EP4171495A1 - Method for coloring anagenic hair with a two component composition - Google Patents

Abstract

The subject of the present disclosure is a method for coloring keratinous material, in particular human hair. In one example, the method includes priming and/or deep cleaning the keratin material and thereafter applying agents (a) and (b) to the keratinous material. The agent (a) comprises at least one organic silicon compound from the group of silanes with one, two or three silicon atoms. An agent (b) comprises a film forming polymer. Either or both of agents (a) and (b) may contain at least one pigment.

Description

METHOD FOR COLORING ANAGENIC HAIR WITH A TWO COMPONENT COMPOSITION

TECHNICAL FIELD

[0001] The subject of the present application is a method for priming and deep cleaning anagenic hair to enable pigment color coatings to provide remanence. Priming and deep cleaning remove sebum, F-layer material, natural oils and other substances from the anagenic hair surfaces. This method enables coloring to provide intimate adherence with the keratinous surfaces of the human hair. The color process comprises the application of at least two different agents (a) and (b). The agent (a) contains at least one organic silicon compound from the group of silanes with one, two or three silicon atoms and furthermore at least one silicone polymer. The agent (a) and/or agent (b) contains at least one pigment.

[0002] The second subject-matter of this application is a multi-component cleaning and packaging unit (kit-of-parts) for coloring keratinous material, in particular human hair, which comprises the materials for priming and deep cleaning as well as agents (a) and (b) separately packaged in two different containers.

BACKGROUND

[0003] Changing the shape and color of keratinous material, especially human hair, is an important area of modern cosmetics. To change the hair color, the expert knows various coloring systems depending on the coloring requirements. Oxidation dyes are usually used for permanent, intensive coloring's with good fastness properties and good grey coverage. Such colorants contain oxidation dye precursors, so-called developer components and coupler components, which, under the influence of oxidizing agents such as hydrogen peroxide, form the actual dyes among themselves. Oxidation dyes are exemplified by very long-lasting coloring results.

[0004] When direct dyes are used, ready-made dyes diffuse from the colorant into the hair fiber. Compared to oxidative hair coloring, the coloring's obtained with direct dyes have a shorter shelf life and quicker wash ability. Coloring with direct dyes usually remain on the hair for a period of between about 5 and about 20 washes. [0005] The use of color pigments is known for short-term color changes on the hair and/or skin. Color pigments are generally understood to be insoluble, coloring substances. These are present undissolved in the color formulation in the form of small particles and are only deposited from the outside on the hair fibers and/or the skin surface. Therefore, they can usually be removed again without residue by a few washes with detergents containing surfactants. Various products of this type are available on the market under the name hair mascara.

[0006] If the user wants a particularly long-lasting color, the use of oxidative dyes has so far been his only option. The hair damage still associated with the use of oxidative dyes also has a negative effect on the user's hair. A continuing challenge is therefore the search for alternative, high-performance coloring processes.

[0007] A prerequisite for a particularly long-lasting coloration on the hair is good wash fastness or remanence, i.e., the film produced on the hair should not wash off because of treatments with aqueous surfactant solutions such as those used in common shampooing. [0008] Apart from shampooing, however, hair is also subject to other stresses in the daily routine, such as the mechanical stress that occurs, for example, when combing, brushing, and styling. A coloring that is in the form of a colored film on the outside of each hair fiber is quite sensitive to the bending, traction and friction of the hair that occurs during combing. [0009] If adhesion is poor or too brittle, the colored film may flake off the hair fiber. In this case, after combing or brushing, the user perceives a reduced color intensity, an irregularity in the coloring and, in the worst case, a mottled color result.

[0010] During the reworking of the coloring processes, it became apparent that the coloring results obtained during these processes still have potential for improvement about their mechanical resistance. The colors obtained in these processes were not yet sufficiently stable to repeated combing and consequently did not yet possess a sufficiently high rub fastness. Therefore, research to develop a high rub fastness coloration product began. However, in the course of this development, it was surprisingly discovered that laboratory investigation did not appropriately represent the coloration issues associated with a person’s hair.

[0011] To date, experimentation to develop keratin fiber coloration such as hair coloration has focused on the use of hair tresses or swatches. These tresses are formed of natural hair but are detached from source (a person) and are usually preprocessed to deliver ease of use for experimental laboratory purposes. Such tresses do not enable experimentation and exploitation of the issues and problems intrinsic with anagenic hair, i.e., hair growing from the scalp of a person. Anagenic hair differs from hair tresses because of hair root, mid-length and tip color differences of anagenic hair, keratin structural differences among and between root, mid and end portions of a living hair, continuous sebum secretions extending from the root to the end portion of each strand of anagenic hair, the individual differences in sebum compositional components from person to person, anagenic hair strand dimension, individualized topographic character of strand surfaces and compositional differences from person to person, the fatty acid or F layer, the variation of curl and color of differing regions of anagenic hair on the scalp, scalp skin issues and environmental factors. Additional differences of anagenic hair relative to hair tresses include but are not limited to lack of cleanliness of anagenic hair, presence of pre-existing hair treatments including but not limited to hair styling formulations, permanent oxidative dye applications, permanent wave and/or curl treatment, application of oils and smoothing compositions and treatments typically applied to anagenic hair. Still other difficulties involve regulatory requirements and the need to avoid tissue damaging and/or environmental attack by sunlight, UV, wind, rain and airborne chemicals, degrading chemicals in water and in hair care and hair dye compositions, as well as sweat and sebum.

[0012] Therefore, improvement of the adherent quality of the dye composition itself has not solved this problem. It has been discovered that the behavior of anagenic hair differs from the behavior of hair in the laboratory because laboratory hair is not continuously bathed in sebum, F-layer materials and natural oils secreted by glands associated with hair follicles, especially those of the human scalp.

SUMMARY

[0013] An aspect of the present invention is directed to solution of problems encountered with anagenic hair. Anagenic hair is hair growing from follicles on the scalp of a person. Sebaceous glands associated with the follicles, sweat glands, pores and dermal excretions bathe anagenic hair in a plethora of substances that repel environmental, bacterial, microscopic pest and foreign agent attack on the hair. Because these substances are continuously delivered to anagenic hair strands, they tend to wash away foreign substances on the strand surfaces, such as but not limited to colored coatings.

[0014] It has been discovered that the combination of priming and/or deep cleaning anagenic hair strands to remove these substances, coupled with certain small molecule compositions that intimately adhere to the resulting bare hair surfaces resists the removal action of the continuous bathing of the hair surfaces by these substances. Surprisingly, it has been discovered that without this combination of aspects, color coatings do not display significant remanence when coated on anagenic hair or its hair tress mimic.

[0015] Therefore, an aspect of the present invention is directed to the combination of deep cleaning and priming coupled with a coloring system with fastness properties (remanence). The color system is based upon pigment particles rather that soluble dye compounds that penetrate the cuticle of the hair shaft. The process or method using the color system involves at least two agents (a) and (b) are applied to the keratinous materials (hair). Here, the agent

(a) contains at least one organic silicon compound (from the group of reactive silanes). The agent (b) comprises a hydrophobic film forming polymer and at least one colorant compound selected from the group including pigments. When anagenic hair and/or mimic hair tresses are primed, deep cleaned and coated with both agents (a) and (b) the resulting coating displays high color intensity and significant remanence.

[0016] In an exemplary embodiment, a method for coloring keratinous material is provided. The method includes applying an agent (a) to the keratinous material that has been primed and deep cleaned. The agent (a) includes at least one organic silicon compound from the group of silanes with one, two or three silicon atoms. The agent (a) further includes at least one silicone polymer. An agent (b) is applied to the keratinous material. The agent (a) and /or

(b) includes at least one pigment and a hydrophobic film forming polymer. DESCRIPTION

[0017] The desirable characteristics of the color coatings on keratin fibers, preferably anagenic hair, may be demonstrated by tests of the coloration on hair tresses prepared from unbleached natural white human hair (hereinafter untreated hair tresses and untreated hair tresses specially prepared with sebum so as to mimic anagenic hair (hereinafter mimic hair tresses) . The two base line forms of hair tresses (untreated and treated hair tresses) are not anagenic hair in that they are cut natural hair so that they are not bathed in sebum secretion. The untreated hair tresses are substantially hydrophobic, have low porosity and have little or no keratin protein surface disruption. The treated hair tresses are substantially less hydrophobic to more hydrophilic than, and have greater porosity than, the untreated hair tresses. The treated hair tresses also display low to mild keratin protein surface disruption. [0018] In contrast to treated and untreated hair tresses, mimic hair tresses are especially treated to demonstrate the sebum, F layer, grubbiness, foulness, and root, mid-length and tip issues associated with anagenic hair and especially those associated with the root segment of anagenic hair, The root segment of anagenic hair is constantly bathed in sebum so that the root segment of anagenic hair shows the most extreme behavior difference relative to treated and untreated hair tresses. To establish the mimicry, untreated hair tresses undergo a series of preparations designed to establish a close comparison with the behavior of anagenic hair, especially the root segments. To this end, the color coatings described herein have been studied with mimic hair tresses, untreated hair tresses. Untreated and mimic hair tresses are accordingly are able to serve as the substrates for experimental development of the embodiments of the color coatings and methods for hair coloration.

[0019] When color coatings are formed onto untreated and onto treated tresses, long lasting remanence is exhibited. However, when the same color coatings are applied to anagenic hair such as the hair of a live salon hair model, remanence disappears. For efficiency of experimental practice, the above described mimic hair tress has been developed to come as close as possible to the behavior of anagenic hair, especially the root segments of anagenic hair. Through use of the mimic hair tress, it has been surprisingly discovered that the combination of the Praeparatur and Fundamenta techniques and the condensed small molecule network coupled with the film of agent (b) preserve remanence for color coatings on mimic hair whereas those color coatings on mimic hair prepared without application of the Praeparatur and/or Fundamenta techniques demonstrate significant to almost full fading during the multiple shampoo applications designed to examine remanence in real life conditions.

[0020] In the following detailed description, chemical formulas list groups with subscripts, superscripts and without subscripts and superscripts. These are synonyms so that for example Cl and Ci both mean the same, a single carbon. Similarly, a C1-C4 alkyl means the same as a Ci -C4 alkyl in that both mean an alkyl formed of one, two, three or four carbons. Similarly, R1 and R¹ mean the same, the first substituent R in contrast to a second R substituent having the definition R2 or R².

[0021] Another object of the present disclosure is a method for coloring keratinous material, in particular human hair, comprising the following steps:

A) Prime and/or Deep clean the keratinous material;

B) Application of an agent (a) to the keratinous material, wherein the agent (a) contains at least one organic silicon compound from the group of silanes with one, two or three silicon atoms,

C) Application of an agent (b) to the keratinous material, the agent (b) comprising a hydrophobic film forming polymer. D) A pigment material may be incorporated in either agent (a) or agent (b), preferably in agent (b).

Keratinous Material

[0022] Keratinous material includes hair, especially anagenic hair and/or hair tresses coated with a synthetic form of sebum. Hair cut from the head of a person is the typical hair used to form hair tresses. Hair tresses are the typical experimental hair substrate used by all research and development organizations investigating treatments of hair. Cut hair and hair tresses are not anagenic hair because they are not continuously bathed in sebum, fatty acid and natural oil secretions produced by the glands surrounding hair follicles on a person’s head and do not always have an intact fatty acid layer. However, hair tresses may be modified to imitate as close as possible anagenic hair by coating the tresses with synthetic sebum and recoating the tresses with sebum during the remanent testing.

Agent (a) and (b)

[0023] In the procedure as contemplated herein, agents (a) and (b) are applied to the keratinous material, in particular human hair. The two means (a) and (b) are different.

[0024] In other words, a first subject of the present disclosure is a method for coloring keratinous material, in particular human hair, comprising the following steps. a) Application of an agent (a) to the keratinous material, wherein the agent (a) contains at least one organic silicon compound from the group of silanes with one, two or three silicon atoms, b) Application of an agent (b) to the keratinous material, the agent (b) comprising a hydrophobic film forming polymer. Either or both of agents (a) and (b) may also comprise pigment material, and preferably pigment material is included with agent (b). The two agents (a) and (b) being different from each other.

Agent (a)

[0025] As a first ingredient essential to the present disclosure, the composition (a) contains at least one organic silicon compound selected from silanes having one, two or three silicon atoms and optionally one or more pigment materials.

[0026] As already described, the organic silicon compounds or organic silanes contained in agent (a) are reactive compounds. [0027] The agent (a) contains the organic silicon compound(s) from the group of silanes in a cosmetic carrier, which may be water-containing, water-poor or also water-free. In addition, the cosmetic carrier can be liquid, gel-like, creamy, powdery, or even solid (e.g., in the form of a tablet or pellet). Preferably, the cosmetic carrier of the product (a) is an aqueous or aqueous-alcoholic carrier. To hair coloration, such carriers are, for example, creams, emulsions, gels, or surfactant-containing foaming solutions, such as shampoos, foam aerosols, foam formulations or other preparations suitable for application to the hair.

[0028] The cosmetic carrier may contain water in circumstances directed to use, which means that the carrier contains at least about 2% by weight of water based on its weight. Preferably, the water content is above about 5 wt. %, further preferably above about 10 wt. % still further preferably above about 15 wt. %. The cosmetic carrier can also be aqueous alcoholic. Aqueous/alcoholic solutions in the context of the present disclosure are aqueous solutions containing from about 2 to about 70% by weight of a Cl -C4 alcohol, more particularly ethanol or isopropanol. The agents as contemplated herein may additionally contain other organic solvents, such as methoxybutanol, benzyl alcohol, ethyl di glycol or 1,2- propylene glycol. Preferred are all water-soluble organic solvents.

[0029] However, the cosmetic carrier for agent (a) preferably is anhydrous in situations involving storage, maintenance, and situations other than immediate use of agent (a). The silanes of agent(a) are reactive in that they hydrolyze and condense to form Si-O-Si networks. The presence of water as part of the carrier will eventually lead to hydrolysis and condensation. In situations in which agent (a) is prepared for use, water may be added to the cosmetic carrier of agent (a) to initiate and promote the hydrolysis and condensation of the silanes. The result of the condensation of the silanes is a silicone network forming a film in situ by oligomerization or polymerization of the organic silicon compound(s). The silicone network also interacts with the hydrophobic film forming polymer of agent (b) by physical combination to form the overall color coating on the keratinous material.

[0030] The term "coloring agent" is used in the context of this present disclosure for a coloring of the keratin material, in particular the hair, caused using pigments. During this coloring process, the coloring compounds are deposited in a particularly homogeneous and smooth hydrophobic film on the surface of the keratin material. The coloring agent is typically part of agent (b), the pigment particles and hydrophobic film. Organic Silicon Compounds

[0031] As the first ingredient essential to the present disclosure, the agent (a) contains at least one organic silicon compound selected from the group including silanes having one, two or three silicon atoms.

[0032] Organic silicon compounds, alternatively called organosilicon compounds, are compounds which either have a direct silicon-carbon bond (Si— C) or in which the carbon is bonded to the silicon atom via an oxygen, nitrogen, or sulfur atom. The organic silicon compounds of the present disclosure are compounds containing one to three silicon atoms. Organic silicon compounds preferably contain one or two silicon atoms.

[0033] According to IUPAC rules, the term silane chemical compounds based on a silicon skeleton and hydrogen. In organic silanes, the hydrogen atoms are completely or partially replaced by organic groups such as (substituted) alkyl groups and/or alkoxy groups. In organic silanes, some of the hydrogen atoms may also be replaced by hydroxy groups.

[0034] The agent (a) contains at least one organic silicon compound selected from silanes having one, two or three silicon atoms wherein the organic silicon compound preferably comprises one or more hydroxyl groups or hydrolysable groups per molecule.

[0035] In a particularly preferred embodiment, a method as contemplated herein is exemplified by the application of an agent (a) to the keratinous material, said agent (a) comprising at least one organic silicon compound selected from silanes having one, two or three silicon atoms, said organic silicon compound further comprising one or more hydroxyl groups or hydrolysable groups per molecule.

[0036] In a particularly preferred embodiment, a method as contemplated herein is exemplified by the application of an agent (a) to the keratinous material, said agent (a) comprising at least one organic silicon compound selected from silanes having one, two or three silicon atoms, said organic silicon compound further comprising one or more basic chemical functions and one or more hydroxyl groups or hydrolysable groups per molecule. [0037] This basic group can be, for example, an amino group, an alkylamino group or a dialkylamino group, which is preferably connected to a silicon atom via a linker. The basic group is preferably an amino group, a C1-C6 alkylamino group or a di(Cl-C6)alkylamino group.

[0038] The hydrolysable group(s) is (are) preferably a C1-C6 alkoxy group, especially an ethoxy group or a methoxy group. It is preferred when the hydrolysable group is directly bonded to the silicon atom. For example, if the hydrolysable group is an ethoxy group, the organic silicon compound preferably contains a structural unit R'R"R"'Si— O — CH_{2 —} CFF. The residues R', R' and R'" represent the three remaining free valences of the silicon atom. [0039] A particularly preferred method as contemplated herein the composition comprises (a) at least one organic silicon compound selected from silanes having one, two or three silicon atoms, the organic silicon compound preferably comprising one or more basic chemical functions and one or more hydroxyl groups or hydrolysable groups per molecule.

[0040] Particularly good results could be obtained if the agent as contemplated herein (a) contains at least one organic silicon compound of formula (I) and/or (II).

[0041] The compounds of formulae (I) and (II) are organic silicon compounds selected from silanes having one, two or three silicon atoms, the organic silicon compound comprising one or more hydroxyl groups and/or hydrolysable groups per molecule.

[0042] In another very particularly preferred embodiment, a method as contemplated herein an agent (a) is applied to the keratinous material (or human hair), the agent (a) comprising at least one organic silicon compound (a) of the formula (I) and/or (II),

RiR₂N-L-Si(OR₃)_a(R4)b Formula I where

Ri, R₂ independently represent a hydrogen atom or a C1-C6 alkyl group, L is a linear or branched divalent C1-C20 alkylene group,

R3 represents a hydrogen atom or a C1-C6 alkyl group

R4 represents a C1-C6 alkyl group a, stands for an integer from 1 to 3, and b stands for the integer 3-a (i.e., 3 minus the value of a),

(R50)c(R6)dSi-(A)e[NR7-(A^,)]f-[0-(A^{, ,})]g-[NR8-(A”]h-Si-(R6^,)d(OR5^,)c’ II

Formula II where

R5, R5', R5" independently represent a hydrogen atom or a C1-C6 alkyl group,

R6, R6' and R6" independently represent a C1-C6 alkyl group,

A, A', A", A'" and A"" independently of one another represent a linear or branched divalent C1-C20 alkylene group, R7 and R5 independently represent a hydrogen atom, a C1-C6 alkyl group, a hydroxy C1-C6 alkyl group, a C2-C6 alkenyl group, an amino C1-C6 alkyl group or a group of formula (III),

-(A"")-Si(R₆")_d"(OR₅")_c" (IP), c, stands for an integer from 1 to 3, d stands for the integer 3-c, c' stands for an integer from 1 to 3, d' stands for the integer 3-c', c" stands for an integer from 1 to 3, d" stands for the integer 3-c", e stands for 0 or 1, f stands for 0 or 1, g stands for 0 or 1, h stands for 0 or 1, provided that at least one of e, f, g, and h is different from 0.

[0043] The substituents Rl, R2, R3, R4, R5, R5', R5", R6, R6', R6", R7, R8, L, A, A', A", A'" and A"" in the compounds of formula (I) and (II) are explained below as examples: Examples of a C1-C6 alkyl group are the groups methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl, and t- butyl, n-pentyl and n-hexyl. Propyl, ethyl, and methyl are preferred alkyl radicals. Examples of a C2-C6 alkenyl group are vinyl, allyl, but-2-enyl, but-3-enyl and isobutenyl, preferred C2-C6 alkenyl radicals are vinyl and allyl. Preferred examples of a hydroxy C1-C6 alkyl group are a hydroxymethyl, a 2-hydroxy ethyl, a 2-hydroxypropyl, a 3-hydroxypropyl, a 4- hydroxybutyl group, a 5-hydroxypentyl and a 6-hydroxyhexyl group; a 2-hydroxyethyl group is particularly preferred. Examples of an amino C1-C6 alkyl group are the aminomethyl group, the 2-aminoethyl group, the 3-aminopropyl group. The 2-aminoethyl group is particularly preferred. Examples of a linear divalent C1-C20 alkyl ene group include the methylene group (— CH2), the ethylene group (— CH2— CH2— ), the propylene group (— CH2— CH2— CH2— ) and the butylene group (— CH2— CH2— CH2— CH2— ). The propylene group (— CH2— CH2— CH2— ) is particularly preferred. From a chain length of 3 C atoms, divalent alkylene groups can also be branched. Examples of branched divalent C2-C2O alkylene groups are (~CH2~CH(CH3)~) and (~CH2-CH(CH3)-CH2-).

[0044] In the organic silicon compounds of the formula (I)

RlR2N-L-Si(OR3)a(R4)_b (I) the radicals Rl and R2 independently of one another represent a hydrogen atom or a C1-C6 alkyl group. In particular, the radicals Rl and R2 both represent a hydrogen atom. [0045] In the middle part of the organic silicon compound is the structural unit or the linker - L- which stands for a linear or branched, divalent C1-C20 alkylene group.

[0046] Preferably -L- stands for a linear, divalent C1-C20 alkylene group. Further preferably -L- stands for a linear divalent C1-C6 alkylene group. Particularly preferred -L- stands for a methylene group (— CH2— ), an ethylene group (— CH2— CH2— ), propylene group (— CH2— CH2— CH2— ) or butylene (— CH2— CH2— CH2— CH2— ). L stands for a propylene group (— CH2-CH2-CH2-).

[0047] The organic silicon compounds of formula (I)

RlR2N-L-Si(OR3)a(R4)_b (I) one end of each carries the silicon-containing group — Si(OR3)a(R4)_b.

In the terminal structural unit — Si(OR3)_a(R4)_b, R3 is hydrogen or C1-C6 alkyl group, and R4 is C1-C6 alkyl group. R3 and R4 independently of each other represent a methyl group or an ethyl group. Here a stands for an integer from 1 to 3, and b stands for the integer 3-a. If a stands for the number 3, then b is equal to 0. If a stands for the number 2, then b is equal to 1. If a stands for the number 1, then b is equal to 2.

[0048] Colors with the best wash fastness values could be obtained if the pretreatment agent contains at least one organic silicon compound corresponding to formula (I): in which R3, R4 independently of one another represent a methyl group or an ethyl group.

[0049] Furthermore, color with the best wash fastness properties could be obtained if the agent as contemplated herein contains at least one organic silicon compound of formula (I) in which the radical a represents the number 3. In this case the rest b stands for the number 0. [0050] In another preferred embodiment, an agent as contemplated herein contains (a) at least one organic silicon compound of formula (I), where R3, R4 independently of one another represent a methyl group or an ethyl group and a stands for the number 3 and b stands for the number 0.

[0051] In another preferred embodiment, a method as contemplated herein the agent (a) contains at least one organic silicon compound of formula (I)

RlR2N-L-Si(OR3)a(R4)_b (I), where Rl, R2 both represent a hydrogen atom, and

L represents a linear, divalent Cl-C6-alkylene group, preferably a propylene group (— CH2— CH2— CH2— ) or an ethylene group (— CH2— CH2— ),

R3 represents a hydrogen atom, an ethyl group, or a methyl group, R4 represents a methyl group or an ethyl group, a stands for the number 3 and b stands for the number 0.

[0052] Organic silicon compounds of the formula (I) which are particularly suitable for solving the problem as contemplated herein are as follows.

- (3-Aminopropyl)triethoxysilan

- (3 -Aminopropyl)trimethoxy silane

-l-(3-Aminopropyl)silantriol

- (2-Aminoethyl)triethoxysilan

- (2 -Aminoethyl)triethoxy silane

- (3 -Diniethylaniinopropy l)triethoxysilan

- (3 -Dimethylaminopropy l)trimet oxysilane

- 1 -(3 -Dimetliylaminopropyl)silantriol

-(2-Dimethylammoethyl)trimet oxysilan.

-(2-Dimethylammoethyl)trimethoxysilane and/or

- 1 - (2 - Dimethy lamino ethy l)silantriol

[0053] In a further preferred embodiment, a method as contemplated herein the agent (a) comprises at least one organic silicon compound of formula (I) selected from the group including (3 -Aminopropyl)tri ethoxy silane, (3 -Aminopropyl)trimethoxy silane, l-(3- Aminopropyl) silantriol, (2- Aminoethyl)tri ethoxy silane, (2 -Aminoethyl)trimethoxy silane 1- (2-Aminoethyl)silantriol, (3-Dimethylaminopropyl)triethoxysilane, (3- Dimethylaminopropyl)trimethoxy silane, l-(3-Dimethylaminopropyl)silantriol (2- Dimethylaminoethyl)triethoxysilane, (2-Dimethylaminoethyl)trimethoxysilane and/or l-(2- Dimethylaminoethyl)silantriol.

[0054] The organic silicon compound of formula (I) is commercially available. (3- aminopropyl)trimethoxysilane, for example, can be purchased from Sigma-Aldrich. Also (3- aminopropyl)triethoxysilane is commercially available from Sigma-Aldrich.

[0055] In a further version, the present disclosure contains at least one organic silicon compound of formula (II) (R50)c(R6)dSi-(A)e[NR7-(A^,)]f-[0-(A^{, ,})]g-[NR8-(A”]h-Si-(R6^,)d(OR5^,)c’ II

[0056] The organosilicon compounds of formula (II) as contemplated herein each carry the silicon-containing groups (R50)_c(R6)_dSi— and — Si(R6')_d'(OR5')_C’ at both ends.

[0057] In the central part of the molecule of formula (II) there are the groups -(A)_e- and — [NR7-(A')]_f- and [0-(A")]_g”'~ and — [NR8-(A"')]_h— . Here, each of the radicals e, f, g, and h can independently of one another stand for the number 0 or 1, with the proviso that at least one of the radicals e, f, g, and h is different from 0. In other words, an organic silicon compound of formula (II) as contemplated herein contains at least one grouping from the group including -(A)- and — [NR7-(A')]- and — [0-(A")]— and — [NR8-(A"')]~.

[0058] In the two terminal structural units (R50)_c(R6)_dSi— and — Si(R6')_d (OR5')_c% the radicals R5, R5', R5" independently of one another represent a hydrogen atom or a C1-C6 alkyl group. The radicals R6, R6' and R6" independently represent a C1-C6 alkyl group. [0059] Here a stands for an integer from 1 to 3, and d stands for the integer 3-c. If c stands for the number 3, then d is equal to 0. If c stands for the number 2, then d is equal to 1. If c stands for the number 1, then d is equal to 2. Analogously c' stands for a whole number from 1 to 3, and d' stands for the whole number 3-c'. If c' stands for the number 3, then d' is 0. If c' stands for the number 2, then d' is 1. If c' stands for the number 1, then d' is 2.

[0060] Coloration with the best wash fastness values could be obtained if the residues c and c' both stand for the number 3. In this case d and d' both stand for the number 0.

[0061] In another preferred embodiment, a method as contemplated herein the agent (a) contains at least one organic silicon compound of formula (II),

(R50)_c(R6)_dSi-(A)_e[NR7-(A^,)]_f-[0-(A”)]g-[NR8-(A”]_h-Si-(R6^,)_ci(0R5^,)_c’ II where R5 and R5' independently represent a methyl group or an ethyl group, c and c' both stand for the number 3 and d and d' both stand for the number 0.

[0062] If c and c' are both the number 3 and d and d' are both the number 0, the organic silicon compound of the present disclosure corresponds to formula (Ila)

(R50)₃Si-(A)e-[NR7-(A^,)]f-[0-(A^{, ,})]_g-[NR8-(A^{, ,}]h-Si(0R5^,)3 Ila [0063] The radicals e, f, g, and h can independently stand for the number 0 or 1, whereby at least one radical from e, f, g, and h is different from zero. The abbreviations e, f, g, and h thus define which of the groupings -(A)_e- and — [NR2-(A')]_f- and — [0-(A")]_g and — [NR8-(A"')]_h- are in the middle part of the organic silicon compound of formula (II).

[0064] In this context, the presence of certain groupings has proved to be particularly beneficial in terms of increasing washability. Particularly good results were obtained when at least two of the residues e, f, g, and h stand for the number 1. Especially preferred e and f both stand for the number 1. Furthermore, g and h both stand for the number 0.

[0065] If e and f both stand for the number 1 and g and h both stand for the number 0, the organic silicon compound as contemplated herein corresponds to formula (lib)

(R50)c(R6)_dSi-(A)-[NR7-(A^,)]-Si-(R6^,)_d(0R5^,)c_’ Db

[0066] The radicals A, A', A", A'" and A"" independently represent a linear or branched divalent C1-C20 alkylene group. Preferably the radicals A, A', A", A'" and A"" independently of one another represent a linear, divalent C1-C20 alkylene group. Further preferably the radicals A, A', A", A'" and A"" independently represent a linear divalent C1-C6 alkylene group. In particular, the radicals A, A', A", A'" and A"" independently of one another represent a methylene group (— CH2— ), an ethylene group (— CH2— CH2— ), a propylene group (— CH2— CH2— CH2— ) or a butylene group (— CH2— CH2— CH2— CH2— ). In particular, the residues A, A', A", A'" and A"" stand for a propylene group (— CH2— CH2— CH2— ).

[0067] If the radical f represents the number 1, then the organic silicon compound of formula (II) as contemplated herein contains a structural grouping — [NR7-(A')]-. If the radical f represents the number 1, then the organic silicon compound of formula (II) as contemplated herein contains a structural grouping — [NR8-(A"')]-.

[0068] Wherein R7 and R8 independently represent a hydrogen atom, a C1-C6 alkyl group, a hydroxy-Cl-C6 alkyl group, a C2-C6 alkenyl group, an amino-Cl-C6 alkyl group or a group of the formula (III)

-(A”’)-Si(R6”)_d(OR5”)_c” preferably the radicals R7 and R8 independently of one another represent a hydrogen atom, a methyl group, a 2-hydroxyethyl group, a 2-alkenyl group, a 2-aminoethyl group or a grouping of the formula (III). [0069] If the radical f represents the number 1 and the radical h represents the number 0, the organic silicon compound as contemplated herein contains the grouping [NR7-(A')] but not the grouping — [NR8-(A"')] If the radical R7 now stands for a grouping of the formula (III), the pretreatment agent (a) contains an organic silicon compound with 3 reactive silane groups.

[0070] In another preferred embodiment, a method as contemplated herein the agent (a) contains at least one organic silicon compound of formula (II),

(R50)_c(R6)_dSi-(A)_e[NR7-(A^,)]_f-[0-(A”)]g-[NR8-(A”]_h-Si-(R6^,)_ci(0R5^,)_c’ II where e and f both stand for the number 1, g and h both stand for the number 0, A and A' independently represent a linear, divalent C1-C6 alkylene group and R7 represents a hydrogen atom, a methyl group, a 2-hydroxyethyl group, a 2-alkenyl group, a 2-aminoethyl group or a group of formula (III).

[0071] In a further preferred embodiment, a method as contemplated herein the agent (a) contains at least one organic silicon compound of the formula (II), where e and f both stand for the number 1, g and h both stand for the number 0, A and A' independently of one another represent a methylene group (— CH2— ), an ethylene group (— CH2 — CH2— ) or a propylene group (— CH2-CH2 — CH2), and R7 represents a hydrogen atom, a methyl group, a 2-hydroxyethyl group, a 2-alkenyl group, a 2-aminoethyl group or a group of formula (III).

[0072] Organic silicon compounds of the formula (II) which are well suited for solving the problem as contemplated herein are

- 3- (trimethoxysilyl)-N- [3- (trimethoxysilyl)propyl]-l -propanamine

- 3 - (Triethoxysily 1)-N- [3- (triethoxysilyl)propyl] - 1 -propanamine

- N-methyl-3- (trimethoxysilyl)-N- [3- (trimethoxysilyl)propyl]-l- propanamine

- N-methyl-3- (triethoxysilyl)-N- [3- (triethoxy silyl)propyl] - 1 - propanamine

- 2-[Bis[3-(trimetlioxysilyl)propyl]amino]-ethanol

- 2 -[bis [3- (triethoxy si lyl)propyl] amino] -ethano 1

- 3 - (Tri ethoxysilyl)-N,N-bis [3- (trimethoxy silyl)propyl] -1 - propanamine

- 3-(Triethoxysilyl)-N,N-bis[3-(triethoxysilyl)propyl]-l-propanamme

- N 1 ,N 1 -B is [3 -(triethoxys ily l)propyl ] - 1 ,2- etlianediamine ,

- H,M-Bis[3-(trimethoxysilyl)propyl]-2-propen- 1 -amine

- N,N-Bis[3-(trietlioxysilyl)propyl]-2-propen- 1-amine

[0073] The organic silicon compounds of formula (II) are commercially available.

[0074] Bis(trimethoxysilylpropyl)amines with the CAS number 82985-35-1 can be purchased from Sigma-Aldrich. Bis[3-(triethoxysilyl)propyl]amines with the CAS number 13497-18-2 can be purchased from Sigma-Aldrich, for example. N-methyl-3-(trimethoxysilyl)-N-[3- (trimethoxysilyl)propyl]-l-pro- panamine is alternatively referred to as bis(3- trimethoxysilylpropyl)-N-methylamine and can be purchased commercially from Sigma- Aldrich or Fluorochem. 3-(triethoxysilyl)-N,N-bis[3-(triethoxysilyl)propyl]-l-propanamine with the CAS number 18784-74-2 can be purchased for example from Fluorochem or Sigma- Aldrich.

[0075] In another preferred embodiment, an agent as contemplated herein contains (a) at least one organic silicon compound of formula (II) selected from the group including 3 -(trimethoxysilyl)-N-[3 -(trimethoxysilyl)propyl]- 1 -propanamine 3-(Triethoxysilyl)-N-[3-(triethoxysilyl)propyl]-l -propanamine N-methyl-3-(trimethoxysilyl)-N-[3-(trimethoxysilyl)propyl]-l-propanamine N-Methyl-3-(triethoxysilyl)-N-[3-(triethoxysilyl)propyl]-l-propanamine 2-[Bis[3-(trimethoxysilyl)propyl]amino]-ethanol

2-[bis[3-(triethoxysilyl)propyl]amino]ethanol

3-(Trimethoxysilyl)-N,N-bis[3-(trimethoxysilyl)propyl]-l-propanamine [0143] 3- (Triethoxysilyl)-N,N-bis[3-(triethoxysilyl)propyl]-l-propanamine [0144] Nl,Nl-bis[3- (trimethoxysilyl)propyl]-l,2-ethanediamine,

N1 ,N1 -bis[3 -(triethoxysilyl)propyl]- 1 ,2-ethanediamine, N,N-bis[3-(trimethoxysilyl)propyl]-2-propen-l-amine and/or N,N-bis[3-(triethoxysilyl)propyl]-2-propen-l -amine.

[0076] In further coloring tests, it has also proved to be particularly advantageous if the agent used on the keratinous material in the method as contemplated herein (a) contains at least one organic silicon compound of formula (IV)

R9Si(ORl0)k(Rll)m (IV).

[0077] The compounds of formula (IV) are organic silicon compounds selected from silanes having one, two or three silicon atoms, the organic silicon compound comprising one or more hydroxyl groups and/or hydrolysable groups per molecule.

[0078] The organic silicon compound(s) of formula (IV) may also be called a silane of the alkyl-alkoxy-silane or alkyl-hydroxy-silane type,

R9Si(ORl0)k(Rll)m (IV), where

R₉ represents a Cl -Cl 2, alkyl group, Rio represents a hydrogen atom or a C1-C6 alkyl group, R₁₁ represents a C1-C6 alkyl group, k is an integer from 1 to 3, and m stands for the integer 3-k.

[0079] In another preferred embodiment, a method as contemplated herein the agent (a) contains at least one organic silicon compound of formula (IV).

R9Si(ORl0)k(Rll)m (IV), where

R9 represents a Cl -Cl 2, alkyl group, R10 represents a hydrogen atom or a C1-C6 alkyl group, R11 represents a C1-C6 alkyl group, k is an integer from 1 to 3, and m stands for the integer 3-k.

[0080] In a further preferred embodiment, a method as contemplated herein the agent (a) contains, in addition to the organic silicon compound(s) of formula (I), at least one further organic silicon compound of formula (IV)

R9Si(ORl0)k(Rll)m (IV), where

R9 represents a Cl -Cl 2, alkyl group, RIO represents a hydrogen atom or a C1-C6 alkyl group, R11 represents a C1-C6 alkyl group, k is an integer from 1 to 3, and m stands for the integer 3-k.

[0081] In a further preferred embodiment, a method as contemplated herein the agent (a) contains, in addition to the organic silicon compound or compounds of the formula (II), at least one further organic silicon compound of the formula (IV)

R9Si(ORl0)k(Rll)m (IV), whereR9 represents a Cl -C 12 alkyl group, R10 represents a hydrogen atom or a C1-C6 alkyl group, R11 represents a C1-C6 alkyl group, k is an integer from 1 to 3, and m stands for the integer 3-k.

[0082] In a further preferred embodiment, a method as contemplated herein the composition contains (a) in addition to the organic silicon compound(s) of formula (I) and/or (II) at least one further organic silicon compound of formula (IV)

R9Si(ORl0)k(Rll)m (IV), where R9 represents a Cl -Cl 2, alkyl group, R10 represents a hydrogen atom or a C1-C6 alkyl group, R11 represents a C1-C6 alkyl group, k is an integer from 1 to 3, and m stands for the integer 3-k.

[0083] In the organic silicon compounds of formula (IV), the radical R9 represents a Cl -Cl 2 alkyl group. This Cl -Cl 2, alkyl group is saturated and can be linear or branched. Preferably R9 stands for a linear Cl-C.sub.8 alkyl group. Preferably R9 stands for a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n- octyl group or an n-dodecyl group. Particularly preferred, R9 stands for a methyl group, an ethyl group or an n-octyl group.

[0084] In the organic silicon compounds of formula (IV), the radical R10 represents a hydrogen atom or a C1-C6 alkyl group. R10 stands for a methyl group or an ethyl group. [0085] In the organic silicon compounds of formula (IV), the radical Ru represents a C1-C6 alkyl group. R11 stands for a methyl group or an ethyl group.

[0086] Furthermore, k stands for a whole number from 1 to 3, and m stands for the whole number 3-k. If k stands for the number 3, then m is equal to 0. If k stands for the number 2, then m is equal to 1. If k stands for the number 1, then m is equal to 2.

[0087] Colors with the best wash fastness values could be obtained if an agent (a) were used in the method which contains at least one organic silicon compound of the formula (IV) in which the radical k stands for the number 3. In this case the rest m stands for the number 0. [0088] Organic silicon compounds of the formula (IV) which are particularly suitable for solving the problem as contemplated herein are

- M ethy ltr imeth oxy s i lane

- Ethyltrimethoxy silane

- n-Hexyltriethoxysilane

- n-Octyltrimethoxysilane

- n-Octyltrietlioxysilane

- n-dodecyltrimethoxysilane and/or

- n-dodecyltrietlioxysilane

[0089] In another preferred embodiment, a method as contemplated herein the agent (a) contains at least one organic silicon compound of formula (IV) selected from the group including

Methyltrimethoxysilane

Methyltri ethoxy silane

Ethyltrimethoxy silane

Ethyltriethoxysilane

Hexyltrimethoxysilane

Hexyltriethoxysilane

Octyltrimethoxysilane

Octyltriethoxysilane

Dodecyltrimethoxysilane and/or

Dodecyltriethoxysilane.

[0090] In an explicitly particularly preferred embodiment, a method as contemplated herein an agent (a) is applied to the keratinous material which contains at least one organic silicon compound of the formula (I) which is selected from the group including (3- aminopropyl)triethoxysilane and (3-aminopropyl)trimethoxysilane, and additionally contains at least one organic silicone compound of formula (IV) selected from the group including methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane and ethyltriethoxysilane.

[0091] The organic silicon compounds described above are reactive compounds. In this context, it has been found preferable if the agent (a) as contemplated herein contains— based on the total weight of the agent (a)— one or more organic silicon compounds from the group of silanes having one, two or three silicon atoms in a total amount of the one or more compounds from about 0.1 to about 95.0% by weight, preferably from about 1.0 to about 90.0% by weight and particularly preferably from about 2.0 to about 90% by weight.

[0092] In a further preferred embodiment, a method as contemplated herein the agent (a)— based on the total weight of agent (a)— contains one or more organic silicon compounds in a total amount of the one or more compounds from about 0.1 to about 95.0% by weight, preferably from about 1.0 to about 90.0% by weight and particularly preferably from about 2.0 to about 90.0% by weight.

[0093] To achieve particularly good coloring results, it is particularly advantageous to use the organic silicon compounds of the formula (I) and/or (II) in certain quantity ranges on average (a). Particularly preferably, the agent (a) contains— based on the total weight of the agent (a)— one or more organic silicon compounds of the formula (I) and/or (II) in a total amount of from about 0.1 to about 60.0% by weight, preferably from about 0.5 to about 55.0% by weight and particularly preferably from about 1.0 to about 55.0% by weight.

[0094] In a further preferred embodiment, a method as contemplated herein the agent (a) contains— based on the total weight of the agent (a) one or more organic silicon compounds of the formula (I) and/or (II) in a total amount of from about 0.1 to about 95.0% by weight, preferably from about 0.5 to about 55.0% by weight and particularly preferably from about 1.0 to about 50.0% by weight.

[0095] Furthermore, it has proven to be particularly preferred if the organic silicon compound(s) of formula (IV) is (are) also present in certain quantity ranges in average (a). Particularly preferably the agent (a) contains— based on the total weight of agent (a) one or more organic silicon compounds of the formula (IV) in a total amount of from about 0.1 to about 95.0% by weight, preferably from about 2.0 to about 90.0% by weight and particularly preferably from about 3.0 to about 85.0% by weight.

[0096] In a further preferred embodiment, a method as contemplated herein the agent (a) contains— based on the total weight of the agent (a) one or more organic silicon compounds of the formula (IV) in a total amount of from about 0.1 to about 95.0% by weight, preferably from about 2.0 to about 90.0% by weight and particularly preferably from about 3.0 to about 85.0% by weight.

[0097] In the course of the work leading to this present disclosure it turned out that particularly stable and uniform films could be obtained on the keratin material if the agent (a) contains two structurally different organic silicon compounds.

[0098] In another preferred embodiment, a method as contemplated herein the agent (a) contains at least two structurally different organic silicon compounds.

[0099] In an explicitly particularly preferred embodiment, a method as contemplated herein an agent (a) is applied to the keratinous material which contains at least one organic silicon compound of the formula (I) which is selected from the group including (3- aminopropyl)triethoxysilane and (3-aminopropyl)trimethoxysilane, and additionally contains at least one organic silicon compound of the formula (IV) which is selected from the group including methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane and ethyltriethoxysilane.

[00100] In a further preferred embodiment, a method as contemplated herein the agent (a) based on the total weight of agent (a) contains from about 0.5 to about 60.0 weight % of at least one first organic silicon compound selected from the group of (3- aminopropyl)trimethoxysilane, (3-aminopropyl)triethoxysilane, (2- aminoethyl)trimethoxy silane, (2-aminoethyl)tri ethoxy silane, (3- dimethylaminopropyl)trimethoxysilane, (3-dimethylaminopropyl)triethoxysilane (2- dimethylaminoethyl)trimethoxysilane and (2-dimethylaminoethyl)triethoxysilane, and from about 3.0 to about 85.0% by weight of at least one second organic silicon compound selected from the group of methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, dodecyltrimethoxysilane and dodecyltriethoxysilane.

[00101] In this version, the agent contains (a) one or more organic silicon compounds of a first group in a total amount of from about 0.5 to about 5.0% by weight. The organic silicon compounds of this first group are selected from the group of (3- aminopropyl)trimethoxysilane, (3-aminopropyl)triethoxysilane, (2- aminoethyl)trimethoxy silane, (2-aminoethyl)tri ethoxy silane, (3- dimethylaminopropyl)trimethoxysilane, (3-dimethylaminopropyl)triethoxysilane (2- dimethylaminoethyl)trimethoxysilane and/or (2-dimethylaminoethyl)triethoxysilane.

[00102] In this version, the agent contains (a) one or more organic silicon compounds of a second group in a total amount of from about 2 wt% to about 10.0% by weight. The organic silicon compounds of this second group are selected from the group of methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, dodecyltrimethoxysilane and/or dodecy ltri ethoxy sil ane .

Pigment

[00103] Pigments may be included in either or both of agents (a) and (b) and preferably are included in agent (b).

[00104] Pigments within the meaning of the present disclosure are coloring compounds which have a solubility in water at about 25 °C of less than about 0.5 g/L, preferably less than about 0.1 g/L, even more preferably less than about 0.05 g/L.

[00105] Water solubility can be determined, for example, by the method described below: about 0.5 g of the pigment are weighed in a beaker. A magnetic stirrer is added. Then one liter of distilled water is added. This mixture is heated to about 25 ^{0 0} C. for one hour while stirring on a magnetic stirrer. If undissolved components of the pigment are still visible in the mixture after this period, the solubility of the pigment is below about 0.5 g/L. If the pigment-water mixture cannot be assessed visually due to the high intensity of the possibly finely dispersed pigment, the mixture is filtered. If a proportion of undissolved pigments remains on the filter paper, the solubility of the pigment is below about 0.5 g/L.

[00106] Suitable color pigments can be of inorganic and/or organic origin.

[00107] In a preferred embodiment, an agent (b) of the present disclosure contains at least one colorant compound from the group of inorganic and/or organic pigments.

[00108] Preferred color pigments are selected from synthetic or natural inorganic pigments. Inorganic color pigments of natural origin can be produced, for example, from chalk, ochre, umber, green earth, burnt Terra di Siena or graphite. Furthermore, black pigments such as iron oxide black, colored pigments such as ultramarine or iron oxide red as well as fluorescent or phosphorescent pigments can be used as inorganic color pigments.

[00109] Particularly suitable are colored metal oxides, hydroxides and oxide hydrates, mixed-phase pigments, sulfur-containing silicates, silicates, metal sulfides, complex metal cyanides, metal sulphates, chromates and/or molybdates. Preferred color pigments are black iron oxide (Cl 77499), yellow iron oxide (Cl 77492), red and brown iron oxide (Cl 77491), manganese violet (Cl 77742), ultramarine (sodium aluminum sulfo silicates, Cl 77007, pigment blue 29), chromium oxide hydrate (CI77289), iron blue (ferric ferrocyanides, CI77510) and/or carmine (cochineal). [00110] As contemplated herein, colored pearlescent pigments are also particularly preferred color pigments. These are usually mica- and/or mica-based and can be coated with one or more metal oxides. Mica belongs to the layer silicates. The most important representatives of these silicates are muscovite, phlogopite, paragonite, biotite, lepidolite and margarite. To produce the pearlescent pigments in combination with metal oxides, the mica, mainly muscovite or phlogopite, is coated with a metal oxide.

[00111] As an alternative to natural mica, synthetic mica coated with one or more metal oxides can also be used as pearlescent pigment. Especially preferred pearlescent pigments are based on natural or synthetic mica (mica) and are coated with one or more of the metal oxides mentioned above. The color of the respective pigments can be varied by varying the layer thickness of the metal oxide(s).

[00112] In a further preferred embodiment, a method as contemplated herein the agent (b) contains at least one colorant compound from the group of pigments selected from the group of colored metal oxides, metal hydroxides, metal oxide hydrates, silicates, metal sulfides, complex metal cyanides, metal sulfates, bronze pigments and/or from colored pigments based on mica or mica which are coated with at least one metal oxide and/or one metal oxychloride.

[00113] In a further preferred embodiment, an agent as contemplated herein contains (b) at least one colorant compound from the group of pigments selected from pigments based on mica or micaceous iron oxide, which is combined with one or more metal oxides from the group of titanium dioxide (Cl 77891), are coated with black iron oxide (Cl 77499), yellow iron oxide (Cl 77492), red and/or brown iron oxide (Cl 77491, Cl 77499), manganese violet (Cl 77742), ultramarine (sodium aluminum sulfo silicates, Cl 77007, pigment blue 29), chromium oxide hydrate (Cl 77289), chromium oxide (Cl 77288) and/or iron blue (ferric ferrocyanides, Cl 77510).

[00114] Examples of particularly suitable color pigments are commercially available under the trade names Rona®, Colorona®, Xirona®, Dichrona® and Timiron® from Merck, Ariabel® and Unipure® from Sensient, Prestige® from Eckart Cosmetic Colors and Sunshine® from Sunstar.

[00115] Particularly preferred color pigments with the trade name Colorona® are, for example:

Colorona Copper, Merck, MICA, Cl 77491 (IRON OXIDES)

Colorona Passion Orange, Merck, Mica, Cl 77491 (Iron Oxides), Alumina

Colorona Patina Silver, Merck, MICA, Cl 77499 (IRON OXIDES), Cl 77891 (TITANIUM DIOXIDE)

Colorona RY, Merck, Cl 77891 (TITANIUM DIOXIDE), MICA, Cl 75470 (CARMINE) Colorona Oriental Beige, Merck, MICA, Cl 77891 (TITANIUM DIOXIDE), Cl 77491 (IRON OXIDES)

Colorona Dark Blue, Merck, MICA, TITANIUM DIOXIDE, FERRIC FERROCYANIDE Colorona Chameleon, Merck, Cl 77491 (IRON OXIDES), MICA Colorona Aborigine Amber, Merck, MICA, Cl 77499 (IRON OXIDES), Cl 77891 (TITANIUM DIOXIDE)

Colorona Blackstar Blue, Merck, Cl 77499 (IRON OXIDES), MICA Colorona Patagonian Purple, Merck, MICA, Cl 77491 (IRON OXIDES), Cl 77891 (TITANIUM DIOXIDE), Cl 77510 (FERRIC FERROCYANIDE)

Colorona Red Brown, Merck, MICA, Cl 77491 (IRON OXIDES), Cl 77891 (TITANIUM DIOXIDE)

Colorona Russet, Merck, Cl 77491 (TITANIUM DIOXIDE), MICA, Cl 77891 (IRON OXIDES)

Colorona Imperial Red, Merck, MICA, TITANIUM DIOXIDE (Cl 77891), D&C RED NO. 30 (Cl 73360)

Colorona Majestic Green, Merck, Cl 77891 (TITANIUM DIOXIDE), MICA, Cl 77288 (CHROMIUM OXIDE GREENS)

Colorona Light Blue, Merck, MICA, TITANIUM DIOXIDE (Cl 77891), FERRIC FERROCYANIDE (Cl 77510)

Colorona Red Gold, Merck, MICA, Cl 77891 (TITANIUM DIOXIDE), Cl 77491 (IRON OXIDES)

Colorona Gold Plus MP 25, Merck, MICA, TITANIUM DIOXIDE (Cl 77891), IRON OXIDES (Cl 77491)

Colorona Carmine Red, Merck, MICA, TITANIUM DIOXIDE, CARMINE Colorona Blackstar Green, Merck, MICA, Cl 77499 (IRON OXIDES)

Colorona Bordeaux, Merck, MICA, Cl 77491 (IRON OXIDES)

Colorona Bronze, Merck, MICA, Cl 77491 (IRON OXIDES)

Colorona Bronze Fine, Merck, MICA, Cl 77491 (IRON OXIDES)

Colorona Fine Gold MP 20, Merck, MICA, Cl 77891 (TITANIUM DIOXIDE), Cl 77491 (IRON OXIDES)

Colorona Sienna Fine, Merck, Cl 77491 (IRON OXIDES), MICA Colorona Sienna, Merck, MICA, Cl 77491 (IRON OXIDES) Colorona Precious Gold, Merck, Mica, Cl 77891 (Titanium dioxide), Silica, Cl 77491 (Iron oxides), Tin oxide

Colorona Sun Gold Sparkle MP 29, Merck, MICA, TITANIUM DIOXIDE, IRON OXIDES, MICA, Cl 77891, Cl 77491 (EU)

Colorona Mica Black, Merck, Cl 77499 (Iron oxides), Mica, Cl 77891 (Titanium dioxide) Colorona Bright Gold, Merck, Mica, Cl 77891 (Titanium dioxide), Cl 77491 (Iron oxides) Colorona Blackstar Gold, Merck, MICA, Cl 77499 (IRON OXIDES)

Other particularly preferred color pigments with the trade name Xirona® are for example: Xirona Golden Sky, Merck, Silica, Cl 77891 (Titanium Dioxide), Tin Oxide Xirona Caribbean Blue, Merck, Mica, Cl 77891 (Titanium Dioxide), Silica, Tin Oxide Xirona Kiwi Rose, Merck, Silica, Cl 77891 (Titanium Dioxide), Tin Oxide Xirona Magic Mauve, Merck, Silica, Cl 77891 (Titanium Dioxide), Tin Oxide.

In addition, particularly preferred color pigments with the trade name Unipure® are for example:

Unipure Red LC 381 EM, Sensient Cl 77491 (Iron Oxides), Silica

Unipure Black LC 989 EM, Sensient, Cl 77499 (Iron Oxides), Silica

Unipure Yellow LC 182 EM, Sensient, Cl 77492 (Iron Oxides), Silica

[00116] In a further embodiment, the means as contemplated herein may also contain

(b) one or more coloring compounds from the group of organic pigments

[00117] The organic pigments as contemplated herein are correspondingly insoluble, organic dyes or color lacquers, which may be selected, for example, from the group of nitroso, nitro-azo, xanthene, anthraquinone, isoindolinone, isoindolinone, quinacridone, perinone, perylene, diketo-pyrrolopyorrole, indigo, thioindido, dioxazine and/or triarylmethane compounds.

[00118] Examples of particularly suitable organic pigments are carmine, quinacridone, phthalocyanine, sorghum, blue pigments with the Color Index numbers Cl 42090, Cl 69800, Cl 69825, Cl 73000, Cl 74100, Cl 74160, yellow pigments with the Color Index numbers Cl 11680, Cl 11710, Cl 15985, Cl 19140, Cl 20040, Cl 21100, Cl 21108, Cl 47000, Cl 47005, green pigments with the Color Index numbers Cl 61565, Cl 61570, Cl 74260, orange pigments with the Color Index numbers Cl 11725, Cl 15510, Cl 45370, Cl 71105, red pigments with the Color Index numbers Cl 12085, Cl 12120, Cl 12370, Cl 12420, Cl 12490, Cl 14700, Cl 15525, Cl 15580, Cl 15620, Cl 15630, Cl 15800, Cl 15850, Cl 15865, Cl 15880, Cl 17200, Cl 26100, Cl 45380, Cl 45410, Cl 58000, Cl 73360, Cl 73915 and/or Cl 75470.

[00119] In a further particularly preferred embodiment, a method as contemplated herein the agent (b) contains at least one colorant compound from the group of organic pigments selected from the group of carmine, quinacridone, phthalocyanine, sorghum, blue pigments with the Color Index numbers Cl 42090, Cl 69800, Cl 69825, Cl 73000, Cl 74100, Cl 74160, yellow pigments with the Color Index numbers Cl 11680, Cl 11710, Cl 15985, Cl 19140, Cl 20040, Cl 21100, Cl 21108, Cl 47000, Cl 47005, green pigments with Color Index numbers Cl 61565, Cl 61570, Cl 74260, orange pigments with Color Index numbers Cl 11725, Cl 15510, Cl 45370, Cl 71105, red pigments with the Color Index numbers Cl 12085, Cl 12120, Cl 12370, Cl 12420, Cl 12490, Cl 14700, Cl 15525, Cl 15580, Cl 15620, Cl 15630, Cl 15800, Cl 15850, Cl 15865, Cl 15880, Cl 17200, Cl 26100, Cl 45380, Cl 45410, Cl 58000, Cl 73360, Cl 73915, Cl 75470 and/or black pigment with Color Index number CI77266.

[00120] The organic pigment can also be a color paint. As contemplated herein, the term color lacquer means particles comprising a layer of absorbed dyes, the unit of particle and dye being insoluble under the above-mentioned conditions. The particles can, for example, be inorganic substrates, which can be aluminum, silica, calcium borosilate, calcium aluminum borosilicate or even aluminum.

[00121] For example, alizarin color varnish can be used.

Due to their excellent light and temperature resistance, the use of the pigments in agent (b) of the method as contemplated herein is particularly preferred. It is also preferred if the pigments used have a certain particle size. As contemplated herein, it is therefore advantageous if the at least one pigment has an average particle size D50 of from about 1.0 to about 50 .mu.m, preferably from about 5.0 to about 45 .mu.m, preferably from about 10 to about 40 .mu.m, from about 14 to about 30 .mu.m. The mean particle size D50D.sub.50, for example, can be determined using dynamic light scattering (DLS).

The pigment or pigments may be used in an amount of from about 0.001 to about 20% by weight, of from about 0.05 to about 5% by weight, each based on the total weight of agent (b).

Agent (b) Film Forming Polymer

To achieve uniform and particularly washfast colorings, it has further proved to be particularly preferred if the agent (b) used in the method as contemplated herein contains at least one film-forming polymer that is hydrophobic at least in its un-neutralized form. The film forming polymer may be an organic or silicone polymer.

[00122] In a further preferred embodiment, a method as contemplated herein agent (b) contains at least one film-forming hydrophobic polymer, preferably an organic polymer.

[00123] Polymers are macromolecules with a molecular weight of at least about 1000 g/mol, preferably of at least about 2500 g/mol, particularly preferably of at least about 5000 g/mol, which include identical, repeating organic units. The polymers of the present disclosure may be synthetically produced polymers which are manufactured by polymerisation of one type of monomer or by polymerisation of different types of monomer which are structurally different from each other. If the polymer is produced by polymerising a type of monomer, it is called a homo-polymer. If structurally different monomer types are used in polymerisation, the resulting polymer is called a copolymer.

[00124] The maximum molecular weight of the polymer depends on the degree of polymerisation (number of polymerised monomers) and the batch size and is determined by the polymerisation method. For the purposes of the present disclosure, it is preferred that the maximum molecular weight of the film-forming hydrophobic polymer (b) is not more than about 107 g/mol, preferably not more than about 106 g/mol and particularly preferably not more than about 105 g/mol.

[00125] A hydrophobic polymer is a polymer that has a solubility in water at about 25 ⁰ C. (760 mmHg) of less than about 1% by weight. A polymer that is hydrophilic in its neutralized form, such as a polycarboxylic acid, is hydrophobic if it meets this solubility when it is in its un-neutralized form.

[00126] The water solubility of the film-forming, hydrophobic polymer can be determined in the following way, for example about 1.0 g of the polymer is placed in a beaker. Make up to about 100 g with water. A magnetic stirrer is added, and the mixture is heated to about 25 ⁰ C. on a magnetic stirrer while stirring. It is stirred for about 60 minutes. The aqueous mixture is then visually assessed. If the polymer-water mixture cannot be assessed visually due to a high turbidity of the mixture, the mixture is filtered. If a proportion of undissolved polymer remains on the filter paper, the solubility of the polymer is less than about 1% by weight.

[00127] As contemplated herein, a film-forming polymer is a polymer which can form a film on a substrate, for example on a keratinic material or a keratinic fiber. The formation of a film can be demonstrated, for example, by looking at the keratin material treated with the polymer under a microscope. [00128] These include acrylic acid-type polymers, polyurethanes, polyesters, polyamides, polyureas, cellulose polymers, nitrocellulose polymers, silicone polymers, acrylamide-type polymers, and polyisoprenes.

[00129] Particularly well suited film-forming, hydrophobic polymers are, for example, polymers from the group of copolymers of acrylic acid, copolymers of methacrylic acid, homopolymers or copolymers of acrylic acid esters, homopolymers or copolymers of methacrylic acid esters, homopolymers or copolymers of acrylic acid amides, homopolymers or copolymers of methacrylic acid amides, copolymers of vinylpyrrolidone, copolymers of vinyl alcohol, copolymers of vinyl acetate, homopolymers or copolymers of ethylene, homopolymers or copolymers of propylene, homopolymers or copolymers of styrene, polyurethanes, polyesters and/or polyamides.

[00130] In a further preferred embodiment, a method as contemplated herein the agent (b) contains at least one film-forming hydrophobic polymer selected from the group of copolymers of acrylic acid, copolymers of methacrylic acid, homopolymers or copolymers of acrylic acid esters, homopolymers or copolymers of methacrylic acid esters, the homopolymers or copolymers of acrylic acid amides, the homopolymers or copolymers of methacrylic acid amides, the copolymers of vinylpyrrolidone, the copolymers of vinyl alcohol, the copolymers of vinyl acetate, the homopolymers or copolymers of ethylene, the homopolymers or copolymers of propylene, the homopolymers or copolymers of styrene, polyurethanes, polyesters and/or polyamides.

[00131] The film-forming hydrophobic polymers, which are selected from the group of synthetic polymers, polymers obtainable by radical polymerisation or natural polymers, have proved to be particularly suitable for solving the problem as contemplated herein.

[00132] Other particularly well-suited film-forming hydrophobic polymers can be selected from the homopolymers or copolymers of olefins, such as cycloolefms, butadiene, isoprene or styrene, vinyl ethers, vinylamides, the esters or amides of (meth)acrylic acid with at least one C1-C20 alkyl group, an aryl group or a C2-C10 hydroxyalkyl group.

[00133] Other film-forming hydrophobic polymers may be selected from the homo- or copolymers of isooctyl (meth)acrylate; isonononyl (meth)acrylate; 2-ethylhexyl (meth)acrylate; lauryl (meth)acrylate; isopentyl (meth)acrylate; n-butyl (meth)acrylate); isobutyl (meth)acrylate; ethyl (meth)acrylate; methyl (meth)acrylate; tert-butyl (meth)acrylate; stearyl (meth)acrylate; hydroxyethyl (meth)acrylate; 2-hydroxypropyl (meth)acrylate; 3-hydroxypropyl (meth)acrylate and/or mixtures thereof. [00134] Other film-forming hydrophobic polymers may be selected from the homo- or copolymers of (meth)acryl amide; N-alkyl-(meth)acrylamides, in those with C2-C18 alkyl groups, such as N-ethyl-acrylamide, N-tert-butyl-acrylamide, le N-octyl-acrylamide; N- di(C 1 -C4)alkyl-(meth)acrylamide.

[00135] Other preferred anionic copolymers are, for example, copolymers of acrylic acid, methacrylic acid or their C1-C6 alkyl esters, as they are marketed under the INCI Declaration Acrylates Copolymers. A suitable commercial product is for example Aculyn® 33 from Rohm & Haas. Copolymers of acrylic acid, methacrylic acid or their C1-C6 alkyl esters and the esters of an ethylenically unsaturated acid and an alkoxylated fatty alcohol are also preferred. Suitable ethylenically unsaturated acids are especially acrylic acid, methacrylic acid and itaconic acid; suitable alkoxylated fatty alcohols are especially steareth- 20 or ceteth-20.

[00136] Very particularly preferred polymers on the market are, for example, Aculyn® 22 (Acrylates/Steareth-20 Methacrylate Copolymer), Aculyn® 28 (Acrylates/Beheneth-25 Methacrylate Copolymer), Structure 20010 (Acryla-tes/Steareth-20 Itaconate Copolymer), Structure 30010 (Acrylates/Ceteth-20 Itaconate Copolymer), Structure Plus®

(Acrylates/ Aminoacrylates CIO-30 Alkyl PEG-20 Itaconate Copolymer), Carbopol® 1342, 1382, Ultrez 20, Ultrez 21 (Acrylates/C 10-30 Alkyl Acrylate Crosspolymer), Synthalen W 2000® (Acrylates/Palmeth-25 Acrylate Copolymer) or the Rohme and Haas distributed Soltex OPT (Acrylates/C 12-22 Alkyl methacrylate Copolymer).

[00137] The homo- and copolymers of N-vinylpyrrolidone, vinylcaprolactam, vinyl- (Cl-C6)alkyl -pyrrole, vinyl-oxazole, vinyl -thiazole, vinylpyrimidine, vinylimidazole can be named as suitable polymers based on vinyl monomers.

[00138] Furthermore, the copolymers octylacrylamide/acrylates/butylaminoethyl- methacrylate copolymer, as commercially marketed under the trade names AMPHOMER® or LOVOCRYL® 47 by NATIONAL STARCH, or the copolymers of acrylates/octylacrylamides marketed under the trade names DERMACRYL® LT and DERMACRYL® 79 by NATIONAL STARCH are particularly suitable.

[00139] Suitable olefin-based polymers include homopolymers and copolymers of ethylene, propylene, butene, isoprene and butadiene.

[00140] In another version, block copolymers can be used as film-forming hydrophobic polymers, which comprise at least one block of styrene or the derivatives of styrene. These block copolymers can be copolymers that contain one or more other blocks in addition to a styrene block, such as styrene/ethylene, styrene/ethylene/butylene, styrene/butylene, styrene/isoprene, styrene/butadiene. Such polymers are commercially distributed by BASF under the trade name "Luvitol HSB".

[00141] Surprisingly, it turned out that particularly good coloring's can be obtained with the anionic direct dyes, if the film-forming hydrophobic polymer also carries anionic charges.

[00142] In a further explicitly particularly preferred embodiment, a method as contemplated herein the agent (b) contains at least one anionic, film-forming, hydrophobic polymer.

[00143] An anionic polymer is a polymer comprising repeating units having at least one carboxylic acid group, one sulphonic acid group and/or their physiologically acceptable salts.

[00144] In other words, an anionic polymer is made from monomers having at least one carboxylic acid group, a sulphonic acid group. In this context, the hydrophobic, film forming copolymers of acrylic acid and the copolymers of methacrylic acid are particularly preferred. The polymers in this group contain the carboxylic acid groups, the sulphonic acid groups or their salts in an amount that ensures that the hydrophobic character of the whole polymer is maintained.

[00145] The film-forming hydrophobic polymer(s) as contemplated herein are preferably used in certain quantity ranges on average (b). In this context, it has proved to be particularly preferred for the solution of the task as contemplated herein if the agent (b)— based on the total weight of agent (b)— contains one or more polymers in a total amount of from about 0.1 to about 25.0% by weight, preferably from about 0.2 to about 20.0% by weight, more preferably from about 0.5 to about 15.0% by weight and very particularly preferably from about 1.0 to about 7.0% by weight.

[00146] In a further preferred embodiment, a method as contemplated herein the agent (b) contains— based on the total weight of agent (b)— one or more film-forming hydrophobic polymers in a total amount of from about 0.1 to about 25.0% by weight, preferably from about 0.2 to about 20.0% by weight, more preferably from about 0.5 to about 15.0% by weight and very particularly preferably from about 1.0 to about 11.0% by weight.

Other Ingredients in Agents (a) and (b)

[00147] The agents (a) and (b) described above may also contain one or more optional ingredients. [00148] The products may also contain one or more surfactants. The term surfactants refer to surface-active substances. A distinction is made between anionic surfactants including a hydrophobic residue and a negatively charged hydrophilic head group, amphoteric surfactants, which carry both a negative and a compensating positive charge, cationic surfactants, which in addition to a hydrophobic residue have a positively charged hydrophilic group, and non-ionic surfactants, which have no charges but strong dipole moments and are strongly hydrated in aqueous solution.

[00149] Zwitterionic surfactants are those surface-active compounds which carry at least one quaternary ammonium group and at least one -COO — or — SO2 group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N,N-dimethylammonium-glycinate, for example the cocoalkyl- dimethylammoniumglycinate, N-acylaminopropyl-N,N-dimethylammoniumglycinate, for example, cocoacylaminopropyl dimethyl ammonium glycinate, and 2-alkyl-3-carboxymethyl- 3 -hydroxy ethyl imidazolines each having 8 to 18 C atoms in the alkyl or acyl group, and cocoacylaminoethyl hydroxyethyl carboxymethyl glycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known under the INCI name cocamidopropyl betaine.

[00150] Ampholytic surfactants are surface-active compounds which, apart from a C.sub.8-C24 alkyl or acyl group, contain at least one free amino group and at least one — COOH- or — SO2H group in the molecule and can form internal salts. Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N- alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each with about 8 to 24 C atoms in the alkyl group. Typical examples of amphoteric or zwitterionic surfactants are alkylbetaines, alkylamidobetaines, amino propionates, aminoglycinate, imidazoliniumbetaines and sulfobetaines.

[00151] Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C12-C18 acylsarcosine.

[00152] The products may also additionally contain at least one non-ionic surfactant. Suitable non-ionic surfactants are alkyl polyglycosides as well as alkylene oxide addition products to fatty alcohols and fatty acids with 2 to 30 mol ethylene oxide per mol fatty alcohol or fatty acid. Preparations with good properties are also obtained if they contain as non-ionic surfactants fatty acid esters of ethoxylated glycerol reacted with at least 2 mol ethylene oxide. The non-ionic surfactants are used in a total quantity of from about 0.1 to about 45% by weight, preferably from about 1 to about 30% by weight and very preferably from about 1 to about 15% by weight— based on the total weight of the respective agent.

[00153] In addition, the products may also contain at least one cationic surfactant. Cationic surfactants are surfactants, i.e., surface-active compounds, each with one or more positive charges. Cationic surfactants contain only positive charges. Usually, these surfactants are composed of a hydrophobic part and a hydrophilic head group, the hydrophobic part usually including a hydrocarbon backbone (e.g., including one or two linear or branched alkyl chains) and the positive charge(s) being in the hydrophilic head group. Examples of cationic surfactants are quaternary ammonium compounds which, as hydrophobic radicals, may carry one or two alkyl chains with a chain length of 8 to 28 C atoms, quaternary phosphonium salts substituted with one or more alkyl chains with a chain length of 8 to 28 C atoms or tertiary sulfonium salts.

[00154] Furthermore, the cationic charge can also be part of a heterocyclic ring (e.g., an imidazolium ring or a pyridinium ring) in the form of an onium structure. In addition to the functional unit carrying the cationic charge, the cationic surfactant may also contain other uncharged functional groups, as is the case for example with esterquats. The cationic surfactants are used in a total quantity of from about 0.1 to about 45 wt. %, preferably from about 1 to about 30 wt. % and most preferably from about 1 to about 15 wt. %— based on the total weight of the respective agent.

[00155] Furthermore, the means as contemplated herein may also contain at least one anionic surfactant. Anionic surfactants are surface-active agents with exclusively anionic charges (neutralized by a corresponding counter cation). Examples of anionic surfactants are fatty acids, alkyl sulphates, alkyl ether sulphates and ether carboxylic acids with 12 to 20 C atoms in the alkyl group and up to 16 glycol ether groups in the molecule.

[00156] The anionic surfactants are used in a total quantity of from about 0.1 to about 45 wt. %, preferably from about 1 to about 30 wt. % and most preferably from about 1 to about 15 wt. %— based on the total weight of the respective agent.

[00157] To adjust the desired pH, agents (a) and (b) may also contain at least one alkalizing agent and/or acidifying agent. The pH values for the purposes of the present disclosure are pH values measured at a temperature of about 22⁰ C.

[00158] As alkalizing agents, agents (a) and (b) may contain for example ammonia, alkanolamines and/or basic amino acids. [00159] The alkanolamines which can be used in the composition of the present disclosure are preferably selected from primary amines having a C2-C6 alkyl base which carries at least one hydroxyl group. Preferred alkanolamines are selected from the group formed by 2-aminoethan-l-ol (monoethanolamine), 3-aminopropan-l-ol, 4-aminobutan-l-ol, 5-aminopentan-l-ol, l-aminopropan-2-ol, l-aminobutan-2-ol, l-aminopentan-2-ol, 1- aminopentan-3-ol, l-aminopentan-4-ol, 3-amino-2-methylpropan-l-ol, l-amino-2- methylpropan-2-ol, 3 -aminopropan- 1 ,2-diol, 2-amino-2-methylpropan- 1 ,3 -diol.

[00160] Alkanolamines particularly preferred as contemplated herein are selected from 2-aminoethan-l-ol and/or 2-amino-2-methylpropan-l-ol. A particularly preferred embodiment the agent as contemplated herein contains an alkanolamine selected from 2- aminoethan-l-ol and/or 2-amino-2-methylpropan-l-ol as alkalizing agent.

[00161] A particularly preferred embodiment the agent as contemplated herein contains an alkanolamine selected from 2-aminoethan-l-ol and/or 2-amino-2-methylpropan- l-ol as alkalizing agent. Preferred amino acids are aminocarboxylic acids, especially . alpha. - (alpha)-aminocarboxylic acids and w-aminocarboxylic acids, whereby .alpha. - aminocarboxylic acids are particularly preferred.

[00162] As contemplated herein, basic amino acids are those amino acids which have an isoelectric point pi of greater than about 7.0.

[00163] Basic a-aminocarboxylic acids contain at least one asymmetric carbon atom. In the context of the present disclosure, both possible enantiomers can be used equally as specific compounds or their mixtures, especially as racemates. However, it is particularly advantageous to use the naturally preferred isomeric form, usually in L-configuration.

[00164] The basic amino acids are preferably selected from the group formed by arginine, lysine, ornithine, and histidine, especially preferably arginine and lysine. In another particularly preferred embodiment, an agent as contemplated herein the alkalizing agent is a basic amino acid from the group arginine, lysine, ornithine and/or histidine.

[00165] In addition, the product may contain other alkalizing agents, especially inorganic alkalizing agents. Inorganic alkalizing agents usable as contemplated herein are preferably selected from the group formed by sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium phosphate, potassium phosphate, sodium silicate, sodium metasilicate, potassium silicate, sodium carbonate and potassium carbonate. [00166] Particularly preferred alkalizing agents are ammonia, 2-aminoethan-l-ol (monoethanolamine), 3-aminopropan-l-ol, 4-aminobutan-l-ol, 5-aminopentan-l-ol, 1- aminopropan-2-ol, l-aminobutan-2-ol, l-aminopentan-2-ol, l-aminopentan-3-ol, 1- aminopentan-4-ol, 3-amino-2-methylpropan-l-ol, l-Amino-2-methylpropan-2-ol, 3- aminopropan-l,2-diol, 2-amino-2-methylpropan-l,3-diol, arginine, lysine, ornithine, histidine, sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium phosphate, potassium phosphate, sodium silicate, sodium metasilicate, potassium silicate, sodium carbonate and potassium carbonate.

[00167] Acidifiers commonly used by experts are, for example, indulgence acids such as citric acid, acetic acid, malic acid, or tartaric acid, as well as diluted mineral acids such as hydrochloric acid, sulfuric acid, or phosphoric acid.

[00168] They may also contain other active substances, auxiliaries and additives, such as solvents, fatty components such as C8-C30 fatty alcohols, C5-C30 fatty acid triglycerides, C.sub.8-C₂0 fatty acid monoglycerides, C.sub.8-C₂0 fatty acid diglycerides and/or hydrocarbons; polymers, structural agents such as glucose, maleic acid and lactic acid; hair conditioning compounds such as phospholipids, for example lecithin and cephalins; perfume oils, dimethylisosorbide and cyclodextrins; fiber structure-improving active substances, in particular mono-, di- and oligosaccharides such as glucose, galactose, fructose, fructose and lactose; dyes for coloring the composition; anti-dandruff active substances such as Piroctone Olamine, Zinc Omadine and Climbazol; amino acids and oligopeptides; protein hydrolysates on animal and/or vegetable basis, as well as in the form of their fatty acid condensation products or optionally anionic or cationically modified derivatives; vegetable oils; sunscreens and UV-blockers; active ingredients such as panthenol, pantothenic acid, pantolactone, allantoin, pyrrolidinonecarboxylic acids and their salts, and bisabolol; polyphenols, in particular hydroxycinnamic acids, 6,7-dihydroxycumarine, hydroxybenzoic acids, catechine, tannine, leukoanthocyanidine, anthocyanidine, flavanone, flavone and flavonols; ceramides or pseudoceramides; vitamins, provitamins and vitamin precursors; plant extracts; fats and waxes such as fatty alcohols, beeswax, montan wax and paraffins; swelling and penetrating substances such as glycerol, propylene glycol monoethyl ether, carbonates, hydrogen carbonates, guanidines, ureas and primary, secondary and tertiary phosphates; opacifiers such as latex, styrene/PVP and styrene/acryl amide copolymers; pearlescent agents such as ethylene glycol mono- and distearate and PEG-3 distearate; and blowing agents such as propane-butane mixtures, N2O, dimethyl ether, CO2 and air.

[00169] The selection of these other substances will be made by the specialist according to the desired properties of the agents. About other optional components and the quantities of these components used, explicit reference is made to the relevant manuals known to the specialist. The additional active ingredients and auxiliary substances are preferably used in the preparations as contemplated herein in quantities of from about 0.0001 to about 25 wt. % each, from about 0.0005 to about 15 wt. %, based on the total weight of the respective agent.

Priming and Deep Cleaning of Keratin Materials

[00170] In the procedure as contemplated herein, agents (a) and (b) are applied to the primed and/or deep cleaned keratinous materials, to human hair and especially to anagenic hair such as a person, usually a female, who visits a professional salon to have a hair coloration performed according to the embodiments of this invention.

[00171] To accomplish remanence of the color coating on keratin material, especially when the keratin material is anagenic hair, the keratin material is processed to prime and/or deep clean the surfaces of the keratin material. The priming and deep cleaning are accomplished through practice of Praeparatur and Fundamenta techniques. These techniques deal with unique issues of anagenic hair such as but not limited to sebum coating on the keratin fiber strand surfaces, bound fatty acid layer (F layer) attached to keratin fiber strand surfaces, grime, grit, foulness and deposits from hair formulations previously applied to anagenic hair. The Praeparatur technique substantially to essentially primes the hair to remove surface crusting and/or glazing and/or sebum while the Fundamenta technique deep cleans the surface character and/or surface structure of keratin material as well as removes the F layer. These techniques may be applied separately and individually or may be applied together in either sequence. Irrespective of use of both or use of one or the other, these techniques are applied to hair before applying agents (a) and (b). It is believed that the combination of one or more of the Praeparatur/Fundamenta techniques coupled with the silanes of agent (a) forming a network intimately adhering to the contours of the treated topographic surfaces of keratin material and the adherence among and between the small molecule network and agent (b) produce a highly remanent color coating on anagenic hair. [00172] The Praeparatur technique includes but are not limited to mild agitation with an aqueous surfactant composition to strong interaction with an aqueous or aqueous organic medium with anionic surfactant and/or rinsing with aqueous media optionally having pH adjustment. Additional procedures include optional mechanical agitation with such surfactant media and combing, brushing, vibrating, ultrasound and similar vibratory action applied to the surfaces of keratin material.

[00173] The Fundamenta method include but are not limited to one or more of a non- thermal equilibrium plasma restructuring of the F layer and hair strand surfaces; phase transfer tenside such as but not limited to a multi-alkyl ammonium halide optionally with alkali, chemical treatment with an oxidizing agent including but not limited to ozone, persulfate or peroxide with optional alkali and optional surfactant cleaning.

[00174] One or both of the Praeparatur and Fundamenta techniques may be applied to keratin fibers such as anagen hair. They may be applied separately, applied to different segments of keratin fibers, may be applied sequentially and/or may be applied simultaneously. The Praeparatur technique typically may be applied first, the anagenic hair and the Fundamenta technique may be applied as needed.

[00175] The Praeparatur technique typically begins formulation of an aqueous surfactant with the preferred surfactant being an anionic sulfate surfactant. About 10 to 40 ml of a concentrated anionic surfactant mixture of sodium lauryl sulfate and sodium lauryl ether (PEGio) sulfate may be combined with about 150 to 200 ml of distilled water. A mimic swatch prepared as described in the experimental section may be submersed in the detersive surfactant and briskly agitated with a fine-tooth comb for several minutes. If a live salon hair model is the subject of the Praeparatur technique, she or he may be asked to place her or his head over a salon wash basin. The salon operator may then first wet the model’s hair with water and then apply the surfactant solution to hair and massage and lather the Praeparatur composition onto the hair and scalp. After a period of time the salon operator may then rinse the product from the hair, and optionally repeat the process again. Depending upon the salon operator’s or lab technician’s visual inspection and touch of the hair, the salon operator/technician may also use a fine-toothed comb or pass a hand held ultrasonic device over segments of the hair treated with surfactant solution. The process is continued with optional elevation of the anionic surfactant concentration and optional pH adjustment until the operator/technician’s visual inspection and touch of the hair indicates sebum, natural oils, grime and minerals have been removed to expose bare hair shafts.

[00176] The Fundamenta technique may be applied separate, alone and independent from the Praeparatur technique or the two may be combined in either order. For a typical combined technique, the Fundamenta technique may be applied following the Praeparatur technique application.

[00177] Plasma Fundamenta procedure. An atmospheric low temperature plasma pen such as Piezobrush® PZ2 (Relyon Plasma, Regensburg, Germany) may be used to treat the hair tress. To accomplish the Fundamenta technique, sections of the salon model’s hair or sections of the mimic tress may be exposed to a device producing a cold (ambient temperature) plasma, for example a Relyon PZ2 Plasma Pen. A typical cold plasma generator passes a stream of air, nitrogen or oxygen through a high energy RF or EMF field to produce ions and with air and oxygen, also ozone. The stream of partially ionized gas may be directed toward the hair. The result is a “cold plasma” of partially ionized gas on the keratin fibers. The “cold plasma” may be splayed over and through segments of the Praeparatur treated hair to deep clean the surfaces of the hair strands. The cold plasma is applied at a suitable distance over a period of 1 to 5 minutes, preferably 1 to 3 minutes to provide the desired effect of deep cleansing. In particular, the plasma generator such as the Piezobrush may be held 5 mm from the tress surface and moved slowly up and down along the tress for 3 minutes on each side to perform the Fundamenta step.

[00178] In an alternate Fundamenta technique, an aqueous solution of at least 10 wt%, preferably at least 20 wt%, more preferably at least 30 wt% of an ammonium cationic surfactant such as choline or a C2 to C24 quaternary ammonium halide salt, more preferably cetyl trimethyl ammonium bromide (CTAB) or stearyl trimethyl ammonium bromide (STAB) in either alkali at a pH of about 10 or in thiol at a pH above 7 is applied to the mimic hair tress or to sections of a salon model’s hair and massaged throughout the tress or hair sections for a period of from about 5 minutes to 30 minutes, preferably 5 minutes to 10 minutes. This treatment is then rinsed with shampoo at acidic pH (with acetic acid) until the CTAB or STAB is removed.

[00179] When the Fundamenta technique is the application of an oxidizing composition it may be performed using the following steps. The developer, peroxide containing composition, is mixed with either a composition containing ammonium hydroxide or monoethanolamine or with a powder containing persulfate salts. This mixture is then applied to the hair and left to act for a period of time of at least 1 minute but less than 1 hour. It is then rinsed out of the hair with water and then optionally a Praeparatur step is performed. [00180] In particular, the following CTAB solution may be prepared, CTAB 0.20 %, sodium carbonate, 1.60 % and water 98.2 %. 50 g of solution can be prepared for each tress that is to be treated in a beaker. This solution may be heated to ( 39°C or 60°C). The tresses are placed in the alkaline surfactant solution for (30 min or 15 min) with stirring performed by a magnetic stirrer. Afterwards tresses may be removed from the surfactant solution and dried. The following acidic cleaning composition is then prepared. Texapon N70 (70% in Water) 14.29%, Isopropanol 25.00%, Acetic acid 3.00%, Water 57.71%. The following steps were then performed. 1. Rinse the treated hair tresses thoroughly for 2 minutes with water (4 L min ¹) at approximately 37+/- 3 °C.

2. Apply acidic cleaning composition to hair, using 0.1 g for each gram of hair tress for 60 seconds with the finger to distributed through the hair tress.

3. Rinse the hair swatch with water for 60 sec with water (4 L min ¹) at approximately 37+/- 3 °C.

4. Repeat steps 2-3 two more times.

5. Blow dry tresses.

6. For treatment of a salon customer’s anagenic hair, the foregoing procedure is modified as appropriate for application of the phase transfer tenside such as CTAB to the hair on the head of a person. In particular, the temperatures of application are maintained at room temperature and the pH adjustments of the media are maintained to be slightly acidic and slightly basic. The amounts to be applied are based upon the ratio of amount weights applied to a tress weighing 1 gram and are accordingly used in proportional amounts relative to the weight of hair on the head of a person, about 100 g.

[00181] Following a practice of either or both of the Praeparatur and Fundamenta technique, the mimic swatch or salon customer or salon model is ready for application of the process for coloring keratin materials.

Process for Coloring Keratin Materials

[00182] Thus, agents (a) and (b) are the ready -to-use agents. The agents (a) and (b) are different.

[00183] In principle, agents (a) and (b) can be applied simultaneously or successively, whereby successive application is preferred.

[00184] The best results were obtained when agent (a) was applied to the keratin materials as a pretreatment agent and then agent (b) was applied as a colorant.

[00185] Therefore, a method for coloring keratinous material, in particular human hair, comprising the following steps in the order given is particularly preferred:

In a first step, applying an agent (a) to the keratinous material, wherein the agent (a) comprises at least one organic silicon compound selected from silanes having one, two or three silicon atoms, and

In a second step, applying an agent (b) to the keratinous material. One or more pigments may be combined with either or both of agents (a) and (b).

[00186] The agents (a) and (b) are particularly preferably applied within one and the same coloring process, which means that there is a period of a maximum of several hours between the application of agents (a) and (b).

[00187] In a further preferred embodiment, a method as contemplated herein first the agent (a) is applied, and then the agent (b) is applied, the time between the application of the agents (a) and (b) being at most about 24 hours, preferably at most about 12 hours and particularly preferably at most about 6 hours.

[00188] Within the scope of the procedure as contemplated herein, the keratin materials, in particular human hair, are first treated with agent (a). Then agent (b) is applied to the keratin materials. Either or both of agents (a) and (b) may contain one or more pigments.

[00189] Preferably, agent (b) contains colorants or coloring compounds such as one or more pigments. A characteristic feature of the pretreatment agent (a) is its content of at least one reactive organic silicon compound. The reactive organic silicon compound(s) (a) functionalize the hair surface as soon as they meet it. In this way a first film is formed. In a second step of the process, agent (b) with pigment is now applied to the hair. During application of the agent (b), the colorant compounds interact with the silane film and are thus bound to the keratin materials.

[00190] Here, the technical application properties of the resulting coloring can be further improved by selecting the optimum process conditions.

[00191] In the context of a further form of execution, a procedure comprising the following steps in the order indicated is particularly preferred.

[00192] (1) Application of agent (a) on the keratinous material, (2) Allow the agent (a) to act for a period of from about 10 seconds to about 10 minutes, preferably from about 10 seconds to about 5 minutes, (3) if necessary, rinse the keratinous material with water, (4) Application of agent (b) on the keratinous material, (5) Allow the agent (b) to act for a period of from about 30 seconds to about 30 minutes, preferably from about 30 seconds to about 10 minutes, and (6) Optionally rinse the keratinous material with water.

[00193] The rinsing of the keratinous material with water in steps (3) and (6) of the method is understood, as contemplated herein, to mean that only water is used for the rinsing method, without any other agents other than agents (a) and (b). [00194] In a first step (1), agent (a) is applied to the keratin materials, especially human hair.

After application, the agent (a) can act on the keratin materials. In this context, application times from about 10 seconds to about 10 minutes, preferably from about 20 seconds to about 5 minutes and especially preferably from about 30 seconds to about 2 minutes on the hair have proven to be particularly beneficial.

[00195] In a preferred embodiment of the method as contemplated herein, the agent (a) can now be rinsed from the keratin materials before the agent (b) is applied to the hair in the subsequent step.

[00196] Coloring's with also good wash fastness were obtained when agent (b) was applied to the keratin materials which were still exposed to agent (a).

[00197] In step (4), agent (b) is now applied to the keratin materials. After application, let the agent (b) act on the hair.

[00198] The method as contemplated herein allows the production of coloring's with particularly good intensity and wash fastness even with a short exposure time of agent (b). Application times from about 10 seconds to about 10 minutes, preferably from about 20 seconds to about 5 minutes and most preferably from about 30 seconds to about 3 minutes on the hair have proven to be particularly beneficial.

[00199] In step (6), agent (b) (and any remaining agent (a)) is rinsed out of the keratin material with water.

[00200] In the context of a further form of execution, a procedure comprising the following steps in the order indicated is particularly preferred.

[00201] (1) Application of agent (a) on the keratinous material, (2) Allow the agent (a) to act for a period of from about 10 seconds to about 10 minutes, preferably from about 10 seconds to about 5 minutes, (3) optionally rinse the keratinous material with water, (4) Application of agent (b) on the keratinous material, (5) Allow the agent (b) to act for a period of from about 30 seconds to about 30 minutes, preferably from about 30 seconds to about 10 minutes, and (6) optionally rinse the keratinous material with water.

[00202] In this embodiment, the sequence of steps (1) to (6) preferably takes place within about 24 hours. Multi-Component Packaging Unit (Kit-of-Parts)

[00203] Within the scope of the procedure as contemplated herein, agents (a) and (b) are applied to the keratin materials, i.e., both agents (a) and (b) are ready-to-use agents. [00204] To increase user comfort, the user is preferably provided with all required resources in the form of a multi-component packaging unit (kit-of-parts).

[00205] A second subject matter of the present disclosure is therefore a multi - component packaging unit (kit-of-parts) for coloring keratinic material, comprehensively packaged separately from one another.

[00206] A first container comprising an agent (a), wherein the agent (a) comprises at least one organic silicon compound selected from the group including silanes having one, two or three silicon atoms, and a second container comprising an agent (b), wherein the agent (b) comprises at least one pigment.

[00207] The organic silicon compounds from the group of silanes with one, two or three silicon atoms contained in agent (a) of the kit correspond to the organic silicon compounds that were also used in agent (a) of the previously described method.

[00208] The pigments contained in agent (b) of the kit correspond to the pigments that were also used in agent (b) of the procedure described above.

[00209] A second subject matter of the present disclosure is therefore a multi - component packaging unit (kit-of-parts) for coloring keratinic material, comprehensively packaged separately from one another.

[00210] A first container comprising an agent (a), wherein the agent (a) comprises at least one organic silicon compound selected from the group including silanes having one, two or three silicon atoms, and A second container comprising agent (b) comprising a hydrophobic polymer and at least one pigment as disclosed in detail in the description presented in this disclosure.

[00211] The agent (a) contains with the organic silicon compound(s) a class of highly reactive compounds which can undergo hydrolysis or oligomerization and/or polymerization in the presence of water as described above. Due to their high reactivity, these organic silicon compounds form a film on the keratin material.

[00212] To avoid premature oligomerization or polymerization, it is of considerable advantage to the user to prepare the ready-to-use agent (a) only shortly before application. [00213] In the context of a further embodiment, a multi-component packaging unit (kit-of-parts) for coloring keratinic material is preferably packaged separately from one another, a first container comprising an agent (al), wherein the agent (al) comprises at least one organic silicon compound selected from the group including silanes having one, two or three silicon atoms, a second container comprising an agent (a2), the agent (a2) comprising water, and a third container containing an agent (b), the agent (b) containing hydrophobic polymer and at least one pigment.

[00214] To provide a formulation that is as stable as possible during storage, the agent (al) itself is preferably packaged with low or no water.

[00215] A kit-of-parts packaging unit as contemplated herein the agent (al)— based on the total weight of the agent (al)— contains a water content of from about 0.001 to about 10.0% by weight, preferably from about 0.5 to about 9.0% by weight, more preferably from about 1.0 to about 8.0% by weight and very particularly preferably from about 1.5 to about 7.0% by weight.

[00216] The agent (a2) contains water. In a preferred embodiment, a multi-component packaging unit (kit-of-parts) as contemplated herein the agent (a2)— based on the total weight of the agent (a2)— has a water content of from about 15 to about 100% by weight, preferably from about 35 to about 100% by weight, more preferably from about 55 to about 100% by weight, still more preferably from about 65 to about 100% by weight and very particularly preferably from about 75 to about 100% by weight.

[00217] Within this version, the ready-to-use agent (a) is now produced by mixing agents (al) and (a2).

[00218] For example, the user can first mix or shake the agent (al) containing the organic silicon compound(s) with the water-containing agent (a2). The user can now apply this mixture of (al) and (a2) to the keratin materials— either directly after their production or after a short reaction time of 10 seconds to 20 minutes. Afterwards, the user can apply agent (b) as described above.

[00219] With respect to the other preferred embodiments of the multi -component packaging unit as contemplated herein, the same applies mutatis mutandis to the procedure as contemplated herein.

[00220] Additionally, the kit-of-parts can include several packaging units for the Praeparatur and Fundamenta techniques.

[00221] The Praeparatur kit may contain separate units of concentrated or ready-to-use forms of anionic surfactants such as sodium lauryl sulfate and sodium lauryl ether (PEG20) sulfate. The concentrations may be as high as at least 80 to 95% surfactant in distilled water. The ready-to-use form will contain about 10-25 wt% surfactant in distilled water. Additionally, packaging units containing aqueous acetic acid and aqueous sodium carbonate may be provided Instructions are provided for steps of mixing each of the anionic surfactants with water to form the ready -to-use Praeparatur formulations. The instructions provide steps for forming surfactant solutions with escalating priming power determined by the dilution of the surfactant units with water, formation of a mixture of surfactants and addition of aqueous sodium carbonate. The instructions also provide steps for rinsing with aqueous acetic acid and with water.

[00222] The Fundamenta kit may contain a Piezoelectric plasma generator pen with associated comb and hair strand separation devices. The Fundamenta kit may also contain packaging units of concentrated or ready-to-use CTAB, carbonate solution, thiol solution and acetic acid solution. The Fundamenta kit also provides instructions for use of the plasma generator pen and CTAB formulations. The instructions follow the procedures described above.

EXAMPLES

General

The compositions described herein within the examples are generally applied to a hair tress. 1 gram of composition is applied to each gram of hair tress, on a flat plate or in a bowl and brushed into the hair to ensure that all of the strands look visibly coated with the composition. The hair tress is then dried by heating with a hair dryer while combing until it is dry to the touch and the hairs are individualized.

Preparation and application of film forming systems to color hair:

As required the compositions used herein are prepared as described in the following sections prior to starting the applications steps.

General description of treatment steps:

• If required apply at least one Praeparatur composition to the hair tresses and then rinse the hair strands. Repeat as required.

• If required perform a Fundamenta step on the hair tresses.

• Application of agent (a) comprising at least one organic silicon compound from the group of silanes with one, two or three silicon atoms. • Application of agent (b) comprising a film forming hydrophobic polymer and a pigment.

After the color composition is applied to the hair tress to assess performance the following was then performed: o Full root simulation color remanence test

Full root simulation color remanence test: This test was used to determine the color remanence of the hair coated with a multicomponent coloring composition under more demanding conditions which are designed to better mimic consumers root hair. Versus the standard color remanence test three changes are made. Rather than using standard natural white hair tresses light blonde hair tresses are used. Prior to using the tresses a sebum mimic was applied to account for the sebum excreted from the scalp onto the hair prior to application of a product. Finally the hair was washed using an extended protocol to mimic the recoating of the hair with sebum originating from the scalp in between hair washes.

Prior to any testing the light blonde hair hair tresses were first prepared to better simulate root hair found on a consumer. 0.1 g of sebum (Hautfett nach BEY, sold by Wfk-Testgewebe GmbH)] was applied to the individual hair tress weighing about 1 g described above. The tress was placed in an oven at 40 °C for 30 minutes.

Any steps that were required to color the hair tress with the required compositions were then performed. The colored coating was then left at room temperature 20 °C -25°C and 50-60 %RH for 20 hours. This lower temperature was chosen to more closely replicate conditions on a consumer hair. After these 20 hours the following was performed.

1. Apply 0.1 g of sebum (Hautfett nach BEY, sold by Wfk-Testgewebe GmbH) to the individual colored hair tress weighing about 1 g described above. The sebum is rubbed into the tress to distribute it evenly.

2. Place the tress in the oven at 40 °C for 30 min.

3. Rinse the hair tress for approximately 10 seconds with water (4 L min ¹) at approximately 37+/- 3 °C.

4. Apply 0.1 g “Wella Professional Brilliance Shampoo for fine and normal hair” without dilution to the individual colored hair tress weighing about 1 g described above. 5. Shampoo is worked into the colored hair tress for about 30 sec with fingers by using a stroking motion into the hair.

6. The shampooed colored hair tress is rinsed with water for approximately 30 seconds.

7. Apply 0.1 g “Wella Professional Brilliance Shampoo for fine and normal hair” without dilution to the individual colored hair tress weighing about 1 g described above.

8. Shampoo is worked into the colored hair tress for about 30 sec with fingers by using a stroking motion into the hair.

9. The shampooed colored hair tress is rinsed with water for approximately 30 seconds.

10. The rinsed colored hair tress is then dried using a hot blow dryer while mechanically separating the fibers in the substrate material until uniformly dry.

Steps 1-10 described above represent one cycle of the Full root simulation color remanence test. These are repeated for a total of 5 cycles. This results in a total of 10 shampoo applications to the hair tress prior to assessment. The visual color remanence assessment, described below is then performed to assess the color remanence after the full root simulation color remanence test.

Color Remanence Assessment

Remanence was assessed visually by comparing the washed samples versus a retained tress which had been colored but not washed. Color remanence was graded as either very strong when the color after washing was either unchanged or remaining very intense, strong where the color remained intense but was noticeably less than the starting color, moderate where the color was still visible but obviously less than the starting color or weak where none or a low level of color . To simplify the results tables shown below they were giving the following annotations, very strong = +++, strong = ++ and moderate = +, weak = 0.

Hair tresses used for testing.

Untreated hair tresses. These were used to reflect root length consumer hair. Light blonde hair was purchased (Farbe 9/0 from Kerling International Haarfabrik GmbH, Backnang, Germany) in the form of 10 cm long, 1,4 cm wide strands. The light blonde hair has in prior testing been shown to be a better mimic of consumers root hair, the hair adjacent to the scalp. Whilst not wishing to be bound to theory, it is thought to be less processed by the supplier prior to preparing hair tresses than the natural white hair tresses. These hair tresses were also used as received. EXAMPLES

Example 1. Impact of Praeparatur and Fundamenta steps

Preparation procedure for agent (a) comprising at least one organic silicon compound from the group of silanes with one, two or three silicon atoms.

The agent (a) was prepared by combining the two different organic silicon compounds from the group of silanes with one, two or three silicon atoms into a solvent such as water and mixing until uniform. The resulting mixture is agent (a).

Preparation procedure for agent (b) comprising a film forming hydrophobic polymer and a pigment.

The agent (b) was prepared by combining the two film forming hydrophobic polymers with water, adjusting the pH as needed and then adding the pigment paste and then mixing until uniform. The resulting mixture is agent (b).

General Coloring Procedure:

Agent (a) was applied to the hair tresses, 1 gram of agent (a) was applied per 1 gram of hair. Application was accomplished by a slow distribution and spreading on the hair tress, for example, with fingers, brush, comb or other manipulation instrument/tool. In some experiments the tresses were then rinsed for 30 seconds, in other experiments they were not rinsed. Then agent (b) was applied to the hair tresses. 1 gram of agent (b) was applied per 1 gram of hair. Application was accomplished by a slow distribution and spreading on the hair tress, for example, with fingers, brush, comb or other manipulation instrument/tool. The slow distribution can be accomplished by application with a syringe or a pipette serially to portions of the hair tress. Excess was removed with absorbent tissue material and the resulting colored hair tress was blow dried while combing using a hair dryer to achieve better hair individualization.

In the following four experiments the curing conditions used after the general coloring procedure were room temperature 20-25°C at 50-60% RH for 24 hours prior to performing the full root simulation color remanence test. The following examples show the impact of using a Praeparatur and a Fundamenta step when using the full root simulation color remanence protocol.

Praeparatur procedure: To the hair which had a pre-treatment of sebum to replicate the hair found on a consumers head, prepared using the protocol described above, either nothing was done, and the hair was then colored, or the following step was performed.

1. Rinse the hair tress for approximately 10 seconds with water (4 L min ¹) at approximately 37+/- 3 °C.

2. Apply 0.1 g “Wella System Professional Deep Cleanser Shampoo” without dilution to the individual hair tress weighing about 1 g described above.

3. Shampoo is worked into the hair tress for about 30 sec with fingers by using a stroking motion into the hair.

4. The shampooed hair tress is rinsed with water for approximately 30 seconds.

5. Apply 0.1 g “Wella System Professional Deep Cleanser Shampoo” without dilution to the individual hair tress weighing about 1 g described above.

6. Shampoo is worked into the hair tress for about 30 sec with fingers by using a stroking motion into the hair.

7. The shampooed hair tress is rinsed with water for approximately 30 seconds.

8. The rinsed hair tress is then dried using a hot blow dryer while mechanically separating the fibers in the substrate material until uniformly dry.

Fundamenta Procedures. One Fundamenta procedure was performed on the hair. In both cases this was performed on the hair which had first had the Prarparatio step described above.

Plasma Fundamenta procedure. An atmospheric low temperature plasma pen, Piezobrush® PZ2 (Relyon Plasma, Regensburg, Germany) was used to treat the hair tress. It was held 5 mm from the tress surface and moved slowly up and down along the tress for 2 minutes on each side to perform the Fundamenta step.

The curing conditions used are detailed in the table below and are the same for the standard color remanence test on untreated hair and for the full root simulation color remanence test on light blonde hair. Composition of pigment paste

These experiments were performed to show the difference between testing remanence on regular lab hair tresses versus a full root hair remanence simulation.

The performance of the control legs, 1 A (with rinsing of agent (a)) and 1C (with no rinsing of agent (a)), is weak after the full root simulation color remanence test. Test leg IB (with rinsing of agent (a)) and ID (with no rinsing of agent (a)) showed strong performance showing the advantage of using a Praeparatur and / or a Fundamenta Step prior to the pre-treatment and color application steps, in this case the combination of the 2 shampoo Praeparatur step followed by the Fundamenta plasma treatment.

MISCELLANEOUS STATEMENTS

The invention has been described broadly and generically herein. Each of the narrower species and subgeneric groupings falling within the generic disclosure also form part of the invention. This includes the generic description of the invention with a proviso or negative limitation removing any patient matter from the genus, regardless of whether or not the excised material is specifically recited herein. The inventions, examples, results and statement of embodiments described, stated and claimed herein may have attributes and embodiments include, but not limited to, those set forth or described or referenced in this application.

The terms and expressions that have been employed are used as terms of description and not of limitation, and there is no intent in the use of such terms and expressions to exclude any equivalent of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the invention as claimed and as provided by the statements of embodiments. Thus, it will be understood that although the present invention has been specifically disclosed by various nonlimiting embodiments and/or preferred nonlimiting embodiments and optional features, any and all modifications and variations of the concepts herein disclosed that may be resorted to by those skilled in the art are considered to be within the scope of this invention as defined by the appended claims and the statements of embodiments.

All patents, publications, scientific articles, web sites and other documents and ministerial references or mentioned herein are indicative of the levels of skill of those skilled in the art to which the invention pertains, and each such referenced document and material is hereby incorporated by reference to the same extent as if it had been incorporated verbatim and set forth in its entirety herein. The right is reserved to physically incorporate into this specification any and all materials and information from any such patent, publication, scientific article, web site, electronically available information, text book or other referenced material or document.

The written description of this patent application includes all claims, examples and statements of embodiments. All claims and statements of embodiments including all original claims are hereby incorporated by reference in their entirety into the written description portion of the specification and the right is reserved to physically incorporated into the written description or any other portion of the application any and all such claims and statements of embodiments. Thus, for example, under no circumstances may the patent be interpreted as allegedly not providing a written description for a claim on the assertion that the precise wording of the claim is not set forth in haec verba in written description portion of the patent.

While the invention has been described in conjunction with the detailed description thereof, the foregoing description is intended to illustrate and not limit the scope of the invention, which is defined by the scope of the appended claims and the statements of embodiments. Thus, from the foregoing, it will be appreciated that, although specific nonlimiting embodiments of the invention have been described herein for the purpose of illustration, various modifications may be made without deviating from the scope of the invention. Other aspects, advantages, and modifications are within the scope of the following claims and the present invention is not limited except as by the appended claims and the statements of embodiments.

The specific methods and compositions described herein are representative of preferred nonlimiting embodiments and are exemplary and not intended as limitations on the scope of the invention. Other objects, aspects, and embodiments will occur to those skilled in the art upon consideration of this specification and are encompassed within the spirit of the invention as defined by the scope of the claims. It will be readily apparent to one skilled in the art that varying substitutions and modifications may be made to the invention disclosed herein without departing from the scope and spirit of the invention. The invention illustratively described herein suitably may be practiced in the absence of any element or elements, or limitation or limitations, which is not specifically disclosed herein as essential. Thus, for example, in each instance herein, in nonlimiting embodiments or examples of the present invention, the terms "comprising", "including", "containing", etc. are to be read expansively and without limitation. The methods and processes illustratively described herein suitably may be practiced in differing orders of steps, and that they are not necessarily restricted to the orders of steps indicated herein or in the claims.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by a person of ordinary skill in the art.

Claims

What is claimed is:

1. A method for coloring keratinous material comprising the steps of: priming and/or deep cleaning the keratinous material, applying an agent (a) to the keratinous material, wherein the agent (a) comprises at least one organic silicon compound from the group of silanes with one, two or three silicon atoms and applying an agent (b) to the keratinous material, wherein agent (b) comprises a film forming polymer, and either or both of agents (a) and (b) further comprise at least one pigment; and the priming and /or deep cleaning of the keratin material comprise the steps of applying the Praeparatur and/or Fundamenta techniques.

2. The method according to claim 1, wherein the agent (a) comprises at least one organic silicon compound or at least two different organic silicon compounds of formula (I) and/or (P)

RlR2N-L-Si(OR3)_a(R4)_b I wherein each of R1_,R2 andR3 independently represents a hydrogen atom or a C1-C6 alkyl group, L is a linear or branched divalent C1-C20 alkylene group, R4 represents a C1-C6 alkyl group, a, stands for an integer from 1 to 3, and b stands for the integer 3 -a, and wherein in the organic silicon compound of formula (II)

(R50)c(R6)dSi-(A)e[NR7-(A^,)]f-[0-(A^{, ,})]g-[NR8-(A”]h-Si-(R6^,)d(OR5^,)c’ II wherein each of R5, R5' and R5" independently represents hydrogen or a C1-C6 alkyl group; each of R6, R6' and R6" independently represents a C1-C6 alkyl group, A, A', A", A'" and

A"" independently represent a linear or branched divalent C1-C20 alkylene group, R7 and R8 independently represent a hydrogen atom, a C1-C6 alkyl group, a hydroxy C1-C6 alkyl group, a C2-C6 alkenyl group, an amino C1-C6 alkyl group or a group of formula (III)

-(A” Si(R6”)_d(OR5” ’ III c, stands for an integer from 1 to 3, d stands for the integer 3-c, c' stands for an integer from 1 to 3, d' stands for the integer 3-c', c" stands for an integer from 1 to 3, d" stands for the integer 3-c", e stands for 0 or 1, f stands for 0 or 1, g stands for 0 or 1, h stands for 0 or 1, provided that at least one of e, f, g, and h is different from 0.

3. The method according to claim 1, wherein the agent (a) comprises the at least one organic silicon compound of formula (I),

RlR2N-L-Si(OR3)_a(R4)_b I where Rl, R2 both represent a hydrogen atom, and L represents a linear, divalent C1-C6- alkylene group, R3, R4 independently represent a methyl group or an ethyl group, a stands for the number 3, and b stands for the number 0.

4. The method according to claim 3, wherein the agent (a) comprises the at least one organic silicon compound of formula (I) selected from the group of (3- Aminopropyl)trimethoxy silane, (3 -Aminopropyl)triethoxysilane, (2- Aminoethyl)trimethoxy silane, (2-Aminoethyl)triethoxysilane, (3- Dimethylaminopropyl)trimethoxy silane, (3 -Dimethylaminopropyl)tri ethoxy silane, (2- dimethylaminoethyl)trimethoxysilane, and (2-Dimethylaminoethyl)triethoxysilane.

5. The method according to claim 2, wherein the agent (a) comprises the at least one organic silicon compound of the formula (II),

(R50)c(R6)dSi-(A)e[NR7-(A^,)]f-[0-(A^,,)]g-[NR8-(A”]h-Si-(R6^,)d(OR5^,)c’ II where e and f both stand for the number 1, g and h both stand for the number 0, A and A' independently represent a linear, divalent C1-C6 alkylene group and R7 represents a hydrogen atom, a methyl group, a 2-hydroxyethyl group, a 2-alkenyl group, a 2-aminoethyl group or a group of formula (III).

6. The method according to claim 1, wherein the agent (a) comprises (a) at least one organic silicon compound of the formula (II) which is selected from the group of 3-(trimethoxysilyl)- N-[3-(trimethoxysilyl)propyl]-l-propanamine, 3 -(triethoxysilyl)-N-[3 -(tri ethoxy silyl)propyl]- 1 -propanamine, N-methyl-3-(trimethoxysilyl)-N-[3-(trimethoxysilyl)propyl]-l-propanamine, N-methyl-3-(triethoxysilyl)-N-[3-(triethoxysilyl)propyl]-l-propanamine, 2-[bis[3- (trimethoxysilyl)propyl]amino]-ethanol, 2-[bis[3-(triethoxysilyl)propyl]amino]ethanol, 3- (trimethoxysilyl)-N,N-bis[3-(trimethoxysilyl)propyl]-l -propanamine, 3-(triethoxysilyl)-N,N- bis[3 -(triethoxysilyl)propyl] - 1 -propanamine, N1 ,N1 -bis[3 -(trimethoxysilyl)propyl] - 1 ,2- ethanediamine, Nl,Nl-bis[3-(triethoxysilyl)propyl]-l,2-ethanediamine, N,N-bis[3- (trimethoxysilyl)propyl]-2-propen-l -amine, and/or N, N-bis[3-(triethoxysilyl)propyl]-2- propen-1 -amine.

7. The method according to claim 1, wherein the agent (a) comprises the at least one organic silicon compound of formula (IV).

R9Si(OR10)k(Rll)m IV where R9 represents a Cl -Cl 2 alkyl group, RIO represents a hydrogen atom or a C1-C6 alkyl group, R11 represents a C1-C6 alkyl group k is an integer from 1 to 3, and m stands for the integer 3-k.

8. The method according to claim 7, wherein the agent (a) comprises the at least one organic silicon compound of formula (IV) selected from the group of methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, dodecyltrimethoxysilane, and/or dodecyltriethoxysilane.

9. The method according to any of the preceding claims, wherein the agent (b) comprises a film forming polymer of organic or silicone composition that is hydrophobic or is hydrophobic when its neutralized hydrophilic salt form and is rendered hydrophobic by conversion to its un-neutralized form, and the film forming polymer is preferably a film forming polymer of organic composition.

10. The method according to any of the preceding claims, wherein the agent (a) based on the total weight of agent (a) comprises: about 0.5 to about 40.0 weight % of at least one first organic silicon compound selected from the group of (3-aminopropyl)trimethoxysilane, (3- aminopropyl)triethoxysilane, (2-aminoethyl)trimethoxysilane, (2-aminoethyl)triethoxysilane, (3 -dimethylaminopropyl)trimethoxy silane, (3-dimethylaminopropyl)triethoxysilane, (2- dimethylaminoethyl)trimethoxysilane, and (2-dimethylaminoethyl)triethoxysilane, and about 0.5 to about 75.0% by weight of at least one second organic silicon compound selected from the group of methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, dodecyltrimethoxysilane and dodecyltriethoxysilane.

11. The method according to any of the preceding claims, wherein the pigment comprises the at least one inorganic pigment selected from the group of colored metal oxides, metal hydroxides, metal oxide hydrates, silicates, metal sulfides, complex metal cyanides, metal sulfates, bronze pigments and/or colored pigments based on mica or mica coated with at least one metal oxide and/or one metal oxychloride and/or metal microflakes.

12. The method according to any of the preceding claims, wherein the pigment comprises the at least one organic pigment selected from the group of carmine, quinacridone, phthalocyanine, sorghum, blue pigments with the Color Index numbers Cl 42090, Cl 69800, Cl 69825, Cl 73000, Cl 74100, Cl 74160, yellow pigments with the Color Index numbers Cl 11680, Cl 11710, Cl 15985, Cl 19140, Cl 20040, Cl 21100, Cl 21108, Cl 47000, Cl 47005, green pigments with Color Index numbers Cl 61565, Cl 61570, Cl 74260, orange pigments with Color Index numbers Cl 11725, Cl 15510, Cl 45370, Cl 71105, red pigments with Color Index numbers Cl 12085, Cl 12120, Cl 12370, Cl 12420, Cl 12490, Cl 14700, Cl 15525, Cl 15580, Cl 15620, Cl 15630, Cl 15800, Cl 15850, Cl 15865, Cl 15880, Cl 17200, Cl 26100, Cl 45380, Cl 45410, Cl 58000, Cl 73360, Cl 73915 and/or Cl 75470.

13. A method according to any of the preceding claims, comprising priming the keratin material with a Praeparatur technique comprising manipulating the keratin material with an aqueous solution of at least one anionic surfactant optionally with basic pH adjustment and repeating at least once the manipulating of the keratin material with the same or higher concentration of anionic surfactant and rinsing the keratin material with water optionally containing dilute acetic acid.

14. A method according to claim 13 wherein the concentration of anionic surfactant is at least 10 wt% relative to the total weight of the aqueous solution.

15. A method according to any of the preceding claims, comprising deep cleaning the keratin material with a Fundamenta technique comprising applying a cold plasma to the surfaces of the keratin material, or applying a phase transfer tenside at optional basic pH to the keratin material, or applying an oxidizing agent to the keratin material, and rinsing the keratin material with an acidic shampoo solution and/or basic shampoo solution.