DE102023205849A1 - Procedure and a kit for conditioning and structural improvement of damaged keratin fibers - Google Patents

Abstract

The present invention relates to a method and a kit for conditioning keratin fibers, in particular hair, in particular for improving the structure of damaged keratin fibers.

Description

The present invention relates to a method and a kit for conditioning keratin fibers, in particular hair, in particular for improving the structure of damaged keratin fibers.

The problem with oxidative treatments of keratin fibers, such as dyeing or bleaching hair, is that the aggressive agents, particularly oxidizing agents, but also alkalizing agents, can cause damage to the keratin fibers. For example, these agents reduce the natural hydrophobicity of the keratin fibers, since the dyeing or bleaching agents have to make the keratin fibers permeable in order to develop their effect inside the fiber. On the one hand, the water-repellent effect is a natural protection of the keratin fibers, especially the hair, and on the other hand, parameters desired by the consumer, such as shine, suppleness, feel and "fall" of the keratin fibers, especially the hair, are closely linked to it.

In addition to damage to the surface of the keratin fibers, the aggressive agents, especially oxidizing agents and alkalizing agents, can also cause permanent damage to the inner fiber structure. In addition to a variety of changes to the keratin fibers, the disulfide bridges found in the keratin fibers are mainly broken down. This structural damage to the keratin fibers manifests itself in a reduced extensibility and elasticity of the fiber, which can be easily demonstrated by determining the tensile elongation (E-modulus).

In order to eliminate or even avoid the disadvantages mentioned, various means and treatment methods are already known.

To reduce damage caused by hair treatment with aggressive agents, active ingredients with a damage-reducing effect can be added. These include, for example, organic acids, especially saturated or unsaturated dicarboxylic acids, such as succinic acid and maleic acid, hydroxycarboxylic acids, such as lactic acid or malic acid, or sulfonic acids, such as taurine. However, such acids lower the pH value of the hair treatment product, which can impair the actual purpose of the hair treatment, such as oxidative coloring or lightening, because an alkaline pH value in the range of pH 9 to about pH 10.5 is normally necessary for a good coloring or lightening result. Silicones and polymers, especially cation polymers, can also improve the properties of damaged keratin fibers, but an increasing proportion of consumers prefer to forego the use of these fully synthetic chemicals in favor of more sustainable raw materials, such as non-synthetic oils and protein hydrolysates. In addition, the conditioning agents mentioned essentially only act on the surface of the keratin fibers without having a lasting restructuring effect.

There are also pre-treatment products on the market that are designed to protect the hair from the effects of aggressive agents. However, these often weigh down the hair or impair the success of the subsequent lightening or coloring of the hair; in particular, the washfastness of the color can be impaired by the pre-treatment product.

There are also numerous post-treatment products that attempt to repair the fiber damage caused by oxidative and/or highly alkaline hair treatment. However, all of these methods require a multi-stage application process, i.e. the application of another hair treatment product either before or after the coloring or lightening process. This is often perceived by consumers as annoying, as the oxidative coloring or lightening treatment itself is very time-consuming with several steps and an exposure time of up to 60 minutes.

The object of the present invention was to provide methods and kits for the conditioning treatment of keratin fibers, in particular human hair, which overcome the disadvantages mentioned and bring about at least partial repair of damage caused by an oxidative treatment or minimize this damage without negatively affecting the desired result of the oxidative fiber treatment.

In particular, procedures and kits should be provided that do not weigh down the hair. Furthermore, the hair protection achieved should be as time-consuming as possible and should be carried out as close to the actual oxidative treatment as possible. Another task was to develop flexible procedures and kits for the conditioning treatment of keratin fibers, in particular for the conditioning treatment of damaged keratin fibers. particularly preferred for the restructuring and damage-reducing treatment of damaged keratin fibers.

The use of carbodiimides and polycarbodiimides in hair care has long been known in the state of the art. EP3342395A2 discloses the use of polycarbodiimides as vehicles to covalently bind cosmetic active ingredients to keratinic surfaces, such as hair or skin. KR20160123549A discloses the use of polycarbodiimides in acidic solution as a vehicle to covalently bind an acrylate or methacrylate (co)polymer to keratinic surfaces, in particular to hair, in order to thereby strengthen the hair. FR1567219A discloses the use of a post-treatment agent for oxidatively dyed hair that contains a carbodiimide or a polycarbodiimide. This post-treatment improves the fastness properties of the dye to various external influences, such as shampooing. WO2022189575A1 discloses the use of polycarbodiimides in combination with an associative polymer and with a pigment or a direct dye to achieve a uniformly colored coating on the hair that has good fastness properties to shampooing, brushing or rubbing. The dyeing process does not cause any hair damage.

Surprisingly, it was found that the spectrum of action of carbodiimides and polycarbodiimides can be extended to the repair of oxidative damage and the improvement of the internal structure of the keratin fibers by subjecting the keratin fibers to an acidic treatment with an inorganic acid after the alkaline treatment with a carbodiimide or polycarbodiimide. The process according to the invention improves the tensile strength of the keratin fibers significantly more than known treatment processes.

1. a) Auftragen einer Zusammensetzung (CDI), die in einem kosmetischen Träger mindestens ein Carbodiimid oder mindestens ein Polycarbodiimid enthält, auf die Keratinfasern,
2. b) Einwirkenlassen für eine Zeit von 30 Sekunden bis 60 Minuten, bevorzugt 1 bis 45 Minuten, besonders bevorzugt 2 bis 30 Minuten, außerordentlich bevorzugt 5 bis 15 Minuten,
3. c) Spülen der Keratinfasern mit Wasser,
4. d) optional Trocknen der Keratinfasern,
5. e) Auftragen einer wässrigen Zusammensetzung (A) auf die Keratinfasern, wobei die Zusammensetzung (A) eine anorganische Säure enthält und einen sauren pH-Wert aufweist, wobei der pH-Wert bevorzugt 0,2 - 6,5, weiter bevorzugt 2,0 - 6,0, besonders bevorzugt 3,0 - 5,5, außerordentlich bevorzugt 4,0 - 5,0, weiter außerordentlich bevorzugt 4,3 - 4,6, beträgt, jeweils gemessen bei 20°C,
6. f) Einwirkenlassen für eine Zeit von 10 Sekunden bis 60 Minuten, bevorzugt 30 Sekunden bis 30 Minuten, besonders bevorzugt 1 bis 20 Minuten, außerordentlich bevorzugt 2 bis 15 Minuten, weiter außerordentlich bevorzugt 5 bis 10 Minuten,
7. g) Spülen der Keratinfasern mit Wasser,
8. h) optional Trocknen der Keratinfasern.

The present invention relates to a method for the conditioning treatment of keratin fibers, in particular human hair, which comprises the following method steps in the order given:

1. a) applying to the keratin fibres a composition (CDI) containing in a cosmetic carrier at least one carbodiimide or at least one polycarbodiimide,
2. b) allowing to act for a time of 30 seconds to 60 minutes, preferably 1 to 45 minutes, particularly preferably 2 to 30 minutes, extremely preferably 5 to 15 minutes,
3. c) Rinsing the keratin fibers with water,
4. d) optional drying of the keratin fibers,
5. e) applying an aqueous composition (A) to the keratin fibers, wherein the composition (A) contains an inorganic acid and has an acidic pH, wherein the pH is preferably 0.2 - 6.5, more preferably 2.0 - 6.0, particularly preferably 3.0 - 5.5, extremely preferably 4.0 - 5.0, more extremely preferably 4.3 - 4.6, in each case measured at 20°C,
6. f) allowing to act for a time of 10 seconds to 60 minutes, preferably 30 seconds to 30 minutes, particularly preferably 1 to 20 minutes, extremely preferably 2 to 15 minutes, further extremely preferably 5 to 10 minutes,
7. g) Rinsing the keratin fibers with water,
8. h) optionally drying the keratin fibers.

According to the invention, "conditioning treatment" of keratin fibers is to be understood as meaning that the fibers have improved after a treatment according to the invention or preferred according to the invention in relation to at least one test parameter compared to the state before the treatment. Suitable test parameters are, for example, extensibility, elasticity, melting point, e.g. measured by means of differential scanning calorimetry (DSC), wet combability or wet combing work and dry combability or dry combing work.

worin

• X₁ und X₂ unabhängig voneinander für ein Sauerstoff-Atom, ein Schwefel-Atom oder eine NH-Gruppe stehen,
• R1 und R2 unabhängig voneinander für eine Gruppe stehen, die ausgewählt ist aus einer Kohlenwasserstoff-Gruppe, bevorzugt aus mindestens einer Alkyl-Gruppe, die optional durch ein oder mehrere Heteroatome unterbrochen sein kann, weiterhin ausgewählt aus Alkoxysilyl-, Hydroxysilyl-, Acetoxysilyl-, Vinylsilyl-, Acrylalkylsilyl-, Methacrylalkylsilyl-, Crotonylalkylsilyl-, Carboxyanhydridoalkylsilyl-, Carboxyalkylsilyl-, Hydroxyalkylsilyl-, Aldehydoalkylsilyl-, Mercaptoalkylsilyl-, Norbornenylsilyl-, Acylpentadienylalkylsilyl-, Maleimidoalkylsilyl-, Sulfonylalkylsilyl-, (Meth)acrylalkyl-, Crotonylalkyl-, Alkylepoxid-, z. B. Propylepoxid- oder Butylepoxid-, und Azacyclopropan-Gruppen sowie Mischungen hiervon;
• - n für eine ganze Zahl im Bereich von 1 bis 200, bevorzugt 2 bis 200, besonders bevorzugt 3 bis 150, weiter besonders bevorzugt 4 bis 100, weiter besonders bevorzugt 4 bis 50, weiter besonders bevorzugt 4 bis 10, außerordentlich bevorzugt 6 bis 7, steht; und
• - A für eine divalente Gruppe steht, die aus den nachstehend dargestellten Substituenten ausgewählt ist:
  
  
  
  
  

In a preferred embodiment of the invention, the at least one polycarbodiimide is selected from compounds of the structural formula (CDI-I)

wherein

• X ₁ and X ₂ independently represent an oxygen atom, a sulfur atom or an NH group,
• R1 and R2 independently of one another represent a group which is selected from a hydrocarbon group, preferably from at least one alkyl group which can optionally be interrupted by one or more heteroatoms, further selected from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydealkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylalkylsilyl, (meth)acrylalkylalkyl, crotonylalkyl, alkylepoxide, e.g. propylepoxide or butylepoxide, and azacyclopropane groups and mixtures thereof;
• - n is an integer in the range from 1 to 200, preferably 2 to 200, particularly preferably 3 to 150, further particularly preferably 4 to 100, further particularly preferably 4 to 50, further particularly preferably 4 to 10, extremely preferably 6 to 7; and
• - A represents a divalent group selected from the substituents shown below:
  
  
  
  
  

• - „Alkyl“-Gruppe steht für eine lineare oder verzweigte, jeweils gesättigte Gruppe, die 1 bis 30 Kohlenstoffatome umfasst;
• - „Aminoalkyl“-Gruppe steht für eine lineare oder verzweigte, jeweils gesättigte Gruppe, die 1 bis 30 Kohlenstoffatome und eine -NH₂-Gruppe umfasst;
• - „Hydroxyalkyl“-Gruppe steht für eine lineare oder verzweigte, jeweils gesättigte Gruppe, die 1 bis 30 Kohlenstoffatome und eine -OH-Gruppe umfasst;
• - „Alkylen“-Gruppe steht für eine divalente lineare oder verzweigte, jeweils gesättigte C1-C4-Kohlenwasserstoff-basierte Gruppe, insbesondere für Methylen, Ethylen, Propylen, Isopropylen, n-Propylen, n-Butylen, iso-Butylen oder tert.-Butylen;
• - „Cycloalkyl“-Gruppe oder „Alicycloalkyl“-Gruppe steht für eine gesättigte monozyklische oder bizyklische, bevorzugt monozyklische, Kohlenwasserstoff-basierte Gruppe, die 3 bis 20 Kohlenstoffatome, bevorzugt 4 bis 15 Kohlenstoffatome, besonders bevorzugt 5 bis 13 Kohlenstoffatome, weiter bevorzugt 6 bis 12 Kohlenstoffatome, weiter bevorzugt 7 bis 10 Kohlenstoffatome umfasst, insbesondere für eine Cyclopropyl-, Cyclopentyl-, Cyclohexyl-, Cycloheptyl- oder Norbornyl-Gruppe, besonders bevorzugt für eine Cyclopropyl-, Cyclopentyl- oder Cyclohexyl-Gruppe, wobei die Cycloalkyl-Gruppe optional mit einer oder mehreren C1-C4-Alkyl-Gruppen, bevorzugt mit Methyl, und/oder optional mit einer oder mehreren C1-C4-AlkylenGruppen, bevorzugt mit Methylen oder mit Isopropylen, substituiert sein kann; besonders bevorzugt ist die Cycloalkyl-Gruppe dann eine Isobornyl-Gruppe;
• - „Cycloalkylen“-Gruppe steht für eine divalente Cycloalkyl-Gruppe gemäß der vorstehenden Definition für „Cycloalkyl“, wobei bevorzugte Cycloalkylen-Gruppen 3 bis 15 Kohlenstoffatome aufweisen;
• - „Aryl“-Gruppe steht für eine monozyklische, bizyklische oder bizyklische aromatische Kohlenwasserstoff-basierte Gruppe, die 6 bis 14 Kohlenstoffatome, bevorzugt 6 bis 12 Kohlenstoffatome umfasst; wobei bevorzugte Aryl-Gruppen ausgewählt sind aus Phenyl, Naphthyl, Anthryl, Phenanthryl und Biphenyl, besonders bevorzugt Phenyl, wobei die Aryl-Gruppe optional mit einer oder mehreren C1-C4-Alkyl-Gruppen, bevorzugt mit Methyl, substituiert sein kann; besonders bevorzugt ist die Aryl-Gruppe dann eine Gruppe, ausgewählt aus Tolyl, Xylyl und Methylnaphthyl;
• - „Arylen“-Gruppe steht für eine divalente Aryl-Gruppe gemäß der vorstehenden Definition für „Aryl“; wobei „Arylen“ bevorzugt für Phenylen steht;
• - „heterozyklische“ Gruppe steht für eine gesättigte oder ungesättigte, nicht-aromatische oder aromatische, monozyklische oder polyzyklische Kohlenwasserstoff-basierte Gruppe, die ein oder mehrere Heteroatome, bevorzugt 1 bis 5 Heteroatome, aufweist, die ausgewählt sind aus O, S oder N, wobei der Heterozyklus 3 bis 20 Ringatome, bevorzugt 5 bis 10 Ringatome, aufweist, wie beispielsweise Imidazolyl, Pyrrolyl und Furanyl;
• - „Heterozykloalkylen“-Gruppe steht für eine divalente heterozyklische Gruppe gemäß der vorstehenden Definition für „heterozyklisch“;
• - „reaktive“ Gruppe steht für eine Gruppe, die in der Lage ist, durch eine chemische Reaktion eine kovalente Bindung mit einer anderen Gruppe, die gleich oder verschieden ist, auszubilden.

For the purposes of this application, the following definitions apply:

• - “Alkyl” group means a linear or branched, saturated group containing 1 to 30 carbon atoms;
• - “Aminoalkyl” group means a linear or branched, saturated group containing 1 to 30 carbon atoms and an -NH ₂ group;
• - “Hydroxyalkyl” group means a linear or branched, saturated group containing 1 to 30 carbon atoms and an -OH group;
• - “Alkylene” group stands for a divalent linear or branched, in each case saturated C1-C4 hydrocarbon-based group, in particular methylene, ethylene, propylene, isopropylene, n-propylene, n-butylene, isobutylene or tert-butylene;
• - “Cycloalkyl” group or “alicycloalkyl” group stands for a saturated monocyclic or bicyclic, preferably monocyclic, hydrocarbon-based group which comprises 3 to 20 carbon atoms, preferably 4 to 15 carbon atoms, particularly preferably 5 to 13 carbon atoms, further preferably 6 to 12 carbon atoms, further preferably 7 to 10 carbon atoms, in particular a cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl or norbornyl group, particularly preferably a cyclopropyl, cyclopentyl or cyclohexyl group, where the cycloalkyl group can optionally be substituted with one or more C1-C4-alkyl groups, preferably with methyl, and/or optionally with one or more C1-C4-alkylene groups, preferably with methylene or with isopropylene; the cycloalkyl group is then particularly preferably an isobornyl group;
• - “cycloalkylene” group represents a divalent cycloalkyl group as defined above for “cycloalkyl”, with preferred cycloalkylene groups having 3 to 15 carbon atoms;
• - "Aryl" group stands for a monocyclic, bicyclic or bicyclic aromatic hydrocarbon-based group which comprises 6 to 14 carbon atoms, preferably 6 to 12 carbon atoms; preferred aryl groups are selected from phenyl, naphthyl, anthryl, phenanthryl and biphenyl, particularly preferably phenyl, where the aryl group can optionally be substituted with one or more C1-C4-alkyl groups, preferably with methyl; particularly preferably the aryl group is then a group selected from tolyl, xylyl and methylnaphthyl;
• - “Arylene” group means a divalent aryl group as defined above for “aryl”; where “arylene” preferably means phenylene;
• - "heterocyclic" group stands for a saturated or unsaturated, non-aromatic or aromatic, monocyclic or polycyclic hydrocarbon-based group having one or more heteroatoms, preferably 1 to 5 heteroatoms, selected from O, S or N, wherein the heterocycle has 3 to 20 ring atoms, preferably 5 to 10 ring atoms, such as imidazolyl, pyrrolyl and furanyl;
• - ‘heterocycloalkylene’ group means a divalent heterocyclic group as defined above for ‘heterocyclic’;
• - “reactive” group means a group that is capable of forming a covalent bond with another group, which may be the same or different, through a chemical reaction.

Carbodiimides and Polycarbodiimides

In the methods according to the invention and preferred according to the invention for the conditioning treatment of keratin fibers, in a first method step a composition (CDI) is applied to the keratin fibers which contains at least one carbodiimide or at least one polycarbodiimide and mixtures thereof.

The composition (CDI) may contain at least two different carbodiimides or polycarbodiimides and mixtures thereof.

A carbodiimide is a compound that has a divalent carbodiimide group of the general structural formula -N=C=N- in the molecule.

A polycarbodiimide is a compound which has two or more carbodiimide groups of the general structural formula -N=C=N- in the molecule; preferably no more than 200 carbodiimide groups, particularly preferably no more than 150 carbodiimide groups, extremely preferably no more than 100 carbodiimide groups are contained in the molecule.

The term “(poly)carbodiimide” includes carbodiimides and polycarbodiimides. According to the invention, polycarbodiimides with 2 to 200 carbodiimide groups, preferably 3 to 150 carbodiimide groups, are preferred. particularly preferably 4 to 100 carbodiimide groups, extremely preferably 4 to 50 carbodiimide groups, further extremely preferably 4 to 10 carbodiimide groups, with 6 to 7 carbodiimide groups also being extremely preferred. Carbodiimide groups are obtainable from two isocyanate groups with elimination of carbon dioxide: RN=C=O + O=C=NR → RN=C=NR + _CO2

Starting from diisocyanates, oligomeric compounds with several carbodiimide groups and optionally isocyanate groups, especially terminal isocyanate groups, are obtainable, so-called polycarbodiimides. Any isocyanate groups still present can be further reacted with alcohols, thiols, primary or secondary amines to form urethane, thiourethane or urea groups. The polycarbodiimides can therefore contain urethane, thiourethane or urea groups in addition to free isocyanate groups.

The production of polycarbodiimides from diisocyanates is known per se and is described, for example, in US2840589A, US2853473A , US2941966A and EP628541A described. In all common manufacturing processes, phosphorus compounds are used as catalysts (carbodiimidization catalysts), such as various phospholene oxides, for example 1-methyl-2-phospholene-1-oxide and/or 1-methyl-3-phospholene-1-oxide, 3-methyl-2-phospholene-1-oxide and/or 3-methyl-3-phospholene-1-oxide, 1-phenyl-2-phospholene-1-oxide and/or 1-phenyl-3-phospholene-1-oxide. Polycarbodiimides can be produced particularly gently and free of by-products by catalysis according to DE2504400A1 , DE2552350A1 and EP609698A1. The carbodiimidization of diisocyanates in the presence of catalysts such as phospholene oxide is already known in principle. It is also known that aromatic isocyanates can be converted to carbodiimides under significantly milder reaction conditions and with smaller amounts of phospholene oxide catalyst. Isocyanate compounds such as di-4,4'-diisocyanatocyclohexylmethane or isophorone diisocyanate, which have secondary isocyanate groups, react slowly and require larger amounts of carbodiimidization catalysts.

The average functionality of carbodiimide units is the average number of carbodiimide units in a polycarbodiimide molecule. The average functionality can also be a fractional number. Preferred methods and kits according to the invention for the conditioning treatment of keratin fibers are characterized in that the polycarbodiimide used therein has an average functionality of 1 to 10, preferably 2 to 7, particularly preferably 3 to 7. If the average functionality is higher than 10, the dispersibility of the polycarbodiimide in water is low.

Preferred methods and kits for the conditioning treatment of keratin fibers according to the invention are characterized in that the polycarbodiimide used therein was obtained by polycondensation from at least one aliphatic, cycloaliphatic or aromatic diisocyanate selected from the group consisting of methylene diisocyanate, dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, dipropyl ether diisocyanate, 2,2-dimethylpentane diisocyanate, 3-methoxyhexane diisocyanate, octamethylene diisocyanate, 2,2,4-trimethylpentane diisocyanate, nonamethylene diisocyanate, decamethylene diisocyanate, 3-butoxyhexane diisocyanate, 1,4-butylene glycol dipropyl ether diisocyanate, thiodihexyl diisocyanate, metaxylylene diisocyanate, paraxylylene diisocyanate, tetramethylxylylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate (H12MDI), Isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), hydrogenated xylylene diisocyanate (H6XDI), 1,12-diisocyanatododecane (DDI), norbornane diisocyanate (NBDI) and 2,4-bis(8-isocyanatoctyl)-1,3-dioctylcyclobutane (OCDI).

Diisocyanates used with particular preference according to the invention are isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), hydrogenated xylylene diisocyanate (H6XDI) and 4,4'-dicyclohexylmethane diisocyanate (H12MDI). The cycloaliphatic diisocyanate 4,4'-dicyclohexylmethane diisocyanate (H12MDI) is very particularly preferred.

The conversion of diisocyanate to polycarbodiimide takes place at a temperature in the range of 160 to 230 °C, preferably in the range of 180 °C to 210 °C, particularly preferably in the range of 185 °C to 205 °C.

For methods and kits preferred according to the invention, it is particularly advantageous if the polycarbodiimide used therein is reacted by further reaction with at least one hydrophilic compound which carries at least a group reactive towards isocyanate and/or carbodiimide groups, so that the resulting polycarbodiimide subsequently carries hydrophilic substituents which increase its water solubility or water dispersibility.

1. a) Umsetzen von wenigstens einem aliphatischen, cycloaliphatischen oder aromatischen Diisocyanat bei einer Temperatur im Bereich von 160 bis 230 °C in Gegenwart von 50 bis 3000 ppm Carbodiimidisierungskatalysator, bezogen auf die molare Menge an Diisocyanat zu einem Polycarbodiimid mit einer mittleren Funktionalität von 1 bis 10 Carbodiimideinheiten, wobei die Reaktionsgase zeitweise oder permanent gezielt aus dem Reaktionsmedium abgeführt werden,
2. b) Umsetzen des in Schritt a) erhaltenen Polycarbodiimids mit mindestens einer hydrophilen Verbindung, die mindestens eine gegenüber Isocyanat- und/oder Carbodiimidgruppen reaktionsfähige Gruppe trägt, die ausgewählt ist aus der Gruppe, bestehend aus Polyethoxymonoolen, Polyethoxydiolen, Polyethoxypolypropoxymonoolen, Polyethoxypolypropoxydiolen, Polyethoxymonoaminen, Polyethoxydiaminen, Polyethoxypolypropoxymonoaminen, Polyethoxypolypropoxydiaminen, Hydroxyalkylsulfonaten, Aminalkylsulfonaten, Polyethoxymonothiolen, Polyethoxydithiolen, Polyethoxymonocarbonsäuren, Polyethoxydicarbonsäuren, Monohydroxycarbonsäuren, Dihydroxycarbonsäuren und den Salzen der vorgenannten Säuren zu einem hydrophilierten Polycarbodiimid,
3. c) gegebenenfalls weiteres Umsetzen der nicht abreagierten Isocyanat-Gruppen mit weiteren gegenüber Isocyanat-Gruppen reaktionsfähigen Verbindungen, wie bevorzugt mit Wasser, mindestens einem C1-C4-Monoalkohol, insbesondere Methanol, Ethanol, n-Propanol, iso-Propanol, n-Butanol, sek.-Butanol und tert.-Butanol, Thiolen, Aminen, Mineralsäuren und Carbonsäuren.

Typically, hydrophilized polycarbodiimides used according to the invention and preferably according to the invention are prepared by a process comprising the following steps:

1. a) reacting at least one aliphatic, cycloaliphatic or aromatic diisocyanate at a temperature in the range from 160 to 230 °C in the presence of 50 to 3000 ppm of carbodiimidization catalyst, based on the molar amount of diisocyanate, to form a polycarbodiimide having an average functionality of 1 to 10 carbodiimide units, wherein the reaction gases are temporarily or permanently removed from the reaction medium in a targeted manner,
2. b) reacting the polycarbodiimide obtained in step a) with at least one hydrophilic compound which carries at least one group reactive towards isocyanate and/or carbodiimide groups, which is selected from the group consisting of polyethoxymonools, polyethoxydiols, polyethoxypolypropoxymonools, polyethoxypolypropoxydiols, polyethoxymonoamines, polyethoxydiamines, polyethoxypolypropoxymonoamines, polyethoxypolypropoxydiamines, hydroxyalkylsulfonates, aminealkylsulfonates, polyethoxymonothiols, polyethoxydithiols, polyethoxymonocarboxylic acids, polyethoxydicarboxylic acids, monohydroxycarboxylic acids, dihydroxycarboxylic acids and the salts of the aforementioned acids to form a hydrophilized polycarbodiimide,
3. c) optionally further reacting the unreacted isocyanate groups with further compounds reactive towards isocyanate groups, such as preferably with water, at least one C1-C4 monoalcohol, in particular methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol and tert-butanol, thiols, amines, mineral acids and carboxylic acids.

Preferably, the reaction of the polycarbodiimide containing isocyanate groups obtained in step a) according to the present invention is carried out such that 10 to 70 mol percent (mol %) of the isocyanate groups present in the polycarbodiimide are reacted with at least one hydrophilic compound as sub-step b1) of step b), wherein the hydrophilic compound is selected from the group consisting of polyethoxymonothiols, polyethoxydithiols, polyethoxymonocarboxylic acids, polyethoxydicarboxylic acids, monohydroxycarboxylic acids, dihydroxycarboxylic acids and the salts of the aforementioned acids, as well as mixtures of these compounds. In sub-step b2) of step b), 30-90 mol% of the remaining isocyanate groups are then reacted with at least one compound which is reactive towards isocyanate groups and which is selected from the group consisting of polyethoxymonothiols, polyethoxydithiols, polyethoxymonocarboxylic acids, polyethoxydicarboxylic acids, monohydroxycarboxylic acids, dihydroxycarboxylic acids, the salts of the aforementioned acids, water, at least one C1-C4 monoalcohol, in particular methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol and tert-butanol, _C1 - _C30 thiols, amines, mineral acids and carboxylic acids, and mixtures of these compounds.

Preferably, the reaction of the polycarbodiimides in sub-step b1) of step b) is carried out with at least one compound selected from the group of compounds corresponding to the formula (EO-1): R ¹ -O-(CH ₂ -CH ₂ -O)mH formula (EO-I), with R ¹ = C1- to C30-alkyl, C2- to C29-acyl or an aryl group
m = 4 to 60, preferably 4-20, particularly preferably 5-15, extremely preferably 6-9. particularly preferably with at least one compound selected from the group corresponding to the formula (EO-I), where R ¹ is a methyl group and m = 4-20, preferably 5-15, particularly preferably 6-9.

A particularly preferred compound of the formula (EO-I) is monomethoxypolyethylene glycol with m = 5-15.

Preferred hydrophilic compounds which can be used for a further reaction of the isocyanate groups present in the polycarbodiimide and not completely reacted with the hydrophilic compounds in sub-step b2) of step b) are water, C ₁ - C ₃₀ monoalcohols and C ₁ - C ₃₀ diols, each with a molecular weight in the range from 32 to 500 g/mol, particularly preferably in the range from 62 to 300 g/mol. Very particular preference is given to C ₁ - C ₃₀ monoalcohols, in particular methanol, ethanol, propanol, 1-butanol, 1-pentanol, 1-hexanol, cyclohexanol, cyclohexylmethanol, 2-ethylhexanol, dodecanol, stearyl alcohol or oleyl alcohol, mixtures thereof with one another and C ₁ - C ₃₀ diols, such as preferably 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, cyclohexanediol, cyclohexanedimethanol, 1,8-octanediol, 1,9-non adiol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, tricyclodecanedimethanol and mixtures thereof.

The hydrophilized polycarbodiimide obtained in process step b) can be dispersed in water and used in this water-dispersed form in the processes and kits according to the invention. The hydrophilized polycarbodiimide obtained in process step b) can also be used as a pure substance in the processes and kits according to the invention. In a preferred embodiment of the processes and kits according to the invention, the aqueous dispersion of the - preferably hydrophilized - polycarbodiimide is adjusted in a step d) to a pH in the range from 7 to 12 (at 20°C), particularly preferably in the range from 8 to 11. Amine solutions, alkalis and conventional buffer solutions can be used for this. The pH can be adjusted in step d) by adding a base selected from the group consisting of alkali hydroxides, ammonia and tertiary amines. Examples of alkali hydroxides are lithium hydroxide, sodium hydroxide and potassium hydroxide. Examples of tertiary amines are a trialkylamine such as triethylamine and ethanolamines. In an alternative embodiment, a buffer selected from the group consisting of phosphate buffers, tris(hydroxymethyl)aminomethane buffers and aminoalkylsulfonic acid buffers can be used to adjust the pH. The aqueous polycarbodiimide dispersions and/or solutions usually have a polycarbodiimide solids content of 10 to 80% by weight, preferably 20 to 60% by weight and particularly preferably 30 to 50% by weight, based on their weight.

worin

• n für eine ganze Zahl im Bereich von 3 bis 50, bevorzugt 4 bis 20, besonders bevorzugt 4 bis 10, außerordentlich bevorzugt 6 bis 7, steht; und
• R2 und R3, unabhängig voneinander, für einen von einer Verbindung, ausgewählt aus der Gruppe bestehend aus einem Monoalkoxy-poly(ethylenglykol) gemäß der allgemeinen Formel (EO-I) mit m = 4 bis 60, und einem von C1 bis C30 Alkohol oder einem C5 bis C90 Monoalkoxyethylenglykol abgeleiteten Rest stehen. Bevorzugte Verbindungen der allgemeinen Formel (XIV) tragen unabhängig voneinander als R2 und R3 Reste abgeleitet von Monomethoxypoly(ethylenglykol) gemäß der allgemeinen Formel (EO-I) mit m = 4-20, bevorzugt 5-15, besonders bevorzugt 6-9 und C1 bis C30 Monoalkoxyethylenglykol. Die besonders bevorzugte Verbindung der allgemeinen Formel (XIV) trägt unabhängig voneinander Reste R2 und R3 abgeleitet von Monomethoxypoly (ethylenglykol) gemäß der allgemeinen Formel (EO-I) mit m = 4-20, bevorzugt 5-15, besonders bevorzugt 6-9, sowie abgeleitet von Monobutoxyethylenglykol.

According to a preferred embodiment of the methods and kits according to the invention, the at least one polycarbodiimide is selected from compounds of the general structural formula (XIV) shown below

wherein

• n is an integer in the range from 3 to 50, preferably 4 to 20, particularly preferably 4 to 10, extremely preferably 6 to 7; and
• R2 and R3, independently of one another, represent a radical derived from a compound selected from the group consisting of a monoalkoxypoly(ethylene glycol) according to the general formula (EO-I) with m = 4 to 60, and a radical derived from C1 to C30 alcohol or a C5 to C90 monoalkoxyethylene glycol. Preferred compounds of the general formula (XIV) independently of one another carry as R2 and R3 radicals derived from monomethoxypoly(ethylene glycol) according to the general formula (EO-I) with m = 4-20, preferably 5-15, particularly preferably 6-9, and C1 to C30 monoalkoxyethylene glycol. The particularly preferred compound of the general formula (XIV) independently of one another carries radicals R2 and R3 derived from monomethoxypoly(ethylene glycol) according to the general formula (EO-I) with m = 4-20, preferably 5-15, particularly preferably 6-9, and derived from monobutoxyethylene glycol.

worin

• n für eine ganze Zahl im Bereich von 3 bis 50, bevorzugt 4 bis 20, besonders bevorzugt 4 bis 10, außerordentlich bevorzugt 6 bis 7, steht; und
• m für eine ganze Zahl im Bereich von 1 - 10, bevorzugt 1 - 5 steht.

According to a preferred embodiment of the methods and kits according to the invention, the at least one polycarbodiimide is selected from compounds of the general structural formula (XIII) shown below

wherein

• n is an integer in the range from 3 to 50, preferably 4 to 20, particularly preferably 4 to 10, extremely preferably 6 to 7; and
• m stands for an integer in the range 1 - 10, preferably 1 - 5.

Further (poly)carbodiimide compounds preferably used according to the invention can optionally contain in their structure one or more reactive groups which are different from carbodiimide groups, wherein these reactive groups are selected from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydealkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylalkylsilyl, (meth)acrylalkylalkyl, crotonylalkyl, alkylepoxide, e.g. propylepoxide or butylepoxide, and azacyclopropane groups. The reactive groups which are different from carbodiimide groups can be present in the (poly)carbodiimide terminally or as a side chain. Preferably, the at least one reactive group other than a carbodiimide group occupies a terminal position in the (poly)carbodiimide. Carbodiimides and polycarbodiimides preferably used according to the invention are characterized in that they have at least one reactive group other than a carbodiimide group in the terminal position, which is selected from an alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydealkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylalkylsilyl, (meth)acrylalkylalkyl, crotonylalkyl, alkylepoxide, e.g. propylepoxide or butylepoxide, or azacyclopropane group.

worin:

• -X₁ und X₂ unabhängig voneinander für ein Sauerstoff-Atom, ein Schwefel-Atom oder eine NH-Gruppe stehen;
• - R1 und R2 unabhängig voneinander für einen Substituenten stehen, der ausgewählt ist aus einer Kohlenwasserstoff-Gruppe, bevorzugt einer Alkyl-Gruppe, die optional durch ein oder mehrere Heteroatome unterbrochen sein kann, weiterhin ausgewählt aus einer Alkoxysilyl-, Hydroxysilyl-, Acetoxysilyl-, Vinylsilyl-, Acrylalkylsilyl-, Methacrylalkylsilyl-, Crotonylalkylsilyl-, Carboxyanhydridoalkylsilyl-, Carboxyalkylsilyl-, Hydroxyalkylsilyl-, Aldehydoalkylsilyl-, Mercaptoalkylsilyl-, Norbornenylsilyl-, Acylpentadienylalkylsilyl-, Maleimidoalkylsilyl-, Sulfonylalkylsilyl-, (Meth)acrylalkyl-, Crotonylalkyl-, Alkylepoxid-, z. B. Propylepoxid- oder Butylepoxid-, und Azacyclopropan-Gruppe,
• - n für eine ganze Zahl im Bereich von 1 bis 200, bevorzugt 2 bis 200, besonders bevorzugt 3 bis 150, weiter besonders bevorzugt 4 bis 100, weiter besonders bevorzugt 4 bis 50, weiter besonders bevorzugt 4 bis 10, außerordentlich bevorzugt 6 bis 7, steht; und
• - A für eine divalente Gruppe steht, die aus den nachstehend dargestellten Substituenten ausgewählt ist:
  
  
  
  
  

According to a preferred embodiment of the methods and kits according to the invention, the at least one carbodiimide or polycarbodiimide is selected from compounds of the general structural formula (CDI-I) shown below

wherein:

• -X ₁ and X ₂ independently represent an oxygen atom, a sulfur atom or an NH group;
• - R1 and R2 independently of one another represent a substituent which is selected from a hydrocarbon group, preferably an alkyl group, which can optionally be interrupted by one or more heteroatoms, further selected from an alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydealkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylalkylsilyl, (meth)acrylalkylalkyl, crotonylalkyl, alkylepoxide, e.g. propylepoxide or butylepoxide, and azacyclopropane group,
• - n is an integer in the range from 1 to 200, preferably 2 to 200, particularly preferably 3 to 150, further particularly preferably 4 to 100, further particularly preferably 4 to 50, further particularly preferably 4 to 10, extremely preferably 6 to 7; and
• - A represents a divalent group selected from the substituents shown below:
  
  
  
  
  

worin

• -X₁ und X₂ unabhängig voneinander für ein Sauerstoff-Atom, ein Schwefel-Atom oder eine NH-Gruppe stehen,
• -Y1 und Y2 unabhängig voneinander für eine divalente organische Gruppe stehen, die ausgewählt ist aus einer gesättigten, aliphatischen C₁ - C₃₆-Gruppe oder einer aromatischen C₆ - C₂₄-Gruppe, wobei die aliphatische oder die aromatische Gruppe optional von mindestens einem Heteroatom, wie einem Stickstoff-Atom, einem Sauerstoff-Atom oder einem Schwefel-Atom, unterbrochen sein kann;
• - Z₁ und Z₂ unabhängig voneinander für eine reaktive Endgruppe oder für eine inerte Endgruppe stehen;
• - wenn Z₁ und/oder Z₂ für eine inerte Endgruppe stehen, so können:
  • - Z₁ und/oder Z₂ unabhängig voneinander für eine lineare, verzweigte oder zyklische C1-C50-Gruppe, die jeweils gesättigt und aliphatisch ist, oder für eine aromatische C6-C18-Gruppe stehen, wobei die aliphatische oder die aromatische Gruppe optional von 1 bis 10 Heteroatomen, ausgewählt aus mindestens einem Stickstoff-Atom, einem Sauerstoff-Atom oder einem Schwefel-Atom, sowie Mischungen hiervon, unterbrochen sein kann; und wobei die aliphatische oder die aromatische Gruppe optional teilweise oder vollständig fluoriert sein kann;
  • - wobei Z₁ und Z₂ jeweils eine Verbindungsgruppe V aufweisen, die Z₁ mit Y₁ und Z₂ mit Y₂ verbindet, wobei die Verbindungsgruppen V ausgewählt sind aus einer Einfachbindung, einer C-C-Einfachbindung, einer C=C-Doppelbindung, einer Amid-Gruppe, einer EsterGruppe, einer Carbonat-Gruppe, einer Thioester-Gruppe, einer Ether-Gruppe, einer Urethan-Gruppe, einer Thiourethan-Gruppe oder einer Harnstoff-Gruppe;
• - wenn Z₁ und/oder Z₂ für eine reaktive Endgruppe stehen, so können Z₁ und Z₂ unabhängig voneinander für eine Alkoxysilyl-, Hydroxysilyl-, Acetoxysilyl-, Vinylsilyl-, Acrylalkylsilyl-, Methacrylalkylsilyl-, Crotonylalkylsilyl-, Carboxyanhydridoalkylsilyl-, Carboxyalkylsilyl-, Hydroxyalkylsilyl-, Aldehydoalkylsilyl-, Mercaptoalkylsilyl-, Norbornenylsilyl-, Acylpentadienylalkylsilyl-, Maleimidoalkylsilyl-, Sulfonylalkylsilyl-, (Meth)acrylalkyl-, Crotonylalkyl-, Alkylepoxid-, z. B. Propylepoxid- oder Butylepoxid-, und Azacyclopropan-Gruppe stehen;
• - Q für ein Organopolymer oder ein Organooligomer mit sich wiederholenden Einheiten von linearen, verzweigten oder zyklischen Gruppen steht, die gesättigt und aliphatisch sind, oder mit sich wiederholenden Einheiten von aromatischen Gruppen, die jeweils durch Carbonat-, Ester-, Ether-, Amid-, Urethan- oder Harnstoffgruppen oder Mischungen hiervon miteinander verknüpft sind;
• - A für eine divalente organische Gruppe steht, die ausgewählt ist aus einer aliphatischen oder einer aromatischen Gruppe mit 2 bis 30 Kohlenstoffatomen, wobei die aliphatische oder die aromatische Gruppe optional von mindestens einem Heteroatom, wie einem Stickstoff-Atom, einem Sauerstoff-Atom oder einem Schwefel-Atom, unterbrochen sein kann;
• - r für Null oder 1 steht;
• - m für eine ganze Zahl im Bereich von 0 bis 200, bevorzugt für Null oder 1 steht;
• - m' für eine ganze Zahl im Bereich von 0 bis 200, bevorzugt für Null oder 1 steht;
• - n für eine ganze Zahl im Bereich von 0 bis 200, bevorzugt für Null oder 1 steht, mit (m + m'·n) > 2.

According to a preferred embodiment of the methods and kits according to the invention, the at least one carbodiimide or polycarbodiimide is selected from compounds of the general structural formula (la) shown below,

wherein

• -X ₁ and X ₂ independently represent an oxygen atom, a sulfur atom or an NH group,
• -Y1 and Y2 independently represent a divalent organic group selected from a saturated, aliphatic C ₁ - C ₃₆ group or an aromatic C ₆ - C ₂₄ group, wherein the aliphatic or aromatic group may optionally be interrupted by at least one heteroatom, such as a nitrogen atom, an oxygen atom or a sulfur atom;
• - Z ₁ and Z ₂ independently represent a reactive end group or an inert end group;
• - if Z ₁ and/or Z ₂ represent an inert end group, then:
  • - Z ₁ and/or Z ₂ independently of one another represent a linear, branched or cyclic C1-C50 group, which is in each case saturated and aliphatic, or an aromatic C6-C18 group, where the aliphatic or aromatic group can optionally be interrupted by 1 to 10 heteroatoms selected from at least one nitrogen atom, one oxygen atom or one sulfur atom, and mixtures thereof; and where the aliphatic or aromatic group can optionally be partially or fully fluorinated;
  • - wherein Z ₁ and Z ₂ each have a linking group V which links Z ₁ to Y ₁ and Z ₂ to Y ₂ , wherein the linking groups V are selected from a single bond, a CC single bond, a C=C double bond, an amide group, an ester group, a carbonate group, a thioester group, an ether group, a urethane group, a thiourethane group or a urea group;
• - when Z ₁ and/or Z ₂ represent a reactive end group, Z ₁ and Z ₂ can independently of one another represent an alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydoalkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkylepoxide, e.g. propylepoxide or butylepoxide, and azacyclopropane group;
• - Q represents an organopolymer or an organooligomer comprising repeating units of linear, branched or cyclic groups which are saturated and aliphatic, or comprising repeating units of aromatic groups each linked to one another by carbonate, ester, ether, amide, urethane or urea groups or mixtures thereof;
• - A represents a divalent organic group selected from an aliphatic or an aromatic group having 2 to 30 carbon atoms, wherein the aliphatic or aromatic group may optionally be interrupted by at least one heteroatom, such as a nitrogen atom, an oxygen atom or a sulfur atom;
• - r stands for zero or 1;
• - m stands for an integer in the range from 0 to 200, preferably zero or 1;
• - m' stands for an integer in the range from 0 to 200, preferably zero or 1;
• - n is an integer in the range 0 to 200, preferably zero or 1, with (m + m'·n) > 2.

Preferably used carbodiimides or polycarbodiimides are compounds of the structural formula (Ia) in which Z ₁ and Z ₂ independently of one another represent a reactive end group, particularly preferably a reactive end group selected from at least one alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydealkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylalkylsilyl, (meth)acrylalkylalkyl, crotonylalkyl, alkylepoxide, e.g. propylepoxide or butylepoxide, or azacyclopropane group. Such (poly)carbodiimide components are commercially available, for example from Stahl BV under the trade names Permutex, RelcaLink or Picassian XL and from Nisshinbo under the trade name Carbodilite with the serial numbers V-02, V-02-L2, SV-02, E-02, V-10, SW-12G, E-03A, E-04DG-T, E-05, V- 04, V-02B, V-04PF and V-05.

worin

• -X₁ und X₂ unabhängig voneinander für ein Sauerstoff-Atom, ein Schwefel-Atom oder eine NH-Gruppe stehen,
• -R₁ und R₂ unabhängig voneinander für eine Kohlenwasserstoff-basierte Gruppe stehen, die optional durch ein oder mehrere Heteroatome unterbrochen sein kann;
• - n und z für eine ganze Zahl im Bereich von 1 bis 20 stehen, mit n+z > 2, und w für eine ganze Zahl im Bereich von 0 bis 3 steht;
• - L₁ unabhängig voneinander für eine divalente aliphatische Kohlenwasserstoff-basierte C1-C18-Gruppe, eine C3-C15-Cycloalkylen-Gruppe, eine C3-C12-Heterocycloalkylen-Gruppe oder eine C6-C14-Arylen-Gruppe, sowie Mischungen hiervon steht;
• - E für eine Gruppe steht, die ausgewählt ist aus -O-R³-O-, -S-R⁴-S-, -R⁵-N(R⁶)-R⁴-N(R⁶)-R⁵-, worin
  • - R³ und R⁴ unabhängig voneinander für eine Kohlenwasserstoff-basierte Gruppe stehen, die optional durch ein oder mehrere Heteroatome unterbrochen sein kann;
  • - R⁵ unabhängig für eine kovalente Bindung oder eine gesättigte divalente Kohlenwasserstoff-basierte Gruppe steht, die optional durch ein oder mehrere Heteroatome unterbrochen sein kann;
  • - R⁶ unabhängig für ein Wasserstoffatom oder eine Kohlenwasserstoff-basierte Gruppe steht, die optional durch ein oder mehrere Heteroatome unterbrochen sein kann.

According to a further preferred embodiment of the methods and kits according to the invention, the at least one carbodiimide or polycarbodiimide is selected from compounds of the general structural formula (II) shown below:

wherein

• -X ₁ and X ₂ independently represent an oxygen atom, a sulfur atom or an NH group,
• -R ₁ and R ₂ independently represent a hydrocarbon-based group which may optionally be interrupted by one or more heteroatoms;
• - n and z are integers in the range 1 to 20, with n+z > 2, and w is integers in the range 0 to 3;
• - L ₁ independently represents a divalent aliphatic hydrocarbon-based C1-C18 group, a C3-C15 cycloalkylene group, a C3-C12 heterocycloalkylene group or a C6-C14 arylene group, and mixtures thereof;
• - E represents a group selected from -OR ³ -O-, -SR ⁴ -S-, -R ⁵ -N(R ⁶ )-R ⁴ -N(R ⁶ )-R ⁵ -, wherein
  • - R ³ and R ⁴ independently represent a hydrocarbon-based group which may optionally be interrupted by one or more heteroatoms;
  • - R ⁵ independently represents a covalent bond or a saturated divalent hydrocarbon-based group which may optionally be interrupted by one or more heteroatoms;
  • - R ⁶ independently represents a hydrogen atom or a hydrocarbon-based group which may optionally be interrupted by one or more heteroatoms.

The term "hydrocarbon-based group" means a saturated or unsaturated, linear or branched group having 1 to 300 carbon atoms, preferably 1 to 250 carbon atoms, particularly preferably 1 to 200 carbon atoms. Preferably, the hydrocarbon-based group is a saturated linear hydrocarbon group.

The hydrocarbon-based group may have one or more cyclic groups. The hydrocarbon-based group may be interrupted by one or more heteroatoms, in particular selected from O, S or N.

The hydrocarbon-based group can be substituted with one or more cationic, anionic or zwitterionic groups, for example with cationic ammonium groups or anionic carboxylate groups. The charge of the entire compound is neutralized by corresponding oppositely charged anions or cations.

The term “heteroatom” stands for an oxygen atom, a sulfur atom or a nitrogen atom and, if the heteroatom is not incorporated into a chain, also for a halogen atom, in particular for Cl, F, Br and I. Preferred heteroatoms are selected from an oxygen, sulfur or nitrogen atom.

Preferably, X1 and X2 independently represent an oxygen atom. Particularly preferably, X1 and X2 each represent an oxygen atom.

Preferred methods and kits according to the invention are characterized in that in the polycarbodiimide of the above structural formula (II) used therein, the substituents R ¹ and R ² are independently selected from dialkylamino alcohols, hydroxycarboxylic acid alkyl esters and (poly)alkylene glycol monoalkyl ethers in which the hydroxyl group is absent, and mixtures thereof.

1. (i) Gruppen gemäß der Strukturformel (III) R⁷-O-C(O)-C(R⁸)(H)- (III), worin R⁷für eine C₁-C₃-Alkyl-Gruppe und R⁸ für ein Wasserstoffatom oder eine C₁-C₃-Alkyl- Gruppe stehen; wobei bevorzugt R⁷für eine Methyl-Gruppe und R⁸ für ein Wasserstoff - atom oder für eine Methyl-Gruppe stehen;
2. (ii) Gruppen gemäß der Strukturformel (IV) R⁹-[O-CH₂-CH(R¹⁰)]_p- (IV), worin R⁹ für eine C₁-C₄-Alkyl-Gruppe, R¹⁰ für ein Wasserstoffatom oder eine C₁-C₄-Alkyl-Gruppe und p für eine ganze Zahl von 1 bis 3 stehen; wobei bevorzugt R⁹ für eine Methyl-, Ethyl- oder Butyl-Gruppe, R¹⁰ für ein Wasserstoffatom oder eine Methyl-Gruppe stehen und p gleich 1 ist;
3. (iii) Gruppen gemäß der Strukturformel (V) (R¹¹)₂N-CH₂-CH(R¹²)- (V), worin R¹¹ für eine C₁-C₄-Alkyl-Gruppe und R¹² für ein Wasserstoffatom oder eine C₁-C₄-Alkyl-Gruppe stehen; wobei bevorzugt R¹¹ für eine Methyl-, Ethyl- oder Butyl-Gruppe und R¹² für ein Wasserstoffatom oder eine Methyl-Gruppe stehen,
4. (iv) Gruppen gemäß der Strukturformel (VI) R¹³-[O-CH₂-CH(R¹⁴)]_q- (VI), worin R¹³ für eine C₁-C₄-Alkyl-Gruppe oder eine Phenyl-Gruppe, R¹⁴ für ein Wasserstoffatom oder eine C₁-C₄-Alkyl-Gruppe und q für eine ganze Zahl von 4 bis 30 stehen; wobei bevorzugt R¹³ für eine Methyl-, Ethyl- oder Butyl-Gruppe und R¹⁴ für ein Wasserstoffatom oder eine Methyl-Gruppe stehen.

Particularly preferred methods and kits according to the invention are characterized in that in the polycarbodiimide of the above structural formula (II) used therein, the substituents R ¹ and R ² are independently selected from groups (i) to (iv), as shown below:

1. (i) Groups according to the structural formula (III) R ⁷ -OC(O)-C(R ⁸ )(H)- (III), wherein R ⁷ represents a C ₁ -C ₃ alkyl group and R ⁸ represents a hydrogen atom or a C ₁ -C ₃ alkyl group; preferably R ⁷ represents a methyl group and R ⁸ represents a hydrogen atom or a methyl group;
2. (ii) Groups according to the structural formula (IV) R ⁹ -[O-CH ₂ -CH(R ¹⁰ )] _p - (IV), wherein R ⁹ represents a C ₁ -C ₄ alkyl group, R ¹⁰ represents a hydrogen atom or a C ₁ -C ₄ alkyl group and p represents an integer from 1 to 3; preferably R ⁹ represents a methyl, ethyl or butyl group, R ¹⁰ represents a hydrogen atom or a methyl group and p is 1;
3. (iii) Groups according to the structural formula (V) (R ¹¹ ) ₂ N-CH ₂ -CH(R ¹² )- (V), wherein R ¹¹ is a C ₁ -C ₄ alkyl group and R ¹² is a hydrogen atom or a C ₁ -C ₄ alkyl group; preferably R ¹¹ is a methyl, ethyl or butyl group and R ¹² is a hydrogen atom or a methyl group,
4. (iv) Groups according to the structural formula (VI) R ¹³ -[O-CH ₂ -CH(R ¹⁴ )] _q - (VI), wherein R ¹³ represents a C ₁ -C ₄ alkyl group or a phenyl group, R ¹⁴ represents a hydrogen atom or a C ₁ -C ₄ alkyl group and q represents an integer from 4 to 30; preferably R ¹³ represents a methyl, ethyl or butyl group and R ¹⁴ represents a hydrogen atom or a methyl group.

Preferably, R ¹ and R ² independently of one another represent a group according to the structural formula (VI), in which R ¹³ represents a C ₁ -C ₄ alkyl group or a phenyl group, preferably a C ₁ -C ₄ alkyl group, particularly preferably a methyl group, R ¹⁴ represents a hydrogen atom or a C ₁ -C ₄ alkyl group, preferably a hydrogen atom, and q is an integer from 4 to 30.

According to a further preferred alternative, methods and kits according to the invention are characterized in that in the polycarbodiimide of the above structural formula (II) used therein, the substituents R ¹ and R ² are different from one another and one of the groups R ¹ or R ² stands for a group according to the above-described structural formula (IV) and the other group R ¹ or R ² stands for a group according to the above-described structural formula (VI). In this preferred embodiment of the invention, in group (IV), R ⁹ stands for a methyl, ethyl or butyl group, R ¹⁰ stands for a hydrogen atom or a methyl group, and p is 1. In this preferred embodiment of the invention, in group (VI), R ¹³ stands for a methyl, ethyl or butyl group, R ¹⁴ stands for a hydrogen atom or a methyl group, and q stands for an integer from 4 to 30.

According to a further preferred alternative, methods and kits according to the invention are characterized in that in the polycarbodiimide of the above structural formula (II) used therein, the substituents R ¹ and R ² are identical and stand for a group according to the structural formula (VI) described above, in which R ¹³ stands for a C ₁ -C ₄ alkyl group or a phenyl group, preferably for a C ₁ -C ₄ alkyl group, particularly preferably for a methyl group, R ¹⁴ stands for a hydrogen atom or a C ₁ -C ₄ alkyl group, preferably for a hydrogen atom and q stands for an integer from 4 to 30.

According to a further preferred alternative, methods and kits according to the invention are characterized in that in the polycarbodiimide of the above structural formula (II) used therein, the index n stands for an integer in the range from 1 to 20, preferably from 2 to 20.

According to a further preferred alternative, methods and kits according to the invention are characterized in that in the polycarbodiimide of the above structural formula (II) used therein, the index z stands for an integer in the range from 1 to 20, preferably from 2 to 20.

According to a further preferred alternative, methods and kits according to the invention are characterized in that in the polycarbodiimide of the above structural formula (II) used therein, the index w stands for the value 1 and the sum n+z stands for an integer in the range from 4 to 10.

According to a further preferred alternative, methods and kits according to the invention are characterized in that in the polycarbodiimide of the above structural formula (II) used therein, the group L ₁ is selected from a divalent aliphatic C ₁ -C ₁₈ hydrocarbon-based group, in particular methylene, ethylene and propylene, further selected from a C ₃ -C ₁₅ cycloalkylene group, such as in particular 4,4'-dicyclohexylenemethane, cyclopentylene, cycloheptylene and cyclohexylene, further selected from a C ₃ -C ₁₂ heterocycloalkylene group, such as imidazolene, pyrrolene and furanylene, or selected from a C ₆ -C ₁₄ arylene group, such as phen-1,3-dioctylcyclobutylene, tetramethylxylylene, isophorone, 1,5-naphthylene, 4,4'-diphenylmethylene, 4,4'-diphenyldimethylmethylene and phenylene, as well as mixtures thereof.

According to a particularly preferred alternative, methods and kits according to the invention are characterized in that in the polycarbodiimide of the above structural formula (II) used therein, the group L ₁ is selected from a C ₃ -C ₁₅ cycloalkylene group, a C ₆ -C ₁₄ arylene group or mixtures thereof. Examples of particularly preferred ones are shown below with the structures (VII-1) to (VII-14):

L ₁ is preferably 4,4'-dicyclohexylenemethane according to the following formula (VII-7)

• - -O-R³-O-; -S-R⁴-S-; -R⁵-N(R^e)-R⁴-N(R^e)-R⁵-; worin
• - R³ und R⁴ unabhängig voneinander für eine divalente Kohlenwasserstoff-basierte Gruppe stehen, die optional durch ein oder mehrere Heteroatome unterbrochen sein kann,
• - R⁵ unabhängig für eine kovalente Bindung oder eine gesättigte divalente Kohlenwasserstoff-basierte Gruppe steht, die optional durch ein oder mehrere Heteroatome unterbrochen sein kann; und
• - R⁶ unabhängig für ein Wasserstoffatom oder eine Kohlenwasserstoff-basierte Gruppe steht, die optional durch ein oder mehrere Heteroatome unterbrochen sein kann.

According to a further preferred alternative, methods and kits according to the invention are characterized in that in the polycarbodiimide of the above structural formula (II) used therein, the group E independently represents a group selected from:

• - -OR ³ -O-; -SR ⁴ -S-; -R ⁵ -N(R ^e )-R ⁴ -N(R ^e )-R ⁵ -; wherein
• - R ³ and R ⁴ independently represent a divalent hydrocarbon-based group which may optionally be interrupted by one or more heteroatoms,
• - R ⁵ independently represents a covalent bond or a saturated divalent hydrocarbon-based group which may optionally be interrupted by one or more heteroatoms; and
• - R ⁶ independently represents a hydrogen atom or a hydrocarbon-based group which may optionally be interrupted by one or more heteroatoms.

According to a further particularly preferred alternative, methods and kits according to the invention are characterized in that in the polycarbodiimide of the above structural formula (II) used therein, the groups R ³ and R ⁴ are selected independently of one another from a C ₆ -C ₁₄ arylene group, preferably selected from a phenylene group, further selected from a C 3 -C 15 cycloalkylene group, such as in particular cyclopropylene and cyclobutylene, further selected from a linear or branched C ₁ -C ₁₈ alkylene group, such as methylene and ethylene, optionally interrupted by one or more heteroatoms, and mixtures thereof. According to a further particularly preferred alternative, methods and kits according to the invention are characterized in that in the polycarbodiimide of the above structural formula (II) used therein, in the substituent E, the groups R ³ and R ⁴ are selected independently of one another are composed of a linear or branched C ₁ -C ₁₈ alkylene group, such as methylene, butylene, propylene or ethylene, optionally interrupted by one or more heteroatoms.

According to a further particularly preferred alternative, methods and kits according to the invention are characterized in that in the polycarbodiimide of the above structural formula (II) used therein, in the substituent E, the group R ⁵ does not represent a single bond, but is selected from a C 6 -C 14 arylene group, preferably selected from a phenylene group, further selected from a C ₃ -C ₁₂ cycloalkylene group, such as in particular cyclopropylene and cyclobutylene, further selected from a linear or branched C ₁ -C ₁₈ alkylene group, such as methylene and ethylene, optionally interrupted by one or more heteroatoms, and mixtures thereof.

According to a further particularly preferred alternative, methods and kits according to the invention are characterized in that in the polycarbodiimide of the above structural formula (II) used therein, in the substituent E, the group R ⁶ is selected from a C ₆ -C ₁₄ arylene group, preferably selected from a phenylene group, further selected from a C ₃ -C ₁₂ cycloalkylene group, such as in particular cyclopropylene and cyclobutylene, further selected from a linear or branched C ₁ -C ₁₈ alkylene group, such as methylene and ethylene, optionally interrupted by one or more heteroatoms, and mixtures thereof.

According to a further particularly preferred alternative, methods and kits according to the invention are characterized in that in the polycarbodiimide of the above structural formula (II) used therein, the substituent E stands for a group -OR ³ -O-, in which R ³ is selected from a C6-C14 arylene group, preferably selected from a phenylene group, further selected from a C ₃ -C ₁₂ cycloalkylene group, such as in particular cyclopropylene and cyclobutylene, further selected from a linear or branched C ₁ -C ₁₈ alkylene group, such as methylene, butylene, propylene or ethylene, optionally interrupted by one or more heteroatoms, and mixtures thereof. According to a further extremely preferred alternative, methods and kits according to the invention are characterized in that in the polycarbodiimide of the above structural formula (II) used therein, the substituent E stands for a group -OR ³ -O-, in which R ³ is selected from a linear or branched C ₁ -C ₁₈ alkylene group, such as methylene, butylene, propylene or ethylene, optionally interrupted by one or more heteroatoms.

worin

• R unabhängig voneinander für eine Gruppe steht, die ausgewählt ist aus einer linearen oder verzweigten C₁-C₂₄-Alkyl-Gruppe, bevorzugt einer Methyl-, Ethyl- oder Butyl-Gruppe, weiterhin ausgewählt aus einer Cycloalkyl-Gruppe mit 3 bis 24 Kohlenstoffatomen und einer Aryl-Gruppe mit 6 bis 24 Kohlenstoffatomen, und
• n für eine ganze Zahl im Bereich von 2 bis 100, bevorzugt im Bereich von 2 bis 50, besonders bevorzugt im Bereich von 3 bis 30 und außerordentlich bevorzugt im Bereich von 5 bis 10 steht.

According to a further particularly preferred alternative, methods and kits according to the invention are characterized in that the polycarbodiimide used therein was obtained by polycondensation of alpha-methylstyryl isocyanates, so that the polycarbodiimide contains alpha-methylstyrylene monomers according to the following structural formula (X):

wherein

• R independently represents a group selected from a linear or branched C ₁ -C ₂₄ alkyl group, preferably a methyl, ethyl or butyl group, further selected from a cycloalkyl group having 3 to 24 carbon atoms and an aryl group having 6 to 24 carbon atoms, and
• n is an integer in the range from 2 to 100, preferably in the range from 2 to 50, particularly preferably in the range from 3 to 30 and extremely preferably in the range from 5 to 10.

In this embodiment, the terms “cycloalkyl” group and “aryl” group correspond to the above definitions.

worin R unabhängig voneinander für eine lineare oder verzweigte Alkyl-Gruppe mit 1 bis 24 Kohlenstoffatomen, bevorzugt für eine Methyl-, Ethyl- oder Butyl-Gruppe, weiterhin für eine Cycloalkyl-Gruppe mit 3 bis 24 Kohlenstoffatomen oder eine Aryl-Gruppe mit 6 bis 24 Kohlenstoffatomen steht.According to a further particularly preferred alternative, methods and kits according to the invention are characterized in that the polycarbodiimide used therein is a tricarbodiimide according to the following structural formula (XI):

wherein R independently represents a linear or branched alkyl group having 1 to 24 carbon atoms, preferably a methyl, ethyl or butyl group, furthermore a cycloalkyl group having 3 to 24 carbon atoms or an aryl group having 6 to 24 carbon atoms.

In this embodiment, the terms “cycloalkyl” group and “aryl” group correspond to the above definitions.

in denen:

• - X¹ und X² jeweils ein Sauerstoff-Atom repräsentieren;
• - R¹ und R² unabhängig voneinander ausgewählt sind aus der Gruppe, bestehend aus Dialkylaminoalkoholen, Alkylestern von Hydroxycarbonsäuren und Monoalkylethern von Polyalkylenglycol, in denen die Hydroxyl-Gruppe entfernt wurde, und Mischungen hiervon, bevorzugt ausgewählt aus Monoalkylethern von Polyalkylenglycol, in denen die Hydroxyl-Gruppe entfernt wurde, besonders bevorzugt ausgewählt aus mindestens einer Komponente der vorstehend beschriebenen Strukturformel (VI), worin
  • - R¹³ für eine C₁-C₄-Alkyl-Gruppe oder eine Phenyl-Gruppe, bevorzugt für eine C₁-C₄-Alkyl-Gruppe, besonders bevorzugt für eine Methyl-Gruppe steht,
  • - R¹⁴ für ein Wasserstoff-Atom oder für eine C₁-C₄-Alkyl-Gruppe, bevorzugt für ein Wasserstoff-Atom steht, und
  • - q für eine ganze Zahl im Bereich von 1 bis 30 steht;
  • - n und z für eine ganze Zahl im Bereich von 1 bis 20 stehen, mit n+z > 2, und w für die Zahl null oder 1 steht;
• - L₁ ausgewählt ist aus einer divalenten aliphatischen C₁-C₁₈ Kohlenwasserstoff-basierten Gruppe, insbesondere Methylen-, Ethylen- und Propylen-, weiterhin ausgewählt aus einer C₃-C₁₅-Cycloalkylen-Gruppe, wie insbesondere 4,4'-Dicyclohexylenmethan, Cyclopentylen-, Cycloheptylen- und Cyclohexylen-, weiterhin ausgewählt aus einer C₃-C₁₂-Heterocycloalkylen-Gruppe, wie Imidazolen-, Pyrrolen- und Furanylen-, oder ausgewählt aus einer C6-C14-Arylen-Gruppe, wie Phen-1,3-dioctylcyclobutylen-, Tetramethylxylylen-, Isophoron-, 1,5-Naphthylen-, 4,4'-Diphenylmethylen-, 4,4'-Diphenyldimethylmethylen- und Phenylen-, sowie Mischungen hiervon, wobei L₁ besonders bevorzugt ausgewählt ist aus einer C3-C15-Cycloalkylen-Gruppe, wie insbesondere 4,4'-Dicyclohexylenmethan, Cyclopentylen-, Cycloheptylen- und Cyclohexylen-,
• - A ausgewählt ist aus einer divalenten aliphatischen C₁-C₁₈-Kohlenwasserstoff-basierten Gruppe, insbesondere Methylen-, Ethylen- und Propylen-, weiterhin ausgewählt aus einer C₃-C₁₅-Cycloalkylen-Gruppe, wie insbesondere 4,4'-Dicyclohexylenmethan, Cyclopentylen-, Cycloheptylen- und Cyclohexylen-, weiterhin ausgewählt aus einer C₃-C₁₂-Heterocycloalkylen-Gruppe, wie Imidazolen-, Pyrrolen- und Furanylen-, oder ausgewählt aus einer C6-C14-Arylen-Gruppe, wie Phen-1,3-dioctylcyclobutylen-, Tetramethylxylylen-, Isophoron-, 1,5-Naphthylen-, 4,4'-Diphenylmethylen-, 4,4'-Diphenyldimethylmethylen- und Phenylen-, sowie Mischungen hiervon, wobei L₁ besonders bevorzugt ausgewählt ist aus einer C3-C15-Cycloalkylen-Gruppe, wie insbesondere 4,4'-Dicyclohexylenmethan, Cyclopentylen-, Cycloheptylen- und Cyclohexylen-,
• - E unabhängig für eine Gruppe steht, die ausgewählt aus:
  • -O-R³-O-; -S-R⁴-S-; -R^S-N(R⁶)-R⁴-N(R⁶)-R⁵-; worin
  • - R³ und R⁴ unabhängig voneinander für eine divalente C6-C14-Arylen-Gruppe, eine C₃-C₁₂-Cycloalkylen-Gruppe, eine lineare oder verzweigte C₁-C₁₈-Alkylen-Gruppe, die optional durch ein oder mehrere Heteroatome unterbrochen ist, und Mischungen hiervon stehen;
  • - R⁵ ausgewählt ist aus einer divalenten C6-C14-Arylen-Gruppe, einer C₃-C₁₂-CycloalkylenGruppe, einer linearen oder verzweigten C₁-C₁₈-Alkylen-Gruppe, optional durch ein oder mehrere Heteroatome unterbrochen, und Mischungen hiervon; und
  • - R⁶ ausgewählt ist aus einer divalenten C6-C14-Arylen-Gruppe, einer C₃-C₁₂-CycloalkylenGruppe, einer linearen oder verzweigten C₁-C₁₈-Alkylen-Gruppe, optional durch ein oder mehrere Heteroatome unterbrochen, und Mischungen hiervon.

According to a further particularly preferred alternative, methods and kits according to the invention are characterized in that the polycarbodiimide used therein is selected from at least one compound according to one of the following structural formulas (CDI-I) or (II),

in which:

• - X ¹ and X ² each represent an oxygen atom;
• - R ¹ and R ² are independently selected from the group consisting of dialkylamino alcohols, alkyl esters of hydroxycarboxylic acids and monoalkyl ethers of polyalkylene glycol in which the hydroxyl group has been removed, and mixtures thereof, preferably selected from monoalkyl ethers of polyalkylene glycol in which the hydroxyl group has been removed, particularly preferably selected from at least one component of the structural formula (VI) described above, wherein
  • - R ¹³ represents a C ₁ -C ₄ alkyl group or a phenyl group, preferably a C ₁ -C ₄ alkyl group, particularly preferably a methyl group,
  • - R ¹⁴ represents a hydrogen atom or a C ₁ -C ₄ alkyl group, preferably a hydrogen atom, and
  • - q is an integer in the range 1 to 30;
  • - n and z are integers in the range 1 to 20, with n+z > 2, and w is zero or 1;
• - L ₁ is selected from a divalent aliphatic C ₁ -C ₁₈ hydrocarbon-based group, in particular methylene, ethylene and propylene, further selected from a C ₃ -C ₁₅ cycloalkylene group, such as in particular 4,4'-dicyclohexylenemethane, cyclopentylene, cycloheptylene and cyclohexylene, further selected from a C ₃ -C ₁₂ heterocycloalkylene group, such as imidazoles, pyrroles and furanylenes, or selected from a C6-C14 arylene group, such as phen-1,3-dioctylcyclobutylene, tetramethylxylylene, isophorone, 1,5-naphthylene, 4,4'-diphenylmethylene, 4,4'-diphenyldimethylmethylene and phenylene, and mixtures thereof, where L ₁ is particularly preferably selected from a C3-C15-cycloalkylene group, such as in particular 4,4'-dicyclohexylenemethane, cyclopentylene, cycloheptylene and cyclohexylene,
• - A is selected from a divalent aliphatic C ₁ -C ₁₈ hydrocarbon-based group, in particular methylene, ethylene and propylene, further selected from a C ₃ -C ₁₅ cycloalkylene group, such as in particular 4,4'-dicyclohexylenemethane, cyclopentylene, cycloheptylene and cyclohexylene, further selected from a C ₃ -C ₁₂ heterocycloalkylene group, such as imidazolene, pyrrolene and furanylene, or selected from a C6-C14 arylene group, such as phen-1,3-dioctylcyclobutylene, tetramethylxylylene, isophorone, 1,5-naphthylene, 4,4'-diphenylmethylene, 4,4'-diphenyldimethylmethylene and phenylene, and mixtures thereof, where L ₁ is particularly preferably selected from a C3-C15-cycloalkylene group, such as in particular 4,4'-dicyclohexylenemethane, cyclopentylene, cycloheptylene and cyclohexylene,
• - E independently stands for a group selected from:
  • -OR ³ -O-; -SR ⁴ -S-; -R ^S -N(R ⁶ )-R ⁴ -N(R ⁶ )-R ⁵ -; wherein
  • - R ³ and R ⁴ independently of one another represent a divalent C 6 -C 14 arylene group, a C ₃ -C ₁₂ cycloalkylene group, a linear or branched C ₁ -C ₁₈ alkylene group which is optionally interrupted by one or more heteroatoms, and mixtures thereof;
  • - R ⁵ is selected from a divalent C6-C14 arylene group, a C ₃ -C ₁₂ cycloalkylene group, a linear or branched C ₁ -C ₁₈ alkylene group, optionally interrupted by one or more heteroatoms, and mixtures thereof; and
  • - R ⁶ is selected from a divalent C 6 -C 14 arylene group, a C ₃ -C ₁₂ cycloalkylene group, a linear or branched C ₁ -C ₁₈ alkylene group, optionally interrupted by one or more heteroatoms, and mixtures thereof.

• - X¹ und X² jeweils ein Sauerstoff-Atom repräsentieren;
• - R¹ und R² unabhängig voneinander ausgewählt sind aus der Gruppe, bestehend aus Dialkylaminoalkoholen, Alkylestern von Hydroxycarbonsäuren und Monoalkylethern von Polyalkylenglycol, in denen die Hydroxyl-Gruppe entfernt wurde, und Mischungen hiervon, bevorzugt ausgewählt aus Monoalkylethern von Polyalkylenglycol, in denen die Hydroxyl-Gruppe entfernt wurde;
• - n und z für eine ganze Zahl im Bereich von 1 bis 20 stehen, mit n+z > 2, und w für die Zahl null oder 1 steht;
• - L₁ ausgewählt ist aus einer divalenten aliphatischen C₁-C₁₈ Kohlenwasserstoff-basierten Gruppe, insbesondere Methylen-, Ethylen- und Propylen-, weiterhin ausgewählt aus einer C₃-C₁₅-Cycloalkylen-Gruppe, wie insbesondere 4,4'-Dicyclohexylenmethan, Cyclopentylen-, Cycloheptylen- und Cyclohexylen-, weiterhin ausgewählt aus einer C₃-C₁₂-Heterocycloalkylen-Gruppe, wie Imidazolen-, Pyrrolen- und Furanylen-, oder ausgewählt aus einer C6-C14-Arylen-Gruppe, wie Phen-1,3-dioctylcyclobutylen-, Tetramethylxylylen-, Isophoron-, 1,5-Naphthylen-, 4,4'-Diphenylmethylen-, 4,4'-Diphenyldimethylmethylen- und Phenylen-, sowie Mischungen hiervon, wobei L₁ besonders bevorzugt ausgewählt ist aus einer C3-C15-Cycloalkylen-Gruppe, wie insbesondere 4,4'-Dicyclohexylenmethan, Cyclopentylen-, Cycloheptylen- und Cyclohexylen-,
• - E unabhängig für eine Gruppe steht, die ausgewählt aus:
  • -O-R³-O-; -S-R⁴-S-; -R^S-N(R⁶)-R⁴-N(R⁶)-R⁵-; worin
  • - R³ und R⁴ unabhängig voneinander für eine divalente C6-C14-Arylen-Gruppe, eine divalente C₃-C₁₂-Cycloalkylen-Gruppe, eine divalente lineare oder verzweigte C₁-C₁₈-Alkylen-Gruppe, die optional durch ein oder mehrere Heteroatome unterbrochen ist, und Mischungen hiervon stehen;
  • - R⁵ ausgewählt ist aus einer divalenten C6-C14-Arylen-Gruppe, einer divalenten C₃-C₁₂-Cycloalkylen-Gruppe, einer divalenten linearen oder verzweigten C₁-C₁₈-Alkylen-Gruppe, optional durch ein oder mehrere Heteroatome unterbrochen, und Mischungen hiervon; und
  • - R⁶ ausgewählt ist aus einer divalenten C6-C14-Arylen-Gruppe, einer divalenten C₃-C₁₂-Cycloalkylen-Gruppe, einer divalenten linearen oder verzweigten C₁-C₁₈-Alkylen-Gruppe, optional durch ein oder mehrere Heteroatome unterbrochen, und Mischungen hiervon.

According to a further particularly preferred alternative, methods and kits according to the invention are characterized in that the polycarbodiimide used therein is selected from at least one compound according to the above structural formula (II), wherein:

• - X ¹ and X ² each represent an oxygen atom;
• - R ¹ and R ² are independently selected from the group consisting of dialkylamino alcohols, alkyl esters of hydroxycarboxylic acids and monoalkyl ethers of polyalkylene glycol in which the hydroxyl group has been removed, and mixtures thereof, preferably selected from monoalkyl ethers of polyalkylene glycol in which the hydroxyl group has been removed;
• - n and z are integers in the range 1 to 20, with n+z > 2, and w is zero or 1;
• - L ₁ is selected from a divalent aliphatic C ₁ -C ₁₈ hydrocarbon-based group, in particular methylene, ethylene and propylene, further selected from a C ₃ -C ₁₅ cycloalkylene group, such as in particular 4,4'-dicyclohexylenemethane, cyclopentylene, cycloheptylene and cyclohexylene, further selected from a C ₃ -C ₁₂ heterocycloalkylene group, such as imidazoles, pyrroles and furanylenes, or selected from a C6-C14 arylene group, such as phen-1,3-dioctylcyclobutylene, tetramethylxylylene, isophorone, 1,5-naphthylene, 4,4'-diphenylmethylene, 4,4'-diphenyldimethylmethylene and phenylene, and mixtures thereof, where L ₁ is particularly preferably selected from a C3 C15-cycloalkylene group, such as in particular 4,4'-dicyclohexylenemethane, cyclopentylene, cycloheptylene and cyclohexylene,
• - E independently stands for a group selected from:
  • -OR ³ -O-; -SR ⁴ -S-; -R ^S -N(R ⁶ )-R ⁴ -N(R ⁶ )-R ⁵ -; wherein
  • - R ³ and R ⁴ independently of one another represent a divalent C 6 -C 14 arylene group, a divalent C ₃ -C ₁₂ cycloalkylene group, a divalent linear or branched C ₁ -C ₁₈ alkylene group which is optionally interrupted by one or more heteroatoms, and mixtures thereof;
  • - R ⁵ is selected from a divalent C6-C14 arylene group, a divalent C ₃ -C ₁₂ cycloalkylene group, a divalent linear or branched C ₁ -C ₁₈ alkylene group, optionally interrupted by one or more heteroatoms, and mixtures thereof; and
  • - R ⁶ is selected from a divalent C 6 -C 14 arylene group, a divalent C ₃ -C ₁₂ cycloalkylene group, a divalent linear or branched C ₁ -C ₁₈ alkylene group, optionally interrupted by one or more heteroatoms, and mixtures thereof.

• - X¹ und X² jeweils ein Sauerstoff-Atom repräsentieren;
• - R¹ und R² unabhängig voneinander ausgewählt sind aus der Gruppe, bestehend aus Monoalkylethern von Polyalkylenglycol, in denen die Hydroxyl-Gruppe entfernt wurde;
• - n und z für eine ganze Zahl im Bereich von 1 bis 20 stehen, mit n+z > 2, und w für die Zahl null oder 1 steht;
• - L₁ für eine C3-C15-Cycloalkylen-Gruppe, wie insbesondere 4,4'-Dicyclohexylenmethan, Cyclopentylen-, Cycloheptylen- und Cyclohexylen-, steht;
• - E unabhängig für eine Gruppe steht, die ausgewählt aus:
  • -O-R³-O-; -S-R⁴-S-; -R^S-N(R⁶)-R⁴-N(R⁶)-R⁵-; worin
  • - R³ und R⁴ unabhängig voneinander für eine divalente C6-C14-Arylen-Gruppe, eine divalente C₃-C₁₂-Cycloalkylen-Gruppe, eine divalente lineare oder verzweigte C₁-C₁₈-Alkylen-Gruppe, die optional durch ein oder mehrere Heteroatome unterbrochen ist, und Mischungen hiervon stehen;
  • - R⁵ ausgewählt ist aus einer divalenten C6-C14-Arylen-Gruppe, einer divalenten C₃-C₁₂-Cycloalkylen-Gruppe, einer divalenten linearen oder verzweigten C₁-C₁₈-Alkylen-Gruppe, optional durch ein oder mehrere Heteroatome unterbrochen, und Mischungen hiervon; und
  • - R⁶ ausgewählt ist aus einer divalenten C6-C14-Arylen-Gruppe, einer divalenten C₃-C₁₂-Cycloalkylen-Gruppe, einer divalenten linearen oder verzweigten C₁-C₁₈-Alkylen-Gruppe, optional durch ein oder mehrere Heteroatome unterbrochen, und Mischungen hiervon.

According to a further particularly preferred alternative, methods and kits according to the invention are characterized in that the polycarbodiimide used therein is selected from at least one compound according to the above structural formula (II), wherein:

• - X ¹ and X ² each represent an oxygen atom;
• - R ¹ and R ² are independently selected from the group consisting of monoalkyl ethers of polyalkylene glycol in which the hydroxyl group has been removed;
• - n and z are integers in the range 1 to 20, with n+z > 2, and w is zero or 1;
• - L ₁ represents a C3-C15 cycloalkylene group, such as in particular 4,4'-dicyclohexylenemethane, cyclopentylene, cycloheptylene and cyclohexylene;
• - E independently stands for a group selected from:
  • -OR ³ -O-; -SR ⁴ -S-; -R ^S -N(R ⁶ )-R ⁴ -N(R ⁶ )-R ⁵ -; wherein
  • - R ³ and R ⁴ independently of one another represent a divalent C 6 -C 14 arylene group, a divalent C ₃ -C ₁₂ cycloalkylene group, a divalent linear or branched C ₁ -C ₁₈ alkylene group which is optionally interrupted by one or more heteroatoms, and mixtures thereof;
  • - R ⁵ is selected from a divalent C6-C14 arylene group, a divalent C ₃ -C ₁₂ cycloalkylene group, a divalent linear or branched C ₁ -C ₁₈ alkylene group, optionally interrupted by one or more heteroatoms, and mixtures thereof; and
  • - R ⁶ is selected from a divalent C 6 -C 14 arylene group, a divalent C ₃ -C ₁₂ cycloalkylene group, a divalent linear or branched C ₁ -C ₁₈ alkylene group, optionally interrupted by one or more heteroatoms, and mixtures thereof.

• - X¹ und X² jeweils ein Sauerstoff-Atom repräsentieren;
• - R¹ und R² unabhängig voneinander ausgewählt sind aus mindestens einer Komponente der Strukturformel (VI), R¹³-[O-CH₂-CH(R¹⁴)]_q- (VI), worin
  • - R¹³ für eine C₁-C₄-Alkyl-Gruppe oder eine Phenyl-Gruppe, bevorzugt für eine C₁-C₄-Alkyl-Gruppe, besonders bevorzugt für eine Methyl-Gruppe steht,
  • - R¹⁴ für ein Wasserstoff-Atom oder für eine C₁-C₄-Alkyl-Gruppe, bevorzugt für ein Wasserstoff-Atom steht, und
  • - q für eine ganze Zahl im Bereich von 1 bis 30 steht;
  • - n und z für eine ganze Zahl im Bereich von 1 bis 20 stehen, mit n+z > 2, und w für die Zahl null oder 1 steht;
• - L₁ für eine C3-C15-Cycloalkylen-Gruppe, wie insbesondere 4,4'-Dicyclohexylenmethan, Cyclopentylen-, Cycloheptylen- und Cyclohexylen-, steht; und
• - E für eine Gruppe -O-R³-O- steht, worin R³ für eine divalente C6-C14-Arylen-Gruppe, eine divalente C₃-C₁₂-Cycloalkylen-Gruppe, eine divalente lineare oder verzweigte C₁-C₁₈-Alkylen-Gruppe, die optional durch ein oder mehrere Heteroatome unterbrochen ist, und Mischungen hiervon steht.

According to a further particularly preferred alternative, methods and kits according to the invention are characterized in that the polycarbodiimide used therein is selected from at least one compound according to the above structural formula (II), wherein:

• - X ¹ and X ² each represent an oxygen atom;
• - R ¹ and R ² are independently selected from at least one component of the structural formula (VI), R ¹³ -[O-CH ₂ -CH(R ¹⁴ )] _q - (VI), wherein
  • - R ¹³ represents a C ₁ -C ₄ alkyl group or a phenyl group, preferably a C ₁ -C ₄ alkyl group, particularly preferably a methyl group,
  • - R ¹⁴ represents a hydrogen atom or a C ₁ -C ₄ alkyl group, preferably a hydrogen atom, and
  • - q is an integer in the range 1 to 30;
  • - n and z are integers in the range 1 to 20, with n+z > 2, and w is zero or 1;
• - L ₁ represents a C3-C15 cycloalkylene group, such as in particular 4,4'-dicyclohexylenemethane, cyclopentylene, cycloheptylene and cyclohexylene; and
• - E represents a group -OR ³ -O-, wherein R ³ represents a divalent C 6 -C 14 arylene group, a divalent C ₃ -C ₁₂ cycloalkylene group, a divalent linear or branched C ₁ -C ₁₈ alkylene group optionally interrupted by one or more heteroatoms, and mixtures thereof.

• - X¹ und X² jeweils ein Sauerstoff-Atom repräsentieren;
• - R¹ und R² unabhängig voneinander ausgewählt sind aus mindestens einer Komponente der Strukturformel (VI), R¹³-[O-CH₂-CH(R¹⁴)]_q- (VI), worin
  • - R¹³ für eine C₁-C₄-Alkyl-Gruppe oder eine Phenyl-Gruppe, bevorzugt für eine C₁-C₄-Alkyl-Gruppe, besonders bevorzugt für eine Methyl-Gruppe steht,
  • - R¹⁴ für ein Wasserstoff-Atom oder für eine C₁-C₄-Alkyl-Gruppe, bevorzugt für ein Wasserstoff-Atom steht, und
  • - q für eine ganze Zahl im Bereich von 1 bis 30 steht;
  • - n und z für eine ganze Zahl im Bereich von 1 bis 20, bevorzugt von 2 bis 20, stehen, mit n+z im Bereich von 4 bis 10, und w für die Zahl null oder 1 steht;
• - L₁ für eine C3-C15-Cycloalkylen-Gruppe, wie insbesondere 4,4'-Dicyclohexylenmethan, Cyclopentylen-, Cycloheptylen- und Cyclohexylen-, besonders bevorzugt für steht; und
• - E für eine Gruppe -O-R³-O- steht, worin R³ für eine divalente lineare oder verzweigte C₁-C₁₈-Alkylen-Gruppe, die optional durch ein oder mehrere Heteroatome unterbrochen ist, bevorzugt für Methylen-, Propylen-, Butylen- oder Ethylen-, steht.

According to a further particularly preferred alternative, methods and kits according to the invention are characterized in that the polycarbodiimide used therein is selected from at least one compound according to the above structural formula (II), wherein:

• - X ¹ and X ² each represent an oxygen atom;
• - R ¹ and R ² are independently selected from at least one component of the structural formula (VI), R ¹³ -[O-CH ₂ -CH(R ¹⁴ )] _q - (VI), wherein
  • - R ¹³ represents a C ₁ -C ₄ alkyl group or a phenyl group, preferably a C ₁ -C ₄ alkyl group, particularly preferably a methyl group,
  • - R ¹⁴ represents a hydrogen atom or a C ₁ -C ₄ alkyl group, preferably a hydrogen atom, and
  • - q is an integer in the range 1 to 30;
  • - n and z are an integer in the range from 1 to 20, preferably from 2 to 20, with n+z in the range from 4 to 10, and w is the number zero or 1;
• - L ₁ represents a C3-C15-cycloalkylene group, such as in particular 4,4'-dicyclohexylenemethane, cyclopentylene, cycloheptylene and cyclohexylene, particularly preferably; and
• - E represents a group -OR ³ -O-, wherein R ³ represents a divalent linear or branched C ₁ -C ₁₈ alkylene group which is optionally interrupted by one or more heteroatoms, preferably methylene, propylene, butylene or ethylene.

• - X¹ und X² jeweils ein Sauerstoff-Atom repräsentieren;
• - R¹ und R² jeweils eine Komponente der Strukturformel (VI) darstellen, R¹³-[O-CH₂-CH(R¹⁴)]_q- (VI), worin
  • - R¹³ für eine Methyl-Gruppe steht,
  • - R¹⁴ für ein Wasserstoff-Atom steht, und
  • - q für eine ganze Zahl im Bereich von 1 bis 4 steht;
  • - n für eine ganze Zahl im Bereich von 4 bis 7 steht, und w für die Zahl 0 steht;
• - L₁ für eine 4,4'-Dicyclohexylenmethan-Gruppe steht.

According to a further particularly preferred alternative, methods and kits according to the invention are characterized in that the polycarbodiimide (II-pref) used therein is selected from at least one compound according to the above structural formula (II), wherein:

• - X ¹ and X ² each represent an oxygen atom;
• - R ¹ and R ² each represent a component of the structural formula (VI), R ¹³ -[O-CH ₂ -CH(R ¹⁴ )] _q - (VI), wherein
  • - R ¹³ stands for a methyl group,
  • - R ¹⁴ stands for a hydrogen atom, and
  • - q is an integer in the range 1 to 4;
  • - n stands for an integer in the range 4 to 7, and w stands for the number 0;
• - L ₁ stands for a 4,4'-dicyclohexylenemethane group.

worin

• - L₁ für 4,4'-Dicyclohexylenmethan steht; und
• - n und z für eine ganze Zahl im Bereich von 1 bis 20, bevorzugt von 2 bis 20, stehen, mit n+z im Bereich von 4 bis 10;
• - E für eine Gruppe -O-R³-O- steht, worin R³ für eine divalente lineare oder verzweigte C₁-C₁₈-Alkylen-Gruppe, die optional durch ein oder mehrere Heteroatome unterbrochen ist, bevorzugt für Methylen-, Propylen-, Butylen- oder Ethylen-, steht;
• - r und s für eine ganze Zahl im Bereich von 4 bis 30 stehen.

According to a further particularly preferred alternative, methods and kits according to the invention are characterized in that the polycarbodiimide used therein is selected from at least one compound according to the above structural formula (XII):

wherein

• - L ₁ is 4,4'-dicyclohexylenemethane; and
• - n and z are an integer in the range from 1 to 20, preferably from 2 to 20, with n+z in the range from 4 to 10;
• - E represents a group -OR ³ -O-, wherein R ³ represents a divalent linear or branched C ₁ -C ₁₈ alkylene group, which is optionally interrupted by one or more heteroatoms, preferably methylene, propylene, butylene or ethylene;
• - r and s represent an integer in the range 4 to 30.

Methods and kits preferred according to the invention for the conditioning treatment of keratinic fibers are characterized in that - apart from an optional substitution of the at least one carbodiimide or polycarbodiimide used according to the invention with at least one acrylate- or methacrylate-based monomer - no additional polymer is contained which comprises acrylic acid, acrylic acid amides, acrylic acid esters, methacrylic acid, methacrylic acid amides and/or methacrylic acid esters as monomer.

The composition (CDI) used according to the invention, which contains at least one carbodiimide or polycarbodiimide, can be designed in many dosage forms.

In a first preferred embodiment, the composition (CDI) used according to the invention is a flowable composition that can be applied directly to the keratin fibers. The flowable composition (CDI) can also be mixed with another composition and then applied to the keratin fibers. For the two aforementioned embodiments, it is preferred if the composition (CDI) and also its mixture with another treatment agent for keratin fibers each have a pH value in the range of 8.5 to 12, preferably 9.5 to 11, each measured at 20°C. Therefore, compositions (CDI) preferably used according to the invention are characterized in that they contain at least one alkalizing agent. Other compositions (CDI) preferably used according to the invention are characterized in that they, based on their weight, 11 - 99 wt.%, preferably 20 - 90 wt.%, particularly preferably 40 - 85 wt.% water.

A composition preferably used according to the invention (CDI) or a composition preferably used according to the invention (pre-CDI) containing at least one carbodiimide or polycarbodiimide, furthermore at least one alkalizing agent, which furthermore contains, based on its weight, 11-99% by weight, preferably 20-90% by weight, particularly preferably 40-85% by weight of water and has a pH in the range from 8.5 to 12, preferably 9.5 to 11, in each case measured at 20°C, can be used in this form as an agent for restructuring damaged keratin fibers. Such an agent for restructuring damaged keratin fibers can be sold in a kit with an aqueous composition (A) which contains an inorganic acid and has an acidic pH. Such a composition (CDI) or (pre-CDI) for restructuring damaged keratin fibers is preferably characterized in that it contains, in each case based on its weight, at least one carbodiimide or at least one polycarbodiimide in a total amount of 0.1 - 20 wt.%, preferably 0.2 - 10 wt.%, particularly preferably 0.5 - 5 wt.%. Compositions (CDI) containing carbodiimide or polycarbodiimide in the lower claimed concentration range, especially in the range of 0.1 - 5 wt.%, are preferably applied undiluted to the keratin fibers. Since carbodiimides and polycarbodiimides are more storage-stable in the alkaline range, especially in the pH range of 8.5 to 12, an alkaline tinting agent containing at least one direct dye is suitable as a dosage form for an alkaline keratin treatment agent in addition to the pure restructuring agent. Further compositions (CDI) preferably used according to the invention are therefore characterized in that they contain at least one direct dye.

Compositions (pre-CDI) containing carbodiimide or polycarbodiimide in the upper claimed concentration range, especially in the range of > 5 - 20 wt. %, based on the weight of the composition (pre-CDI), are preferably suitable for being applied to the keratin fibers only after dilution. Dilution can be carried out in particular by adding the composition (pre-CDI) to a keratin treatment agent before this is applied to the keratin fibers. Suitable keratin treatment agents which are mixed with a composition (pre-CDI) used according to the invention, usually immediately before their application to the keratin fibers, are, for example, bleaching powder, coloring powder, bleaching pastes, bleaching creams, coloring creams, but also conditioners, hair treatments and shampoos. Bleaching powder, coloring powder, bleaching pastes, bleaching creams and coloring creams usually have an alkaline pH value from the outset. In a further preferred embodiment of the invention, they can therefore also contain at least one carbodiimide or polycarbodiimide themselves and thus represent a composition used according to the invention (CDI). In order to achieve the desired lightening or coloring effect, the keratin treatment agents mentioned, i.e. bleaching powder, coloring powder, bleaching pastes, bleaching creams or coloring creams, must be mixed with an aqueous solution containing hydrogen peroxide immediately before or immediately after application to the keratin fibers.

Such an agent for lightening or coloring keratin fibers and simultaneously restructuring the damaged keratin fibers or preventing keratin damage can be sold as a multi-part kit and preferably comprises a composition (CDI) or (pre-CDI), furthermore an agent selected from a bleaching powder, a coloring powder, a bleaching paste, a bleaching cream and a coloring cream, furthermore an aqueous solution containing hydrogen peroxide and furthermore - for after-treatment - an aqueous composition (A) which contains an inorganic acid and has an acidic pH value.

Another preferred subject of the invention is a kit K1, comprising a bleaching powder containing at least one carbodiimide or polycarbodiimide, physically separated therefrom an aqueous solution containing hydrogen peroxide and furthermore - for aftertreatment - an aqueous composition (A) which contains an inorganic acid and has an acidic pH. Another preferred subject of the invention is a method for lightening keratin fibers and simultaneously restructuring the damaged keratin fibers or preventing keratin damage using the aforementioned kit K1.

In a further preferred embodiment of the aforementioned kit K1 and the method, the bleaching powder contains at least one alkalizing agent (kit K2) in addition to the at least one carbodiimide or polycarbodiimide. A further preferred subject matter of the invention is a method for applying lightening of keratin fibers and simultaneous restructuring of damaged keratin fibers or prevention of keratin damage using the aforementioned K2 kit.

In a further preferred embodiment of the aforementioned kit K1 and the method, the kit comprises, in addition to the bleaching powder with the at least one carbodiimide or polycarbodiimide and the acid composition (A), physically separated therefrom, a bleaching cream which contains water and at least one alkalizing agent and has a pH in the range of 8.0 to 12.0, measured at 20°C (kit K3).

The bleaching powder of the K3 kit can contain at least one alkalizing agent (Kit 3-A). The bleaching powder of the K3 kit can also contain no alkalizing agent (Kit 3-B). The bleaching cream of the K3 kit can contain at least one carbodiimide or polycarbodiimide (Kit 3-C).

Another preferred subject matter of the invention is a method for lightening keratin fibers and simultaneously restructuring the damaged keratin fibers or preventing keratin damage using one of the aforementioned kits K3-A, K3-B or K3-C. Another preferred subject matter of the invention is a kit comprising a bleaching paste which contains a) at least one carbodiimide or polycarbodiimide, b) at least one persalt, c) at least one alkalizing agent and d) at least one oil, furthermore an aqueous hydrogen peroxide-containing solution and furthermore - for aftertreatment - an aqueous composition (A) which contains an inorganic acid and has an acidic pH value (kit 4). Another preferred subject matter of the invention is a method for lightening keratin fibers and simultaneously restructuring the damaged keratin fibers or preventing keratin damage using the aforementioned kit K4.

• a) mindestens ein Carbodiimid oder Polycarbodiimid, b) mindestens ein Alkalisierungsmittel und
• c) Wasser enthält und einen pH-Wert im Bereich von 8,0 bis 12,0, gemessen bei 20°C, aufweist, physikalisch getrennt davon weiterhin eine wässrige Wasserstoffperoxid-haltige Lösung und weiterhin - zur Nachbehandlung - eine wässrige Zusammensetzung (A), die eine anorganische Säure enthält und einen sauren pH-Wert aufweist (Kit K5-A). Als weiterer Kit-Bestandteil kann ein Blondierpulver zugegen sein, das mindestens ein Persalz (Kit K5-B) und optional mindestens ein Alkalisierungsmittel (Kit K5-C) und/oder mindestens ein (Poly)carbodiimid (Kits K5-D, K5-E) enthält. Ein weiterer bevorzugter Gegenstand der Erfindung ist ein Verfahren zur Aufhellung von Keratinfasern und gleichzeitiger Restrukturierung der geschädigten Keratinfasern oder Prävention der Keratinschädigung unter Verwendung eines der vorgenannten Kits K5-A bis K5-E.

Another preferred subject of the invention is a kit comprising a bleaching cream which

• a) at least one carbodiimide or polycarbodiimide, b) at least one alkalizing agent and
• c) contains water and has a pH value in the range of 8.0 to 12.0, measured at 20°C, physically separated from this an aqueous solution containing hydrogen peroxide and furthermore - for aftertreatment - an aqueous composition (A) which contains an inorganic acid and has an acidic pH value (Kit K5-A). A further kit component can be a bleaching powder which contains at least one persalt (Kit K5-B) and optionally at least one alkalizing agent (Kit K5-C) and/or at least one (poly)carbodiimide (Kits K5-D, K5-E). Another preferred subject matter of the invention is a method for lightening keratin fibers and simultaneously restructuring the damaged keratin fibers or preventing keratin damage using one of the aforementioned kits K5-A to K5-E.

Another preferred subject of the invention is a kit comprising a coloring cream which contains a) at least one carbodiimide or polycarbodiimide, b) at least one alkalizing agent, c) at least one dye selected from oxidation dye precursors and direct dyes and mixtures thereof, and d) water and has a pH in the range from 8.0 to 12.0, measured at 20°C, physically separated therefrom, an aqueous solution containing hydrogen peroxide and furthermore - for aftertreatment - an aqueous composition (A) which contains an inorganic acid and has an acidic pH (kit K6). Another preferred subject of the invention is a method for the oxidative coloring of keratin fibers and simultaneous restructuring of the damaged keratin fibers or prevention of keratin damage using the aforementioned kit K6.

Another preferred subject of the invention is a kit comprising a dye powder which contains a) at least one carbodiimide or polycarbodiimide, b) at least one alkalizing agent and c) at least one dye selected from oxidation dye precursors and direct dyes and mixtures thereof, physically separated therefrom, an aqueous solution containing hydrogen peroxide and furthermore - for aftertreatment - an aqueous composition (A) which contains an inorganic acid and has an acidic pH value (kit K7). Another preferred subject of the invention is a method for the oxidative coloring of keratin fibers and simultaneous restructuring of the damaged keratin fibers or prevention of keratin damage using the aforementioned kit K7.

The time specification “immediately before” means a period of time from 1 second to a maximum of 30 minutes, preferably from 1 to 10 minutes before application to the keratin fibers.

The time specification “immediately afterwards” means a period of time from 1 second to a maximum of 1 hour, preferably from 1 to 10 minutes after application to the keratin fibres.

Conditioners, hair treatments and shampoos usually have an acidic pH value from the outset. Carbodiimides and polycarbodiimides are not long-term stable in this regard. If conditioners, hair treatments or shampoos are mixed with a composition (CDI) or (pre-CDI) used according to the invention before being applied to the keratin fibers, they should preferably be applied to the keratin fibers immediately after mixing.

Another preferred subject matter of the invention is a kit comprising a composition (CDI) or (pre-CDI) containing at least one carbodiimide or polycarbodiimide, furthermore at least one alkalizing agent, which furthermore contains, based on its weight, 11-99% by weight, preferably 20-90% by weight, particularly preferably 40-85% by weight of water and has a pH in the range from 8.5 to 12, preferably 9.5 to 11, in each case measured at 20°C, physically separated therefrom, furthermore a hair conditioner and furthermore - for aftertreatment - an aqueous composition (A) which contains an inorganic acid and has an acidic pH (kit K8). Another preferred subject matter of the invention is a method for conditioning keratin fibers and simultaneously restructuring the damaged keratin fibers or preventing keratin damage using the aforementioned kit K8.

Another preferred subject of the invention is a kit comprising a composition (CDI) containing at least one carbodiimide or polycarbodiimide, furthermore at least one alkalizing agent, which furthermore contains, based on its weight, 11-99% by weight, preferably 20-90% by weight, particularly preferably 40-85% by weight of water and has a pH in the range from 8.5 to 12, preferably 9.5 to 11, in each case measured at 20°C, physically separated therefrom, furthermore a shampoo and furthermore - for aftertreatment - an aqueous composition (A) which contains an inorganic acid and has an acidic pH (kit K9). Another preferred subject of the invention is a method for cleaning keratin fibers and simultaneously restructuring the damaged keratin fibers or preventing keratin damage using the aforementioned kit K9.

Another preferred subject of the invention is a kit comprising a composition (pre-CDI) which, based on its weight, contains at least one carbodiimide or at least one polycarbodiimide in a total amount of 0.5-20% by weight, preferably 1-15% by weight, particularly preferably 3-12% by weight, furthermore water and at least one alkalizing agent and has a pH in the range of 8.5 to 12, preferably 9.5 to 11, in each case measured at 20°C and, physically separated therefrom for aftertreatment, an aqueous composition (A) which contains an inorganic acid and has an acidic pH (kit K10). Another preferred subject of the invention is a method for conditioning keratin fibers and simultaneously restructuring the damaged keratin fibers or preventing keratin damage using the aforementioned kit K10.

A further preferred subject matter of the invention is a kit comprising a composition (pre-CDI) which, based on its weight, contains at least one carbodiimide or at least one polycarbodiimide in a total amount of 0.5 - 20 wt. %, preferably 1 - 15 wt. %, particularly preferably 3 - 12 wt. %, furthermore water and at least one alkalizing agent and has a pH in the range of 8.5 to 12, preferably 9.5 to 11, in each case measured at 20°C and, physically separated therefrom, a bleaching powder or an alkalizing cream which optionally contains at least one carbodiimide or at least one polycarbodiimide, furthermore an aqueous hydrogen peroxide-containing solution and furthermore - for aftertreatment - an aqueous composition (A) which contains an inorganic acid and has an acidic pH (kits K11-A to K11-D). Another preferred subject matter of the invention is a method for conditioning keratin fibers and simultaneous restructuring of the damaged keratin fibers or prevention of keratin damage using one of the aforementioned kits K11-A to K11-D.

A further preferred subject matter of the invention is a kit comprising a composition (pre-CDI) which, based on its weight, contains at least one carbodiimide or at least one polycarbodiimide in a total amount of 0.5 - 20 wt. %, preferably 1 - 15 wt. %, particularly preferably 3 - 12 wt. %, furthermore water and at least one alkalizing agent and has a pH in the range of 8.5 to 12, preferably 9.5 to 11, in each case measured at 20°C and, physically separated therefrom, a coloring cream or a coloring powder which optionally contains at least one carbodiimide or at least one polycarbodiimide, furthermore an aqueous hydrogen peroxide-containing solution and furthermore - for aftertreatment - an aqueous composition (A) which contains an inorganic acid and has an acidic pH (Kit K12). Another preferred subject matter of the invention is a method for conditioning keratin fibers and simultaneous restructuring of the damaged keratin fibers or prevention of keratin damage using the aforementioned Kit K12.

The following are preferred ingredients used in methods and kits according to the invention and preferred methods and kits for the conditioning treatment of keratin fibers.

Typically, agents for oxidative color change have an alkaline pH value to accelerate the reaction during oxidative application, which is adjusted with alkalizing agents such as alkanolamines, ammonia or inorganic bases.

The compositions (CDI) used according to the invention also preferably contain at least one alkalizing agent. Compositions (CDI) used particularly preferably according to the invention contain at least one alkalizing agent in such an amount that the composition (CDI) has a pH in the range from 8.5 to 12, preferably 9.5 to 11, in each case measured at 20°C.

The alkalizing agents preferably suitable for adjusting the pH of the agents used in the methods and kits according to the invention are selected from ammonia, alkanolamines, alkali hydroxides, basic amino acids, alkali metal metasilicates, alkali metal disilicates, alkali phosphates and dialkalimonohydrogenphosphates and mixtures of these substances. Particularly preferred alkalizing agents are selected from alkanolamines, alkali hydroxides, basic amino acids, alkali metal metasilicates, alkali metal disilicates, alkali phosphates and dialkalimonohydrogenphosphates and mixtures of these substances. The alkali metal ions in the aforementioned alkalizing salts are preferably lithium, sodium or potassium, in particular sodium or potassium.

The basic amino acids that can be used as alkalizing agents are preferably selected from the group L-arginine, D-arginine, D,L-arginine, L-lysine, D-lysine, D,L-lysine and mixtures thereof. Particularly preferred basic amino acids are L-arginine, L-lysine and mixtures thereof.

The alkali hydroxides that can be used as alkalizing agents are preferably selected from sodium hydroxide and potassium hydroxide and mixtures thereof. Potassium hydroxide is extremely preferred according to the invention.

The alkanolamines which can be used as alkalizing agents preferably have 2 to 9 carbon atoms in the molecule and are particularly preferably selected from primary amines having a C ₂ -C ₆ alkyl parent structure which carries at least one hydroxyl group. Particularly preferred alkanolamines are selected from the group consisting of 2-aminoethane-1-ol (monoethanolamine), 3-aminopropane-1-ol, 4-aminobutane-1-ol, 5-aminopentane-1-ol, 1-aminopropane-2-ol, 1-aminobutane-2-ol, 1-aminopentane-2-ol, 1-aminopentane-3-ol, 1-aminopentane-4-ol, 3-amino-2-methylpropane-1-ol, 1-amino-2-methylpropane-2-ol, 3-aminopropane-1,2-diol, and 2-amino-2-methylpropane-1,3-diol, and mixtures thereof. Alkanolamines which are particularly preferred according to the invention are selected from the group consisting of 2-aminoethane-1-ol, 2-amino-2-methylpropane-1-ol and 2-amino-2-methylpropane-1,3-diol; 2-aminoethane-1-ol is particularly preferred. However, secondary amines such as diisopropanolamine (1,1'-iminodipropane-2-ol) are also suitable alkalizing agents according to the invention. Agents used in particularly preferred methods and kits according to the invention contain 2-aminoethane-1-ol, potassium hydroxide, L-arginine, L-lysine and mixtures thereof as alkalizing agents. Agents which are particularly preferably used contain a mixture of 2-aminoethane-1-ol, potassium hydroxide, L-arginine and L-lysine.

Agents used in particularly preferred methods and kits according to the invention are characterized in that at least one alkalizing agent is contained in a total amount of 0.5 - 10 wt.%, preferably 0.7 - 7 wt.%, particularly preferably 1.0 - 5 wt.%, extremely preferably 1.2 - 3 wt.%, in each case based on the weight of the agent. This can be the agent (CDI), synonymously the composition (CDI), or an agent for the oxidative color change of keratin fibers.

Persalts preferably used according to the invention are selected from sodium percarbonates and inorganic salts of a peroxosulfuric acid and mixtures thereof.

Sodium percarbonates are sodium carbonate-hydrogen peroxide complexes. Commercially available sodium percarbonate has the average composition 2 Na ₂ CO ₃ . 3 H ₂ O ₂ . Sodium percarbonate is a white, water-soluble powder that easily breaks down into sodium carbonate and "active" oxygen, which has a bleaching and oxidizing effect.

Peroxosulfuric acids include peroxodisulfuric acid and peroxomonosulfuric acid (Caro's acid).

Preferably, the at least one inorganic salt of a peroxosulfuric acid is selected from ammonium peroxodisulfate, alkali metal peroxodisulfates, ammonium peroxomonosulfate, alkali metal peroxomonosulfates and alkali metal hydrogen peroxomonosulfates. Particularly preferred are ammonium peroxodisulfate, potassium peroxodisulfate, sodium peroxodisulfate and potassium hydrogen peroxomonosulfate. Furthermore, it has proven particularly preferred in the work on the present invention if the bleaching powder used according to the invention contains at least two different peroxodisulfates. Preferred peroxodisulfate salts are combinations of ammonium peroxodisulfate and potassium peroxodisulfate and/or sodium peroxodisulfate. Preferred bleaching powders used according to the invention contain at least one oxidizing agent selected from sodium percarbonates and inorganic salts of a peroxosulfuric acid and mixtures thereof, in a total amount of 5 - 85 wt.%, preferably 10 - 75 wt.%, particularly preferably 15 - 65 wt.%, extremely preferably 20 - 55 wt.%, in each case based on the weight of the bleaching powder.

In a preferred embodiment, the agent preferably used according to the invention for the oxidative color change of keratin fibers contains at least one oxidation dye precursor of the developer type and at least one oxidation dye precursor of the coupler type. Oxidation dye precursors can be divided into two categories based on their reaction behavior, so-called developer components and coupler components. Coupler components do not form a significant coloration on their own in the context of oxidative coloring, but always require the presence of developer components. Developer components can form the actual dye with themselves.

The developer and coupler components are usually used in free form. However, in the case of substances with amino groups, it may be preferable to use them in salt form, in particular in the form of hydrochlorides, hydrobromides, hydrogen sulfates or sulfates.

Particularly preferred developer components are selected from at least one compound from the group formed by p-phenylenediamine, p-toluenediamine, 2-(2-hydroxyethyl)-p-phenylenediamine, 2-(1,2-dihydroxyethyl)-p-phenylenediamine, N,N-bis-(2-hydroxyethyl)-p-phenylenediamine, 2-methoxymethyl-p-phenylenediamine, N-(4-amino-3-methylphenyl)-N-[3-(1H-imidazol-1-yl)propyl]amine, N,N'-bis-(2-hydroxyethyl)-N,N'-bis-(4-aminophenyl)-1,3-diamino-propan-2-ol, bis-(2-hydroxy-5-aminophenyl) methane, 1,3-bis-(2,5-diaminophenoxy)propan-2-ol, N,N'-bis-(4-aminophenyl)-1,4-diazacycloheptane, 1,10-bis-(2,5-diaminophenyl)-1,4,7,10-tetraoxadecane, p-aminophenol, 4-amino-3-methylphenol, 4-amino-2-aminomethylphenol, 4-amino-2-(1,2-dihydroxyethyl)phenol and 4-amino-2-(diethylaminomethyl)phenol, 4,5-diamino-1-(2-hydroxyethyl)pyrazole, 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, the physiologically acceptable salts of these compounds as well as mixtures of these developer components and developer component salts.

Very particularly preferred developer components are selected from 4,5-diamino-1-(2-hydroxyethyl)pyrazole, p-toluenediamine, 2-(2-hydroxyethyl)-p-phenylenediamine, 2-methoxymethyl-p-phenylenediamine, N-(4-amino-3-methylphenyl)-N-[3-(1H-imidazol-1-yl)propyl]amine and mixtures of these compounds and their physiologically acceptable salts. 4,5-diamino-1-(2-hydroxyethyl)pyrazole, p-toluenediamine, 2-(2-hydroxyethyl)-p-phenylenediamine, 2-methoxymethyl-p-phenylenediamine and mixtures of these compounds and their physiologically acceptable salts are particularly preferred.

Preferably, at least one developer component or its salt is contained in a total amount of 0.01 to 5 wt. %, preferably 0.1 to 4 wt. %, particularly preferably 0.2 to 3.0 wt. %, extremely preferably 0.5 to 2.0 wt. %, in each case based on the weight of the oxidative color-changing agent (M1) used according to the invention.

Preferably, at least one coupler component or its salt is present in a total amount of 0.001 to 4 wt. %, preferably 0.01 to 3 wt. %, particularly preferably 0.05 to 2 wt. %, preferably 0.1 to 1 wt. %, based in each case on the weight of the oxidative color-changing agent (M1) used according to the invention.

The total amount of oxidation dye precursors or their salts in the agent (M1) according to the invention is preferably 0.011 to 9% by weight, preferably 0.11 to 7% by weight, particularly preferably 0.25 to 5% by weight, extremely preferably 0.6 to 3.0% by weight, in each case based on the weight of the oxidative color-changing agent (M1) used according to the invention. Coupler components in the sense of the invention allow at least one substitution of a chemical residue of the coupler by the oxidized form of the developer component. A covalent bond is formed between the coupler and developer components. Couplers are preferably cyclic compounds which carry at least two groups on the cycle, selected from (i) optionally substituted amino groups and/or (ii) hydroxyl groups. If the cyclic compound is a six-membered ring (preferably aromatic), the said groups are preferably in the ortho position or meta position to one another.

• - 3-Aminophenol (m-Aminophenol) und/oder dessen Derivate,
• - 3-Aminoanilin (m-Diaminobenzol) und/oder dessen Derivate,
• - 2-Aminoanilin (1,2-Diaminobenzol; o-Diaminobenzol) und/oder dessen Derivate,
• - 2-Aminophenol (o-Aminophenol) und/oder dessen Derivate,
• - Naphthalinderivate mit mindestens einer Hydroxygruppe,
• - Di- beziehungsweise Trihydroxybenzol und/oder deren Derivate,
• - Pyridinderivate,
• - Pyrimidinderivate,
• - Monohydroxyindol-Derivate und/oder Monoaminoindol-Derivate,
• - Monohydroxyindolin-Derivate und/oder Monoaminoindolin-Derivate,
• - Pyrazolonderivate, wie beispielsweise 1-Phenyl-3-methylpyrazol-5-on,
• - Morpholinderivate, wie beispielsweise 6-Hydroxybenzomorpholin oder 6-Aminobenzomorpholin,
• - Chinoxalinderivate, wie beispielsweise 6-Methyl-1,2,3,4-tetrahydrochinoxalin.

Preferred oxidative color-changing agents used according to the invention are characterized in that the at least one oxidation dye precursor of the coupler type is selected from one of the following classes:

• - 3-aminophenol (m-aminophenol) and/or its derivatives,
• - 3-aminoaniline (m-diaminobenzene) and/or its derivatives,
• - 2-aminoaniline (1,2-diaminobenzene; o-diaminobenzene) and/or its derivatives,
• - 2-aminophenol (o-aminophenol) and/or its derivatives,
• - naphthalene derivatives containing at least one hydroxy group,
• - di- or trihydroxybenzene and/or their derivatives,
• - pyridine derivatives,
• - pyrimidine derivatives,
• - monohydroxyindole derivatives and/or monoaminoindole derivatives,
• - monohydroxyindoline derivatives and/or monoaminoindoline derivatives,
• - Pyrazolone derivatives, such as 1-phenyl-3-methylpyrazol-5-one,
• - Morpholine derivatives, such as 6-hydroxybenzomorpholine or 6-aminobenzomorpholine,
• - Quinoxaline derivatives, such as 6-methyl-1,2,3,4-tetrahydroquinoxaline.

Mixtures of two or more compounds from one or more of these classes are also preferred according to the invention in this embodiment.

Additional coupler components which are particularly preferred according to the invention are selected from 3-aminophenol, 5-amino-2-methylphenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 5-amino-4-chloro-2-methylphenol, 5-(2-hydroxyethyl)amino-2-methylphenol, 2,4-dichloro-3-aminophenol, 2-aminophenol, 3-phenylenediamine, 2-(2,4-diaminophenoxy)ethanol, 1,3-bis-(2,4-diaminophenoxy)propane, 1-beta-hydroxyethyl-3,4-methylenedioxyaniline, 1-methoxy-2-amino-4-(2'-hydroxyethylamino)benzene (= 2-amino-4-hydroxyethylaminoanisole), 1,3-bis(2,4-diaminophe-nyl)propane, 2,6-Bis(2'-hydroxyethylamino)-1-methylbenzene, 2-({3-[(2-hydroxyethyl)amino]-4-meth-oxy-5-methylphenyl}amino)ethanol, 2-({3-[(2-hydroxyethyl)amino]-2-methoxy-5-methylphenyl}-amino)ethanol, 2-({3-[(2-Hydroxyethyl)amino]-4,5-dimethylphenyl}amino)ethanol, 2-[3-morpholin-4-ylphenyl)amino]ethanol, 3-amino-4-(2-methoxyethoxy)-5-methylphenylamine, 1-amino-3-bis-(2-hydroxyethyl)aminobenzene, resorcinol, 2-methylresorcinol, 4-Chlororesorcinol, 1,2,4-Trihydroxybenzene, 2-Amino-3-hydroxypyridine, 3-Amino-2-methylamino-6-methoxypyridine, 2,6-Dihydroxy-3,4-dimethylpyridine, 3,5-diamino-2,6-dimethoxypyridine, 1-phenyl-3-methylpyrazol-5-one, 1-naphthol, 1,5-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 4-hydroxyindole, 6-hydroxyindole, 7-hydroxyindole, 4-hydroxyindoline, 6-hydroxyindoline, 7-hydroxyindoline or mixtures of these compounds or the physiologically acceptable salts of the aforementioned compounds.

Particularly preferred are 3-aminophenol, resorcinol, 2-methylresorcinol, 5-amino-2-methylphenol, 2-(2,4-diaminophenoxy)ethanol, 1,3-bis(2,4-diaminophenoxy)propane, 1-methoxy-2-amino-4-(2'-hydroxyethylamino)benzene, 2-amino-3-hydroxypyridine, 1-naphthol and 1-beta-hydroxyethyl-3,4-methylene dioxyaniline, as well as their physiologically acceptable salts and mixtures of the components mentioned. It may be preferable to avoid resorcinol and resorcinol derivatives.

In order to achieve a balanced and subtle nuance formation or to mattify undesirable residual color impressions caused by melanin degradation products, in particular in the reddish or bluish range, it is preferred according to the invention if further color-imparting components are contained in the oxidative color-changing agent used according to the invention.

In a further embodiment, the oxidative color-changing agents used according to the invention can therefore additionally contain at least one direct dye. In a further embodiment, non-oxidative color-changing agents used according to the invention can also additionally contain at least one direct dye. These are dyes that are absorbed directly onto the hair and do not require an oxidative process to form the color. Direct dyes are usually nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols.

Direct dyes can be anionic, cationic or non-ionic. The direct dyes are preferably contained in an amount of 0.001 to 2% by weight, based on the weight of the oxidative or non-oxidative color-changing agent used according to the invention.

Preferred anionic direct dyes are the compounds known under the international names or trade names Acid Yellow 1, Yellow 10, Acid Yellow 23, Acid Yellow 36, Acid Orange 7, Acid Red 33, Acid Red 52, Pigment Red 57:1, Acid Blue 7, Acid Green 50, Acid Violet 43, Acid Black 1, Acid Black 52, Bromophenol Blue and Tetrabromophenol Blue. Preferred cationic direct dyes are cationic triphenylmethane dyes, for example Basic Blue 7, Basic Blue 26, Basic Violet 2 and Basic Violet 14, aromatic systems substituted with a quaternary nitrogen group, such as Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 and Basic Brown 17, cationic anthraquinone dyes such as HC Blue 16 (Bluequat B) and direct dyes containing a heterocycle having at least one quaternary nitrogen atom, in particular Basic Yellow 87, Basic Orange 31 and Basic Red 51. The cationic direct dyes sold under the trademark Arianor are also preferred cationic direct dyes according to the invention. Nonionic direct dyes that are particularly suitable are nonionic nitro and quinone dyes and neutral azo dyes. Preferred non-ionic direct dyes are the compounds known under the international names or trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, HC Orange 1, Disperse Orange 3, HC Red 1, HC Red 3, HC Red 10, HC Red 11, HC Red 13, HC Red BN, HC Blue 2, HC Blue 11, HC Blue 12, Disperse Blue 3, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9, as well as 1,4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1,4-bis-(2-hydroxyethyl)-amino-2-nitrobenzene, 3-nitro-4-(2-hydroxyethyl)aminophenol, 2-(2-hydroxyethyl)amino-4,6-dinitrophenol, 4-[(2-hydroxyethyl)amino]-3-nitro-1-methylbenzene, 1-amino-4-(2-hydroxyethyl)amino-5-chloro-2-nitrobenzene, 4-amino-3-nitrophenol, 1-(2'-ureidoethyl)amino-4-nitrobenzene, 2-[(4-amino-2-nitrophenyl)amino]-benzoic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, 2-hydroxy-1,4-naphthoquinone, picramic acid and its salts, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-4-nitrophenol. According to the invention, it is very particularly preferred to contain at least one cationic direct dye selected from Basic Blue 7, Basic Blue 26, Basic Violet 2, Basic Violet 14, Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16, Basic Brown 17, HC Blue 16 (Bluequat B), Basic Yellow 87, Basic Orange 31 and Basic Red 51 and mixtures thereof.

A hair conditioner preferably used according to the invention contains at least one cationic component selected from cationic surfactants and cationic polymers and mixtures thereof, optionally in combination with at least one fatty component selected from oils, linear, saturated fatty alcohols with 12 to 30 carbon atoms, glycerol trifatty acid esters with a melting point above 28°C and waxes and mixtures of these fatty components. These hair conditioners usually contain water, usually with at least 50% by weight of water, based on their weight, but can also be anhydrous and then preferably contain at least one polyol that is liquid at 25°C, such as 1,2-propylene glycol, glycerin or dipropylene glycol.

A shampoo preferably used according to the invention contains water and at least one anionic surfactant, optionally in combination with at least one nonionic surfactant and/or with at least one amphoteric surfactant.

Table 1 below lists possible kits according to the invention for the conditioning treatment of keratin fibers, preferably hair: Table 1 Comp. for upstream mixing step (before step a) compartment for process step a) Comp. for step a) compartment for process step a) compartment for process step a) Comp. for step e) Kit No. bleaching or coloring powder with CDI H ₂ O ₂ if necessary, alkalizing cream, may contain CDI acid (A) K1, K2, K3, K7 alkalizing cream with CDI H ₂ O ₂ possibly blond booster, may contain CDI acid (A) K5-A to K5-E; K3 coloring cream with CDI H ₂ O ₂ acid (A) K6 alkaline tinting with CDI acid (A) K13 Pre-CDI Conditioner/Curator/Treatment acid (A) K8 Pre-CDI shampoo acid (A) K9 Pre-CDI acid (A) K10 Pre-CDI H ₂ O ₂ Bleaching powder and/or alkalizing cream can independently contain CDI acid (A) K11-A to K11-D Pre-CDI H ₂ O ₂ coloring cream (or coloring powder) acid (A) K12

Methods and kits for the conditioning treatment of keratin fibers preferred according to the invention are characterized in that the composition (CDI), based on its weight, contains 0-15% by weight, preferably 0.5-10% by weight, particularly preferably 1-8% by weight, extremely preferably 2 to 5% by weight, of water.

In another embodiment of the invention, preferred methods and kits for the conditioning treatment of keratin fibers are characterized in that the composition (CDI), based on its weight, contains 11-99% by weight, preferably 20-90% by weight, particularly preferably 40-85% by weight of water.

In a further embodiment of the invention, preferred methods and kits for the conditioning treatment of keratin fibers are characterized in that the composition (CDI) contains at least one alkalizing agent.

In a further embodiment of the invention, preferred methods and kits for the conditioning treatment of keratin fibers are characterized in that the composition (CDI), based on its weight, contains at least one carbodiimide or polycarbodiimide in a total amount of 0.1 - 20 wt.%, preferably 0.2 - 10 wt.%, particularly preferably 0.5 - 5 wt.%.

In a further embodiment of the invention, preferred methods and kits for the conditioning treatment of keratin fibers are characterized in that the composition (CDI) has a pH in the range of 8.5 to 12, preferably 9.5 to 11, each measured at 20°C.

In a further embodiment of the invention, preferred methods and kits for the conditioning treatment of keratin fibers are characterized in that the composition (CDI) contains at least one oxidizing agent other than atmospheric oxygen, which is preferably selected from hydrogen peroxide, persulfates, percarbamide and sodium percarbonate and mixtures thereof, with hydrogen peroxide, persulfates and hydrogen peroxide-persulfate mixtures being particularly preferred.

In another embodiment of the invention, preferred methods and kits for the conditioning treatment of keratin fibers are characterized in that the composition (CDI) does not contain an oxidizing agent other than atmospheric oxygen.

In a further embodiment of the invention, preferred methods and kits for the conditioning treatment of keratin fibers are characterized in that the composition (CDI) contains at least one direct dye.

In a further embodiment of the invention, preferred methods and kits for the conditioning treatment of keratin fibers are characterized in that the inorganic acid contained in the composition (A) is selected from phosphoric acid, dihydrogen phosphate salts, hydrochloric acid, sulfuric acid, hydrogen sulfate salts, carbonic acid, nitric acid and mixtures thereof.

In a further embodiment of the invention, preferred methods for the conditioning treatment of keratin fibers are characterized in that the rinsing water in step c) has a temperature in the range of 15 - 40 °C, preferably 18 - 40 °C, particularly preferably 20 - 35 °C, extremely preferably 25 - 32 °C.

1. i) eine Zusammensetzung (CDI-x) oder (pre-CDI), die in einem kosmetischen Träger mindestens ein Carbodiimid oder mindestens ein Polycarbodiimid enthält und die, wie für die in Zusammensetzung (CDI) einem der Ansprüche 1 - 11 beschrieben, ausgestaltet ist, und
2. ii) eine wässrige Zusammensetzung (A), die eine anorganische Säure enthält und einen sauren pH-Wert, gemessen bei 20°C, aufweist und die, wie in einem der Ansprüche 1 oder 12 beschrieben, ausgestaltet ist.

In a further embodiment of the invention, preferred kits for the conditioning treatment of keratin fibers, in particular human hair, are characterized in that they comprise at least the following compartments, which are physically separated from one another:

1. i) a composition (CDI-x) or (pre-CDI) which contains at least one carbodiimide or at least one polycarbodiimide in a cosmetic carrier and which is designed as described for the composition (CDI) in any of claims 1-11, and
2. ii) an aqueous composition (A) which contains an inorganic acid and has an acidic pH, measured at 20°C, and which is designed as described in any one of claims 1 or 12.

1. 1. Verfahren zur konditionierenden Behandlung von keratinischen Fasern, insbesondere menschlichen Haaren, das folgende Verfahrensschritte in der angegebenen Reihenfolge umfasst:
   1. a) Auftragen einer Zusammensetzung (CDI), die in einem kosmetischen Träger mindestens ein Carbodiimid oder mindestens ein Polycarbodiimid enthält, auf die Keratinfasern,
   2. b) Einwirkenlassen für eine Zeit von 30 Sekunden bis 60 Minuten, bevorzugt 1 bis 45 Minuten, besonders bevorzugt 2 bis 30 Minuten, außerordentlich bevorzugt 5 bis 15 Minuten,
   3. c) Spülen der Keratinfasern mit Wasser,
   4. d) optional Trocknen der Keratinfasern,
   5. e) Auftragen einer wässrigen Zusammensetzung (A) auf die Keratinfasern, wobei die Zusammensetzung (A) eine anorganische Säure enthält und einen sauren pH-Wert aufweist, wobei der pH-Wert bevorzugt 0,2 - 6,5, weiter bevorzugt 2,0 - 6,0, besonders bevorzugt 3,0 - 5,5, außerordentlich bevorzugt 4,0 - 5,0, weiter außerordentlich bevorzugt 4,3 - 4,6, beträgt, jeweils gemessen bei 20°C,
   6. f) Einwirkenlassen für eine Zeit von 10 Sekunden bis 60 Minuten, bevorzugt 30 Sekunden bis 30 Minuten, besonders bevorzugt 1 bis 20 Minuten, außerordentlich bevorzugt 2 bis 15 Minuten, weiter außerordentlich bevorzugt 5 bis 10 Minuten,
   7. g) Spülen der Keratinfasern mit Wasser,
   8. h) optional Trocknen der Keratinfasern.
2. 2. Verfahren zur konditionierenden Behandlung nach Punkt 1, dadurch gekennzeichnet, dass das mindestens eine Polycarbodiimid ausgewählt ist aus Verbindungen der Strukturformel (CDI-I)
   
   worin
   • X1 und X2 unabhängig voneinander für ein Sauerstoff-Atom, ein Schwefel-Atom oder eine NH-Gruppe stehen,
   • die ausgewählt ist aus einer Kohlenwasserstoff-Gruppe, bevorzugt aus mindestens einer Alkyl-Gruppe, die optional durch ein oder mehrere Heteroatome unterbrochen sein kann, weiterhin ausgewählt aus Alkoxysilyl-, Hydroxysilyl-, Acetoxysilyl-, Vinylsilyl-, Acrylalkylsilyl-, Methacrylalkylsilyl-, Crotonylalkylsilyl-, Carboxyanhydridoalkylsilyl-, Carboxyalkylsilyl-, Hydroxyalkylsilyl-, Aldehydoalkylsilyl-, Mercaptoalkylsilyl-, Norbornenylsilyl-, Acylpentadienylalkylsilyl-, Maleimidoalkylsilyl-, Sulfonylalkylsilyl-, (Meth)acrylalkyl-, Crotonylalkyl-, Alkylepoxid-, z. B. Propylepoxid- oder Butylepoxid-, und Azacyclopropan-Gruppen sowie Mischungen hiervon;
   • - n für eine ganze Zahl im Bereich von 1 bis 200, bevorzugt 2 bis 200, besonders bevorzugt 3 bis 150, weiter besonders bevorzugt 4 bis 100, weiter besonders bevorzugt 4 bis 50, weiter besonders bevorzugt 4 bis 10, außerordentlich bevorzugt 6 bis 7, steht; und
   • - A für eine divalente Gruppe steht, die aus den nachstehend dargestellten Substituenten ausgewählt ist:
     
     
     
     
     
3. 3. Verfahren zur konditionierenden Behandlung nach Punkt 1 oder 2, dadurch gekennzeichnet, dass das Carbodiimid oder Polycarbodiimid ausgewählt ist aus Verbindungen der nachstehend dargestellten allgemeinen Strukturformel (II):
   
   worin
   • -X₁ und X₂ unabhängig voneinander für ein Sauerstoff-Atom, ein Schwefel-Atom oder eine NH-Gruppe stehen,
   • -R₁ und R₂ unabhängig voneinander für eine Kohlenwasserstoff-basierte Gruppe stehen, die optional durch ein oder mehrere Heteroatome unterbrochen sein kann;
   • - n und z für eine ganze Zahl im Bereich von 1 bis 20 stehen, mit n+z > 2, und w für eine ganze Zahl im Bereich von null bis 3 steht;
   • - L₁ unabhängig voneinander für eine divalente aliphatische Kohlenwasserstoff-basierte C1-C18-Gruppe, eine C3-C15-Cycloalkylen-Gruppe, eine C3-C12-Heterocycloalkylen-Gruppe oder eine C6-C14-Arylen-Gruppe, sowie Mischungen hiervon steht;
   • - E für eine Gruppe steht, die ausgewählt ist aus -O-R³-O-, -S-R⁴-S-, -R⁵-N(R⁶)-R⁴-N(R⁶)-R⁵-, worin
     • - R³ und R⁴ unabhängig voneinander für eine Kohlenwasserstoff-basierte Gruppe stehen, die optional durch ein oder mehrere Heteroatome unterbrochen sein kann;
     • - R⁵ unabhängig für eine kovalente Bindung oder eine gesättigte divalente Kohlenwasserstoff-basierte Gruppe steht, die optional durch ein oder mehrere Heteroatome unterbrochen sein kann;
     • - R⁶ unabhängig für ein Wasserstoffatom oder eine Kohlenwasserstoff-basierte Gruppe steht, die optional durch ein oder mehrere Heteroatome unterbrochen sein kann.
4. 4. Verfahren nach einem der Punkte 1 bis 3, dadurch gekennzeichnet, dass das mindestens eine Polycarbodiimid ausgewählt ist aus Verbindungen der nachstehend dargestellten allgemeinen Strukturformel (XIV)
   
   worin
   • n für eine ganze Zahl im Bereich von 3 bis 50, bevorzugt 4 bis 20, besonders bevorzugt 4 bis 10, außerordentlich bevorzugt 6 bis 7, steht; und
   • R2 und R3, unabhängig voneinander, für einen von einer Verbindung, ausgewählt aus der Gruppe, bestehend aus einem Monoalkoxy-poly(ethylenglykol) gemäß der allgemeinen Formel (EO-I) steht: R¹-O-(CH₂-CH₂-O)_m-H Formel (EO-I), mit
   • R¹ = C1- bis C30-Alkyl, C2- bis C29-Acyl- oder einer Aryl-Gruppe m = 4 bis 60, bevorzugt 4-20, besonders bevorzugt 5-15, außerordentlich bevorzugt 6-9.
5. 5. Verfahren nach einem der Punkte 1 bis 4, dadurch gekennzeichnet, dass das mindestens eine Polycarbodiimid ausgewählt ist aus Verbindungen der nachstehend dargestellten allgemeinen Strukturformel (XIV)
   
   worin
   • n für eine ganze Zahl im Bereich von 4 bis 10, bevorzugt 6 bis 7, steht; und
   • R2 und R3, unabhängig voneinander, für einen von einer Verbindung, ausgewählt aus der Gruppe, bestehend aus einem Monoalkoxy-poly(ethylenglykol) gemäß der allgemeinen Formel (EO-I) steht:
   • R¹-O-(CH₂-CH₂-O)_m-H Formel (EO-I), mit
   • R¹ = Methyl und
   • m = 4-20, bevorzugt 5-15, besonders bevorzugt 6-9.
6. 6. Verfahren zur konditionierenden Behandlung nach einem der Punkte 1 bis 5, dadurch gekennzeichnet, dass die Zusammensetzung (CDI), bezogen auf ihr Gewicht, 0 - 15 Gew.-%, bevorzugt 0,5 - 10 Gew.-%, besonders bevorzugt 1 - 8 Gew.-%, außerordentlich bevorzugt 2 bis 5 Gew.-%, Wasser enthält.
7. 7. Verfahren zur konditionierenden Behandlung nach einem der Punkte 1 bis 6, dadurch gekennzeichnet, dass die Zusammensetzung (CDI), bezogen auf ihr Gewicht, 11 - 99 Gew.-%, bevorzugt 20 - 90 Gew.-%, besonders bevorzugt 40 - 85 Gew.-% Wasser enthält.
8. 8. Verfahren zur konditionierenden Behandlung nach einem der Punkte 1 bis 7, dadurch gekennzeichnet, dass die Zusammensetzung (CDI) mindestens ein Alkalisierungsmittel enthält.
9. 9. Verfahren zur konditionierenden Behandlung nach einem der Punkte 1 bis 8, dadurch gekennzeichnet, dass die Zusammensetzung (CDI), bezogen auf ihr Gewicht, mindestens ein Carbodiimid oder Polycarbodiimid in einer Gesamtmenge von 0,1 - 20 Gew.-%, bevorzugt 0,2 - 10 Gew.-%, besonders bevorzugt 0,5 - 5 Gew.-% enthält.
10. 10. Verfahren zur konditionierenden Behandlung nach einem der Punkte 1 bis 9, dadurch gekennzeichnet, dass die Zusammensetzung (CDI) einen pH-Wert im Bereich von 8,5 bis 12, bevorzugt 9,5 bis 11, aufweist, jeweils gemessen bei 20°C.
11. 11. Verfahren nach einem der Punkte 1 - 10, dadurch gekennzeichnet, dass die Zusammensetzung (CDI) mindestens ein von Luftsauerstoff verschiedenes Oxidationsmittel enthält, das bevorzugt ausgewählt ist aus Wasserstoffperoxid, Persulfaten, Percarbamid und Natriumpercarbonat sowie Mischungen hiervon, wobei Wasserstoffperoxid, Persulfate und Wasserstoffperoxid-Persulfat-Mischungen besonders bevorzugt sind.
12. 12. Verfahren nach einem der Punkte 1 - 10, dadurch gekennzeichnet, dass die Zusammensetzung (CDI) kein von Luftsauerstoff verschiedenes Oxidationsmittel enthält.
13. 13. Verfahren nach einem der Punkte 1 - 12, dadurch gekennzeichnet, dass die Zusammensetzung (CDI) mindestens einen direktziehenden Farbstoff enthält.
14. 14. Verfahren zur konditionierenden Behandlung nach einem der Ansprüche 1 bis 13, dadurch gekennzeichnet, dass die Zusammensetzung (CDI) unmittelbar vor der Applikation auf die Keratinfasern durch Vermischen einer Zusammensetzung (Pre-CDI), enthaltend mindestens ein Carbodiimid oder Polycarbodiimid gemäß einem der Ansprüche 1 - 5, und einem Haarbehandlungsmittel, ausgewählt aus einem Conditioner, einem Shampoo, einem Aufhellungsmittel und einem Färbemittel, hergestellt wird.
15. 15. Verfahren nach Punkt 14, dadurch gekennzeichnet, dass die Zusammensetzung (Pre-CDI), bezogen auf ihr Gewicht, mindestens ein Carbodiimid oder mindestens ein Polycarbodiimid in einer Gesamtmenge von 0,5 - 20 Gew.-%, bevorzugt 1 - 15 Gew.-%, besonders bevorzugt 3 - 12 Gew.-%, weiterhin Wasser und mindestens ein Alkalisierungsmittel enthält und einen pH-Wert im Bereich von 8,5 bis 12, bevorzugt 9,5 bis 11, aufweist, jeweils gemessen bei 20°C.
16. 16. Verfahren nach einem der Punkte 1 bis 15, dadurch gekennzeichnet, dass - abgesehen von einer optionalen Substitution des mindestens einen erfindungsgemäß eingesetzten Carbodiimids oder Polycarbodiimids mit mindestens einem Acrylat- oder Methacrylat-basierten Monomer- kein zusätzliches Polymer enthalten ist, das als Monomer Acrylsäure, Acrylsäureamide, Acrylsäureester, Methacrylsäure, Methacrylsäureamide und/oder Methacrylsäureester umfasst.
17. 17. Verfahren nach einem der Punkte 1 bis 16, dadurch gekennzeichnet, dass die in der Zusammensetzung (A) enthaltene anorganische Säure ausgewählt ist aus Phosphorsäure, Dihydrogenphosphatsalzen, Salzsäure, Schwefelsäure, Hydrogensulfatsalzen, Kohlensäure, Salpetersäure sowie Mischungen hiervon.
18. 18. Verfahren nach einem der Punkte 1 - 17, dadurch gekennzeichnet, dass das Spülwasser in Schritt c) eine Temperatur im Bereich von 15 - 40°C, bevorzugt 18 - 40°C, besonders bevorzugt 20 - 35 °C, außerordentlich bevorzugt 25 - 32 °C, aufweist.
19. 19. Kit zur konditionierenden Behandlung von keratinischen Fasern, insbesondere menschlichen Haaren, das mindestens folgende Kompartimente umfasst, die physisch getrennt voneinander vorliegen:
    1. i) eine Zusammensetzung (CDI-x) oder (pre-CDI), die in einem kosmetischen Träger mindestens ein Carbodiimid oder mindestens ein Polycarbodiimid enthält und die, wie für die in Zusammensetzung (CDI) einem der Punkte 1 - 16 beschrieben, ausgestaltet ist, und
    2. ii) eine wässrige Zusammensetzung (A), die eine anorganische Säure enthält und einen sauren pH-Wert, gemessen bei 20°C, aufweist und die, wie in einem der Punkte 1 oder 17 beschrieben, ausgestaltet ist.
20. 20. Kit zur konditionierenden Behandlung von keratinischen Fasern nach Punkt 19, dadurch gekennzeichnet, dass es mindestens ein weiteres physisch getrenntes Kompartiment umfasst, das eine Haarbehandlungszusammensetzung enthält, die ausgewählt ist aus einer Wasserstoffperoxid-haltigen Entwicklerlösung für oxidative Haarfarbveränderungsmittel, einem Conditioner und einem Shampoo.

The subject matter of the present invention is characterized by the following points:

1. 1. Process for the conditioning treatment of keratin fibres, in particular human hair, comprising the following process steps in the order given:
   1. a) applying to the keratin fibres a composition (CDI) containing in a cosmetic carrier at least one carbodiimide or at least one polycarbodiimide,
   2. b) allowing to act for a time of 30 seconds to 60 minutes, preferably 1 to 45 minutes, particularly preferably 2 to 30 minutes, extremely preferably 5 to 15 minutes,
   3. c) Rinsing the keratin fibers with water,
   4. d) optional drying of the keratin fibers,
   5. e) applying an aqueous composition (A) to the keratin fibers, wherein the composition (A) contains an inorganic acid and has an acidic pH, wherein the pH is preferably 0.2 - 6.5, more preferably 2.0 - 6.0, particularly preferably 3.0 - 5.5, extremely preferably 4.0 - 5.0, more extremely preferably 4.3 - 4.6, in each case measured at 20°C,
   6. f) allowing to act for a time of 10 seconds to 60 minutes, preferably 30 seconds to 30 minutes, particularly preferably 1 to 20 minutes, extremely preferably 2 to 15 minutes, further extremely preferably 5 to 10 minutes,
   7. g) Rinsing the keratin fibers with water,
   8. h) optionally drying the keratin fibers.
2. 2. Process for conditioning treatment according to item 1, characterized in that the at least one polycarbodiimide is selected from compounds of the structural formula (CDI-I)
   
   wherein
   • X1 and X2 independently represent an oxygen atom, a sulfur atom or an NH group,
   • which is selected from a hydrocarbon group, preferably from at least one alkyl group, which can optionally be interrupted by one or more heteroatoms, further selected from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydealkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkylepoxide, e.g. propylepoxide or butylepoxide, and azacyclopropane groups and mixtures thereof;
   • - n is an integer in the range from 1 to 200, preferably 2 to 200, particularly preferably 3 to 150, further particularly preferably 4 to 100, further particularly preferably 4 to 50, further particularly preferably 4 to 10, extremely preferably 6 to 7; and
   • - A represents a divalent group selected from the substituents shown below:
     
     
     
     
     
3. 3. Process for conditioning treatment according to point 1 or 2, characterized in that the carbodiimide or polycarbodiimide is selected from compounds of the general structural formula (II) shown below:
   
   wherein
   • -X ₁ and X ₂ independently represent an oxygen atom, a sulfur atom or an NH group,
   • -R ₁ and R ₂ independently represent a hydrocarbon-based group which may optionally be interrupted by one or more heteroatoms;
   • - n and z are integers in the range 1 to 20, with n+z > 2, and w is integers in the range zero to 3;
   • - L ₁ independently represents a divalent aliphatic hydrocarbon-based C1-C18 group, a C3-C15 cycloalkylene group, a C3-C12 heterocycloalkylene group or a C6-C14 arylene group, and mixtures thereof;
   • - E represents a group selected from -OR ³ -O-, -SR ⁴ -S-, -R ⁵ -N(R ⁶ )-R ⁴ -N(R ⁶ )-R ⁵ -, wherein
     • - R ³ and R ⁴ independently represent a hydrocarbon-based group which may optionally be interrupted by one or more heteroatoms;
     • - R ⁵ independently represents a covalent bond or a saturated divalent hydrocarbon-based group which may optionally be interrupted by one or more heteroatoms;
     • - R ⁶ independently represents a hydrogen atom or a hydrocarbon-based group which may optionally be interrupted by one or more heteroatoms.
4. 4. Process according to one of points 1 to 3, characterized in that the at least one polycarbodiimide is selected from compounds of the general structural formula (XIV) shown below
   
   wherein
   • n is an integer in the range from 3 to 50, preferably 4 to 20, particularly preferably 4 to 10, extremely preferably 6 to 7; and
   • R2 and R3, independently of one another, represent one of a compound selected from the group consisting of a monoalkoxy-poly(ethylene glycol) according to the general formula (EO-I): R ¹ -O-(CH ₂ -CH ₂ -O) _m -H formula (EO-I), with
   • R ¹ = C1- to C30-alkyl, C2- to C29-acyl or an aryl group m = 4 to 60, preferably 4-20, particularly preferably 5-15, extremely preferably 6-9.
5. 5. Process according to one of points 1 to 4, characterized in that the at least one polycarbodiimide is selected from compounds of the general structural formula (XIV) shown below
   
   wherein
   • n is an integer in the range from 4 to 10, preferably 6 to 7; and
   • R2 and R3, independently of one another, represent one of a compound selected from the group consisting of a monoalkoxy-poly(ethylene glycol) according to the general formula (EO-I):
   • R ¹ -O-(CH ₂ -CH ₂ -O) _m -H formula (EO-I), with
   • R ¹ = methyl and
   • m = 4-20, preferably 5-15, particularly preferably 6-9.
6. 6. Process for conditioning treatment according to one of points 1 to 5, characterized in that the composition (CDI), based on its weight, contains 0 - 15 wt.%, preferably 0.5 - 10 wt.%, particularly preferably 1 - 8 wt.%, extremely preferably 2 to 5 wt.%, of water.
7. 7. Process for conditioning treatment according to one of points 1 to 6, characterized in that the composition (CDI), based on its weight, contains 11 - 99 wt.%, preferably 20 - 90 wt.%, particularly preferably 40 - 85 wt.% water.
8. 8. Process for conditioning treatment according to one of points 1 to 7, characterized in that the composition (CDI) contains at least one alkalizing agent.
9. 9. Process for conditioning treatment according to one of points 1 to 8, characterized in that the composition (CDI), based on its weight, contains at least one carbodiimide or polycarbodiimide in a total amount of 0.1 - 20 wt.%, preferably 0.2 - 10 wt.%, particularly preferably 0.5 - 5 wt.%.
10. 10. Process for conditioning treatment according to one of points 1 to 9, characterized in that the composition (CDI) has a pH in the range of 8.5 to 12, preferably 9.5 to 11, each measured at 20°C.
11. 11. Process according to one of items 1 - 10, characterized in that the composition (CDI) contains at least one oxidizing agent other than atmospheric oxygen, which is preferably selected from hydrogen peroxide, persulfates, percarbamide and sodium percarbonate and mixtures thereof, with hydrogen peroxide, persulfates and hydrogen peroxide-persulfate mixtures being particularly preferred.
12. 12. Process according to one of items 1 - 10, characterized in that the composition (CDI) does not contain an oxidizing agent other than atmospheric oxygen.
13. 13. Process according to one of items 1 - 12, characterized in that the composition (CDI) contains at least one direct dye.
14. 14. Process for conditioning treatment according to one of claims 1 to 13, characterized in that the composition (CDI) is prepared immediately before application to the keratin fibers by mixing a composition (pre-CDI) containing at least one carbodiimide or polycarbodiimide according to one of claims 1 to 5 and a hair treatment agent selected from a conditioner, a shampoo, a lightening agent and a dye.
15. 15. Process according to item 14, characterized in that the composition (pre-CDI), based on its weight, contains at least one carbodiimide or at least one polycarbodiimide in a total amount of 0.5 - 20 wt. %, preferably 1 - 15 wt. %, particularly preferably 3 - 12 wt. %, furthermore water and at least one alkalizing agent and has a pH in the range of 8.5 to 12, preferably 9.5 to 11, in each case measured at 20°C.
16. 16. Process according to one of items 1 to 15, characterized in that - apart from an optional substitution of the at least one carbodiimide or polycarbodiimide used according to the invention with at least one acrylate- or methacrylate-based monomer - no additional polymer is contained which comprises acrylic acid, acrylic acid amides, acrylic acid esters, methacrylic acid, methacrylic acid amides and/or methacrylic acid esters as monomer.
17. 17. Process according to one of items 1 to 16, characterized in that the inorganic acid contained in the composition (A) is selected from phosphoric acid, dihydrogen phosphate salts, hydrochloric acid, sulfuric acid, hydrogen sulfate salts, carbonic acid, nitric acid and mixtures thereof.
18. 18. Method according to one of items 1 - 17, characterized in that the rinsing water in step c) has a temperature in the range of 15 - 40 °C, preferably 18 - 40 °C, particularly preferably 20 - 35 °C, extremely preferably 25 - 32 °C.
19. 19. Kit for the conditioning treatment of keratin fibres, in particular human hair, comprising at least the following compartments, which are physically separated from each other:
    1. i) a composition (CDI-x) or (pre-CDI) which contains at least one carbodiimide or at least one polycarbodiimide in a cosmetic carrier and which is designed as described for the composition (CDI) in any of items 1 to 16, and
    2. ii) an aqueous composition (A) which contains an inorganic acid and has an acidic pH, measured at 20°C, and which is designed as described in any of items 1 or 17.
20. 20. Kit for conditioning treatment of keratinic fibers according to item 19, characterized in that it comprises at least one further physically separate compartment containing a hair treatment composition selected from a hydrogen peroxide-containing developer solution for oxidative hair color changers, a conditioner and a shampoo.

The examples presented below are intended to illustrate the subject matter of the invention without limiting it thereto.

1. Preparation of a hydrophilized polycarbodiimide preferably used according to the invention

raw materials:

Cycloaliphatic diisocyanate H12MDI: 4,4'-diisocyanatodicyclohexylmethane, CAS No. 79103-62-1: (Desmodur®-W, Bayer MaterialScience AG, Leverkusen, DE) Carbodiimidization catalyst 1, 1-MPO: technical mixture of 1-methyl-2-phospholene-1-oxide and 1-methyl-3-phospholene-1-oxide, CAS No. 872-45-7 and 930-38-1: (Clariant AG, Muttenz, CH)
Monomethoxy-poly(ethylene glycol) 750, MPEG 750: CAS no. 9004-74-4: (Aldrich, DE) Butoxyethanol: CAS no. 111-76-2: (SysKem Chemie GmbH, Wuppertal, DE)

• Diisocyanat und Carbodiimidisierungskatalysator werden in einem beheizbaren Reaktionsgefäß (2 L Glaskolben oder 5L-Edelstahlreaktor) vorgelegt und unter Rühren im Stickstoffstrom binnen 2 Stunden auf 180°C erhitzt. Danach wird der Stickstoffstrom beendet, und das Reaktionsgemisch wird innerhalb 1 Stunde auf 200°C erhitzt und weitergerührt. Optional wird in gewissen Zeitabständen Vakuum angelegt, um das Reaktionsprodukt CO₂ abzuführen, und danach der Druckausgleich durch Stickstoffzufuhr sichergestellt. Der Reaktionsverlauf wird durch Probenentnahmen und anschließende Titration des NCO-Gehalts (Ausgangswert bei H12MDI: 32 Gew.-%) kontrolliert. Der typische Zielbereich des NCO-Gehalts liegt bei 5.5-9.5% und entspricht einem mittleren Carbodiimidisierungsgrad von 4-7. Dies bedeutet, dass 4 bis 7 Carbodiimidgruppen pro Polycarbodiimidmolekül vorhanden sind.

General procedure for the carbodiimidization reaction (step a):

• Diisocyanate and carbodiimidization catalyst are placed in a heatable reaction vessel (2 L glass flask or 5 L stainless steel reactor) and heated to 180°C within 2 hours while stirring in a nitrogen stream. The nitrogen stream is then stopped and the reaction mixture is heated to 200°C within 1 hour and stirred further. Optionally, a vacuum is applied at certain intervals to remove the reaction product CO ₂ and then pressure equalization is ensured by supplying nitrogen. The course of the reaction is monitored by taking samples and then titrating the NCO content (initial value for H12MDI: 32 wt.%). The typical target range of the NCO content is 5.5-9.5% and corresponds to an average degree of carbodiimidization of 4-7. This means that 4 to 7 carbodiimide groups are present per polycarbodiimide molecule.

1. 876 g Monomethoxypoly(ethylenglykol) 750 (MPEG 750) werden in einem 15 L Edelstahlkessel vorgelegt und unter Rühren und in einer Stickstoffatmosphäre auf 140°C erhitzt. Dazu werden 2748 g des Polycarbodiimids aus Beispiel 2 (NCO-Wert von 6,2 Gew.-%) zugegeben. Das Reaktionsgemisch wird eine Stunde bei 140°C weitergerührt (NCO-Gehalt von 3,3 Gew.-%). Anschließend werden 376 g Butoxyethanol zugegeben und für 1 weitere Stunde gerührt (NCO-Gehalt von 0 Gew.-%). Danach wird auf 95°C abgekühlt, mit 6000 g Wasser vermischt und eine Stunde lang weitergerührt. Man erhält eine fast transparent aussehende Dispersion mit einem pH-Wert von 9, einer mittleren Teilchengröße von 35 nm (Volumenmittel) und einem Feststoffgehalt von 40 Gew.-%.

Preparation of a hydrophilized polycarbodiimide (step b) and a polycarbodiimide dispersion (step c):

1. 876 g of monomethoxypoly(ethylene glycol) 750 (MPEG 750) are placed in a 15 L stainless steel vessel and heated to 140°C while stirring in a nitrogen atmosphere. 2748 g of the polycarbodiimide from Example 2 (NCO content of 6.2% by weight) are added. The reaction mixture is stirred for one hour at 140°C (NCO content of 3.3% by weight). 376 g of butoxyethanol are then added and stirred for a further hour (NCO content of 0% by weight). The mixture is then cooled to 95°C, mixed with 6000 g of water and stirred for one hour. An almost transparent-looking dispersion with a pH of 9, an average particle size of 35 nm (volume average) and a solids content of 40% by weight is obtained.

Inventive method for conditioning hair bleaching and for reducing hair damage caused by bleaching

Surprisingly, by adding 0.8 grams of a polycarbodiimide-containing cream to 10 grams of bleaching powder and 20 grams of hydrogen peroxide-containing aqueous solution (developer with 9% by weight H ₂ O ₂ ), a significant increase in the tensile strength of the hair was found compared to hair treated without polycarbodiimide-containing cream. Table 2: Composition (pre-CDI), composition (CDI), amounts in % by weight Ceteareth-50 2.00 Ceteareth-20 2.00 cocamidopropyl betaine 1.50 cetearyl alcohol 8.00 Coconut fatty alcohol (Lorol technical from BASF) 5.00 Polycarbodiimide according to (II-pref) or (XIV) 12.00 Monoethanolamine (2-aminoethanol) 1.50 water, demineralized 68.00 Total 100.00 Table 3: Bleaching powder (quantities in % by weight) hydrated sodium silicate, molar ratio SiO2/Na2O = 2.65 37,500 basic magnesium carbonate 9,000 hydroxyethylcellulose 0.250 carboxymethylcellulose 2,300 potassium stearate 0.600 sodium hexametaphosphate 0.400 Silica (hydrophilic pyrogenic silica) 0.500 Trisodium Dicarboxymethyl Alaninate 1,400 ammonium persulfate 9,950 potassium persulfate 32,000 Polyquaternium-4 0.300 2-octyldodecanol 1,000 perfume 0.600 Paraffinum Liquidum 4,200 Total 100,000 Table 4: Oxidizing agent-containing developer (“Developer”) for the bleaching powder from Table 2 ingredient sample weight (wt.%) sodium benzoate 0.04 Dipicolinic acid (2,6-dicarboxypyridine) 0.10 disodium pyrophosphate 0.10 potassium hydroxide 0.12 etidronic acid 0.15 paraffin oil 17.00 sodium cetearyl sulfate 0.50 cetearyl alcohol 3.50 PEG-40 Castor Oil 0.70 hydrogen peroxide 6.00 water, demineralized ad 100.00 Table 5: Acid composition (A) for post-treatment (pH 1.29) ingredient sample weight (wt.%) sulfuric acid (20 wt.%) 2.50 water, demineralized 97.50

The test strands come from Kerling International, Backnang, European Natural Hair 7/0, Lot #2005, Blend 138.

The bleaching powder is carefully mixed with developer and polycarbodiimide-containing cream to obtain an application mixture (CDI) used according to the invention.

To prepare the placebo bleaching agent not according to the invention, the weight of polycarbodiimide-containing cream according to Table 2 was replaced by the same weight of water.

The respective application mixture is applied to dry hair strands (virgin hair) and left to work for 45 minutes.

After the exposure time has elapsed, the application mixture is washed out for 90 seconds with water at a temperature in the range of 20 - 35 °C, preferably 25 - 32 °C.

The towel-dried hair is immersed in the sulphuric acid solution according to Table 5 for 2 minutes, then rinsed with water for 90 seconds and blow-dried.

In another series of measurements, non-bleached virgin hair (ENH 7/0) was immersed in the sulphuric acid solution according to Table 5 for 2 minutes, then rinsed with water for 90 seconds and blow-dried. Rinsing was not used.

Before measuring the tensile strength, the treated hair strands are stored for 5 days.

Determination of Young's modulus or tensile strength

The Young's modulus, also called the elastic modulus (E-modulus) or tensile strength, is defined as the ratio of stress to strain in the Hooke's range. Hooke's law of elasticity states that the longitudinal change of a material body (the strain) is linearly related to the force that causes the deformation (the stress). For wet hair, this range is between about 0 and 2% strain. The elastic modulus is a measure of the strength of a fiber (the higher the elastic modulus, the stronger the fiber).

The tensile strengths were determined using a tensile strain tester from Dia-Stron Ltd., Great Britain (stress-strain system MTT 690 with control unit UV 1000).

The addition of polycarbodiimide followed by treatment with sulfuric acid significantly improved the tensile strength of the keratin fibers.

Treatment with sulphuric acid alone had no effect on the tensile strength. Table 6: Young's modulus (N/m ² ] in the elastic range - paired two-sample Student t-test (after bleaching) product average standard deviation N Diff. Stdabw. Diff. t FG p confidence -95.000% confidence +95,000% virgin hair PCDI-1 2.31E+09 1.64E+08 after 1 bleaching PCDI-1 1.90E+09 1.64E+08 48 4.07E+08 7.89E+07 35.7 47 0.000 3.84E+08 4.30E+08 virgin hair PCDI-2 2.34E+09 1.64E+08 after 1 bleaching PCDI-2 1.92E+09 1.60E+08 50 4.20E+08 8.81E+07 33.7 49 0.000 3.95E+08 4.45E+08 virgin hair placebo 2.29E+09 1.71E+08 after 1 bleaching placebo 1.79E+09 1.61E+08 50 4.98E+08 9.37E+07 37.6 49 0.000 4.71E+08 5.24E+08 Table 7: Differences in Young's modulus (N/m ² ] in the elastic range - Tukey HSD test (after two bleaching processes) Variable difference [N/m ² ] 2x ultra bleached versus virgin hair (without outlier values in A22-166 Hookean 24-01-2023.stw). Approximate probabilities for post-hoc tests Error: MQ(between) = 151E14, FG = 337.00 {1} -908E6 {2} -828E6 {3} -836E6 {4} -714E6 {5} -724E6 {6} -904E6 {7} -860E6 PCDI-1 0.000 0.000 0.000 0.999 0.000 0.000 PCDI-2 0.000 0.001 0.000 0.999 0.000 0.000 placebo 0.479 0.858 0.949 0.000 0.000 0.589 Table 8: Differences in Young's modulus (N/m ² ] in the elastic range - Tukey HSD test (after two bleaching processes) Variable difference [N/m ² ] 2x ultra-bleached versus virgin hair (without outlier values in A22-166 Hookean 24-01-2023.stw). Homogeneous groups, Alpha = 0.05000 Error: MQ(between) = 151E14, FG = 337.00 Difference [N/m ² ] 1 2 3 PCDI-1 -7.13E+08 **** **** PCDI-2 -7.25E+08 **** placebo -8.61 E+08 **** ****

QUOTES INCLUDED IN THE DESCRIPTION

This list of documents listed by the applicant was generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA accepts no liability for any errors or omissions.

Cited patent literature

• EP 3342395A2 [0010]
• KR 20160123549A [0010]
• FR 1567219A [0010]
• WO 2022189575A1 [0010]
• US 2853473A [0022]
• US 2941966A [0022]
• EP 628541A [0022]
• DE 2504400A1 [0022]

Claims (15)

Method for the conditioning treatment of keratin fibers, in particular human hair, which comprises the following method steps in the order given: a) applying a composition (CDI) which contains at least one carbodiimide or at least one polycarbodiimide in a cosmetic carrier to the keratin fibers, b) allowing to act for a time of 30 seconds to 60 minutes, preferably 1 to 45 minutes, particularly preferably 2 to 30 minutes, extremely preferably 5 to 15 minutes, c) rinsing the keratin fibers with water, d) optionally drying the keratin fibers, e) applying an aqueous composition (A) to the keratin fibers, wherein the composition (A) contains an inorganic acid and has an acidic pH, wherein the pH is preferably 0.2 - 6.5, more preferably 2.0 - 6.0, particularly preferably 3.0 - 5.5, extremely preferably 4.0 - 5.0, further extremely preferably 4.3 - 4.6, each measured at 20°C, f) allowing to act for a time of 10 seconds to 60 minutes, preferably 30 seconds to 30 minutes, particularly preferably 1 to 20 minutes, extremely preferably 2 to 15 minutes, further extremely preferably 5 to 10 minutes, g) rinsing the keratin fibers with water, h) optionally drying the keratin fibers. Conditioning treatment procedure according to claim 1 , characterized in that the at least one polycarbodiimide is selected from compounds of the structural formula (CDI-I)

wherein X1 and X2 independently of one another represent an oxygen atom, a sulfur atom or an NH group which is selected from a hydrocarbon group, preferably from at least one alkyl group which can optionally be interrupted by one or more heteroatoms, further selected from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydealkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkylepoxide, e.g. propylepoxide or butylepoxide, and azacyclopropane groups and mixtures thereof; - n is an integer in the range from 1 to 200, preferably 2 to 200, particularly preferably 3 to 150, further particularly preferably 4 to 100, further particularly preferably 4 to 50, further particularly preferably 4 to 10, extremely preferably 6 to 7; and - A is a divalent group selected from the substituents shown below:

Conditioning treatment procedure according to claim 1 or 2 , characterized in that the carbodiimide or polycarbodiimide is selected from compounds of the general structural formula (II) shown below:

wherein - X ₁ and X ₂ independently of one another represent an oxygen atom, a sulfur atom or an NH group, - R ₁ and R ₂ independently of one another represent a hydrocarbon-based group which can optionally be interrupted by one or more heteroatoms; - n and z represent an integer in the range from 1 to 20, with n+z > 2, and w represents an integer in the range from zero to 3; - L ₁ independently of one another represents a divalent aliphatic hydrocarbon-based C1-C18 group, a C3-C15 cycloalkylene group, a C3-C12 heterocycloalkylene group or a C6-C14 arylene group, and mixtures thereof; - E represents a group selected from -OR ³ -O-, -SR ⁴ -S-, -R ⁵ -N(R ⁶ )-R ⁴ -N(R ⁶ )-R ⁵ -, wherein - R ³ and R ⁴ independently represent a hydrocarbon-based group which may optionally be interrupted by one or more heteroatoms; - R ⁵ independently represents a covalent bond or a saturated divalent hydrocarbon-based group which may optionally be interrupted by one or more heteroatoms; - R ⁶ independently represents a hydrogen atom or a hydrocarbon-based group which may optionally be interrupted by one or more heteroatoms. Conditioning treatment method according to one of the Claims 1 until 3 , characterized in that the composition (CDI) contains, based on its weight, 0 - 10 wt.% water. Conditioning treatment method according to one of the Claims 1 until 3 , characterized in that the composition (CDI), based on its weight, contains 11 - 99 wt.%, preferably 20 - 90 wt.%, particularly preferably 40 - 85 wt.% water. Conditioning treatment method according to one of the Claims 1 until 5 , characterized in that the composition (CDI) contains at least one alkalizing agent. Conditioning treatment method according to one of the Claims 1 until 6 , characterized in that the composition (CDI), based on its weight, contains at least one carbodiimide or polycarbodiimide in a total amount of 0.1 - 20 wt.%, preferably 0.2 - 10 wt.%, particularly preferably 0.5 - 5 wt.%. Conditioning treatment method according to one of the Claims 1 until 7 , characterized in that the composition (CDI) has a pH in the range of 8.5 to 12, preferably 9.5 to 11, each measured at 20°C. Method according to one of the Claims 1 - 8 , characterized in that the composition (CDI) contains at least one oxidizing agent other than atmospheric oxygen, which is preferably selected from hydrogen peroxide, persulfates, percarbamide and sodium percarbonate and mixtures thereof, with hydrogen peroxide, persulfates and hydrogen peroxide-persulfate mixtures being particularly preferred. Method according to one of the Claims 1 - 8 , characterized in that the composition (CDI) does not contain an oxidizing agent other than atmospheric oxygen. Method according to one of the Claims 1 - 10 , characterized in that the composition (CDI) contains at least one direct dye. Method according to one of the Claims 1 until 11 , characterized in that the inorganic acid contained in the composition (A) is selected from phosphoric acid, dihydrogen phosphate salts, hydrochloric acid, sulfuric acid, hydrogen sulfate salts, carbonic acid, nitric acid and mixtures thereof. Method according to one of the Claims 1 - 12 , characterized in that the rinsing water in step c) has a temperature in the range of 15 - 40 °C, preferably 18 - 40 °C, particularly preferably 20 - 35 °C, extremely preferably 25 - 32 °C. Kit for the conditioning treatment of keratin fibres, in particular human hair, comprising at least the following compartments, which are physically separated from one another: (i) a composition (CDI-x) containing, in a cosmetic carrier, at least one carbodiimide or at least one polycarbodiimide and which, as described for the composition (CDI), is in one of the Claims 1 - 11 and ii) an aqueous composition (A) containing an inorganic acid and having an acidic pH measured at 20°C and which, as described in any of the Claims 1 or 12 described, designed. Kit for conditioning treatment of keratin fibers after claim 14 , characterized in that it comprises at least one further physically separate compartment containing a hair treatment composition selected from a hydrogen peroxide-containing developer solution for oxidative hair color changers, a conditioner and a shampoo.