WO2005116112A1 - Polycondensat a base de cystine - Google Patents

Polycondensat a base de cystine Download PDF

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Publication number
WO2005116112A1
WO2005116112A1 PCT/EP2005/003698 EP2005003698W WO2005116112A1 WO 2005116112 A1 WO2005116112 A1 WO 2005116112A1 EP 2005003698 W EP2005003698 W EP 2005003698W WO 2005116112 A1 WO2005116112 A1 WO 2005116112A1
Authority
WO
WIPO (PCT)
Prior art keywords
polycondensate
formula
hair
cystine
group
Prior art date
Application number
PCT/EP2005/003698
Other languages
German (de)
English (en)
Inventor
Sabine Kainz
Ursula Huchel
Olaf Lammerschop
Andre HÄTZELT
Ina KRÜGERMANN
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Priority to EP05728200A priority Critical patent/EP1749045A1/fr
Publication of WO2005116112A1 publication Critical patent/WO2005116112A1/fr

Links

Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/88—Polyamides
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/04—Preparations for permanent waving or straightening the hair
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/12—Preparations containing hair conditioners

Definitions

  • the invention relates to a method for producing a polycondensate from cystine or a salt thereof and an activated dicarboxylic acid.
  • the invention further relates to the polycondensate itself, its use for restructuring keratin fibers, and cosmetic agents for hair treatment which contain such a polycondensate.
  • Keratin fibers, especially hair are an important part of everyday life as an integral part of the human body and as an essential part of human clothing and home textiles.
  • the treatment with washing, cleaning, styling and coloring products for cleaning and design purposes, as well as their exposure to environmental influences such as ozone, salt and chlorine water, IR, UV and heat radiation (blow-drying) lead to over time cumulative damage to the fibers and thus to a reduction in their quality.
  • both cleaning hair with shampoos and decorating the hairstyle by dyeing or perming are interventions that influence the natural structure and properties of the hair. Consequently, after such a treatment, for example, the wet and dry combability, hold, fullness, shine and tactility of the hair can be unsatisfactory.
  • the hold of the color on the hair can continue to be unsatisfactory, particularly with frequent shampooing, so that there is a gradual bleeding of the color.
  • care products with a sufficiently strong and long-lasting effect increases.
  • Care products of this type influence the natural structure and properties of the hair. After such treatments, for example, the wet and dry combability of the hair, the hold and the fullness of the hair can be improved or the hair can be protected from an increased split rate.
  • the hair is treated with special active ingredients, for example quaternary ammonium salts or special polymers. Depending on the formulation, this treatment improves the combability, hold and fullness of the hair and reduces the split rate.
  • active substances available both for separate aftertreatment agents and for combination preparations generally act preferentially on the hair surface.
  • Hair care products are known which give the hair shine, hold, fullness or better wet or dry combability or prevent split ends.
  • the internal structural cohesion of the hair fibers which can be greatly influenced in particular in oxidative and reductive processes such as coloring and perms.
  • Keratinic fibers are particularly exposed to deformation processes such as hair perms.
  • a negative side effect of permanent hair waving is often embrittlement and dulling of the hair.
  • other properties such as wet and dry combability, grip, smoothness, softness, gloss and tear resistance are also influenced in an undesirable manner.
  • Nourishing additives and film formers are often added to the permanent waving agent without, however, significantly improving the hair structure.
  • high-molecular polymers are used, for example, which attach to the top layer of skin and hair and there produce an external, subjectively perceptibly improved grip on the hair.
  • the structural damage to the interior of the hair which is caused by the reduction process in the case of perms, cannot be reduced, however, because the substances cannot penetrate the hair due to their size.
  • EP 723 772 describes that alkalizing agents such as basic amino acids together with cationic polymers in the waving agent cause the hair to swell more. On the one hand it leads to stronger shaping and longer durability of the perm, but on the other hand it also leads to hair damage.
  • the published patent application GB 216 041 9 describes a method in which hair is first treated with a reducing agent which is then rinsed out. Then an aqueous protein hydrolyzate, preferably with a molecular weight greater than 50,000 daltons, is applied to the areas to be treated, after which the Neutralization takes place. Subjectively, the area treated in this way felt better, but there was no reduction in hair damage inside.
  • the object of the present invention was to provide an improved active substance for the restructuring of keratin fibers, which has advantages over the prior art.
  • the active ingredient should be technically easily and inexpensively accessible and have an improved fiber-reinforcing effect. It should, for example, be advantageously applicable in the context of conventional permanent wave treatments and should be able to reduce the damage to the hair fibers associated therewith.
  • This object is achieved by providing a polycondensate which can be obtained by a process in which free or in the form of one of its salts cystine is reacted with an activated dicarboxylic acid.
  • the invention thus firstly relates to a process for the preparation of a polycondensate, in which cystine or a salt thereof with an activated dicarboxylic acid of the formula (I)
  • A denotes a bond or a divalent saturated or mono- or polyunsaturated aliphatic or aromatic hydrocarbon radical having 1 to 20 carbon atoms, which means with one or can be substituted by several halogen, hydroxyl or free or de-dated carboxy groups and the shortest connection between the two carbonyl groups adjacent to group A consists of up to 12 carbon atoms,
  • X represents a halogen atom, a 1-imidazolyl group, an acyloxy group R-C (O) -O- or another group which is suitable for activating a carboxyl group HO-C (O) -A-, and
  • Y has the same meanings as X, where X and Y can be the same or different.
  • cystine can form salts with both acids and bases.
  • salts are suitable which are formed from cystine by the action of bases, for example alkali or alkaline earth metal hydroxides or ammonia and amines.
  • bases for example alkali or alkaline earth metal hydroxides or ammonia and amines.
  • alkali metal, alkaline earth metal and ammonium salts of cystine are particularly suitable according to the invention, it being possible for 1 to 4 hydrogen atoms in the cation of the latter to be substituted by alkyl radicals having 1 to 4 carbon atoms.
  • the lithium, sodium, potassium, cesium, calcium and triethylammonium salts of cystine are preferred.
  • X and Y are preferably selected from chlorine, bromine and the acetoxy group.
  • X and Y together represent an oxygen bridge linking the carbon atoms of the carbonyl carbon atoms.
  • the activated dicarboxylic acid of the formula (I) is an acid anhydride.
  • a in formula (I) is a divalent saturated aliphatic hydrocarbon radical having 2 to 6 carbon atoms and in particular the ethane-1,2-diyl radical.
  • derivatization is preferably understood to be an esterification with an alcohol having 1 to 4 carbon atoms.
  • the reaction of the cystine or one of its salts with an activated dicarboxylic acid of the formula (I) is preferably carried out in a molar ratio of 2: 1 to 1: 2, in particular 1: 1 to 1: 1, 2.
  • reaction is carried out as interfacial condensation in a reaction mixture which comprises two liquid phases which are essentially immiscible with one another.
  • an essentially immiscible organic phase which comprises at least one solvent which is selected from methylene chloride, chloroform, ethyl acetate, toluene, alkanes with 5 to 8 carbon atoms, in particular n-octane, and ethers with 5 to 16 carbon atoms, especially methyl tert-butyl ether.
  • the organic phase can be lighter or heavier than the aqueous phase.
  • the cystine when using an aqueous phase the cystine can dissolve sufficiently and at the same time a sufficient amount of free amino groups are available for reaction with the activated dicarboxylic acid of formula (I), it is expedient if the aqueous phase is alkaline.
  • the aqueous phase is kept in a pH range between 8 and 14, in particular between 10 and 13, during the entire reaction by continuously adding a base.
  • Suitable bases are, for example, aqueous solutions of alkali or alkaline earth metal hydroxides or ammonia, preferably sodium hydroxide solution or potassium hydroxide solution.
  • the process according to the invention is carried out particularly advantageously such that the reaction takes place with the introduction of shear energy, in particular with intensive stirring.
  • the reaction is carried out at a temperature of from 0 to 50 ° C., but in particular from 2 to 20 ° C.
  • the reaction temperature should be chosen so that the solvent used is in the liquid state.
  • cystine or a salt thereof is initially introduced in dissolved form, and then an activated dicarboxylic acid of the formula (I), dissolved in methylene chloride, is metered in.
  • cystine or a salt thereof is presented, for example, in the form of a 1 to 30% by weight solution, but in particular a 15 to 25% by weight solution, based on the total weight of the solution.
  • solids can separate out during the reaction and form, for example, at the interface between the aqueous and organic phases.
  • the reaction mixture is worked up in the event that the process according to the invention has been carried out in a two-phase system with an aqueous and organic phase, preferably in such a way that any solid which may have formed is first separated off in a suitable manner, e.g. by filtration or centrifugation.
  • the organic phase is then separated off.
  • the organic phase can be washed with water, which is preferably made alkaline.
  • the aqueous phase from the reaction is then optionally combined with the wash water and, if appropriate, with the previously separated solid and then largely or completely freed from the water. This is done in a manner known per se, for example by evaporation under reduced pressure or by freeze-drying (lyophilization).
  • the remaining residue is the polycondensate according to the invention.
  • the reaction of cystine or its salt with an activated dicarboxylic acid of the formula (I) takes place in the melt.
  • the reactants are initially introduced in solid form and the mixture is then heated, with stirring, to a temperature at which the reactants are in liquid form.
  • the temperature naturally depends on the type of reactants chosen. However, heating to 150 to 200 ° C is usually sufficient. It is of course also possible to initially only provide one reaction partner, convert it into the molten state and meter in the second reaction component in the solid or likewise molten state.
  • the reaction mixture is kept in the molten state with stirring for some time, usually 1 to 5 hours, and then cooled and worked up.
  • Another object of the invention is a polycondensate which can be obtained by a process as described above.
  • all animal hair such as e.g. Wool, horsehair, angora hair, furs, feathers and silk and products or textiles made from them can be used.
  • the method according to the invention is preferably suitable for shaping human hair and wigs made therefrom. Because of the gentle process conditions, it is particularly suitable for deforming the hair on the living body, e.g. in connection with the production of permed hair or the straightening of curly hair.
  • Restructuring in the sense of the present invention means in particular a fiber reinforcement, an increase in tear strength and / or a reduction in the damage to keratin fibers caused by the most varied of influences.
  • the restoration of natural strength plays an important role.
  • Restructured fibers can be characterized, for example, by an increased tensile strength, an increased strength, an increased elasticity and / or an increased volume, which can be shown in greater abundance, for example, in a hairstyle.
  • they can have an improved gloss, an improved grip and / or easier combability.
  • the polycondensate according to the invention is suitable for strengthening, protecting and repairing keratin fibers and very particularly for improving the hair structure and / or strengthening human hair.
  • fiber properties such as strength, elasticity or volume are positively influenced in the sense of an increase in these properties.
  • the polycondensate is also suitable for styling purposes, such as shaping and maintaining shape, and for increasing the color fastness, in particular the wash fastness of colored keratin fibers, in particular colored human hair. Under washing fastness, the preservation of color is one to understand dyed keratin fiber with regard to color shade and / or color intensity if the dyed fiber is exposed to the influence of aqueous agents, in particular surfactant-containing agents such as shampoos.
  • the polycondensate according to the invention is also suitable for protecting fibers from the damaging influence of light.
  • the invention thus also relates to the use of a polycondensate according to the invention for restructuring keratin fibers.
  • a polycondensate according to the invention is brought into contact with a keratinic fiber. This is preferably done in the form of a preparation which can be obtained by adding the polycondensate according to the invention to a conventional hair treatment composition.
  • the invention therefore furthermore relates to a cosmetic agent for hair treatment, comprising a polycondensate according to the invention in a physiologically compatible carrier.
  • the polycondensate according to the invention is a mixture of substances which, in addition to polymeric constituents, can also contain cystine and / or the dicarboxylic acid used, preferably succinic acid and salts.
  • the content of cystine and / or dicarboxylic acid can be influenced via the quantitative ratio of the starting materials used in the production of the polycondensate and via the manner in which the reaction product is worked up.
  • the polycondensate according to the invention can a) preferably 30 to 60% by weight, but in particular 35 to 50% by weight of polymeric constituents, b) preferably 0.5 to 7% by weight, but especially 2 to 4 wt .-% cystine and c) preferably contain 2 to 20 wt .-%, but especially 3 to 10 wt .-% succinic acid, each based on the total weight of the polycondensate.
  • the amounts given for the polymeric constituents relate to values which were determined by means of GPC based on a polyethylene glycol standard.
  • Polycondensate salts contain, for example, chlorides in an amount of 10 to 20 wt .-% Cl, based on the total weight of the polycondensate.
  • a product is known from US Pat. No. 5,646,239 which is formed by reacting a cystine ester with a dicarboxylic acid halide and subsequent saponification of the ester groups.
  • the inventors of the present invention have found that this product known from the US document differs from the polycondensate which can be obtained from cystine and the otherwise identical dicarboxylic acid halide by the process of the present invention. This could be shown, for example, by the fact that both substances show different effects when examining their cosmetic effects on hair. For example, a clearly superior restructuring and hair-strengthening effect was observed for the polycondensate obtainable according to the present invention when used on damaged hair.
  • Synthesis example 6 Production of a polycondensate from cystine and succinic anhydride by reaction in the melt:
  • tension values, gradients, elastic modulus, elongation at break and tensile strength at break of the wet hair were determined with the aid of a tension-stretching device from Dia-Stron (MTT 670).
  • the hair cross-sectional area of the wet individual hair was determined by means of contactless projection measurement using laser technology known in the prior art.
  • a universal dimension meter of the type UMD5000A from Zimmer was used for this.
  • the t-test a statistical evaluation with which the series of measurements are compared on both sides, in pairs, gives percentage probabilities with which the series of measurements are differentiated (distinction 90-95%: series of measurements tend to be different,> 95%: series of measurements significantly differentiated ).
  • the hair is then rinsed with water for 5 minutes.
  • the damage to the hair by the permanent wave method is clearly evident in the increase in the hair cross-sectional area, the reduction in the modulus of elasticity, the gradient, the tension values and the work values. An increase in the elongation at break can also be observed.
  • Example according to the invention double permanent hair with 1% product from synthesis example 1 in the cold wave, as described under 3.2: steps f) with 1% product from synthesis example 1, g), c); Repetition of steps f) with 1% product from synthesis example 1, g), c); then d) and e).
  • composition according to the invention The influence of the composition according to the invention on hair was investigated by means of tensile strain measurement in the wet state.
  • Parameter improvement 1 by treatment with a polycondensate comparison material according to the invention

Abstract

La présente invention concerne un procédé pour préparer un polycondensat comprenant la conversion de cystine ou d'un sel de celle-ci, avec un acide dicarboxylique actif de formule (I) X-C(O)-A-C(O)-Y, selon une proportion molaire de 10:1 à 1:10. Selon l'invention, dans la formule (I): A représente une liaison ou un radical hydrocarbure aliphatique ou aromatique bivalent saturé ou mono- ou polyinsaturé qui comprend de 1 à 20 atomes de carbone et peut être substitué avec un ou plusieurs groupes carboxy dérivés ou libres, ou groupes halogène ou hydroxy; et la liaison la plus courte entre les deux groupes A de groupes carbonyle voisins, est composée d'au maximum 12 atomes de carbone; X est un atome d'halogène, un groupe 1-imidazolyle, un groupe acyloxy R-C(O)-O- ou un autre groupe qui convient pour activer un groupe carboxyle HO-C(O)-A-; Y a les mêmes correspondances que X, X et Y pouvant être identiques ou différents; et le sel est de préférence un sel de métal alcalin, un sel de métal alcalino-terreux ou un sel d'ammonium; et dans le cation, les 1 à 4 derniers atomes d'hydrogène peuvent être substitués par 1 à 4 atomes de carbone. L'invention a également pour objet le polycondensat lui-même, son utilisation pour restructurer des fibres de kératine, et des agents cosmétiques de traitement capillaire, qui contiennent un polycondensat de ce type.
PCT/EP2005/003698 2004-05-18 2005-04-08 Polycondensat a base de cystine WO2005116112A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP05728200A EP1749045A1 (fr) 2004-05-18 2005-04-08 Polycondensat a base de cystine

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE200410024505 DE102004024505A1 (de) 2004-05-18 2004-05-18 Cystin-basiertes Polykondensat
DE102004024505.3 2004-05-18

Publications (1)

Publication Number Publication Date
WO2005116112A1 true WO2005116112A1 (fr) 2005-12-08

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PCT/EP2005/003698 WO2005116112A1 (fr) 2004-05-18 2005-04-08 Polycondensat a base de cystine

Country Status (3)

Country Link
EP (1) EP1749045A1 (fr)
DE (1) DE102004024505A1 (fr)
WO (1) WO2005116112A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3178523A1 (fr) * 2015-12-08 2017-06-14 MAG Cosmetics GmbH Produit de traitement pour cheveux, produit de soin pour cheveux et leur utilisation
CN113817119A (zh) * 2021-09-28 2021-12-21 长春工业大学 一种双硫键和多重氢键协同作用的自愈合水性聚氨酯的制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5646239A (en) * 1993-07-21 1997-07-08 Flamel Technologies Organic products containing reactive thiol functions, one method for preparing same, and biomaterials containing said products
EP1142925A1 (fr) * 1998-12-25 2001-10-10 Mitsui Chemicals, Inc. Procedes servant a preparer une resine absorbant l'eau
EP1374831A1 (fr) * 2001-03-13 2004-01-02 Ajinomoto Co., Inc. Produits cosmetiques ou preparations a usage externe pour la peau

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5646239A (en) * 1993-07-21 1997-07-08 Flamel Technologies Organic products containing reactive thiol functions, one method for preparing same, and biomaterials containing said products
EP1142925A1 (fr) * 1998-12-25 2001-10-10 Mitsui Chemicals, Inc. Procedes servant a preparer une resine absorbant l'eau
EP1374831A1 (fr) * 2001-03-13 2004-01-02 Ajinomoto Co., Inc. Produits cosmetiques ou preparations a usage externe pour la peau

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3178523A1 (fr) * 2015-12-08 2017-06-14 MAG Cosmetics GmbH Produit de traitement pour cheveux, produit de soin pour cheveux et leur utilisation
CN113817119A (zh) * 2021-09-28 2021-12-21 长春工业大学 一种双硫键和多重氢键协同作用的自愈合水性聚氨酯的制备方法

Also Published As

Publication number Publication date
DE102004024505A1 (de) 2005-12-15
EP1749045A1 (fr) 2007-02-07

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