EP1339383A2 - Agents cosmetiques, pharmaceutiques et dermatologiques - Google Patents
Agents cosmetiques, pharmaceutiques et dermatologiquesInfo
- Publication number
- EP1339383A2 EP1339383A2 EP01998320A EP01998320A EP1339383A2 EP 1339383 A2 EP1339383 A2 EP 1339383A2 EP 01998320 A EP01998320 A EP 01998320A EP 01998320 A EP01998320 A EP 01998320A EP 1339383 A2 EP1339383 A2 EP 1339383A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- copolymers
- vinyl
- optionally
- composition according
- Prior art date
- Legal status (The legal status 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 status listed.)
- Withdrawn
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
-
- 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
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- A61K8/8158—Homopolymers or copolymers of amides or imides, e.g. (meth) acrylamide; Compositions of derivatives of such polymers
-
- 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
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- A61K8/817—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions or derivatives of such polymers, e.g. vinylimidazol, vinylcaprolactame, allylamines (Polyquaternium 6)
- A61K8/8182—Copolymers of vinyl-pyrrolidones. Compositions of derivatives of such polymers
-
- 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
- A61K8/86—Polyethers
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P17/00—Drugs for dermatological disorders
- A61P17/16—Emollients or protectives, e.g. against radiation
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/54—Polymers characterized by specific structures/properties
-
- 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
- A61Q5/006—Antidandruff preparations
-
- 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
- A61Q5/02—Preparations for cleaning 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
- A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
Definitions
- the present invention relates to cosmetic, pharmaceutical and dermatological compositions containing comb-shaped copolymers based on acryloyldimethyltauric acid.
- polyelectrolytes play a major role as thickeners and gel formers.
- the prior art is particularly thickeners based on poly (meth) acrylic acid and its water-soluble copolymers.
- the variety of possible structures and the associated diverse application possibilities are not least expressed in a large number of patents that have been registered worldwide since the mid-1970s.
- a major disadvantage of the thickeners based on poly (meth) acrylic acid is the strong pH dependence of the thickening performance.
- a sufficiently high viscosity is generally only built up when the pH of the formulation is set above pH 6, ie the poly (meth) acrylic acid is present in neutralized form.
- the corresponding agents are sensitive to UV radiation and shear and also impart a sticky feeling on the skin.
- acryloyldimethyl taurate-based thickener systems show excellent properties in pH ranges below pH 6, ie in a pH range in which it is no longer possible to work with conventional poly (meth) acrylate thickeners.
- High UV and shear stability, excellent viscoelastic properties, easy processing and a favorable toxicological profile of the main monomer make acryloyldimethyltaurate-based thickener systems modern, new representatives with high potential for the future.
- Comb polymers based on acryloyldimethyltauric acid (AMPS) - which are suitable as thickeners, consistency agents, emulsifiers, solubilizers, dispersants, lubricants, adhesives, conditioners and / or stabilizers - are ideally suited for the formulation of cosmetic, pharmaceutical and dermatological agents.
- the invention therefore relates to cosmetic, pharmaceutical and dermatological compositions comprising at least one copolymer which can be obtained by radical copolymerization of
- the copolymers according to the invention preferably have a molecular weight of 10 3 g / mol to 10 9 g / mol, particularly preferably 10 4 to 10 7 g / mol, particularly preferably 5 * 10 4 to 5 * 10 6 g / mol.
- the Acryloyldimethyltauraten can be the inorganic or organic salts of Acryloyldimethyltaurinklare (Acrylamidopropyl-2-methyl-2-sulfonic acid).
- the Li + , Na + , K + , Mg ++ , Ca ++ , Al +++ and / or NH + salts are preferred.
- the monoalkylammonium, dialkylammonium, trialkylammonium and / or tetraalkylammonium salts are likewise preferred, it being possible for the alkyl substituents of the amines, independently of one another, to be (C 1 -C 22 ) alkyl radicals or (C 2 -CIO) hydroxyalkyl radicals. Furthermore, one to three times ethoxylated ammonium compounds with different degrees of ethoxylation are preferred. It should be noted that mixtures of two or more of the above representatives are also within the meaning of the invention.
- the degree of neutralization of acryloyldimethyltauric acid can be between 0 and 100%, a degree of neutralization of above 80% is particularly preferred.
- the content of acryloyldimethyltauric acid or acryloyldimethyltaurates is at least 0.1% by weight, preferably 20 to 99.5% by weight, particularly preferably 50 to 98% by weight.
- comonomers B All olefinically unsaturated, non-cationic monomers whose reaction parameters allow copolymerization with acryloyldimethyltauric acid and / or acryloyldimethyltaurates in the respective reaction media can be used as comonomers B).
- Preferred comonomers B) are unsaturated carboxylic acids and their anhydrides and salts, and also their esters with aliphatic, olefinic, cycloaliphatic, arylaliphatic or aromatic alcohols with a carbon number of 1 to 30.
- Particularly preferred unsaturated carboxylic acids are acrylic acid, methacrylic acid, styrene sulfonic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid and senecioic acid.
- Preferred counterions are Li + , Na + , K + , Mg ++ , Ca ++ , Al +++ , NH 4 + , monoalkylammonium, dialkylammonium, trialkylammonium and / or tetraalkylammonium radicals
- the alkyl substituents of the amines can independently of one another be (C 1 -C 22 ) -alkyl radicals or (C 2 -C 10 ) -hydroxyalkyl radicals.
- one to three times ethoxylated ammonium compounds with different degrees of ethoxylation can also be used.
- the degree of neutralization of the carboxylic acids can be between 0 and 100%.
- comonomers B) are open-chain N-vinylamides, preferably N-vinylformamide (VIFA), N-vinylmethylformamide, N-vinylmethylacetamide (VIMA) and N-vinylacetamide; cyclic N-vinylamides (N-vinyllactams) with a ring size of 3 to 9, preferably N-vinylpyrrolidone (NVP) and N-vinylcaprolactam; Amides of acrylic and methacrylic acid, preferably acrylamide, methacrylamide, N, N-dimethyl-acrylamide, N, N-diethylacrylamide and N, N-diisopropylacrylamide; alkoxylated acrylic and methacrylamides, preferably hydroxyethyl methacrylate, hydroxymethyl methacrylamide, hydroxyethyl methacrylamide, hydroxypropyl methacrylamide and succinic acid mono- [2- (methacryloyloxy) e
- the proportion by weight of comonomers B), based on the total mass of the copolymers, can be 0 to 99.8% by weight and is preferably 0.5 to 80% by weight, particularly preferably 2 to 50% by weight.
- Suitable comonomers C) are all olefinically unsaturated monomers with a cationic charge which are capable of forming copolymers in the selected reaction media with acryloyldimethyltauric acid or its salts.
- the resulting distribution of the cationic charges over the chains can be statistical, alternating, block-like or gradient-like.
- cationic comonomers C) also include those which carry the cationic charge in the form of a betaine, zwitterionic or amphoteric structure.
- Comonomers C) in the sense of the invention are also amino-functionalized precursors which are converted into their corresponding quaternary (e.g. reaction with dimethyl sulfate, methyl chloride), zwitterionic (e.g. reaction with hydrogen peroxide), betaine (e.g. reaction with chloroacetic acid) or amphomeric derivatives by polymer-analogous reactions can.
- DMAC Diallyldimethylammonium chloride
- the proportion by weight of the comonomers C), based on the total mass of the copolymers, can be 0.1 to 99.8% by weight, preferably 0.5 to 30% by weight and particularly preferably 1 to 20% by weight.
- Suitable polymerizable, silicon-containing components D) are all at least mono-olefinically unsaturated compounds which are capable of radical copolymerization under the reaction conditions chosen in each case are.
- the distribution of the individual silicone-containing monomers across the resulting polymer chains does not necessarily have to be statistical.
- the formation of, for example, block (also multiblock) or gradient-like structures is also within the meaning of the invention. Combinations of two or more different silicone-containing representatives are also possible.
- the use of silicone-containing components with two or more polymerization-active groups leads to the formation of branched or cross-linked structures.
- Preferred silicone-containing components are those of the formula (I).
- R 1 represents a polymerizable function from the group of vinylically unsaturated compounds, which is suitable for building polymer structures by radical means.
- a suitable chemical bridge Z is required to bind the silicone-containing polymer chain to the reactive end group R 1 .
- Preferred bridges Z are -O-, - ((Ci - C 50 ) alkylene) -, - ((C 6 - C 30 ) arylene) -, - ((C 5 - C 8 ) cycloalkylene) -, - ((C ⁇ -C 5 o) alkenylene) -, - (polypropylene oxide) n -, - (polyethylene oxide) 0 -, - (polypropylene oxide) n (polyethylene oxide) 0 -, where n and o independently of one another represent numbers from 0 to 200 and the distribution of EO / PO units can be statistical or block-shaped.
- bridge groupings Z are - ((C ⁇ - C 10 ) alkyl) - (Si (OCH 3 ) 2 ) - and - (Si (OCH 3 ) 2 ) -.
- the polymer middle part is represented by silicone-containing repeat units.
- the radicals R 3 , R 4 , R 5 and R 6 independently of one another are -CH 3 , -O-CH 3 , -C 6 H 5 or -OC 6 H 5 .
- the indices w and x represent stoichiometric coefficients which, independently of one another, are 0 to 500, preferably 10 to 250.
- the distribution of the repeating units over the chain can not only be purely statistical, but can also be block-like, alternating or gradient-like.
- R 2 can symbolize on the one hand an aliphatic, olefinic, cycloaliphatic, arylaliphatic or aromatic (Ci - C 5 o) carbon hydrogen radical (linear or branched) or -OH, -NH 2 , -N (CH3) 2, -R 7 or for the
- Structure unit [-ZR 1 ] stand. The meaning of the two variables Z and R 1 has already been explained. R 7 stands for further Si-containing groups. preferred
- R 7 radicals are -O-Si (CH 3 ) 3 , -O-Si (Ph) 3 , -O-Si (O-Si (CH 3 ) 3 ) 2CH 3 ) and
- R 2 is an element of the group [-ZR 1 ], it is a bifunctional, monomers that crosslink the resulting
- Polymer structures can be used.
- Formula (l) describes not only vinylically functionalized, silicone-containing
- Particularly preferred silicone-containing components are the following acrylic or methacrylic modified silicone-containing components:
- the content of silicon-containing components can be up to 99.9% by weight, preferably 0.5 to 30% by weight, particularly preferably 1 to 20% by weight.
- Suitable polymerizable, fluorine-containing components E) are all at least mono-olefinically unsaturated compounds which are capable of radical copolymerization under the reaction conditions chosen in each case.
- the distribution of the individual fluorine-containing monomers across the resulting polymer chains need not necessarily be statistical.
- the formation of, for example, block (also multiblock) or gradient-like structures is also within the meaning of the invention.
- Combinations of two or more different fluorine-containing components E) are also possible, it being clear to the expert that monofunctional representatives lead to the formation of comb-shaped structures, whereas di-, tri- or polyfunctional components E) lead to at least partially crosslinked structures.
- Preferred fluorine-containing components E) are those of the formula (II).
- R 1 represents a polymerizable function from the group of vinylically unsaturated compounds, which is suitable for building polymer structures by radical means.
- a suitable chemical bridge Y is required to link the fluorine-containing group to the reactive end group R 1 .
- Preferred bridges Y are -O-, _c (O) -, -C (O) -O-, -S-, -O-CH 2 -CH (O -) - CH 2 OH, -O-CH 2 -CH (OH) -CH 2 -O-, -O-SOz-O-, -OS (O) -O-, -PH-, -P (CH 3 ) -, -PO 3 -, -NH-, -N (CH 3 ) -, -O- (C 1 -C 5 o) alkyl-O-, -O-phenyl-O-, -O-benzyl-O-, -O- (C 5 -C 8 ) cycloalkyl- O-, -O- (C 1 -C 50 ) alkenyl-O-,
- R and s are stoichiometric coefficients that independently represent numbers from 0 to 200.
- the content of fluorine-containing components can be up to 99.9% by weight, preferably 0.5 to 30% by weight, particularly preferably 1 to 20% by weight.
- the macromonomers F) are at least simple olefinically functionalized polymers with one or more discrete repeating units and a number average molecular weight greater than or equal to 200 g / mol. Mixtures of chemically different macromonomers F) can also be used in the copolymerization. Both Macromonomers are polymeric structures that are composed of one or more repeating unit (s) and have a molecular weight distribution that is characteristic of polymers.
- Preferred macromonomers F) are compounds of the formula (III).
- R 1 represents a polymerizable function from the group of vinylically unsaturated compounds which are suitable for building polymeric structures by radical means.
- a suitable bridging group Y is required to bind the polymer chain to the reactive end group.
- Preferred bridges Y are -O-, -C (O) -, -C (O) -O-, -S-, -O-CH 2 -CH (O -) - CH 2 OH, -O-CH 2 - CH (OH) -CH 2 O-, -O-SO 2 -O-, -O-SO 2 -O-, -O-SO-O-, -PH-, -P (CH 3 ) -, -PO 3 -, -NH- and -N (CH 3 ) -, particularly preferably -O-.
- the polymer middle part of the macromonomer is represented by the discrete repeat units A, B, C and D. preferred
- Repeating units A, B, C and D are derived from acrylamide, methacrylamide, ethylene oxide, propylene oxide, AMPS, acrylic acid, methacrylic acid, methyl methacrylate, acrylonitrile, maleic acid, vinyl acetate, styrene, 1,3-butadiene, isoprene, isobutene, diethylacrylamide and diisopropylacrylamide.
- the indices v, w, x and z in formula (III) represent the stoichiometric
- Coefficients relating to the repetition units A, B, C and D. v, w, x. And z are, independently of one another, 0 to 500, preferably 1 to 30, the sum of the four coefficients on average having to be ⁇ 1.
- the distribution of the repeating units over the macromonomer chain can be statistical, block-like, alternating or gradient-like.
- R 2 denotes a linear or branched aliphatic, olefinic, cycloaliphatic, arylaliphatic or aromatic (CrC ⁇ o) hydrocarbon residue, OH, -NH 2 , -N (CH 3 ) 2 or is identical to the structural unit [-YR 1 ].
- R 2 equal to [-YR 1 ]
- these are difunctional macromonomers which are suitable for crosslinking the copolymers.
- Particularly preferred macromonomers F) are acrylic or methacrylic monofunctionalized alkyl ethoxylates of the formula (IV).
- R 3 , R 4 , R ⁇ and R ⁇ independently of one another denote hydrogen or n-aliphatic, iso-aliphatic, olefinic, cycloaliphatic, arylaliphatic or aromatic (CrCsoJ hydrocarbon radicals.
- R 3 and R 4 are preferably H or —CH 3 , particularly preferably H; R 5 is H or -CH 3 ; and R ⁇ is equal to an n-aliphatic, iso-aliphatic, olefinic, cycloaliphatic, arylaliphatic or aromatic (-C-C 30 ) hydrocarbon radical.
- v and w are again the stoichiometric coefficients relating to the ethylene oxide units (EO) and propylene oxide units (PO), v and w are independently 0 to 500, preferably 1 to 30, the sum of v and w on average having to be> 1.
- the distribution of the EO and PO units over the macromonomer chain can be statistical, block-like, alternating or gradient-like.
- Y stands for the bridges mentioned above.
- Also particularly suitable as macromonomers F) are esters of (meth) acrylic acid with
- the molecular weight of the macromonomers F) is preferably 200 g / mol to 10 6 g / mol, particularly preferably 150 to 10 4 g / mol and particularly preferably 200 to 5000 g / mol.
- suitable macromonomers up to 99.9% by weight can be used.
- Fractions of 1 to 20% by weight and 75 to 95% by weight are particularly preferred.
- Preferred copolymers are those which can be obtained by copolymerizing at least components A), C) and D).
- copolymers are those which can be obtained by copolymerizing at least components A), C) and E).
- copolymers are those which can be obtained by copolymerizing at least components A), D) and F).
- copolymers are those which can be obtained by copolymerizing at least components A) and F).
- the copolymerization is carried out in the presence of at least one polymeric additive G), the additive G) being added to the polymerization medium in whole or in part in solution before the actual copolymerization.
- the use of several additives G) is also according to the invention.
- Crosslinked additives G) can also be used.
- additives G) or their mixtures only have to be wholly or partly soluble in the chosen polymerization medium.
- additive G) has several functions. On the one hand, it prevents the formation of over-crosslinked polymer fractions in the copolymer being formed in the actual polymerization step and, on the other hand, the additive becomes G) attacked statistically by active radicals according to the generally known mechanism of graft copolymerization. As a result, depending on the additive G), more or less large amounts of it are incorporated into the copolymers.
- suitable additives G) have the property of changing the solution parameters of the copolymers which form during the radical polymerization reaction in such a way that the average molecular weights are shifted to higher values. Compared with analog copolymers which were produced without the addition of additives G), those which were produced with the addition of additives G) advantageously show a significantly higher viscosity in aqueous solution.
- Preferred additives G) are homo- and copolymers soluble in water and / or alcohols, preferably in t-butanol. Copolymers are also to be understood as meaning those with more than two different types of monomers. Particularly preferred additives G) are homopolymers and copolymers of N-vinylformamide, N-vinyl acetamide, N-vinyl pyrrolidone, ethylene oxide, propylene oxide, acryloyldimethyltauric acid, N-vinyl caprolactam, N-vinyl methylacetamide, acrylamide, acrylic acid, methacrylic acid, N-vinyl morpholide, hydroxyethyl methacrylate, Diallyldimethylammonium chloride (DADMAC) and / or [2- (methacryloyloxy) ethyl] trimethylammonium chloride (MAPTAC); Polyalkylene glycols and / or alkyl polyglycols.
- Particularly preferred additives G) are polyvinylpyrrolidones (such as Luviskol K15 ®, K20 ® and K30 ® from BASF), poly (N-vinylformamides), poly (N-vinylcaprolactams) and copolymers of N-vinylpyrrolidone, N-vinylformamide and / or acrylic acid which can also be partially or completely saponified.
- polyvinylpyrrolidones such as Luviskol K15 ®, K20 ® and K30 ® from BASF
- poly (N-vinylformamides) poly (N-vinylcaprolactams)
- copolymers of N-vinylpyrrolidone, N-vinylformamide and / or acrylic acid which can also be partially or completely saponified.
- the molecular weight of the additives G) is preferably 10 2 to 10 7 g / mol, particularly preferably 0.5 * 10 4 to 10 6 g / mol.
- the amount of polymeric additive G) used is, based on the total mass of the monomers to be polymerized during the copolymerization, preferably 0.1 to 90% by weight, particularly preferably 1 to 20% by weight and particularly preferably 1.5 to 10% by weight .-%.
- the copolymers according to the invention are crosslinked, ie they contain comonomers with at least two polymerizable vinyl groups.
- Preferred crosslinkers are methylene bisacrylamide; methylenebismethacrylamide; Esters of unsaturated mono- and polycarboxylic acids with polyols, preferably diacrylates and triacrylates or methacrylates, particularly preferably butanediol and ethylene glycol diacrylate or methacrylate, trimethylolpropane triacrylate (TMPTA) and trimethylolpropane trimethacrylate (TMPTMA); Allyl compounds, preferably allyl (meth) acrylate, triallyl cyanurate, maleic acid diallyl ester, polyallyl ester, tetraallyloxyethane, triallylamine, tetraallylethylene diamine; Allyl esters of phosphoric acid; and / or vinylphosphonic acid derivatives.
- TMPTA trimethylolpropane triacrylate
- TMPTMA trimethylolpropane trimethacrylate
- Allyl compounds preferably allyl (meth) acryl
- Trimethylolpropane triacrylate is particularly preferred as the crosslinking agent.
- the proportion by weight of crosslinking comonomers, based on the total mass of the copolymers, is preferably up to 20% by weight, particularly preferably 0.05 to 10% by weight and particularly preferably 0.1 to 7% by weight.
- All organic or inorganic solvents can be used as the polymerization medium which are largely inert with respect to radical polymerization reactions and which advantageously permit the formation of medium or high molecular weights.
- Water is preferred; lower alcohols; preferably methanol, ethanol, propanols, iso-, sec- and t-butanol, particularly preferably t-butanol; Hydrocarbons with 1 to 30 carbon atoms and mixtures of the aforementioned compounds.
- the polymerization reaction is preferably carried out in the temperature range between 0 and 150 ° C., particularly preferably between 10 and 100 ° C., both under normal pressure and under elevated or reduced pressure. If necessary, the polymerization can also be carried out under a protective gas atmosphere, preferably under nitrogen.
- high-energy electromagnetic radiation mechanical energy or the usual chemical polymerization initiators, such as organic peroxides, for example benzoyl peroxide, tert-butyl hydroperoxide, Methyl ethyl ketone peroxide, cumene hydroperoxide, dilauroyl peroxide or azo initiators such as azodiisobutyronitrile (AIBN)
- organic peroxides for example benzoyl peroxide, tert-butyl hydroperoxide, Methyl ethyl ketone peroxide, cumene hydroperoxide, dilauroyl peroxide or azo initiators such as azodiisobutyronitrile (AIBN)
- AIBN azodiisobutyronitrile
- inorganic peroxy compounds such as (NH 4 ) 2 S 2 O 8 , K 2 SO 8 or H 2 O 2 , optionally in combination with reducing agents (e.g.
- sodium bisulfite, ascorbic acid, iron (II) sulfate etc.) or redox systems which contain an aliphatic or aromatic sulfonic acid (eg benzenesulfonic acid, toluenesulfonic acid etc.) as reducing component.
- an aliphatic or aromatic sulfonic acid eg benzenesulfonic acid, toluenesulfonic acid etc.
- All solvents can be used as the polymerization medium which are largely inert with respect to radical polymerization reactions and which allow the formation of high molecular weights.
- Water and lower, tertiary alcohols or hydrocarbons having 3 to 30 carbon atoms are preferably used.
- t-butanol is used as the reaction medium.
- Mixtures of two or more representatives of the potential solvents described are of course also in accordance with the invention. This also includes emulsions of immiscible solvents (e.g. water / hydrocarbons).
- reaction control which lead to the polymer structures according to the invention are suitable (solution polymerization, emulsion process, precipitation process, high-pressure process, suspension process, bulk polymerisation, gel polymerisation, etc.).
- Precipitation polymerization is particularly suitable, particularly preferably precipitation polymerization in tert-butanol.
- the following list shows 67 copolymers which are particularly suitable for the formulation of the agents according to the invention.
- the various copolymers No. 1 to No. 67 can be obtained according to the following production processes 1, 2, 3 and 4.
- Butanol can be produced.
- the monomers were initially introduced into t-butanol, the reaction mixture was rendered inert and then the reaction after heating to 60 ° C. by addition of the corresponding t-butanol-soluble initiator (preferably dilauroyl peroxide) started. After the reaction has ended (2 hours), the polymers are isolated by suction extraction of the solvent and subsequent vacuum drying.
- t-butanol-soluble initiator preferably dilauroyl peroxide
- These polymers can be prepared in water using the gel polymerization process.
- the monomers are dissolved in water, the reaction mixture is rendered inert, and the reaction is then started after heating to 65 ° C. by adding suitable initiator or initiator systems (preferably Na 2 S 2 ⁇ 8 ).
- suitable initiator or initiator systems preferably Na 2 S 2 ⁇ 8 .
- the polymer gels are then crushed and the polymers isolated after drying.
- Process 3 These polymers can be prepared in water using the emulsion process.
- the monomers are mixed in a water / organ mixture.
- Solvent preferably cyclohexane
- emulsifier emulsifier
- the reaction mixture is rendered inert by means of N 2 and the reaction is then started after heating to 80 ° C. by adding suitable initiator or initiator systems (preferably Na 2 S 2 O 8 ).
- suitable initiator or initiator systems preferably Na 2 S 2 O 8 .
- the polymer emulsions are then evaporated (cyclohexane acts as a tug for water), thereby isolating the polymers.
- These polymers can be prepared by the solution process in organic solvents (preferably toluene, for example also partially alcohols).
- organic solvents preferably toluene, for example also partially alcohols.
- the monomers are initially introduced in the solvent, the reaction mixture is rendered inert, and the reaction is then started after heating to 70 ° C. by adding suitable initiator or initiator systems (preferably dilauroyl peroxide).
- suitable initiator or initiator systems preferably dilauroyl peroxide.
- the polymers are isolated by evaporation of the solvent and subsequent vacuum drying. Polymers with hydrophobic side chains, uncrosslinked
- the described, optionally feasible grafting of the copolymers with other polymers leads to products with a particular polymer morphology which result in optically clear gels in aqueous systems.
- a potential disadvantage of the copolymers without grafting is more or less strong opalescence in aqueous solution. This is based on previously unavoidable, over-crosslinked polymer fractions that arise during the synthesis and are only insufficiently swollen in water. As a result, light-scattering particles form, the size of which is well above the wavelength of visible light and are therefore the cause of opalescence.
- the described grafting process which can be carried out as an option, significantly reduces or completely avoids the formation of over / replaced polymer components compared to conventional techniques.
- copolymers show advantageous properties both in crosslinked and in uncrosslinked form. While networked systems e.g. excellent property profiles with regard to emulsion stabilization could be thickened, especially with the help of the uncrosslinked variants, surfactant-containing solutions. The same applies to electrolyte-containing systems which are known to be very difficult or impossible to thicken with polyelectrolytes.
- copolymers have a wide range of uses and are suitable, for example, for use in formulations, emulsions, suspensions, dispersions and powders in aqueous-alcoholic, aqueous-surfactant formulations.
- the copolymers can be used as thickeners for agents on an aqueous or aqueous-alcoholic basis, for example hair gels.
- the copolymers are furthermore suitable as stabilizers, dispersants and consistency agents for aqueous surfactant preparations, for example shampoos, shower baths, shower gels, foam baths and the like.
- the thickening effect of the copolymers in aqueous surfactants is enhanced by an association of the polymer side chains and the surfactants and can be controlled by the choice of the side chains of the copolymers and by the choice of the surfactants.
- the suspending or dispersing and stabilizing action of the copolymers in aqueous surfactant is achieved by the association of the polymer side chains or functional groups in the main and side chain and the liquid components insoluble in aqueous surfactant, for example silicone oils or the insoluble components. for example zinc pyrethione.
- the copolymers are also suitable as thickeners and dispersants, as emulsifiers, suspending agents with a thickening effect and as consistency agents for emulsions and suspensions, and as lubricants, adhesives, thickeners, Dispersant and emulsifier of decorative, solid-containing preparations. Mixtures of the copolymers can also be used.
- the emulsifying, stabilizing and / or consistency effect of the copolymers in emulsions is caused or enhanced by an association of the polymer side chains with one another, and by an interaction of the polymer side chains with the hydrophobic oil components.
- the emulsions can be both water-in-oil emulsions and oil-in-water emulsions, microemulsions and multiple emulsions.
- the preparation of the emulsions can be carried out in a known manner, i.e. for example by hot, hot / cold or PIT emulsification.
- the non-aqueous proportion of the emulsions which largely consists of the emulsifier, the thickener and the oil body, is usually 5 to 95% by weight, preferably 15 to 75% by weight.
- the emulsions can contain 5 to 95% by weight, preferably 25 to 85% by weight, of water, depending on whether lotions with a comparatively low viscosity or creams and ointments with a high viscosity are to be produced.
- the copolymers are used in rinse-off products, preferably shampoos, shower baths, shower gels and foam baths.
- the copolymers are used in leave-on products, preferably skin care products, day creams, night creams, skin care creams, nutritional creams, body lotions, ointments, sunscreens, lip care products and deodorants.
- surfactant-free, aqueous agents and emulsions for example for hair treatments and hair rinses, hair gels but also for permanent wave agents, hair colorants, and for decorative cosmetics, for example make-ups, eye shadows, lipsticks, mascara and the like.
- compositions according to the invention contain, based on the finished compositions, preferably 0.01 to 10% by weight, particularly preferably 0.1 to 5% by weight, particularly preferably 0.5 to 3% by weight, of copolymers.
- the agents according to the invention can contain anionic, cationic, non-ionic, hermaphrodite and / or amphoteric surfactants.
- the total amount of the surfactants used in the agents according to the invention (for example in the case of rinse-off products), based on the finished agents, is preferably 2 to 70% by weight, particularly preferably 5 and 40% by weight, particularly preferably 12 up to 35% by weight.
- Preferred anionic surfactants are (C 2 -C 20) -alkyl and alkylene-carboxylates, alkyl ether carboxylates, fatty alcohol sulfates, fatty alcohol ether sulfates, alkyl amide sulfates and sulfonates, fatty acid alkyl amide polyglycol ether sulfates, alkane sulfonates, hydroxy alkanesulfonate, isolefinsulfonate, olefinsulfonate, olefinsulfonate, isolefinsulfonates, olefinsulfonate, olefinsulfonate, olefinsulfonate, isocyanates, and , Sulfosuccinates, sulfosuccinic acid semiesters and diesters, fatty alcohol ether phosphates, protein-fatty acid condensation products, alkyl monoglyceride sulfates and sulf
- the proportion by weight of the anionic surfactants is preferably 2 to 30% by weight, particularly preferably 5 to 25% by weight, particularly preferably 12 to 22% by weight, based on the finished compositions.
- Preferred cationic surfactants are quaternary ammonium salts, such as di (C ⁇ o-C 24 ) alkyl dimethylammonium chloride or bromide, preferably di (C 2 -C 8 8 ) alkyl dimethylammonium chloride or bromide; (C ⁇ 0 -C 24 ) alkyl dimethyl ethyl ammonium chloride or bromide; (C 10 -C 24 ) alkyl trimethyl ammonium chloride or bromide, preferably cetyl trimethyl ammonium chloride or bromide and (C2o-C 22 ) alkyl trimethyl ammonium chloride or bromide; (C 10 -C 24 ) alkyl dimethylbenzyl ammonium chloride or bromide, preferably (Ci2-C ⁇ 8 ) alkyl dimethylbenzyl ammonium chloride; N- (-C ⁇ -C ⁇ 8 ) alkyl pyridinium chloride or -bromide, preferably N
- the proportion by weight of the cationic surfactants is preferably 1 to 10% by weight, particularly preferably 2 to 7% by weight, particularly preferably 3 to 5% by weight.
- Preferred nonionic surfactants are fatty alcohol ethoxylates
- Alkylpolyethylene glycols Alkylphenolpolyethylenglykole;
- Alkylmercaptanpolyethylenglykole Fatty amine ethoxylates (alkylamino polyethylene glycols); Fatty acid ethoxylates (acyl polyethylene glycols);
- Saccharoseester Sorbitol ester and the polyglycol ether.
- the weight fraction of the nonionic surfactants in the agents according to the invention is preferably in the range from 1 to
- Preferred amphoteric surfactants are N- (-C 2 -C 18 ) -alkyl-ß-aminopropionate and N- (Ci 2 - C ⁇ 8 ) -alkyl-ß-iminodipropionate as alkali and mono-, di- and trialkylammonium salts; N-acylaminoalkyl-N, N-dimethyl-acetobetaine, preferably N- (C 8 -C 8 ) -acyl-aminopropyl-N, N-dimethylacetobetaine; (C 12 -C 8 ) alkyl dimethyl sulfopropyl betaine; Amphoteric surfactants based on imidazoline (trade name: Miranol ® , Steinapon ® ), preferably the sodium salt of 1- ( ⁇ -carboxymethyloxyethyl) -1- (carboxymethyl) -2-lauryl-imidazolinium; Amine oxide, for example (C
- the weight fraction of the amphoteric surfactants is preferably 0.5 to 20% by weight, particularly preferably 1 to 10% by weight.
- Preferred surfactants are lauryl sulfate, laureth sulfate, cocoamidopropyl betaine, sodium cocoyl glutamate, lauroamphoacetate.
- the agents additionally contain co-surfactants from the group of alkyl betaines, alkyl amido betaines, aminopropionates, aminoglycinates, imidazolinium betaines and sulfobetaines, amine oxides, fatty acid alkanolamides and polyhydroxyamides as foam-enhancing agents.
- the agents according to the invention can contain oil bodies, emulsifiers and co-emulsifiers, as well as other additives commonly used in cosmetics, such as e.g. cationic polymers, film formers, superfatting agents, stabilizers, biogenic agents, glycerin, preservatives, pearlescent agents, colorants and fragrances, solvents, opacifiers, also protein derivatives such as gelatin, collagen hydrolyzates, polypeptides on a natural and synthetic basis, egg yolk, lecithin, lanolin and lanolin derivatives, fatty alcohol , Silicones, deodorising agents, substances with keratolytic and keratoplastic effects, enzymes and carrier substances.
- antimicrobial agents can be added to the agents according to the invention
- Oil body means any fatty substance that is liquid at room temperature (25 ° C).
- the fat phase can comprise one or more oils, which are preferably selected from the following oils: Silicone oils, volatile or non-volatile, linear, branched or ring-shaped, possibly organically modified; Phenyl silicones, silicone resins and rubbers that are solid or liquid at room temperature; Mineral oils such as paraffin or petroleum jelly; Oils of animal origin, such as perhydrosqualene or lanolin; Oils of vegetable origin, such as liquid triglycerides, for example sunflower, corn, soybean, rice, jojoba, babusscu, pumpkin, grape seed, sesame, walnut, apricot, macadamia, avocado, sweet almond , Meadow foam, castor oil, triglycerides of caprylic / capric acids, olive oil, peanut oil, rapeseed oil and coconut oil; synthetic oils, such as purcellin oil, isoparaffins, linear and / or branched fatty alcohols and
- the non-ionic co-emulsifiers include Storage products of 0 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide to linear
- Suitable ionogenic co-emulsifiers are e.g. anionic emulsifiers, such as mono-, di- or tri-phosphoric acid esters, but also cationic emulsifiers, such as mono-, di- and tri-alkyl quats and their polymeric derivatives.
- Suitable cationic polymers are those known under the INCI name "Polyquaternium", in particular Polyquaternium-31, Polyquaternium-16, Polyquaternium-24, Polyquaternium-7, Polyquaternium-22, Polyquaternium-39, Polyquaternium-28, Polyquaternium-2, Polyquaternium -10, Polyquaternium-11, as well as Polyquaternium 37 & mineral oil & PPG trideceth (Salcare SC95), PVP-dimethylaminoethyl methacrylate copolymer, guar hydroxypropyltriammonium chlorides, as well as calcium alginate and ammonium alginate.
- Polyquaternium in particular Polyquaternium-31, Polyquaternium-16, Polyquaternium-24, Polyquaternium-7, Polyquaternium-22, Polyquaternium-39, Polyquaternium-28, Polyquaternium-2, Polyquaternium -10, Polyquaternium-11, as well as Polyquaternium 37 & mineral oil & P
- Cationic cellulose derivatives; cationic starch and copolymers can be used; ; quaternized vinylpyrrolidone / vinylimidazole polymers; condensation products of polyglycols and amines; quaternized collagen polypeptides; quaternized wheat polypeptides; polyethyleneimines; cationic silicone polymers such as amidomethicones;
- Suitable silicone compounds are, for example, dimethylpolysiloxane, methylphenylpolysiloxanes, cyclic silicones and amino, fatty acid, alcohol, polyether, epoxy, fluorine and / or alkyl-modified silicone compounds, and also polyalkylsiloxanes, polyalkylarylsiloxanes, polyether siloxane copolymers, as in US 5104 645 and the writings described therein, which can be both liquid and resinous at room temperature.
- suitable film formers are water-soluble polyurethanes, for example C10-polycarbamylpolyglyceryl esters, polyvinyl alcohol, polyvinylpyrrolidone, copolymers, for example vinylpyrrolidone / vinyl acetate copolymer, water-soluble acrylic acid polymers / Copolymers or their esters or salts, for example partial ester copolymers of acrylic / methacrylic acid and polyethylene glycol ethers of fatty alcohols, such as acrylate / steareth-20-methacrylate copolymer, water-soluble cellulose, for example hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, water-soluble quaterniums, polyquaterniums, carboxyvinyl polymers, such as carbovinyl polymers ere and their salts, polysaccharides, for example polydextrose and glucan.
- water-soluble polyurethanes for example C10-poly
- Substances such as, for example, polyethoxylated lanolin derivatives, lecithin derivatives, polyol fatty acid esters, monoglycerides and fatty acid alkanolamides can be used as superfatting agents, the latter simultaneously serving as foam stabilizers.
- polyethoxylated lanolin derivatives such as, for example, polyethoxylated lanolin derivatives, lecithin derivatives, polyol fatty acid esters, monoglycerides and fatty acid alkanolamides
- foam stabilizers for example, isopropyl palmitate, glycerin and / or sorbitol are available as a moisturizing substance.
- Metal salts of fatty acids such as e.g. Magnesium, aluminum and / or zinc stearate can be used.
- Biogenic active substances are understood to mean, for example, plant extracts and vitamin complexes.
- formulations according to the invention can be organic
- Alcohols with 1 to 4 carbon atoms such as ethanol, propanol, isopropanol, n-butanol, i-butanol, t-butanol, glycerol and mixtures of the alcohols mentioned are preferably used.
- Other preferred alcohols are polyethylene glycols with a relative
- polyethylene glycol with a relative molecular weight between 200 and 600 and in amounts of up to 45% by weight and of polyethylene glycol with a relative molecular weight between 400 and 600 in amounts of 5 to 25% by weight is preferred
- suitable solvents are, for example, triacetin (glycerol triacetate) and 1-methoxy-2-propanol.
- the agents according to the invention can be mixed with conventional ceramides, pseudoceramides, fatty acid-N-alkylpolyhydroxyalkylamides, cholesterol, cholesterol fatty acid esters, fatty acids, triglycerides, cerebrosides, phospholipids and similar substances as a care additive.
- Suitable UV filters are e.g. 4-aminobenzoic acid; 3- (4'-trimethylammonium) benzylidene-borane-2-one methyl sulfate; 3,3,5-trimethyl-cyclohexyl salicylate; 2-hydroxy-4-methoxybenzophenone; 2-phenylbenzimidazole-5-sulfonic acid and its potassium, sodium and triethanolamine salts; 3,3 '- (1,4-phenylenedimethine) bis (7,7-dimethyl-2-oxobicyclo [2.2.1] heptane-1-methanesulfonic acid and its salts; 1- (4-tert-butylphenyl) -3- (4-methoxypheny ⁇ ) propan-1, 3-dione, 3- (4'-sulfo) -benzy ⁇ den-bornan- 2-one and its salts; 2-cyan-3,3-diphenyl-acrylic acid- (2nd -ethylhexyl ester); poly
- pigments / micropigments e.g. microfine titanium dioxide, mica titanium oxide, iron oxides, mica iron oxide, zinc oxide, silicon oxides, ultramarine blue, chromium oxides can be used.
- Suitable antioxidants are, for example, superoxide dismutase, tocopherol (vitamin E) and ascorbic acid (vitamin C).
- suitable preservatives are phenoxyethanol, parabens, pentanediol or sorbic acid.
- the dyes which can be used are those which are suitable and approved for cosmetic purposes.
- Suitable antifungal active ingredients are preferably ketoconazole, oxiconazole, terbinafine, bifonazole, butoconazole, cloconazole, clotrimazole, econazole, enilconazole, fenticonazole, isoconazole, miconazole, sulconazole, tioconazole fluonazole, ionifoneazonazole, ioconazole, ioconazole, ioconazole, ioconazole, ioconazole, ionoconazole, ioconazole, ionoconazole, ionoconazole, ionoconazole, ionoconazole, ionoconazole, ionoconazole, ionoconazole, ionoconazole, ionoconazole, ionoconazole, ionoconazole, i
- cellulose ethers and other cellulose derivatives e.g. carboxymethyl cellulose, hydroxyethyl cellulose
- gelatin starch and starch derivatives
- sodium alginates fatty acid polyethylene glycol esters
- agar agar tragacanth or dextrins
- Various materials are used as synthetic polymers, e.g.
- Polyvinyl alcohols polyacrylamides, polyvinylamides, polysulfonic acids, polyacrylic acid, polyacrylic acid esters, polyvinyl pyrrolidone, polyvinyl methyl ether, polyethylene oxides, copolymers of maleic anhydride and vinyl methyl ether, as well as various mixtures and copolymers from the above. Compounds, including their various salts and esters. These polymers can optionally be cross-linked or uncross-linked.
- the described copolymers containing acryloyldimethyltauric acid can also be used without the use of an additional co-emulsifier and / or without the use of an additional consistency agent.
- the use of co-emulsifiers and / or consistency enhancers is therefore not mandatory, but possible.
- a combination with other known co-emulsifiers and / or Consistency agents may be desirable for setting special cosmetic profiles and for exploiting synergistic effects.
- the agents according to the invention are usually adjusted to a pH in the range 2 to 12, preferably pH 3 to 8.
- the nature of the agents according to the invention is extremely advantageous: the emulsions are creamy and ointment-like and do not have the gel-like or even gelatin-like appearance of certain prior art emulsions in which the outer aqueous phase is thickened.
- the cosmetic feeling on the skin is also very good: when applied, the emulsion gives a feeling of freshness and comfort, while at the same time having a rich and nourishing effect; it is soft and comfortable and in no way sticky.
- copolymers used in the examples are representatives of the particularly preferred copolymers No. 1 to No. 67 already listed in the description.
- the preparation was carried out according to processes 1, 2, 3 or 4 using the preferred initiators and solvents.
- Example 1 O / W - skin milk
- composition A copolymer No. 34 1.00%
- V Add components from G to I one after the other VI adjust pH if necessary
- Emulsogen HCO 040 (Clariant) 0.50% PEG-40 Hydrogenated Castor Oil perfumee qs
- Emulsogen HCO 040 (Clariant) 0.50%
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Abstract
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
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EP14001712.0A EP2944658A1 (fr) | 2000-12-01 | 2001-11-28 | Agents cosmétiques, pharmaceutiques et dermatologiques |
EP10000386.2A EP2186836B1 (fr) | 2000-12-01 | 2001-11-28 | Composition cosmétique, pharmaceutique et dermatologique. |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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DE10059826A DE10059826A1 (de) | 2000-12-01 | 2000-12-01 | Kosmetische, pharmazeutische und dermatologische Mittel |
DE10059826 | 2000-12-01 | ||
PCT/EP2001/013867 WO2002043689A2 (fr) | 2000-12-01 | 2001-11-28 | Agents cosmetiques, pharmaceutiques et dermatologiques |
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EP10000386.2A Division EP2186836B1 (fr) | 2000-12-01 | 2001-11-28 | Composition cosmétique, pharmaceutique et dermatologique. |
EP14001712.0A Division EP2944658A1 (fr) | 2000-12-01 | 2001-11-28 | Agents cosmétiques, pharmaceutiques et dermatologiques |
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EP10000386.2A Expired - Lifetime EP2186836B1 (fr) | 2000-12-01 | 2001-11-28 | Composition cosmétique, pharmaceutique et dermatologique. |
EP14001712.0A Withdrawn EP2944658A1 (fr) | 2000-12-01 | 2001-11-28 | Agents cosmétiques, pharmaceutiques et dermatologiques |
EP01998320A Withdrawn EP1339383A2 (fr) | 2000-12-01 | 2001-11-28 | Agents cosmetiques, pharmaceutiques et dermatologiques |
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EP10000386.2A Expired - Lifetime EP2186836B1 (fr) | 2000-12-01 | 2001-11-28 | Composition cosmétique, pharmaceutique et dermatologique. |
EP14001712.0A Withdrawn EP2944658A1 (fr) | 2000-12-01 | 2001-11-28 | Agents cosmétiques, pharmaceutiques et dermatologiques |
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US (2) | US7399478B2 (fr) |
EP (3) | EP2186836B1 (fr) |
JP (1) | JP2002265321A (fr) |
BR (2) | BRPI0117227B1 (fr) |
DE (1) | DE10059826A1 (fr) |
ES (1) | ES2490217T3 (fr) |
WO (1) | WO2002043689A2 (fr) |
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-
2000
- 2000-12-01 DE DE10059826A patent/DE10059826A1/de not_active Withdrawn
-
2001
- 2001-09-27 JP JP2001295996A patent/JP2002265321A/ja not_active Withdrawn
- 2001-11-28 BR BRPI0117227-1A patent/BRPI0117227B1/pt not_active IP Right Cessation
- 2001-11-28 ES ES10000386.2T patent/ES2490217T3/es not_active Expired - Lifetime
- 2001-11-28 EP EP10000386.2A patent/EP2186836B1/fr not_active Expired - Lifetime
- 2001-11-28 US US10/433,116 patent/US7399478B2/en not_active Expired - Fee Related
- 2001-11-28 EP EP14001712.0A patent/EP2944658A1/fr not_active Withdrawn
- 2001-11-28 EP EP01998320A patent/EP1339383A2/fr not_active Withdrawn
- 2001-11-28 BR BRPI0115843A patent/BRPI0115843B1/pt not_active IP Right Cessation
- 2001-11-28 WO PCT/EP2001/013867 patent/WO2002043689A2/fr active Application Filing
-
2008
- 2008-04-29 US US12/150,532 patent/US7943157B2/en not_active Expired - Fee Related
Non-Patent Citations (1)
Title |
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See references of WO0243689A2 * |
Also Published As
Publication number | Publication date |
---|---|
US20040109835A1 (en) | 2004-06-10 |
DE10059826A1 (de) | 2002-06-13 |
EP2186836A1 (fr) | 2010-05-19 |
US7943157B2 (en) | 2011-05-17 |
JP2002265321A (ja) | 2002-09-18 |
BRPI0115843B1 (pt) | 2016-03-08 |
US7399478B2 (en) | 2008-07-15 |
WO2002043689A3 (fr) | 2002-10-24 |
WO2002043689A2 (fr) | 2002-06-06 |
EP2186836B1 (fr) | 2014-06-25 |
EP2944658A1 (fr) | 2015-11-18 |
US20080207773A1 (en) | 2008-08-28 |
BR0115843A (pt) | 2003-10-07 |
ES2490217T3 (es) | 2014-09-03 |
BRPI0117227B1 (pt) | 2015-06-02 |
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