EP1495060A1 - Polyurethannes reticules de polytetrahydrofurane - Google Patents

Polyurethannes reticules de polytetrahydrofurane

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Publication number
EP1495060A1
EP1495060A1 EP03720405A EP03720405A EP1495060A1 EP 1495060 A1 EP1495060 A1 EP 1495060A1 EP 03720405 A EP03720405 A EP 03720405A EP 03720405 A EP03720405 A EP 03720405A EP 1495060 A1 EP1495060 A1 EP 1495060A1
Authority
EP
European Patent Office
Prior art keywords
weight
active hydrogen
acid
per molecule
hydrogen atoms
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Withdrawn
Application number
EP03720405A
Other languages
German (de)
English (en)
Inventor
Son Nguyen-Kim
Ellen Pfrommer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP1495060A1 publication Critical patent/EP1495060A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
    • C08G18/722—Combination of two or more aliphatic and/or cycloaliphatic polyisocyanates
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04—Dispersions; Emulsions
    • A61K8/046—Aerosols; Foams
    • 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
    • A61K8/87—Polyurethanes
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6625—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/34
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34

Definitions

  • the present invention relates to crosslinked polyurethanes based on polytetrahydrofurans and their use in cosmetic and / or pharmaceutical preparations.
  • hair treatment agents which are present, for example, as hair setting agents or hair spray, are used for setting, improving the structure and shaping the hair.
  • the hair treatment compositions consist primarily of a solution of film-forming resins or synthetic polymers. So far, the following film formers have mainly been used in hair treatment agents: shellac, homopolymers and copolymers of N-vinylpyrrolidone, copolymers of vinyl ethers / maleic acid half-esters, of (eth) acrylic acid or its esters and amides and crotonic acid with vinyl esters.
  • the hair treatment agents are sprayed onto the hair in the form of solutions, preferably as ethanolic solutions. After the solvent has evaporated, the hair is held in the desired shape by the remaining polymer at the points of mutual contact.
  • the polymers should be so hydrophilic that they can be washed out of the hair, on the other hand, they should be hydrophobic so that the hair treated with the polymers maintain their shape even at high atmospheric humidity and do not stick together.
  • the previously known polymeric film formers such as polyvinylpyrrolidones
  • polyvinylpyrrolidones mostly have the disadvantage of excessive water absorption with increased atmospheric humidity. This property leads, among other things, to undesired sticking of the hair and to a loss of strength and therefore a breakdown of the hairstyle.
  • the resistance to high air humidity is improved, for example in the case of copolymers of N-vinylpyrrolidone and vinyl acetate, the production effect of the film suffers and can even lead to unpleasant dusting and a flaky coating.
  • the washability when cleaning the hair is made more difficult.
  • the present invention has for its object to provide auxiliaries for cosmetic and pharmaceutical preparations.
  • the object of the present invention is to provide new cosmetic compositions, in particular hair treatment compositions based on polyurethane, which on the one hand can be used as hair fixatives and on the other hand also have good washability (redispersibility). They should give the hair smoothness and smoothness.
  • polymeric film formers which give the hair the desired flexibility and at the same time have little or no stickiness.
  • the object of the invention is achieved by crosslinked polyurethanes
  • crosslinked polyurethanes according to the invention are suitable as cosmetic and / or pharmaceutical auxiliaries, in particular as film formers.
  • EP 656 021 B1 describes the use of
  • EP 656 021 B1 does not describe polyurethanes with polytetrahydrofranes.
  • the polyurethanes according to the invention have good flexibility with low stickiness at the same time.
  • EP-A-619 111 describes the use of polyurethanes based on organic diisocyanates, diols and 2,2-hydroxymethyl-substituted carboxylates of the formula
  • A represents a hydrogen atom or a C 1 -C 2 o -alkyl group
  • A represents a hydrogen atom or a C 1 -C 2 o -alkyl group
  • the carboxylic acid groups are neutralized with an organic or inorganic base.
  • the diols have a molecular weight in the range from 300 to 20,000, polytetrahydrofurans also being mentioned as a suitable diol component.
  • none of the exemplary embodiments describes a polyurethane based on a polytetrahydrofuran. Films based on these polyurethanes are soft and sticky and the hair fixers based on them are in need of improvement.
  • Polyurethanes with cationic groups form hygroscopic films that are sticky. Therefore, they generally do not meet the gloss and natural appearance demands made of hair setting polymer.
  • WO 01/16200 describe water-soluble or water-dispersible polyurethanes from an oligomer a)
  • Isocyanate groups reactive groups which is selected from
  • the oligomer comprises at least two urethane and / or urea groups per molecule and additionally at least two further functional groups which are selected from hydroxyl, primary and / or secondary amino groups
  • polyurethanes contain at least one of the oligomers as component a) in built-in (polymerized) form.
  • EP 938 889 A2 describes an aqueous cosmetic composition containing at least one water-soluble or water-dispersible polyurethane
  • At least one polymer with two active hydrogen atoms per molecule which is selected from polytetrahydrofuran, polysiloxanes and mixtures thereof,
  • polyurethane contains no unit derived from a primary or secondary amine which has an ionogenic or ionic group.
  • the polyurethanes described in EP 938 889 A2 are essentially uncrosslinked.
  • polyurethanes according to the invention are cross-linked.
  • the present invention relates to a crosslinked polyurethane
  • the invention relates to a crosslinked polyurethane
  • E) a compound different from B) and C) which contains at least 2 active hydrogen atoms and has a molecular weight of 60 to 5000
  • Component A) is polytetrahydrofuran of the general formula
  • polytetrahydrofurans usually have a number average molecular weight in the range from 200 to 3000, preferably 250 to 2000, in particular 600 to 1500.
  • Suitable polytetrahydrofurans can be obtained by cationic polymerization of tetrahydrofuran in the presence of acidic catalysts, e.g. Sulfuric acid or fluorosulfuric acid. Such production processes are known to the person skilled in the art.
  • acidic catalysts e.g. Sulfuric acid or fluorosulfuric acid.
  • Component B) is a compound that is more than
  • 3 to 20 in particular 3 to 10, especially 3 to 5 OH and / or, NH groups.
  • Triols and higher polyols with 3 to 100, preferably 3 to 70, carbon atoms are preferably used as component B).
  • Preferred triplets are e.g. Glycerin and trimethylol propane.
  • Preferred triols B) are also the triesters of hydroxycarboxylic acids with trihydric alcohols. These are preferably triglycerides of hydroxycarboxylic acids, such as e.g. Lactic acid, hydroxystearic acid and ricinoleic acid.
  • Naturally occurring mixtures are also suitable which contain hydroxycarboxylic acid triglycerides, in particular castor oil.
  • Preferred higher polyols B) are, for example, erythritol, pentaerythritol and sorbitol.
  • Preferred triamines B) are, for example, diethylenetriamine, N, N'-diethyl-diethylenetria in etc.
  • Preferred higher-quality polyamines are, for example, triethylenetetramine etc. and ⁇ , ⁇ -diamino polyethers which can be prepared by amination of polyalkylene oxides with ammonia.
  • the compounds mentioned as component B) can be used individually or in mixtures.
  • Polysiloxanes with more than 2 active hydrogen atoms can also be used as component B).
  • the polysiloxanes B) are, for example, compounds of the formula II
  • s stands for a value of 5 to 200, preferably 10 to 100
  • polyalkylene oxide-containing silicone derivatives are those which contain the following structural elements:
  • radicals R 1 can be identical or different, and either come from the group of aliphatic hydrocarbons with 1 to 20 carbon atoms, are cyclic aliphatic hydrocarbons with 3 to -20 C atoms, or are aromatic in nature
  • R 2 , R 3 , R 5 can be identical or different, and either come from the group of aliphatic hydrocarbons with 1 to 20 carbon atoms, cyclic aliphatic hydrocarbons with 3 to 20 C atoms, or aromatic in nature or the same R 6 are:
  • a, b can be integers between 0 and 50 with the proviso that the sum of a and b is greater than 0
  • R H, -CH 3 , -Si-0 -Si - CH 3 i
  • the groups R 1 are preferably selected from the following group: methyl, ethyl, propyl, butyl, isobutyl, pentyl, isopentyl, hexyl, octyl, decyl, dodecyl and octadecyl, cycloaliphatic radicals, especially cyclohexyl, aromatic groups, especially phenyl or naphthyl, mixed aromatic-aliphatic radicals such as benzyl or phenylethyl and tolyl and xylyl.
  • Methyl, ethyl and phenyl are particularly preferred.
  • the groups R 2 , R 3 and R 5 are preferably selected from the following group: methyl, ethyl, propyl, butyl, isobutyl, pentyl, isopentyl, hexyl, octyl, decyl, dodecyl and octadecyl, cycloaliphatic radicals, especially cyclohexyl, aromatic groups especially phenyl or naphthyl, mixed aromatic-aliphatic radicals such as benzyl or phenylethyl as well as tolyl and xylyl and R 6 .
  • Preferred radicals R 2 and R 6 are those in which the sum of a + b is between 5 and 30.
  • silicone derivative B) containing polyalkylene oxide compounds of the following formula are used as the silicone derivative B) containing polyalkylene oxide:
  • R 4 -H; -C0CH 3 , alkyl with C 1 -C 4 , -OH
  • n 1 to 6, in particular 2 to 4, preferably 3 where y is selected so that at least 3 OH groups are present in the molecule, that is for
  • x and y are integers such that the molecular weight of the polysiloxane block is between 1000 and 10000,
  • a, b can be integers between 0 and 50, with the proviso that the sum of a and b is greater than 0.
  • Silicone-containing polyamino compounds can also be used as component B).
  • a stands for an integer from 0 to 100
  • b stands for an integer from 2 to 8
  • R 13 and R i4 independently of one another represent Ci to Cs alkylene, the order of the alkylene oxide units is arbitrary and v and w independently of one another represent an integer from 0 to 200, the sum of v and w being> 0, Polysiloxanes of the general formula IV.2
  • R i5 represents a Ci to Cs alkylene radical
  • R 16 and R X7 independently of one another represent hydrogen, Ci- to Cs-alkyl or C 5 - to Cs-cycloalkyl, the sequence of the siloxane units is arbitrary, c, d and e independently of one another represent 0 to 100, the sum of c, d and e is at least 3, and where d and e are selected such that there are at least 3 active hydrogen molecules, f is an integer from 2 to 8,
  • the order of the alkylene oxide units is arbitrary and g and h independently of one another represent an integer from 0 to 200, the sum of g and h> 0,
  • R18 f * Q r is a C ⁇ ⁇ to C 8 alkylene radical
  • R 13 and R i4 are preferably, independently of one another, a C to C 4 alkylene radical.
  • Rl * 3 and R i4 independently of one another represent a C 2 - to C 3 -alkylene radical.
  • the molecular weight of the compound of the formula IV.1 is preferably in a range from about 300 to 100,000.
  • formula IV.1 a is preferably an integer from 1 to 20, such as 2 to 10.
  • the end groups of the polysiloxanes with repeating units of the general formula IV.1 are preferably selected from (CH 3 ) 3 SiO, H, Ci to Cs alkyl and mixtures thereof.
  • Suitable alkoxylated siloxane amines of the formula IV.1 are e.g. in WO-A-97/32917, to which full reference is made here.
  • Commercially available compounds are e.g. the Silsoft® brands from Witco, e.g. Silsoft® A-843.
  • radical R i5 is preferably a C to C 4 alkylene radical.
  • R 16 and R i7 are preferably, independently of one another, hydrogen or C 1 -C 4 -alkyl.
  • the sum of c, d and e is preferably chosen such that the molecular weight of the compound of the formula IV.2 is in a range from about 300 to 100,000, preferably 500 to 50,000.
  • the total number of alkylene oxide units of the radical of formula V i.e. the sum of g and h, in a range from about 3 to 200, preferably 5 to 80.
  • the R i8 radical is preferably C 2 -C 4 -alkyl.
  • the radical R 19 is preferably hydrogen or C 1 -C 4 -alkyl.
  • a suitable compound of formula IV.2 is e.g. Silsoft® A-858 from Witco.
  • Component C) is a compound which has at least 2 active hydrogen atoms and at least one ionogenic and / or ionic group per molecule, which are anionogenic, anionic, cationogenic and / or cationic groups.
  • Preferred compounds C) with two active hydrogen atoms and at least one anionogenic and / or anionic group per molecule are, for example, compounds with carboxylate and / or Sulfonate groups.
  • component c 2,2-hydroxymethyl-alkylcarboxylic acids, such as dimethylolpropanoic acid, and mixtures which contain 2,2-hydroxymethyl-alkylcarboxylic acids, such as dimethylolpropanoic acid, are particularly preferred.
  • Suitable diamines and / or diols C) with anionogenic or anionic groups are compounds of the formula
  • R is a C-Ci 8 ⁇ alkylene group and Me is Na or K.
  • w and x independently of one another represent an integer from 1 to 8, in particular 1 to 6, and M represents Li, Na or K, and compounds of the formula
  • w and x have the meanings given above, y and z independently of one another are an integer from 0 to 50, at least one of the two variables y or z> 0.
  • the order of the alkylene oxide units is arbitrary.
  • the last-mentioned compounds preferably have a number average molecular weight in the range from about 400 to 3000.
  • a suitable connection of this type is e.g. Poly ESP 520 from Raschig.
  • the polyurethanes can also contain compounds C) which contain two active hydrogen atoms and at least one cationogenic and / or cationic group, preferably at least one nitrogenous group.
  • the nitrogen-containing group is preferably a tertiary amino group or a quaternary ammonium group.
  • compounds of the general formulas are preferred
  • R 7 and R 8 which may be the same or different, represent C 2 -C 8 -alkylene
  • R 9 , R i2 and R l * 3 which may be the same or different, represent Ci-C ß- alkyl, Phenyl or phenyl -CC ⁇ C 4 alkyl
  • R ° and R U which may be the same or different, are H or Ci-C ß alkyl
  • o is 1, 2 or 3
  • ® for chloride, bromide , Iodide, Ci-C ß- alkyl sulfate or S ⁇ 4 2 ⁇ / 2 is.
  • N- (C ** - to Cg-alkydiethanolamines, such as methyldiethanolamine, and N-alkyldialkylenetriamines, such as ⁇ -methyldipropylenetriamine, are particularly preferred. These are preferably used in combination with dimethylolpropanoic acid as component c). Also suitable as component C) are mixtures which contain two or more of the abovementioned compounds with anionic and / or anionogenic groups, two or more of the abovementioned compounds with cationic and / or cationogenic groups or mixtures which contain at least one of the abovementioned compounds contain anionic or anionogenic groups and at least one of the aforementioned compounds with cationic or cationogenic groups.
  • mixtures are preferably used which contain dimethylolpropanoic acid and N-methyldiethanolamine.
  • the polyurethanes contain predominantly or exclusively anionogenic and / or anionic groups as ionogenic and / or ionic groups.
  • the polyurethanes contain predominantly or exclusively cationogenic and / or cationic groups as ionogenic and / or ionic groups.
  • the polyurethanes thus preferably contain a component c) which contains predominantly, preferably at least 80% by weight, in particular at least 90% by weight, based on the total amount of component c), either anionogenic (anionic) compounds or cationogenic ( cationic) compounds.
  • the diisocyanates D) are preferably selected from aliphatic, cycloaliphatic and / or aromatic diisocyanates, such as tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diphenyl diisocyanate, 2,4- and 2,6-tolylene diisocyanate and their mixtures of isomers, o-, m- and p-xylylene diisocyanate, 1,1 5-naphthylene diisocyanate, 1,4-cyclohexylene diisocyanate, dicyclohexyl methane diisocyanate and mixtures thereof, in particular isophore diisocyanate, hexamethylene diisocyanate and / or dicyclohexyl methane diisocyanate. Hexamethylene diisocyanate is particularly preferably used. If desired, up to 3 mol% of the compounds mentioned can be replaced by triisocyanates.
  • Component E) is a compound different from B) and C), which contains at least 2 active hydrogen atoms and has a molecular weight of 60 to 5000.
  • Diols whose molecular weight is in a range from about 62 to 500 g / mol are preferably used as component E). These include, for example, diols having 2 to 18 carbon atoms, preferably 2 to 10 carbon atoms, such as 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,5-pentanediol, 1 , 10-decanediol, 2-methyl-l, 3-propanediol, 2,2-dimethyl-l, 3-propanediol, di-, tri-, tetra-, penta- and hexaethylene glycol, neopentyl glycol, cyclohexanedimethylol and mixtures thereof.
  • diols having 2 to 18 carbon atoms, preferably 2 to 10 carbon atoms such as 1,2-ethanediol, 1,3
  • Preferred amino alcohols E) are, for example, 2-aminoethanol, 2- (N-methylamino) ethanol, 3-aminopropanol, 4-aminobutanol, 1-ethylaminobutan-2-ol, 2-amino-2-methyl-1-propanol, 4-methyl - 4-aminopentan-2-ol etc.
  • Preferred polyamines E) are e.g. Diamines such as ethylenediamine, propylenediamine, 1,4-diaminobutane, 1,5-diaminopentane and 1,6-diaminohexane.
  • the compounds mentioned as component E) can be used individually or in mixtures. 1,2-Ethanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, cyclohexanedimethylol and mixtures thereof are particularly preferably used.
  • Component E) is preferably a polymer having a number average molecular weight in the range from about 300 to 5000, preferably about 400 to 4000, in particular 500 to 3000.
  • Useful polymers E) are, for example Polyester ⁇ - diols, polyetherols, polysiloxanes and mixtures thereof.
  • Polyetherols are preferably polyalkylene glycols, e.g. Polyethylene glycols, polypropylene glycols etc., copolymers of ethylene oxide and propylene oxide or block copolymers of ethylene oxide, propylene oxide and butylene oxide, which contain the alkylene oxide units randomly distributed or copolymerized in the form of blocks.
  • ⁇ , ⁇ -diamino polyethers which can be prepared by amination of polyalkylene oxides with ammonia. Polyester diols and mixtures containing them are preferably used as component E).
  • Preferred polyester diols have a number average molecular weight in the range from about 400 to 5000, preferably 500 to 3000, in particular 600 to 2000.
  • Suitable polyester diols are all those which are customarily used for the production of polyurethanes, in particular those based on aromatic dicarboxylic acids, such as terephthalic acid, isophthalic acid, phthalic acid, Na- or K-sulfoisophthalic acid etc., aliphatic dicarboxylic acids, such as adipic acid or Succinic acid etc., and cycloaliphatic dicarboxylic acids, such as 1,2-, 1,3- or 1,4-cyclohexanedicarboxylic acid.
  • aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, Na- or K-sulfoisophthalic acid etc.
  • aliphatic dicarboxylic acids such as adipic acid or Succinic acid etc.
  • cycloaliphatic dicarboxylic acids such as 1,2-, 1,3- or 1,4-cyclohexanedicarboxylic acid.
  • Suitable diols are in particular aliphatic diols, such as ethylene glycol, propylene glycol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, polyethylene glycols, polypropylene glycols, 1,4-dimethylolcyclohexane.
  • Polyester diols based on aromatic and aliphatic dicarboxylic acids and aliphatic diols are preferred, in particular those in which the aromatic dicarboxylic acid accounts for 10 to 95 mol%, in particular 40 to 90 mol%, of the total dicarboxylic acid content (remainder aliphatic dicarboxylic acids).
  • polyester diols are the reaction products of phthalic acid / diethylene glycol, isophthalic acid / 1,4-butanediol, isophthalic acid / adipic acid / 1,6-hexanediol, 5-NaSO 3 -isophthalic acid / phthalic acid / adipic acid / 1,6-hexanediol, adipic acid / ethylene glycol, Isophthalic acid / adipic acid / neopentylglycol, isophthalic acid / adipic acid / neopentylglycol / diethylene glycol / dirnethylolcyclohexane and 5-NaS0 3 -isophthalic acid / isophthalic acid / adipic acid / neopenty1-glycol / diethylene glycol / dimethylolcyclocyclohexane, isiphen
  • component E) are also polyesterdiols based on linear or branched, C ⁇ - to C 3 o -.
  • Preferred carboxylic acids and hydroxycarboxylic acids are, for example,vestic acid, dodecanedioic acid, suberic acid, pimelic acid, sebacic acid, tetrahedronic acid, citric acid, ricinoleic acid, hydroxystearic acid and mixtures thereof.
  • 1,4-Butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,4-dimethylolcyclohexane, diethylene glycol and mixtures thereof are preferably used as the diol component for the production of these polyester diols.
  • R 4 and R 5 independently of one another represent C 1 -C 4 -alkyl, benzyl or phenyl,
  • E i and E 2 independently of one another represent OH or NHR 6 , where R 6 represents hydrogen, C ⁇ - to Cg-alkyl or C 5 - to Cs-cycloalkyl, i and 1 independently of one another represent 2 to 8,
  • k 3 to 50
  • Suitable alkyl radicals are e.g. Methyl, ethyl, n-propyl, isopropyl, n-butyl, t. Butyl, n-pentyl, n-hexyl etc.
  • Suitable cycloalkyl radicals are e.g. Cyclopentyl, Cyclohexyl, Cycloheptyl, 10 Cyclooctyl etc.
  • R 4 and R 5 are both methyl.
  • These polysiloxanes E) preferably have a number average molecular weight in the range from about 300 to 10,000, preferably 400 to 5000.
  • Suitable compounds E) are also the polydimethylsiloxanes described in EP-A-227 816, to which reference 20 is hereby made.
  • components B) or E) contains a polysiloxane.
  • Crosslinked polyurethanes are very particularly preferred
  • TMP Trimethylolpropane
  • the polyurethanes used in the agents according to the invention are produced by reacting the compounds of components A), B), C), D) and optionally E).
  • the temperature is in a range from about 60 to 140 ° C., preferably about
  • the reaction can be carried out without a solvent or in a suitable inert solvent or solvent mixture.
  • suitable solvents are aprotic polar solvents, e.g. Tetrahydrofuran, ethyl acetate, N-methylpyrrolidone, dimethylformamide and preferably ketones, such as acetone and
  • the reaction is preferably carried out under an inert gas atmosphere, such as. B. under nitrogen.
  • the components are used in amounts such that the ratio of the NCO equivalent of the compounds of component e) to the equivalent of the active hydrogen atom of components a), b), c) and d) in
  • resulting polyurethanes still have free isocyanate groups, these are finally inactivated by adding amines, preferably amino alcohols.
  • amines preferably amino alcohols.
  • Suitable amino alcohols are the 5 described above as component C), preferably 2-amino-2-methyl-1-propanol.
  • the polyurethanes containing acid groups can be converted into a water-soluble or water-dispersible form by partial or complete neutralization with a base.
  • the salts of the polyurethanes obtained generally have better water solubility or dispersibility in water than the non-neutralized polyurethanes.
  • Alkali metal bases such as sodium hydroxide solution, potassium hydroxide solution, soda, sodium hydrogen carbonate, potassium carbonate or potassium hydrogen carbonate and alkaline earth metal bases such as Calcium hydroxide, calcium oxide, magnesium hydroxide or magnesium carbonate as well as ammonia and amine can be used.
  • Suitable amines are, for example, Ci-C 6 -alkylamine, preferably n-propylamine and n-butylamine, dialkylamines, preferably diethylpropylamine and dipropylmethylamine, trialkylamines, preferably triethylamine and tri-isopropylamine, C 1 -C 6 -alkyldiethyanolamines, preferably methylamine or Ethyldiethanol-amine and di-Ci-C ⁇ -Alkylethanolainine.
  • 2-Amino-2-methyl-1-propanol, diethylaminopropylamine and triisopropanol-a in have proven particularly suitable for use in hair treatment compositions for neutralizing the polyurethanes containing acid groups.
  • the polyurethanes containing acid groups can also be neutralized with the aid of mixtures of several bases, for example mixtures of sodium hydroxide solution and triisopropanolamine.
  • the neutralization can be partial, for example 20 to 40% or complete, ie 100%.
  • a water-miscible organic solvent is used in the production of the polyurethanes, this can subsequently be carried out by customary processes known to the skilled worker, e.g. by distillation under reduced pressure. Water can also be added to the polyurethane before the solvent is separated off. After replacing the solvent with water, a solution or dispersion of the polymer is obtained from which, if desired, the polymer can be obtained in a conventional manner, e.g. by spray drying.
  • the polyurethanes according to the invention have K values (measured according to E. Fikentscher, Cellulose-Chemie 13 (1932), pp. 58-64, on a 1% solution in N-methylpyrrolidone) in a range from 15 to 90, preferably 20 to 60, on.
  • Your glass transition temperature is generally at least 0 ° C, preferably at least 20 ° C, particularly preferably at least 25 ° C and especially at least 30 ° C.
  • the polyurethanes according to the invention are particularly suitable as coating compositions for keratin-containing surfaces (hair, skin and nails). If the polyurethanes according to the invention are water-dispersible, they can be used in the form of aqueous microdispersions with particle diameters of usually 1 to 150 nm, preferably 5 to 100 nm. The solids contents of the preparations are usually in a range from about 0.5 to 20% by weight, preferably 1 to 12% by weight. These microdispersions generally do not require any emulsifiers or surfactants to stabilize them.
  • the polyurethanes according to the invention can preferably be in the form of a hair treatment composition, in particular in the form of a hairspray.
  • the K value of these polymers is preferably in a range from 23 to 90, in particular 25 to 60.
  • the cosmetic compositions contain the polyurethanes in an amount in the range from 0.2 to 20% by weight, based on the total weight of the composition.
  • a hair treatment agent It is preferably a hair treatment agent.
  • These are usually in the form of an aqueous dispersion or in the form of an alcoholic or aqueous-alcoholic solution.
  • suitable alcohols are ethanol, propanol, isopropanol etc.
  • the invention relates to a hair cosmetic composition containing
  • the hair treatment compositions generally contain customary cosmetic auxiliaries, for example plasticizers, such as glycerol and glycol; Emollients, perfumes; UV absorbers; dyes; Thickeners; antistatic agents; Combing agents; Preservatives; and foam stabilizers.
  • the polyurethanes according to the invention are formulated as a hairspray, they contain a sufficient amount of a blowing agent, for example a low-boiling hydrocarbon or ether, such as propane, butane, isobutane or dimethyl ether. Compressed gases such as nitrogen, air or carbon dioxide can also be used as blowing agents.
  • the amount of blowing agent can be kept low so as not to unnecessarily increase the VOC content. It is then generally not more than 55% by weight, based on the total weight of the composition. If desired, however, higher VOC contents of 85% by weight and above are also possible.
  • the polyurethanes described above can also be used in combination with other hair polymers in the compositions. Such polymers are in particular:
  • non-ionic, water-soluble or water-dispersible polymers or oligers such as polyvinyl caprolactam, e.g. Luviskol Plus (BASF), or polyvinylpyrrolidone and their copolymers, in particular with vinyl esters, such as vinyl acetate, e.g. Luviskol VA 37 (BASF); Polyamides, e.g. based on itaconic acid and aliphatic diamines;
  • - Amphoteric or zwitterionic polymers such as the octyl acrylamide / methyl methacrylate / tert available under the names Amphomer® (Delft National).
  • -Butylaminoethylmethacry- lat / 2-hydroxypropyl methacrylate copolymers and zwitterionic polymers as disclosed for example in German patent applications DE 39 29 973, DE 21 50 557, DE 28 17 369 and DE 37 08 451.
  • Acrylamidopropyltrimethylammonium chloride / acrylic acid or methacrylic acid copolymers and their alkali and ammonium salts are preferred zwitterionic polymers.
  • Other suitable zwitterionic polymers are methacroylethylbetaine / methacrylate copolymers, which are commercially available under the name Amersette® (AMERCHOL);
  • Anionic polymers such as vinyl acetate / crotonic acid copolymers, such as those under the names Resyn®
  • Luviflex® (NATIONAL STARCH), Luviset® (BASF) and Gafset® (GAF) are on the market, vinylpyrrolidone / vinyl acrylate copolymers, obtained for example under the trademark Luviflex® (BASF).
  • a preferred polymer is the vinylpyrrolidone / acrylate terpolymer available under the name Luviflex® VBM-35 (BASF), acrylic acid / ethyl acrylate / N-tert.
  • Butyllacrylamide terpolymers which are sold, for example, under the name Ultrahold® strong (BASF) , as well as Luvimer® (BASF, terpolymer from t-butyl acrylate, ethyl acrylate and methacrylic acid), or
  • cationic (quaternized) polymers for example cationic polyacrylate copolymers based on N-vinyllactarnene and their derivatives (N-vinylpyrrolidone, N-vinylcaprolactam etc.) as well as customary cationic hair conditioner polymers, for example Luviquat® (copolymer of vinylpyrrolidone and vinylimidazolium methochloride®), (Copolymer of quaternized N-vinylimidazole, N-vinylpyrrolidone and N-vinylcaprolactam), Merquat® (polymer based on dimethyldiallylammonium chloride), Gafquat® (quaternary Polymers formed by the reaction of polyvinylpyrrolidone with quaternary ammonium compounds), Polymer JR (hydroxyethyl cellulose with cationic groups), polyquaternium types (CTFA names), etc .;
  • nonionic, siloxane containing, water soluble or dispersible polymers e.g. Polyether siloxanes, such as Tegopren® (from Goldschmidt) or Belsil® (from Wacker).
  • the crosslinked polyurethanes according to the invention based on at least one polytetrahydrofuran are preferably used as a mixture with another hair polymer containing amide groups.
  • These include e.g. the polyurethanes described in DE-A-42 25 045, the previously described vinylpyrrolidone / acrylate terpolymers and acrylic acid / ethyl acrylate / N-tert.
  • the other hair polymers are preferably in amounts up to
  • a preferred hair treatment composition contains:
  • a blowing agent preferably dimethyl ether
  • the agent according to the invention can contain as component d) at least one other hair polymer which is soluble or dispersible in water.
  • the proportion of this component is then generally about 0.1 to 15% by weight, preferably 0.1 to 10% by weight, based on the total weight of the composition.
  • Crosslinked polyurethanes which contain no polymerized siloxane groups can preferably be used.
  • the agent according to the invention can be used as component e) at least one water-insoluble silicone, in particular a polydimethylsiloxane, e.g. the Abil® types from Goldschmidt.
  • the proportion of this component is then generally about 0.001 to 0.2% by weight, preferably 0.01 to 0.1% by weight, based on the total weight of the composition.
  • the agent according to the invention can contain at least one nonionic, siloxane-containing, water-soluble or water-dispersible polymer, in particular selected from the polyether siloxanes described above.
  • the proportion of this component is then generally about 0.001 to 2% by weight, based on the total weight of the composition.
  • the agent according to the invention can additionally optionally contain a defoamer, e.g. silicone-based.
  • a defoamer e.g. silicone-based.
  • the amount of defoamer is generally up to about 0.001% by weight based on the total amount of the agent.
  • a particularly preferred hair treatment composition contains:
  • the hair polymer d) containing amide groups is a polymer which contains one or more monomers containing amide groups in copolymerized form.
  • Preferred amide group-containing monomers are N-vinyl-lacta e, which are preferably selected from N-vinylpyrrolidone, N-vinylcaprolactam, their derivatives, which may have, for example, one or more C 1 -C 4 -alkyl substituents, and mixtures thereof.
  • the hair polymers d) then preferably contain these in copolymerized amounts in an amount of at least 30% by weight.
  • a polymer mixture which has at least one such copolymer is also suitable.
  • the Luviskol® brands from BASF Aktiengesellschaft, such as Luviskol VA37 and Luviskol plus, are particularly preferred.
  • the hair polymer d) containing amide groups is a silicone-free polyurethane, such as is used e.g. in DE-A-42 25 045, DE-A-42 41 118 and EP-A-619 111.
  • the agents according to the invention have the advantage that, on the one hand, they give the hair the desired strength and, on the other hand, the polymers are easy to wash out (redispersible), and they also give the hair smoothness and / or shine.
  • hair treatment compositions with a VOC content of less than 85% by weight, preferably less than 60% by weight, and also purely aqueous formulations can be produced, even if they are formulated as a hairspray.
  • the previously crosslinked polyurethanes of a polytetrahydrofuran and / or polysiloxane according to the invention are also suitable as auxiliaries in pharmacy, e.g. as a coating agent and / or binder for solid pharmaceutical forms. They can also be used in creams and as tablet coating agents and tablet binders. They are also suitable for use as coating agents for the textile, paper, printing, leather and adhesive industries.
  • Examples 1 to 5 are comparative examples
  • the flexibility was determined by measuring the modulus of elasticity
  • the stickiness was determined as follows.
  • a film (approx. 30 ⁇ m film layer thickness) was applied to a glass plate and stored overnight at 40 ° C. and 75% relative atmospheric humidity. The stickiness of the film was determined by a specialist panel.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Veterinary Medicine (AREA)
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  • Epidemiology (AREA)
  • Birds (AREA)
  • Manufacturing & Machinery (AREA)
  • Engineering & Computer Science (AREA)
  • Dispersion Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Cosmetics (AREA)
  • Medicinal Preparation (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne un polyuréthanne réticulé composé des éléments suivants : A) au moins un polytétrahydrofurane de formule (I) ; B) au moins un composé comportant plus de deux atomes d'hydrogène actifs par molécule ; C) au moins un composé comportant plus de deux atomes d'hydrogène actifs par molécule et au moins un groupe ionogène et/ou ionique par molécule, ces groupes étant des groupes anionogènes, anioniques, cationogènes ou cationiques ; D) au moins un diisocyanate ; E) éventuellement un composé différent de B) et de C), comportant au moins deux atomes d'hydrogène actifs et ayant un poids moléculaire de 60 à 5000, ledit polyuréthanne pouvant être composé alternativement des sels de ces éléments.
EP03720405A 2002-04-04 2003-04-02 Polyurethannes reticules de polytetrahydrofurane Withdrawn EP1495060A1 (fr)

Applications Claiming Priority (3)

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DE10214971 2002-04-04
DE10214971A DE10214971A1 (de) 2002-04-04 2002-04-04 Vernetzte Polyurethane
PCT/EP2003/003430 WO2003085019A1 (fr) 2002-04-04 2003-04-02 Polyurethannes reticules de polytetrahydrofurane

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EP1495060A1 true EP1495060A1 (fr) 2005-01-12

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US (1) US20050148753A1 (fr)
EP (1) EP1495060A1 (fr)
JP (1) JP2005527665A (fr)
AU (1) AU2003224024A1 (fr)
DE (1) DE10214971A1 (fr)
WO (1) WO2003085019A1 (fr)

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JP4560703B2 (ja) * 2003-03-19 2010-10-13 東洋紡績株式会社 導電性ロールおよびこれを用いた電子写真装置
DE102004036146A1 (de) * 2004-07-26 2006-03-23 Basf Ag Vernetzte Polytetrahydrofuran-haltige Polyurethane
DE102004062201A1 (de) * 2004-12-23 2006-07-13 Basf Ag Urethanverbindung, die ein Polyethergruppen-haltiges Siliconderivat und einen Stickstoffheterocyclus eingebaut enthält
DE102005043173A1 (de) * 2005-09-09 2007-03-15 Basf Ag Polyurethandispersion, enthaltend Alkanolamine
EP2027162A1 (fr) * 2006-01-23 2009-02-25 Basf Se Procede de fabrication de polymeres en solvant aqueux
ES2405624T3 (es) 2006-03-31 2013-05-31 Basf Se Método para la preparación de polímeros de acrilato
KR20090014188A (ko) * 2006-05-04 2009-02-06 바스프 에스이 중화된 산기-함유 중합체 및 그의 용도
EP2105120A1 (fr) * 2008-03-26 2009-09-30 Bayer MaterialScience AG Préparations cosmétiques destinées à être appliquées sur la peau
JP2010018811A (ja) * 2009-09-24 2010-01-28 Toyobo Co Ltd ポリウレタン樹脂、導電性ロールおよび電子写真装置
JP2017528536A (ja) * 2014-06-24 2017-09-28 スリーエム イノベイティブ プロパティズ カンパニー ポリウレタンエアゾール組成物、物品、及び関連する方法
US11622929B2 (en) 2016-03-08 2023-04-11 Living Proof, Inc. Long lasting cosmetic compositions
WO2019055440A1 (fr) 2017-09-13 2019-03-21 Living Proof, Inc. Compositions cosmétiques longue durée
CA3074845A1 (fr) 2017-09-13 2019-03-21 Living Proof, Inc. Compositions de protection de couleur

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US5554686A (en) * 1993-08-20 1996-09-10 Minnesota Mining And Manufacturing Company Room temperature curable silane-terminated polyurethane dispersions
DE19807908A1 (de) * 1998-02-25 1999-08-26 Basf Ag Kosmetisches Mittel
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DE19847791A1 (de) * 1998-10-16 2000-04-20 Bayer Ag Wäßrige Polyurethandispersionen
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DE10214971A1 (de) 2003-10-16
WO2003085019A1 (fr) 2003-10-16
AU2003224024A1 (en) 2003-10-20
WO2003085019A8 (fr) 2004-01-15
JP2005527665A (ja) 2005-09-15
US20050148753A1 (en) 2005-07-07
AU2003224024A8 (en) 2003-10-20

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