WO2015010945A1 - Polymère - Google Patents

Polymère Download PDF

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Publication number
WO2015010945A1
WO2015010945A1 PCT/EP2014/065075 EP2014065075W WO2015010945A1 WO 2015010945 A1 WO2015010945 A1 WO 2015010945A1 EP 2014065075 W EP2014065075 W EP 2014065075W WO 2015010945 A1 WO2015010945 A1 WO 2015010945A1
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Prior art keywords
repeating units
units derived
weight
group
formula
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PCT/EP2014/065075
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English (en)
Inventor
Axel Böttcher
Ewelina BURAKOWSKA-MEISE
Wolfgang Denuell
David Graham
Peter Hössel
Wolfgang Jahnel
Stefan LAST
Volker Wendel
Jan Mirko STACHOWIAK
Son Nguyen-Kim
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Basf Se
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Publication of WO2015010945A1 publication Critical patent/WO2015010945A1/fr

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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
    • C08F226/00—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
    • C08F226/06—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 by a heterocyclic ring containing nitrogen
    • C08F226/10—N-Vinyl-pyrrolidone
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/285—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety
    • C08F220/286—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety and containing polyethylene oxide in the alcohol moiety, e.g. methoxy polyethylene glycol (meth)acrylate

Definitions

  • the present invention relates to a new polymer, a process for making it and its use as thickening agent (also called thickener).
  • the polymer comprises repeating units derived from acrylic acid and/or methacrylic acid, repeating units derived from a monomer which is, in a wider sense, an ethoxylated or propoxylated fatty alcohol substituted with a hydrophobic moiety, repeating units derived from vinyl pyrrolidone and repeating units derived from 1 -vinyl imidazole.
  • Thickening agents are substances which are used to increase the viscosity, respectively the overall rheological profile of aqueous formulations, e. g. shower gels, shampoos, hair relaxers, emulsions (o/w, w/o, multiple emulsions) for several application purposes (face/body/baby/depilatories) and various other cosmetic formulations.
  • aqueous formulations e. g. shower gels, shampoos, hair relaxers, emulsions (o/w, w/o, multiple emulsions) for several application purposes (face/body/baby/depilatories) and various other cosmetic formulations.
  • emulsions o/w, w/o, multiple emulsions
  • face/body/baby/depilatories face/body/baby/depilatories
  • polymeric and non-polymeric thickening agents are substances which are used to increase the viscosity, respectively the overall rheological profile of
  • One method is precipitation polymerization. Monomers are dissolved in a volatile, low boiling solvent such as heptane, petrol, methylene chloride. Then, polymerization is carried out and the polymer produced is obtained as a precipitate. Examples of polymers produced in this way are polyacrylic acid based thickeners, also called carbomers. Examples of commercially available carbomers are Carbopol ® 980, Carbopol ® Ultrez 10 and 30, Rheocare ® C Plus, TegoCarbomer ® 931. Furthermore hydrophobically modified polymers can be produced by precipitation polymerization.
  • Examples are acrylates/C 10-30 alkyl acrylate crosspolymers, commercially available as Pemulen ® TR-types, Carbopol ® Ultrez 20 and 21 .
  • the solvents used in the precipitation polymerization method are difficult to handle and need to be recycled, which is a costly process. Additionally the polymers need to be isolated from the l solvents and dried.
  • the polymers produced are usually obtained in the form of a powder. Polymer powders have handling disadvantages, e. g. dust issues, dilution time etc.
  • Another method is emulsion polymerization.
  • monomers are emulsified in water.
  • a dispersion of a polymer in water is obtained.
  • these dispersions have a content of about 30 % by weight of dispersed polymer.
  • Polymers of the ASE type (alkali swellable emulsion) and of the HASE type (hydrophobically modified alkali swellable emulsion) are made by emulsion polymerization.
  • LDP liquid dispersion polymers
  • IEP inverse emulsion polymers
  • monomers are dissolved in water which is the discontinuous phase of a water in oil emulsion.
  • the polymerization is carried out in the individual aqueous solution droplets, resulting in polymer dispersions in oil.
  • the water used in this process can either be removed by distillation or it can remain in the dispersion.
  • WO 99/29735 discloses a non-aqueous, heterogeneous polymerization process with vinyl monomers in an oil as solvent. N-vinylpyrrolidone is used as vinyl monomer. It is disclosed that the dispersions of polymers in oils that are obtained may be used in cosmetic compositions.
  • Emulsion polymers can only be made using water insoluble monomers that are not too hydrophobic. Additionally emulsion polymers including acidic monomers like acrylic acid need to be neutralized to a pH value of 6 or higher after polymerization, often even 6.5 or higher, which is not a desired pH level for many modern cosmetic applications. The reason for this is that the monomer in its deprotonated form is highly soluble in water and therefore not suitable for emulsion polymerization and that, on the other hand, only the partially neutralized polymer has a significant thickening effect due to the repulsion of the negatively charged groups in the polymeric molecule.
  • the thickening agents known in the art have disadvantages. Their thickening mechanism combines repulsive effects with associative effects but is available only in media which have a relatively high pH value as explained in the previous paragraph. LDPs can only be made from water soluble monomers. This clearly limits flexibility with respect to the monomers that can be used to make LDPs. The thickening mechanism of LDPs is predominantly driven by repulsion effects. Only small amounts of so called associative monomers can be incorporated. Examples of associative monomers are lauryl acrylate, stearyl methacrylate and their ethoxylated derivatives. In general, associative monomers are monomers that provide physical crosslinking of the copolymers made including the associative monomer. E. g. a copolymer including repeating units derived from lauryl acrylate will, when dissolved in water, form a network which is physically crosslinked by the attraction of the hydrophobical lauryl moieties.
  • WO 2008/087326 discloses an anionic copolymer containing at least one surface-active monomer and its use as a thickening agent.
  • the copolymer disclosed has a thickening effect in solutions with a high content of electrolytes, i. e. it has a high electrolyte tolerance.
  • the problem underlying the present invention is to provide a polymer that can be used as thickening agent in cosmetic formulations.
  • this polymer shall have a high electrolyte tolerance.
  • A) 5 - 40 preferably 10 - 35, more preferably 15 - 30, more preferably 20 to 25, % by weight repeating units derived from acrylic acid,
  • R is selected from the group consisting of the moiety according to formula (II), the moiety according to formula (III), the maleic moiety, the itaconic moiety, the crotonic moiety and the vinylphthalic moiety, wherein in each case the oxygen radical of the moiety makes the chemical bond to the rest of the molecule according to formula (I), preferably R is the moiety according to formula (II) or the moiety according to formula (Hi),
  • R1 is hydrogen or methyl, preferably hydrogen, m is 0 to 50, preferably 1 to 50, more preferably 10 to 40, and most preferably 20 to 30,
  • R' is a hydrophobic moiety selected from linear or branched alkyl, alkylaryl or arylalkyl radicals, preferably having at least 6 C-atoms, R ' preferably is selected from linear alkyl radicals having 8 to 20 carbon atoms, still more preferred from linear alkyl radicals having 12 to 18 carbon atoms, and most preferably from linear alkyl radicals having 16 to 18 carbon atoms,
  • G 0 - 10, preferably 0 to 5, more preferably 0 to 2, % by weight repeating units derived from a further monomer having at least one vinyl group.
  • This polymer is a first subject of the present invention.
  • the monomers used to make the polymer according to the present invention are commercially available or can be made using standard methods of organic chemistry.
  • the monomer according to formula (I) can be made from the unsaturated acid underlying this monomer plus ethylene oxide or propylene oxide plus the alcohol underlying this monomer.
  • the acid is either reacted with ethylene oxide or propylene oxide and the resulting intermediate is reacted with the alcohol or the alcohol is reacted with ethylene oxide or propylene oxide and the resulting intermediate is reacted with the acid.
  • the crosslinker according to the present invention is selected from the group consisting of pentaerythrite triallylether (preferably used in an amount of 0.1-1 % by weight) and trimethylolpropane trimethacrylate (preferably used in an amount of 0.1- 5 % by weight)
  • Pentaerythrite triallylether has the following formula:
  • trimethylolpropane trimethacrylate has the following formula:
  • the polymer according to the present invention does not contain a crosslinker it is difficult to determine the average molar mass of it. This is so because the polymer according to the present invention has the tendency to form physically crosslinked networks through the association of the repeating units derived from monomer C.
  • the thickening property of the polymer according to the present invention shows that it really is a polymer having a significant degree of polymerization.
  • R is selected from the group consisting of the moiety according to formula (II), the moiety according to formula (III), the maleic moiety, the itaconic moiety, the crotonic moiety and the vinylphthalic moiety, wherein in each case the oxygen radical of the moiety makes the chemical bond to the rest of the molecule according to formula (I),
  • R1 is hydrogen or methyl, m is 0 to 50,
  • R' is a hydrophobic moiety selected from linear or branched alkyl, alkylaryl or arylalkyl radicals,
  • polymer according to the present invention is a polymer comprising
  • R is selected from the group consisting of the moiety according to formula (II) and the moiety according to formula (III)
  • R1 is hydrogen, m is 1 to 50, more preferably 10 to 40, and most preferably 20 to 30,
  • R' is a hydrophobic moiety selected from linear or branched alkyl, alkylaryl or arylalkyi radicals having at least 6 C-atoms, R ' preferably is selected from linear alkyl radicals having 8 to 20 carbon atoms, still more preferred from linear alkyl radicals having 12 to 18 carbon atoms, and most preferably from linear alkyl radicals having 16 to 18 carbon atoms,
  • G 0 - 10, preferably 0 to 5, more preferably 0 to 2, % by weight repeating units derived from a further monomer having at least one vinyl group,
  • crosslinker F is selected from the group consisting of pentaerythrite triallylether (preferably used in an amount of 0.1 -1 % by weight) and trimethylolpropane trimethacrylate (preferably used in an amount of 0.1 - 5 % by weight).
  • R is selected from the group consisting of the moiety according to formula (II) and the moiety according to formula (III)
  • R1 is hydrogen, m is 10 to 40, preferably 20 to 30,
  • R' is selected from linear alkyl radicals having 8 to 20 carbon atoms, preferably from linear alkyl radicals having 12 to 18 carbon atoms, and most preferably from linear alkyl radicals having 16 to 18 carbon atoms, D) 55 to 65, % by weight repeating units derived from vinyl pyrrolidone,
  • G 0 - 10, preferably 0 to 5, more preferably 0 to 2, % by weight repeating units derived from a further monomer having at least one vinyl group,
  • crosslinker F is selected from the group consisting of pentaerythrite triallylether (preferably used in an amount of 0.1 -1 % by weight) and trimethylolpropane trimethacrylate (preferably used in an amount of 0.1 - 5 % by weight).
  • R is selected from the group consisting of the moiety according to formula (II) and the moiety according to formula (III)
  • R1 is hydrogen, m is 20 to 30, R' is selected from linear alkyl radicals having 12 to 18 carbon atoms, preferably from linear alkyl radicals having 16 to 18 carbon atoms,
  • G 0 to 5, preferably 0 to 2, % by weight repeating units derived from a further monomer having at least one vinyl group,
  • crosslinker F is selected from the group consisting of pentaerythrite triallylether (preferably used in an amount of 0.1 -1 % by weight) and trimethylolpropane trimethacrylate (preferably used in an amount of 0.1 - 5 % by weight).
  • the polymer according to the present invention in a preferred embodiment in which this polymer comprises repeating units derived from AA (acrylic acid), MAA (methacrylic acid), VP (N-vinyl pyrrolidone), VI (1 -vinyl imidazole) and LUMA (PEG 25 stearyl methacrylate), has the following structural formula. In this formula the numbers of m, n, o, p and q have to be chosen so that the weight-% ratios of the polymer according to the present invention are fulfilled. It is believed that the sequence of the repeating units in the polymer chain is a statistical sequence.
  • the repeating units derived from VP increase the flexibility and the hydrophilicity of the polymer.
  • the film forming capabilities of the repeating units derived from VP support positive sensorial aspects of the polymer according to the present invention.
  • the polymer according to the present invention comprises acidic COOH groups. It also comprises basic nitrogen atoms in the repeating units derived from vinyl imidazole. Therefore, depending on the pH value of the medium surrounding the polymer according to the present invention, the structure of the polymer according to the present invention may comprise deprotonated COOH groups, i. e. anionic COO " groups. It may also comprise protonated, cationic vinyl imidazolinium moieties.
  • the counterions to balance this overall charge of the polymer according to the present invention can be various counterions depending on what counterions have been brought into contact with the polymer according to the present invention.
  • anionic counterions are halogen anions, especially chloride.
  • counterions as citrate, lactate, glycolate, benzoate, formate, acetate etc. can be present.
  • the counterions to balance this overall charge of the polymer according to the present invention can be various counterions depending on what counterions have been brought into contact with the polymer according to the present invention.
  • Non-limiting examples of anionic counterions are alkali cations, especially sodium cations and potassium cations. Furthermore nitrogen based counterions as ammonium ions or aminomethyl propanol derived ions and similar ions can be present.
  • the term "the polymer according to the present invention” not only comprises the polymer according to the present invention which has no overall charge but it also comprises the polymer according to the present invention which has been neutralized either by acids or by bases so that it has an overall charge which is either negative or positive and which is balanced by suitable counterions being present in the surrounding of the polymer according to the present invention.
  • the polymer according to the present invention can be made by a precipitation process using an oil as solvent.
  • the process according to the present invention for making the polymer according to the present invention comprises the steps
  • the solvent being selected from the group consisting of at least one cosmetically acceptable emollient, at least one nonionic surfactant and mixtures thereof,
  • the solvent used in the process according to the present invention may comprise further substances apart from the substances named in the previous paragraph. It may comprise low amounts of water, organic solvents or other substances.
  • the solvent has a purity of at least 90 % by weight, more preferably at least 95 % by weight, more preferably 98 % by weight, more preferably 99 % by weight, more preferably 99.5 % by weight.
  • the copolymerization may be initiated regulated and stopped by means known in the art.
  • This process is another subject of the present invention.
  • the solvent used in the process according to the present invention has a water content of less than 5 % by weight, preferably less than 2, more preferred less than 1 , and most preferred less than 0.5 % by weight.
  • the cosmetically acceptable emollient according to the present invention can be any cosmetically acceptable emollient. Based on their chemical structures, such emollients can be categorized as esters, hydrocarbons, glycerides, ethers, fatty alcohols, silicone derivatives and other emollients.
  • emollients examples include vegetable oils, fatty acid alkyl esters based on C6-C22 fatty acids, mineral oils, silicone oils and their mixtures.
  • Cosmetically acceptable refers to those kinds of organic oils or blends of oils which can be used in such compositions which come into intense and/or direct contact to the human skin, scalp, hair or nails, without harming them.
  • Examples illustrating the nature of suitable emollients without limiting the invention to these examples are: C6-C22-Fatty alcohols, Guerbet alcohols based on fatty alcohols having 6 to 18, preferably 8 to 10, carbon atoms, esters of linear C6-C22-fatty acids with linear or branched C6-C22-fatty alcohols or esters of branched C6-C13-carboxylic acids with linear or branched C6-C22-fatty alcohols, such as, for example, myristyl myristate, myristyl palmitate, myristyl stearate, myristyl isostearate, myristyl oleate, myristyl behenate, myristyl erucate, cetyl myristate, cetyl palmitate, cetyl stearate, cetyl isostearate, cetyl oleate, cetyl behenate, cetyl erucate, stearyl myr
  • esters of linear C6-C22-fatty acids with branched alcohols in particular 2-ethylhexanol, esters of C18-C38- alkylhydroxy carboxylic acids with linear or branched C6-C22-fatty alcohols, in particular dioctylmalate, esters of linear and/or branched fatty acids with polyhydric alcohols (such as, for example, propylene glycol, dimerdiol or trimertriol) and/or Guerbet alcohols, triglycerides based on C6-C10-fatty acids, liquid mono-/di-/triglyceride mixtures based on C6-C18-fatty acids, esters of C6-C22-fatty alcohols and/or Guerbet alcohols with aromatic carboxylic acids, in particular benzoic acid, esters of C2- C12- dicarboxylic acids with linear or branched alcohols having 1 to 22 carbon atoms or polyols having 2 to 10 carbon atom
  • Finsolv® TN linear or branched, symmetrical or asymmetrical dialkyl ethers having 6 to 22 carbon atoms per alkyl group, such as, for example, dicaprylyl ether (Cetiol® OE), ring-opening products of epoxidized fatty acid esters with polyols and/or silicone oils (cyclomethicones, silicone methicone grades, etc.).
  • Further preferred emollients are selected from silicone oils, including hydrophobically modified silicone oils (e.g. Dow Corning® 2502 by Dow Corning).
  • Suitable as emollient are also vegetable oils.
  • Preferred cosmetic acceptable emollients are selected from
  • Especially preferred emollients according to the present teaching are selected from groups iii), iv), v) and/or vi) as well as any mixture thereof.
  • the preferred chain length of the alk(en)yl groups in each case is C 6 to C 2 2-
  • the cosmetically acceptable emollient is a triglyceride of at least one fatty acid having 6 to 22 carbon atoms.
  • the cosmetically acceptable emollient is a diester of adipic acid of at least one fatty acid having 6 to 22 carbon atoms.
  • the surfactant to be used in the process according to the present invention can be any nonionic surfactant.
  • nonionic surfactants which may be used as surfactant according to the present invention are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, mixed ethers and mixed formals, optionally partially oxidized alk(en)yl oligoglycosides and glucuronic acid derivatives, fatty acid N-alkylglucamides, protein hydrolyzates (especially wheat-based vegetable products), polyol fatty acid esters, sugar esters, sorbitan esters, polysorbates, amine oxides, fatty acid mono- and diethanolamides and polyglycerol fatty acid esters. If the nonionic surfactants contain polyglycol ether chains, they may have a conventional homolog distribution, but preferably have a narrow homolog distribution.
  • R1 is an alkyl or alkenyl group having 6 to 22 carbon atoms, preferably having 12 to 22 carbon atoms,
  • R2 is either hydrogen or a methyl group
  • m is 1 to 50, preferably 1 to 20, more preferably 2 to 15,
  • R3 is hydrogen or a (hydrophobic) linear alkyl group having 1 to 22 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 4 carbon atoms.
  • R1 is a linear, primary alkyl or alkenyl group having 6 to 22 carbon atoms, preferably having 12 to 22 carbon atoms, i. e. R1 is derived from a fatty alcohol.
  • the total amount of monomers A to G compared to the amount of monomers A to G plus the amount of solvent is preferably 10 - 60 % by weight, more preferably 20 to 50, more preferably 30 to 50 % by weight.
  • the process according to the present invention is carried out in such a way that the amount of polymer obtained is at least 99 % by weight, preferably at least 99.9 % by weight of the amount of monomers A to G used.
  • the polymer is not isolated but the dispersion obtained is the desired product.
  • this dispersion comprises at least one cosmetically acceptable emollient or at least one nonionic surfactant or mixtures thereof it may be used as raw material for cosmetic formulations that will then contain, apart from further components, the polymer according to the present invention and at least one cosmetically acceptable emollient or at least one nonionic surfactant or mixtures thereof.
  • a further subject of the present invention is a dispersion comprising
  • the polymer according to the present invention preferably in amount of 10 - 60 % by weight, more preferably 20 to 50, more preferably 30 to 50 % by weight, and
  • a solvent being selected from the group consisting of at least one cosmetically acceptable emollient, at least one nonionic surfactant and mixtures thereof.
  • a further subject of the present invention is a cosmetic composition
  • a cosmetic composition comprising
  • the polymer according to the present invention preferably in an amount of 0.05 - 10% by weight, more preferably 0.1 - 5.0 % by weight, and • a solvent being selected from the group consisting of at least one cosmetically acceptable emollient, at least one nonionic surfactant and mixtures thereof, preferably in amount of 0.05 - 50 % by weight, more preferably 0.1 - 5 % by weight, and
  • the cosmetic composition according to the present invention is a clear gel, a gel cream, a lamellar or non-lamellar care emulsion, a microemulsion, a dispersion (e. g. a make up composition or a sun protection composition), a surfactant based shampoo or body wash composition.
  • the polymer according to the present invention can be applied in different fields.
  • the polymer may be used as hair styling polymer.
  • the main application of the polymer according to the present invention is its use as thickener in cosmetic compositions.
  • the polymer according to the present invention can be made with the efficient process according to the present invention.
  • % means % by weight.
  • EO means ethylene oxide
  • PEG means polyethylene glycol.
  • PEG-140 means polyethylene glycol having an average degree of polymerization of 140 ethylene glycol units (number average).
  • Polymers were prepared having the composition given in the following table.
  • the polymers were prepared in the following way.
  • the monomers were dissolved in the emollient or surfactant listed in the following table.
  • the relative amount of each monomer was chosen according to the previous table. Polymerization was initiated and resulted in dispersions A to F according to the following table.
  • Dispersions A, B and C are the processes used to make the dispersions in more detail.
  • Dispersions A, B and C are the processes used to make the dispersions in more detail.
  • the initiator 2,2'-azobis(2.4-dimethyl valeronitrile) was dissolved in a small portion of the matrix (emollient or surfactant) (1 to 10% of the matrix) and thus resulted in solution 1 .
  • the monomers were diluted in a portion of 20 to 40% of the matrix and thus resulted in solution 2.
  • the remaining emollient (or surfactant) was charged into the reaction vessel and heated to 60°C.
  • To initiate polymerization the monomer solution (solution 2) was added at 60°C within 3 hours. Simultaneously the initiator solution (solution 1 ) was added within 5 hours. A temperature of about 60°C was kept during this time. Subsequently the reaction mixture was kept for 5 hours at 80°C.
  • Dispersions D, E and F are Dispersions D, E and F:
  • the initiator 2,2'-azobis(2.4-dimethyl valeronitrile) was dissolved in a small portion of the matrix (1 to 10% of the matrix) and thus resulted in solution 1 .
  • the monomers were mixed to a homogeneous solution (solution 2).
  • the remaining emollient (or surfactant) was charged into the reaction vessel and heated to 60°C.
  • the monomers (solution 2) were slowly added at 60°C (within 3 to 6 hours).
  • the initiator solution (solution 1 ) was added within 5 to 6 hours. Subsequently the reaction mixture was kept for 5 hours at 80°C.
  • capric acid decanoic acid
  • caprylic acid octanoic acid
  • Dispersion D or Carbomer (crosslinked polyacrylic acid) or Polyurethane-39 (copolymer of PEG-140 and hexamethylene diisocyanate endcapped with different alkoxylated fatty alcohols [C12-14 + 10EO, C16-18 + 1 1 EO and C18-20 + 1 1 EO]; abbreviation: PU-39) as thickening agent.
  • the pH value was adjusted with citric acid and sodium hydoxide solution.
  • Formulations A, C and D show that in each case the polymer according to the present invention is the most effective thickening agent resulting in the highest viscosity in comparison with the conventional thickening agents. Furthermore the formulations demonstrate the polymers according to the present invention can be combined with several cosmetic ingredients including anionic surfactants (formulation A) and nonionic surfactants (formulations C and D). Formulation C contains 2 % by weight of sodium chloride and demonstrates that the polymers according to the present invention have a high electrolyte tolerance.
  • the present invention targets the use of polymers in cosmetic formulations.
  • the structures are intended to optimize a) the viscosity performance at lower pH values (around 5) and b) the electrolyte tolerance of the cosmetic formulation.
  • the lower pH values are of increasing interest because of the trend towards acid based preservatives - e.g. benzoic acid, sorbis acid resp. their salts that usually need pH of 5 or lower - and the natural pH of skin.
  • Increased electrolyte tolerance is a common demand for several applications - not only in the cosmetic field.
  • Sample A is prepared with acrylic acid, for process reasons combined with methyl methacrylate (MMA).
  • Sample B combines acrylic acid with methacrylic acid (MAA).
  • Samples prepared with AA only or combining AA with MAA are processable. In pure water their performance differs only slightly. In the critical formulation C the difference is obvious and relevant.

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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)
  • Cosmetics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

La présente invention concerne un nouveau polymère, un procédé de fabrication de celui-ci et son utilisation comme agent épaississant (aussi appelé épaississant). Le polymère comprend des unités répétées dérivées d'acide acrylique et/ou d'acide méthacrylique, des unités répétées dérivées d'un monomère qui est, dans un sens plus large, un alcool gras éthoxylé ou propoxylé substitué avec une partie hydrophobe, des unités répétées dérivées de vinylpyrrolidone et des unités répétées dérivées de vinylimidazole.
PCT/EP2014/065075 2013-07-24 2014-07-15 Polymère WO2015010945A1 (fr)

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EP13177870.6 2013-07-24
EP13177870 2013-07-24

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2020230600A1 (ja) * 2019-05-14 2021-11-25 株式会社日本触媒 薬剤用添加剤

Citations (4)

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