EP0424765B1 - Dispersions de copolymérisats contenant des groupes perfluoroalkyles - Google Patents

Dispersions de copolymérisats contenant des groupes perfluoroalkyles Download PDF

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EP0424765B1
EP0424765B1 EP90119662A EP90119662A EP0424765B1 EP 0424765 B1 EP0424765 B1 EP 0424765B1 EP 90119662 A EP90119662 A EP 90119662A EP 90119662 A EP90119662 A EP 90119662A EP 0424765 B1 EP0424765 B1 EP 0424765B1
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dispersions
alkyl
aqueous dispersions
weight
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EP0424765A3 (en
EP0424765A2 (fr
Inventor
Jutta Dr. Röttger
Karl-Heinz Dr. Passon
Werner Dr. Maurer
Rolf-Volker Dr. Meyer
Wilfried Dipl.-Ing. Kortmann
Peter Dipl.-Ing. Selinger
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Bayer AG
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Bayer AG
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine

Definitions

  • Aqueous dispersions of copolymers and graft copolymers which are prepared with the use of perfluoroalkyl (meth) acrylates have been described many times in the literature (cf., for example, JP-A 83/59277, BE-A 677 859, DE-A 3 407 361, DE-A 3 407 362, DE-A 1 953 345 and DE-A 1 953 349) and are used as phobicizers on many substrates.
  • alkyl (meth) acrylates as comonomers in the preparation of perfluoroalkyl copolymer dispersions and the use of these dispersions for textile treatment are also known (cf. for example US Pat. Nos. 2,803,615 and 3,062,765), often in addition to an oleophobic finish hydrophobization is also obtained.
  • compositions for the hydrophobic / oleophobic finishing of textiles are described in which (co) polymers with fluoroalkyl groups are combined with glycerol- ⁇ -esters of C1-C6-carboxylic acids will.
  • the copolymers can also contain fluorine-free comonomers from a large group of different types of compounds; however, the use of long-chain, fluorine-free (meth) acrylates is not apparent from this publication. The reworking of examples from this publication resulted in unsatisfactory oleophobic values.
  • the object was therefore to develop highly effective finishing agents which bring about the desired oleophobic / hydrophobic properties without increasing the fluorine-containing component and which therefore also cause the disadvantages not described above,
  • the present invention now relates to aqueous dispersions of copolymers and graft copolymers of ethylenically unsaturated perfluoroalkyl monomers with at least 6 carbon atoms in the perfluoro chain and perfluoroalkyl group-free ethylenically unsaturated monomers, characterized in that the dispersions additionally contain ester compounds which have at least 6 linearly linked carbon atoms have and either contain 1,2-substituted vinyl groups or are free of vinyl groups, and their use for the treatment of textiles, leather and paper.
  • the aqueous dispersions have solids contents of copolymers of about 10% by weight to 30% by weight and particle sizes of about 250 to 450 nm.
  • Examples include: acrylic and methacrylic acid esters of behenyl alcohol, stearyl alcohol, oleyl alcohol, nonyl or octyl alcohol or isomer mixtures of such alcohols.
  • Particularly preferred monomers (III) are vinyl esters such as vinyl acetate or vinyl propionate as well as acrylic and methacrylic acid esters of C1-C4 alcohols.
  • Preferred copolymers contain the individual types of comonomers in the quantitative ratios listed below; Perfluoroalkyl monomers of the formulas (I) 15 to 70% by weight, preferably 25 to 60% by weight, Comonomers of the formula (II) 5 to 35% by weight, preferably 10 to 25% by weight, Comonomers of the formulas (III) 15 to 65% by weight, preferably 20 to 55% by weight.
  • water-insoluble comonomers are preferred; to ensure some adhesion to the various substrates in the oleophobic / hydrophobic finish, water-soluble comonomers can also be used in proportions of up to 10% by weight, preferably up to 2% by weight.
  • the esters (IV) contain at least 6 carbon atoms in the chain.
  • esters (IV) described in items 1 to 3 can advantageously also be used as mixtures.
  • the ester compounds used according to the invention are known. In the preparation of the copolymer according to the invention, the ester compounds can either be used directly, since the preparation is carried out by the emulsion polymerization process, but more advantageously in the form of their aqueous emulsions.
  • the aqueous emulsions contain the ester compounds mentioned in concentrations of 5 to 40% by weight, preferably 10 to 30% by weight.
  • emulsifiers for the preparation of the emulsions it is possible to use both nonionic, anionic and cationic types and anionic / nonionic or cationic / nonionic combinations of the surface-active compounds in concentrations of 2 to 25, preferably 5 to 15% by weight, based on the one to be emulsified Use compound or mixtures thereof.
  • the methods for emulsification are generally known.
  • ester compounds are used to prepare the perfluoroalkyl copolymer dispersions according to the invention in amounts of 2 to 50, preferably 5 to 35,% by weight, based on the total amount of the monomers used for the copolymerization.
  • aqueous dispersions according to the invention can contain further polymers, as described, for example, in DE-A 3 407 361 and 3 407 362, in particular hydrophobic vinyl polymers (V) and / or polycondensates (VI), as described, for example, in DE-A 956 990 are contained, optionally as a graft base, preferably in amounts of 8% by weight to 30% by weight, based on the copolymer of (I), (II) and (III).
  • Suitable vinyl polymers (V) are, for example, copolymers of (meth) acrylates, such as isobutyl methacrylate or butyl acrylate, which contain at least one comonomer with a hydrophobic alkyl radical, such as, for example, stearyl methacrylate.
  • Suitable polycondensates (VI) are, for example, urea resins and melamine resins, such as those e.g. can be obtained by reacting hexamethylolmelamine pentamethyl ether with fatty acids and optionally with methyl dialkoanolamine, as described, for example, in EP-A 324 354.
  • a special embodiment is the combination of such a melamine condensate with paraffin fractions or paraffin waxes.
  • the dispersions according to the invention are prepared in a manner known per se, for example the procedure for emulsion polymerization in water is employed.
  • auxiliary solvents in the copolymerization, which are described, for example, in US Pat. No. 3,062,765. It is also possible to use auxiliary solvents which are immiscible with water, such as alkyl acetate, alkyl propionate or chlorofluorocarbons. The use of ethyl acetate or methyl propionate is particularly advantageous.
  • the auxiliary solvent is removed by distillation after completion of the polymerization.
  • the emulsions are produced in stirring units, ultrasound apparatus or homogenizers.
  • radical formers e.g. aliphatic azo compounds such as azodiisobutyronitrile and organic or inorganic peroxides are suitable, which are used in conventional amounts.
  • Organic peroxides which may be mentioned are: diacyl peroxides such as dibenzoyl peroxide, hydroperoxides such as tert-butyl hydroperoxide and percarbonates such as dicyclohexyl percarbonate.
  • the alkaline salts of peroxidic sulfuric acid are particularly suitable as inorganic peroxides.
  • the polymerization temperatures are up to 100 ° C., preferably 50 to 100 ° C., in particular 60 to 90 ° C.
  • Suitable starter systems are e.g. Mixtures of peroxidisulfates and reducing sulfur compounds such as bisulfites or thiosulfates or combinations of diacyl peroxides with tert. Amines.
  • the known chain transfer agents based on mercapto compounds or aliphatic aldehydes can be used to adjust the molecular weights or the molecular weight distributions.
  • anionic, cationic or nonionic emulsifiers and combinations of ionic and nonionic emulsifiers can be used to stabilize the dispersions according to the invention and also to prepare the monomer emulsions.
  • cationic emulsifiers are quaternary ammonium or pyridinium salts, e.g. Stearyldimethylbenzylammonium chloride or N, N, N-trimethyl-N-perfluorooctanesulfonamidopropylammonium chloride.
  • anionic emulsifiers are alkyl sulfonates, alkylarylsulfonates, fatty alcohol sulfates or sulfosuccinic acid esters, furthermore perfluoroalkyl group-containing emulsifiers such as ammonium or tetraethylammonium salts of perfluorooctanesulfonic acid or the potassium salt of N-ethyl-N-perfluorooctanesulfonylglycine.
  • the storage stability of the copolymer dispersions is particularly increased by non-ionic emulsifiers.
  • nonionic emulsifiers are polyglycol ethers, e.g. Ethylene oxide / propylene oxide copolymers, including those with a block structure, and alkoxylation products, in particular ethoxylation products of fatty alcohols, alkylphenols, fatty acids, fatty acid amides, sorbitol monooleate.
  • the polymerization of (I), (II) and (III) is carried out in the presence of (IV) and optionally (V) and / or (VI).
  • (V) and (VI) are preferably used in the form of aqueous dispersions.
  • the dispersions according to the invention are outstandingly suitable for the treatment of natural and synthetic materials such as leather, paper, fibers, filaments, yarns, nonwovens, woven fabrics, knitted fabrics and knitted fabrics, in particular carpets, made in particular of cellulose and its derivatives, but also made of polyester, polyamide and polyacrylonitrile materials, wool or silk, to which the dispersions according to the invention impart oleophobic and hydrophobic properties.
  • natural and synthetic materials such as leather, paper, fibers, filaments, yarns, nonwovens, woven fabrics, knitted fabrics and knitted fabrics, in particular carpets, made in particular of cellulose and its derivatives, but also made of polyester, polyamide and polyacrylonitrile materials, wool or silk, to which the dispersions according to the invention impart oleophobic and hydrophobic properties.
  • the dispersions according to the invention can also be used in combination with other fluorine-containing or fluorine-free dispersions.
  • the copolymers and graft copolymers according to the invention are preferably in the form of aqueous dispersions containing the ester compounds used according to the invention, in combination with aqueous colloidal suspensions of organosiloxanes, as described, for example, in DE-A 3 307 420, and optionally in an additional combination with other fluorine-containing dispersions.
  • the dispersions according to the invention have significantly improved oleophobic and hydrophobic effects on the substrates equipped with them, such as textiles, leather and paper.
  • natural and synthetic materials such as leather, paper, fibers, filaments, yarns, nonwovens, fabrics, knitted fabrics and knitted fabrics, in particular carpets, made in particular of cellulose and its derivatives, but also made of polyester, polyamide and polyacrylonitrile materials, wool or silk can be successfully rendered oleophobic and hydrophobic.
  • finishing is carried out according to known methods, such as pull-out or padding methods, for example between room temperature and 40 ° C., but also by splashing, spraying or foam application with a subsequent temperature treatment at 80 to 180 ° C., preferably 120 to 150 ° C.
  • glycerol monooleate mixture of approx. 50% monoglyceride, approx. 38% di- and 12% triglyceride
  • C12-C14-alkyldimethylbenzylammonium chloride approximately 50% in water
  • the agitator is replaced by a ULTRA-TURRAX dispersing device and 1,008 parts by weight of deionized water (temperature: 60 to 70 ° C) are added dropwise within 45 to 60 minutes (speed of the dispersing device: 10,000 rpm).
  • deionized water temperature: 60 to 70 ° C
  • speed of the dispersing device 10,000 rpm
  • Glycerol trioleate is emulsified using the same procedure as described in Example A.
  • 1,200 parts by weight of deionized water at 60 ° C are mechanically agitated in a 2 liter flat ground vessel using a ULTRATURRAX dispersing device (10,000 rpm).
  • the organic phase is metered into this template via a heatable dropping funnel (60 ° C.) within about 30 minutes.
  • the dispersing device is left to run for a further 5 minutes.
  • the solids content in the finished emulsion is approximately 21.5%.
  • Solution 2 is prepared at 50 ° C, solution 3 at 30 ° C.
  • Solutions 1 and 2 are combined at 50 ° C. and emulsified in an emulsifying machine until the particle size is constant at 40 to 50 ° C.
  • the emulsion obtained is placed in a reactor equipped with a stirrer, reflux condenser and internal thermometer and allowed to cool to 30 ° C.
  • Solution 3 is then metered in at 30 ° C. and stirred at 30 to 40 ° C. for 15 minutes.
  • the mixture is then heated to 60 ° C. within half an hour and stirred at 60 to 70 ° C. for one hour. Then allowed to react for three hours at 70 to 80 ° C and distilled off the ethyl acetate from an additional attached distillation apparatus.
  • the mixture is stirred for a further two hours at 83 to 85 ° C and three hours at 85 to 90 ° C.
  • Solids content 14.4% Fluorine content in the solid: 20.1% Average particle size: (after light scattering) 367 nm
  • copolymer dispersion is prepared as described in Example 2a), with the only difference that the emulsion of glycerol monooleate prepared according to Example A is not added to solution 1, but only after polymerization and Distillation of the finished copolymer dispersion is added in the same proportions as described in Example 2a).
  • Example 2a The preparation is carried out as in Example 2a) with the solutions mentioned there, with the only difference that Solution 1 does not contain an aqueous emulsion of an ester compound to be used according to the invention prepared according to Example A.
  • Example 2a The preparation is carried out as in Example 2a) with the solutions mentioned there with the only difference that solution 1 contains the same amount of an emulsion prepared according to Example B instead of an aqueous emulsion of an ester compound prepared according to Example A.
  • Solids content 15.5%
  • Fluorine content in the solid 17.9%
  • Average particle size (after light scattering) 295 nm
  • Example 2a The preparation is carried out as in Example 2a) with the solutions mentioned there, with the only difference that solution 1 contains the same amount of an emulsion prepared according to Example C instead of an aqueous emulsion of an ester compound prepared according to Example A.
  • An aqueous dispersion according to Example 1 is produced. 40 parts by weight of this dispersion are mixed with 60 parts by weight of an aqueous colloidal suspension of organosiloxanes, as described in DE-A-3 307 420.
  • a 2.5% aqueous dilution of this mixture is applied to a polyamide carpet (tufted fabric with 30% residual moisture, pile weight: 500 g / m2) (spray application) in such a way that a coating of 1% by weight of the above mixture ( based on the pile weight) remains on the carpet.
  • dispersions prepared according to Examples 2 to 8 are used for finishing polyamide carpets.
  • the copolymer dispersions according to the invention show a marked improvement in both the oleophobic and the hydrophobic effect.
  • the soiling behavior of the carpets finished with these copolymer dispersions is also improved and corresponds to increased requirements.

Claims (10)

  1. Dispersions aqueuses de copolymérisats et de copolymérisats greffés de monomères perfluoralkylés à nonsaturation éthylénique ayant au moins 6 atomes de carbone dans la chaîne perfluorée et de monomères à non-saturation éthylénique dépourvus de groupes perfluoralkyle, caractérisées en ce qu'elles contiennent en outre des composés du type d'esters qui présentent au moins 6 atomes de carbone en liaison linéaire les uns avec les autres et qui contiennent des groupes vinylique substitués en positions 1,2 ou qui sont dépourvus de groupes vinyliques.
  2. Dispersions aqueuses de copolymérisats et de copolymérisats greffés suivant la revendication 1, caractérisées en ce qu'elles contiennent comme composés du type d'esters
    a) des esters et/ou des esters partiels synthétiques ou naturels d'acides gras saturés, non saturés et/ou substitués ayant une longueur de chaîne de C₆ à C₂₂ avec des mono-, des di-, des tri- et des polyols,
    b) des esters et/ou des esters partiels d'acides di-, tri- et tétracarboxyliques avec des alcools gras saturés ou non saturés ayant une longueur de chaîne de C₆ à C₂₂,
    c) des polyesters à base d'alcools polyvalents et d'un acide polycarboxylique, ayant des poids moléculaires d'environ 1000 à 8000.
  3. Dispersions aqueuses suivant la revendication 1, caractérisées en ce que les (méth)acrylates de perfluoralkyle répondent aux formules
    Figure imgb0034
     et
    Figure imgb0035
     ainsi que
    Figure imgb0036
     dans lesquelles
    R₁   est un groupe alkyle en C₁ à C₄,
    R₂   est de l'hydrogène ou un groupe méthyle,
    m   a une valeur de 1 à 4 et
    n   a une valeur de 6 à 12.
  4. Dispersions aqueuses suivant la revendication 1, caractérisées en ce que les monomères dépourvus de groupes perfluoralkyle répondent aux formules
    Figure imgb0037
     et
    Figure imgb0038
     ou bien
    Figure imgb0039
     ou bien
    Figure imgb0040
     dans lesquelles
    R₃   est de l'hydrogène, un groupe méthyle ou du fluor,
    R₄   est un reste alkyle en C₈ à C₂₂,
    R₅   est un reste alkyle en C₁ à C₇,
    R₆   est un reste alkyle en C₁ à C₇,
    Figure imgb0041
     -CH₂-OH, -CH₂-OCH₃ ou
    Figure imgb0042
    R₇   représente H, CH₃, F ou Cl et
    R₈   représente Cl, F, OR₁, un groupe phényle,
    Figure imgb0043
     ou CN
    R₉   est un reste alkyle en C₁ à C₄.
  5. Dispersions aqueuses suivant la revendication 1 ou 4, caractérisées en ce que les comonomères dépourvus de groupes perfluoralkyle sont des esters de vinyle ou des esters acryliques et méthacryliques d'alcanols en C₁ à C₄ et des esters acryliques et méthacryliques d'alcanols en C₁₂ à C₂₂.
  6. Dispersions aqueuses suivant la revendication 1, caractérisées en ce qu'on utilise comme substrat de greffage des polymères vinyliques et/ou des polycondensats hydrophobes.
  7. Dispersions aqueuses suivant la revendication 1, caractérisées en ce que la proportion de composés du type d'esters contenus en outre et non incorporés par polymérisation, comportant au moins 6 atomes de carbone, se situe entre 2 et 50 % en poids, de préférence entre 5 et 35 % en poids, par rapport aux monomères utilisés.
  8. Procédé d'apprêtage de matières textiles, de tapis, de cuir et de papier, caractérisé en ce qu'on utilise des dispersions aqueuses suivant la revendication 1.
  9. Procédé suivant la revendication 8, caractérisé en ce qu'on utilise des associations des dispersions suivant la revendication 1, avec d'autres dispersions de polymérisats contenant du fluor.
  10. Procédé suivant la revendication 8, caractérisé en ce qu'on utilise des associations des dispersions suivant la revendication 1, avec des dispersions de polysiloxane.
EP90119662A 1989-10-27 1990-10-13 Dispersions de copolymérisats contenant des groupes perfluoroalkyles Expired - Lifetime EP0424765B1 (fr)

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Application Number Priority Date Filing Date Title
DE3935859A DE3935859A1 (de) 1989-10-27 1989-10-27 Dispersionen von perfluoralkylgruppen enthaltende copolymerisate
DE3935859 1989-10-27

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EP0424765A2 EP0424765A2 (fr) 1991-05-02
EP0424765A3 EP0424765A3 (en) 1992-07-29
EP0424765B1 true EP0424765B1 (fr) 1994-08-03

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JP (1) JPH03174418A (fr)
CA (1) CA2028503C (fr)
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Publication number Priority date Publication date Assignee Title
DE19907766B4 (de) * 1998-03-06 2009-04-09 Nippon Mektron, Ltd. Wäßrige Emulsion, Verfahren zu deren Herstellung sowie Wasser- und ölabweisendes Mittel

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DE3935859A1 (de) 1991-05-02
EP0424765A3 (en) 1992-07-29
CA2028503A1 (fr) 1991-04-28
JPH03174418A (ja) 1991-07-29
DE59006687D1 (de) 1994-09-08
CA2028503C (fr) 2001-12-18
EP0424765A2 (fr) 1991-05-02
US5093398A (en) 1992-03-03

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