EP1921203B1 - Verfahren zur Behandlung von Füllfasern mit wässrigen Dispersionen von Organopolysiloxanen - Google Patents

Verfahren zur Behandlung von Füllfasern mit wässrigen Dispersionen von Organopolysiloxanen Download PDF

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EP1921203B1
EP1921203B1 EP07120032A EP07120032A EP1921203B1 EP 1921203 B1 EP1921203 B1 EP 1921203B1 EP 07120032 A EP07120032 A EP 07120032A EP 07120032 A EP07120032 A EP 07120032A EP 1921203 B1 EP1921203 B1 EP 1921203B1
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radical
organopolysiloxanes
carbon atoms
radicals
process according
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French (fr)
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EP1921203A1 (de
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Konrad Alfons Dr. Wierer
Otto Dr. Schneider
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Wacker Chemie AG
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Wacker Chemie 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
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
    • D06M13/503—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms without bond between a carbon atom and a metal or a boron, silicon, selenium or tellurium atom
    • D06M13/507—Organic silicon compounds without carbon-silicon bond
    • 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
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • D06M15/6436—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing amino groups
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
    • D06B1/00—Applying liquids, gases or vapours onto textile materials to effect treatment, e.g. washing, dyeing, bleaching, sizing or impregnating
    • D06B1/02—Applying liquids, gases or vapours onto textile materials to effect treatment, e.g. washing, dyeing, bleaching, sizing or impregnating by spraying or projecting
    • 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
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/32—Polyesters
    • 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
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/34—Polyamides
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2201/00—Cellulose-based fibres, e.g. vegetable fibres
    • D10B2201/20—Cellulose-derived artificial fibres
    • D10B2201/22—Cellulose-derived artificial fibres made from cellulose solutions
    • D10B2201/24—Viscose
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2321/00—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D10B2321/02—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polyolefins
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
    • D10B2331/02—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyamides
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
    • D10B2331/04—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyesters, e.g. polyethylene terephthalate [PET]

Definitions

  • the invention relates to a process for the treatment of filler fibers with aqueous dispersions of organopolysiloxanes.
  • Emulsions of crosslinked silicones are known. For the crosslinking of silicones (heavy) metal-containing or metal-free catalysts and crosslinkers are needed. In part, inhibitors are also used to control reactivity and pot life to prevent undesired too early gelation.
  • DE 102004038148 A1 (corresponding WO 2006/015740 A1 ) describes the preparation of highly viscous silicones (10,000 to 50,000,000 mPa ⁇ s) in emulsion by reacting silanol-terminated organopolysiloxanes with ⁇ -aminomethylalkoxysilanes. However, no elastomeric silicone films which are insoluble in toluene are obtained.
  • EP 510 631 A describes the preparation and equipment of a fiber finishing agent based on copolyesters grafted with polyorganosiloxanes for a soft feather-like Gripping on polyester filling fibers.
  • the side grafting of polyorganosiloxanes to the polyester backbone gives a finishing agent that gives a smooth, low-friction feel to fibers, especially polyester filler fibers.
  • DE 35 03 457 A discloses a process for impregnating organic fibers in which an organopolysiloxane having amino groups such as aminoethylaminopropyl groups is cross-linked with hydrogensiloxane in the presence of metal-containing catalysts such as dibutyltin dilaurate.
  • EP 1 096 059 A For example, there is described an aqueous emulsion for treating polyester fibers containing a mixture of an emulsion of an amino functional organopolysiloxane with alkoxy groups and an emulsion of an amino functional organopolysiloxane with hydroxy groups.
  • the two organopolysiloxanes must first be complex by reaction of ⁇ , ⁇ -Dihydroxydimethylpolysiloxanen with N- (2-aminoethyl) (3-aminopropyl) methyldimethoxysilane or by reacting ⁇ , ⁇ -Dihydroxydimethylpolysiloxanen or cyclic dimethylpolysiloxanes with the hydrolysis or condensation product of N - (2-aminoethyl) (3-aminopropyl) -methyldimethoxysilane. It is from high molecular weight linear polysiloxanes, but no crosslinked films which are insoluble in toluene, prepared.
  • the object was to provide a process for the treatment of filler fibers with aqueous dispersions of organopolysiloxanes without the use of metal-containing catalysts.
  • Another object of the present invention was to provide a process for treating filler fibers with aqueous dispersions of organopolysiloxanes in which the aqueous dispersions of organopolysiloxanes form elastomeric films which are insoluble in toluene after removal of the water, and this treatment gives the filler fibers a permanent soft feel and a permanent soft touch gives good buoyancy.
  • a further object was to provide a process for the treatment of filler fibers with aqueous dispersions of organopolysiloxanes, in which the dispersions are obtained by a simple process in which no complex chemical reactions have to take place, in which the treatment of the filling fibers can be carried out with short residence times and at in which the treatment of the filling fibers can be carried out even at low temperatures and the filler fibers thus treated have a lower yellowing.
  • Another object was to provide for the treatment of filler fibers aqueous dispersions of organopolysiloxanes which are finely divided, stable and preferably pH-neutral (range pH about 5-9) and which are free or nearly free of volatile organic compounds (VOC). The object is achieved by the invention.
  • reaction - aqueous dispersions are obtained with high molecular weight partially crosslinked polymer particles, which after removal of the water, preferably by evaporation, yield an elastic film with formation of a high molecular elastic network and give the filler fibers thus treated a permanent soft feel.
  • the reaction of organopolysiloxane (1) with silane (2) can be carried out both before the emulsion is prepared and by first emulsifying the organopolysiloxane (1), which is then mixed with the silane (2) in the emulsion droplet. responding.
  • the dispersions according to the invention already contain precrosslinked organopolysiloxanes, elastomeric films being formed after the removal of the water and containing crosslinked organopolysiloxanes which branched out into high molecular weight or dendrimer-like hyperbranched structures. On these elastomeric films, a viscosity measurement is not possible.
  • the polymeric siloxane networks of the elastomeric films are typically insoluble in organic solvents such as toluene but may swell therein, but this is also to be understood as insoluble within the scope of this invention. This is in contrast to uncrosslinked organopolysiloxanes, which may also be highly viscous, but where a viscosity measurement is possible and which are soluble in organic solvents such as toluene.
  • the dispersions according to the invention are preferably aqueous suspensions or aqueous emulsions of organopolysiloxanes.
  • the dispersions of the invention form on drying - without addition of catalyst or change in pH - an elastic silicone network.
  • organopolysiloxanes having condensable groups and crosslinking agents (2).
  • These components preferably react with each other even at room temperature. To support this reaction no metal-containing additional catalysts are needed.
  • the reaction also preferably proceeds in the neutral range, ie in the pH range of about 5 to 9, which results from the components themselves. Due to the high reactivity is also a targeted guided chemical reaction not necessary and preferably also no heating.
  • the dispersion of the invention is characterized by its high storage stability, even at elevated temperature, and by their high shear stability.
  • the process according to the invention has the advantage that dispersions with a high solids content and filler content can be obtained.
  • the content of non-volatile substances in the dispersion is preferably about 1 to 99% by weight, preferably 30 to 95% by weight, particularly preferably more than 50% by weight, based on the total weight of the dispersion.
  • no metal-containing catalysts are used, i. It is preferable that no transition metals of VIII.
  • Subgroup of the Periodic Table and their compounds and no metals of the III, IV and V main group of the Periodic Table and their compounds are used, wherein the elements C, Si, N, and P in this definition not as Metals apply.
  • hydrocarbon radicals R are alkyl radicals, such as the methyl, ethyl, n-propyl, iso-propyl, 1-n-butyl, 2-n-butyl, isobutyl, tert-butyl, n-pentyl, iso-pentyl, neo-pentyl, tert-pentyl; Hexyl radicals, such as the n-hexyl radical; Heptyl radicals, such as the n-heptyl radical; Octyl radicals, such as the n-octyl radical and iso-octyl radicals, such as the 2,2,4-trimethylpentyl radical; Nonyl radicals, such as the n-nonyl radical; Decyl radicals, such as the n-decyl radical; Dodecyl radicals, such as the n-dodecyl radical; Octadecyl radicals, such as the
  • the radicals R are preferably the methyl, ethyl, octyl and phenyl radicals, particularly preferably the methyl and ethyl radicals.
  • N or O-substituted hydrocarbon radicals R are hydrocarbon radicals which are substituted by amino groups, and Polyethoxy or polypropoxy or polyethoxy-polypropoxy groups are substituted.
  • radicals R which are substituted by amino groups are radicals of the formula -R 6 -NR 7 2 , wherein R 6 has the meaning given above and R 7 is the same or different and represents a hydrogen atom or an alkyl or aminoalkyl or iminoalkyl radical.
  • a preferred example is the N- (2-aminoethyl) (3-aminopropyl) radical.
  • R 1 is a hydrogen atom.
  • alkyl radicals R 1 are the alkyl radicals listed above at R, wherein the methyl or ethyl radical is preferred.
  • R 2 is a hydrogen atom.
  • alkyl radicals R having 1 to 8 carbon atoms are also fully applicable to alkyl radicals R 3 .
  • Preferred examples of alkyl radicals R 3 are the methyl and ethyl radicals.
  • hydrocarbon radicals R such as alkyl, cycloalkyl, aryl, alkaryl and aralkyl radicals, apply in their entirety to hydrocarbon radicals R 4 .
  • alkyl radicals R 4 are methyl, ethyl, butyl, hexyl and octyl radicals, a preferred example of cycloalkyl radicals R 4 is the cyclohexyl radical.
  • R 5 is the radical of the formula -CH 2 -CH 2 -O-CH 2 -CH 2 -.
  • radicals Y are the morpholino, piperazino, piperidino and cyclohexylamino radicals.
  • the radical R 6 is an alkylene radical, preferably a radical of the formula -CH 2 CH 2 CH 2 -.
  • Preferred organopolysiloxanes (1) are siloxanes of the general formula (R 1 O) R 2 SiO (SiR 2 O) e SiR 2 (OR 1 ) (IV) wherein R and R 1 have the meaning given above, and e is an integer from 1 to 1000, with the proviso that 25 to 100%, preferably 50 to 100% of all radicals R 1 are hydrogen atoms used.
  • organopolysiloxanes (1) are resins of the general formula [(R 3 SiO 1/2 ) f (R 2 SiO 2/2 ) g (R 1 SiO 3/2 ) h (SiO 4/2 ) k ] (V) where R has the meaning given above and additionally R in formula (V) can also be (OR 1 ) with the meaning given above, with the proviso that at least one radical -OR 1 , where R 1 is a hydrogen atom, contained per molecule, f, g, h and k are an integer from 0 to 1000 and h / (f + g + h + k) is preferably> 0.2.
  • siloxanes (1) are commercially available silanol-terminated polydimethylsiloxanes and alkoxy-terminated polydimethylsiloxanes.
  • siloxanes (1) are commercially available functionalized siloxanes, such as amine oils, e.g. Amine oils having 3- (2-aminoethyl) aminopropyl functions, glycol oils, phenyl or phenylmethyl oils containing silanol or alkoxy groups.
  • organopolysiloxanes (1) are resinous siloxanes, for example methylsilicone resins, with 80 mol% CH 3 SiO 3/2 and 20 mol% (CH 3 ) 2 SiO 2/2 and a molecular weight of about 5000 g / mol or 98 mol% CH 3 SiO 3/2 and 2 mol% (CH 3 ) 2 SiO 2/2 and a molecular weight of about 5000 g / mol, or eg methylphenylsilicone resins with 65 mol% C 6 H 5 SiO 3/2 and 35 mol% (CH 3 ) 2 SiO 2/2 , whose remaining free valencies R 1 O groups of the above meaning carry.
  • resinous siloxanes for example methylsilicone resins, with 80 mol% CH 3 SiO 3/2 and 20 mol% (CH 3 ) 2 SiO 2/2 and a molecular weight of about 5000 g / mol or 98 mol% CH 3 SiO 3/2 and 2 mol
  • organopolysiloxane (1) or various kinds of organopolysiloxane (1) can be used.
  • the organopolysiloxanes (1) used preferably have viscosities of 1 mPa.s to 5,000,000 mPa.s at 25 ° C, preferably 50 mPa.s to 100,000 mPa.s at 25 ° C and particularly preferably 100 mPa.s to 10,000 mPa at 25 ° C.
  • one kind of silane (2) or various kinds of silane (2) may be used.
  • radical -CR 2 2 -Y in silane (2) of the formula (II) is preferably a radical of the formula -CH 2 -Y.
  • radicals -CR 2 2 -Y in silane (2) of the formula (II) are the aminomethyl, methylaminomethyl, dimethylaminomethyl, diethylaminomethyl, dibutylaminomethyl, cyclohexylaminomethyl, morpholinomethyl, piperidinomethyl, piperazinomethyl, (( diethoxymethylsilyl) methyl) cyclohexylaminomethyl, ((Triethoxysilyl) methyl) cyclohexylaminomethyl, anilinomethyl, 3-dimethylaminopropylaminomethyl and Bis (3-dimethylaminopropyl) aminomethyl.
  • silanes (II) are Dibutylaminomethyltriethoxysilan, Dibutylaminomethyltributoxysilan, cyclohexylaminomethyltrimethoxysilane, cyclohexylaminomethyltriethoxysilane, Anilinomethyltriethoxysilan, morpholinomethyltriethoxysilane, Morpholinomethyltrimethoxysilan, Morpholinomethyltriisopropoxysilan, 3-dimethylaminopropyl-aminomethyltrimethoxysilane, Ethylcarbamoylmethyltrimethoxysilan, Morpholinomethyltributoxysilan, Morpholinomethyltrialkoxysilan wherein the alkoxy group is a C 1 -C 4 -alkoxy radical, in particular a Is a mixture of methoxy and ethoxy radical, Bis (dimethylaminopropyl) aminomethyl
  • the silanes (2) of the formula (II) may contain up to 30% by weight of difunctional silanes of the formula (R 3 O) 2 RSiCR 2 2 -Y (II ') or their hydrolysates contain.
  • the silane of formula (II ') is chain extending for organopolysiloxanes (1) but does not interfere with the crosslinking reaction of silane of formula (II) with the chain extended organopolysiloxane (1).
  • Crosslinked organopolysiloxanes according to the invention are obtained.
  • the degree of crosslinking depends on the ratio of the equivalents used -OR 3 in silane (2) of the formula (II) to -OR 1 in organopolysiloxane (1) of the formula (I).
  • silane (2) or its partial hydrolysates is preferably present in amounts of at least 0.6 equivalents of -OR 3 , preferably at least 0.7 equivalents of -OR 3 , particularly preferably 0 , 6 to 2 equivalents of -OR 3 , especially 0.65 to 1 equivalent of -OR 3 , more preferably of 0.7 to 0.99 equivalents of -OR 3 , per equivalent of -OR 1 in organopolysiloxane (1) used, wherein R 1 in (1) is preferably a hydrogen atom.
  • the crosslinking frequency depends both on the chain lengths of the organopolysiloxanes (1) and on the stoichiometry of the SiOR 1 groups of the organopolysiloxane (1) and the SiOR 3 groups of the silane (2) which react with one another. High levels of crosslinking are achieved when the same number of SiOR 1 groups of the organopolysiloxane (1) and SiOR 3 groups of the silane (2) react with each other. Losses due to volatility or side reactions may require a stoichiometric ratio other than 1.0: 1.0. If desired, a stoichiometric excess of SiOR 3 - of silane (2) to SiOR 1 - groups of organopolysiloxane (1) can be used. Surprisingly, it was found that even with a stoichiometric deficit of SiOR 3 - from silane (2) to SiOR 1 groups of organopolysiloxane (1), for example 0.7: 1.0, elastic films can be achieved.
  • the dispersions according to the invention are prepared by intensive mixing of organopolysiloxanes (1) with silanes (2), Water (3), Emulsifiers (4), optionally further silanes (5), and optionally other substances (6) with each other.
  • the preparation can be discontinuous or continuous, such as in DE 102004023911 A or in WO 2005100453 is described.
  • silanes (2) are known to contain hydrolysis-sensitive groups, especially when R 3 is a hydrogen atom or a methyl or ethyl radical, even in the presence of Water surprisingly crosslinked organopolysiloxanes obtained by reaction with a plurality of organopolysiloxanes (1).
  • the components (1) and (2) are premixed with each other, then the (or) the emulsifier (s) (4) is added and then the water (3) and optionally further substances (5) and (6) are incorporated. It is also possible to meter the components (1) and (2) and (3) to (6) in sequence into the emulsifying apparatus. In special cases it may e.g. due to the siloxane viscosity or reactivity, it is advantageous to mix silane (2) with an organopolysiloxane (1) and then incorporate another organopolysiloxane (1), or vice versa, depending on how more favorable rheological properties result for the processing of the components.
  • silanes (2) it may be advantageous first to convert the component (1) with emulsifier (4) and the water (3) into a stiff phase, and then to pass the silane (2) neat or diluted in an inert substance ( 6) before further dilution with water if necessary.
  • silane (2) in the finished emulsion of organopolysiloxanes (1) so as to achieve the desired reaction and crosslinking of the organopolysiloxane (1) in the emulsion.
  • the silane (2) may be previously partially or completely hydrolyzed by adding water.
  • the by-product alcohol R 3 OH can be partially or completely removed by suitable known measures, such as distillation, membrane processes or other separation processes.
  • water (3) is used in amounts of preferably from 1 to 99% by weight, particularly preferably from 5 to 95% by weight, based in each case on the total weight of all the ingredients of the dispersion.
  • the process for the preparation of dispersions can be carried out continuously.
  • the organopolysiloxanes (1) required for the preparation of the dispersion are preferably prepared continuously and passed on continuously to the emulsifying apparatus, and mixed continuously with silanes (2), emulsifiers (4) and at least part of the water as dispersant (3) before emulsification, and This mixture is continuously fed to a first high shear mixer and it is formed in this mixer, a viscous phase, wherein the pressure and the temperature are measured after this mixer and adjusted so that a high quality and finely divided as possible dispersion.
  • silanes (5) and other substances (6) can be added before or after the first high-shear mixer.
  • the emulsion may be further diluted by mixing in water.
  • inventive method can be used as emulsifiers (4) all previously known, ionic and nonionic emulsifiers both individually and as mixtures of different emulsifiers with which previously aqueous dispersions, especially aqueous emulsions of organopolysiloxanes could be produced.
  • Preferred emulsifiers are nonionic emulsifiers, in particular the alkyl polyglycol ethers listed under 6.
  • the constituent (4) may consist of one of the abovementioned emulsifiers or of a mixture of two or more of the abovementioned emulsifiers; it may be used in pure form or as solutions of one or more emulsifiers in water or organic solvents.
  • the emulsifiers (4) in amounts of preferably 0.1 to 60 wt .-%, particularly preferably 0.5 to 30 wt .-%, each based on the total weight of organopolysiloxanes (1) and silanes (2 ).
  • organopolysiloxane (1) or the silane (2) or the resulting crosslinked organopolysiloxane itself acts as an emulsifier
  • the addition of separate emulsifier (4) can be dispensed with.
  • silanes (5) of the formula (III) can be used.
  • Z in formula (III) is preferably a radical of the formula -NR 7 2 , wherein R 7 is the same or different and represents a hydrogen atom or an alkyl or aminoalkyl or Iminoalkylrest.
  • a preferred example of the radical Z is the radical of the formula -NH (CH 2 ) 2 NH 2 .
  • x is 2.
  • R 6 in formula (III) is a radical of the formula -CH 2 CH 2 CH 2 -.
  • silane (5) examples are (3-methacryloxypropyl) trimethoxysilane, 3-aminopropyltrimethoxysilane, 3- (cyclohexylamino) propyltrimethoxysilane N- (2-aminoethyl) (3-aminopropyl) methyldimethoxysilane, N- (2-aminoethyl) (3-aminopropyl) methyl diethoxysilane, N- (2-aminoethyl) (3-aminopropyl) trimethoxysilane, N- (2-aminoethyl) (3-aminopropyl) triethoxysilane and (3-glycidoxypropyl) triethoxysilane.
  • water-miscible liquids that can be used as further substances (6) are acids, such as formic acid, acetic acid, propionic acid, oxalic acid and citric acid and silicone or non-silicone emulsions.
  • the dispersions can be prepared as dispersions of undiluted crosslinked organopolysiloxanes, but sometimes for reasons of handling, dilution with organic solvents or low-viscosity oligomers / polymers is recommended.
  • water-immiscible liquids which can be used as further substances (6) are therefore organic solvents, such as toluene, n-hexane, n-heptane and technical gasoline fractions and low-viscosity oligomers / polymers, such as silicone oils, preferably siloxanes, such as dimethylpolysiloxanes ,
  • water-soluble solids that can be used as further substances (6) are ammonium phosphates and polyphosphates, ammonium formates and lithium formate, which may act as antistatic agents and / or flame retardants.
  • water-insoluble solids which can be used as further substances (6) are reinforcing and non-reinforcing and flame-retardant fillers.
  • reinforcing fillers ie fillers with a BET surface area of at least 50 m 2 / g, are fumed silica, precipitated silica or silicon-aluminum mixed oxides having a BET surface area of more than 50 m 2 / g and silicone particles, such as MQ resins.
  • the fillers mentioned may be hydrophobic.
  • non-reinforcing and also flame-retardant fillers are powders of quartz, chalk, cristobalite, diatomaceous earth, calcium silicate, zirconium silicate, montmorillonites, such as bentonites, zeolites, metal oxides, such as Aluminum or zinc oxide or their mixed oxides or titanium dioxide, metal hydroxides, such as aluminum hydroxide, barium sulfate, calcium carbonate, gypsum, silicon nitride, silicon carbide and boron nitride.
  • the emulsification process for preparing the dispersion is preferably carried out at temperatures below 120.degree. C., preferably at 5.degree. C. to 100.degree. C., more preferably at 10.degree. C. to 80.degree.
  • the temperature increase is preferably due to the entry of mechanical shear energy needed for the emulsification process.
  • the temperature increase is not needed to accelerate a chemical process.
  • the dispersion is preferably carried out at the pressure of the surrounding atmosphere, but may also be carried out at higher or lower pressures.
  • the dispersion which is used for the process according to the invention has the advantage that it can be prepared without the addition of catalysts, in particular without the addition of metal catalysts.
  • the reaction of (1) with (2) preferably proceeds completely in a few minutes to several hours, where methoxysilanes also react faster than ethoxysilanes.
  • the condensation can be accelerated by acids and bases.
  • the alcohols which are obtained as condensation by-products in the preparation of the dispersion can remain in the dispersion or can also be removed, for example by distillation under reduced pressure, membrane processes or by extraction.
  • the measured by light scattering in the dispersions average particle size is in the range 0.001 to 100 microns, preferably 0.002 to 10 microns.
  • the pH values can vary from 1 to 14, preferably 3 to 9, particularly preferably 5 to 9.
  • filler fibers which are treated with the dispersions according to the invention are those of polyester, polyamide, polylactate (PLA), polybutyric acid, polyolefins, viscose, modal and lyocell.
  • the filling fibers are preferably staple fibers or crimped staple fibers, from which a bulky cotton wool is produced by opening and laying on cards. These can be used as wadding, filling material or cushioning material in pillows, upholstery, blankets, comforters, mattresses, sleeping bags, insulating clothing (eg coats, sports anoraks).
  • the filling fibers can be treated by contacting the filler fibers with the dispersions of the invention by dipping, spraying, rolling, printing, padding or curtain casting, preferably by spraying the aqueous dispersions onto the filler fibers by spraying, dipping, padding or curtain-coating be applied. Thereafter, the water (3) is removed.
  • the water is preferably removed by drying the filler fibers at a temperature of from 1 to 230 ° C., preferably from 30 to 180 ° C., more preferably in the temperature range from 70 to 120 ° C.
  • the drying time depends on parameters such as temperature, air circulation, substrate thickness and application quantity.
  • the dispersions according to the invention remain after drying as a film on the surface of the filling fibers.
  • the process according to the invention has the advantage that the filler fibers treated with the dispersions according to the invention have a permanent soft feel, increased elasticity, gloss and smoothness, reduction of frictional resistance and improved hydrophobicity and dirt repellency.
  • the film obtained by the evaporation of the water from the dispersion adheres well to the filler fibers and gives the surface of the Filling fibers a particularly soft smoothness and elasticity with a return force. Due to the good permanent adhesion on the fiber, the filling fiber can be well carded and there is hardly any abrasion / deposition of silicone polymers on the card fittings, which would cause a parking of the cards and increased cleaning.
  • wet fiber is removed and separated from it in a sling (salad spinner) so much liquid that a weight gain of 70% is maintained.
  • a drying oven for 10 minutes (optionally at 120 or 170 ° C) or, optionally, the treated fibers are spread at 23 ° C for 24 hours and dried.
  • emulsifier in an Ultra-Turrax T 50 emulsifier (Janke & Kunkel / IKA) is from 5 g Isotridecyldecaethoxylat, 85% in water, commercially available under the trade name Lutensol TO 109 (BASF), and 8 g of deionized water an emulsifier to which 100 g of a freshly prepared homogeneous siloxane polymer / silane mixture consisting of 99.65 g of polydimethylsiloxane diol containing 1100 ppm by weight of terminal OH groups as siloxane (1) and 0.39 g of N-morpholinomethyl triethoxysilane (molecular weight 263.4) as silane (2), is metered.
  • a freshly prepared homogeneous siloxane polymer / silane mixture consisting of 99.65 g of polydimethylsiloxane diol containing 1100 ppm by weight of terminal OH groups as siloxane
  • a milky white emulsion having an average particle size of 309 nm.
  • the solids content of the emulsion is 50.7%, the pH is 6.0.
  • the emulsion is homogeneous and stable even after 6 months storage at room temperature.
  • Evaporation of the emulsion gives, after a drying time of 24 h / 25 ° C., a gel-like elastic film which adheres well to glass or aluminum.
  • Example 1 example Siloxane (1) in g Silane (2) in g Fixed content (%) pH Particle size (nm) Film evaluation after drying 24 h / 25 ° C B2 99.56 (1a) 0.44 50.5 7 478 very elastic, transparent B3 99.40 (1a) 0.60 49.9 7 481 elastic, transparent B4 99,22 (1a) 0.79 50.5 6.5 --- elastic, opaque B5 94.0 (1a) 6.0 49.8 8th --- not very elastic, opaque B6 20.0 (1b) 80.0 (1a) 0.37 52.0 7 2810 very elastic, transparent
  • the solid content is determined at 150 ° C to constant weight with device: Mettler Toledo HR 73.
  • the particle sizes are determined with Coulter N4 plus.
  • silane (2) is used:
  • the elasticity of the films produced from the emulsion decreases from B1 to B5 as the amount of silane (2) increases.
  • the viscosity increase was measured after mixing the components siloxane (1) and silane (2) according to Example B3, ie, ⁇ , ⁇ -dihydroxypolydimethylsiloxane with morpholinomethyltriethoxysilane.
  • morpholinomethyltriethoxysilane was replaced by the component indicated in Table 3 in V2a - V2f (analogously to Comparative Experiments V1a - V1f) and the viscosity increase was likewise measured. The results are summarized in Table 3.
  • Table 3 Measurement of Viscosity Increase comparison Siloxane (1) in g Replacement of silane (2) Viscosity at 23 ° C measured with Brookfiled [mPa ⁇ s] in g immediately after mixing after 2 h after 24 h after 2 days after 6 days v2a 99.40 0.60 VTMO 1) 5410 5740 5680 5720 5810 v2c 99.40 0.60 GF95-H 2) 6100 6240 6200 6200 6390 v2d 99.40 0.60 Resin 3) 5860 5980 5960 5950 6020 V2e 99.40 0.60 Resin 3) + KOH to pH 11 5950 6530 7480 7960 9280 V2f 99.40 0.60 VTMO 1) + GF95-H 2) 5810 6580 8710 12650 36700 analogously to Example 3 99.40 0.60 According to the invention: morpholinomethyltriethoxysilane 350000 736000 not measurable, networked, elastic not measurable, networked, elastic not
  • T 50 (Janke & Kunkel / IKA) is from 9.38 g Isotridecyldecaethoxylat (Lutensol TO 109, Fa., BASF AG), 3.90 g castor oil G 1300 (Atlas) and 4, 55 g of water, a stiff emulsifier prepared to the 125.28 g of a freshly prepared homogeneous polymer / silane mixture of 124.63 g of polydimethylsiloxane with a content of terminal OH groups of 765 ppm by weight as organopolysiloxane (1) and 0.86 g N-Morpholylmethylmethyldiethoxysilane is metered. It is then diluted in portions with a total of 106.65 g of water, whereupon a stable emulsion having an average particle size of 275 nm is obtained.
  • the silicone content of the emulsion is 50%.
  • a michig-white emulsion having an average particle size of 210 nm is obtained.
  • To the emulsion is added 1 g of N- (2-aminoethyl) (3-aminopropyl) methyldimethoxysilane as component (5) and 0.4 g of 80% acetic acid as component (6) with stirring.
  • the solids content of the emulsion is 66%, the pH 7.5.
  • the emulsion is homogeneous and stable even after 6 months storage at room temperature.
  • a michig-white emulsion having an average particle size of 210 nm.
  • To the emulsion is added 1 g of N- (2-aminoethyl) (3-aminopropyl) -methyldimethoxysilane as component (5) and 0.4 g of 80% strength acetic acid as further component (6) with stirring.
  • the solids content of the emulsion is 66%, the pH 7.5.
  • the emulsion is homogeneous and stable even after 6 months storage at room temperature.
  • the emulsions of Examples 7 and 8 and Comparative Experiments 4 and 5 were respectively crimped polyester staple fibers with a titer of 61 dtex and 50 mm staple length after laboratory description and dried at 3 different temperatures of 23 °, 120 ° and 170 °. After this drying, the finished fibers were conditioned in a climatic room at 23 ° C 50% humidity for 24 hours and judged manually by 5 people by the handle (dryness, softness, slipperiness, bulkiness and recoil behavior). For this purpose, the samples were strung together according to the handle judgment and set a grading scale of 1 -5 with 5 as the softest, most sliding spring-like grip with the best resilience and 1 as a dry grip with noticeable permanent deformation and low restoring force. The results are summarized in Table 5.
  • the handle of the fibers treated with Examples 7 and 8 is judged to be softer, more slippery, less abrasive, and bulkier. In particular, the good feel is significantly improved even at room temperature, but especially at 120 ° C drying compared to the non-inventive Comparative Experiments 4 and 5.
  • Table 5 Comparison of the handle of crimped polyester staple fibers equipped with the following emulsions finishes Handle after drying at 23 ° C 120 ° C 170 ° C Example 7 2.5 3.5 4.5 Example 8 3.5 4 5 Comparison 4 1.5 2 3 Comparison 5 1.5 2 3
  • the finished fibers were split and half of the samples were placed in a rinse net and washed with mild detergent at 40 ° C (color wash setting). After the wash cycle, the nets were emptied and the fibers dried and conditioned in a climate chamber at 23 ° C 50% H-heuchte.
  • the extractable portion is considerably lower in Examples 7 and 8 at 1.78% and 1.61% than in noninventive Comparative Experiments 4 and 5 and thus an indication of a higher permanence of the formed silicone film according to the invention on the fiber, also towards organic solvent ,

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EP07120032A 2006-11-08 2007-11-06 Verfahren zur Behandlung von Füllfasern mit wässrigen Dispersionen von Organopolysiloxanen Expired - Fee Related EP1921203B1 (de)

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KR101230637B1 (ko) * 2008-06-30 2013-02-06 코오롱인더스트리 주식회사 해양용 폴리에스테르 원사
US8518170B2 (en) 2008-12-29 2013-08-27 Honeywell International Inc. Boron-comprising inks for forming boron-doped regions in semiconductor substrates using non-contact printing processes and methods for fabricating such boron-comprising inks
US8324089B2 (en) 2009-07-23 2012-12-04 Honeywell International Inc. Compositions for forming doped regions in semiconductor substrates, methods for fabricating such compositions, and methods for forming doped regions using such compositions
KR101297806B1 (ko) * 2009-12-30 2013-08-19 코오롱인더스트리 주식회사 해양용 폴리에스테르 원사 및 그의 제조 방법
CN102812086A (zh) * 2010-03-26 2012-12-05 日本电气株式会社 含有磷化合物和聚硅氧烷化合物的聚乳酸树脂组合物及由其制成的模塑制品
DE102011079911A1 (de) 2011-07-27 2013-01-31 Wacker Chemie Ag Kosmetische Zusammensetzungen
US8629294B2 (en) 2011-08-25 2014-01-14 Honeywell International Inc. Borate esters, boron-comprising dopants, and methods of fabricating boron-comprising dopants
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US20080107814A1 (en) 2008-05-08
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