EP0270842A2 - Process for the manufacture of needled non-woven floor coverings - Google Patents

Process for the manufacture of needled non-woven floor coverings Download PDF

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Publication number
EP0270842A2
EP0270842A2 EP87116301A EP87116301A EP0270842A2 EP 0270842 A2 EP0270842 A2 EP 0270842A2 EP 87116301 A EP87116301 A EP 87116301A EP 87116301 A EP87116301 A EP 87116301A EP 0270842 A2 EP0270842 A2 EP 0270842A2
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EP
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Prior art keywords
weight
needle
copolymers
floor coverings
carbon atoms
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EP87116301A
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German (de)
French (fr)
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EP0270842A3 (en
EP0270842B1 (en
Inventor
Erich Dr. Penzel
Josef Dr. Peterhans
Karl-Clemens Dr. Peters
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BASF SE
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BASF SE
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Classifications

    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/44—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties the fleeces or layers being consolidated by mechanical means, e.g. by rolling
    • D04H1/46—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties the fleeces or layers being consolidated by mechanical means, e.g. by rolling by needling or like operations to cause entanglement of fibres
    • D04H1/48—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties the fleeces or layers being consolidated by mechanical means, e.g. by rolling by needling or like operations to cause entanglement of fibres in combination with at least one other method of consolidation
    • D04H1/488—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties the fleeces or layers being consolidated by mechanical means, e.g. by rolling by needling or like operations to cause entanglement of fibres in combination with at least one other method of consolidation in combination with bonding agents
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4326—Condensation or reaction polymers
    • D04H1/4334—Polyamides
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
    • D04H1/587—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives characterised by the bonding agents used
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
    • D04H1/64—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives the bonding agent being applied in wet state, e.g. chemical agents in dispersions or solutions
    • 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
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/47—Oxides or hydroxides of elements of Groups 5 or 15 of the Periodic Table; Vanadates; Niobates; Tantalates; Arsenates; Antimonates; Bismuthates
    • 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
    • D06M15/244—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons
    • D06M15/248—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons containing chlorine
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
    • D06N3/0063—Inorganic compounding ingredients, e.g. metals, carbon fibres, Na2CO3, metal layers; Post-treatment with inorganic compounds

Definitions

  • flame-retardant needle-punched non-woven floor coverings There are two options for the manufacture of flame-retardant needle-punched non-woven floor coverings: Use of flame-retardant fibers or finishing nonwovens made from conventional organic fibers with flame retardants or flame retardant binders.
  • Commercially available binders are aqueous dispersions based on styrene-butadiene copolymer or polyacrylate, but binders based on butadiene-styrene copolymers are generally less suitable if the aim is flame retardancy.
  • Flame retardant additives are mostly organic halogen compounds, organic phosphorus compounds and antimony trioxide.
  • the finishing and consolidation of needle-punched non-woven floor coverings is usually done with full bath impregnation of the nonwovens.
  • the dispersion is diluted and the needle punch is immersed in the bath.
  • the binder application is generally 20 to 30% by weight (solid), based on the weight of the fiber.
  • Flame retardant additives to the impregnation liquor for example organic halogen and / or phosphorus compounds, have no binding effect. Adding them to binder disposition therefore leads to an incorporation in the binder and thus to a reduction in the binding strength. If the flame retardant is soluble in the binder, the binder is also made more sticky by the addition and the tendency towards contamination of the bonded nonwoven is increased.
  • its refractive index which differs from that of the binder in general, means that the binder does not form a clear, transparent film after drying, but - depending on the amount of additive and layer thickness - forms a cloudy to opaque film.
  • this effect at least affects the brilliance, a so-called color veiling.
  • this can be avoided by using additives with a grain size that is significantly less than the wavelength of visible light. Such fine-particle additives are hardly available.
  • the third disadvantage of almost all common halogenated organic and mineral flame retardants is their relatively high specific weight, which easily leads to their settling in the low-viscosity impregnation liquor and to their deposition on the bottom of the application pan, in containers and pipelines.
  • binders have been used which contain copolymerized vinyl chloride.
  • a certain disadvantage with these binders is that only relatively small amounts of chlorine are obtained in the polymer with vinyl chloride without too much stiffening of the handle of the bound nonwoven.
  • Copolymers of vinyl chloride and acrylic esters with more than 60 to 70% by weight of vinyl chloride also cannot be filmed at room temperature.
  • copolymers of vinylidene chloride and acrylic esters are cheaper.
  • large amounts of chlorine can be introduced into the polymer without difficulties in film formation.
  • the flame retardant effect does not necessarily improve with an increasing amount of vinylidene chloride, since it is not only the amount of halogen that is important for the fire behavior.
  • the tendency to yellowing increases with an increasing amount of vinylidene chloride.
  • EP-A-0 180 868 describes dispersions of copolymers of 10 to 50% by weight of vinylidene chloride which, in addition to acrylic esters, can optionally contain vinyl chloride in copolymerized form.
  • the dispersions are suitable as binders for paints and plasters. They are unsuitable as binders for needle-punched non-woven floor coverings because they are uncrosslinked and uncrosslinkable polymers which - if they have sufficient softness for this purpose - would lead to an unbearable susceptibility to dirt on the coverings when they were walked on.
  • crosslinking comonomers such as N-methylol (meth) acrylamides, the cleaning resistance of nonwovens can also be considerably improved, as was shown in DE 1 086 208 or DE-AS 1 047 431.
  • GB-PS 1 054 877 it is known to produce flame-retardant, bonded nonwovens using a binder mixture which, based on the fibers, 20 to 200% by weight of polymers based on acrylic acid esters and / or butadiene, 15 to 150% by weight % of at least 80% of their weight of copolymerized vinylidene chloride-containing copolymers and 15 to 150% by weight of antimony trioxide.
  • the vinylidene chloride polymers which do not act as binders can preferably be used in powder form. Such mixtures are unsuitable for the production of needle-punched non-woven floor coverings using the full bath impregnation method.
  • the minimum film formation temperature (MFT) of dispersions III, E, F, and O determined in accordance with DIN 53 787, is: Example 3, E MFT: 39 ° C, Example 3, F MFT: 30 ° C and Example 3, O MFT: over 50 ° C.
  • needle-punched nonwoven floor coverings can advantageously be produced by making needle-punched nonwovens with aqueous dispersions of copolymers with a minimum film-forming temperature of 5 to 25 ° C. 15 to 35% of their weight vinylidene chloride 10 to 45% of their weight vinyl chloride 8 to 72% of their weight esters of (meth) acrylic acid with alkanols containing 1 to 12 carbon atoms or optionally vinyl esters containing aliphatic carboxylic acids or mixtures of these monomers with 2 to 3 carbon atoms 1 to 7% of their weight of ⁇ , ⁇ -monoolefinically unsaturated mono- and / or dicarboxylic acids containing 3 to 5 carbon atoms and / or their amides 2 to 5% of their weight of N-methylol- (meth) acrylamide and / or their alkyl ethers with 1 to 4 carbon atoms in the alkyl groups, 0 to 3% of their weight vinyl sul
  • the aqueous copolymer dispersions can be prepared by known methods of emulsion polymerization e.g. be prepared with the emulsion feed of the monomers in a closed pressure vessel in a conventional manner. Their manufacture is not the subject of this invention.
  • the usual water-soluble, radical-forming polymerization initiators, such as alkali persulfates, can advantageously be used in combination with water-soluble reducing agents, such as formaldehyde sulfoxylate or sodium pyrosulfite.
  • All anionic and nonionic emulsifiers customary for emulsion polymerization can be used as emulsifiers.
  • the copolymer dispersions preferably contain an amount of emulsifier of only 2 to 4% by weight, based on the copolymers, and their LD value is preferably above 70%, the surface tension preferably being in the range from 35 to 55 dynes / cm.
  • Preferred emulsifiers for the copolymer dispersions used as binders are disulfonates, alone or together with other customary anionic and / or nonionic emulsifiers.
  • Copolymer dispersions produced in this way are coagulate-free, finely divided and shear-stable and have a relatively high surface tension in the range from 40 to 50 dynes / cm.
  • the sodium salts of paraffin disulfonic acid and alkyl diphenyl ether disulfonic acid are mentioned as preferred disulfonates.
  • the amount of vinylidene chloride is 15 to 35% by weight, that of vinyl chloride 10 to 45% by weight. Only the combination of both chlorine-containing monomers gives the desired flame-retardant behavior.
  • the amount of esters of acrylic acid is 8 to 72% by weight, with ethyl, butyl and 2-ethylhexyl acrylate being particularly preferred.
  • vinyl esters vinyl acetate and vinyl propionate are of particular interest.
  • esters of methacrylic acid with alkanols containing 1 to 4 carbon atoms are also suitable.
  • the amount of unsaturated mono- and / or dicarboxylic acids and / or their amides is 1 to 7% by weight, preferably 3 to 5% by weight.
  • acrylic acid, methacrylic acid, acrylamide and methacrylamide as well as itaconic acid and their Mono- and diamides of particular importance.
  • vinylsulfonic acid - mostly as an alkali metal salt, in particular as a sodium salt - is also used.
  • 2 to 5% by weight, preferably 2 to 3% by weight, of the N-methylol- (meth) acrylamides and their ethers are used.
  • N-Methylolacrylamide and N-Methylol-methacrylamide are preferred here.
  • the copolymer has a minimum film-forming temperature (MFT) of +5 to + 25 ° C, determined in accordance with DIN 53 787.
  • MFT minimum film-forming temperature
  • the incorporation of the fibers is beneficial, but the dirtiness of the floor covering bound with the dip version is very high.
  • the ability to be soiled is very low, but the strengthening of the nonwoven, ie the binding of the fibers, is insufficient.
  • the needle-punched non-woven floor covering is too stiff, so that it is no longer easy to install, especially in cool conditions after unwinding from the roll. Both properties are well balanced in the claimed temperature range, especially in the range of 10 to 20 ° C.
  • the copolymer dispersions are first mixed with finely divided antimony oxides suspended in water, the quantitative ratio of copolymers (solid) to the suspended antimony oxides usually being from 100 to 2 to 100 to 15, preferably from 100 to 5 to 100 to 10, is.
  • the antimony oxides are said to be finely divided; they usually have an average particle size of 5 to 50, preferably 10 to 20 nm.
  • the needle felt is treated with such a mixture, e.g. passed through or impregnated on the back and the treated needle felt then dried at elevated temperature, usually in the range from 100 to 150 ° C., preferably from 110 to 130 ° C., in a conventional manner.
  • the needled nonwovens used are the needled nonwovens that are customary for the production of needled nonwoven floor coverings, which usually have a thickness of 0.3 to 1.0 cm, a basis weight of 300 to 2000 g / m2 and needling of 100 to 500 / cm2. They generally consist of staple fibers made of polyamides or polypropylene with a staple length of 5 to 12 cm. Fiber inclusion, dirt resistance and appearance of the needled nonwoven floor coverings produced according to the invention are the often consider the corresponding properties of needle-punched non-woven floor coverings that have been consolidated with commercially available binders. In addition, the needled nonwoven floor coverings produced according to the invention are flame-retardant.
  • the combustibility of the bonded needle-punched non-woven floor coverings is determined in accordance with DIN 75 200 (the corresponding US regulation is MVSS 302). The speed at which a 250 mm long sample burns is measured. Flame retardant samples have a low burning rate.
  • the fiber integration is tested with the Lisson pedal test according to DIN draft 54 322.
  • DIN draft 54 322 In the case of needle-punched non-woven floor coverings made of polypropylene fibers, the corrugated profile of the pedal feet described in the DIN draft is used. In deviation from the DIN draft, needle-punched non-woven floor coverings made of polyamide fibers with the more aggressive pyramid profile were tested. The test is ended after 250 cycles of the bicycle. In deviation from the DIN draft, the surface is assessed optically, the change in the surface being compared with standards and graded. 1 means very good and 5 very bad.
  • the floor coverings are laid out in a busy corridor.
  • the pads are dry cleaned weekly with a vacuum cleaner.
  • the contamination is assessed after three weeks. It is graded by comparison with standards. The grade 1 means very good, the grade 5 very bad.
  • the surface of the binder can be damaged when rubbing a consolidated needle-punched non-woven floor covering with a metal pin. This can be seen from the bright lines that appear. This process is called "writing" and is particularly critical for polypropylene nonwovens. If no writing is observed, grade 1 (very good) is awarded. The grading scale ends at 5.
  • Example 1 and Comparative Examples A to D are intended to show that copolymers of vinylidene chloride and vinyl chloride behave more favorably in flame retardant finishes than those copolymers which each contain only one of these monomers in copolymerized form.
  • the aqueous dispersion is prepared in a pressure-resistant polymerization kettle with a volume of 50 l, equipped with a heating and cooling jacket, a blade stirrer, a feed kettle of 50 l content and a feed vessel of 4 l content.
  • the following are introduced as a template into the kettle: 10.0 kg of water, 0.08 kg of sodium peroxydisulfate, 0.1 kg of a 40% aqueous solution of the sodium salt of C14-paraffin sulfonic acid and 1.67 kg of feed I.
  • Feed I is an aqueous emulsion of 9.3 kg of water, 5 kg of vinylidene chloride, 5 kg of vinyl chloride, 9 kg of n-butyl acrylate, 0.6 kg of acrylic acid, 2.67 kg of a 15% strength aqueous solution of N-methylol methacrylamide, 0.4 kg of a 25% aqueous solution of the sodium salt of vinylsulfonic acid, 0.1 kg of sodium pyrophosphate and 0.01 kg of ascorbic acid, emulsified with 1.33 kg of a 45% aqueous solution of the sodium salt of C12-alkyl-diphenyl ether disulfonic acid.
  • Feed II is a solution of 0.1 kg sodium peroxydisulfate in 1 kg water.
  • the reaction vessel is heated to 70.degree. C. and feeds I and II, which are added within 4 hours, are started continuously at 45.degree.
  • the reaction mixture is then kept at 70 ° C. for a further 3 hours, flushed with nitrogen and cooled.
  • the solids content is 45.6%, the LD value 88%, the OSP 43.0 dyn / cm and the MFT 8 ° C.
  • the solids content of the copolymer dispersion is 44.8%, the LD value 81%, the OSP 43.8 dyn / cm and the MFT 8 ° C.
  • Example 2 The procedure is as in Example 1, but the vinyl chloride is replaced by the corresponding molar amount of additional vinylidene chloride.
  • the solids content of the copolymer dispersion is 46.0%, the LD value 92%, the OSP 40.0 dyn / cm and the MFT 10 ° C.
  • Example 2 The procedure is as given in Example 1, but vinylidene chloride is replaced by vinyl chloride with the same amount of chlorine.
  • the solids content of the copolymer dispersion is 45.5%, the LD value 76%, the OSP 40.0 dyn / cm and the MFT 25 ° C.
  • Example 2 The procedure is as in Example 1, but vinyl chloride is replaced by vinylidene chloride with the same amount of chlorine.
  • the solids content of the copolymer dispersion is 46.1%, the LD value 90%, the OSP 46.6 dyn / cm and the MFT ⁇ 2 ° C.
  • the procedure is as given in Example 1.
  • the template has the composition specified there, feed I, however, consists of 5.9 kg of water, 6 kg of vinylidene chloride, 2.6 kg of vinyl chloride, 10 kg of ethyl acrylate, 0.4 kg of methacrylamide and 6.67 kg of a 15% strength aqueous solution of N. -Methylol methacrylamide, 0.4 kg of a 25% aqueous solution of the sodium salt of vinyl sulfonic acid, 0.1 kg of sodium pyrophosphate and 0.01 kg of ascorbic acid emulsified with 1.33 kg of a 45% aqueous solution of the sodium salt of C12-alkyldiphenyl ether disulfonic acid.
  • Feed II has the same composition as in Example 1.
  • the solids content of the copolymer dispersion is 45.6%, the LD value 51%, the OSP 36.8 dynes / cm and the MFT 19 ° C.
  • Example 2 The procedure described in Example 1 is followed, but the following monomer mixture is used in feed I: 4 kg of vinylidene chloride, 4 kg of vinyl chloride, 11 kg of isobutyl acrylate, 0.5 kg of methacrylic acid and 1 kg of a 48% strength aqueous solution of N-methylolacrylamide.
  • the solids content of the copolymer dispersion is 45.0%, the LD value 89%, the OSP 50.3 dym / cm and the MFT 20 ° C.
  • the solids content of the copolymer dispersion is 45.7%, the LD value 92%, the OSP 45.6 dyn / cm and the MFT 18 ° C.
  • the template consists of 11.8 kg of water, 0.051 kg of sodium peroxydisulfate and 0.087 kg of a 35% strength aqueous solution of the sodium salt of the sulfuric acid half-ester of para-isooctylphenol reacted with 25 mol of ethylene oxide.
  • Feed I consists of 12.54 kg of water, 3.28 kg of vinylidene chloride, 3.28 kg of vinyl chloride, 6.56 kg of n-butyl acrylate, 6.56 kg of vinyl propionate, 0.308 kg of acrylic acid and 3.414 kg of a 15% aqueous solution of N- Methylol methacrylamide, emulsified with 1.365 kg of a 45% solution of the sodium salt of C12 alkyl diphenyl ether disulfonic acid.
  • Feed II consists of a solution of 0.133 kg sodium peroxydisulfate in 1.28 kg water.
  • the solids content is 42.4%, the LD value 91%, the OSP 43.1 dyn / cm and the MFT 5 ° C.
  • Comparative example E is a commercially available 50% aqueous dispersion of a copolymer of 40 parts of butadiene and 60 parts of styrene
  • comparative example F is a commercially available 40% dispersion of a copolymer mainly of butyl acrylate and acrylonitrile.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Artificial Filaments (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)

Abstract

Needle-bonded floor coverings are consolidated and flameproofed by treatment with mixtures of aqueous dispersions of copolymers which contain vinylidene chloride and vinyl chloride as copolymerised units and suspended finely divided antimony oxides and drying at elevated temperature.

Description

Es ist allgemein bekannt, daß man durch Zusätze von halogenhaltigen, organischen Substanzen eine Verminderung der Brennbarkeit von Substraten erreichen kann. Dabei ist Brom erheblich wirksamer als Chlor. Ferner ist der Synergismus zwischen Halogenverbindungen und Antimonoxid bekannt. In Gegenwart von Antimonoxid kann man die Menge an Halogenverbindungen drastisch reduzieren, um die gleiche flammwidrige Ausrüstung zu erreichen. Auch Phosphorverbindungen in Verbindung mit Halogenverbindungen werden häufig zu flammfesten Ausrüstungen, insbesondere bei Textilien, verwendet. Eine ausführliche Darstellung der chemischen Prozesse beim Brand, der Wirkung der verschiedenen Flammschutzmittel im Brenngeschehen und der flammwidrigen Ausrüstung verschiedener Substrate findet man in dem Buch von J.W. Lyons "The Chemistry and Uses of Fire Retardants", New York 1970.It is generally known that the flammability of substrates can be reduced by adding halogen-containing organic substances. Bromine is considerably more effective than chlorine. The synergism between halogen compounds and antimony oxide is also known. In the presence of antimony oxide, the amount of halogen compounds can be drastically reduced to achieve the same flame retardant finish. Phosphorus compounds in conjunction with halogen compounds are also frequently used for flame-retardant finishes, particularly in the case of textiles. A detailed description of the chemical processes during fire, the effect of the various flame retardants in the burning process and the flame-retardant finishing of various substrates can be found in the book by J.W. Lyon's "The Chemistry and Uses of Fire Retardants", New York 1970.

Für die Herstellung von schwer brennbaren Nadelvliesbodenbelägen bestehen zwei Möglichkeiten: Verwendung schwer brennbarer Fasern oder Ausrüsten von Vliesstoffen aus konventionellen organischen Fasern mit Flammschutzmitteln oder flammwidrigen Bindemitteln. Handelsübliche Bindemittel sind wäßrige Dispersionen auf Styrol-Butadien-Copolymerisat- oder Polyacrylat-Basis, wobei Bindemittel auf Basis von Butadien-Styrol-Copolymerisaten im allgemeinen weniger geeignet sind, wenn man Flammwidrigkeit anstrebt. Flammhemmende Zusatzstoffe sind meist organische Halogenverbindungen, organische Phosphorverbindungen und Antimontrioxid.There are two options for the manufacture of flame-retardant needle-punched non-woven floor coverings: Use of flame-retardant fibers or finishing nonwovens made from conventional organic fibers with flame retardants or flame retardant binders. Commercially available binders are aqueous dispersions based on styrene-butadiene copolymer or polyacrylate, but binders based on butadiene-styrene copolymers are generally less suitable if the aim is flame retardancy. Flame retardant additives are mostly organic halogen compounds, organic phosphorus compounds and antimony trioxide.

Die Ausrüstung und Verfestigung von Nadelvliesbodenbelägen erfolgt meist unter Vollbadimprägnierung der Vliese. Dabei wird die Dispersion verdünnt und das Nadelvlies in das Bad eingetaucht. Der Binderauftrag liegt im allgemeinen bei 20 bis 30 Gew.% (Feststoff), bezogen auf das Fasergewicht.The finishing and consolidation of needle-punched non-woven floor coverings is usually done with full bath impregnation of the nonwovens. The dispersion is diluted and the needle punch is immersed in the bath. The binder application is generally 20 to 30% by weight (solid), based on the weight of the fiber.

Flammschutzmittel-Zusätze zur Imprägnierflotte, z.B. organische Halogen-und/oder Phosphorverbindungen haben keine Bindewirkung. Ihre Zumischung zur Binderdisposition führt daher zu einer Einlagerung in das Bindemittel und damit zur Verminderung der Bindefestigkeit. Ist das Flamm­schutzmittel im Bindemittel löslich, so wird außerdem das Bindemittel durch den Zusatz klebriger gemacht und dadurch die Verschmutzungsneigung des gebundenen Vlieses erhöht.Flame retardant additives to the impregnation liquor, for example organic halogen and / or phosphorus compounds, have no binding effect. Adding them to binder disposition therefore leads to an incorporation in the binder and thus to a reduction in the binding strength. If the flame retardant is soluble in the binder, the binder is also made more sticky by the addition and the tendency towards contamination of the bonded nonwoven is increased.

Ist es im Bindemittel unlöslich, so führt sein im allgemeinen gegenüber dem Bindemittel unterschiedlicher Brechungsindex dazu, daß das Bindemittel nach dem Trocknen keinen klaren, transparenten, sondern - je nach Menge des Zusatzes und Schichtdicke - einen trüben bis undurchsichtigen Film bildet. Im Nadelvliesbodenbelag bewirkt dieser Effekt zumindest eine Beeinträchtigung der Brillanz, eine sogenannte Farbverschleierung. Diese kann im Prinzip dadurch vermieden werden, daß man Zusatzstoffe mit einer Korngröße verwendet, die wesentlich geringer ist als die Wellenlänge des sichtbaren Lichts. Derartig feinteilige Additive stehen aber kaum zur Verfügung.If it is insoluble in the binder, its refractive index, which differs from that of the binder in general, means that the binder does not form a clear, transparent film after drying, but - depending on the amount of additive and layer thickness - forms a cloudy to opaque film. In the needle-punched non-woven floor covering, this effect at least affects the brilliance, a so-called color veiling. In principle, this can be avoided by using additives with a grain size that is significantly less than the wavelength of visible light. Such fine-particle additives are hardly available.

Der dritte Nachteil fast aller gängigen halogenorganischen und mineralischen Flammschutzadditive ist ihr relativ hohes spezifisches Gewicht, das leicht zu ihrem Absetzen in der dünnflüssigen Imprägnier­flotte und zu ihrer Ablagerung auf dem Boden der Auftragswanne, in Behältern und Rohrleitungen führt.The third disadvantage of almost all common halogenated organic and mineral flame retardants is their relatively high specific weight, which easily leads to their settling in the low-viscosity impregnation liquor and to their deposition on the bottom of the application pan, in containers and pipelines.

Man hat daher schon Bindemittel verwendet, die Vinylchlorid einpolymerisiert enthalten. Ein gewisser Nachteil bei diesen Bindemitteln besteht darin, daß man mit Vinylchlorid nur relativ geringe Mengen Chlor in das Polymerisat bekommt ohne den Griff des gebundenen Vlieses zu stark zu versteifen. Copolymerisate aus Vinylchlorid und Acrylestern mit mehr als 60 bis 70 Gew.% Vinylchlorid lassen sich zudem bei Raumtemperatur nicht verfilmen. In dieser Hinsicht sind Copolymere aus Vinylidenchlorid und Acrylestern günstiger. Hier lassen sich große Mengen Chlor in das Polymerisat einbrigen, ohne daß Schwierigkeiten bei der Filmbildung auftreten. Allerdings wurde beobachtet, daß die Flammschutzwirkung nicht unbedingt mit steigender Vinylidenchloridmenge verbessert wird, da für das Brandverhalten nicht allein die Menge an Halogen von Bedeutung ist. Ferner steigt mit zunehmender Menge an Vinylidenchlorid die Neigung zur Vergilbung.Therefore, binders have been used which contain copolymerized vinyl chloride. A certain disadvantage with these binders is that only relatively small amounts of chlorine are obtained in the polymer with vinyl chloride without too much stiffening of the handle of the bound nonwoven. Copolymers of vinyl chloride and acrylic esters with more than 60 to 70% by weight of vinyl chloride also cannot be filmed at room temperature. In this regard, copolymers of vinylidene chloride and acrylic esters are cheaper. Here, large amounts of chlorine can be introduced into the polymer without difficulties in film formation. However, it was observed that the flame retardant effect does not necessarily improve with an increasing amount of vinylidene chloride, since it is not only the amount of halogen that is important for the fire behavior. Furthermore, the tendency to yellowing increases with an increasing amount of vinylidene chloride.

In der EP-A-0 180 868 sind Dispersionen von Copolymeren aus 10 bis 50 Gew.% Vinylidenchlorid beschrieben, die neben Acrylestern gegebenenfalls Vinylchlorid einpolymerisiert enthalten können. Die Dispersionen eignen sich als Bindemittel für Anstrichfarben und Putze. Als Bindemittel für Nadelvliesbodenbeläge sind sie ungeeignet, da es sich um unvernetzte und unvernetzbare Polymere handelt, die - sofern sie für diesen Verwendungszweck eine ausreichende Weichheit besitzen - zu einer untragbaren Schmutzanfälligkeit der Beläge beim Begehen führen würden. Durch Einpolymerisieren von vernetzend wirkenden Comonomeren, wie z.B. N-Methylol-(meth)-acrylamide, kann zudem, wie in DE 1 086 208 oder DE-AS 1 047 431 gezeigt wurde, die Reinigungsbeständigkeit von Vliesstoffen erheblich verbessert werden.EP-A-0 180 868 describes dispersions of copolymers of 10 to 50% by weight of vinylidene chloride which, in addition to acrylic esters, can optionally contain vinyl chloride in copolymerized form. The dispersions are suitable as binders for paints and plasters. They are unsuitable as binders for needle-punched non-woven floor coverings because they are uncrosslinked and uncrosslinkable polymers which - if they have sufficient softness for this purpose - would lead to an unbearable susceptibility to dirt on the coverings when they were walked on. By polymerizing crosslinking comonomers, such as N-methylol (meth) acrylamides, the cleaning resistance of nonwovens can also be considerably improved, as was shown in DE 1 086 208 or DE-AS 1 047 431.

Aus der GB-PS 1 054 877 ist es bekannt, schwer entflammbare, gebundene Faservliese unter Verwendung eines Bindemittelgemisches herzustellen, das, bezogen auf die Fasern, 20 bis 200 Gew.% Polymerisate auf Basis von Acrylsäureestern und/oder Butadien, 15 bis 150 Gew.% von wenigstens 80 % ihres Gewichts Vinylidenchlorid einpolymerisiert enthaltenden Misch­polymerisaten und 15 bis 150 Gew.% Antimontrioxid enthalten. Die dabei nicht als Bindemittel wirkenden Vinylidenchloridpolymerisate können bevorzugt in Pulverform eingesetzt sein. Solche Mischungen sind ungeeignet zur Herstellung von Nadelvliesbodenbelägen nach dem Verfahren der Vollbadimprägnierung. Sowohl die pulverförmigen chlorhaltigen Flammschutz­mittel als auch Antimontrioxid beeinträchtigen das Aussehen des Nadelvliesbodenbelags. Er zeigt eine Farbverschleierung von grau bis weiß, je nach zugesetzter Menge. Außerdem wird die Bindekraft durch die festen Zusätze erheblich beeinträchtigt.From GB-PS 1 054 877 it is known to produce flame-retardant, bonded nonwovens using a binder mixture which, based on the fibers, 20 to 200% by weight of polymers based on acrylic acid esters and / or butadiene, 15 to 150% by weight % of at least 80% of their weight of copolymerized vinylidene chloride-containing copolymers and 15 to 150% by weight of antimony trioxide. The vinylidene chloride polymers which do not act as binders can preferably be used in powder form. Such mixtures are unsuitable for the production of needle-punched non-woven floor coverings using the full bath impregnation method. Both the powdered chlorine-containing flame retardants and antimony trioxide impair the appearance of the needle-punched non-woven floor covering. It shows a color veil from gray to white, depending on the amount added. In addition, the binding power is significantly affected by the solid additives.

Außerdem sind aus der US-PS 3 787 232 vernetzbare Bindemittel für die Verfestigung von Vliesstoffen und zur Ausrüstung von Textilien und Papier bekannt, die Vinylchlorid und/oder Vinylidenchlorid einpolymerisiert enthalten. Dabei werden, wie aus den Beispielen hervorgeht, Copolymere die allein Vinylchlorid einpolymerisiert enthalten, vorgezogen, wenngleich drei der Beispiele wäßrige Dispersionen von Copolymeren aus Vinylchlorid und Vinylidenchlorid betreffen. Diese Dispersionen (Beispiele III, E, F und O) sind jedoch nicht als Bindemittel für Faservliese geeignet, da diese Mischpolymerisate bei Raumtemperatur zu steif sind und die Dipersionen bei Raumtemperatur keinen zusammenhängenden Film bilden. Die Mindest-Filmbilde-Temperatur (MFT) der Dispersionen III, E, F, und O, bestimmt nach DIN 53 787, betragen:
Beispiel 3,E MFT: 39°C,
Beispiel 3,F MFT: 30°C und
Beispiel 3,O MFT: über 50°C.In addition, US Pat. No. 3,787,232 crosslinkable binders for the consolidation of nonwovens and for finishing textiles and paper are known which contain copolymerized vinyl chloride and / or vinylidene chloride. As can be seen from the examples, copolymers which alone contain copolymerized vinyl chloride are preferred, although three of the examples relate to aqueous dispersions of copolymers of vinyl chloride and vinylidene chloride. However, these dispersions (Examples III, E, F and O) are not suitable as binders for nonwoven fabrics, since these copolymers are too stiff at room temperature and the dispersions do not form a coherent film at room temperature. The minimum film formation temperature (MFT) of dispersions III, E, F, and O, determined in accordance with DIN 53 787, is:
Example 3, E MFT: 39 ° C,
Example 3, F MFT: 30 ° C and
Example 3, O MFT: over 50 ° C.

Es wurde nun gefunden, daß man Nadelvliesbodenbeläge mit Vorteil herstellen kann, indem man Nadelvliese mit wäßrigen Dispersionen von Copolymeren einer Mindest-Filmbilde-Temperatur von 5 bis 25°C aus
15 bis 35 % ihres Gewichts Vinylidenchlorid
10 bis 45 % ihres Gewichts Vinylchlorid
8 bis 72 % ihres Gewichts Estern der (Meth)Acrylsäure mit 1 bis 12 C-Atome enthaltenden Alkanolen oder gegebenenfalls Vinyl­estern 2 bis 3 C-Atome enthaltender aliphatischer Carbonsäuren oder Gemische dieser Monomerer
1 bis 7 % ihres Gewichts α,β-monoolefinisch ungesättigten 3 bis 5 C-Atome enthaltende Mono- und/oder Dicarbonsäuren und/oder deren Amide
2 bis 5 % ihres Gewichts N-Methylol-(meth)acrylamid und/oder deren Alkylether mit 1 bis 4 C-Atomen in den Alkylgruppen,
0 bis 3 % ihres Gewichts Vinylsulfonsäure
im Gemisch mit suspendierten feinteiligen Antimonoxiden behandelt und dann bei erhöhter Temperatur trocknet.It has now been found that needle-punched nonwoven floor coverings can advantageously be produced by making needle-punched nonwovens with aqueous dispersions of copolymers with a minimum film-forming temperature of 5 to 25 ° C.
15 to 35% of their weight vinylidene chloride
10 to 45% of their weight vinyl chloride
8 to 72% of their weight esters of (meth) acrylic acid with alkanols containing 1 to 12 carbon atoms or optionally vinyl esters containing aliphatic carboxylic acids or mixtures of these monomers with 2 to 3 carbon atoms
1 to 7% of their weight of α, β-monoolefinically unsaturated mono- and / or dicarboxylic acids containing 3 to 5 carbon atoms and / or their amides
2 to 5% of their weight of N-methylol- (meth) acrylamide and / or their alkyl ethers with 1 to 4 carbon atoms in the alkyl groups,
0 to 3% of their weight vinyl sulfonic acid
treated in a mixture with suspended fine-particle antimony oxides and then dried at elevated temperature.

Die wäßrigen Copolymer-Dispersionen können nach bekannten Verfahren der Emulsionspolymerisation z.B. mit Emulsionszulauf der Monomeren im geschlossenen Druckkessel in an sich üblicher Weise hergestellt sein. Ihre Herstellung ist nicht Gegenstand dieser Erfindung. Es können die üblichen wasserlöslichen, radikalbildenden Polymerisationsinitiatoren, wie Alkalipersulfate, vorteilhaft in Kombination mit wasserlöslichen Reduktionsmitteln, wie Formaldehydsulfoxylat oder Natriumpyrosulfit, verwendet werden.The aqueous copolymer dispersions can be prepared by known methods of emulsion polymerization e.g. be prepared with the emulsion feed of the monomers in a closed pressure vessel in a conventional manner. Their manufacture is not the subject of this invention. The usual water-soluble, radical-forming polymerization initiators, such as alkali persulfates, can advantageously be used in combination with water-soluble reducing agents, such as formaldehyde sulfoxylate or sodium pyrosulfite.

Als Emulgiermittel können alle für die Emulsionspolymerisation üblichen anionischen und nichtionischen Emulgatoren verwendet worden sein. Dabei enthalten die Copolymer-Dispersionen vorzugsweise eine Emulgatormenge von nur 2 bis 4 Gew.%, bezogen auf die Copolymeren, und ihr LD-Wert liegt vorzugsweise über 70 %, wobei die Oberflächenspannung vorzugsweise im Bereich von 35 bis 55 dyn/cm liegt. Als Emulgatoren für die als Bindemittel eingesetzten Copolymer-Dispersionen werden Disulfonate allein oder zusammen mit anderen üblichen anionischen und/oder nichtionischen Emulgatoren bevorzugt. Damit hergestellte Copolymer-Dispersionen sind koagulatfrei, feinteilig und scherstabil und haben eine verhältnismäßig hohe Oberflächenspannung im Bereich von 40 bis 50 dyn/cm. Als bevorzugte Disulfonate seinen die Natriumsalze von Paraffindisulfonsäure und Alkyl-­Diphenyletherdisulfonsäure genannt.All anionic and nonionic emulsifiers customary for emulsion polymerization can be used as emulsifiers. The copolymer dispersions preferably contain an amount of emulsifier of only 2 to 4% by weight, based on the copolymers, and their LD value is preferably above 70%, the surface tension preferably being in the range from 35 to 55 dynes / cm. Preferred emulsifiers for the copolymer dispersions used as binders are disulfonates, alone or together with other customary anionic and / or nonionic emulsifiers. Copolymer dispersions produced in this way are coagulate-free, finely divided and shear-stable and have a relatively high surface tension in the range from 40 to 50 dynes / cm. The sodium salts of paraffin disulfonic acid and alkyl diphenyl ether disulfonic acid are mentioned as preferred disulfonates.

Die Menge an Vinylidenchlorid beträgt 15 bis 35 Gew.%, diejenige an Vinyl­chlorid 10 bis 45 Gew.%. Erst die Kombination von beiden chlorhaltigen Monomeren gibt das gewünschte flammwidrige Verhalten. Die Menge an Estern der Acrylsäure beträgt 8 bis 72 Gew.%, wobei Ethyl-, Butyl- und 2-Ethyl­hexylacrylat besonders bevorzugt sind. Bei den Vinylestern sind Vinyl­acetat und Vinylpropionat von besonderem Interesse. Ferner geeignet sind Ester der Methacrylsäure mit 1 bis 4 C-Atome enthaltenden Alkanolen. Die Menge an ungesättigten Mono- und/oder Dicarbonsäuren und/oder deren Amiden beträgt 1 bis 7 Gew.% vorzugsweise 3 bis 5 Gew.%. Hier sind Acrylsäure, Methacrylsäure, Acrylamid und Methacrylamid sowie Itaconsäure und deren Mono- und Diamide von besonderer Bedeutung. Häufig ist es zur Verbesserung der Stabilität der wäßrigen Dispersion vorteilhaft, wenn bis zu 3 Gew.% Vinylsulfonsäure - meist als Alkali-, insbesondere als Natrium-Salz - mitverwendet werden. Von den N-Methylol-(meth)acrylamiden und deren Ethern werden 2 bis 5 Gew.%, vorzugsweise 2 bis 3 Gew.%, eingesetzt. Hier werden N-Methylolacrylamid und N-Methylol-methacrylamid bevorzugt. Wichtig für die Gebrauchseigenschaften des Nadelvliesbodenbelages ist, daß das Mischpolymerisat eine Mindest-Filmbilde-Temperatur (MFT) bestimmt nach DIN 53 787 von +5 bis +25°C aufweist. Bei tieferen Mindest-Filmbilde-Temperaturen ist zwar die Einbindung der Fasern günstig, jedoch ist die Anschmutzbarkeit des mit der Dipsersion gebundenen Bodenbelags sehr hoch. Bei höheren Mindest-Filmbilde-Temperaturen des Mischpolymerisates ist zwar die Anschmutzbarkeit sehr gering, dafür ist aber die Verfestigung des Vliesstoffes, d.h. die Bindung der Fasern, unzureichend. Ferner ist der Nadelvliesbodenbelag zu steif, so daß er besonders unter kühlen Bedingungen nach dem Abwickeln von der Rolle nicht mehr leicht zu verlegen ist. Im beanspruchten Temperaturbereich sind beide Eigenschaften gut ausgewogen, insbesondere im Bereich von 10 bis 20°C.The amount of vinylidene chloride is 15 to 35% by weight, that of vinyl chloride 10 to 45% by weight. Only the combination of both chlorine-containing monomers gives the desired flame-retardant behavior. The amount of esters of acrylic acid is 8 to 72% by weight, with ethyl, butyl and 2-ethylhexyl acrylate being particularly preferred. In the case of vinyl esters, vinyl acetate and vinyl propionate are of particular interest. Also suitable are esters of methacrylic acid with alkanols containing 1 to 4 carbon atoms. The amount of unsaturated mono- and / or dicarboxylic acids and / or their amides is 1 to 7% by weight, preferably 3 to 5% by weight. Here are acrylic acid, methacrylic acid, acrylamide and methacrylamide as well as itaconic acid and their Mono- and diamides of particular importance. To improve the stability of the aqueous dispersion, it is often advantageous if up to 3% by weight of vinylsulfonic acid - mostly as an alkali metal salt, in particular as a sodium salt - is also used. 2 to 5% by weight, preferably 2 to 3% by weight, of the N-methylol- (meth) acrylamides and their ethers are used. N-Methylolacrylamide and N-Methylol-methacrylamide are preferred here. It is important for the performance properties of the needle-punched non-woven floor covering that the copolymer has a minimum film-forming temperature (MFT) of +5 to + 25 ° C, determined in accordance with DIN 53 787. At lower minimum film-forming temperatures, the incorporation of the fibers is beneficial, but the dirtiness of the floor covering bound with the dip version is very high. At higher minimum film-forming temperatures of the copolymer, the ability to be soiled is very low, but the strengthening of the nonwoven, ie the binding of the fibers, is insufficient. Furthermore, the needle-punched non-woven floor covering is too stiff, so that it is no longer easy to install, especially in cool conditions after unwinding from the roll. Both properties are well balanced in the claimed temperature range, especially in the range of 10 to 20 ° C.

Zum Behandeln der Nadelvliese werden die Copolymer-Dispersionen zunächst mit in Wasser suspendierten feinteiligen Antimonoxiden gemischt, wobei das Mengenverhältnis von Copolymeren (fest) zu den suspendierten Antimonoxiden meist von 100 zu 2 bis 100 zu 15, vorzugsweise von 100 zu 5 bis 100 zu 10, beträgt. Die Antimonoxide sollen feinteilig sein; sie haben meist eine mittlere Teilchengröße von 5 bis 50, vorzugsweise von 10 bis 20 nm. Von besonderem Interesse ist Sb₂O₅ einer mittleren Teilchengröße im Bereich von 10 bis 20 nm, wie es z.B. als handelsübliche wäßrige Sb₂O₅-Suspension (®Nyacol A 1530 (® = eingetragenes Warenzeichen)) einer mittleren Teilchengröße (Teilchendurchmesser) von 14 bis 15 nm zur Verfügung steht. Mit einem derartigen Gemisch wird das Nadelvlies behandelt, z.B. hindurchgeführt oder rückseitig imprägniert und das behandelte Nadelvlies dann bei erhöhter Temperatur, meist im Bereich von 100 bis 150°C, vorzugsweise von 110 bis 130°C, in an sich üblicher Weise getrocknet.To treat the needled nonwovens, the copolymer dispersions are first mixed with finely divided antimony oxides suspended in water, the quantitative ratio of copolymers (solid) to the suspended antimony oxides usually being from 100 to 2 to 100 to 15, preferably from 100 to 5 to 100 to 10, is. The antimony oxides are said to be finely divided; they usually have an average particle size of 5 to 50, preferably 10 to 20 nm. Of particular interest is Sb₂O₅ an average particle size in the range of 10 to 20 nm, as e.g. is available as a commercially available aqueous Sb₂O₅ suspension (®Nyacol A 1530 (® = registered trademark)) with an average particle size (particle diameter) of 14 to 15 nm. The needle felt is treated with such a mixture, e.g. passed through or impregnated on the back and the treated needle felt then dried at elevated temperature, usually in the range from 100 to 150 ° C., preferably from 110 to 130 ° C., in a conventional manner.

Als Nadelvliese werden bei dem neuen Verfahren die für die Herstellung von Nadelvlies-Bodenbelägen üblichen genadelten Vliese eingesetzt, die meist eine Dicke von 0,3 bis 1,0 cm, ein Flächengewicht von 300 bis 2000 g/m² und eine Nadelung von 100 bis 500/cm² aufweisen. Sie bestehen im all­gemeinen aus Stapelfasern aus Polyamiden oder Polypropylen mit einer Stapellänge von 5 bis 12 cm. Fasereinbindung, Schmutzresistenz und Aussehen der erfindungsgemäß herstellten Nadelvliesbodenbeläge sind den entsprechenden Eigenschaften von Nadelvliesbodenbelägen, die mit handelsüblichen Bindemitteln verfestigt wurden, oft überlegen. Darüber hinaus sind die erfindungsgemäß herstellten Nadelvliesbodenbeläge flammwidrig.In the new process, the needled nonwovens used are the needled nonwovens that are customary for the production of needled nonwoven floor coverings, which usually have a thickness of 0.3 to 1.0 cm, a basis weight of 300 to 2000 g / m² and needling of 100 to 500 / cm². They generally consist of staple fibers made of polyamides or polypropylene with a staple length of 5 to 12 cm. Fiber inclusion, dirt resistance and appearance of the needled nonwoven floor coverings produced according to the invention are the often consider the corresponding properties of needle-punched non-woven floor coverings that have been consolidated with commercially available binders. In addition, the needled nonwoven floor coverings produced according to the invention are flame-retardant.

Zur Prüfung der Eigenschaften der erfindungsgemäß verfestigten Nadelvlies­bodenbeläge wurden folgende Untersuchungen durchgeführt:The following tests were carried out to test the properties of the needled nonwoven floor coverings consolidated according to the invention:

Die Brennbarkeit der gebundenen Nadelvliesbodenbeläge wird nach DIN 75 200 bestimmt (die entsprechende US-Vorschrift ist die MVSS 302). Dabei wird die Geschwindigkeit gemessen, in der eine 250 mm lange Probe abbrennt. Flammwidrig ausgerüstete Proben haben eine niedrige Brenngeschwindigkeit.The combustibility of the bonded needle-punched non-woven floor coverings is determined in accordance with DIN 75 200 (the corresponding US regulation is MVSS 302). The speed at which a 250 mm long sample burns is measured. Flame retardant samples have a low burning rate.

Die Fasereinbindung wird mit dem Tretradversuch nach Lisson gemäß dem DIN-Entwurf 54 322 geprüft. Bei Nadelvliesbodenbelägen aus Polypropylen­fasern wird das in dem DIN-Entwurf beschriebene Wellenprofil der Tretradfüße verwendet. Abweichend von dem DIN-Entwurf wurden Nadelvlies­bodenbeläge aus Polyamidfasern mit dem aggresiveren Pyramidenprofil geprüft. Nach 250 Hin- und Hergängen des Tretrades wird die Prüfung beendet. Abweichend von dem DIN-Entwurf erfolgt die Beurteilung der Oberfläche optisch, wobei die Veränderung der Oberfläche mit Standards verglichen und benotet wird. Dabei bedeutet 1 sehr gut und 5 sehr schlecht.The fiber integration is tested with the Lisson pedal test according to DIN draft 54 322. In the case of needle-punched non-woven floor coverings made of polypropylene fibers, the corrugated profile of the pedal feet described in the DIN draft is used. In deviation from the DIN draft, needle-punched non-woven floor coverings made of polyamide fibers with the more aggressive pyramid profile were tested. The test is ended after 250 cycles of the bicycle. In deviation from the DIN draft, the surface is assessed optically, the change in the surface being compared with standards and graded. 1 means very good and 5 very bad.

Um die Anschmutzbarkeit zu prüfen, werden die Bodenbeläge in einem viel begangenen Korridor ausgelegt. Die Beläge werden wöchentlich mit dem Staubsauger trocken gereinigt. Nach drei Wochen wird die Verschmutzung beurteillt. Es erfolgt eine Benotung durch Vergleich mit Standards. Die Note 1 bedeutet sehr gut, die Note 5 sehr schlecht.In order to check the dirtiness, the floor coverings are laid out in a busy corridor. The pads are dry cleaned weekly with a vacuum cleaner. The contamination is assessed after three weeks. It is graded by comparison with standards. The grade 1 means very good, the grade 5 very bad.

An einem in Brillant-tiefblau gefärbten Nadelvliesbodenbelag wird beurteilt, ob durch die Vollbadimprägnierung ein Grauschleier entstanden ist. Kann kein Grauschleier festgestellt werden, wird die Note 1 gleich sehr gut, vergeben. Die Notenskala reicht bis 3.It is assessed on a needle-felt floor covering colored in brilliant deep blue whether a gray haze has arisen as a result of the full bath impregnation. If no gray veil can be found, the grade 1 is awarded very well. The grading scale extends to 3.

Beim Reiben eines verfestigten Nadelvliesbodenbelags mit einem Metallstift kann der Binder an der Oberfläche beschädigt werden. Erkennbar wird dies an entstehenden hellen Strichen. Dieser Vorgang wird als "Schreiben" bezeichnet und ist besonders kritisch bei Vliesen aus Polypropylen. Wird kein Schreiben beobachtet, so wird die Note 1 (sehr gut) vergeben. Die Notenskala endet mit 5.The surface of the binder can be damaged when rubbing a consolidated needle-punched non-woven floor covering with a metal pin. This can be seen from the bright lines that appear. This process is called "writing" and is particularly critical for polypropylene nonwovens. If no writing is observed, grade 1 (very good) is awarded. The grading scale ends at 5.

Beispiel 1 und die Vergleichsbeispiele A bis D sollen zeigen, daß Copolymere aus Vinylidenchlorid und Vinylchlorid in der Flammfest­ausrüstung sich günstiger verhalten als solche Copolymere, die jeweils nur eines dieser Monomeren einpolymerisiert enthalten.Example 1 and Comparative Examples A to D are intended to show that copolymers of vinylidene chloride and vinyl chloride behave more favorably in flame retardant finishes than those copolymers which each contain only one of these monomers in copolymerized form.

Beispiel 1example 1

Die Herstellung der wäßrigen Dispersion erfolgt in einem druckfesten Polymerisationskessel mit einem Volumen von 50 l, ausgerüstet mit Heiz- und Kühlmantel, einem Blattrührer, einem Zulaufkessel von 50 l Inhalt und einem Zulaufgefäß von 4 l Inhalt. In den Kessel werden als Vorlage eingebracht: 10,0 kg Wasser, 0,08 kg Natriumperoxidisulfat, 0,1 kg einer 40 %igen wäßrigen Lösung des Natriumsalzes von C₁₄-Paraffinsulfon­säure und 1,67 kg von Zulauf I.The aqueous dispersion is prepared in a pressure-resistant polymerization kettle with a volume of 50 l, equipped with a heating and cooling jacket, a blade stirrer, a feed kettle of 50 l content and a feed vessel of 4 l content. The following are introduced as a template into the kettle: 10.0 kg of water, 0.08 kg of sodium peroxydisulfate, 0.1 kg of a 40% aqueous solution of the sodium salt of C₁₄-paraffin sulfonic acid and 1.67 kg of feed I.

Zulauf I ist eine wäßrige Emulsion aus 9,3 kg Wasser, 5 kg Vinylidenchlorid, 5 kg Vinylchlorid, 9 kg n-Butylacrylat 0,6 kg Acrylsäure, 2,67 kg einer 15 %igen wäßrigen Lösung von N-Methylolmethacrylamid, 0,4 kg einer 25-%igen wäßrigen Lösung des Natriumsalzes der Vinylsulfonsäure, 0,1 kg Natriumpyrophosphat und 0,01 kg Ascorbinsäure, emulgiert mit 1,33 kg einer 45 %igen wäßrigen Lösung des Natriumsalzes von C₁₂-Alkyl-Diphenyletherdisulfonsäure.Feed I is an aqueous emulsion of 9.3 kg of water, 5 kg of vinylidene chloride, 5 kg of vinyl chloride, 9 kg of n-butyl acrylate, 0.6 kg of acrylic acid, 2.67 kg of a 15% strength aqueous solution of N-methylol methacrylamide, 0.4 kg of a 25% aqueous solution of the sodium salt of vinylsulfonic acid, 0.1 kg of sodium pyrophosphate and 0.01 kg of ascorbic acid, emulsified with 1.33 kg of a 45% aqueous solution of the sodium salt of C₁₂-alkyl-diphenyl ether disulfonic acid.

Zulauf II ist eine Lösung von 0,1 kg Natriumperoxidisulfat in 1 kg Wasser.Feed II is a solution of 0.1 kg sodium peroxydisulfate in 1 kg water.

Man heizt das Reaktionsgefäß auf 70°C auf und beginnt bei 45°C mit dem kontinuierlichen Zuführen der Zuläufe I und II, die innerhalb von 4 Stunden zugegeben werden. Anschließend wird das Reaktionsgemisch weitere 3 Stunden auf 70°C gehalten, mit Stickstoff gespült und gekühlt. Der Feststoffgehalt beträgt 45,6 %, der LD-Wert 88 %, die OSP 43,0 dyn/cm und die MFT 8°C.The reaction vessel is heated to 70.degree. C. and feeds I and II, which are added within 4 hours, are started continuously at 45.degree. The reaction mixture is then kept at 70 ° C. for a further 3 hours, flushed with nitrogen and cooled. The solids content is 45.6%, the LD value 88%, the OSP 43.0 dyn / cm and the MFT 8 ° C.

Vergleichsbeispiel AComparative Example A

Es wird wie in Beispiel 1 angegeben gearbeitet, jedoch Vinylidenchlorid durch die entsprechende molare Menge an zusätzlichem Vinylchlorid ersetzt.The procedure is as given in Example 1, but vinylidene chloride is replaced by the corresponding molar amount of additional vinyl chloride.

Der Feststoffgehalt der Copolymer-Dispersion beträgt 44,8 %, der LD-Wert 81%, die OSP 43,8 dyn/cm und die MFT 8°C.The solids content of the copolymer dispersion is 44.8%, the LD value 81%, the OSP 43.8 dyn / cm and the MFT 8 ° C.

Vergleichsbeispiel BComparative Example B

Man arbeitet wie in Beispiel 1 angegeben, ersetzt jedoch das Vinylchlorid durch die entsprechende molare Menge an zusätzlichem Vinylidenchlorid. Der Feststoffgehalt der Copolymer-Dispersion beträgt 46,0 %, der LD-Wert 92 %, die OSP 40,0 dyn/cm und die MFT 10°C.The procedure is as in Example 1, but the vinyl chloride is replaced by the corresponding molar amount of additional vinylidene chloride. The solids content of the copolymer dispersion is 46.0%, the LD value 92%, the OSP 40.0 dyn / cm and the MFT 10 ° C.

Vergleichsbeispiel CComparative Example C

Man arbeitet wie in Beispiel 1 angegeben, ersetzt jedoch bei gleicher Chlormenge Vinylidenchlorid durch Vinylchlorid. Der Feststoffgehalt der Copolymer-Dispersion beträgt 45,5 %, der LD-Wert 76 %, die OSP 40,0 dyn/cm und die MFT 25°C.The procedure is as given in Example 1, but vinylidene chloride is replaced by vinyl chloride with the same amount of chlorine. The solids content of the copolymer dispersion is 45.5%, the LD value 76%, the OSP 40.0 dyn / cm and the MFT 25 ° C.

Vergleichsbeispiel DComparative Example D

Man arbeitet wie in Beispiel 1 angegeben, ersetzt jedoch bei gleicher Chlormenge Vinylchlorid durch Vinylidenchlorid. Der Feststoffgehalt der Copolymer-Dispersion beträgt 46,1 %, der LD-Wert 90 %, die OSP 46,6 dyn/cm und die MFT <2°C.The procedure is as in Example 1, but vinyl chloride is replaced by vinylidene chloride with the same amount of chlorine. The solids content of the copolymer dispersion is 46.1%, the LD value 90%, the OSP 46.6 dyn / cm and the MFT <2 ° C.

Alle Dispersionen werden mit 8 Gew.% (fest/fest) einer handelsüblichen wäßrigen Sb₂O₅-Suspension (mittlere Teilchengröße 14 bis 15 nm) gemischt und mit dem Gemisch ein 6 mm dickes Nadelvlies aus Polyamid behandelt unter Hindurchführen des Vlieses und Abquetschen. Die so behandelten Vlieses werden 0,5 Stunden bei 120°C getrocknet und dann ihre Brennbarkeit nach DIN 75 200 bestimmt. Die Ergebnisse der Brennversuche zeigt Tabelle 1.All dispersions are mixed with 8% by weight (solid / solid) of a commercially available aqueous Sb₂O₅ suspension (average particle size 14 to 15 nm) and treated with the mixture a 6 mm thick non-woven fabric made of polyamide while passing the fleece and squeezing. The fleece treated in this way is dried at 120 ° C. for 0.5 hours and then its flammability is determined in accordance with DIN 75 200. The results of the burning tests are shown in Table 1.

Beispiel 2Example 2

Man arbeitet wie in Beispiel 1 angegeben. Die Vorlage hat die dort angegebene Zusammensetzung, Zulauf I hingegen besteht aus 5,9 kg Wasser, 6 kg Vinylidenchlorid, 2,6 kg Vinylchlorid, 10 kg Ethylacrylat, 0,4 kg Methacrylamid 6,67 kg einer 15 %igen wäßrigen Lösung von N-Methylolmethacrylamid, 0,4 kg einer 25 %igen wäßrigen Lösung des Natriumsalzes der Vinylsulfonsäure, 0,1 kg Natriumpyrophosphat und 0,01 kg Ascorbinsäure emulgiert mit 1,33 kg einer 45 %igen wäßrigen Lösung des Natriumsalzes von C₁₂-Alkyldiphenyletherdisulfonsäure. Zulauf II hat die gleiche Zusammensetzung wie in Beispiel 1. Der Feststoffgehalt der Copolymer-Dispersion beträgt 45,6 %, der LD-Wert 51 %, die OSP 36,8 dyn/cm und die MFT 19°C.The procedure is as given in Example 1. The template has the composition specified there, feed I, however, consists of 5.9 kg of water, 6 kg of vinylidene chloride, 2.6 kg of vinyl chloride, 10 kg of ethyl acrylate, 0.4 kg of methacrylamide and 6.67 kg of a 15% strength aqueous solution of N. -Methylol methacrylamide, 0.4 kg of a 25% aqueous solution of the sodium salt of vinyl sulfonic acid, 0.1 kg of sodium pyrophosphate and 0.01 kg of ascorbic acid emulsified with 1.33 kg of a 45% aqueous solution of the sodium salt of C₁₂-alkyldiphenyl ether disulfonic acid. Feed II has the same composition as in Example 1. The solids content of the copolymer dispersion is 45.6%, the LD value 51%, the OSP 36.8 dynes / cm and the MFT 19 ° C.

Beispiel 3Example 3

Man arbeitet wie in Beispiel 1 angegeben, setzt jedoch bei Zulauf I folgende Monomerenmischung ein: 4 kg Vinylidenchlorid, 4 kg Vinylchlorid, 11 kg iso-Butylacrylat, 0,5 kg Methacrylsäure und 1 kg einer 48 %igen wäßrigen Lösung von N-Methylolacrylamid. Der Festgehalt der Copolymer-Dispersion beträgt 45,0 %, der LD-Wert 89 %, die OSP 50,3 dym/cm und die MFT 20°C.The procedure described in Example 1 is followed, but the following monomer mixture is used in feed I: 4 kg of vinylidene chloride, 4 kg of vinyl chloride, 11 kg of isobutyl acrylate, 0.5 kg of methacrylic acid and 1 kg of a 48% strength aqueous solution of N-methylolacrylamide. The solids content of the copolymer dispersion is 45.0%, the LD value 89%, the OSP 50.3 dym / cm and the MFT 20 ° C.

Beispiel 4Example 4

Man arbeitet wie in Beispiel 1 angegeben, setzt jedoch bei Zulauf I folgende Monomerenmischung ein: 4 kg Vinylidenchlorid, 9 kg Vinylchlorid, 6 kg 2-Ethylhexylacrylat, 0,2 kg Acrylamid, 0,4 kg Acrylsäure und 2,67 kg einer 15 %igen wäßrigen N-Methylolmethacrylamid-Lösung.The procedure is as described in Example 1, but the following monomer mixture is used in feed I: 4 kg of vinylidene chloride, 9 kg of vinyl chloride, 6 kg of 2-ethylhexyl acrylate, 0.2 kg of acrylamide, 0.4 kg of acrylic acid and 2.67 kg of a 15% aqueous N-methylol methacrylamide solution.

Der Feststoffgehalt der Copolymer-Dispersion beträgt 45,7 %, der LD-Wert 92 %, die OSP 45,6 dyn/cm und die MFT 18°C.The solids content of the copolymer dispersion is 45.7%, the LD value 92%, the OSP 45.6 dyn / cm and the MFT 18 ° C.

Beispiel 5Example 5

Man arbeitet wie in Beispiel 1 angegeben. Die Vorlage besteht jedoch aus 11,8 kg Wasser, 0,051 kg Natriumperoxidisulfat und 0,087 kg einer 35 %igen wäßrigen Lösung des Natriumsalzes des Schwefelsäurehalbesters von mit 25 Mol Ethylenoxid umgesetztem para-Isooctylphenol. Zulauf I besteht aus 12,54 kg Wasser, 3,28 kg Vinylidenchlorid, 3,28 kg Vinylchlorid, 6,56 kg n-Butylacrylat 6,56 kg Vinylpropionat, 0,308 kg Acrylsäure und 3,414 kg einer 15 %igen wäßrigen Lösung von N-Methylolmethacrylamid, emulgiert mit 1,365 kg einer 45 %igen Lösung des Natriumsalzes von C₁₂-Alkyldiphenyl­etherdisulfonsäure. Zulauf II besteht aus einer Lösung von 0,133 kg Natriumperoxidisulfat in 1,28 kg Wasser.The procedure is as given in Example 1. However, the template consists of 11.8 kg of water, 0.051 kg of sodium peroxydisulfate and 0.087 kg of a 35% strength aqueous solution of the sodium salt of the sulfuric acid half-ester of para-isooctylphenol reacted with 25 mol of ethylene oxide. Feed I consists of 12.54 kg of water, 3.28 kg of vinylidene chloride, 3.28 kg of vinyl chloride, 6.56 kg of n-butyl acrylate, 6.56 kg of vinyl propionate, 0.308 kg of acrylic acid and 3.414 kg of a 15% aqueous solution of N- Methylol methacrylamide, emulsified with 1.365 kg of a 45% solution of the sodium salt of C₁₂ alkyl diphenyl ether disulfonic acid. Feed II consists of a solution of 0.133 kg sodium peroxydisulfate in 1.28 kg water.

Der Feststoffgehalt beträgt 42,4 %, der LD-Wert 91 %, die OSP 43,1 dyn/cm und die MFT 5°C.The solids content is 42.4%, the LD value 91%, the OSP 43.1 dyn / cm and the MFT 5 ° C.

Das Ergebnis der Brennversuche und die Beurteilung der Verfestigung ist in Tabelle 2 angegeben. Es wurden hier außerdem noch zwei Vergleichsbeispiele aufgenommen: Vergleichsbeispiel E ist eine handelsübliche 50 %ige wäßrige Dispersion eines Copolymerisats aus 40 Teilen Butadien und 60 Teilen Styrol, Vergleichsbeispiel F ist eine handelsübliche 40 %ige Dispersion eines Copolymerisates vorwiegend aus Acrylsäurebutylester und Acrylnitril.

Figure imgb0001
Figure imgb0002
 The result of the firing tests and the assessment of the hardening is given in Table 2. Two comparative examples were also included here: Comparative example E is a commercially available 50% aqueous dispersion of a copolymer of 40 parts of butadiene and 60 parts of styrene, comparative example F is a commercially available 40% dispersion of a copolymer mainly of butyl acrylate and acrylonitrile.
Figure imgb0001
Figure imgb0002

Claims (5)

1. Verfahren zum Verfestigen und Flammfestausrüsten von Nadelvliesboden­belägen durch Behandeln der Nadelvliese mit wäßrigen Dispersionen von Copolymeren einer Mindest-Filmbilde-Temperatur von 5 bis 25°C aus
15 bis 35 % ihres Gewichts Vinylidenchlorid
10 bis 45 % ihres Gewichts Vinylchlorid
8 bis 72 % ihres Gewichts Estern der (Meth)Acrylsäure mit 1 bis 12 C-Atome enthaltenden Alkanolen oder Vinylestern 2 bis 3 C-Atome enthaltender aliphatischer Carbonsäuren oder Gemische dieser Monomeren
1 bis 7 % ihres Gewichts α,β-monoolefinisch ungesättigten 3 bis 5 C-Atome enthaltenden Mono- und/oder Dicarbonsäuren und/oder deren Amide
2 bis 5 % ihres Gewichts N-Methylol-(meth)acrylamid und/oder deren Alkylether mit 1 bis 4 C-Atomen in den Alkylgruppen,
0 bis 3 % ihres Gewichts Vinylsulfonsäure
im Gemisch mit suspendierten feinteiligen Antimonoxiden und Trocknen der behandelten Nadelvliese bei erhöhter Temperatur.1. Process for solidifying and flame-retarding needle-punched non-woven floor coverings by treating the needle-punched nonwovens with aqueous dispersions of copolymers with a minimum film-forming temperature of 5 to 25 ° C.
15 to 35% of their weight vinylidene chloride
10 to 45% of their weight vinyl chloride
8 to 72% of their weight esters of (meth) acrylic acid with alkanols containing 1 to 12 carbon atoms or vinyl esters containing aliphatic carboxylic acids or mixtures of these monomers with 2 to 3 carbon atoms
1 to 7% of their weight of α, β-monoolefinically unsaturated mono- and / or dicarboxylic acids containing 3 to 5 carbon atoms and / or their amides
2 to 5% of their weight of N-methylol- (meth) acrylamide and / or their alkyl ethers with 1 to 4 carbon atoms in the alkyl groups,
0 to 3% of their weight vinyl sulfonic acid
in a mixture with suspended fine-particle antimony oxides and drying the treated needled nonwovens at elevated temperature. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Mindest-­Filmbilde-Temperatur der Copolymeren 10 bis 20°C beträgt.2. The method according to claim 1, characterized in that the minimum film-forming temperature of the copolymers is 10 to 20 ° C. 3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß das Mengenverhältnis von Copolymeren der wäßrigen Dispersionen zu den suspendierten Antimonoxiden von 2 bis 15 %, bezogen auf Polymerisat, beträgt.3. The method according to claim 1 or 2, characterized in that the quantitative ratio of copolymers of the aqueous dispersions to the suspended antimony oxides is from 2 to 15%, based on the polymer. 4. Verfahren nach den Ansprüchen 1 bis 3, dadurch gekennzeichnet, daß als fein suspendiertes Antimonoxid Sb₂O₅ einer Teilchengröße von 5 bis 50 nm eingesetzt wird.4. Process according to claims 1 to 3, characterized in that Sb₂O₅ having a particle size of 5 to 50 nm is used as the finely suspended antimony oxide. 5. Verfestigte und flammfest ausgerüstete Nadelvliesbodenbeläge hergestellt nach dem Verfahren der Ansprüche 1 bis 4.5. Solidified and flame-retardant needle-punched non-woven floor coverings produced by the method of claims 1 to 4.
EP87116301A 1986-11-20 1987-11-05 Process for the manufacture of needled non-woven floor coverings Expired - Lifetime EP0270842B1 (en)

Priority Applications (1)

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AT87116301T ATE81362T1 (en) 1986-11-20 1987-11-05 PROCESS FOR MANUFACTURING NEEDLE FLEECE FLOOR COVERINGS.

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DE19863639573 DE3639573A1 (en) 1986-11-20 1986-11-20 METHOD FOR STRENGTHENING AND FLAME RETARDING OF NEEDLE PLANT FLOOR COVERINGS
DE3639573 1986-11-20

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1990006393A1 (en) * 1988-11-25 1990-06-14 Cellulosa Composite Products Limited A process for treating fibours cellulosic webs and liquids for use therein

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1574864A (en) * 1967-05-13 1969-07-18
US3904570A (en) * 1973-09-19 1975-09-09 Stauffer Chemical Co Flame-retardant binder comprising vinylidene halide-bis(hydrocarbyl) vinyl phosphonate polymer latices blended with antimony oxide
US4610920A (en) * 1985-06-27 1986-09-09 National Starch And Chemical Corporation Binders for nonwovens

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1574864A (en) * 1967-05-13 1969-07-18
US3904570A (en) * 1973-09-19 1975-09-09 Stauffer Chemical Co Flame-retardant binder comprising vinylidene halide-bis(hydrocarbyl) vinyl phosphonate polymer latices blended with antimony oxide
US4610920A (en) * 1985-06-27 1986-09-09 National Starch And Chemical Corporation Binders for nonwovens

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1990006393A1 (en) * 1988-11-25 1990-06-14 Cellulosa Composite Products Limited A process for treating fibours cellulosic webs and liquids for use therein

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ATE81362T1 (en) 1992-10-15
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EP0270842B1 (en) 1992-10-07

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