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EP0379100B1 - Flame-resistant carrier web for bitumen webs, and process for producing the same - Google Patents

Flame-resistant carrier web for bitumen webs, and process for producing the same Download PDF

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Publication number
EP0379100B1
EP0379100B1 EP90100667A EP90100667A EP0379100B1 EP 0379100 B1 EP0379100 B1 EP 0379100B1 EP 90100667 A EP90100667 A EP 90100667A EP 90100667 A EP90100667 A EP 90100667A EP 0379100 B1 EP0379100 B1 EP 0379100B1
Authority
EP
European Patent Office
Prior art keywords
melamine
formaldehyde
carrier web
consolidated
sulfamate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP90100667A
Other languages
German (de)
French (fr)
Other versions
EP0379100A1 (en
Inventor
Peter Dr. Heidel
Wilhelm Dr. Adam
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hoechst AG
Original Assignee
Hoechst AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hoechst AG filed Critical Hoechst AG
Publication of EP0379100A1 publication Critical patent/EP0379100A1/en
Application granted granted Critical
Publication of EP0379100B1 publication Critical patent/EP0379100B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING 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
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40Non-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
    • D04H1/44Non-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
    • D04H1/46Non-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
    • D04H1/48Non-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
    • D04H1/488Non-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
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING 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
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40Non-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
    • D04H1/42Non-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
    • D04H1/4209Inorganic fibres
    • D04H1/4218Glass fibres
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING 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
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40Non-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
    • D04H1/42Non-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
    • D04H1/4326Condensation or reaction polymers
    • D04H1/435Polyesters
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING 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
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40Non-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
    • D04H1/44Non-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
    • D04H1/46Non-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
    • D04H1/498Non-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 entanglement of layered webs
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING 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
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40Non-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
    • D04H1/58Non-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
    • D04H1/64Non-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
    • D04H1/645Impregnation followed by a solidification process
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING 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
    • D04H13/00Other non-woven fabrics
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/60Nonwoven fabric [i.e., nonwoven strand or fiber material]
    • Y10T442/659Including an additional nonwoven fabric
    • Y10T442/66Additional nonwoven fabric is a spun-bonded fabric
    • Y10T442/662Needled
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/60Nonwoven fabric [i.e., nonwoven strand or fiber material]
    • Y10T442/682Needled nonwoven fabric
    • Y10T442/684Containing at least two chemically different strand or fiber materials
    • Y10T442/685Containing inorganic and polymeric strand or fiber materials

Definitions

  • the present invention relates to a multi-layer, flame-retardant carrier sheet and its production, and to a bituminized roofing and sealing sheet containing this carrier sheet.
  • carrier sheets for roofing and sealing sheets which concern their further processing into roofing and sealing sheets and the behavior of the latter during and after laying on the documents.
  • High strength of the carrier web in a wide temperature range is intended to ensure high processing and dimensional stability when bituminizing and the fire behavior, assessed according to DIN 4102, part 7, is to be met.
  • the carrier sheet should also ensure high dimensional stability of the finished roofing and waterproofing membrane when laid on the roof or other substrates, as well as high flexibility and a certain amount of stretch to compensate for irregularities and weather-related dimensional changes of the covered substrate.
  • Carrier sheets for bituminized roofing and waterproofing sheets are described, for example, in European laid-open publications 0 176 847 and 242 524. They preferably consist of two nonwovens, for example a glass fiber mat and a polyester fiber mat, which are connected to one another by needling. The needled laminate is then finally consolidated with a binder, acrylate-butadiene or acrylate-butadiene-styrene copolymers being generally used.
  • German Offenlegungsschrift 26 19 087 e.g. described for polyester spunbonded binders, consisting of an acrylate-butadiene-styrene copolymer with an addition of 5 to 30 wt .-% of a melamine-formaldehyde precondensate.
  • a method for producing flame-resistant nonwovens is known from German publication 11 49 688.
  • a flame retardant is applied to the nonwoven at the same time as the binder.
  • tetrahydrophosphonium chloride is used as the flame retardant, which is applied together with a binder system made from natural rubber latex and a melamine-formaldehyde precondensate.
  • the fleece is also consolidated with a melamine-formaldehyde precondensate.
  • the nonwovens equipped in this way are, however, poorly suited for the production of flame-retardant bitmunised roofing and waterproofing membranes in accordance with DIN 4107, Part 7, since for this purpose they must contain a very large amount of flame retardants, for example antimony trioxide or phosphorus compounds. This high proportion of flame retardants leads to a very strong reduction in the flexibility of the nonwovens, so that in this respect they no longer meet the requirements for the production of roofing and waterproofing membranes.
  • flame retardants for example antimony trioxide or phosphorus compounds.
  • the present invention now relates to a carrier sheet for the production of roofing and sealing sheets, which does not have the disadvantages of the known materials, in which high mechanical stability is combined with very good fire behavior even at elevated temperatures.
  • the carrier web according to the invention consists of a glass fiber mat and a hat made of synthetic fibers, which are needled together and which are finally consolidated with a polymer-free, low-formaldehyde melamine-formaldehyde precondensate which has a molar ratio of melamine to formaldehyde of 1: 1.0 to 1: 3.5.
  • the glass fiber mat contained in the carrier web according to the invention can in the usual way with the usual binders, i.e. usually polymer binders or melamine resins are pre-consolidated.
  • the synthetic fiber fleece contained in the carrier web according to the invention can be produced from all types of synthetic fibers which have sufficient strength.
  • synthetic fibers which have sufficient strength.
  • aliphatic and aromatic polyamides, polyacrylonitrile and in particular polyester fibers are suitable.
  • fiber types that have high strength, high modulus and low heat shrinkage, so that the dimension of the carrier web remains constant during further processing into roofing and waterproofing membranes.
  • a particularly preferred synthetic fiber material consists of polyethylene terephthalate, especially the high-strength and low-shrink types.
  • the synthetic fiberylies consist of flame-retardant polyesters.
  • Examples of commercially available synthetic fibers from which the Synthetic fiber fleece can be constructed are (R) Trevira, in particular the high-strength types and the flame-resistant type (R) Trevira CS.
  • the synthetic fiber fleece can be constructed from staple fibers, advantageously with cutting lengths between 1 and 100 mm, or from continuous fibers. Tangled nonwovens made from continuous fibers are particularly preferred, in particular types which have undergone a certain degree of pre-consolidation through a calendering process, such as the so-called spunbonds.
  • the low-formaldehyde melamine-formaldehyde precondensate with which the carrier web according to the invention is finally consolidated has a molar ratio of melamine to formaldehyde of 1: 1.0 to 1: 3.5, preferably 1: 1.2 to 1: 3.
  • the partially etherified precondensates are partially etherified with lower alkanols, ie those with 1 to 4 carbon atoms, but especially with methanol.
  • the degree of etherification of the partially etherified precondensates is characterized in that they have 0.2 to 0.85, preferably 0.6 to 0.8, mol of ether groups per mole of formaldehyde.
  • Particularly preferred low-formaldehyde partially etherified melamine-formaldehyde precondensates have a molar ratio of melamine to formaldehyde of 1: 2 to 1: 3 and have 0.6 to 0.8 mol of methyl ether groups per mol of formaldehyde.
  • Sulfamate-modified low-formaldehyde melamine-formaldehyde precondensates contain, based on solid resin, 1 to 20% by weight, preferably 5 to 15% by weight, of sulfamate, calculated as sodium sulfamate.
  • Particularly preferred sulfamate-modified melamine-formaldehyde precondensates have a molar ratio of melamine to formaldehyde of 1: 1.2 to 1: 2 and, based on solid resin, have 5 to 15% by weight sulfamate, calculated as sodium sulfamate.
  • the melamine-formaldehyde precondensate contained in the carrier web according to the invention additionally contains a small amount, i.e. 1 to 5% by weight, based on solid resin, contains further modifying agents, in particular modifying agents which increase plasticity, as long as this does not reduce the necessary flame resistance to an unacceptable degree.
  • Plasticizing additives of this type are e.g. Di- and triethylene glycol and their ethers or polyethylene glycols with molecular weights up to 2000.
  • support webs according to the invention which have been solidified with a melamine-formaldehyde precondensate without additional plasticizing modifiers.
  • Carrier webs according to the invention which have a combination of several preferred features are also particularly preferred.
  • the carrier web according to the invention has the advantage over known carrier webs that it exhibits improved fire behavior with a high degree of flexibility which is very accommodating for further processing. In this respect, it is considerably superior to both the nonwoven materials known from DE-AS 1 149 688 and the nonwoven materials produced using a binder according to DE-OS 26 19 087.
  • the mechanical strength of the carrier web according to the invention under the influence of heat (temperature range, e.g. 180 ° C.), as occurs during further processing into roofing and waterproofing membranes, has also been significantly improved.
  • one of the above-specified is used Synthetic fiber nonwovens needled with an optionally pre-consolidated glass fiber nonwoven and then with an aqueous melamine-formaldehyde precondensate of the above specification, to which about 0.5 to 3% of a known hardener, for example a hardener based on p-toluenesulfonic acid, has expediently been added Spraying, splashing or, preferably, dipping impregnated to the required resin absorption of 5 to 40, preferably 15 to 30,% by weight, based on unimpregnated material, optionally squeezed and then dried in a heating oven, generally at temperatures between 80 to 200, preferably 120 to 180 ° C, hardened in the course of 5 to 30 minutes.
  • a known hardener for example a hardener based on p-toluenesulfonic acid
  • the carrier web according to the invention can be used for very different purposes with particular advantage. It can e.g. can be used as decorative supports due to their flame retardancy. Their use as a carrier material for bituminized roofing and waterproofing membranes is particularly preferred.
  • the use according to the invention of the low-formaldehyde melamine-formaldehyde precondensates specified above also offers advantages in the production of the carrier web according to the invention: namely, glass nonwovens with a relatively low binder content can be used. Since the character of the binder plays a minor role with a low binder content, e.g. cheaper glass fleeces with a lower binder content, which need not be flame-retardant, can be used.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Laminated Bodies (AREA)
  • Nonwoven Fabrics (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
  • Road Signs Or Road Markings (AREA)
  • Working-Up Tar And Pitch (AREA)
  • Paints Or Removers (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Manufacturing Of Multi-Layer Textile Fabrics (AREA)

Abstract

A carrier web of a sheet-like fiber material consisting of a glass fiber mat and a mat of synthetic fibers, which and are needled together and are end-consolidated with a polymer-free low-formaldehyde melamine-formaldehyde precondensate, and a process for its preparation are described. The carrier web is preferably end-consolidated with a melamine-formaldehyde precondensate which is partly etherified and/or sulfamate-modified.

Description

Die vorliegende Erfindung betrifft eine mehrschichtige, schwer brennbare Trägerbahn und ihre Herstellung sowie eine diese Trägerbahn enthaltende bituminierte Dach- und Dichtungsbahn.The present invention relates to a multi-layer, flame-retardant carrier sheet and its production, and to a bituminized roofing and sealing sheet containing this carrier sheet.

An Trägerbahnen für Dach- und Dichtungsbahnen werden verschiedene wichtige Anforderungen gestellt, die ihre Weiterverarbeitung zu Dach- und Dichtungsbahnen und das Verhalten der letzteren beim und nach dem Verlegen auf den Unterlagen betreffen. Hohe Festigkeit der Trägerbahn in einem weiten Temperaturbereich soll eine hohe Verarbeitungs- und Dimensionsstabilität beim Bituminieren sicherstellen und das Brandverhalten, beurteilt nach DIN 4102, Teil 7, soll erfüllt werden. Gleichzeitig soll die Trägerbahn auch hohe Dimensionsstabilität der fertigen Dach- und Dichtungsbahn bei der Velegung auf dem Dach oder sonstigen Untergründen sowie hohe Flexibilität und eine gewisse Dehnbarkeit zum Ausgleich von Unregelmäßigkeit und witterungsbedingten Dimensionsänderungen des gedeckten Untergrunds gewährleisten.Various important requirements are placed on carrier sheets for roofing and sealing sheets, which concern their further processing into roofing and sealing sheets and the behavior of the latter during and after laying on the documents. High strength of the carrier web in a wide temperature range is intended to ensure high processing and dimensional stability when bituminizing and the fire behavior, assessed according to DIN 4102, part 7, is to be met. At the same time, the carrier sheet should also ensure high dimensional stability of the finished roofing and waterproofing membrane when laid on the roof or other substrates, as well as high flexibility and a certain amount of stretch to compensate for irregularities and weather-related dimensional changes of the covered substrate.

Trägerbahnen für bituminierte Dach- und Dichtungsbahnen sind z.B. in den Europäischen Offenlegungsschriften 0 176 847 und 242 524 beschrieben. Sie bestehen vorzugsweise aus zwei Vliesstoffen, z.B. einer Glasfasermatte und einer Polyesterfasermatte, die durch Nadlung miteinander verbunden sind. Der vernadelte Schichtstoff wird dann noch mit einem Bindemittel endverfestigt, wobei in der Regel Acrylat-Butadien- oder Acrylat-Butadien-Styrol-Copolymerisate eingesetzt werden.Carrier sheets for bituminized roofing and waterproofing sheets are described, for example, in European laid-open publications 0 176 847 and 242 524. They preferably consist of two nonwovens, for example a glass fiber mat and a polyester fiber mat, which are connected to one another by needling. The needled laminate is then finally consolidated with a binder, acrylate-butadiene or acrylate-butadiene-styrene copolymers being generally used.

In der deutschen Offenlegungsschrift 26 19 087 werden z.B. für Polyesterspinnvliese Bindemittel beschrieben, bestehend aus einem Acrylat-Butadien-Styrol-Copolymerisat mit einem Zusatz von 5 bis 30 Gew.-% eines Melamin-Formaldehyd-Vorkondensats.In German Offenlegungsschrift 26 19 087 e.g. described for polyester spunbonded binders, consisting of an acrylate-butadiene-styrene copolymer with an addition of 5 to 30 wt .-% of a melamine-formaldehyde precondensate.

Diese bekannten Bindemittel sind im Hinblick auf die textiltechnologischen Daten wie Festigkeit, Weiterreißfestigkeit usw optimiert, ihr Brandverhalten war jedoch bisher nur von geringem Interesse. Die aus mit diesen Bindemittelsystemen verfestigten Schichtstoffen hergestellten Bitumenschweißbahnen sind daher nur bedingt brandhemmend im Sinne der DIN 4107, Teil 7.These known binders have been optimized with regard to textile technology data such as strength, tear propagation resistance etc., however, their fire behavior has so far been of little interest. The bituminous welding sheets made from laminates solidified with these binder systems are therefore only fire-retardant to a limited extent within the meaning of DIN 4107, Part 7.

Aus der deutschen Auslegeschrift 11 49 688 ist ein Verfahren zur Herstellung flammfester Vliesstoffe bekannt. Bei diesem Verfahren wird ein Flammschutzmittel gleichzeitig mit dem Bindemittel auf das Vlies aufgebracht. In einem der Beispiele dieser Druckschrift wird als Flammschutzmittel Tetrahydrophosphoniumchlorid eingesetzt, das gemeinsam mit einem Bindersystem aus Naturkautschuklatex und einem Melamin-Formaldehyd-Vorkondensat appliziert wird. Die Nachverfestigung des Vlieses erfolgt ebenfalls mit einem Melamin-Formaldehyd-Vorkondensat.A method for producing flame-resistant nonwovens is known from German publication 11 49 688. In this method, a flame retardant is applied to the nonwoven at the same time as the binder. In one of the examples in this publication, tetrahydrophosphonium chloride is used as the flame retardant, which is applied together with a binder system made from natural rubber latex and a melamine-formaldehyde precondensate. The fleece is also consolidated with a melamine-formaldehyde precondensate.

Die so ausgerüsteten Vliese sind jedoch für die Herstellung von nach DIN 4107, Teil 7 flammfesten bitmunierten Dach- und Dichtungsbahnen schlecht geeignet, da sie für diesen Zweck eine sehr hohe Menge von Flammschutzmitteln z.B. Antimontrioxid oder Phosphorverbindungen enthalten müssen. Dieser hohe Anteil von Flammschutzmitteln führt zu einer sehr starken Herabsetzung der Flexibilität der Vliese, so daß sie in dieser Hinsicht den Anforderungen zur Herstellung von Dach- und Dichtungsbahnen nicht mehr genügen.The nonwovens equipped in this way are, however, poorly suited for the production of flame-retardant bitmunised roofing and waterproofing membranes in accordance with DIN 4107, Part 7, since for this purpose they must contain a very large amount of flame retardants, for example antimony trioxide or phosphorus compounds. This high proportion of flame retardants leads to a very strong reduction in the flexibility of the nonwovens, so that in this respect they no longer meet the requirements for the production of roofing and waterproofing membranes.

Die vorliegende Erfindung betrifft nun eine Trägerbahn zur Herstellung von Dach- und Dichtungsbahnen, die die Nachteile der bekannten Materialien nicht aufweist, in welcher vielmehr hohe mechanische Stabilität auch bei erhöhten Temperaturen mit sehr gutem Brandverhalten kombiniert ist.The present invention now relates to a carrier sheet for the production of roofing and sealing sheets, which does not have the disadvantages of the known materials, in which high mechanical stability is combined with very good fire behavior even at elevated temperatures.

Die erfindungsgemäße Trägerbahn besteht aus einer Glasfasermatte und einer Hatte aus Synthesefasern, die miteinander vernadelt und die mit einem polymerisatfreien formaldehydarmen Melamin-Formaldehyd-Vorkondensat endverfestigt sind das ein Molverhältnis von Melamin zu Formaldehyd von 1:1,0 bis 1:3,5 aufweist. Die in der erfindungsgemäßen Trägerbahn enthaltene Glasfasermatte kann in üblicher Weise mit den üblichen Bindern, d.h. meist Polymerisatbindern oder auch Melaminharzen vorverfestigt sein. Wegen der hohen Bindekraft der erfindungsgemäß eingesetzten formaldehydarmen Melamin-Formaldehyd-Vorkondensate ist es jedoch möglich, den für die Vorverfestigung des Glasvlieses benutzten Binderanteil deutlich zu senken, ohne daß die Endfestigkeit der erfindungsgemäßen Trägerbahn unzulässig reduziert wird.The carrier web according to the invention consists of a glass fiber mat and a hat made of synthetic fibers, which are needled together and which are finally consolidated with a polymer-free, low-formaldehyde melamine-formaldehyde precondensate which has a molar ratio of melamine to formaldehyde of 1: 1.0 to 1: 3.5. The glass fiber mat contained in the carrier web according to the invention can in the usual way with the usual binders, i.e. usually polymer binders or melamine resins are pre-consolidated. Because of the high binding power of the low-formaldehyde melamine-formaldehyde precondensates used according to the invention, however, it is possible to significantly reduce the proportion of binder used for the pre-consolidation of the glass nonwoven without the final strength of the carrier web according to the invention being unduly reduced.

Das in der erfindungsgemäßen Trägerbahn enthaltene Synthesefaservlies kann aus allen Synthesefasertypen, die eine ausreichende Festigkeit haben, hergestellt sein. In Betracht kommen beispielsweise aliphatische und aromatische Polyamide, Polyacrylnitril und insbesondere Polyesterfasern. Zweckmäßigerweise werden dabei solche Fasertypen eingesetzt, die eine hohe Festigkeit, hohen Modul und einen niedrigen Hitzeschrumpf aufweisen, damit bei der Weiterverarbeitung zu Dach- und Dichtungsbahnen die Dimension der Trägerbahn konstant bleibt. Besonders bevorzugtes Synthesefasermaterial besteht aus Polyethylenterephthalat, insbesondere den hochfesten und schrumpfarmen Typen. Es ist im Prinzip auch möglich, aber nicht unbedingt erforderlich, daß das Synthesefaserylies aus schwer brennbaren Polyestern besteht. Beispiele für handelsübliche Synthesefasern, aus denen das Synthesefaservlies aufgebaut sein kann, sind (R)Trevira, insbesondere die hochfesten Typen und die schwer brennbare Type (R)Trevira CS.The synthetic fiber fleece contained in the carrier web according to the invention can be produced from all types of synthetic fibers which have sufficient strength. For example, aliphatic and aromatic polyamides, polyacrylonitrile and in particular polyester fibers are suitable. It is expedient to use fiber types that have high strength, high modulus and low heat shrinkage, so that the dimension of the carrier web remains constant during further processing into roofing and waterproofing membranes. A particularly preferred synthetic fiber material consists of polyethylene terephthalate, especially the high-strength and low-shrink types. In principle, it is also possible, but not absolutely necessary, that the synthetic fiberylies consist of flame-retardant polyesters. Examples of commercially available synthetic fibers from which the Synthetic fiber fleece can be constructed are (R) Trevira, in particular the high-strength types and the flame-resistant type (R) Trevira CS.

Das Synthesefaservlies kann aus Stapelfasern, zweckmäßigerweise mit Schnittlängen zwischen 1 und 100 mm oder aus Endlosfasern aufgebaut sein. Besonders bevorzugt sind Wirrvliese aus Endlosfasern, insbesondere Typen, die durch einen Kalandrierungsprozeß eine gewisse Vorverfestigung erfahren haben, wie z.B. die sogenannten Spunbonds.The synthetic fiber fleece can be constructed from staple fibers, advantageously with cutting lengths between 1 and 100 mm, or from continuous fibers. Tangled nonwovens made from continuous fibers are particularly preferred, in particular types which have undergone a certain degree of pre-consolidation through a calendering process, such as the so-called spunbonds.

Das formaldehydarme Melamin-Formaldehyd-Vorkondensat, mit dem die erfindungsgemäße Trägerbahn endverfestigt ist, hat ein Molverhältnis von Melamin zu Formaldehyd von 1:1,0 bis 1:3,5, vorzugsweise 1:1,2 bis 1:3. Von diesem formaldehydarmen Melamin-Formaldehyd-Vorkondensaten sind solche bevorzugt, die teilverethert und/oder sulfamatmodifiziert sind. Die teilveretherten Vorkondensate sind mit niederen Alkanolen, d.h. solchen mit 1 bis 4 Kohlenstoffatomen, insbesondere aber mit Methanol teilverethert. Der Veretherungsgrad der teilveretherten Vorkondensate ist dadurch gekennzeichnet, daß sie pro Mol Formaldehyd 0,2 bis 0,85, vorzugsweise 0,6 bis 0,8 Mol Ethergruppen aufweisen. Besonders bevorzugte formaldehydarme teilveretherte Melamin-Formaldehyd-Vorkondensate haben ein Molverhältnis von Melamin zu Formaldehyd von 1:2 bis 1:3 und weisen pro Mol Formaldehyd 0,6 bis 0,8 Mol Methylethergruppen auf. Sulfamatmodifizierte formaldehydarme Melamin-Formaldehyd-Vorkondensate, mit denen die erfindungsgemäße Trägerbahn endverfestigt sein kann, enthalten, bezogen auf Festharz, 1 bis 20 Gew.-%, vorzugsweise 5 bis 15 Gew.-% Sulfamat, gerechnet als Natriumsulfamat. Besonders bevorzugte sulfamatmodifizierte Melamin-Formaldehyd-Vorkondensate haben ein Molverhältnis Melamin zu Formaldehyd von 1:1,2 bis 1:2 und weisen, bezogen auf Festharz 5 bis 15 Gew.-% Sulfamat auf, gerechnet als Natriumsulfamat.The low-formaldehyde melamine-formaldehyde precondensate with which the carrier web according to the invention is finally consolidated has a molar ratio of melamine to formaldehyde of 1: 1.0 to 1: 3.5, preferably 1: 1.2 to 1: 3. Of these low-formaldehyde melamine-formaldehyde precondensates, preference is given to those which are partially etherified and / or modified with sulfamate. The partially etherified precondensates are partially etherified with lower alkanols, ie those with 1 to 4 carbon atoms, but especially with methanol. The degree of etherification of the partially etherified precondensates is characterized in that they have 0.2 to 0.85, preferably 0.6 to 0.8, mol of ether groups per mole of formaldehyde. Particularly preferred low-formaldehyde partially etherified melamine-formaldehyde precondensates have a molar ratio of melamine to formaldehyde of 1: 2 to 1: 3 and have 0.6 to 0.8 mol of methyl ether groups per mol of formaldehyde. Sulfamate-modified low-formaldehyde melamine-formaldehyde precondensates, with which the carrier web according to the invention can be finally consolidated, contain, based on solid resin, 1 to 20% by weight, preferably 5 to 15% by weight, of sulfamate, calculated as sodium sulfamate. Particularly preferred sulfamate-modified melamine-formaldehyde precondensates have a molar ratio of melamine to formaldehyde of 1: 1.2 to 1: 2 and, based on solid resin, have 5 to 15% by weight sulfamate, calculated as sodium sulfamate.

Für spezielle Einsatzgebiete kann es zweckmäßig sein, wenn das in der erfindungsgemäßen Trägerbahn enthaltene Melamin-Formaldehyd-Vorkondensat zusätzlich geringe Menge, d.h. ca. 1 bis 5 Gew.-% bezogen auf Festharz, weitere Modifizierungsmittel, insbesondere die Plastizität steigernde Modifizierungsmittel enthält, solange dadurch die erforderliche Schwerbrennbarkeit nicht in unvertretbarem Maß herabgesetzt wird. Plastifizierende Zusätze dieser Art sind z.B. Di- und Triethylenglykol sowie deren Ether oder Polyethylenglykole mit Molgewichten bis zu 2000. Besonders bevorzugt sind jedoch erfindungsgemäße Trägerbahnen, die mit einem Melamin-Formaldehyd-Vorkondensat ohne zusätzliche plastifizierende Modifizierungsmittel endverfestigt sind.For special areas of application, it may be expedient if the melamine-formaldehyde precondensate contained in the carrier web according to the invention additionally contains a small amount, i.e. 1 to 5% by weight, based on solid resin, contains further modifying agents, in particular modifying agents which increase plasticity, as long as this does not reduce the necessary flame resistance to an unacceptable degree. Plasticizing additives of this type are e.g. Di- and triethylene glycol and their ethers or polyethylene glycols with molecular weights up to 2000. However, particular preference is given to support webs according to the invention which have been solidified with a melamine-formaldehyde precondensate without additional plasticizing modifiers.

Besonders bevorzugt sind auch solche erfindungsgemäßen Trägerbahnen, die eine Kombination mehrerer bevorzugter Merkmale aufweisen.Carrier webs according to the invention which have a combination of several preferred features are also particularly preferred.

Die erfindungsgemäße Trägerbahn zeigt gegenüber bekannten Trägerbahnen den Vorteil, daß sie bei einer der Weiterverarbeitung sehr entgegenkommenden hohen Flexibilität ein verbessertes Brandverhalten zeigt. Sie ist in dieser Hinsicht sowohl den aus der DE-AS 1 149 688 bekannten als auch den unter Einsatz eines Bindemittels gemäß DE-OS 26 19 087 hergestellten Vliesmaterialien erheblich überlegen. Auch die mechanische Belastbarkeit der erfindungsgemäßen Trägerbahn unter Wärmeeinwirkung (Temperaturbereich z.B. 180°C), wie sie bei der Weiterverarbeitung zu Dach- und Dichtungsbahnen auftritt, ist wesentlich verbessert. Das gleiche gilt für die Weiterreißfestigkeit der erfindungsgemäßen Trägerbahn, die gegenüber Trägerbahnen, die mit Polyacrylatbindern endverfestigt sind, um ca. 25 % gesteigert ist.The carrier web according to the invention has the advantage over known carrier webs that it exhibits improved fire behavior with a high degree of flexibility which is very accommodating for further processing. In this respect, it is considerably superior to both the nonwoven materials known from DE-AS 1 149 688 and the nonwoven materials produced using a binder according to DE-OS 26 19 087. The mechanical strength of the carrier web according to the invention under the influence of heat (temperature range, e.g. 180 ° C.), as occurs during further processing into roofing and waterproofing membranes, has also been significantly improved. The same applies to the tear propagation resistance of the carrier web according to the invention, which is increased by approximately 25% compared to carrier webs which are finally consolidated with polyacrylate binders.

Zur Herstellung der oben beschriebenen erfindungsgemäßen Trägerbahn wird eins der oben spezifizierten Synthesefaservliese mit einem gegebenenfalls vorverfestigten Glasfaservlies vernadelt und anschließend mit einem wäßrigen Melamin-Formaldehyd-Vorkondensat der oben angegebenen Spezifikation, dem zweckmäßigerweise ca. 0,5 bis 3 % eines bekannten Härters, z.B. einem Härter auf Basis von p-Toluolsulfonsäure zugesetzt worden ist, durch Besprühen, Pflatschen oder vorzugsweise Tauchen imprägniert auf die erforderliche Harzaufnahme von 5 bis 40 vorzugsweise 15 bis 30 Gew.-% bezogen auf unimprägniertes Material abgequetscht, gegebenenfalls zwischengetrocknet und anschließend in einem Wärmeofen, in der Regel bei Temperaturen zwischen 80 bis 200, vorzugsweise 120 bis 180°C, im Verlaufe von 5 bis 30 Minuten ausgehärtet. Auch die Herstellung der erfindungsgemäßen Trägerbahn ist Gegenstand der vorliegenden Patentanmeldung.To produce the carrier web according to the invention described above, one of the above-specified is used Synthetic fiber nonwovens needled with an optionally pre-consolidated glass fiber nonwoven and then with an aqueous melamine-formaldehyde precondensate of the above specification, to which about 0.5 to 3% of a known hardener, for example a hardener based on p-toluenesulfonic acid, has expediently been added Spraying, splashing or, preferably, dipping impregnated to the required resin absorption of 5 to 40, preferably 15 to 30,% by weight, based on unimpregnated material, optionally squeezed and then dried in a heating oven, generally at temperatures between 80 to 200, preferably 120 to 180 ° C, hardened in the course of 5 to 30 minutes. The production of the carrier web according to the invention is also the subject of the present patent application.

Die erfindungsgemäße Trägerbahn kann für sehr unterschiedliche Zwecke mit besonderem Vorteil eingesetzt werden. Sie kann z.B. aufgrund ihrer Schwerbrennbarkeit als Dekorationsträger eingesetzt werden. Besonders bevorzugt ist ihr Einsatz als Trägermaterial für bituminierte Dach- und Dichtungsbahnen.The carrier web according to the invention can be used for very different purposes with particular advantage. It can e.g. can be used as decorative supports due to their flame retardancy. Their use as a carrier material for bituminized roofing and waterproofing membranes is particularly preferred.

Der erfindungsgemäße Einsatz der oben spezifizierten formaldehydarmen Melamin-Formaldehyd-Vorkondensate bietet auch Vorteile bei der Herstellung der erfindungsgemäßen Trägerbahn: Es können nämlich Glasvliese mit relativ niedrigem Bindemittelgehalt verwendet werden. Da bei niedrigem Bindemittelgehalt der Charakter des Bindemittels eine geringere Rolle spielt, können z.B. preiswertere Glasvliese mit niedrigerem Bindemittelgehalt, die nicht schwer brennbar sein müssen, verwendet werden.The use according to the invention of the low-formaldehyde melamine-formaldehyde precondensates specified above also offers advantages in the production of the carrier web according to the invention: namely, glass nonwovens with a relatively low binder content can be used. Since the character of the binder plays a minor role with a low binder content, e.g. cheaper glass fleeces with a lower binder content, which need not be flame-retardant, can be used.

Claims (14)

  1. A carrier web of a sheet-like fiber material composed of a glass fiber mat and a mat of synthetic fibers which are needled to one another and end-consolidated with a polymer-free melamine-formaldehyde precondensate which has a molar ratio of melamine to formaldehyde of 1:1.0 to 1:3.5.
  2. The carrier web as claimed in claim 1, wherein the synthetic fiber mat consists of polyester fibers.
  3. The carrier web as claimed in at least one of claims 1 and 2, wherein the synthetic fiber mat is a spun-bond material.
  4. The carrier web as claimed in at least one of claims 1 to 3, end-consolidated with a melamine-formaldehyde precondensate which is partly etherified and/or sulfamate-modified.
  5. The carrier web as claimed in at least one of claims 1 to 4, end-consolidated with a melamine-formaldehyde precondensate which is either partly etherified or sulfamate-modified.
  6. The carrier web as claimed in at least one of claims 1 to 5, end-consolidated with a melamine-formaldehyde precondensate which is partly etherified with lower alcohols.
  7. The carrier web as claimed in at least one of claims 1 to 6, end-consolidated with a partly etherified melamine-formaldehyde precondensate which contains 0.2 to 0.85 mol of alkane ether groups per mole of formaldehyde.
  8. The carrier web as claimed in at least one of claims 1 to 7, end-consolidated with a melamine-formaldehyde precondensate which has a molar ratio of melamine to formaldehyde of 1:2 to 1:3 and contains 0.6 to 0.8 mol of methyl ether groups per mole of formaldehyde.
  9. The carrier web as claimed in at least one of claims 1 to 5, end-consolidated with a melamine-formaldehyde precondensate which contains 1 to 20% by weight of sulfamate, calculated as sodium sulfamate and based on the solid resin.
  10. The carrier web as claimed in at least one of claims 1 to 5 and 9, end-consolidated with a melamine-formaldehyde precondensate which has a molar ratio of melamine to formaldehyde of 1:1.2 to 1:2 and contains 5 to 15% by weight of sulfamate, calculated as sodium sulfamate and based on the solid resin.
  11. A process for the production of the carrier web as claimed in claim 1 by needling a synthetic fiber nonwoven to a glass fiber nonwoven, which is preconsolidated if appropriate, and subsequently end-consolidating, which comprises impregnating the two-layered structure with an essentially aqueous solution of a polymer-free melamine-formaldehyde precondensate which has a molar ratio of melamine to formaldehyde of 1:1.0 to 1:3.5 and to which about 0.5 to 5% by weight of a customary hardener has been added, squeezing off the structure to a resin uptake of 5 to 40% by weight, based on the non-resinated material, and then hardening the structure at elevated temperature.
  12. The process as claimed in claim 11, wherein a melamine-formaldehyde precondensate which is partly etherified and/or sulfamate-modified is employed.
  13. The process as claimed in at least one of claims 11 and 12, wherein the melamine-formaldehyde precondensate is either partly etherified or sulfamate-modified.
  14. The use of the carrier web as claimed in claim 1 for the production of bituminized roofing and sealing webs.
EP90100667A 1989-01-17 1990-01-13 Flame-resistant carrier web for bitumen webs, and process for producing the same Expired - Lifetime EP0379100B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3901152A DE3901152A1 (en) 1989-01-17 1989-01-17 FLAME RESISTANT CARRIER RAIL FOR BITUMEN RAILWAYS AND METHOD FOR THEIR PRODUCTION
DE3901152 1989-01-17

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EP0379100A1 EP0379100A1 (en) 1990-07-25
EP0379100B1 true EP0379100B1 (en) 1995-05-10

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EP (1) EP0379100B1 (en)
JP (1) JPH02233240A (en)
AT (1) ATE122412T1 (en)
AU (1) AU4796790A (en)
CA (1) CA2007882A1 (en)
DE (2) DE3901152A1 (en)
FI (1) FI900214A0 (en)
NO (1) NO173515C (en)
ZA (1) ZA90284B (en)

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DE10151411A1 (en) * 2001-10-18 2003-05-08 Johns Manville Europe Gmbh Laminate with improved properties
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US7199065B1 (en) 1999-07-30 2007-04-03 Johns Manville Non-woven laminate composite
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DE19952432A1 (en) * 1999-10-30 2001-06-21 Johns Manville Int Inc Two or three layer laminates of synthetic non-woven fabric and woven glass fabric or scrim, for use in bituminized roofing webs and sealing membranes, in which the layers are bonded by needling and consolidated with a binder
DE19952432B4 (en) * 1999-10-30 2004-10-07 Johns Manville International, Inc., Denver laminate
DE10151411A1 (en) * 2001-10-18 2003-05-08 Johns Manville Europe Gmbh Laminate with improved properties
DE10151411B4 (en) * 2001-10-18 2006-09-14 Johns Manville Europe Gmbh Laminate with improved properties
EP2309046A1 (en) 2009-10-08 2011-04-13 Johns Manville Multilayer fabric materials for roofing applications

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ATE122412T1 (en) 1995-05-15
JPH02233240A (en) 1990-09-14
NO173515C (en) 1993-12-22
EP0379100A1 (en) 1990-07-25
AU4796790A (en) 1990-07-26
CA2007882A1 (en) 1990-07-17
NO900231D0 (en) 1990-01-16
US5171629A (en) 1992-12-15
NO173515B (en) 1993-09-13
FI900214A0 (en) 1990-01-15
DE3901152A1 (en) 1990-07-19
ZA90284B (en) 1990-11-28
NO900231L (en) 1990-07-18
DE59009035D1 (en) 1995-06-14

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