EP0111076B1 - Flame-resistant flexible material - Google Patents
Flame-resistant flexible material Download PDFInfo
- Publication number
- EP0111076B1 EP0111076B1 EP83109548A EP83109548A EP0111076B1 EP 0111076 B1 EP0111076 B1 EP 0111076B1 EP 83109548 A EP83109548 A EP 83109548A EP 83109548 A EP83109548 A EP 83109548A EP 0111076 B1 EP0111076 B1 EP 0111076B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- flame
- flexible material
- printed
- resistant
- pattern
- 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
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- 239000000463 material Substances 0.000 title claims abstract description 27
- 239000011230 binding agent Substances 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 5
- 150000002367 halogens Chemical class 0.000 claims abstract description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical class [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000004753 textile Substances 0.000 claims description 17
- 239000004831 Hot glue Substances 0.000 claims description 5
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 4
- 239000004952 Polyamide Substances 0.000 claims description 3
- 229920001971 elastomer Polymers 0.000 claims description 3
- 239000000806 elastomer Substances 0.000 claims description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 3
- 238000005187 foaming Methods 0.000 claims description 3
- 229920000058 polyacrylate Polymers 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- 229920002635 polyurethane Polymers 0.000 claims description 3
- 239000004814 polyurethane Substances 0.000 claims description 3
- 239000003063 flame retardant Substances 0.000 description 46
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 31
- 239000004744 fabric Substances 0.000 description 10
- 239000010410 layer Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000000835 fiber Substances 0.000 description 5
- 238000007639 printing Methods 0.000 description 5
- 239000002131 composite material Substances 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 229920000126 latex Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 229920003043 Cellulose fiber Polymers 0.000 description 2
- 239000005696 Diammonium phosphate Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 238000010000 carbonizing Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- BSBSDQUZDZXGFN-UHFFFAOYSA-N cythioate Chemical compound COP(=S)(OC)OC1=CC=C(S(N)(=O)=O)C=C1 BSBSDQUZDZXGFN-UHFFFAOYSA-N 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 2
- 235000019838 diammonium phosphate Nutrition 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002557 mineral fiber Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 210000002268 wool Anatomy 0.000 description 2
- BQHQZFUAEAVJRE-UHFFFAOYSA-N 2-fluorobuta-1,3-diene Chemical compound FC(=C)C=C BQHQZFUAEAVJRE-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 229920000784 Nomex Polymers 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 206010053615 Thermal burn Diseases 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007596 consolidation process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000009970 fire resistant effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000004761 kevlar Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 239000004763 nomex Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 238000010022 rotary screen printing Methods 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Classifications
-
- 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
- D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
- D06M23/16—Processes for the non-uniform application of treating agents, e.g. one-sided treatment; Differential treatment
-
- 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
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/30—Flame or heat resistance, fire retardancy properties
Definitions
- the invention relates to flame-retardant, flexible materials, in particular textiles.
- FR-A-2 125410 describes a flame-retardant flexible material in which a solution of diammonium phosphate is printed as a pattern in the form of dots or lines in such a way that zones of high concentration alternate with zones in which there is little or no flame retardant. Instead of the usual uniform distribution by immersing the substance in a highly dilute solution of diammonium phosphate, a point concentration of this flame retardant is to be achieved here.
- a flame retardant in the form of dots is printed on textiles. It is a specific brominated phosphoric acid ester and not a pigmented flame retardant.
- DE-A-2 105 019 describes fabrics in which at least two auxiliaries of different functions are applied to the surface of a fabric. B. patch-like zones is applied and the other aid is applied distributed at least in a part of the rest of the area. One of the two aids of different functions can also be a means of flame retarding the fabric.
- the invention has for its object to provide flexible, in particular textile, materials using pigment or powder flame retardants in combination with binders in a flame retardant manner that good wearing properties result with excellent protection. This also includes the possibility of using flame retardants that have not previously been used for textiles.
- this object is achieved with a flame-retardant flexible material in which the flame retardant is printed in the form of piles or dams in that the piles or dams of the printed pattern have a height of 0.01 to 1 mm and a diameter or one Have a width of 0.05 to 2 mm and cover 20 to 80% of the surface of the flexible carrier and either a powdered flame retardant, which forms a fire-resistant layer by foaming, or powdered flame retardant in the form of bromine compounds or combinations of antimony trioxide with a halogen dispenser and in contain a binder in both cases.
- the piles or dams of the printed powdery flame retardant preferably have a diameter or a width of 0.2 to 1 mm.
- the design of the print ensures that the printed pattern of the flame retardant covers only 20 to 80%, preferably 30 to 70%, of the surface of the flexible carrier.
- the powdered flame retardants can be carbonizing and fire-suffocating as well as barrier layer-forming flame retardants.
- So-called intumescent agents are also very suitable, they contain substances that foam up when they heat up, carbonize from 200 to 300 ° C, solidify and form a fine-pored, well-insulating cushion.
- the pigment-like flame retardants known for plastics can also be used, the flame-retardant effect of which can be enhanced by so-called synergists or certain plasticizers or the binders.
- Self-extinguishing plastics especially those with a higher halogen content, can also be used alone or in combination with other known flame retardants.
- powdered flame retardants can be used, which are compatible with one another in combination with the textile fabric serving as a carrier and are described, for example, in Römpps Chemie-Lexikon, 8th edition, (1981) under the keyword “flame retardants” and the literature references listed here.
- Suitable, in particular polymeric, binders suitable for printing on the powdered flame retardants chemically belong, for example, to the group of polyurethanes, polyacrylates or elastomers. The latter can also be halogenated, in particular chlorinated or fluorinated.
- Hotmelt adhesives based on polyamides, polyesters or ethylene-vinyl acetate copolymers (EVA) are also very suitable.
- the polymeric binders and hot melt adhesives are usually in the form of a dispersion.
- the polymeric, solidified, for example crosslinked or vulcanized, binders then remain in the printed pattern. Their proportion in the printed pattern of the flame retardant can make up 5 to 200, in particular 10 to 50% by weight, based on the flame retardant.
- the backing layer for the flame-retardant flexible material according to the invention is for most areas of application, in particular for the production of protective suits, as a rule a textile fabric made of mineral, synthetic or natural fibers. Woven or knitted fabrics are particularly preferred because of their small thickness and high strength.
- the choice of the backing textile depends on the intended use. In the case of light protective clothing, a composite or mixed fabric made of synthetic or natural fibers and mineral fibers is recommended, with the mineral fiber side being provided with the printed pattern of the flame retardant. The simultaneous weaving of these materials is also suitable.
- the use of flame-retardant or particularly tear-resistant fibers, such as aramids (KEV-LAR, NOMEX) or polyimides, can be useful for certain purposes.
- the flexible backing material can be printed not only on one side, but also on both sides, and the adhesive effect of the polymeric binder before it solidifies can be used to produce a composite material which has an interrupted layer from the regularly printed pattern of the bound flame retardant between two flexible, in particular air-permeable backing layers up to about 1 mm thick. Then, for example, these nubs of the flame retardant lie between two webs and are better protected.
- This composite material can be produced by allowing another substrate layer web to run into the flexible carrier layer immediately after printing on a web, then drying the composite material and laminating it together under the action of pressure and heat.
- the manufacture of the flame-retardant flexible material according to the invention takes place in such a way that a paste made from, for example, powdered flame retardant, optionally with liquid flame retardants, synergists or plasticizers, a solution or dispersion of the polymeric binder and, if appropriate, customary printing aids is applied to the flexible carrier layer by rotary screen printing in one certain pattern is applied, dried and solidified.
- a paste made from, for example, powdered flame retardant, optionally with liquid flame retardants, synergists or plasticizers, a solution or dispersion of the polymeric binder and, if appropriate, customary printing aids is applied to the flexible carrier layer by rotary screen printing in one certain pattern is applied, dried and solidified.
- the polymeric binder is e.g.
- the latex of optionally halogenated elastomers such as natural, synthetic or silicone rubber, chloroprene or fluoroprene
- the piles or dams of the bound flame retardant applied in a specific pattern must be removed to remove the volatile ones Latex ingredients are dried.
- Hot melt adhesives in particular based on polyamides, polyesters or EVA, can also be used as dry powder in addition to as a dispersion. Then the printed piles of flame retardants and hot melt adhesive must be exposed to heat radiation shortly after printing before the printed web is driven into the so-called drying tunnel for final consolidation.
- the foaming intumescent material which foams when heated, is printed in such a pattern or spacing between the centers of the flame retardants that the print pattern foams together under the action of heat to form a closed protective layer before the textile carrier suffers considerable damage or loses its strength. Once present, the foam can withstand extreme loads for an astonishingly long time. If you applied the fire protection coating by coating or impregnation, you would get a board from the flexible textile carrier that would only be suitable for stationary applications. The printed lumps or dams, on the other hand, only slightly change the handle and the air or water vapor permeability of the textile material. When using a clear flexible support, e.g. B. a glass fiber fabric or a film, remains a considerable light transmission despite the printed points of the insulation protection.
- a clear flexible support e.g. B. a glass fiber fabric or a film
- the flame-retardant flexible materials according to the invention offer the same protection as with a full-surface treatment, while the air permeability is still very remarkable and the grip is hardly changed.
- the color of the flexible carrier is also retained on the unprinted side.
- the flexible materials, which are flame-retardant according to the invention can be processed into protective clothing for extreme conditions in both civil and military fields.
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Laminated Bodies (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Fireproofing Substances (AREA)
- Paper (AREA)
- Manufacturing Of Multi-Layer Textile Fabrics (AREA)
Abstract
Description
Die Erfindung betrifft flammwidrig ausgerüstete, flexible Materialien, insbesondere Textilien.The invention relates to flame-retardant, flexible materials, in particular textiles.
Bei der Raumausstattung von Hotels, Theatern und Kongreßzentren, bei Bussen und Flugzeugen spielen flammhemmend ausgerüstete Textilien eine große Rolle als präventiver Schutz. Die derzeit für textile Flächengebilde verwendeten Flammschutzmittel bzw. flammwidrigen Ausrüstungen lassen sich in folgende Gruppen einteilen:
- - Carbonisierende und dehydratisierende Mittel, die bei Cellulosefasern, z.B. Baumwolle, zur Abspaltung von Wasser führen, während ein schwer entflammbares Kohlenstoffgerüst zurückbleibt. Derartige Mittel sind als Pyrovatex° und Probano im Handel. Der Griff der Textilien wird zwar nicht beeinträchtigt, aber meist leidet die Festigkeit.
- - Es gibt auch ähnliche flammwidrige Ausrüstungen speziell für Wolle.
- - Unabhängig von der chemischen Natur der Faser werden beispielsweise Krustenbildner verwendet, die die Sauerstoffzufuhr reduzieren. Sie werden aber selten allein eingesetzt und spielen bei Textilien keine große Rolle.
- - Ähnliches gilt für wasserabspaltende Mittel, z.B. Aluminiumhydroxid, die unter Bildung von Wasserdampf, der als Schutzgas wirkt, Energie verbrauchen. Ihre wirksame Menge zum Schutz eines textilen Materials ist relativ hoch.
- - Radikalfänger, die die Kettenreaktion der Verbrennung unterbrechen, sind universal einsetzbar und spielen vor allem bei Kunststoffen eine große Rolle. Es handelt sich meist um Bromverbindungen oder 'um Kombinationen von Antimontrioxid mit einem Halogenspender.
- - Carbonizing and dehydrating agents that lead to the elimination of water in cellulose fibers, such as cotton, while leaving a flame-retardant carbon structure. Such agents are commercially available as Pyrovatex ° and Proban o . The feel of the textiles is not impaired, but the firmness usually suffers.
- - There are also similar flame retardant equipment specifically for wool.
- - Regardless of the chemical nature of the fiber, crust formers are used, for example, which reduce the oxygen supply. However, they are rarely used alone and do not play a major role in textiles.
- - The same applies to water-releasing agents, such as aluminum hydroxide, which consume energy to form water vapor, which acts as a protective gas. Their effective amount for protecting a textile material is relatively high.
- - Radical scavengers, which interrupt the chain reaction of the combustion, can be used universally and play a particularly important role in plastics. They are mostly bromine compounds or ' combinations of antimony trioxide with a halogen donor.
Sieht man von den Ausrüstungen ab, die jeweils nur auf eine Faser, z. B. Cellulosefasern oder Wolle ansprechen, so ist festzustellen, daß alle anderen Flammschutzmittel den Charakter von Textilien nachteilig verändern. Der Griff wird hart bzw. brettig, und die Fähigkeit Luft und Wasserdampf hindurch zu lassen bzw. Feuchtigkeit auch nur zu transportieren, wird stark beeinträchtigt. Demzufolge leiden die Trageigenschaften beträchtlich. Der Grund dafür ist insbesondere bei dem Bindemittel zu suchen, das das pigmentförmige Flammschutzmittel fixiert, aber auch das Gewebe verklebt.Apart from the equipment, each of which only on one fiber, for. B. cellulose fibers or wool, it should be noted that all other flame retardants adversely change the character of textiles. The handle becomes hard or boardy, and the ability to let air and water vapor through or even to transport moisture is severely impaired. As a result, the wearing properties suffer considerably. The reason for this is particularly to be found in the binder that fixes the pigment-like flame retardant but also glues the fabric.
Die FR-A-2 125410 beschreibt ein flammwidrig ausgerüstetes flexibles Material, bei dem eine Lösung von Diammoniumphosphat als Muster in Form von Punkten oder Linien so aufgedruckt ist, das Zonen hoher Konzentration mit Zonen abwechseln, in denen sich nur wenig oder kein Flammschutzmittel befindet. Anstelle der üblichen gleichmäßigen Verteilung durch Eintauchen des Stoffes in eine stark verdünnte Lösung von Diammoniumphosphat soll hier eine punktförmige Konzentration dieses Flammschutzmittels erreicht werden.FR-A-2 125410 describes a flame-retardant flexible material in which a solution of diammonium phosphate is printed as a pattern in the form of dots or lines in such a way that zones of high concentration alternate with zones in which there is little or no flame retardant. Instead of the usual uniform distribution by immersing the substance in a highly dilute solution of diammonium phosphate, a point concentration of this flame retardant is to be achieved here.
Auch nach der FR-A-2 328 790 wird auf Textilien ein Flammschutzmittel in Form von Punkten aufgedruckt. Dabei handelt es sich um einen bestimmten bromierten Phosphorsäureester und kein pigmentförmiges Flammschutzmittel.Even according to FR-A-2 328 790, a flame retardant in the form of dots is printed on textiles. It is a specific brominated phosphoric acid ester and not a pigmented flame retardant.
Die DE-A-2 105 019 beschreibt Gewebe, bei denen wenigstens zwei Hilfsmittel verschiedener Funktion auf die Oberfläche eines Gewebes aufgebracht werden, wobei das eine Hilfsmittel in Form von kleinen gleichmäßig auf der Oberfläche des Gewebes verteilten, z. B. fleckenartigen Zonen aufgebracht wird und das andere Hilfsmittel wenigstens auf einem Teil des restlichen Gebiets verteilt aufgebracht wird. Eines der beiden Hilfsmittel verschiedener Funktion kann auch ein Mittel zur Flammfestausrüstung des Gewebes sein.DE-A-2 105 019 describes fabrics in which at least two auxiliaries of different functions are applied to the surface of a fabric. B. patch-like zones is applied and the other aid is applied distributed at least in a part of the rest of the area. One of the two aids of different functions can also be a means of flame retarding the fabric.
Der Erfindung liegt die Aufgabe zugrunde, flexible, insbesondere textile, Materialien unter Verwendung von pigment- oder pulverförmigen Flammschutzmitteln in Kombination mit Bindemitteln in einer Weise flammwidrig auszurüsten, daß gute Trageeigenschaften bei hervorragender Schutzwirkung resultieren. Hierzu gehört auch die Möglichkeit der Verwendung von Flammschutzmitteln, die bisher nicht für Textilien verwendet wurden.The invention has for its object to provide flexible, in particular textile, materials using pigment or powder flame retardants in combination with binders in a flame retardant manner that good wearing properties result with excellent protection. This also includes the possibility of using flame retardants that have not previously been used for textiles.
Erfindungsgemäß wird diese Aufgabe bei einem flammwidrig ausgerüsteten flexiblen Material, bei dem das Flammschutzmittel in Form von Häufchen oder Dämmen aufgedruckt ist, dadurch gelöst, daß die Häufchen oder Dämme des aufgedruckten Musters eine Höhe von 0,01 bis 1 mm und einen Durchmesser bzw. eine Breite von 0,05 bis 2 mm haben und 20 bis 80% der Oberfläche des flexiblen Trägers bedecken und entweder ein pulverförmiges Flammschutzmittel, das durch Aufschäumen eine feuerfeste Schicht bildet, oder pulverförmige Flammschutzmittel in Form von Bromverbindungen oder Kombinationen von Antimontrioxid mit einem Halogenspender sowie in beiden Fällen ein Bindemittel enthalten.According to the invention, this object is achieved with a flame-retardant flexible material in which the flame retardant is printed in the form of piles or dams in that the piles or dams of the printed pattern have a height of 0.01 to 1 mm and a diameter or one Have a width of 0.05 to 2 mm and cover 20 to 80% of the surface of the flexible carrier and either a powdered flame retardant, which forms a fire-resistant layer by foaming, or powdered flame retardant in the form of bromine compounds or combinations of antimony trioxide with a halogen dispenser and in contain a binder in both cases.
Die Häufchen oder Dämme des aufgedruckten pulverförmigen Flammschutzmittels haben vorzugsweise einen Durchmesser bzw. eine Breite von 0,2 bis 1 mm. Durch die Gestaltung des Drukkes wird dafür gesorgt, daß das aufgedruckte Muster des Flammschutzmittels nur 20 bis 80%, vorzugsweise 30 bis 70% der Oberfläche des flexiblen Trägers bedeckt.The piles or dams of the printed powdery flame retardant preferably have a diameter or a width of 0.2 to 1 mm. The design of the print ensures that the printed pattern of the flame retardant covers only 20 to 80%, preferably 30 to 70%, of the surface of the flexible carrier.
Bei den pulverförmigen Flammschutzmitteln kann es sich sowohl um verkohlungsfördernde und feuererstickende als auch sperrschichtbildende Flammschutzmittel handeln. Gut geeignet sind auch die sogenannten Dämmschichtbildner, die Substanzen enthalten, die sich beim Erwärmen schaumig aufblähen, ab 200 bis 300°C verkohlen, sich dabei verfestigen und ein feinporiges gut isolierendes Polster bilden. Brauchbar sind ferner die für Kunststoffe bekannten pigmentförmigen Flammschutzmittel, deren flammhemmende Wirkung noch durch sogenannte Synergisten oder bestimmte Wichmacher bzw. die Bindemittel verstärkt werden kann. Auch selbstverlöschende Kunststoffe, insbesondere solche mit höherem Halogengehalt, sind allein oder in Kombination mit anderen bekannten Flammschutzmitteln brauchbar. Im Rahmen der Erfindung sind also alle pulverförmigen Flammschutzmittel verwendbar, die in Kombination mit dem als Träger dienenden textilen Flächengebilde und untereinander verträglich und beispielsweise in Römpps Chemie-Lexikon, 8. Aufl., (1981) unter dem Stichwort «Flammschutzmittel» und den hier aufgeführten Literaturstellen beschrieben sind.The powdered flame retardants can be carbonizing and fire-suffocating as well as barrier layer-forming flame retardants. So-called intumescent agents are also very suitable, they contain substances that foam up when they heat up, carbonize from 200 to 300 ° C, solidify and form a fine-pored, well-insulating cushion. The pigment-like flame retardants known for plastics can also be used, the flame-retardant effect of which can be enhanced by so-called synergists or certain plasticizers or the binders. Self-extinguishing plastics, especially those with a higher halogen content, can also be used alone or in combination with other known flame retardants. So are within the scope of the invention all powdered flame retardants can be used, which are compatible with one another in combination with the textile fabric serving as a carrier and are described, for example, in Römpps Chemie-Lexikon, 8th edition, (1981) under the keyword “flame retardants” and the literature references listed here.
Für das Aufdrucken der pulverförmigen Flammschutzmittel geeignete, insbesondere polymere, Bindemittel gehören chemisch beispielsweise zur Gruppe der Polyurethane, Polyacrylate oder Elastomere. Letztere können auch halogeniert, insbesondere chloriert oder fluoriert, sein. Sehr geeignet sind ferner Schmelzkleber auf Basis von Polyamiden, Polyestern oder Äthylen-Vinylacetat-Copolymeren (EVA). Beim Druck liegen die polymeren Bindemittel und die Schmelzkleber meist als Dispersion vor. In dem aufgedruckten Muster verbleiben dann aber nur die polymeren, verfestigten, beispielsweise vernetzten oder vulkanisierten, Bindemittel. Ihr Anteil in dem aufgedruckten Muster des Flammschutzmittels kann 5 bis 200, insbesondere 10 bis 50 Gew.%, bezogen auf das Flammschutzmittel, ausmachen.Suitable, in particular polymeric, binders suitable for printing on the powdered flame retardants chemically belong, for example, to the group of polyurethanes, polyacrylates or elastomers. The latter can also be halogenated, in particular chlorinated or fluorinated. Hotmelt adhesives based on polyamides, polyesters or ethylene-vinyl acetate copolymers (EVA) are also very suitable. When printing, the polymeric binders and hot melt adhesives are usually in the form of a dispersion. However, only the polymeric, solidified, for example crosslinked or vulcanized, binders then remain in the printed pattern. Their proportion in the printed pattern of the flame retardant can make up 5 to 200, in particular 10 to 50% by weight, based on the flame retardant.
Die Trägerschicht für das flammwidrig ausgerüstete flexible Material nach der Erfindung ist für die meisten Anwendungsgebiete, insbesondere für die Herstellung von Schutzanzügen, in der Regel ein textiles Flächengebilde aus Mineral-, Synthese- oder Naturfasern. Gewebe oder Gewirke werden wegen ihrer geringen Dicke bei hoher Festigkeit besonders bevorzugt. Die Auswahl des Trägertextils richtet sich nach dem gewünschten Verwendungszweck. Im Falle leichter Schutzbekleidung empfiehlt sich ein Verbundwerkstoff bzw. Mischgewebe aus Synthese- oder Naturfasern und Mineralfasern, wobei die Mineralfaserseite mit dem aufgedruckten Muster des Flammschutzmittels versehen wird. Auch die gleichzeitige Verwebung dieser Materialien ist gut geeignet. Die Mitverwendung von schwer entflammbaren bzw. besonders reißfesten Fasern, wie Aramiden (KEV-LAR, NOMEX) oder Polyimiden, kann für bestimmte Verwendungszwecke nützlich sein.The backing layer for the flame-retardant flexible material according to the invention is for most areas of application, in particular for the production of protective suits, as a rule a textile fabric made of mineral, synthetic or natural fibers. Woven or knitted fabrics are particularly preferred because of their small thickness and high strength. The choice of the backing textile depends on the intended use. In the case of light protective clothing, a composite or mixed fabric made of synthetic or natural fibers and mineral fibers is recommended, with the mineral fiber side being provided with the printed pattern of the flame retardant. The simultaneous weaving of these materials is also suitable. The use of flame-retardant or particularly tear-resistant fibers, such as aramids (KEV-LAR, NOMEX) or polyimides, can be useful for certain purposes.
Das flexible Trägermaterial kann nicht nur einseitig, sondern auch beidseitig bedruckt werden und die Klebewirkung des polymeren Bindemittels vor seiner Verfestigung läßt sich nutzen, um ein Verbundmaterial herzustellen, das zwischen zwei flexiblen, insbesondere luftdurchlässigen Trägerschichten eine unterbrochene Schicht aus dem regelmäßig aufgedruckten Muster des gebundenen Flammschutzmittels von bis zu etwa 1 mm Dicke aufweist. Dann liegen beispielsweise diese Noppen des Flammschutzmittels zwischen zwei Bahnen und sind besser geschützt. Dieses Verbundmaterial läßt sich herstellen, indem man unmittelbar nach dem Bedrucken einer Bahn der flexiblen Trägerschicht eine weitere Trägerschichtbahn zulaufen läßt, dann das Verbundmaterial trocknet und durch Einwirkung von Druck und Hitze zusammenkaschiert.The flexible backing material can be printed not only on one side, but also on both sides, and the adhesive effect of the polymeric binder before it solidifies can be used to produce a composite material which has an interrupted layer from the regularly printed pattern of the bound flame retardant between two flexible, in particular air-permeable backing layers up to about 1 mm thick. Then, for example, these nubs of the flame retardant lie between two webs and are better protected. This composite material can be produced by allowing another substrate layer web to run into the flexible carrier layer immediately after printing on a web, then drying the composite material and laminating it together under the action of pressure and heat.
Allgemein geschieht die Herstellung des erfindungsgemäßen flammwidrig ausgerüsteten flexiblen Materials in der Weise, daß eine Paste aus dem beispielsweise pulverförmigen Flammschutzmittel, gegebenenfalls mitflüssigen Flammschutzmitteln, Synergisten oder Weichmachern, einer Lösung oder Dispersion des polymeren Bindemittels und gegebenenfalls üblichen Druckhilfsmitteln durch Rotationssiebdruck auf die flexible Trägerschicht in einem bestimmten Muster aufgetragen, getrocknet und verfestigt wird. Wird das polymere Bindemittel z.B. in Form von Polyurethan- oder Polyacrylatlatices, dem Latex von gegebenenfalls halogenierten Elastomeren, wie Natur-, Synthese- oder Siliconkautschuk, Chloropren oder Fluoropren eingesetzt, dann müssen nach dem Druck die in einem bestimmten Muster aufgetragenen Häufchen oder Dämme des gebundenen Flammschutzmittels zur Entfernung der flüchtigen Latexbestandteile getrocknet werden. Je nach der chemischen Natur des Bindemittels können sie anschließend auch noch Druck und/oder Wärme ausgesetzt werden, um verfestigt, d.h. vernetzt oder vulkanisiert zu werden, sofern sich dabei nicht schon das Flammschutzmittel verändert, z.B. funktionsgemäß zersetzt.In general, the manufacture of the flame-retardant flexible material according to the invention takes place in such a way that a paste made from, for example, powdered flame retardant, optionally with liquid flame retardants, synergists or plasticizers, a solution or dispersion of the polymeric binder and, if appropriate, customary printing aids is applied to the flexible carrier layer by rotary screen printing in one certain pattern is applied, dried and solidified. If the polymeric binder is e.g. used in the form of polyurethane or polyacrylate latices, the latex of optionally halogenated elastomers, such as natural, synthetic or silicone rubber, chloroprene or fluoroprene, then the piles or dams of the bound flame retardant applied in a specific pattern must be removed to remove the volatile ones Latex ingredients are dried. Depending on the chemical nature of the binder, they can then also be subjected to pressure and / or heat in order to solidify, i.e. to be crosslinked or vulcanized, provided the flame retardant does not change, e.g. functionally decomposed.
Schmelzkleber, insbesondere auf Basis von Polyamiden, Polyestern oder EVA, können außer als Dispersion auch als Trockenpulver eingesetzt werden. Dann müssen die aufgedruckten Häufchen aus Flammschutzmitteln und Schmelzkleber unmittelbar nach dem Druck kurz einer Wärmestrahlung ausgesetzt werden, bevor man die bedruckte Bahn zur endgültigen Verfestigung in den sogenannten Trockenkanal fährt.Hot melt adhesives, in particular based on polyamides, polyesters or EVA, can also be used as dry powder in addition to as a dispersion. Then the printed piles of flame retardants and hot melt adhesive must be exposed to heat radiation shortly after printing before the printed web is driven into the so-called drying tunnel for final consolidation.
Die sich beim Erwärmen schaumig aufblähenden Dämmschichtbildner werden in einem solchen Muster bzw. Abstand der Flammschutzmittelpunkte aufgedruckt, daß das Druckmuster unter der Hitzeeinwirkung zu einer geschlossenen Schutzschicht zusammenschäumt, bevor der textile Träger erheblichen Schaden erleidet bzw. seine Festigkeit verliert. Einmal vorhanden, hält der Schaum dann extremen Belastungen während erstaunlich langer Zeit stand. Würde man den Brandschutzanstrich durch Beschichten bzw. Imprägnieren auftragen, so erhielte man aus dem flexiblen textilen Träger ein Brett, das nur für stationäre Anwendungen geeignet wäre. Die aufgedruckten Klümpchen oder Dämme hingegen verändern den Griff und die Luft- bzw. Wasserdampfdurchlässigkeit des textilen Materials nur wenig. Bei Verwendung eines durchsichtigen flexiblen Trägers, z. B. eines Glasfasergewebes oder auch einer Folie, bleibt trotz der aufgedruckten Punkte des Dämmschutzbildners noch eine beträchtliche Lichtdurchlässigkeit erhalten.The foaming intumescent material, which foams when heated, is printed in such a pattern or spacing between the centers of the flame retardants that the print pattern foams together under the action of heat to form a closed protective layer before the textile carrier suffers considerable damage or loses its strength. Once present, the foam can withstand extreme loads for an astonishingly long time. If you applied the fire protection coating by coating or impregnation, you would get a board from the flexible textile carrier that would only be suitable for stationary applications. The printed lumps or dams, on the other hand, only slightly change the handle and the air or water vapor permeability of the textile material. When using a clear flexible support, e.g. B. a glass fiber fabric or a film, remains a considerable light transmission despite the printed points of the insulation protection.
Es hat sich gezeigt, daß die erfindungsgemäßen flammwidrig ausgerüsteten flexiblen Materialien den gleichen Schutz bieten, wie bei einer vollflächigen Behandlung, während die Luftdurchlässigkeit noch immer sehr beachtlich und der Griff kaum verändert ist. Auch der Farbton des flexiblen Trägers bleibt auf der unbedruckten Seite erhalten. Die erfindungsgemäß flammwidrig ausgerüsteten flexiblen Materialien erlauben die Verarbeitung zu Schutzbekleidung für extreme Bedingungen im zivilen wie im militärischen Bereich.It has been shown that the flame-retardant flexible materials according to the invention offer the same protection as with a full-surface treatment, while the air permeability is still very remarkable and the grip is hardly changed. The color of the flexible carrier is also retained on the unprinted side. The flexible materials, which are flame-retardant according to the invention, can be processed into protective clothing for extreme conditions in both civil and military fields.
Claims (9)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT83109548T ATE42779T1 (en) | 1982-11-11 | 1983-09-26 | FLAME RETARDANT FLEXIBLE MATERIAL. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3241820A DE3241820C2 (en) | 1982-11-11 | 1982-11-11 | Flame retardant, flexible textile material or the like |
DE3241820 | 1982-11-11 |
Publications (3)
Publication Number | Publication Date |
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EP0111076A2 EP0111076A2 (en) | 1984-06-20 |
EP0111076A3 EP0111076A3 (en) | 1986-12-03 |
EP0111076B1 true EP0111076B1 (en) | 1989-05-03 |
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Application Number | Title | Priority Date | Filing Date |
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EP83109548A Expired EP0111076B1 (en) | 1982-11-11 | 1983-09-26 | Flame-resistant flexible material |
Country Status (3)
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EP (1) | EP0111076B1 (en) |
AT (1) | ATE42779T1 (en) |
DE (2) | DE3241820C2 (en) |
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US20030054141A1 (en) * | 2001-01-25 | 2003-03-20 | Worley James Brice | Coated articles having enhanced reversible thermal properties and exhibiting improved flexibility, softness, air permeability, or water vapor transport properties |
KR101680533B1 (en) * | 2010-02-26 | 2016-11-29 | 코오롱인더스트리 주식회사 | Artificial leather |
JP2014523976A (en) * | 2011-06-28 | 2014-09-18 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Pattern-forming flame-retardant flexible substrates and methods for producing them |
Family Cites Families (3)
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CA941692A (en) * | 1970-02-03 | 1974-02-12 | Shunya Ida | Specific processed cloths and a method of producing the same |
GB1339649A (en) * | 1971-02-12 | 1973-12-05 | Raduner & Co Ag | Flameproofing of sheet materials |
IT1043567B (en) * | 1975-10-22 | 1980-02-29 | Anic Spa | METHOD TO FIREPROOF NONWOVEN FABRICS |
-
1982
- 1982-11-11 DE DE3241820A patent/DE3241820C2/en not_active Expired - Fee Related
-
1983
- 1983-09-26 AT AT83109548T patent/ATE42779T1/en active
- 1983-09-26 EP EP83109548A patent/EP0111076B1/en not_active Expired
- 1983-09-26 DE DE8383109548T patent/DE3379794D1/en not_active Expired
Also Published As
Publication number | Publication date |
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DE3241820A1 (en) | 1984-05-17 |
DE3241820C2 (en) | 1994-04-21 |
EP0111076A3 (en) | 1986-12-03 |
ATE42779T1 (en) | 1989-05-15 |
DE3379794D1 (en) | 1989-06-08 |
EP0111076A2 (en) | 1984-06-20 |
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