DE19600877A1 - Ammonium phosphate-based flameproofing agent free of afterglow - Google Patents
Ammonium phosphate-based flameproofing agent free of afterglowInfo
- Publication number
- DE19600877A1 DE19600877A1 DE1996100877 DE19600877A DE19600877A1 DE 19600877 A1 DE19600877 A1 DE 19600877A1 DE 1996100877 DE1996100877 DE 1996100877 DE 19600877 A DE19600877 A DE 19600877A DE 19600877 A1 DE19600877 A1 DE 19600877A1
- Authority
- DE
- Germany
- Prior art keywords
- component
- flame retardant
- retardant according
- ammonium phosphate
- ammonium
- 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.)
- Withdrawn
Links
- 239000004254 Ammonium phosphate Substances 0.000 title claims abstract description 15
- 235000019289 ammonium phosphates Nutrition 0.000 title claims abstract description 15
- 229910000148 ammonium phosphate Inorganic materials 0.000 title claims abstract description 12
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 title description 3
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 12
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052796 boron Inorganic materials 0.000 claims abstract description 7
- 239000003063 flame retardant Substances 0.000 claims description 39
- 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 claims description 33
- 239000000203 mixture Substances 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 8
- 235000010338 boric acid Nutrition 0.000 claims description 8
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 7
- 229920000877 Melamine resin Polymers 0.000 claims description 6
- 229960002645 boric acid Drugs 0.000 claims description 6
- 229920001568 phenolic resin Polymers 0.000 claims description 6
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 5
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 5
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 5
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 5
- 239000004327 boric acid Substances 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 5
- 239000000600 sorbitol Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- VKFFEYLSKIYTSJ-UHFFFAOYSA-N tetraazanium;phosphonato phosphate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[O-]P([O-])(=O)OP([O-])([O-])=O VKFFEYLSKIYTSJ-UHFFFAOYSA-N 0.000 claims description 4
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 150000001639 boron compounds Chemical class 0.000 claims description 3
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 239000000155 melt Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims description 2
- 239000004386 Erythritol Substances 0.000 claims description 2
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 claims description 2
- 229930195725 Mannitol Natural products 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 239000012736 aqueous medium Substances 0.000 claims description 2
- 125000005619 boric acid group Chemical class 0.000 claims description 2
- 229910052810 boron oxide Inorganic materials 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 claims description 2
- 235000019414 erythritol Nutrition 0.000 claims description 2
- 229940009714 erythritol Drugs 0.000 claims description 2
- 230000036571 hydration Effects 0.000 claims description 2
- 238000006703 hydration reaction Methods 0.000 claims description 2
- 239000000594 mannitol Substances 0.000 claims description 2
- 235000010355 mannitol Nutrition 0.000 claims description 2
- MOWNZPNSYMGTMD-UHFFFAOYSA-N oxidoboron Chemical class O=[B] MOWNZPNSYMGTMD-UHFFFAOYSA-N 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 235000000346 sugar Nutrition 0.000 claims description 2
- 150000008163 sugars Chemical class 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims 2
- 239000007864 aqueous solution Substances 0.000 claims 1
- 239000007900 aqueous suspension Substances 0.000 claims 1
- 239000004568 cement Substances 0.000 claims 1
- 238000001816 cooling Methods 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 239000000320 mechanical mixture Substances 0.000 claims 1
- 239000000178 monomer Substances 0.000 claims 1
- 150000002894 organic compounds Chemical class 0.000 claims 1
- 239000011505 plaster Substances 0.000 claims 1
- 238000009736 wetting Methods 0.000 claims 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000004744 fabric Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical class [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 description 3
- IUTYMBRQELGIRS-UHFFFAOYSA-N boric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OB(O)O.NC1=NC(N)=NC(N)=N1 IUTYMBRQELGIRS-UHFFFAOYSA-N 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- -1 Melamine borate Chemical class 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- AXFZAZQUMXZWJV-UHFFFAOYSA-N diazanium;phosphono phosphate Chemical compound [NH4+].[NH4+].OP(O)(=O)OP([O-])([O-])=O AXFZAZQUMXZWJV-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- KCZIUKYAJJEIQG-UHFFFAOYSA-N 1,3,5-triazin-2-amine Chemical class NC1=NC=NC=N1 KCZIUKYAJJEIQG-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000271 Kevlar® Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 239000011111 cardboard Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000011093 chipboard Substances 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 239000007799 cork Substances 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000009970 fire resistant effect Effects 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 239000004761 kevlar Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 239000006012 monoammonium phosphate Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000011120 plywood Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011814 protection agent Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000011122 softwood Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/06—Organic materials
- C09K21/12—Organic materials containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
-
- 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
- D06M11/68—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 phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof
- D06M11/70—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 phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof with oxides of phosphorus; with hypophosphorous, phosphorous or phosphoric acids or their salts
- D06M11/71—Salts of phosphoric acids
-
- 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
- D06M11/68—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 phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof
- D06M11/72—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 phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof with metaphosphoric acids or their salts; with polyphosphoric acids or their salts; with perphosphoric acids or their salts
-
- 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
- D06M11/80—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 boron or compounds thereof, e.g. borides
- D06M11/82—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 boron or compounds thereof, e.g. borides with boron oxides; with boric, meta- or perboric acids or their salts, e.g. with borax
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/144—Alcohols; Metal alcoholates
- D06M13/148—Polyalcohols, e.g. glycerol or glucose
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
Description
Flammschutzmittel, die als wirksame Komponente Ammoniumphosphate enthalten, sind seit langem bekannt. Auch die Kombination von Ammoniumphosphaten mit Borverbindungen, wie Melaminborat, ist als Flammschutzmittel bekannt.Flame retardants that contain ammonium phosphates as an effective component have been known for a long time. Also the combination of ammonium phosphates with boron compounds, such as Melamine borate, is known as a flame retardant.
Die DE-A-38 01 456 beschreibt zum Beispiel flammwidrig ausgerüstete Polyurethanmassen, die als Flammschutzmittel ein Phenol oder Melamin-Formaldehyd-Kondensat, Pentaerythrit sowie ein Ammoniumphosphat und Dicyandiamid enthalten. Die EP-A-0 555 136 beschreibt ein intumeszierendes Flammschutzmittel aus Zuckeralkoholen und Diammoniumdiphosphat.DE-A-38 01 456 describes, for example, flame-retardant polyurethane compositions, the flame retardant is a phenol or melamine-formaldehyde condensate, pentaerythritol as well as an ammonium phosphate and dicyandiamide. EP-A-0 555 136 describes an intumescent flame retardant made from sugar alcohols and diammonium diphosphate.
In der DE-A-31 00 626 werden schwer entflammbare Kunststoffe mit einem besonderen strukturellen Aufbau beschrieben, die Ammoniumphosphat, Ammoniumpolyphosphat, Borax und/oder Melamin enthalten. Die DE-A-37 02 667 wiederum beschreibt eine Formmasse, die als Flammschutz und Brandschutzmittel eine Mischung aus primärem und sekundärem Ammoniumphosphat enthält. Auch bei der DE-A-40 34 046, die flammwidrige Polyurethan- Weichschaumstoffe beschreibt, wird modifiziertes und nichtmodifiziertes Ammoniumpolyphos phat in Kombination mit Melamin und Blähgraphit als Flammschutzmittel verwendet. Selbstverlöschende Polyurethane, die als Flammschutzmittel eine Phosphor- und eine Stickstoffkomponente enthalten, beschreibt die DE-A-40 03 230, wobei die Phosphorkom ponente aus in Wasser schwer löslichem Ammoniumpolyphosphat besteht und die Stickstoff komponente, z. B. Amino-1,3,5-triazine, beinhaltet.DE-A-31 00 626 describes flame-retardant plastics with a special one Structural structure described, the ammonium phosphate, ammonium polyphosphate, borax and / or melamine. DE-A-37 02 667 in turn describes a molding compound which as a flame retardant and fire protection agent, a mixture of primary and secondary Contains ammonium phosphate. Also in DE-A-40 34 046, the flame-retardant polyurethane Soft foams describes modified and unmodified ammonium polyphos phat used in combination with melamine and expanded graphite as a flame retardant. Self-extinguishing polyurethanes, which have a phosphor and a flame retardant Containing nitrogen component, describes DE-A-40 03 230, the phosphorus component consists of ammonium polyphosphate, which is sparingly soluble in water, and the nitrogen component, e.g. B. Amino-1,3,5-triazines.
Alle diese bisher bekannten Flammschutzmittel zeigen jedoch Nachteile, die deren Verwendung stark einschränken bzw. sogar unmöglich erscheinen lassen, da sie nachglimmen und gegebenenfalls zusätzlich die entsprechenden Normen nicht erfüllen, nicht lagerstabil sind oder eine zu starke Rauchentwicklung aufweisen. Das Nachglimmen ist beispielsweise bei Motorisolierungen im Automobilbau von großem Nachteil.However, all of these previously known flame retardants have disadvantages in their use severely restrict or even make it seem impossible because they glow and if necessary, additionally do not meet the relevant standards, are not stable in storage or have too much smoke. The afterglow is, for example, at Motor insulation in automotive engineering is a major disadvantage.
Aufgabe der Erfindung war es daher, ein lagerstabiles, universell einsetzbares und äußerst wirksames intumeszierendes Flammschutzmittel zu finden, das alle Anforderungen erfüllt, insbesondere das Nachglimmen zu verhindern oder zumindest stark zu reduzieren. Diese Aufgabe wird mit den Merkmalen des Anspruches 1 gelöst.The object of the invention was therefore to provide a storage-stable, universally applicable and extremely Find effective intumescent flame retardant that meets all requirements especially to prevent afterglow or at least to reduce it strongly. This The object is achieved with the features of claim 1.
Da sowohl Kombinationen von Ammoniumpolyphosphat mit Melaminborat als auch von Zuckeralkoholen mit Diammoniumdiphosphat nachglimmen, ist es äußerst überraschend, daß die erfindungsgemäßen Flammschutzmittel ein Nachglimmen wirkungsvoll verhindern.Since both combinations of ammonium polyphosphate with melamine borate and of Afterglow sugar alcohols with diammonium diphosphate, it is extremely surprising that the flame retardants according to the invention effectively prevent afterglow.
Als Ammoniumphosphatkomponente können prinzipiell alle Ammoniumortho-, -di- und -polyphosphate verwendet werden, doch sind insbesondere das Tetraammoniumdiphosphat sowie polymere Ammoniumphosphate bevorzugt.In principle, all ammonium ortho-, di- and -polyphosphates are used, but especially the tetraammonium diphosphate as well as polymeric ammonium phosphates are preferred.
Die Polyalkoholkomponente umfaßt alle Polyalkohole mit zwei und mehr OH-Gruppen pro Molekül, wobei Erythrit, Pentaerythrit, Sorbit, Mannit und andere Zucker bevorzugt sind und sich vor allem Pentaerythrit und Sorbit als besonders wirksam gezeigt haben.The polyalcohol component includes all polyalcohols with two and more OH groups per Molecule, with erythritol, pentaerythritol, sorbitol, mannitol and other sugars being preferred and Pentaerythritol and sorbitol have been shown to be particularly effective.
Als Borkomponente findet bevorzugt Orthoborsäure (H₃BO₃) Verwendung. Es kommen aber auch Boroxide sowie deren Hydrationsprodukte und sonstige Borverbindungen, wie Salze der Borsäure, z. B. Melaminborat, in Betracht, aus denen sich in wäßrigem Milieu gegebenenfalls Borsäuren bilden können.Orthoboric acid (H₃BO₃) is preferably used as the boron component. But it will come also boron oxides and their hydration products and other boron compounds, such as salts of Boric acid, e.g. B. melamine borate, from which, if appropriate, in an aqueous medium Can form boric acids.
Das erfindungsgemäße Flammschutzmittel kann zum Schutz aller brennbaren Stoffe als Tränk-, Imprägnier- oder Beschichtungsmittel für faserige, kugelige, plättchen-, kristall- oder pulverförmige, massive oder poröse, stückige, hohlkörperartige, schaumstoffartige oder flächige, organische, brennbare Teilchen oder Teile verwendet werden. Dabei kann das erfindungsgemäße Flammschutzmittel allein oder in Kombination mit Bindemitteln eingesetzt werden. Bindemittel können Phenol- oder Melaminformaldehyd-Kondensationsprodukte, sonstige organische polymerisierbare oder kondensierbare Verbindungen, aber auch an organische Mittel, wie z. B. Wasserglasbinder etc., sein. Besondere Wirksamkeit wurde dort erreicht, wo feinteilige Stoffe wie Fasern, Späne, Holz, Kork, Körner, Fruchtschalen, Stärkeprodukte, Eiweißprodukte oder Cellulosezubereitungen mit dem erfindungsgemäßen Flammschutzmittel behandelt und anschließend durch Zusatz von Bindemitteln zu Formkörpern verarbeitet werden. Das Flammschutzmittel kann aber auch mit dem verwendeten Bindemittel gemischt werden und zum Einsatz kommen, oder aber die feinteiligen Stoffe werden mit dem Flammschutzmittel homogenisiert und danach erst mit dem Bindemittel versetzt.The flame retardant according to the invention can be used as an impregnating, Impregnating or coating agent for fibrous, spherical, platelet, crystal or powdery, solid or porous, lumpy, hollow body, foam or flat, organic, flammable particles or parts are used. It can Flame retardants according to the invention used alone or in combination with binders will. Binders can be phenol or melamine formaldehyde condensation products, other organic polymerizable or condensable compounds, but also on organic agents such as B. water glass binder, etc. Particular effectiveness was there reached where finely divided substances such as fibers, chips, wood, cork, grains, fruit peels, Starch products, protein products or cellulose preparations with the invention Flame retardants treated and then by adding binders to moldings are processed. The flame retardant can also be used with the binder are mixed and used, or the finely divided substances are mixed with the Flame retardant homogenized and only then mixed with the binder.
Die Zusammensetzung des erfindungsgemäßen Flammschutzmittels kann innerhalb gewisser Grenzen schwanken, ohne daß sich die Wirksamkeit des Flammschutzmittels wesentlich verändert.The composition of the flame retardant according to the invention can be within certain limits Limits fluctuate without significantly reducing the effectiveness of the flame retardant changed.
Das erfindungsgemäße Flammschutzmittel enthält vorzugsweise 65 bis 75 Gew.% der Ammoniumphosphatkomponente, 10 bis 40 Gew.%, besonders 20 bis 30 Gew.% der Polyalkoholkomponente und 2 bis 15 Gew.%, besonders 4 bis 6 Gew.% der Borkomponente.The flame retardant according to the invention preferably contains 65 to 75% by weight of the Ammonium phosphate component, 10 to 40% by weight, especially 20 to 30% by weight of the Polyalcohol component and 2 to 15 wt.%, Especially 4 to 6 wt.% Of the boron component.
In der einfachsten Form besteht das erfindungsgemäße Flammschutzmittel aus einer homogenen Mischung der feinpulverigen Inhaltsstoffe. Es kann aber auch dadurch erhalten werden, daß man zwei der Wirkstoffe mit einer konzentrierten Lösung oder Suspension des dritten Stoffes benetzt, anschließend trocknet und pulverisiert. Auch kann die Schmelze eines Inhaltsstoffes mit den anderen Inhaltsstoffen vermischt, die Mischung abgekühlt und anschließend gemahlen werden.In its simplest form, the flame retardant according to the invention consists of a homogeneous mixture of fine powdery ingredients. But it can also get it be that two of the active ingredients with a concentrated solution or suspension of third substance wetted, then dried and pulverized. The melt can also be one Ingredient mixed with the other ingredients, the mixture cooled and are then ground.
Wenn das pulverförmige erfindungsgemäße Flammschutzmittel schnell auf Temperaturen über 250°C erhitzt wird oder Flammengasen ausgesetzt wird, dann wird durch Aufschäumen eine Dämmschicht gebildet, die einen besonders effektiven Schutz gegen Entflammen darstellt. Aufgrund dieses auch als Intumeszenz bezeichneten Verhaltens werden daher die erfindungs gemäßen Flammschutzmittel, z. B. in gegebenenfalls verstärkten Formteilen in Formkörpern aus gebundenen Teilchen, wie z. B. Holz, Fasern, Pappe, Kunststoffe usw., in gebundenen, beschichteten bzw. imprägnierten Vliesen, Geweben, Gewirken, starren oder flexiblen Schaumstoffen und dergleichen verwendet.If the powdered flame retardant according to the invention quickly to temperatures Is heated to 250 ° C or is exposed to flame gases, then by foaming one Insulation layer formed, which represents a particularly effective protection against ignition. Because of this behavior, also known as intumescence, the invention contemporary flame retardants, e.g. B. in optionally reinforced moldings in moldings bound particles, such as As wood, fibers, cardboard, plastics, etc., in bound, coated or impregnated nonwovens, woven fabrics, knitted fabrics, rigid or flexible Foams and the like are used.
Im folgenden soll die Erfindung beispielhaft erläutert werden. Die angegebenen Teile und Prozente beziehen sich auf das Gewicht, sofern nichts anderes angegeben ist.The invention will be explained below by way of example. The specified parts and Percentages are by weight unless otherwise stated.
In einem geeigneten Mischaggregat werden 350 Teile Tetraammoniumpyrophosphat, 125 Teile Sorbit und 25 Teile Borsäure homogen miteinander vermischt. Die Mischung wird dann auf einer Stiftmühle gemahlen und verpackt.350 parts of tetraammonium pyrophosphate and 125 parts are in a suitable mixing unit Sorbitol and 25 parts of boric acid homogeneously mixed together. The mixture is then on ground and packed in a pin mill.
Ein Zwangsmischer wird mit 350 Teilen Ammoniumpolyphosphat und 125 Teilen Sorbit beschickt, und beide Komponenten werden miteinander vermischt. Bei laufendem Misch werkzeug werden dann 50 Teile einer heißen 50%igen Borsäurelösung auf die vorgelegten Komponenten aufgesprüht. Es bildet sich ein feines Granulat. Das Granulat wird in einem Durchlauftrommeltrockner getrocknet, anschließend gemahlen und verpackt.A compulsory mixer is used with 350 parts of ammonium polyphosphate and 125 parts of sorbitol loaded, and both components are mixed together. With mixing in progress 50 parts of a hot 50% boric acid solution are then placed on the tool Components sprayed on. A fine granulate is formed. The granules are in one Continuous drum dryer dried, then ground and packed.
Ein Schmelzkessel wird mit 350 Teilen Monoammoniumposphat beschickt und geschmolzen. In die Schmelze werden nacheinander 125 Teile Pentaerythrit und 25 Teile Borsäure eingetragen und untergemischt. Die Mischung wird ausgegossen und abgekühlt. Die erstarrte Mischung wird anschließend grob gebrochen, dann fein gemahlen und verpackt.A melting pot is charged with 350 parts of monoammonium phosphate and melted. 125 parts of pentaerythritol and 25 parts of boric acid are successively introduced into the melt registered and mixed. The mixture is poured out and cooled. The froze The mixture is then roughly broken, then finely ground and packed.
Ein Reißwollefaservlies wird mit dem erfindungsgemäßen Flammschutzmittel nach Beispiel 1 und danach mit einem Phenol-Formaldehyd-Kondensationsprodukt bepudert. Das derart vorbehandelte Vlies wird in einer heizbaren Presse verdichtet und bei 140°C ausgehärtet. Man erhält ein flächiges, leichtes Preßteil, welches dem "NORDTEST NT FIRE 002" entspricht und keinerlei Nachglimmen zeigt.A tear wool fleece is made with the flame retardant according to the invention according to Example 1 and then powdered with a phenol-formaldehyde condensation product. That way Pretreated fleece is compressed in a heatable press and cured at 140 ° C. Man receives a flat, light pressed part, which corresponds to the "NORDTEST NT FIRE 002" and shows no afterglow.
Eine Beschichtungsmasse auf Kunstharzbasis wird mit 20% des erfindungsgemäßen Flammschutzmittels nach Beispiel 2 vermischt. Eine phenolharzverleimte Sperrholzplatte wird mit der Beschichtungsmasse satt beschichtet. Die Beschichtung wird getrocknet und hinterläßt einen 0,5 mm dicken Belag auf der Plattenoberfläche. Diese Oberfläche wird mit einem Erdgasgebläse beflammt. Es bildet sich eine bis zu 10 mm dicke Schicht aus isolierendem und feuerabweisendem Intumeszenzschaum aus, hinter der das Holz gegen Durchbrennen geschützt ist.A coating composition based on synthetic resin is 20% of the invention Flame retardant mixed according to Example 2. A plywood sheet glued with phenolic resin is used fully coated with the coating compound. The coating is dried and left behind a 0.5 mm thick coating on the plate surface. This surface comes with a Flame for natural gas blowers. A layer of insulating and up to 10 mm thick is formed fire-resistant intumescent foam, behind which the wood is protected against burning is.
Ein Polyamidgewebe (Kevlargewebe) wird einseitig mit dem erfindungsgemäßen Flammschutz mittel nach Beispiel 3 beschichtet. Ein zweites Gewebe wird mit einem flüssigen Phenolharz benetzt und dann mit der benetzten Seite auf die mit dem erfindungsgemäßen Mittel beschichtete Seite gelegt. Beide Gewebe werden jetzt zusammengepreßt und durch Erhitzen miteinander verklebt. Das so erhaltene Flächengebilde wird mit der Flamme eines Erdgasgeblä ses beflammt. Das mit dem erfindungsgemäßen Flammschutzmittel behandelte Gewebe wird durch Beflammung verkohlt, dabei aber nicht zerstört.A polyamide fabric (Kevlar fabric) is one-sided with the flame retardant according to the invention coated according to Example 3. A second fabric is made with a liquid phenolic resin wetted and then with the wetted side to the agent according to the invention coated side. Both tissues are now pressed together and heated glued together. The sheet thus obtained is blown with a natural gas blower it flames. The fabric treated with the flame retardant according to the invention becomes charred by flame but not destroyed.
In einem geeigneten Mischaggregat werden 100 kg getrocknete Weichholzspäne vorgelegt und mit 25 kg des erfindungsgemäßen Flammschutzmittels gemäß Beispiel 3 vermischt. Die Mischung wird dann zusätzlich mit 15 kg Melamin-Formaldehydharz versetzt und homogeni siert. Die erhaltene Mischung wird auf einer heizbaren Presse zu einer Platte verpreßt. Diese Spanholzplatte von 20 mm Dicke widersteht einer 30minütigen Beflammung mit einem Erdgasgebläse, ohne durchzubrennen. Bei Abschalten des Gebläses ist nach 20 sec kein Nachglimmen mehr zu erkennen.100 kg of dried softwood shavings are placed in a suitable mixing unit and mixed with 25 kg of the flame retardant according to the invention according to Example 3. The The mixture is then additionally mixed with 15 kg of melamine-formaldehyde resin and homogeneous siert. The mixture obtained is pressed into a plate on a heatable press. This Chipboard with a thickness of 20 mm withstands 30 minutes of exposure to flame Natural gas blower without blowing. When the fan is switched off, there is no after 20 seconds Afterglow to see more.
Claims (10)
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DE1996100877 DE19600877A1 (en) | 1996-01-12 | 1996-01-12 | Ammonium phosphate-based flameproofing agent free of afterglow |
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DE102004043219A1 (en) * | 2004-09-03 | 2006-03-23 | Wolfgang Christ | Flat fibrous material and process for its production |
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