Compositions comprising ammonium polyphosphate

Abstract

The present invention relates to a composition comprising, as component (A), 0.1 to 99.9% by weight of phase II ammonium polyphosphate and, as component (B), 0.1 to 99.9% by weight of phase I and / or phase III, IV, V and / or VI ammonium polyphosphate, the sum of the components being 100% by weight, and to its use in intumescent coatings.

Description

Technical Field

[0001] The present invention relates to compositions comprising ammonium polyphosphate. Background Art

[0002] Ammonium polyphosphate is widely used as a flame retardant. In addition, ammonium polyphosphate can also be used to prevent the generation of nitrous gases in (acid) baths containing free nitric acid and used for metal surface treatment (EP-A-0004560).

[0003] Ammonium polyphosphate can exist in several crystalline forms (I to VI), wherein the ammonium polyphosphate of crystalline form I can be synthesized from a condensing agent and phosphoric acid or a phosphate.

[0004] Ammonium polyphosphate in form II is a slightly water-soluble product and is known as a flame retardant component for use in synthetic resins. It is usually prepared from phosphorus pentoxide.

[0005] A known method for preparing ammonium polyphosphate in crystalline form II is characterized in that ammonium polyphosphate in crystalline form I is subjected to a heat treatment for a specific period of time (C.Y. Shen et al., Journal of American Chemical Society, Vol. 91, p. 62 (1969)). Methods for preparing crystal forms II and IV are also proposed therein.

[0006] M. Watanabe, M. Sakurai and M. Takahashi, Phosphorus Research Bulletin 2003, 16, pp. 39-46, describe ammonium polyphosphate in form I and form V.

[0007] M. Watanabe, N. Narita, M. Sakurai, H. Suzuki, Bulletin of the Chemical Society of Japan 2000, 73, 115-119 and RC Sheridan, JF McCullough, NES Tahlheber, CY Shen in Inorganic Syntheses, John Wiley & Sons, Inc, 1979, 278-280 and KR Waerstad, GH McClellan, J. Agric. Food Chem. 1976, 24, 412-415 describe different processes for the preparation of ammonium polyphosphate of form II.

[0008] US-A-3,978,195 claims a process for preparing essentially water-insoluble chain ammonium polyphosphate, wherein equimolar amounts of ammonium orthophosphate and phosphorus pentoxide are reacted in the presence of ammonia at a temperature of 170 to 350° C. in a reactor equipped with mixing tools, with continuous mixing, kneading and comminution.

[0009] In another process described in EP-A-0537475, ammonium orthophosphate, phosphorus pentoxide and gaseous ammonia are reacted with one another in a first stage, so that the intermediate is further condensed and dried in a second stage on a tray dryer under an ammonia atmosphere.

[0010] Ammonium polyphosphate is generally difficult to prepare in high-purity and homogeneous form; in particular, its residual moisture content and hygroscopic properties present considerable problems in storage and transport.

[0011] Today, the known ammonium polyphosphates are frequently used in intumescent formulations, which are then used as flame-retardant coatings.

[0012] While conventional flame retardant formulations are primarily used to protect less heat-sensitive substrates, such as steel, aluminum, and / or concrete, there is a growing demand for insulating (protecting) less thermally stable substrates. These can be organic and inorganic materials. These can be of polymeric and non-polymeric nature.

[0013] Thermal insulation at low temperatures is essential for all substrates, as not only are the pyrolysis reactions that occur suppressed, but in the case of inert substrates (such as steel), the insulation effect is increased throughout the fire due to the expansion that occurs at low temperatures. This allows for significantly longer flame retardancy times to be achieved, or the amount applied to be significantly reduced. Summary of the Invention

[0014] It was therefore an object of the present invention to provide ammonium polyphosphates which are stable and easy to handle and lead to increased substrate protection, in particular when used in intumescent coatings.

[0015] This object is achieved by the following composition, comprising:

[0016] 0.1% to 99.9% by weight of phase II ammonium polyphosphate as component (A), and

[0017] As component (B), 0.1% to 99.9% by weight of phase I and / or phase III, IV, V and / or VI ammonium polyphosphate, the sum of the components being 100% by weight.

[0018] The composition preferably contains 60% to 99.9% by weight of component A and 0.1% to 40% by weight of component B.

[0019] More preferably, the composition contains 65% to 92% by weight of component A and 8% to 35% by weight of component B.

[0020] Compositions wherein component A is a phase II ammonium polyphosphate and component B is a phase I ammonium polyphosphate are preferred.

[0021] Component A is preferably of the formula (NH4) n+2 P n O 3n+1 Phase II ammonium polyphosphate, wherein n=300 to 100,000.

[0022] Component A is more preferably of the formula (NH4) n+2 P n O 3n+1 Phase II ammonium polyphosphate, wherein n=1000 to 25000.

[0023] Component B is preferably of the formula (NH4) n+2 P n O 3n+1 Phase I ammonium polyphosphate, wherein n=5 to 100.

[0024] The composition according to the invention preferably has

[0025] — a residual moisture content (water content) according to ISO 760 of less than 0.5%,

[0026] —0.3 to 0.9 g / cm 3 The bulk density,

[0027] - less than 1.5% water solubility (10% suspension in water at 25°C),

[0028] - a viscosity of less than 40 mPas (Brookfield DV3T, speed 50 rpm, spindle 1),

[0029] - Particle size d from 1 to 50 μm 50 , which is measured by laser diffraction,

[0030] - Particle size d from 10 to 60 μm 90 , which is measured by laser diffraction, and

[0031] - pH 4 to 8 (10% suspension in water at 25°C).

[0032] In the composition according to the invention, the ammonium polyphosphate is preferably microencapsulated with organofunctional (poly)silanes, (poly)siloxanes, (poly)silazanes, modified waxes, polyurethanes, polyepoxides, urea-formaldehyde resins, melamine-formaldehyde resins, emulsions based on (meth)acrylate resins, based on styrene / acrylate copolymers, urethanes, based on ethylene / nonyl acetate copolymers, based on rubber and / or mixtures thereof.

[0033] Preference is given to compositions which further contain up to 10% by weight, based on the amount of components (A) and (B):

[0034] ammonium sulfate, triethylammonium sulfate, tetramethylammonium sulfate, trimethylammonium sulfate, dimethyl sulfate, diethyl sulfate, dipropyl sulfate, sodium octyl sulfate, sodium decyl sulfate, sodium octadecyl sulfate, lauryl sulfate, urea sulfate, melamine sulfate, hydroxylamine sulfate, hydrazine sulfate, potassium sulfate, potassium hydrogen sulfate, sodium sulfate, sodium hydrogen sulfate, magnesium sulfate, magnesium hydrogen sulfate, calcium sulfate, calcium hydrogen sulfate, barium sulfate, potassium aluminum sulfate, aluminum sulfate, iron (III) sulfate, iron (II) sulfate, cobalt sulfate, titanium sulfate, zinc sulfate, tin sulfate, cerium sulfate, lithium sulfate, trimethylsulfonium methyl sulfate, or mixtures thereof.

[0035] The invention also relates to the use of the composition according to at least one of claims 1 to 10 for reducing the initial reaction temperature of intumescent coatings, for increasing the flame retardancy of intumescent coatings, as a flame retardant for clearcoats and intumescent coatings, for or as a flame retardant for wood and other cellulosic products, for or as a reactive and / or non-reactive flame retardant for polymers, gelcoats and / or unsaturated polyester resins, for producing flame-retardant polymer molding compounds, for producing flame-retardant polymer moldings, for rendering polyesters and pure and blended cellulosic textiles flame-retardant, for polyurethane foams, for polyolefins, for unsaturated polyesters and phenolic resins, and for rendering textiles flame-retardant.

[0036] The invention also relates to the use of the composition according to at least one of claims 1 to 10 in or for plug connectors, current-carrying components in power distributors (residual current protection), circuit boards, potting compounds, power connectors, circuit breakers, lamp covers, LED lamp covers, capacitor covers, coil elements, ventilation devices, grounding contacts, plugs, in / on printed circuit boards, covers for plugs, battery covers, cables, flexible circuit boards, charging cables, motor covers, textile coatings and other products.

[0037] In particular, the present invention relates to the use of a composition according to at least one of claims 1 to 10 for flame-retardant coatings on steel, wood, wood-based materials, paper, mineral wool, plasterboard, plastics, metals, alloys, textiles made of synthetic or natural fibers and other materials and / or as a solder mask and for electrical switches and circuits.

[0038] Particular preference is given to the use of the composition according to at least one of claims 1 to 10 for coating steel structures, such as steel beams and steel supports, ceilings, walls, cables, pipes, ducts, cables and bulkheads, doors, curtains, flue grilles, shutters, safety cabinets, installation cabinets and other articles.

[0039] The invention also relates to a flame-retardant coating material comprising a film-forming binder, a blowing agent, a composition according to one or more of claims 1 to 10 as a foam-forming substance, a carbon-forming substance, auxiliaries and additives, and optionally a thickener, a dispersing additive and a solvent and / or a solvent mixture.

[0040] Such flame-retardant coatings preferably contain a film-forming binder, a blowing agent, a composition according to one or more of claims 1 to 10 as a foam-forming substance, at least one polyol as a carbon-forming substance, auxiliaries and / or additives, thickeners, dispersing additives and solvents and / or solvent mixtures.

[0041] The present invention particularly preferably comprises the following flame retardant coating:

[0042] 5% to 69.4% by weight of a film-forming binder,

[0043] 5% to 25% by weight of a blowing agent,

[0044] 5% to 40% by weight of a composition according to one or more of claims 1 to 10 as foam-forming substance,

[0045] 5% to 25% by weight of carbon-forming substances,

[0046] 5% to 40% by weight of auxiliaries and / or additives,

[0047] 0.5 to 10% by weight of a thickener,

[0048] 0.1% to 10% by weight of wetting and / or dispersing additives, and

[0049] 10% to 40% by weight of solvents and / or solvent mixtures, wherein the components add up to up to 100% by weight.

[0050] The film-forming binder preferably comprises a copolymer based on styrene and acrylic esters, a copolymer based on acrylic esters, a vinyltoluene / acrylate copolymer, a styrene / acrylate polymer, a homopolymer based on vinyl acetate, a copolymer based on vinyl acetate, ethylene and vinyl chloride, a copolymer based on vinyl acetate and a vinyl ester of a long-chain branched carboxylic acid, a copolymer based on vinyl acetate and di-n-butyl maleate and / or acrylic esters, a vinyl / acrylate copolymer, a self-crosslinking polyurethane dispersion, a terpene and / or a polyterpene and / or a mixture thereof;

[0051] The blowing agent is melamine, melamine-formaldehyde condensate, guanidine, their salts, melamine condensation products and / or dicyandiamide;

[0052] The carbon-forming substance is starch, modified starch, polyol (polyol), such as saccharide and polysaccharide, and / or thermoplastic or thermosetting polymer resin binder, such as phenolic resin, urea resin, polyurethane, polyvinyl chloride, poly(meth)acrylate, polyvinyl acetate, polyvinyl alcohol, silicone resin and / or rubber;

[0053] The auxiliary agents and additives are glass fibers, mineral fibers, metal fibers, carbon fibers, kaolin, talc, aluminum oxide, aluminum hydroxide, magnesium hydroxide and other metal oxides, precipitated silica, silicates and / or powdered cellulose;

[0054] The thickeners and / or rheological additives are (modified) cellulose, silica, bentonite, castor oil derivatives, fat derivatives, polyamides, poly(meth)acrylates, polyacrylamides, polyethers, polyurethanes, polyvinyl alcohol, polyvinyl pyrrolidone, sugar polymers, such as gum arabic, alginate, xanthan and / or agar-agar;

[0055] The wetting and dispersing additive is an alkylphenol ethoxylate, polyacrylic acid and / or polyurethane;

[0056] The organic solvent and / or solvent mixture is an aromatic hydrocarbon, preferably xylene and / or alkylbenzene,

[0057] Preference is given to toluene and ethylbenzene; alcohols, preferably methanol, and / or alkanols, preferably 2-methyl-1-propanol; ketones, such as acetone or butanone, alkanoic esters and / or polyethers, preferably polyglycolethers.

[0058] The polyol is preferably a mixture of tripentaerythritol and / or a polycondensate of pentaerythritol and / or an ester based on pentaerythritol with a polyol, polyvinyl acetate, polyvinyl alcohol, sorbitol and / or an ethylene oxide-propylene oxide polyol.

[0059] The invention also relates to a process for preparing a mixture according to one or more of claims 1 to 10, characterized in that component (A) and component (B), each in powder form or as granules, are mixed with one another, or dissolved component (B) is introduced into component (A).

[0060] Another method for preparing the mixture according to the invention is characterized in that equimolar amounts of ammonium dihydrogen orthophosphate and urea are heated to a temperature of 250 to 300° C. for a period of 0.5 to 4 hours.

[0061] Another method for preparing the mixture according to the invention is characterized in that equimolar amounts of ammonium orthophosphate and urea are heated to a temperature of 250 to 305° C. under a moist ammonia atmosphere for a period of 0.1 to 4 hours.

[0062] An alternative process for preparing the mixture according to the invention is characterized in that equimolar amounts of ammonium orthophosphate and urea are heated to a temperature of 320 to 350° C. for a period of 0.1 to 4 hours under a moist ammonia atmosphere with simultaneous addition of component (B).

[0063] One preferred area of ​​application of ammonium polyphosphate is in intumescent formulations, which are then used as flame-retardant coatings.

[0064] Intumescent coatings, also known as flame-retardant coatings forming an insulation layer, are characterized in that they foam under the action of the corresponding heat in the event of a fire, and this foaming of the flame-retardant coating hinders or at least prevents the transfer of heat to substrates, such as steel structures, roofs, walls, cables, pipes and the like.

[0065] The insulating layer formed by the coating of the present invention already has excellent strength and thermal insulation properties and is characterized by an earlier onset of reaction compared to conventional coating formulations. Therefore, the intumescent coating composition according to the present invention is suitable for the effective protection of steel structures and other materials, as well as for the protection of heat-sensitive substrates.

[0066] For example, steel-frame buildings offer many advantages over conventional construction methods, but also have a serious disadvantage: in the event of a fire, the temperature of unprotected steel rises rapidly to such a high degree that it softens, loses rigidity, and thus compromises the stability of the structure (risk of collapse, preventing escape from the building, etc.). Consequently, thermal insulation of the steel is recommended. For example, intumescent coatings can be applied to various structures to delay the thermal effects of a fire. Such coatings slow the rate of temperature increase of the corresponding substrate to which they are applied, thereby extending the time before the structure collapses due to the heat from the fire. This additional time increases the chances of extinguishing the fire and cooling the building, and extends the time available for escape.

[0067] Optionally, one or more reactive flame retardants may be added to the composition according to the invention. In the present case, one example is a reactive organophosphorus compound, such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide (DOPO) and its derivatives and adducts.

[0068] The compositions of the present invention may preferably further comprise a phosphinate (EP-A-1544206).

[0069] The use of the above-mentioned phosphinates or diphosphinates reduces the onset temperature of the expansion reaction by more than 15° C. compared to formulations without phosphinate.

[0070] The organic solvent is preferably an aromatic hydrocarbon, preferably xylene and / or alkylbenzene, preferably ethylbenzene; an alcohol, preferably methanol, and / or an alkanol, more preferably 2-methyl-1-propanol; a polyether, preferably a polyglycol ether, more preferably α-isotridecyl-ω-hydroxy-polyglycol ether.

[0071] In the composition, additional additives can be added, for example thickening agents and / or rheological additives, and fillers. The rheological additives used, for example anti-settling agents, anti-flow agents (anti-running agent) and thixotropic agents, are preferably polyhydroxycarboxylic acid amides, urea derivatives, the salt of unsaturated carboxylic acid esters, the alkylammonium salts of acidic phosphoric acid derivatives, the amine salts of p-toluenesulfonic acid, the amine salts of sulfonic acid derivatives, and aqueous or organic solutions or mixtures of the compound. In addition, the rheological additives based on pyrogenic silica or precipitated silica or based on silanized pyrogenic silica or precipitated silica can be used. The rheological additives preferably comprise pyrogenic silica, modified and unmodified sheet silicates, precipitated silica, cellulose ethers, polysaccharides, polyurethanes and acrylate thickeners, urea derivatives, castor oil derivatives, polyamides, fatty acid amides and polyolefins, with the condition that they are solid forms, powdered cellulose and / or suspension media, for example xanthan gum.

[0072] Such flame retardant coatings (intumescent coatings) are primarily used in the form of paintable, spreadable or roller-applicable lacquers for protecting a wide variety of substrates, preferably steel beams and columns, roofs, walls, cables, pipes, cable ducts, cable and composite bulkheads, doors, curtains, smoke claddings, shutters, safety cabinets, installation cabinets and the like.

[0073] The present invention particularly relates to the use of the flame-retardant coating according to the invention on steel, wood, wood-based materials, paper, mineral wool, gypsum board, plastics, metals, alloys, textiles made of synthetic or natural fibers, and other suitable materials, and / or as a solder mask, and in electrical switches and circuits. The flame-retardant coating according to the invention is highly suitable for structural fire protection of hollow and H-section profiles and for workshop applications; it is also suitable for areas where improved weathering resistance is required.

[0074] The mixtures according to the invention are very suitable for the above-mentioned use in intumescent formulations, and then as flame-retardant coatings.

[0075] The mixtures according to the invention can also preferably be used or employed as intumescent coatings on polyolefins.

[0076] Preferred polyolefins are, for example, polymers of mono- and diolefins (e.g. ethylene, propylene, isobutylene, butene, 4-methylpentene, isoprene, butadiene, styrene), for example polypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polystyrene, poly(p-methylstyrene) and / or poly(α-methylstyrene), polyisoprene or polybutadiene and polyethylene (optionally crosslinked), for example high-density polyethylene (HDPE), high-density high-molecular-weight polyethylene (HDPE-HMW), high-density ultra-high-molecular-weight polyethylene (HDPE-UHMW), medium-density polyethylene (HMDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), very low-density polyethylene (VLDPE), branched low-density polyethylene (BLDPE), and polymers of cycloolefins, for example polymers of cyclopentene or norbornene.

[0077] Preferred polymers are furthermore mixtures (blends) of the polyolefins listed above, such as polypropylene (PP) with polyisobutylene, polyethylene with polyisobutylene, polypropylene with polyethylene (eg PP / HDPE / LDPE) and mixtures of various types of polyethylene (eg LDPE / HDPE).

[0078] Polymers which can preferably be used are further copolymers of monoolefins and dienes with one another and with other vinyl monomers, for example ethylene-propylene copolymers; LLDPE, VLDPE and mixtures thereof with LDPE; propylene-but-1-ene copolymers, propylene-isobutylene copolymers, ethylene-but-1-ene copolymers, ethylene-hexene copolymers, ethylene-methylpentene copolymers, ethylene-heptene copolymers, ethylene-octene copolymers, propylene-butadiene copolymers, isobutylene-isoprene copolymers, ethylene-alkyl acrylate copolymers, ethylene-alkyl methacrylate copolymers, ethylene-vinyl acetate copolymers. ester copolymers, copolymers of styrene or α-methylstyrene with a diene or acrylic derivative, such as styrene-butadiene, styrene-acrylonitrile, styrene-alkyl methacrylate, styrene-butadiene-alkyl acrylate and alkyl methacrylate, styrene-maleic anhydride, styrene-acrylonitrile-methyl acrylate; high impact resistant mixtures of styrene copolymers and another polymer, such as a polyacrylate, a diene polymer or an ethylene-propylene-diene terpolymer; and block copolymers of styrene, such as styrene-butadiene-styrene, styrene-isoprene-styrene, styrene-ethylene graft copolymers of ethylene / butylene-styrene or styrene-ethylene / propylene-styrene, and styrene or α-methylstyrene, for example, styrene grafted onto polybutadiene, styrene grafted onto polybutadiene-styrene copolymer or polybutadiene-acrylonitrile copolymer, styrene and acrylonitrile (or methacrylonitrile) grafted onto polybutadiene; styrene, acrylonitrile and methyl methacrylate grafted onto polybutadiene; styrene and maleic anhydride grafted onto polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide grafted onto polybutadiene; styrene and maleimide grafted onto polybutadiene; Styrene and alkyl acrylates or alkyl methacrylates grafted onto polyacrylic acid copolymers, styrene and acrylonitrile grafted onto ethylene-propylene-diene terpolymers, styrene and acrylonitrile grafted onto polyalkyl acrylates or polyalkyl methacrylates, styrene and acrylonitrile grafted onto acrylate-butadiene copolymers and mixtures thereof, such as those known, for example, as so-called ABS, MBS, ASA or AES polymers; and their copolymers with carbon monoxide or ethylene-acrylic acid copolymers and their salts (ionomers) and terpolymers of ethylene with propylene and a diene, such as hexadiene, dicyclopentadiene or ethylidene norbornene;and mixtures of such copolymers with one another and / or with other polymers, for example polypropylene-ethylene-propylene copolymers, LDPE-ethylene-vinyl acetate copolymers, LDPE-ethylene-acrylic acid copolymers, LLDPE-ethylene-vinyl acetate copolymers, LLDPE-ethylene-acrylic acid copolymers, as well as alternating or random polyalkylene-carbon monoxide copolymers and mixtures thereof with other polymers, such as polyamides.;

[0079] The mixtures according to the invention can also be used with thermoplastic polymers, such as polyesters, polystyrenes or polyamides, and thermosetting polymers, such as unsaturated polyester resins, epoxy resins, polyurethanes or acrylates.

[0080] Suitable polyesters are derived from dicarboxylic acids and their esters with diols and / or from hydroxycarboxylic acids or the corresponding lactones. Particular preference is given to using terephthalic acid and ethylene glycol, propane-1,3-diol and butane-1,3-diol.

[0081] Suitable polyesters include polyethylene terephthalate, polybutylene terephthalate (available from Celanese 2500, 2002; obtained from BASF ), poly(1,4-dihydroxymethylcyclohexane terephthalate), polyhydroxybenzoates and block polyetheresters derived from polyethers having hydroxyl end groups; and polyesters modified with polycarbonate or MBS.

[0082] The polymers are preferably polymers of monoolefins and diolefins, such as polypropylene, polyisobutylene, poly-1-butene, poly-4-methyl-1-pentene, polyisoprene or polybutadiene, and addition polymers of cyclic olefins, such as cyclopentene or norbornene; and polyethylene (which may optionally be cross-linked), such as high-density polyethylene (HDPE), high-density high molecular weight polyethylene (HDPE-HMW), high-density ultra-high molecular weight polyethylene (HDPE-UHMW), medium-density polyethylene (MDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), branched low-density polyethylene (BLDPE) and mixtures thereof.

[0083] The polymers are preferably copolymers of monoolefins and diolefins with each other or with other vinyl monomers, for example ethylene-propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene-1-butene copolymers, propylene-isobutylene copolymers, ethylene-1-butene copolymers, ethylene-hexene copolymers, ethylene-methylpentene copolymers, ethylene-heptene copolymers, ethylene-octene copolymers, propylene-butadiene copolymers, isobutylene-isoprene copolymers, ethylene-alkyl acrylate copolymers, ethylene-alkyl methacrylate copolymers, ethylene-vinyl acetate copolymers and mixtures thereof with monoxide. Copolymers of polypropylene, ethylene-propylene copolymers, LDPE / ethylene-vinyl acetate copolymers, LDPE / ethylene-acrylic acid copolymers, LLDPE / ethylene-vinyl acetate copolymers, LLDPE / ethylene-acrylic acid copolymers, and alternating or random polyalkylene / carbon monoxide copolymers, and mixtures thereof with other polymers, such as polyamides.

[0084] The polymers are preferably hydrocarbon resins (eg C5-C9), including their hydrogenated modifications (eg tackifying resins) and mixtures of polyolefins and starches.

[0085] The polymer is preferably polystyrene ( 143E (BASF), poly(p-methylstyrene), poly(α-methylstyrene)).

[0086] The polymer is preferably a copolymer of styrene or α-methylstyrene with a diene or acrylic derivative, such as styrene-butadiene, styrene-acrylonitrile, styrene-alkyl methacrylate, styrene-butadiene-alkyl acrylate and methacrylate, styrene-maleic anhydride, styrene-acrylonitrile-methacrylate; a high-impact mixture of a styrene copolymer and another polymer, such as a polyacrylate, a diene polymer or an ethylene-propylene-diene terpolymer; and a block copolymer of styrene, such as styrene-butadiene-styrene, styrene-isoprene-styrene, styrene-ethylene / butylene-styrene or styrene-ethylene / propylene-styrene.

[0087] The polymers are preferably graft copolymers of styrene or α-methylstyrene, for example styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymers, styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene, styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene, styrene and maleimide on polybutadiene, styrene and alkyl acrylate / methacrylate on polybutadiene, styrene and acrylonitrile on ethylene-propylene-diene terpolymers, styrene and acrylonitrile on polyalkyl acrylate or polyalkyl methacrylate, styrene and acrylonitrile on acrylate-butadiene copolymers, and mixtures thereof, such as those known as ABS, MBS, ASA or AES polymers.

[0088] The styrene polymer is preferably a relatively coarse-pored foam, such as EPS (expanded polystyrene), e.g. (BASF) and / or foams with relatively fine pores, such as XPS (extruded rigid polystyrene foam), e.g. (BASF). Polystyrene foam is preferred, e.g. XPS, (Dow Chemical) and the like.

[0089] The polymer is preferably a halogenated polymer, such as polychloroprene, chloroprene rubber, chlorinated and brominated copolymers of isobutylene-isoprene (halogenated butyl rubber), chlorinated or chlorosulfonated polyethylene, copolymers of ethylene and chlorinated vinyl, epichlorohydrin homopolymers and copolymers, in particular polymers of halogenated vinyl compounds, such as polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride; and copolymers thereof, such as vinyl chloride-vinylidene chloride, vinyl chloride-vinyl acetate or vinylidene chloride-vinyl acetate.

[0090] The polymers are preferably polymers derived from α,β-unsaturated acids and their derivatives, such as polyacrylates and polymethacrylates, polymethyl methacrylate impact-modified with butyl acrylate, polyacrylamide and polyacrylonitrile, and copolymers of the monomers mentioned with one another or with other unsaturated monomers, such as acrylonitrile-butadiene copolymers, acrylonitrile-alkyl acrylate copolymers, acrylonitrile-alkoxyalkyl acrylate copolymers, acrylonitrile-vinyl halide copolymers or acrylonitrile-alkyl methacrylate-butadiene terpolymers.

[0091] The polymer is preferably a polymer derived from unsaturated alcohols and amines or their acyl derivatives or acetals, such as polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate or polyvinyl maleate, polyvinyl butyral, polyallyl phthalate, polyallyl melamine; and copolymers thereof with olefins.

[0092] The polymers are preferably homopolymers and copolymers of cyclic ethers, such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or copolymers thereof with bisglycidyl ethers.

[0093] The polymer is preferably a polyacetal, such as polyoxymethylene, and polyoxymethylene containing a comonomer such as ethylene oxide; polyacetal modified with thermoplastic polyurethane, acrylate or MBS.

[0094] The polymers are preferably polyphenylene ethers and polyphenylene sulfides and mixtures thereof with styrene polymers or polyamides.

[0095] The polymers are preferably polyurethanes derived from polyethers, polyesters and polybutadienes having both terminal hydroxyl groups and aliphatic or aromatic polyisocyanates, and their precursors.

[0096] The polymers are preferably polyamides and copolyamides derived from diamines and dicarboxylic acids and / or from aminocarboxylic acids or the corresponding lactams, for example nylon-2 / 12, nylon-4, nylon-4 / 6, nylon-6, nylon-6 / 6, nylon-6 / 9, nylon-6 / 10, nylon-6 / 12, nylon-6 / 66, nylon-7, nylon-7,7, nylon-8, nylon-8,8, nylon-9, nylon-9,9, nylon-10, Nylon 10,9, nylon 10,10, nylon 11, nylon 12, aromatic polyamides based on meta-xylene, diamines, and adipic acid; polyamides prepared from hexamethylenediamine and isophthalic acid and / or terephthalic acid (polyhexamethylene isophthalamide, polyhexamethylene terephthalamide), optionally with elastomers as modifiers, such as poly-2,4,4-trimethylhexamethylene terephthalimide or poly-metaphenylene isophthalamide. Block copolymers of the above polyamides with polyolefins, olefin copolymers, ionomers, or chemically bonded or grafted elastomers; or polyethers, such as polyethylene glycol, polypropylene glycol, or polybutylene glycol. Furthermore, EPDM- or ABS-modified polyamides or copolyamides; and polyamides condensed during processing ("RIM polyamide systems").

[0097] The polymers are preferably polyureas, polyimides, polyamideimides, polyetherimides, polyesterimides, polyhydantoins and polybenzimidazoles.

[0098] The polymers are preferably polyesters derived from dicarboxylic acids and diols, and / or hydroxycarboxylic acids, or the corresponding lactones, for example polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dihydroxymethylcyclohexane terephthalate, polyhydroxybenzoates, and block polyetheresters derived from polyethers having hydroxyl end groups; also polyesters modified with polycarbonate or MBS.

[0099] The polymers are preferably polycarbonates and polyester carbonates.

[0100] The polymers are preferably polysulfones, polyethersulfones and polyetherketones.

[0101] The polymers are preferably crosslinked polymers which are derived from aldehydes on the one hand and from phenols, ureas or melamines on the other hand, such as phenol-formaldehyde, urea-formaldehyde and melamine-formaldehyde resins.

[0102] The polymers are preferably drying and non-drying alkyd resins.

[0103] The polymers are preferably unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyols and vinyl compounds as crosslinkers, and their halogenated flame-retardant versions.

[0104] The polymer is preferably a crosslinkable acrylic resin derived from a substituted acrylate, for example from an epoxy acrylate, a urethane acrylate or a polyester acrylate.

[0105] The polymers are preferably alkyd resins, polyester resins and acrylate resins which have been crosslinked with melamine resins, urea-formaldehyde resins, isocyanates, isocyanurates, polyisocyanates or epoxy resins.

[0106] The polymer is preferably a crosslinked epoxy resin derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds, for example products of bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, which are crosslinked with the aid of conventional hardeners, such as anhydrides or amines, with or without accelerators.

[0107] The polymer is preferably a mixture of the above-mentioned polymers (polymer blend), for example PP / EPDM (polypropylene / ethylene-propylene-diene rubber), polyamide / EPDM or ABS (polyamide / ethylene-propylene-diene rubber or acrylonitrile-butadiene-styrene), PVC / EVA (polyvinyl chloride / ethylene-vinyl acetate), PVC / ABS (polyvinyl chloride / acrylonitrile-butadiene-styrene), PVC / MBS (polyvinyl chloride / methacrylate-butadiene-styrene), PC / ABS (polycarbonate / acrylonitrile-butadiene-styrene), PBTP / ABS (polybutylene terephthalate / acrylonitrile-butadiene styrene), Polybutylene terephthalate), PC / ASA (polycarbonate / acrylate-styrene-acrylonitrile), PC / PBT (polycarbonate / polybutylene terephthalate), PVC / CPE (polyvinyl chloride / chlorinated polyethylene), PVC / acrylate (polyvinyl chloride / acrylate), POM / thermoplastic PUR (polyoxymethylene / thermoplastic polyurethane), PC / thermoplastic PUR (polycarbonate / thermoplastic polyurethane), POM / acrylate (polyoxymethylene / acrylate), POM / MBS (polyoxymethylene / methacrylate-butadiene-styrene), PPO / HIPS (polyphenylene ether / high-impact polystyrene), PPO / PA 6,6 (polyphenylene ether / nylon 6,6) and copolymers, PA / HDPE (polyamide / high-density polyethylene), PA / PP (polyamide / polyethylene), PA / PPO (polyamide / polyphenylene ether), PBT / PC / ABS (polybutylene terephthalate / polycarbonate / acrylonitrile butadiene styrene) and / or PBT / PET / PC (polybutylene terephthalate / polyethylene terephthalate / polycarbonate).

[0108] The mixtures according to the invention can accordingly also be used in or on textiles without impairing their properties.

[0109] The mixture according to the invention can be applied to flexible materials, in particular textile materials, in a randomly distributed manner or in a specific pattern, for example a dot pattern. Such textiles are used, for example, in the interior decoration of hotels, theaters and conference centers, and in vehicles (buses, trains, cars, airplanes, etc.).

[0110] The mixtures according to the invention can be used together with other flame retardants, such as for example in Described under “Flammschutzmittel (flame retardants)” in Chemie-Lexikon, 9th edition (1996), pages 1369 to 1371.

[0111] In general, the mixtures according to the invention, acting alone or in combination with other substances, may have the effect of promoting carbonization, extinguishing fire, forming a barrier layer, forming an insulating layer or some other kind of effect.

[0112] For all of the above-mentioned applications in and on polymers, especially polyolefins, as well as in or for the formation of insulating layers, intumescent coatings and textiles, further additives may be added, especially antioxidants, antistatic agents, blowing agents, further flame retardants, heat stabilizers, impact modifiers, processing aids, lubricants, light stabilizers, anti-drip agents, compatibilizers, reinforcing agents, fillers, nucleating agents, additives for laser marking, hydrolysis stabilizers, chain extenders, pigments and / or plasticizers.

[0113] The intumescent formulation - which is then used as a fire retardant coating - is prepared as follows:

[0114] a) initially adding the solvent or solvent mixture at room temperature and dissolving the corresponding resin therein while stirring, and then adding coating additives, such as dispersing additives and optionally defoamers, while stirring,

[0115] b) adding the foam-forming substance, blowing agent and carbon-forming substance, as well as auxiliaries and additives (such as titanium dioxide, fibers and fillers) while stirring at low speed,

[0116] c) Sprinkle thixotropic agent while stirring,

[0117] d) dispersing with high shear force for at least 25 minutes while maintaining the temperature at 50°C to 60°C,

[0118] e) Homogeneous dispersion is carried out for at least 5 minutes and the desired viscosity is established by adding solvent or solvent mixture.

[0119] These formulations can be used, for example, in the method for preparing a flame-retardant coating for forming an insulating layer according to the present invention. In this case, the silicone resin emulsion (binder) is mixed with an agent for forming foam in the event of a fire and optionally other auxiliaries and additives in a high shear dissolver and adjusted to the desired viscosity.

[0120] The coating composition of the present invention can be applied directly to the surface to be coated or through a primer coat. The coating composition is generally applied in liquid form at a temperature of -10 to 60° C. For example, the application can be achieved by airless spraying, casting (using a mold), painting or smoothing.

[0121] The coating composition according to the invention can be applied to a variety of substrates. Steel and aluminum substrates are preferred according to the invention, as well as composite materials, such as glass fiber reinforced plastics. DETAILED DESCRIPTION

[0122] The present invention is illustrated in a non-limiting manner in the following examples.

[0123] First, a mixture of ammonium polyphosphate was prepared by mixing the amount of crystalline Phase II ammonium polyphosphate disclosed in Table 1 with the corresponding amount of crystalline Phase I ammonium polyphosphate in a tumble mixer (from Heidolph) at 320 revolutions per minute (rpm) for 5 hours.

[0124] In Example 1, pure crystalline Phase II ammonium polyphosphate was used.

[0125] In Example 11, pure crystalline Phase I ammonium polyphosphate was used.

[0126] The mixtures thus obtained exhibited the properties reproduced in Table 1.

[0127]

[0128] The above values ​​are determined as follows:

[0129] Viscosity

[0130] To determine the viscosity, a 10% by weight suspension of the corresponding products from Examples 1 to 11 was prepared in water at 25° C. and stirred. The viscosity was determined by means of a Brookfield viscometer in accordance with DIN ISO 2555 (spindle 61, 100 rpm).

[0131] Conductivity

[0132] To determine the pH, a 10% by weight suspension of the corresponding products from Examples 1 to 11 was prepared in water at 25° C. and stirred for 5 minutes. The conductivity was determined potentiometrically (conductometer from Knick, Model 703).

[0133] pH

[0134] To determine the pH, a 10% by weight suspension of the corresponding products from Examples 1 to 11 was prepared in water at 25° C. and stirred for 5 minutes. The pH was determined potentiometrically (Metrohm, LL Aquatrode Plus WOC).

[0135] Acid value

[0136] To determine the acid number, a 10% by weight suspension of the corresponding product from Examples 1 to 11 was prepared in water at 25° C. and stirred for 5 minutes. The acid number was determined in accordance with ISO 2114.

[0137] water solubility

[0138] A 10% by weight suspension of ammonium polyphosphate or a mixture thereof is prepared in water at 25° C., stirred and filtered. The dry residue of the filtrate (10% suspension) based on the amount used corresponds to the water solubility of this ammonium polyphosphate.

[0139] Quality loss

[0140] Quality loss can be expressed in various ways:

[0141] 1) Temperature at which 2% mass loss occurs (°C)

[0142] 2) Mass loss at 300°C, expressed in %

[0143] The mass loss was determined by thermogravimetric analysis under a nitrogen atmosphere using an MA35M-230N instrument from Sartorius.

[0144] The bulk density of the flame retardant mixture is determined in accordance with EN ISO; DIN 53468 at 25°C.

[0145] Particle size d 50 It was determined with the aid of a Malvern Mastersizer.

[0146] As is apparent from Examples 1 to 11 in Table 1, some of the properties of the products described therein are adversely affected by the addition of Phase I ammonium polyphosphate to Phase II ammonium polyphosphate. For example, solubility increases to greater than 3%, and conductivity increases significantly. As a further disadvantage, as the Phase I ammonium polyphosphate content in the mixture increases, the acid value rises to greater than 5 mg KOH / g, and thermal stability decreases.

[0147] When corresponding coatings are used in areas exposed to weathering or other external influences, the action of moisture can lead to leaching of the ammonium polyphosphate, which is no longer available for the swelling reaction. This would be expected to result in a reduction in the swelling effect. For this reason, it is beneficial to keep the solubility of the APP low.

[0148] The increased salt concentration in the solution, which is associated with the solubility of short-chain ammonium (poly)phosphates, can be demonstrated in particular by measuring the electrical conductivity.

[0149] Furthermore, during storage of intumescent systems with aqueous binders, high salt loadings can lead to an undesirably shortened storage stability by impairing the dispersion stability, manifesting itself in an irreversible increase in viscosity.

[0150] For example, when Examples 1, 4 and 6 were incorporated into the intumescent formulation described in WO2017153227A1, good compatibility was observed.

[0151] By comparison with the use of pure Phase II APP (Example 1), in Examples 4 and 6, no increase in viscosity in the final product could be detected after 24 hours. No increase in the flame retardancy time (dry layer thickness of 2000 μm) of the intumescent coatings produced using the crystalline mixtures (Examples 4 and 6) could be observed. The foam properties also showed slight inhomogeneity and reduced stability. This could lead to detachment of the foam during fire tests, especially when applied in relatively high layer thicknesses.

[0152]

[0153] In contrast, if the mixtures according to the invention are used in solvent-based intumescent coatings, a clear increase in the insulating effect is observed.

[0154] The products from Examples 1 and 4 were used to prepare the solution-based intumescent formulations of Examples 12 and 13.

[0155] Example 12

[0156] The ammonium polyphosphate from Example 1 was used to prepare an intumescent formulation having the following composition:

[0157] 28 parts by weight of the ammonium polyphosphate obtained from Example 1,

[0158] 10 parts by weight of resin (Omnova, Ultra 100),

[0159] 8 parts by weight of melamine (OCI, ),

[0160] 8 parts by weight of pentaerythritol (Perstorp, PT 40),

[0161] 9 parts by weight of titanium dioxide (Cristal, 696),

[0162] 6 parts by weight of chloroparaffin (Dover Chemicals, NP70),

[0163] and 100 parts by weight of a thickener ( VP 031), adjuvants and additives (butyldiglycol acetate (BDGA), ), dispersing additives, paint additives, solvents ( 100 / 140, xylene).

[0164] Example 13

[0165] The procedure is as in Example 12, except that instead of 28 parts by weight of the ammonium polyphosphate from Example 1, 28 parts by weight of a mixture of phase II ammonium polyphosphate (85% by weight) and phase I ammonium polyphosphate (15% by weight) from Example 4 are used.

[0166] Each of the intumescent formulations in Examples 12 and 13 was prepared as follows:

[0167] a) Initially add the solvent at room temperature and add the paint additive (from BYK) while stirring -2163), dispersing aids and optional defoamers,

[0168] b) adding the respective mixtures obtained from Example 1 or 4, the blowing agent, the carbon source, titanium dioxide, the filler while stirring at low speed, followed by the thixotropic agent,

[0169] c) The mixture is dispersed with high shear for 20 to 60 minutes while maintaining a temperature of 30 to 70° C., and then the desired viscosity is established by adding solvent under low shear.

[0170] The intumescent formulation thus prepared was applied as an intumescent coating to coated steel panels (S235JR no. 1.0122, in accordance with standard EN 10025-2:2004; dimensions: 280×280×5 mm) and fire tested analogously to DIN 4102 part 8, fire curve ISO 834, with a dry film thickness of 2000 μm. Figure 1 The time course of the temperature of the back side of the plate is shown.

[0171] The inventors have found that, surprisingly, when the mixture from Example 4 is used, the temperature on the back side of the plate reaches T 临界 = 500°C for 109 minutes, which is significantly longer than the 100 minutes for the pure material from Example 1. This means that, in the use according to the invention, the critical softening temperature of the steel is reached only later, and the protective effect is therefore more effective. The structural integrity of the steel structure can therefore be maintained for a longer period of time.

[0172] This is therefore a performance gain of 9%. In the case of Example 1, it takes 32 minutes to reach a temperature of only 300°C on the back side, whereas in the case of Example 4 it takes 48 minutes; this means that the fire protection time is increased by 50%.

[0173] If, as Figure 2As shown in , plotting the temperature difference on the back side of the steel of Examples 12 and 13 over time, it can be seen that the insulation effect of Example 13 is higher throughout the fire process. A maximum temperature difference of 45°C is observed after about 27 minutes.

[0174] In the case of the inventive mixtures from Examples 12 and 13, the initial reaction occurs, in particular, at lower temperatures compared to Example 1. Consequently, the insulating effect begins earlier (faster), and substrates coated with the intumescent formulations according to the invention can be thermally insulated better. This can result in longer-lasting and / or more effective fire protection systems when the described systems are used in structural steel construction. Due to the longer flame retardancy, building residents have longer to leave in the event of a fire, and firefighters can extinguish the fire in a safe environment.

[0175] Taking into account the early onset of the insulating effect, the intumescent formulations according to the invention can now be used to render flame-retardant substrates that, until now, could not be protected against heat due to their low melting point. For example, polymers and other substrates that soften or release flammable and / or toxic pyrolysis gases even at low temperatures (e.g. 300°C) can also be protected.

[0176] From another perspective, the advantages of the intumescent formulation according to the present invention are also obvious:

[0177]

[0178] For example, in Example 1 (comparative example), the substrate temperature reached 250° C. after only 17 minutes, whereas in Example 4 according to the invention, this temperature was not reached until 29 minutes. Thus, the intumescent coating according to the invention is almost twice as effective as pure phase II ammonium polyphosphate within the appropriate temperature range.

[0179] Therefore, in the case of non-metallic substrates (e.g. thermoplastics), which generally have a melting point or decomposition temperature of 300°C or less, fire spread can be very effectively prevented. Practical examples here are structural material panels such as roof panels, partition walls, etc., or composite materials that are used in extreme environments (battery enclosures or pressurized hydrogen storage facilities).

[0180] The longer flame retardancy times at lower temperatures resulting from the use of the mixtures according to the invention advantageously lead to material savings; it is likewise possible to apply lower layer thicknesses to achieve the same effect.

[0181] In the relatively low temperature range, at 250°C, the performance improvement percentage is 71%.

[0182] The mixtures of ammonium polyphosphates of different crystalline phases according to the invention are therefore very suitable for the preparation of faster-acting intumescent coatings which additionally have an increased material efficiency.

[0183] The intumescent coatings of Examples 12 and 13 based on Examples 1 and 4 were applied to sheet materials made of various plastics and fire tested according to DIN 4102 Part 8, fire curve ISO 834, with a dry film thickness of 2000 μm.

[0184] Example 14

[0185] imposed on A3K (BASF; melting temperature according to ISO 11357: 260° C.):

[0186] With the intumescent formulation of Example 12, the critical softening temperature of the polymer of 260°C was reached after only 21 minutes, but with the intumescent formulation according to the invention from Example 13, this temperature was reached only after 35 minutes. Thus, the flame retardancy time was extended by 67% when the intumescent formulation according to the invention was used.

[0187] Example 15

[0188] imposed on 2205 polycarbonate sheet (Covestro; melting temperature according to ISO 11357: 300° C.):

[0189] With the intumescent formulation of Example 12, the critical softening temperature of the polymer of 300°C was reached after only 37 minutes, but with the intumescent formulation according to the invention from Example 13, this temperature was reached only after 58 minutes. Thus, the flame retardancy time was extended by 57% when the intumescent formulation according to the invention was used.

[0190] Example 16

[0191] Applied to in-house prepared glass fiber filled composite panels (DICY-cured bisphenol A epoxy resin):

[0192] With the intumescent formulation of Example 12, the critical decomposition temperature of the substrate of 320°C was reached after only 62 minutes, but with the intumescent formulation according to the invention from Example 13, this temperature was reached only after 74 minutes. Thus, the flame retardancy time was extended by 19% when the intumescent formulation according to the invention was used.

[0193] Example 17

[0194] Applied to aluminum plate

[0195] With the intumescent formulation of Example 12, the critical softening temperature of the substrate of 320°C was reached after only 62 minutes, but with the intumescent formulation according to the invention from Example 13, this temperature was reached only after 74 minutes. Thus, the flame retardancy time was extended by 19% when the intumescent formulation according to the invention was used.

[0196] The mixture from inventive example 4 was also used to prepare a solvent-based intumescent formulation (Table 3) using the following resins:

[0197] Example 18: Styrene-acrylate copolymer Ultra100 (Omnova / Synthomer)

[0198] Example 19: Methacrylate copolymer TB 080 (Evonik)

[0199] Example 20: Methacrylate LP 65 / 11 (Evonik)

[0200] Example 21: Styrene-acrylate copolymer AC 80 (Omnova / Synthomer)

[0201] Example 22: Methacrylate SC 124 / 50WS (Allnex)

[0202] Example 23: Methacrylate LP 63 / 11 (Evonik)

[0203] Table 3: Solvent-based intumescent formulations with various resins

[0204]

[0205] 1 Use Example 7

[0206] Table 3 describes the flexibility of the flame retardant mixtures according to the invention. Although in some cases no extension of the FRT was observed up to 500°C, earlier activation was manifested by an earlier onset of the initial reaction across the panel.

[0207] Furthermore, the preferred foam properties related to surface adhesion, expansion, uniformity and cell size were maintained in all experiments.

[0208] It has been found here that the inventive mixture from Example 4 leads in each case to a longer time for reaching the critical temperature in the corresponding intumescent formulations according to the invention than the mixture from Example 1.

[0209] The inventive mixtures of phase II ammonium polyphosphate with phase I ammonium polyphosphate are therefore very suitable for preparing effective intumescent formulations.

Claims

1. A composition consisting of: 65% to 92% by weight of phase II ammonium polyphosphate as component (A), and 8% to 35% by weight of ammonium polyphosphate of phase I as component (B), the sum of the components being 100% by weight; and Optionally, the composition comprises up to 10% by weight, based on the amount of components (A) and (B), of ammonium sulfate, triethylammonium sulfate, tetramethylammonium sulfate, trimethylammonium sulfate, dimethyl sulfate, diethyl sulfate, dipropyl sulfate, sodium octyl sulfate, sodium decyl sulfate, sodium octadecyl sulfate, lauryl sulfate, urea sulfate, melamine sulfate, hydroxylamine sulfate, hydrazine sulfate, potassium sulfate, potassium hydrogen sulfate, sodium sulfate, sodium hydrogen sulfate, magnesium sulfate, magnesium hydrogen sulfate, calcium sulfate, calcium hydrogen sulfate, barium sulfate, potassium aluminum sulfate, aluminum sulfate, iron (III) sulfate, iron (II) sulfate, cobalt sulfate, titanium sulfate, zinc sulfate, tin sulfate, cerium sulfate, lithium sulfate, trimethylsulfonium methyl sulfate, or mixtures thereof.

2. The composition according to claim 1, characterized in that Component A is a compound having the formula (NH4) n+2 P n O 3n+1 Phase II ammonium polyphosphate, wherein n = 300 to 100,000.

3. The composition according to claim 2, characterized in that Component A is a compound having the formula (NH4) n+2 P n O 3n+1 Phase II ammonium polyphosphate, wherein n = 1000 to 25000.

4. The composition according to any one of claims 1 to 3, characterized in that Component B is a compound having the formula (NH4) n+ 2P n O 3n+1 Phase I ammonium polyphosphate, wherein n = 5 to 100.

5. The composition according to any one of claims 1 to 3, characterized in that They have: - less than 1.5% water solubility, using the following conditions: 10% suspension in water at 25°C, -Viscosity less than 40 mPas using the following conditions: Brookfield DV3T, speed 50 rpm, spindle 1, and - pH 4 to 8, using the following conditions: 10% suspension in water at 25°C.

6. The composition according to any one of claims 1 to 3, characterized in that The ammonium polyphosphate has been microencapsulated with organofunctional (poly)silanes, (poly)siloxanes, (poly)silazanes, modified waxes, polyurethanes, polyepoxides, urea-formaldehyde resins, melamine-formaldehyde resins, emulsions based on (meth)acrylate resins, based on styrene / acrylate copolymers, urethanes, rubbers and / or mixtures thereof.

7. Use of the composition according to any one of claims 1 to 6 for reducing the initial reaction temperature of intumescent coatings, for increasing the flame retardancy of intumescent coatings, as a flame retardant for clearcoats and intumescent coatings, for or as a flame retardant for wood and other cellulosic products, for or as a reactive and / or non-reactive flame retardant for polymers, gelcoats, for producing flame-retardant polymer molding compounds, for producing flame-retardant polymer moldings, for rendering polyesters and pure and blended cellulosic fabrics flame-retardant by impregnation, for polyurethane foams, for polyolefins, for unsaturated polyesters and phenolic resins, and for rendering textiles flame-retardant.

8. The use according to claim 7, wherein the composition is used or employed as a reactive and / or non-reactive flame retardant for unsaturated polyester resins.

9. Use of the composition according to any one of claims 1 to 6 in or for the following substances: plug connectors, current-carrying components in power distributors for residual current protection, circuit boards, potting compounds, power connectors, circuit breakers, lamp covers, capacitor covers, coil elements, ventilation equipment, earthing contacts, plugs, in / on the following substances: covers for plugs, battery covers, cables, motor covers and textile coatings.

10. The use according to claim 9, wherein the composition is used for LED lamp covers.

11. The use according to claim 9, wherein the composition is used in a charging cable.

12. Use of the composition according to any one of claims 1 to 6 for flame-retardant coatings on wood-based materials, paper, mineral wool, plasterboard, plastics, metals, textiles made of synthetic or natural fibers and other suitable materials and / or as solder resists and for electrical switches and circuits.

13. Use according to claim 12, wherein the composition is used for flame retardant coatings on alloys.

14. Use of the composition according to any one of claims 1 to 6 for coating steel structures, ceilings, walls, ducts, cables and modular bulkheads, doors, curtains, flue grilles, shutters, safety cabinets, installation cabinets and other articles.

15. Use according to claim 14, wherein the steel construction is selected from the group consisting of steel beams and steel supports.

16. A flame-retardant coating comprising a film-forming binder, a blowing agent, a composition according to any one of claims 1 to 6 as a foam-forming substance, a carbon-forming substance, auxiliaries and additives, and a solvent and / or a solvent mixture, The auxiliary agents and additives are glass fibers, mineral fibers, metal fibers, carbon fibers, kaolin, talc, aluminum oxide, aluminum hydroxide, magnesium hydroxide and other metal oxides, precipitated silica, silicates and / or powdered cellulose.

17. The flame retardant coating according to claim 16, wherein the flame retardant coating optionally comprises a thickener and / or a dispersing additive.

18. The flame retardant coating according to claim 17, comprising: 5% to 69.4% by weight of a film-forming binder, 5% to 25% by weight of a blowing agent, 5% to 40% by weight of a composition according to any one of claims 1 to 6 as a foam-forming substance, 5% to 25% by weight of carbon-forming substances, 5% to 40% by weight of auxiliaries and additives, 0.5% to 10% by weight of a thickener, 0.1 to 10 wt% of a dispersing additive, and 10% to 40% by weight of solvents and / or solvent mixtures, wherein the sum of the components is 100% by weight.

19. The flame retardant coating according to any one of claims 16 to 18, characterized in that: The film-forming binder comprises a copolymer based on styrene and acrylic esters, a copolymer based on acrylic esters, a vinyltoluene / acrylate copolymer, a homopolymer based on vinyl acetate, a copolymer based on vinyl acetate, ethylene and vinyl chloride, a copolymer based on vinyl acetate and a vinyl ester of a long-chain branched carboxylic acid, a copolymer based on vinyl acetate and di-n-butyl maleate and / or acrylic esters, a vinyl / acrylate copolymer, a self-crosslinking polyurethane dispersion, a terpene and / or a polyterpene and / or a mixture thereof; The blowing agent is melamine, melamine-formaldehyde condensate, guanidine, their salts, melamine condensation products and / or dicyandiamide; The carbon-forming substance is starch, modified starch, polyol, and / or thermoplastic or thermosetting polymer resin binder, silicone resin and / or rubber; The thickener is modified cellulose, silica, bentonite, castor oil derivatives, fat derivatives, polyamide, poly(meth)acrylate, polyacrylamide, polyether, polyurethane, polyvinyl alcohol, polyvinyl pyrrolidone, sugar polymer; The dispersing additive is alkylphenol ethoxylate, polyacrylic acid and / or polyurethane; The solvents and / or solvent mixtures are aromatic hydrocarbons, alcohols, ketones, alkanoates and / or polyethers.

20. The flame retardant coating of claim 19, wherein the polyol is a sugar.

21. The flame retardant coating of claim 20, wherein the saccharide is a polysaccharide.

22. The flame retardant coating according to claim 19, wherein the thermoplastic or thermosetting polymer resin binder is selected from phenolic resin, urea-formaldehyde resin, polyurethane, polyvinyl chloride, poly(meth)acrylate, polyvinyl acetate and polyvinyl alcohol.

23. The flame retardant coating of claim 19, wherein the sugar polymer is gum arabic.

24. The flame retardant coating of claim 19, wherein the aromatic hydrocarbon is xylene.

25. The flame retardant coating of claim 19, wherein the aromatic hydrocarbon is an alkylbenzene.

26. The flame retardant coating according to claim 25, wherein the alkylbenzene is toluene or ethylbenzene.

27. The flame retardant coating of claim 19, wherein the alcohol is methanol.

28. The flame retardant coating of claim 19, wherein the alcohol is an alkanol.

29. The flame retardant coating of claim 28, wherein the alkanol is 2-methyl-1-propanol.

30. The flame retardant coating of claim 19, wherein the ketone is acetone or butanone.

31. The flame retardant coating of claim 19, wherein the polyether is a polyglycol ether.

Images