TWI830717B - Flame retardant mixture - Google Patents

Abstract

The invention relates to a mixture containing as component A at least one organic phosphinic acid salt and as component B at least one alkali metal stannate (M’₂ SnO₃ ), alkali metal hydroxyl stannate (M’₂ Sn(OH)₆ ), alkaline earth metal stannate (M’’SnO₃ ) and/or alkaline earth metal hydroxy stannate (M’’Sn(OH)₆ ). The invention relates also to the use of such a mixture.

Description

flame retardant mixture

This invention relates to non-corrosive flame retardant mixtures and their uses.

Especially for thermoplastic polymers, salts of phosphinic acid (phosphinates) have proven to be effective flame retardant additives (DE-A-2252258 and DE-A-2447727). Calcium and aluminum phosphinate have been described for their activity as being particularly effective in polyesters and having less negative impact on the engineering properties of polymer molding compositions than, for example, alkali metal salts (EP-A-0699708). Furthermore, synergistic combinations of phosphinates with certain nitrogen-containing compounds have been found to be more effective as flame retardants across the entire polymer spectrum than the phosphinate itself (PCT/EP97/01664 and DE-A- 19734437 and DE-A-19737727).

DE-A-19614424 describes phosphinates in polyesters and polyamides in combination with nitrogen synergists. DE-A-19933901 describes phosphinates in combination with melamine polyphosphate as flame retardants for polyesters and polyamides. However, when using these extremely effective flame retardants, there are instances of partial polymer degradation and polymer discoloration, especially at processing temperatures above 300°C and under hot and humid conditions. Examples of weathering during storage.

Thermoplastics are mainly processed in melt. Almost no plastic can withstand changes in structure and physical state when exposed to heat and shear without undergoing a change in chemical structure. The result will be cross-linking, oxidation, molecular weight changes, and consequent changes in physical and technical properties. To reduce the burden on the polymer during processing, different additives are added depending on the plastic in question.

By using flame retardants, further destabilization during melt processing is possible. Flame retardants must often be added at high rates to ensure that the plastic is fully flame retardant according to international standards. The chemical reactivity of flame retardants required for flame retardant effects at high temperatures can cause them to negatively affect the processing stability of plastics. For example, it may increase polymer degradation, cross-linking reactions, outgassing or discoloration.

The incorporation of flame retardants, especially the incorporation of phosphinates, can cause increased wear on processing machinery such as, for example, extruders and injection molding machines. Particularly affected parts are the metal parts of the plastifying unit during mixing and/or injection molding and the metal parts of the mold. The higher the processing temperature of the polymer, the greater the rate at which wear will occur.

Generally speaking, hard fillers (such as fiberglass) along with corrosive-eliminating products (eg, from flame retardants) cause wear on the metal surfaces of the tools. Depending on the material quality of the metal surface and depending on the plastic used, this wear necessitates relatively frequent replacement of the heating jacket, the conveying screw, and the injection mold in the conveying unit. Due to the abrasive nature of fiberglass-reinforced thermoplastic polymers, the possibilities for protecting conveyor screws from corrosion are limited because highly corrosion-resistant steel does not have the hardness required to process fiberglass-reinforced polymers.

Corrosion according to DIN EN ISO 8044 is a physicochemical interaction between a metal and its environment, which may result in a change in the properties of the metal, thereby significantly damaging the function of the metal, the environment or the technical system of which the metal forms part.

WO-A-2009/109318 describes a method of making polyamide and polyester molding compositions that are flame retardant, non-corrosive and easily flowable. Various additives may be used to reduce, but not prevent, corrosion and/or wear caused by flame retardants.

US-A-2010/0001430 describes flame retardant polyamides with zinc stannate which exhibit significantly reduced corrosiveness. Still, a certain level of wear can be measured here.

DE-A-102010048025 describes a flame retardant/stabilizer combination for thermoplastic polymers that exhibits high flame retardancy and has good mechanical properties while exhibiting no discoloration or weathering due to polymer degradation and decomposition reactions. It was noted that this flame retardant/stabilizer combination exhibited low corrosion.

DE-A-02015004662 describes a method for producing flame-retardant and non-corrosive polyamide compounds containing phosphinates, synergists and inorganic zinc compounds. Disadvantages of this invention arise especially when polyamides are processed at high temperatures. The stabilization and anti-corrosion effects are limited and/or the molding compound discolors to brownish black.

The market requires stable and non-corrosive flame retardant compounds that are within eco-toxicity regulations. Increasingly, applications can use high-temperature polymers that must be flame retardant and non-corrosive and can be pigmented in all colors.

It is therefore an object of the present invention to provide flame-retardant polymers that are halogen-free, exhibit high stability, good mechanical properties and no measurable corrosion and no reactions leading to discoloration during processing.

This object is achieved by using mixtures of salts of dialkylphosphinic acids (component A) and selected metal stannates (component B). The mixture may also contain additional components.

The object of the present invention is therefore a mixture containing: at least one organic phosphinate as component A and at least one alkali metal stannate (M' ₂ SnO ₃ ), alkali metal hydroxystannate (M' ₂ Sn (OH) ₆ ), alkaline earth metal stannate (M″SnO ₃ ) and/or alkaline earth metal hydroxystannate (M″Sn(OH) ₆ ) as component B.

In this mixture, it is preferred that M' is one of Na or K, and M" is one of Mg, Ca or Ba.

Preferably, at least one organic phosphinate corresponds to formula (I) Wherein R ¹ and R ² are the same or different, and each is H, linear or branched C ₁ -C ₁₈ alkyl, C ₆ -C ₁₈ aryl, C ₇ -C ₁₈ aryl alkyl or C ₇ - C ₁₈ alkylaryl, or R ¹ and R ² form one or more rings with each other, M is Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn , Li, Na, K and/or protonated nitrogen base; m is 1 to 4.

Preferably, R ¹ and R ² are the same or different, and each is methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, 2-pentyl, 3 -Pentyl, 2-methylbutyl, 3-methylbutyl (isoamyl), 3-methylbut-2-yl, 2-methylbut-2-yl, 2,2-dimethyl Propyl (neopentyl), hexyl, heptyl, octyl, nonyl, decyl, cyclopentyl, cyclopentylethyl, cyclohexyl, cyclohexylethyl, phenyl, phenylethyl, tolyl and /or tolyl.

Preferably, in formula (I), M is calcium, aluminum, zinc, titanium or iron ion.

Preferably, component B has a surface area of 20 to 200 m2/g BET.

Preferably, the mixture contains 40 to 99.9% by weight of component A and 0.1 to 60% by weight of component B.

More preferably, the mixture contains 70 to 99.9% by weight of component A and 0.1 to 30% by weight of component B. In particular, the mixture contains 90 to 99.5% by weight of component A and 0.5 to 10% by weight of component B.

Preferably, a mixture of one or more of items 1 to 8 of the patent application contains 0 to 79.9% by weight of nitrogen and/or phosphorus/nitrogen containing a salt of phosphorous acid of formula (II) and/or phosphorus-containing synergists or flame retardants as additional component C: [HP(=O)O ₂ ] ^2- M''' ^m+ (II) where M''' is Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na and/or K; 0 to 3% by weight of phosphonite or phosphonite and phosphonite A mixture of phosphites as further component D; 0 to 3% by weight of esters or salts of long-chain aliphatic carboxylic acids (fatty acids) usually with a chain length of C ₁₄ to C ₄₀ as further component E, The sum of these components is always 100% by weight; and from 0 to 20% by weight of short-chain polymeric (telomeric) phosphinate as further component F.

Preferably, the mixture contains 40 to 98.9% by weight of component A, 1 to 39.9% by weight of component B, 0.1 to 59% by weight of component C, 0 to 2% by weight of component D, 0 to 2% by weight of component E, and 0 to 20% by weight of component F.

More preferably, the mixture contains 50 to 94.5% by weight of component A, 5 to 39.5% by weight of component B, 0.5 to 45% by weight of component C, 0 to 2% by weight of component D, 0 to 2% by weight of component E, and 0 to 20% by weight of component F.

More preferably, the mixture contains 60 to 94% by weight of component A, 5 to 30% by weight of component B, 1 to 35% by weight of component C, 0 to 2% by weight of component D, 0 to 2% by weight of component E, and 0 to 20% by weight of component F.

Optimally, the mixture contains 60 to 89.7% by weight of component A, 5 to 20% by weight of component B, 5 to 20% by weight of component C, 0.1 to 2% by weight of component D, and 0.1 to 2% by weight of component E, and 0.1 to 20% by weight of component F.

Preferably, in the mixture of the present invention, component C includes the reaction product of phosphorous acid and an aluminum compound.

Preferably, component C includes aluminum phosphite [Al(H ₂ PO ₃ ) ₃ ], secondary aluminum phosphite [Al ₂ (HPO ₃ ) ₃ ], basic aluminum phosphite [Al(OH)(H ₂ PO ₃ ) ₂ *2aq], aluminum phosphite tetrahydrate [Al ₂ (HPO ₃ ) ₃ *4aq], aluminum phosphonate, Al ₇ (HPO ₃ ) ₉ (OH) ₆ (1,6- Hexamethylene diamine) _1.5 *12H ₂ O, Al ₂ (HPO ₃ ) ₃ *xAl ₂ O ₃ *nH ₂ O (where x = 1 - 2.27 and n = 1 - 50) and/or Al ₄ H ₆ P ₁₆ O ₁₈ , or aluminum phosphite containing formula (III), (IV) and/or (V), wherein formula (III) contains: Al ₂ (HPO ₃ ) ₃ x (H ₂ O) _q and q are 0 to 4 ; Formula (IV) contains Al _2.00 M _z (HPO ₃ ) _y (OH) _v x (H ₂ O) _w and M is an alkali metal ion, z is 0.01 to 1.5, y is 2.63 to 3.5, v is 0 to 2 , and w is 0 to 4; Formula (V) includes Al _2.00 (HPO ₃ ) _u (H ₂ PO ₃ ) _t x (H ₂ O) _s , and u is 2 to 2.99, and t is 2 to 0.01, and s is 0 to 4, or the aluminum phosphite includes a mixture of aluminum phosphite of formula (III), a poorly soluble aluminum salt and a nitrogen-free foreign ion; a mixture of aluminum phosphite of formula (IV) and an aluminum salt; formula (IV) ) to (V) a mixture of aluminum phosphite and aluminum phosphite [Al(H ₂ PO ₃ ) ₃ ], a mixture of secondary aluminum phosphite [Al ₂ (HPO ₃ ) ₃ ], and basic aluminum phosphite A mixture of [Al(OH)(H ₂ PO ₃ ) ₂ *2aq], a mixture with aluminum phosphite tetrahydrate [Al ₂ (HPO ₃ ) ₃ *4aq], a mixture with aluminum phosphonate, and Al ₇ ( Mixture of HPO ₃ ) ₉ (OH) ₆ (1,6-hexanediamine) _1.5 *12H ₂ O, and Al ₂ (HPO ₃ ) ₃ *xAl ₂ O ₃ *nH ₂ O (where x = 1 - 2.27 and n = 1 - 50) and/or a mixture with Al ₄ H ₆ P ₁₆ O ₁₈ .

Preferably, component C contains the condensation product of melamine and/or the reaction product of melamine and polyphosphoric acid and/or the reaction product of the condensation product of melamine and polyphosphoric acid, or a mixture thereof; or it contains melem, mellamine. or It includes nitrogen-containing phosphates of the formula (NH ₄ ) _y H _3-y PO ₄ and/or (NH ₄ PO ₃ ) _z (where y ranges from 1 to 3 and z ranges from 1 to 10000).

Preferably, the phosphonite (component D) has the following general formula R-[P(OR ₁ ) ₂ ] _m (VI) where R is a monovalent or polyvalent aliphatic, aromatic or heteroaromatic organic group, and compounds in which R ₁ is structure (VII) Or two groups R ₁ form a bridging group of structure (VIII) Where A is a direct bond, O, S, C ₁ -C ₁₈ alkylene group (linear or branched chain), C ₁ -C ₁₈ alkylene group (linear or branched chain), where R ₂ appears each time independently C ₁ -C ₁₂ alkyl (linear or branched), C ₁ -C ₁₂ alkoxy and/or C ₅ -C ₁₂ cycloalkyl, and n is 0 to 5, and m is 1 to 4 .

Preferably, component E includes alkali metal salts, alkaline earth metal salts, aluminum salts and/or zinc salts of long-chain fatty acids with 14 to 40 carbon atoms and/or long-chain fatty acids with 14 to 40 carbon atoms and Reaction products of polyols such as ethylene glycol, glycerol, trimethylolpropane and/or neopentylerythritol.

The short-chain polymeric phosphinic acid (component F) is preferably a metal salt of the following: ethylbutylphosphinic acid, dibutylphosphinic acid, ethylhexylphosphinic acid, butylhexylphosphinic acid, ethyl Octylphosphinic acid, 2-butylethylphosphinic acid, 1-ethylbutyl-butylphosphinic acid, ethyl-1-methylpentyl-phosphinic acid, di-butylphosphinic acid Phosphonic acid (di-1-methyl-propylphosphinic acid), propyl-hexylphosphinic acid, dihexylphosphinic acid, hexyl-nonylphosphinic acid, propyl-nonylphosphinic acid, dinonyl Phosphinic acid, dipropylphosphinic acid, butyl-octylphosphinic acid, hexyl-octylphosphinic acid, dioctylphosphinic acid, ethylcyclopentylethylphosphinic acid, butylcyclopentylphosphinic acid Pentyl ethyl phosphinic acid, ethyl cyclohexyl ethyl phosphinic acid, butyl cyclohexyl ethyl phosphinic acid, ethyl phenethyl phosphinic acid, butyl phenethyl phosphinic acid, ethyl 4- Methylphenylethylphosphinic acid, butyl 4-methylphenylethylphosphinic acid, butylcyclopentylphosphinic acid, butylcyclohexylethylphosphinic acid, butylphenylphosphinic acid, ethyl 4-Tolylphosphinic acid and/or butyl 4-tolylphosphinic acid, and wherein the metal is Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr At least one of the group of , Mn, Li, Na and/or K.

The present invention also includes the use of a mixture of one or more of items 1 to 20 of the patent application as an adhesive; as a crosslinker in the curing of epoxy resin, polyurethane or unsaturated polyester resin agent or accelerator; as a polymer stabilizer, as a crop protection composition, as a chelating agent, as a mineral oil additive, as an anti-corrosion agent, in cleaning and cleaning composition applications, and in electronic device applications.

The present invention also includes the use of a mixture of at least one of items 1 to 20 of the patent application as a flame retardant, especially as a flame retardant for transparent coatings and intumescent coatings, and for wood and other fibers. Flame retardants for base products, reactive or non-reactive flame retardants as polymers, for the manufacture of flame retardant polymer molding compositions, for the manufacture of flame retardant polymer moldings and/or for borrowing Impregnation makes polyester, pure cellulose fabrics and blended cellulose fabrics flame retardant and serves as a synergist.

The present invention also encompasses flame-retardant thermoplastic or thermosetting polymer molding compositions or polymer moldings, films, filaments, fibers or polymer shapes containing from 0.5 to 45% by weight of as claimed in claims 1 to 20 A mixture of at least one of the items, 55 to 99.5% by weight of a thermoplastic or thermosetting polymer or a mixture thereof, 0 to 55% by weight of additives, and 0 to 55% by weight of fillers or reinforcing materials, wherein the sum of these components is 100% by weight.

Preferably, the flame-retardant thermoplastic or thermosetting polymer molded composition or polymer molded article, film, filament, fiber or polymer formed body contains 1 to 30% by weight of the polycarbonate as described in items 1 to 20 of the patent application. A mixture of at least one of the following, 10 to 95% by weight of thermoplastic or thermosetting polymers or mixtures thereof, 2 to 30% by weight of additives and 2 to 30% by weight of fillers or reinforcing materials, where the sum of these components is 100% by weight %.

Preferably, in the flame-retardant thermoplastic or thermosetting polymer molding composition or polymer molding, film, filament, fiber or polymer shaped body as claimed in claim 23 or 24, the polymerization Materials include polyester, polyamide, thermoplastic elastomer, thermoplastic polyurethane, thermoplastic polyester elastomer, styrenic, polyketone, polyolefin, polyacrylate and/or polyethylene Polymer blends or other blends of amide or polyester; and thermosetting polymers based on epoxy, acrylate, vinyl ester, unsaturated polyester and/or phenolic resin.

At least, the present invention includes one or more of the flame-retardant plastic molding compositions, films, filaments, fibers or polymer shapes as specified in items 23 to 25 of the patent application, which are used in or Used in the following: connectors, power wetted parts in current distributors (RCCB), boards, potting compounds, power connectors, circuit breakers, lamp housings, LED housings, condenser housings, spools and Fans, protective contacts, connectors, covers for circuit boards, connectors, cables, flexible circuit boards, mobile phone chargers, hoods, textile coatings, for electrical appliances/electronics Moldings in the form of components in the sector, especially components for printed circuit boards, housings, films, cables, switches, distribution boards, relays, resistors, capacitors, coils, lamps, diodes, LEDs, transistors, Connectors, controllers, memories and sensors come in the form of large-area components, especially shell components used in cabinets, and in the form of intricately designed components with complex geometries.

Organic phosphinic acid salts correspond to formula (I), are also known as phosphinates, and are known in the prior art. For the purposes of the present invention, short chain dialkyl phosphinates are preferred, especially the aluminum salt of diethylphosphinic acid.

The mixtures according to the invention can be used in different plastics and polymers.

The plastic is preferably a thermoplastic polymer of the following types: high impact polystyrene, polyphenylene ether, polyamide, polyester, polycarbonate, and blends or polymer blends of the following types: ABS (propylene) nitrile-butadiene-styrene) or PC/ABS (polycarbonate/acrylonitrile-butadiene-styrene) or PPE/HIPS (polyphenylene ether/HI polystyrene) plastic. The plastic is preferably polyamide, polyester, thermoplastic polyester elastomer and PPE/HIPS blend.

The polymers are preferably derived from the following group: thermoplastic polymers such as polyesters, polystyrenes, polyamides, polyketones or polyurethanes and/or thermosetting polymers.

The polymer is preferably a polymer of monoolefins and dienes, such as polypropylene, polyisobutylene, polybutene-1, poly-4-methylpentene-1, polyisoprene or polybutadiene. Polymers; and addition polymers of cyclic olefins, such as cyclopentene or norbornene; and polyethylene (which is optionally cross-linked), such as high-density polyethylene (HDPE), high-density polyethylene Molle mass polyethylene (HDPE-HMW), high density ultra-high molar mass polyethylene (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE) , branched low-density polyethylene (BLDPE), and mixtures thereof.

The polymer is preferably a copolymer of monoolefins and diolefins with each other or with other vinyl monomers, such as ethylene-propylene copolymers, linear low-density polyethylene (LLDPE), and copolymers with low-density polyethylene (LDPE). Mixture, propylene-butene-1 copolymer, propylene-isobutylene copolymer, ethylene-butene-1 copolymer, ethylene-hexene copolymer, ethylene-methylpentene copolymer, ethylene-heptene copolymer, ethylene - Octene copolymer, propylene-butadiene copolymer, isobutylene-isoprene copolymer, ethylene-alkyl acrylate copolymer, ethylene-alkyl methacrylate copolymer, ethylene-vinyl acetate copolymer and their Copolymers with carbon monoxide, or ethylene-acrylic acid copolymers and their salts (ionomers), and ethylene and propylene and dienes (such as hexadiene, dicyclopentadiene or ethylidene norbornene) Terpolymers; and mixtures of these copolymers, such as polypropylene/ethylene-propylene copolymer, LDPE/ethylene-vinyl acetate copolymer, LDPE/ethylene-acrylic acid copolymer, LLDPE/ethylene-vinyl acetate copolymers, LLDPE/ethylene-acrylic acid copolymers and alternating or random polyolefin/carbon monoxide copolymers and mixtures with other polymers such as polyamides. The polymer is preferably a hydrocarbon resin (eg C ₅ -C ₉ ), including its hydrogenated modifications (eg adhesive resin) and a mixture of polyolefin and starch.

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

The polymer is preferably a copolymer of styrene or α-methylstyrene and diene or acrylic derivatives, such as styrene-butadiene, styrene-acrylonitrile, styrene-alkyl methacrylate, Styrene-butadiene-alkyl acrylate and styrene-butadiene-alkyl methacrylate, styrene-maleic anhydride, styrene-acrylonitrile-methyl acrylate; styrene copolymers and other polymers More impact-resistant blends of polyacrylates, diene polymers or ethylene-propylene-diene terpolymers; and block copolymers of styrene, such as styrene-butadiene-styrene, styrene -Isoprene-styrene, styrene-ethylene/butylene-styrene or styrene-ethylene/propylene-styrene.

The polymer is preferably a graft copolymer of styrene or α-methylstyrene, such as styrene grafted to polybutadiene, polybutadiene-styrene or polybutadiene-propylene. Styrene of nitrile copolymer, styrene and acrylonitrile (or methacrylonitrile) grafted to polybutadiene; styrene, acrylonitrile and methyl methacrylate grafted to polybutadiene; grafted Styrene and maleic anhydride in polybutadiene; Styrene, acrylonitrile and maleic anhydride or maleic imide grafted into polybutadiene; Grafted into polybutadiene Styrene and maleimide, styrene grafted to polybutadiene and alkyl acrylate or alkyl methacrylate, styrene grafted to ethylene-propylene-diene terpolymer and Acrylonitrile, styrene and acrylonitrile grafted to polyalkyl acrylate or polyalkyl methacrylate, styrene and acrylonitrile grafted to acrylate-butadiene copolymer, and mixtures thereof, as known For example ABS, MBS, ASA or AES polymers.

The styrenic polymer is preferably a relatively coarse-pored foam such as EPS (expanded polystyrene), such as Styropor (BASF) and/or a relatively fine-pored foam such as XPS (extruded rigid polystyrene). foam), such as Styrodur ^® (BASF). ^{Preferred are polystyrene foams such as Austrotherm ® _ _ _} The polymer is preferably a halogenated polymer, such as polychlorine, chlorinated rubber and chlorinated and brominated copolymers of isobutylene-isoprene (halobutyl rubber), chlorinated or chlorosulfonated polyethylene, ethylene and copolymers of chlorinated vinyl, epichlorohydrin homopolymers and copolymers, especially polymers of halogenated vinyl compounds, such as polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride; and Its copolymers, such as vinyl chloride-vinylidene chloride, vinyl chloride-vinyl acetate or vinylidene chloride-vinyl acetate.

The polymer is preferably a polymer derived from α,β-unsaturated acid and its derivatives, such as butyl acrylate impact-modified polyacrylate and polymethacrylate, polymethyl methacrylate, poly Acrylamide and polyacrylonitrile, and copolymers of the above monomers with each other or with other unsaturated monomers, such as, for example, acrylonitrile-butadiene copolymer, acrylonitrile-alkyl acrylate copolymer, acrylonitrile-acrylic acid alkoxy Alkyl ester copolymer, acrylonitrile-vinyl halide copolymer or acrylonitrile-alkyl methacrylate-butadiene terpolymer.

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 benzoate. Vinyl maleate, polyvinyl butyraldehyde, polyallyl phthalate, polyallyl melamine; and their copolymers with olefins.

The polymers are preferably homopolymers and copolymers of cyclic ethers, such as polyalkylene glycol, polyethylene oxide, polypropylene oxide, or their copolymers with bisglycidyl ether.

The polymers are preferably polyacetals, such as polyoxymethylene, and polyoxymethylene containing comonomers such as ethylene oxide; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.

The polymer is preferably polyphenylene ether and polyphenylene sulfide and their mixtures with styrene polymers or polyamide. The polymers are preferably polyurethanes derived from polyethers, polyesters, and polybutadiene with two terminal hydroxyl groups, as well as aliphatic or aromatic polyisocyanates, and their precursors.

The polymers are preferably polyamides and copolyamides derived from diamines and dicarboxylic acids, and/or derived from aminocarboxylic acids or corresponding lactamides, such as nylon 2/12, nylon 4 (Poly-4-aminobutyric acid, Nylon ^® 4 from DuPont), Nylon 4/6 (Poly (tetramethylene hexamethylene glycol)), Nylon ^® 4/6 from DuPont), Nylon 6 (polycaprolactam, poly-6-aminocaproic acid, Nylon ^® 6 (from DuPont), Akulon ^® K122 (from DSM); Zytel ^® 7301 (from DuPont); Durethan ^® B 29 (from from Bayer), Nylon 6/6 (poly(N,N'-hexamethylene adipamide), Nylon ^® 6/6 (from DuPont), Zytel ^® 101 (from DuPont); Durethan ^® A30, Durethan ^® AKV, Durethan ^® AM (from Bayer); Ultramid ^® A3 (from BASF)), Nylon 6/9 (poly(hexamethylene nonenamide), Nylon ^® 6/9, from DuPont), Nylon 6/10 (poly(hexamethylene dodecanediamide), Nylon ^® 6/10 from DuPont), nylon 6/12 (poly(hexamethylene dodecanediamide) amine), Nylon ^® 6/12, available from DuPont), Nylon 6/66 (poly(hexamethylene adipamide-co-caprolactam), Nylon ^® 6/66, available from DuPont), Nylon 7 (poly-7-aminoheptanoic acid, Nylon ^® 7, available from DuPont), Nylon 7,7 (polyheptamethylene peptidamide, Nylon ^® 7,7, available from DuPont), Nylon 8 (poly-8-aminooctanoic acid, Nylon ^® 8, available from DuPont), Nylon 8,8 (polyoctamethylene suberamide, Nylon ^® 8,8, available from DuPont), Nylon 9 (poly-9-aminononanoic acid, Nylon ^® 9, available from DuPont), Nylon 9,9 (polynonamethylene nonanediamide, Nylon ^® 9,9, available from DuPont), Nylon 10 ( Poly-10-aminodecanoic acid, Nylon ^® 10, available from DuPont), Nylon 10,9 (poly(decamethylene nonanediamide), Nylon ^® 10,9, available from DuPont), Nylon 10 , 10 (polydecamethylenedecanediamide, Nylon ^® 10,10, available from DuPont), nylon 11 (poly-11-aminoundecanoic acid, Nylon ^® 11, available from DuPont), nylon 12 (Polylauryl lactams, Nylon ^® 12 (from DuPont), Grillamid ^® L20 (from Ems Chemie)), aromatic polyamides derived from m-xylene, diamines and adipic acid; from hexylene Polyamides (polyhexamethylene isophthalamide, polyhexamethylene terephthalamide) prepared from methyldiamine, isophthalic acid and/or terephthalic acid, and optional elastomers are used as modifiers Agents, such as poly-2,4,4-trimethylhexamethylene p-phthalamide or polym-phenylene isophthalamide; the above-mentioned polyamide and polyolefin, olefin copolymer, ionomer, or Block copolymers of chemically bonded or grafted elastomers; or block copolymers with polyethers, such as polyethylene glycol, polypropylene glycol, or polybutylene glycol. In addition, polyamides or copolyamides modified with ethylene-propylene-diene rubber (EPDM) or modified with ABS; and polyamides condensed during processing ("RIM polyamide systems").

The polymer is preferably polyurea, polyimide, polyamidimide, polyetherimide, polyesterimide, polyglycolide, and polybenzimidazole.

The polymer is preferably a polyester derived from dicarboxylic acids and glycols and/or derived from hydroxycarboxylic acids or corresponding lactones, such as polyethylene terephthalate, polybutylene terephthalate ( ^Celanex® 2500, Celanex ^® 2002 from Celanese; Ultradur ^® from BASF), poly-1,4-dihydroxymethylcyclohexane terephthalate, polyhydroxybenzoates, and polyhydroxybenzoates derived from Polyether block polyetherester; and polyester modified by polycarbonate or MBS.

The polymer is preferably polycarbonate and polyestercarbonate.

The polymers are preferably polyethylene, polyetherether and polyetherketone; cross-linked polymers derived from aldehydes on the one hand and phenol, urea or melamine on the other hand, such as phenol-formaldehyde, urea-formaldehyde and melamine-formaldehyde resins; drying and non-drying alkyd resins.

The polymer is preferably an unsaturated polyester resin, which is a copolyester derived from saturated and unsaturated dicarboxylic acids and polyols and uses vinyl compounds as cross-linking agents, and its halogenated flame retardant modifications .

The polymer preferably comprises a crosslinkable acrylic resin derived from a substituted acrylate, for example from an epoxy acrylate, a urethane acrylate or a polyester acrylate. Preferably, the polymer is alkyd resin, polyester resin and acrylate resin cross-linked with melamine resin, urea resin, isocyanate, isocyanate, polyisocyanate or epoxy resin.

The polymer is preferably a cross-linked epoxy resin derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds, such as bisphenol A diepoxypropyl ether, bisphenol F diepoxy Products of propyl ether which are cross-linked using customary hardeners such as anhydrides or amines with or without accelerators.

The polymer is preferably a mixture (polyblend) of the above-mentioned polymers, for example, PP/EPDM (polypropylene/ethylene-propylene-diene rubber), polyamide/EPDM or ABS (polyamide/ethylene-diene rubber). 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 Diester/acrylonitrile-butadiene-styrene), 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 Ethylene), PA/PPO (polyamide/polyphenylene ether), PBT/PC/ABS (polybutylene terephthalate/polycarbonate/acrylonitrile-butadiene-styrene) and/or PBT/ PET/PC (polybutylene terephthalate/polyethylene terephthalate/polycarbonate).

Preferably, the flame retardant-stabilizer combination is used in the plastic molding composition in a total amount of 2 to 50% by weight based on the plastic molding composition.

The best method is to use a flame retardant-stabilizer combination in the plastic molding composition in a total amount of 10 to 30% by weight based on the plastic molding composition.

Finally, the invention also relates to polymer shapes, films, threads and fibers, each of which contains a flame retardant-stabilizer combination according to the invention.

The polymer shapes, films, threads and fibers are high-impact polystyrene, polyphenylene ether, polyamide, polyester, polycarbonate, and blends or polymer blends of the following types: ABS (propylene) nitrile-butadiene-styrene) or PC/ABS (polycarbonate/acrylonitrile-butadiene-styrene), polyamide, polyester and/or ABS.

More preferably, the polymer contains one or more polyamides to which fillers and/or reinforcing agents have been provided.

The polyamide is preferably in the form of moldings, films, filaments and/or fibers.

The use of the present invention preferably includes the following compositions: 30 to 93% by weight polyamide Mixtures of components A) to E) from 2 to 40% by weight 5 to 50% by weight of fillers and/or reinforcing agents 0 to 40% by weight of other additives.

Surprisingly, it has been found that the combination of a salt of dialkylphosphinic acid and an alkaline earth metal stannate according to the present invention exhibits high flame retardancy combined with improved processing stability of the molded composition without discoloration . An effect of preventing corrosion to this extent without discoloration reaction has not yet been described in the art.

Preferably, component D) contains a phosphonite or a mixture of phosphonite and phosphite.

Preferred salts of phosphorous acid (component C)) are those which are sparingly soluble or insoluble in water. Particularly preferred salts of phosphorous acid are aluminum salts, calcium salts, and zinc salts.

More preferably, component C) is the reaction product of phosphorous acid and aluminum compounds.

The better ones are CAS numbers 15099-32-8, 119103-85-4, 220689-59-8, 56287-23-1, 156024-71-4, 71449-76-8, and 15099-32-8. Aluminum phosphate.

The preferred one is the following type of aluminum phosphite: Al ₂ (HPO ₃ ) ₃ * 0.1 - 30 Al ₂ O ₃ * 0 - 50 H ₂ O, more preferably Al ₂ (HPO ₃ ) ₃ * 0.2 - 20 Al ₂ O ₃ * 0 - 50 H ₂ O, preferably Al ₂ (HPO ₃ ) ₃ * 1 - 3 Al ₂ O ₃ * 0 - 50 H ₂ O.

The preferred one is a mixture of aluminum phosphite and aluminum hydroxide, with a composition of 5 to 95% by weight Al ₂ (HPO ₃ ) ₃ *nH ₂ O and 95 to 5% by weight Al(OH) ₃ , and more preferably 10 to 95% by weight Al 2 (HPO 3 ) 3 *nH 2 O. 90 wt% Al ₂ (HPO ₃ ) ₃ *nH ₂ O and 90 to 10 wt% Al(OH) ₃ , optimally 35 to 65 wt% Al ₂ (HPO ₃ ) ₃ *nH ₂ O and 65 to 35 wt% % Al(OH) ₃ and n = 0 to 4 in each case.

Aluminum phosphite preferably has a particle size of 0.2 to 100 μm.

Preferred aluminum phosphites are conventionally produced by reacting an aluminum source with a phosphorus source and optionally a template in a solvent at 20 to 200°C for a period of up to four days. For this purpose, the aluminum and phosphorus sources are mixed, heated under hydrothermal conditions or under reflux, and the solids are separated by filtration, washed and dried.

Preferred aluminum sources are aluminum isopropoxide, aluminum nitrate, aluminum chloride, and aluminum hydroxide (i.e., pseudodiaspore).

Preferred phosphorus sources are phosphorous acid, aluminum (acid) phosphite, alkali metal phosphites or alkaline earth metal phosphites.

Preferred alkali metal phosphites are disodium phosphite, disodium phosphite hydrate, trisodium phosphite, and potassium hydrogen phosphite.

A preferred disodium phosphite hydrate is ^Brüggolen® H10 from Brüggemann.

Preferred templates are 1,6-hexanediamine, guanidine carbonate or ammonia.

The preferred alkaline earth metal phosphite is calcium phosphite.

The preferred ratio of aluminum to phosphorus to solvent is 1:1:3.7 to 1:2.2:100 moles. The aluminum to template ratio is 1:0 to 1:17 moles.

The preferred pH of the reaction solution is 3 to 9.

The preferred solvent is water.

Component B is preferably calcium stannate, calcium hydroxystannate, magnesium stannate, magnesium hydroxystannate or blends thereof.

Suitable component C is also a compound of formulas (IX) to (XIV) or a mixture thereof wherein R ⁵ to R ⁷ are hydrogen; C ₁ -C ₈ alkyl; C ₅ -C ₁₆ cycloalkyl or C ₅ -C ₁₆ alkyl cycloalkyl, possibly via hydroxyl or via C ₁ -C ₄ hydroxyalkyl Functional group substitution; C ₂ -C ₈ alkenyl; C ₁ -C ₈ alkoxy, C ₁ -C ₈ hydroxyl, C ₁ -C ₈ hydroxyl; C ₆ -C ₁₂ aryl or C ₆ -C ₁₂ Arylalkyl; -OR ⁸ and -N(R ⁸ )R ⁹ ; and N-alicyclic group or N-aromatic group, R ⁸ is hydrogen; C ₁ -C ₈ alkyl; C ₅ -C ₁₆ cycloalkyl or C ₅ -C ₁₆ alkyl cycloalkyl, possibly substituted by hydroxyl or by C ₁ -C ₄ hydroxyalkyl functional group; C ₂ -C ₈ alkenyl; C ₁ -C ₈ alkoxy, C ₁ -C ₈ acylyl group, C ₁ -C ₈ acyloxy group or C ₆ -C ₁₂ aryl group or C ₆ -C ₁₂ arylalkyl group, R ⁹ to R ¹³ are the same groups as R ⁸ , and -OR ⁸ , m and n are independently 1, 2, 3 or 4, and Oligoesters of carboxylic acids. Particularly suitable component C is benzoguanamine, hydroxyethyl isocyanate, allantoin, glycoluril, melamine, melamine cyanurate, dicyandiamide and /or guanidine.

Preferably, M in formulas (I) and (II) is calcium, aluminum or zinc.

Protonated nitrogen bases preferably mean protonated bases of ammonia, melamine, triethanolamine, especially NH ₄ ⁺ .

Suitable phosphinates are described in PCT/WO97/39053, to which reference is expressly made.

Particularly preferred phosphinates are aluminum phosphinate, calcium phosphinate, and zinc phosphinate.

In this application, it is particularly preferred to use the same salt of phosphinic acid as the salt of phosphorous acid - in other words, for example, aluminum dialkylphosphinate and aluminum phosphinate are used together, or zinc dialkylphosphinate is used together. and zinc phosphite.

Combinations according to the invention comprising components A and B and optionally C, D, E and F can be combined with additives such as, for example, antioxidants, UV absorbers and photostabilizers, metal deactivators, peroxides Material destroying compounds, polyamide stabilizers, basic costabilizers, nucleating agents, fillers and reinforcements, additional flame retardants, and other additives are blended.

Suitable antioxidants are, for example, alkylated monophenols, such as 2,6-di-tert-butyl-4-cresol; alkylthiocresols, such as 2,4-dioctylthiomethyl-6-th Tributylphenol; hydroquinone and alkylated hydroquinone, such as 2,6-di-tert-butyl-4-methoxyphenol; tocopherols, such as α-tocopherol, β-tocopherol, γ-tocopherol, Delta-tocopherol and its mixtures (vitamin E); hydroxylated thiobiphenyl ethers, such as 2,2'-thiobis(6-tert-butyl-4-cresol), 2,2'-thiobiphenyl ethers Bis(4-octylphenol), 4,4'-sulfobis(6-tert-butyl-3-cresol), 4,4'-sulfobis(6-tert-butyl-2-methyl Phenol), 4,4'-bisulfide (3,6-di-pentylphenol), 4,4'-bis(2,6-dimethyl-4-hydroxyphenyl) disulfide; alkylene Bisphenols, such as 2,2'-methylenebis(6-tert-butyl-4-cresol); O-benzyl compounds, N-benzyl compounds and S-benzyl compounds, such as 3,5 ,3',5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether; hydroxybenzylated malonate, such as 2,2-bis(3,5-di-tert-butyl ether) hydroxy-2-hydroxybenzyl)di(octadecyl)malonate; hydroxybenzyl aromatic compounds, such as 1,3,5-bis-(3,5-di-tert-butyl)-4-hydroxy Benzyl)-2,4,6-trimethylbenzene, 1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene, 2, 4,6-Shen-(3,5-di-tert-butyl-4-hydroxybenzyl)phenol; trisulfhydryl compounds, such as 2,4-dioctylmercapto-6(3,5-di-tert-butyl) Butyl-4-hydroxyanilino)-1,3,5-tricarboxylate; benzylphosphonate, such as dimethyl 2,5-di-tert-butyl-4-hydroxybenzylphosphonate; acyl group Aminophenol, 4-hydroxylaurylamide, 4-hydroxy-stearanilide, N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamic acid Octyl ester; ester of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid and monohydric or polyhydric alcohols; β-(5-tert-butyl-4-hydroxyphenyl) Esters of tolyl)propionic acid and monohydric or polyhydric alcohols; esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid and monohydric or polyhydric alcohols; 3,5-di-tertiary alcohols Esters of butyl-4-hydroxyphenyl acetic acid and monohydric or polyhydric alcohols; amide of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, such as N,N'- Bis(3,5-di-tert-butyl-4-hydroxyphenylpropyl)hexamethylenediamine, N,N'-bis(3,5-di-tert-butyl-4-hydroxy Phenylpropanyl)trimethylenediamine, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropanyl)hydrazine.

Suitable UV absorbers and light stabilizers are, for example, 2-(2'-hydroxyphenyl)-benzotriazole, such as 2-(2'-hydroxy-5'-tolyl)benzotriazole; 2-hydroxy Benzophenones, such as 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4-tris Hydroxy, 2'-hydroxy-4,4'-dimethoxy derivatives; optionally substituted esters of benzoic acid, such as 4-tert-butylphenyl salicate, phenyl salicate, octylbenzene salicylate Ester, benzoylresorcinol, bis(4-tert-butylbenzoyl)-resorcinol, benzoylresorcinol, 3,5-di-tert-butyl-4- 2,4-di-tert-butylphenyl hydroxybenzoate, cetyl 3,5-di-tert-butyl-4-hydroxybenzoate, 3,5-di-tert-butyl-4-hydroxybenzoate Octearyl benzoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate; acrylic esters such as α-cyano-β ,β-ethyl diphenyl acrylate or isooctyl ester, α-methoxymethyl-cinnamic acid methyl ester, α-cyano-β-methyl-p-methoxycinnamic acid methyl ester or butyl ester, α-Methoxymethyl-p-methoxycinnamic acid methyl ester, N-(β-methoxymethyl-β-cyanovinyl)-2-methylindoline.

Additional nickel compounds, such as nickel complexes of 2,2'-sulfide-bis[4(1,1,3,3-tetramethylbutyl)phenol] (such as 1:1 or 1:2 complexes substances, optionally with additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldiglycolamine), nickel dibutyldithiocarbamate, 4-hydroxy-3,5-di- Nickel salts of monoalkyl tert-butylbenzylphosphonate (such as methyl or ethyl ester), nickel complexes of ketoximes, such as nickel complexes of 2-hydroxy-4-tolyl-undecyl ketoxime nickel complex of 1-phenyl-4-lauryl-5-hydroxypyrazole (optional with additional ligands); sterically hindered amines, such as bis(2,2,6,6 sebacate -tetramethylpiperidinyl) ester; oxalamide, such as 4,4'-dioctyloxyoxalanilide; 2-(2-hydroxyphenyl)-1,3,5-tricarboxamide, such as 2,4 ,6-Shen(2-hydroxy-4-octyloxyphenyl)-1,3,5-three 𠯤. Suitable metal deactivators are, for example, N,N'-diphenyloxalamide, N-salicyl-N'-salicyloylhydrazine, N,N'-bis(salicyloylhydrazine) Hydrazine, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine, 3-sulfacylamino-1,2,4-triazole, bis(benzylidene) base)-oxanilide, oxanilide, isophthaloyl dihydrazine, decanediyl diphenyl dihydrazine, N,N'-dimethyl hexadiyl dihydrazine , N,N'-bis(sauroyl)oxayl dihydrazine, N,N'-bis(sauroyl)thiopropionyl dihydrazine.

Suitable peroxide destroying compounds are, for example, esters of β-thiodipropionic acid (eg lauryl, stearyl, myristyl or tridecyl), mercaptobenzimidazole, zinc salt of 2-mercaptobenzimidazole , zinc dibutyldithiocarbamate, bis(octadecyl) disulfide, tetra(β-dodecylmercapto)-neopenterythritol propionate.

Suitable polyamide stabilizers are, for example, copper salts and divalent manganese salts in combination with iodide and/or phosphorus compounds.

Suitable alkaline co-stabilizers are melamine, polyvinylpyrrolidone, dicyandiamine, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, Alkali metal salts and alkaline earth metal salts of high fatty acids, such as calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate, potassium palmitate, antimony pyrocatechuate pyrocatecholate) or tin pyrocatecholate (tin pyrocatecholate).

Suitable nucleating agents are, for example, 4-tert-butylbenzoic acid, adipic acid and diphenylacetic acid.

Fillers and reinforcements include, for example, calcium carbonate, silicates, glass fiber, carbon fiber, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and metal hydroxides, carbon black, graphite and others.

Additional flame retardants are: Magnesium oxide, calcium oxide, aluminum oxide, zinc oxide, manganese oxide, tin oxide, aluminum hydroxide, diaspore, dihydrotalcite, hydrocalumite, magnesium hydroxide, calcium hydroxide, zinc hydroxide, Tin oxide hydrate, manganese hydroxide, zinc borate, zinc basic silicate and/or zinc stannate; Melamine, melem, melonamine, di(melamine) pyrophosphate, melamine polyphosphate, melamine polyphosphate, melonamine polyphosphate and/or melemine polyphosphate and/or their mixed polysalts and /or diammonium hydrogen phosphate, ammonium dihydrogen phosphate and/or ammonium polyphosphate; Aryl phosphates, phosphonates, salts of hypophosphorous acid and/or red phosphorus; aluminum hypophosphite, zinc hypophosphite, calcium hypophosphite, sodium phosphite, monophenylphosphinic acid and its salts, dialkylphosphine Acids and their salts, as well as monoalkylphosphinic acid and its salts, 2-carboxyethylalkylphosphinic acid and its salts, 2-carboxyethylmethylphosphinic acid and its salts, 2-carboxyethylaryl Phosphinic acid and its salts, 2-carboxyethylphenylphosphinic acid and its salts, oxa-10-phosphaphenanthrene (DOPO) and its salts, and adducts added to p-benzoquinone, or Conic acid and its salts.

Other additives include, for example, plasticizers, expandable graphite, lubricants, emulsifiers, pigments, optical brighteners, flame retardants, antistatic agents, and foaming agents.

These additional additives can be added to the polymer before, together with or after the addition of the flame retardant. These additives and flame retardants can be metered in as solids, solutions or melts, as solid or liquid mixtures, or as masterbatches/concentrates.

Among phosphonites, the following free radicals are preferred: R is C ₄ -C ₁₈ alkyl (linear or branched chain), C ₄ -C ₁₈ alkyl (linear or branched chain), C ₅ -C ₁₂ cycloalkyl, C ₅ -C ₁₂ cycloalkyl, C ₆ -C ₂₄ aryl or C ₆ -C ₂₄ heteroaryl, C ₆ -C ₂₄ aryl or C ₆ -C ₂₄ heteroaryl Aryl, which may also have additional substitutions; R ₁ is a compound of structure (VII) or (VIII), wherein R ₂ is independently C ₁ -C ₈ alkyl (linear or branched), C ₁ -C ₈ alkoxy, cyclohexyl; A is a direct bond, O, C ₁ -C ₈ alkylene (linear or branched chain), C ₁ -C ₈ alkylene (linear or branched), and n is 0 to 3 m is 1 to 3.

Among the phosphonites, the following free radicals are particularly preferred: R is cyclohexyl, phenyl, phenyl, biphenyl and biphenyl R ₁ is a compound of structure (VII) or (VIII), wherein R ₂ is independently C ₁ -C ₈ alkyl (straight chain or branched), C ₁ -C ₈ alkoxy, cyclohexyl A is a direct bond, O, C ₁ -C ₆ alkylene (straight chain or branched) branched chain), and n is 1 to 3 m is 1 or 2.

Another claimant is a mixture P(OR ₁ ) ₃ (XV) of a compound according to the patent scope of the above application and a phosphite of formula (XV), wherein R ₁ is as defined above.

According to the above information, the preferred one is Friedel-Crafts through aromatic or heteroaromatic (such as benzene, biphenyl or diphenyl ether) and phosphorus trihalide (preferably phosphorus trichloride) Compounds prepared by Hu-Qua reaction in the presence of catalysts (such as aluminum chloride, zinc chloride, ferric chloride, etc.) and subsequent reactions with masterbatch phenols of structures (VII) and (VIII). Also expressly included are mixtures with phosphites, which are formed after the stated reaction sequence from an excess of phosphorus trihalides and the above-mentioned phenols.

From the perspective of this compound group, the better ones are the following structures (XVI) and (XVII) wherein n may be 0 or 1, and the mixtures may optionally further comprise compounds (XVIII) or (XIX) in proportions:

Suitable components E) are the esters or salts of long-chain aliphatic carboxylic acids (fatty acids) generally having a chain length from C ₁₄ to C ₄₀ . These esters are the reaction products of the above-mentioned carboxylic acids and commonly used polyols such as ethylene glycol, glycerol, trimethylolpropane or neopentylerythritol. Useful salts of the above-mentioned carboxylic acids include in particular alkali metal salts or alkaline earth metal salts, or aluminum and zinc salts.

Component E preferably contains an ester or salt of stearic acid, such as glyceryl monostearate or calcium stearate.

Component E preferably comprises the reaction product of montanacetic acid and ethylene glycol.

The reaction products are preferably mixtures of ethylene glycol monomontan wax ester, ethylene glycol dimontan wax ester, montan wax acid, and ethylene glycol.

Component E preferably comprises the reaction product of montanacetic acid and calcium salt.

The reaction product is more preferably a mixture of 1,3-butanediol monomontan wax ester, 1,3-butanediol dimontan wax ester, montan wax acid, 1,3-butanediol, calcium montanate, and calcium salts .

The proportions of components A) and B) in the flame retardant combination depend essentially on the intended field of application and can vary widely. Depending on the field of application, the flame retardant combination contains 40 to 99.9% by weight of component A and 0.1 to 60% by weight of component B. From 0 to 79.9% by weight of component C are added, and from 0 to 3% by weight of components D and E are added independently of each other. Component F can be added in the range of 0 to 20% by weight.

The total amount of the flame retardant/stabilizer combination in the polyamide molding composition is preferably 0.5 to 45% by weight based on the polymeric molding composition. The amount of polymer in this case is from 55 to 99.5% by weight.

The total amount of the flame retardant combination in the polymeric molding composition is preferably 1 to 30% by weight based on the polymeric molding composition. The amount of polymer in this case is from 10 to 95% by weight.

The polymer moldings, films, filaments and fibers preferably contain a flame retardant/stabilizer combination in a total amount of 0.5 to 45% by weight, based on the polymer content. The amount of polymer in this case is from 55 to 99.5% by weight.

The polymer moldings, films, filaments and fibers preferably contain a combination of flame retardants in a total amount of 1 to 30% by weight, based on the polymer content. The amount of polymer in this case is from 10 to 95% by weight.

The above-mentioned additives can be introduced into the polymer during a wide range of different processing steps. For example, in the case of polyamides the additives can be mixed into the polymer melt as early as the beginning, or at the end of the polymer/polycondensation reaction, or in subsequent mixing operations. Furthermore, there are processing operations where additives are only added at a later stage. This is carried out in particular when pigments or additive masterbatches are used. It is also possible to apply rollers (especially with powdered additives) to polymer pellets that may be warmed by the drying operation.

Finally, the present invention also relates to a method for manufacturing a flame-retardant polymer molded article, wherein the flame-retardant polymer molded composition of the invention is formed by injection molding (for example, an injection molding machine (Aarburg Allrounder type)) and compression, development Foam injection molding, internal gas pressure injection molding, blow molding, film casting, calendering, lamination or coating at elevated temperatures are processed to produce flame retardant polymer molded articles.

Preferably, the polyamide is an amino acid type and/or a diamine dicarboxylic acid type polyamide.

Preferred polyamides are polyamide-6 and/or polyamide 66, and polyphthalamide.

Preferably, the polyamide is unchanged, colored, filled, unfilled, strengthened, unstrengthened, or modified in other ways.

Example

1. Components used Commercially available polymers (pellets): Polyamide 6.6 (PA 6.6-GV): Ultramid ^® A27 (from BASF, D) Polyphthalamide (PPA): Vestamid ^® HT plus M1000 and M3000 (from Evonik, D) Polybutylene terephthalate (PBT): Ultradur B4500 (from BASF, D) Glass fiber, PPG HP 3610 EC 10 4.5 mm (from PPG Ind. Fiber Glass, NL) Zinc borate Firebrake ^® 500 from Borax, USA Zinc stannate Flamtard ^® H and Flamtard ^® S from William Blythe, UK Component A: Aluminum salt of diethylphosphinic acid, hereafter referred to as DEPAL1 With component F Component A: Aluminum salt of diethylphosphinic acid with 0.1% short-chain polymer, hereafter referred to as DEPAL2 Aluminum salt of diethylphosphinic acid with 2.5% short-chain polymer, hereafter referred to as DEPAL3 Group Part B: Calcium stannate, available from William Blythe, UK, Magnesium stannate, Barium stannate Component C: Aluminum salt of phosphorous acid, hereafter called PHOPAL Melamine polyphosphate (called MPP), Melapur ^® 200 (available from BASF , D) Component D: Sandostab ^® P-EPQ from Clariant GmbH, D Hostanox 010 from Clariant GmbH, D Component E: Licowax ^® E from Clariant Produkte (Deutschland) GmbH, D (montanacetic acid ester) 2. Manufacturing, processing and testing of flame retardant polymeric molding compositions

The flame retardant component is mixed with phosphonite, lubricant and stabilizer in the ratio specified in the table, and passed through the side inlet of a twin-screw extruder (Leistritz ZSE 27/44D) at a temperature of 260 to 310°C into PA 6.6 at 300 to 340°C, into PPA at 300 to 340°C, and into PBT at 230 to 260°C. Fiberglass is added via the second side inlet. The homogenized polymer strands were pulled out, cooled in a water bath, and then pelletized. Processability is evaluated based on strand breakage that occurs during mixing.

After sufficient drying, the molded compositions were processed into test specimens on an injection molding machine (Arburg 320 C Allrounder) at a melt temperature of 230 to 340°C, and the flame retardancy was determined using the UL 94 test (Underwriter Laboratories) Testing and Grading.

The UL 94 combustion classification is as follows: V-0: Afterflame time shall not be longer than 10 seconds, the total afterflame time of 10 applied combustion shall not be more than 50 seconds, no burning drop (flaming drop), no sample is completely consumed, and the application The afterglow time of the sample after combustion must not be longer than 30 seconds V-1: The afterburning time after the end of the applied combustion shall not be longer than 30 seconds, the total afterburning time of 10 applied combustion shall not be more than 250 seconds, and the ember time of the sample after the end of the applied combustion shall not be longer than 60 seconds. Other standards are the same as V-0 V-2: Cotton ignites due to burning drippings, other standards are the same as V-1 Not Classifiable (ncl): Does not comply with combustion class V-2.

The fluidity of the molding composition is determined by determining the melt volume flow rate (MVR) at 275°C/2.16 kg. A sharp increase in the MVR value indicates polymer degradation. MVR is also affected by filler.

Tensile strength (N/mm ² ), elongation at break, and breaking strength are measured in accordance with DIN EN ISO 527 (%), impact strength [kJ/m ² ] and notched impact strength [kJ/m ² ] are measured in accordance with DIN EN ISO 527 (%). Measured according to DIN EN ISO 179.

Visually evaluate the color of the specimen. The reference material is the color of natural polyamide processed with flame retardants and fiberglass as mentioned above. Any change in color is recorded as slight, moderate, or severe brown discoloration.

Corrosion was studied using the platelet method. The small plate method developed at DKI (Deutsches Kunststoffinstitut now Fraunhofer LBF, Darmstadt, Germany) is used for comparative evaluation of metallic materials and modeling studies of corrosion strength and wear strength of plasticized molding compositions. In this test, two specimens were arranged in pairs in a mold to form a rectangular gap with a length of 12 mm, a width of 10 mm, and an adjustable height from 0.1 mm to a maximum of 1 mm for the passage of the polymer melt (Fig. 1 ). The polymer melt is extruded (or injected) from the plasticized assembly through the gap, with most of the shear stress and shear rate in the gap.

One parameter of wear is the weight loss of the specimen, which is determined by measuring the difference in weighing of the specimen using an A&D Analytical "electronic balance" with a deviation of 0.1 mg. The mass of the specimens was determined before and after the corrosion test using 25 kg of polymer yield on 1.2379 steel or 10 kg of polymer yield on CK 45 steel.

After a previously defined yield (usually 25 or 10 kg), the sample plate is removed and physically/chemically cleaned to remove adhering polymers. Physical cleaning is accomplished by rubbing with a soft material (cotton) to remove the thermal polymer mass. Chemical cleaning was performed by heating the specimen in m-cresol at 60°C for 20 minutes. The polymeric composition that remains adhered after the boiling operation is removed by wiping it off with a soft cotton pad.

Unless otherwise stated, all tests in a specific series are performed under the same conditions (temperature planning, screw geometry, injection molding parameters, etc.) taking into account compatibility.

All quantities are reported as weight % and are based on the polymeric molding composition including the flame retardant combination and adjuvants.

Table 1 shows examples of flame retardant PA 66 molded compositions. C1 and C2 are comparative compositions that reveal the current state of technology. The composition systems of the present invention are shown as B1 to B4. The use of calcium stannate or magnesium stannate (component B) results in corrosion reduction benefits. No measurable corrosion. Compositions B1 to B4 also showed improved flame retardancy. Up to UL 94 classification V-0 can also be obtained with thin specimens. Smoother processing of the inventive mixtures (B1 to B4) and reduced line breaks provide more economical processing. Since no discoloration occurs during processing of the inventive mixtures (B1 to B4), the range of applications becomes wider and tinting or dyeing will be easier.

Table 2 shows examples of flame retardant semi-aromatic polyamide molding compositions. C3 and C4 are comparative compositions that reveal the current state of technology. The composition systems of the present invention are shown as B5 to B9. All of the above-mentioned stannates are extremely good at preventing corrosion. The benefit of B5 to B9 over the comparative compositions can be seen in the discoloration. While formulations with Flametard S showed severe discoloration limiting application due to lack of color options, the alkaline earth metals of the present invention surprisingly did not show any discoloration of the injection molded parts. It also improves flame retardancy and can meet the highest UL 94 level V-0 in all thicknesses.

Comparing C4 to B6, improvements in impact strength and notch impact strength can be seen using the inventive mixture. Molding compositions with the flame retardant mixtures B5 to B9 of the invention comply with the strict fire protection requirements according to UL 94 and exhibit good mechanical properties and do not show any corrosion during processing and do not show any discoloration of the compounds.

Table 3 shows examples of flame retardant polybutylene terephthalate molding compositions. C5 shows the current state of the art in flame retardant formulations. During machining, a high degree of corrosion of the machining tools was noticed. The molding composition B10 of the present invention shows no corrosion and meets the strict fire protection requirements according to UL 94 V0 as well as mechanical properties.

Figure 1 shows the mold used for thermoplastic wear research using the DKI small plate method.

Claims (32)

A mixture containing as component A at least one salt of organic phosphinic acid, wherein the at least one salt of organic phosphinic acid corresponds to formula (I)

Wherein R ¹ and R ² are the same or different, and each is H, linear or branched C ₁ -C ₁₈ alkyl, C ₆ -C ₁₈ aryl, C ₇ -C ₁₈ aryl alkyl or C ₇ - C ₁₈ alkylaryl, or R ¹ and R ² form one or more rings with each other, M is Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn , Li, Na, K and/or protonated nitrogen base; m is 1 to 4, and at least one alkaline earth metal stannate (M"SnO ₃ ) and/or alkaline earth metal hydroxystannate (M"Sn ( OH) ₆ ) as component B, wherein M″ is one of Mg, Ca or Ba. For example, the mixture in item 1 of the patent application scope, wherein R ¹ and R ² are the same or different, and each is methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl , 2-pentyl, 3-pentyl, 2-methylbutyl, 3-methylbutyl (isopentyl), 3-methylbut-2-yl, 2-methylbut-2-yl, 2,2-Dimethylpropyl (neopentyl), hexyl, heptyl, octyl, nonyl, decyl, cyclopentyl, cyclopentylethyl, cyclohexyl, cyclohexylethyl, phenyl, phenylethyl, tolyl and/or tolylethyl. For example, the mixture of any one of items 1 to 2 of the patent application, wherein M is calcium, aluminum, zinc, titanium or iron ion. For example, the mixture according to any one of items 1 to 2 of the patent scope, wherein component B has a surface area of 20 to 200 m ² /g BET. For example, the mixture of any one of items 1 to 2 of the patent scope contains 40 to 99.9% by weight of component A and 0.1 to 60% by weight of component B. For example, the mixture of any one of items 1 to 2 of the patent scope contains 70 to 99.9% by weight of component A and 0.1 to 30% by weight of component B. For example, the mixture of any one of items 1 to 2 of the claimed patent scope contains 80 to 99% by weight of component A and 1 to 20% by weight of component B. For example, the mixture of any one of items 1 to 2 of the patent application, which contains 0 to 79.9% by weight of nitrogen-containing synergists and/or phosphorus/nitrogen flame retardants and/or contains phosphorous acid with formula (II) Phosphorus-containing synergist or flame retardant of salt as additional component C: [HP(=O)O ₂ ] ^2- M''' ^m+ (II) where M''' is Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na and/or K, 0 to 3% by weight of phosphonite or phosphonite and phosphonite A mixture of phosphates as further component D and 0 to 3% by weight of esters or salts of long-chain aliphatic carboxylic acids (fatty acids) usually with chain lengths from C ₁₄ to C ₄₀ as further component E, these groups The sum of the components always amounts to 100% by weight, and from 0 to 20% by weight of short-chain polymeric phosphinic acid salts as further component F, where component F is different from component A and is selected from the following Metal salts: ethylbutylphosphinic acid, dibutylphosphinic acid, ethylhexylphosphinic acid, butylhexylphosphinic acid, ethyloctylphosphinic acid, second butylethylphosphinic acid, 1-ethylbutyl-butylphosphinic acid, ethyl-1-methylpentyl-phosphinic acid, di-butylphosphinic acid (di-1-methyl-propylphosphinic acid) , propyl-hexylphosphinic acid, dihexylphosphinic acid, hexyl-nonylphosphinic acid, propyl-nonylphosphinic acid, dinonylphosphinic acid, dipropylphosphinic acid, butyl-octyl Phosphinic acid, hexyl-octylphosphinic acid, dioctylphosphinic acid, ethylcyclopentylethylphosphinic acid, butylcyclopentylethylphosphinic acid, ethylcyclohexylethylphosphinic acid Acid, butylcyclohexylethylphosphinic acid, ethylphenylethylphosphinic acid, butylphenylethylphosphinic acid, ethyl 4-methylphenylethylphosphinic acid, butyl 4-methylbenzene Ethylphosphinic acid, butylcyclopentylphosphinic acid, butylcyclohexylethylphosphinic acid, butylphenylphosphinic acid, ethyl 4-tolylphosphinic acid and/or butyl 4-tolylphosphinic acid Phosphinic acid, and the least of the group wherein the metal is Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na and/or K One. For example, the mixture of item 8 of the patent application scope, wherein the mixture contains 40 to 98.9% by weight of component A, 1 to 39.9% by weight of component B, 0.1 to 59% by weight of component C, 0 to 2% by weight of component C. Component D, 0 to 2% by weight of component E, and 0 to 20% by weight of component F. For example, the mixture of item 8 of the patent application scope, wherein the mixture contains 50 to 94.5% by weight of component A, 5 to 39.5% by weight of component B, 0.5 to 45% by weight of component C, 0 to 2% by weight of component C. Component D, 0 to 2% by weight of component E, and 0 to 20% by weight of component F. For example, the mixture of item 8 of the patent application scope, wherein the mixture contains 60 to 94% by weight of component A, 5 to 30% by weight of component B, 1 to 35% by weight of component C, 0 to 2% by weight of component C. Component D, 0 to 2% by weight of component E, and 0 to 20% by weight of component F. For example, the mixture of item 8 of the patent application, wherein the mixture contains 60 to 89.7% by weight of component A, 5 to 20% by weight of component B, 5 to 20% by weight of component C, 0.1 to 2% by weight Component D, 0.1 to 2% by weight of component E, and 0.1 to 20% by weight of component F. For example, the mixture of item 8 of the patent application, wherein component C includes the reaction product of phosphorous acid and an aluminum compound. For example, in the mixture of item 8 of the patent application, component C includes aluminum phosphite [Al(H ₂ PO ₃ ) ₃ ], secondary aluminum phosphite [Al ₂ (HPO ₃ ) ₃ ], and basic aluminum phosphite [ Al(OH)(H ₂ PO ₃ ) ₂ *2aq], aluminum phosphite tetrahydrate [Al ₂ (HPO ₃ ) ₃ *4aq], aluminum phosphonate, Al ₇ (HPO ₃ ) ₉ (OH) ₆ (1 ,6-hexanediamine) _1.5 *12H ₂ O, Al ₂ (HPO ₃ ) ₃ *xAl ₂ O ₃ *nH ₂ O (where x=1-2.27 and n=1-50) and/or Al ₄ H ₆ P ₁₆ O ₁₈ , or aluminum phosphite containing formula (III), (IV) and/or (V), wherein formula (III) contains: Al ₂ (HPO ₃ ) ₃ x (H ₂ O) _q and q are 0 to 4; Formula (IV) includes Al _2.00 M _z (HPO ₃ ) _y (OH) _v x(H ₂ O) _w and M is an alkali metal ion, z is 0.01 to 1.5, y is 2.63 to 3.5, v is 0 to 2, and w is 0 to 4; formula (V) includes Al _2.00 (HPO ₃ ) _u (H ₂ PO ₃ ) _t x(H ₂ O) _s , and u is 2 to 2.99, and t is 2 to 0.01, and s is 0 to 4, or the aluminum phosphite includes a mixture of aluminum phosphite of formula (III) and a poorly soluble aluminum salt and nitrogen-free foreign ions; a mixture of aluminum phosphite of formula (IV) and an aluminum salt; Mixtures of aluminum phosphite of formulas (IV) to (V) and aluminum phosphite [Al(H ₂ PO ₃ ) ₃ ], mixtures of secondary aluminum phosphite [Al ₂ (HPO ₃ ) ₃ ], and basic A mixture of aluminum phosphite [Al(OH)(H ₂ PO ₃ ) ₂ *2aq], a mixture of aluminum phosphite tetrahydrate [Al ₂ (HPO ₃ ) ₃ *4aq], a mixture of aluminum phosphonate, and A mixture of Al ₇ (HPO ₃ ) ₉ (OH) ₆ (1,6-hexanediamine) _1.5 *12H ₂ O, and Al ₂ (HPO ₃ ) ₃ *xAl ₂ O ₃ *nH ₂ O (where x=1 -2.27 and n=1-50) mixtures and/or mixtures with Al ₄ H ₆ P ₁₆ O ₁₈ . For example, the mixture of item 8 of the patent application, wherein component C includes the condensation product of melamine and/or the reaction product of melamine and polyphosphoric acid and/or the reaction product of the condensation product of melamine and polyphosphoric acid, or a mixture thereof; or contains honey; Melem, melam, melon, dimelamine pyrophosphate, melamine polyphosphate, melem polyphosphate, melam polyphosphate, honey polyphosphate Polyamine and/or its mixed polysalts; or containing the formula (NH ₄ ) _y H _3-y PO ₄ and/or (NH ₄ PO ₃ ) _z (where y is 1 to 3 and z is 1 to 10000) Nitrogen phosphate. For example, the mixture of item 8 of the patent application, wherein the phosphonite (component D) has the following general formula R-[P(OR ₁ ) ₂ ] _m (VI) where R is a monovalent or polyvalent aliphatic or aromatic Or heteroaromatic organic radicals, and R ₁ is a compound of structure (VII)

Or two groups R ₁ form a bridging group of structure (VIII)

Where A is a direct bond, O, S, C ₁ -C ₁₈ alkylene group (linear or branched chain), C ₁ -C ₁₈ alkylene group (linear or branched chain), where R ₂ appears each time independently C ₁ -C ₁₂ alkyl (linear or branched), C ₁ -C ₁₂ alkoxy and/or C ₅ -C ₁₂ cycloalkyl, and n is 0 to 5, and m is 1 to 4 . Such as the mixture of claim 8, wherein component E includes alkali metal salts, alkaline earth metal salts, aluminum salts and/or zinc salts of long-chain fatty acids with 14 to 40 carbon atoms and/or 14 to 40 carbon atoms. The reaction product of long-chain fatty acids of carbon atoms and polyhydric alcohols such as ethylene glycol, glycerol, trimethylolpropane and/or neopentylerythritol. For example, the mixture of item 8 of the patent application, wherein the component A is an aluminum salt of diethylphosphinic acid, and the short-chain polymerized phosphinic acid (component F) is the following metal salt: ethylbutylphosphinic acid Phosphonic acid, dibutylphosphinic acid, ethylhexylphosphinic acid, butylhexylphosphinic acid, ethyloctylphosphinic acid, second butylethylphosphinic acid, 1-ethylbutyl-butyl Phosphinic acid, ethyl-1-methylpentyl-phosphinic acid, di-butylphosphinic acid (di-1-methyl-propylphosphinic acid), propyl-hexylphosphinic acid , dihexylphosphinic acid, hexyl-nonylphosphinic acid, propyl-nonylphosphinic acid, dinonylphosphinic acid, dipropylphosphinic acid, butyl-octylphosphinic acid, hexyl-octylphosphinic acid Phosphinic acid, dioctylphosphinic acid, ethylcyclopentylethylphosphinic acid, butylcyclopentylethylphosphinic acid, ethylcyclohexylethylphosphinic acid Acid, butylcyclohexylethylphosphinic acid, ethylphenylethylphosphinic acid, butylphenylethylphosphinic acid, ethyl 4-methylphenylethylphosphinic acid, butyl 4-methylbenzene Ethylphosphinic acid, butylcyclopentylphosphinic acid, butylcyclohexylethylphosphinic acid, butylphenylphosphinic acid, ethyl 4-tolylphosphinic acid and/or butyl 4-tolylphosphinic acid Phosphinic acid, and the least of the group wherein the metal is Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na and/or K One. A use of the mixture according to any one of items 1 to 18 of the patent application, as an adhesive; as a cross-linking agent or catalyst in the curing of epoxy resin, polyurethane or unsaturated polyester resin Accelerator; as polymer stabilizer, as crop protection composition, as chelating agent, as mineral oil additive, as anti-corrosion agent, in cleaning and cleaning composition applications, and in electronic device applications. A use of a mixture according to any one of items 1 to 18 of the patent application as a flame retardant for the manufacture of flame retardant polymer molding compositions, for the manufacture of flame retardant polymer moldings and / Or used to make polyester and pure cellulose fabrics and blended cellulose fabrics flame retardant through impregnation, and as a synergist. A use of a mixture as in any one of items 1 to 18 of the patent application, as a flame retardant for clearcoat and intumescent coating, as a flame retardant for wood and other cellulose products Flame retardants for products, and reactive or non-reactive flame retardants as polymers. A flame-retardant thermoplastic or thermosetting polymer molding composition, which contains 0.5 to 45% by weight of the mixture of any one of items 1 to 18 of the patent application, 55 to 99.5% by weight of a thermoplastic or thermosetting polymer, or Its mixture, 0 to 55% by weight of additives and 0 to 55% by weight of fillers or reinforcing materials, where the sum of these components is 100% by weight. A polymer molding comprising 0.5 to 45% by weight of a mixture as in any one of items 1 to 18 of the patent application, 55 to 99.5% by weight of a thermoplastic or thermosetting polymer or a mixture thereof, 0 to 55% by weight additives and 0 to 55% by weight of fillers or reinforcing materials, where the total of these components is 100% by weight. A polymer film comprising 0.5 to 45% by weight of the mixture of any one of items 1 to 18 of the patent application, 55 to 99.5% by weight of a thermoplastic or thermosetting polymer or a mixture thereof, 0 to 55% by weight of Additives and 0 to 55% by weight of fillers or reinforcing materials, where the sum of these components is 100% by weight. A filament comprising 0.5 to 45% by weight of a mixture as specified in items 1 to 18 of the patent application, 55 to 99.5% by weight of a thermoplastic or thermosetting polymer or a mixture thereof, and 0 to 55% by weight of additives And 0 to 55 weight % fillers or reinforcing materials, where the sum of these components is 100% by weight. A fiber containing 0.5 to 45% by weight of the mixture of any one of items 1 to 18 of the patent application, 55 to 99.5% by weight of a thermoplastic or thermosetting polymer or a mixture thereof, 0 to 55% by weight of additives, and 0 to 55% by weight of fillers or reinforcing materials, where the sum of these components is 100% by weight. A polymer shaped body comprising 0.5 to 45% by weight of the mixture of any one of items 1 to 18 of the patent application, 55 to 99.5% by weight of a thermoplastic or thermosetting polymer or a mixture thereof, 0 to 55% by weight Additives and 0 to 55% by weight of fillers or reinforcing materials, where the total of these components is 100% by weight. For example, if the flame-retardant thermoplastic or thermosetting polymer molded composition or polymer molded article, polymer film, filament, fiber or polymer formed body in any one of items 22 to 27 of the patent application, the polymer includes polyethylene ester, polyamide, thermoplastic elastomer, thermoplastic polyurethane, thermoplastic polyester elastomer, styrenics, polyketone, polyolefin, polyacrylate and/or containing polyamide or polyester Polymer blends or other blends, and thermosetting polymers based on epoxy, acrylate, vinyl ester, unsaturated polyester and/or phenolic resins. For example, the flame-retardant thermoplastic or thermosetting polymer molded composition, polymer molded article, polymer film, filament, fiber or polymer formed body in any one of the 22 to 27 patent claims, which contains polymerized The molding composition is a mixture of any one of items 1 to 18 of the patent application with a content of 10 to 30% by weight on a basis basis. For example, the flame-retardant thermoplastic or thermosetting polymer molded composition, polymer molded article, polymer film, filament, fiber or polymer formed body in any one of the patented items 22 to 27 is used in Or used in the following: connectors, power wetted parts (RCCB) in distributors, boards, potting compounds, circuit breakers, lamp housings, condenser housings, spools and fans , Protective contacts, connectors, covers for middle/upper circuit boards, connectors, cables, flexible circuit boards, mobile phone chargers, hoods, textile coatings, used in the electrical/electronic sector Moldings in the form of components. For example, the flame-retardant thermoplastic or thermosetting polymer molded composition, polymer molded article, polymer film, filament, fiber or polymer formed body in any one of the patented items 22 to 27 is used in Or used in the following: components for printed circuit boards, housings, films, cables, switches, distribution boards, relays, resistors, capacitors, coils, lamps, diodes, LEDs, transistors, connectors , controllers, memories and sensors, in the form of large-area components. For example, the flame-retardant thermoplastic or thermosetting polymer molded composition, polymer molded article, polymer film, filament, fiber or polymer formed body in any one of the patented items 22 to 27 is used in Or for the following: shell parts for cabinets and in the form of intricately designed components with complex geometries.

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