Flame retardant thermoplastic compositions, methods of manufacture thereof and articles comprising the same

0001Cross-reference of related applications This application claims priority over US Provisional Application No. 61 / 651,487 filed May 24, 2012 and US Provisional Application No. 61 / 748,795 filed January 4, 2013, all of which. The contents are incorporated herein by reference. This disclosure relates to a flame-retardant thermoplastic composition, a method for producing the same, and an article containing the same. This disclosure specifically relates to flame-retardant polyesters and flame-retardant polyester blends. This disclosure also specifically relates to flame-retardant polyphenylene ethers and flame-retardant polyphenylene ether blends.

0002In electronic and electrical equipment such as laptops, ebooks and tablets, metal panels have been replaced with materials that are lighter and offer a stronger combination of mechanical properties. These lighter materials reduce weight and cost, allowing the manufacture of complex designs. Although these lightweight materials can be used in the manufacture of panels with a thin cross-sectional thickness, it is desirable to increase the rigidity of the material in order to prevent warpage and at the same time improve impact resistance. Further, in order to reduce the risk of fire, it is desirable to improve the flame retardancy of the material.

0003A flame retardant composition comprising a polyphenylene ether-polysiloxane copolymer or a combination comprising a polyphenylene ether-polysiloxane copolymer and a polyphenylene ether homopolymer, an impact resistance improver, and a phosphazene flame retardant is disclosed herein. ..

0004A method for forming a flame retardant composition by mixing a polyphenylene ether-polysiloxane copolymer or a combination containing a polyphenylene ether-polysiloxane copolymer and a polyphenylene ether homopolymer, an impact resistance improving agent, and a phosphazene flame retardant. Is also disclosed here.

0005<figref num="1">A series of micrographs at different magnifications showing the dispersion of the phosphazene flame retardant in polyphenylene ether are shown.</figref>

0006<figref num="2">FIG. 6 is a bar graph showing melt viscosity rate (MVR) data for flame retardant compositions containing polyphenylene ether-polysiloxane copolymers, polystyrene and phenoxyphosphazene flame retardants.</figref>

0007<figref num="3">FIG. 6 is a bar graph showing melt viscosity (MV) data of a flame retardant composition containing a polyphenylene ether-polysiloxane copolymer, polystyrene and a phenoxyphosphazene flame retardant.</figref>

0008<figref num="4">FIG. 3 is a bar graph showing notched Izod data, Charpy impact data and multiaxial impact data of a flame retardant composition comprising a polyphenylene ether-polysiloxane copolymer, polystyrene and a phenoxyphosphazene flame retardant.</figref>

0009<figref num="5">FIG. 6 is a bar graph showing nominal fracture strain data for flame retardant compositions containing polyphenylene ether-polysiloxane copolymers, polystyrene and phenoxyphosphazene flame retardants.</figref>

0010<figref num="6">FIG. 6 is a bar graph showing the thermal deformation temperature and the Vicat softening temperature of a composition containing a polyphenylene ether-polysiloxane copolymer, polystyrene and a phenoxyphosphazene flame retardant.</figref>

0011<figref num="7">It is a graph which shows that the flame retardancy of a composition containing 30% by mass of a phenoxyphosphazene flame retardant is the same as that of a comparative composition.</figref>

0012The singular representation herein includes a plurality of referents. "Combination" includes formulations, mixtures, mixtures, reaction products and the like. Unless otherwise defined, the technical and scientific terms herein have the same meaning as commonly understood by one of ordinary skill in the art. Compounds are described using standard nomenclature. "And combinations thereof" also includes designated components and / or other components that are not specifically specified but have substantially the same function.

0013Unless otherwise specified, all numbers or expressions referring to component amounts, reaction conditions, etc. in this specification and claims are modified with "about" in all cases. Should be understood as a thing. Various numerical ranges are disclosed in this patent application. These ranges are continuous and include all numbers between the minimum and maximum values. End points of all ranges for the same property or component can be combined independently and include the listed end points. Unless otherwise stated, the various numerical ranges specified in this application are approximations. "Exceeding 0" Up to a certain value means that the specified component is present in excess of 0 and up to a specified large amount (including it).

0014"Contains" includes "consisting (consisting)" and "consisting essentially (consisting)". As used herein, "and or" means both "and" and "or (or)". For example, "A and or B" is interpreted to mean A, B or A and B.

0015Unless otherwise stated, all ASTM tests and data are from ASTM Standard 2003 edition. All cited references are incorporated herein by reference. For clarification, the "terephthalic acid group", "isophthalic acid group", "butanediol group" and "ethylene glycol group" have the following meanings. The "terephthalic acid group" in the composition is a divalent 1,4-benzene radical (-1,4- (C) that remains after removing the carboxyl group from terephthalic acid.₆H₄)-). The "isophthalic acid group" is a divalent 1,3-benzene radical (-(-1,3-C) that remains after removing the carboxyl group from isophthalic acid.₆H₄)-). The "butanediol group" is a divalent butanediol radical (-(C) that remains after removing the hydroxyl group from butanediol.₄H₈)-). The "ethylene glycol group" is a divalent ethylene radical (-(C) that remains after removing the hydroxyl group from ethylene glycol.₂H₄)-). For example with respect to "terephthalic acid groups", "isophthalic acid groups", "ethylene glycol groups", "butanediol groups" and "diethylene glycol groups" used in other contexts to indicate the mass% of groups in the composition. , "Isophthalic acid group" is the formula (-O (CO) C₆H₄A group having (CO)-), the "terephthalic acid group" is of the formula (-O (CO) C₆H₄A group having (CO)-), a diethylene glycol group has the formula (-O (C)₂H₄) O (C₂H₄The group having)-) is represented by the formula (-O (C).₄H₈The group having)-), the "ethylene glycol group" is of the formula (-O (C)₂H₄)-) Means each group.

0016Another flame-retardant composition comprising a polyphenylene ether and / or a polyphenylene ether blend and a phenoxyphosphazene flame-retardant compound is disclosed herein. The polyphenylene ether blend comprises polyamide, polystyrene and / or polyphenylene ether sulfide. The flame-retardant composition also exhibits an appropriate combination of rigidity and ductility, and a low melt viscosity that represents easy processability. The flame-retardant composition can be used for electronic products such as notebook personal computers, electronic books, and tablet personal computers.

0017In certain embodiments, the flame retardant composition comprises poly (phenylene ether). Suitable polys (phenylene ethers) include those containing the repeating structural unit of equation (1) below:<chemistry num="1"><img id="000002" he="55" wi="149" file="JP5965543B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>In the formula, Z¹Halogen and hydrocarbyl groups are not tertiary hydrocarbyl, respectively.₁-C₁₂Hydrocalvir, C₁-C₁₂Hydrocarbircio, C₁-C₁₂Hydrocarbyloxy, or C where at least two carbon atoms separate the halogen and oxygen atoms₂-C₁₂Halohydrocarbyloxy; Z²Independently, hydrogen, halogen, and hydrocarbyl groups are not tertiary hydrocarbyl, unsubstituted or substituted C.₁-C₁₂Hydrocalvir, C₁-C₁₂Hydrocarbircio, C₁-C₁₂Hydrocarbyloxy, or C where at least two carbon atoms separate the halogen and oxygen atoms₂-C₁₂It is halohydrocarbyloxy. As used herein, "hydrocarbyl" refers to residues that contain only carbon and hydrogen, whether used alone or as a prefix, suffix or fragment of another term. The residues may be aliphatic or aromatic, linear, cyclic, bicyclic, branched, saturated or unsaturated. It may also include combinations of aliphatic, aromatic, linear, cyclic, bicyclic, branched chain, saturated and unsaturated hydrocarbon moieties. However, if the hydrocarbyl residue is described as a substitution, it may optionally contain a heteroatom on the carbon and hydrogen members of the substitution residue. Thus, when specifically described as a substitution, the hydrocarbyl residue may contain one or more carbonyl groups, amino groups, hydroxyl groups, etc., or within the skeleton of the hydrocarbyl residue. May contain a heteroatom. As an example, Z¹May be a di-n-butylaminomethyl group formed by the reaction of the terminal 3,5-dimethyl-1,4-phenyl group with the di-n-butylamine component of the oxidation polymerization catalyst.

0018In some embodiments, the intrinsic viscosity of the poly (phenylene ether) is from about 0.25 to about 1 dL / g as measured in chloroform at a temperature of 25 ° C. Within this range, the intrinsic viscosity of poly (phenylene ether) may be about 0.3 to about 0.65 dL / g, more specifically about 0.35 to 0.5 dL / g, and even more specifically. It may be about 0.4 to about 0.5 dL / g.

0019In some embodiments, the poly (phenylene ether) is a poly (2,6-dimethyl-1,4-phenylene ether) prepared with a morpholine-containing catalyst, and the poly (2,6-dimethyl-) to toluene. Purified samples of poly (2,6-dimethyl-1,4-phenylene ether) prepared by dissolving (1,4-phenylene ether) and precipitating from methanol, reslurry and isolation are available in 250-1,000,000 atomic weight units. It has a monomodal molecular weight distribution in the molecular weight range of, and 2.2% by mass of poly (2,6-dimethyl-1,4-phenylene ether) having a molecular weight of more than 15 times the number average molecular weight of the entire purified sample. Including the following. In some embodiments, the purified sample after separation into six equal poly (2,6-dimethyl-1,4-phenylene ether) weight fractions that reduce the molecular weight is a poly containing a terminal morpholine-substituted phenoxy group (2,6-dimethyl-1,4-phenylene ether). Contains the first, highest molecular weight fraction containing at least 10 mol% (2,6-dimethyl-1,4-phenylene ether). Poly (2,6-dimethyl-1,4-phenylene ether) according to these embodiments is further described in US Patent Application Publication No. 2011/0003962A1 by Carrillo et al.

0020In some embodiments, the poly (phenylene ether) is essentially free of integrated diphenoquinone residues. In this context, "essentially free" means less than 1% by weight of poly (phenylene ether) molecules containing residues of diphenoquinone. As described in Hay's US Pat. No. 3,306,874, the synthesis of poly (phenylene ether) by oxidative polymerization of monohydric phenol produces not only the desired poly (phenylene ether) but also diphenoquinone as a by-product. To. For example, if the monohydric phenol is 2,6-dimethylphenol, 3,3', 5,5'-tetramethyldiphenoquinone is produced. The diphenoquinone is typically "rebalanced" within the poly (phenylene ether) by heating the polymerization reaction mixture to produce a poly (phenylene ether) containing terminal or internal diphenoquinone residues. , Diphenoquinone is incorporated into the poly (phenylene ether) structure). For example, poly (phenylene ether) is prepared by oxidative polymerization of 2,6-dimethylphenol and poly (2,6-dimethyl-1,4-phenylene ether) and 3,3', 5,5'-tetramethyldi. When producing phenoquinone, rebalancing of the reaction mixture can produce a poly (phenylene ether) with integrated diphenoquinone terminal and internal residues.

0021However, such rebalancing reduces the molecular weight of poly (phenylene ether). Therefore, if a higher molecular weight poly (phenylene ether) is desired, it may be desirable to separate the diphenoquinone from the poly (phenylene ether) without rebalancing into the poly (phenylene ether) chain. Such separation is achieved, for example, by precipitating poly (phenylene ether) in a solvent or solvent mixture insoluble in poly (phenylene ether) but soluble in diphenoquinone. For example, poly (phenylene ether) is prepared by oxidative polymerization of 2,6-dimethylphenol in toluene, and poly (2,6-dimethyl-1,4-phenylene ether) and 3,3', 5,5' -When producing a toluene solution containing tetramethyldiphenoquinone, poly (2,6-dimethyl-1,4-phenylene ether) essentially free of diphenoquinone is a volume of the toluene solution and methanol or methanol / methanol. Obtained by mixing with about 1 to about 4 volumes of water mixture.

0022Alternatively, the amount of diphenoquinone by-product produced during oxidative polymerization is at least 95% by weight in at least 50 minutes, starting oxidative polymerization in the presence of less than 10% by weight of monovalent phenol. Minimization (by adding valent phenol) and / or rebalancing of diphenoquinone to the poly (phenylene ether) chain is to isolate the poly (phenylene ether) within 200 minutes after completion of oxidative polymerization (eg,). Can be minimized (by). These methods are described in US Patent Application Gazette No. 2009/0211967, US A1 of Delsman et al. An alternative method that takes advantage of the temperature-dependent solubility of diphenoquinone in toluene is the temperature of a toluene solution containing diphenoquinone and poly (phenylene ether), where diphenoquinone is almost insoluble but poly (phenylene ether) is soluble at about 25. Insoluble diphenoquinone can be removed by solid-liquid separation (eg filtration) at ° C.

0023In some embodiments, the poly (phenylene ether) comprises 2,6-dimethyl-1,4-phenylene ether units, 2,3,6-trimethyl-1,4-phenylene ether units or a combination thereof. .. In some embodiments, the poly (phenylene ether) is poly (2,6-dimethyl-1,4-phenylene ether). In some embodiments, the poly (phenylene ether) has an intrinsic viscosity of about 0.35 to about 0.5 dL / g, specifically about 0.35 to about 0.46 dL / g, as measured in chloroform at 25 ° C. Contains poly (2,6-dimethyl-1,4-phenylene ether).

0024The poly (phenylene ether) may typically contain a molecule having an aminoalkyl-containing terminal group (s) present at the ortho position with respect to the hydroxy group. There are also often TMDQ end groups typically obtained from 2,6-dimethylphenol-containing reaction mixtures in which a tetramethyldiphenoquinone (TMDQ) by-product is present. The poly (phenylene ether) may be in the form of homopolymers, copolymers, graft copolymers, ionomers, block copolymers, or combinations thereof.

0025The flame-retardant composition contains about 5 to about 90% by mass of poly (phenylene ether) based on its total mass. Within this range, the amount of poly (phenylene ether) may be about 10 to about 85% by mass, more specifically about 30 to about 80% by mass, based on the total mass of the flame retardant composition. It may be%.

0026The flame-retardant composition may also contain a poly (phenylene ether) -polysiloxane block copolymer reaction product containing a poly (phenylene ether) -polysiloxane block copolymer and a poly (phenylene ether) homopolymer. ..

0027Therefore, the flame-retardant composition may contain a polyphenylene ether, a poly (phenylene ether) -polysiloxane copolymer, or a combination thereof.

0028For the sake of brevity, the poly (phenylene ether) -polysiloxane block copolymer reaction product is sometimes referred to herein as the "reaction product". The poly (phenylene ether) -polysiloxane block copolymer reaction product is synthesized by oxidative polymerization of a mixture of monohydric phenol and hydroxyaryl-terminated polysiloxane. This oxidative polymerization produces a poly (phenylene ether) -polysiloxane block copolymer as the desired product and a poly (phenylene ether) homopolymer as a by-product. Therefore, the poly (phenylene ether) -polysiloxane block copolymer is a "poly (phenylene ether) -polysiloxane block copolymer reaction product" containing both a poly (phenylene ether) homopolymer and a poly (phenylene ether) -polysiloxane block copolymer. Incorporated into flame-retardant compositions as "things".

0029The poly (phenylene ether) -polysiloxane block copolymer comprises a poly (phenylene ether) block and a polysiloxane block. The poly (phenylene ether) block is a residue of monovalent phenol polymerization. In some embodiments, the poly (phenylene ether) block comprises a phenylene ether repeating unit having the structure detailed in formula (1) above and the related description.

0030The polysiloxane block is a residue of the hydroxyaryl-terminated polysiloxane. In some embodiments, the polysiloxane block has the structure of equation (2) below.<chemistry num="2"><img id="000003" he="33" wi="121" file="JP5965543B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>(In the formula, R¹And R²Are independent of hydrogen and C₁-C₁₂Hydrocarbyl or C₁-C₁₂It contains a repeating unit having halohydrocarbyl), and further has the structure of equation (3) below.<chemistry num="3"><img id="000004" he="35" wi="149" file="JP5965543B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>(In the formula, Y is hydrogen, C₁-C₁₂Hydrocalvir, C₁-C₁₂Hydrocarbyloxy or halogen, R³And R⁴Are independent of hydrogen and C₁-C₁₂Hydrocarbyl or C₁-C₁₂Includes terminal units with halohydrocarbyl). In some embodiments, the polysiloxane repeating unit is dimethylsiloxane (-Si (CH).₃)₂O-) Including units. In some embodiments, the polysiloxane block has the structure of formula (4):<chemistry num="4"><img id="000005" he="39" wi="156" file="JP5965543B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>In the formula, n is about 20 to about 60 on average.

0031The hydroxyaryl-terminated polysiloxane contains at least one hydroxyaryl-terminated group. In some embodiments where a poly (phenylene ether) -polysiloxane diblock copolymer is formed, the hydroxyaryl-terminated polysiloxane has a single hydroxyaryl-terminated group. In other embodiments where a poly (phenylene ether) -polysiloxane diblock copolymer and / or a poly (phenylene ether) -polysiloxane-poly (phenylene ether) triblock copolymer is formed, the hydroxyaryl-terminated polysiloxane is two hydroxy. It has an aryl terminal group. In addition, the hydroxyaryl-terminated polysiloxane can have three or more hydroxyaryl-terminated groups and may have a branched structure capable of forming the corresponding branched-chain block copolymer.

0032In some embodiments, the hydroxyaryl-terminated polysiloxane has an average of about 20 to about 80, specifically about 25 to about 70, and more specifically about 30 to about 60. More specifically, it contains about 35 to about 50, and even more specifically, about 40 to about 50 siloxane repeating units. The number of siloxane repeat units in the polysiloxane block is essentially unaffected by copolymerization and isolation conditions and is therefore equal to the number of siloxane repeat units in the hydroxyaryl-terminated polysiloxane starting material. If found to be unequal, the average number of siloxane repeat units per molecule of hydroxyaryl-terminated polysiloxane is nuclear magnetic resonance (NMR) that compares the signal intensity associated with the siloxane repeat unit with that associated with the hydroxyaryl end group. ) Can be determined by the method. For example, when the hydroxyaryl-terminated polysiloxane is eugenol-capped polydimethylsiloxane, proton nuclear magnetic resonance () that compares the integral of dimethylsiloxane resonance proton with the integral of eugenol methoxy group proton.¹The average number of siloxane repeating units is determined by the 1 H NMR) method.

0033In some embodiments, the poly (phenylene ether) -polysiloxane block copolymer reaction product has a mass average molecular weight of at least 30,000 atomic mass units. The mass average molecular weight of the reaction product may be, for example, 30,000 to about 150,000 atomic mass units, specifically about 35,000 to about 120,000 atomic mass units, and more specifically about 40,000 to about 40,000. It may be about 90,000 atomic mass units, and more specifically, about 45,000 to about 70,000 atomic mass units. In some embodiments, the poly (phenylene ether) -polysiloxane block copolymer reaction product has a number average molecular weight of about 10,000 to about 50,000 atomic weight units, specifically about 10,000 to about 30,000 atomic weight units. More specifically, it is about 14,000 to about 24,000 atomic mass units.

0034In some embodiments, the intrinsic viscosity of the poly (phenylene ether) -polysiloxane block copolymer reaction product is at least 0.3 dL / g as measured by an Ubbelohde viscometer in chloroform at 25 ° C. In some embodiments, the intrinsic viscosity is 0.3 to about 0.5 dL / g, specifically 0.31 to about 0.5 dL / g, and more specifically about 0.35 to about 0.47 dL / g. ..

0035The composition comprises from about 40 to about 70% by weight of its total mass the poly (phenylene ether) -polysiloxane block copolymer reaction product. Within this range, the amount of the reaction product may be from about 45 to about 65% by weight, specifically from about 50 to about 61% by weight.

0036The poly (phenylene ether) may be mixed with a vinyl aromatic resin. Vinyl aromatic resins are derived from polymer precursors containing at least 25% by weight structural units derived from the monomers of formula (5):<chemistry num="5"><img id="000006" he="28" wi="150" file="JP5965543B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>In the formula, R⁵Is hydrogen, lower alkyl or halogen; Z¹Is vinyl, halogen or lower alkyl; p is 0 to about 5. These polymers include homopolymers of styrene, chlorostyrene and vinyltoluene; styrene and one or more of the monomers exemplified by acrylonitrile, butadiene, α-methylstyrene, ethylvinylbenzene, divinylbenzene and maleic anhydride. , Random copolymers; and rubber-modified polystyrenes containing blends and grafts (where rubber is polybutadiene, or rubber-like copolymers containing about 70-98% styrene and about 2-30% diene monomers). .. Polystyrene is miscible with polyphenylene ethers in all proportions, and any of these blends contains about 5 to about 95% by weight of polystyrene, most often about 25 to about 75% by weight, based on the total weight of the polymer. Polystyrene may be included. In certain embodiments, the flame retardant composition comprises 10-40% by weight, specifically 15-35% by weight of polystyrene, based on its total mass.

0037The poly (phenylene ether) may be mixed with polyamide. Typical polyamides are polypyrrolidone (nylon-4), polycaprolactam (nylon-6), polycapril lactam (nylon-8), polyhexamethylene adipamide (nylon-6,6), polyundecanolactam. (Nylon-11), Polydodecanolactam (Nylon-12), Polyhexamethylene azelaamide (Nylon-6,9), Polyhexamethylene sebacamide (Nylon-6,10), Polyhexamethylene isophthalamide (Nylon-6,10) Nylon-6, I), polyhexamethylene terephthalamide (nylon-6, T), polyamide with hexamethylenediamine and n-dodecanedioic acid (nylon-6,12), terephthalic acid and / or isophthalic acid with trimethylhexamethylene Polyamides obtained from diamines, polyamides obtained from adipic acid and metaxylene diamine, polyamides obtained from adipic acid, azelaic acid and 2,2-bis- (p-aminocyclohexyl) propane, terephthalic acid and 4,4 Examples include polyamides obtained from'-diamino-dicyclohexylmethane and combinations containing one or more of these polyamides. The composition may contain two or more polyamides. The polyamide may contain, for example, nylon-6 and nylon-6,6.

0038The above-mentioned polyamide copolymers are also suitable for use in blends with polyphenylene ethers. Typical polyamide copolymers are hexamethylene adipamide and caprolactam copolymer (nylon-6,6 / 6), caproamide and undecamide copolymer (nylon-6 / 11), caproamide and dodecamide copolymer (nylon). -6/12), Copolymer of hexamethylene adipamide and hexamethylene isophthalamide (nylon-6,6 / 6, I), Copolymer of hexamethylene adipamide and hexamethylene terephthalamide (nylon-6,6) / 6, T), copolymers of hexamethylene adipamide and hexamethylene azelaamide (nylon-6,6 / 6,9) and combinations thereof.

0039Polyphenylene ether may also be mixed with polyarylene sulfide. Polyarylene sulfide is a known polymer containing multiple structural units of formula (6):<chemistry num="6"><img id="000007" he="10" wi="150" file="JP5965543B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>In the formula, R is an aromatic radical such as phenylene, biphenylene, naphthylene, oxydiphenyl, diphenylsulfone, or a lower alkyl radical thereof, or a lower alkoxy radical thereof, or a halogen-substituted derivative thereof. The lower alkyl and alkoxy substituents typically have from about 1 to about 6 carbon atoms such as, for example, methyl, ethyl, propyl, isobutyl, n-hexyl and the like. Preferably, the polyarylene sulfide is a polyphenylene sulfide having a repeating structural unit of the formula (7).<chemistry num="7"><img id="000008" he="20" wi="148" file="JP5965543B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>

0040The melt index of the polyarylene sulfide is preferably about 10 g to about 10,000 g / 10 min, measured according to ASTM D-1238-74 (315.6 ° C, load 5 kg). In another embodiment, the intrinsic viscosity of the polyarylene sulfide is more preferably about 0.05 to about 0.4 as measured in a 1-chloronaphthalene solution at a temperature of 206 ° C and a polymer concentration of 0.4 g / 100 mL. Is about 0.1 to about 0.35.

0041Suitable polyarylene sulfides are in accordance with US Pat. No. 3,354,129, ie, in hot polar organic compounds, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 2,5-dibromobenzene and 2, At least one polyhalo-substituted cyclic compound containing unsaturated between adjacent ring atoms, such as 5-dichlorotoluene, may be prepared by reacting with an alkali metal sulfide. Alkali metal sulfides are generally monosulfides of sodium, potassium, lithium, rubidium and cesium. Polar organic compounds will generally dissolve substantially both alkali metal sulfides and polyhalo-substituted aromatic compounds or other reaction by-products. The polymer can also be produced by the method described in British Patent No. 962,941 in which the metal salt of halothiophenol is heated to the polymerization temperature.

0042A suitable mixture or blend of polyarylene ether and polyarylene sulfide is more preferably about 10% by weight or more, preferably about 20% by mass or more, based on the total amount of the thermoplastic resin in the composition. Contains about 25% by weight or more of polyarylene sulfide. In general, the amount of polyarylene sulfide is preferably about 99% by mass or less, preferably about 80% by mass or less, and most preferably about 70% by mass or less, based on the total amount of the thermoplastic resin. The amount of polyarylene ether is generally about 1% by mass or more, preferably about 5% by mass or more, and more preferably about 10% by mass or more, based on the total amount of the thermoplastic resin in the composition. Most preferably, it is about 15% by mass or more. In general, the amount of polyarylene ether is about 90% by mass or less, preferably about 50% by mass or less, more preferably about 35% by mass or less, and most preferably about about 90% by mass or less, based on the total amount of the thermoplastic resin. It is desirable that it is 28% by mass or less.

0043The amount of the thermoplastic resin in the composition is about 15% by mass or more, preferably about 20% by mass or more, and more preferably about 25% by mass or more, based on the total mass of the composition. Most preferably, it is about 35% by mass or more. The amount thereof is preferably about 85% by mass or less, preferably about 70% by mass or less, and more preferably about 65% by mass or less with respect to the total mass of the composition.

0044The flame-retardant composition may further contain an impact resistance improving agent. Impact resistance improvers are (i) elastomeric with a Tg of 10 ° C or less, more specifically -10 ° C or less, and even more specifically -40 ° C to -80 ° C (ie). Includes an elastomeric-modified graft copolymer comprising a (rubbery) polymeric substrate and (ii) a rigid polymeric substrate grafted onto the elastomeric polymeric substrate. As is known, an elastomer-modified graft copolymer can be prepared by first supplying an elastomeric polymer and then polymerizing the constituent monomers of the rigid phase in the presence of the elastomer to obtain a graft copolymer. The graft can be connected to the elastomer core as a graft branch or as a shell. The shell may simply physically enclose the core, or it may be partially or essentially completely grafted onto the core.

0045Materials used as the elastomeric phase include, for example, conjugated diene rubber; copolymers of conjugated diene containing 50% by weight or less of copolymerizable monomer; ethylene propylene copolymer (EPR) or ethylene-propylene-diene monomer rubber (EPDM). Olefin rubber; ethylene-vinyl acetate rubber; silicone rubber; elastomeric C_1-8Alkyl (meth) acrylate; C_1-8Elastomeric copolymers of alkyl (meth) acrylates with butadiene and / or styrene; or combinations containing at least one of these elastomers.

0046Conjugated diene monomers for preparing the elastomer phase include those of formula (8):<chemistry num="8"><img id="000009" he="19" wi="140" file="JP5965543B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>In the formula, X^{b b}Are independent of hydrogen and C₁-C₅Alkyl and the like. Examples of available conjugated diene monomers are butadiene, isoprene, 1,3-heptadiene, methyl-1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-pentadiene. Examples include combinations containing at least one of these conjugated diene monomers, such as 1,3- and 2,4-hexadiene. Specific conjugated diene homopolymers include polybutadiene and polyisoprene.

0047Copolymers of conjugated diene rubbers, such as those produced by aqueous radical emulsion polymerization of conjugated diene and at least one monomer copolymerizable therewith, can also be used. Examples of the monomer useful for copolymerization with the conjugated diene include a monovinyl aromatic monomer containing a condensed aromatic ring structure such as vinylnaphthalene and vinylanthracene, or a monomer of the following formula (9):<chemistry num="9"><img id="000010" he="29" wi="137" file="JP5965543B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>In the formula, X^cAre independent of hydrogen and C₁-C₁₂Alkyl, C₃-C₁₂Cycloalkyl, C₆-C₁₂Aryl, C₇-C₁₂Aralkill, C₇-C₁₂Alkylaryl, C₁-C₁₂Alkoxy, C₃-C₁₂Cycloalkoxy, C₆-C₁₂Aryloxy, chloro, bromo or hydroxy; R is hydrogen, C₁-C₅It is alkyl, bromo or chloro. As monovinyl aromatic monomers that can be used, styrene, 3-methylstyrene, 3,5-diethylstyrene, 4-n-propylstyrene, α-methylstyrene, α-methylvinyltoluene, α-chlorostyrene, α-bromo Examples include styrene, dichlorostyrene, dibromostyrene, tetrachlorostyrene and the like, and combinations containing at least one of these compounds. Styrene and / or α-methylstyrene can be used as a monomer copolymerizable with a conjugated diene monomer.

0048Other monomers copolymerizable with conjugated diene are itaconic acid, acrylamide, N-substituted acrylamide or methacrylamide, maleic anhydride, maleimide, N-alkyl-, aryl- or haloaryl-substituted maleimide, glycidyl (meth) acrylate, And monovinyl monomers such as the monomer of general formula (10):<chemistry num="10"><img id="000011" he="15" wi="136" file="JP5965543B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>In the formula, R is hydrogen, C₁-C₅Alkyl, bromo or chloro, X^cIs cyano, C₁-C₁₂Alkoxycarbonyl, C₁-C₁₂Such as aryloxycarbonyl or hydroxycarbonyl. Examples of monomers of formula (21a) are acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, β-chloroacrylonitrile, α-bromoacrylonitrile, acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl. Examples include (meth) acrylates, t-butyl (meth) acrylates, n-propyl (meth) acrylates, isopropyl (meth) acrylates, 2-ethylhexyl (meth) acrylates, and combinations containing at least one of these monomers. .. Monomers such as n-butyl acrylate, ethyl acrylate and 2-ethylhexyl acrylate are commonly used as copolymerizable monomers with conjugated diene monomers. The combination of the monovinyl monomer and the monovinyl aromatic monomer described above can also be used.

0049In certain embodiments, the flame-retardant composition comprises rubber-modified polystyrene. Rubber-modified polystyrene contains polystyrene and polybutadiene. Rubber-modified polystyrene is also referred to as "impact resistant polystyrene" or "HIPS". In some embodiments, the rubber-modified polystyrene is 80-96% by mass, specifically 88-94% by mass, and 4-20% by mass, specifically, of its mass. Contains 6-12% by weight of polybutadiene. In some embodiments, the effective gel content of the rubber-modified polystyrene is 10-35%. Suitable rubber-modified polystyrene is commercially available, for example, from SABIC Innovative Plastics as HIPS3190.

0050The flame-retardant composition is about 3 to about 40% by mass, specifically about 5 to about 30% by mass, more specifically about 7 to about 35% by mass, based on the total mass. Contains the rubber-modified polystyrene.

0051The (meth) acrylate monomer used in the elastomer phase is C_1-8Alkyl (meth) acrylates, especially C_4-6Crosslinked particulate emulsion homopolymers or copolymers of alkyl acrylates, including, for example, n-butyl acrylate, t-butyl acrylate, n-propyl acrylate, isopropyl acrylate, 2-ethylhexyl acrylate, and at least one of these monomers. It is a combination. C_1-8The alkyl (meth) acrylate monomer may optionally be polymerized in a mixture of 15% by weight or less of the comonomer of formula (8), (9) or (10) with respect to its total mass. Examples of the comonomer include, but are not limited to, butadiene, isoprene, styrene, methyl methacrylate, phenyl methacrylate, phenethyl methacrylate, N-cyclohexylacrylamide, vinyl methyl ether or acrylonitrile, and combinations containing at least one of these comonomer. Be done. Further, optionally, 5% by mass or less of the polyfunctional crosslinked comonomer may be present with respect to the total mass of the monomers. Such polyfunctional crosslinked comonomers include, for example, alkylenediol di (meth) acrylates such as divinylbenzene and glycol bis acrylate, alkylene triol tri (meth) acrylate, polyester di (meth) acrylate, bisacrylamide, triallyl cyanurate, and tri. Allyl isocyanurate, allyl (meth) acrylate, diallyl maleate, diallyl fumarate, diallyl adipate, triallyl ester of citric acid, triallyl ester of phosphate, etc., and combinations containing at least one of these bridging agents Can be mentioned.

0052The elastomeric phase can be a mass process, emulsification process, suspension process, solution process or bulk-suspension process, emulsification-bulk process, bulk-solution process or other using a continuous process, semi-batch process or batch process. It can be polymerized by a combination process such as technology. The particle size of the elastomeric substrate is not important. For example, for an emulsion-based polymerized rubber lattice, an average particle size of 0.001 to 25 μm, specifically 0.01 to 15 μm, and more specifically 0.1 to 8 μm can be used. As the bulk polymerized rubber substrate, a particle size of 0.5 to 10 μm, specifically 0.6 to 1.5 μm can be used. The particle size can be measured by a simple light transmission method or capillary hydrodynamic chromatography (CHDF). The elastomeric phase is fine particle and moderately crosslinked conjugated butadiene or C._4-6It may be an alkyl acrylate rubber, specifically having a gel content of more than 70%. Also, butadiene and styrene and / or C_4-6Combinations with alkyl acrylate rubbers are also useful.

0053The elastomer phase is 5 to 95% by weight, more specifically 20 to 90% by weight, and even more specifically 40 to 85% by weight of the elastomer-modified graft copolymer with respect to the total weight of the graft copolymer. The rest is a rigid graft phase.

0054The rigid phase of an elastomer-modified graft copolymer can be formed by graft-polymerizing a combination containing a monovinyl aromatic monomer and optionally at least one comonomer in the presence of at least one elastomeric polymer substrate. The monovinyl aromatic monomer of the above formula (9) is halostyrene such as styrene, α-methylstyrene or dibromostyrene, vinyltoluene, vinylxylene, butylstyrene, parahydroxystyrene, methoxystyrene or the like, or these monovinyl aromatic monomers. Can be used in rigid graft phases containing combinations containing at least one of. Useful comonomer includes, for example, the monovinyl monomer described above and / or the monomer of the general formula (10). In some embodiments, R is hydrogen or C₁-C₂Alkyl and X^cIs cyano or C₁-C₁₂It is an alkoxycarbonyl. The comonomer used in the rigid phase includes acrylonitrile, methacrylonitrile, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and at least one of these comonomer. Combinations including one can be mentioned.

0055The relative ratio of monovinyl aromatic monomer to comonomer in the rigid graft phase can vary widely depending on the type of elastomer substrate, the type of monovinyl aromatic monomer, the type of comonomer and the desired properties of the impact resistance improver. The rigid phase generally contains less than 100% by weight, specifically 30-100% by weight, more specifically 50-90% by weight of monovinyl aromatic monomers, with the rest of the rigid phase being comonomer.

0056Depending on the abundance of the elastomer-modified polymer, a separate matrix or continuous phase of the ungrafted rigid polymer or copolymer can be obtained at the same time as the elastomer-modified graft copolymer. Such impact resistance improvers typically include 40-95% by weight of elastomer-modified graft copolymers and 5-65% by weight of graft copolymers based on their total mass. In another embodiment, these impact resistance improvers are 50 to 85% by weight, more specifically 75 to 85% by weight of the rubber modified graft copolymer and 15 to 50% by weight, based on their total weight. More specifically, it contains 15 to 25% by weight of a graft copolymer.

0057In certain embodiments, the aromatic vinyl copolymer comprises a "free" styrene-acrylonitrile copolymer (SAN), i.e., a styrene-acrylonitrile copolymer that has not been grafted onto another polymer chain. In certain embodiments, the free styrene-acrylonitrile copolymer may have a molecular weight of 50,000 to 200,000 daltons on a polystyrene standard molecular weight basis and may contain varying ratios of styrene and acrylonitrile. The free SAN may contain, for example, 75% by weight styrene and 25% by weight acrylonitrile relative to the total weight of the free SAN copolymer. The liberated SAN can optionally be present in the composition containing it by the addition of a grafted rubber impact resistance improver, and / or the liberated SAN is said to be independent of other impact resistance improvers. It can exist in things.

0058Another particular type of elastomer-modified impact resistance improver is with structural units derived from at least one silicone rubber monomer;₂C = C (R^d) C (O) OCH₂CH₂R^e(R^dIs hydrogen or C₁-C₈Straight or branched alkyl group, R^eIs a branched chain C₃-C₁₆It contains a branched chain acrylate rubber monomer (of an alkyl group); a first graft-linked monomer; a polymerizable alkenyl-containing organic material; and a second graft-linked monomer. Examples of the silicone rubber monomer include cyclic siloxane, tetraalkoxysilane, trialkoxysilane, (acryloxy) alkoxysilane, (mercaptoalkyl) alkoxysilane, vinylalkoxysilane or allylalkoxysilane, or a combination thereof. For example, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane, tetramethyltetravinylcyclotetrasiloxane, octaphenylcyclotetrasiloxane, octamethylcyclotetrasiloxane and / or Examples thereof include tetraethoxysilane.

0059Branched chain acrylate rubber monomers include isooctyl acrylates, 6-methyloctyl acrylates, 7-methyloctyl acrylates, 6-methylheptyl acrylates and the like, or combinations containing at least one of these. The polymerizable alkenyl-containing organic material may be, for example, a monomer of formula (9) or (10) (eg, styrene, α-methylstyrene, acrylonitrile, methacrylonitrile), or a non-branched (meth) acrylate (eg, methyl). It may be methacrylate, 2-ethylhexyl methacrylate, methyl acrylate, ethyl acrylate, n-propyl acrylate, etc.), or a combination thereof.

0060The first graft-linked monomer may be (acryloxy) alkoxysilane, (mercaptoalkyl) alkoxysilane, vinylalkoxysilane or allylalkoxysilane, or a combination thereof, eg, (γ-methacryloxypropyl) (dimethoxy). ) Methylsilane and / or (3-mercaptopropyl) trimethoxysilane. The second graft-linked monomer is a polyethylene unsaturated compound having at least one allyl group, such as allyl methacrylate, triallyl cyanurate, triallyl isocyanurate, or a combination containing at least one of these.

0061The silicone-acrylate impact resistance improver is a silicone rubber latex obtained by reacting a silicone rubber monomer with a first graft connecting monomer at a temperature of 30 to 110 ° C in the presence of a surfactant such as dodecylbenzene sulfonic acid. Can be prepared by emulsion polymerization to form. Alternatively, a cyclic siloxane such as cyclooctamethyltetrasiloxane and tetraethoxyorthosilicate can be reacted with a first graft-linked monomer such as (γ-methacryloxypropyl) methyldimethoxysilane. Then, optionally, the branched acrylate rubber monomer is polymerized with the silicone rubber particles in the presence of a crosslinked monomer such as allyl methacrylate and a free radical-forming polymerization catalyst such as benzoyl peroxide. The latex is then reacted with a polymerizable alkenyl-containing organic material and a second graft-linked monomer. A silicone-acrylate rubber impact resistance improving agent can be produced by separating the latex particles of the graft silicone-acrylate rubber mixture from the aqueous phase by coagulation (treatment with a coagulant) and drying them until they become fine powder. This method is generally used for producing a silicone-acrylate impact resistance improver having a particle size of 100 nm to 2 μm.

0062Known processes in the formation of the above-mentioned elastomeric modified graft copolymers include mass process, emulsification process, suspension process, solution process or bulk-suspension process, emulsification-using continuous process, semi-batch process or batch process. Combination processes such as bulk process, bulk-solution process or other techniques can be mentioned.

0063In certain embodiments, the aforementioned types of impact resistance improvers are Cs such as alkali metal salts (eg, sodium stearate, lithium stearate, sodium oleate, potassium oleate, etc._6-30It is prepared by an emulsification polymerization process that does not contain basic materials such as alkali metal salts of fatty acids), alkali metal carbonates, amines (dodecyldimethylamine, dodecylamine, etc.) and ammonium salts of amines. Such materials are commonly used as surfactants in emulsion polymerization and can catalyze transesterification and / or degradation of polycarbonate. Alternatively, an ionic sulfate, sulfonate or phosphate surfactant can be used to prepare the impact resistance improver, especially its elastomeric substrate portion. Useful surfactants include, for example, C_1-22Alkyl or C_7-25Alkylaryl sulfonate, C_1-22Alkyl or C_7-25Alkylaryl sulfate, C_1-22Alkyl or C_7-25Included are alkylaryl phosphates, substituted silicates or combinations containing at least one of these. Certain surfactants are C_6-16, Specifically C_8-12It is an alkyl sulfonate. This emulsion polymerization process is described and disclosed in various patents and documents of companies such as Rohm &amp; Haas and General Electric. In carrying out, any of the above impact resistance improving agents can be used, provided that they do not contain alkali metal salts of fatty acids, alkali metal carbonates and other basic materials.

0064A particular impact resistance improver of this type is a methyl methacrylate-butadiene-styrene (MBS) impact resistance improver prepared with the butadiene substrate using the above-mentioned sulfonate, sulfate or phosphate as a surfactant. In addition to ABS and MBS, other examples of elastomer-modified graft copolymers include, but are not limited to, acrylonitrile-styrene-butyl acrylate (ASA), methyl methacrylate-acrylonitrile-butadiene-styrene (MABS) and acrylonitrile-ethylene. -Propylene-diene-styrene (AES) can be mentioned. If an impact resistance improver is present, its amount in the flame retardant composition may be 5-30% by weight based on the total mass of the composition.

0065In certain embodiments, the flame retardant composition may comprise a reinforcing filler. Examples of reinforcing fillers include glass fibers, carbon fibers, metal fibers and the like.

0066The glass fiber may be a flat fiber or a round fiber. The cross section of the flat glass fiber perpendicular to the fiber vertical axis is elliptical, and that of the round fiber is circular. Glass fibers are made from "E glass", "A glass", "C glass", "D glass", "R glass", "S-glass" and E glass derivatives free of fluorine and / or boron. May be good. The glass fiber may be a woven fabric or a non-woven fabric. The diameter of the glass fiber may be about 3 to about 25 μm, specifically about 4 to about 20 μm, and more specifically about 8 to about 15 μm.

0067The carbon fibers may be carbon nanotubes or carbon fibers derived from pitch or polyacrylonitrile. The carbon nanotubes may be single-walled carbon nanotubes or multi-walled carbon nanotubes. The diameter of the carbon nanotubes may be about 2.7 nm to about 100 nm, and the aspect ratio may be about 5 to about 100. Aspect ratio is defined as the ratio of length to diameter.

0068Carbon fibers derived from pitch and polyacrylonitrile have a different microstructure than carbon nanotubes. The diameter of the carbon fibers is about 3 to about 25 μm, specifically about 4 to about 20 μm, more specifically about 8 to about 15 μm, and an aspect ratio of about 0.5 to about 0.5 to. It may be about 100.

0069The metal fiber may be a whisker (diameter less than 100 nm), or its diameter may be in the range of μm. The diameter of the metal fiber in the μm range may be about 3 to about 30 μm. Typical metal fibers include stainless steel, aluminum, iron, nickel, copper, etc., or combinations containing at least one of these metals.

0070The flame-retardant composition is about 15 to about 45% by mass, specifically about 20 to about 40% by mass, more specifically about 28 to about 33% by mass, based on the total mass. Contains reinforcing filler.

0071In addition, the flame-retardant composition may contain an inorganic filler. In certain embodiments, the inorganic filler functions as a synergist. The coercive agent added to the flame-retardant composition makes it easier to improve the flame-retardant properties with respect to a comparative composition containing the same amount of the same component except for the covalent agent. Examples of inorganic fillers include mica, talc, calcium carbonate, dolomite, wollastonite, barium sulphate, silica, kaolin, feldspar, barite, etc., or combinations containing at least one of these inorganic fillers. The average particle size of the inorganic filler may be about 0.1 to about 20 μm, specifically about 0.5 to about 10 μm, and more specifically about 1 to about 3 μm.

0072The abundance of the inorganic filler is about 0.1 to about 20% by mass, specifically about 0.5 to about 15% by mass, and more specifically about about 50% by mass, based on the total mass of the flame-retardant composition. It is 1 to about 5% by mass. A typical inorganic filler is talc.

0073Further, the flame-retardant composition may optionally be an antioxidant, an ozone deterioration inhibitor, a stabilizer, a heat stabilizer, a mold release agent, a dye, a colorant, a pigment, a fluidity improver, or an additive thereof. Additives such as combinations containing at least one of the above may be included.

0074As mentioned above, the flame retardant composition contains a flame retardant. The flame retardant is a phosphazene compound. In certain embodiments, the flame retardant is a phenoxyphosphazene oligomer.

0075The phosphazene compound used in the flame-retardant composition is an organic compound having an -P = N- bond in the molecule. In certain embodiments, the phosphazene compounds are represented by the cyclic phenoxyphosphazene of formula (11); the chain phenoxyphosphazene of formula (12); At least one of the compounds selected from the group consisting of a cross-linked phenoxyphosphazene compound obtained by cross-linking at least one selected from the phenoxyphosphazenes to be prepared with a cross-linking group represented by the following formula (11) and at least one of the compounds selected from the group. Including seeds:<chemistry num="11"><img id="000012" he="73" wi="137" file="JP5965543B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>In equation (11), m represents an integer from about 3 to about 25, and R₁And R₂Can be the same or different, independently hydrogen, halogen, C_1-12Alkoxy or C_1-12It is alkyl.

0076The chain phenoxyphosphazene is expressed by the following equation (12):<chemistry num="12"><img id="000013" he="65" wi="138" file="JP5965543B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>In equation (12), X¹Is -N = P (OPh)₃Represents a group or -N = P (O) OPh group; Y¹Is -P (OPh)₄Group or -P (O) (OPh)₂Represents a group; n represents an integer from 3 to 10000; Ph represents a phenyl group; R¹And R²Can be the same or different, independently hydrogen, halogen, C_1-12Alkoxy or C_1-12It is alkyl.

0077In addition, the phenoxyphosphazene may have a cross-linking group represented by the following formula (13):<chemistry num="13"><img id="000014" he="32" wi="129" file="JP5965543B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>In equation (13), A is -C (CH)₃)₂-,-SO₂Represents-, -S- or -O-; q is 0 or 1.

0078In one embodiment, the phenoxyphosphazene compound has a structure represented by formula (14):<chemistry num="14"><img id="000015" he="63" wi="151" file="JP5965543B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>In the formula, R₁~ R₆May be the same or different, aryl group, condensed aryl group, aralkyl group, C_1-12Alkoxy, C_1-12It may be alkyl or a combination thereof.

0079In one embodiment, the phenoxyphosphazene compound has a structure represented by formula (15):<chemistry num="15"><img id="000016" he="39" wi="147" file="JP5965543B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry> Commercially available phenoxyphosphazenes having the above-mentioned structure are LY202 (registered trademark) manufactured and sold by Lanin Chemical, FP-110R (registered trademark) manufactured and sold by Fushimi Pharmaceutical Co., Ltd., and Otsuka Chemical Co., Ltd. SPB-100 (registered trademark) manufactured and sold by Co., Ltd.

0080The cyclic phenoxyphosphazene compound represented by the formula (11) is obtained by reacting ammonium chloride and phosphorus pentachloride at about 120 to about 130 ° C to obtain a mixture containing cyclic and linear chlorophosphazene, and hexachlorocyclotri. Phenoxycyclotriphosphazene, octaphenoxycyclotetraphosphazene and decafenoxycyclopenta obtained by extracting cyclic chlorophosphazene such as phosphazene, octachlorocyclotetraphosphazene and decachlorocyclopentaphosphazene and then substituting it with a phenoxy group. It may be exemplified by a compound such as phosphazene. The cyclic phenoxyphosphazene compound may be a compound in which m in the formula (11) represents an integer of about 3 to about 8.

0081The chain phenoxyphosphazene compound represented by the formula (12) has a degree of polymerization of about 3 to 3 after ring-opening polymerization of hexachlorocyclotriphosphazene obtained by the above method at about 220 to about 250 ° C. It is exemplified by a compound obtained by substituting about 10000 chain dichlorophosphazene with a phenoxy group. The n value of the formula (12) of the chain phenoxyphosphazene compound is about 3 to about 1000, specifically about 5 to about 100, and more specifically about 6 to about 25.

0082The crosslinked phenoxyphosphazene compound is a compound having a crosslinked structure of 4,4'-sulfonyldiphenylene (bisphenol S residue), a compound having a crosslinked structure of a 2,2- (4,4'-diphenylene) isopropylidene group, and the like. It is exemplified by a compound having a crosslinked structure of a 4,4'-diphenylene group, such as a compound having a crosslinked structure of a 4,4'-oxydiphenylene group, and a compound having a crosslinked structure of a 4,4'-thiodiphenylene group. obtain. The phenylene group content of the crosslinked phenoxyphosphazene compound is based on the total number of phenyl groups and phenylene groups contained in the cyclic phosphazene compound represented by the formula (11) and / or the chain phenoxyphosphazene compound represented by the formula (12). Generally, it is about 50 to about 99.9% by mass, and specifically, it is about 70 to about 90% by mass. Cross-linked phenoxyphosphazene compounds that do not contain any free hydroxyl groups in the molecule may be particularly suitable. In a typical embodiment, the phosphazene compound comprises a cyclic phosphazene.

0083The flame-retardant composition is about 1 to about 20% by mass, specifically about 2 to about 16% by mass, more specifically about 2.5 to about 14% by mass, based on the total mass. It is desirable to include a phosphazene compound.

0084In certain embodiments, the flame retardant composition may comprise a drop inhibitor. Fluorinated polyolefins and / or polytetrafluoroethylene may be used as anti-dripping agents. For example, anti-dripping agents such as fibril-forming or non-fibril-forming fluoropolymers such as polytetrafluoroethylene (PTFE) can also be used. The anti-dripping agent may be encapsulated with a hard copolymer such as styrene acrylonitrile (SAN). PTFE encapsulated within a SAN is known as TSAN. The encapsulated fluoropolymer may be made, for example, by polymerizing the encapsulated polymer in an aqueous dispersion in the presence of the fluoropolymer. TSAN can provide significant advantages in that it can be more easily dispersed in the composition compared to PTFE. Suitable TSANs may include, for example, about 50% by weight PTFE and about 50% by weight SAN based on the total weight of the encapsulated fluoropolymer. The SAN may contain, for example, about 75% by weight styrene and about 25% by weight acrylonitrile relative to the total weight of the copolymer. Alternatively, the fluoropolymer may be premixed with a second polymer, such as an aromatic polycarbonate resin, or SAN in some way to form a cohesive material used as an anti-dripping agent. Either method may be used to produce the encapsulated fluoropolymer.

0085The anti-dripping agent may be added in the form of relatively large particles having a number average particle size of about 0.3 to about 0.7 mm, specifically about 0.4 to about 0.6 mm. The amount of the anti-dripping agent may be 0.01% by mass to about 5.0% by mass with respect to the total mass of the flame-retardant composition.

0086In addition, the flame-retardant composition may contain an inorganic filler. In certain embodiments, the inorganic filler functions as a synergist. In certain embodiments, a small portion of the inorganic filler may be added to the flame-retardant composition in addition to a covalent agent, which may be another inorganic filler. The coercive agent added to the flame-retardant composition makes it easier to improve the flame-retardant characteristics with respect to a comparative composition containing the same amount of the same component except for the covalent agent. Examples of inorganic fillers include mica, talc, calcium carbonate, dolomite, wollastonite, barium sulphate, silica, kaolin, feldspar, barite, etc., or combinations containing at least one of these inorganic fillers. The average particle size of the inorganic filler may be about 0.1 to about 20 μm, specifically about 0.5 to about 10 μm, and more specifically about 1 to about 3 μm. ..

0087Using additives such as antioxidants, ozone degradation agents, mold release agents, heat stabilizers, smoothing agents, viscosity denaturing agents, free radical deactivators and other polymers or copolymers (such as impact resistance improvers) You may.

0088The flame retardant composition can be prepared by mixing the components under conditions that produce a close mixture. All components may be added to the treatment system first, or certain additives may be premixed with one or more components.

0089In certain embodiments, the flame retardant composition is made by mixing a polycarbonate copolymer with a phosphazene compound. The mixture may be a dry mixture, a melt mixture, a solution mixture or a combination comprising at least one of these mixed forms.

0090In certain embodiments, the flame retardant composition may be dry mixed in an apparatus such as a Henschel mixer or Waring blender to form a mixture, which may then be fed to an extruder to melt and mix the mixture. In another embodiment, a portion of the polycarbonate copolymer may be premixed with the phosphazene compound to form a dry preblend. The dried pre-blend is then melt-mixed with the remaining polyamide composition in the extruder. In certain embodiments, a portion of the flame retardant composition may first be charged into the extruder supply port and the rest of the composition may be supplied through a port downstream of the supply port.

0091Mixing of flame-retardant compositions is performed using shear forces, tensile forces, compressive forces, ultrasonic energies, electromagnetic energies, thermal energies or combinations containing at least one of these forces or energy forms, as described above. Single shaft screw, multi-axis screw, mesh co-rotation or reverse rotation screw, non-mesh co-rotation or reverse rotation screw, reciprocating screw, pinned screw, pinned barrel, roll, ram, spiral rotor, or at least of these It is done in a processing device that is added by a combination including one.

0092Mixing by force as described above, single-screw or multi-screw screw extruder, Buss kneader, Henschel, helicone, Ross mixer, Banbury, roll mill, molding machine (injection molding machine, vacuum forming machine, blow molding machine, etc.) or these It may be done within a combination that includes at least one of the machines.

0093The flame retardant composition may be introduced into the melt mixing apparatus in the form of a masterbatch. In such a process, the masterbatch may be introduced into the mixer downstream of where the remaining flame retardant composition is introduced.

0094In certain embodiments, the flame-retardant compositions disclosed herein are used, for example, in the preparation of molded articles such as durable products, electrical and electronic components and automotive components. The composition can be converted to articles using common thermoplastic processes such as film and sheet extrusion, injection molding, gas assisted injection molding, extrusion molding, compression molding and blow molding.

0095The composition was tested for one or more of UL94 flame retardancy, Izod impact strength, melt viscosity and thermal deformation temperature. Details of these tests used in the examples are known to those of skill in the art and can be summarized as follows.

0096The flammability test was conducted in accordance with the method of the Insurer Research Institute Bulletin 94 "Flammability Test of Plastic Materials, UL94". Several grades are applicable based on burning rate, fire extinguishing time, drip-proof performance and flammability of the droplets. The test sample is a rod with dimensions of 125 mm (length) x 13 mm (width) x 13 mm or less (thickness). The thickness of the rod was 0.6 mm or 0.8 mm. Materials are classified as UL94HB (horizontal combustion), V0, V1, V2, 5VA and / or 5VB based on the test results obtained in 5 samples according to this method, the compositions herein. Tested and classified only for V0, V1 and V2. Each standard is as follows.

0097V0: A sample arranged so that the long axis is 180 ° C with respect to the flame, the burning time and / or the smoldering time after removing the ignition flame is 10 seconds or less, and from the sample arranged vertically. , No burning droplets are produced to ignite the cotton wool. The flame extinguishing time of the five rods is the flame extinguishing time when each of the five rods is burned twice, and the total flame extinguishing time of the first flame extinguishing time (t1) and the second flame extinguishing time (t2) ( The maximum of t1 + t2) is 50 seconds or less.

0098V1: In the sample arranged so that the long axis is 180 ° C with respect to the flame, the burning time and / or the smoldering time after removing the ignition flame is 30 seconds or less, and from the sample arranged vertically. , No burning droplets are produced to ignite the cotton wool. The flame extinguishing time of the five rods is the flame extinguishing time when each of the five rods is burned twice, and the total flame extinguishing time of the first flame extinguishing time (t1) and the second flame extinguishing time (t2) ( The maximum of t1 + t2) is 250 seconds or less.

0099V2: A sample placed so that the long axis is 180 ° C with respect to the flame, the average burning time and / or the average smoldering time after removing the ignition flame is 30 seconds or less, but from the vertically placed sample, cotton wool Combustion droplets are generated to ignite. The flame extinguishing time of the five rods is the flame extinguishing time when each of the five rods is burned twice, and the total flame extinguishing time of the first flame extinguishing time (t1) and the second flame extinguishing time (t2) ( The maximum of t1 + t2) is 250 seconds or less.

0100In certain embodiments, the flame-retardant composition is particularly useful for the production of flame-retardant articles that pass UL94 vertical combustion tests, especially UL94 5VB standards. In the UL94 vertical combustion test, the flame is applied to a vertically fixed specimen placed on cut cotton. To achieve grade 5VB, combustion must stop within 60 seconds after applying the flame 5 times to the test rod, and there must be no droplets igniting the cut cotton. Various embodiments of the compositions described herein meet UL94 5 VB standards.

0101Izod impact strength is used to compare the impact resistance of plastic materials. The impact strength of the notched Izod was determined using a molded 3.2 mm thick notched Izod impact rod at both temperatures of 23 ° C and 0 ° C. It was also calculated in accordance with ASTM D256. Results are shown in units J / m.

0102Thermal deformation temperature (HDT) is a relative measure of the load bearing capacity of a material under high temperature, short-term conditions. This test measures the effect of temperature on stiffness: the standard test piece is given a defined surface stress and the temperature rises at a constant rate. HDT conforms to ASTM D648 and is required to be flatwise under 1.82 MPa stress on a 3.2 mm thick rod. Results are shown in units of ° C.

0103The flame retardant composition is illustrated by the following examples.

0104Example 1 This example was performed to demonstrate the use of polyphenylene ether and phosphazene flame retardants in flame retardant compositions. The flame retardant used in these experiments was Rabitle manufactured by Fushimi Pharmaceutical Co., Ltd. It is FP-110. The components used in the flame-retardant composition are shown in Tables 1A and 1B. In the comparative examples of Table 1B, resorcinol diphosphate is used as the flame retardant, and in the examples (including the disclosed invention), the phosphazene flame retardant is used. Additional compositions are shown in Tables 4A, 4B and 4C. A control sample in which the flame retardant is resorcinol diphosphate (Comparative Examples in Table 1B) contains phosphorus and polyphenylene ether in an amount of 1.9% by mass and 64% by mass, respectively. (See Tables 1B, 4A and 4B, respectively.) Note that the mass% of polyphenylene ether is a percentage of the total of polyphenylene ether and impact resistant polystyrene in the formulation (PPE + HIPS in PPE + HIPS). %). Also note that the control samples in Table 4C are made with bisphenol A diphosphate (BPADP) instead of resorcinol diphosphate (RDP). All NORYL compositions disclosed in Tables 1A, 4A and 4C are commercially available from Sabic Innovative Plastics.<tables num="1A"><img id="000017" he="103" wi="159" file="JP5965543B2_D0001.tif" img-format="tif" img-content="drawing" /></tables><tables num="1B"><img id="000018" he="69" wi="159" file="JP5965543B2_D0001.tif" img-format="tif" img-content="drawing" /></tables>

0105The process conditions are shown in Tables 2 and 3 below.<tables num="2"><img id="000019" he="104" wi="121" file="JP5965543B2_D0001.tif" img-format="tif" img-content="drawing" /></tables>

0106Polyphenylene ether, HIPS and phenoxyphosphazene were supplied from the upstream main throat. RDP was supplied from a liquid injection feeder between barrel zones 5 and 6. All additives (release agents, antioxidants, etc.) were premixed with polyphenylene ether powder in a high speed blender and then fed to the extruder. Table 3 shows the details of the molding conditions.<tables num="3"><img id="000020" he="111" wi="119" file="JP5965543B2_D0001.tif" img-format="tif" img-content="drawing" /></tables><tables num="4A"><img id="000021" he="79" wi="159" file="JP5965543B2_D0001.tif" img-format="tif" img-content="drawing" /></tables><tables num="4B"><img id="000022" he="204" wi="159" file="JP5965543B2_D0001.tif" img-format="tif" img-content="drawing" /></tables><tables num="4C"><img id="000023" he="213" wi="127" file="JP5965543B2_D0001.tif" img-format="tif" img-content="drawing" /></tables>

0107From Table 4B, it can be seen that the Vicat softening and thermal deformation temperatures (HDTs) of all samples containing phosphazene flame retardants are higher than those containing resorcinol di-phosphate flame retardants. Similarly, the notched Izod impact and Charpy notched impact properties (at both room temperature and low temperature) of flame retardant compositions containing phosphazene flame retardants are compared to compositions containing resorcinol di-phosphate flame retardants. It is excellent.

0108Multiaxial impact (at both room temperature and low temperature) with compositions containing phosphazene flame retardants is far superior to compositions containing resorcinol di-phosphate flame retardants. The nominal breaking strains of certain compositions (# 3, # 4, # 8 and # 11 in Table 4B) are also higher than in controls (# 1).

0109The significant improvement in impact and heat can be explained by the very finely dispersed regions of the phosphazene flame retardant in the matrix, as shown in FIG. The finely dispersed regions, unlike resorcinol di-phosphate, do not dissolve phosphazenes in the polyphenylene ether phase and therefore do not affect the glass transition temperature and thermal performance of the flame retardant composition, giving good impact properties. Indicates to do.

0110It can be clearly seen that the flow (MVR and MV) in the phosphazene-based composition is significantly lower than that in the resorcinol di-phosphate flame retardant based composition. It is worth mentioning that the throughput during extrusion of the composition containing the phosphazene flame retardant (~ 22 kg / h) was higher than that of the resorcinol di-phosphate flame retardant composition (~ 18 kg / h).

0111From Table 4B, it can be seen that samples # 2 to 11 have improved flow rates and thermal deformation temperatures while maintaining flame retardant properties. From the melt viscosity rate (MVR) at a temperature of 280 ° C and a load of 5 kg, the viscosity of the sample containing phosphazene is 20-40 cm with a melt flow rate.³It can be seen that it is as low as / 10 minutes. A sample containing an alternative flame retardant (ie, control sample # 1 containing RDP) has a melt viscosity rate (MVR) of 52 cm at 280 ° C and a load of 5 k.³/ 10 minutes. This is an improvement of almost 25%.

0112Similarly, the thermal deformation temperature measured at 1.8 MPa according to ISO75 / Af is from 80 ° C to over 95 ° C, specifically above 100 ° C, and more specifically 105 ° in the control sample. It has improved to over C.

0113From Table 4C, the electrical properties of the compositions containing phosphazene FR (# 2, # 4) show that the compositions containing BPADP as flame retardants (control NORYL).^* N1250 and NORYL^* You will find that it is equivalent to NH6020).

0114Example 2 This example was performed to demonstrate the production and properties of a polyphenylene ether-polysiloxane copolymer composition containing a polystyrene blend and a phenoxyphosphazene flame retardant. The various compositions in this example were designed to contain the same concentration of phosphorus.

0115Table 5 shows the components of various examples and control samples (comparative compositions) demonstrating flame-retardant compositions. As shown in Table 5 (Examples 2, 4, 6 vs. Examples 1, 3, 5), the use of solid phosphazene flame retardants in polyphenylene ether-polysiloxane-polystyrene blends was evaluated and the corresponding polyphenylene ether-poly Compared with siloxane-polystyrene blend. Polystyrene was added in the form of an impact resistance improver. An additional example (Example 7) was performed to evaluate the performance of the blend containing no impact resistance improver. The blend was extruded with a ZSK 28mm twin-screw extruder from the technical research line with a maximum throughput of 14-16kg / h and a torque of about 70%. Control samples of the polyphenylene ether system (Example 1) and the polyphenylene ether-polysiloxane copolymer system (Example 2) were mixed with resorcinol di-phosphate as a flame retardant, and all other formulations were in the phosphazene flame retardant system. is there. Since phosphazene significantly improves impact strength, the use of 40% lower phosphazene input (relative to resorcinol di-phosphate input) (Examples 5-7) was also investigated. The phosphorus contents of the phosphazene flame retardant and resorcinol di-phosphate are ~ 13.4% by mass and ~ 10.9% by mass, respectively.

0116The process parameters for the compositions in Table 5 are shown in Tables 6 and 7. Table 6 shows the extrusion conditions and Table 7 shows the molding conditions.<tables num="5"><img id="000024" he="107" wi="158" file="JP5965543B2_D0001.tif" img-format="tif" img-content="drawing" /></tables><tables num="6"><img id="000025" he="102" wi="132" file="JP5965543B2_D0001.tif" img-format="tif" img-content="drawing" /></tables>

0117Polyphenylene ether-polysiloxane copolymer, polystyrene, impact resistance improver and phenoxyphosphazene were supplied from the upstream main throat. All additives (release agents, antioxidants, etc.) were premixed with polyphenylene ether powder in a super blender and then fed to the extruder. Details of the molding conditions are shown in Table 7.<tables num="7"><img id="000026" he="103" wi="141" file="JP5965543B2_D0001.tif" img-format="tif" img-content="drawing" /></tables>

0118The properties of the various compositions in Table 5 (Examples 1-7) are shown in Tables 8 and 9. Tables 8 and 9 and FIGS. 2 to 7 show the characteristics of the samples in Table 5 (Examples 1 to 7).<tables num="8"><img id="000027" he="180" wi="159" file="JP5965543B2_D0001.tif" img-format="tif" img-content="drawing" /></tables><tables num="9"><img id="000028" he="224" wi="69" file="JP5965543B2_D0001.tif" img-format="tif" img-content="drawing" /></tables>

0119Table 8 and FIGS. 4 (Examples 2-8) compared to a polyphenylene ether sample containing resorcinol di-phosphate (Control Example 1) by using a phenoxyphosphazene flame retardant and / or a polyphenylene ether-polysiloxane copolymer. As shown in, it is observed that the impact strength is significantly increased at room temperature. The combination of polyphenylene ether-polysiloxane copolymer and phenoxyphosphazene flame retardant provides the best impact properties. (See Example 4 vs. Examples 1, 2 and 3.) High impact is also observed with formulations containing 40% low input phenoxyphosphazene flame retardants. (See Example 5 vs. Example 1; Example 6 vs. Example 2; Example 6 vs. Example 5.)

0120The impact properties (Charpy and multiaxial) of blends containing polyphenylene ether-polysiloxane copolymers and phenoxyphosphazene flame retardants (Examples 4, 6-8) were performed even when the amount of impact resistance improver was reduced (implemented). Higher compared to Example 7), control blends (Examples 1 and 2) or corresponding polyphenylene ether-based formulations (Example 5).

0121Also, by using a phenoxyphosphazene flame retardant, it is shown in Table 8 and FIG. 5 (Examples 3 and 4) as compared with a polyphenylene ether type or a polyphenylene ether-polysiloxane copolymer type control (Examples 1 and 2). As such, it was also observed that the nominal breaking strain was significantly increased. The combination of the polyphenylene ether-polysiloxane copolymer with the phenoxyphosphazene flame retardant gave the best nominal fracture strain properties (Example 4 vs. Examples 1, 2, 3). Nominal fracture strain was observed to be high or equivalent even with formulations containing a 40% by weight low input of phenoxyphosphazene flame retardant (Example 5 vs. Example 1; Example 6 vs. Example 2 or Example 6). Against Example 5). Nominal fracture strain was minimized when the impact resistance improver was removed along with the 40% low input phenoxyphosphazene flame retardant (Example 7). 40% low input Phosphazene The UL-94V0 performance of the composition containing FR at 1.0 mm was lower than that of the control, but the UL-94V1 performance at 1.5 and 1.0 mm was comparable to that of the control (Example 1 vs. Example 5, Example 2 pair). Example 6). With a 30% lower input of phosphazene (Example 8), UL-94V-0 combustion performance at 1.0 mm is considered to be optimal.

0122The compositions disclosed herein are for a variety of different articles such as computer housings, housings for electronic products (televisions, mobile phones, tablet computers, etc.), automobile parts (interior panels, etc.), aircraft parts, etc. Can be conveniently used in manufacturing.

0123It should be noted that all ranges detailed herein include the end point. Numerical values from different ranges can be combined.

0124"Contains" includes "consisting (consisting)" and "consisting essentially (consisting)".

0125"And or" includes both "and" and "or (or)". For example, "A and or B" is interpreted to mean A, B or A and B.

0126Although the present invention has been described with reference to typical embodiments, it will be appreciated by those skilled in the art that various modifications can be made and the elements can be replaced with equivalents without departing from the scope of the invention. There will be. Also, many changes can be made to adapt a particular situation or material to what the invention teaches, without departing from the essential scope of the invention. Therefore, the present invention is intended to include all embodiments included in the claims, without being limited to the specific embodiments disclosed as the best embodiments considered for its practice. Will be done.