Flame-retardant polyester molded composition

Abstract

The present invention relates to a thermoplastic molding composition comprising a thermoplastic polyester, a metal salt of formula (I), a halogen-containing flame retardant, and an anti-drip agent; to a method for producing fibers, foils, and molded articles, which method comprises using this thermoplastic molding composition; and to a fiber, foil, or molded article obtained from this thermoplastic molding composition. [Case 1] TIFF2023504245000022.tif4990

Description

[Technical Field]

[0001] The present invention relates to a thermoplastic molding composition comprising a thermoplastic polyester, a method for producing fibers, foils and molded articles using the thermoplastic molding composition, and fibers, foils or molded articles obtained from the thermoplastic molding composition. [Background technology]

[0002] Reinforced or unreinforced thermoplastic polyesters are used in the manufacture of electronic components such as connectors, frames, moving parts, transformers, and micromotors. Many of these applications require flame retardancy, which is typically provided by flame retardant systems based on a combination of brominated flame retardants and antimony trioxide as a synergistic agent. However, this type of flame retardant system has limitations because the highly synergistic antimony trioxide tends to significantly increase smoke output, impairing visibility during a fire and hindering people's evacuation. Furthermore, antimony trioxide has a very high bulk density, increasing the specific gravity of molded parts and negatively affecting electrical properties such as the tracking index (CTI). This is particularly undesirable in the transportation and aviation sectors. Additionally, some ecolabels require the removal of antimony trioxide from thermoplastic components.

[0003] There is a clear need for flame-retardant plastics with low or no antimony trioxide content, but such plastics typically require a significant increase in the amount of brominated flame retardants added.

[0004] WO 2012 / 088080 relates to a flame-retardant thermoplastic composition free of antimony trioxide, comprising a) at least one thermoplastic polyester or polyamide, (b) at least one brominated flame retardant, and (c) at least one metal phosphonate or metal phosphinate. A suitable metal phosphonate or metal phosphinate is one of the following formulas.

[0005] [ka] (In the formula, Me is a metal, and R 1 and R 2 x is the same or different linear, branched, or cyclic C1-C6 alkyl or benzyl, n is the valence of the metal and can be 1, 2, 3, or 4 (x is 1 for metal phosphonates and 0 for metal phosphinates).

[0006] WO 2018 / 073813 relates to a composition comprising a polyester and a mixture of a flame retardant having at least two components: calcium hypophosphite and a bromine-containing polymer. This composition is substantially antimony trioxide-free, meaning that the concentration of antimony trioxide in the composition is considerably lower than the permissible amount used in plastic composites with halogenating additives, for example, 1.0% by mass or less, more preferably 0.5% by mass or less, for example 0.0 to 0.3% by mass (based on the total mass of the composition). Most preferably, the composition is completely antimony trioxide-free.

[0007] WO 2018 / 073819 relates to a composition comprising polyester and a mixture of a flame retardant having at least two components: aluminum hypophosphite and a bromine-containing polymer. This composition is substantially free of antimony trioxide. Here, "substantially free" is as defined in WO 2018 / 073818.

[0008] EP 1 657 972 A1 relates to the phosphinate complex of formula (I).

[0009] [ka] (In the formula, M is a metal from Group 2, Group 3, Group 12, or Group 13 of the periodic table, x is 2 or 3, and n is 10 or greater.)

[0010] Furthermore, EP 1 657 972 A1 relates to the phosphinate complex of formula (II).

[0011] [Chemical formula] (In the formula, M is a metal of Group 2, Group 3, Group 12, or Group 13 of the periodic table of elements, x is 2 or 3, R is a hydrogen atom or a 2-hydroxyphenyl residue, B is a Lewis base, y is 1 or 2, and n is 1 to 100).

[0012] EP 1 657 972 A1 further relates to a flame retardant or polymer containing the above phosphinate complex, and a method for using the phosphinate complex as a flame retardant, particularly in prepared products such as polyesters, polyamides, epoxy resins, and base materials for fibers and conductor substrates.

[0013] US 4,317,769 relates to a flame retardant containing an alkali metal salt and / or an alkaline earth metal salt of a cyclic phosphorus compound represented by Formula I

[0014] [Chemical formula] (In the formula, each of X1 to X8 represents hydrogen, halogen, cyano, acyl, alkyl, halogen-substituted alkyl, aryl, halogen-substituted aryl, or aralkyl).

[0015] JP 2001 139 586 A relates to a method for producing a monohydroxy organic cyclic phosphorus compound and its metal salt, which have high purity and quality and can be safely and highly yieldingly used in a sintering process as a stabilizer, flame retardant, etc. for organic polymers, particularly electronic materials or optical materials. This monohydroxy organic cyclic phosphorus compound has the following general formula (1)

[0016] [Chemical formula] (In the formula, X1, X2, and X3 are each H, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group). [Prior art documents] [Patent Documents]

[0017] [Patent Document 1] WO 2012 / 088080 [Patent Document 2] WO 2018 / 073813 [Patent Document 3] WO 2018 / 073819 [Patent Document 4] WO 2018 / 073818 [Patent Document 5] EP 1 657 972 A1 [Patent Document 6] US 4,317,769 [Patent Document 7] JP 2001 139 586 A [Overview of the project] [Problems that the invention aims to solve]

[0018] In view of the related technologies described above, the object of the present invention is to provide a flame-retardant thermoplastic molding composition based on thermoplastic polyester, free of antimony trioxide, characterized by high flame retardancy and / or high glow-wire resistance. Here, glow-wire resistance means that the flame-retardant composition does not reproducibly ignite at a glow-wire temperature of at least 750°C at various wall thicknesses (plaques) according to the IEC 60695-2-13 GWIT test. Ignition means that the flame is visible for more than 5 seconds. In the case of the glow-wire final product test (GWEPT according to IEC 60695-2-11), ignition means that the flame is visible for more than 2 seconds (IEC 60335-1). [Means for solving the problem]

[0019] The purpose of this is, A) 10-98% by mass of thermoplastic polyester, B) 0.5 to 20% by mass of the following metal salt (I)

[0020] [ka] (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 Each of these is independently either hydrogen or a C1-C4 alkyl group. x is 1, 2, 3, or 4. Met is a metal or metalloid of Group 1, 2, 13, 14, or 15 of the Periodic Table (IUPAC), a transition metal of Groups 3-12 of the Periodic Table (IUPAC), a lanthanide metal, or an oxide derivative of one of the aforementioned metals, metalloids, or transition metals. C) 1.5 to 30% by mass, C1) Halogen-containing flame retardant C2) Anti-dripping agent Flame retardant combination obtained from, D) Other additives at 0-40% by mass This is achieved by providing a thermoplastic molding composition containing, where the sum of the mass percentages of components A) to D) is 100%.

[0021] Furthermore, this objective is achieved by a method for producing fibers, foils, and molded articles, including the use of the thermoplastic molding composition of the present invention, and by fibers, foils, or molded articles, preferably injection-molded electronic components, obtained from the thermoplastic molding composition of the present invention.

[0022] The inventors of this invention, - Metal salt of formula (I), - Halogen-containing flame retardants, and - Drip prevention agent It has been found that using a synergistic mixture yields a molded composition free of antimony trioxide with high flame retardancy (low afterflame time and low flaming droplet in the UL94-V test, and / or high glow-wire resistance according to DIN ISO 60695-2-12). [Modes for carrying out the invention]

[0023] Therefore, the present invention preferably relates to the thermoplastic molding composition of the present invention, wherein the thermoplastic molding composition does not contain antimony trioxide (Sb2O3).

[0024] Component A) The molding composition of the present invention comprises, as component A), 10 to 98% by mass, preferably 25 to 95% by mass, and particularly 31 to 80% by mass of at least one thermoplastic polyester, where the sum of the mass percentages of components A) to D) is 100%.

[0025] Preferred thermoplastic polyester A) is a semi-crystalline or amorphous polyester based on dicarboxylic acids and diols, having a viscosity number of 50-150 mL / g, more preferably 80-150 mL / g, as determined in a 0.5% by mass solution in phenol / dichlorobenzene (1:1) at 25°C according to DIN 53728 / ISO 307.

[0026] The dicarboxylic acid used is preferably an aliphatic or aromatic dicarboxylic acid having 4 to 18 carbon atoms, and more preferably selected from the group consisting of phthalic acid, terephthalic acid, dimethylterephthalic acid, isophthalic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-2,3-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, cyclohexanedicarboxylic acid, cyclohexenediacetic acid, diphenyl-4,4'-dicarboxylic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, dodecanediic acid, and sebacic acid, or mixtures thereof.

[0027] Preferred dicarboxylic acids are aromatic dicarboxylic acids from the group of carboxylic acids listed above. More preferred are terephthalic acid, naphthalenedicarboxylic acid, preferably 2,6-naphthalenedicarboxylic acid and isophthalic acid, and mixtures thereof. More preferred dicarboxylic acids are terephthalic acid and 2,6-naphthalenedicarboxylic acid, and mixtures thereof.

[0028] 30 mol% or less, preferably 10 mol% or less, of the above aromatic dicarboxylic acid may be replaced with aliphatic or alicyclic dicarboxylic acids, such as adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, and cyclohexanedicarboxylic acid. Most preferably, no aliphatic or alicyclic dicarboxylic acids are present. Most preferably, the dicarboxylic acid is terephthalic acid.

[0029] The diol is preferably selected from the group consisting of alicyclic diols having 6 to 20 carbon atoms, most preferably 6 carbon atoms, and aliphatic diols having 2 to 20 carbon atoms, more preferably 2 to 6 carbon atoms, most preferably ethylene glycol, diethylene glycol, triethylene glycol, 1,4-cyclohexenedimethanol, propane-1,3-diol, propene-1,2-diol, butane-1,2-diol, butane-1,4-diol, pentene-1,5-diol, hexene-1,6-diol, 3-methylpentene-2-4-diol, 2-methylpentene- The diol is selected from the group consisting of 1,4-diol, 2,2,4-trimethylpentene-1,3-diol, hexane-1,3-diol, hexane-1,4-diol, 2,2-bis(4-hydroxycyclohexyl)propane, 2,4-dihydroxy-1,1,3,3-tetramethylcyclobutane isosorbitol, poly(alkylene oxide) glycol containing a total of 3 to 12 carbon atoms, each containing 3 or 4 or fewer oxygen atoms and the remaining atoms being hydrocarbon atoms, preferably poly(oxyethylene)diol, poly(oxypropylene)diol or poly(oxytetramethylene)diol, and mixtures thereof. More preferably, the diol is an aliphatic diol, particularly ethylene glycol, butane-1,4-diol or propane-1,3-diol, poly(oxyethylene)diol, poly(oxypropylene)diol or poly(oxytetramethylene)diol, and mixtures thereof.

[0030] Particularly preferred thermoplastic polyester A) is terephthalate derived from an alkanediol having 2 to 6 carbon atoms, especially ethylene glycol, butane-1,4-diol, or propane-1,3-diol. Therefore, polyethylene terephthalate, polybutylene terephthalate, and polypropylene terephthalate, and mixtures thereof are particularly preferred.

[0031] Furthermore, polyethylene terephthalate and / or polybutylene terephthalate containing 1,6-hexanediol and / or 2-methyl-1,5-pentanediol in an amount of 1% by mass or less, preferably 0.7% by mass or less, as other monomer units is preferred.

[0032] As described above, the thermoplastic molding composition may include a polyester mixture as component A), for example, a mixture of polybutylene terephthalate and polyethylene terephthalate. The proportion of polyethylene terephthalate in the mixture is, for example, 50% by mass or less, preferably 10 to 35% by mass, based on 100% by mass of component A.

[0033] In a further embodiment, PET recycled (also called scrap PET) optionally mixed with polyalkylene terephthalate such as PBT is used.

[0034] Recyclers generally consist of the following: 1) Known as post-industrial recyclables: These materials are production waste generated during polycondensation or processing, such as sprues from injection molding, starting materials from injection molding or extrusion, or edge trims from extruded sheets or films; 2) Post-consumer recyclables: These materials are plastic products that are collected and processed after use by the end consumer. Low-mold PET bottles for mineral water, soft drinks, and juices make up the vast majority in terms of quantity.

[0035] Both types of recyclete may be used in the form of regrind or pelletized material. In the latter case, the crude recyclete is separated, purified, and then melted in an extruder to form pellets. This usually facilitates measurement for processing and free flow, and for further processing steps. The above-mentioned thermoplastic polyester is commercially available or prepared by processes known in the art. Usually, the polyester is produced by reacting one or more dicarboxylic acids, or their esters or other ester-forming derivatives, with the above-mentioned dihydroxy compounds by methods known per se. Furthermore, component A) can be a blend of at least one of the above-mentioned polyesters and at least one blend component.

[0036] Suitable blend components are selected from the group consisting of polycarbonate and liquid crystal polyester, copolymers of polybutylene adipate and terephthalate, and aliphatic polyesters such as epsilon-polycaprolactone. One or more blend components are present in an amount of 0 to 30% by mass (total amount of blend components) based on the total amount of component A). When one or more blend components are present, the blend components are present in an amount of 0.1 to 30% by mass (total amount of blend components) based on the total amount of component A).

[0037] Component B) The molding composition of the present invention contains, as component B), 0.5 to 20% by mass, preferably 3 to 17% by mass, more preferably 5 to 15% by mass of at least one metal salt of formula (I), where the total mass percentages of components A) to D) are 100%.

[0038] [Chemical formula] (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently hydrogen or C1-C4 alkyl, x is 1, 2, 3 or 4, Met is a metalloid of any of the metals in groups 1, 2, 13, 14, or 15 of the periodic table (IUPAC), a transition metal in groups 3 to 12 of the periodic table (IUPAC), a lanthanide metal, or an oxy derivative of any of the aforementioned metal metalloids or transition metals.

[0039] Preferably, in the metal salt B), Met in formula (I) is a metalloid of a metal from group 13, 14, or 15 of the periodic table (IUPAC), a transition metal from group 3 to 12 of the periodic table (IUPAC), a lanthanide metal, or an oxy derivative of any of the aforementioned metal metalloids or transition metals. More preferably, Met is selected from the group consisting of Al, Ge, Sn, Bi, Ti, V, Cr, Mn, Fe, La, Ce, OTi, OV, OCr, OSn, and OBi. Most preferably, Met is Al and x is 3.

[0040] R in equation (I) in metal salts 1 , R 2 , R 3 , R 4 , R 5 and R 6 Preferably, it is hydrogen. That is, most preferably, it is a metal salt of formula (Ia).

[0041] [ka] (In the formula, x is 2, 3, or 4, preferably 3) Met is Al, Ge, Sn, Bi, Ti, V, Cr, Mn, Fe, La, Ce, OTi, OV, OCr, OSn, and OBi, preferably Al).

[0042] The metal salts of formulas (I) and (Ia), respectively, are metal salts of 10-hydroxy-9,10-dihydro-9-oxa-10-phosphophenantrenoxide (DOPO acid).

[0043] The aforementioned metal salts are prepared, for example, starting from commercially available DOPO acids, which are reacted with suitable metal salts containing the metal Met as defined in formulas (I) and (Ia), respectively. Suitable metal salts are, for example, hydroxides, halides, especially chlorides, or sulfates of the metal Met as referred to in formulas (I) and (Ia), respectively.

[0044] Component C) The molding composition of the present invention comprises, as component C), 1.5 to 30% by mass, preferably 2 to 23% by mass, more preferably 15 to 22% by mass. C1) Halogen-containing flame retardant C2) Drip inhibitor It comprises at least one flame retardant combination obtained from, where the sum of the mass percentages of components A) to D) is 100%.

[0045] Preferably, component C) comprises 95 to 99.95% by mass, preferably 96 to 99.50% by mass, more preferably 97 to 99.0% by mass of C1), and 0.05 to 5% by mass, preferably 0.1 to 2% by mass, more preferably 0.25 to 3% by mass of C2).

[0046] Component C2) Any anti-dripping agent known in the art can be used as the anti-dripping agent C2). Preferably, the anti-dripping agent C2) is a compound selected from the group consisting of fluorine-containing polymers, siloxane-based anti-dripping agents, and mixtures thereof. More preferably, the anti-dripping agent contains a fluorine-containing polymer or a siloxane.

[0047] Preferred fluorine-containing polymers are selected from the group consisting of poly(tetrafluoroethylene) (PTFE), tetrafluoroethylene / hexafluoropropylene copolymer, tetrafluoroethylene / ethylene copolymer, poly(vinylidene fluoride), poly(chlorotrifluoroethylene), and mixtures thereof. The preferred fluorine-containing polymer is poly(tetrafluoroethylene) (PTFE). The poly(tetrafluoroethylene) can be used as PTFE powder. Fluorine-containing polymers are commercially available or prepared by processes known in the art.

[0048] A suitable siloxane is preferably a siloxane-based anti-dropping agent containing polydimethylsiloxane. Suitable siloxane-based anti-dropping agents are commercially available.

[0049] Component C1) Component C1) is a halogen-containing flame retardant, preferably a bromine-containing flame retardant or a chlorine-containing flame retardant, more preferably a bromine-containing flame retardant.

[0050] Suitable halogen-containing flame retardants are known to those skilled in the art. Preferred halogen-containing flame retardants are oligomers and polymers.

[0051] Preferred bromine-containing flame retardants include brominated diphenyl esters, brominated trimethylphenylindanes (e.g., FR 1808 from DSB), tetrabromobisphenol A, brominated oligocarbonates, and preferably brominated oligocarbonates of tetrabromobisphenol A having the following formula (wherein n is greater than 2):

[0052] [ka] (For example, Great Lakes' BC 52 or BC 58), Polypentabromobenzylacrylate as shown in the following formula (where n is greater than 4):

[0053] [ka] (For example, ICL-IP's FR 1025), The oligomeric reaction product of tetrabromo-bis-phenol A and epoxide in the following formula (where n is greater than 3):

[0054] [ka] (For example, DSB's FR 2300 and 2400), Preferably, the group consists of brominated oligostyrene and brominated polystyrene having an average degree of polymerization (number mean) of 3 to 90, more preferably 5 to 60, as measured by vapor pressure osmotic pressure measurement in toluene.

[0055] A preferred brominated oligostyrene has the following formula (I)

[0056] [ka] (wherein R is hydrogen, or an aliphatic moiety, particularly an alkyl moiety, such as CH3 or C2H5, and n is the number of repeating chain units, preferably 124 or less, more preferably 10 to 100, R 1 (This may be H, or bromine, or a fragment of a conventional free radical generator).

[0057] Brominated oligostyrenes preferably contain 40-80% by mass, more preferably 55-70% by mass, of bromine. Products mainly composed of polydibromostyrene are preferred. This substance can be melted without decomposition and is soluble in, for example, tetrahydrofuran. These can be produced, for example, by cyclic bromination of an optionally aliphatic hydrogenated styrene oligomer of the type obtained by thermal polymerization of styrene (according to DT-OS 25 37 385), or by free radical oligomerization of suitable brominated styrenes. Brominated oligostyrenes can also be produced by ionic oligomerization of styrene and subsequent bromination.

[0058] Brominated polystyrene is typically obtained by the process described in EP-A 47 549.

[0059] [ka]

[0060] The commercially available brominated polystyrenes that can be obtained by the above process are mainly ring-substituted tribromation products. n' (see III) generally has a value of 125 to 1500, which corresponds to a molecular weight of 42500 to 235000, preferably 130000 to 135000.

[0061] The bromine content (based on the content of ring-substituted bromine) is generally at least 50% by mass, preferably at least 60% by mass, and particularly 65% ​​by mass.

[0062] Commercially available powdered products generally have a glass transition temperature of 160-200°C and can be purchased, for example, as HP 7010 from Albemarle and Pyrocheck PB 68 from Ferro Corporation.

[0063] Furthermore, it is also possible to use a mixture of brominated oligomer styrene and brominated polystyrene in any mixing ratio.

[0064] A suitable chlorine-containing flame retardant is, for example, dechloran plus, as shown in the formula below.

[0065] [ka]

[0066] Further halogenated flame retardants are disclosed, for example, in EP-A-1477520 or WO 2013 / 085789.

[0067] Component D) The molding composition of the present invention comprises, as component D), 0 to 40% by mass of one or more other additives, preferably 0.1 to 35% by mass, more preferably 0.5 to 32% by mass, where the total mass percentage of components A) to D) is 100%.

[0068] In the context of this invention, the term "additive" encompasses both additives and processing agents.

[0069] Suitable additives D) include fibrous or particulate fillers D1), such as glass fibers, aramid fibers and potassium titanate fibers, glass beads, amorphous silica, calcium silicate, calcium metasilicate, magnesium carbonate, kaolin, chalk, quartz powder, mica, barium sulfate, feldspar, talc, magnesium hydroxide, and wollastonite, particularly wollastonite needles, and mixtures of the aforementioned fillers.

[0070] Further preferred fillers are laser-absorbing fillers, such as carbon fibers, carbon black, graphite, graphene, or carbon nanotubes. The amount of laser-absorbing filler is generally less than 1% by mass, preferably less than 0.01% by mass, based on the thermoplastic molding composition.

[0071] Needle-shaped mineral fillers are also suitable. For the purposes of the present invention, needle-shaped mineral fillers are mineral fillers having strongly developed needle-like properties. An example is needle-shaped wollastonite. Needle-shaped minerals preferably have an L / D (length / diameter) ratio of 8:1 to 35:1, more preferably 9:1 to 11:1.

[0072] Preferred fibrous fillers are glass fibers, aramid fibers, potassium titanate fibers, and mixtures thereof, with glass fibers being particularly preferred. Glass fibers are even more preferably present in the form of E-glass. These can be used in the form of roving or chopped glass.

[0073] Preferred particulate or needle-shaped mineral fillers include talc, magnesium hydroxide, wollastonite, particularly wollastonite needles, and mixtures thereof.

[0074] Most preferably, and especially most preferably, are glass fibers in the form of E-glass.

[0075] Fibrous fillers and particulate fillers (and laser-absorbing fillers and needle-shaped mineral fillers) can be surface-pretreated with silane compounds.

[0076] Suitable silane compounds are those with the general formula (X(DH2) n ) x -Si-(OC m H 2m+1 ) 4-K (In the formula, x is between 1 and 2, n is 2 to 10, preferably 3 to 4. m is 1 to 5, preferably 1 to 2. k is a value between 1 and 3, preferably 1.

[0077] Preferred silane compounds are aminopropyltrimethoxysilane, aminobutyltrimethoxysilane, aminopropyltriethoxysilane, aminobutyltriethoxysilane, and the corresponding silanes containing a glycidyl group as a substituent.

[0078] The amount of silane compound or surface coating used is generally 0.05 to 5% by mass, preferably 0.1 to 1.5% by mass, and particularly 0.2 to 0.5% by mass (based on filler).

[0079] Further additives D) that can be used in the thermoplastic molding composition according to the present invention are elastomer polymers D2) often called "impact modifiers," "elastomers," or "rubber."

[0080] Very generally, these are copolymers preferably composed of at least two of the following monomers: ethylene, propylene, butadiene, isobutene, isoprene, chloroprene, vinyl acetate, styrene, acrylonitrile, and an acrylic ester or methacrylic ester having preferably 1 to 18 carbon atoms in the alcohol component.

[0081] This type of polymer is known in the field of technology.

[0082] Preferred types of elastomer polymers include ethylene propylene (EPM) rubber, ethylene-propylene-diene (EPDM) rubber, EPM rubber grafted with a reactive carboxylic acid or its derivative, EPDM rubber grafted with a reactive carboxylic acid or its derivative, and copolymers of ethylene with acrylic acid and / or methacrylic acid and / or esters of these acids, wherein the rubber may further include monomers, homopolymers or copolymers and graft polymers containing dicarboxylic acids or derivatives of these acids and / or epoxy groups, emulsion polymers such as ABS polymers and / or ASA polymers, or homogeneous polymers, i.e., single-shell elastomers preferably composed of 1,3-butadiene, isoprene and n-butyl acrylate or copolymers thereof.

[0083] ABS and / or ASA polymers are used, for example, in a mixture with polyethylene terephthalate in an amount of 40% by mass or less based on a thermoplastic molding composition, for example, for impact modification of PBT, and optionally in a mixture with polyethylene terephthalate in an amount of 40% by mass or less based on a thermoplastic molding composition. These types of blended products are commercially available, for example, under the trademark Ultradur® S of BASF SE.

[0084] Further preferred components D) are halogen-free flame retardants D3), particularly halogen-free phosphorus and / or nitrogen-containing flame retardants. Preferred halogen-free flame retardants are known to those skilled in the art and are disclosed, for example, in EP-A-1477520.

[0085] Further preferred components D) are lubricants, mold release agents, and plasticizers, which are commonly used as processing aids D4).

[0086] Suitable lubricants and release agents include long-chain fatty acids (e.g., stearic acid or behenic acid), their metal salts (e.g., calcium stearate or zinc stearate), or montan wax (a mixture of straight-chain saturated carboxylic acids having a chain length of 28 to 32 carbon atoms), calcium montanate or sodium montanate, or ester wax (long-chain monovalent wax acid (C)). 22 ~C 34 ) and monounsaturated fatty acids or wax alcohols (C 24 ~C 32 Examples include reaction products with (), amide waxes (reaction products of technical fatty acids, fatty acid esters or triacylglycerols with ammonia or monovalent or polyvalent amines and amino alcohols), and also low molecular weight polyethylene wax and low molecular weight polypropylene wax. The lubricant and release agent are preferably used in an amount of 0 to 1% by mass, preferably 0.1 to 0.9% by mass, based on the thermoplastic molding composition.

[0087] Further preferred components D) are, as conventional processing aids D5), metal deactivators, nucleating agents, acid scavengers, carbon black, oxidation retarders (antioxidants), aids that neutralize the decomposition of the composition by heat and ultraviolet light, and colorants such as dyes and pigments.

[0088] Suitable examples of oxidation retarders and heat stabilizers include sterically hindered phenols and / or phosphites, thiosyntheticists, hydroquinones, aromatic secondary amines such as diphenylamine, various substituted members of this group, and mixtures thereof, preferably in amounts of 0 to 1% by mass, and more preferably 0.1 to 0.9% by mass, based on the thermoplastic molding composition.

[0089] UV stabilizers include, for example, various substituted resorcinols, salicylates, benzotriazoles, and benzophenones. The UV stabilizer is used in an amount of preferably 0 to 2% by mass, preferably 0.1 to 1.9% by mass, based on the thermoplastic molding composition.

[0090] The colorants that can be added are inorganic or organic pigments and dyes, such as anthraquinones. Suitable colorants are described, for example, in EP 1 722 984 B1, EP 1 353 986 B1, or DE 100 54 859 A1. The colorants are used in an amount of 0 to 1% by mass, preferably 0.1 to 0.9% by mass, based on the thermoplastic molding composition.

[0091] A further class of processing aids is an ester or amide of a saturated or unsaturated aliphatic carboxylic acid having 10 to 40 carbon atoms, preferably 16 to 23, and a saturated aliphatic alcohol or amine having 2 to 40 carbon atoms, preferably 2 to 6.

[0092] Carboxylic acids can be monobasic or dibasic. Examples mentioned include pelargonic acid, palmitic acid, lauric acid, margaric acid, dodecanediic acid, behenic acid, stearic acid, capric acid, and montanic acid (a mixture of fatty acids having 30 to 40 carbon atoms), with stearic acid, capric acid, and montanic acid being particularly preferred.

[0093] Aliphatic alcohols can be monovalent to tetravalent. Examples of alcohols include n-butanol, n-octanol, stearyl alcohol, ethylene glycol, propylene glycol, neopentyl glycol, and pentaerythritol, and glycerol, with pentaerythritol and glycerol being preferred.

[0094] Aliphatic amines can be monobasic or tribasic. Examples include stearylamine, ethylenediamine, propylenediamine, hexamethylenediamine, and di(6-aminohexyl)amine, with ethylenediamine and hexamethylenediamine being preferred. Preferred esters or amides are correspondingly glycerol distearate, glycerol tristearate, ethylenediamine distearate, glycerol monopalmitate, glycerol trilaurate, glycerol monobehenate, and pentaerythritol tetrastearate. Furthermore, mixtures of various esters or amides, or combinations of esters and amides, can be used in any mixing ratio.

[0095] The thermoplastic molding composition of the present invention can be manufactured by processes known in the art, for example, by mixing the starting components in a conventional mixing apparatus such as a screw extruder, Brabender mixer, or Banbury mixer, and then extruding the mixture. The extruded material can be cooled and crushed. Alternatively, the individual components can be pre-mixed (for example, by applying the individual components to the pelletizing material in a drum, etc.), and then the remaining starting materials can be added individually and / or similarly in the form of a mixture and / or in the form of a masterbatch. The mixing temperature is generally 230-320°C. Component B) can alternatively be added by hot-feed or directly to the inlet of the extruder.

[0096] The molding composition of the present invention is characterized by good electrical properties and flame retardancy. Furthermore, the molding composition of the present invention is characterized by high glow-wire resistance (glow-wire resistance is defined above).

[0097] Accordingly, the present invention further relates to a method for producing fibers, foils, and molded articles, including the use of the thermoplastic molding composition according to the present invention, and to fibers, foils, or molded articles, preferably injection-molded electronic components, obtained from the thermoplastic molding composition according to the present invention.

[0098] Molded articles produced from the molding compositions of the present invention may be used, for example, in the manufacture of internal and external components having load-bearing or mechanical functions in any of the fields of electrical, furniture, sports, mechanical engineering, public health and sanitation, medical, power engineering and drive technology, automobiles and other means of transport, or in the manufacture of housing materials for equipment and devices for telecommunications, home appliances, household appliances, mechanical engineering, heating elements or fasteners for installation work, or for containers and ventilation components of any type.

[0099] In particular, the thermoplastic molding composition of the present invention is suitable for use in plugs, switches, housing components, housing covers, headlamps (bezels), shower heads, fittings, smoothing irons, rotary switches, stove controls, fryer lids, door handles, (rearview) mirror housings, (tailgate) screen wipers, and sheaths for optical conductors.

[0100] Devices that can be manufactured in the electrical and electronic fields by the thermoplastic molding composition according to the present invention include plugs, plug components, plug connectors, cable harness components, circuit mounts, circuit mount components, three-dimensional injection molded circuit mounts, electrical connector elements, mechatronics components, and optoelectronic components.

[0101] Possible applications in automotive interiors include dashboards, steering column switches, seat components, headrests, center consoles, gearbox components, and door modules; and possible applications in automotive exteriors include door handles, headlamp components, exterior mirror components, front wiper components, front wiper protective housings, decorative grilles, roof rails, roof frames, and exterior body components.

[0102] Possible applications of the thermoplastic molding composition of the present invention in the kitchen and household sectors include the manufacture of kitchen equipment components, such as fryers, smoothing irons, and buttons, and also applications in the garden and leisure sectors, such as components for irrigation systems or garden equipment.

[0103] The present invention will be further explained by the following embodiments. [Examples]

[0104] Manufacturing of molded compositions / test samples The molded composition was manufactured by melt compounding. For this purpose, the individual components were mixed in a flat temperature profile using a twin-screw extruder ZSK 26 (Berstorff) with a rotation speed of 20 kg / h and a temperature of approximately 250-270°C, extruded in the form of strands, cooled to a pellet-forming state, and then pelletized.

[0105] Using an Arburg 420C injection molding machine, the test specimens listed in the table below were injection molded at a melting temperature of approximately 250-290°C and a mold temperature of approximately 80°C.

[0106] The flame retardancy of the molded material was measured using the UL94-V method (Underwriters Laboratories Inc. safety standard, "Flammable Test of Plastic Materials for Equipment and Parts", pp. 14-18, North-brook 1998).

[0107] Glow-wire resistance was determined by calculating the glow-wire flammability index (GWFI) in accordance with IEC 60695-2-12.

[0108] The GWFI was determined by performing a glow-wire test on three test specimens (e.g., a test plate or circular disc with a shape of 60 × 60 × 1.0 mm). The maximum temperature was determined by the glow-wire at temperatures between 550°C and 960°C, at which point the material did not ignite during the contact time with the glow-wire in the subsequent three tests. The test specimen was pressed against a heated glow-wire with a force of 1 Newton for 30 seconds. The penetration of the glow-wire was limited to 7 mm. The test was considered successful if the test specimen glowed after the glow-wire was removed in less than 30 seconds and the tissue paper placed beneath the test specimen did not ignite.

[0109] Glow-wire resistance was further determined by measuring the glow-wire ignition temperature (GWIT) according to DIN EN 60695-2-13. The GWIT test determined the highest temperature at which ignition did not occur during the glow-wire contact time in subsequent three tests. GWIT tests were performed on three test specimens (e.g., plates with a shape of 60 × 60 × 1.5 mm) using glow-wires at temperatures between 550 and 960°C. The specified GWIT was 25K higher than the determined highest temperature. A flame with a burning time exceeding 5 seconds was used as the ignition criterion.

[0110] The resistance to voltage exposure (comparative tracking index = CTI value) was determined by determining the resistance to voltage exposure in accordance with IEC 60112.

[0111] The following components were used in the examples.

[0112] Ingredient A: BASF SE's Ultradur® B4520 (130cm) 3 PBT with viscosity number according to DIN 53728 per g.

[0113] Ingredient B1: The aluminum salt of (commercially available) DOPO acid (10-hydroxy-9,10-dihydro-9-oxa-10-phosphophenantrenoxide = DOPOX) was prepared by the following procedure: In a glass valve, 355.2 g (8.610 mol) of NaOH was partially dissolved in 1 L of deionized water with stirring. This solution was cooled. Meanwhile, in a 20 L beaker, 2000 g (8.610 mol) of DOPOX was suspended in 10 L of deionized water. Next, the prepared NaOH solution was partially added to the DOPOX suspension over 60 minutes with stirring, and washed with deionized water. This formed a brownish-black solution, which was stirred until the solid was completely dissolved. Subsequently, 693.4 g (2.870 mol) of aluminum chloride hexahydrate was partially dispersed in 2.5 L of deionized water and then partially added to the reaction mixture over 60 minutes, thereby causing the final product to precipitate as a solid. The reaction mixture was stirred at room temperature for 2 hours, and after 24 hours, the solid was filtered and suspended in 12 L of deionized water under vigorous stirring. The solid was then filtered again, washed with deionized water, and vacuum-dried at 130°C.

[0114] Component B2: The iron(III) salt of (commercially available) DOPO acid (10-hydroxy-9,10-dihydro-9-oxa-10-phosphophenantrenoxide = DOPOX) was prepared by the following procedure: The previous day, 177.6 g (4.31 mol) of NaOH was partially dissolved in 0.5 L of deionized water while stirring. This solution was cooled. The reaction vessel was kept sealed and stored until use.

[0115] In a 20 L beaker, 1000 g (4.31 mol) of DOPOX was suspended in 5 L of deionized water. The prepared NaOH solution was partially added to the DOPOX suspension over 60 minutes with stirring, and washed with deionized water. This formed a brownish-black solution, which was stirred until the solid was completely dissolved. Meanwhile, 386.39 g (1.43 mol) of iron chloride hexahydrate was partially dispersed in 1 L of deionized water, then partially added to the reaction mixture over 60 minutes, and washed with deionized water. The solid precipitated immediately. The reaction mixture was stirred at room temperature for 2 hours and allowed to stand overnight to precipitate the solid. The solid was filtered and vigorously stirred in 6 L of deionized water for 1 hour. The solid was filtered and washed with deionized water. The solid was then vacuum-dried first at 80°C and then at 130°C.

[0116] Component C1 / a: Brominated flame retardant based on tetrabromobisphenol A (BC-52™ trademark of Lanxess).

[0117] Component C2: Commercially available PTFE powder (3M-Dyneon GmbH) was used.

[0118] Component C3: Commercially available calcium hypophosphate (Phoslite IP-C® from Italmatch Chemicals SPA) was used.

[0119] Component D: Short glass fibers with a diameter of 10 μm, PPG 3786 (PPG Industries, Inc.), were used.

[0120] [Table 1]

[0121] As is clear from the data shown in Table 1, the composition of the present invention exhibits superior values ​​in terms of fire behavior according to UL94-V (V-0 classification) compared to the prior art (comparative example V1, which is self-extinguishing (no flame droplets are generated)).

Claims

1. A) 10-80% by mass of thermoplastic polyester, B) 3 to 20% by mass of the metal salt of formula (I) below 【Chemistry 1】 (In the formula, R １ , R ２ , R ３ , R ４ , R ５ and R ６ Each of them independently consists of hydrogen or C １ ~C ４ It is alkyl, x is 1, 2, 3 or 4, Met is a metalloid of a metal in Group 1, 2, 13, 14, or 15 of the Periodic Table (IUPAC), a transition metal in Groups 3 to 12 of the Periodic Table (IUPAC), a lanthanide metal, or an oxy derivative of one of the aforementioned metals, metalloids, or transition metals. C) 15-30% by mass, C1) Halogen-containing flame retardant C2) Dripping inhibitor Flame retardant combination obtained from, D) 0-50% by mass of other additives Includes, The sum of the mass percentages of components A) to D) is 100%, A thermoplastic molding composition that does not contain antimony trioxide (Sb ２ O ３ ).

2. The thermoplastic molding composition according to claim 1, wherein Met in the metal salt B) is a metalloid of a metal from group 13, 14, or 15 of the periodic table (IUPAC), a transition metal from group 3 to 12 of the periodic table (IUPAC), a lanthanide metal, or an oxy derivative of any of the aforementioned metal, metalloid, or transition metal.

3. The thermoplastic molding composition according to claim 1 or 2, wherein Met is selected from the group consisting of Al, Ge, Sn, Bi, Ti, V, Cr, Mn, Fe, La, Ce, OTi, OV, OCr, OSn, and OBi.

4. R １ , R ２ , R ３ , R ４ , R ５ and R ６ A thermoplastic molding composition according to any one of claims 1 to 3, wherein is hydrogen.

5. The thermoplastic molding composition according to any one of claims 1 to 4, wherein the thermoplastic polyester A) has a viscosity number of 50 to 180 mL / g as determined in a 0.5% by mass solution in phenol / o-dichlorobenzene (1:1) at 25°C according to DIN 53728 / ISO 307, and is a semicrystalline or amorphous polyester based on dicarboxylic acids and diols.

6. The thermoplastic molding composition according to claim 5, wherein the dicarboxylic acid is an aliphatic or aromatic dicarboxylic acid having 4 to 18 carbon atoms.

7. The thermoplastic molding composition according to claim 5 or 6, wherein the diol is selected from the group consisting of alicyclic diols having 6 to 20 carbon atoms and aliphatic diols having 2 to 20 carbon atoms.

8. The thermoplastic molding composition according to any one of claims 1 to 7, wherein component C) comprises 95 to 99.95% by mass of C1) and 0.05 to 5% by mass of C2).

9. The thermoplastic molding composition according to any one of claims 1 to 8, wherein the anti-dripping agent C2) is a compound selected from the group consisting of a fluorine-containing polymer, a siloxane-based anti-dripping agent, and mixtures thereof.

10. The thermoplastic molding composition according to claim 9, wherein the fluorine-containing polymer is selected from the group consisting of poly(tetrafluoroethylene), tetrafluoroethylene / hexafluoropropylene copolymer, tetrafluoroethylene / ethylene copolymer, poly(vinylidene fluoride), poly(chlorotrifluoroethylene), and mixtures thereof, and the siloxane-based anti-dropping agent comprises polydimethylsiloxane.

11. The thermoplastic molding composition according to any one of claims 1 to 10, wherein component C1) is a bromine-containing flame retardant or a chlorine-containing flame retardant.

12. The bromine-containing flame retardant is brominated diphenyl ether, brominated trimethylphenylindan, tetrabromobisphenol A, hexabromocyclododecane, brominated oligocarbonate, Polypentabromebenzylate as shown in the formula below 【Chemistry 2】 (In the formula, n is greater than 4.) The oligomeric reaction product of tetrabromobisphenol A and epoxide shown in the following formula 【Transformation 3】 (In the formula, n is greater than 3.) The thermoplastic molding composition according to claim 11, wherein a mixture of brominated oligostyrene and brominated polystyrene is selected from the group consisting of brominated oligostyrene and brominated polystyrene having an average degree of polymerization (number mean) of 3 to 90 as measured by vapor pressure osmotic pressure measurement in toluene, and a mixture of brominated oligomer styrene and brominated polystyrene in any mixing ratio is also available.

13. A method for producing fibers, foils, and molded articles, comprising using a thermoplastic molding composition according to any one of claims 1 to 12.

14. Fibers, foils, or molded articles obtained from the thermoplastic molding composition according to any one of claims 1 to 12.

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