Improved polyether ester

Abstract

The present invention provides copolyetherester compositions that are flame resistant and exhibit reduced smoke generation when exposed to heat or flame.

Description

[Technical Field]

[0001] Cross-reference of related applications This application claims priority to U.S. Provisional Patent Applications No. 63 / 039,098, No. 63 / 039,133, and No. 63 / 039,171, filed on 15 June 2020 under Section 365 of the U.S. Patent Act, each of which is incorporated herein by reference in its entirety.

[0002] This invention relates to copolyether esters, and more particularly to flame-retardant copolyether esters. [Background technology]

[0003] Several patents, patent applications, and publications are referenced herein to provide a more detailed description of the context of the technical field to which the present invention relates. The entire disclosures of each of these patents, patent applications, and publications are incorporated herein by reference.

[0004] Copolyether esters are a group of elastomer polyesters having a hard segment containing polyester blocks and a soft segment containing long-chain polyetherdiols. They are widely used in applications where resilience and elasticity are required.

[0005] Typical copolyether esters are produced by reacting one or more diacid moieties with short-chain diols and long-chain polyetherdiols.

[0006] Copolyether esters exhibit excellent elasticity, maintenance of mechanical properties at low temperatures, and good fatigue performance.

[0007] Non-halogenated flame retardants ("NHFR") copolyether esters are continuously in demand. Dialkylphosphinates are well-known non-halogenated flame retardant molecules. U.S. Patent No. 7,420,007 [Clariant Produkte (Deutschland) GmbH] defines formula (I):

[0008]

Chem.

[0009] (wherein, R 1 , R 2 are the same or different and are linear or branched C1-C6-alkyl, M is Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, K and / or a protonated nitrogen base, and m is from 1 to 4) The use of the dialkylphosphinate of as a flame retardant in a number of different polymers such as polyether esters is described.

[0010] U.S. Patent Application Publication No. 2013 / 0190432 describes the use of aluminum diethylphosphinate together with an aluminum salt of phosphorous acid as a combination of flame retardants in nylon-6,6, nylon-6T / 6,6, nylon-4,6, copolyether esters and PBT.

[0011] The use of flame retardants in polymer resins can significantly reduce flammability but unfortunately can result in high smoke generation when exposed to heat or flame. This is a concern as smoke can significantly contribute to damage and mortality in fires.

Summary of the Invention

Problems to be Solved by the Invention

[0012] There is a need for a combination of a resin and a flame retardant that exhibits not only reduced flammability but also reduced smoke generation when exposed to heat and / or flame.

Means for Solving the Problems

[0013] In a first aspect, the present invention (1) At least one polymer selected from copolyether esters, polyamide elastomers, thermoplastic polyolefin elastomers, styrene elastomers, thermoplastic polyurethanes, and thermoplastic vulcanized products, (2) Aluminum diethylphosphinate and (3) Zinc diethylphosphinate and (4) 2 to 20% by weight of a phosphate selected from aluminum phosphate, zinc phosphate, and mixtures thereof The present invention provides a flame-retardant polymer composition containing, where the weight percentage is based on the total weight of the composition.

[0014] In a second aspect, the present invention is (1) at least one copolyether ester, (2) Aluminum diethylphosphinate and (3) Zinc diethylphosphinate and (4) 2 to 20% by weight of a phosphate selected from aluminum phosphate, zinc phosphate, and mixtures thereof The present invention provides a flame-retardant copolyether ester composition containing, where wt% is based on the total weight of the composition.

[0015] In a third aspect, the present invention is (1) at least one copolyether ester, (2) Aluminum diethylphosphinate and (3) Zinc diethylphosphinate and (4) 2 to 20% by weight of a phosphate selected from aluminum phosphate, zinc phosphate, and mixtures thereof We provide molded articles made from a flame-retardant copolyether ester composition containing, where the weight percentage is based on the total weight of the composition.

[0016] In a fourth aspect, the present invention relates to a light- or electrically conductive core, (1) at least one copolyether ester, (2) Aluminum diethylphosphinate and (3) Zinc diethylphosphinate and (4) 2 to 20% by weight of a phosphate selected from aluminum phosphate, zinc phosphate, and mixtures thereof The present invention provides a cable comprising a sheath made from a flame-retardant copolyether ester composition containing, where wt% is based on the total weight of the composition.

[0017] In a fifth aspect, the present invention provides a method for producing a composition of the present invention, comprising the step of melting and mixing the enumerated components in an extruder. [Modes for carrying out the invention]

[0018] Definitions and Abbreviations PBT (Polybutylene Terephthalate) PTMEG (Polytetramethylene Ether Glycol) Copolyether esters or TPCs: Thermoplastic elastomers resulting from the reaction of at least one diol, at least one diacid, and at least one poly(alkylene oxide)diol. DEPAl aluminum diethylphosphinate DEPZn Zinc Diethylphosphinate Phosphite, as used herein, is synonymous with “salt of phosphite” or “salt of phosphonic acid” of aluminum and / or zinc.

[0019] The inventors have surprisingly found that when a copolyether ester is combined with 2 to 16% by weight of a phosphate selected from DEPAl, DEPZn, and aluminum phosphate salts, zinc phosphate salts, and mixtures thereof, a composition with good flame retardancy and reduced smoke generation when exposed to heat and / or flame is obtained.

[0020] The inventors have also found that, surprisingly, adding a phosphate selected from aluminum phosphite, zinc phosphite, and mixtures thereof to a flame-retardant copolyether ester composition containing DEPAl and DEPZn reduces smoke generation from the composition when exposed to heat and / or flame.

[0021] DEPAl and DEPZn are well known for imparting flame retardancy to polymer formulations. The inventors have found that the addition of phosphate reduces smoke generation. Since the addition of phosphate appears to slightly reduce the flame retardancy imparted by DEPAl and DEPZn, the phosphate needs to be added in an amount that reduces smoke generation without excessively impairing flame retardancy. The inventors have found that adding 2 to 16% by weight of phosphate based on the total weight of the composition yields acceptable flame retardancy and reduction in smoke generation.

[0022] Copolyether esters suitable for the compositions of the present invention are polymers produced by reacting a C2-C6 diol with an aromatic diacid moiety and a poly(alkylene oxide) diol.

[0023] The poly(alkylene oxide)diol is preferably selected from poly(ethylene oxide)diol, poly(propylene oxide)diol, poly(tetramethylene oxide)diol ("PTMEG"), and mixtures thereof. Poly(propylene oxide)diol and poly(tetramethylene oxide)diol may be linear or branched. If they are branched at a terminal hydroxyl-containing carbon, they are preferably end-capped with ethylene glycol or poly(ethylene oxide)diol. Poly(propylene oxide)diol and poly(tetramethylene oxide)diol ("PTMEG") and mixtures thereof are particularly preferred, with PTMEG being particularly preferred.

[0024] The C2-C6 diol is preferably selected from ethylene glycol, propylene glycol, butylene glycol, and mixtures thereof, with butylene glycol being particularly preferred.

[0025] The aromatic diacid is preferably selected from terephthalate, isoterephthalate, and mixtures thereof, with terephthalate being particularly preferred.

[0026] Particularly preferred copolyether esters are: 1. Copolyether esters made from butylenediol, terephthalate and PTMEG, 2. Copolyether esters made from butylenediol, terephthalate, and poly(propylene oxide)diol, 3. Copolyether esters made from propylenediol, terephthalate and PTMEG, and 4. Copolyether esters made from propylenediol, terephthalate, and poly(propylene oxide)diol Selected from.

[0027] Copolyether esters made from butylenediol, terephthalate, and PTMEG are particularly preferred.

[0028] The softness of the copolyether ester is influenced by the chain length (i.e., molecular weight) of the poly(alkylene oxide) diol and the relative amount of poly(alkylene oxide) diol used to produce the polymer.

[0029] In preferred embodiments, the poly(alkylene oxide)diol has a molecular weight of 2000 g / mol or about 2000 g / mol.

[0030] In another preferred embodiment, the poly(alkylene oxide)diol constitutes 40% to 80% by weight, more preferably 50% to 75% by weight, and particularly preferably 72.5% by weight of the copolyether ester, based on the total weight of the copolyether ester.

[0031] In a particularly preferred embodiment, the copolyether ester comprises 40% to 80% by weight, more preferably 50 to 75% by weight, and especially preferably 72.5% by weight of the copolyether ester, with a molecular weight of 2000 g / mol or about 2000 g / mol of poly(alkylene oxide)diol.

[0032] Particularly preferred polyether esters contain 72.5% by weight or about 72.5% by weight (weight percentage is based on the total weight of the copolyether ester elastomer) of polytetramethylene oxide preferably having an average molecular weight of about 2000 g / mol as a polyether block segment, and the short-chain ester units of the copolyether ester are polybutylene terephthalate segments.

[0033] In addition to at least one copolyether ester, the composition of the present invention comprises aluminum diethylphosphinate ("DEPAl") and zinc diethylphosphinate ("DEPZn").

[0034] The total phosphinate concentration is preferably 5 to 50% by weight, more preferably 10 to 40% by weight, and particularly preferably 10 to 25% by weight, based on the total weight of the copolyether ester composition.

[0035] The preferred combination of phosphinates is: 5-20% by weight of DEPAl and 5-20% by weight of DEPZn, 8-15% by weight of DEPAl and 8-15% by weight of DEPZn, 10% by weight of DEPAl and 10% by weight of DEPZn, 8-15% by weight of DEPAl and 2-6% by weight of DEPZn, 15% by weight of DEPAl and 5% by weight of DEPZn, 15-25% by weight of DEPAl and 15-25% by weight of DEPZn, 20% by weight of DEPAl and 20% by weight of DEPZn Here, the weight percentage is based on the total weight of the composition.

[0036] Filling with more than 40% by weight of total phosphinate results in compositions with inferior mechanical properties. While such high filling levels may be appropriate for some applications, it is generally preferable that the total phosphinate concentration does not exceed 40% by weight.

[0037] In a preferred embodiment, DEPAl has a D95 (by volume %) in acetone, measured using laser diffraction techniques with a Malvern Mastersizer 2000 particle size analyzer, with a particle size of ≤10 microns.

[0038] In a preferred embodiment, DEPZn has a D95 of ≤10 microns (by volume %) in acetone, measured using laser diffraction techniques with a Malvern Mastersizer 2000 particle size analyzer.

[0039] In another preferred embodiment, DEPAl and DEPZn have a D95 of ≤10 microns (by volume %) in acetone, measured using laser diffraction techniques with a Malvern Mastersizer 2000 particle size analyzer.

[0040] The composition of the present invention further comprises 2 to 16% by weight of an aluminum salt of phosphite, a zinc salt of phosphite, or both, where the weight percentage is based on the total weight of the composition. Phosphite is also called phosphonic acid or HP(=O)(OH)2.

[0041] Phosphorous acid has tautomers, as shown below.

[0042] [ka]

[0043] Aluminum phosphite salts are also called aluminum phosphite.

[0044] Preferred aluminum phosphites are those having CAS numbers [15099 32-8], [119103-85-4], [220689-59-8], [CAS56287-23-1], [156024-71-4], [71449-76-8] and [15099-32-8]. Particularly preferred are aluminum phosphites of the type Al2(HPO3)3*0.1~30Al2O3*0~50H2O, more preferably Al2(HPO3)3*0.2~20Al2O3*0~50H2O, and most preferably Al2(HPO3)3*1~3Al2O3*0~50H2O.

[0045] Particularly preferred are mixtures of aluminum phosphite and aluminum hydroxide having a composition of 5-95 wt% Al2(HPO3)3*nH2O and 95-5 wt% Al(OH)3, more preferably 10-90 wt% Al2(HPO3)*nH2O and 90-10 wt% Al(OH)3, and most preferably 35-65 wt% Al2(HPO3)3*nH2O and 65-35 wt% Al(OH)3, where n=0-4 in each case.

[0046] Particularly preferred is aluminum phosphite having CAS number [CAS56287-23-1].

[0047] In preferred embodiments, the phosphate has a D95 of ≤10 microns (by volume %) in acetone, measured using laser diffraction techniques with a Malvern Mastersizer 2000 particle size analyzer.

[0048] In preferred embodiments, aluminum phosphite has a D95 of ≤10 microns (by volume %) in acetone, measured using laser diffraction techniques with a Malvern Mastersizer 2000 particle size analyzer.

[0049] Aluminum phosphite [56287-23-1] having a D95 of ≤10 microns (measured by laser diffraction technique using a Malvern Mastersizer 2000 particle size analyzer, volume %) in acetone is particularly preferred.

[0050] The zinc salt of phosphite is referred to herein as zinc phosphite. Zinc phosphite having CAS number [CAS14332-59-3] is particularly preferred, as shown below.

[0051] [ka]

[0052] In preferred embodiments, zinc phosphite has a particle size of ≤10 microns D95 (by volume %) in acetone, measured using laser diffraction techniques with a Malvern Mastersizer 2000 particle size analyzer. Alternatively, zinc phosphite preferably has a particle size of 0.1 to 100 microns, and particularly preferably 0.1 to 30 microns.

[0053] Zinc phosphite [14332-59-3] having a D95 of ≤10 microns (measured by laser diffraction technique using a Malvern Mastersizer 2000 particle size analyzer, volume %) in acetone is particularly preferred.

[0054] In preferred compositions of the present invention, aluminum phosphite [CAS 56287-23-1] and zinc phosphite [CAS 14332-59-3] are used.

[0055] The total phosphate concentration is 2 to 20% by weight, more preferably 10% by weight or less, based on the total weight of the copolyether ester composition. Higher phosphate filling amounts exceeding 10% by weight can provide good smoke reduction, but may impair the flame retardant properties of the composition, making it unsuitable for specific applications. In preferred embodiments, the total phosphate concentration is 5 to 10% by weight, based on the total weight of the composition.

[0056] The compositions of the present invention may further comprise at least one nitrogen-containing synergistic agent and / or a phosphorus-containing flame retardant and / or a nitrogen-containing flame retardant. More preferably, the compositions further comprise at least one melamine derivative selected from melamine salts having organic or inorganic acids and mixtures thereof. More particularly preferably, the compositions of the present invention further comprise at least one component selected from melamine salts having boric acid, cyanuric acid, phosphoric acid and / or pyro / polyphosphate and mixtures thereof. Melamine pyrophosphate is particularly preferred.

[0057] Some preferred compositions of the present invention are listed below. Weight percentages (W%) are based on the total weight of the composition.

[0058] Preferred compositions of the present invention, (1) at least one copolyether ester, (2) DEPAl, (3) DEPZn, (4) 2-16% by weight of aluminum phosphite, especially [CAS56287-23-1] This is a copolyether ester composition containing [a specific compound].

[0059] Another preferred composition of the present invention is, (1) at least one copolyether ester, (2) DEPAl, (3) DEPZn, (4) 2-10% by weight of aluminum phosphite, especially [CAS56287-23-1] This is a copolyether ester composition containing [a specific compound].

[0060] Another preferred composition of the present invention is, (1) at least one copolyether ester, (2) DEPAl, (3) DEPZn, (4) at least 5% by weight of aluminum phosphite, particularly [CAS56287-23-1] This is a copolyether ester composition containing [a specific compound].

[0061] Another preferred composition of the present invention is, (1) at least one copolyether ester, (2) DEPAl, (3) DEPZn, (4) 2-16% by weight of zinc phosphite, especially [CAS14332-59-3] This is a copolyether ester composition containing [a specific compound].

[0062] Another preferred composition of the present invention is, (1) at least one copolyether ester, (2) DEPAl, (3) DEPZn, (4) 2-10% by weight of zinc phosphite, especially [CAS14332-59-3] This is a copolyether ester composition containing [a specific compound].

[0063] Another preferred composition of the present invention is, (1) at least one copolyether ester, (2) DEPAl, (3) DEPZn, (4) 2-8% by weight of aluminum phosphite, especially [CAS 56287-23-1] and 2-8% by weight of zinc phosphite, especially [CAS 14332-59-3] This is a copolyether ester composition containing [a specific compound].

[0064] Another preferred composition of the present invention is, (1) at least one copolyether ester, (2) 8-12% by weight, especially 10% by weight of DEPAl, (3) 8-12% by weight, especially 10% by weight of DEPZn, (4) 2-8% by weight of aluminum phosphite, especially [CAS 56287-23-1] and 2-8% by weight of zinc phosphite, especially [CAS 14332-59-3] This is a copolyether ester composition containing [a specific compound].

[0065] Another preferred composition of the present invention is, (1) at least one copolyether ester, (2) 12-16% by weight, especially 15% by weight of DEPAl, (3) 2-6% by weight, especially 5% by weight of DEPZn, (4) 2-8% by weight, especially 5% by weight of aluminum phosphite, especially [CAS56287-23-1] This is a copolyether ester composition containing [a specific compound].

[0066] Another preferred composition of the present invention is, (1) at least one copolyether ester, (2) 12-16% by weight, especially 15% by weight of DEPAl, (3) 2-6% by weight, especially 5% by weight of DEPZn, (4) 2-8% by weight, especially 5% by weight of zinc phosphite, especially [CAS14332-59-3] This is a copolyether ester composition containing [a specific compound].

[0067] Another preferred composition of the present invention is, (1) at least one copolyether ester, (2) 12-16% by weight, especially 15% by weight of DEPAl, (3) 2-6% by weight, especially 5% by weight of DEPZn, (4) 2-8% by weight, especially 4% by weight, of aluminum phosphite, especially [CAS56287-23-1] and 2-8% by weight, especially 4% by weight, of zinc phosphite, especially [CAS14332-59-3] This is a copolyether ester composition containing [a specific compound].

[0068] Another preferred composition of the present invention is, (1) at least one copolyether ester, (2) 18-22% by weight, especially 20% by weight of DEPAl, (3) 18-22% by weight, especially 20% by weight of DEPZn, (4) 6-10% by weight, especially 8% by weight, of aluminum phosphite, especially [CAS56287-23-1] and 6-10% by weight, especially 8% by weight, of zinc phosphite, especially [CAS14332-59-3] This is a copolyether ester composition containing [a specific compound].

[0069] Another preferred composition of the present invention is, (1) at least one copolyether ester, (2) 18-22% by weight, especially 20% by weight of DEPAl, (3) 18-22% by weight, especially 20% by weight of DEPZn, (4) 6-10% by weight, especially 8% by weight of aluminum phosphite, especially [CAS56287-23-1] This is a copolyether ester composition containing [a specific compound].

[0070] Another preferred composition of the present invention is, (1) at least one copolyether ester, (2) 18-22% by weight, especially 20% by weight of DEPAl, (3) 18-22% by weight, especially 20% by weight of DEPZn, (4) 6-10% by weight, especially 8% by weight of zinc phosphite, especially [CAS14332-59-3] This is a copolyether ester composition containing [a specific compound].

[0071] Preferred compositions of the present invention, (1) at least one copolyether ester, (2) DEPAl, (3) DEPZn, (4) 2-16% by weight of aluminum phosphite [CAS 56287-23-1] This is a copolyether ester composition containing [a specific compound].

[0072] Another preferred composition of the present invention is, (1) at least one copolyether ester, (2) DEPAl, (3) DEPZn, (4) 2-10% by weight of aluminum phosphite [CAS 56287-23-1] This is a copolyether ester composition containing [a specific compound].

[0073] Another preferred composition of the present invention is, (1) at least one copolyether ester, (2) DEPAl, (3) DEPZn, (4) At least 5% by weight of aluminum phosphite [CAS 56287-23-1] This is a copolyether ester composition containing [a specific compound].

[0074] Another preferred composition of the present invention is, (1) at least one copolyether ester, (2) DEPAl, (3) DEPZn, (4) 2-16% by weight of zinc phosphite [CAS 14332-59-3] This is a copolyether ester composition containing [a specific compound].

[0075] Another preferred composition of the present invention is, (1) at least one copolyether ester, (2) DEPAl, (3) DEPZn, (4) 2-10% by weight of zinc phosphite [CAS 14332-59-3] This is a copolyether ester composition containing [a specific compound].

[0076] Another preferred composition of the present invention is, (1) at least one copolyether ester, (2) DEPAl, (3) DEPZn, (4) 2-8% by weight of aluminum phosphite [CAS 56287-23-1] and 2-8% by weight of zinc phosphite [CAS 14332-59-3] This is a copolyether ester composition containing [a specific compound].

[0077] Another preferred composition of the present invention is, (1) at least one copolyether ester, (2) 8-12% by weight, especially 10% by weight of DEPAl, (3) 8-12% by weight, especially 10% by weight of DEPZn, (4) 2-8% by weight of aluminum phosphite [CAS 56287-23-1] and 2-8% by weight of zinc phosphite [CAS 14332-59-3] This is a copolyether ester composition containing [a specific compound].

[0078] Another preferred composition of the present invention is, (1) at least one copolyether ester, (2) 12-16% by weight, especially 15% by weight of DEPAl, (3) 2-6% by weight, especially 5% by weight of DEPZn, (4) 2-8% by weight, especially 5% by weight, of aluminum phosphite [CAS 56287-23-1] This is a copolyether ester composition containing [a specific compound].

[0079] Another preferred composition of the present invention is, (1) at least one copolyether ester, (2) 12-16% by weight, especially 15% by weight of DEPAl, (3) 2-6% by weight, especially 5% by weight of DEPZn, (4) 2-8% by weight, especially 5% by weight, of zinc phosphite [CAS14332-59-3] This is a copolyether ester composition containing [a specific compound].

[0080] Another preferred composition of the present invention is, (1) at least one copolyether ester, (2) 12-16% by weight, especially 15% by weight of DEPAl, (3) 2-6% by weight, especially 5% by weight of DEPZn, (4) 2-8% by weight, especially 4% by weight, of aluminum phosphite [CAS 56287-23-1] and 2-8% by weight, especially 4% by weight, of zinc phosphite [CAS 14332-59-3] This is a copolyether ester composition containing [a specific compound].

[0081] Another preferred composition of the present invention is, (1) at least one copolyether ester, (2) 18-22% by weight, especially 20% by weight of DEPAl, (3) 18-22% by weight, especially 20% by weight of DEPZn, (4) 6-10% by weight, especially 8% by weight, of aluminum phosphite [CAS 56287-23-1] and 6-10% by weight, especially 8% by weight, of zinc phosphite [CAS 14332-59-3] This is a copolyether ester composition containing [a specific compound].

[0082] Another preferred composition of the present invention is, (1) at least one copolyether ester, (2) 18-22% by weight, especially 20% by weight of DEPAl, (3) 18-22% by weight, especially 20% by weight of DEPZn, (4) 6-10% by weight, especially 8% by weight, of aluminum phosphite [CAS 56287-23-1] This is a copolyether ester composition containing [a specific compound].

[0083] Another preferred composition of the present invention is, (1) at least one copolyether ester, (2) 18-22% by weight, especially 20% by weight of DEPAl, (3) 18-22% by weight, especially 20% by weight of DEPZn, (4) 6-10% by weight, especially 8% by weight, of zinc phosphite [CAS 14332-59-3] This is a copolyether ester composition containing [a specific compound].

[0084] Another preferred composition of the present invention is, (1) at least one copolyether ester, (2) 10% by weight of DEPAl, (3) 10% by weight of DEPZn, (4) 2-8% by weight of aluminum phosphite [CAS 56287-23-1] and 2-8% by weight of zinc phosphite [CAS 14332-59-3] This is a copolyether ester composition containing [a specific compound]. (201714332593).

[0085] Another preferred composition of the present invention is, (1) at least one copolyether ester, (2) 15% by weight of DEPAl, (3) 5% by weight of DEPZn, (4) 5% by weight of aluminum phosphite [CAS 56287-23-1] This is a copolyether ester composition containing [a specific compound].

[0086] Another preferred composition of the present invention is, (1) at least one copolyether ester, (2) 15% by weight of DEPAl, (3) 5% by weight of DEPZn, (4) 5% by weight of zinc phosphite [CAS 14332-59-3] This is a copolyether ester composition containing [a specific compound].

[0087] Another preferred composition of the present invention is, (1) at least one copolyether ester, (2) 15% by weight of DEPAl, (3) 5% by weight of DEPZn, (4) 4 wt% aluminum phosphite [CAS 56287-23-1] and 4 wt% zinc phosphite [CAS 14332-59-3] This is a copolyether ester composition containing [a specific compound].

[0088] Another preferred composition of the present invention is, (1) at least one copolyether ester, (2) 20% by weight of DEPAl, (3) 20% by weight of DEPZn, (4) 8 wt% aluminum phosphite [CAS 56287-23-1] and 8 wt% zinc phosphite [CAS 14332-59-3] This is a copolyether ester composition containing [a specific compound].

[0089] Another preferred composition of the present invention is, (1) at least one copolyether ester, (2) 20% by weight of DEPAl, (3) 20% by weight of DEPZn, (4) 8% by weight of aluminum phosphite [CAS 56287-23-1] This is a copolyether ester composition containing [a specific compound].

[0090] Another preferred composition of the present invention is, (1) at least one copolyether ester, (2) 20% by weight of DEPAl, (3) 20% by weight of DEPZn, (4) 8% by weight of zinc phosphite [CAS 14332-59-3] This is a copolyether ester composition containing [a specific compound].

[0091] Another preferred composition of the present invention is, (1) at least one copolyether ester, (2) 5-20% by weight of DEPAl, (3) 5-20% by weight of DEPZn, (4) 2 to 10% by weight of phosphate selected from aluminum phosphite [CAS 56287-23-1], zinc phosphite [CAS 14332-59-3] and mixtures thereof. This is a copolyether ester composition containing [a specific compound].

[0092] Some particularly preferred compositions include, or consist of, the components listed above in addition to one or more optional additives such as antioxidants, heat stabilizers, UV stabilizers, mineral fillers, glass fibers, colorants, lubricants, plasticizers, and impact resistant agents. If present, each optional additive is present in an amount of 0.01 to 5% by weight, and the total amount of all optional additives in the composition is 0.01 to 10% by weight based on the total weight of the composition.

[0093] The compositions of the present invention exhibit good flammability. Flammability can be assessed by methods known to those skilled in the art. One method is the limiting oxygen index ("LOI") according to test method ISO 4589-1 / -2, using a test rod in the shape of a rectangular bar with dimensions of 125 mm in length × 13 mm in width and an average thickness of about 1.7 ± 0.1 mm. Preferably, when measured according to test method ISO 4589-1 / -2 using a test rod in the shape of a rectangular bar with dimensions of 125 mm in length × 13 mm in width and an average thickness of about 1.7 ± 0.1 mm, the compositions of the present invention exhibit an LOI of 20 or higher, more preferably 21 or higher, and even more preferably 23 or higher.

[0094] Another parameter that can be used to evaluate flammability is the LOI (LOI) of a composition containing DEPAL + DEPZn + phosphate. ex This is the ratio of the LOI (LOI0) of the same composition without phosphates. Preferably, the composition of the present invention, when measured using a test rod in the shape of a rectangular rod with dimensions of 125 mm length × 13 mm width and an average thickness of about 1.7 ± 0.1 mm according to the test method ISO 4589-1 / -2, shows a ratio of about 0.75 or more, more preferably 0.9 or more, and most preferably 1.0 or more, of the LOI of the composition incorporating DEPAl + DEPZn and metal phosphates to the LOI of the composition without metal phosphates.

[0095] The composition of the present invention achieves a good combination of good flammability and reduced smoke generation.

[0096] The smoke density test can be carried out in an NBS smoke chamber in accordance with the ISO 5659 test standard. The test specimens are prepared as plaques having an area of 75 mm × 75 mm and a thickness of 2 mm. The test specimens are mounted horizontally in the chamber and exposed to a constant heat radiation of 25 kW / m 2 on the upper surface through a radiator cone and a heat flux meter for about 40 minutes in the presence of a pilot flame. The smoke generated over time is collected in the chamber, and the attenuation of the light passing through the smoke is measured with a photometric system equipped with a 6.5 V incandescent lamp, a photomultiplier tube, and a high-precision photodetector. The results are measured with respect to the light transmittance over time and reported with respect to the specific optical density D s . D s is inversely proportional to the light transmittance and is given for a specific optical path length equal to the thickness of the formed test specimen. The smoke generation is measured as the maximum specific optical density D s,max and the total smoke generation amount VOF4 in the first 4 minutes of the test. VOF4 is calculated as D s1min + D s2min + D s3min +(D s4min / 2), where D s1min , D s2min , D s3min and D s4min are the values of the specific optical density recorded at the 1-minute, 2-minute, 3-minute, and 4-minute time points, respectively. Any dripping from the plaque test specimens that occurs during the test is recorded. The weight of the dripping material is subtracted from the weight of the 75 mm × 75 mm × 2 mm test plaque. This difference is reported in grams as the "mass retained" during the experimental time. The normalized D s,max can be calculated by dividing D s,max by the mass retained during the experimental time and is reported as D s,max,ret .

[0097] D s,max / g units of the mass retained (D s,maxA low value for mass retained in g) and VOF4 is desirable, indicating a material that does not significantly reduce visibility during a fire, thus enabling the rapid escape of people from confined spaces. In the absence of any smoke, the light transmittance is 100%, and D s It is 0.

[0098] Parameters, VOF4 and [D s,max The performance of the smoke can be evaluated using the retained mass in units of gram.

[0099] The compositions of the present invention preferably exhibit a VOF4 of 1000 or less, more preferably 800 or less, and more particularly 750 or less, as measured according to the ISO 5659 test standard and using a plaque having an area of ​​75 mm × 75 mm and a thickness of 2 mm.

[0100] The composition of the present invention preferably has a D content of 40 or less, more preferably 35 or less, and more particularly 30 or less, measured according to the ISO 5659 test standard and using a plaque having an area of ​​75 mm × 75 mm and a thickness of 2 mm. s,max This indicates the retained mass in units of gram ( / g).

[0101] Another parameter that can be used to evaluate the performance of the smoke is the D of the composition containing DEPAl + DEPZn and metal phosphate. s,max,ret (D s,max,ret ex ) of composition D without metal phosphates s,max,ret (D s,max,ret This is the ratio to 0). The composition of the present invention preferably contains DEPAl + DEPZn and metal phosphate, and is measured according to the ISO 5659 test standard and using a plaque having an area of ​​75 mm × 75 mm and a thickness of 2 mm, with a ratio of 0.81 or less, more preferably 0.76 or less, and more particularly 0.6 or 0.5 or less. s,max,ret Composition D without metal phosphates s,max,ret This shows the ratio to the given value.

[0102] In a more particularly preferred embodiment, the composition of the present invention has a Line of Influence (LOI) of 20 or more, more preferably 21 or more, and more preferably 23 or more, when measured using a test rod in the shape of a rectangular bar with dimensions of 125 mm in length × 13 mm in width and an average thickness of about 1.7 ± 0.1 mm, according to the test method ISO 4589-1 / -2, and a Line of Influence (LOI) of 40 or less, more preferably 35 or less, and more preferably 30 or less, when measured using a plaque with an area of ​​75 mm × 75 mm and a thickness of 2 mm, according to the test standard ISO 5659, and s,max It has a retained mass in units of / g.

[0103] The present invention is further illustrated by specific embodiments in the following examples, which provide further details about the compositions, uses, and processes described herein. These examples, which illustrate preferred modes currently conceivable for carrying out the present invention, are intended to illustrate the invention and not to limit it. [Examples]

[0104] material The flame-retardant polymer compositions described herein and comparative compositions were prepared using the following materials.

[0105] Copolyether ester (TPC): A copolyether ester elastomer containing approximately 72.5 weight percent of polytetramethylene oxide as a polyether block segment, having an average molecular weight of approximately 2000 g / mol, wherein the weight percentage is based on the total weight of the copolyether ester elastomer, and the short-chain ester units of the copolyether ester are polybutylene terephthalate segments. The copolyether ester elastomer contained up to 6 weight percent of heat stabilizers, antioxidants, and metal deactivators based on the total weight of the elastomer and additives.

[0106] DEPAl: Aluminum diethylphosphinate with a D90max of 7.506 microns (measured by laser diffraction technique using a Malvern Mastersizer 2000 particle size analyzer, volume %) in acetone.

[0107] DEPZn: Zinc diethylphosphinate.

[0108] Aluminum phosphite: phosphorous acid, aluminum salt [CAS 56287-23-1].

[0109] Zinc phosphite: Phosphorous acid, zinc salt [CAS 14332-59-3].

[0110] Test method Mechanical properties Mechanical tensile stress-strain performance was measured at room temperature according to the ISO 527 test method. Specimens were prepared from the compositions listed in the table by melt-extruding narrow, flat strips in a standard extruder with a barrel temperature set to approximately 170°C to 190°C, and then cutting the resulting flat strips into the shape of ISO 5275A tensile test bars with an average thickness of approximately 1.7 ± 0.1 mm. The specimens were allowed to settle at room temperature for at least 24 hours before testing. Tensile stress and elongation were measured at a rate of 200 mm / min. The modulus of elasticity was measured from the same specimen at a rate of 1 mm / min in the low-strain region.

[0111] Flame retardant Flammability tests were performed according to the Limiting Oxygen Index ("LOI") test method ISO 4589-1 / -2. Test specimens were prepared from the compositions listed in the table by melt-extruding narrow, flat strips in a standard extruder with a barrel temperature set to approximately 170°C to 190°C, and then cutting the resulting flat strips into rectangular rods with dimensions of 125 mm in length and 13 mm in width, and an average thickness of approximately 1.7 ± 0.1 mm. The test specimens were conditioned at room temperature and 50% relative humidity for at least 72 hours prior to testing. According to this test, the test specimen is fixed vertically at the center of a glass chimney at room temperature in an atmosphere of a mixture of oxygen and nitrogen (where the relative concentrations of oxygen and nitrogen can be varied) slowly supplied upward through a glass column. The upper end of the test specimen is ignited with a pilot light and burns downward. The combustion behavior of the test specimen is observed, and the duration of combustion is compared. LOI (Liquid Intake) is the minimum oxygen concentration, expressed as a volume percentage, required to sustain the combustion of a sample, indicated by a target burn time of less than 180 seconds after ignition. A high LOI is desirable and indicates that the substance is difficult to ignite and flammable. Flammability was measured for all compositions after pre-conditioning for at least 88 hours at 23°C and 50% relative humidity immediately before use.

[0112] smoke density Smoke density tests were conducted in an NBS smoke chamber supplied by Fire Testing Technologies, in accordance with the ISO 5659 test standard. Test specimens were prepared from the composition shown in the table by melt-extruding narrow, flat strips in a standard extruder with a barrel temperature set to approximately 170°C to 190°C, and then compression-molding the strips to form plaques with an area of ​​75 mm × 75 mm and a thickness of 2 mm. The test specimens were mounted horizontally in the chamber and measured for approximately 40 minutes in the presence of a pilot flame, via a radiator cone and heat flux meter, at a top surface density of 25 kW / m². 2The sample is exposed to constant thermal radiation. The smoke generated over time is collected in a chamber, and the attenuation of light rays passing through the smoke is measured using a photometric system equipped with a 6.5V incandescent light bulb, a photomultiplier tube, and a high-precision photodetector. The results are measured in terms of light transmittance over time, and the specific optical density D s It will be reported regarding D s This is inversely proportional to the light transmittance and given for a specific optical path length equal to the thickness of the molded specimen. Comparison between material compositions is given by the maximum specific optical density D s,max This is done by measuring the total smoke output (VOF4) during the first four minutes of the test. VOF4 is D s1min +D s2min +D s3min +(D s4min Calculated as / 2), in the formula, D s1min , D s2min , D s3min and D s4min These are the relative optical density values ​​recorded at the 1-minute, 2-minute, 3-minute, and 4-minute mark, respectively. s,max The VOF4 value is automatically calculated by the NBS smoke chamber software. s,max A low VOF4 value is desirable, indicating a material that does not significantly reduce visibility during a fire, thus enabling the rapid escape of people from confined spaces. In the absence of any smoke, the light transmittance is 100%, and Ds is 0.

[0113] Any leakage from the plaque specimen during the test is recorded. The weight of the leaked material is subtracted from the weight of the 75mm x 75mm x 2mm test plaque. This difference is reported in grams as the "held mass" during the experiment. Normalized D s,max D is the mass held during the experiment. s,max It can be calculated by dividing by D s,max,ret It is reported as such.

[0114] Experimental data The compositions indicated by "CE" are comparative, while the compositions indicated by "E" are those of the present invention.

[0115] Table 1 Table 1 shows the flammability (LOI) and smoke generation (D) of comparative compositions having 10% by weight of DEPAl and 10% by weight of DEPZn, and the composition of the present invention, based on the total weight of the composition. s,max , VOF4 and D s,max (Retained mass, in grams) is shown. Comparative composition CE15 contains DEPAl and DEPZn, but does not contain phosphates. Flammability is good (LOI=26), but smoke generation is high (D s,max (Mass held, in grams = 48). Adding 2.5% and 5% by weight of aluminum phosphite resulted in reasonable flammability (LOI of 23 and 28, respectively) and a significant reduction in smoke generation (LOI of 22 and 38, respectively). s,max Compositions (E20 and E13) are obtained (retained mass, in grams). Compositions E15 and E17 also maintain flammability that meets provisional standards (LOI of 24 and 23, respectively) and show significantly reduced smoke generation (LOI of 26 and 17, respectively). s,max (Retained mass, in grams). As the total phosphate content increases further in compositions E21 and E22, the flammability decreases (20 LOI in both compositions), but smoke generation is significantly reduced (17 and 26 D, respectively). s,max (The mass held, in grams)

[0116] Table 2 Table 2 shows the flammability (LOI) and smoke generation (D) of a comparative composition having 15% by weight of DEPAl and 5% by weight of DEPZn, and the composition of the present invention, based on the total weight of the composition. s,max , VOF4 and D s,max (Retained mass, in grams) is shown. Comparative composition CE16 contains DEPAl and DEPZn, but does not contain phosphates. Flammability is good (LOI=28), but smoke generation is high (D s,max (Mass held, in grams = 59). Adding 5% by weight of aluminum phosphite resulted in reasonable flammability (LOI of 25) and a significant reduction in smoke generation (D of 26). s,maxComposition (E23) is obtained (retained mass, in grams). Compositions E24 and E25 either show improved performance (E25) or maintain good flammability (LOI of 30 and 25, respectively) and significantly reduced smoke generation (LOI of 27 and 22, respectively). s,max (The mass held, in grams)

[0117] Table 3 Table 3 shows the flammability (LOI) and smoke generation (D) of comparative compositions having 20% ​​by weight of DEPAl and 20% by weight of DEPZn, and the composition of the present invention, based on the total weight of the composition. s,max , VOF4 and D s,max (Retained mass, in grams) is shown. Comparative composition CE17 contains DEPAl and DEPZn, but does not contain phosphates. Flammability is good (LOI=32), but smoke generation is high (D s,max (Mass held, in grams = 43). Adding 8% by weight of aluminum phosphite resulted in reasonable flammability (LOI of 27) and a significant reduction in smoke generation (D of 32). s,max Composition (E14) is obtained (retained mass, in grams). Composition E16 contains 8 wt% zinc phosphite and exhibits good flammability (LOI of 27) and significantly reduced smoke generation (D of 18). s,max (The mass held, in grams) was retained.

[0118] While certain preferred embodiments of the present invention have been described and illustrated above, the present invention is not intended to be limited to such embodiments. Various modifications can be made without departing from the scope and spirit of the invention, as set forth in the following claims.

[0119] [Table 1]

[0120] [Table 2]

[0121] Table 3

Claims

1. (1) At least one polymer selected from copolyether esters, polyamide elastomers, thermoplastic polyolefin elastomers, styrene elastomers, thermoplastic polyurethanes, and thermoplastic vulcanized products, (2) Aluminum diethylphosphinate ("DEPAl"), (3) Zinc diethylphosphinate ("DEPZn") and (4) 2 to 20% by weight of a phosphate selected from aluminum phosphite, zinc phosphite, and mixtures thereof A flame-retardant polymer composition comprising, wherein the weight percentage is based on the total weight of the composition.

2. (1) at least one copolyether ester, (2) Aluminum diethylphosphinate ("DEPAl"), (3) Zinc diethylphosphinate ("DEPZn") and (4) 2 to 20% by weight of a phosphate selected from aluminum phosphite, zinc phosphite, and mixtures thereof A flame-retardant copolyether ester composition comprising a flame-retardant polymer composition, wherein the weight percentage is based on the total weight of the composition.

3. The aforementioned copolyether ester is C ２ ~C ６ The composition according to claim 1 or 2, which is produced by reacting a diol with an aromatic diacid moiety and a poly(alkylene oxide) diol.

4. The composition according to any one of claims 1 to 3, wherein the copolyether ester is prepared using a poly(alkylene oxide) diol selected from poly(ethylene oxide) diol, poly(propylene oxide) diol, poly(tetramethylene oxide) diol ("PTMEG") and a mixture of two or more thereof.

5. The aforementioned copolyether ester is selected from ethylene glycol, propylene glycol, butylene glycol, and mixtures of two or more thereof. ２ ~C ６ A composition according to any one of claims 1 to 4, prepared using a diol.

6. The composition according to any one of claims 1 to 5, wherein the copolyether ester is prepared using an aromatic diacid selected from terephthalate, isoterephthalate, and mixtures thereof.

7. The composition according to any one of claims 1 to 6, wherein the copolyether ester is made from butylene glycol, terephthalate, and PTMEG.

8. The composition according to any one of claims 1 to 7, wherein the total amount of DEPAl and DEPZn is 5 to 40% by weight based on the total weight of the composition.

9. The composition according to any one of claims 1 to 7, comprising 5 to 20% by weight of DEPAl and 5 to 20% by weight of DEPZn based on the total weight of the composition.

10. The composition according to any one of claims 1 to 7, comprising 8 to 15% by weight of DEPAl and 8 to 15% by weight of DEPZn based on the total weight of the composition.

11. The composition according to any one of claims 1 to 7, comprising 8 to 15% by weight of DEPAl and 2 to 6% by weight of DEPZn based on the total weight of the composition.

12. The composition according to any one of claims 1 to 7, comprising 15 to 25% by weight of DEPAl and 15 to 25% by weight of DEPZn based on the total weight of the composition.

13. A composition according to any one of claims 1 to 12, comprising aluminum phosphite [CAS56287-23-1].

14. A composition according to any one of claims 1 to 12, comprising zinc phosphite [CAS14332-59-3].

15. A composition according to any one of claims 1 to 12, comprising aluminum phosphite [CAS56287-23-1] and zinc phosphite [CAS14332-59-3].

16. The composition according to any one of claims 1 to 15, wherein the total phosphate concentration is 20% by weight or less based on the total weight of the composition.

17. The composition according to any one of claims 1 to 16, wherein the total phosphate concentration is 5 to 10% by weight based on the total weight of the composition.

18. (1) at least one copolyether ester, (2) 5 to 20% by weight of aluminum diethylphosphinate ("DEPAl") (3) 5-20% by weight of zinc diethylphosphinate ("DEPZn") (4) 2 to 10% by weight of phosphate selected from aluminum phosphite [CAS56287-23-1], zinc phosphite [CAS14332-59-3] and mixtures thereof. A flame-retardant polymer composition comprising, wherein the weight percentage is based on the total weight of the composition.

19. The composition according to any one of claims 1 to 18, wherein when measured using a test rod in the shape of a rectangular bar with dimensions of 125 mm in length and 13 mm in width and an average thickness of about 1.7 ± 0.1 mm, according to the test method ISO 4589-1 / -2, the composition has a line of interest (LOI) of 20 or more.

20. The composition according to any one of claims 1 to 19, wherein when measured using a test rod in the shape of a rectangular bar with dimensions of 125 mm in length and 13 mm in width and an average thickness of about 1.7 ± 0.1 mm, according to the test method ISO 4589-1 / -2, the composition has an LOI of 23 or more.

21. The composition according to any one of claims 1 to 20, wherein the ratio of the LOI of the composition to the LOI of the composition without the phosphate of component (4) is 0.75 or greater when measured using a test rod in the shape of a rectangular rod having dimensions of 125 mm in length × 13 mm in width and an average thickness of about 1.7 ± 0.1 mm, according to test method ISO 4589-1 / -2.

22. When measured according to the ISO 5659 test standard and using a plaque with an area of ​​75 mm x 75 mm and a thickness of 2 mm, the D value is 40 or less. ｓ，ｍａｘ Mass held in units of / g (D s,max The method described in any one of claims 1 to 21, having (mass retained in g) The composition of.

23. When measured according to the ISO 5659 test standard and using a plaque with an area of ​​75 mm x 75 mm and a thickness of 2 mm, the D value is 30 or less. ｓ，ｍａｘ Mass held in units of / g (D s,max The method described in any one of claims 1 to 22, having (mass retained in g) The composition of.

24. When measured using a plaque having an area of 75 mm × 75 mm and a thickness of 2 mm in accordance with the ISO 5659 test standard, D of the composition ｓ，ｍａｘ，ｒｅｔ of the composition without the phosphite of the component (4), D ｓ，ｍａｘ，ｒｅｔ The ratio to is 0.81 or less. The composition according to any one of claims 1 to 23.

25. (2') The composition according to any one of claims 1 to 24, further comprising 0.2 to 16% by weight of an aluminum salt of ethylbutylphosphinic acid, dibutylphosphinic acid, ethylhexylphosphinic acid, butylhexylphosphinic acid, dihexylphosphinic acid, or a mixture of two or more thereof.

26. When measured using a rectangular rod with dimensions of 125 mm in length and 13 mm in width, and an average thickness of approximately 1.7 ± 0.1 mm, according to the test method ISO 4589-1 / -2, the LOI is 19 or higher, and when measured using a plaque with an area of ​​75 mm x 75 mm and a thickness of 2 mm, according to the ISO 5659 test standard, the D is 45 or lower. ｓ，ｍａｘ，ｒｅｔ A composition according to any one of claims 1 to 18, having the following characteristics.

27. The composition according to any one of claims 1 to 26, wherein the DEPAl has a D95 of ≤10 microns (by volume %) in acetone, measured using laser diffraction techniques with a Malvern Masteriser 2000 particle size analyzer.

28. The composition according to any one of claims 1 to 26, wherein the DEPZn has a D95 of ≤10 microns (by volume %) in acetone, measured using laser diffraction techniques with a Malvern Masteriser 2000 particle size analyzer.

29. The composition according to any one of claims 1 to 26, wherein the DEPAl and the DEPZn have a D95 of ≤10 microns (by volume %) in acetone, measured using laser diffraction techniques with a Malvern Masteriser 2000 particle size analyzer.

30. The composition according to any one of claims 1 to 29, wherein the phosphate has a D95 of ≤10 microns (by volume %) in acetone, measured using laser diffraction technique with a Malvern Masteriser 2000 particle size analyzer.

31. A composition according to any one of claims 1 to 30, comprising aluminum phosphite having a D95 of ≤10 microns (by volume %) in acetone, measured using laser diffraction techniques with a Malvern Masteriser 2000 particle size analyzer.

32. A composition according to any one of claims 1 to 31, comprising aluminum phosphite [56287-23-1] having a D95 of ≤10 microns (by volume %) in acetone, measured using laser diffraction techniques with a Malvern Masteriser 2000 particle size analyzer.

33. A composition according to any one of claims 1 to 32, comprising zinc phosphite having a particle size of ≤10 microns and a D95 (by volume in acetone, measured using laser diffraction techniques with a Malvern Masteriser 2000 particle size analyzer).

34. A composition according to any one of claims 1 to 29, comprising zinc phosphite having a particle size of 0.1 to 100 microns.

35. The composition according to any one of claims 1 to 34, further comprising at least one nitrogen-containing synergistic agent and / or a phosphorus-containing flame retardant and / or a nitrogen-containing flame retardant.

36. The composition according to any one of claims 1 to 34, further comprising at least one melamine derivative selected from melamine salts having organic or inorganic acids and mixtures thereof.

37. The composition according to any one of claims 1 to 34, further comprising at least one component selected from boric acid, cyanuric acid, phosphoric acid and / or pyro / polyphosphate and melamine salts having mixtures thereof.

38. The composition according to any one of claims 1 to 34, further comprising melamine pyrophosphate.

39. A molded article made from a flame-retardant polymer composition according to any one of claims 1 to 38.

40. A cable comprising an optical or electrical conductive core and a sheath made from a flame-retardant polymer composition according to any one of claims 1 to 38.

41. A method for preparing the composition according to any one of claims 1 to 38, The process of melting and mixing the listed components in an extruder. A method that includes this.

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