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    • 专利摘要:
    COMPOSITION AND ARTICLE. The present disclosure provides a composition that includes a thermoplastic elastomer and a flame retardant composed of a metal hydrate and an oligomeric phosphate ester. The weight ratio of metal hydrate to oligomeric phosphate ester is greater than 1.45: 1. The composition can be a component of an article such as a coated wire or a coated cable, with the composition present in the coating.
    公开号:BR112012002247B1
    申请号:R112012002247-4
    申请日:2009-07-31
    公开日:2020-10-27
    发明作者:Xiangyang Tai；Yudong Qi；Jing Chen；Robert F. Eaton；Weiguang Yao
    申请人:Dow Global Technologies Inc；
    IPC主号:
    专利说明:

    Historic
    [001] The present disclosure relates to thermoplastic / flame retardant elastomers.
    [002] Materials containing halogen such as poly (vinyl chloride) (PVC) find widespread use in wire and cable applications. Ecological and health concerns drive efforts to find viable alternatives to PVC. Thermoplastic elastomers are seen as potential halogen-free substitutes for PVC since thermoplastic elastomers and PVC are similar in many physical and mechanical aspects. However, wire and cable applications require flame retardancy. The addition of flame retardants to elastomers often degrades the desired physical and mechanical properties of the thermoplastic elastomer.
    [003] A halogen-free flame retardant thermoplastic elastomer would be desirable, with physical and mechanical properties suitable for applications in wires and cables, and in particular, flexible wires / cables. summary
    [004] The present disclosure provides a composition. In an embodiment the composition provided includes from about 12% by weight to about 50% by weight of a thermoplastic elastomer and from about 48% by weight to about 75% by weight of a flame retardant. The thermoplastic elastomer has a Shore hardness less than 50D. The flame retardant includes a metal hydrate and an oligomeric phosphate ester. The weight ratio of metal hydrate to oligomeric phosphate ester is greater than 1.45: 1.
    [005] The present disclosure provides another composition. In one embodiment the composition provided includes a thermoplastic elastomer, a polar olefin-based polymer, and a flame retardant comprising a metal hydrate and an oligomeric phosphate ester.
    [006] The present disclosure provides an article. In an embodiment the article provided includes at least one component consisting of a composition comprising a thermoplastic elastomer and a flame retardant. The thermoplastic elastomer has a Shore hardness less than 50D. The flame retardant includes a metal hydrate and an oligomeric phosphate ester. The weight ratio of metal hydrate to oligomeric phosphate ester is greater than 1.45: 1.
    [007] In an embodiment, the article comprises a conductive metal and a coating on the conductive metal. The coating includes the composition. Brief description of the drawings
    [008] Figure 1 is a schematic representation of a wire shaping machine according to an embodiment of the present disclosure.
    [009] Figure 2 is a schematic representation of a flame test apparatus according to an embodiment of the present disclosure. Detailed Description
    [010] All references to the Periodic Table of Elements here will refer to the Periodic Table of Elements published and registered by CRC Press, Inc., 2003. Likewise, any references to a Group or Groups will be to a Group or Groups shown in this Table Periodic Table of Elements using the IUPAC system to number groups. Unless stated to the contrary, implicit in context, or customary in the technique, all parts and percentages are based on weight. For United States patent practice purposes, the contents of any patent, patent application, or publication referred to herein are hereby incorporated by reference in their entirety (or the equivalent US version thereof is also incorporated by reference) especially with respect to the disclosure of synthetic techniques, product and processing designs, polymers, catalysts, definitions (to the extent not inconsistent with any definitions provided herein) and general knowledge in the art.
    [011] In this disclosure, the numerical ranges are approximate and, therefore, may include values outside the target ranges if indicated differently. The numerical ranges include all values of the same including the lower value and the upper value, in increments of one unit, as long as there is a separation of at least two units between any lower value and any higher value. As an example, if a composition, physical or other property, such as, for example, molecular weight, melt index, etc., is from 100 to 1000, it is intended that all individual values, such as 100, 101, 102, etc., and sub-ranges, such as 100 to 144, 155 to 170, 197 to 200, etc., are expressly listed. For ranges containing values less than one (1) or containing fractional numbers greater than one (1) (for example, 1.1, 1.5, etc.), a unit is considered to be 0.0001, 0.001 or 0.1, when appropriate. For ranges containing single-digit numbers less than ten (for example, 1 to 5), a unit is considered to be 0.1. These are just examples of what is specifically intended, and all possible combinations of numerical value between the minimum and the maximum enumerated value are considered to be expressly stated in this disclosure. Within this disclosure, numerical ranges are provided for, among other things, the amounts of thermoplastic elastomer, flame retardants, UV stabilizers, additives, and various other components in the composition, and the various characteristics and properties for which these components are defined. .
    [012] Unless specifically stated to the contrary, when used with respect to a chemical compound, the singular includes all isomeric forms and vice versa (for example, "hexane" includes individually or collectively all hexane isomers). The terms, "compound" and "complex" are used to allow exchange and / or substitution to refer to organic, inorganic and organometallic compounds. The term "atom" refers to the smallest constituent of an element regardless of ionic state, that is, whether or not it has a partial charge or charge or whether it is attached to another atom. The term "amorphous" refers to a polymer lacking a crystalline melting point determined by differential scanning calorimetry (DSC) or an equivalent technique.
    [013] The terms, "comprising", "including", "having" and its derivatives are not intended to exclude the presence of any additional component, step or procedure, whether or not it is specifically disclosed. In order to avoid any doubt, all compositions claimed through the use of the term "comprising" may include any additive, adjuvant, or compound, polymeric or not, additional, unless otherwise stated. In contrast, the term, "consisting essentially of" excludes any other component, step or procedure from the scope of any subsequent mention, except those that are not essential to operability. The term "consisting of" excludes any component, step or procedure not specifically described or listed. Unless otherwise stated, the term "or" refers to members listed individually as well as in any combination.
    [014] "Composition" and similar terms mean a combination or mixture of two or more components.
    [015] "Mixture", "polymeric mixture" and similar terms mean a mixture of two or more polymers. Such a mixture may or may not be miscible. Such a mixture may or may not be separated in stages. Such a mixture may or may not contain one or more domain configurations, determined from electronic transmission spectroscopy, light scattering, X-ray scattering, and any other method known in the art.
    [016] The term "polymer" (and similar terms) is a macromolecular compound prepared by reacting (ie, polymerizing) monomers of the same or different types. "Polymer" includes homopolymers and copolymers.
    [017] In an incorporation, a composition is provided. The composition includes a thermoplastic elastomer and a flame retardant. The flame retardant is composed of a metal hydrate and an oligomeric phosphate ester. The weight ratio of metal hydrate to oligomeric phosphate ester is greater than 1.45: 1. The weight ratio is based on the total weight of the composition.
    [018] In an embodiment, the thermoplastic elastomer has a Shore hardness less than 50D.
    [019] When used here, a "thermoplastic elastomer is a polymer (1) that has the ability to stretch beyond its original length and contracts substantially to its original length when released and (2) softens when exposed to heat and substantially returns to its original condition when cooled to room temperature. The present thermoplastic elastomers are not crosslinked, or are non-crosslinked. The present thermoplastic elastomers are distinct from and do not include "thermoset polymers" that solidify or "deform" irreversibly when heated. Non-limiting examples of suitable thermoplastic elastomers include: thermoplastic polyurethane ("TPU"), thermoplastic polyester elastomer (TPEE), polyamide elastomer, and any combination thereof.
    [020] In one embodiment, the thermoplastic elastomer excludes polymers based on non-polar olefins such as non-polar ethylene-based polymers and non-polar propylene-based polymers.
    [021] When used here, a "thermoplastic polyurethane" (or "TPU") is the reaction product of a polyisocyanate, one or more polymeric diols, and optionally one or more difunctional chain extenders. TPU can be prepared by prepolymer, quasi-polymer, or one-step methods.
    [022] The polyisocyanate can be a diisocyanate. The diisocyanate forms a hard segment in the TPU and can be an aromatic, aliphatic and cycloaliphatic diisocyanate and combinations of two or more of these compounds. A non-limiting example of a diisocyanate structural unit (OCN-R-
    CNO) is represented by the formula (I) below: (I) in which R is an alkylene, cycloalkylene, or arylene group. Representative examples of these diisocyanates can be found in US Patent Nos. 4,385,133, 4,522,975 and 5,167,899. Non-limiting examples of suitable diisocyanates include 4,4'-diphenyl methane diisocyanate, p-phenylene diisocyanate, 1,3-bis (methyl isocyanate) -cyclohexane, 1,4-diisocyanate-cyclohexane, hexamethylene diisocyanate , 1,5-naphthalene diisocyanate, 3,3'-dimethyl-4,4 '-biphenyl diisocyanate, 4,4'-diisocyanate-di-cyclohexyl methane, 2,4-toluene diisocyanate, and 4, 4'-diisocyanato-diphenyl methane.
    [023] The polymeric diol forms soft segments in the resulting TPU. The polymeric diol has a numerical average molecular weight in the range of 200 to 10,000 g / mol. More than one polymeric diol can be used. Non-limiting examples of suitable polymeric diols include polyether diols (producing a "polyether TPU"), polyester diols (producing a "polyester TPU"), hydroxy-terminated polycarbonates (producing a "polycarbonate TPU"), polybutadienes terminated by hydroxy, hydroxy-terminated copolymers of dialkyl siloxane and alkylene oxides, such as ethylene oxide and propylene oxide, natural oil diols, and any combination thereof. One or more of the foregoing polymeric diols may be mixed with an amine-terminated polyether and / or an amino-terminated polybutadiene / acrylonitrile copolymer.
    [024] The difunctional extenders can be normal or branched chain aliphatic diols having 2 to 10 carbon atoms, inclusive, in the chain. Examples of such diols include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, and the like, 1,4-cyclohexane dimethanol, hydroquinone bis ( hydroxyethyl) ether, cyclohexylenediols (1,4-, 1,3-, and 1,2- isomers), isopropylidene bis (cyclohexanols), diethylene glycol, dipropylene glycol, ethanolamine, N-methyl-diethanolamine, and the like , and mixing any of the above. As noted earlier, in some cases, smaller proportions (less than about 20 percent equivalent) of the difunctional extender can be replaced with trifunctional extenders, without decreasing the thermoplasticity value of the resulting TPU, examples of which are glycerol, trimethylolpropane, and the like .
    [025] The chain extender is incorporated into the polyurethane in quantities determined by the selection of the specific reagent components, the desired amounts of the hard and soft segments, and the index sufficient to provide good mechanical properties, such as modulus and resistance to rupture. The polyurethane compositions used in the practice of this disclosure can contain from 2 to 25, or from 3 to 20, or from 4 to 18% by weight of the component chain extender.
    [026] Optionally, small amounts of compounds with monohydroxyl or monoamino functionality, often called "chain switch", can be used to control molecular weight. Examples of chain switches include propanols, butanols, pentanols, and hexanols. When used, chain switches are typically present in minimum amounts of 0.1 to 2 weight percent of the entire reaction mixture leading to the polyurethane composition.
    [027] The equivalent proportions of polymeric diol for said extender can vary considerably depending on the desired hardness for the TPU product. Generally speaking, the equivalent proportions fall within the respective range of about 1: 1 to about 1:20, or about 1: 2 to about 1:10. At the same time, the overall ratio of isocyanate equivalents to equivalents of materials containing active hydrogen is within the range of 0.90: 1 to 1.10: 1, or, 0.95: 1 to 1.05: 1.
    [028] Additives can be used to modify the properties of the polyurethane used in the practice of this disclosure. Additives can be included in conventional amounts already known in the art and in the literature. Usually, additives are used to provide specific properties desired for polyurethanes such as various antioxidants, ultraviolet inhibitors, waxes, thickening agents and fillers. When fillers are used, they can be organic or inorganic, but are generally inorganic such as clay, talc, calcium carbonate, silica and the like. Also, fibrous additives, such as fiberglass or carbon fiber, can also be added to impart certain properties.
    [029] In an incorporation, the TPU has a density greater than or equal to 0.90 g / cm3, or greater or equal to 0.95 g / cm3, or greater than 1.00 g / cm3Nother -> y / cm. In another embodiment, the TPU has a density less than 1.30 g / cm 3, or less than 1.25 g / cm 3 and less than or equal to 1.20 g / cm 3. In another embodiment, TPU has a density of 0.90 g / cm3a i, 30 g / cm3, or from 0.95 g / cm3 to 1.25 g / cm3, or from 1.0 g / cm3 to 1.20 g / cm3.
    [030] In an embodiment, TPU has a melting index greater than or equal to 0.1 g / 10 min (measured by ASTM D-1238-04, 190 ° C, 8.7 kg). In another embodiment, the TPU has a melting index less than or equal to 100 g / 10 min, or less than or equal to 50 g / 10 min, or less than or equal to 20 g / 10 min (ASTM D-1238-04, 190 ° C, 8.7 kg). In another embodiment, the TPU has a melting index of 0.1 g / 10 min at 100 g / 10 min, or 0.5 g / 10 min at 50 g / 10 min, or 1 g / 10 min at 20 g / 10 min.
    [031] Non-limiting examples of TPUs include PELLETHANE ™ thermoplastic polyurethane, TECOFLEX ™ thermoplastic polyurethanes, TECOPLAST ™ thermoplastic polyurethanes, TECOPLILIC ™ thermoplastic polyurethanes, TECOTHANE ™ thermoplastic polyurethanes, ULTROPLASTIC thermoplastics and Advanced polyurethanes. Materials, CARBOTHANE ™ thermoplastic polyurethanes obtainable from Noveon; ELASTOLLAN ™ thermoplastic polyurethanes and other thermoplastic polyurethanes obtainable from BASF; and commercial thermoplastic polyurethanes obtainable from Bayer, Huntsman, and Merquinsa.
    [032] In an embodiment, the thermoplastic elastomer is a TPU with a Shore hardness of about 60A less than 50D. Shore hardness is measured according to ASTM D2240.
    [033] In an embodiment, the thermoplastic elastomer includes a thermoplastic polyester elastomer (TPEE). When used herein, "thermoplastic polyester elastomer" is a thermoplastic elastomer comprising a hard polyester segment and a soft polyoxyalkylene glycol segment. Non-limiting examples of suitable hard segments include poly (butylene terephthalate) (PBT), and poly (butylene naphthalate) (PBN). Non-limiting examples of suitable soft segments include poly (tetramethylene glycol) (PTMG), polycaprolactone (PCL), and poly (butylene adipate) (PBA). The TPEE has a Shore hardness value in the range of 25D less than 50D. Non-limiting examples of commercial TPEE include ARNITEL ™ from DSM, and HYTREL ™ from DuPont.
    [034] In an embodiment, the thermoplastic elastomer includes polyamide elastomer. When used herein, "polyamide elastomer" is a thermoplastic elastomer comprising a hard polyamide segment and a soft segment which is a polyether and / or a polyester. The polyamide ester has a Shore hardness in the range of 80A to less than 50D. Non-limiting examples of suitable polyamide elastomer include PEBAX ™ from Arkema.
    [035] The composition may include one or more than one thermoplastic elastomer. In one embodiment, the composition includes a first thermoplastic elastomer and a second thermoplastic elastomer, the second thermoplastic elastomer different from the first thermoplastic elastomer.
    [036] In an embodiment, the present composition includes the thermoplastic elastomer in an amount less than about 48% by weight, or about 50% by weight, or about 55% by weight, and an increased amount of the thermoplastic elastomer of about 75% by weight, or about 70% by weight, or about 65% by weight or about 60% by weight. The weight percentage is based on the total weight of the composition.
    [037] The present composition includes a flame retardant. The flame retardant is composed of a metal hydrate and an oligomeric phosphate ester. In an embodiment, the flame retardant is an intumescent flame retardant. An "intumescent flame retardant" is a flame retardant that produces a carbonaceous foam residue formed on a surface of a polymeric material during exposure to fire.
    [038] The flame retardant includes a metal hydrate. Without being bound by any particular theory, metal hydroxide is a water generating agent (or a water vapor generating agent) to provide foaming during combustion of the present composition. Non-limiting examples of suitable metal hydrates include magnesium hydroxide, aluminum hydroxide, alumina monohydrate, hydromagnesite, hydrated zinc borate, and any combination thereof.
    [039] The flame retardant may contain one or more metal hydrates. In an embodiment, the flame retardant includes a first metal hydrate and a second metal hydrate, the second metal hydrate different from the first metal hydrate.
    [040] In an embodiment, the metal hydrate is aluminum hydroxide and / or magnesium hydroxide.
    [041] The metal hydrate is present in the composition in an amount less than about 30% by weight, or about 35% by weight, or about 37% by weight and an amount greater than about 60% by weight , or about 50% by weight, or about 45-6 by weight. The weight percentage is based on the total weight of the composition.
    [042] The flame retardant also includes an oligomeric phosphate ester (OPE). When used herein, "oligomeric phosphate ester" is a compound of structure (II):
    in which R is independently a divalent alkylene or linear, branched or cyclic C1 -C2 alkylene or a divalent C6-C30 arylene radical having one or more aromatic nuclei, or a substituted derivative of any one thereof; Z is independently selected from the group consisting of (I) linear, branched or cyclic C1-C20Z alkylidene or alkylene monovalent (II) C6-C30 arylene monovalent radicals having one or more aromatic nuclei or substituted derivatives of any of them, or (III) a hydrogen radical; each m is independently zero or 1, preferably 1; and n is about 1 to about 10 (inclusive), or any subset thereof, or about 1 to about 7, or about 1 to about 3. The term "n" can represent the average number of repeating units for an aromatic phosphate ester oligomer where the aromatic phosphate ester oligomer composition contains a statistical distribution of phosphate compounds that typically results from an oligomerization process. As a result, "n" does not have to be an integer for a particular aromatic phosphate ester oligomer composition.
    [043] Arylene mono- or bivalent radicals in R and Z are based on and include phenylene, biphenylene, 2,2-diphenyl propane, naphthylene, anthracylene, and substituted derivatives thereof, and the like. Non-limiting examples of arylene radicals from which Z or R can be derived include the remnants of resorcinol, 1-bis (4-hydroxy phenyl) -1-phenyl ethane ("Bisphenol-AP" or "Bis-AP"), 9, 9-bis (4-hydroxy phenyl) fluorine ("BHPF") or bisphenol A. In an embodiment, R is selected from a linear, branched or cyclic C1-C20 alkylidene or alkylene radical, or C6-C30 arylene bivalent radical having one or more aromatic nuclei or substituted derivative of any one thereof; Z is a monovalent arylene radical of C6, each m is 1, and n is from about 1 to about 3.
    [044] Non-limiting examples of oligomeric phosphate esters include resorcinol tetrafenyl diphosphate, bisphenol A tetrafenyl diphosphate, resorcinol diphosphate, resorcinol diphenyl phosphate (RDP), bisphenol A (BPAPP) diphosphate (BAPP), diphenyl A phosphate (BPAPP), bisphenol A ), bisphenol A diphosphate (BADP), 1,3-phenylene bisphosphate (2,6-dimethyl phenyl), and any combination thereof.
    [045] The flame retardant may contain one or more oligomeric phosphate esters. In an embodiment, the flame retardant includes more than one OPE, such as a first OPE and a second OPE, the second OPE different from the first OPE.
    [046] OPE is present in the composition in an amount less than about 5% by weight, or about 10% by weight, or about 15% by weight and a greater amount of about 35% by weight, or about 30% by weight, or about 25% by weight. The weight percentage is based on the total weight of the composition.
    [047] In an incorporation, the flame retardant is devoid of halogen or is also halogen free.
    [048] In an incorporation, the flame retardant is devoid of nitrogen or is also free of nitrogen.
    [049] In an incorporation, the OPE is devoid of halogen or is also halogen free.
    [050] In an incorporation, the OPE is devoid of nitrogen or is also free of nitrogen.
    [051] The flame retardant has a weight ratio of metal hydrate to organic phosphate greater than 1.45: 1, or greater than 1.45-12.0: 1, or 1.5-9.0: 1, or 1.7-6: 1, or 2.0- 4.0: 1. Table 1 below provides non-limiting examples of weight ratios for flame retardant components and total flame retardant load. Table 1
    FR = flame retardant; MH = metal hydrate; OPE = oligomeric phosphate ester; % by weight based on the total weight of the composition.
    [052] Surprisingly, applicants have found that the composition with (1) the flame retardant charge and (2) the MH: OPE weight ratio greater than 1.45: 1 unexpectedly produces a thermoplastic / flame retardant elastomer composition. flame that passes the rigorous VW-1 test for wire and cable applications. In addition, the composition advantageously has a V-1 rating or better based on UL-94.
    [053] In an embodiment, the composition contains from about 12% by weight to about 50% by weight of the thermoplastic elastomer, and from about 48% by weight to about 75% by weight of the flame retardant. In addition, the flame retardant includes from about 30% by weight to about 45% by weight of metal hydrate (MH) and from about 5% by weight to about 35% by weight of oligomeric phosphate ester (OPE) . The weight ratio of MH: OPE is greater than 1.45: 1.
    [054] In an embodiment, the composition is molded into a plate. The plate has a tensile strength of about 25 MPa to about 10 MPa. Tensile strength is measured according to ASTM D638.
    [055] In an embodiment, the composition is molded into a plate. The plate has a tensile elongation at break of about 200% to about 700%, or about 300% to 650%, measured according to ASTM D638. Surprisingly, applicants have found that provision of a thermoplastic elastomer with a Shore hardness less than 50D unexpectedly produces a composition with excellent flexibility, i.e., a tensile elongation at break of about 200% to about 700%. In an additional embodiment, the composition has a Shore hardness of less than 50D.
    [056] The present patent application provides another composition. In one embodiment, a composition is provided that includes a thermoplastic elastomer, a polar olefin-based polymer, and a flame retardant. The flame retardant includes a metal hydrate and an oligomeric phosphate ester. The thermoplastic elastomer and flame retardant can be any of the respective thermoplastic elastomers and flame retardants disclosed herein.
    [057] In an embodiment, the weight ratio of metal hydrate to oligomeric phosphate ester is greater than 1.45: 1.
    [058] When used herein, an "olefin-based polymer" is a polymer containing, in polymerized form, a majority weight percentage of an olefin, for example, ethylene or propylene, based on the total weight of the polymer. Non-limiting examples of olefin-based polymers include ethylene-based polymers and propylene-based polymers. A "polar olefin-based polymer" is an olefin-based polymer containing one or more polar groups (sometimes referred to as polar functionalities). When used herein, a "polar group" is any group that confers a dipolar moment of attachment to an essentially non-polar olefin molecule. Exemplary polar groups include carbonyls, carboxylic acid groups, carboxylic acid anhydride groups, carboxylic ester groups, epoxy groups, sulfonyl groups, nitrile groups, amide groups, silane groups and the like, and these groups can be introduced into the olefin-based polymer either by grafting or by copolymerization.
    [059] Examples of polar olefin-based polymers include copolymers of ethylene / acrylic acid (EAA), ethylene / methacrylic acid (EMA), ethylene / acrylate or methacrylate, ethylene / vinyl acetate (EVA), poly (ethylene-co-vinyl trimethoxy silane), olefinic polymers grafted with anhydride or silane, poly (ethylene alt-ethylene tetra fluorine) (ETFE), poly (ethylene-co-tetra fluorine ethylene-co-hexa fluorine-propylene) (EFEP), poly (vinylidene fluoride) (PVDF), poly (vinyl fluoride) (PVF), and the like. Commercial incorporations of polar olefin-based polymers include ethylene / vinyl acetate (EVA) resins ELVAX ™ from DuPont, ethylene / ethyl acetate (EAA) copolymer AMPLIFY ™ from The Dow Chemical Company, ethylene / acrylic acid copolymers PRIMACOR ™ from The Dow Chemical Company, and copolymer of poly (ethylene-co-vinyl trimethoxy silane) from The Dow Chemical Company.
    [060] In an embodiment, the polar ethylene-based polymer is ethylene / vinyl acetate (EVA) copolymer. EVA has a vinyl acetate content of about 3% by weight to about 45% by weight, based on the total weight of EVA. EVA can form a continuous layer (or matrix) or a co-continuous phase with the thermoplastic elastomer. The flame retardant is dispersed throughout the continuous phase or throughout the co-continuous phase.
    [061] In an embodiment, EVA is present in the composition in an amount less than about 1% by weight, or about 5% by weight, or about 10% by weight and in an amount greater than about 30% by weight , or about 25% by weight, or about 20% by weight. In an additional embodiment, the composition contains from 10% by weight to 15% by weight of EVA. The weight percentage is based on the total weight of the composition.
    [062] In an embodiment, the composition contains from about 12% by weight to about 50% by weight of the thermoplastic elastomer, from about 1% by weight to about 30% by weight of EVA, and about 48% by weight to about 75% by weight of the flame retardant. In addition, the flame retardant includes from about 30% by weight to about 60% by weight of the metal hydrate and from about 5% by weight to about 35% by weight of the oligomeric phosphate ester. The ratio of metal hydrate to oligomeric phosphate ester can be any ratio, or any range of reasons, discussed above. The amount of flame retardant and the weight ratio MH: OPE provide the composition with a classification V-1 or better determined according to UL-94.
    [063] In an embodiment, the composition is molded into a plate. The plate has a tensile strength of about 2.5 MPa to about 10 MPa. Tensile strength is measured according to ASTM D638.
    [064] In an incorporation, the composition is molded on a plate. The plate has a tensile elongation at break of about 200% to about 700%, or about 300% to 650%, measured according to ASTM D638.
    [065] In an embodiment, the composition with the polar olefin-based polymer has a Shore hardness less than 50D.
    [066] Any of the preceding compositions may include one or more of the following additives: an anti-drip agent, a hindered amine light stabilizer (having at least one secondary or tertiary amine group) ("HALS"), UV light absorbers ( such as o-hydroxy phenyl triazines), antioxidants, curing agents, reinforcers and retardants, processing aids, fillers, coupling agents, antistatic agents, nucleating agents, sliding agents, plasticizers, lubricants, viscosity controlling agents, tackiness, non-stick agents, surfactants, extender oils, acid purgers, metal deactivators, and any combination thereof.
    [067] In an incorporation, the composition is drip-free. When used herein, the term "drip-free composition" means a composition that, when exposed to heat or flame, does not produce any vertical drop of melted particles that ignite cotton located under the composition.
    [068] In an embodiment, the present composition includes an anti-dripping agent. The anti-dripping agent prevents the composition from dripping when exposed to fire. The anti-dripping agent can be any anti-dripping agent known in the art. Non-limiting examples of suitable anti-dripping agents include fluorinated resins, such as poly (ethylene tetra fluoride), poly (vinylidene fluoride) or ethylene tetra fluorine / ethylene fluorine copolymers and ethylene / tetra fluorine ethylene copolymers / styrene copolymer / acrylonitrile grafted with teflon (T-SAN), fluorinated polyolefin, lithium salt, sodium, potassium or cesium sulfonate of 1, 1,2,2-tetra fluorine ethane or sulfonate of 1, 1,2,3,3, 3-hexa fluorine propane. Additional non-limiting examples of suitable anti-dripping agents include silicone resins, silicone oil, phosphoric acid, phosphoric acid, hypophosphoric acid, hypophosphoric acid, phosphoric acid, phosphonic acid, metaphosphoric acid, hexametaphosphoric acid, thiophosphoric acid, fluorine phosphoric acid, phosphoric fluoride, phosphorus fluorine acid, phosphorus diflouror acid, hypophosphorus fluorine acid, and hypophosphoric acid The anti-dripping agent can be one or more of the aforementioned anti-dripping agents. In an embodiment, the anti-dripping agent is halogen free.
    [069] In an embodiment, the present embodiment includes a hindered amine light stabilizer (HALS). Non-limiting examples of appropriate HALS include: TINUVIN® 770 (bis- (2,2,6,6-tetramethyl-4-piperidinyl sebacate)), TINUVIN® 144 (bis- (1,2,2,6 , 6-pentamethyl-4-piperidinyl) -4-n-butyl-2- (3,5-ditherciobutyl -4-hydroxy benzyl)), and SANDUVOR® PR-31 ([4-methoxy phenyl) -methylene] -bis - (1,2,2,6,6-pentamethyl-4-piperidinyl) propanedioic acid ester).
    [070] In an embodiment, the present composition includes an antioxidant. Non-limiting examples of suitable antioxidants include hindered phenols such as tetrakis [methylene (3,5-ditherciobutyl-4-hydroxyhydrocinamate)] methane, bis [(beta- (3,5- ditherciobutyl-4-hydroxy benzyl) sulfide) -methyl carboxy ethyl)], 4,4'-thio bis (2-methyl-6-terciobutyl phenol), 4,4'-thio bis (2-terciobutyl-5-methyl phenol), 2,2'-thio bis (4-methyl-6-terciobutyl phenol), and bis (3,5-ditherciobutyl-4-hydroxy) diethyl thio hydrocinamate; phosphites and phosphonites such as tris phosphite (2,4-ditherciobutyl phenyl) and ditherciobutyl phenylphonite; thiocompounds such as dilauryl dipropionate uncle, dimyristyl dipropionate uncle, and distearyl dipropionate uncle; various siloxanes; Polymerized 2,2,4-trimethyl-1,2-dihydroquinoline, n, n'-bis (1,4-dimethyl pentyl-p-phenylenediamine), alkylated diphenylamines, 4,4'-bis (alpha, alpha- dimethyl benzyl) diphenylamine, diphenyl-p-phenylenediamine, mixed di-aryl-p-phenylenediamines, and other hindered amine stabilizers or antidegraders. Antioxidants can be used in amounts of 0.1 to 5% by weight, based on the weight of the composition.
    [071] In an embodiment, the present composition includes a processing aid. Non-limiting examples of suitable processing aids include metal salts of carboxylic acids such as zinc stearate and calcium stearate; fatty acids such as stearic acid, oleic acid, or erucic acid; fatty amides such as stearamide, oleamide, erucamide, or N, N'-ethylene bis stearamide; polyethylene wax; oxidized polyethylene wax; ethylene oxide polymers; copolymers of ethylene oxide and propylene oxide; vegetable waxes; nonionic surfactants; and polysiloxanes. Processing aids can be used in amounts of 0.05 to 5% by weight, based on the weight of the composition.
    [072] In an embodiment, the composition is devoid of halogen or is also halogen free.
    [073] The present compositions may comprise two or more incorporations disclosed herein.
    [074] The present disclosure provides an article. In an embodiment, the article provided includes a component comprising the present composition. In particular, the article includes a component composed of a composition including a thermoplastic elastomer, a flame retardant, and optionally a polar olefin-based polymer. The thermoplastic elastomer has a Shore hardness less than 50D. The flame retardant includes a metal hydrate and an oligomeric phosphate ester with a weight ratio of MH: OPE greater than 1.45: 1. The weight percentage of each individual component in the composition can be any value or range previously disclosed here.
    [075] In an embodiment, the article includes a conductive metal and a coating on the conductive metal. This forms a coated metallic conductor. When used herein, a "conductive metal" is at least one metallic wire and / or at least one metallic cable. The coated metallic conductor can be flexible, semi-rigid, or rigid.
    [076] A coating (also referred to as a "shirt" or "lining") is over the metallic conductor. The coating includes the composition. The composition can be any composition disclosed herein. When used here, "over" includes direct contact or indirect contact between the cladding and the metallic conductor. "Direct contact" is a configuration whereby the coating immediately contacts the metallic conductor, without any intermediate layers and / or without any materials located between the coating and the metallic conductor. "Indirect contact" is a configuration by which intermediate layers and / or intermediate structures are located between the metallic conductor and the coating. The cladding can completely or partially cover or encircle or enclose the metallic conductor differently. The coating may be the only component involving the metallic conductor. Alternatively, the coating may be a layer of a multilayer shirt or liner covering the metallic conductor.
    [077] In an embodiment, the article is a coated metallic conductor. Surprisingly, applicants have discovered a wire jacket or jacket composed of the present composition that exhibits strong flame retardancy and excellent flexibility (evidenced by the high tensile strength range at break) for applications in flexible spinning. Non-limiting examples of coated metallic conductors include flexible wiring for consumer electronic devices, power cable, power charger wire for cell phones and / or computers, flexible computer data conductors, flexible power conductors, electrical wiring material appliances, and accessory cords for consumer electronics.
    [078] In an embodiment, the coated metallic conductor has a VW-1 classification determined according to method 1080 of UL-1581.
    [079] The article may comprise two or more incorporations disclosed herein. Combination
    [080] The present composition can be prepared by combining the individual components. Non-limiting examples of combination equipment include internal batch mixers, such as a Haake Rheometer mixer, a Banbury ™ or Bolling ™ internal mixer. Alternatively, one or two-bladed continuous mixers can be used, such as a Farrel ™ continuous blender, a Werner and Pfleiderer ™ two-bladed mixer or Buss ™ continuous kneading extruder. The type of mixer used, and the operating conditions of the mixer, will affect the properties of the composition such as viscosity, volumetric resistivity, and smoothness of the extruded surface.
    [081] When using a paddle mixer, the individual components can be introduced into it by means of a main loading funnel, a side feeder, or a combination thereof.
    [082] In an incorporation, the metal hydrate is separated into two portions, a first portion is mixed with thermoplastic elastomer (and optionally with the polar olefin-based polymer) and introduced into the paddle mixer through the main loading funnel. The second portion is introduced into the paddle mixer through the side feeder.
    [083] In an incorporation, a portion of the metal hydrate is introduced into the paddle mixer through the main loading funnel together with the polar olefin-based polymer. Another portion of the metal hydrate is mixed with the thermoplastic elastomer and introduced into the paddle mixer through the side feeder.
    [084] In an incorporation, the metal hydrate is mixed with the polar olefin-based polymer to form a standard mixture. The standard mixture formed is then mixed with the thermoplastic elastomer and the organic phosphate.
    [085] An article such as a coated wire or cable coated with a jacket and / or insulating layer comprising the composition disclosed herein can be prepared with various types of extruders, of the types of one or two spindles. A description of a conventional extruder can be found in U.S. Patent No. 4,857,600. An example of co-extrusion and an extruder can be found in U.S. Patent No. 5,575,965. A typical extruder has a loading funnel at its upstream end and a die at its downstream end. The hopper feeds a barrel, which contains a spindle. At the downstream end, between the spindle end and the die, there is a screen and a carrier plate. The spindle portion is considered to be divided into three sections, the feed section, the compression section and the dosing section, and two zones, the rear heating zone and the frontal heating zone, the operating sections and zones from upstream to downstream. Alternatively, there may be multiple heating zones (more than two) along the axis operating from upstream to downstream. If there is more than one barrel, the barrels are connected in series. The length to diameter ratio of each barrel is in the range of about 15: 1 to about 30: 1. In a wire jacket where the polymeric insulation is cross-linked after extrusion, the cable often passes immediately through a heated vulcanization zone downstream of the extrusion die. The heated curing zone can be maintained at a temperature in the range of about 200 ° C to about 350 ° C, or in the range of about 170 ° C to about 250 ° C. The heated zone can be heated by pressurized water vapor, or by inductively heated pressurized nitrogen gas.
    [086] The wire and cable constructions (ie, coated metallic conductor) of this disclosure are made by extruding the present composition over a bundle of insulated conductors to form a jacket (or jacket) around the insulated conductors. The thickness of the jacket depends on the requirements of the desired end-use application. Typical jacket thickness is about 0.010 inch to about 0.200 inch, or about 0.020 inch to about 0.050 inch. The present composition can be extruded into the jacket of the previously prepared composition. Usually, the present composition is in the form of pellets to facilitate its feeding in the extruder. The wire and cable jacket can be extruded directly from the composition extruder without going through the separate pelletizing step of the present composition. This one-step composition / extrusion process would eliminate a heating history step for the composition.
    [087] Non-limiting incorporations of the composition and article are provided below.
    [088] The present disclosure provides a composition. In an embodiment, a composition is provided comprising from about 12% by weight to about 50% by weight of a thermoplastic elastomer and from about 48% by weight to about 75% by weight of a flame retardant. The thermoplastic elastomer has a Shore hardness less than 50D. The flame retardant comprises a metal hydrate and an oligomeric phosphate ester. The weight ratio of metal hydrate to oligomeric phosphate ester is greater than 1.45: 1.
    [089] In one embodiment, the thermoplastic elastomer of the composition is selected from the group consisting of thermoplastic polyurethane, thermoplastic polyester elastomer, polyamide elastomer, and combinations thereof.
    [090] In an embodiment, the oligomeric phosphate ester is selected from the group consisting of resorcinol bis (diphenyl phosphate), bisphenol A bis (diphenyl phosphate), bisphenol A polyphosphate and combinations thereof.
    [091] In an embodiment, the composition comprises from about 30% by weight to about 60% by weight of the metal hydrate and from about 5% by weight to about 35% by weight of oligomeric phosphate ester.
    [092] In an embodiment, the metal hydrate to oligomeric phosphate ester ratio is 1.5-12.0: 1.
    [093] In an embodiment, the composition comprises a second thermoplastic elastomer.
    [094] In an embodiment, the composition comprises a component selected from the group consisting of an antioxidant, a processing stabilizer, and combinations thereof.
    [095] In an embodiment, the composition has a Shore hardness less than 50D.
    [096] In an embodiment, the composition has a V-1 rating or better, determined according to the UL-94 flame test.
    [097] In one embodiment, the composition is a plate having a tensile strength of about 2.5 MPa to about 10 MPa measured according to ASTM D638.
    [098] In one embodiment, the composition of a tensile elongation at break of about 200% to about 700% measured according to ASTM D638.
    [099] The present disclosure provides another composition. In an embodiment, a composition is provided which comprises a thermoplastic elastomer, a polar olefin-based polymer, and a flame retardant. The flame retardant comprises a metal hydrate and an oligomeric phosphate ester.
    [100] In an embodiment, the ratio of metal hydrate to oligomeric phosphate ester is greater than 1.45: 1.
    [101] In an embodiment, the composition comprises from about 12% by weight to about 50% by weight of the thermoplastic elastomer, from about 1% by weight to about 30% by weight of ethylene / vinyl acetate copolymer, from about 48% by weight to about 75% by weight of the flame retardant, from about 30% by weight to about 45% by weight of metal hydrate, and from about 5% by weight to about 35% by weight of oligomeric phosphate ester.
    [102] In an embodiment, the composition has a Shore hardness less than 50D.
    [103] In an embodiment, the composition comprises a component selected from the group consisting of an antioxidant, a processing stabilizer, and combinations thereof.
    [104] In an embodiment, the composition has a V-1 rating or better, determined according to the UL-94 flame test.
    [105] The present disclosure provides an article. In an embodiment, an article is provided which comprises at least one component consisting of a composition comprising a thermoplastic elastomer and a flame retardant. The thermoplastic elastomer has a Shore hardness less than 50D. The flame retardant comprises a metal hydrate and an oligomeric phosphate ester. The ratio of metal hydrate to oligomeric phosphate ester is greater than 1.45: 1.
    [106] In an embodiment, the composition in the article comprises a polar olefin-based polymer.
    [107] In an embodiment, the oligomeric phosphate ester present in the article is selected from the group consisting of resorcinol bis (diphenyl phosphate), bisphenol A bis (diphenyl phosphate), bisphenol A polyphosphate and combinations thereof.
    [108] In an embodiment, the article comprises a metallic conductor and a coating on the metallic conductor. The coating comprises the composition.
    [109] In one embodiment, the coating has a Shore hardness less than 50D.
    [110] In one embodiment, the coating has a tensile strength at break of about 200% to about 700% measured according to ASTM D638.
    [111] In an embodiment, the coated metallic conductor is selected from the group consisting of a flexible wire, a power cable, an apparatus wiring material, and combinations thereof.
    [112] In an embodiment, the coated metal conductor has a VW-1 rating determined according to method 1080 of UL-1581. Testing methods
    [113] Tensile elongation at break is measured according to ASTM D638. Traction elongation is measured by adjusting the crosshead speed to 50 mm / minute with the% elongation measured using an extensometer with an initial gauge length of 25 mm to measure rupture strain and tensile properties calculated via standard calculation using load and cross-sectional area of specimen with ASTM D638 as method.
    [114] Tensile strength at break is measured according to ASTM D638.
    [115] The modulus of elasticity of 2% is measured according to ASTM D638. For modulus of elasticity, an initial 58 mm (2.25 ") jaw separation and a test speed of 50 mm / minute are used to provide a specimen deformation rate of around 100% / minute The 1% modulus data are determined using a 1% deformation piston displacement method (0.01 minute = 0.6 second deflection) with ASTM D638 as the method.
    [116] UL-94 is the test of insurance laboratory bulletin 94 (UL) for flammability of plastic materials for parts in devices and appliances. The tested material is classified as UL 94 V-0 if: • None of the five specimens burns within 10 seconds at any time after removing the burner flame. • The total burning time of the 10 ignition test does not exceed 50 seconds. • No test body burns either with a flame or plastic drain after the fixer. • No incandescent molten material should fall that would cause the cotton to burn under any test body. • The burning of the posterior plastic flow of any specimen does not exceed 30 seconds.
    [117] The tested material is classified as UL 94 V-l if: • None of the five specimens burns within 30 seconds at any time after removing the burner flame. • The total burning time of the 10 ignition test does not exceed 250 seconds. • No test body burns either with a flame or plastic drain after the fixer. • No incandescent molten material should fall that would cause the cotton to burn under any test body. • The burning of the posterior plastic flow of any specimen does not exceed 60 seconds.
    [118] The tested material is classified as UL 94 V-2 if: • None of the five specimens burns within 30 seconds at any time after removing the burner flame. • The total burning time of the 10 ignition test does not exceed 250 seconds. • No test body burns either with a flame or plastic drain after the fixer. • Only such burnt parts can fall from the test body, which burn only momentarily, some of which burn the cotton underneath. • The burning of the posterior plastic flow of any specimen does not exceed 60 seconds.
    [119] VW-1 is an insurance laboratory flame rating (UL) for yarns and liners. It indicates "vertical yarn, class 1", which is the highest flame or jacket rating can be given under the UL 1441 specification. The test is performed by placing the yarn or jacket in a vertical position. The flame is placed under the wire or shirt for a period of time, and then removed. The characteristics of the shirt are then noted. The VW-1 flame test is determined according to method 1080 of UL-1581. Non-limiting examples of this disclosure are provided.
    [120] Examples
    [121] Ingredients Table 2
    Processing
    [122] The ingredients shown in Table 2 are used to prepare the composition in Table 3 using a laboratory Haake mixer. The model number is HAAKE Rheomix 6000S, with Polylab Drive RheoDrive7 as the driving system.
    [123] With a cylinder rotor, at a rotor speed of 10 rpm, component A and / or component B are added to the mixing vessel and mixed for 2 minutes to achieve a homogeneous molten state. Then, components C and D are added to the container in 2 minutes, followed by 5 min of mixing at 55 rpm. After mixing, the composite is removed from the mixing vessel and cooled to room temperature.
    [124] A compression-molded plate is prepared by compression molding at 185 ° C. The preheating time is about 3 min, followed by 2 min of pressing at 15 MPa. The plate is cooled to room temperature and cut into specimens for the tensile test by ASTM D-638 Type IV.
    [125] VW-1 test wire simulated by compression molding is prepared. Figure 1 shows the schematic structure of the molding machine. A single copper conductor with a diameter of 0.5 mm is placed in the center of each notch. The temperature of the hot press is set at 185 ° C. The preheating time is about 3 min followed by 2 min of pressure at 13 MPa. The plate is cooled to room temperature and cut into a strip of wire (203 mm x 2.5 mm x 2 mm), annealed at 23 ± 2 ° C and a relative humidity of 50 ± 2 percent for at least 24 hours before flame retardancy test. test
    [126] The test is performed on an Instron ™ traction analyzer (Instron model 5565) according to ASTM D638.
    [127] The Shore hardness test is carried out according to ASTM D2240.
    [128] The simulated FR VW-1 test is performed in a standard UL 94 chamber, with a methane gas flow rate of 105 mL / min, back pressure less than 10 mm of water. The blue flame with yellow burner tip is 20 ± 1 mm high. The wire strip is hung on the fastener, with a vertical longitudinal axis applying a 50 g load on the lower end. A paper banner (2 cm x 0.5 cm) is applied to the top of the wire. The distance from the bottom of the flame (highest point of the burner oracle) to the bottom of the flag is 18 c. The flame is applied continuously for 45 seconds. After the flame time (AFT), the unburned wire length (UCL) and the percentage of unburned flag area (unburned flag) are recorded during and after combustion. 4 or 5 specimens are tested for each formulation.
    [129] As shown in Table 3 (the component ratios in Table 3 are in% by weight of the total composition), with ATH + RDP above 48%, and ATH / RDP greater than 1.45: 1 (by weight) ), all formulations from Example 1 to Example 9 easily pass the simulated VW-1 test, whether they are mixtures of TPU / EVA in examples 1, 1-1, 2 or 7, or TPU as polymeric material in examples 3, 4, 5, 6, 8, 9. The addition of antioxidants and processing stabilizer does not deteriorate FR performance. In all nine examples, the after flame time (AFT) is short, the unburned length (UCL) on the wire strip is so long that the flame has little chance of touching the flag at the top of the specimen. Great swelling of the specimen is observed under the flag, showing very effective swelling for examples 1-9.
    [130] As shown in comparative example 2, without oligomeric phosphate ester the entire specimen burns together with the flag at the top. The residual wire after combustion is simply metallic oxide, with a visual size the same as before ignition, showing no swelling. When the metal hydrate / oligomeric phosphate ester ratio is not above 1.45: 1, as in comparative example 1, the flame retardancy is insufficient to pass the simulated VW-1 test.

    权利要求:
    Claims (10)
    [0001]
    1. Composition comprising thermoplastic elastomer and flame retardant, said composition being characterized by the fact that it comprises: - from 12% by weight to 50% by weight of a thermoplastic elastomer with a Shore hardness less than 50D as measured according to ASTM D2240; - from 1 to 30% by weight of ethylene vinyl acetate; - from 48% by weight to 75% by weight of a flame retardant comprising a metal hydrate and an oligomeric phosphate ester, the oligomeric phosphate ester being a compound of structure (II):
    [0002]
    2. Composition according to claim 1, characterized in that the thermoplastic elastomer is selected from the group consisting of thermoplastic polyurethane, thermoplastic polyester elastomer, polyamide elastomer and combinations thereof.
    [0003]
    Composition according to any one of claims 1-2, characterized in that the oligomeric phosphate ester is selected from the group consisting of resorcinol bis (diphenyl phosphate), bisphenol A bis (diphenyl phosphate), bisphenol polyphosphate A and combinations thereof.
    [0004]
    4. Composition according to claim 1, characterized in that it comprises the flame retardant comprising from 30% by weight to 45% by weight of metal hydrate based on the total weight of the flame retardant; and from 5% by weight to 35% by weight of oligomeric phosphate ester based on the total weight of the retardant.
    [0005]
    5. Article, characterized by the fact that it comprises: - at least one component composed of a composition comprising a thermoplastic elastomer with a Shore hardness less than 50D, the thermoplastic elastomer comprising at least 12% by weight to 50% by weight of the composition to 30-O by weight of ethylene vinyl acetate; and a flame retardant comprising a metal hydrate and an oligomeric phosphate ester, the flame retardant comprising at least 48-6 by weight at 75% by weight of the composition, the oligomeric phosphate ester being a compound of structure (II):
    [0006]
    6. Article according to claim 5, characterized in that it comprises a conductive metal and a coating on the conductive metal, the coating comprising the composition.
    [0007]
    7. Article according to claim 6, characterized in that the coated metal conductor has a VW-1 classification determined according to the 1080 method of UL-1581.
    [0008]
    8. Composition according to claim 1, characterized by the fact that it is formed within a plate and the plate has a stress elongation at break of 200% to 700% as measured according to ASTMD638.
    [0009]
    9. Article according to claim 6, characterized in that the thermoplastic elastomer comprises a thermoplastic polyurethane.
    [0010]
    10. Article according to claim 6, characterized in that the coating has a stress elongation at break of 200% to 700% as measured according to ASTM D638.
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    同族专利:
    公开号 | 公开日
    TW201103956A|2011-02-01|
    BR112012002247A2|2016-06-14|
    EP2459632A4|2013-01-23|
    US20120132457A1|2012-05-31|
    JP2013501081A|2013-01-10|
    EP2459632A1|2012-06-06|
    EP2459632B1|2017-04-26|
    CA2769007C|2018-01-16|
    CN102549056B|2014-10-29|
    KR101726900B1|2017-04-13|
    US8987597B2|2015-03-24|
    JP5458174B2|2014-04-02|
    CA2769007A1|2011-02-03|
    CN102549056A|2012-07-04|
    MX2012001402A|2012-04-20|
    KR20120053017A|2012-05-24|
    WO2011011921A1|2011-02-03|
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    法律状态:
    2018-04-17| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2018-07-03| B07A| Technical examination (opinion): publication of technical examination (opinion)|
    2018-12-18| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application according art. 36 industrial patent law|
    2019-06-04| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application according art. 36 industrial patent law|
    2019-10-22| B07A| Technical examination (opinion): publication of technical examination (opinion)|
    2020-06-02| B09A| Decision: intention to grant|
    2020-10-27| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 10 (DEZ) ANOS CONTADOS A PARTIR DE 27/10/2020, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    PCT/CN2009/073020|WO2011011921A1|2009-07-31|2009-07-31|Flame retardant thermoplastic elastomer|
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