• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
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    • 专利摘要:
    COMPOSITION The present invention relates to a composition comprising at least one thermoplastic polyamide resin, one thermoplastic polyester resin, reinforcement or filler fillers and a flame retardant. Said composition does not comprise a polyamide and polyester compatibilizing agent, such as a polymeric type agent, namely any epoxy resin. Such a flame-retardant polyamide / polyester composition has good compatibility and good mechanical and flame retardant properties, especially a good ability to not form flames in the presence of incandescent agents, for example in the field of household appliances, electrical engineering and electronics
    公开号:BR112014004395B1
    申请号:R112014004395-7
    申请日:2012-08-20
    公开日:2020-07-28
    发明作者:Mok-Keun Lim
    申请人:Performance Polyamides, Sas；
    IPC主号:
    专利说明:

    [001] The present invention relates to a composition comprising at least a thermoplastic polyamide resin, a thermoplastic polyester resin, reinforcement or filler fillers and a flame retardant. Said composition does not comprise a polyamide and polyester compatibilizing agent, such as a polymeric type agent, namely any epoxy resin. Such a flame-retardant polyamide / polyester composition has good compatibility and good mechanical and flame retardant properties, especially a good ability to not form flames in the presence of incandescent agents, for example in the field of household appliances, electrical engineering and electronics. PREVIOUS TECHNIQUE
    [002] Polyamide resin has good mechanical, chemical and thermal properties and is therefore used in several areas. However, the polyamide resin has poor dimensional stability and the mechanical properties of the polyamide resin decrease with water absorption. As a result, an attempt has been made to improve the properties of the polyamide resin by mixing the polyamide resin in the molten state with another thermoplastic resin such as a polyester resin, to form a mixture in the molten state. However, considering that a thermoplastic polyamide resin shows a low compatibility with a thermoplastic polyester resin, a mixture formed only from the two resins shows a treatment ability and properties that are weak.
    [003] From US patent No. 4 150 674 it is known to use a lactam terpolymer as a compatibility agent when mixing a polyamide resin with a polyester resin and to use the product thus obtained for fabrics. In addition, US Patent No. 5,055,509 describes the introduction of arylphosphonyl azide as a compatibility agent. However, the effects of the compatibility of these compounds have not been clearly verified and the products thus obtained do not produce the desired properties.
    [004] US Patent No. 5,296,550, US Patent No. 5,475,058, and EP 664 320 and EP 984 087 applications describe a composition that improves compatibility between the two resins by adding an obtained olefinic resin by copolymerization by grafting an ethylene type monomer, for example styrene or methacrylate, with a monomer having a glycidyl group, for example glycidyl methacrylate. However, this composition has disadvantages such as reduced stiffness compared to polyamide or polyester resins.
    [005] CC Huang et al., Polymer, 1997, 38 (7), 2135-2141 and CC Huang et al., Polymer, 1997, 38 (17), 4287-4293, describe mixtures of poly (butylene terephthalate) and polyamide-6,6 using a bisphenol-A type epoxy resin in the solid state with an epoxy equivalent weight (EEW) of 2060 g / eq. J. An et al., Journal of Applied Polymer Science, 1996, 60, 1803-1810, describe PBT and PA-6 (polyamide-6) alloys with varying amounts of E-44 epoxy resin (EEW = 210 g / eq). KC Chiou et al, Journal of Applied Polymer Science: Part B: Polymer Physics, 2000, 38, 23-33, uses a multifunctional epoxy resin (EEW = 110 to 130 g / eq) as a coupling agent to make PA mixes compatible 6 / PBT. However, if an epoxy resin of a low epoxy equivalent weight is used in polymer blends, the treatment suitability and properties of polymer blends are still unsatisfactory and must be improved.
    [006] In addition, formulations are sought especially in the electrical and electronic domains that are capable of not forming flames when in the presence of a nearby incandescent object; this property being different from the classic fireproof properties measured by UL-94 tests. Thus, it is evident that the presence of a compatibilizing agent between polyamide and polyester, such as epoxy resin, is harmful for this property of not forming flames.
    [007] There is thus a need to develop fireproof polyamide / polyester formulations showing good compatibility and good mechanical and flame retardant properties, especially a good ability to not form flames in the presence of incandescent agents, for example in the field of household appliances, electrotechnics and electronics. INVENTION
    [008] The applicant has developed a formulation comprising polyamide and polyester, flame retardants and reinforcing or filling fillers and presenting all the advantages mentioned above.
    [009] The present invention relates to a composition comprising at least: (a) a thermoplastic polyamide resin; (b) a thermoplastic polyester resin; (c) a reinforcement or filling load; and (d) a flame retardant, the composition not comprising a polyamide and polyester compatibilizing agent, as an agent of the polymeric and organic type, namely any epoxy resin.
    [010] The composition according to the present invention does not therefore comprise a polyamide and polyester compatibilizing agent typically used for this purpose as the compounds already described, especially epoxy resins typically comprising at least two epoxy groups per molecule. For information purposes only, these epoxy resins are generally resins of the DGEBA type (bisphenol A diglycidyl ether), the DGEBF type (bisphenol F diglycidyl ether), or the hydrogen BPA type (hydrogenated bisphenol A), for example. (A) POLYAMIDE RESIN
    [011] The polyamide resin included in the composition of the present invention can be any thermoplastic polyamide resin. Examples of a polyamide resin can comprise a polyamide-6 that can be obtained as a product of polymerization by opening the cycle of lactams such as s-caprolactam and w-dodecalactam; polyamide polymers that can be obtained from amino acids such as aminocaproic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid; aliphatic, cycloaliphatic or aromatic diamines such as ethylenediamine, tetramethylenediamine, hexamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylamethylamethyl, methylamethylamine p-xylenediamine, 1,3-bis-aminomethylcyclohexane, 1,4-bisaminomethylcyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, bis (4-aminocyclohexane) methane, bis ( 4-methyl-4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminopropyl) piperazine, aminoethylpiperidine, etc. ; polyamide polymers that can be obtained from aliphatic, cycloaliphatic or aromatic dicarboxylic acids such as adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methyltereftálico and 5-methylisoftálico acid; and copolymers of polyamide resins, which can be used alone or in combination of two or more types.
    [012] In certain embodiments, examples of polyamide resin may comprise polyamide-6, polyamide-66, polyamide-610, polyamide-11, polyamide-12, polytherephthalamide, polyisophthalamide, and polyamide. .
    [013] The polyamide matrix may be, in particular, a polymer comprising branched, hyper-branched star or H-chain macromoleculars and, if necessary, linear macromolecular chains. Polymers containing such star or H macromolecular chains are described, for example, in FR2743077, FR2779730, US5959069, EP0632703, EP0682057 and EP0832149.
    [014] According to another particular embodiment of the invention, the polyamide matrix of the present invention can be a random tree-type polymer, preferably a copolyamide having a random tree structure. The copolyamides of the statistical tree structure as well as the process for obtaining them are described in particular in WO 99/03909. The matrix of the present invention can also be a composition comprising a linear thermoplastic polymer and a star, H and / or tree thermoplastic polymer, as described above. The matrix of the invention can also comprise a hyper-branched copolyamide, of the type described in WO 00/68298. The composition of the invention may also comprise any combination of linear, star, H, tree, hyperbranched copolyamide polymer as described above.
    [015] In one embodiment, the relative viscosity of the polyamide resin can vary between 2.0 to 3.7 (a solution of 1 g of polymers in 100 ml of 90% formic acid, measured at 25 ° C) . In another embodiment, the number average molecular weight of the polyamide resin can vary between 5,000 and 70,000.
    [016] In one embodiment, the content of the polyamide resin can be chosen according to the desired properties. In one embodiment, the polyamide resin can be included in an amount of 1 to 98% by weight with respect to the total weight of the composition, more preferably in proportions between 40 and 70% by weight.
    [017] The weight ratio of polyamide in the composition is preferably more important than the weight ratio of polyester in said composition. (B) POLYESTER RESIN
    [018] The polyester resin comprised in the composition of the present invention can be a polymer compound that has ester bonds in its skeleton. Examples of polyester resin may comprise a homopolymer or a copolymer that can be obtained by condensing a dicarboxylic acid or its derivatives which can form an ester, with a diol or its derivatives being able to form an ester or a mixture thereof.
    [019] In one embodiment, an example of dicarboxylic acid can comprise an aromatic dicarboxylic acid such as terephthalic acid, isophthalic acid, phthalic acid, 1,4-, 1,5-, 2-dicarboxylic acid , 6-or 2,7-naphthalene, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 5-sodiosulfoisophthalic acid, etc. ; an aliphatic dicarboxylic acid such as adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, etc. ; a cycloaliphatic dicarboxylic acid such as 1,3-cyclohexane dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, etc. ; and their derivatives can form an ester, but are not limited to that. In certain embodiments, said dicarboxylic acid can be used in the form of a derivative that can form an ester as a derivative substituted by an alkylalkoxy, or a halogen, etc., and an ester obtained from a lower alcohol, for example dimethyl ester.
    [020] In another embodiment, examples of said diols may comprise an aliphatic glycol having 2 to 20 carbon atoms with ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1.5 -pentanediol, 1,6-hexanediol, decamethylene glycol, cyclohexanedimethanol, cyclohexanediol, etc. ; a long chain glycol with a molecular weight of 400 to 6,000 such as polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol, etc .; and their derivatives can form an ester, but are not limited to that. In certain embodiments, said diols can be used in the form of their derivatives and can form an ester as a derivative substituted by an alkyl, alkoxy or halogen group, etc.
    [021] In a certain embodiment, examples of homopolymers or copolymers can comprise polybutylene terephthalate, polybutylene (terephthalate / isophthalate), polybutylene (terephthalate / adipate), polybutylene (terephthalate / sebacate), polybutylene (terephthalate / decanate), polybutylene (decatephthalate) / decanate). polybutylene naphthalate, polyethylene terephthalate, polyethylene (terephthalate / isophthalate), polyethylene (terephthalate / adipate), polyethylene (terephthalate / 5-sodiosulfoisophthalate), polyethylene terephthalate, polyetherylene terephthalate, terephthalate polycyclohexanedimethylene, but not limited to that.
    [022] In another embodiment, examples of the polyester resin other than the compounds described above may comprise a polyester resin copolymerized with a copolymerizable monomer, for example a hydroxycarboxylic acid such as glycolic acid, hydroxybenzoic acid, hydroxyphenylacetic acid, naphthylglycolic acid, etc. ; and a lactone compound such as propriolactone, butyrolactone, caprolactone, valerolactone, etc. In yet another embodiment, examples of the polyester resin can comprise a polyester resin derived from compounds forming a multifunctional ester such as trimethylolpropane, trimethylolethane, pentaerythritol, trimellitic acid, trimethic acid, pyromelitic acid or a resin polyester with a branched or cross-linked structure in an amount where the polyester resin maintains a thermoplasticity.
    [023] The content of the polyester resin can be chosen according to the desired properties. In one embodiment, the polyester resin can be included in an amount of 1 to 98% by weight with respect to the total weight of the composition, more preferably in proportions between 5 and 40% by weight.
    [024] The polyester resin may in particular be a recycled polyester, especially from end-of-life articles or production waste. These polyesters can come from textile articles, bottles, films or technical plastics, namely composites. Polyesters can be used directly or after one or more possible treatments, namely hydrolysis or to separate the fillers and additives from the polyester compositions. The residues can be broken or crushed in the form of fragments, powders or granules, for example.
    [025] According to the invention, it is possible to use a mixture of polyester and recycled polyester in the composition. (c) REINFORCEMENT OR FILLING LOADS
    [026] The composition may comprise fibrous and / or non-fibrous fillers.
    [027] As fibrous fillers, glass fibers, carbon fibers, natural fibers, aramid fibers, and nanotubes, especially carbon, can be mentioned. Hemp and flax can be mentioned as natural fibers. Among the non-fibrous fillers, we can also mention all particular, lamellar fillers and / or exfoliable or non-exfoliable nanocharges such as aluminum, carbon black, aluminum silicate clays, montmorillonites, zirconium phosphate, kaolin , calcium carbonate, diatoms, graphite, mica, silicon, titanium dioxide, zeolites, talc, wollastonite, polymeric fillers such as particles of dimethylacrylates, glass spheres or glass powder.
    [028] It is perfectly possible according to the invention that the composition comprises various types of reinforcement charges. Preferably, the most used load can be fiberglass, of the chopped type, especially with a diameter between 7 to 14 pm. These fillers may have a surface gum that ensures mechanical adhesion between the fibers and the polyamide matrix.
    [029] The weight concentration of the filler or filler is advantageously between 1% and 60% of the weight in relation to the total weight of the composition, preferably between 15 and 50%. (D) IGNIPLE AGENT
    [030] The composition according to the present invention can especially comprise flame retardants generally used in the field of polyamide; that is, compounds that make it possible to reduce flame propagation and / or flame retardant properties well known to those skilled in the art. These flame retardants are generally used in flame retardant compositions and are described, for example, in US6344158, US6365071, US6211402 and US6255371 and cited herein by reference.
    [031] Advantageously, the composition comprises at least one flame retardant selected from the group comprising: -fire retardants containing phosphorus, such as: -phosphine oxides, such as triphenylphosphine oxide, oxide of tri- (3-hydroxypropyl) phosphine, and tri- (3-hydroxy-2-methylpropyl) phosphine oxide. -phosphonic acids or their salts or phosphonic acids or their salts, such as, for example, the zinc, magnesium, calcium, aluminum, or manganese phosphine acids, especially the aluminum salt of diethylphosphonic acid, or the zinc salt of dimethylphosphine acid. -cyclic phosphonates, such as cyclic diphosphate esters, such as for example Antiblaze 1045. -organic phosphates, such as triphenyl phosphate. -organic phosphates such as ammonium polyphosphates and sodium polyphosphates. -red phosphorus, whether it is, for example, stabilized or coated, in powder or in batch form. -fire retardants such as organic compounds with nitrogen, such as, for example, triazines, cyanuric and / or isocyanuric acid, melamine or its derivatives, such as melamine cyanurate, oxalate, phthalate, borate , sulphate, phosphate, polyphosphate and / or melamine pyrophosphate, condensed melamine products such as melem, melam and melon, tris isocyanurate (hydroxyethyl), benzoguanamine, guanidine, allantoin and glycoluryl. -the flame retardants containing halogenated derivatives, such as: -the bromine derivatives, such as, for example PBDPO (polybromodiphenyloxides), BrPS (brominated polystyrene and polystyrene), poly (pentabromobenzylacrylate), brominated indane, tetradecarbomodifenoxibene 120), ethane-1,2-bis (pentabromophenyl) or Saytex 8010 from Albemarle, tetrabromobisphenol A and brominated epoxy oligomers. Especially among brominated derivatives, we can mention polydibromo styrene such as Chemtura's PDBS-80, brominated polystyrenes such as Saybe HP 3010 from Albemarle or FR-803P from Dead Sea Bromine Group, decabromodiphenyleter (DBPE) or FR-1210 from Dead Sea Bromine Group, octabromodiphenyleter (OBPE), 2,4,6-tris (2,4,6-tribromophenoxy) -1,3,5 triazine or FR-245 from Dead Sea Bromine Group, poly (pentabromobenzylacrylate) or FR -1025 from Dead Sea Bromine Group and oligomers or polymers with epoxy or tetrabromobisphenol-A terminations, such as F-2300 and F2400 from Dead Sea Bromine Group. -chlorinated compounds, such as for example a chlorinated cycloaliphatic compound like Dechlorane plus ® (sold by OxyChem, see CAS 13560-89-9).
    [032] These compounds can be used alone or in combination, sometimes synergistically. Particularly preferred is a synergistic combination of phosphorus-containing compounds, such as phosphine oxides, phosphonic acids or their salts or phosphonic acids or their salts, and cyclic phosphonates, with nitrogen derivatives such as melam, melem, phosphate melamine, melamine polyphosphates, melamine pyrophosphates or ammonium polyphosphates.
    [033] Especially preferred is a composition according to the invention comprising a compound F1 of the formula: [R1R2P (= O) -O] z-Mz + where: R1 and R2 are identical or different and represent a straight or branched alkyl chain comprising 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms and / or an aryl radical; M represents a calcium, magnesium, aluminum and / or zinc ion, preferably a magnesium and / or aluminum ion; Z represents 2 or 3, preferably 3.
    [034] The composition of the invention may also comprise a compound F2 which is a product of the reaction between phosphoric acid and melamine and / or a product of the reaction between phosphoric acid and a condensed melamine product.
    [035] The composition of the invention can also comprise compounds F1 and F2.
    [036] Such an ignition system is described in particular in US patent 6255371. The composition can comprise 1 to 70% by weight of the ignition system, preferably 5 to 40%, even more preferably between 10 to 30%, particularly between 15 30%, in relation to the total weight of the composition. Preferably, the weight ratio of compounds F1 and F2 is between 1: 1 and 4: 1, preferably about 3: 2, respectively.
    [037] R1 and R2 can be identical or different and represent a methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl and / or aryl, such as a phenyl. M is preferably an aluminum ion. The phosphonic acid of the F1 compounds can be chosen, for example, from the group consisting of dimethyl phosphonic acid, ethyl methyl phosphonic acid, phosphonic diethyl acid and phosphonic methyl-n-propyl acid or mixtures thereof. Different phosphonic acids can be used in combination.
    [038] The phosphonic acid salts according to the invention can be prepared according to the usual methods well known to those skilled in the art, such as that described in patent EP 0699708. The phosphonic acid salts according to the invention can be used in different forms depending on the nature of the polymer and the desired properties. For example, to obtain good dispersion in the polymer, a phosphonic acid salt can be in the form of fine particles.
    [039] The compound F2 is a product of the reaction between phosphoric acid and melamine and / or a product of the reaction between phosphoric acid and a condensed melamine product. Different F2 compounds can be used in combination. Condensed melamine products are for example melam, melem and melom. Even more condensed compounds can also be used. Preferably, the compound F2 can be selected, for example, from the group consisting of the following reaction products: melamine polyphosphate, melam polyphosphate and melem polyphosphate, or a mixture thereof. It is particularly preferable to use a melamine polyphosphate with chains of length greater than 2, and in particular greater than 10.
    [040] These compounds are described in particular in WO 9839306. Compounds F2 can also be obtained by processes other than those based on direct reaction with a phosphoric acid. For example, melamine polyphosphate can be prepared by reacting melamine with polyphosphoric acid (see WO 9845364), but also by condensing melamine phosphate and melamine pyrophosphate (see WO 9808898).
    [041] Preferably, the flameproofing system of the present invention comprises a compound F1 in which R1 = R2 = ethyl, M = aluminum and Z = 3; and a compound F2: melamine polyphosphate. The weight ratio of compounds F1 and F2 can be 3: 2, respectively.
    [042] It is also possible to add other compounds that participate in flame retardation to the formulation, such as zinc borate, zinc oxide and magnesium hydroxide.
    [043] In general, the composition may comprise between 1 to 40% by weight of flame retardants, in relation to the total weight of the composition, preferably between 1 to 20% by weight, more preferably between 1 to 10% by weight . OTHER COMPOUNDS AND ADDITIVES
    [044] In certain embodiments, depending on the desired final property, a resin alloy composition may further comprise other polymer resins, for example polyethylene, polystyrene, polypropylene, ABS resin, polycarbonate, polyphenylene sulfide, polyphenylene oxide, polyacetal, polysulfone, polyethersulfone, polyetherimide, polyetherketone, a polylactic acid resin, a polysulfone resin, an elastomeric resin or mixtures thereof.
    [045] The composition may also comprise impact resistance modifying agents. These are generally polymers of elastomers that can be used for this purpose. Resilience modifying agents are generally defined as having an ASTM D-638 tensile modulus less than about 500 MPa. Examples of suitable elastomers are ethylene-acrylic ester-maleic anhydride, ethylene-propylene-maleic anhydride, EPDM (ethylene-propylene-diene monomer) with eventually a grafted maleic anhydride. The elastomer weight concentration is advantageously between 0.1 and 30% based on the total weight of the composition.
    [046] It is preferable that the shock modifying agents comprise functional groupings reactive with the polyamide. For example, ethylene terpolymers, methacrylate acrylic and glycidyl ester, ethylene and butyl acrylate copolymers, ethylene, n-butyl acrylate and methacrylate glycidyl copolymers, ethylene and anhydride copolymers can be mentioned. maleic, styrene-maleimide copolymers implanted with maleic anhydride, styrene-ethylene-butylene-styrene copolymers modified with maleic anhydride, styrene-acrylonitrile butadiene styrene copolymers implanted with maleic anhydrides and their hydrogenated versions. The weight proportion of these agents in the total composition is in particular between 0.1 and 40%.
    [047] In an embodiment, in a framework that does not infringe the purpose of the present invention, additives such as antioxidants, thermal stabilizers, UV radiation absorbers, such as aromatic amines, hindered phenols, phosphorus and sulfur, etc., dispersing agents , dyes, dyes, pigments, surfactants, release agents, lubricants, plasticizers, gloss-enhancing agents, which are generally used as plastic treatment agents can be used to transmit various effects. COMPOSITION MANUFACTURING
    [048] The composition of the resin alloy of polyamide resin and polyester resin can be obtained by mixing the compounds in the molten state with the help of a traditional extruder, for example, a single screw extruder or a double screw extruder. A general range of the cylinder temperature inside the extruder can be adjusted taking into account the melting point of the resin. In an illustrative embodiment, when a polyamide-6 resin is used, the temperature can be set to 250 ° C, and when a polyamide-66 resin is used, the temperature can be set to 280 ° C.
    [049] In addition, the resin alloy composition of the present application can be treated in the desired forms such as a granulate, a plate, a fiber, a filament, a film, a sheet, a tube, a concave body or a box by treatment processes such as traditional calendering molding, compression molding, blow molding, injection molding or melting molding, but the treatment forms or processes are not limited to these.
    [050] The composition according to the present invention can be used according to the general use of a polyamide resin or a polyester resin. For example, it can be applied in various ways to general precision machinery accessories, automotive accessories, electrical and electronic accessories, construction materials, films, fibers and sports equipment.
    [051] The examples described below serve to explain in more detail the characteristics and advantages of the object of the present disclosure, but without being limited to the examples presented below. The object of the present disclosure should not be limited to the specific embodiment and the examples described here. In the light of the present disclosure, a technician in the field can easily perceive that it is possible to modify, replace, add and combine a part of the constitutions described in the present disclosure differently from the different exemplary embodiments and examples. EXPERIMENTAL PART
    [052] In the following examples and comparative examples, the resin alloy composition of the present invention and the comparative composition are prepared respectively, and their properties are then compared from that of the superior effects of the polyamide resin alloy composition. and the polyester resin of the present invention are described in detail.
    [053] Initially, each component used in the examples and the comparative examples of the present invention are classified and explained below and are indicated with reference symbols. Thermoplastic polyamide-66 {trade name: Technyl 23A, manufactured by Rhodia}. Polyester: polyethylene terephthalate resin {trade name: ESLON PET-2211, manufactured by Woongjin Chemical}. Red phosphor: FR4260 master blend Glass fibers DGEBA type epoxy resin {epoxy equivalent weight: 3000 g / eq}, manufactured by Kukdo Chemical, Co., Ltd. Impact resistance modifying agent: Lotader 3210
    [054] The above components are mixed uniformly in a super mixer according to each mixing ratio of the examples and comparative examples. A twin screw extruder (internal diameter of e 30 mm, L / D = 30) is used. The cylinder temperatures inside the extruder are adjusted to about 280 ° C, taking into account the melting point of the resin used and the gas inside the spindle is exhausted at a spindle rotation speed of 250 to 300 tr / min and a vacuum pump pressure of 50 to 70 cm Hg.
    [055] The components are perfectly mixed inside the extruder cylinder and the extrudate formed is quenched in a cold water bath and granulated to a prescribed size using a granulator.
    [056] An injection machine (German, ENGEL) with a clamping force of 80 tonnes and an injection volume of 189.44 cc (6.4 oz) and used to prepare the sample for various property tests.
    [057] After sample preparation of the composition for molding under the conditions of a molding temperature of the general range taking into account the melting point of the resin used, a molding temperature of 80 ° C, an injection pressure of 50 to 80 bar, an injection speed of 40 to 60 mm / sec., an injection duration of three seconds and a cooling duration of fifteen seconds.
    [058] The global properties are reported in Table 1 below: TABLE 1

    [059] In the GWIT test, the ability to not form a flame following the application of an incandescent wire according to IEC 60695-2-13 in 1.0 mm thick beakers at a temperature of 750 ° C. The standard provides that when the sample successfully passes the test at 750 ° C the temperature is increased by 25 ° C and the sample is therefore classified with a GWIT of 775 ° C. It is concluded that the composition successfully passes the test when there is no inflammation during the application of the incandescent wire. It is concluded that the composition failed the test if there is inflammation during the application of the incandescent wire, that is, production of flames with permanence of more than 5 seconds. The test is successful when the three different test tubes confirm the same temperature in succession.
    [060] Another comparative example was carried out similarly to example 1, but without flame retardant or glass fibers. It is not possible to obtain an extruded strip as polyamide and polyester are incompatible. No granulate could be obtained.
    [061] It is thus observed that with the absence of a compatibilizing agent between polyamide and polyester, such as epoxy resin, better flameproofing properties are obtained, namely GWIT in relation to a known composition of the prior art, at the same time that the mechanical properties are remarkably maintained; and this using a relatively small amount of flame retardants in the formulation.
    [062] A composition similar to that of example 1, but comprising another fireproofing system, namely a compound F1 in which R1 = R2 = ethyl, M = aluminum and Z = 3; and a compound F2: melamine polyphosphate (the weight ratio of compounds F1 and F2 is 3: 2 respectively) was produced and tested. Mechanical properties equivalent or superior to the composition of example 1 are observed, while presenting a VO class in the UL94 @ 0.8mm test and passing the GWIT test, 775 ° C, 2 mm.
    权利要求:
    Claims (8)
    [0001]
    1. COMPOSITION, characterized by comprising at least: (a) from 40% to 70% by weight, in relation to the total weight of the composition, of a thermoplastic polyamide resin; (b) from 5% to 40% by weight, based on the total weight of the composition, of a thermoplastic polyester resin; (c) 15% to 50% by weight, based on the total weight of the composition, of a reinforcement or filler; and (d) from 1% to 20% by weight, based on the total weight of the composition, of a flame retardant, and (e) from 0.1% to 30% by weight, based on the total weight of the composition, from an impact resistance modifier, the composition being free of a compatibilizing agent for polyamide and polyester.
    [0002]
    2. COMPOSITION according to claim 1, characterized in that said polyamide resin comprises one or more elements chosen from the group consisting of polyamide-6, polyamide-66, polyamide-610, polyamide-11, polyamide-12, polytherephthalamide, polyisophthalamide and polyamides.
    [0003]
    COMPOSITION according to any one of claims 1 to 2, characterized in that said polyester resin comprises one or more elements chosen from the group consisting of polybutylene terephthalate, polybutylene (terephthalate / isophthalate), polybutylene (terephthalate / adipate ), polybutylene (terephthalate / sebacate), polybutylene (terephthalate / decanedicarboxylate), polybutylene naphthalate, polyethylene terephthalate, polyethylene (terephthalate / isophthalate), polyethylene (terephthalate / adipate), polyethylene (terephthalate / terephthalate) / 5-sodiosulfoisophthalate), polypropylene terephthalate, polyethylene naphthalate and polycyclohexanedimethylene terephthalate.
    [0004]
    COMPOSITION according to any one of claims 1 to 3, characterized in that said polyester resin is a recycled resin.
    [0005]
    COMPOSITION according to any one of claims 1 to 4, characterized in that the reinforcing or filling loads are fibrous or non-fibrous.
    [0006]
    6. COMPOSITION according to any one of claims 1 to 5, characterized in that the fibrous fillers are chosen from the group consisting of: glass fibers, carbon fibers, natural fibers, aramid fibers and nanotubes.
    [0007]
    7. COMPOSITION according to any one of claims 1 to 6, characterized in that it comprises at least one flame retardant chosen from the group consisting of: * phosphorus-containing flame retardants, such as: phosphine oxides, phosphonic acids or their salts or phosphonic acids or their salts cyclic phosphonates organic phosphates inorganic phosphates red phosphorus * flame retardant agents such as nitrogen-containing organic compounds, such as triazines, cyanuric and / or isocyanuric acid, melamine or its derivatives, such as melamine cyanurate, oxalate, phthalate, borate, sulfate, phosphate, polyphosphate and / or melamine pyrophosphate, melamine condensed products, such as melem, melam and melon, tri (hydroxyethyl) isocyanurate, benzoguanamine, guanidine, allantoin and glycoluryl; * flame retardant agents containing halogenated derivatives, such as: bromine derivatives, and chlorinated compounds.
    [0008]
    COMPOSITION according to one of Claims 1 to 7, characterized in that it comprises, as an flame retardant, a combination containing: phosphorus-containing compounds, such as phosphine oxides, phosphonic acids or their phosphonic acids or salts or their cyclic salts and phosphonates; with nitrogen derivatives, such as melam, melem, melamine phosphate, melamine polyphosphates, melamine pyrophosphates or ammonium polyphosphates.
    类似技术:
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    同族专利:
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    法律状态:
    2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-09-17| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-02-11| B25A| Requested transfer of rights approved|Owner name: PERFORMANCE POLYAMIDES, SAS (FR) |
    2020-05-26| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-07-28| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 20/08/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1157554|2011-08-26|
    FR1157554|2011-08-26|
    PCT/EP2012/066181|WO2013030024A1|2011-08-26|2012-08-20|Flame-retardant composition of a polyamide and polyester resin alloy|
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