Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
  • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
  • B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/49—Phosphorus-containing compounds
  • C08K5/51—Phosphorus bound to oxygen
  • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
  • C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K7/00—Use of ingredients characterised by shape
  • C08K7/02—Fibres or whiskers
  • C08K7/04—Fibres or whiskers inorganic
  • C08K7/14—Glass
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2077/00—Use of PA, i.e. polyamides, e.g. polyesteramides or derivatives thereof, as moulding material
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
  • B29L2031/00—Other particular articles
  • B29L2031/34—Electrical apparatus, e.g. sparking plugs or parts thereof
  • B29L2031/36—Plugs, connectors, or parts thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
  • C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
  • C08J2477/06—Polyamides derived from polyamines and polycarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2201/00—Properties
  • C08L2201/02—Flame or fire retardant/resistant
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
  • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

Definitions

• the invention relates to a flame retardant polyamide composition, a process for moulding the flame retardant polyamide composition, and moulded parts made of the flame retardant polyamide composition.
• the invention in particular relates to halogen free flame retardant moulding compositions for high performance applications.
• high performance applications often semi-crystalline polyamides with high melting temperatures are used, if not excluded or prohibited by even higher temperature requirements.
• flame retardancy halogen free flame retardants can be used, although with such flame retardants it is more difficult to achieve the required flame retardancy level, compared to halogen containing flame retardants used in the past. Because of the high temperatures involved in either the processing and/or the applications of these moulding compositions, the selection of flame retardants that can be used is limited, and even the better performing flame retardants commercially available have their limitations and problems. This becomes even more pronounced in more critical applications involving large production series of precision parts with small dimensions.
• compositions should have high flow, the products should preferably have a good weld line strength, a good surface appearance, e.g. high gloss, staining free and blooming free, and have a good flame retardancy rating, such as according to UL94 test methods.
• the processing should preferably not induce corrosion of the injection moulding equipment.
• Plate-out is the outgassing of solid material from the moulding composition and deposition thereof inside the mould. Accumulation of such deposition can block the outgassing openings of the mould. This becomes apparent from burning spots on the moulded parts : through fast injection of the moulding material in the mould, the gas comprised by the mould cannot escape and gets compressed quickly, resulting in heating up of the gas to such high temperatures that the parts can get burned.
• Plate out is different from blooming or staining.
• Blooming is the migration of solid material from the composition to the surface after exposure of a moulded part to hot and humid conditions.
• Staining is the migration of solid material from a composition to the surface upon contacting of a moulded part with a liquid.
• the aim of the present invention is to provide a halogen free flame retardant moulding composition that has a good balance in properties, and has a good plate out performance.
• the moulded parts made of the composition also have a good surface appearance and low tendency for blooming and staining.
• composition according to the invention comprising
• polyamide (A) a semi-crystalline semi-aromatic polyamide (referred to as polyamide (A), or (A)) having a melting temperature (referred to as TmA) and having a number average molecular weight (referred to as Mn-B) in the range between 7,500 and 30,000 g/mol;
• polyamide (B) a semi-crystalline aliphatic polyamide (referred to as polyamide (B), or (B)) having a melting temperature (referred to as TmB); and having a number average molecular weight (referred to as Mn-B) in the range between 7,500 and 50,000 g/mol; and
• a halogen free flame retardant system comprising a metal salt of a phosphinic acid and/or a diphosphinic acid (together referred to as metal (di)phosphinate), wherein
• the TmA is higher than TmB and
• composition according to the invention comprising the above combination of components with the said features is that the composition can be moulded at less severe moulding conditions than corresponding compositions based on a semi-aromatic polyamide only, while still having a good flow at those moulding conditions and resulting in moulded parts with good flame retardancy properties, weld strength and surface appearance, and most importantly reduced plate out, when compared with the corresponding compositions only based on a semi- aromatic polyamide, or when compared with corresponding compositions only based on an aliphatic polyamide composition even though said composition would still not have a comparable flame retardancy level.
• the flow of the semi-aromatic polyamide based composition could be improved by using aliphatic polyamides with lower Mn, which can be used in lower amounts, but this results in loss of flame retardancy properties.
• the flow of the semi-aromatic polyamide based composition could be increased by using higher processing temperatures but this would result in even more extensive plate out.
• Combining an aromatic polyamide and an aliphatic polyamide in a ratio beyond the above range, and/or with number average molecular weights beyond the ranges indicated above for the invention does not solve the problem of plating and/or introduces other problems, such as loss in flame retardancy properties and/or insufficient flow and surface appearance.
• the semi-crystalline semi-aromatic polyamide (A) has a number average molecular weight (Mn-A) of in the range of 10,000 - 25,000 g/mol, more preferably in the range of 12,500 - 20,000 g/mol.
• the semi- crystalline aliphatic polyamide (B) has a number average molecular weight (Mn-B) in the range of 10,000 - 40,000 g/mol, more preferably in the range of 15,000 - 30,000 g/mol.
• Mn-A number average molecular weight of 10,000 - 25,000 g/mol, more preferably in the range of 12,500 - 20,000 g/mol.
• the semi- crystalline aliphatic polyamide (B) has a number average molecular weight (Mn-B) in the range of 10,000 - 40,000 g/mol, more preferably in the range of 15,000 - 30,000 g/mol.
• the number average molecular weight (Mn) as referred to herein is determined by measuring the molecular weight distribution by gel permeation chromatography (GPC), more particular with Size Exclusion Chromatography (SEC) combined with triple detection method.
• GPC gel permeation chromatography
• SEC Size Exclusion Chromatography
• a GPC apparatus is coupled to viscometry, refractive index and light scattering detection (90 degrees).
• the measurements are performed using hexafluoroisopropanol comprising 0.1 wt% potassium trifluoro acetate, relative to the weight of the hexafluoroisopropanol, as solvent, and employing a Size Exclusion Chromatograph equipped with 3 PFG linear XL silica columns;
• the weight average molecular weight is calculated from the measured molecular weight distribution using TriSEC 3.0 software of the company Viscotek.
• the Mn and Mw are expressed in g/mol.
• the triple detection method has the advantage in that this method gives absolute values and does not need an external reference.
• any semi-crystalline semi-aromatic polyamide used for making moulding compositions can be used.
• (A) comprises repeat units derived from terephthalic acid, and optionally another aromatic dicarboxylic acid and/or aliphatic dicarboxylic acid, and aliphatic diamines selected from aliphatic linear or branched diamines comprising 4-12 carbon atoms.
• An aromatic dicarboxylic acid that suitably is combined with terephthalic acid is, for example, isophthalic acid.
• An example of an aliphatic dicarboxylic acid, that can be combined with terephthalic acid, and optionally with the other aromatic dicarboxylic acid, in the semi-crystalline semi-aromatic polyamide (A) is adipic acid.
• the semi-crystalline semi-aromatic polyamide (A) suitably has a high melting temperature.
• Tm-A is at least 270°C, more preferably at least 280°C. Still more preferably Tm-A is in the range of 290-350 °C, or even better at least 300 - 340 °C.
• a higher melting temperature for polyamide (A) results in a product with better retention of mechanical and other properties at high temperature. The product can nevertheless be processed at such process conditions that a good flame retardancy and low plate out is achieved.
• melting temperature is herein understood the melting temperature (Tm) as determined by the method according to ISO-1 1357-3.2, 2009, in an N2 atmosphere with a heating and cooling rate of 10°C/min, from the peak value of the melting peak in the second heating cycle. In case there are multiple melting peaks, the peak value is to be taken from the highest melting peak.
• a semi-crystalline semi-aromatic polyamide with a higher melting temperature can generally be achieved by using a higher content in terephthalic acid and/or shorter chain diamines in the polyamide.
• the person skilled in the art of making polyamide moulding compositions will be capable of making and selecting such polyamides. Suitable examples include PA8T, PA9T, PA10T, PA12T, PA6T/6I, PA6T/66, PA6T/46, and copolyamides thereof.
• the semi-crystalline aliphatic polyamide (B) also suitably has a high melting temperature, though always remaining blow that of (A).
• Tm-B is at least 220 °C.
• Tm-B is in the range of 250-300 °C.
• semi-crystalline aliphatic polyamide (B) also a wide variety of polyamides can be used.
• a polyamide with a high melting point is used such as either polyamide 4,6, polyamide 4,8, polyamide 4,10, or polyamide 6,6 or any mixture or copolymer thereof.
• the weight ratio of (A) : (B) is in the range of 55 : 45 - 72.5 : 27.5.
• the semi-crystalline semi-aromatic polyamide (A) and the semi-crystalline aliphatic polyamide (B) used in the composition according to the invention are at least miscible with each other to a certain extend.
• (A) and (B) have a negative X parameter.
• the formula as used by Ellis is applicable for blends of aliphatic and semi-aromatic polyamides, defined as A x B 1-x /A y B z Ci-y- z , where A X B 1-X represents the aliphatic polyamide and A y B z Ci- y - z represents the aromatic polyamide, and wherein A, B and C represent the methylene, amide, and phenyl repeat units, x, 1 -x, y, z and 1 -y-z represent the relative amounts of these repeat units in the polyamides.
• Suitable salts of (di)phosphinic acids that can be used in the composition according to the present invention are, for example, a phosphinate of the formula (I), a disphosphinate of the formula (II),
• R 1 and R 2 are identical or different or are Ci - C 6 alkyl, linear or branched, and/or aryl;
• R 3 is Ci - Cio-alkylene, linear or branched, C 6 - Ci 0 - arylene, -alkylarylene or -arylalkylene;
• M is one or more of calcium ions, magnesium ions, aluminum ions and zinc ions, m is 2 to 3; n is 1 or 3; x is 1 or 2.
• R 1 and R 2 may be identical or different and are preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, tent- butyl, n-pentyl and/or phenyl.
• R 3 is preferably methylene, ethylene, n-propylene, isopropylene, n-butylene, tert-butylene, n-pentylene, n-octylene, n-dodecylene, or phenylene or naphthylene, or methylphenylene, ethylphenylene, tert-butylphenylene, methylnaphthylene, ethylnaphthylene or tert-butylnaphthylene, or phenylmethylene, phenylethylene, phenylpropylene or phenylbutylene.
• M is preferably aluminum ions or zinc ions.
• the flame retardant system (C) comprises an aluminum
• (di)phosphinate Suitable examples thereof are methylethyl(di)phosphinate and/or aluminum diethyl(di)phosphinate.
• flame retardant system (C) is present in an amount of 1 - 100 parts by weight (pbw) relative to 100 pbw of (A) + (B).
• the amount of (C) is in the range of 5 - 50 parts by weight (pbw) relative to 100 pbw of (A) + (B).
• the flame retardant system (C) is also suitably present in an amount in the range of at least 5 wt.% and/or at most 30 wt.%, more particular at least 5 wt.% and/or at most 25 wt.%.
• the weight percentages (wt.%) are relative to the total weight of the flame retardant polyamide composition.
• the amount of the metal (di)phosphinate comprised by the flame retardant polyamide composition is preferably in the range of 5 -25 wt.%, more preferably 7.5 - 20 wt.%, relative to the total weight of the composition.
• the composition may comprise one or more other flame retardants than the metal (di)phosphinates, and/or one or more flame retardant synergists.
• Flame retardant synergists generally used in combination with metal (di)phosphinate flame retardants include metal borates, such as Znborate and BaBorate.
• the composition comprises at most 1 wt.%, more preferably at most 0.5 wt.%, and even better 0 - 0.1 wt.% ZnBorate.
• the advantage of a lower content or even absence of ZnBorate is that the staining of the composition is improved, compared to the corresponding composition comprising a higher ZnBorate content.
• the polyamide composition of the present invention may optionally comprise further components, such as inorganic fillers, fibrous reinforcing agents, other polymers, as well as additives selected from, for example, acid scavengers, impact modifiers, plasticizers, stabilizers (such as, for example, thermal stabilizers, oxidative stabilizers, UV light stabilizers and chemical stabilizers), processing aids (such as, for example, mould release agents and nucleating agents), solid lubricants, colorants (such as carbon black, other pigments, dyes), nanoclays, etc.
• An impact modifier is advantageously included to further improve impact resistance for e.g. housings for electronic devices.
• inorganic reinforcing agents and/or fillers examples include one or more of glass fibres, which may be flat glass fibres, glass flakes, kaolin, clay, talc, mica, wollastonite, calcium carbonate, silica, carbon fibres, potassium titanate, etc. Glass fibres and carbon fibres are preferred.
• the inorganic reinforcing agent and/or filler used in the present invention if used at all, is suitably present in amount from, for example, about 5 wt.% up to about 60 wt.%, based on the total weight of the composition.
• the flame retardant polyamide composition comprises 5 - 25 wt.% of flame retardant (C), and 5 - 60 wt.% of glass or carbon fibre reinforcement, wherein the wt.% are relative to the total weight of the composition.
• the total amount of fibrous reinforcing agents and fillers in the composition is in the range of 45-60 wt.%, for example about 50 wt.% or about 55 wt.%.
• Such a high amount is preferred in case a high stiffness is required, such as for example, for use in housings for electronic devices such as for notebooks, mobile phones and PC tablets.
• the amount of the inorganic reinforcing agents and/or fillers is suitably up to about 45 wt.%, or more preferably up to about 40 wt.%, based on the total weight of the composition.
• the flame retardant polyamide composition consists of
• the flame retardant polyamide composition consists of
• weight percentages are relative to the total weight of the composition, and the sum of (A)-(E) is 100 %.
• compositions according to the invention can be prepared by a process, wherein the semi-aromatic polyamide, the aliphatic polyamide, the flame retardant system and optional additional ingredients are melt-blended. Part of the materials may be mixed in a melt-mixer, and the rest of the materials may then be added and further melt-mixed until uniform. Melt-blending may be carried out using any appropriate method known to those skilled in the art. Suitable methods may include using a single or twin-screw extruder, blender, kneader, Banbury mixer, moulding machine, etc. Twin-screw extrusion is preferred, particularly when the process is used to prepare compositions that contain additives such as flame retardants, and reinforcing agents.
• compositions of the present invention have a high melt flow and may be conveniently formed into a variety of articles using injection moulding, rotomoulding and other melt-processing techniques.
• the articles are useful in SMT applications among others and include connectors, such as memory cards, (CPU) sockets, I/O, FPC, motherboard and automotive connectors, and housings and stiffener frames for electronic devices, for example housings and stiffener frames for notebooks, mobile phones, stiffeners and PC tablets.
• the invention also relates to a process for the production of moulded parts from the flame retardant polyamide composition according to the invention, or any embodiment thereof, as described above, by injection moulding, comprising a step wherein the composition is heated in an injection moulding machine to form a polymer melt.
• the melt is heated to a temperature of at most 10°C above TmA, i.e. above the melting temperature of the semi-crystalline semi-aromatic polyamide comprised by the composition.
• TmA i.e. above the melting temperature of the semi-crystalline semi-aromatic polyamide comprised by the composition.
• the polymer melt is injected into a mould with a mould temperature of at least 100°C.
• the temperature of the mould is in the range of 1 10 - 150°C.
• a mould temperature of 100°C and higher has the advantage that the resulting product has an improved gloss.
• the invention also relates to an article or moulded product made from a composition according to the present invention, or any specific embodiment thereof.
• the article is a plastic part of a connector or a housing or stiffener frame for an electronic device.
• PA-46 PA-46 based aliphatic polyamide according to the invention with a melting temperature of 290°C
• PA-66 PA-66 based aliphatic polyamide according to the invention with a melting temperature of 260°C
• Flame retardant polyamide compositions were prepared on a twin screw extruder.
• the temperature of the extruded melt was typically about 340 °C, so well above 325 °C.
• the melt temperature was about 310 °C. After the melt compounding the resulting melt was extruded into strands, cooled an cut into granules.
• the flame retardant polyamide compositions were injection moulded into appropriate test moulds using a standard injection moulding machine.
• the settings were such that the melts of the compositions reached a temperature of about 310 °C.
• Comparative Experiments A, B and D the settings were such that the melts of the compositions reached a temperature of about 340 °C.
• Comparative Experiments A, B and D could not be processed in a proper manner with a melt temperature much lower than 340 °C, and certainly not below 325 °C.
• the Examples l-lll and Comparative Experiments C could be processed with a melt temperature above 325 °C, but when processed at the conditions used for Comparative Experiments A, B and D this resulted in deteriorated products with bad properties.

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Manufacturing & Machinery (AREA)
• Mechanical Engineering (AREA)
• Materials Engineering (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Injection Moulding Of Plastics Or The Like (AREA)

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• 2012
  • 2012-07-24 JP JP2014522057A patent/JP6387569B2/ja active Active
  • 2012-07-24 CN CN201280037537.4A patent/CN103717676B/zh active Active
  • 2012-07-24 KR KR1020147004196A patent/KR101908167B1/ko active Active
  • 2012-07-24 US US14/234,288 patent/US20150361263A1/en not_active Abandoned
  • 2012-07-24 EP EP12738134.1A patent/EP2736975B1/en not_active Revoked
  • 2012-07-24 WO PCT/EP2012/064467 patent/WO2013014144A1/en not_active Ceased
• 2017
  • 2017-12-28 US US15/857,194 patent/US11015054B2/en active Active

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