EP3652254A1 - Compositions de polyamide ignifuges de couleur noire et leur utilisation - Google Patents

Compositions de polyamide ignifuges de couleur noire et leur utilisation

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Publication number
EP3652254A1
EP3652254A1 EP18739830.0A EP18739830A EP3652254A1 EP 3652254 A1 EP3652254 A1 EP 3652254A1 EP 18739830 A EP18739830 A EP 18739830A EP 3652254 A1 EP3652254 A1 EP 3652254A1
Authority
EP
European Patent Office
Prior art keywords
component
flame
polyamide compositions
proportion
compositions according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP18739830.0A
Other languages
German (de)
English (en)
Inventor
Harald Bauer
Sebastian HÖROLD
Martin Sicken
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Clariant International Ltd
Original Assignee
Clariant Plastics and Coatings Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Clariant Plastics and Coatings Ltd filed Critical Clariant Plastics and Coatings Ltd
Publication of EP3652254A1 publication Critical patent/EP3652254A1/fr
Pending legal-status Critical Current

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    • 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
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0066—Flame-proofing or flame-retarding additives
    • 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
    • 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
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
    • 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
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/10—Reinforcing macromolecular compounds with loose or coherent fibrous material characterised by the additives used in the polymer mixture
    • 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
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
    • C08K5/3462—Six-membered rings
    • C08K5/3465—Six-membered rings condensed with carbocyclic rings
    • C—CHEMISTRY; METALLURGY
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    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C—CHEMISTRY; METALLURGY
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    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C08K5/34922—Melamine; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
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    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C08K5/34928—Salts
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    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C—CHEMISTRY; METALLURGY
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    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • 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
    • 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
    • C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
    • 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
    • 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
    • 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
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C08K2003/327—Aluminium phosphate
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general
    • 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
    • C08L2203/00—Applications
    • C08L2203/12—Applications used for fibers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • 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

Definitions

  • the present invention relates to flame retardant polyamide compositions and moldings produced therefrom.
  • Flammable plastics generally have to be equipped with flame retardants in order to achieve the high flame retardance requirements demanded by plastics processors and in part by the legislation. Preference also for ecological reasons - are non-halogenated
  • phosphinates the salts of phosphinic acids (phosphinates) have proven to be particularly effective for thermoplastic polymers (DE 2 252 258 A and DE 2 447 727 A).
  • synergistic combinations of phosphinates with certain nitrogen-containing compounds are known which act more effectively in a whole series of polymers as flame retardants than the phosphinates alone (WO-2002/28953 A1 and DE 197 34 437 A1 and DE 197 37 727 A1).
  • dialkylphosphinates containing a small amount of selected telomers are suitable as flame retardants for polymers, the polymer only undergoing very little degradation upon incorporation of the flame retardant into the polymer matrix. Flame retardants must often be added in high dosages in order to ensure a sufficient flame retardancy of the plastic according to international standards. Due to their chemical reactivity, which for the
  • Flame retardancy at high temperatures is required Flame retardants, especially at higher dosages, affect the processing stability of plastics. It can lead to increased polymer degradation, crosslinking reactions, outgassing or discoloration. From WO 2014/135256 A1 polyamide molding compositions are known which have a significantly improved thermal stability, a reduced tendency to migrate and a good electrical and mechanical properties.
  • thermoplastic molding compositions which contain a gray or black colorant in addition to a gray or black colored fibrous filler.
  • thermoplastics also polyamides can be used.
  • Polyamide compositions that achieve all the required properties at the same time, such as good electrical values (CTI, GWFI), a deep black color (color) and an effective flame retardancy, characterized by the shortest possible afterburning times (UL-94, time).
  • good electrical values CTI, GWFI
  • color color
  • effective flame retardancy characterized by the shortest possible afterburning times (UL-94, time).
  • the invention relates to flame-retardant polyamide compositions containing
  • Polyamide having a melting point of less than or equal to 290 ° C, preferably of less than or equal to 280 ° C and most preferably of less than or equal to 250 ° C, as component A,
  • R 1 and R 2 are ethyl
  • M is Al, Fe, TiOp or Zn
  • n 2 to 3, preferably 2 or 3
  • R 3 is ethyl
  • Met is Al, Fe, TiOq or Zn
  • n 2 to 3, preferably 2 or 3
  • the proportion of component A is usually 25 to 95 wt .-%, preferably 25 to 75 wt .-%. In the polyamide composition according to the invention, the proportion of
  • Component B usually 1 to 45 wt .-%, preferably 20 to 40 wt .-%.
  • the proportion of component C is usually 1 to 35 wt .-%, preferably 5 to 20 wt .-%.
  • the proportion of component D is usually 0.01 to 3 wt .-%, preferably 0.05 to
  • the proportion of component E is usually 0.001 to 1 wt .-%, preferably 0.01 to
  • the proportion of component F is usually 1 to 25 wt .-%, preferably 2 to 10 wt .-%.
  • the proportion of component G is usually from 0.01 to 20% by weight, preferably from 0.01 to
  • the proportion of component B is from 1 to 45% by weight
  • the proportion of component E is 0.001 to 1% by weight
  • component G is 0.01 to 20 wt .-%, wherein the
  • Percentages are based on the total amount of
  • the proportion of component A is from 25 to 75% by weight
  • the proportion of component B is from 20 to 40% by weight
  • the proportion of component E is from 0.01 to 0.6% by weight
  • the proportion of component G is from 0.1 to 8% by weight
  • Percentages are based on the total amount of
  • Preferred salts of component C are those in which M m + Zn 2+ , Fe 3+ or in particular Al 3+ .
  • Preferred salts of component D are zinc, iron or in particular aluminum salts.
  • Preferably used salts of component E are those in which Met n + Zn 2+ , Fe 3+ or in particular Al 3+ .
  • the above-described flame-retardant polyamide compositions contain inorganic phosphonate as further component H.
  • inorganic phosphonates used according to the invention or also salts of phosphorous acid
  • the inorganic phosphonate (component H) preferably corresponds to the general formulas (IV) or (V) [(HO) PO 2 ] 2 -p / 2 cat P + (IV)
  • Kat is a p-valent cation, in particular a cation of an alkali metal, alkaline earth metal, an ammonium cation and / or a cation of Fe, Zn or particular AI including the cation AI ( OH) or Al (OH) 2, and p is 1, 2, 3 or 4.
  • the inorganic phosphonate (component H) is preferably also aluminum phosphites of the formulas (VI), (VII) and / or (VIII)
  • Aluminum phosphite tetrahydrate [Al 2 (HPO 3) 3 * 4aq] to give aluminum phosphonate to Al7 (HPO 3) 9 (OH) 6 (1,6-hexanediamine) i, 5 * 12H 2 O, by ⁇ 2 ( ⁇ 3 ) 3 * ⁇ 2 ⁇ 3 * ⁇ 2 ⁇ with x 2.27 - 1 and / or AUHePieOis.
  • Preferred inorganic phosphonates are water-insoluble or sparingly soluble salts.
  • Particularly preferred inorganic phosphonates are aluminum, calcium and zinc salts.
  • component H is a
  • Reaction product of phosphorous acid and an aluminum compound is Reaction product of phosphorous acid and an aluminum compound.
  • Particularly preferred components H are aluminum phosphites with the
  • the preparation of the preferably used aluminum phosphites is carried out by reacting an aluminum source with a phosphorus source and optionally a template in a solvent at 20-200 ° C for a period of up to 4 days.
  • the aluminum source and the phosphorus source are mixed for 1 to 4 hours, heated under hydrothermal conditions or at reflux, filtered off, washed and z. B. at 1 10 ° C dried.
  • Preferred aluminum sources are aluminum isopropoxide, aluminum nitrate, aluminum chloride, aluminum hydroxide (eg pseudoboehmite).
  • Preferred sources of phosphorus are phosphorous acid, (acidic)
  • Preferred Alkaliphosphite are disodium phosphite, Dinatriumphosphithydrat, trisodium phosphite, Kaliumhydrogenphosphit Preferred Dinatriumphosphithydrat is Brüggolen ® H10 Fa. Brüggemann.
  • Preferred templates are 1, 6-hexanediamine, guanidine carbonate or ammonia.
  • Preferred alkaline earth metal phosphite is calcium phosphite.
  • the preferred ratio of aluminum to phosphorus to solvent is thereby 1: 1: 3.7 to 1: 2.2: 100 mol.
  • the ratio of aluminum to template is 1: 0 to 1: 17 mol.
  • the preferred pH of the reaction solution is 3 to 9.
  • Preferred solvent is water.
  • the same salt of phosphinic acid as the phosphorous acid is used in the application, so z.
  • aluminum diethylphosphinate together with aluminum phosphite or Zinkdiethylphosphinat together with zinc phosphite is used in the application, so z.
  • the above-described flame retardant polyester compositions contain, as component H, a compound of the formula (III)
  • Me is Fe, TiOr, Zn or in particular Al,
  • o is 2 to 3, preferably 2 or 3
  • Preferred compounds of the formula III are those in which Me 'is Fe 3+ or in particular Al 3+ .
  • Component H is preferably in an amount of 0.005 to 10 wt .-%, in particular in an amount of 0.02 to 5 wt .-%, based on the
  • Polyannide compositions achieve a rating of V0 according to UL-94, especially measured on moldings of 3.2 mm to 0.4 mm thickness.
  • Polyamide compositions have a Glow Wire Flammability Index according to IEC-60695-2-12 of at least 960 ° C, in particular measured
  • the polyamide compositions of the invention contain as component A one or more polyamides having a melting point of less than or equal to 290 ° C.
  • the melting point is determined by means of differential scanning caloimetry (DSC) at a heating rate of 10 K / second.
  • the polyamides of component A are usually around
  • aliphatic to homo- or copolyamides derived from (cyclo) aliphatic dicarboxylic acids or their polyamide-forming derivatives, such as their salts, and of (cyclo) aliphatic diamines or of (cyclo) aliphatic amino carboxylic acids or their polyamide-forming derivatives, such as their salts , deduce.
  • the polyamides used as component A according to the invention are thermoplastic polyamides.
  • thermoplastic polyamides are based on Hans
  • polyamides used according to the invention as component A can be prepared by various processes and from very different building blocks be synthesized and in particular application alone or in combination with processing aids, stabilizers or polymers
  • Alloy partners preferably elastomers, to materials equipped with specially selected property combinations. are also suitable
  • Monomerbausteine various chain regulators for setting a desired molecular weight or monomers with reactive groups for later intended post-treatments can be used.
  • Polyamides to be preferably used as component A are partially crystalline aliphatic polyamides starting from aliphatic diamines and
  • aliphatic dicarboxylic acids and / or cycloaliphatic lactams with at least 5 ring members or corresponding amino acids can be prepared.
  • Suitable starting materials are aliphatic dicarboxylic acids, preferably adipic acid, 2,2,4- and 2,4,4-trimethyladipic acid, azelaic acid and / or sebacic acid, aliphatic diamines, preferably tetramethylenediamine, hexamethylenediamine, 1, 9-nonanediamine, 2,2,4- and 2,4,4-trimethylhexamethylenediamine, the isomeric diaminodicyclohexylmethanes, diaminodicyclohexylpropanes, bisaminomethylcyclohexane,
  • Aminocarboxylic acids preferably aminocaproic acid or the corresponding Lactams are considered.
  • Copolyamides of several of the monomers mentioned are included. Particularly preferred are caprolactams, most preferably ⁇ -caprolactam is used.
  • the aliphatic homo- or copolyamides used according to the invention are preferably polyamide 12, polyamide 4, polyamide 4.6, polyamide 6, polyamide 6.6, polyamide 6.9, polyamide 6.10, polyamide 6.12, polyamide 6.66, polyamide 7.7, polyamide 8.8, polyamide 9.9, polyamide 10.9, polyamide 10/10, polyamide 1 1 or nylon 12. These are, for example under the trade name nylon ®, Fa. DuPont, Ultramid ®, Fa. BASF, Akulon ® K122, Fa. DSM, Zytel ® 7301,
  • PA6 PA6.6
  • other aliphatic homo- or copolyamide-based compounds in which a
  • Polyamide group in the polymer chain 3 to 1 1 come methylene groups.
  • Flame-retardant polyamide compositions in which one or more polyamides is selected as component A from the group consisting of PA 6, PA 6.6, PA 4.6, PA 12, PA 6.10 are preferably used.
  • Flame-retardant polyamide compositions in which polyamide 6.6 or polymer blends of polyamide 6.6 and polyamide 6 are used as component A are particularly preferred. Very particular preference is given to flame retardants
  • fillers and / or preferably reinforcing materials are used, preferably glass fibers. It is also possible to use mixtures of two or more different fillers and / or reinforcing materials.
  • Preferred fillers are mineral particulate fillers based on talc, mica, silicate, quartz, titanium dioxide, wollastonite, kaolin, amorphous silicas, nanoscale minerals, particularly preferably montmorillonites or nano-boehmites, magnesium carbonate, chalk, feldspar, glass beads and / or barium sulfate. Particular preference is given to mineral particulate fillers based on talc, wollastonite and / or kaolin.
  • needle-shaped mineral fillers are also particularly preferably used. Under needle-shaped mineral fillers is understood according to the invention a mineral filler with pronounced needle-like character. Preferred are needle-shaped wollastonites.
  • the mineral has a length to diameter ratio of 2: 1 to 35: 1, more preferably from 3: 1 to 19: 1, particularly preferably from 4: 1 to 12: 1.
  • the average particle size of the acicular mineral fillers used according to the invention as component B is preferably less than 20 ⁇ m, more preferably less than 15 ⁇ m, particularly preferably less than 10 ⁇ m, determined using a CILAS granulometer.
  • the components B preferably used according to the invention are reinforcing materials. This may, for example, to
  • Reinforcement based on carbon fibers and / or glass fibers act.
  • the filler and / or reinforcing material may in a preferred
  • Be surface-modified embodiment preferably with a
  • Adhesive or a primer system particularly preferably on
  • Silane In particular when glass fibers are used, in addition to silanes, polymer dispersions, film formers, branching agents and / or
  • Fiber processing aids are used.
  • the glass fibers preferably used according to the invention as component B may be short glass fibers and / or long glass fibers. As a short or long glass fibers, cut fibers can be used. Short glass fibers can also be used in the form of ground glass fibers.
  • glass fibers can also be used in the form of continuous fibers, for example in the form of rovings, monofilaments,
  • Filament yarns or twines or glass fibers can be used in the form of textile fabrics, for example as glass fabrics, as
  • Glass braid or as a glass mat Glass braid or as a glass mat.
  • Polyamide matrix range from 0.05 to 10 mm, preferably from 0.1 to 5 mm. After incorporation into the polyamide matrix, the length of the glass fibers has decreased. Typical fiber lengths for short glass fibers after the
  • Incorporation into the polyamide matrix ranges from 0.01 to 2 mm, preferably from 0.02 to 1 mm.
  • the diameters of the individual fibers can vary within wide ranges. Typical diameters of the individual fibers range from 5 to 20 ⁇ m.
  • the glass fibers can have any cross-sectional shapes, for example round, elliptical, n-cornered or irregular cross-sections. Glass fibers with mono- or multilobal cross-sections can be used.
  • Glass fibers can be used as continuous fibers or as cut or ground glass fibers.
  • the glass fibers themselves can be selected, for example, from the group of E-glass fibers, A-glass fibers, C-glass fibers, D-glass fibers, M-glass fibers, S-glass fibers,
  • the glass fibers are preferably provided with a size which preferably contains polyurethane as film former and aminosilane as adhesion promoter.
  • Particularly preferably used E glass fibers have the following chemical composition: S1O2 50-56%; AI2O3 12-16%; CaO 16-25%; MgO ⁇ 6%; B2O3 6-13%; F ⁇ 0.7%; Na 2 O 0.3-2%; K2O 0.2-0.5%; Fe 2 Os 0.3%.
  • R glass fibers have the following chemical composition: S1O2 50-65%; AI2O3 20-30%; CaO 6-16%; MgO 5-20%; Na 2 O 0.3-0.5%; K2O 0.05-0.2%; Fe 2 Os 0.2-0.4%, T1O2 0.1-0.3%.
  • Particularly preferably used ECR glass fibers have the following chemical composition: S1O2 57.5-58.5%; AI2O3 17.5-19.0%; CaO 11, 5-13.0%; MgO 9.5-1 1, 5.
  • the salts of diethylphosphinic acid used according to the invention as component C are known flame retardants for polymeric molding compositions.
  • Salts of diethylphosphinic acid with fractions of the phosphinic and phosphonic acid salts used according to the invention as components D and E are known flame retardants.
  • the preparation of this combination of substances is z. B. in US 7,420,007 B2 described.
  • Component C may contain small amounts of salts of component D and salts of component E, for example up to 10 wt .-% of
  • Component D preferably 0.01 to 6% by weight, and in particular 0.2 to 2.5% by weight thereof, and up to 10% by weight of component E, preferably 0.01 to 6% by weight, and in particular from 0.2 to 2.5% by weight thereof, based on the amount of components C, D and E.
  • component E preferably 0.01 to 6% by weight, and in particular 0.2 to 2.5% by weight thereof, and up to 10% by weight of component E, preferably 0.01 to 6% by weight, and in particular from 0.2 to 2.5% by weight thereof, based on the amount of components C, D and E.
  • Ethylphosphonic acid are as additives to diethylphosphinates in
  • Flame retardants for polymeric molding compositions also known, for example from WO 2016/065971 A1.
  • the use of the polyphosphate derivatives of melamine according to the invention as component F with a degree of condensation of greater than or equal to 20 as flame retardants is also known.
  • DE 10 2005 016 195 A1 discloses a stabilized flame retardant containing 99 to 1% by weight.
  • Phosphinic acid and / or a phosphinic acid salt can be combined.
  • Preferred flame retardant polyamide compositions according to the invention contain, as component F, a melamine polyphosphate whose average degree of condensation is from 20 to 200, in particular from 40 to 150.
  • the average is
  • Polyamide compositions contain as component F a
  • Melaminpolyphosphat having a decomposition temperature greater than or equal to 320 ° C, in particular greater than or equal to 360 ° C and most preferably greater than or equal to 400 ° C.
  • component F preference is given to using melamine polyphosphates which are known from WO 2006/027340 A1 (corresponding to EP 1 789 475 B1) and WO 2000/002869 A1 (corresponding to EP 1 095 030 B1).
  • melamine polyphosphates whose mean condensation ridge (number average) is> 20, whose decomposition temperature is greater than 320 ° C, the molar ratio of 1, 3,5-triazine compound to phosphorus less than 1, 1, in particular 0.8 to 1, 0 and their pH of a 10% slurry in water at 25 ° C 5 or higher, preferably 5.1 to 6.9.
  • components C, D, E and F are in particulate form, the average particle size (dso) being 1 to 100 ⁇ m.
  • the polyamide compositions according to the invention contain one or more black colorants.
  • a colorant is generally understood to mean all colorants according to DIN ISO 18451, which can be classified into inorganic and organic colorants as well as natural and synthetic (see Rompps Chemie Lexikon, 1981, 8th edition, page 1237).
  • Dyes and pigments which are preferably used as component G include carbon black, graphite, graphene, nigrosines, bone charcoal, black color pigments or combinations of complementary red to yellow pigments with green, blue or violet pigments or mixtures of one or more of these compounds.
  • the carbon blacks suitable as component G include in particular carbon blacks having a pore volume (DBP dibutyl phthalate adsorption) according to DIN ISO 18451 of at least 30 ml / 100 g, preferably of at least 50 ml / 100 g.
  • Further carbon blacks used as component G preferably have a BET specific surface area (according to ISO 4652) of at least 20 to 1000 m 2 / g, preferably from 30 to 300 m 2 / g. Further carbon blacks preferably used as component G have an average primary particle size of from 5 to 50 nm, in particular from 10 to 35 nm.
  • Such carbon black types are z. B. under the trademarks Printex XE2 ® (Evonik GmbH) or Ketjenblack ® EC 600JD (Akzo) available as well as the Furnace carbon blacks such as Printex ® 90, 75, 80, 85, 95 and 60-A.
  • graphite can also be used as component G. This can be crushed by grinding.
  • the particle size is usually in the range of 0.01 ⁇ to 1 mm, preferably in the range of 1 to 250 ⁇ .
  • Graphites are very soft (Mohs hardness 1) and have a greyish to black intrinsic color.
  • black agents suitable as component G are graphenes.
  • Commercially available graphenes are e.g. B. the Vor-x ® products (Vorbeck
  • the thickness of graphenes is usually from 1 to 5 nm, the diameter from 20 to 1000 nm and the BET specific surface area from 500 to 1000 m 2 / g (N 2 ).
  • Black agents preferably used as component G are nigrosines. This is generally understood to mean a group of black or gray indulene-related phenazine dyes (azine dyes) in various embodiments. Nigrosines can be water-soluble, fat-soluble or sparingly soluble. Technically, nigrosine is obtained by heating nitrobenzene, aniline and hydrochloric aniline with metallic iron and FeC.
  • Nigrosine can be used as a free base or as a salt (for example as a hydrochloride).
  • Bone coal can be prepared by heating degreased bone meal under exclusion of air to about 700 ° C. From a mixture of
  • Bone charcoal and sugar or syrup is produced by charring with concentrated sulfuric acid the so-called bone black or Cologne black.
  • Finely ground Bone charcoal is suitable for coloring thermoplastic molding compounds. It is also possible to use modified bone carbon as component G. Are z. If, for example, mineral components are dissolved out of the bone char with the help of hydrochloric acid, a blacker bone charcoal remains, which is mixed with a little bit of Berlin blue and is available as black or Parisian black.
  • Suitable colorants which can be used as component G are generally classified according to the Color Index (C.I.), in which case, in addition to systematic or trivial names, C.I. Designation is added.
  • C.I. Color Index
  • Black color pigments which can be used according to the invention as component G, z.
  • Example iron oxide black (Fe3O4), spinel black (Cu, (Cr, Fe) 2O4), manganese black (mixture of manganese dioxide, silica and
  • Iron oxide cobalt black or antimony black.
  • red to yellow pigments with correspondingly complementary green, blue or violet pigments or mixtures thereof are used, in order to obtain a black color of the polyamide composition, as desired.
  • Preferred pigments are copper phthalocyanine pigments which have a green or blue color.
  • the green color is generally achieved by substitution of hydrogen by chlorine atoms on macrocyclic tetraamine.
  • pigments are manganese violet pigments (pyrophosphates of ammonium and manganese (III) of the formula MnNH 4 P 2 O 7, which give bluer or redder tones by varying the stoichiometric composition), Ultramarine pigments (sodium, aluminum silicates), blue and green pigments based on z.
  • manganese violet pigments pyrophosphates of ammonium and manganese (III) of the formula MnNH 4 P 2 O 7, which give bluer or redder tones by varying the stoichiometric composition
  • Ultramarine pigments sodium, aluminum silicates
  • blue and green pigments based on z.
  • chromium oxides or cobalt oxides with spinel structure are -blue under the trade names Heliogen ®, Heliogen ® -Green,
  • Sicopal ® -Green, Sicopal ® -Blue (BASF SE brands) as well as ultramarine, chromium or manganese violet pigments are commercially available.
  • Preferred pigments are in accordance with CI Part 1 Pigment blue 15, Pigment blue 15: 2, Pigment blue 15: 4, Pigment blue 16, Pigment blue 28, Pigment blue 29, Pigment blue 36, Pigment green 17, Pigment green 24, Pigment green 50 , Pigment violet 15 and pigment violet 16, wherein pigment blue 15: 1 and 15: 3 and pigment green 7 and 36 are particularly preferred.
  • component G Preferably used as component G are black pigments or dyes which are selected from the group of carbon black, graphite, graphene, nigrosines, bone charcoal, black color pigments or combinations
  • the polyamide compositions according to the invention preferably have a black coloration, which is characterized by the numbers 9004, 9005, 901 1, 9017 and 9021 of the RAL color table, in particular by RAL 9005 ("jet black").
  • the polyamide compositions according to the invention may contain further additives as component I.
  • Preferred components I for the purposes of the present invention are antioxidants, UV stabilizers,
  • Gamma ray stabilizers for antioxidants, antistatic agents, emulsifiers, nucleating agents, plasticizers, processing aids, impact modifiers, of component G
  • Preferred metals for this purpose are the elements of FIG. 2.
  • Main group the 3rd main group, the 2nd subgroup, the 4th subgroup and the subgroup Villa of the Periodic Table and cerium and / or lanthanum.
  • Melamine poly (metal phosphates) are preferably melamine poly (zinc phosphates), melamine poly (magnesium phosphates) and / or melamine poly (calcium phosphates).
  • melamine poly metal phosphates
  • melamine-intercalated aluminum, zinc or magnesium salts of condensed phosphates are also preferred.
  • Bis-melamine-zinc diphosphate and / or bis-melamine alumotriphosphate Bis-melamine-zinc diphosphate and / or bis-melamine alumotriphosphate.
  • Subgroup Villa of the Periodic Table and of cerium and / or lanthanum with anions of the oxo acids of the fifth main group (phosphates, pyrophosphates and polyphosphates).
  • Aluminum phosphates Preference is given to aluminum phosphates, aluminum monophosphates; Aluminum orthophosphates (AIPO4), aluminum hydrogen phosphate (Al2 (HPO4) 3) and / or aluminum dihydrogen phosphate
  • calcium phosphate, zinc phosphate, titanium phosphate and / or iron phosphate Preference is given to calcium hydrogen phosphate, calcium hydrogen phosphate dihydrate, magnesium hydrogen phosphate, titanium hydrogen phosphate (TIHC) and / or zinc hydrogen phosphate
  • Calcium dihydrogen pyrophosphate, magnesium pyrophosphate zinc pyrophosphate and / or aluminum pyrophosphate are examples of magnesium pyrophosphate and / or aluminum pyrophosphate.
  • the quantitative ratio of the components C is preferably
  • the further additives are known per se as additives to polyamide compositions and can be used alone or mixed or in the form of masterbatches.
  • the abovementioned components A, B, C, D, E, F, G and, if appropriate, H and / or I can be processed in a wide variety of combinations with the flameproofed polyamide composition according to the invention. It is thus possible to mix the components into the polyamide melt at the beginning or at the end of the polycondensation or in a subsequent compounding process. Furthermore, there are processing processes in which individual
  • Drying process possibly warm up warm polymer granules.
  • two or more of the components of the polyamide compositions of the present invention may be combined by mixing prior to incorporation into the polyamide matrix.
  • conventional mixing units can be used, in which the components in a suitable mixer, for. B. 0.01 to 10 hours at 0 to 300 ° C mixed.
  • Polyamide compositions can also be prepared granules, which can then be introduced into the polyamide matrix.
  • Polyamide composition with granulation and / or binder in a suitable mixer or a granulating are processed into granules.
  • the initially formed crude product can be dried in a suitable dryer or tempered for further grain buildup.
  • the polyamide composition according to the invention or two or more components thereof may be prepared in one embodiment by roll compaction.
  • the polyamide composition according to the invention or two or more components thereof may in one embodiment be prepared by mixing, extruding, chopping (or breaking) the ingredients.
  • the polyamide composition of the present invention or two or more components thereof may be prepared by spray granulation in one embodiment.
  • the flame-retardant polymer molding composition according to the invention is preferably in granular form, for. B. as an extrudate or as a compound before.
  • the granules preferably have a cylindrical shape with a circular, elliptical or irregular base, spherical shape, pillow shape, cube shape, cuboid shape, prism shape.
  • Typical length to diameter ratio of the granules are 1 to 50 to 50 to 1, preferably 1 to 5 to 5 to 1.
  • the granules preferably have a diameter of 0.5 to 15 mm, more preferably of 2 to 3 mm and preferably a length of 0.5 to 15 mm, particularly preferably 2 to 5 mm.
  • the invention also relates to moldings produced from the above-described flame-retardant polyamide composition containing the components A, B, C, D, E, F and G and optionally the components H and / or I.
  • the molded parts according to the invention may be any desired formations.
  • Examples are fibers, films or moldings, available from the Flame-retardant Polyamidformnnassen invention by any molding process, in particular by injection molding or extrusion.
  • the preparation of the inventive flame-retardant polyamide molded body can be carried out by any molding process. Examples include injection molding, pressing, foam injection, gas injection molding, blow molding,
  • the molded parts are preferably injection-molded parts or extruded parts.
  • the flame-retardant polyamide compositions according to the invention are suitable for the production of fibers, films and moldings, in particular for applications in the electrical and electronics sector.
  • the invention preferably relates to the use of the flame-retardant polyamide compositions according to the invention in or for connectors, current-carrying parts in power distributors (Fl protection), circuit boards, potting compounds, power connectors, circuit breakers, lamp housings, LED housings,
  • the invention likewise preferably relates to the use of the flame-retardant polyamide compositions according to the invention for the production of
  • the wall thickness of the shaped bodies according to the invention can typically be up to 10 mm. Particularly suitable are moldings with less than 1.5 mm wall thickness, more preferably less than 1 mm wall thickness and particularly preferably less than 0.5 mm wall thickness.
  • Polyamide 6.6 (PA 6.6-GV; melting range of 255-260 ° C): Ultramid ® A27 (BASF)
  • Polyamide 6 (melting range of 217-222 ° C): Durethan ® B29 (Lanxess) polyamide 6T / 6,6 (melting range 310-320 ° C): Vestamid ® HT plus 1000 (Evonik)
  • Nigrosine Cl Solvent black 7 (Nigrosine BAP, Lanxess, Leverkusen, Germany)
  • the flame retardant components were mixed in the proportions shown in the tables with the colorant and the side feeder of a twin-screw extruder (Leistritz ZSE 27 / 44D) at temperatures of 260 to 310 ° C in PA 6.6 or at 250 to 275 ° C in PA 6 or at 310 to 330 ° C PA 6T / 6.6 incorporated.
  • the glass fibers were added via a second side feed. The homogenized polymer strand was stripped off, cooled in a water bath and then granulated.
  • Injection molding machine type Arburg 320 C Allrounder
  • mass temperatures 250 to 320 ° C to test specimens processed and based on the UL 94 test
  • the Glow Wire Flammability Index (GWIT Index) was standardized
  • the polyamide compositions of Examples 1A to 5C according to the invention are molding compounds which achieve the UL 94 V-0 fire rating at 0.4 mm, CTI 600 volts and GWFI 960 ° C. simultaneously, and deep black
  • Comparative Examples V3a and V3B resulted in a marked reddish color in the moldings.
  • the polyamide compositions according to the invention of Examples 6A to 10B are molding compositions which reach the fire classification UL 94 V-0 at 0.4 mm, while having CTI 600 volts and GWFI 960 ° C, and deep black
  • Comparative Examples V8a and V8B resulted in a distinct reddish in the color of the moldings.
  • G G1 2 2 2 2 2 2 2 2 2
  • Test specimens could not be produced from any of the PA molding compositions of Comparative Examples V1 1 -V18 since the PA molding compositions proved to be unprocessable.
  • the polyamide strands foamed during production and no test specimens suitable for the measurements could be produced.
  • antimony trioxide can be adjusted V-0, but no deep black color.

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Abstract

La présente invention concerne des compositions de polyamide ignifuges contenant du polyamide ayant un point de fusion inférieur ou égal à 290 °C en tant que constituant A, des substances de charge et/ou des substances de renfort en tant que constituant B ; un sel d'acide phosphinique de formule (I) en tant que constituant C, où R1 et R2 sont éthyle, M est Al, Fe, TiOp ou Zn, m vaut de 2 à < 4, et p = (4 - m) / 2 ; un composé choisi dans le groupe des sels d'Al, de Fe, de TiOp ou de Zn de l'acide éthylbutylphosphinique, de l'acide dibutylphosphinique, de l'acide éthylhexylphosphinique, de l'acide butylhexylphosphinique et/ou de l'acide dihexylphosphinique en tant que constituant D ; un sel d'acide phosphinique de formule II en tant que constituant E où R3 est éthyle, Met est Al, Fe, TiOq ou Zn, n vaut de 2 à < 4 , et q = (4 - n) / 2 ; un polyphosphate de mélamine ayant un degré de condensation moyen de 2 à 200 en tant que constituant F; et un colorant de couleur noire en tant que constituant G. Les compositions de polyamide de couleur noire peuvent être employées pour la production de fibres, de films et de corps moulés, notamment pour des applications dans le domaine électrique et électronique.
EP18739830.0A 2017-07-14 2018-07-06 Compositions de polyamide ignifuges de couleur noire et leur utilisation Pending EP3652254A1 (fr)

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PCT/EP2018/068319 WO2019011788A1 (fr) 2017-07-14 2018-07-06 Compositions de polyamide ignifuges de couleur noire et leur utilisation

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DE102017215777A1 (de) * 2017-09-07 2019-03-07 Clariant Plastics & Coatings Ltd Flammschutzmittelkombinationen für Polymerzusammensetzungen und deren Verwendung
CN111662323A (zh) * 2019-03-07 2020-09-15 黎杰 二烷基次膦酸-烷基亚磷酸金属复合盐,其制备方法和用途
CN111171556A (zh) * 2019-12-25 2020-05-19 金发科技股份有限公司 一种聚酰胺组合物及其制备方法
WO2021206146A1 (fr) * 2020-04-09 2021-10-14 株式会社クラレ Composition de résine de polyamide colorée et corps moulé correspondant
EP3926002A1 (fr) 2020-06-15 2021-12-22 Clariant International Ltd Combinaison de stabilisateur et d'agent ignifuge pour polymères thermoplastiques
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