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WO2004000921A1 - Compositions de polyamides stabilisees - Google Patents

Compositions de polyamides stabilisees Download PDF

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Publication number
WO2004000921A1
WO2004000921A1 PCT/EP2003/006167 EP0306167W WO2004000921A1 WO 2004000921 A1 WO2004000921 A1 WO 2004000921A1 EP 0306167 W EP0306167 W EP 0306167W WO 2004000921 A1 WO2004000921 A1 WO 2004000921A1
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Prior art keywords
carbon atoms
alkyl
hydroxy
triazine
phenyl
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English (en)
Inventor
Hui Chin
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BASF Schweiz AG
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Ciba Spezialitaetenchemie Holding AG
Ciba SC Holding AG
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Priority to AU2003246417A priority Critical patent/AU2003246417A1/en
Publication of WO2004000921A1 publication Critical patent/WO2004000921A1/fr
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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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • 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
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines

Definitions

  • the present invention relates to stabilized polyamide compositions, in particular polyamide fibers, films, molded articles and the like.
  • the present invention relates to stabilized polyamide compositions comprising an s-triazine ultraviolet light absorber and a copper salt in the absence of carbon black.
  • Polyamides, or nylons are a widely used class of thermoplastic engineering resins characterized by excellent lubricity, wear resistance and chemical resistance.
  • suitable stabilization systems to protect nylons from the deleterious effects of heat, light and oxygen.
  • Polyamides have been stabilized against the deleterious effects of heat and light by the addition of small amounts of copper salts, for example in combination with alkali metal halide salts, for example as in U.S. Pat. Nos. 2,630,421 and 2,705,227.
  • Copper salts exhibit some problems when used as an additive in nylons, for example as described in U.S. Pat. Nos. 2,960,498, 3,359,235, 4,745,006 and GB 1 ,148,244.
  • WO 96/28503 discloses stabilized polyamide compositions that contain heat- stabilizing additives combined with at least one inorganic black pigment.
  • a polyamide composition stabilized against the deleterious effects of heat, light and oxygen, comprising an effective stabilizing amount of
  • the black pigment excluded from the present compositions is for example carbon black.
  • the term "essentially no black pigment” means levels of black pigment may be present that do not materially affect the basic characteristics of the polyamide compositions.
  • the present compositions comprise no black pigment.
  • the s-triazines of the instant invention are typical commercial s-triazine UV absorbers based on 4,6-bis-(2,4-diaryl)-2-(2,4-dihydroxyphenyl)-s-triazine such as Tinuvin ® 400 or Tinuvin ® 1577, Ciba Specialty Chemicals Corp., or Cyasorb® 1164, Cytec Corporation, or they are red-shifted s-triazines as disclosed for example in U.S. Patent Nos. 5,556,973 and 5,354,794, or they are high molar extinction s-triazines as disclosed in U.S. Pat. No. 6,255,483, the disclosures of which are hereby incorporated by reference.
  • the s-triazine UV absorbers of component (b) are of formula (IV), (V), (VI), (VII), (VIII) or (IX)
  • X and Y are independently phenyl, naphthyl, or said phenyl or said naphthyl substituted by one to three alkyl of 1 to 6 carbon atoms, by halogen, by hydroxy or by alkoxy of 1 to 6 carbon atoms or by mixtures thereof; or X and Y are independently ⁇ or Z 2 ;
  • R T is hydrogen, straight or branched chain alkyl of 1 to 24 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, halogen, -SR 3 , -SOR 3 or -SO2R3; or said alkyl, said cycloalkyl or said phenylalkyl substituted by one to three halogen, -R 4 , - OR 5)
  • R 3 is alkyl of 1 to 20 carbon atoms, alkenyl of 3 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenyl
  • R 4 is aryl of 6 to 10 carbon atoms or said aryl substituted by one to three halogen, alkyl of 1 to 8 carbon atoms, alkoxy of 1 to 8 carbon atoms or combinations thereof; cycloalkyl of 5 to 12 carbon atoms; phenylalkyl of 7 to 15 carbon atoms or said phenylalkyl substituted on the phenyl ring by one to three halogen, alkyl of 1 to 8 carbon atoms, alkoxy of 1 to 8 carbon atoms or combinations thereof; or straight or branched chain alkenyl of 2 to 18 carbon atoms;
  • R 5 is defined as is R ; or R 5 is also hydrogen or straight or branched chain alkyl of 1 to 24 carbon atoms, alkenyl of 2 to 24 carbon atoms; or R 5 is a group for formula
  • T is hydrogen, oxyl, hydroxyl, -OT ⁇ alkyl of 1 to 24 carbon atoms, said alkyl substituted by one to three hydroxy; benzyl or alkanoyl of 2 to 18 carbon atoms;
  • Ti is alkyl of 1 to 24 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, alkenyl of 2 to 24 carbon atoms, cycloalkenyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, a radical of a saturated or unsaturated bicyclic or tricyclic hydrocarbon of 7 to 12 carbon atoms or aryl of 6 to 10 carbon atoms or said aryl substituted by one to three alkyl of 1 to 4 carbon atoms;
  • R 6 is straight or branched chain alkyl of 1 to 18 carbon atoms, straight or branched chain alkenyl of 2 to 12 carbon atoms, phenoxy, alkylamino of 1 to 12 carbon atoms, arylamino of 6 to 12 carbon atoms, -R 7 COOH or -NH-R 8 -NCO;
  • R 7 is alkylene of 2 to 14 carbon atoms or phenylene
  • R 8 is alkylene of 2 to 24 carbon atoms, phenylene, tolylene, diphenylmethane or a group
  • R ⁇ and RV are the same or different and are as defined for Ri;
  • R 2 ' and R 2 " are the same or different and are as defined for R 2
  • X, X', Y and Y' are the same or different and are as defined for X and Y;
  • t is 0 to 9;
  • L is straight or branched alkylene of 1 to 12 carbon atoms, cycloalkylene of 5 to 12 carbon atoms or alkylene substituted or interrupted by cyclohexylene or phenylene; or L is benzylidene; or L is -S-, -S-S-, -S-E-S-, -SO-, -SO 2 -, -SO-E-SO-, -SO 2 -E-SO 2 -, -CH 2 -NH-E- NH-CH 2 - or
  • E is alkylene of 2 to 12 carbon atoms, cycloalkylene of 5 to 12 carbon atoms or alkylene interrupted or terminated by cycloalkylene of 5 to 12 carbon atoms;
  • n 2, 3 or 4;
  • Q is straight or branched alkylene of 2 to 16 carbon atoms; or said alkylene substituted by one to three hydroxy groups; or said alkylene interrupted by one to three
  • -CH CH- or -O-; or said alkylene both substituted and interrupted by combinations of the groups mentioned above; or Q is xylylene or a group -CONH-R 8 -NHCO-, -CH 2 CH(OH)CH 2 O- R9-OCH 2 CH(OH)CH2-, -CO-R10-CO-, or -(CH 2 ) m -COO-R 11 -OOC-(CH 2 )m- ! where m is 1 to 3; or Q is
  • R is alkylene of 2 to 50 carbon atoms; or said alkylene interrupted by one to ten -O-, phenylene or a group -phenylene-G-phenylene in which G is -O-, -S-, -SO 2 -, -CH 2 - or -C(CH 3 ) 2 -;
  • R 10 is alkylene of 2 to 10 carbon atoms, or said alkylene interrupted by one to four -O-
  • R 10 is arylene of 6 to 12 carbon atoms
  • Ru is alkylene of 2 to 20 carbon atoms or said alkylene interrupted by one to eight
  • Q is a group -[(CH 2 ) m COO] 3 -R 12 where m is 1 to 3, and R 12 is an alkanetriyl of 3 to 12 carbon atoms;
  • Q is a group -[(CH 2 ) m COO] 4 -R 13 where m is 1 to 3, and R 14 is an alkanetetrayi of 4 to 12 carbon atoms;
  • Z t is a group of formula
  • Z 2 is a group of formula
  • ⁇ and r 2 are independently of each other 0 or 1 ;
  • Ri5, Rie. Ri7 > Ri ⁇ , Ri9, R20, R21, R22 and R 23 are independently of one another hydrogen, hydroxy, cyano, alkyl of 1 to 20 carbon atoms, alkoxy of 1 to 20 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, cycloalkoxy of 5 to 12 carbon atoms, halogen, haloalkyl of 1 to 5 carbon atoms, sulfo, carboxy, acylamino of 2 to 12 carbon atoms, acyloxy of 2 to 12 carbon atoms, alkoxycarbonyl of 2 to 12 carbon atoms or aminocarbonyl; or R 17 and R ⁇ 8 or R 22 and R 23 together with the phenyl radical to which they are attached are a cyclic radical interrupted by one to three -O- or -NR 5 -.
  • the invention pertains to compounds of formula (IV) where X and Y are the same or different and are phenyl or said phenyl substituted by one to three alkyl of 1 to 6 carbon atoms, halogen, hydroxy or alkoxy of 1 to 12 carbon atoms; or X and Y are Z ⁇ or Z 2 ;
  • ⁇ is hydrogen, straight or branched chain alkyl of 1 to 24 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms or halogen;
  • R 2 is hydrogen, straight or branched chain alkyl of 1 to 24 carbon atoms or cycloalkyl of 5 to 12 carbon atoms; or said alkyl or said cycloalkyl substituted by one to three -R 4 , -OR 5 , -COOR 5 , -OCOR 5 or combinations thereof; or said alkyl or cycloalkyl interrupted by one to three epoxy, -O-, -COO-, -OCO- or -CO-;
  • R 4 is aryl of 6 to 10 carbon atoms or said aryl substituted by one to three halogen, alkyl of 1 to 8 carbon atoms, alkoxy of 1 to 8 carbon atoms or combinations thereof; cycloalkyl of 5 to 12 carbon atoms; phenylalkyl of 7 to 15 carbon atoms or said phenylalkyl substituted on the phenyl ring by one to three halogen, alkyl of 1 to 8 carbon atoms, alkoxy of 1 to 8 carbon atoms or combinations thereof;
  • R 5 is defined as is R ; or R 5 is also hydrogen or straight or branched chain alkyl of 1 to 24 carbon atoms;
  • Z ⁇ is a group of formula
  • Z 2 is a group of formula
  • R22 and R 23 are independently of one another hydrogen, hydroxy, cyano, alkyl of 1 to 20 carbon atoms, alkoxy of 1 to 20 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, cycloalkoxy of 5 to 12 carbon atoms, halogen, haloalkyl of 1 to 5 carbon atoms, sulfo, carboxy, acylamino of 2 to 12 carbon atoms, acyloxy of 2 to 12 carbon atoms, or alkoxycarbonyl of 2 to 12 carbon atoms or aminocarbonyl.
  • the s-triazine UV absorber is also of formula (V) where
  • X is phenyl, naphthyl or said phenyl or said naphthyl substituted by one to three alkyl of 1 to 6 carbon atoms, by halogen, by hydroxy or by alkoxy of 1 to 6 carbon atoms or by mixtures thereof; or X is Z- ⁇ .
  • the s-triazine UV absorber is also of formula (VI) or (VII) or (VIII).
  • the s-triazine UV absorber is also of formula (IX) where X and Y are independently phenyl or said phenyl substituted by one to three alkyl of 1 to 6 carbon atoms, by halogen, by hydroxy or by alkoxy of 1 to 6 carbon atoms or by mixtures thereof; or X and Y are independently Z ⁇ or Z 2 ; and
  • L is straight or branched alkylene of 1 to 12 carbon atoms, cycloalkylene of 5 to 12 carbon atoms or alkylene substituted or interrupted by cyclohexylene or phenylene.
  • the instant s-triazine UV absorber is of formula (IV) where X and Y are the same or different and are phenyl or said phenyl substituted by one to three alkyl of 1 to 6 carbon atoms; Z ⁇ or Z 2 ;
  • R ⁇ is hydrogen or phenylalkyl of 7 to 15 carbon atoms
  • R 2 is hydrogen, straight or branched chain alkyl of 1 to 18 carbon atoms; or said alkyl substituted by one to three -R , -OR 5 or mixtures thereof; or said alkyl interrupted by one to eight -O- or -COO-;
  • R 4 is aryl of 6 to 10 carbon atoms
  • R 5 is hydrogen
  • Z-i is a group of formula
  • Z 2 is a group of formula
  • Ru, Ri5. Ri ⁇ . i7, Rie, Rig, R20, R21, R 22 and R 23 are each hydrogen.
  • the s-triazine UV absorber of this invention is a compound which is
  • the s-triazine UV absorber of component (b) is
  • the s-triazine UV absorber is for example 4,6-diphenyl-2-(4-hexyloxy-2- hydroxyphenyl)-s-triazine, sold commercially as Tinuvin ® 1577, available from Ciba Specialty Chemicals, CAS #147315-50-2.
  • Straight or branched chain alkyl is for example methyl, ethyl, propyl, isopropyl, n- butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1 ,3- dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1 ,1 ,3,3-tetramethylbutyl, 1 - methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, 1 ,1 ,3-trimethylhexyl, 1 ,1 ,3,3- tetramethylpentyl, nonyl, decyl, undecyl, 1 -methylundecyl, dodecyl, 1 ,1 ,3,3,
  • Cycloalkyl or said cycloalkyl substituted by one to three alkyl is for example cyclopentyl, methylcyclopentyl, dimethylcyclopentyl, cyclohexyl, methyicyclohexyl, dimethylcyclohexyl, trimethylcyclohexyl, tert-butylcyclohexyl, cycloheptyl or cyclooctyl.
  • Phenyl substituted by one to three alkyl is for example o-, m- or p-methylphenyl, 2,3- dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4- dimethylphenyl, 3,5-dimethylphenyl, 2-methyl-6-ethylphenyl, 4-tert-butylphenyl, 2-ethylphenyl or 2,6-diethylphenyl.
  • Phenylalkyl is for example, benzyl, ⁇ -methylbenzyl, , ⁇ -dimethylbenzyl or 2-phenyl- ethyl.
  • Phenylalkyl substituted on the phenyl ring by one to three alkyl of is for example 2- methylbenzyl, 3-methylbenzyl, 4-methyIbenzyl, 2,4-dimethylbenzyl, 2,6-dimethylbenzyl or 4- tert-butylbenzyl.
  • Straight or branched chain alkoxy is for example methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, pentyloxy, isopentyloxy, hexyloxy, heptyloxy, octyloxy, decyloxy, tetrad ecy I oxy, hexadecyloxy or octadecyloxy.
  • Cycloalkoxy is for example, cyclopentyloxy, methylcyclopentyloxy, dimethylcyclopentyloxy, cyclohexyloxy, methylcyclohexyloxy, dimethylcyclohexyloxy, trimethylcyclohexyloxy, tert-butylcyclohexyloxy, cycloheptyloxy or cyclooctyloxy.
  • the present s-triazines are known and may be prepared for example as disclosed in, WO 96/28431 and United States Patent Nos. 3,843,371 ; 4,619,956; 4,740,542; 5,096,489; 5,106,891 ; 5,298,067; 5,300,414; 5,354,794; 5,461 ,151 ; 5,476,937; 5,489,503; 5,543,518; 5,556,973; 5,597,854; 5,681 ,955; 5,726,309; 5,736,597; 5,942,626; 5,959,008; 5,998,116; 6,013,704; 6,060,543; 6,187,919; 6,242,598 and 6,255,483.
  • the relevant disclosures of the U.S. Patents are hereby incorporated by reference.
  • Copper salts useful in the present invention include both cuprous and cupric salts of inorganic and organic acids, as well as mixtures of one or more thereof. Useful salts can be in anhydrous form. Hydrated forms of copper salts are also of interest. Copper salts may be of an alkanoic acid, for example acetic, butyric, lauric, palmitic, stearic, and the like. Other organic anions of copper salts include citrate, lactate, oleate, oxalate, tartrate, benzoate, salicylate, and the like. Suitable inorganic anions include for example chloride, bromide, iodide, nitrate, and the like.
  • Specific copper salts of this invention include copper (I) chloride, copper (I) bromide, copper (I) iodide, copper (II) acetate, copper (II) chloride, copper (II) bromide, copper (II) nitrate, copper (II) sulfate and mixtures thereof.
  • Polyamides are for example those prepared by the polymerization of a monoamino- monocarboxylic acid or a lactam thereof having at least 2 carbon atoms between the amino and carboxylic acid group, of substantially equimolar proportions of a diamine which contains at least 2 carbon atoms between the amino groups and a dicarboxylic acid, or of a monoaminocarboxylic acid or a lactam thereof as defined above together with substantially equimolar proportions of a diamine and a dicarboxylic acid.
  • substantially equimolar proportions includes both strictly equimolar proportions and slight departures therefrom which are involved in conventional techniques for stabilizing the viscosity of the resultant polyamides.
  • the dicarboxylic acid may be used in the form of a functional derivative thereof, for example, an ester or acid chloride.
  • Examples of the aforementioned monoamino-monocarboxylic acids or lactams thereof which are useful in preparing the polyamides include those compounds containing from 2 to 16 carbon atoms between the amino and carboxylic acid groups, said carbon atoms forming a ring containing the -CO-NH- group in the case of a lactam.
  • aminocarboxylic acids and lactams there may be mentioned ⁇ -aminocaproic acid, butyrolactam, pivaloiactam, ⁇ -caprolactam, capryllactam, enantholactam, undecanolactam, dodecanolactam and 3- and 4-aminobenzoic acids.
  • Diamines suitable for use in the preparation of the polyamides include the straight chain and branched chain alkyl, aryl and alkaryl diamines.
  • Illustrative diamines are trimethylenediamine, tetramethylenediamine, pentamethylenediamine, octamethylenediamine, hexamethylenediamine, trimethylhexamethylenediamine, m- phenylenediamine and m-xylylenediamine.
  • the dicarboxylic acids may for example be represented by the formula
  • B is a divalent aliphatic or aromatic group containing at least 2 carbon atoms.
  • aliphatic acids are sebacic acid, octadecanedioic acid, suberic acid, glutaric acid, pimelic acid and adipic acid.
  • Both crystalline and amorphous polyamides may be employed, where the crystalline species often exhibits superior solvent resistance.
  • Typical examples of the polyamides or nylons, as these are often called, include, for example, polyamide-6 (polycaprolactam), 6,6 (polyhexamethylene adipamide), 11 , 12, 4,6, 6,10 and 6,12 as well as polyamides from terephthalic acid and/or isophthalic acid and trimethylhexamethylenediamine; from adipic acid and m-xylylenediamines; from adipic acid, azelaic acid and 2,2-bis(p- aminophenyl)propane or 2,2-bis-(p-aminocyclohexyl)propane and from terephthalic acid and 4,4'-diaminodicyclohexylmethane.
  • Present polyamides are for example polyamide-6, 4,6, 6,6, 6,9, 6,10, 6,12, 11 and 12, for example polyamide-6 and polyamide-6, 6.
  • the copper compound is present for example from about 1 ppm (parts per million), based on polyamide to about 500 ppm.
  • the copper compound is present in the following ranges: from about 10 ppm to about 300 ppm, from about 100 ppm to about 300 ppm, from about 150 ppm to about 300 ppm, from about 150 ppm to about 500 ppm, from about 200 ppm to about 500 ppm, from about 300 ppm to about 500 ppm, from about 10 ppm to about 500 ppm, from about 10 ppm to 150 ppm, or from about 10 ppm to about 100 ppm.
  • the s-triazine ultraviolet light absorbers are present from about 0.1 % to about 2% by weight, based on the weight of polyamide.
  • the s-triazine UV absorbers are for example about 0.5% by weight, based on the weight of the polyamide.
  • the s-triazine UV absorbers are present from about 0.1 % to about 1.5%, from about 0.1 % to about 1 %, or from about 0.1 to 0.5% by weight, based on the weight of the polyamide.
  • the s- triazine UV absorbers are present from about 0.5% to about 2%, from about 1.0% to about 2%, or from about 1.5% to about 2% by weight, based on the weight of the polyamide.
  • the stabilized polyamide compositions may further include at least one alkali metal halide.
  • Alkali metal halides are for example salts of group la alkali metals, for example lithium, sodium, potassium, etc., with group Vila halogens, for example fluorine, chlorine, bromine and iodine.
  • group Vila halogens for example fluorine, chlorine, bromine and iodine.
  • the present alkali metal halides are potassium iodide, potassium bromide, potassium chloride, sodium iodide, sodium bromide, sodium chloride, or mixtures thereof.
  • the present alkali metal halide is potassium bromide, potassium iodide, or a mixture of potassium bromide and potassium iodide.
  • Alkali metals halides may be present in the stabilized compositions of this invention from about 100 ppm to about 10,000 ppm based on polyamide, for example from about 500 ppm to about 2000 ppm based on polyamide.
  • alkali metal halides may be present from about 100 ppm to about 5000 ppm, from about 100 ppm to about 2000 ppm, from about 100 ppm to about 1000 ppm, or from about 100 ppm to about 500 ppm, based on polyamide.
  • alkali metal halides may be present from about 500 ppm to about 10,000 ppm, from about 1000 ppm to about 10,000, from about 2000 ppm to 10,000 ppm, or from about 5000 ppm to about 10,000 ppm based on polyamide.
  • the compositions of the present invention may further include alkali metal salts and alkaline earth metal salts of higher fatty acids, for example, calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate, antimony pyrocatecholate or zinc pyrocatecholate.
  • the compositions of the present invention may further include zinc stearate.
  • Fatty acid salts may be present in the polyamide compositions of this invention at for example the same levels as the copper compound.
  • the resulting stabilized compositions of the invention may optionally also contain from about 0.01 to about 10%, for example from about 0.025 to about 5%, for instance from about 0.1 to about 3% by weight of various conventional stabilizer coadditives, such as the materials listed below, or mixtures thereof.
  • Alkylated monophenols for example 2,6-di-tert-butyl-4-methylphenol, 2-tert- butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-( ⁇ -methylcyclohexyi)- 4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert- butyl-4-methoxymethylphenol, nonylphenols which are linear or branched in the side chains, for example, 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6-(1-methylundec-1-yl)phenol, 2,4-
  • Alkylthiomethylphenols for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di- dodecylthiomethyl-4-nonylphenol.
  • Hvdroquinones and alkylated hvdroquinones for example 2,6-di-tert-butyI-4- methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4- octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di- tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis-(3,5-di-tert-butyl-4- hydroxyphenyl) adipate.
  • Tocopherols for example ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol, ⁇ - tocopherol and mixtures thereof (Vit
  • Hydroxylated thiodiphenyl ethers for example 2,2'-thiobis(6-tert-butyl-4- methylphenol), 2,2'-thiobis(4-octylphenol), 4,4'-thiobis(6-tert-butyl-3-methylphenol), 4,4'- thiobis(6-tert-butyl-2-methylphenol), 4,4'-thiobis-(3,6-di-sec-amylphenol), 4,4'-bis(2,6- dimethyl-4-hydroxyphenyl)disuifide.
  • 2,2'-thiobis(6-tert-butyl-4- methylphenol 2,2'-thiobis(4-octylphenol), 4,4'-thiobis(6-tert-butyl-3-methylphenol), 4,4'- thiobis(6-tert-butyl-2-methylphenol), 4,4'-thiobis-(3,6-di-sec-amylphenol), 4,4'-bis
  • Alkylidenebisphenols for example 2,2'-methylenebis(6-tert-butyl-4- methylphenol), 2,2'-methylenebis(6-tert-butyl-4-ethylphenol), 2,2'-methylenebis[4-methyl-6- ( -methylcyclohexyl)phenol], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'- methylenebis(6-nonyl-4-methylphenol), 2,2'-methylenebis(4,6-di-tert-butylphenol), 2,2'- ethylidenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2'- methylenebis[6-( ⁇ -methylbenzyl)-4-nonylphenol], 2,2'-methylenebis[6-( ⁇ , -dimethylbenzyl)-
  • Benzyl compounds for example 3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tridecyl-4-hydroxy-3,5-di- tert-butylbenzylmercaptoacetate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine, 1 ,3,5-tri-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, di-(3,5-di-tert-butyl-4- hydroxybenzyl) sulfide, 3,5-di-tert-butyl-4-hydroxybenzyl-mercapto-acetic acid isooctyl ester, bis-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl
  • Hydroxybenzylated malonates for example dioctadecyl-2,2-bis-(3,5-di-tert- butyl-2-hydroxybenzyl)-malonate, di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)- malonate, di-dodecylmercaptoethyl-2,2-bis-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, bis[4-(1 ,1 ,3,3-tetramethylbutyl)phenyl]-2,2-bis(3 ) 5-di-tert-butyl-4-hydroxybenzyl)malonate.
  • Aromatic hvdroxybenzyl compounds for example 1 ,3,5-tris-(3,5-di-tert-butyl- 4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1 ,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6- tetramethylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.
  • Triazine compounds for example 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl- 4-hydroxyanilino)-1 ,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-
  • Benzylphosphonates for example dimethyl-2,5-di-tert-butyl-4- hydroxybenzylphosphonate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy- 3-methylbenzylphosphonate, the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4- hydroxybenzylphosphonic acid.
  • Acylaminophenols for example 4-hydroxy-lauric acid anilide, 4-hydroxy- stearic acid anilide, 2,4-bis-octylmercapto-6-(3,5-tert-butyl-4-hydroxyanilino)-s-triazine and octyl-N-(3,5-di-tert-butyl-4-hydroxyphenyl)-carbamate.
  • esters of ⁇ -(3,5-di-tert-butyl-4-hvdroxyphenyl)propionic acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1 ,6- hexanediol, 1 ,9-nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1 -phospha
  • esters of ⁇ -(5-tert-butyl-4-hvdroxy-3-methylphenyl)propionic acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1 ,6- hexanediol, 1 ,9-nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1 -phospha-2
  • esters of ⁇ -(3,5-dicvclohexyl-4-hvdroxyphenyl)propionic acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, octanol, octadecanol, 1 ,6-hexanediol, 1 ,9- nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'- bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1 -phospha-2,6,7-trioxabicyclo[2.2.2]o
  • esters of 3,5-di-tert-butyl-4-hvdroxyphenyl acetic acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, octanol, octadecanol, 1 ,6-hexanediol, 1 ,9- nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'- bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1 -phospha-2,6,7-trioxabicyclo[2.2.2]octane
  • antioxidants for example N,N'-di-isopropyl-p-phenylenediamine, N,N'-di-sec-butyi-p-phenylenediamine, N,N'-bis(1 ,4-dimethylpentyl)-p-phenylenediamine, N,N'-bis(1 -ethyl-3-methylpentyl)-p-phenylenediamine, N,N'-bis(1 -methylheptyl)-p- phenylenediamine, N,N'-dicyclohexyl-p-phenylenediamine, N,N'-diphenyI-p- phenylenediamine, N,N'-bis(2-naphthyl)-p-phenylenediamine, N-isopropyl-N'-phenyl-p- phenylenediamine, N-(1
  • 2-Hydroxybenzophenones for example the 2,2'-dihydroxy, 4-hydroxy, 4- methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy and 2'- hydroxy-4,4'-dimethoxy derivatives.
  • Esters of substituted and unsubstituted benzoic acids as for example 4-tert- butyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis(4- tert-butylbenzoyl) resorcinol, benzoyl resorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4- hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl- 4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.
  • Nickel compounds for example nickel complexes of 2,2'-thio-bis-[4-(1 ,1 ,3,3- tetramethylbutyl)phenol], such as the 1 :1 or 1 :2 complex, with or without additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of the monoalkyl esters, e.g. the methyl or ethyl ester, of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid, nickel complexes of ketoximes, e.g. of 2- hydroxy-4-methylphenyl undecylketoxime, nickel complexes of 1 -phenyl-4-lauroyl-5- hydroxypyrazole, with or without additional ligands.
  • additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldi
  • Sterically hindered amine stabilizers for example 4-hydroxy-2,2,6,6- tetramethylpiperidine, 1 -allyl-4-hydroxy-2,2,6,6-tetramethylpiperidine, 1 -benzyl-4-hydroxy- 2,2,6,6-tetramethylpiperidine, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(2,2,6,6- tetramethyl-4-piperidyl) succinate, bis(1 ,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis(1- octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1 ,2,2,6,6-pentamethyl-4-piperidyl) n- butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of 1-(2-hydroxyethyl)- 2,2,6,6-tetramethylpiperidine
  • the sterically hindered amine may also be one of the compounds described in U.S. Pat. No. 5,980,783, the relevant parts of which are hereby incorporated by reference, that is compounds of component l-a), l-b), l-c), l-d), l-e), l-f), l-g), l-h), l-i), l-j), l-k) or l-l), in particular the light stabilizer 1 -a-1 , 1 -a-2, 1-b-1 , 1-c-1 , 1-c-2, 1-d-1 , 1-d-2, 1-d-3, 1 -e-1 , 1-f-1 , 1-g-1 , 1 -g- 2 or 1 -k-1 listed on columns 64-72 of said U.S. Pat. No. 5,980,783.
  • the sterically hindered amine may also be one of the compounds described in EP 782994, for example compounds as described in claims 10 or 38 or in Examples 1-12 or D-1 to D
  • Oxamides for example 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'- dioctyloxy-5,5'-di-tert-butoxanilide, 2,2'-didodecyloxy-5,5'-di-tert-butoxanilide, 2-ethoxy-2'- ethyloxanilide, N,N'-bis(3-dimethylaminopropyl)oxamide, 2-ethoxy-5-tert-butyl-2'-ethoxanilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butoxaniIide, mixtures of o- and p-methoxy- disubstituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides.
  • Metal deactivators for example N.N'-diphenyloxamide, N-salicylal-N'-salicyloyl hydrazine, N,N'-bis(salicyloyl) hydrazine, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1 ,2,4-triazole, bis(benzylidene)oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, N,N'-diacetyladipoyl dihydrazide, N,N'-bis(salicyloyl)oxalyl dihydrazide, N,N'-bis(salicyloyl)thiopropionyl dihydrazide.
  • Phosphites and phosphonites for example triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)-pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis
  • Tris(2,4-di-tert-butylphenyl) phosphite (lrgafos ® 168, Ciba Specialty Chemicals Corp.), tris(nonylphenyl) phosphite,
  • Hydroxylamines for example N,N-dibenzylhydroxylamine, N,N- diethylhydroxylamine, N,N-dioctylhydroxylamine, N,N-dilaurylhydroxylamine, N,N- ditetradecylhydroxylamine, N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydroxylamine, N-heptadecyl-N-octadecylhydroxylamine, N-methyl- N-octadecylhydroxylamine and the N,N-dialkylhydroxylamine derived from hydrogenated tallow amine.
  • Nitrones for example N-benzyl- ⁇ -phenylnitrone, N-ethyl- ⁇ -methylnitrone, N-octyl- ⁇ -heptylnitrone, N-lauryl- ⁇ -undecylnitrone, N-tetradecyl- ⁇ -tridcylnitrone, N-hexadecyl- ⁇ - pentadecylnitrone, N-octadecyl- ⁇ -heptadecylnitrone, N-hexadecyl- ⁇ -heptadecylnitrone, N- ocatadecyl- ⁇ -pentadecylnitrone, N-heptadecyl- ⁇ -heptadecylnitrone, N-octadecyl- ⁇ - hexadecylnitrone, N-methyl- ⁇ -heptadecylnitrone and the nitrone
  • Amine oxides for example amine oxide derivatives as disclosed in U.S. Patent Nos. 5,844,029 and 5,880,191 , didecyl methyl amine oxide, tridecyl amine oxide, tridodecyl amine oxide and trihexadecyl amine oxide.
  • Thiosynerqists for example dilauryl thiodipropionate or distearyl thiodipropionate.
  • Peroxide scavengers for example esters of ⁇ -thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2- mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis( ⁇ -dodecylmercapto)propionate.
  • esters of ⁇ -thiodipropionic acid for example the lauryl, stearyl, myristyl or tridecyl esters
  • mercaptobenzimidazole or the zinc salt of 2- mercaptobenzimidazole zinc dibutyldithiocarbamate
  • dioctadecyl disulfide pentaerythritol tetrakis( ⁇ -dodecyl
  • Polyamide stabilizers for example copper salts in combination with iodides and/or phosphorus compounds and salts of divalent manganese, for example Cul.
  • Basic co-stabilizers for example melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids, for example, calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate, antimony pyrocatecholate or zinc pyrocatecholate.
  • Basic co-stabilizers for example melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids, for example, calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium
  • Nucleating agents for example inorganic substances such as talcum, metal oxides such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of, for example, alkaline earth metals; organic compounds such as mono- or polycarboxylic acids and the salts thereof, e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymeric compounds such as ionic copolymers (ionomers).
  • inorganic substances such as talcum, metal oxides such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of, for example, alkaline earth metals
  • organic compounds such as mono- or polycarboxylic acids and the salts thereof, e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate
  • polymeric compounds such as ionic copolymers (ionomers).
  • Fillers and reinforcing agents for example calcium carbonate, silicates, glass fibres, glass bulbs, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, wood flour and flours or fibers of other natural products, synthetic fibers.
  • Dispersing Agents such as polyethylene oxide waxes or mineral oil.
  • additives for example plasticizers, lubricants, emulsifiers, pigments, dyes, optical brighteners, rheology additives, catalysts, flow-control agents, slip agents, crosslinking agents, crosslinking boosters, halogen scavengers, smoke inhibitors, flameproofing agents, antistatic agents, clarifiers such as substituted and unsubstituted bisbenzylidene sorbitols, benzoxazinone UV absorbers such as 2,2'-p-phenylene-bis(3,1 - benzoxazin-4-one), Cyasorb ® 3638 (CAS# 18600-59-4), and blowing agents.
  • plasticizers for example plasticizers, lubricants, emulsifiers, pigments, dyes, optical brighteners, rheology additives, catalysts, flow-control agents, slip agents, crosslinking agents, crosslinking boosters, halogen scavengers, smoke inhibitors, flameproofing agents, antistatic agents, clar
  • the present polyamide compositions are prepared by melt blending techniques well known to those skilled in the art, for example by blending methods which results in the formation of an intimate blend of the components.
  • Suitable procedures include solution blending and melt blending.
  • the polyamide and the various components are intimately mixed using conventional mixing equipment such as a mill, a Banbury mixer, a Brabender Torque Rheometer, a single or twin screw extruder, continuous mixers, kneaders, etc.
  • the components may be intimately mixed in the form of granules and/or powder in a high shear mixer.
  • the components may be dry blended followed by extrusion to obtain the polymer composition of the present invention.
  • the present invention also pertains to a method of stabilizing a polyamide composition against the deleterious effects of heat, light and oxygen, which method comprises incorporating into said polyamide composition an effective stabilizing amount of at least one compound selected from the group consisting of the s-triazine UV absorbers and a copper salt, where essentially no black pigment is present.
  • the present polyamide films, fibers and molded articles are useful for example as insulation, transparent films, bristles, cloth, coated fabrics, coatings, filaments, textiles, yarns and tire cord.
  • Polyamide-6 powder (ULTRAMID BS-700-F Powder) is blended with additives with a Turbula mixer for 15-20 minutes. Total formulation size is 2000 g. The mixtures are then extruded with a 27 mm Leistritz twin screw extruder. The extrusion is conducted under conditions such that the zone temperatures are 475, 500, 500°F, with a die temperature of 500°F. The obtained resin is pelletized with a cutter. The pelletized resin composition is dried overnight in a vacuum oven (at 82°C, nitrogen bleed) prior to fiber spinning.
  • Accelerated weathering utilizes an Atlas CI-65 xenon arc weatherometer (XAW), operated according to ASTM G26-90 method C. This method utilizes a xenon arc Weatherometer operated at an irradiance of 0.35 W/m 2 and a black panel temperature of 63°C.
  • XAW Atlas CI-65 xenon arc weatherometer
  • lrgafos ® 168 is tris(2,4-di-tert-butylphenyl) phosphite
  • Irganox ® HP-136 is 3-(3,4-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one
  • Irganox ® 1098 is N,N'-hexane-1 ,6-diylbis-(3-(3,5-di-tert-butyl-4-hydroxyphenylpropionamide))
  • Irganox ® 3790 is tris-(4-t-butyl-2,6-dimethyl-3-hydroxybenzyl) isocyanurate(CAS 40601 -76-1 )
  • Tinuvin ® 234 is 2-(2-hydroxy-3,5-di- ⁇ -cumyl)-2H-benzotriazole
  • Irgafos ® 38 is bis(2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite
  • Irgafos ® P-EPQ is tetrakis(2,4-di-tert-butylphenyl)4,4'-biphenylene-diphosphonite
  • Irgastab ® FS042 is N,N-di(alkyl)hydroxylamine produced by the direct oxidation of N,N- di(hydrogenated tallow)amine
  • Tinuvin ® 1577 is 4,6-diphenyl-2-(4-hexyloxy-2-hydroxyphenyl)-s-triazine
  • Iodide Stabilizer is 80% Kl
  • Irganox ® 565 is 2,6-di-t-butyl-4-(4,6-bis(octylthio)-1 ,3,5-triazin-2-ylamino) phenol
  • Brugggolen ® H3336 is an halogen alkyl phosphate copper compound available from
  • Brueggeman CGL 374 is an oligomeric hindered amine stabilizer
  • CGL 0066 is a piperazine based hindered amine stabilizer
  • NYLOSTAB SEED is 1 ,3-benzenedicarboxamide-N,N'-bis-(2,2,6,6-tetramethyl-4-piperidinyl),
  • Chimassorb ® 1 19 is R ._ NH _( CH ⁇ _ N _( CH ⁇ _ N _( CH x_ NH _ R .
  • Tinuvin ® 770 is
  • Tinuvin 144 is
  • Formulation No. 33 is of present invention.
  • the formulations of the present invention provide outstanding stabilization against the effects of heat, light and oxygen.

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Abstract

La présente invention concerne des compositions de polyamides, plus particulièrement des fibres, films et articles moulés en polyamide. Elles sont effectivement stabilisées par incorporation d'une combinaison d'au moins un absorbeur d'UV à base de s-triazine et d'un sel de cuivre en l'absence de noir de carbone.
PCT/EP2003/006167 2002-06-19 2003-06-12 Compositions de polyamides stabilisees Ceased WO2004000921A1 (fr)

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JP2009149763A (ja) * 2007-12-20 2009-07-09 Unitika Ltd 低揮発性ポリアミド樹脂組成物
WO2010081625A2 (fr) 2009-01-19 2010-07-22 Basf Se Pigments noirs organiques et leur préparation
WO2012084898A1 (fr) 2010-12-20 2012-06-28 Rhodia Acetow Gmbh Module photovoltaique
WO2012084899A1 (fr) 2010-12-20 2012-06-28 Rhodia Acetow Gmbh Module de source lumineuse a led (diode electroluminescente)
EP2927273A1 (fr) * 2014-04-02 2015-10-07 Ems-Patent Ag Masse de moulage en polyamide, corps moulé fabriqué à partir de celle-ci et utilisation des masses de moulage en polyamide
EP3263639A1 (fr) * 2016-06-27 2018-01-03 Clariant International Ltd Utilisation d'une composition d'additif pour la préparation de polymères de polycondensation
US20220056214A1 (en) * 2019-03-14 2022-02-24 Mitsubishi Gas Chemical Company, Inc. Polyimide resin composition
WO2022207787A1 (fr) * 2021-04-01 2022-10-06 Basf Se Mélange stabilisateur
EP4397716A4 (fr) * 2021-09-03 2025-01-01 Mitsubishi Gas Chemical Company, Inc. Composition de résine et article moulé

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US20020028861A1 (en) * 2000-02-01 2002-03-07 Andrews Stephen Mark Method of content protection with durable UV absorbers
WO2002042281A1 (fr) * 2000-11-27 2002-05-30 Ciba Specialty Chemicals Holding Inc. Derives 2-(2-hydroxyphenyl)-2h-benzotriazole a substitution aryle ou heteroaryle en position 5 en tant qu'absorbeurs uv

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US20020028861A1 (en) * 2000-02-01 2002-03-07 Andrews Stephen Mark Method of content protection with durable UV absorbers
EP1038912A2 (fr) * 2000-06-22 2000-09-27 Ciba SC Holding AG Stabilisateurs à poids moléculaire élevé d'amines hydrocarbyloxylées
WO2002042281A1 (fr) * 2000-11-27 2002-05-30 Ciba Specialty Chemicals Holding Inc. Derives 2-(2-hydroxyphenyl)-2h-benzotriazole a substitution aryle ou heteroaryle en position 5 en tant qu'absorbeurs uv

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009149763A (ja) * 2007-12-20 2009-07-09 Unitika Ltd 低揮発性ポリアミド樹脂組成物
WO2010081625A2 (fr) 2009-01-19 2010-07-22 Basf Se Pigments noirs organiques et leur préparation
WO2012084898A1 (fr) 2010-12-20 2012-06-28 Rhodia Acetow Gmbh Module photovoltaique
WO2012084899A1 (fr) 2010-12-20 2012-06-28 Rhodia Acetow Gmbh Module de source lumineuse a led (diode electroluminescente)
EP2927273A1 (fr) * 2014-04-02 2015-10-07 Ems-Patent Ag Masse de moulage en polyamide, corps moulé fabriqué à partir de celle-ci et utilisation des masses de moulage en polyamide
US20150284531A1 (en) * 2014-04-02 2015-10-08 Ems-Patent Ag Polyamide moulding composition, moulded articles produced therefrom and also use of the polyamide moulding compositions
CN104974513A (zh) * 2014-04-02 2015-10-14 Ems专利股份公司 聚酰胺模塑组合物和由其制造的模塑制品以及聚酰胺模塑组合物的用途
US9644081B2 (en) * 2014-04-02 2017-05-09 Ems-Patent Ag Polyamide moulding composition, moulded articles produced therefrom and also use of the polyamide moulding compositions
EP3263639A1 (fr) * 2016-06-27 2018-01-03 Clariant International Ltd Utilisation d'une composition d'additif pour la préparation de polymères de polycondensation
WO2018001704A1 (fr) * 2016-06-27 2018-01-04 Clariant International Ltd Utilisation d'une composition d'additif pour la préparation de polymères de polycondensation
US10920069B2 (en) 2016-06-27 2021-02-16 Clariant Plastics & Coatings Ltd Use of an additive composition for the preparation of polycondensation polymers
US20220056214A1 (en) * 2019-03-14 2022-02-24 Mitsubishi Gas Chemical Company, Inc. Polyimide resin composition
WO2022207787A1 (fr) * 2021-04-01 2022-10-06 Basf Se Mélange stabilisateur
EP4397716A4 (fr) * 2021-09-03 2025-01-01 Mitsubishi Gas Chemical Company, Inc. Composition de résine et article moulé

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