US20110130492A1 - Stabilization of polyether polyol, polyester polyol or polyurethane compositions - Google Patents

Stabilization of polyether polyol, polyester polyol or polyurethane compositions Download PDF

Info

Publication number
US20110130492A1
US20110130492A1 US13/024,404 US201113024404A US2011130492A1 US 20110130492 A1 US20110130492 A1 US 20110130492A1 US 201113024404 A US201113024404 A US 201113024404A US 2011130492 A1 US2011130492 A1 US 2011130492A1
Authority
US
United States
Prior art keywords
tinuvin
tert
irganox
butyl
formula
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.)
Abandoned
Application number
US13/024,404
Inventor
Dietmar Mäder
Pierre Rota-graziosi
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.)
Individual
Original Assignee
Individual
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 Individual filed Critical Individual
Priority to US13/024,404 priority Critical patent/US20110130492A1/en
Publication of US20110130492A1 publication Critical patent/US20110130492A1/en
Abandoned legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • 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
    • 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
    • C08K5/20—Carboxylic acid amides
    • 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
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3432—Six-membered rings
    • C08K5/3435—Piperidines
    • 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
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • 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
    • C08K5/13—Phenols; Phenolates
    • 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
    • C08K5/13—Phenols; Phenolates
    • C08K5/134—Phenols containing ester groups
    • C08K5/1345—Carboxylic esters of phenolcarboxylic acids

Definitions

  • the present invention pertains to compositions comprising a polyether polyol, a polyester polyol or a polyurethane susceptible to light induced degradation, and a mixture of at least two different light stabilizers, one of them being a specific UV-absorber and/or hindered amine light stabilizer.
  • DE 101 48 702 A1 pertains to stabilizer blends comprising an antioxidant, a HALS compound, a UV-absorber and a phosphorus compound.
  • the initial yellowness of thermoplastic polyurethane stabilized with such a blend of stabilizers is not so great.
  • WO 03/095543 relates to stabilizer mixtures for polymer substrates comprising benzylidene-bis-malonates and at least one compound selected from the group consisting of UV-absorbers, hindered amine stabilizers, sterically hindered phenols, organophosphines, organophosphites and organophosphonites.
  • stabilizer mixtures provide protection of polymeric substrates against the damaging influence of light exposure by long term storage of polymers.
  • EP 0714931 A discloses a mixture of Tinuvin® 312, Tinuvin® 770 and Chimassorb® 81 in a polyurethane.
  • WO 2004/068217 A describes a polyurethane composition comprising Tinuvin® 144, Tinuvin® 765 and Irganox® 1010.
  • WO 03/078148 A relates to a polyurethane composition comprising Tinuvin® 144, Tinuvin® 765 and Uvinul® 3040.
  • the polyether polyol, polyester polyol or polyurethane compositions according to the present invention have an excellent initial color after processing, good light stability and also good gas fading resistance.
  • the present invention pertains to a composition
  • a composition comprising
  • R 1 and R 2 are each independently C 1 -C 4 alkyl or C 1 -C 4 alkyoxy
  • composition of this invention must contain either (i) a UV-absorber of formula (I) and a hindered amine of formula (II); or (ii) a UV-absorber of formula (I) and a UV-absorber or/and a hindered amine different from formulae (I) and (II); or (iii) a hindered amine of formula (II) and a UV-absorber or/and a hindered amine different from formulae (I) and (II).
  • a UV-absorber of formula (I) and a hindered amine of formula (II) or a UV-absorber or/and a hindered amine different from formulae (I) and (II).
  • further UV-absorbers or/and hindered amines may be present.
  • composition that comprises as component (c) a hindered amine light stabilizer of formula HA-1 to HA-11 or a UV-absorber of formula UV-1 to UV-8 as defined below.
  • composition comprising as component (c) a hindered amine light stabilizer of formula HA-1 to HA-11 or a UV-absorber of formula UV-1 to UV-7.
  • compositions of the instant invention preferably contain further additives.
  • Such further additives may for example be:
  • Alkylated monophenols for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-di-methylphenol, 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-( ⁇ -methylcyclohexyl)-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, 2,2,4-
  • 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, 2,4-dodecylthiomethyl-6-tert-butylphenol, 2,4-dodecylthiomethyl-6-methylphenol.
  • Hydroquinones and alkylated hydroquinones for example 2,6-di-tert-butyl-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.
  • 2,6-di-tert-butyl-4-methoxyphenol 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-
  • Tocopherols for example ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol and mixtures thereof (vitamin E).
  • 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)-disulfide.
  • 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-
  • 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)-4-nonylphenol
  • O-, N- and S-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, bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate, bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.
  • 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 hydroxybenzyl 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)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine, 2,4,6-tris-(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, 2,4,6-tris-tris
  • Benzylphosphonates for example dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl3,5-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-hydroxylauranilide, 4-hydroxystearanilide, octyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.
  • esters of ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)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, trimethylol-propane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo
  • esters of ⁇ -(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with mono- or poly-hydric 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-2,6,7-trioxabicyclo
  • esters of ⁇ -(3,5-dicyclohexyl-4-hydroxyphenyl)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]octane.
  • esters of 3,5-di-tert-butyl-4-hydroxyphenyl 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-butyl-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′-diphenyl-p-phenylenediamine, N,N′-bis(2-naphthyl)-p-phenylenediamine, N-isopropyl-N′-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl-p-phenylenediamine, N,N′-bis(
  • 2-(2′-Hydroxyphenyl)benzotriazoles for example 2-(2′-hydroxy-5′-methylphenyl)benzotriazole, 2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)benzotriazole, 2-(5′-tert-butyl-2′-hydroxyphenyl)benzotriazole, 2-(2′-hygroxy-5′-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole, 2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3′-tert-butyl-2′-hydroxy-5′-methylphenyl)-5-chlorobenzotriazole, 2-(3′-sec-butyl-5′-tert-butyl-2′-hydroxyphenyl)benzotriazole, 2-(2′-hydroxy-4′-octyl
  • R 3′-tert-butyl-4′-hydroxy-5′-2H-benzotriazol-2-ylphenyl, 2-[2′-hydroxy-3′-( ⁇ , ⁇ -dimethylbenzyl)-5′-(1,1,3,3-tetramethylbutyl)phenyl]-benzotriazole; 2-[2′-hydroxy-3′-(1,1,3,3-tetramethylbutyl)-5′-( ⁇ , ⁇ -dimethylbenzyl)phenyl]benzotriazole.
  • Esters of substituted and unsubstituted benzoic acids for example 4-tert-butylphenyl 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.
  • Acrylates for example ethyl ⁇ -cyano- ⁇ , ⁇ -diphenylacrylate, isooctyl ⁇ -cyano- ⁇ , ⁇ -diphenylacrylate, methyl ⁇ -carbomethoxycinnamate, methyl ⁇ -cyano- ⁇ -methyl-p-methoxycinnamate, butyl ⁇ -cyano- ⁇ -methyl-p-methoxycinnamate, methyl ⁇ -carbomethoxy-p-methoxycinnamate and N-( ⁇ -carbomethoxy- ⁇ -cyanovinyl)-2-methylindoline.
  • Nickel compounds for example nickel complexes of 2,2′-thiobis[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-methylphenylundecylketoxime, nickel complexes of 1-phenyl-4-Iauroyl-5-hydroxypyrazole, with or without additional ligands.
  • additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate,
  • Further hindered amine light stabilizers for example bis(2,2,6,6-tetramethyl-4-piperidyl)succinate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, the condensate of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, linear or cyclic condensates of N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-triazine, tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, 1,1′-(1,2-ethaned
  • 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, 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-butoxanilide, 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-hydroxyphenylpropionyphydrazine, 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.
  • N,N′-diphenyloxamide N-s
  • Phosphites and phosphonites for example triphenyl phosphite, diphenylalkyl phosphites, phenyldialkyl phosphites, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylpentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,4-dicumylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphi
  • 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,N-dialkylhydroxylamine derived from hydrogenated tallow amine.
  • Nitrones for example N-benzyl-alpha-phenylnitrone, N-ethyl-alpha-methylnitrone, N-octyl-alpha-heptylnitrone, N-lauryl-alpha-undecylnitrone, N-tetradecyl-alpha-tridecylnitrone, N-hexadecyl-alpha-pentadecylnitrone, N-octadecyl-alpha-heptadecylnitrone, N-hexadecyl-alpha-heptadecylnitrone, N-ocatadecyl-alpha-pentadecylnitrone, N-heptadecyl-alpha-hepta-decylnitrone, N-octadecyl-alpha-hexadecylnitrone, nitrone derived from N,N-dialky
  • Thiosynergists 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
  • Basic co-stabilisers 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-stabilisers 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 ric
  • Fillers and reinforcing agents for example calcium carbonate, silicates, glass fibres, glass bulbs, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood flour and flours or fibers of other natural products, synthetic fibers.
  • additives for example plasticisers, lubricants, emulsifiers, pigments, rheology additives, catalysts, flow-control agents, optical brighteners, flameproofing agents, antistatic agents and blowing agents.
  • Anti-gas fading agents for example 1,1,1′,1′-tetramethyl-4,4′-(methylene-di-p-phenylene)disemicarbazide; 1,6-hexamethylene bis(N,N-dimethylsemicarbazide); 11-[6-[[(2,2-dimethylhydrazino)carbonyl]amino]hexyl]-10,12-dioxo-, bis(2 ,2-d imethylhydrazide).
  • the further additives are added, for example, in concentrations of 0.01 to 10%, relative to the total weight of the composition of this invention.
  • such further stabilizers are antioxidants, further light-stabilizers and/or processing stabilizers.
  • Such further stabilizers are phenolic and/or aminic antioxidants, further hindered amine light stabilizers, further UV-absorbers, phosphites, phosphonites and/or benzofuranones.
  • compositions where the further stabilizers are further hindered amine light stabilizers, further UV-absorbers, phenolic antioxidants and/or phosphites.
  • component (b) is a combination of a UV-absorber of formula (I) and a hindered amine light stabilizer of formula (II).
  • compositions wherein the UV-absorber of formula (I) is a compound of formula (Ia).
  • An embodiment of the present invention is a composition, wherein component (b) is a UV-absorber of formula (I) and component (c) is a hindered amine light stabilizer.
  • Another embodiment of the present invention is a composition, wherein component (b) is a hindered amine light stabilizer of formula (II) and component (c) is a UV-absorber.
  • compositions wherein the overall amount of component (b) and (c) is 0.01% to 5%, based on the weight of the composition.
  • compositions wherein the overall amount of component (b) and (c) is 0.5% to 2%, based on the weight of the composition.
  • compositions wherein the ratio of components (b):(c) or of the compounds of formulae (I):(II) respectively is from 10:1 to 1:10.
  • compositions wherein the ratio of components (b):(c) or of the compounds of formulae (I):(II) respectively is from 3:1 to 1:3.
  • compositions according to this invention do not contain benzylidene-bis-malonates.
  • benzylidene-bis-malonates are disclosed in WO 03/095543.
  • the present invention also pertains to the use of a mixture of component (b) and (c) as defined herein as stabilizer for a polyether polyol, a polyester polyol or a polyurethane against degradation by light, oxygen and/or heat.
  • the further additives and/or stabilizers may be as defined herein.
  • the present invention also pertains to a process for stabilizing a polyether polyol, a polyester polyol or a polyurethane against degradation by light, oxygen and/or heat, which process comprises incorporating into said material a mixture of component (b) and (c) as defined herein.
  • the further additives and/or stabilizers may be as defined herein.
  • Hindered amine light stabilizers are preferably compounds containing at least one group of formula (III)
  • G 1 and G 2 are independently alkyl of 1 to 4 carbon atoms, or G 1 and G 2 together are pentamethylene; preferably G 1 and G 2 are each methyl. specifies the border of a chemical group and does not have a chemical meaning by itself.
  • the hindered amine light stabilizers useful as component (c) may be the ones mentioned in 2.6. herein above and the ones disclosed in WO 01/62836, WO 02/02706 and DE 10008367, which are incorporated here by reference.
  • Preferred hindered amine light stabilizers are compounds of formulae (100)-(104) or 7-Oxa-3,20-diazadispiro[5.1.11.2]heneicosan-21-one, 2,2,4,4-tetramethyl-20-(oxiranylmethyl)-, polymer with (chloromethyl)oxirane;
  • E is hydrogen, C 1 -C 18 alkyl, C 1 -C 18 alkoxy or C 1 -C 18 alkoxy substituted by 1 OH;
  • n 1 is 1 or 2;
  • R 3 is C 1 -C 25 alkyl or —CO—R 10 ;
  • R 3 is C 2 -C 14 alkylene or —CO—R 11 —CO—;
  • R 10 is C 1 -C 23 alkyl
  • R 11 is C 2 -C 14 -alkylene
  • n 2 is 2 to 4.
  • n 3 1 to 3
  • R 5 is hydrogen or C 1 -C 12 alkyl
  • R 4 is the group T 1 ,
  • n 4 is 2 to 8
  • n 5 is 1 to 50;
  • R 6 is morpholino, piperidino, 1-piperizinyl, alkylamino of 1 to 8 carbon atoms, especially branched alkylamino of 3 to 8 carbon atoms such as tert-octylamino, —N(alkyl)T 2 with alkyl of 1 to 8 carbon atoms, or —N(alkyl) 2 of 2 to 16 carbon atoms,
  • R 7 is hydrogen, acyl of 2 to 4 carbon atoms, carbamoyl substituted by alkyl of 1 to 4 carbon atoms, s-triazinyl substituted once by chlorine and once by R 6 , or s-triazinyl substituted twice by R 6 with the condition that the two R 6 substituents may be different;
  • R 8 is chlorine, amino substituted by alkyl of 1 to 8 carbon atoms or by T 2 , —N(alkyl)T 2 with alkyl of 1 to 8 carbon atoms, —N(alkyl) 2 of 2 to 16 carbon atoms, or the group T 3 ,
  • R 12 is hydrogen, acyl of 2 to 4 carbon atoms, carbamoyl substituted by alkyl of 1 to 4 carbon atoms, s-triazinyl substituted twice by —N(alkyl) 2 of 2 to 16 carbon atoms or s-triazinyl substituted twice by —N(alkyl)T 2 with alkyl of 1 to 8 carbon atoms;
  • a l is hydrogen or C 1 -C 4 alkyl
  • a 2 is a direct bond or C 1 -C 10 alkylene
  • a 3 is C 1 -C 4 alkyl or C 1 -C 4 alkoxy and
  • n 6 is a number from 2 to 50, preferably 2 to 20;
  • n 8 is 2 to 12.
  • component (c) Of particular interest as component (c) are UV-absorbers of the hydroxyphenyl-triazine, benzotriazole, benzophenone, oxanilide, acrylate and cyanacrylate classes.
  • the hydroxyphenyl triazine UV absorber usually is selected from known compounds, described e.g. in GB-A-975966, EP-A-434608, U.S. Pat. No. 4,619,956, U.S. Pat. No. 5,298,067, EP-A-530135, EP-A-520938, EP-A-531258, U.S. Pat. No. 5,556,973, U.S. Pat. No. 5,959,008, U.S. Pat. No. 6,184,375, U.S. Pat. No. 6,117,997; preferred are compounds as described in U.S. Pat. No. 5,998,116, U.S. Pat. No. 6,255,483, U.S. Pat. No. 6,060,543.
  • hydroxyphenyl triazine UV absorbers are compounds conforming to formula (200), (201) or (202)
  • 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 are independently Z 1 or Z 2 ;
  • R 13 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 17 , —SOR 17 or —SO 2 R 17 ; or said alkyl, said cycloalkyl or said phenylalkyl substituted by one to three halogen, —R 18 , —OR 19 , —N(R 19 ) 2 , —COR 19 , —COOR 19 , —OCOR 19 , —CN, —NO 2 , —SR 19 , —SOR 19 , —SO 2 R 19 or —P(O)(OR 19 ) 2 , morpholinyl, piperidinyl, 2,2,6,6-tetramethylpiperidinyl, piperazinyl or N-methylpiperidinyl groups or combinations thereof; or said alkyl or said cyclo
  • R 17 is alkyl of 1 to 20 carbon atoms, alkenyl of 3 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, aryl of 6 to 10 carbon atoms or said aryl substituted by one or two alkyl of 1 to 4 carbon atoms;
  • R 18 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 19 is defined as is R 18 ; or R 19 is also hydrogen or straight or branched chain alkyl of 1 to 24 carbon atoms, alkenyl of 2 to 24 carbon atoms; or R 19 is a group for formula
  • T is hydrogen, oxyl, hydroxyl, —OT 4 , alkyl of 1 to 24 carbon atoms, said alkyl substituted by one to three hydroxy; benzyl or alkanoyl of 2 to 18 carbon atoms;
  • T 4 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 o 10 carbon atoms or said aryl substituted by one to three alkyl of 1 to 4 carbon atoms;
  • R 14 is hydrogen, straight or branched chain alkyl of 1 to 24 carbon atoms or cycloalkyl of 5 to 12 carbon atoms or R 20 ; or said alkyl or said cycloalkyl substituted by one to four halogen, hydroxy, epoxy, glycidyloxy, furyloxy, —R 18 , —OR 19 , —N(R 19 ) 2 , —CON(R 19 ) 2 , —COR 19 , —COOR 19 , —OCOR 19 , —OCOC(R 19 ) ⁇ C(R 19 ) 2 , —C(R 19 ) ⁇ CCOOR 19 , —CN, —NCO, or
  • R 21 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 22 COOH or —NH—R 23 —NCO;
  • R 22 is alkylene of 2 to 14 carbon atoms or phenylene
  • R 23 is alkylene of 2 to 24 carbon atoms, phenylene, tolylene, diphenylmethane or a group
  • R 13 , R 15 and R 13 ′′ are the same or different and are as defined for R 13 ;
  • R 14 , R 16 and R 14 ′′ are the same or different and are as defined for R 14 ;
  • Z 1 is a group of formula
  • Z 2 is a group of formula
  • r 13 and r 14 are independetly of each other 0 or 1;
  • R 20 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 , R 30 , R 31 and R 32 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 26 and R 27 or R 31 and R 32 together with the phenyl radical to which they are attached are a cyclic radical interrupted by one to three —O— or —NR 19 —.
  • hydroxyphenyltriazines are the compounds (a1)-(a19)
  • UV-absorber of the benzotriazole class are compounds of formula (206) and/or (207),
  • R 33 is hydrogen, halogen, C 1 -C 4 alkyl or C 1 -C 8 alkoxy;
  • R 34 is hydrogen, C 1 -C 18 alkyl or C 1 -C 8 alkyl substituted by phenyl;
  • R 35 is C 1 -C 12 alkyl, —CH 2 CH 2 —CO—R 37 or C 1 -C 8 alkyl substituted by phenyl;
  • R 37 is a monovalent polyethylene oxide residue
  • R 36 is a divalent polyethylene oxide residue
  • benzotriazoles are the compounds (b1)-(b23)
  • the phenolic antioxidant may be a compound of formula (300), (301) or (302)
  • R 38 and R 39 are independently C 1 -C 8 alkyl, R 47 is C 1 -C 18 alkyl;
  • phenolic antioxidant may be any compound listed in items 1.1-1.17 in the list of stabilizers given above.
  • the phosphite may be a compound of formula (400) or (401)
  • R 40 , R 41 , R 42 and R 43 are independently C 1 -C 8 alkyl; or R 40 and R 42 may independently be hydrogen;
  • R 44 , R 45 and R 46 are independently hydrogen or C 1 -C 8 alkyl
  • the phosphite may be any phosphite compound listed in item 4 in the list of stabilizers given above.
  • alkyl may comprise within the limits of the given number of carbon atoms, 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, 2-methylheptyl, 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 or dodecyl.
  • alkylene comprises within the limits of the given number of carbon atoms, for example methylene and the branched and unbranched isomers of ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene and tetradecylene.
  • alkoxy may comprise within the limits of the given number of carbon atoms, for example methoxy and ethoxy and the branched and unbranched isomers of propoxy, butoxy, pentoxy, hexoxy, heptoxy, octoxy, nonoxy, decoxy, undecoxy, dodecoxy, tridecoxy, tetradecoxy, pentadecoxy, hexadecoxy, heptadecoxy and octadecoxy.
  • halogen comprises for example chlorine, bromine and iodine.
  • aryl comprises for example phenyl and naphthyl.
  • alkenyl examples include vinyl, allyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl and dodecenyl.
  • n 7 is 2 to 50, preferably 2 to 20, particular preference is given to the commercial product TINUVIN® 622.
  • n 8 is 2 to 12; particular preference is given to the commercial product UVASORB® HA-88.
  • n 9 is 2 to 50, preferably 2 to 20, the endgroups preferably being
  • n 10 is 2 to 50, preferably 2 to 20, the endgroups preferably being
  • n 11 is 2 to 50, preferably 2 to 20, with the endgroups preferably being
  • n 12 is 2 to 50, preferably 2 to 20, with the endgroups preferably being
  • n 14 is 2 to 50, preferably 2 to 20, with the endgroups preferably being
  • n 15 is 2 to 50, for example 2 to 25;
  • the end group bonded to the nitrogen can be, for example, hydrogen and the end group bonded to the 2-hydroxypropylene radical can be, for example,
  • UV-absorbers Of interest are the following UV-absorbers:
  • n 13 is 2 to 20, for example 3 to 10; preferably, this compound is a mixture of polyethylene glycol and mono- and diesters; particular preference is given to the commercial product TINUVIN® 213.
  • UV-absorbers UV-1 to UV-7 are of particular interest.
  • the phenolic antioxidant is N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N
  • phosphite is N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoe
  • Preferred embodiements of this invention are a polyether polyol, a polyester polyol or a polyurethane comprising one of the following blends of commercially available additives:
  • Tinuvin® 234/Tinuvin® 144
  • Tinuvin® 312/Tinuvin 144
  • Tinuvin® 120/Tinuvin® 144/Irganox® 1726/Irgafos® 126 Tinuvin® 120/Tinuvin® 144/Irganox® 1726/Irgafos® 126.
  • polyether polyol a polyester polyol or a polyurethane comprising one of the following blends of commercially available additives:
  • Tinuvin® 234/Tinuvin® 144
  • Tinuvin® 120/Tinuvin® 144 Tinuvin® 120/Tinuvin® 144.
  • a polyether polyol, a polyester polyol or a polyurethane comprises one of the following blends of commercially available additives:
  • TINUVIN® 328/TINUVIN® 144/Irganox® 1010/Irgafos® 126 are examples of TINUVIN® 328/TINUVIN® 144/Irganox® 1010/Irgafos® 126.
  • polyether polyol a polyester polyol or a polyurethane comprising one of the following blends of commercially available additives:
  • polyether polyol a polyester polyol or a polyurethane comprising one of the following blends of commercially available additives:
  • Tinuvin® 312/Tinuvin® 144/Irganox® 1010/Irgafos® 126 Tinuvin® 312/Tinuvin® 144/Irganox® 1010/Irgafos® 126.
  • polyether polyol a polyester polyol or a polyurethane comprising the one of the following blends of commercially available additives:
  • stabilizers and stabilizer blends mentioned are suitable as stabilizers for polyether polyol, polyester polyol or polyurethane against oxidative, thermal and/or light-induced degradation and as reducer of fogging contribution of the polymer.
  • the polyether polyol, polyester polyol or polyurethane composition of the present invention may be also a foam (flexible, rigid, integral), a microcellular foam, a cast PU, a PU skin, a PU hot melt adhesive, a silylated polyurethane (SPUR), a thermoplasic polyurethane (TPU) a PU elastomer, artifical leather, PU skin, PU stray coating or reaction injection molding (RIM).
  • polyether polyol, polyester polyol or polyurethane composition of the present invention are not foamed.
  • the polyurethanes are obtained, for example, by reacting polyethers, polyesters and polybutadienes which contain terminal hydroxyl groups, i.e. polyols, with aliphatic or aromatic polyisocyanates.
  • Polyethers and polyesters having terminal hydroxyl groups are known and are prepared, for example, by polymerizing epoxides such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin with themselves, for example in the presence of BF 3 , or by addition reaction of these epoxides, alone or as a mixture or in successsion, with starting components containing reactive hydrogen atoms, such as alcohols, ammonia or amines, for example ethylene glycol, propylene 1,3- and 1,2-glycol, trimethylolpropane, 4,4′-dihydroxydiphenylpropane, aniline, ethanolamine or ethylenediamine.
  • epoxides such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin
  • starting components containing reactive hydrogen atoms such as alcohols, ammonia
  • Sucrose polyethers are also suitable in accordance with the invention. In many cases preference is given to those polyethers which predominantly (up to 90% by weight, based on all the OH groups present in the polyether) contain primary OH groups. Furthermore, polyethers modified by vinyl polymers, as are formed, for example, by polymerizing styrene and acrylonitrile in the presence of polyethers, are suitable, as are polybutadienes containing OH groups.
  • These compounds generally have molecular weights of 40 and are polyhydroxy compounds, especially compounds containing from two to eight hydroxyl groups, especially those of molecular weight from 800 to 10,000, preferably from 1000 to 6000, for example polyethers containing at least 2, generally 2 to 8, but preferably 2 to 4, hydroxyl groups, as are known for the preparation of homogeneous polyurethanes and cellular polyurethanes.
  • Suitable polyisocyanates are aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates, for example ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, cyclobutane 1,3-diisocyanate, cyclohexane 1,3- and -1,4-diisocyanate and also any desired mixtures of these isomers, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane, 2,4- and 2,6-hexahydrotolylene diisocyanate and also any desired mixtures of these isomers, hexahydro-1,3- and/or -1,4-phenylene diisocyanate, perhydro-2,4′- and/or -4,4′-diphenylmethanediisocyan
  • isocyanate group-containing distillation residues as they are or dissolved in one or more of the above-mentioned polyisocyanates, which are obtained in the course of the industrial preparation of isocyanates. It is additionally possible to use any desired mixtures of the above-mentioned polyisocyanates.
  • polyisocyanates which are readily obtainable industrially, for example aromatic isocyanates such as 2,4- and 2,6-tolylene diisocyanate and any desired mixtures of these isomers (“TDI”), polyphenyl-polymethylene-polyisocyanates as prepared by aniline-formaldehyde condensation followed by phosgenization (“crude MDI”), and polyisocyanates containing carbodiimide, urethane, allophanate, isocyanurate, urea or biuret groups (“modified polyisocyanates”).
  • aromatic isocyanates such as 2,4- and 2,6-tolylene diisocyanate and any desired mixtures of these isomers
  • CAMDI polyphenyl-polymethylene-polyisocyanates as prepared by aniline-formaldehyde condensation followed by phosgenization
  • modified polyisocyanates polyisocyanates containing carbodiimide, urethane, allophanate, isocyanurate,
  • Polyurethane is preferably prepared from liquid starting components, i.e. the starting materials to be reacted with one another being mixed together in a one-shot process.
  • incorporación of the additives and/or stabilizer blends into the polyether polyol, polyester polyol or polyurethane is carried out by known methods, for example before or during compounding, extrusion, co-extrusion or can also be added before or during polymerisation or before crosslinking.
  • the additives and/or stabilizer blends are added before polymerisation, they can be dissolved in one or all reactants. They are preferably dissolved in the polyether polyol or polyester polyol.
  • compositions of this invention will help to fulfil needs and/or requirements for the polyurethane industry, in providing polyurethane (PU) compounds, thermoplastic PU, cast PU, reaction injection molding (RIM), spray coating, PU skin.
  • PU polyurethane
  • RIM reaction injection molding
  • compositions according to the invention can be advantageously used for various purposes and for the preparation of various shaped articles. Examples are:
  • Bushes for motor vehicle electrics, insulants, printed circuits, potting, semiconductors, switches, switch gears, medium and high voltage transformers.
  • Bonding of textile onto foam direct glazing of vehicle windscreens, glazing replacement, fastening of various car components, vacuum lamination of foil to fiberboard.
  • Binding agent for re-milled rubber waste the composite materials are mainly used as molded tiles, playgrounds (in-situ), running tracks (in-situ).
  • V-3-A Automotive applications, in particular as instrument clusters, sound insulation, carpeting, seating, decorative trim, exterior applications such as weather stripping, exterior trim, light lens units, and windshield assemblies, recreational vehicle side walls.
  • V-3-B Textile applications, in particular lamination, profile wrapping.
  • V-3-C Furniture industry, in particular for bonding bond solid wood, wood composites, metal hardware, and decorative plastic laminates.
  • V-3-D Construction industry, in particular assembly of door and window frames and corner covering for linoleum flooring.
  • Adhesives for shoe bond upper to sole
  • toe caps porosity
  • furniture do it yourself and automotive.
  • Household appliances cables outdoor electrical cables, industrial cables and wire.
  • Pneumatic transport systems ventilation systems, pneumatic control units, pneumatic breaks, hydraulic tubes, corrugated pipes, fire hoses, vacuum cleaner tubes.
  • TPUs are made from both aromatic and aliphatic TPUs. Typical applications are barrier film, adhesive film, seam tape, inter layer in security glass.
  • Ear tags are Ear tags, wheels, horse shoes, plugs, wrist watch straps.
  • Gear shift knobs bearing sockets, cable plugs, bushings, casings, friction bearings.
  • Hydraulic seals stripper rings, gaskets, pneumatic seals, membranes.
  • RIM in particular bumpers, sunroof, front and rear skirts, door sill scuff plates.
  • TPU in particular front and rear skirts, doorsill scuff plates, cable sheeting, gearshift knob, instrument panel.
  • Cast PU systems in particular spring aids, spring isolation, seat damping, top mounts, roll restrictors, emergency wheel, body mounts, stops in door systems.
  • Shoes/shoe-soles insoles, spats, adhesives, structural adhesives.
  • Articles for the leisure time such as sports and fitness devices, gymnastics mats, ski-boots, inline-skates, skis, big foot, athletic surfaces (e.g. tennis grounds).
  • a further embodiment of the present invention relates to a shaped article, in particular artificial leather, shock-absorbers, rollers of inline-skates and footwear, containing a composition as described above.
  • Percentages and ratios mean weight percent and weight ratios.
  • thermoplastic polyurethane (TPU) pellets (Desmopan® 385 S of Bayer Material Science®) are mixed to homogeneity in a tumble mixer with 0.33% of pentaerythritol tetrakis 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (Irganox® 1010), 0.17% of bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite (Irgafos® 126), and with the light stabilizer combinations given in the tables below.
  • This blend is then extruded in a twin-screw extruder of Berstorff® at a temperature of at most 180° C. After drawing the extrudate through a waterbath to cool, it is granulated.
  • test panels 64 mm ⁇ 40 mm ⁇ 2 mm test panels are moulded from these granules by means of an injection-moulding machine (Arburg® 320 S) at a temperature of at most 180° C. (mold temperature 50° C.). The samples are exposed in a Weatherometer (WOM) bpt 63° C., 0.35 W/m2.
  • WOM Weatherometer
  • TPU pellets 4 g are dissolved 22 g DMF as a solvent.
  • TPU films are prepared by drawing film with a 250 micron doctor blade. The DMF solvent is evaporated and the films are dried. The final film thickness is about 40 micron.
  • WOM Weatherometer
  • the color quality is reported in terms of Yellowness Index (YI) determined on the TPU samples in accordance with the ASTM 1926-70 Yellowness Test.
  • YI Yellowness Index

Abstract

The present invention pertains to compositions comprising
    • (a) a polyether polyol, a polyester polyol or a polyurethane,
    • (b) a UV-absorber of formula (I) and/or a hindered amine liaht stabilizer of formula (II)
Figure US20110130492A1-20110602-C00001
wherein R1 and R2 are each independently C1-C4alkyl or C1-C4alkyoxy, and
    • (c) at least one further UV-absorber and/or hindered amine light stabilizer if only one of the components (I) and (II) is present
      with the proviso that component (c) is not a compound of formula (A)-(D) as defined in claim 1.

Description

  • This application is a continuation of application Ser. No. 11/630,230, pending, which is a national stage of international app. No. PCT/EP 2005/052843, filed Jun. 20, 2005, the contents of which applications are incorporated herein by reference.
  • The present invention pertains to compositions comprising a polyether polyol, a polyester polyol or a polyurethane susceptible to light induced degradation, and a mixture of at least two different light stabilizers, one of them being a specific UV-absorber and/or hindered amine light stabilizer.
  • DE 101 48 702 A1 pertains to stabilizer blends comprising an antioxidant, a HALS compound, a UV-absorber and a phosphorus compound. The initial yellowness of thermoplastic polyurethane stabilized with such a blend of stabilizers is not so great.
  • WO 03/095543 relates to stabilizer mixtures for polymer substrates comprising benzylidene-bis-malonates and at least one compound selected from the group consisting of UV-absorbers, hindered amine stabilizers, sterically hindered phenols, organophosphines, organophosphites and organophosphonites. Such stabilizer mixtures provide protection of polymeric substrates against the damaging influence of light exposure by long term storage of polymers.
  • EP 0714931 A discloses a mixture of Tinuvin® 312, Tinuvin® 770 and Chimassorb® 81 in a polyurethane.
  • WO 2004/068217 A describes a polyurethane composition comprising Tinuvin® 144, Tinuvin® 765 and Irganox® 1010.
  • WO 03/078148 A relates to a polyurethane composition comprising Tinuvin® 144, Tinuvin® 765 and Uvinul® 3040.
  • There is a strong demand from the polyurethane industry to have systems with excellent initial color and good light fastness. This is especially important for the shoe industry where good color stability is required, e.g. for thermoplastic polyurethane (TPU). Furthermore, there is a need for non-yellowing or low-yellowing polyurethane hot melt adhesives and silylated polyurethane (SPUR) sealants and artificial leather, especially based on aromatic isocyanates.
  • The polyether polyol, polyester polyol or polyurethane compositions according to the present invention have an excellent initial color after processing, good light stability and also good gas fading resistance.
  • The present invention pertains to a composition comprising
      • (a) a polyether polyol, a polyester polyol or a polyurethane,
      • (b) a UV-absorber of formula (I) and/or a hindered amine light stabilizer of formula (II)
  • Figure US20110130492A1-20110602-C00002
  • wherein R1 and R2 are each independently C1-C4alkyl or C1-C4alkyoxy, and
      • (c) at least one further UV-absorber and/or hindered amine light stabilizer if only one of the components (I) and (II) is present
        with the proviso that component (c) is not a compound of formula (A)-(D)
  • Figure US20110130492A1-20110602-C00003
  • As evident from this definition, the composition of this invention must contain either (i) a UV-absorber of formula (I) and a hindered amine of formula (II); or (ii) a UV-absorber of formula (I) and a UV-absorber or/and a hindered amine different from formulae (I) and (II); or (iii) a hindered amine of formula (II) and a UV-absorber or/and a hindered amine different from formulae (I) and (II). Of course, also in case (i) further UV-absorbers or/and hindered amines may be present.
  • Of interest is an instant composition that comprises as component (c) a hindered amine light stabilizer of formula HA-1 to HA-11 or a UV-absorber of formula UV-1 to UV-8 as defined below.
  • Of particular interest is an instant composition comprising as component (c) a hindered amine light stabilizer of formula HA-1 to HA-11 or a UV-absorber of formula UV-1 to UV-7.
  • In addition to the light stabilizers (b) and/or (c) the compositions of the instant invention preferably contain further additives.
  • Such further additives may for example be:
  • 1. Antioxidants
  • 1.1. Alkylated monophenols, for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-di-methylphenol, 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-(α-methylcyclohexyl)-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-dimethyl-6-(1′-methylheptadec-1′-yl)phenol, 2,4-dimethyl-6-(1′-methyltridec-1′-yl)phenol and mixtures thereof.
  • 1.2. 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, 2,4-dodecylthiomethyl-6-tert-butylphenol, 2,4-dodecylthiomethyl-6-methylphenol.
  • 1.3. Hydroquinones and alkylated hydroquinones, for example 2,6-di-tert-butyl-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.
  • 1.4. Tocopherols, for example α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol and mixtures thereof (vitamin E).
  • 1.5. 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)-disulfide.
  • 1.6. 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-(α-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-(α-methylbenzyl)-4-nonylphenol], 2,2′-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol], 4,4′-methylenebis(2,6-di-tert-butylphenol), 4,4′-methylenebis(6-tert-butyl-2-methylphenol), 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane, ethylene glycol bis[3,3-bis(3′-tert-butyl-4′-hydroxphenyl)butyrate], bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopentadiene, bis[2-(3′-tert-butyl-2′-hydroxy-5′-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate, 1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane, 2,2-bis(3,5-di-tert-butyl-4-hydroxyphenyl)propane, 2,2-bis-(5-tert-butyl-4-hydroxy2-methylphenyl)-4-n-dodecylmercaptobutane, 1,1,5,5-tetra(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.
  • 1.7. O-, N- and S-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, bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate, bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.
  • 1.8. 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.
  • 1.9. Aromatic hydroxybenzyl 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.
  • 1.10. 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)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine, 2,4,6-tris-(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, 2,4,6-tris-(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexahydro-1,3,5-triazine, 1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzypisocyanurate. 1.11. Benzylphosphonates, for example dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl3,5-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.
  • 1.12. Acylaminophenols, for example 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.
  • 1.13. Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)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, trimethylol-propane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
  • 1.14. Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with mono- or poly-hydric 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-2,6,7-trioxabicyclo[2.2.2]octane; 3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]-undecane.
  • 1.15. Esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)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]octane.
  • 1.16. Esters of 3,5-di-tert-butyl-4-hydroxyphenyl 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.
  • 1.17. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid e.g. N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide, N,N′-bis(3,5-di-tert-butyl-4-hydroxy-phenylpropionyl)trimethylenediamide, N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazide, N,N′-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxamide (Naugard®XL-1, supplied by Uniroyal).
  • 1.18. Ascorbic acid (vitamin C) 1.19. Aminic antioxidants, for example N,N′-di-isopropyl-p-phenylenediamine, N,N′-di-sec-butyl-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′-diphenyl-p-phenylenediamine, N,N′-bis(2-naphthyl)-p-phenylenediamine, N-isopropyl-N′-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine, N-(1-methylheptyl)-N′-phenyl-p-phenylenediamine, N-cyclohexyl-N′-phenyl-p-phenylenediamine, 4-(p-toluenesulfamoyl)diphenylamine, N,N′-dimethyl-N,N′-di-sec-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, for example p,p′-di-tert-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol, bis(4-methoxyphenyl)amine, 2,6-di-tert-butyl-4-dimethylaminomethylphenol, 2,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, N,N,N′,N′-tetra-methyl-4,4′-diaminodiphenylmethane, 1,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(phenylamino)propane, (o-tolyl)biguanide, bis[4-(1′,3′-dimethylbutyl)phenyl]amine, tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- and dialkylated tert-butyl/tert-octyldiphenylamines, a mixture of mono- and dialkylated nonyldiphenylamines, a mixture of mono- and dialkylated dodecyldiphenylamines, a mixture of mono- and dialkylated isopropyl/isohexyldiphenylamines, a mixture of mono- and dialkylated tert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, a mixture of mono- and dialkylated tert-butyl/tert-octylphenothiazines, a mixture of mono- and dialkylated tert-octylphenothiazines, N-allylphenothiazine, dinonylphenothiazine, mono-nonylphenothiazine, a mixture of mono- and dialkylated nonylphenothiazine, N,N,N′,N′-tetraphenyl-1,4-diaminobut-2-ene, a mixture of one of the above disclosed unsubstituted or substituted diphenylamine with one of the above disclosed unsubstitutued or substituted phenothiazine.
  • 2. Other UV Absorbers and Light Stabilizers
  • 2.1. 2-(2′-Hydroxyphenyl)benzotriazoles, for example 2-(2′-hydroxy-5′-methylphenyl)benzotriazole, 2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)benzotriazole, 2-(5′-tert-butyl-2′-hydroxyphenyl)benzotriazole, 2-(2′-hygroxy-5′-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole, 2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3′-tert-butyl-2′-hydroxy-5′-methylphenyl)-5-chlorobenzotriazole, 2-(3′-sec-butyl-5′-tert-butyl-2′-hydroxyphenyl)benzotriazole, 2-(2′-hydroxy-4′-octyloxyphenyl)benzotriazole, 2-(3′,5′-di-tert-amyl-2′-hydroxphenyl)benzotriazole, 2-(3′,5′-bis(α,α-dimethylbenzyl)-2′-hydroxyphenyl)benzotriazole, 2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)-5-chlorobenzotriazole, 2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)carbonylethyl]-2′-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)-5-chlorobenzotriazole, 2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)benzotriazole, 2-(3′-tert-butyl-2′-hydroxy-5′-(2-octylmcarbonylethyl)phenyl)benzotriazole, 2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)carbonylethyl]-2′-hydroxyphenyl)benzotriazole, 2-(3′-dodecyl-2′-hydroxy-5′-methylphenyl)benzotriazole, 2-(3′-tert-butyl-2′-hydroxy-5′-(2-isooctyloxycarbonylethyl)phenylbenzotriazole, 2,2′-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazole-2-ylphenol]; the transesterification product of 2-[3′-tert-butyl-5′-(2-methoxycarbonylethyl)-2′-hydroxyphenyl]-2H-benzotriazole with polyethylene glycol 300;
  • Figure US20110130492A1-20110602-C00004
  • where R=3′-tert-butyl-4′-hydroxy-5′-2H-benzotriazol-2-ylphenyl, 2-[2′-hydroxy-3′-(α,α-dimethylbenzyl)-5′-(1,1,3,3-tetramethylbutyl)phenyl]-benzotriazole; 2-[2′-hydroxy-3′-(1,1,3,3-tetramethylbutyl)-5′-(α,α-dimethylbenzyl)phenyl]benzotriazole.
  • 2.1a. 4-Hydroxybenzoates, for example 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, 3,5-di-tert-butyl-4-hydroxybenzoate.
  • 2.2. 2-Hydroxybenzophenones and Formamidines, for example the 4-hydroxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2′,4′-trihydroxy and 2′-hydroxy-4,4′-dimethoxy benzophenones; N-alkyl-N,N′-diarylformamidines, for example, benzoic acid, 4-[[(methylphenylamino)methylene]amino] ethyl ester [Tinuvin 101 (RTM), Ciba Specialty Chemicals Inc.]; benzoic acid, 4-[[(ethylphenylamino)methylene]amino] ethyl ester; 2-propenoic acid, 3-(4-methoxyphenyl)-, 2-ethylhexyl ester [Uvinul 3088 (RTM), BASF]; 2-propenoic acid, 2-cyano-3,3-diphenyl-, ethyl ester [Uvinul 3035 (RTM), BASF]; or 2-propenoic acid, 2-cyano-3,3-diphenyl-, 2-ethylhexyl ester [Uvinul 3039 (RTM), BASF].
  • 2.3. Esters of substituted and unsubstituted benzoic acids, for example 4-tert-butylphenyl 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.
  • 2.4. Acrylates, for example ethyl α-cyano-β,β-diphenylacrylate, isooctyl α-cyano-β,β-diphenylacrylate, methyl α-carbomethoxycinnamate, methyl α-cyano-β-methyl-p-methoxycinnamate, butyl α-cyano-β-methyl-p-methoxycinnamate, methyl α-carbomethoxy-p-methoxycinnamate and N-(β-carbomethoxy-β-cyanovinyl)-2-methylindoline.
  • 2.5. Nickel compounds, for example nickel complexes of 2,2′-thiobis[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-methylphenylundecylketoxime, nickel complexes of 1-phenyl-4-Iauroyl-5-hydroxypyrazole, with or without additional ligands.
  • 2.6. Further hindered amine light stabilizers, for example bis(2,2,6,6-tetramethyl-4-piperidyl)succinate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, the condensate of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, linear or cyclic condensates of N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-triazine, tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, 1,1′-(1,2-ethanediyl)-bis(3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione, bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate, bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)succinate, linear or cyclic condensates of N,N′-bis(2,2,6,6-tetramethyl-4-piperidyphexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate of 2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazine and 1,2-bis(3-aminopropylamino)ethane, the condensate of 2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazine and 1,2-bis(3-aminopropylamino)ethane, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione, 3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyr rolidine-2,5-dione, 3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione, a mixture of 4-hexadecyloxy- and 4-stearyloxy-2,2,6,6-tetramethylpiperidine, a condensate of N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, a condensate of 1,2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro-1,3,5-triazine as well as 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No. [136504-96-6]); a condensate of 1,6-hexanediamine and 2,4,6-trichloro-1,3,5-triazine as well as N,N-dibutylamine and 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No. [192268-64-7]); N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimide, N-(1,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimide, 2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro[4,5]decane, a reaction product of 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro-[4,5]decane and epichlorohydrin, 1,1-bis(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)-2-(4-methoxyphenypethene, N,N′-bis-formyl-N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine, a diester of 4-methoxymethylenemalonic acid with 1,2,2,6,6-pentamethyl-4-hydroxypiperidine, poly[methylpropyl-3-oxy-4-(2,2,6,6-tetramethyl-4-piperidyl)]siloxane, a reaction product of maleic acid anhydride-a-olefin copolymer with 2,2,6,6-tetramethyl-4-aminopiperidine or 1,2,2,6,6-pentamethyl-4-aminopiperidine; HA-6) as defined below.
  • 2.7. 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, 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-butoxanilide, mixtures of o- and p-methoxy-disubstituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides.
  • 2.8. 2-(2-Hydroxyphenyl)-1,3,5-triazines, for example 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-propyloxphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-tridecyloxwhenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-butyloxypropoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropyloxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine, 2-[4-(dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)phenyl]-4,6-bis(2,4-dimethyl-phenyl)-1,3,5-triazine, 2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine, 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine, 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazine, 2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine, 2-{2-hydroxy-4-[3-(2-ethylhexyl-1-oxy)-2-hydroxypropyloxy]phenyl}-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.
  • 3. 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-hydroxyphenylpropionyphydrazine, 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.
  • 4. Phosphites and phosphonites, for example triphenyl phosphite, diphenylalkyl phosphites, phenyldialkyl phosphites, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylpentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,4-dicumylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl)-pentaerythritol diphosphite, bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl) 4,4′-biphenylene diphosphonite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz[d,g]-1,3,2-dioxaphosphocin , bis(2,4-di-tert-butyl-6-methylphenyl)methyl phosphite, bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz[d,g]-1,3,2-dioxaphosphocin, 2,2′,2″-nitrilo-[triethyltris(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)phosphite], 2-ethylhexyl(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)phosphite, 5-butyl-5-ethyl-2-(2,4,6-tri-tert-butylphenoxy)-1,3,2-dioxaphosphirane.
  • 5. 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,N-dialkylhydroxylamine derived from hydrogenated tallow amine.
  • 6. Nitrones, for example N-benzyl-alpha-phenylnitrone, N-ethyl-alpha-methylnitrone, N-octyl-alpha-heptylnitrone, N-lauryl-alpha-undecylnitrone, N-tetradecyl-alpha-tridecylnitrone, N-hexadecyl-alpha-pentadecylnitrone, N-octadecyl-alpha-heptadecylnitrone, N-hexadecyl-alpha-heptadecylnitrone, N-ocatadecyl-alpha-pentadecylnitrone, N-heptadecyl-alpha-hepta-decylnitrone, N-octadecyl-alpha-hexadecylnitrone, nitrone derived from N,N-dialkylhydroxylamine derived from hydrogenated tallow amine.
  • 7. Thiosynergists, for example dilauryl thiodipropionate or distearyl thiodipropionate.
  • 8. Peroxide scavengers, for example esters of β-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((β-dodecylmercapto)propionate.
  • 9. Basic co-stabilisers, 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.
  • 10. Fillers and reinforcing agents, for example calcium carbonate, silicates, glass fibres, glass bulbs, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood flour and flours or fibers of other natural products, synthetic fibers.
  • 11. Other additives, for example plasticisers, lubricants, emulsifiers, pigments, rheology additives, catalysts, flow-control agents, optical brighteners, flameproofing agents, antistatic agents and blowing agents.
  • 12. Benzofuranones and indolinones, for example those disclosed in U.S. Pat. No. 4,325,863; U.S. Pat. No. 4,338,244; U.S. Pat. No. 5,175,312; U.S. Pat. No. 5,216,052; U.S. Pat. No. 5,252,643; DE-A-4316611; DE-A-4316622; DE-A-4316876; EP-A-0589839; EP-A-0591102 or EP-A-1291384 or 3-[4-(2-acetoxyethoxy)phenyl]-5,7-di-tert-butylbenzofuran-2-one, 5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one, 3,3′-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)-benzofuran-2-one], 5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one, 3-(4-acetm-3,5-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one, 3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butylbenzofuran-2-one, 3-(3,4-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one, 3-(2,3-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one or 3-(2-acetyl-5-isooctylphenyl)-5-isooctylbenzofuran-2-one.
  • 13. Anti-gas fading agents, for example 1,1,1′,1′-tetramethyl-4,4′-(methylene-di-p-phenylene)disemicarbazide; 1,6-hexamethylene bis(N,N-dimethylsemicarbazide); 11-[6-[[(2,2-dimethylhydrazino)carbonyl]amino]hexyl]-10,12-dioxo-, bis(2 ,2-d imethylhydrazide).
  • The further additives are added, for example, in concentrations of 0.01 to 10%, relative to the total weight of the composition of this invention.
  • Preferably, such further stabilizers are antioxidants, further light-stabilizers and/or processing stabilizers.
  • More preferably, such further stabilizers are phenolic and/or aminic antioxidants, further hindered amine light stabilizers, further UV-absorbers, phosphites, phosphonites and/or benzofuranones.
  • Of outstanding interest are compositions, where the further stabilizers are further hindered amine light stabilizers, further UV-absorbers, phenolic antioxidants and/or phosphites.
  • Of interest are also such compositions, wherein component (b) is a combination of a UV-absorber of formula (I) and a hindered amine light stabilizer of formula (II).
  • Preferred are compositions, wherein the UV-absorber of formula (I) is a compound of formula (Ia).
  • Figure US20110130492A1-20110602-C00005
  • An embodiment of the present invention is a composition, wherein component (b) is a UV-absorber of formula (I) and component (c) is a hindered amine light stabilizer.
  • Another embodiment of the present invention is a composition, wherein component (b) is a hindered amine light stabilizer of formula (II) and component (c) is a UV-absorber.
  • Of interest are compositions, wherein the overall amount of component (b) and (c) is 0.01% to 5%, based on the weight of the composition.
  • Of special interest are compositions, wherein the overall amount of component (b) and (c) is 0.5% to 2%, based on the weight of the composition.
  • Preferred are compositions, wherein the ratio of components (b):(c) or of the compounds of formulae (I):(II) respectively is from 10:1 to 1:10.
  • Most preferred are compositions, wherein the ratio of components (b):(c) or of the compounds of formulae (I):(II) respectively is from 3:1 to 1:3.
  • Preferably, the compositions according to this invention do not contain benzylidene-bis-malonates. Such benzylidene-bis-malonates are disclosed in WO 03/095543.
  • The present invention also pertains to the use of a mixture of component (b) and (c) as defined herein as stabilizer for a polyether polyol, a polyester polyol or a polyurethane against degradation by light, oxygen and/or heat.
  • Preferred is the use of such mixtures that additionally comprise further additives and/or stabilizers. The further additives and/or stabilizers may be as defined herein.
  • The present invention also pertains to a process for stabilizing a polyether polyol, a polyester polyol or a polyurethane against degradation by light, oxygen and/or heat, which process comprises incorporating into said material a mixture of component (b) and (c) as defined herein.
  • Preferred is a process for stabilizing a polyether polyol, a polyester polyol or a polyurethane against degradation by light, oxygen and/or heat, which process comprises incorporating into said material a mixture comprising component (b) and (c) as defined herein and additionally comprises further additives and/or stabilizers. The further additives and/or stabilizers may be as defined herein.
  • Hindered amine light stabilizers are preferably compounds containing at least one group of formula (III)
  • Figure US20110130492A1-20110602-C00006
  • wherein G1 and G2 are independently alkyl of 1 to 4 carbon atoms, or G1 and G2 together are pentamethylene; preferably G1 and G2 are each methyl.
    Figure US20110130492A1-20110602-P00001

    specifies the border of a chemical group and does not have a chemical meaning by itself.
  • The hindered amine light stabilizers useful as component (c) may be the ones mentioned in 2.6. herein above and the ones disclosed in WO 01/62836, WO 02/02706 and DE 10008367, which are incorporated here by reference.
  • Preferred hindered amine light stabilizers are compounds of formulae (100)-(104) or 7-Oxa-3,20-diazadispiro[5.1.11.2]heneicosan-21-one, 2,2,4,4-tetramethyl-20-(oxiranylmethyl)-, polymer with (chloromethyl)oxirane;
  • Figure US20110130492A1-20110602-C00007
  • wherein
  • E is hydrogen, C1-C18alkyl, C1-C18alkoxy or C1-C18alkoxy substituted by 1 OH;
  • n1 is 1 or 2;
  • when n1 is 1, R3 is C1-C25alkyl or —CO—R10;
  • when n1 is 2, R3 is C2-C14alkylene or —CO—R11—CO—;
  • R10 is C1-C23alkyl;
  • R11 is C2-C14-alkylene;
  • n2 is 2 to 4;
  • n3 is 1 to 3,
  • R5 is hydrogen or C1-C12alkyl;
  • R4 is the group T1,
  • T1 is
  • Figure US20110130492A1-20110602-C00008
  • n4 is 2 to 8,
  • n5 is 1 to 50;
  • R6 is morpholino, piperidino, 1-piperizinyl, alkylamino of 1 to 8 carbon atoms, especially branched alkylamino of 3 to 8 carbon atoms such as tert-octylamino, —N(alkyl)T2 with alkyl of 1 to 8 carbon atoms, or —N(alkyl)2 of 2 to 16 carbon atoms,
  • T2 is
  • Figure US20110130492A1-20110602-C00009
  • R7 is hydrogen, acyl of 2 to 4 carbon atoms, carbamoyl substituted by alkyl of 1 to 4 carbon atoms, s-triazinyl substituted once by chlorine and once by R6, or s-triazinyl substituted twice by R6 with the condition that the two R6 substituents may be different;
  • R8 is chlorine, amino substituted by alkyl of 1 to 8 carbon atoms or by T2, —N(alkyl)T2 with alkyl of 1 to 8 carbon atoms, —N(alkyl)2 of 2 to 16 carbon atoms, or the group T3,
  • T3 is
  • Figure US20110130492A1-20110602-C00010
  • R12 is hydrogen, acyl of 2 to 4 carbon atoms, carbamoyl substituted by alkyl of 1 to 4 carbon atoms, s-triazinyl substituted twice by —N(alkyl)2 of 2 to 16 carbon atoms or s-triazinyl substituted twice by —N(alkyl)T2 with alkyl of 1 to 8 carbon atoms;
  • Al is hydrogen or C1-C4alkyl,
  • A2 is a direct bond or C1-C10alkylene,
  • A3 is C1-C4alkyl or C1-C4alkoxy and
  • n6 is a number from 2 to 50, preferably 2 to 20;
  • n8 is 2 to 12.
  • Of particular interest as component (c) are UV-absorbers of the hydroxyphenyl-triazine, benzotriazole, benzophenone, oxanilide, acrylate and cyanacrylate classes.
  • The hydroxyphenyl triazine UV absorber usually is selected from known compounds, described e.g. in GB-A-975966, EP-A-434608, U.S. Pat. No. 4,619,956, U.S. Pat. No. 5,298,067, EP-A-530135, EP-A-520938, EP-A-531258, U.S. Pat. No. 5,556,973, U.S. Pat. No. 5,959,008, U.S. Pat. No. 6,184,375, U.S. Pat. No. 6,117,997; preferred are compounds as described in U.S. Pat. No. 5,998,116, U.S. Pat. No. 6,255,483, U.S. Pat. No. 6,060,543.
  • Examples for hydroxyphenyl triazine UV absorbers are compounds conforming to formula (200), (201) or (202)
  • Figure US20110130492A1-20110602-C00011
  • wherein
  • 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 are independently Z1 or Z2;
  • R13 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, —SR17, —SOR17 or —SO2R17; or said alkyl, said cycloalkyl or said phenylalkyl substituted by one to three halogen, —R18, —OR19, —N(R19)2, —COR19, —COOR19, —OCOR19, —CN, —NO2, —SR19, —SOR19, —SO2R19 or —P(O)(OR19)2, morpholinyl, piperidinyl, 2,2,6,6-tetramethylpiperidinyl, piperazinyl or N-methylpiperidinyl groups or combinations thereof; or said alkyl or said cycloalkyl interrupted by one to four phenylene, —O—, —NR19—, —CONR19—, —COO—, —OCO— or —CO groups or combinations thereof; or said alkyl or said cycloalkyl both substituted and interrupted by combinations of the groups mentioned above;
  • R17 is alkyl of 1 to 20 carbon atoms, alkenyl of 3 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, aryl of 6 to 10 carbon atoms or said aryl substituted by one or two alkyl of 1 to 4 carbon atoms;
  • R18 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;
  • R19 is defined as is R18; or R19 is also hydrogen or straight or branched chain alkyl of 1 to 24 carbon atoms, alkenyl of 2 to 24 carbon atoms; or R19 is a group for formula
  • Figure US20110130492A1-20110602-C00012
  • T is hydrogen, oxyl, hydroxyl, —OT4, alkyl of 1 to 24 carbon atoms, said alkyl substituted by one to three hydroxy; benzyl or alkanoyl of 2 to 18 carbon atoms;
  • T4 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 o 10 carbon atoms or said aryl substituted by one to three alkyl of 1 to 4 carbon atoms;
  • R14 is hydrogen, straight or branched chain alkyl of 1 to 24 carbon atoms or cycloalkyl of 5 to 12 carbon atoms or R20; or said alkyl or said cycloalkyl substituted by one to four halogen, hydroxy, epoxy, glycidyloxy, furyloxy, —R18, —OR19, —N(R19)2, —CON(R19)2, —COR19, —COOR19, —OCOR19, —OCOC(R19)═C(R19)2, —C(R19)═CCOOR19, —CN, —NCO, or
  • Figure US20110130492A1-20110602-C00013
  • or combinations thereof; or said alkyl or said cycloalkyl interrupted by one to four epoxy, —O—, —NR19—, —CONR19—, —COO—, —OCO—, —CO—, —C(R19)═C(R19)COO—, —OCOC(R19)═C(R19)—, —C(R19)═C(R19)—, phenylene or phenylene-G-phenylene in which G is —O—, —S—, —SO2—, —CH2— or —C(CH3)2— or combinations thereof, or said alkyl or said cycloalkyl both substituted and interrupted by combinations of the groups mentioned above; or R14 is —SO2R17 or —COR21;
  • R21 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, —R22COOH or —NH—R23—NCO;
  • R22 is alkylene of 2 to 14 carbon atoms or phenylene;
  • R23 is alkylene of 2 to 24 carbon atoms, phenylene, tolylene, diphenylmethane or a group
  • Figure US20110130492A1-20110602-C00014
  • R13, R15 and R13″ are the same or different and are as defined for R13;
  • R14, R16 and R14″ are the same or different and are as defined for R14;
  • Z1 is a group of formula
  • Figure US20110130492A1-20110602-C00015
  • Z2 is a group of formula
  • Figure US20110130492A1-20110602-C00016
  • where
  • r13 and r14 are independetly of each other 0 or 1;
  • R20, R24, R25, R26, R27, R28, R29, R30, R31 and R32 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 R26 and R27 or R31 and R32 together with the phenyl radical to which they are attached are a cyclic radical interrupted by one to three —O— or —NR19—.
  • Examples of hydroxyphenyltriazines are the compounds (a1)-(a19)
  • a1) 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine,
  • a2) 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,
  • a3) 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,
  • a4) 2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine,
  • a5) 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine,
  • a6) 2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,
  • a7) 2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,
  • a8) 2-[2-hydroxy-4-(2-hydroxy-3-butyloxypropoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,
  • a9) 2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropyloxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,
  • a10) 2-(2-hydroxy-4-[2-ethylhexyl]oxyphenyl)-4,6-di(4-phenylphenyl)-1,3,5-triazine,
  • a11) 2-(2-hydroxy-4-[2-heptylcarbonyloxyethoxy]phenyl)-4,6-diphenyl-1,3,5-triazine,
  • a12) 2-(2,4-dihydroxyphenyl)-4,6-diphenyl-1,3,5-triazine,
  • a13) 2-[4-(dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)1,3,5-triazine,
  • a14) 2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxpropoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,
  • a15) 2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine,
  • a16) 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine,
  • a17) 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazine,
  • a18) 2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine,
  • a19) 2-{2-hydroxy-4-[3-(2-ethylhexyl-1-oxy)-2-hydroxypropyloxy]phenyl}-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.
  • Examples of UV-absorber of the benzotriazole class are compounds of formula (206) and/or (207),
  • Figure US20110130492A1-20110602-C00017
  • wherein
  • R33 is hydrogen, halogen, C1-C4alkyl or C1-C8alkoxy;
  • R34 is hydrogen, C1-C18alkyl or C1-C8alkyl substituted by phenyl;
  • R35 is C1-C12alkyl, —CH2CH2—CO—R37 or C1-C8alkyl substituted by phenyl;
  • R37 is a monovalent polyethylene oxide residue;
  • R36 is a divalent polyethylene oxide residue;
  • Examples of benzotriazoles are the compounds (b1)-(b23)
  • b1) 2-(2′-hydroxy-6-methylphenyl)benzotriazole,
  • b2) 2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)benzotriazole,
  • b3) 2-(5′-tert-butyl-2′-hydroxyphenyl)benzotriazole,
  • b4) 2-(2′-hydroxy-5′-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole,
  • b5) 2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)-5-chlorobenzotriazole,
  • b6) 2-(3′-tert-butyl-2′-hydroxy-5′-methylphenyl)-5-chlorobenzotriazole,
  • b7) 2-(3′-sec-butyl-5′-tert-butyl-2′-hydroxyphenyl)benzotriazole,
  • b8) 2-(2′-hydroxy-4′-octyloxyphenyl)benzotriazole,
  • b9) 2-(3′,5′-di-tert-amyl-2′-hydroxyphenyl)benzotriazole,
  • b10) 2-(3′,5′-bis(a,a-dimethylbenzyl)-2′-hydroxyphenyl)benzotriazole,
  • b11) 2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)-5-chlorobenzotriazole,
  • b12) 2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)carbonylethyl]-2′-hydroxyphenyl)-5-chlorobenzotriazole,
  • b13) 2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)-5-chlorobenzotriazole,
  • b14) 2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)benzotriazole,
  • b15) 2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)benzotriazole,
  • b16) 2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)carbonylethyl]-2′-hydroxyphenyl)benzotriazole,
  • b17) 2-(3′-dodecyl-2′-hydroxy-5′-methylphenyl)benzotriazole,
  • b18) 2-(3′-tert-butyl-2′-hydroxy-5′-(2-isooctyloxycarbonylethyl)phenylbenzotriazole,
  • b19) 2,2′-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazole-2-ylphenol],
  • b20) the transesterification product of 2-[3′-tert-butyl-5′-(2-methoxycarbonylethyl)-2′-hydroxyphenyl]-2H-benzotriazole with polyethylene glycol 300,
  • b21)
  • Figure US20110130492A1-20110602-C00018
  • where R =3′-tert-butyl-4′-hydroxy-5′-2H-benzotriazol-2-ylphenyl,
  • b22) 2-[2′-hydroxy-3′-(α,α-dimethylbenzyl)-5′-(1,1,3,3-tetramethylbutyl)phenyl]benzotriazole,
  • b23) 2-[2′-hydroxy-3′-(1,1,3,3-tetramethylbutyl)-5′-(α,α-dimethylbenzyl)phenyl]benzotriazole.
  • The phenolic antioxidant may be a compound of formula (300), (301) or (302)
  • Figure US20110130492A1-20110602-C00019
  • wherein R38 and R39 are independently C1-C8alkyl, R47 is C1-C18alkyl;
  • or the phenolic antioxidant may be any compound listed in items 1.1-1.17 in the list of stabilizers given above.
  • The phosphite may be a compound of formula (400) or (401)
  • Figure US20110130492A1-20110602-C00020
  • wherein R40, R41, R42 and R43 are independently C1-C8alkyl; or R40 and R42 may independently be hydrogen;
  • R44, R45 and R46 are independently hydrogen or C1-C8alkyl;
  • or the phosphite may be any phosphite compound listed in item 4 in the list of stabilizers given above.
  • The term alkyl may comprise within the limits of the given number of carbon atoms, 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, 2-methylheptyl, 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 or dodecyl.
  • In the context of the description of the present invention, the term alkylene comprises within the limits of the given number of carbon atoms, for example methylene and the branched and unbranched isomers of ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene and tetradecylene.
  • The term alkoxy may comprise within the limits of the given number of carbon atoms, for example methoxy and ethoxy and the branched and unbranched isomers of propoxy, butoxy, pentoxy, hexoxy, heptoxy, octoxy, nonoxy, decoxy, undecoxy, dodecoxy, tridecoxy, tetradecoxy, pentadecoxy, hexadecoxy, heptadecoxy and octadecoxy.
  • The term halogen comprises for example chlorine, bromine and iodine.
  • The term aryl comprises for example phenyl and naphthyl.
  • Examples of alkenyl are vinyl, allyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl and dodecenyl.
  • Of special interest are the following hindered amine light stabilizers:
  • Figure US20110130492A1-20110602-C00021
  • n7 is 2 to 50, preferably 2 to 20, particular preference is given to the commercial product TINUVIN® 622.
  • Figure US20110130492A1-20110602-C00022
  • this compound is described in U.S. Pat. No. 4,477,615; n8 is 2 to 12; particular preference is given to the commercial product UVASORB® HA-88.
  • Figure US20110130492A1-20110602-C00023
  • n9 is 2 to 50, preferably 2 to 20, the endgroups preferably being
  • Figure US20110130492A1-20110602-C00024
  • particular preference is given to the commercial product CYASORB® UV-3529.
  • Figure US20110130492A1-20110602-C00025
  • n10 is 2 to 50, preferably 2 to 20, the endgroups preferably being
  • Figure US20110130492A1-20110602-C00026
  • particular preference is given to the commercial product CYASORB® UV-3346.
  • Figure US20110130492A1-20110602-C00027
  • n11 is 2 to 50, preferably 2 to 20, with the endgroups preferably being
  • Figure US20110130492A1-20110602-C00028
  • particular preference is given to the commercial product CHIMASSORB® 944.
  • Figure US20110130492A1-20110602-C00029
  • n12 is 2 to 50, preferably 2 to 20, with the endgroups preferably being
  • Figure US20110130492A1-20110602-C00030
  • particular preference is given to the commercial product CHIMASSORB® 2020.
  • Figure US20110130492A1-20110602-C00031
  • n14 is 2 to 50, preferably 2 to 20, with the endgroups preferably being
  • Figure US20110130492A1-20110602-C00032
  • particular preference is given to the commercial product Tinuvin® NOR 371.
  • HA-11) 7-Oxa-3,20-diazadispiro[5.1.11.2]heneicosan-21-one, 2,2,4,4-tetramethyl-20-(oxiranylmethyl)—, polymer with (chloromethyl)oxirane, for example
  • Figure US20110130492A1-20110602-C00033
  • n15 is 2 to 50, for example 2 to 25; the end group bonded to the nitrogen can be, for example, hydrogen and the end group bonded to the 2-hydroxypropylene radical can be, for example,
  • Figure US20110130492A1-20110602-C00034
  • particular preference is given to the commercial product Hostavin® N30.
  • Of interest are the following UV-absorbers:
  • Figure US20110130492A1-20110602-C00035
  • n13 is 2 to 20, for example 3 to 10; preferably, this compound is a mixture of polyethylene glycol and mono- and diesters; particular preference is given to the commercial product TINUVIN® 213.
  • Figure US20110130492A1-20110602-C00036
  • Of particular interest are the UV-absorbers UV-1 to UV-7.
  • Preferably, the phenolic antioxidant is
  • Figure US20110130492A1-20110602-C00037
  • Preferably, phosphite is
  • Figure US20110130492A1-20110602-C00038
  • The additives and stabilizers mentioned herein are mainly commercially available.
  • Preferred embodiements of this invention are a polyether polyol, a polyester polyol or a polyurethane comprising one of the following blends of commercially available additives:
  • Tinuvin® 234/Tinuvin® 144;
  • Tinuvin® 101/Tinuvin® 144;
  • Tinuvin® 312/Tinuvin 144;
  • Tinuvin® 120/Tinuvin ® 144;
  • Tinuvin® 312/Tinuvin® 622/Irganox® 1010;
  • Tinuvin® 312/Tinuvin® 123/Irganox® 1010;
  • Tinuvin® 312/Chimassorb® 119/Irganox® 1010;
  • Tinuvin® 312/Chimassorb® 944/Irganox® 1010;
  • Tinuvin® 312/Chimassorb® 2020/Irganox® 1010;
  • Tinuvin® 312/Cyasorb@ UV 3529/Irganox® 1010;
  • Tinuvin® 312/Cyasorb® UV 3346/Irganox® 1010;
  • Tinuvin® 312/Uvasorb® HA88/Irganox® 1010;
  • Tinuvin® 312/Tinuvin® 622/Irganox® 1010/Irgafos® 126;
  • Tinuvin® 312/Tinuvin® 123/Irganox® 1010/Irgafos® 126;
  • Tinuvin® 312/Chimassorb® 119/Irganox® 1010/Irgafos® 126;
  • Tinuvin® 312/Chimassorb® 944/Irganox® 1010/Irgafos® 126;
  • Tinuvin® 312/Chimassorb® 2020/Irganox® 1010/Irgafos® 126;
  • Tinuvin® 312/Cyasorb® UV 3529/Irganox® 1010/Irgafos® 126;
  • Tinuvin® 312/Cyasorb® UV 3346/Irganox® 1010/Irgafos® 126;
  • Tinuvin® 312/Uvasorb® HA88/Irganox® 1010/Irgafos® 126;
  • Tinuvin® 312/Tinuvin® 622/Irganox® 245;
  • Tinuvin® 312/Tinuvin® 123/Irganox® 245;
  • Tinuvin® 312/Chimassorb® 119/Irganox® 245;
  • Tinuvin® 312/Chimassorb® 944/Irganox® 245;
  • Tinuvin® 312/Chimassorb® 2020/Irganox® 245;
  • Tinuvin® 312/Cyasorb® UV 3529/Irganox® 245;
  • Tinuvin® 312/Cyasorb® UV 3346/Irganox® 245;
  • Tinuvin® 312/Uvasorb® HA88/Irganox® 245;
  • Tinuvin® 312/Tinuvin® 622/Irganox® 245/Irgafos® 126;
  • Tinuvin® 312/Tinuvin® 123/Irganox® 245/Irgafos® 126;
  • Tinuvin® 312/Chimassorb® 119/Irganox® 245/Irgafos® 126;
  • Tinuvin® 312/Chimassorb® 944/Irganox® 245/Irgafos® 126;
  • Tinuvin® 312/Chimassorb® 2020/Irganox® 245/Irgafos® 126;
  • Tinuvin® 312/Cyasorb® UV 3529/Irganox® 245/Irgafos® 126;
  • Tinuvin® 312/Cyasorb® UV 3346/Irganox® 245/Irgafos® 126;
  • Tinuvin® 312/Uvasorb® HA88/Irganox® 245/Irgafos® 126;
  • Tinuvin® 312/Tinuvin® 622/Irganox® 1726;
  • Tinuvin® 312/Tinuvin® 123/Irganox® 1726;
  • Tinuvin® 312/Chimassorb® 119/Irganox® 1726;
  • Tinuvin® 312/Chimassorb® 944/Irganox® 1726;
  • Tinuvin® 312/Chimassorb® 2020/Irganox® 1726;
  • Tinuvin® 312/Cyasorb® UV 3529/Irganox® 1726;
  • Tinuvin® 312/Cyasorb® UV 3346/Irganox® 1726;
  • Tinuvin® 312/Uvasorb® HA88/Irganox® 1726;
  • Tinuvin® 312/Tinuvin® 622/Irganox® 1726/Irgafos® 126;
  • Tinuvin® 312/Tinuvin® 123/Irganox® 1726/Irgafos® 126;
  • Tinuvin® 312/Chimassorb® 119/Irganox® 1726/Irgafos® 126;
  • Tinuvin® 312/Chimassorb® 944/Irganox® 1726/Irgafos® 126;
  • Tinuvin® 312/Chimassorb® 2020/Irganox® 1726/Irgafos® 126;
  • Tinuvin® 312/Cyasorb® UV 3529/Irganox® 1726/Irgafos® 126;
  • Tinuvin® 312/Cyasorb® UV 3346/Irganox® 1726/Irgafos® 126;
  • Tinuvin® 312/Uvasorb® HA88/Irganox® 1726/Irgafos® 126;
  • Tinuvin® 312/Tinuvin® 144/Irganox® 1010;
  • Tinuvin® 234/Tinuvin® 144/Irganox® 1010;
  • Tinuvin® 101/Tinuvin® 144/Irganox® 1010;
  • Tinuvin® 571/Tinuvin® 144/Irganox® 1010;
  • Tinuvin® 213/Tinuvin® 144/Irganox® 1010;
  • Tinuvin® 328/Tinuvin® 144/Irganox® 1010;
  • Uvinul® 3039/Tinuvin® 144/Irganox® 1010;
  • Uvinul® 3088/Tinuvin® 144/Irganox® 1010;
  • Tinuvin® 120/Tinuvin® 144/Irganox® 1010;
  • Tinuvin® 312/Tinuvin® 144/Irganox® 1010/Irgafos® 126;
  • Tinuvin® 234/Tinuvin® 144/Irganox® 1010/Irgafos® 126;
  • Tinuvin® 101/Tinuvin® 144/Irganox® 1010/Irgafos® 126;
  • Tinuvin® 571/Tinuvin® 144/Irganox® 1010/Irgafos® 126;
  • Tinuvin® 213/Tinuvin® 144/Irganox® 1010/Irgafos® 126;
  • Tinuvin® 328/Tinuvin® 144/Irganox® 1010/Irgafos® 126;
  • Uvinul® 3039/Tinuvin® 144/Irganox® 1010/Irgafos® 126;
  • Uvinul® 3088/Tinuvin® 144/Irganox® 1010/Irgafos® 126;
  • Tinuvin® 120/Tinuvin® 144/Irganox® 1010/Irgafos® 126;
  • Tinuvin® 312/Tinuvin® 144/Irganox® 245;
  • Tinuvin® 234/Tinuvin® 144/ Irganox® 245;
  • Tinuvin® 101/Tinuvin® 144/ Irganox® 245;
  • Tinuvin® 571/Tinuvin® 144/ Irganox® 245;
  • Tinuvin® 213/Tinuvin® 144/ Irganox® 245;
  • Tinuvin® 328/Tinuvin® 144/ Irganox® 245;
  • Uvinul® 3039/Tinuvin® 144/ Irganox® 245;
  • Uvinul® 3088/Tinuvin® 144/ Irganox® 245;
  • Tinuvin® 120/Tinuvin® 144/ Irganox® 245;
  • Tinuvin® 312/Tinuvin® 144/Irganox® 245/Irgafos® 126;
  • Tinuvin® 234/Tinuvin® 144/Irganox® 245/Irgafos® 126;
  • Tinuvin® 101/Tinuvin® 144/Irganox® 245/Irgafos® 126;
  • Tinuvin® 571/Tinuvin® 144/Irganox® 245/Irgafos® 126;
  • Tinuvin® 213/Tinuvin® 144/Irganox® 245/Irgafos® 126;
  • Tinuvin® 328/Tinuvin® 144/Irganox® 245/Irgafos® 126;
  • Uvinul® 3039/Tinuvin® 144/Irganox® 245/Irgafos® 126;
  • Uvinul® 3088/Tinuvin® 144/Irganox® 245/Irgafos® 126;
  • Tinuvin® 120/Tinuvin® 144/Irganox® 245/Irgafos® 126;
  • Tinuvin® 312/Tinuvin® 144/Irganox® 1726;
  • Tinuvin® 234/Tinuvin® 144/Irganox® 1726;
  • Tinuvin® 101/Tinuvin® 144/Irganox® 1726;
  • Tinuvin® 571/Tinuvin® 144/Irganox® 1726;
  • Tinuvin® 213/Tinuvin® 144/Irganox® 1726;
  • Tinuvin® 328/Tinuvin® 144/Irganox® 1726;
  • Uvinul® 3039/Tinuvin® 144/Irganox® 1726;
  • Uvinul® 3088/Tinuvin® 144/Irganox® 1726;
  • Tinuvin® 120/Tinuvin® 144/Irganox® 1726;
  • Tinuvin® 312/Tinuvin® 144/Irganox® 1726/Irgafos® 126;
  • Tinuvin® 234/Tinuvin® 144/Irganox® 1726/Irgafos® 126;
  • Tinuvin® 101/Tinuvin® 144/Irganox® 1726/Irgafos® 126;
  • Tinuvin® 571/Tinuvin® 144/Irganox® 1726/Irgafos® 126;
  • Tinuvin® 213/Tinuvin® 144/Irganox® 1726/Irgafos® 126;
  • Tinuvin® 328/Tinuvin® 144/Irganox® 1726/Irgafos® 126;
  • Uvinul® 3039/Tinuvin® 144/Irganox® 1726/Irgafos® 126;
  • Uvinul® 3088/Tinuvin® 144/Irganox® 1726/Irgafos® 126;
  • Tinuvin® 120/Tinuvin® 144/Irganox® 1726/Irgafos® 126.
  • More particular preference is given to a polyether polyol, a polyester polyol or a polyurethane comprising one of the following blends of commercially available additives:
  • Tinuvin® 312/Tinuvin® 144
  • Tinuvin® 312/Tinuvin® 144/Irganox® 1010;
  • Tinuvin® 312/Tinuvin® 144/Irganox® 245;
  • Tinuvin® 312/Tinuvin® 144/Irganox® 245/Irgafos® 126;
  • Tinuvin® 234/Tinuvin® 144;
  • Tinuvin® 101/Tinuvin® 144;
  • Tinuvin® 312/Tinuvin® 144/Irganox® 1010/Irgafos® 126;
  • Tinuvin® 234/Tinuvin® 144/Irganox® 1010/Irgafos® 126;
  • Tinuvin® 120/Tinuvin® 144.
  • For example, a polyether polyol, a polyester polyol or a polyurethane comprises one of the following blends of commercially available additives:
  • TINUVIN® 234/TINUVIN® 144/Irganox® 1010/Irgafos® 126;
  • TINUVIN® 312/TINUVIN® 770/Irganox® 1010/Irgafos® 126;
  • TINUVIN® 312/TINUVIN® 622/Irganox® 1010/Irgafos® 126;
  • TINUVIN® 312/TINUVIN® 144/Irganox® 1010/Irgafos® 126;
  • TINUVIN® 328/TINUVIN® 144/Irganox® 1010/Irgafos® 126.
  • Most preference is given to a polyether polyol, a polyester polyol or a polyurethane comprising one of the following blends of commercially available additives:
  • Tinuvin® 312/Tinuvin® 144/Irganox® 1010/Irgafos® 126;
  • Tinuvin® 234/Tinuvin® 144/Irganox® 1010/Irgafos® 126;
  • Tinuvin® 312/Tinuvin® 144/Irganox® 1010/Irgafos® 126;
  • Tinuvin® 312/Tinuvin® 144/Irganox® 1010;
  • Tinuvin® 234/Tinuvin® 144/Irganox® 1010;
  • Tinuvin® 312/Tinuvin® 144/Irganox® 1010.
  • Most particular preference is given to a polyether polyol, a polyester polyol or a polyurethane comprising one of the following blends of commercially available additives:
  • Tinuvin® 312/Tinuvin® 144/Irganox® 1010/Irgafos® 126;
  • Tinuvin® 234/Tinuvin® 144/Irganox® 1010/Irgafos® 126;
  • Tinuvin® 312/Tinuvin® 144/Irganox® 1010/Irgafos® 126.
  • Of special interest is a polyether polyol, a polyester polyol or a polyurethane comprising the one of the following blends of commercially available additives:
  • Tinuvin® 312/Tinuvin® 234/Tinuvin® 144/Irganox® 1010/Irgafos® 126;
  • Tinuvin® 312/Tinuvin® 234/Tinuvin® 622/Irganox® 1010.
  • The stabilizers and stabilizer blends mentioned are suitable as stabilizers for polyether polyol, polyester polyol or polyurethane against oxidative, thermal and/or light-induced degradation and as reducer of fogging contribution of the polymer.
  • The polyether polyol, polyester polyol or polyurethane composition of the present invention may be also a foam (flexible, rigid, integral), a microcellular foam, a cast PU, a PU skin, a PU hot melt adhesive, a silylated polyurethane (SPUR), a thermoplasic polyurethane (TPU) a PU elastomer, artifical leather, PU skin, PU stray coating or reaction injection molding (RIM).
  • For example, polyether polyol, polyester polyol or polyurethane composition of the present invention are not foamed.
  • The polyurethanes are obtained, for example, by reacting polyethers, polyesters and polybutadienes which contain terminal hydroxyl groups, i.e. polyols, with aliphatic or aromatic polyisocyanates.
  • Polyethers and polyesters having terminal hydroxyl groups are known and are prepared, for example, by polymerizing epoxides such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin with themselves, for example in the presence of BF3, or by addition reaction of these epoxides, alone or as a mixture or in successsion, with starting components containing reactive hydrogen atoms, such as alcohols, ammonia or amines, for example ethylene glycol, propylene 1,3- and 1,2-glycol, trimethylolpropane, 4,4′-dihydroxydiphenylpropane, aniline, ethanolamine or ethylenediamine. Sucrose polyethers are also suitable in accordance with the invention. In many cases preference is given to those polyethers which predominantly (up to 90% by weight, based on all the OH groups present in the polyether) contain primary OH groups. Furthermore, polyethers modified by vinyl polymers, as are formed, for example, by polymerizing styrene and acrylonitrile in the presence of polyethers, are suitable, as are polybutadienes containing OH groups.
  • These compounds generally have molecular weights of 40 and are polyhydroxy compounds, especially compounds containing from two to eight hydroxyl groups, especially those of molecular weight from 800 to 10,000, preferably from 1000 to 6000, for example polyethers containing at least 2, generally 2 to 8, but preferably 2 to 4, hydroxyl groups, as are known for the preparation of homogeneous polyurethanes and cellular polyurethanes.
  • It is of course possible to employ mixtures of the above compounds containing at least two isocyanate-reactive hydrogen atoms, in particular with a molecular weight of 400-10,000.
  • Suitable polyisocyanates are aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates, for example ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, cyclobutane 1,3-diisocyanate, cyclohexane 1,3- and -1,4-diisocyanate and also any desired mixtures of these isomers, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane, 2,4- and 2,6-hexahydrotolylene diisocyanate and also any desired mixtures of these isomers, hexahydro-1,3- and/or -1,4-phenylene diisocyanate, perhydro-2,4′- and/or -4,4′-diphenylmethanediisocyanate, 1,3-and1,4-phenylene diisocyanate, 2,4- and 2,6-tolylene diisocyanate, and also any desired mixtures of these isomers, diphenylmethane 2,4′- and/or -4,4′-diisocyanate, naphthylene 1,5-diisocyanate, triphenylmethane 4,4′,4″-triisocyanate, polyphenyl-polymethylene polyisocyanates as are obtained by aniline-formaldehyde condensation followed by phosgenization, m- and p-isocyanatophenylsulfonyl isocyanates, perchlorinated aryl polyisocyanates, polyisocyanates containing carbodiimide groups, polyisocyanates containing allophanate groups, polyisocyanates containing isocyanurate groups, polyisocyanates containing urethane groups, polyisocyanates containing acylated urea groups, polyisocyanates containing biuret groups, polyisocyanates containing ester groups, reaction products of the above-mentioned isocyanates with acetals, and polyisocyanates containing polymeric fatty acid radicals.
  • It is also possible to employ the isocyanate group-containing distillation residues as they are or dissolved in one or more of the above-mentioned polyisocyanates, which are obtained in the course of the industrial preparation of isocyanates. It is additionally possible to use any desired mixtures of the above-mentioned polyisocyanates.
  • Particular preference is given in general to the polyisocyanates which are readily obtainable industrially, for example aromatic isocyanates such as 2,4- and 2,6-tolylene diisocyanate and any desired mixtures of these isomers (“TDI”), polyphenyl-polymethylene-polyisocyanates as prepared by aniline-formaldehyde condensation followed by phosgenization (“crude MDI”), and polyisocyanates containing carbodiimide, urethane, allophanate, isocyanurate, urea or biuret groups (“modified polyisocyanates”).
  • Polyurethane is preferably prepared from liquid starting components, i.e. the starting materials to be reacted with one another being mixed together in a one-shot process.
  • Incorporation of the additives and/or stabilizer blends into the polyether polyol, polyester polyol or polyurethane is carried out by known methods, for example before or during compounding, extrusion, co-extrusion or can also be added before or during polymerisation or before crosslinking. In case the additives and/or stabilizer blends are added before polymerisation, they can be dissolved in one or all reactants. They are preferably dissolved in the polyether polyol or polyester polyol.
  • The compositions of this invention will help to fulfil needs and/or requirements for the polyurethane industry, in providing polyurethane (PU) compounds, thermoplastic PU, cast PU, reaction injection molding (RIM), spray coating, PU skin.
  • The compositions according to the invention can be advantageously used for various purposes and for the preparation of various shaped articles. Examples are:
  • V) Adhesive, Coating and Elastomer
  • V-1) PU Elastomer
  • V-1-A) Electrical and Electronic Industry
  • Bushes, cable connections, components for electrical control and adjustment, electromagnetic switches, hard and elastomeric encapsulants, gear shift cable castings for motor vehicle electrics, insulants, printed circuits, potting, semiconductors, switches, switch gears, medium and high voltage transformers.
  • V-1-B) Heavy-Duty Industry
  • Wheels, conveyor belts, sieves and linings.
  • V-1-C) Leisure
  • Skate board roller.
  • V-2) Adhesives
  • V-2-A) Automotive
  • Bonding of textile onto foam, direct glazing of vehicle windscreens, glazing replacement, fastening of various car components, vacuum lamination of foil to fiberboard.
  • V-2-B) Building and Civil Engineering
  • Bonding of sandwich insulation panels, flooring, roofs, sealing of car parks, concrete pavements, industrial floors, one component sealant for vertical joints (precast concrete panels, expansion joints), pourable joint sealants for vertical surfaces (floor-to-wall joints).
  • V-2-C) Carpentry
  • Furniture assembly and profile lamination of wood to plastic.
  • V-2-D) Flexible Packaging
  • Film-to-film and film-to-foil lamination.
  • V-2-E) Footwear
  • Bonding of shoe soles.
  • V-2-F) General Industry
  • Electronics industry, household goods, loudspeaker acoustic panels, office furniture, metal window frames, air conditioning systems, buses, containers, lorries, metal/sheet metal constructions, railway carriages, sewerage works, silos and ventilation systems.
  • V-2-G) Insulated Glazing
  • V-2-H) Rubbercrumb
  • Binding agent for re-milled rubber waste; the composite materials are mainly used as molded tiles, playgrounds (in-situ), running tracks (in-situ).
  • V-2-J) Sandwich Construction
  • Binding of similar substrates together or to other materials such as metals, plastics and rigid foam; used in a variety of laminated panels, such as panels for buildings, caravans, partition walls, refrigerated trucks, containers and cold storages.
  • V-3) Polyurethane Hotmelts
  • V-3-A) Automotive applications, in particular as instrument clusters, sound insulation, carpeting, seating, decorative trim, exterior applications such as weather stripping, exterior trim, light lens units, and windshield assemblies, recreational vehicle side walls.
  • V-3-B) Textile applications, in particular lamination, profile wrapping.
  • V-3-C) Furniture industry, in particular for bonding bond solid wood, wood composites, metal hardware, and decorative plastic laminates.
  • V-3-D) Construction industry, in particular assembly of door and window frames and corner covering for linoleum flooring.
  • VI) TPU
  • VI-1) Adhesive Grade
  • Adhesives for shoe (bond upper to sole), toe caps (powder), furniture, do it yourself and automotive.
  • VI-2) Extrusion Grades
  • VI-2-A) Cable and Wire Applications
  • Household appliances cables, outdoor electrical cables, industrial cables and wire.
  • VI-2-B) Hoses and Tubes
  • Pneumatic transport systems, ventilation systems, pneumatic control units, pneumatic breaks, hydraulic tubes, corrugated pipes, fire hoses, vacuum cleaner tubes.
  • VI-2-C) Profile Applications
  • Round cords, tooth belts, gaskets, bowden cables, stripper blades, cables.
  • VI-3) Film and Sheet
  • These are made from both aromatic and aliphatic TPUs. Typical applications are barrier film, adhesive film, seam tape, inter layer in security glass.
  • VI-3-A) Optical Applications of Aliphatic TPU
  • Security laminates, security display screens.
  • VI-3-B) Non-Optical Applications of Aliphatic TPU
  • Traffic and warning signs, protective films for exterior automotive applications, industrial tapes, industrial boats and balloons, film for food packaging, aerospace.
  • VI-3-C) Melt Coatings
  • Belts for food transportation and industrial goods.
  • VI-4) Injection Molding
  • VI-4-A) General Purpose
  • Ear tags, wheels, horse shoes, plugs, wrist watch straps.
  • VI-4-B) Hi-Performance/Special Compounds
  • Transparent soles for sport shoes, frames for ski goggles, technical parts, screens (mining).
  • VI-4-C) Automotive Applications
  • Gear shift knobs, bearing sockets, cable plugs, bushings, casings, friction bearings.
  • VI-4-D) Seal Applications
  • Hydraulic seals, stripper rings, gaskets, pneumatic seals, membranes.
  • VII) Automotive Applications
  • Bumpers, dashboards, battery, rear and front linings, moldings parts under the hood, hat shelf, trunk linings, interior linings, air bag covers, electronic moldings for fittings (lights), panes for dashboards, headlamp glass, instrument panel, exterior linings, upholstery, automotive lights, head lights, parking lights, rear lights, stop lights, interior and exterior trims; door panels; gas tank; glazing front side; rear windows; seat backing, exterior panels, wire insulation, profile extrusion for sealing, cladding, pillar covers, chassis parts, exhaust systems, fuel filter/filler, fuel pumps, fuel tank, body side moldings, convertible tops, exterior mirrors, exterior trim, fasteners/fixings, front end module, glass, hinges, lock systems, luggage/roof racks, pressed/stamped parts, seals, side impact protection, sound deadener/insulator and sunroof.
  • VII-1) Flexible Foam, in particular arm rest, head restraints, acoustic foam carpet, seats.
  • VII-2) Semi-rigid foam, in particular roof liners, hat racks, door panels, arm rest, instrument panel, head-impact, side-impact.
  • VII-3) Rigid foam, in particular foam filling of cavities.
  • VII-4) Flexible integral foam, in particular steering wheel, air filter, gearshift knob, spoiler, cable sheeting, head restraints.
  • VII-5) RIM, in particular bumpers, sunroof, front and rear skirts, door sill scuff plates.
  • VII-6) TPU, in particular front and rear skirts, doorsill scuff plates, cable sheeting, gearshift knob, instrument panel.
  • VII-7) Cast PU systems, in particular spring aids, spring isolation, seat damping, top mounts, roll restrictors, emergency wheel, body mounts, stops in door systems.
  • VIII) Footwear
  • Shoes/shoe-soles (insoles, spats, adhesives, structural adhesives).
  • IX) Furniture
  • X) Support Devices
  • Articles for the leisure time such as sports and fitness devices, gymnastics mats, ski-boots, inline-skates, skis, big foot, athletic surfaces (e.g. tennis grounds).
  • XI) Others
  • Composite panels, insulation board and block, technical insulation, pipe insulation, food boxes (fruit, vegetables, meat, fish), synthetic paper, labels for bottles, couches, human artificial joints, printing plates (flexographic), printed circuit boards, display technologies, screw tops, tops and stoppers for bottles, and cans.
  • For Example
  • 1) PU elastomers
  • 2) PU skin
  • 3) PU spray coating
  • 4) Thermoplastic polyurethane (TPU)
  • 5) PU artificial leather
  • 6) Silylated polyurethane (SPUR)
  • 7) PU hot melt adhesives
  • 8) Cast PU
  • 9) PU foam (flexible, rigid, integral)
  • 10) PU microcelluar
  • 11) Reaction injection molding (RIM).
  • Thus, a further embodiment of the present invention relates to a shaped article, in particular artificial leather, shock-absorbers, rollers of inline-skates and footwear, containing a composition as described above.
    • EXAMPLES
  • Figure US20110130492A1-20110602-C00039
  • Percentages and ratios mean weight percent and weight ratios.
  • Compounding:
  • 2.5 kg of thermoplastic polyurethane (TPU) pellets (Desmopan® 385 S of Bayer Material Science®) are mixed to homogeneity in a tumble mixer with 0.33% of pentaerythritol tetrakis 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (Irganox® 1010), 0.17% of bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite (Irgafos® 126), and with the light stabilizer combinations given in the tables below. This blend is then extruded in a twin-screw extruder of Berstorff® at a temperature of at most 180° C. After drawing the extrudate through a waterbath to cool, it is granulated.
  • Injection Molding:
  • 64 mm×40 mm×2 mm test panels are moulded from these granules by means of an injection-moulding machine (Arburg® 320 S) at a temperature of at most 180° C. (mold temperature 50° C.). The samples are exposed in a Weatherometer (WOM) bpt 63° C., 0.35 W/m2.
  • Film Preparation
  • 4 g of TPU pellets are dissolved 22 g DMF as a solvent. TPU films are prepared by drawing film with a 250 micron doctor blade. The DMF solvent is evaporated and the films are dried. The final film thickness is about 40 micron.
  • Light Expoure
  • The samples are exposed in a Weatherometer (WOM) bpt 63° C., 0.35 W/m2nm at λ=340 nm.
  • Kalahari exposure is done according to VW Test PV 3929 with xenon light exposure at 75 W/m2 at λ=300-400 nm.
  • Color Measurement:
  • The color quality is reported in terms of Yellowness Index (YI) determined on the TPU samples in accordance with the ASTM 1926-70 Yellowness Test. Low YI values denote little discoloration, high YI values severe discoloration of the samples. The whiter the TPU the better the TPU is stabilized.
  • TABLE 1
    Determination of initial color and light stability obtained with various
    light stabilizer systems. (Measured according to ASTM 1926-70).
    2 mm plaques, Weatherometer (WOM) bpt 63° C., 0.35 W/m2
    Initial Color
    (YI: yellowness
    Formulation % Light stabilizers* index) 72 h 144 h 240 h 316 h 460 h
    1 blank 11.9 35.8 49.4 55.9 60.0 66.4
    2 0.50% TINUVIN ® 234 14.2 13.8 16.1 20.6 23.9 28.5
    0.50% TINUVIN ® 144
    3 0.50% TINUVIN ® 312 10.9 12.4 17.6 26.7 34.4 42.1
    0.50% TINUVIN ® 622
    4 0.50% TINUVIN ® 312 9.6 9.9 13.7 20.3 25.4 32.8
    0.50% TINUVIN ® 144
    *All formulations in Table 1 contain 0.33% IRGANOX ® 1010 and 0.17% IRGAFOS ® 126
  • TABLE 2
    Determination of initial color and light stability
    obtained with various light stabilizer systems.
    (Measured according to ASTM 1926-70).
    Film, Weatherometer (WOM) bpt 63° C., 0.35 W/m2
    Formulation % Light stabilizers* 15 h 41 h 108 h
    5 blank 3.1 6.3 34.1
    6 0.50% TINUVIN 234 2.3 3.6 5.5
    0.50% TINUVIN 144
    7 0.50% TINUVIN 312 2.7 2.9 5.4
    0.50% TINUVIN 622
    8 0.50% TINUVIN 312 2.2 3.5 5.5
    0.50% TINUVIN 144
    *All formulations in Table 2 contain 0.33% IRGANOX ® 1010 and 0.17% IRGAFOS ® 126
  • TABLE 3
    Determination of initial color and light stability
    obtained with various light stabilizer systems.
    (Measured according to ASTM 1926-70).
    2 mm plaques, Kalahari exposure (VW Test PV 3929)
    Formulation % Light stabilizers* 96 h 144 h
    9 blank 53.9 58.7
    10 0.50% TINUVIN 234 18.9 22.1
    0.50% TINUVIN 144
    11 0.33% TINUVIN 234 23.4 27.0
    0.67% TINUVIN 144
    12 0.75% TINUVIN 312 16.8 23.3
    0.25% TINUVIN 144
    13 0.67% TINUVIN 312 17.4 22.6
    0.33% TINUVIN 144
    14 0.50% TINUVIN 312 18.8 22.3
    0.50% TINUVIN 144
    15 0.33% TINUVIN 312 23.4 28.8
    0.67% TINUVIN 144
    16 0.33% TINUVIN 234 15.9 21.3
    0.33% TINUVIN 312
    0.33% TINUVIN 144
    17 0.25% TINUVIN 234 17.9 23.6
    0.25% TINUVIN 312
    0.50% TINUVIN 144
    18 0.50% TINUVIN 328 19.5 23.4
    0.50% TINUVIN 144
    19 0.33% TINUVIN 328 19.3 25.0
    0.67% TINUVIN 144
    *All formulations in Table 3 contain 0.33% IRGANOX ® 1010 and 0.17% IRGAFOS ® 126

Claims (18)

1. A composition comprising
(a) a polyether polyol, a polyester polyol or a polyurethane,
(b) a UV-absorber of formula (I) and/or a hindered amine light stabilizer of formula (II)
Figure US20110130492A1-20110602-C00040
wherein R1 and R2 are each independently C1-C4alkyl or C1-C4alkyoxy, and
(c) at least one further hindered amine light stabilizer and/or UV-absorber selected from the group consisting of hydroxyphenyl-triazine, benzophenone, oxanilide, acrylate and cyanacrylate classes if only one of the components (I) and (II) is present
with the proviso that component (c) is not a compound of formula (A)-(D)
Figure US20110130492A1-20110602-C00041
2. A composition according to claim 1, comprising as component (c) a hindered amine light stabilizer of formula HA-1 to HA-11 or a UV-absorber of formula UV-5 to UV-8
Figure US20110130492A1-20110602-C00042
Figure US20110130492A1-20110602-C00043
Figure US20110130492A1-20110602-C00044
HA-11) 7-oxa-3,20-diazadispiro[5.1.11.2]heneicosan-21-one, 2,2,4,4-tetramethyl-20-(oxiranylmethyl)—, polymer with (chloromethyl)oxirane
Figure US20110130492A1-20110602-C00045
3. A composition according to claim 1, comprising further additives.
4. A composition according to claim 1, comprising further stabilizers.
5. A composition according to claim 4, comprising as further stabilizers antioxidants, light-stabilizers and/or processing stabilizers.
6. A composition according to claim 5, comprising as further stabilizers phenolic and/or aminic antioxidants, hindered amine light stabilizers, UV-absorbers, phosphites, phosphonites and/or benzofuranones.
7. A composition according to claim 6, comprising as further stabilizers hindered amine light stabilizers, UV-absorbers, phenolic antioxidants and/or phosphites.
8. A composition according to claim 1, wherein component (b) is a combination of a UV-absorber of formula (I) and a hindered amine light stabilizer of formula (II).
9. A composition according to claim 1, wherein the UV-absorber of formula (I) is a compound of formula (Ia)
Figure US20110130492A1-20110602-C00046
10. A composition according to claim 1, wherein component (b) is a UV-absorber of formula (I) and component (c) is a hindered amine light stabilizer.
11. A composition according to claim 1, wherein component (b) is a hindered amine light stabilizer of formula (II) and component (c) is a UV-absorber.
12. A composition according to claim 1, wherein the overall amount of component (b) and (c) is 0.01% to 5%, based on the weight of the composition.
13. A composition according to claim 1, wherein the overall amount of component (b) and (c) is 0.5% to 2%, based on the weight of the composition.
14. A composition according to claim 1, wherein the ratio of components (b):(c) or of the compounds of formulae (I):(II) respectively is from 10:1 to 1:10.
15. A composition according to claim 1, wherein the ratio of components (b):(c) or of the compounds of formulae (I):(II) respectively is from 3:1 to 1:3.
16. A process for stabilizing a polyether polyol, a polyester polyol or a polyurethane against degradation by light, oxygen and/or heat, which process comprises incorporating therein a mixture of components (b) and (c) as defined in claim 1.
17. A process according to claim 16, whereby the mixture additionally comprises further additives and/or further stabilizers.
18. A composition according to claim 6, comprising as further stabilizers hindered amine light stabilizers, UV-absorbers, phenolic antioxidants and/or phosphites; the phosphites being selected from the group consisting of
Figure US20110130492A1-20110602-C00047
US13/024,404 2004-06-30 2011-02-10 Stabilization of polyether polyol, polyester polyol or polyurethane compositions Abandoned US20110130492A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US13/024,404 US20110130492A1 (en) 2004-06-30 2011-02-10 Stabilization of polyether polyol, polyester polyol or polyurethane compositions

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
EP04103062.8 2004-06-30
EP04103062 2004-06-30
EP04104456.1 2004-09-15
EP04104456 2004-09-15
PCT/EP2005/052843 WO2006003092A1 (en) 2004-06-30 2005-06-20 Stabilization of polyether polyol, polyester polyol or polyurethane compositions
US63023007A 2007-06-20 2007-06-20
US13/024,404 US20110130492A1 (en) 2004-06-30 2011-02-10 Stabilization of polyether polyol, polyester polyol or polyurethane compositions

Related Parent Applications (2)

Application Number Title Priority Date Filing Date
PCT/EP2005/052843 Continuation WO2006003092A1 (en) 2004-06-30 2005-06-20 Stabilization of polyether polyol, polyester polyol or polyurethane compositions
US63023007A Continuation 2004-06-30 2007-06-20

Publications (1)

Publication Number Publication Date
US20110130492A1 true US20110130492A1 (en) 2011-06-02

Family

ID=34971573

Family Applications (2)

Application Number Title Priority Date Filing Date
US11/630,230 Active 2027-10-16 US7910642B2 (en) 2004-06-30 2005-06-20 Stabilization of polyether polyol, polyester polyol or polyurethane compositions
US13/024,404 Abandoned US20110130492A1 (en) 2004-06-30 2011-02-10 Stabilization of polyether polyol, polyester polyol or polyurethane compositions

Family Applications Before (1)

Application Number Title Priority Date Filing Date
US11/630,230 Active 2027-10-16 US7910642B2 (en) 2004-06-30 2005-06-20 Stabilization of polyether polyol, polyester polyol or polyurethane compositions

Country Status (13)

Country Link
US (2) US7910642B2 (en)
EP (1) EP1765928B1 (en)
JP (1) JP5165370B2 (en)
KR (1) KR101267891B1 (en)
AT (1) ATE409205T1 (en)
BR (1) BRPI0512939B1 (en)
CA (1) CA2570540C (en)
DE (1) DE602005009956D1 (en)
ES (1) ES2314674T3 (en)
MX (1) MXPA06015139A (en)
MY (1) MY139524A (en)
TW (1) TWI394779B (en)
WO (1) WO2006003092A1 (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9051478B2 (en) 2010-07-22 2015-06-09 Basf Se Additive combination for sealants applications
FR3093335A1 (en) * 2019-02-28 2020-09-04 Valeo Systemes D'essuyage Coating composition for wiper blade for wiper blade and associated wiper blade
US10899117B2 (en) * 2016-11-29 2021-01-26 Toppan Printing Co., Ltd. Decorative sheet and method of producing decorative sheet
US11148403B2 (en) 2015-09-04 2021-10-19 Toppan Printing Co., Ltd. Decorative sheet
WO2024023618A1 (en) * 2022-07-29 2024-02-01 3M Innovative Properties Company Polyurethanes, polishing articles and polishing systems therefrom and method of use thereof

Families Citing this family (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101163735B (en) * 2005-04-19 2011-12-07 西巴特殊化学品控股有限公司 Polyether polyols, polyester polyols and polyurethanes of low residual aldehyde content
DE102006011933B4 (en) * 2006-03-15 2010-04-15 Baerlocher Gmbh Stabilizer compositions for halogen-containing polymers having improved initial color and improved color retention, polymer compositions containing them and shaped articles, and methods for stabilizing halogen-containing polymers
US7886825B2 (en) 2006-09-18 2011-02-15 Schlumberger Technology Corporation Formation fluid sampling tools and methods utilizing chemical heating
JP4895276B2 (en) * 2006-09-29 2012-03-14 住化スタイロンポリカーボネート株式会社 Antistatic polycarbonate resin composition
JP2009066241A (en) * 2007-09-14 2009-04-02 Sri Sports Ltd Golf ball
DE102008042632A1 (en) 2008-10-06 2010-04-08 Wacker Chemie Ag Crosslinkable compositions based on organosilicon compounds
JP2010120838A (en) * 2008-10-24 2010-06-03 Central Glass Co Ltd Water-absorbing thin film, and cover glass for display unit including the same
US9469798B1 (en) 2009-09-10 2016-10-18 Line-X Llc Mine seal
DE102009054788A1 (en) 2009-12-16 2011-06-22 tesa SE, 20253 Process for the stabilization of polyacrylate PSAs in admixture with adhesive resins
MX2012011843A (en) 2010-04-16 2012-11-12 Valspar Sourcing Inc Coating compositions for packaging articles and methods of coating.
US20110253950A1 (en) * 2010-04-17 2011-10-20 Bruce Nash Surface Finishing Product and Method for Its Application
EP2655459B1 (en) 2010-12-20 2016-11-09 Dow Global Technologies LLC Curable compositions containing isocyanate functional components and having improved durability in the cured state
EP3878912B1 (en) 2011-02-07 2023-04-05 Swimc Llc Coating compositions for containers and other articles and methods of coating
KR101353359B1 (en) * 2011-11-29 2014-01-21 주식회사 지코 Stabilizer composition for polyurethan and producing method thereof
BR112014017086A8 (en) * 2012-01-17 2017-07-04 Bayer Ip Gmbh compact light-resistant polyurethane molded parts
CN104486946A (en) 2012-05-16 2015-04-01 Vegro有限责任公司 A strong insecticidal net
KR102093405B1 (en) 2012-08-09 2020-03-25 에스더블유아이엠씨 엘엘씨 Container coating system
RU2618704C2 (en) 2012-08-09 2017-05-11 Вэлспар Сорсинг, Инк. Compositions for containers and other products and their application methods
JP6287030B2 (en) 2013-10-10 2018-03-07 ブリヂストンスポーツ株式会社 Golf ball manufacturing method
TWI513762B (en) * 2014-04-09 2015-12-21 Fdc Lees Chemical Industry Co Stabilizers with hindered phenolic group and hindered amine, and their compositions
KR102429146B1 (en) 2014-04-14 2022-08-04 에스더블유아이엠씨 엘엘씨 Methods of preparing compositions for containers and other articles and methods of using same
EP3163631B1 (en) * 2014-06-27 2021-01-06 Mitsui Chemicals Tohcello, Inc. Resin composition for solar cell encapsulating material, solar cell encapsulating material, and solar cell module
TWI614275B (en) 2015-11-03 2018-02-11 Valspar Sourcing Inc Liquid epoxy resin composition for preparing a polymer
WO2017189761A1 (en) 2016-04-28 2017-11-02 Medtronic, Inc. Hydrolytically stable polymer compositions, articles, and methods
KR102020185B1 (en) 2016-08-15 2019-09-09 미쓰비시 신도 가부시키가이샤 Free cutting copper alloy and manufacturing method of free cutting copper alloy
US11661531B2 (en) 2019-01-31 2023-05-30 Synthomer Adhesives Technology LLC Hygiene adhesives comprising low volatile tackifier compositions
WO2022119885A1 (en) * 2020-12-02 2022-06-09 Huntsman International Llc A thermoplastic polyurethane resin composition
TW202237726A (en) * 2021-01-12 2022-10-01 瑞士商克萊瑞特國際股份有限公司 Stabilizer composition for silyl-modified polymer sealants

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4935275A (en) * 1987-04-27 1990-06-19 Toyoda Gosei Co., Ltd. Polyurethane material for decorative parts
US6881774B2 (en) * 2001-09-11 2005-04-19 Ciba Specialty Chemicals Corp. Stabilization of synthetic polymers
US7148278B2 (en) * 2000-10-06 2006-12-12 Acushnet Company Urethane elastomers with improved color stability

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5798545A (en) * 1980-12-11 1982-06-18 Mitsubishi Gas Chem Co Inc Acetal resin composition
JPH02283748A (en) * 1989-04-25 1990-11-21 Asahi Chem Ind Co Ltd Thermoplastic resin composition
CA2103709A1 (en) * 1991-02-19 1992-08-20 Robert B. Barbee Powder coating compositions
WO1993004102A1 (en) * 1991-08-27 1993-03-04 Eastman Kodak Company Thermosetting powder coating compositions
ATE149555T1 (en) * 1993-07-01 1997-03-15 Eastman Chem Co HEAT CURRENT COATING AGENTS
CA2166306A1 (en) * 1993-07-01 1995-01-12 Robert B. Barbee Powder coating compositions
FR2727423B1 (en) 1994-11-29 1997-01-03 Atohaas Holding Cv COMPOSITION FOR CAST PLATES BASED ON INTERPENETRATE POLYURETHANE AND POLY (METHYL METHACRYLATE) ARRAYS, CAST PLATES OBTAINED FROM THIS COMPOSITION AND THEIR MANUFACTURING METHOD
JP2881153B2 (en) * 1994-12-13 1999-04-12 三洋化成工業株式会社 Window frame shield material
JP2000129145A (en) * 1998-10-22 2000-05-09 Asahi Glass Co Ltd Composition curable at room temperature
US20030197151A1 (en) * 2000-05-31 2003-10-23 Francois Gugumus Stabilizer mixtures
DE10148702A1 (en) 2001-10-02 2003-04-10 Basf Ag Stabilizer mixture, used for stabilizing polyurethane for e.g. sheet, shoe sole, roller, fiber, hose, cable, sealant or tire production, contains antioxidant, hindered amine light stabilizer, UV absorber and phosphorus compound
AU2003225785B2 (en) 2002-03-13 2008-05-08 Insight Equity A.P.X., Lp Injection molding of lens
US7081213B2 (en) 2002-05-14 2006-07-25 Clariant Finance (Bvi) Limited Stabilizer mixtures for the protection of polymer substrates
WO2004068217A2 (en) 2003-01-24 2004-08-12 Vision-Ease Lens, Inc. Photochromic polyurethane film of improved fatigue resistance

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4935275A (en) * 1987-04-27 1990-06-19 Toyoda Gosei Co., Ltd. Polyurethane material for decorative parts
US7148278B2 (en) * 2000-10-06 2006-12-12 Acushnet Company Urethane elastomers with improved color stability
US6881774B2 (en) * 2001-09-11 2005-04-19 Ciba Specialty Chemicals Corp. Stabilization of synthetic polymers

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9051478B2 (en) 2010-07-22 2015-06-09 Basf Se Additive combination for sealants applications
US11148403B2 (en) 2015-09-04 2021-10-19 Toppan Printing Co., Ltd. Decorative sheet
US10899117B2 (en) * 2016-11-29 2021-01-26 Toppan Printing Co., Ltd. Decorative sheet and method of producing decorative sheet
FR3093335A1 (en) * 2019-02-28 2020-09-04 Valeo Systemes D'essuyage Coating composition for wiper blade for wiper blade and associated wiper blade
WO2024023618A1 (en) * 2022-07-29 2024-02-01 3M Innovative Properties Company Polyurethanes, polishing articles and polishing systems therefrom and method of use thereof

Also Published As

Publication number Publication date
KR101267891B1 (en) 2013-05-31
TW200604270A (en) 2006-02-01
DE602005009956D1 (en) 2008-11-06
BRPI0512939A (en) 2008-04-15
CA2570540A1 (en) 2006-01-12
US7910642B2 (en) 2011-03-22
ATE409205T1 (en) 2008-10-15
US20080033080A1 (en) 2008-02-07
BRPI0512939B1 (en) 2016-07-19
MXPA06015139A (en) 2007-03-15
WO2006003092A1 (en) 2006-01-12
TWI394779B (en) 2013-05-01
JP2008504422A (en) 2008-02-14
ES2314674T3 (en) 2009-03-16
KR20070034571A (en) 2007-03-28
EP1765928B1 (en) 2008-09-24
CA2570540C (en) 2012-04-17
EP1765928A1 (en) 2007-03-28
MY139524A (en) 2009-10-30
JP5165370B2 (en) 2013-03-21

Similar Documents

Publication Publication Date Title
US7910642B2 (en) Stabilization of polyether polyol, polyester polyol or polyurethane compositions
EP1853660B1 (en) Stabilization of polyol or polyurethane compositions against thermal oxidation
US10259931B2 (en) 3-phenyl-benzofuran-2-one derivatives containing phosphorus as stabilizers
EP1874853B1 (en) Polyether polyols, polyester polyols and polyurethanes of low residual aldehyde content
US10683409B2 (en) Additive mixture for stabilization of polyol and polyurethane
US10072136B2 (en) 3-phenyl-benzofuran-2-one diphosphite derivatives as stabilizers
US9550886B2 (en) Stabilizer and composition including the same
US11767338B2 (en) 3-phenyl-benzofuran-2-one diphosphate derivatives as stabilizers
US10113052B2 (en) 5H-furan-2-one derivatives stabilization of organic material
EP2828353B1 (en) Isoindolo[2,1-a]quinazoline derivatives for stabilization of organic materials
US20070185250A1 (en) Stabilization of polyether polyols, polyester polyols and polyurethanes
US8569405B2 (en) Additive mixtures for styrenic polymers
US20240052141A1 (en) An organic material based shaped article

Legal Events

Date Code Title Description
STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION