Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
  • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
  • C08K5/3477—Six-membered rings
  • C08K5/3492—Triazines
  • C08K5/34926—Triazines also containing heterocyclic groups other than triazine groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L59/00—Compositions of polyacetals; Compositions of derivatives of polyacetals
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L59/00—Compositions of polyacetals; Compositions of derivatives of polyacetals
  • C08L59/02—Polyacetals containing polyoxymethylene sequences only

Definitions

• the invention relates to compositions based on polyoxymethylene, blends of polycarbonate with acrylonitrile-butadiene-styrene terpolymer, or functional acrylate resin and crosslinking agent, which are stabilized by addition of a compound of the class of 3,3,5,5-tetraalkyl-piperazin-2,6-dione, new compounds of this class, the use of the novel compounds as stabilizers for organic material against harmful effects of light, oxygen and/or heat, and organic material stabilized correspondingly.
• the invention therefore pertains to a composition
• a composition comprising
• s is from the range 1 to 8;
• A is C 1 -C 18 alkyl; C 2 -C 18 alkyl which is substituted by NH 2 , hydroxy, halogen and/or OR 10 or interrupted by —O—, —NH— and/or —NR 10 —; or A is C 1 -C 18 alkyl substituted by —COOR 11 or phenyl;
• A is C 2 -C 10 alkylene; C 4 -C 12 alkenylene; C 3 -C 15 alkylene substituted by one or more OH and/or interrupted by one or more oxygen, phenylene, C 1 -C 4 alkylphenylene, —COO—, —CONH—,
• A is C 3 -C 10 alkantriyl; C 3 -C 12 alkantriyl substituted by OH and/or interrupted by oxygen, —NH— or —NR 10 —; or one of the groups of the formulae (IIa)-(IIId)
• A is C 4 -C 10 alkantetryl; C 4 -C 12 alkantetryl substituted by OH and/or interrupted by oxygen, —NH— or —NR 10 —; or one of the groups of the formulae (IVa)-(IVd)
• A is C 5 -C 10 alkanepentayl; C 5 -C 12 alkanepentayl substituted by OH and/or interrupted by oxygen, —NH— or —NR 10 —; or one of the groups of the formulae (Va)-(Vc)
• A is C 6 -C 10 alkanehexayl; C 6 -C 12 alkanehexayl substituted by OH and/or interrupted by oxygen, —NH— or —NR 10 —; or one of the groups of the formulae (VIa)-(VIf)
• A is C 7 -C 10 alkaneheptayl; C 7 -C 12 alkaneheptayl substituted by OH and/or interrupted by oxygen, —NH— or —NR 10 —; or one of the groups of the formulae (VIIa)-(VIId)
• A is C 8 -C 10 alkaneoctayl; C 8 -C 12 alkaneoctayl substituted by OH and/or interrupted by oxygen, —NH— or —NR 10 —; or one of the groups of the formulae (VIIIa)-(VIIIb)
• the index i is zero or 1;
• R 1 , R 2 , R 3 and R 4 independently of each other, are C 1 -C 4 alkyl, or R 1 and R 2 or R 3 and R 4 , together with the carbon atom to which they are bound, form a cyclopentyl or cyclohexyl ring;
• R 5 is hydrogen; C 1 -C 18 alkyl; oxyl; OH; CH 2 CN; C 1 -C 18 alkoxy; C 5 -C 12 cycloalkoxy; C 3 -C 8 alkenyl; C 3 -C 8 alkynyl; C 7 -C 12 phenylalkyl; C 7 -C 15 phenylalkyl, which is substituted on the phenyl ring by 1, 2 or 3 radicals selected from C 1 -C 4 alkyl and C 1 -C 4 alkoxy; C 7 -C 15 phenylalkoxy; C 7 -C 15 phenylalkoxy, which is substituted on the phenyl ring by 1, 2 or 3 radicals selected from C 1 -C 4 alkyl and C 1 -C 4 alkoxy; or R 5 is C 1 -C 8 alkanoyl; C 3 -C 5 alkenoyl; C 1 -C 18 alkanoyloxy
• R 8 and R 9 , and R 28 , R 29 , R 30 , R 31 , R 32 and R 33 are C 1 -C 4 alkylene;
• R 10 is C 1 -C 8 alkyl, C 1 -C 8 alkanoyl, C 5 -C 12 cycloalkyl, C 7 -C 15 phenylalkyl which is unsubstituted or substituted on the phenyl ring by a radical selected from C 1 -C 4 alkyl and C 1 -C 4 alkoxy; or R 10 is C 1 -C 8 alkyl or C 1 -C 8 alkanoyl substituted by OH, C 1 -C 12 alkoxy and/or a residue benzophenonyl or benzophenonyloxy, wherein one or both phenyl rings of the benzophenone moiety are unsubstituted or substituted by OH, halogen, C 1 -C 4 alkyl and/or C 1 -C 18 alkoxy;
• R 11 is C 1 -C 18 alkyl; C 2 -C 18 alkyl which is substituted by NH 2 , NHR 10 , N(R 10 ) 2 , nitro, hydroxy and/or C 1 -C 18 alkoxy; C 3 -C 18 alkenyl; C 5 -C 12 cycloalkyl; C 5 -C 12 cycloalkyl which is substituted by C 1 -C 4 alkyl and/or interrupted by —O—;
• R 12 , R 13 and R 14 independently of each other, are C 2 -C 10 alkylene; C 3 -C 12 alkylene substituted by OH and/or interrupted by oxygen, phenylene, C 1 -C 4 alkylphenylene, —NH— or —NR 10 —; C 4 -C 12 alkenylene;
• R 15 and R′ 15, independently of each other, are is C 2 -C 10 alkylene; C 3 -C 12 alkylene substituted by OH and/or interrupted by oxygen, phenylene, C 1 -C 4 alkylphenylene, —NH— or —NR 10 —;
• R 16 is C 3 -C 10 alkantriyl; C 3 -C 12 alkantriyl substituted by OH and/or interrupted by oxygen, —NH— or —NR 10 —;
• R 17 is C 4 -C 10 alkantetryl; C 4 -C 12 alkantetryl substituted by OH and/or interrupted by oxygen, —NH— or —NR 10 —;
• R 18 is C 5 -C 10 alkanepentayl; C 5 -C 12 alkanepentayl substituted by OH and/or interrupted by oxygen, —NH— or —NR 10 —;
• R 19 is C 6 -C 10 alkanehexayl; C 6 -C 12 alkanehexayl substituted by OH and/or interrupted by oxygen, —NH— or —NR 10 —;
• X is —O—, —NH— or —N(R 10 )—;
• X 1 , X 2 , X 3 , X 4 , X 5 , X 6 , X 7 and X 8 are —O— or —NH—;
• Y is —O— or a residue of the formula
• Z stands for halogen, NH 2 , NHR 10 , N(R 10 ) 2 or C 1 -C 4 alkoxy;
• Z 1 has one of the meanings given for Z or is —X—R′ 15 —XH and
• Z 2 is H or a residue of the formula
• Alkylene, cycloalkylene or alkenylene residues may be bonded on different carbon atoms or on the same carbon atom thus embracing alkylidene, cycloalkylidene and alkenylidene, respectively.
• All residues, where appropriate, may be straight chain or branched unless otherwise indicated.
• Hetero atoms are non-carbon atoms, for instance N, O, S or P atoms.
• Alkyl or alkylene interrupted by hetero groups such as oxygen or cycloalkylene may be interrupted by one or more of these groups as long as no linkages of the type O—O, O—N etc. occur.
• the index s is the valency of A; for example, A as alkyl is a monovalent, A as alkylene a divalent, A as alkanetriyl a trivalent, A as alkanetetryl a tetravalent, A as alkanepentayl a pentavalent, A as alkanehexayl a hexavalent, A as alkaneheptayl a heptavalent, and A as alkaneoctayl an octovalent saturated hydrocarbon residue.
• a residue which is interrupted is interrupted in a carbon-carbon single bond.
• a residue which is interrupted and/or substituted may be a residue interrupted in one or more carbon-carbon single bonds by one or more divalent interrupting groups, a residue substituted by one or more monovalent substituents, or a residue which is both interrupted in one or more carbon-carbon single bonds by one or more divalent interrupting groups and substituted by one or more monovalent substituents.
• examples for A as C 3 -C 15 alkylene substituted by one or more OH and/or interrupted by oxygen, phenylene, C 1 -C 4 alkylphenylene, —COO—, —CONH—, —NH— or —NR 10 — include groups of the formulae CH 2 CH(OH)CH 2 , CH 2 —C(CH 2 OH) 2 —CH 2 , (CH 2 ) 2 —N(CHO)—(CH 2 ) 2 , (CH 2 ) 2 —NH—(CH 2 ) 2 , (CH 2 ) 2 —O—(CH 2 ) 2 , (CH 2 ) 2 —O—(CH 2 ) 2 —O—(CH 2 ) 2 , CH 2 —CO—O—(CH 2 ) 2 —O—(CH 2 ) 2 —O—CO—CH 2 , CH 2 —CO—O—(CH 2 ) 6 —O—CO—CH 2 , CH 2 —CO—O—
• Halogen is preferably chloro or bromo, especially chloro.
• C 6 -C 12 aryl is preferably phenyl or naphthyl, especially phenyl.
• the compounds of the invention can be pure or mixtures of compounds.
• R 1 R 2 , R 3 , R 4 , R 5 , R 10 as alkyl are, within the definitions given, for example methyl, ethyl, propyl such as n- or isopropyl, butyl such as n-, iso-, sec- and tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl or octadecyl.
• R 8 , R 9 , R 12 , R 13 , R 14 , R 15 , R′ 15 and R 28 -R 33 as alkylene are, within the definitions given, for example methylene, 1,2-ethylene, 1,1-ethylene, 1,3-propylene, 1,2-propylene, 1,1-propylene, 2,2-propylene, 1,4-butylene, 1,3-butylene, 1,2-butylene, 1,1-butylene, 2,2-butylene, 2,3-butylene, or -C 5 H,O—, —C 6 H 12 —, C 7 H 14 , —C 8 H 16 —, —C 9 H 18 —, —C 10 H 20 —, —C 11 H 22 —, —C 12 H 24 —, —C 13 H 26 —, —C 14 H 28 -, —C 15 H 30 —, —C 16 H 32 —, —C 17 H 34 —, —C 18 H 36 —.
• R 8 , R 9 and R 28 -R 33 are especially preferred as methylene.
• the cycloalkyl part is, for example, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl or cyclododecyl.
• C 5 -C 12 -Cycloalkenyl includes cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, cyclononenyl, cyclodecenyl, cycloundecenyl, cyclododecenyl.
• C 1 -C 4 alkyl or akloxy substituted cycloalkyl or phenyl include inter alia 2- or 4-methylcyclohexyl, dimethylcyclohexyl, trimethylcyclohexyl, t-butylcyclohexyl, methylphenyl, methoxyphenyl, dimethylphenyl.
• Phenylalkyl or phenylalkoxy are alkyl or alkoxy each of which is substituted by phenyl.
• R 5 , R 10 as phenylalkyl or phenylalkoxy are, within the definitions given, for example benzyl, benzyloxy, a-methylbenzyl, a-methylbenzyloxy, cumyl, cumyloxy.
• R 5 and R 10 as alkanoyl are, for example, formyl, acetyl, propionyl, butyryl, pentanoyl, octanoyl; R 5 as alkanoyl is preferred as C 2 -C 8 alkanoyl, especially acetyl.
• Residues alkenoyl such as in the definition of R 5 , are most preferably acryloyl or methacryloyl.
• Residues alkenyl such as in the definition of R 5 , are most preferably allyl.
• X is preferably NH; X 1 -X 6 are most preferably O; Z is most preferred as N(R 10 ) 2 ; i is most preferred as zero.
• the index p is preferably from the range 2-6.
• a preferred blend of polycarbonate with acrylonitrile-butadiene-styrene terpolymer is a blend of 10 to 90 parts by weight of polycarbonate with 90 to 10 parts by weight of acrylonitrile-butadiene-styrene terpolymer.
• W is a divalent phenolic radical.
• W can be derived, for example, from hydroquinone, resorcinol, dihydroxybiphenylene or bisphenols in the broadest sense of the term, such as bis(hydroxyphenyl)alkanes, cycloalkanes, sulfides, ethers, ketones, sulfones, sulfoxides, ⁇ , ⁇ ′-bis(hydroxyphenyl)diisopropylbenzenes, for example the compounds 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxy-phenyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxy-phenyl)propane, 2,2-
• composition of the invention preferably contains as further component (C) a UV absorber from the class of the benzotriazoles, o-hydroxyphenyl-s-triazines and/or benzophenones, examples of which are listed below.
• composition wherein in the compound of formula I (component B) s is from the range 2 to 6;
• A is C 2 -C 10 alkylene; C 3 -C 12 alkylene substituted by OH and/or interrupted by oxygen, —NH— or —NR 10 —; or a group of the formula —R 8 —COO—R 12 —OCO—R 9 — (IIa);
• A is a group of the formula (IIIa)
• A is one of the groups of the formulae (IVa) or (IVd)
• A is a group of the formula (Va)
• A is one of the groups of the formulae (VIb)-(VIf)
• the index is zero is 1;
• R 1 , R 2 , R 3 and R 4 independently of each other, are methyl;
• R 5 is hydrogen; C 1 -C 18 alkyl; oxyl; OH; C 1 -C 18 alkoxy; C 5 -C 12 cycloalkoxy; C 3 -C 8 alkenyl; or R 5 is
• C 1 -C 8 alkanoyl C 3 -C 5 alkenoyl; C 1 -C 18 alkanoyloxy; glycidyl; or a group —CH 2 CH(OH)—G, in which G is hydrogen, methyl or phenyl;
• R 8 and R 9 , and R 28 , R 29 , R 30 , R 31 , R 32 and R 33 , independently of each other, are methylene;
• R 10 is C 1 -C 8 alkyl, C 1 -C 8 alkanoyl, C 5 -C 12 C 12 cycloalkyl;
• R 12 is C 2 -C 10 alkylene; or C 3 -C 12 alkylene interrupted by oxygen, —NH— or —NR 10 —;
• R 15 and R′ 15 are is C 2 -C 10 alkylene;
• R 17 is C 4 -C 10 alkantetryl
• R 18 is C 5 -C 10 alkanepentayl
• X is —O—, —NH— or —N(R 10 )—;
• X 1 , X 2 , X 3 , X 4 , X 5 , X 6 , X 7 and X 8 independently of each other, are —O— or —NH—;
• Z stands for NHR 10 , N(R 10 ) 2 or C 1 -C 4 alkoxy.
• s is from the range 1 to 8, preferably 2 to 8;
• R 1 , R 2 , R 3 and R 4 are C 1 -C 4 alkyl;
• R 5 is hydrogen; C 1 -C 18 alkyl; oxyl; OH; CH 2 CN; C 1 -C 18 alkoxy; C 5 -C 12 cycloalkoxy; C 3 -C 8 alkenyl; C 3 -C 8 alkynyl; C 7 -C 12 phenylalkyl; C 7 -C 15 phenylalkyl, which is substituted on the phenyl ring by 1, 2 or 3 radicals selected from C 1 -C 4 alkyl and C 1 -C 4 alkoxy; C 7 -C 15 phenylalkoxy; C 7 -C 15 phenylalkoxy, which is substituted on the phenyl ring by 1, 2 or 3 radicals selected from C 1 -C 4 alkyl and C 1 -C 4 alkoxy; or R 5 is C 1 -C 8 alkanoyl; C 3 -C 5 alkenoyl; C 1 -C 18 alkanoyloxy
• A is C 2 -C 18 alkylene substituted by OR 30 , wherein R 30 is C 1 -C 8 alkyl or C 1 -C 8 alkanoyl substituted by a residue benzophenonyl or benzophenonyloxy, wherein one or both phenyl rings of the benzophenone moiety are unsubstituted or substituted by OH, halogen, C 1 -C 4 alkyl and/or C 1 -C 18 alkoxy;
• A is C 3 -C 15 alkylene substituted by one or more OH and/or interrupted by one or more oxygen, phenylene, C 1 -C 4 alkylphenylene, —COO—, —CONH—,
• A also embraces C 2 -C 10 alkylene; C 2 -C 10 alkylene interrupted by phenylene or C 1 -C 4 alkylphenylene;
• A is C 3 -C 10 alkantriyl; C 3 -C 12 alkantriyl substituted by OH and/or interrupted by oxygen, —NH— or —NR 10 —; or one of the groups of the formulae (IIIa)-(IIId)
• A is C 4 -C 10 alkantetryl; C 4 -C 12 alkantetryl substituted by OH and/or interrupted by oxygen, —NH— or —NR 10 —; or one of the groups of the formulae (IVa)-(IVd)
• A is C 5 -C 10 alkanepentayl; C 5 -C 12 alkanepentayl substituted by OH and/or interrupted by oxygen, —NH— or —NR 10 —; or one of the groups of the formulae (Va)-(Vc)
• A is C 6 -C 10 alkanehexayl; C 6 -C 12 alkanehexayl substituted by OH and/or interrupted by oxygen, —NH— or —NR 10 —; or one of the groups of the formulae (VIa)-(VIf)
• A is C 7 -C 10 alkaneheptayl; C 7 -C 12 alkaneheptayl substituted by OH and/or interrupted by oxygen, —NH— or —NR 10 —; or one of the groups of the formulae (VIIa)-(VIId)
• A is C 8 -C 10 alkaneoctayl; C 8 -C 12 alkaneoctayl substituted by OH and/or interrupted by oxygen, —NH— or —NR 10 —; or one of the groups of the formulae (VIIIa)-(VIIIb)
• the index i is zero or 1;
• R 8 and R 9 , and R 28 , R 29 , R 30 , R 31 , R 32 and R 33 are methylene, and when R 5 is not hydrogen, additionally embrace ethylene;
• R 10 is C 1 -C 8 alkyl, C 1 -C 8 alkanoyl, C 5 -C 12 cycloalkyl, C 7 -C 15 phenylalkyl which is unsubstituted or substituted on the phenyl ring by a radical selected from C 1 -C 4 alkyl and C 1 -C 4 alkoxy;
• R 12 , R 13 and R 14 independently of each other, are C 2 -C 10 alkylene; C 3 -C 12 alkylene substituted by OH and/or interrupted by oxygen, phenylene, C 1 -C 4 alkylphenylene, —NH— or —NR 10 —; C 4 -C 12 alkenylene;
• R 15 and R′ 15 are is C 2 -C 10 alkylene; C 3 -C 12 alkylene substituted by OH and/or interrupted by oxygen, phenylene, C 1 -C 4 alkylphenylene, —NH— or —NR 10 —;
• R 1 is C 3 -C 10 alkantriyl; C 3 -C 12 alkantriyl substituted by OH and/or interrupted by oxygen, —NH— or —NR 10 —;
• R 17 is C 4 -C 10 alkantetryl; C 4 -C 12 alkantetryl substituted by OH and/or interrupted by oxygen, —NH— or —NR 10 —;
• R 18 is C 5 -C 10 alkanepentayl; C 5 -C 12 alkanepentayl substituted by OH and/or interrupted by oxygen, —NH— or —NR 10 —;
• R 19 is C 6 -C 10 alkanehexayl; C 6 -C 12 alkanehexayl substituted by OH and/or interrupted by oxygen, —NH— or —NR 10 —;
• X is —O—, —NH— or —N(R 10 )—;
• X 1 , X 2 , X 3 , X 4 , X 5 , X 6 independently of each other, are —O— or —NH—;
• Y is —O— or a residue of the formula
• Z stands for halogen, NH 2 , NHR 10 , N(R 10 ) 2 or C 1 -C 4 alkoxy;
• Z 1 has one of the meanings given for Z or is —X—R′ 15 —XH and
• Z 2 is H or a residue of the formula
• R 1 , R 2 , R 3 and R 4 independently of each other, are methyl or ethyl;
• R 5 is hydrogen; C 1 -C 18 alkyl; oxyl; OH; CH 2 CN; C 1 -C 18 alkoxy; C 5 -C 12 cycloalkoxy; C 3 -C 8 alkenyl; C 7 -C 12 phenylalkyl; C 7 -C 15 phenylalkoxy; or R 5 is C 1 -C 8 alkanoyl; C 3 -C 5 alkenoyl; C 1 -C 18 alkanoyloxy; glycidyl; or a group —CH 2 CH(OH)—G, in which G is hydrogen, methyl or phenyl;
• A is C 3 -C 12 alkylene substituted by OH and/or interrupted by oxygen, —NH— or —NR 10 —;
• A also embraces C 2 -C 10 alkylene; C 2 -C 10 alkylene interrupted by phenylene or C 1 -C 4 alkylphenylene;
• A is C 3 -C 10 alkantriyl; or one of the groups of the formulae (IIIa)-(IIId)
• A is C 4 -C 10 alkantetryl; or one of the groups of the formulae (IVa)-(IVd)
• A is C 5 -C 10 alkanepentayl; or a group of the formula (Va)
• A is C 6 -C 10 alkanehexayl; or one of the groups of the formulae (VIb)-(VIf)
• A is C 7 -C 10 alkaneheptayl
• A is C 8 -C 10 alkaneoctayl; or one of the groups of the formulae (VIIIa)-(VIIIb); the index i is zero or 1;
• R 8 and R 9 , and R 28 , R 29 , R 30 , R 31 , R 32 and R 33 are methylene;
• R 10 is C 1 -C 8 alkyl, C 1 -C 8 alkanoyl, C 5 -C 12 cycloalkyl, C 7 -C 15 phenylalkyl;
• R 12 , R 13 and R 14 independently of each other, are C 2 -C 10 alkylene; C 3 -C 12 alkylene substituted by OH and/or interrupted by oxygen, —NH— or —NR 10 —; C 4 -C 12 alkenylene;
• R 15 and R′ 15 are is C 2 -C 10 alkylene; C 3 -C 12 alkylene substituted by OH and/or interrupted by oxygen, phenylene, C 1 -C 4 alkylphenylene, —NH— or —NR 10 —;
• R 16 is C 3 -C 10 alkantriyl
• R 17 is C 4 -C 10 alkantetryl
• R 18 is C 5 -C 10 alkanepentayl
• X is —O—, —NH— or —N(R 10 )—;
• X 1 , X 2 , X 3 , X 4 , X 5 independently of each other, are —o— or —NH—;
• Z stands for halogen, NH 2 , NHR 10 , N(R 10 ) 2 or C 1 -C 4 alkoxy.
• R 1 , R 2 , R 3 and R 4 independently of each other, are methyl or ethyl;
• R 5 is hydrogen; C 1 -C 18 alkyl; oxyl; OH; CH 2 CN; C 1 -C 18 alkoxy; C 5 -C 12 cycloalkoxy; C 3 -C 8 alkenyl; C 7 -C 12 phenylalkyl; C 7 -C 15 phenylalkoxy; or R 5 is C 1 -C 8 alkanoyl; C 3 -C 5 alkenoyl; C 1 -C 18 alkanoyloxy; glycidyl; or a group —CH 2 CH(OH)—G, in which G is hydrogen, methyl or phenyl;
• A is C 3 -C 12 alkylene substituted by OH and/or interrupted by oxygen, —NH— or —NR 10 —;
• A also embraces C 2 -C 10 alkylene
• A is C 3 -C 10 alkantriyl; or one of the groups of the formulae (IIIa), (IIIb) or (IIId);
• A is C 4 -C 10 alkantetryl; or one of the groups of the formulae (IVa), (IVb) or (IVd);
• A is C 5 -C 10 alkanepentayl
• A is one of the groups of the formulae (VIb)-(VIf);
• the index i is zero or 1;
• R 8 and R 9 , and R 28 , R 29 , R 30 , R 31 , R 32 and R 33 , independently of each other, are methylene;
• R 10 is C 1 -C 8 alkyl, C 1 -C 8 alkanoyl, C 5 -C 12 cycloalkyl;
• R 12 is C 2 -C 10 alkylene; C 3 -C 12 alkylene substituted by OH and/or interrupted by oxygen, —NH— or —NR 10 —;
• R 15 and R′ 15 are is C 2 -C 10 alkylene;
• R 16 is C 3 -C 10 alkantriyl
• R 17 is C 4 -C 10 alkantetryl
• X is —O—, —NH— or —N(R 10 )—;
• X 1 , X 2 , X 3 , X 4 independently of each other, are —O— or —NH—;
• Z stands for NHR 10 or N(R 10 ) 2 .
• R 1 , R 2 , R 3 and R 4 are methyl
• R 5 is hydrogen; C 1 -C 8 alkyl; C 1 -C 18 alkoxy; cyclohexyloxy; allyl; benzyl; acetyl; C 3 -C 4 alkenoyl; glycidyl;
• A is C 3 -C 10 alkylene substituted by OH or interrupted by oxygen, —NH— or —NR 10 —; or a group of the formula —R 8 —COO—R 12 —OCO—R 9 — (IIa); and when R 5 is not hydrogen, A also embraces C 2 -C 10 alkylene;
• A is a group of the formula (IIIa);
• A is a group of the formula (IVa) or (IVd);
• A is a groups of the formula (VIe); the index i is zero;
• R 8 and R 9 , and R 28 , R 29 , R 30 , R 31 , R 32 and R 33 are methylene;
• R 10 is C 1 -C 8 alkyl, formyl, acetyl, or cyclohexyl;
• R 12 is C 2 -C 10 alkylene; or C 3 -C 10 alkylene interrupted by oxygen;
• R 15 and R′ 15 are is C 2 -C 10 alkylene;
• R 17 is C 4 -C 10 alkantetryl
• X is —NH—
• X 1 , X 2 , X 3 , X 4 are —O—;
• Z stands for N(R 10 ) 2 .
• Compounds thus obtained may be further derivatized by applying suitable synthetic methods known in the art, e.g. in analogy to methods described in EP-A-375612, U.S. Pat. Nos. 5,204,473, 5,004,770, and Kurumada et al., J. Polym. Sci., Poly. Chem. Ed. 23,1477 (1985), as well as U.S. Pat. No. 5,449,776, example 8, and publications cited therein, for the modification of piperidine derivatives.
• novel compounds of present invention can be employed with advantage for stabilizing organic material against the damaging effect of light, oxygen and/or heat. They are notable for high substrate compatibility and good persistence in the substrate.
• Polymers of monoolefins and diolefins for example polypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for instance of cyclopentene or norbornene, polyethylene (which optionally can be crosslinked), for example high density polyethylene (HDPE), high density and high molecular weight polyethylene (HDPE-HMW), high density and ultrahigh molecular weight polyethylene (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), (VLDPE) and (ULDPE).
• HDPE high density polyethylene
• HDPE-HMW high density and high molecular weight polyethylene
• HDPE-UHMW high density and ultrahigh molecular weight polyethylene
• MDPE medium density polyethylene
• LDPE low density polyethylene
• LLDPE linear low density poly
• Polyolefins i.e. the polymers of monoolefins exemplified in the preceding paragraph, preferably polyethylene and polypropylene, can be prepared by different, and especially by the following, methods:
• a catalyst that normally contains one or more than one metal of groups IVb, Vb, VIb or VIII of the Periodic Table.
• These metals usually have one or more than one ligand, typically oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls that may be either ⁇ - or ⁇ -coordinated.
• These metal complexes may be in the free form or fixed on substrates, typically on activated magnesium chloride, titanium(III) chloride, alumina or silicon oxide.
• These catalysts may be soluble or insoluble in the polymerisation medium.
• the catalysts can be used by themselves in the polymerisation or further activators may be used, typically metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes, said metals being elements of groups Ia, IIa and/or IIIa of the Periodic Table.
• the activators may be modified conveniently with further ester, ether, amine or silyl ether groups.
• These catalyst systems are usually termed Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC).
• Copolymers of monoolefins and diolefins with each other or with other vinyl monomers for example ethylene/propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene/but-1-ene copolymers, propylene/isobutylene copolymers, ethylene/but-1-ene copolymers, ethylene/hexene copolymers, ethylene/methylpentene copolymers, ethylene/heptene copolymers, ethylene/octene copolymers, propylene/butadiene copolymers, isobutylene/isoprene copolymers, ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylate copolymers, ethylene/vinyl acetate copolymers and their copolymers with carbon monoxide or ethylene/acrylic acid copolymers and their salts
• Hydrocarbon resins for example C 5 -C 9
• hydrogenated modifications thereof e.g. tackifiers
• mixtures of polyalkylenes and starch
• Copolymers of styrene or a-methylstyrene with dienes or acrylic derivatives for example styrene/butadiene, styrene/acrylonitrile, styrene/alkyl methacrylate, styrene/butadiene/alkyl acrylate, styrene/butadiene/alkyl methacrylate, styrene/maleic anhydride, styrene/acrylonitrile/methyl acrylate; mixtures of high impact strength of styrene copolymers and another polymer, for example a polyacrylate, a diene polymer or an ethylene/propylene/diene terpolymer; and block copolymers of styrene such as styrene/butadiene/styrene, styrene/isoprene/styrene, styren
• Graft copolymers of styrene or x-methylstyrene for example styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene and maleimide on polybutadiene; styrene and alkyl acrylates or methacrylates on polybutadiene; styrene and acrylonitrile on ethylene/propylene/diene terpolymers; styrene and alkyl
• Halogen-containing polymers such as polychloroprene, chlorinated rubbers, chlorinated and brominated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated or sulfochlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers, especially polymers of halogen-containing vinyl compounds, for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, as well as copolymers thereof such as vinyl chloride/vinylidene chloride, vinyl chloride/vinyl acetate or vinylidene chloride/vinyl acetate copolymers.
• halogen-containing polymers such as polychloroprene, chlorinated rubbers, chlorinated and brominated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated
• Copolymers of the monomers mentioned under 9) with each other or with other unsaturated monomers for example acrylonitrile/butadiene copolymers, acrylonitrile/alkyl acrylate copolymers, acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halide copolymers or acrylonitrile/alkyl methacrylate/butadiene terpolymers.
• Polymers derived from unsaturated alcohols and amines or the acyl derivatives or acetals thereof for example polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well as their copolymers with olefins mentioned in 1) above.
• Polyacetals such as polyoxymethylene and those polyoxymethylenes which contain ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.
• Polyamides and copolyamides derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides starting from m-xylene diamine and adipic acid; polyamides prepared from hexamethylenediamine and isophthalic or/and terephthalic acid and with or without an elastomer as modifier, for example poly-2,4,4,-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide; and also block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, e.g. with polyethylene glycol, polypropylene glycol or polytet
• Polyesters derived from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or the corresponding lactones for example polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylolcyclohexane terephthalate and polyhydroxybenzoates, as well as block copolyether esters derived from hydroxyl-terminated polyethers; and also polyesters modified with polycarbonates or MBS.
• Crosslinkable acrylic resins derived from substituted acrylates for example epoxy acrylates, urethane acrylates or polyester acrylates.
• crosslinked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds, e.g. products of diglycidyl ethers of bisphenol A and bisphenol F, which are crosslinked with customary hardeners such as anhydrides or amines, with or without accelerators.
• Natural polymers such as cellulose, rubber, gelatin and chemically modified homologous derivatives thereof, for example cellulose acetates, cellulose propionates and cellulose butyrates, or the cellulose ethers such as methyl cellulose; as well as rosins and their derivatives.
• Blends of the aforementioned polymers for example PP/EPDM, Polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR, PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA/PP, PAIPPO, PBT/PC/ABS or PBT/PET/PC.
• polyblends for example PP/EPDM, Polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR, PC/thermoplastic PUR, POM/acrylate, POM/MBS,
• compositions comprising
• Effects of degradation inter alia may be discoloration, molecular breakdown or buildup.
• the invention likewise embraces a method of stabilizing organic material against thermal, oxidative and/or actinic breakdown/buildup, which comprises applying or adding at least one compound of the formula I′ to this material.
• the compounds of the formula I or I′ are added to the material to be stabilized in amounts of from 0.1 to 10%, preferably from 0.01 to 5%, in particular from 0.01 to 2% (based on the material to be stabilized). Particular preference is given to the use of the novel compounds in amounts of from 0.05 to 1.5%, especially from 0.1 to 0.5%.
• novel compositions may as additional component C comprise one or more conventional additives such as, for example, those indicated below.
• 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-dimethyl-phenol, 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′-
• Alkylthiomethylphenols for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioc-tylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl-4-nonylphenol.
• Hydroquinones and alkylated hydroguinones for example 2,6-di-tert-butyl-4-methoxy-phenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octade-cyloxyphenol, 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-methoxy-phenol 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-dip
• 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-butyl-phenol), 2,2′-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2′-methylenebis[6-( ⁇ -methylbenzyl)-4-nonylphenol], 2,2′-methylenebis[6-( ⁇ , ⁇ -dimethylbenzyl)
• O—, N— and S-benzyl compounds for example 3,5,3′,5′-tetra-tert-butyl-4,4′-dihydroxydi-benzyl 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-hydroxy-benzyl)sulfide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.
• S-benzyl compounds for example 3,5,3′,5′-tetra-tert-butyl-4,4
• 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-te-tramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.
• Hydroxybenzylated malonates for example dioctadecyl-2,2-bis-(3,5-di-tert-butyl-2-hydroxybenzyl)-malonate, di-octadecyl-2-(3-tert-
• Aromatic hydroxybenzyl compounds for example 1,3,5-tris-(3,5-di-tert-butyl-4-hydroxy-benzyl)-2,4,6-trimethylbenzene, 1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetrame-thylbenzene, 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-hydroxy-benzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate,
• Benzvlphosphonates 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.
• esters of ⁇ -(3,5-di-tert-butyl-4-hvdroxyphenyl)propionic acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N′-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethyihexanediol, trimethylol-propane, 4-hydroxymethyl-1-phospha
• esters of ⁇ -(5-tert-butyl-4-hvdroxy-3-methylnhenyl)propionic acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexane-diol, 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,
• esters of ⁇ -(3,5-dicyclohexyl-4-hvdroxyyhenyl)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)ox-amide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]o
• esters of 3,5-di-tert-butyl-4-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)ox-amide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
• 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-N-phenyl
• 2-(2′-Hydroxyphenyl)benzotriazoles for example 2-(2′-hydroxy-5′-methylphenyl)-benzo-triazole, 2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)benzotriazole, 2-(5′-tert-butyl-2′-hydroxyphenyl)benzotriazole, 2-(2′-hydroxy-5′-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole, 2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)-5-chloro-benzotriazole, 2-(3′-tert-butyl-2′-hydroxy-5′-methylphenyl)-5-chloro-benzotriazole, 2-(3′-sec-butyl-5′-tert-butyl-2′-hydroxyphenyl)benzotriazole, 2-(2′-hydroxy-4′-o
• esters of substituted and unsubstituted benzoic acids as for example 4-tertbutyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis(4-tert-butylbenzoyl) resorcinol, benzoyl resorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.
• Nickel compounds for example nickel complexes of 2,2′-thio-bis-[4-(1,1,3,3-tetrame-thylbutyl)phenol], such as the 1:1 or 1:2 complex, with or without additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of the monoalkyl esters, e.g. the methyl or ethyl ester, of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid, nickel complexes of ketoximes, e.g. of 2-hydroxy-4-methylphenyl undecylketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additional ligands.
• additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithi
• Sterically hindered amines for example bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)succinate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-pi-peridyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, 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-oc
• Oxamides for example 4,4′-dioctyloxyoxanilide, 2,2′-diethoxyoxanilide, 2,2′-dioctyloxy-5,5′-di-tert-butoxanilide, 2,2′-didodecyloxy-5,5′-di-tert-butoxanilide, 2-ethoxy-2′-ethyloxanilide, N,N′-bis(3-dimethylaminopropyl)oxamide, 2-ethoxy-5-tert-butyl-2′-ethoxanilide and its mixture with 2-ethoxy-2′-ethyl-5,4′-di-tert-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-hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, N,N′-diacetyladipoyl dihydrazide, N,N′-bis(salicyloyl)oxalyl dihydrazide, N,N′-bis(salicyloyl)thiopropionyl dihydrazide.
• Phosphites and phosphonites for example triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)-pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, diis
• Tris(2,4-di-tert-butylphenyl) phosphite (Irgafos®168, Ciba-Geigy), tris(nonylphenyl) phosphite,
• Hydroxylamines for example, N,N-dibenzylhydroxylamine, N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine, N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhy-droxylamine, N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derived from hydrogenated tallow amine.
• Nitrones for example, N-benzyl-alpha-phenyl-nitrone, N-ethyl-alpha-methyl-nitrone, N-octyl-alpha-heptyl-nitrone, N-lauryl-alpha-undecyl-nitrone, N-tetradecyl-alpha-tridcyl-nitrone, N-hexadecyl-alpha-pentadecyl-nitrone, N-octadecyl-alpha-heptadecyl-nitrone, N-hexadecyl-alpha-heptadecyl-nitrone, N-ocatadecyl-alpha-pentadecyl-nitrone, N-heptadecyl-alpha-heptadecyl-nitrone, N-octadecyl-alpha-hexadecyl-nitron
• Thiosyner ists, for example, dilauryl thiodipropionate or distearyl thiodipropionate.
• Peroxide scavengers for example esters of P-thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2-mercapto-benzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis(5-dodecylmercapto)propionate.
• esters of P-thiodipropionic acid for example the lauryl, stearyl, myristyl or tridecyl esters
• mercaptobenzimidazole or the zinc salt of 2-mercapto-benzimidazole zinc dibutyldithiocarbamate
• dioctadecyl disulfide pentaerythritol tetrakis(5-dodecylmercap
• Polvamide stabilisers for example, copper salts in combination with iodides and/or phosphorus compounds and salts of divalent manganese.
• 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 zink 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
• Nucleating agents for example, inorganic substances such as talcum, metal oxides such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of, preferably, alkaline earth metals; organic compounds such as mono- or polycarboxylic acids and the salts thereof, e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymeric compounds such as ionic copolymers (ionomers).
• inorganic substances such as talcum, metal oxides such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of, preferably, alkaline earth metals
• organic compounds such as mono- or polycarboxylic acids and the salts thereof, e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate
• polymeric compounds such as ionic copolymers (ionomers
• Fillers and reinforcing agents for example, calcium carbonate, silicates, glass fibres, glass bulbs, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, 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.
• the conventional additives are judiciously employed in amounts of 0.1-10% by weight, for example 0.2-5% by weight, based on the material to be stabilized.
• Costabilizers optionally to be added to the stabilizer mixture of the invention are preferably further light stabilizers, for instance those of the 2-hydroxyphenyl-benztriazole, 2-hydroxyphenyl-triazine, benzophenone or oxalanilide classes, e.g. as described in EP-A-453396, EP-A-434608, U.S. Pat. No. 5,298,067, WO 94/18278, GB-A-2297091 and WO 96/28431, and/or further hindered amines derived from 2,2,6,6-tetraalkylpiperidine containing at least one group of the formula
• G is hydrogen or methyl, especially hydrogen
• examples of tetraalkylpiperidine derivatives which can be used as costabilizers with mixtures of the invention are given in EP-A-356 677, pages 3-17, sections a) to f). These sections of this EP-A are regarded as part of the present description.
• Especially preferred as costabilizers are 2-hydroxyphenyl-benztriazoles and/or 2-hydroxyphenyl-triazines.
• the organic materials to be protected are preferably natural, semisynthetic or, preferably, synthetic organic materials.
• synthetic organic polymers or mixtures of such polymers especially thermoplastic polymers such as polyolefins, especially polyethylene and polypropylene (PP), and coating compositions.
• thermoplastic polymers such as polyolefins, especially polyethylene and polypropylene (PP)
• PP polypropylene
• coating compositions Of special importance are also polycarbonates and blends thereof, for example the polymers listed above under items 19 and 28.
• incorporation into the materials can be effected, for example, by mixing in or applying the compounds of the formula I′ and, if desired, further additives by the methods which are customary in the art. Where polymers are involved, especially synthetic polymers, incorporation can take place prior to or during the shaping operation, or by applying the dissolved or dispersed compound to the polymer, with or without subsequent evaporation of the solvent. In the case of elastomers, these can also be stabilized as latices.
• a further possibility for incorporating the compounds of the formula I′ into polymers is to add them before, during or directly after the polymerization of the corresponding monomers or prior to crosslinking.
• the compound of the formula can be added as it is or else in encapsulated form (for example in waxes, oils or polymers).
• the compounds of the formula I′ can also act as a regulator of the chain length of the polymers (chain terminator).
• the compounds of the formula I or I′ can also be added in the form of a masterbatch containing said compound in a concentration, for example, of from 2.5 to 25% by weight to the polymers that are to be stabilized.
• emulsion or dispersion e.g. to latices or emulsion polymers
• Novel polymer compositions can be employed in various forms and/or processed to give various products, for example as (to give) films, fibres, tapes, moulding compositions, profiles, or as binders for coating materials, adhesives or putties.
• Other materials to be stabilized according to the invention are recording materials. By such materials are meant, for example, those described in Research Disclosure 1990, 31429 (pages 474-480) for photographic reproduction and other reprographic techniques.
• novel recording materials comprise, for example, those for pressure-sensitive copying systems, microcapsule photocopier systems, heat-sensitive copier systems, photographic material and ink-jet printing.
• the novel photographic material can be a black and white or a colour photographic material; colour photographic material is preferred. Further details on the structure of colour photographic material, and the components which can be employed in the novel material, can be found, inter alia, in U.S. Pat. No. 5,538,840, column 27, line 25, to column 106, line 16, and in the publications cited therein; these passages of U.S. Pat. No. 5,538,840 are hereby incorporated by reference.
• Application of the novel stabilizers of the formula I′ is essentially as described for UV absorbers or hindered amine stabilizers in this reference. Further important components, especially couplers, are described in U.S. Pat. No. 5,578,437.
• novel mixtures comprising compounds of the formula (I) as stabilizers for coatings, for example for paints.
• the invention therefore also relates to those compositions whose component (A) is a film-forming binder for coatings.
• the novel coating composition preferably comprises 0.01-10 parts by weight of (B), in particular 0.05-10 parts by weight of (B), especially 0.1-5 parts by weight of (B), per 100 parts by weight of solid binder (A).
• concentration of the novel stabilizer (component (B)) in the outer layer can be relatively high, for example from 1 to 15 parts by weight of (B), in particular 3-10 parts by weight of (B), per 100 parts by weight of solid binder (A).
• the binder (component (A)) can in principle be any binder which is customary in industry, for example those described in Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A18, pp. 368-426, VCH, Weinheim 1991. In general, it is a film-forming binder based on a thermoplastic or thermosetting resin, predominantly on a thermosetting resin. Examples thereof are alkyd, acrylic, polyester, phenolic, melamine, epoxy and polyurethane resins and mixtures thereof.
• Component (A) can be a cold-curable or hot-curable binder; the addition of a curing catalyst may be advantageous. Suitable catalysts which accelerate curing of the binder are described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, Vol. Al18, p.469, VCH Verlagsgesellschaft, Weinheim 1991.
• component (A) is a binder comprising a functional acrylate resin and a crosslinking agent.
• Examples of coating compositions containing specific binders are:
• polyurethane paints based on aliphatic or aromatic urethaneacrylates or polyurethaneacrylates having free amino groups within the urethane structure and melamine resins or polyether resins, if necessary with curing catalyst;
• thermoplastic polyacrylate paints based on thermoplastic acrylate resins or externally crosslinking acrylate resins in combination with etherified melamine resins;
• paint systems especially for clearcoats, based on malonate- blocked isocyanates with melamine resins (e.g. hexamethoxymethylmelamine) as crosslinker (acid catalyzed);
• melamine resins e.g. hexamethoxymethylmelamine
• UV-curable systems based on oligomeric urethane acrylates, or oligomeric urethane acrylates in combination with other oligomers or monomers;
• the coating composition according to the invention preferably comprises as component (C) a known light stabilizer of the sterically hindered amine type, the 2-(2-hydroxyphenyl)-1,3,5-triazine and/or 2-hydroxyphenyl-2H-benzotriazole type as explained above, examples are mentioned in the above list in sections 2.1, 2.6 and 2.8. Further examples for light stabilizers of the 2-(2-hydroxyphenyl)-1,3,5-triazine type advantageously to be added can be found e.g. in the publications U.S. Pat. No. 4,619,956, EP-A-434608, U.S. Pat. Nos.
• Component (C) is preferably used in an amount of 0.05-5 parts by weight per 100 parts by weight of the solid binder.
• the coating composition can also comprise further components, examples being solvents, pigments, dyes, plasticizers, stabilizers, thixotropic agents, drying catalysts and/or levelling agents.
• examples are those described in Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Vol. Al18, pp. 429-471, VCH, Weinheim 1991.
• Possible drying catalysts or curing catalysts are, for example, organometallic compounds, amines, amino-containing resins and/or phosphines.
• organometallic compounds are metal carboxylates, especially those of the metals Pb, Mn, Co, Zn, Zr or Cu, or metal chelates, especially those of the metals Al, Ti or Zr, or organometallic compounds such as organotin compounds, for example.
• metal carboxylates are the stearates of Pb, Mn or Zn, the octoates of Co, Zn or Cu, the naphthenates of Mn and Co or the corresponding linoleates, resinates or tallates.
• metal chelates are the aluminium, titanium or zirconium chelates of acetylacetone, ethyl acetylacetate, salicylaldehyde, salicylaldoxime, o-hydroxyacetophenone or ethyl trifluoroacetylacetate, and the alkoxides of these metals.
• organotin compounds are dibutyltin oxide, dibutyltin dilaurate or dibutyltin dioctoate.
• amines are, in particular, tertiary amines, for example tributylamine, triethanolamine, N-methyldiethanolamine, N-dimethylethanolamine, N-ethylmorpholine, N-methylmorpholine or diazabicyclooctane (triethylenediamine) and salts thereof.
• quaternary ammonium salts for example trimethylbenzylammonium chloride.
• Amino-containing resins are simultaneously binder and curing catalyst. Examples thereof are amino-containing acrylate copolymers.
• the curing catalyst used can also be a phosphine, for example triphenylphosphine.
• the novel coating compositions can also be radiation-curable coating compositions.
• the binder essentially comprises monomeric or oligomeric compounds containing ethylenically unsaturated bonds, which after application are cured by actinic radiation, i.e. converted into a crosslinked, high molecular weight form.
• the system is UV-curing, it generally contains a photoinitiator as well.
• the novel stabilizers can also be employed without the addition of sterically hindered amines.
• the coating compositions according to the invention can be applied to any desired substrates, for example to metal, wood, plastic or ceramic materials. They are preferably used as topcoat in the finishing of automobiles. If the topcoat comprises two layers, of which the lower layer is pigmented and the upper layer is not pigmented, the novel coating composition can be used for either the upper or the lower layer or for both layers, but preferably for the upper layer.
• novel coating compositions can be applied to the substrates by the customary methods, for example by brushing, spraying, pouring, dipping or electrophoresis; see also Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A18, pp. 491-500.
• the coatings can be cured at room temperature or by heating.
• the coatings are preferably cured at 50-150° C., and in the case of powder coatings or coil coatings even at higher temperatures.
• the coatings obtained in accordance with the invention have excellent resistance to the damaging effects of light, oxygen and heat; particular mention should be made of the good light stability and weathering resistance of the coatings thus obtained, for example paints.
• the invention therefore also relates to a coating, in particular a paint, which has been stabilized against the damaging effects of light, oxygen and heat by a content of the compound of the formula (I) according to the invention.
• the paint is preferably a topcoat for automobiles.
• the invention furthermore relates to a process for stabilizing a coating based on organic polymers against damage by light, oxygen and/or heat, which comprises mixing with the coating composition a mixture comprising a compound of the formula (I), and to the use of mixtures comprising a compound of the formula (I) in coating compositions as stabilizers against damage by light, oxygen and/or heat.
• the coating compositions can comprise an organic solvent or solvent mixture in which the binder is soluble.
• the coating composition can otherwise be an aqueous solution or dispersion.
• the vehicle can also be a mixture of organic solvent and water.
• the coating composition may be a high-solids paint or can be solvent-free (e.g. a powder coating material). Powder coatings are, for example, those described in Ullmann's Encyclopedia of Industrial Chemistry, 5th Ed., A18, pages 438-444.
• the powder coating material may also have the form of a powder-slurry (dispersion of the powder preferably in water).
• the pigments can be inorganic, organic or metallic pigments.
• the novel coating compositions preferably contain no pigments and are used as a clearcoat. Likewise preferred is the use of the coating composition as a topcoat for applications in the automobile industry, especially as a pigmented or unpigmented topcoat of the paint finish. Its use for underlying coats, however, is also possible.
• a 200 ml portion of CH 2 Cl 2 and 200 ml portion of water is added to the mixture under stirring and the organic layer is collected, dried over Na 2 SO 4 and charged, together with 400 ml of xylene and 22.8 g of di-ethylen glycol, in a round bottomed flask equipped with a stirrer, thermometer, condenser drying tube and gas inlet tube.
• the solution is heated up to reflux temperature and 0.2 g of di-buthyl tin oxide are added to the mixture and left to react for 12 hours, then cooled down to 25° C.
• the resulting solid is then charged in a round bottomed flask equipped with a stirrer, thermometer, condenser drying tube and gas inlet tube togheter with 600 ml of tert-amyl alcohol and 52 g of para-formaldehyde.
• the mixture is warmed up to 75° C. and 78 g of formic acid is added dropwise under stirring and left to react for 3 hours keeping the temperature at 75° C., then cooled to 25° C.
• To the mixture are added under stirring 2000 ml of CH 2 Cl 2 and 74 g of a solution of 50% NaOH in water and left to react for 1 hour at 40° C., then cooled down to 25° C.
• a 20.5 g portion of the product of Example A25 is added dropwise over a 30′ period time in a three necked flask equipped with a stirrer, thermometer, condenser, containing 100 ml of CH 2 Cl 2 and 9.2 g of cyanuric choride cooled down to 5° C. and left to react under stirring for 3 hours.
• a solution of 2 g of NaOH in 8 ml of water are added to the reaction mixture and left to reach room temperature.
• Example A25 A 80 g portion of the product of Example A25 is added dropwise over 30 minutes in a three necked flask equipped with a stirrer, thermometer, condenser, containing 360 ml of CH 2 Cl2 and 36 g of cyanuric choride cooled to 5° C. and left to react under stirring for 3 hours. A solution of 8.6 g of NaOH in 9 ml of water is added to the reaction mixture and left to reach room temperature.
• reaction mixture is then heated up to 142° C. for 16 hours, cooled down to 20° C. and washed with 400 ml of water.
• the organic layer is then concentrated under vacuum obtaining a white solid of m.p. 68-77° C.
• the mixtures obtained are extruded at a temperature of 200-230° C. to give polymer granules which are then converted into plaques of 2 mm thickness by injection moulding at 200-220° C.
• the mixtures are extruded at 200-220° C. to give polymer granules which are subsequently converted to stretched tapes of 50 ⁇ m thickness and 2.5 mm width, using a semi-industrial type of apparatus (®Leonard-Sumirago (VA)—Italy) and waking under the following conditions: Extruder temperature: 200-230° C. Head temperature: 240-260° C. Stretch ratio: 1:6
• the tapes thus prepared are mounted on a white card and exposed in a Weather-O-Meter 65 WR (ASTM D 2565-85) with a black panel temperature of (63 ⁇ 3)° C.
• the residual tenacity is measured, by means of a constant velocity tensometer, on a sample taken after various light exposure times; from this, the exposure time (in hours) required to halve the initial tenacity (T 50 ) is measured.
• the mixtures are extruded at 190-230° C. to give granules; these are subsequently converted into fibres using a a semi-industrial type of apparatus (Leonard-SumiragoTM (VA), Italy) under the following conditions: Extruder temperature: 200-230° C. Head temperature: 255° C. Stretch ratio: 1:3.5 Count: 11 dtex per filament
• the fibres stabilized according to the invention have excellent tenacity.
• Some of the films are treated with pesticides by storing them before WOM exposure for 20 days at 30° C. over a concentrated solution of VAPAMTM in water (1:1 relation in parts by volume) without direct contact with the solution.
• VAPAMTM (BASLINI SpA, Treviglio/BG, Italy) is an aqueous solution of 382 g per liter of metam-sodium having the formula CH 3 —NH—CS—SNa.
• the stabilizer of the invention provides effective stabilization for PE films both with and without pesticide treatment.
• Accelerated weathering is performed using an Atlas Ci65A Weather-o-meter (XAW), operated in either “Dry XAW” mode (ASTM G26-90 method C). After regular intervals, the color change ⁇ E according to DIN 6174 is determined. Results are compiled in table 5.
• XAW Atlas Ci65A Weather-o-meter
• ASTM G26-90 method C the color change ⁇ E according to DIN 6174 is determined. Results are compiled in table 5.
• Samples are prepared from commercial PC/ABS-blend (CycoloyTM MC 8002; 50/50 wt/wt blend of PC and ABS as described in example B5 except that TiO 2 (TionaTM RCL-4 rutile; SCM chemicals) is used as pigment. Weathering and assessment is done as described in example B5; results are compiled in table 6.
• PC/ABS samples stabilized according to the invention show an excellent color stability.
• Gloss 2′′ ⁇ 2′′ injection molded plaques are removed and replaced at each interval. Measurement device is BYK-Gardner Haze-Gloss Laboratory Reference Instrument.
• Chip impact testing 10 replicate bars are used for each test interval, impacting the exposed face. Test conducted per ASTM D4508-90 using TMI Monitor/impact Tester. PC/ABS samples stabilized according to the invention with 0.5% by weight of the compound of example A4 or A17 show excellent gloss retention and impact strength.
• the light-stabilizers to be tested are dissolved in 30 g of Solvesso®100 and tested in a clearcoat having the following composition (parts by weight): Synthacryl ® SC 303 1) 27.51 Synthacryl ® SC 370 2) 23.34 Maprenal ® 650 3) 27.29 Butyl acetate/Butanol (37/8) 4.33 Isobutanol 4.87 Solvesso ® 150 4) 2.72 Crystal Oil K-30 5) 8.74 Levelling assistant Baysilon ® MA 6) 1.20 100.00
• 1% of the light-stabilizers to be tested is added to the clearcoat, based on the solids content of the varnish.
• a clearcoat containing no light-stabilizers is used.
• the clearcoat is diluted with Solvesso® 100 to spray viscosity and is applied by spraying to a prepared aluminium panel (®Uniprime Epoxy, silver-metallic basecoat) which is baked at 130° C., for 30 minutes, to give a dry film thickness of 40-50 ⁇ m of clearcoat.
• Molded test specimens are prepared by injection molding thermoplastic olefin (TPO) pellets containing pigments, a phosphite, a phenolic antioxidant or hydroxylamine (HA), a metal stearate, ultraviolet light absorbers (UVA) or a hindered amine stabilizers (HALS) or a mixture of UV absorbers and hindered amine stabilizers as described below.
• TPO thermoplastic olefin
• Pigmented TPO pellets are prepared from pure pigment or pigment concentrates, stabilizers, co-additives and commercially available thermoplastic olefin by mixing the components in a Superior/MPM 1′′ single screw extruder with a general all-purpose screw (24:1 UD) at 400° F. (200° C.), cooled in a water bath and pelletized. The resulting pellets are molded into 60 mil (0.006 inch thick) 2′′ ⁇ 2′′ plaques at about 375° F. (190° C.) on a BOY 30M Injection Molding Machine.
• Pigmented TPO formulations composed of polypropylene blended with a rubber modifier where the rubber modifier is an in-situ reacted copolymer or blended product containing copolymers of propylene and ethylene with or without a ternary component such as ethylidene norbornene are stabilized with a base stabilization system consisting of an N,N-dialkylhydroxylamine or a hindered phenolic antioxidant with or without an organophosphorous compound.
• Formulations contain thermoplastic olefin pellets and one or more of the following components;
• HALS hindered amine stabilizer
• the components are dry blended in a tumble dryer prior to extrusion and molding.
• Test plaques are mounted in metal frames and exposed in an Atlas Ci65 Xenon Arc Weather-o-meter at 70° C. black panel temperature, 0.55 W/m 2 at 340 nanometers and 50% relative humidity with intermittent light/dark cycles and water spray (Society of Automotive Engineers—SAE J 1960 Test Procedure). Specimens are tested at approximately 625 kilojoule intervals by performing color measurements on an Applied Color Systems spectrophotometer by reflectance mode according to ASTM D 2244-79. Data collected include delta E, L*, a* and b* values. Gloss measurements are conducted on a BYK-GARDNER Haze/Gloss Meter at 60° according to ASTM D523.
• Test specimens prepared from a commercially available polyolefin blend (Polytrope TPP 518-01; commercial supplier A. Schulman, Inc.; Akron, Ohio, U.S.A.) as 60 mil thick 2′′ ⁇ 2′′ injection molded plaques are exposed to UV radiation under SAE J 1960—Exterior Automotive conditions.
• Control sample contains as stabilizer formulation the compound A as indicated in the following table, 0.2% by weight of compound B and 0.1% of a 1:1 mixture of tris(2,4-di-t-butylphenyl)phosphite and 1 part of pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] in the final resin formulation as commonly used in the industry to impart UV stability.
• Samples 1-3 stabilized according to the invention contain 0.05% dialkylhydroxylamine in the final resin formulation as base stabilization and 0.2% by weight of compound C costabilizer.
• Compound A is Bis(2,2,6,6-tetramethylpiperidine-4-yl) sebacate;
• compound B is Poly [[6-[(1,1,3,3-tetramethyl butyl) amino]-1,3,5-triazine-2,4-diyl][[(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]]; CAS-No. 70624-18-9;
• compound C is of the formula R—NH—(CH 2 ) 3 —N(R)—(CH 2 ) 2 —N(R)—(CH 2 ) 3 —NH—R, with R being
• All of the samples contain talc at 15%, 2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole at 0.2%, 0.1% calcium stearate and as color package 0.25% Red 3B and Pigment Red 177, C.I. # 65300.

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• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
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• Health & Medical Sciences (AREA)
• Hydrogenated Pyridines (AREA)
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• Paints Or Removers (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Anti-Oxidant Or Stabilizer Compositions (AREA)
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