US20030197151A1 - Stabilizer mixtures - Google Patents

Stabilizer mixtures Download PDF

Info

Publication number
US20030197151A1
US20030197151A1 US10/276,120 US27612002A US2003197151A1 US 20030197151 A1 US20030197151 A1 US 20030197151A1 US 27612002 A US27612002 A US 27612002A US 2003197151 A1 US2003197151 A1 US 2003197151A1
Authority
US
United States
Prior art keywords
rtm
formula
compound
tinuvin
hydrogen
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
US10/276,120
Inventor
Francois Gugumus
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.)
BASF Performance Products LLC
Original Assignee
Ciba Specialty Chemicals Corp
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 Ciba Specialty Chemicals Corp filed Critical Ciba Specialty Chemicals Corp
Assigned to CIBA SPECIALTY CHEMICALS CORP. reassignment CIBA SPECIALTY CHEMICALS CORP. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: GUGUMUS, FRANCOIS
Publication of US20030197151A1 publication Critical patent/US20030197151A1/en
Priority to US11/052,714 priority Critical patent/US20050143500A1/en
Priority to US11/498,351 priority patent/US20060270764A1/en
Priority to US12/317,014 priority patent/US20090105379A1/en
Priority to US12/607,102 priority patent/US7820744B2/en
Abandoned legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
    • C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
    • C09K15/26—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing nitrogen and sulfur
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
    • C08K5/3462—Six-membered rings
    • 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
    • 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
    • C08K5/34922—Melamine; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • 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
    • 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
    • C08K5/35—Heterocyclic compounds having nitrogen in the ring having also oxygen in the ring
    • C08K5/353—Five-membered rings
    • 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
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond

Definitions

  • the present invention relates to a stabilizer mixture containing a specific sterically hindered amine ester or amide, and two different low molecular weight sterically hindered amines.
  • Stabilizer mixtures containing blends of sterically hindered amines are for example described in U.S. Pat. No. 4,692,468, U.S. Pat. No. 4,863,981, U.S. Pat. No. 5,719,217, U.S. Pat. No. 5,919,399, U.S. Pat. No. 5,965,643, U.S. Pat. No. 5,980,783, U.S. Pat. No. 6,015,849 and U.S. Pat. No. 6,020,406.
  • the present invention relates to a stabilizer mixture containing the components (A) and (B)
  • component (A) is
  • a 1 is hydrogen or C 1 -C 4 alkyl
  • a 2 is a direct bond or C 1 -C 10 alkylene
  • n 1 is a number from 2 to 50;
  • n 2 and n 2 * are a number from 2 to 50;
  • a 3 and A 4 independently of one another are hydrogen or C 1 -C 8 alkyl, or A 3 and A 4 together form a C 2 -C 14 alkylene group, and
  • n 3 independently of one another are a number from 1 to 50;
  • n 4 is a number from 2 to 50
  • a 5 is hydrogen or C 1 -C 4 alkyl
  • radicals A 6 and A 7 independently of one another are C 1 -C 4 alkyl or a group of the formula (a-I)
  • a 8 is hydrogen, C 1 -C 8 alkyl, O ⁇ , —OH, —CH 2 CN, C 1 -C 18 alkoxy, C 5 -C 12 cycloalkoxy, C 3 -C 6 alkenyl, C 7 -C 9 phenylalkyl unsubstituted or substituted on the phenyl by 1, 2 or 3 C 1 -C 4 alkyl; or C 1 -C 8 acyl,
  • radicals A 7 are a group of the formula (a-I); and component (B) is formed by two different low molecular weight sterically hindered amine compounds containing a group of the formula (I) or (II);
  • the compounds of component (B) have a molecular weight up to 1,000 g/mol, for example 155 to 800 g/mol or 155 to 1,000 g/mol or 300 to 800 g/mol or 300 to 1,000 g/mol.
  • the two different compounds of component (B) are preferably selected from the group consisting of the following classes
  • E 1 is hydrogen, C 1 -C 8 alkyl, O ⁇ , —OH, —CH 2 CN, C 1 -C 18 alkoxy, C 5 -C 12 cycloalkoxy, C 3 -C 6 alkenyl, C 7 -C 9 phenylalkyl unsubstituted or substituted on the phenyl by 1, 2 or 3 C 1 -C 4 alkyl; or C 1 -C 8 acyl,
  • m 1 is 1, 2 or 4,
  • E 2 is C 1 -C 14 alkylene or a group of the formula (b-I)
  • E 3 is C 1 -C 10 alkyl or C 2 -C 10 alkenyl
  • E 4 is C 1 -C 10 alkylene
  • E 5 and E 6 independently of one another are C 1 -C 4 alkyl, cyclohexyl or methylcyclohexyl
  • E 2 is C 4 -C 10 alkanetetrayl
  • two of the radicals E 7 are —COO—(C 1 -C 20 alkyl), and
  • E 9 and E 10 together form C 2 -C 14 alkylene
  • E 11 is hydrogen or a group -Z 1 -COO-Z 2 ,
  • Z 1 is C 2 -C 14 alkylene
  • Z 2 is C 1 -C 24 alkyl
  • E 12 has one of the meanings of E 1 ;
  • radicals E 14 independently of one another are hydrogen or C 1 -C 12 alkyl
  • E 15 is C 1 -C 10 alkylene or C 3 -C 10 alkylidene
  • radicals E 16 independently of one another have one of the meanings of E 1 ;
  • E 17 is C 1 -C 24 alkyl
  • E 18 has one of the meanings of E 1 ;
  • E 19 , E 20 and E 21 independently of one another are a group of the formula (b-III)
  • E 22 has one of the meanings of E 1 ;
  • E 24 is hydrogen, C 1 -C 12 alkyl or C 1 -C 12 alkoxy
  • m 2 is 1, 2 or 3
  • E 25 has one of the meanings of E 1 , and
  • E 26 is C 2 -C 22 alkylene
  • E 26 is a group of the formula (b-IV)
  • radicals E 27 independently of one another are C 2 -C 12 alkylene, and the radicals E 28 independently of one another are C 1 -C 12 alkyl or C 5 -C 12 cycloalkyl;
  • the radicals E 29 independently of one another have one of the meanings of E 1 , and E 30 is C 2 -C 22 alkylene, C 5 -C 7 cycloalkylene, C 1 -C 4 alkylenedi(C 5 -C 7 cycloalkylene), phenylene or phenylenedi(C 1 -C 4 alkylene); or
  • E 31 is C 1 -C 10 alkyl, C 5 -C 12 cycloalkyl, C 1 -C 4 alkyl-substituted C 5 -C 12 cycloalkyl, phenyl or C 1 -C 10 alkyl-substituted phenyl,
  • E 32 is C 3 -C 10 alkylene
  • E 33 has one of the meanings of E 1 , and
  • m 3 is a number from 2 to 6.
  • One of the preferred embodiments of this invention relates to stabilizer mixtures wherein the two compounds of component (B) are selected from different classes.
  • component (B) are:
  • alkyl having up to 25 carbon atoms examples include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1,3-dimethyl-butyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl, tridecyl
  • a 8 , E 1 , E 8 , E 12 , E 13 , E 16 , E 18 , E 22 , E 23 , E 25 , E 29 and E 33 is C 1 -C 4 alkyl, especially methyl.
  • alkoxy having up to 18 carbon atoms are methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, pentoxy, isopentoxy, hexoxy, heptoxy, octoxy, decyloxy, dodecyloxy, tetradecyloxy, hexadecyloxy and octadecyloxy.
  • One of the preferred meanings of E 1 is octoxy.
  • E 24 is preferably C 1 -C 4 alkoxy.
  • C 5 -C 12 cycloalkyl examples are cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cyclododecyl.
  • C 1 -C 4 Alkyl-substituted C 5 -C 12 cycloalkyl is for example methylcyclohexyl or dimethylcyclohexyl.
  • C 5 -C 12 cycloalkoxy examples are cyclopentoxy, cyclohexoxy, cycloheptoxy, cyclooctoxy, cyclodecyloxy and cyclododecyloxy.
  • C 1 -C 10 Alkyl-substituted phenyl is for example methylphenyl, dimethylphenyl, trimethylphenyl or tert-butylphenyl.
  • C 7 -C 9 phenylalkyl are benzyl and phenylethyl.
  • C 7 -C 9 Phenylalkyl which is substituted on the phenyl radical by 1, 2 or 3 C 1 -C 4 alkyl is for example methylbenzyl, dimethylbenzyl, trimethylbenzyl or tert-butylbenzyl.
  • alkenyl having up to 10 carbon atoms are allyl, 2-methallyl, butenyl, pentenyl and hexenyl. Allyl is preferred.
  • the carbon atom in position 1 is preferably saturated.
  • acyl containing not more than 8 carbon atoms are formyl, acetyl, propionyl, butyryl, pentanoyl, hexanoyl, heptanoyl, octanoyl, acryloyl, methacryloyl and benzoyl.
  • C 1 -C 8 Alkanoyl, C 3 -C 8 alkenyl and benzoyl are preferred.
  • Acetyl and acryloyl are especially preferred.
  • alkylene having up to 22 carbon atoms examples include methylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, 2,2-dimethyltrimethylene, hexamethylene, trimethylhexamethylene, octamethylene and decamethylene.
  • C 3 -C 10 alkylidene is the group
  • C 4 -C 10 alkanetetrayl is 1,2,3,4-butanetetrayl.
  • C 5 -C 7 cycloalkylene is cyclohexylene.
  • C 1 -C 4 alkylenedi(C 5 -C 7 cycloalkylene) is methylenedicyclohexylene.
  • phenylenedi(C 1 -C 4 alkylene) is methylene-phenylene-methylene or ethylene-phenylene-ethylene.
  • n 1 , n 2 , n 2 * and n 4 are preferably a number from 2 to 25, in particular 2 to 20.
  • n 3 is preferably a number from 1 to 25, in particular 1 to 20.
  • m 3 is preferably a number from 2 to 6 or 2 to 5, in particular 2 to 4.
  • Component (A) is preferably TINUVIN 622 (RTM), HOSTAVIN N 30 (RTM) or FERRO AM 806 (RTM).
  • the compounds of component (B) are preferably selected from the group consisting of DASTIB 845 (RTM), TINUVIN 770 (RTM), TINUVIN 765 (RTM), TINUVIN 144 (RTM), TINUVIN 123 (RTM), ADK STAB LA 52 (RTM), ADK STAB LA 57 (RTM), ADK STAB LA 62 (RTM), ADK STAB LA 67 (RTM), HOSTAVIN N 20 (RTM), HOSTAVIN N 24 (RTM), SANDUVOR 3050 (RTM), DIACETAM 5 (RTM), SUMISORB TM 61 (RTM), UVINUL 4049 (RTM), SANDUVOR PR 31(RTM), GOODRITE UV 3034 (RTM), GOODRITE UV 3150 (RTM), GOODRITE UV 3159 (RTM), GOODRITE 3110 ⁇ 128 (RTM), UVINUL 4050 H (RTM), UVASIL 299 LM (RTM) and UVASIL 2000 LM
  • terminal groups which saturate the free valences in the compounds of the formulae (A-1), (A-2-a), (A-2-b), (A-4) and (B-11) depend on the processes used for their preparation.
  • the terminal groups can also be modified after the preparation of the compounds.
  • a 1 is hydrogen or methyl
  • a dicarboxylic acid diester of the formula Y—OOC-A 2 -COO—Y in which Y is, for example, methyl, ethyl or propyl, and A 2 is as defined above
  • the terminal group bonded to the 2,2,6,6-tetramethyl-4-oxypiperidin-1-yl radical is hydrogen or —CO-A 2 -COO—Y
  • the terminal group bonded to the diacyl radical is —O—Y or
  • the terminal group bonded to the nitrogen can be, for example, hydrogen and the terminal group bonded to the 2-hydroxypropylene radical can be, for example, a
  • the terminal group bonded to the dimethylene radical can be, for example, —OH
  • the terminal group bonded to the oxygen can be, for example, hydrogen.
  • the terminal groups can also be polyether radicals.
  • the end group bonded to the —CH 2 — residue can be, for example, hydrogen and the end group bonded to the —CH(CO 2 A 7 ) residue can be, for example, —CH ⁇ CH—COOA 7 .
  • the terminal group bonded to the silicon atom can be, for example, (E 31 ) 3 Si—O—, and the terminal group bonded to the oxygen can be, for example, —Si(E 31 ) 3 .
  • the compounds of the formula (B-11) can also be in the form of cyclic compounds if m 3 is a number from 3 to 6, i.e. the free valences shown in the structural formula then form a direct bond.
  • a 8 is preferably hydrogen, C 1 -C 4 alkyl, C 1 -C 10 alkoxy, cyclohexyloxy, allyl, benzyl or acetyl.
  • E 1 , E 8 , E 12 , E 13 , E 16 , E 18 , E 22 , E 23 , E 25 , E 29 and E 33 are preferably hydrogen, C 1 -C 4 alkyl, C 1 -C 10 alkoxy, cyclohexyloxy, allyl, benzyl or acetyl.
  • a 8 , E 1 , E 8 , E 12 , E 13 , E16, E 18 , E 22 , E 23 , E 25 , E 29 and E 33 are in particular hydrogen or methyl and E 1 additionally is C 1 -C 8 alkoxy.
  • a 1 is hydrogen or methyl
  • a 2 is a direct bond or C 2 -C 6 alkylene
  • n 1 is a number from 2 to 25;
  • n 2 and n 2 * are a number from 2 to 25;
  • a 3 and A 4 independently of one another are hydrogen or C 1 -C 4 alkyl, or A 3 and A 4 together form a C 9 -C 13 alkylene group, and
  • n 3 independently of one another are a number from 1 to 25;
  • n 4 is a number from 2 to 25,
  • a 5 and A 6 independently of one another are C 1 -C 4 alkyl
  • a 7 is C 1 -C 4 alkyl or a group of the formula (a-I)
  • m 1 is 1, 2 or 4,
  • E 2 is C 2 -C 10 alkylene or a group of the formula (b-I)
  • E 3 is C 1 -C 4 alkyl
  • E 4 is C 1 -C 6 alkylene
  • E 5 and E 6 independently of one another are C 1 -C 4 alkyl
  • E 2 is C 4 -C 8 alkanetetrayl
  • two of the radicals E 7 are —COO—(C 10 -C 15 alkyl), and
  • two of the radicals E 7 are a group of the formula (b-II);
  • E 9 and E 10 together form C 9 -C 13 alkylene
  • E 11 is hydrogen or a group -Z 1 -COO-Z 2 ,
  • Z 1 is C 2 -C 6 alkylene
  • Z 2 is C 10 -C 16 alkyl
  • E 14 is hydrogen
  • E 15 is C 2 -C 6 alkylene or C 3 -C 5 alkylidene
  • E 17 is C 10 -C 14 alkyl
  • E 24 is C 1 -C 4 alkoxy
  • m 2 is 1, 2 or 3
  • E 26 is a group of the formula (b-IV)
  • radicals E 27 independently of one another are C 2 -C 6 alkylene, and
  • radicals E 28 independently of one another are C 1 -C 4 alkyl or C 5 -C 8 cycloalkyl;
  • E 30 is C 2 -C 8 alkylene
  • E 31 is C 1 -C 4 alkyl
  • E 32 is C 3 -C 6 alkylene
  • m 3 is a number from 2 to 6.
  • a particularly preferred embodiment of this invention relates to a stabilizer mixture wherein
  • component (A) is a compound of the formula (A-1-a), (A-2-a), (A-2-b), (A-3-a) or (A-4-a);
  • n 1 is a number from 2 to 20;
  • n 2 and n 2 * are a number from 2 to 20;
  • n 3 independently of one another are a number from 1 to 20;
  • n 4 is a number from 2 to 20
  • radicals A 7 are a group of the formula (a-I)
  • a 8 is hydrogen, C 1 -C 8 alkyl, O ⁇ , —OH, —CH 2 CN, C 1 -C 18 alkoxy, C 5 -C 12 cycloalkoxy, C 3 -C 6 alkenyl, C 7 -C 9 phenylalkyl unsubstituted or substituted on the phenyl by 1, 2 or 3 C 1 -C 4 alkyl; or C 1 -C 8 acyl,
  • component (B) is formed by two different compounds selected from the group consisting of compounds of the formulae (B-1-a), (B-1-b), (B-1-c), (B-1-d), (B-2-a), (B-3-a), (B-3-b), (B-4-a), (B-4-b), (B-5), (B-6-a), (B-7), (B-8-a), (B-9-a), (B-9-b), (B-9-c), (B-10-a) and (B-11-a);
  • E 1 is hydrogen, C 1 -C 8 alkyl, O ⁇ , —OH, —CH 2 CN, C 1 -C 18 alkoxy, C 5 -C 12 cycloalkoxy, C 3 -C 6 alkenyl, C 7 -C 9 phenylalkyl unsubstituted or substituted on the phenyl by 1, 2 or 3 C 1 -C 4 alkyl; or C 1 -C 8 acyl;
  • E 8 has one of the meanings of E 1 ;
  • E 12 has one of the meanings of E 1 ;
  • E 13 has one of the meanings of E 1 ;
  • E 16 has one of the meanings of E 1 ;
  • E 18 has one of the meanings of E 1 ;
  • E 22 has one of the meanings of E 1 ;
  • E 23 has one of the meanings of E 1 ;
  • E 25 has one of the meanings of E 1 ;
  • E 29 has one of the meanings of E 1 ;
  • a particularly preferred embodiment of this invention also relates to a stabilizer mixture wherein one of the two different compounds forming component (B) is a compound of the formula (B-1-b) with E 1 being hydrogen.
  • Another preferred embodiment of this invention relates to a stabilizer mixture wherein
  • component (A) is a compound of the formula (A-1-a) with n 1 being a number from 2 to 20 or a compound of the formula (A-2-a) or (A-2-b) wherein n 2 and n 2 * are a number from 2 to 20; and
  • one of the two different compounds forming component (B) is a compound of the formula (B-1-b) with E 1 being hydrogen.
  • a further particularly preferred embodiment of this invention is a stabilizer mixture wherein
  • component (A) is a compound of the formula (A-1-a) with n 1 being a number from 2 to 20 or a compound of the formula (A-2-a) or (A-2-b) wherein n 2 and n 2 * are a number from 2 to 20;
  • one of the two different compounds forming component (B) is a compound of the formula (B-1-b) with E 1 being hydrogen;
  • the other of the two different compounds forming component (B) is a compound of the formula (B-1-a) with E 1 being hydrogen, (B-1-b) with E 1 being methyl, (B-1-d) with E 1 being hydrogen or methyl, (B-3-a) with E 12 being hydrogen, (B-3-b) with E 12 being hydrogen, (B-4-b) with E 13 being hydrogen, (B-5) with E 16 being hydrogen, (B-6-a) with E 18 being hydrogen or methyl, (B-8-a) with E 23 being methyl, (B-9-c) with E 25 being hydrogen or methyl, (B-10-a) with E 29 being hydrogen, or (B-11-a) with E 33 being hydrogen.
  • Examples of stabilizer mixtures according to the present invention are the following combinations of commercial products:
  • stabilizer mixtures are those wherein in the above combinations 1 to 324 the commercial product TINUVIN 622 (RTM) is replaced by a compound of the formula (A-2-a) and/or (A-2-b)
  • n 2 and n 2 * are a number from 2 to 20.
  • stabilizer mixtures are those wherein in the above combinations 1 to 324 the commercial product TINUVIN 622 (RTM) is replaced by a compound of the formula (A-4-a)
  • n 4 is a number from 2 to 20, and at least 50% of the radicals A 7 are a group of the formula
  • Combinations of particular interest are numbers 1, 4, 7, 8, 12, 13 and 15 to 24, and the corresponding combinations wherein TINUVIN 622 (RTM) is replaced by a compound of the formula (A-2-a) and/or (A-2-b).
  • TINUVIN 770 corresponds to the compound of the formula (B-1-b) wherein E 1 is hydrogen.
  • TINUVIN 765 corresponds to the compound of the formula (B-1-b) wherein E 1 is methyl.
  • TINUVIN 123 corresponds to the compound of the formula (B-1-b) wherein E 1 is octyloxy.
  • TINUVIN 144 corresponds to the compound of the formula (B-1-c) wherein E 1 is methyl.
  • HOSTAVIN N 24 corresponds to the compound of the formula (B-3-b) wherein E 12 is hydrogen.
  • RTM The commercial product SANDUVOR 3050 (RTM) corresponds to the compound of the formula (B-3-b-1) shown below, wherein E 12 is hydrogen.
  • the commercial product SUMISORB TM 61 corresponds to the compound of the formula (B-4-b) wherein E 13 is hydrogen.
  • UVASIL 299 LM (RTM) or UVASIL 2000 LM (RTM) contains as active ingredient the compound of the formula (B-11-a) wherein R 16 is hydrogen.
  • the compound of the formula (B-3-b-1) has the following structure:
  • the stabilizer mixture according to this invention is suitable for stabilizing organic materials against degradation induced by light, heat or oxidation.
  • organic materials are the following:
  • 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:
  • 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 ⁇ -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
  • Halogen-containing polymers such as polychloroprene, chlorinated rubbers, chlorinated and brominated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated or sulfo-chlorinated 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), chlor
  • Copolymers of the monomers mentioned under 9) with each other or with other unsaturated monomers for example acrylonitrilel butadiene copolymers, acrylonitrile/alkyl acrylate copolymers, acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halide copolymers or acrylonitrile/alkyl methacrylate/butadiene terpolymers.
  • 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, 619, 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 polytetram
  • 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, polyalkylene naphthalate (PAN) 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, PA/PPO, 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
  • Naturally occurring and synthetic organic materials which are pure monomeric compounds or mixtures of such compounds, for example mineral oils, animal and vegetable fats, oil and waxes, or oils, fats and waxes based on synthetic esters (e.g. phthalates, adipates, phosphates or trimellitates) and also mixtures of synthetic esters with mineral oils in any weight ratios, typically those used as spinning compositions, as well as aqueous emulsions of such materials.
  • synthetic esters e.g. phthalates, adipates, phosphates or trimellitates
  • Aqueous emulsions of natural or synthetic rubber e.g. natural latex or latices of carboxylated styrene/butadiene copolymers.
  • This invention therefore additionally relates to a composition
  • a composition comprising an organic material subject to degradation induced by light, heat or oxidation and the stabilizer mixture described herein above.
  • a further embodiment of the present invention is a method for stabilizing an organic material against degradation induced by light, heat or oxidation, which comprises incorporating into the organic material the stabilizer mixture described herein above.
  • the organic material is preferably a synthetic polymer, in particular from one of the above groups.
  • Polyolefins are preferred and polyethylene, polypropylene, a polyethylene copolymer and a polypropylene copolymer are particularly preferred.
  • the compounds of components (A) and (B) may be added to the organic material to be stabilized either individually or mixed with one another.
  • Each of the compounds of components (A) and (B) may be present in the organic material in an amount of preferably 0.005 to 5%, in particular 0.01 to 1% or 0.05 to 1%, relative to the weight of the organic material.
  • the weight ratio of the components (A):(B) is preferably 10:1 to 1:100, in particular 10:1 to 1:10 or 5:1 to 1:5. Further examples for the weight ratio are also 1:1 to 1:10, for example 1:2 to 1:5.
  • the weight ratio of the two components forming component (B) is for example 1:10 to 10:1 or 1:5 to 5:1, preferably 1:2 to 2:1, in particular 1:1.
  • the above components can be incorporated into the organic material to be stabilized by known methods, for example before or during shaping or by applying the dissolved or dispersed compounds to the organic material, if necessary with subsequent evaporation of the solvent.
  • the components can be added to the organic material in the form of a powder, granules or a masterbatch, which contains these components in, for example, a concentration of from 2.5 to 25% by weight.
  • the compounds of components (A) and (B) can be blended with each other before incorporation in the organic material. They can be added to a polymer before or during the polymerization or before the crosslinking.
  • the materials stabilized according to this invention can be used in a wide variety of forms, for example as films, fibres, tapes, moulding compositions, profiles or as binders for paints, adhesives or putties.
  • the stabilized material may additionally also contain various conventional additives, for example:
  • 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
  • Alkylthiomethylphenols for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctyl-thiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl-4-nonylphenol.
  • 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)
  • 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.
  • 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-tetramethylbutyl)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-butyl-4-hydroxy-5
  • 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
  • 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.
  • 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, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-triox
  • esters of ⁇ -(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis-(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-triox
  • 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.
  • 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
  • R 3′-tert-butyl-4′-hydroxy-5′-2H-benzotraizol-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.
  • 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-lauroyl-5-hydroxypyrazole, with or without additional ligands.
  • additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate,
  • 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.
  • N,N′-diphenyloxamide N
  • 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, dilsodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,4-di-cumylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaeryth
  • 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-heptadecylnitrone, N-octadecyl-alpha-hexadecylnitrone, nitrone derived from N,N
  • 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( ⁇ -dodecylmercap
  • Polyamide 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 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
  • Nucleatina 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 copoly
  • 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 weight ratio of the total amount of components (A) and (B) to the total amount of the conventional additives can be, for example, 100:1 to 1:100 or 10:1 to 1:10.
  • TINUVIN 770 (RTM):
  • the material thus obtained is compression molded in a laboratory press between two aluminum foils for 6 minutes at 260° C. to a 0.5 mm thick film which is cooled immediately to room temperature in a water-cooled press. Samples of 60 mm ⁇ 25 mm are cut out of these 0.5 mm films and are exposed in a WEATHER-OMETER Ci 65 (black panel temperature 63 ⁇ 2° C., without water-spraying).
  • T 0.1 The exposure time (T 0.1 ) corresponding to the formation of a carbonyl absorbance of 0.1 is a measure for the efficiency of the light stabilizer system.
  • the values obtained are summarized in Table 1. High T 0.1 values are desired.
  • TABLE 1 T 0.1 in hours
  • the amount amount of the of the light light stabilizers stabilizers used is used is 0.075% 0.05% Light stabilizer system each*). each*).
  • TINUVIN 770 RTM + TINUVIN 765 (RTM) 1780 3095 TINUVIN 770 (RTM) + TINUVIN 144 (RTM) 1990 2815 TINUVIN 770 (RTM) + TINUVIN 123 (RTM) 1780 2650 TINUVIN 770 (RTM) + HOSTAVIN N 20 2760 3205 (RTM) TINUVIN 770 (RTM) + ADK STAB LA 57 2245 3045 (RTM) TINUVIN 770 (RTM) + GOODRITE UV 3034 2440 3570 (RTM) TINUVIN 770 (RTM) + GOODRITE UV 3150 2715 3230 (RTM) TINUVIN 770 (RTM) + Compound (B-6-a-1) 1930 3095 TINUVIN 770 (RTM) + Compound (B-6-a-2) 2000 3400 TINUVIN 770 (RTM) + Compound (B-10-a-1) 3510 3940 TINUVIN 770 (RTM) +
  • the material thus obtained is compression molded in a laboratory press between two aluminum foils for 6 minutes at 260° C. to a 0.5 mm thick film which is cooled immediately to room temperature in a water-cooled press. Samples of 60 mm ⁇ 25 mm are cut out of these 0.5 mm films and are exposed in a WEATHER-OMETER Ci 65 (black panel temperature 63 ⁇ 2° C., without water-spraying).
  • T 0.1 The exposure time (T 0.1 ) corresponding to the formation of a carbonyl absorbance of 0.1 is a measure for the efficiency of the light stabilizer system.
  • the values obtained are summarized in the following tables. High T 0.1 values are desired.
  • TABLE 2A T 0.1 T 0.1 T 0.1 in hours in hours in hours
  • RTM Light Light Light stabilizer stabilizer stabilizer system in system in system in combi- combi- combi- nation nation with with with with TINUVIN TINUVIN TINUVIN 622 622 622 622 (RTM) (RTM)
  • RTM The amount amount amount of the of the of the stabilizers stabilizers stabilizers of the of the of the light light light T 0.1 stabilizer stabilizer stabilizer in hours system system system system The is 0.05% is 0.07
  • TINUVIN 770 RTM + 4635 6025 TINUVIN 144 (RTM) TINUVIN 770 (RTM) + 4935 6080 TINUVIN 123 (RTM) TINUVIN 770 (RTM) + 5105 6005 HOSTAVIN N 24 (RTM) TINUVIN 770 (RTM) + 5450 6800 ADK STAB LA 57 (RTM) TINUVIN 770 (RTM) + 6925 7735 GOODRITE UV 3034 (RTM) TINUVIN 770 (RTM) + 6530 7335 Compound (B-6-a-2) TINUVIN 770 (RTM) + 6040 6905 Compound (B-1-a-1) TINUVIN 770 (RTM) + 5070 >6495 SANDUVOR 3050 (RTM)
  • TINUVIN 770 (RTM) + 4815 >7260 TINUVIN 765 (RTM) TINUVIN 770 (RTM) + 5695 7145 TINUVIN 144 (RTM) TINUVIN 770 (RTM) + 4670 7080 TINUVIN 123 (RTM) TINUVIN 770 (RTM) + 5390 6710 HOSTAVIN N 24 (RTM) TINUVIN 770 (RTM) + 6655 >7260 ADK STAB LA 52 (RTM) TINUVIN 770 (RTM) + 5040 6760 ADK STAB LA 62 (RTM) TINUVIN 770 (RTM) + 5010 6205 ADK STAB LA 67 (RTM) TINUVIN 770 (RTM) + 5825 >7260 Compound (B-10-a-1) TINUVIN 770 (RTM) + 6125 7215 Compound (B-1-a-1) TINUVIN 770 (RTM) + 5690 >7260 SANDUV

Abstract

A stabilizer mixture containing the components (A) and (B) wherein component (A) is for example a compound of the formula (A-1) wherein A1 is hydrogen or C1-C4alkyl, A2 is a direct bond or C1-C10alkylene, and n1 is a number from 2 to 50; and component (B) is formed by two different low molecular weight sterically hindered amine compounds containing a group of the formula (I) and (II); with the proviso that components (A) and (B) are different.
Figure US20030197151A1-20031023-C00001

Description

  • The present invention relates to a stabilizer mixture containing a specific sterically hindered amine ester or amide, and two different low molecular weight sterically hindered amines. [0001]
  • Stabilizer mixtures containing blends of sterically hindered amines are for example described in U.S. Pat. No. 4,692,468, U.S. Pat. No. 4,863,981, U.S. Pat. No. 5,719,217, U.S. Pat. No. 5,919,399, U.S. Pat. No. 5,965,643, U.S. Pat. No. 5,980,783, U.S. Pat. No. 6,015,849 and U.S. Pat. No. 6,020,406. [0002]
  • The present invention relates to a stabilizer mixture containing the components (A) and (B) [0003]
  • wherein [0004]
  • component (A) is [0005]
  • a compound of the formula (A-1) [0006]
    Figure US20030197151A1-20031023-C00002
  • wherein [0007]  
  • A[0008] 1 is hydrogen or C1-C4alkyl,
  • A[0009] 2 is a direct bond or C1-C10alkylene, and
  • n[0010] 1 is a number from 2 to 50;
  • at least one compound of the formulae (A-2-a) and (A-2-b) [0011]
    Figure US20030197151A1-20031023-C00003
    Figure US20030197151A1-20031023-C00004
  • wherein [0012]  
  • n[0013] 2 and n2* are a number from 2 to 50;
  • a compound of the formula (A-3) [0014]
    Figure US20030197151A1-20031023-C00005
  • wherein [0015]  
  • A[0016] 3 and A4 independently of one another are hydrogen or C1-C8alkyl, or A3 and A4 together form a C2-C14alkylene group, and
  • the variables n[0017] 3 independently of one another are a number from 1 to 50; or
  • a compound of the formula (A-4) [0018]
    Figure US20030197151A1-20031023-C00006
  • wherein [0019]  
  • n[0020] 4 is a number from 2 to 50,
  • A[0021] 5 is hydrogen or C1-C4alkyl,
  • the radicals A[0022] 6 and A7 independently of one another are C1-C4alkyl or a group of the formula (a-I)
    Figure US20030197151A1-20031023-C00007
  • wherein A[0023]   8 is hydrogen, C1-C8alkyl, O−, —OH, —CH2CN, C1-C18alkoxy, C5-C12cycloalkoxy, C3-C6alkenyl, C7-C9phenylalkyl unsubstituted or substituted on the phenyl by 1, 2 or 3 C1-C4alkyl; or C1-C8acyl,
  • with the proviso that at least 50% of the radicals A[0024] 7 are a group of the formula (a-I); and component (B) is formed by two different low molecular weight sterically hindered amine compounds containing a group of the formula (I) or (II);
    Figure US20030197151A1-20031023-C00008
  • with the proviso that components (A) and (B) are different. [0025]
  • Preferably the compounds of component (B) have a molecular weight up to 1,000 g/mol, for example 155 to 800 g/mol or 155 to 1,000 g/mol or 300 to 800 g/mol or 300 to 1,000 g/mol. [0026]
  • The two different compounds of component (B) are preferably selected from the group consisting of the following classes [0027]
  • β-1) a compound of the formula (B-1) [0028]
    Figure US20030197151A1-20031023-C00009
  • in which [0029]  
  • E[0030] 1 is hydrogen, C1-C8alkyl, O−, —OH, —CH2CN, C1-C18alkoxy, C5-C12cycloalkoxy, C3-C6alkenyl, C7-C9phenylalkyl unsubstituted or substituted on the phenyl by 1, 2 or 3 C1-C4alkyl; or C1-C8acyl,
  • m[0031] 1 is 1, 2 or 4,
  • if m[0032] 1 is 1, E2 is C1-C25alkyl,
  • if m[0033] 1 is 2, E2 is C1-C14alkylene or a group of the formula (b-I)
    Figure US20030197151A1-20031023-C00010
  • wherein E[0034] 3 is C1-C10alkyl or C2-C10alkenyl, E4 is C1-C10alkylene, and E5 and E6 independently of one another are C1-C4alkyl, cyclohexyl or methylcyclohexyl, and
  • if m[0035] 1 is 4, E2 is C4-C10alkanetetrayl;
  • β-2) a compound of the formula (B-2) [0036]
    Figure US20030197151A1-20031023-C00011
  • in which [0037]  
  • two of the radicals E[0038] 7 are —COO—(C1-C20alkyl), and
  • two of the radicals E[0039] 7 are a group of the formula (b-II)
    Figure US20030197151A1-20031023-C00012
  • with E[0040] 8 having one of the meanings of E1;
  • β-3) a compound of the formula (B-3) [0041]
    Figure US20030197151A1-20031023-C00013
  • in which [0042]  
  • E[0043] 9 and E10 together form C2-C14alkylene,
  • E[0044] 11 is hydrogen or a group -Z1-COO-Z2,
  • Z[0045] 1 is C2-C14alkylene, and
  • Z[0046] 2 is C1-C24alkyl, and
  • E[0047] 12 has one of the meanings of E1;
  • β-4) a compound of the formula (B-4) [0048]
    Figure US20030197151A1-20031023-C00014
  • wherein [0049]  
  • the radicals E[0050] 13 independently of one another have one of the meanings of E1,
  • the radicals E[0051] 14 independently of one another are hydrogen or C1-C12alkyl, and
  • E[0052] 15 is C1-C10alkylene or C3-C10alkylidene;
  • β-5) a compound of the formula (B-5) [0053]
    Figure US20030197151A1-20031023-C00015
  • wherein [0054]  
  • the radicals E[0055] 16 independently of one another have one of the meanings of E1;
  • β-6) a compound of the formula (B-6) [0056]
    Figure US20030197151A1-20031023-C00016
  • in which [0057]  
  • E[0058] 17 is C1-C24alkyl, and
  • E[0059] 18 has one of the meanings of E1;
  • β-7) a compound of the formula (B-7) [0060]
    Figure US20030197151A1-20031023-C00017
  • in which [0061]  
  • E[0062] 19, E20 and E21 independently of one another are a group of the formula (b-III)
    Figure US20030197151A1-20031023-C00018
  • wherein E[0063] 22 has one of the meanings of E1;
  • β-8) a compound of the formula (B-8) [0064]
    Figure US20030197151A1-20031023-C00019
  • wherein [0065]  
  • the radicals E[0066] 23 independently of one another have one of the meanings of E1,
  • and E[0067] 24 is hydrogen, C1-C12alkyl or C1-C12alkoxy;
  • β-9) a compound of the formula (B-9) [0068]
    Figure US20030197151A1-20031023-C00020
  • wherein [0069]  
  • m[0070] 2 is 1, 2 or 3,
  • E[0071] 25 has one of the meanings of E1, and
  • when m[0072] 2 is 1, E26 is a group
    Figure US20030197151A1-20031023-C00021
  • when m[0073] 2 is 2, E26 is C2-C22alkylene, and
  • when m[0074] 2 is 3, E26 is a group of the formula (b-IV)
    Figure US20030197151A1-20031023-C00022
  • wherein the radicals E[0075] 27 independently of one another are C2-C12alkylene, and the radicals E28 independently of one another are C1-C12alkyl or C5-C12cycloalkyl;
  • β-10) a compound of the formula (B-10) [0076]
    Figure US20030197151A1-20031023-C00023
  • wherein [0077]  
  • the radicals E[0078] 29 independently of one another have one of the meanings of E1, and E30 is C2-C22alkylene, C5-C7cycloalkylene, C1-C4alkylenedi(C5-C7cycloalkylene), phenylene or phenylenedi(C1-C4alkylene); or
  • β-11) a compound of the formula (B-11) [0079]
    Figure US20030197151A1-20031023-C00024
  • in which [0080]  
  • E[0081] 31 is C1-C10alkyl, C5-C12cycloalkyl, C1-C4alkyl-substituted C5-C12cycloalkyl, phenyl or C1-C10alkyl-substituted phenyl,
  • E[0082] 32 is C3-C10alkylene,
  • E[0083] 33 has one of the meanings of E1, and
  • m[0084] 3 is a number from 2 to 6.
  • One of the preferred embodiments of this invention relates to stabilizer mixtures wherein the two compounds of component (B) are selected from different classes. [0085]
  • Examples of component (B) are: [0086]
  • A compound selected from the class β-1 and a compound selected from the class β-3, β-4, β-5, β-6, β-7, β-8, β-9, β-10 or β-11, preferably the class β-3, β-5, β-6, β-10 or β-11. [0087]
  • A compound selected from the class β-3 and a compound selected from the class β-4, β-5, β-6, β-7, β-9, β-10 or β-11, preferably β-5, β-6, β-10 or β-11. [0088]
  • A compound selected from the class β-5 and a compound selected from the class β-6, β-7, β-8, β-9, β-10 or β-11, preferably β-6, β-10 or β-11. [0089]
  • A compound selected from the class β-6 and a compound selected from the class β-10 or β-11. [0090]
  • A compound selected from the class β-7 and a compound selected from the class β-8, β-10 or β-11. [0091]
  • A compound selected from the class β-9 and a compound selected from the class β-10 or β-11. [0092]
  • A compound selected from the class β-10 and a compound selected from the class β-11. [0093]
  • Examples of alkyl having up to 25 carbon atoms are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1,3-dimethyl-butyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, eicosyl and docosyl. One of the preferred definitions of A[0094] 8, E1, E8, E12, E13, E16, E18, E22, E23, E25, E29 and E33 is C1-C4alkyl, especially methyl.
  • Examples of alkoxy having up to 18 carbon atoms are methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, pentoxy, isopentoxy, hexoxy, heptoxy, octoxy, decyloxy, dodecyloxy, tetradecyloxy, hexadecyloxy and octadecyloxy. One of the preferred meanings of E[0095] 1 is octoxy. E24 is preferably C1-C4alkoxy.
  • Examples of C[0096] 5-C12cycloalkyl are cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cyclododecyl. C5-C8Cycloalkyl, especially cyclohexyl, is preferred.
  • C[0097] 1-C4Alkyl-substituted C5-C12cycloalkyl is for example methylcyclohexyl or dimethylcyclohexyl.
  • Examples of C[0098] 5-C12cycloalkoxy are cyclopentoxy, cyclohexoxy, cycloheptoxy, cyclooctoxy, cyclodecyloxy and cyclododecyloxy. C5-C8Cycloalkoxy, in particular cyclopentoxy and cyclohexoxy, is preferred.
  • C[0099] 1-C10Alkyl-substituted phenyl is for example methylphenyl, dimethylphenyl, trimethylphenyl or tert-butylphenyl.
  • Examples of C[0100] 7-C9phenylalkyl are benzyl and phenylethyl.
  • C[0101] 7-C9Phenylalkyl which is substituted on the phenyl radical by 1, 2 or 3 C1-C4alkyl is for example methylbenzyl, dimethylbenzyl, trimethylbenzyl or tert-butylbenzyl.
  • Examples of alkenyl having up to 10 carbon atoms are allyl, 2-methallyl, butenyl, pentenyl and hexenyl. Allyl is preferred. The carbon atom in position 1 is preferably saturated. [0102]
  • Examples of acyl containing not more than 8 carbon atoms are formyl, acetyl, propionyl, butyryl, pentanoyl, hexanoyl, heptanoyl, octanoyl, acryloyl, methacryloyl and benzoyl. C[0103] 1-C8Alkanoyl, C3-C8alkenyl and benzoyl are preferred. Acetyl and acryloyl are especially preferred.
  • Examples of alkylene having up to 22 carbon atoms are methylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, 2,2-dimethyltrimethylene, hexamethylene, trimethylhexamethylene, octamethylene and decamethylene. [0104]
  • An example of C[0105] 3-C10alkylidene is the group
    Figure US20030197151A1-20031023-C00025
  • An example of C[0106] 4-C10alkanetetrayl is 1,2,3,4-butanetetrayl.
  • An example of C[0107] 5-C7cycloalkylene is cyclohexylene.
  • An example of C[0108] 1-C4alkylenedi(C5-C7cycloalkylene) is methylenedicyclohexylene.
  • An example of phenylenedi(C[0109] 1-C4alkylene) is methylene-phenylene-methylene or ethylene-phenylene-ethylene.
  • n[0110] 1, n2, n2* and n4 are preferably a number from 2 to 25, in particular 2 to 20. n3 is preferably a number from 1 to 25, in particular 1 to 20.
  • m[0111] 3 is preferably a number from 2 to 6 or 2 to 5, in particular 2 to 4.
  • The compounds described above as components (A) and (B) are essentially known and commercially available. All of them can be prepared by known processes. [0112]
  • The preparation of the compounds of component (A) is disclosed for example in U.S. Pat. No. 4,233,412, U.S. Pat. No. 4,340,534, WO-A-98/51,690 and EP-A-1,803. [0113]
  • The preparation of the compounds of component (B) is disclosed for example in U.S. Pat. No. 5,679,733, U.S. Pat. No. 3,640,928, U.S. Pat. No. 4,198,334, U.S. Pat. No. 5,204,473, U.S. Pat. No. 4,619,958, U.S. Pat. No. 4,110,306, U.S. Pat. No. 4,110,334, U.S. Pat. No. 4,689,416, U.S. Pat. No. 4,408,051, SU-A-768,175 (Derwent 88-138,751/20), U.S. Pat. No. 5,049,604, U.S. Pat. No. 4,769,457, U.S. Pat. No. 4,356,307, U.S. Pat. No. 4,619,956, U.S. Pat. No. 5,182,390, GB-A-2,269,819, U.S. Pat. No. 4,292,240, U.S. Pat. No. 5,026,849, U.S. Pat. No. 5,071,981, U.S. Pat. No. 4,547,538, U.S. Pat. No. 4,976,889 and U.S. Pat. No. 5,051,458. [0114]
  • Component (A) is preferably TINUVIN 622 (RTM), HOSTAVIN N 30 (RTM) or FERRO AM 806 (RTM). [0115]
  • The compounds of component (B) are preferably selected from the group consisting of DASTIB 845 (RTM), TINUVIN 770 (RTM), TINUVIN 765 (RTM), TINUVIN 144 (RTM), TINUVIN 123 (RTM), ADK STAB LA 52 (RTM), ADK STAB LA 57 (RTM), ADK STAB LA 62 (RTM), ADK STAB LA 67 (RTM), HOSTAVIN N 20 (RTM), HOSTAVIN N 24 (RTM), SANDUVOR 3050 (RTM), DIACETAM 5 (RTM), SUMISORB TM 61 (RTM), UVINUL 4049 (RTM), SANDUVOR PR 31(RTM), GOODRITE UV 3034 (RTM), GOODRITE UV 3150 (RTM), GOODRITE UV 3159 (RTM), GOODRITE 3110×128 (RTM), UVINUL 4050 H (RTM), UVASIL 299 LM (RTM) and UVASIL 2000 LM (RTM). [0116]
  • The meanings of the terminal groups which saturate the free valences in the compounds of the formulae (A-1), (A-2-a), (A-2-b), (A-4) and (B-11) depend on the processes used for their preparation. The terminal groups can also be modified after the preparation of the compounds. [0117]
  • If the compounds of the formula (A-1) are prepared, for example, by reacting a compound of the formula [0118]
    Figure US20030197151A1-20031023-C00026
  • in which A[0119] 1 is hydrogen or methyl, with a dicarboxylic acid diester of the formula Y—OOC-A2-COO—Y, in which Y is, for example, methyl, ethyl or propyl, and A2 is as defined above, the terminal group bonded to the 2,2,6,6-tetramethyl-4-oxypiperidin-1-yl radical is hydrogen or —CO-A2-COO—Y, and the terminal group bonded to the diacyl radical is —O—Y or
    Figure US20030197151A1-20031023-C00027
  • In the compounds of the formula (A-2-a), the terminal group bonded to the nitrogen can be, for example, hydrogen and the terminal group bonded to the 2-hydroxypropylene radical can be, for example, a [0120]
    Figure US20030197151A1-20031023-C00028
  • group. [0121]
  • In the compounds of the formula (A-2-b), the terminal group bonded to the dimethylene radical can be, for example, —OH, and the terminal group bonded to the oxygen can be, for example, hydrogen. The terminal groups can also be polyether radicals. [0122]
  • In the compounds of the formula (A-4), the end group bonded to the —CH[0123] 2— residue can be, for example, hydrogen and the end group bonded to the —CH(CO2A7) residue can be, for example, —CH═CH—COOA7.
  • In the compounds of the formula (B-11), the terminal group bonded to the silicon atom can be, for example, (E[0124] 31)3Si—O—, and the terminal group bonded to the oxygen can be, for example, —Si(E31)3.
  • The compounds of the formula (B-11) can also be in the form of cyclic compounds if m[0125] 3 is a number from 3 to 6, i.e. the free valences shown in the structural formula then form a direct bond.
  • A[0126] 8 is preferably hydrogen, C1-C4alkyl, C1-C10alkoxy, cyclohexyloxy, allyl, benzyl or acetyl.
  • E[0127] 1, E8, E12, E13, E16, E18, E22, E23, E25, E29 and E33 are preferably hydrogen, C1-C4alkyl, C1-C10alkoxy, cyclohexyloxy, allyl, benzyl or acetyl.
  • A[0128] 8, E1, E8, E12, E13, E16, E18, E22, E23, E25, E29 and E33 are in particular hydrogen or methyl and E1 additionally is C1-C8alkoxy.
  • According to a preferred embodiment [0129]
  • A[0130] 1 is hydrogen or methyl,
  • A[0131] 2 is a direct bond or C2-C6alkylene, and
  • n[0132] 1 is a number from 2 to 25;
  • n[0133] 2 and n2* are a number from 2 to 25;
  • A[0134] 3 and A4 independently of one another are hydrogen or C1-C4alkyl, or A3 and A4 together form a C9-C13alkylene group, and
  • the variables n[0135] 3 independently of one another are a number from 1 to 25;
  • n[0136] 4 is a number from 2 to 25,
  • A[0137] 5 and A6 independently of one another are C1-C4alkyl, and
  • A[0138] 7 is C1-C4alkyl or a group of the formula (a-I)
  • with the proviso that at least 50% of the radicals A[0139] 7 are a group of the formula (a-I).
  • According to a further preferred embodiment [0140]
  • m[0141] 1 is 1, 2 or 4,
  • if m[0142] 1 is 1, E2 is C12-C20alkyl,
  • if m[0143] 1 is 2, E2 is C2-C10alkylene or a group of the formula (b-I)
  • E[0144] 3 is C1-C4alkyl,
  • E[0145] 4 is C1-C6alkylene, and
  • E[0146] 5 and E6 independently of one another are C1-C4alkyl, and
  • if m[0147] 1 is 4, E2 is C4-C8alkanetetrayl;
  • two of the radicals E[0148] 7 are —COO—(C10-C15alkyl), and
  • two of the radicals E[0149] 7 are a group of the formula (b-II);
  • E[0150] 9 and E10 together form C9-C13alkylene,
  • E[0151] 11 is hydrogen or a group -Z1-COO-Z2,
  • Z[0152] 1 is C2-C6alkylene, and
  • Z[0153] 2 is C10-C16alkyl;
  • E[0154] 14 is hydrogen, and
  • E[0155] 15 is C2-C6alkylene or C3-C5alkylidene;
  • E[0156] 17 is C10-C14alkyl;
  • E[0157] 24 is C1-C4alkoxy;
  • m[0158] 2 is 1, 2 or 3,
  • when m[0159] 2 is 1, E26 is a group
    Figure US20030197151A1-20031023-C00029
  • when m[0160] 2 is 2, E26 is C2-C6alkylene, and
  • when m[0161] 2 is 3, E26 is a group of the formula (b-IV)
  • the radicals E[0162] 27 independently of one another are C2-C6alkylene, and
  • the radicals E[0163] 28 independently of one another are C1-C4alkyl or C5-C8cycloalkyl;
  • E[0164] 30 is C2-C8alkylene; and
  • E[0165] 31 is C1-C4alkyl,
  • E[0166] 32 is C3-C6alkylene, and
  • m[0167] 3 is a number from 2 to 6.
  • A particularly preferred embodiment of this invention relates to a stabilizer mixture wherein [0168]
  • component (A) is a compound of the formula (A-1-a), (A-2-a), (A-2-b), (A-3-a) or (A-4-a); [0169]
    Figure US20030197151A1-20031023-C00030
  • wherein n[0170] 1 is a number from 2 to 20;
    Figure US20030197151A1-20031023-C00031
    Figure US20030197151A1-20031023-C00032
  • wherein n[0171] 2 and n2* are a number from 2 to 20;
    Figure US20030197151A1-20031023-C00033
  • wherein the variables n[0172] 3 independently of one another are a number from 1 to 20;
    Figure US20030197151A1-20031023-C00034
  • wherein n[0173] 4 is a number from 2 to 20, and
  • at least 50% of the radicals A[0174] 7 are a group of the formula (a-I)
    Figure US20030197151A1-20031023-C00035
  • wherein A[0175] 8 is hydrogen, C1-C8alkyl, O−, —OH, —CH2CN, C1-C18alkoxy, C5-C12cycloalkoxy, C3-C6alkenyl, C7-C9phenylalkyl unsubstituted or substituted on the phenyl by 1, 2 or 3 C1-C4alkyl; or C1-C8acyl,
  • and the remaining radicals A[0176] 7 are ethyl; and
  • component (B) is formed by two different compounds selected from the group consisting of compounds of the formulae (B-1-a), (B-1-b), (B-1-c), (B-1-d), (B-2-a), (B-3-a), (B-3-b), (B-4-a), (B-4-b), (B-5), (B-6-a), (B-7), (B-8-a), (B-9-a), (B-9-b), (B-9-c), (B-10-a) and (B-11-a); [0177]
    Figure US20030197151A1-20031023-C00036
  • wherein E[0178] 1 is hydrogen, C1-C8alkyl, O−, —OH, —CH2CN, C1-C18alkoxy, C5-C12cycloalkoxy, C3-C6alkenyl, C7-C9phenylalkyl unsubstituted or substituted on the phenyl by 1, 2 or 3 C1-C4alkyl; or C1-C8acyl;
    Figure US20030197151A1-20031023-C00037
  • in which two of the radicals E[0179] 7 are —COO—C13H27 and two of the radicals E7 are
    Figure US20030197151A1-20031023-C00038
  • and E[0180]   8 has one of the meanings of E1;
    Figure US20030197151A1-20031023-C00039
  • wherein E[0181] 12 has one of the meanings of E1;
    Figure US20030197151A1-20031023-C00040
  • wherein E[0182] 13 has one of the meanings of E1;
    Figure US20030197151A1-20031023-C00041
  • wherein E[0183] 16 has one of the meanings of E1;
    Figure US20030197151A1-20031023-C00042
  • wherein E[0184] 18 has one of the meanings of E1;
    Figure US20030197151A1-20031023-C00043
  • in which E[0185] 19, E20 and E21 independently of one another are a group of the formula (b-III)
    Figure US20030197151A1-20031023-C00044
  • wherein E[0186] 22 has one of the meanings of E1;
    Figure US20030197151A1-20031023-C00045
  • wherein E[0187] 23 has one of the meanings of E1;
    Figure US20030197151A1-20031023-C00046
  • wherein E[0188] 25 has one of the meanings of E1;
    Figure US20030197151A1-20031023-C00047
  • wherein E[0189] 29 has one of the meanings of E1;
    Figure US20030197151A1-20031023-C00048
  • wherein m[0190] 3 is a number from 2 to 6 and E33 has one of the meanings of E1.
  • A particularly preferred embodiment of this invention also relates to a stabilizer mixture wherein one of the two different compounds forming component (B) is a compound of the formula (B-1-b) with E[0191] 1 being hydrogen.
  • Another preferred embodiment of this invention relates to a stabilizer mixture wherein [0192]
  • component (A) is a compound of the formula (A-1-a) with n[0193] 1 being a number from 2 to 20 or a compound of the formula (A-2-a) or (A-2-b) wherein n2 and n2* are a number from 2 to 20; and
  • one of the two different compounds forming component (B) is a compound of the formula (B-1-b) with E[0194] 1 being hydrogen.
  • A further particularly preferred embodiment of this invention is a stabilizer mixture wherein [0195]
  • component (A) is a compound of the formula (A-1-a) with n[0196] 1 being a number from 2 to 20 or a compound of the formula (A-2-a) or (A-2-b) wherein n2 and n2* are a number from 2 to 20;
  • one of the two different compounds forming component (B) is a compound of the formula (B-1-b) with E[0197] 1 being hydrogen; and
  • the other of the two different compounds forming component (B) is a compound of the formula (B-1-a) with E[0198] 1 being hydrogen, (B-1-b) with E1 being methyl, (B-1-d) with E1 being hydrogen or methyl, (B-3-a) with E12 being hydrogen, (B-3-b) with E12 being hydrogen, (B-4-b) with E13 being hydrogen, (B-5) with E16 being hydrogen, (B-6-a) with E18 being hydrogen or methyl, (B-8-a) with E23 being methyl, (B-9-c) with E25 being hydrogen or methyl, (B-10-a) with E29 being hydrogen, or (B-11-a) with E33 being hydrogen.
  • Examples of stabilizer mixtures according to the present invention are the following combinations of commercial products: [0199]
  • 1. TINUVIN 622 (RTM)+TINUVIN 770 (RTM)+TINUVIN 765 (RTM) [0200]
  • 2. TINUVIN 622 (RTM)+TINUVIN 770 (RTM)+TINUVIN 144 (RTM) [0201]
  • 3. TINUVIN 622 (RTM)+TINUVIN 770 (RTM)+TINUVIN 123 (RTM) [0202]
  • 4. TINUVIN 622 (RTM)+TINUVIN 770 (RTM)+compound of the formula (B-3-a) wherein E[0203] 12 is hydrogen
  • 5. TINUVIN 622 (RTM)+TINUVIN 770 (RTM)+HOSTAVIN N 24 (RTM) [0204]
  • 6. TINUVIN 622 (RTM)+TINUVIN 770 (RTM)+DIACETAM 5 (RTM) [0205]
  • 7. TINUVIN 622 (RTM)+TINUVIN 770 (RTM)+ADK STAB LA 52 (RTM) [0206]
  • 8. TINUVIN 622 (RTM)+TINUVIN 770 (RTM)+ADK STAB LA 57 (RTM) [0207]
  • 9. TINUVIN 622 (RTM)+TINUVIN 770 (RTM)+ADK STAB LA 62 (RTM) [0208]
  • 10. TINUVIN 622 (RTM)+TINUVIN 770 (RTM)+ADK STAB LA 67 (RTM) [0209]
  • 11. TINUVIN 622 (RTM)+TINUVIN 770 (RTM)+GOODRITE UV 3034 (RTM) [0210]
  • 12. TINUVIN 622 (RTM)+TINUVIN 770 (RTM)+GOODRITE UV 3150 (RTM) [0211]
  • 13. TINUVIN 622 (RTM)+TINUVIN 770 (RTM)+GOODRITE UV 3159 (RTM) [0212]
  • 14. TINUVIN 622 (RTM)+TINUVIN 770 (RTM)+compound of the formula (B-9-a) wherein E[0213] 25 is hydrogen
  • 15. TINUVIN 622 (RTM)+TINUVIN 770 (RTM)+UVINUL 4049 (RTM) [0214]
  • 16. TINUVIN 622 (RTM)+TINUVIN 770 (RTM)+compound of the formula (B-10-a) wherein E[0215] 29 is hydrogen
  • 17. TINUVIN 622 (RTM)+TINUVIN 770 (RTM)+compound of the formula (B-1-a) wherein E[0216] 1 is hydrogen
  • 18. TINUVIN 622 (RTM)+TINUVIN 770 (RTM)+SUMISORB TM 61 (RTM) [0217]
  • 19. TINUVIN 622 (RTM)+TINUVIN 770 (RTM)+SANDUVOR 3050 (RTM) [0218]
  • 20. TINUVIN 622 (RTM)+TINUVIN 770 (RTM)+SANDUVOR PR-31 (RTM) [0219]
  • 21. TINUVIN 622 (RTM)+TINUVIN 770 (RTM)+UVASIL 299 LM (RTM) [0220]
  • 22. TINUVIN 622 (RTM)+TINUVIN 770 (RTM)+UVASIL 2000 LM (RTM) [0221]
  • 23. TINUVIN 622 (RTM)+TINUVIN 770 (RTM)+compound of the formula (B-6-a) wherein E[0222] 18 is hydrogen
  • 24. TINUVIN 622 (RTM)+TINUVIN 770 (RTM)+compound of the formula (B-6-a) wherein E[0223] 18 is methyl
  • 25. TINUVIN 622 (RTM)+TINUVIN 770 (RTM)+compound of the formula (B-7) with E[0224] 19, E20 and E21 being a group of the formula (b-III) wherein E22 is hydrogen.
  • 26. TINUVIN 622 (RTM)+TINUVIN 765 (RTM)+TINUVIN 144 (RTM) [0225]
  • 27. TINUVIN 622 (RTM)+TINUVIN 765 (RTM)+TINUVIN 123 (RTM) [0226]
  • 28. TINUVIN 622 (RTM)+TINUVIN 765 (RTM)+compound of the formula (B-3-a) wherein E[0227] 12 is hydrogen
  • 29. TINUVIN 622 (RTM)+TINUVIN 765 (RTM)+HOSTAVIN N 24 (RTM) [0228]
  • 30. TINUVIN 622 (RTM)+TINUVIN 765 (RTM)+DIACETAM 5 (RTM) [0229]
  • 31. TINUVIN 622 (RTM)+TINUVIN 765 (RTM)+ADK STAB LA 52 (RTM) [0230]
  • 32. TINUVIN 622 (RTM)+TINUVIN 765 (RTM)+ADK STAB LA 57 (RTM) [0231]
  • 33. TINUVIN 622 (RTM)+TINUVIN 765 (RTM)+ADK STAB LA 62 (RTM) [0232]
  • 34. TINUVIN 622 (RTM)+TINUVIN 765 (RTM)+ADK STAB LA 67 (RTM) [0233]
  • 35. TINUVIN 622 (RTM)+TINUVIN 765 (RTM)+GOODRITE UV 3034 (RTM) [0234]
  • 36. TINUVIN 622 (RTM)+TINUVIN 765 (RTM)+GOODRITE UV 3150 (RTM) [0235]
  • 37. TINUVIN 622 (RTM)+TINUVIN 765 (RTM)+GOODRITE UV 3159 (RTM) [0236]
  • 38. TINUVIN 622 (RTM)+TINUVIN 765 (RTM)+compound of the formula (B-9-a) wherein E[0237] 25 is hydrogen
  • 39. TINUVIN 622 (RTM)+TINUVIN 765 (RTM)+UVINUL 4049 (RTM) [0238]
  • 40. TINUVIN 622 (RTM)+TINUVIN 765 (RTM)+compound of the formula (B-10-a) wherein E[0239] 29 is hydrogen
  • 41. TINUVIN 622 (RTM)+TINUVIN 765 (RTM)+compound of the formula (B-1-a) wherein E[0240] 1 is hydrogen
  • 42. TINUVIN 622 (RTM)+TINUVIN 765 (RTM)+SUMISORB TM 61 (RTM) [0241]
  • 43. TINUVIN 622 (RTM)+TINUVIN 765 (RTM)+SANDUVOR 3050 (RTM) [0242]
  • 44. TINUVIN 622 (RTM)+TINUVIN 765 (RTM)+SANDUVOR PR-31 (RTM) [0243]
  • 45. TINUVIN 622 (RTM)+TINUVIN 765 (RTM)+UVASIL 299 LM (RTM) [0244]
  • 46. TINUVIN 622 (RTM)+TINUVIN 765 (RTM)+UVASIL 2000 LM (RTM) [0245]
  • 47. TINUVIN 622 (RTM)+TINUVIN 765 (RTM)+compound of the formula (B-6-a) wherein E[0246] 18 is hydrogen
  • 48. TINUVIN 622 (RTM)+TINUVIN 765 (RTM)+compound of the formula (B-6-a) wherein E[0247] 18 is methyl
  • 49. TINUVIN 622 (RTM)+TINUVIN 765 (RTM)+compound of the formula (B-7) with E[0248] 19, E20 and E21 being a group of the formula (b-III) wherein E22 is hydrogen.
  • 50. TINUVIN 622 (RTM)+TINUVIN 144 (RTM)+TINUVIN 123 (RTM) [0249]
  • 51. TINUVIN 622 (RTM)+TINUVIN 144 (RTM)+compound of the formula (B-3-a) wherein E[0250] 12 is hydrogen
  • 52. TINUVIN 622 (RTM)+TINUVIN 144 (RTM)+HOSTAVIN N 24 (RTM) [0251]
  • 53. TINUVIN 622 (RTM)+TINUVIN 144 (RTM)+DIACETAM 5 (RTM) [0252]
  • 54. TINUVIN 622 (RTM)+TINUVIN 144 (RTM)+ADK STAB LA 52 (RTM) [0253]
  • 55. TINUVIN 622 (RTM)+TINUVIN 144 (RTM)+ADK STAB LA 57 (RTM) [0254]
  • 56. TINUVIN 622 (RTM)+TINUVIN 144 (RTM)+ADK STAB LA 62 (RTM) [0255]
  • 57. TINUVIN 622 (RTM)+TINUVIN 144 (RTM)+ADK STAB LA 67 (RTM) [0256]
  • 58. TINUVIN 622 (RTM)+TINUVIN 144 (RTM)+GOODRITE UV 3034 (RTM) [0257]
  • 59. TINUVIN 622 (RTM)+TINUVIN 144 (RTM)+GOODRITE UV 3150 (RTM) [0258]
  • 60. TINUVIN 622 (RTM)+TINUVIN 144 (RTM)+GOODRITE UV 3159 (RTM) [0259]
  • 61. TINUVIN 622 (RTM)+TINUVIN 144 (RTM)+compound of the formula (B-9-a) wherein E[0260] 25 is hydrogen
  • 62. TINUVIN 622 (RTM)+TINUVIN 144 (RTM)+UVINUL 4049 (RTM) [0261]
  • 63. TINUVIN 622 (RTM)+TINUVIN 144 (RTM)+compound of the formula (B-10-a) wherein E[0262] 29 is hydrogen
  • 64. TINUVIN 622 (RTM)+TINUVIN 144 (RTM)+compound of the formula (B-1-a) wherein E[0263] 1 is hydrogen
  • 65. TINUVIN 622 (RTM)+TINUVIN 144 (RTM)+SUMISORB TM 61 (RTM) [0264]
  • 66. TINUVIN 622 (RTM)+TINUVIN 144 (RTM)+SANDUVOR 3050 (RTM) [0265]
  • 67. TINUVIN 622 (RTM)+TINUVIN 144 (RTM)+SANDUVOR PR-31 (RTM) [0266]
  • 68. TINUVIN 622 (RTM)+TINUVIN 144 (RTM)+UVASIL 299 LM (RTM) [0267]
  • 69. TINUVIN 622 (RTM)+TINUVIN 144 (RTM)+UVASIL 2000 LM (RTM) [0268]
  • 70. TINUVIN 622 (RTM)+TINUVIN 144 (RTM)+compound of the formula (B-6-a) wherein E[0269] 18 is hydrogen
  • 71. TINUVIN 622 (RTM)+TINUVIN 144 (RTM)+compound of the formula (B-6-a) wherein E[0270] 18 is methyl
  • 72. TINUVIN 622 (RTM)+TINUVIN 144 (RTM)+compound of the formula (B-7) with E[0271] 19, E20 and E21 being a group of the formula (b-III) wherein E22 is hydrogen.
  • 73. TINUVIN 622 (RTM)+TINUVIN 123 (RTM)+compound of the formula (B-3-a) wherein E[0272] 12 is hydrogen
  • 74. TINUVIN 622 (RTM)+TINUVIN 123 (RTM)+HOSTAVIN N 24 (RTM) [0273]
  • 75. TINUVIN 622 (RTM)+TINUVIN 123 (RTM)+DIACETAM 5 (RTM) [0274]
  • 76. TINUVIN 622 (RTM)+TINUVIN 123 (RTM)+ADK STAB LA 52 (RTM) [0275]
  • 77. TINUVIN 622 (RTM)+TINUVIN 123 (RTM)+ADK STAB LA 57 (RTM) [0276]
  • 78. TINUVIN 622 (RTM)+TINUVIN 123 (RTM)+ADK STAB LA 62 (RTM) [0277]
  • 79. TINUVIN 622 (RTM)+TINUVIN 123 (RTM)+ADK STAB LA 67 (RTM) [0278]
  • 80. TINUVIN 622 (RTM)+TINUVIN 123 (RTM)+GOODRITE UV 3034 (RTM) [0279]
  • 81. TINUVIN 622 (RTM)+TINUVIN 123 (RTM)+GOODRITE UV 3150 (RTM) [0280]
  • 82. TINUVIN 622 (RTM)+TINUVIN 123 (RTM)+GOODRITE UV 3159 (RTM) [0281]
  • 83. TINUVIN 622 (RTM)+TINUVIN 123 (RTM)+compound of the formula (B-9-a) wherein E[0282] 25 is hydrogen
  • 84. TINUVIN 622 (RTM)+TINUVIN 123 (RTM)+UVINUL 4049 (RTM) [0283]
  • 85. TINUVIN 622 (RTM)+TINUVIN 123 (RTM)+compound of the formula (B-10-a) wherein E[0284] 29 is hydrogen
  • 86. TINUVIN 622 (RTM)+TINUVIN 123 (RTM)+compound of the formula (B-1-a) wherein E[0285] 1 is hydrogen
  • 87. TINUVIN 622 (RTM)+TINUVIN 123 (RTM)+SUMISORB TM 61 (RTM) [0286]
  • 88. TINUVIN 622 (RTM)+TINUVIN 123 (RTM)+SANDUVOR 3050 (RTM) [0287]
  • 89. TINUVIN 622 (RTM)+TINUVIN 123 (RTM)+SANDUVOR PR-31 (RTM) [0288]
  • 90. TINUVIN 622 (RTM)+TINUVIN 123 (RTM)+UVASIL 299 LM (RTM) [0289]
  • 91. TINUVIN 622 (RTM)+TINUVIN 123 (RTM)+UVASIL 2000 LM (RTM) [0290]
  • 92. TINUVIN 622 (RTM)+TINUVIN 123 (RTM)+compound of the formula (B-6-a) wherein E[0291] 18 is hydrogen
  • 93. TINUVIN 622 (RTM)+TINUVIN 123 (RTM)+compound of the formula (B-6-a) wherein E[0292] 18 is methyl
  • 94. TINUVIN 622 (RTM)+TINUVIN 123 (RTM)+compound of the formula (B-7) with E[0293] 19, E20 and E21 being a group of the formula (b-III) wherein E22 is hydrogen.
  • 95. TINUVIN 622 (RTM)+compound of the formula (B-3-a) wherein E[0294] 12 is hydrogen+HOSTAVIN N 24 (RTM)
  • 96. TINUVIN 622 (RTM)+compound of the formula (B-3-a) wherein E[0295] 12 is hydrogen+DIACETAM 5 (RTM)
  • 97. TINUVIN 622 (RTM)+compound of the formula (B-3-a) wherein E[0296] 12 is hydrogen+ADK STAB LA 52 (RTM)
  • 98. TINUVIN 622 (RTM)+compound of the formula (B-3-a) wherein E[0297] 12 is hydrogen+ADK STAB LA 57 (RTM)
  • 99. TINUVIN 622 (RTM)+compound of the formula (B-3-a) wherein E[0298] 12 is hydrogen+ADK STAB LA 62 (RTM)
  • 100. TINUVIN 622 (RTM)+compound of the formula (B-3-a) wherein E[0299] 12 is hydrogen+ADK STAB LA 67 (RTM)
  • 101. TINUVIN 622 (RTM)+compound of the formula (B-3-a) wherein E[0300] 12 is hydrogen+GOODRITE UV 3034 (RTM)
  • 102. TINUVIN 622 (RTM)+compound of the formula (B-3-a) wherein E[0301] 12 is hydrogen+GOODRITE UV 3150 (RTM)
  • 103. TINUVIN 622 (RTM)+compound of the formula (B-3-a) wherein E[0302] 12 is hydrogen+GOODRITE UV 3159 (RTM)
  • 104. TINUVIN 622 (RTM)+compound of the formula (B-3-a) wherein E[0303] 12 is hydrogen+compound of the formula (B-9-a) wherein E25 is hydrogen
  • 105. TINUVIN 622 (RTM)+compound of the formula (B-3-a) wherein E[0304] 12 is hydrogen+UVINUL 4049 (RTM)
  • 106. TINUVIN 622 (RTM)+compound of the formula (B-3-a) wherein E[0305] 12 is hydrogen+compound of the formula (B-10-a) wherein E29 is hydrogen
  • 107. TINUVIN 622 (RTM)+compound of the formula (B-3-a) wherein E[0306] 12 is hydrogen+compound of the formula (B-1-a) wherein E1 is hydrogen
  • 108. TINUVIN 622 (RTM)+compound of the formula (B-3-a) wherein E[0307] 12 is hydrogen+SUMISORB TM 61 (RTM)
  • 109. TINUVIN 622 (RTM)+compound of the formula (B-3-a) wherein E[0308] 12 is hydrogen+SANDUVOR 3050 (RTM)
  • 110. TINUVIN 622 (RTM)+compound of the formula (B-3-a) wherein E[0309] 12 is hydrogen+SANDUVOR PR-31 (RTM)
  • 111. TINUVIN 622 (RTM)+compound of the formula (B-3-a) wherein E[0310] 12 is hydrogen+UVASIL 299 LM (RTM)
  • 112. TINUVIN 622 (RTM)+compound of the formula (B-3-a) wherein E[0311] 12 is hydrogen+UVASIL 2000 LM (RTM)
  • 113. TINUVIN 622 (RTM)+compound of the formula (B-3-a) wherein E[0312] 12 is hydrogen+compound of the formula (B-6-a) wherein E18 is hydrogen
  • 114. TINUVIN 622 (RTM)+compound of the formula (B-3-a) wherein E[0313] 12 is hydrogen+compound of the formula (B-6-a) wherein E18 is methyl
  • 115. TINUVIN 622 (RTM)+compound of the formula (B-3-a) wherein E[0314] 12 is hydrogen+compound of the formula (B-7) with E19, E20 and E21 being a group of the formula (b-III) wherein E22 is hydrogen.
  • 116. TINUVIN 622 (RTM)+HOSTAVIN N 24 (RTM)+DIACETAM 5 (RTM) [0315]
  • 117. TINUVIN 622 (RTM)+HOSTAVIN N 24 (RTM)+ADK STAB LA 52 (RTM) [0316]
  • 118. TINUVIN 622 (RTM)+HOSTAVIN N 24 (RTM)+ADK STAB LA 57 (RTM) [0317]
  • 119. TINUVIN 622 (RTM)+HOSTAVIN N 24 (RTM)+ADK STAB LA 62 (RTM) [0318]
  • 120. TINUVIN 622 (RTM)+HOSTAVIN N 24 (RTM)+ADK STAB LA 67 (RTM) [0319]
  • 121. TINUVIN 622 (RTM)+HOSTAVIN N 24 (RTM)+GOODRITE UV 3034 (RTM) [0320]
  • 122. TINUVIN 622 (RTM)+HOSTAVIN N 24 (RTM)+GOODRITE UV 3150 (RTM) [0321]
  • 123. TINUVIN 622 (RTM)+HOSTAVIN N 24 (RTM)+GOODRITE UV 3159 (RTM) [0322]
  • 124. TINUVIN 622 (RTM)+HOSTAVIN N 24 (RTM)+compound of the formula (B-9-a) wherein E[0323] 25 is hydrogen
  • 125. TINUVIN 622 (RTM)+HOSTAVIN N 24 (RTM)+UVINUL 4049 (RTM) [0324]
  • 126. TINUVIN 622 (RTM)+HOSTAVIN N 24 (RTM)+compound of the formula (B-10-a) wherein E[0325] 29 is hydrogen
  • 127. TINUVIN 622 (RTM)+HOSTAVIN N 24 (RTM)+compound of the formula (B-1-a) wherein E[0326] 1 is hydrogen
  • 128. TINUVIN 622 (RTM)+HOSTAVIN N 24 (RTM)+SUMISORB TM 61 (RTM) [0327]
  • 129. TINUVIN 622 (RTM)+HOSTAVIN N 24 (RTM)+SANDUVOR 3050 (RTM) [0328]
  • 130. TINUVIN 622 (RTM)+HOSTAVIN N 24 (RTM)+SANDUVOR PR-31 (RTM) [0329]
  • 131. TINUVIN 622 (RTM)+HOSTAVIN N 24 (RTM)+UVASIL 299 LM (RTM) [0330]
  • 132. TINUVIN 622 (RTM)+HOSTAVIN N 24 (RTM)+UVASIL 2000 LM (RTM) [0331]
  • 133. TINUVIN 622 (RTM)+HOSTAVIN N 24 (RTM)+compound of the formula (B-6-a) wherein E[0332] 18 is hydrogen
  • 134. TINUVIN 622 (RTM)+HOSTAVIN N 24 (RTM)+compound of the formula (B-6-a) wherein E[0333] 18 is methyl
  • 135. TINUVIN 622 (RTM)+HOSTAVIN N 24 (RTM)+compound of the formula (B-7) with E[0334] 19, E20 and E21 being a group of the formula (b-III) wherein E22 is hydrogen.
  • 136. TINUVIN 622 (RTM)+DIACETAM 5 (RTM)+ADK STAB LA 52 (RTM) [0335]
  • 137. TINUVIN 622 (RTM)+DIACETAM 5 (RTM)+ADK STAB LA 57 (RTM) [0336]
  • 138. TINUVIN 622 (RTM)+DIACETAM 5 (RTM)+ADK STAB LA 62 (RTM) [0337]
  • 139. TINUVIN 622 (RTM)+DIACETAM 5 (RTM)+ADK STAB LA 67 (RTM) [0338]
  • 140. TINUVIN 622 (RTM)+DIACETAM 5 (RTM)+GOODRITE UV 3034 (RTM) [0339]
  • 141. TINUVIN 622 (RTM)+DIACETAM 5 (RTM)+GOODRITE UV 3150 (RTM) [0340]
  • 142. TINUVIN 622 (RTM)+DIACETAM 5 (RTM)+GOODRITE UV 3159 (RTM) [0341]
  • 143. TINUVIN 622 (RTM)+DIACETAM 5 (RTM)+compound of the formula (B-9-a) wherein E[0342] 25 is hydrogen
  • 144. TINUVIN 622 (RTM)+DIACETAM 5 (RTM)+UVINUL 4049 (RTM) [0343]
  • 145. TINUVIN 622 (RTM)+DIACETAM 5 (RTM)+compound of the formula (B-10-a) wherein E[0344] 29 is hydrogen
  • 146. TINUVIN 622 (RTM)+DIACETAM 5 (RTM)+compound of the formula (B-1-a) wherein E[0345] 1 is hydrogen
  • 147. TINUVIN 622 (RTM)+DIACETAM 5 (RTM)+SUMISORB TM 61 (RTM) [0346]
  • 148. TINUVIN 622 (RTM)+DIACETAM 5 (RTM)+SANDUVOR 3050 (RTM) [0347]
  • 149. TINUVIN 622 (RTM)+DIACETAM 5 (RTM)+SANDUVOR PR-31 (RTM) [0348]
  • 150. TINUVIN 622 (RTM)+DIACETAM 5 (RTM)+UVASIL 299 LM (RTM) [0349]
  • 151. TINUVIN 622 (RTM)+DIACETAM 5 (RTM)+UVASIL 2000 LM (RTM) [0350]
  • 152. TINUVIN 622 (RTM)+DIACETAM 5 (RTM)+compound of the formula (B-6-a) wherein E[0351] 18 is hydrogen
  • 153. TINUVIN 622 (RTM)+DIACETAM 5 (RTM)+compound of the formula (B-6-a) wherein E[0352] 18 is methyl
  • 154. TINUVIN 622 (RTM)+DIACETAM 5 (RTM)+compound of the formula (B-7) with E[0353] 19, E20 and E21 being a group of the formula (b-III) wherein E22 is hydrogen.
  • 155. TINUVIN 622 (RTM)+ADK STAB LA 52 (RTM)+ADK STAB LA 57 (RTM) [0354]
  • 156. TINUVIN 622 (RTM)+ADK STAB LA 52 (RTM)+ADK STAB LA 62 (RTM) [0355]
  • 157. TINUVIN 622 (RTM)+ADK STAB LA 52 (RTM)+ADK STAB LA 67 (RTM) [0356]
  • 158. TINUVIN 622 (RTM)+ADK STAB LA 52 (RTM)+GOODRITE UV 3034 (RTM) [0357]
  • 159. TINUVIN 622 (RTM)+ADK STAB LA 52 (RTM)+GOODRITE UV 3150 (RTM) [0358]
  • 160. TINUVIN 622 (RTM)+ADK STAB LA 52 (RTM)+GOODRITE UV 3159 (RTM) [0359]
  • 161. TINUVIN 622 (RTM)+ADK STAB LA 52 (RTM)+compound of the formula (B-9-a) wherein E[0360] 25 is hydrogen
  • 162. TINUVIN 622 (RTM)+ADK STAB LA 52 (RTM)+UVINUL 4049 (RTM) [0361]
  • 163. TINUVIN 622 (RTM)+ADK STAB LA 52 (RTM)+compound of the formula (B-10-a) wherein E[0362] 29 is hydrogen
  • 164. TINUVIN 622 (RTM)+ADK STAB LA 52 (RTM)+compound of the formula (B-1-a) wherein E[0363] 1 is hydrogen
  • 165. TINUVIN 622 (RTM)+ADK STAB LA 52 (RTM)+SUMISORB TM 61 (RTM) [0364]
  • 166. TINUVIN 622 (RTM)+ADK STAB LA 52 (RTM)+SANDUVOR 3050 (RTM) [0365]
  • 167. TINUVIN 622 (RTM)+ADK STAB LA 52 (RTM)+SANDUVOR PR-31 (RTM) [0366]
  • 168. TINUVIN 622 (RTM)+ADK STAB LA 52 (RTM)+UVASIL 299 LM (RTM) [0367]
  • 169. TINUVIN 622 (RTM)+ADK STAB LA 52 (RTM)+UVASIL 2000 LM (RTM) [0368]
  • 170. TINUVIN 622 (RTM)+ADK STAB LA 52 (RTM)+compound of the formula (B-6-a) wherein E[0369] 18 is hydrogen
  • 171. TINUVIN 622 (RTM)+ADK STAB LA 52 (RTM)+compound of the formula (B-6-a) wherein E[0370] 18 is methyl
  • 172. TINUVIN 622 (RTM)+ADK STAB LA 52 (RTM)+compound of the formula (B-7) with E[0371] 19, E20 and E21 being a group of the formula (b-III) wherein E22 is hydrogen.
  • 173. TINUVIN 622 (RTM)+ADK STAB LA 57 (RTM)+ADK STAB LA 62 (RTM) [0372]
  • 174. TINUVIN 622 (RTM)+ADK STAB LA 57 (RTM)+ADK STAB LA 67 (RTM) [0373]
  • 175. TINUVIN 622 (RTM)+ADK STAB LA 57 (RTM)+GOODRITE UV 3034 (RTM) [0374]
  • 176. TINUVIN 622 (RTM)+ADK STAB LA 57 (RTM)+GOODRITE UV 3150 (RTM) [0375]
  • 177. TINUVIN 622 (RTM)+ADK STAB LA 57 (RTM)+GOODRITE UV 3159 (RTM) [0376]
  • 178. TINUVIN 622 (RTM)+ADK STAB LA 57 (RTM)+compound of the formula (B-9-a) wherein E[0377] 25 is hydrogen
  • 179. TINUVIN 622 (RTM)+ADK STAB LA 57 (RTM)+UVINUL 4049 (RTM) [0378]
  • 180. TINUVIN 622 (RTM)+ADK STAB LA 57 (RTM)+compound of the formula (B-10-a) wherein E[0379] 29 is hydrogen
  • 181. TINUVIN 622 (RTM)+ADK STAB LA 57 (RTM)+compound of the formula (B-1-a) wherein E[0380] 1 is hydrogen
  • 182. TINUVIN 622 (RTM)+ADK STAB LA 57 (RTM)+SUMISORB TM 61 (RTM) [0381]
  • 183. TINUVIN 622 (RTM)+ADK STAB LA 57 (RTM)+SANDUVOR 3050 (RTM) [0382]
  • 184. TINUVIN 622 (RTM)+ADK STAB LA 57 (RTM)+SANDUVOR PR-31 (RTM) [0383]
  • 185. TINUVIN 622 (RTM)+ADK STAB LA 57 (RTM)+UVASIL 299 LM (RTM) [0384]
  • 186. TINUVIN 622 (RTM)+ADK STAB LA 57 (RTM)+UVASIL 2000 LM (RTM) [0385]
  • 187. TINUVIN 622 (RTM)+ADK STAB LA 57 (RTM)+compound of the formula (B-6-a) wherein E[0386] 18 is hydrogen
  • 188. TINUVIN 622 (RTM)+ADK STAB LA 57 (RTM)+compound of the formula (B-6-a) wherein E[0387] 18 is methyl
  • 189. TINUVIN 622 (RTM)+ADK STAB LA 57 (RTM)+compound of the formula (B-7) with E[0388] 19, E20 and E21 being a group of the formula (b-III) wherein E22 is hydrogen.
  • 190. TINUVIN 622 (RTM)+ADK STAB LA 62 (RTM)+ADK STAB LA 67 (RTM) [0389]
  • 191. TINUVIN 622 (RTM)+ADK STAB LA 62 (RTM)+GOODRITE UV 3034 (RTM) [0390]
  • 192. TINUVIN 622 (RTM)+ADK STAB LA 62 (RTM)+GOODRITE UV 3150 (RTM) [0391]
  • 193. TINUVIN 622 (RTM)+ADK STAB LA 62 (RTM)+GOODRITE UV 3159 (RTM) [0392]
  • 194. TINUVIN 622 (RTM)+ADK STAB LA 62 (RTM)+compound of the formula (B-9-a) wherein E[0393] 25 is hydrogen
  • 195. TINUVIN 622 (RTM)+ADK STAB LA 62 (RTM)+UVINUL 4049 (RTM) [0394]
  • 196. TINUVIN 622 (RTM)+ADK STAB LA 62 (RTM)+compound of the formula (B-10-a) wherein E[0395] 29 is hydrogen
  • 197. TINUVIN 622 (RTM)+ADK STAB LA 62 (RTM)+compound of the formula (B-1-a) wherein E[0396] 1 is hydrogen
  • 198. TINUVIN 622 (RTM)+ADK STAB LA 62 (RTM)+SUMISORB TM 61 (RTM) [0397]
  • 199. TINUVIN 622 (RTM)+ADK STAB LA 62 (RTM)+SANDUVOR 3050 (RTM) [0398]
  • 200. TINUVIN 622 (RTM)+ADK STAB LA 62 (RTM)+SANDUVOR PR-31 (RTM) [0399]
  • 201. TINUVIN 622 (RTM)+ADK STAB LA 62 (RTM)+UVASIL 299 LM (RTM) [0400]
  • 202. TINUVIN 622 (RTM)+ADK STAB LA 62 (RTM)+UVASIL 2000 LM (RTM) [0401]
  • 203. TINUVIN 622 (RTM)+ADK STAB LA 62 (RTM)+compound of the formula (B-6-a) wherein E[0402] 18 is hydrogen
  • 204. TINUVIN 622 (RTM)+ADK STAB LA 62 (RTM)+compound of the formula (B-6-a) wherein E[0403] 18 is methyl
  • 205. TINUVIN 622 (RTM)+ADK STAB LA 62 (RTM)+compound of the formula (B-7) with E[0404] 19, E20 and E21 being a group of the formula (b-III) wherein E22 is hydrogen.
  • 206. TINUVIN 622 (RTM)+ADK STAB LA 67 (RTM)+GOODRITE UV 3034 (RTM) [0405]
  • 207. TINUVIN 622 (RTM)+ADK STAB LA 67 (RTM)+GOODRITE UV 3150 (RTM) [0406]
  • 208. TINUVIN 622 (RTM)+ADK STAB LA 67 (RTM)+GOODRITE UV 3159 (RTM) [0407]
  • 209. TINUVIN 622 (RTM)+ADK STAB LA 67 (RTM)+compound of the formula (B-9-a) wherein E[0408] 25 is hydrogen
  • 210. TINUVIN 622 (RTM)+ADK STAB LA 67 (RTM)+UVINUL 4049 (RTM) [0409]
  • 211. TINUVIN 622 (RTM)+ADK STAB LA 67 (RTM)+compound of the formula (B-10-a) wherein E[0410] 29 is hydrogen
  • 212. TINUVIN 622 (RTM)+ADK STAB LA 67 (RTM)+compound of the formula (B-1-a) wherein E[0411] 1 is hydrogen
  • 213. TINUVIN 622 (RTM)+ADK STAB LA 67 (RTM)+SUMISORB TM 61 (RTM) [0412]
  • 214. TINUVIN 622 (RTM)+ADK STAB LA 67 (RTM)+SANDUVOR 3050 (RTM) [0413]
  • 215. TINUVIN 622 (RTM)+ADK STAB LA 67 (RTM)+SANDUVOR PR-31 (RTM) [0414]
  • 216. TINUVIN 622 (RTM)+ADK STAB LA 67 (RTM)+UVASIL 299 LM (RTM) [0415]
  • 217. TINUVIN 622 (RTM)+ADK STAB LA 67 (RTM)+UVASIL 2000 LM (RTM) [0416]
  • 218. TINUVIN 622 (RTM)+ADK STAB LA 67 (RTM)+compound of the formula (B-6-a) wherein E[0417] 18 is hydrogen
  • 219. TINUVIN 622 (RTM)+ADK STAB LA 67 (RTM)+compound of the formula (B-6-a) wherein E[0418] 18 is methyl
  • 220. TINUVIN 622 (RTM)+ADK STAB LA 67 (RTM)+compound of the formula (B-7) with E[0419] 19, E20 and E21 being a group of the formula (b-III) wherein E22 is hydrogen.
  • 221. TINUVIN 622 (RTM)+GOODRITE UV 3034 (RTM)+GOODRITE UV 3150 (RTM) [0420]
  • 222. TINUVIN 622 (RTM)+GOODRITE UV 3034 (RTM)+GOODRITE UV 3159 (RTM) [0421]
  • 223. TINUVIN 622 (RTM)+GOODRITE UV 3034 (RTM)+compound of the formula (B-9-a) wherein E[0422] 25 is hydrogen
  • 224. TINUVIN 622 (RTM)+GOODRITE UV 3034 (RTM)+UVINUL 4049 (RTM) [0423]
  • 225. TINUVIN 622 (RTM)+GOODRITE UV 3034 (RTM)+compound of the formula (B-10-a) wherein E[0424] 29 is hydrogen
  • 226. TINUVIN 622 (RTM)+GOODRITE UV 3034 (RTM)+compound of the formula (B-1-a) wherein E[0425] 1 is hydrogen
  • 227. TINUVIN 622 (RTM)+GOODRITE UV 3034 (RTM)+SUMISORB TM 61 (RTM) [0426]
  • 228. TINUVIN 622 (RTM)+GOODRITE UV 3034 (RTM)+SANDUVOR 3050 (RTM) [0427]
  • 229. TINUVIN 622 (RTM)+GOODRITE UV 3034 (RTM)+SANDUVOR PR-31 (RTM) [0428]
  • 230. TINUVIN 622 (RTM)+GOODRITE UV 3034 (RTM)+UVASIL 299 LM (RTM) [0429]
  • 231. TINUVIN 622 (RTM)+GOODRITE UV 3034 (RTM)+UVASIL 2000 LM (RTM) [0430]
  • 232. TINUVIN 622 (RTM)+GOODRITE UV 3034 (RTM)+compound of the formula (B-6-a) wherein E[0431] 18 is hydrogen
  • 233. TINUVIN 622 (RTM)+GOODRITE UV 3034 (RTM)+compound of the formula (B-6-a) wherein E[0432] 18 is methyl
  • 234. TINUVIN 622 (RTM)+GOODRITE UV 3034 (RTM)+compound of the formula (B-7) with E[0433] 19, E20 and E21 being a group of the formula (b-III) wherein E22 is hydrogen.
  • 235. TINUVIN 622 (RTM)+GOODRITE UV 3150 (RTM)+GOODRITE UV 3159 (RTM) [0434]
  • 236. TINUVIN 622 (RTM)+GOODRITE UV 3150 (RTM)+compound of the formula (B-9-a) wherein E[0435] 25 is hydrogen
  • 237. TINUVIN 622 (RTM)+GOODRITE UV 3150 (RTM)+UVINUL 4049 (RTM) [0436]
  • 238. TINUVIN 622 (RTM)+GOODRITE UV 3150 (RTM)+compound of the formula (B-10-a) wherein E[0437] 29 is hydrogen
  • 239. TINUVIN 622 (RTM)+GOODRITE UV 3150 (RTM)+compound of the formula (B-1-a) wherein E[0438] 1 is hydrogen
  • 240. TINUVIN 622 (RTM)+GOODRITE UV 3150 (RTM)+SUMISORB TM 61 (RTM) [0439]
  • 241. TINUVIN 622 (RTM)+GOODRITE UV 3150 (RTM)+SANDUVOR 3050 (RTM) [0440]
  • 242. TINUVIN 622 (RTM)+GOODRITE UV 3150 (RTM)+SANDUVOR PR-31 (RTM) [0441]
  • 243. TINUVIN 622 (RTM)+GOODRITE UV 3150 (RTM)+UVASIL 299 LM (RTM) [0442]
  • 244. TINUVIN 622 (RTM)+GOODRITE UV 3150 (RTM)+UVASIL 2000 LM (RTM) [0443]
  • 245. TINUVIN 622 (RTM)+GOODRITE UV 3150 (RTM)+compound of the formula (B-6-a) wherein E[0444] 18 is hydrogen
  • 246. TINUVIN 622 (RTM)+GOODRITE UV 3150 (RTM)+compound of the formula (B-6-a) wherein E[0445] 18 is methyl
  • 247. TINUVIN 622 (RTM)+GOODRITE UV 3150 (RTM)+compound of the formula (B-7) with E[0446] 19, E20 and E21 being a group of the formula (b-III) wherein E22 is hydrogen.
  • 248. TINUVIN 622 (RTM)+GOODRITE UV 3159 (RTM)+compound of the formula (B-9-a) wherein E[0447] 25 is hydrogen
  • 249. TINUVIN 622 (RTM)+GOODRITE UV 3159 (RTM)+UVINUL 4049 (RTM) [0448]
  • 250. TINUVIN 622 (RTM)+GOODRITE UV 3159 (RTM)+compound of the formula (B-10-a) wherein E[0449] 29 is hydrogen
  • 251. TINUVIN 622 (RTM)+GOODRITE UV 3159 (RTM)+compound of the formula (B-1-a) wherein E[0450] 1 is hydrogen
  • 252. TINUVIN 622 (RTM)+GOODRITE UV 3159 (RTM)+SUMISORB TM 61 (RTM) [0451]
  • 253. TINUVIN 622 (RTM)+GOODRITE UV 3159 (RTM)+SANDUVOR 3050 (RTM) [0452]
  • 254. TINUVIN 622 (RTM)+GOODRITE UV 3159 (RTM)+SANDUVOR PR-31 (RTM) [0453]
  • 255. TINUVIN 622 (RTM)+GOODRITE UV 3159 (RTM)+UVASIL 299 LM (RTM) [0454]
  • 256. TINUVIN 622 (RTM)+GOODRITE UV 3159 (RTM)+UVASIL 2000 LM (RTM) [0455]
  • 257. TINUVIN 622 (RTM)+GOODRITE UV 3159 (RTM)+compound of the formula (B-6-a) wherein E[0456] 18 is hydrogen
  • 258. TINUVIN 622 (RTM)+GOODRITE UV 3159 (RTM)+compound of the formula (B-6-a) wherein E[0457] 18 is methyl
  • 259. TINUVIN 622 (RTM)+GOODRITE UV 3159 (RTM)+compound of the formula (B-7) with E[0458] 19, E20 and E21 being a group of the formula (b-III) wherein E22 is hydrogen.
  • 260. TINUVIN 622 (RTM)+compound of the formula (B-9-a) wherein E[0459] 25 is hydrogen+UVINUL 4049 (RTM)
  • 261. TINUVIN 622 (RTM)+compound of the formula (B-9-a) wherein E[0460] 25 is hydrogen+compound of the formula (B-10-a) wherein E29 is hydrogen
  • 262. TINUVIN 622 (RTM)+compound of the formula (B-9-a) wherein E[0461] 25 is hydrogen+compound of the formula (B-1-a) wherein E1 is hydrogen
  • 263. TINUVIN 622 (RTM)+compound of the formula (B-9-a) wherein E[0462] 25 is hydrogen+SUMISORB TM 61 (RTM)
  • 264. TINUVIN 622 (RTM)+compound of the formula (B-9-a) wherein E[0463] 25 is hydrogen+SANDUVOR 3050 (RTM)
  • 265. TINUVIN 622 (RTM)+compound of the formula (B-9-a) wherein E[0464] 25 is hydrogen+SANDUVOR PR-31 (RTM)
  • 266. TINUVIN 622 (RTM)+compound of the formula (B-9-a) wherein E[0465] 25 is hydrogen+UVASIL 299 LM (RTM)
  • 267. TINUVIN 622 (RTM)+compound of the formula (B-9-a) wherein E[0466] 25 is hydrogen+UVASIL 2000 LM (RTM)
  • 268. TINUVIN 622 (RTM)+compound of the formula (B-9-a) wherein E[0467] 25 is hydrogen+compound of the formula (B-6-a) wherein E18 is hydrogen
  • 269. TINUVIN 622 (RTM)+compound of the formula (B-9-a) wherein E[0468] 25 is hydrogen+compound of the formula (B-6-a) wherein E18 is methyl
  • 270. TINUVIN 622 (RTM)+compound of the formula (B-9-a) wherein E[0469] 25 is hydrogen+compound of the formula (B-7) with E19, E20 and E21 being a group of the formula (b-III) wherein E22 is hydrogen.
  • 271. TINUVIN 622 (RTM)+UVINUL 4049 (RTM)+compound of the formula (B-10-a) wherein E[0470] 29 is hydrogen
  • 272. TINUVIN 622 (RTM)+UVINUL 4049 (RTM)+compound of the formula (B-1-a) wherein E[0471] 1 is hydrogen
  • 273. TINUVIN 622 (RTM)+UVINUL 4049 (RTM)+SUMISORB TM 61 (RTM) [0472]
  • 274. TINUVIN 622 (RTM)+UVINUL 4049 (RTM)+SANIDUVOR 3050 (RTM) [0473]
  • 275. TINUVIN 622 (RTM)+UVINUL 4049 (RTM)+SANDUVOR PR-31 (RTM) [0474]
  • 276. TINUVIN 622 (RTM)+UVINUL 4049 (RTM)+UVASIL 299 LM (RTM) [0475]
  • 277. TINUVIN 622 (RTM)+UVINUL 4049 (RTM)+UVASIL 2000 LM (RTM) [0476]
  • 278. TINUVIN 622 (RTM)+UVINUL 4049 (RTM)+compound of the formula (B-6-a) wherein E[0477] 18 is hydrogen
  • 279. TINUVIN 622 (RTM)+UVINUL 4049 (RTM)+compound of the formula (B-6-a) wherein E[0478] 18 is methyl
  • 280. TINUVIN 622 (RTM)+UVINUL 4049 (RTM)+compound of the formula (B-7) with E[0479] 19, E20 and E21 being a group of the formula (b-III) wherein E22 is hydrogen.
  • 281. TINUVIN 622 (RTM)+compound of the formula (B-10-a) wherein E[0480] 29 is hydrogen+compound of the formula (B-1-a) wherein E1 is hydrogen
  • 282. TINUVIN 622 (RTM)+compound of the formula (B-10-a) wherein E[0481] 29 is hydrogen+SUMISORB TM 61 (RTM)
  • 283. TINUVIN 622 (RTM)+compound of the formula (B-10-a) wherein E[0482] 29 is hydrogen+SANDUVOR 3050 (RTM)
  • 284. TINUVIN 622 (RTM)+compound of the formula (B-10-a) wherein E[0483] 29 is hydrogen+SANDUVOR PR-31 (RTM)
  • 285. TINUVIN 622 (RTM)+compound of the formula (B-10-a) wherein E[0484] 29 is hydrogen+UVASIL 299 LM (RTM)
  • 286. TINUVIN 622 (RTM)+compound of the formula (B-10-a) wherein E[0485] 29 is hydrogen+UVASIL 2000 LM (RTM)
  • 287. TINUVIN 622 (RTM)+compound of the formula (B-10-a) wherein E[0486] 29 is hydrogen+compound of the formula (B-6-a) wherein E18 is hydrogen
  • 288. TINUVIN 622 (RTM)+compound of the formula (B-10-a) wherein E[0487] 29 is hydrogen+compound of the formula (B-6-a) wherein E18 is methyl
  • 289. TINUVIN 622 (RTM)+compound of the formula (B-10-a) wherein E[0488] 29 is hydrogen+compound of the formula (B-7) with E19, E20 and E21 being a group of the formula (b-III) wherein E22 is hydrogen.
  • 290. TINUVIN 622 (RTM)+compound of the formula (B-1-a) wherein E[0489] 1 is hydrogen+SUMISORB TM 61 (RTM)
  • 291. TINUVIN 622 (RTM)+compound of the formula (B-1-a) wherein E[0490] 1 is hydrogen+SANBUVOR 3050 (RTM)
  • 292. TINUVIN 622 (RTM)+compound of the formula (B-1-a) wherein E[0491] 1 is hydrogen+SANDUVOR PR-31 (RTM)
  • 293. TINUVIN 622 (RTM)+compound of the formula (B-1-a) wherein E[0492] 1 is hydrogen+UVASIL 299 LM (RTM)
  • 294. TINUVIN 622 (RTM)+compound of the formula (B-1-a) wherein E[0493] 1 is hydrogen+UVASIL 2000 LM (RTM)
  • 295. TINUVIN 622 (RTM)+compound of the formula (B-1-a) wherein E[0494] 1 is hydrogen+compound of the formula (B-6-a) wherein E18 is hydrogen
  • 296. TINUVIN 622 (RTM)+compound of the formula (B-1-a) wherein E[0495] 1 is hydrogen+compound of the formula (B-6-a) wherein E18 is methyl
  • 297. TINUVIN 622 (RTM)+compound of the formula (B-1-a) wherein E[0496] 1 is hydrogen+compound of the formula (B-7) with E19, E20 and E21 being a group of the formula (b-III) wherein E22 is hydrogen.
  • 298. TINUVIN 622 (RTM)+SUMISORB TM 61 (RTM)+SANDUVOR 3050 (RTM) [0497]
  • 299. TINUVIN 622 (RTM)+SUMISORB TM 61 (RTM)+SANDUVOR PR-31 (RTM) [0498]
  • 300. TINUVIN 622 (RTM)+SUMISORB TM 61 (RTM)+UVASIL 299 LM (RTM) [0499]
  • 301. TINUVIN 622 (RTM)+SUMISORB TM 61 (RTM)+UVASIL 2000 LM (RTM) [0500]
  • 302. TINUVIN 622 (RTM)+SUMISORB TM 61 (RTM)+compound of the formula (B-6-a) wherein E[0501] 18 is hydrogen
  • 303. TINUVIN 622 (RTM)+SUMISORB TM 61 (RTM)+compound of the formula (B-6-a) wherein E[0502] 18 is methyl
  • 304. TINUVIN 622 (RTM)+SUMISORB TM 61 (RTM)+compound of the formula (B-7) with E[0503] 19, E20 and E21 being a group of the formula (b-III) wherein E22 is hydrogen.
  • 305. TINUVIN 622 (RTM)+SANDUVOR 3050 (RTM)+SANDUVOR PR-31 (RTM) [0504]
  • 306. TINUVIN 622 (RTM)+SANDUVOR 3050 (RTM)+UVASIL 299 LM (RTM) [0505]
  • 307. TINUVIN 622 (RTM)+SANDUVOR 3050 (RTM)+UVASIL 2000 LM (RTM) [0506]
  • 308. TINUVIN 622 (RTM)+SANDUVOR 3050 (RTM)+compound of the formula (B-6-a) wherein E[0507] 18 is hydrogen
  • 309. TINUVIN 622 (RTM)+SANDUVOR 3050 (RTM)+compound of the formula (B-6-a) wherein E[0508] 18 is methyl
  • 310. TINUVIN 622 (RTM)+SANDUVOR 3050 (RTM)+compound of the formula (B-7) with E[0509] 19, E20 and E21 being a group of the formula (b-III) wherein E22 is hydrogen.
  • 311. TINUVIN 622 (RTM)+SANDUVOR PR-31 (RTM)+UVASIL 299 LM (RTM) [0510]
  • 312. TINUVIN 622 (RTM)+SANDUVOR PR-31 (RTM)+UVASIL 2000 LM (RTM) [0511]
  • 313. TINUVIN 622 (RTM)+SANDUVOR PR-31 (RTM)+compound of the formula (B-6-a) wherein E[0512] 18 is hydrogen
  • 314. TINUVIN 622 (RTM)+SANDUVOR PR-31 (RTM)+compound of the formula (B-6-a) wherein E[0513] 18 is methyl
  • 315. TINUVIN 622 (RTM)+SANDUVOR PR-31 (RTM)+compound of the formula (B-7) with E[0514] 19, E20 and E21 being a group of the formula (b-III) wherein E22 is hydrogen.
  • 316. TINUVIN 622 (RTM)+UVASIL 299 LM (RTM)+compound of the formula (B-6-a) wherein E[0515] 18 is hydrogen
  • 317. TINUVIN 622 (RTM)+UVASIL 299 LM (RTM)+compound of the formula (B-6-a) wherein E[0516] 18 is methyl
  • 318. TINUVIN 622 (RTM)+UVASIL 299 LM (RTM)+compound of the formula (B-7) with E[0517] 19, E20 and E21 being a group of the formula (b-III) wherein E22 is hydrogen.
  • 319. TINUVIN 622 (RTM)+UVASIL 2600 LM (RTM)+compound of the formula (B-6-a) wherein E[0518] 18 is hydrogen
  • 320. TINUVIN 622 (RTM)+UVASIL 2000 LM (RTM)+compound of the formula (B-6-a) wherein E[0519] 18 is methyl
  • 321. TINUVIN 622 (RTM)+UVASIL 2000 LM (RTM)+compound of the formula (B-7) with E[0520] 19, E20 and E21 being a group of the formula (b-III) wherein E22 is hydrogen.
  • 322. TINUVIN 622 (RTM)+compound of the formula (B-6-a) wherein E[0521] 18 is hydrogen+compound of the formula (B-6-a) wherein E18 is methyl
  • 323. TINUVIN 622 (RTM)+compound of the formula (B-6-a) wherein E[0522] 18 is hydrogen+compound of the formula (B-7) with E19, E20 and E21 being a group of the formula (b-III) wherein E22 is hydrogen.
  • 324. TINUVIN 622 (RTM)+compound of the formula (B-6-a) wherein E[0523] 18 is methyl+compound of the formula (B-7) with E19, E20 and E21 being a group of the formula (b-III) wherein E22 is hydrogen.
  • Further examples of stabilizer mixtures are those wherein in the above combinations 1 to 324 the commercial product TINUVIN 622 (RTM) is replaced by a compound of the formula (A-2-a) and/or (A-2-b) [0524]
    Figure US20030197151A1-20031023-C00049
  • wherein n[0525] 2 and n2* are a number from 2 to 20.
  • Additional examples of stabilizer mixtures are those wherein in the above combinations 1 to 324 the commercial product TINUVIN 622 (RTM) is replaced by a compound of the formula (A-4-a) [0526]
    Figure US20030197151A1-20031023-C00050
  • wherein n[0527] 4 is a number from 2 to 20, and at least 50% of the radicals A7 are a group of the formula
    Figure US20030197151A1-20031023-C00051
  • and the remaining radicals A[0528] 7 are ethyl.
  • Combinations of particular interest are numbers 1, 4, 7, 8, 12, 13 and 15 to 24, and the corresponding combinations wherein TINUVIN 622 (RTM) is replaced by a compound of the formula (A-2-a) and/or (A-2-b). [0529]
  • Further combinations of particular interest are numbers 3, 4, 8, 17 and 31. [0530]
  • The commercial product TINUVIN 622 (RTM) corresponds to the compound of the formula (A-1-a). [0531]
  • The commercial product TINUVIN 770 (RTM) corresponds to the compound of the formula (B-1-b) wherein E[0532] 1 is hydrogen.
  • The commercial product TINUVIN 765 (RTM) corresponds to the compound of the formula (B-1-b) wherein E[0533] 1 is methyl.
  • The commercial product TINUVIN 123 (RTM) corresponds to the compound of the formula (B-1-b) wherein E[0534] 1 is octyloxy.
  • The commercial product TINUVIN 144 (RTM) corresponds to the compound of the formula (B-1-c) wherein E[0535] 1 is methyl.
  • The commercial product ADK STAB LA 57 (RTM) corresponds to the compound of the formula (B-1-d) wherein E[0536] 1 is hydrogen.
  • The commercial product ADK STAB LA 52 (RTM) corresponds to the compound of the formula (B-1-d) wherein E[0537] 1 is methyl.
  • The commercial product ADK STAB LA 67 (RTM) corresponds to the compound of the formula (B-2-a) wherein E[0538] 8 is hydrogen.
  • The commercial product ADK STAB LA 62 (RTM) corresponds to the compound of the formula (B-2-a) wherein E[0539] 1 is methyl.
  • The commercial product HOSTAVIN N 24 (RTM) corresponds to the compound of the formula (B-3-b) wherein E[0540] 12 is hydrogen.
  • The commercial product SANDUVOR 3050 (RTM) corresponds to the compound of the formula (B-3-b-1) shown below, wherein E[0541] 12 is hydrogen.
  • The commercial product DIACETAM 5 (RTM) corresponds to the compound of the formula (B-4-a) wherein E[0542] 13 is hydrogen.
  • The commercial product SUMISORB TM 61 corresponds to the compound of the formula (B-4-b) wherein E[0543] 13 is hydrogen.
  • The commercial product UVINUL 4049 (RTM) corresponds to the compound of the formula (B-5) wherein E[0544] 16 is hydrogen.
  • The commercial product SANDUVOR PR 31 (RTM) corresponds to the compound of the formula (B-8-a) wherein E[0545] 23 is methyl.
  • The commercial product GOODRITE 3034 (RTM) corresponds to the compound of the formula (B-9-b) wherein E[0546] 25 is hydrogen.
  • The commercial product GOODRITE 3150 (RTM) corresponds to the compound of the formula (B-9-c) wherein E[0547] 25 is hydrogen.
  • The commercial product GOODRITE 3159 (RTM) corresponds to the compound of the formula (B-9-c) wherein E[0548] 25 is methyl.
  • The commercial product UVASIL 299 LM (RTM) or UVASIL 2000 LM (RTM) contains as active ingredient the compound of the formula (B-11-a) wherein R[0549] 16 is hydrogen.
  • The compound of the formula (B-3-b-1) has the following structure: [0550]
    Figure US20030197151A1-20031023-C00052
  • The stabilizer mixture according to this invention is suitable for stabilizing organic materials against degradation induced by light, heat or oxidation. Examples of such organic materials are the following: [0551]
  • 1. 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). [0552]
  • 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: [0553]
  • a) radical polymerisation (normally under high pressure and at elevated temperature). [0554]
  • b) catalytic polymerisation using 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 π- or σ-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). [0555]
  • 2. Mixtures of the polymers mentioned under 1), for example mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (for example PP/HDPE, PP/LDPE) and mixtures of different types of polyethylene (for example LDPE/HDPE). [0556]
  • 3. 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 (ionomers) as well as terpolymers of ethylene with propylene and a diene such as hexadiene, dicyclopentadiene or ethylidene-norbornene; and mixtures of such copolymers with one another and with polymers mentioned in 1) above, for example polypropylene/ethylene-propylene copolymers, LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic acid copolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or random polyalkylene/carbon monoxide copolymers and mixtures thereof with other polymers, for example polyamides. [0557]
  • 4. Hydrocarbon resins (for example C[0558] 5-C9) including hydrogenated modifications thereof (e.g. tackifiers) and mixtures of polyalkylenes and starch.
  • 5. Polystyrene, poly(p-methylstyrene), poly(α-methylstyrene). [0559]
  • 6. Copolymers of styrene or α-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, styrene/ethylene/butylene/styrene or styrene/ethylene/propylene/styrene. [0560]
  • 7. Graft copolymers of styrene or α-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 acrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styrene and acrylonitrile on acrylate/butadiene copolymers, as well as mixtures thereof with the copolymers listed under 6), for example the copolymer mixtures known as ABS, MBS, ASA or AES polymers. [0561]
  • 8. Halogen-containing polymers such as polychloroprene, chlorinated rubbers, chlorinated and brominated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated or sulfo-chlorinated 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. [0562]
  • 9. Polymers derived from α,β-unsaturated acids and derivatives thereof such as polyacrylates and polymethacrylates; polymethyl methacrylates, polyacrylamides and polyacrylonitriles, impact-modified with butyl acrylate. [0563]
  • 10. Copolymers of the monomers mentioned under 9) with each other or with other unsaturated monomers, for example acrylonitrilel butadiene copolymers, acrylonitrile/alkyl acrylate copolymers, acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halide copolymers or acrylonitrile/alkyl methacrylate/butadiene terpolymers. [0564]
  • 11. 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. [0565]
  • 12. Homopolymers and copolymers of cyclic ethers such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or copolymers thereof with bisglycidyl ethers. [0566]
  • 13. Polyacetals such as polyoxymethylene and those polyoxymethylenes which contain ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS. [0567]
  • 14. Polyphenylene oxides and sulfides, and mixtures of polyphenylene oxides with styrene polymers or polyamides. [0568]
  • 15. Polyurethanes derived from hydroxyl-terminated polyethers, polyesters or polybutadienes on the one hand and aliphatic or aromatic polyisocyanates on the other, as well as precursors thereof. [0569]
  • 16. 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, 619, 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 polytetramethylene glycol; as well as polyamides or copolyamides modified with EPDM or ABS; and polyamides condensed during processing (RIM polyamide systems). [0570]
  • 17. Polyureas, polyimides, polyamide-imides, polyetherimids, polyesterimids, polyhydantoins and polybenzimidazoles. [0571]
  • 18. 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, polyalkylene naphthalate (PAN) and polyhydroxybenzoates, as well as block copolyether esters derived from hydroxyl-terminated polyethers; and also polyesters modified with polycarbonates or MBS. [0572]
  • 19. Polycarbonates and polyester carbonates. [0573]
  • 20. Polysulfones, polyether sulfones and polyether ketones. [0574]
  • 21. Crosslinked polymers derived from aldehydes on the one hand and phenols, ureas and melamines on the other hand, such as phenol/formaldehyde resins, urea/formaldehyde resins and melamine/formaldehyde resins. [0575]
  • 22. Drying and non-drying alkyd resins. [0576]
  • 23. Unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols and vinyl compounds as crosslinking agents, and also halogen-containing modifications thereof of low flammability. [0577]
  • 24. Crosslinkable acrylic resins derived from substituted acrylates, for example epoxy acrylates, urethane acrylates or polyester acrylates. [0578]
  • 25. Alkyd resins, polyester resins and acrylate resins crosslinked with melamine resins, urea resins, isocyanates, isocyanurates, polyisocyanates or epoxy resins. [0579]
  • 26. 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. [0580]
  • 27. 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. [0581]
  • 28. Blends of the aforementioned polymers (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, PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS or PBT/PET/PC. [0582]
  • 29. Naturally occurring and synthetic organic materials which are pure monomeric compounds or mixtures of such compounds, for example mineral oils, animal and vegetable fats, oil and waxes, or oils, fats and waxes based on synthetic esters (e.g. phthalates, adipates, phosphates or trimellitates) and also mixtures of synthetic esters with mineral oils in any weight ratios, typically those used as spinning compositions, as well as aqueous emulsions of such materials. [0583]
  • 30. Aqueous emulsions of natural or synthetic rubber, e.g. natural latex or latices of carboxylated styrene/butadiene copolymers. [0584]
  • This invention therefore additionally relates to a composition comprising an organic material subject to degradation induced by light, heat or oxidation and the stabilizer mixture described herein above. [0585]
  • A further embodiment of the present invention is a method for stabilizing an organic material against degradation induced by light, heat or oxidation, which comprises incorporating into the organic material the stabilizer mixture described herein above. [0586]
  • The organic material is preferably a synthetic polymer, in particular from one of the above groups. Polyolefins are preferred and polyethylene, polypropylene, a polyethylene copolymer and a polypropylene copolymer are particularly preferred. [0587]
  • The compounds of components (A) and (B) may be added to the organic material to be stabilized either individually or mixed with one another. [0588]
  • Each of the compounds of components (A) and (B) may be present in the organic material in an amount of preferably 0.005 to 5%, in particular 0.01 to 1% or 0.05 to 1%, relative to the weight of the organic material. [0589]
  • The weight ratio of the components (A):(B) is preferably 10:1 to 1:100, in particular 10:1 to 1:10 or 5:1 to 1:5. Further examples for the weight ratio are also 1:1 to 1:10, for example 1:2 to 1:5. [0590]
  • The weight ratio of the two components forming component (B) is for example 1:10 to 10:1 or 1:5 to 5:1, preferably 1:2 to 2:1, in particular 1:1. [0591]
  • The above components can be incorporated into the organic material to be stabilized by known methods, for example before or during shaping or by applying the dissolved or dispersed compounds to the organic material, if necessary with subsequent evaporation of the solvent. The components can be added to the organic material in the form of a powder, granules or a masterbatch, which contains these components in, for example, a concentration of from 2.5 to 25% by weight. [0592]
  • If desired, the compounds of components (A) and (B) can be blended with each other before incorporation in the organic material. They can be added to a polymer before or during the polymerization or before the crosslinking. [0593]
  • The materials stabilized according to this invention can be used in a wide variety of forms, for example as films, fibres, tapes, moulding compositions, profiles or as binders for paints, adhesives or putties. [0594]
  • The stabilized material may additionally also contain various conventional additives, for example: [0595]
  • 1. Antioxidants [0596]
  • 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. [0597]
  • 1.2. Alkylthiomethylphenols, for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctyl-thiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl-4-nonylphenol. [0598]
  • 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. [0599]
  • 1.4. Tocopherols, for example α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol and mixtures thereof (vitamin E). [0600]
  • 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. [0601]
  • 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′-hydroxyphenyl)butyrate], bis(3-tert-butyl-4hydroxy-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. [0602]
  • 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. [0603]
  • 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. [0604]
  • 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. [0605]
  • 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-hydroxybenzyl)isocyanurate. [0606]
  • 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. [0607]
  • 1.12. Acylaminophenols, for example 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate. [0608]
  • 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, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane. [0609]
  • 1.14. Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis-(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-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. [0610]
  • 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. [0611]
  • 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. [0612]
  • 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-hydroxyphenylpropionyl)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). [0613]
  • 1.18. Ascorbic acid (vitamin C) [0614]
  • 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′-tetramethyl-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, N,N,N′,N′-tetraphenyl-1,4-diaminobut-2-ene, N,N-bis(2,2,6,6-tetramethylpiperid-4-yl-hexamethylenediamine, bis(2,2,6,6-tetramethylpiperid-4-yl)sebacate, 2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol. [0615]
  • 2. UV Absorbers and Light Stabilisers [0616]
  • 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′-hydroxy-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′-hydroxyphenyl)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-octyloxycarbonylethyl)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; [0617]
    Figure US20030197151A1-20031023-C00053
  • where R=3′-tert-butyl-4′-hydroxy-5′-2H-benzotraizol-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. [0618]
  • 2.2. 2-Hydroxybenzophenones, for example the 4hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2′,4′-trihydroxy and 2′-hydroxy-4,4′-dimethoxy derivatives. [0619]
  • 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. [0620]
  • 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. [0621]
  • 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-lauroyl-5-hydroxypyrazole, with or without additional ligands. [0622]
  • 2.6. 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. [0623]
  • 2.7. 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-propyl-oxyphenyl)-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-tridecyloxyphenyl)-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-dimethylphenyl)-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. [0624]
  • 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-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. [0625]
  • 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, dilsodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,4-di-cumylphenyl)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. [0626]
  • The following phosphites are especially preferred: [0627]
  • Tris(2,4-di-tert-butylphenyl) phosphite (Irgafos®168, Ciba-Geigy), tris(nonylphenyl) phosphite, [0628]
    Figure US20030197151A1-20031023-C00054
    Figure US20030197151A1-20031023-C00055
  • 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. [0629]
  • 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-heptadecylnitrone, N-octadecyl-alpha-hexadecylnitrone, nitrone derived from N,N-dialkylhydroxylamine derived from hydrogenated tallow amine. [0630]
  • 7. Thiosynergists, for example dilauryl thiodipropionate or distearyl thiodipropionate. [0631]
  • 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. [0632]
  • 9. Polyamide stabilisers, for example copper salts in combination with iodides and/or phosphorus compounds and salts of divalent manganese. [0633]
  • 10. 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. [0634]
  • 11. Nucleatina 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). Especially preferred are 1,3:2,4-bis(3′,4′-dimethylbenzylidene)sorbitol, 1,3:2,4-di(paramethyldibenzylidene)sorbitol, and 1,3:2,4-di(benzylidene)sorbitol. [0635]
  • 12. 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. [0636]
  • 13. Other additives, for example plasticisers, lubricants, emulsifiers, pigments, rheology additives, catalysts, flow-control agents, optical brighteners, flameproofing agents, antistatic agents and blowing agents. [0637]
  • 14. 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 or EP-A-0591102 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-acetoxy-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. [0638]
  • The weight ratio of the total amount of components (A) and (B) to the total amount of the conventional additives can be, for example, 100:1 to 1:100 or 10:1 to 1:10. [0639]
  • The examples below illustrate the invention in greater detail. All percentages and parts are by weight, unless stated otherwise. [0640]
  • Light Stabilizers Used in the Following Examples 1 and 2: [0641]
  • TINUVIN 622 (RTM) [0642]
    Figure US20030197151A1-20031023-C00056
  • Mixture (A-2): [0643]
  • Mixture of the compounds (A-2-a) and (A-2-b) in a weight ratio of 4:1 [0644]
    Figure US20030197151A1-20031023-C00057
  • Compound (B-1-a-1): [0645]
    Figure US20030197151A1-20031023-C00058
  • TINUVIN 770 (RTM): [0646]
    Figure US20030197151A1-20031023-C00059
  • TINUVIN 765 (RTM): [0647]
    Figure US20030197151A1-20031023-C00060
  • TINUVIN 123 (RTM): [0648]
    Figure US20030197151A1-20031023-C00061
  • TINUVIN 144 (RTM): [0649]
    Figure US20030197151A1-20031023-C00062
  • ADK STAB LA 52 (RTM): [0650]
    Figure US20030197151A1-20031023-C00063
  • ADK STAB LA 57 (RTM): [0651]
    Figure US20030197151A1-20031023-C00064
  • ADK STAB LA 62 (RTM): [0652]
    Figure US20030197151A1-20031023-C00065
  • in which two of the radicals E[0653] 7 are —COO—C13H27 and two of the radicals E7 are
    Figure US20030197151A1-20031023-C00066
  • ADK STAB LA 67 (RTM): [0654]
    Figure US20030197151A1-20031023-C00067
  • in which two of the radicals E[0655] 7 are —COO—C13H27 and two of the radicals E7 are
    Figure US20030197151A1-20031023-C00068
  • HOSTAVIN N 20 (RTM): [0656]
    Figure US20030197151A1-20031023-C00069
  • SANDUVOR 3050 (RTM): [0657]
    Figure US20030197151A1-20031023-C00070
  • HOSTAVIN N 24 (RTM): [0658]
    Figure US20030197151A1-20031023-C00071
  • UVINUL 4049 H (RTM): [0659]
    Figure US20030197151A1-20031023-C00072
  • Compound (B-6-a-1): [0660]
    Figure US20030197151A1-20031023-C00073
  • Compound (B-6-a-2): [0661]
    Figure US20030197151A1-20031023-C00074
  • SANDUVOR PR 31 (RTM): [0662]
    Figure US20030197151A1-20031023-C00075
  • GOODRITE UV 3034 (RTM): [0663]
    Figure US20030197151A1-20031023-C00076
  • GOODRITE UV 3150 (RTM) [0664]
    Figure US20030197151A1-20031023-C00077
  • Compound (B-10-a-1): [0665]
    Figure US20030197151A1-20031023-C00078
  • Compound (B-7-1): [0666]
    Figure US20030197151A1-20031023-C00079
  • in which E[0667] 19, E20 and E21 are the group
    Figure US20030197151A1-20031023-C00080
    • EXAMPLE 1
  • Light Stabilization of Polypropylene Homopolymer Films. [0668]
  • 100 parts of unstabilized polypropylene powder (melt flow index: 2.4 g/10 minutes at 230° C. and 2160 g) are homogenized at 200° C. for 10 minutes in a Brabender plastograph with 0.05 parts of pentaerythrityl-tetrakis{3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate}, 0.05 parts of tris{2,4-di-tert-butylphenyl}phosphite, 0.1 parts of Ca stearate, 0.25 parts of titanium dioxide (anatase) and the stabilizer system indicated Table 1. The material thus obtained is compression molded in a laboratory press between two aluminum foils for 6 minutes at 260° C. to a 0.5 mm thick film which is cooled immediately to room temperature in a water-cooled press. Samples of 60 mm×25 mm are cut out of these 0.5 mm films and are exposed in a WEATHER-OMETER Ci 65 (black panel temperature 63±2° C., without water-spraying). [0669]
  • Periodically, these samples are removed from the exposure apparatus and their carbonyl content is measured with an infrared spectrophotometer. [0670]
  • The exposure time (T[0671] 0.1) corresponding to the formation of a carbonyl absorbance of 0.1 is a measure for the efficiency of the light stabilizer system. The values obtained are summarized in Table 1. High T0.1 values are desired.
    TABLE 1
    T0.1
    in hours
    Light
    stabilizer
    system in
    combi-
    nation
    with
    TINUVIN
    T0.1 622
    in hours (RTM)
    The The
    amount amount
    of the of the
    light light
    stabilizers stabilizers
    used is used is
    0.075% 0.05%
    Light stabilizer system each*). each*).
    Without 185 —
    TINUVIN 770 (RTM) + TINUVIN 765 (RTM) 1780 3095
    TINUVIN 770 (RTM) + TINUVIN 144 (RTM) 1990 2815
    TINUVIN 770 (RTM) + TINUVIN 123 (RTM) 1780 2650
    TINUVIN 770 (RTM) + HOSTAVIN N 20 2760 3205
    (RTM)
    TINUVIN 770 (RTM) + ADK STAB LA 57 2245 3045
    (RTM)
    TINUVIN 770 (RTM) + GOODRITE UV 3034 2440 3570
    (RTM)
    TINUVIN 770 (RTM) + GOODRITE UV 3150 2715 3230
    (RTM)
    TINUVIN 770 (RTM) + Compound (B-6-a-1) 1930 3095
    TINUVIN 770 (RTM) + Compound (B-6-a-2) 2000 3400
    TINUVIN 770 (RTM) + Compound (B-10-a-1) 3510 3940
    TINUVIN 770 (RTM) + Compound (B-1-a-1) 1715 3520
    TINUVIN 770 (RTM) + SANDUVOR 3050 1630 3040
    (RTM)
    TINUVIN 770 (RTM) + SANDUVOR PR-31 1885 2730
    (RTM)
    HOSTAVIN N 20 (RTM) + ADK STAB LA 57 2485 2765
    (RTM)
    HOSTAVIN N 20 (RTM) + Compound (B-6-a-1) 2625 3010
    HOSTAVIN N 20 (RTM) + UVINUL 4049 H 2655 3245
    (RTM)
    HOSTAVIN N 20 (RTM) + Compound (B-1-a-1) 2510 3055
    HOSTAVIN N 20 (RTM) + SANDUVOR 2120 3140
    PR-31 (RTM)
    ADK STAB LA 57 (RTM) + TINUVIN 765 2290 2705
    (RTM)
    ADK STAB LA 57 (RTM) + GOODRITE 2305 2930
    UV 3150 (RTM)
    ADK STAB LA 57 (RTM) + Compound 2255 2745
    (B-6-a-2)
    ADK STAB LA 57 (RTM) + UVINUL 4049 H 2400 2735
    (RTM)
    ADK STAB LA 57 (RTM) + SANDUVOR 1670 2655
    PR-31 (RTM)
    GOODRITE UV 3150 (RTM) + Compound 2390 3040
    (B-6-a-1)
    GOODRITE UV 3150 (RTM) + Compound 2155 2670
    (B-6-a-2)
    GOODRITE UV 3150 (RTM) + SANDUVOR 2075 2840
    PR-31 (RTM)
    Compound (B-6-a-1) + TINUVIN 765 (RTM) 2230 3010
    Compound (B-6-a-1) + Compound (B-6-a-2) 2235 2980
    Compound (B-6-a-1) + UVINUL 4049 H (RTM) 2465 3235
    Compound (B-6-a-1) + Compound (B-1-a-1) 2225 2775
    Compound (B-10-a-1) + UVINUL 4049 H (RTM) 3430 4055
    Compound (B-10-a-1) + SANDUVOR PR-31 2710 3255
    (RTM)
    Compound (B-1-a-1) + TINUVIN 765 (RTM) 2365 3060
    Compound (B-1-a-1) + UVINUL 4049 H (RTM) 2475 3205
    Compound (B-1-a-1) + SANDUVOR PR-31 1845 2550
    (RTM)
    Compound (B-1-a-1) + Compound (B-6-a-2) 2240 2650
    • EXAMPLE 2
  • Light Stabilization of Polypropylene Homopolymer Films. [0672]
  • 100 parts of unstabilized polypropylene powder (melt flow index: 3.8 g/10 minutes at 230° C. and 2160 g) are homogenized at 200° C. for 10 minutes in a Brabender plastograph with 0.05 parts of pentaerythrityl {tetrakis-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate}, 0.05 parts of tris{2,4-di-tert-butylphenyl)phosphite}, 0.1 parts of Ca stearate, 0.25 parts of titanium dioxide (anatase) and the stabilizer system indicated in Tables 2A to 2H. The material thus obtained is compression molded in a laboratory press between two aluminum foils for 6 minutes at 260° C. to a 0.5 mm thick film which is cooled immediately to room temperature in a water-cooled press. Samples of 60 mm×25 mm are cut out of these 0.5 mm films and are exposed in a WEATHER-OMETER Ci 65 (black panel temperature 63±2° C., without water-spraying). [0673]
  • Periodically, these samples are removed from the exposure apparatus and their carbonyl content is measured with an infrared spectrophotometer. [0674]
  • The exposure time (T[0675] 0.1) corresponding to the formation of a carbonyl absorbance of 0.1 is a measure for the efficiency of the light stabilizer system. The values obtained are summarized in the following tables. High T0.1 values are desired.
    TABLE 2A
    T0.1 T0.1 T0.1
    in hours in hours in hours
    Light Light Light
    stabilizer stabilizer stabilizer
    system in system in system in
    combi- combi- combi-
    nation nation nation
    with with with
    TINUVIN TINUVIN TINUVIN
    622 622 622
    (RTM) (RTM) (RTM)
    The The The
    amount amount amount
    of the of the of the
    stabilizers stabilizers stabilizers
    of the of the of the
    light light light
    T0.1 stabilizer stabilizer stabilizer
    in hours system system system
    The is 0.05% is 0.075% is 0.09%
    amount each each each
    of the and the and the and the
    light amount of amount of amount
    stabilizers TINUVIN TINUVIN TINUVIN
    Light used 622 622 622
    stabilizer is 0.1% (RTM) is (RTM) is (RTM) is
    system each*). 0.10%*). 0.05%*). 0.02%*).*
    Without 300
    TINUVIN 770 (RTM) + 4635 7530 7585 6235
    TINUVIN 144 (RTM)
    TINUVIN 770 (RTM) + 4935 7940 7170 7130
    TINUVIN 123 (RTM)
    TINUVIN 770 (RTM) + 5105 7455 7030 6890
    HOSTAVIN N 24
    (RTM)
    TINUVIN 770 (RTM) + 6710 6945 7865 8010
    ADK STAB LA 52
    (RTM)
    TINUVIN 770 (RTM) + 5450 7225 7225 7280
    ADK STAB LA 57
    (RTM)
    TINUVIN 770 (RTM) + 5915 6700 7190 7025
    ADK STAB LA 67
    (RTM)
    TINUVIN 770 (RTM) + 6925 >8340 >8340 7360
    GOODRITE UV 3034
    (RTM)
    TINUVIN 770 (RTM) + 6325 7965 7625 7025
    GOODRITE UV 3150
    (RTM)
    TINUVIN 770 (RTM) + 6040 7400 7540 7025
    Compound (B-1-a-1)
    TINUVIN 770 (RTM) + 5070 7005 6990 5735
    SANDUVOR 3050
    (RTM)
    TINUVIN 770 (RTM) + 5745 7470 6765 6705
    SANDUVOR PR-31
    (RTM)
  • [0676]
    TABLE 2B
    T0.1 in hours
    Light stabilizer
    T0.1 system in combination
    in hours with Mixture (A-2)
    The amount The amount of the
    of the light stabilizers of the light
    stabilizers stabilizer system is 0.075%
    used is each and the amount of
    Light stabilizer system 0.1% each*). Mixture (A-2) is 0.05%*).
    Without 300 —
    TINUVIN 770 (RTM) + 4635 6025
    TINUVIN 144 (RTM)
    TINUVIN 770 (RTM) + 4935 6080
    TINUVIN 123 (RTM)
    TINUVIN 770 (RTM) + 5105 6005
    HOSTAVIN N 24 (RTM)
    TINUVIN 770 (RTM) + 5450 6800
    ADK STAB LA 57 (RTM)
    TINUVIN 770 (RTM) + 6925 7735
    GOODRITE UV 3034 (RTM)
    TINUVIN 770 (RTM) + 6530 7335
    Compound (B-6-a-2)
    TINUVIN 770 (RTM) + 6040 6905
    Compound (B-1-a-1)
    TINUVIN 770 (RTM) + 5070 >6495
    SANDUVOR 3050 (RTM)
  • [0677]
    TABLE 2C
    T0.1 in hours
    Light stabilizer
    T0.1 system in combination
    in hours with TINUVIN 622 (RTM)
    The amount The amount of
    of the the stabilizers of
    the light the light stabilizer system
    stabilizers is 0.075% each and the
    used is amount of TINUVIN 622
    Light stabilizer system 0.1% each*). (RTM) is 0.05%*).
    Without 315 —
    TINUVIN 770 (RTM) + 4815 >7260
    TINUVIN 765 (RTM)
    TINUVIN 770 (RTM) + 5695 7145
    TINUVIN 144 (RTM)
    TINUVIN 770 (RTM) + 4670 7080
    TINUVIN 123 (RTM)
    TINUVIN 770 (RTM) + 5390 6710
    HOSTAVIN N 24 (RTM)
    TINUVIN 770 (RTM) + 6655 >7260
    ADK STAB LA 52 (RTM)
    TINUVIN 770 (RTM) + 5040 6760
    ADK STAB LA 62 (RTM)
    TINUVIN 770 (RTM) + 5010 6205
    ADK STAB LA 67 (RTM)
    TINUVIN 770 (RTM) + 5825 >7260
    Compound (B-10-a-1)
    TINUVIN 770 (RTM) + 6125 7215
    Compound (B-1-a-1)
    TINUVIN 770 (RTM) + 5690 >7260
    SANDUVOR 3050 (RTM)
    TINUVIN 770 (RTM) + 5100 6475
    SANDUVOR PR-31 (RTM)
  • [0678]
    TABLE 2D
    T0.1 in hours
    Light stabilizer
    T0.1 system in combination
    in hours with TINUVIN 622 (RTM)
    The amount The amount of
    of the the stabilizers of
    the light the light stabilizer system
    stabilizers is 0.075% each and the
    used is amount of TINUVIN 622
    Light stabilizer system 0.1% each*). (RTM) is 0.05%*).
    Without 315 —
    TINUVIN 765 (RTM) + 4930 7180
    TINUVIN 144 (RTM)
    TINUVIN 765 (RTM) + 4640 >7260
    TINUVIN 123 (RTM)
    TINUVIN 765 (RTM) + 6580 >7260
    HOSTAVIN N 20 (RTM)
    TINUVIN 765 (RTM) + 5325 7040
    HOSTAVIN N 24 (RTM)
    TINUVIN 765 (RTM) + 5605 >7260
    ADK STAB LA 52 (RTM)
    TINUVIN 765 (RTM) + 5360 6905
    ADK STAB LA 57 (RTM)
    TINUVIN 765 (RTM) + 4620 >7260
    ADK STAB LA 62 (RTM)
    TINUVIN 765 (RTM) + 4840 6625
    ADK STAB LA 67 (RTM)
    TINUVIN 765 (RTM) + 6550 >7260
    GOODRITE UV 3034 (RTM)
    TINUVIN 765 (RTM) + 5715 >7260
    GOODRITE UV 3150 (RTM)
    TINUVIN 765 (RTM) + 5105 >7260
    Compound (B-6-a-1)
    TINUVIN 765 (RTM) + 6145 >7260
    Compound (B-1-a-1)
    TINUVIN 765 (RTM) + 5425 >7260
    SANDUVOR 3050 (RTM)
    TINUVIN 765 (RTM) + 4920 6675
    SANDUVOR PR-31 (RTM)
  • [0679]
    TABLE 2E
    T0.1 in hours
    Light stabilizer
    T0.1 system in combination
    in hours with TINUVIN 622 (RTM)
    The amount The amount of
    of the the stabilizers of
    the light the light stabilizer system
    stabilizers is 0.075% each and the
    used is amount of TINUVIN 622
    Light stabilizer system 0.1% each*). (RTM) is 0.05%*).
    Without 330
    TINUVIN 144 (RTM) + 3185 5765
    TINUVIN 123 (RTM)
    TINUV1N 144 (RTM) + 4295 6150
    HOSTAVIN N 20 (RTM)
    TINUVIN 144 (RTM) + 3725 5720
    HOSTAVIN N 24 (RTM)
    TINUVIN 144 (RTM) + 4195 5635
    ADK STAB LA 52 (RTM)
    TINUVIN 144 (RTM) + 4870 6350
    ADK STAB LA 57 (RTM)
    TINUVIN 144 (RTM) + 2815 5695
    ADK STAB LA 62 (RTM)
    TINUVIN 144 (RTM) + 3910 4940
    ADK STAB LA 67 (RTM)
    TINUVIN 144 (RTM) + 4185 6115
    GOODRITE UV 3034 (RTM)
    TINUVIN 144 (RTM) + 4290 5725
    GOODRITE UV 3150 (RTM)
    TINUVIN 144 (RTM) + 5515 6565
    Compound (B-6-a-1)
    TINUVIN 144 (RTM) + 5100 6810
    Compound (B-6-a-2)
    TINUVIN 144 (RTM) + 5380 6585
    Compound (B-10-a-1)
    TINUVIN 144 (RTM) + 5470 6305
    Compound (B-1-a-1)
    TINUVIN 144 (RTM) + 4030 5200
    SANDUVOR 3050 (RTM)
    TINUVIN 144 (RTM) + 3105 5890
    SANDUVOR PR-31 (RTM)
  • [0680]
    TABLE 2F
    T0.1 in hours
    Light stabilizer
    T0.1 system in combination
    in hours with TINUVIN 622 (RTM)
    The amount The amount of
    of the the stabilizers of
    the light the light stabilizer system
    stabilizers is 0.075% each and the
    used is amount of TINUVIN 622
    Light stabilizer system 0.1% each*). (RTM) is 0.05%*).
    Without 330
    TINUVIN 123 (RTM) + 4455 5715
    HOSTAVIN N 20 (RTM)
    TINUVIN 123 (RTM) + 3490 5265
    HOSTAVIN N 24 (RTM)
    TINUVIN 123 (RTM) + 4620 5610
    ADK STAB LA 52 (RTM)
    TINUVIN 123 (RTM) + 4275 5670
    ADK STAB LA 57 (RTM)
    TINUVIN 123 (RTM) + 3380 5185
    ADK STAB LA 62 (RTM)
    TINUVIN 123 (RTM) + 3470 5355
    ADK STAB LA 67 (RTM)
    TINUVIN 123 (RTM) + 4520 >6280
    GOODRITE UV 3034 (RTM)
    TINUVIN 123 (RTM) + 4260 5635
    GOODRITE UV 3150 (RTM)
    TINUVIN 123 (RTM) + 4760 6145
    Compound (B-6-a-1)
    TINUVIN 123 (RTM) + 5115 6365
    Compound (B-6-a-2)
    TINUVIN 123 (RTM) + 5785 6700
    Compound (B-10-a-1)
    TINUVIN 123 (RTM) + 4345 6115
    Compound (B-1-a-1)
    TINUVIN 123 (RTM) + 3650 5040
    SANDUVOR 3050 (RTM)
    TINUVIN 123 (RTM) + 3655 5390
    SANDUVOR PR-31 (RTM)
    TINUVIN 123 (RTM) + 4305 5205
    Compound (B-7-1)
  • [0681]
    TABLE 2G
    T0.1 in hours
    Light stabilizer
    T0.1 system in combination
    in hours with TINUVIN 622 (RTM)
    The amount The amount of
    of the the stabilizers of
    the light the light stabilizer system
    stabilizers is 0.075% each and the
    used is amount of TINUVIN 622
    Light stabilizer system 0.1% each*). (RTM) is 0.05%*).
    Without 325
    HOSTAVIN N 20 (RTM) + 3695 4565
    HOSTAVIN N 24 (RTM)
    HOSTAVIN N 20 (RTM) + 4375 5525
    ADK STAB LA 52 (RTM)
    HOSTAVIN N 20 (RTM) + 4485 5535
    ADK STAB LA 57 (RTM)
    HOSTAVIN N 20 (RTM) + 3810 5315
    ADK STAB LA 62 (RTM)
    HOSTAVIN N 20 (RTM) + 3655 5045
    ADK STAB LA 67 (RTM)
    HOSTAVIN N 20 (RTM) + 5005 5610
    GOODRITE UV 3034 (RTM)
    HOSTAVIN N 20 (RTM) + 3950 5050
    GOODRITE UV 3150 (RTM)
    HOSTAVIN N 20 (RTM) + 5025 >5890
    Compound (B-6-a-1)
    HOSTAVIN N 20 (RTM) + 5465 >5890
    Compound (B-6-a-2)
    HOSTAVIN N 20 (RTM) + 5405 >5890
    Compound (B-10-a-1)
    HOSTAVIN N 20 (RTM) + 5410 >5890
    Compound (B-1-a-1)
    HOSTAVIN N 20 (RTM) + 3985 5090
    SANDUVOR 3050 (RTM)
    HOSTAVIN N 20 (RTM) + 4085 5255
    SANDUVOR PR-31 (RTM)
    HOSTAVIN N 20 (RTM) + 4200 5220
    Compound (B-7-1)
  • [0682]
    TABLE 2H
    T0.1 in hours
    Light stabilizer
    T0.1 system in combination
    in hours with TINUVIN 622 (RTM)
    The amount The amount of
    of the the stabilizers of
    the light the light stabilizer system
    stabilizers is 0.075% each and the
    used is amount of TINUVIN 622
    Light stabilizer system 0.1% each*). (RTM) is 0.05%*).
    Without 325
    ADK STAB LA 57 (RTM) + 4035 5020
    HOSTAVIN N 24 (RTM)
    ADK STAB LA 57 (RTM) + 3855 4985
    ADK STAB LA 52 (RTM)
    ADK STAB LA 57 (RTM) + 4320 4890
    GOODRITE UV 3150 (RTM)
    ADK STAB LA 57 (RTM) + 3970 4430
    SANDUVOR PR-31 (RTM)
    ADK STAB LA 57 (RTM) + 3765 4475
    Compound (B-7-1)

Claims (17)

1. A stabilizer mixture containing the components (A) and (B) wherein
component (A) is
a compound of the formula (A-1)
Figure US20030197151A1-20031023-C00081
 wherein
A1 is hydrogen or C1-C4alkyl,
A2 is a direct bond or C1-C10alkylene, and
n1 is a number from 2 to 50;
at least one compound of the formulae (A-2-a) and (A-2-b)
Figure US20030197151A1-20031023-C00082
n2 and n2* are a number from 2 to 50;
a compound of the formula (A-3)
Figure US20030197151A1-20031023-C00083
 wherein
A3 and A4 independently of one another are hydrogen or C1-C8alkyl, or A3 and A4 together form a C2-C14alkylene group, and
the variables n3 independently of one another are a number from 1 to 50; or
a compound of the formula (A-4)
Figure US20030197151A1-20031023-C00084
 wherein
n4 is a number from 2 to 50,
A5 is hydrogen or C1-C4alkyl,
the radicals A6 and A7 independently of one another are C1-C4alkyl or a group of the formula (a-I)
Figure US20030197151A1-20031023-C00085
wherein A8 is hydrogen, C1-C8alkyl, O−, —OH, —CH2CN, C1-C18alkoxy, C5-C12cycloalkoxy, C3-C6alkenyl, C7-C9phenylalkyl unsubstituted or substituted on the phenyl by 1, 2 or 3 C1-C4alkyl; or C1-C8acyl,
with the proviso that at least 50% of the radicals A7 are a group of the formula (a-I); and component (B) is formed by two different low molecular weight sterically hindered amine compounds containing a group of the formula (I) or (II);
Figure US20030197151A1-20031023-C00086
with the proviso that components (A) and (B) are different.
2. A stabilizer mixture according to claim 1 wherein the two different compounds of component (B) are selected from the group consisting of the classes
β-1) a compound of the formula (B-1)
Figure US20030197151A1-20031023-C00087
 in which
E1 is hydrogen, C1-C8alkyl, O−, —OH, —CH2CN, C1-C18alkoxy, C5-C12cycloalkoxy, C3-C6alkenyl, C7-C9phenylalkyl unsubstituted or substituted on the phenyl by 1, 2 or 3 C1-C4alkyl; or C1-C8acyl,
m1 is 1, 2 or 4,
if m1 is 1, E2 is C1-C25alkyl,
if m1 is 2, E2 is C1-C14alkylene or a group of the formula (b-I)
Figure US20030197151A1-20031023-C00088
wherein E3 is C1-C10alkyl or C2-C10alkenyl, E4 is C1-C10alkylene, and E5 and E6 independently of one another are C1-C4alkyl, cyclohexyl or methylcyclohexyl, and
if m1 is 4, E2 is C4-C10alkanetetrayl;
β-2) a compound of the formula (B-2)
Figure US20030197151A1-20031023-C00089
 in which
two of the radicals E7 are —COO—(C1-C20alkyl), and
two of the radicals E7 are a group of the formula (b-II)
Figure US20030197151A1-20031023-C00090
with E8 having one of the meanings of E1;
β-3) a compound of the formula (B-3)
Figure US20030197151A1-20031023-C00091
 in which
E9 and E10 together form C2-C14alkylene,
E11 is hydrogen or a group -Z1-COO-Z2,
Z1 is C2-C14alkylene, and
Z2 is C1-C24alkyl, and
E12 has one of the meanings of E1;
β-4) a compound of the formula (B-4)
Figure US20030197151A1-20031023-C00092
 wherein
the radicals E13 independently of one another have one of the meanings of E1, the radicals E14 independently of one another are hydrogen or C1-C12alkyl, and
E15 is C1-C10alkylene or C3-C10alkylidene;
β-5) a compound of the formula (B-5)
Figure US20030197151A1-20031023-C00093
 wherein
the radicals E16 independently of one another have one of the meanings of E1;
β-6) a compound of the formula (B-6)
Figure US20030197151A1-20031023-C00094
 in which
E17 is C1-C24alkyl, and
E18 has one of the meanings of E1;
β-7) a compound of the formula (B-7)
Figure US20030197151A1-20031023-C00095
 in which
E19, E20 and E21 independently of one another are a group of the formula (b-III)
Figure US20030197151A1-20031023-C00096
wherein E22 has one of the meanings of E1;
β-8) a compound of the formula (B-8)
Figure US20030197151A1-20031023-C00097
 wherein
the radicals E23 independently of one another have one of the meanings of E1, and E24 is hydrogen, C1-C12alkyl or C1-C12alkoxy;
β-9) a compound of the formula (B-9)
Figure US20030197151A1-20031023-C00098
 wherein
m2 is 1, 2 or 3,
E25 has one of the meanings of E1, and
when m2 is 1, E26 is a group
Figure US20030197151A1-20031023-C00099
when m2 is 2, E26 is C2-C22alkylene, and
when m2 is 3, E26 is a group of the formula (b-IV)
Figure US20030197151A1-20031023-C00100
wherein the radicals E27 independently of one another are C2-C12alkylene, and the radicals E28 independently of one another are C1-C12alkyl or C5-C12cycloalkyl;
β-10) a compound of the formula (B-10)
Figure US20030197151A1-20031023-C00101
 wherein
the radicals E29 independently of one another have one of the meanings of E1, and E30 is C2-C22alkylene, C5C7cycloalkylene, C1-C4alkylenedi(C5-C7cycloalkylene), phenylene or phenylenedi(C1-C4alkylene); or
β-11) a compound of the formula (B-11)
Figure US20030197151A1-20031023-C00102
 in which
E31 is C1-C10alkyl, C5-C12cycloalkyl, C1-C4alkyl-subsbtuted C5-C12cycloalkyl, phenyl or C1-C10alkyl-substituted phenyl,
E32 is C3-C10alkylene,
E33 has one of the meanings of E1, and
m3 is a number from 2 to 6.
3. A stabilizer mixture according to claim 1 wherein
A1 is hydrogen or methyl,
A2 is a direct bond or C2-C6alkylene, and
n1 is a number from 2 to 25;
n2 and n2* are a number from 2 to 25;
A3 and A4 independently of one another are hydrogen or C1-C4alkyl, or A3 and A4 together form a C9-C13alkylene group, and
the variables n3 independently of one another are a number from 1 to 25;
n4 is a number from 2 to 25,
A5 and A6 independently of one another are C1-C4alkyl, and
A7 is C1-C4alkyl or a group of the formula (a-I)
with the proviso that at least 50% of the radicals A7 are a group of the formula (a-I).
4. A stabilizer mixture according to claim 2 wherein
m1 is 1, 2 or 4,
if m1 is 1, E2 is C12-C20alkyl,
if m1 is 2, E2 is C2-C10alkylene or a group of the formula (b-I)
E3 is C1-C4alkyl,
E4 is C1-C6alkylene, and
E5 and E6 independently of one another are C1-C4alkyl, and
if m1 is 4, E2 is C4-C8alkanetetrayl;
two of the radicals E7 are —COO—(C10-C15alkyl), and
two of the radicals E7 are a group of the formula (b-II);
E9 and E10 together form C9-C13alkylene,
E11 is hydrogen or a group -Z1-COO-Z2,
Z1 is C2-C6alkylene, and
Z2 is C10-C16alkyl;
E14 is hydrogen, and
E15 is C2-C6alkylene or C3-C5alkylidene;
E17 is C10-C14alkyl;
E24 is C1-C4alkoxy;
m2 is 1, 2 or 3,
when m2 is 1, E26 is a group
Figure US20030197151A1-20031023-C00103
when m2 is 2, E26 is C2-C6alkylene, and
when m2 is 3, E26 is a group of the formula (b-IV)
the radicals E27 independently of one another are C2-C6alkylene, and
the radicals E28 independently of one another are C1-C4alkyl or C5-C8cycloalkyl;
E30 is C2-C8alkylene; and
E31 is C1-C4alkyl,
E32 is C3-C6alkylene, and
m3 is a number from 2 to 6.
5. A stabilizer mixture according to claim 1 wherein
component (A) is a compound of the formula (A-1-a), (A-2-a), (A-2-b), (A-3-a) or (A-4-a);
Figure US20030197151A1-20031023-C00104
wherein n1 is a number from 2 to 20;
Figure US20030197151A1-20031023-C00105
wherein n2 and n2* are a number from 2 to 20;
Figure US20030197151A1-20031023-C00106
wherein the variables n3 independently of one another are a number from 1 to 20;
Figure US20030197151A1-20031023-C00107
wherein n4 is a number from 2 to 20, and at least 50% of the radicals A7 are a group of the formula (a-I)
Figure US20030197151A1-20031023-C00108
wherein A8 is hydrogen, C1-C8alkyl, O−, —OH, —CH2CN, C1-C18alkoxy, C5-C12cycloalkoxy, C3-C6alkenyl, C7-C9phenylalkyl unsubstituted or substituted on the phenyl by 1, 2 or 3 C1-C4alkyl; or C1-C8acyl,
and the remaining radicals A7 are ethyl; and
component (B) is formed by two different compounds selected from the group consisting of compounds of the formulae (B-1-a), (B-1-b), (B-1-c), (B-1-d), (B-2-a), (B-3-a), (B-3-b), (B-4-a), (B-4-b), (B-5), (B-6-a), (B-7), (B-8-a), (B-9-a), (B-9-b), (B-9-c), (B-10-a) and (B-11-a);
Figure US20030197151A1-20031023-C00109
wherein E1 is hydrogen, C1-C8alkyl, O−, —OH, —CH2CN, C1-C18alkoxy, C5-C12cycloalkoxy, C3-C6alkenyl, C7-C9phenylalkyl unsubstituted or substituted on the phenyl by 1, 2 or 3 C1-C4alkyl; or C1-C8acyl;
Figure US20030197151A1-20031023-C00110
in which two of the radicals E7 are —COO—C13H27 and
two of the radicals E7 are
Figure US20030197151A1-20031023-C00111
 and E8 has one of the meanings of E1;
Figure US20030197151A1-20031023-C00112
wherein E12 has one of the meanings of E1;
Figure US20030197151A1-20031023-C00113
wherein E13 has one of the meanings of E1;
Figure US20030197151A1-20031023-C00114
wherein E16 has one of the meanings of E1;
Figure US20030197151A1-20031023-C00115
wherein E18 has one of the meanings of E1;
Figure US20030197151A1-20031023-C00116
in which E19, E20 and E21 independently of one another are a group of the formula (b-III)
Figure US20030197151A1-20031023-C00117
wherein E22 has one of the meanings of E1;
Figure US20030197151A1-20031023-C00118
wherein E23 has one of the meanings of E1;
Figure US20030197151A1-20031023-C00119
wherein E25 has one of the meanings of E1;
Figure US20030197151A1-20031023-C00120
wherein E29 has one of the meanings of E1;
Figure US20030197151A1-20031023-C00121
wherein m3 is a number from 2 to 6 and E33 has one of the meanings of E1.
6. A stabilizer mixture according to claim 1 wherein A8 is hydrogen, C1-C4alkyl, C1-C10alkoxy, cyclohexyloxy, allyl, benzyl or acetyl.
7. A stabilizer mixture according to claim 2 wherein E1, E8, E12, E13, E16, E18, E22, E23, E25, E29 and E33 are hydrogen, C1-C4alkyl, C1-C10alkoxy, cyclohexyloxy, allyl, benzyl or acetyl.
8. A stabilizer mixture according to claim 5 wherein A8, E1, E8, E12, E13, E16, E18, E22, E23, E25, E29 and E33 are hydrogen or methyl and E1 additionally is C1-C8alkoxy.
9. A stabilizer mixture according to claim 5 wherein one of the two different compounds forming component (B) is a compound of the formula (B-1-b) with E1 being hydrogen.
10. A stabilizer mixture according to claim 5 wherein
component (A) is a compound of the formula (A-1-a) with n1 being a number from 2 to 20 or a compound of the formula (A-2-a) or (A-2-b) wherein n2 and n2* are a number from 2 to 20; and
one of the two different compounds forming component (B) is a compound of the formula (B-1-b) with E1 being hydrogen.
11. A stabilizer mixture according to claim 5 wherein component (A) is a compound of the formula (A-1-a) with n1 being a number from 2 to 20 or a compound of the formula (A-2-a) or (A-2-b) wherein n2 and n2* are a number from 2 to 20;
one of the two different compounds forming component (B) is a compound of the formula (B-1-b) with E1 being hydrogen; and
the other of the two different compounds forming component (B) is a compound of the formula (B-1-a) with E1 being hydrogen, (B-1-b) with E1 being methyl, (B-1-d) with E1 being hydrogen or methyl, (B-3-a) with E12 being hydrogen, (B-3-b) with E12 being hydrogen, (B-4-b) with E13 being hydrogen, (B-5) with E16 being hydrogen, (B-6-a) with E18 being hydrogen or methyl, (B-8-a) with E23 being methyl, (B-9-c) with E25 being hydrogen or methyl, (B-10-a) with E29 being hydrogen, or (B-11-a) with E33 being hydrogen.
12. A stabilizer mixture according to claim 5 wherein
component (A) is a compound of the formula (A-1-a) with n1 being a number from 2 to 20,
component (B) is a compound of the formula (B-1-b) wherein E1 is hydrogen, and
component (C) is a compound of the formula (B-1-b) wherein E1 is octyloxy; or
component (A) is a compound of the formula (A-1-a) with n1 being a number from 2 to 20,
component (B) is a compound of the formula (B-1-b) wherein E1 is hydrogen, and
component (C) is a compound of the formula (B-3-a) wherein E12 is hydrogen; or
component (A) is a compound of the formula (A-1-a) with n1 being a number from 2 to 20,
component (B) is a compound of the formula (B-1-b) wherein E1 is hydrogen, and
component (C) is a compound of the formula (B-1-d) wherein E1 is hydrogen; or
component (A) is a compound of the formula (A-1-a) with n1 being a number from 2 to 20,
component (B) is a compound of the formula (B-1-b) wherein E1 is hydrogen, and
component (C) is a compound of the formula (B-1-a) wherein E1 is hydrogen; or
component (A) is a compound of the formula (A-1-a) with n1 being a number from 2 to 20,
component (B) is a compound of the formula (B-1-b) wherein E1 is methyl, and
component (C) is a compound of the formula (B-1-d) wherein E1 is methyl.
13. A composition comprising an organic material subject to degradation induced by light, heat or oxidation and a stabilizer mixture according to claim 1.
14. A composition according to claim 13 wherein the organic material is a synthetic polymer.
15. A composition according to claim 13 wherein the organic material is a polyolefin.
16. A composition according to claim 13 wherein the organic material is polyethylene, polypropylene, a polyethylene copolymer or a polypropylene copolymer.
17. A method for stabilizing an organic material against degradation induced by light, heat or oxidation, which comprises incorporating into the organic material a stabilizer mixture according to claim 1.
US10/276,120 2000-05-31 2001-05-22 Stabilizer mixtures Abandoned US20030197151A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US11/052,714 US20050143500A1 (en) 2000-05-31 2005-01-19 Stabilizer mixtures
US11/498,351 US20060270764A1 (en) 2000-05-31 2006-08-03 Stabilizer mixtures
US12/317,014 US20090105379A1 (en) 2000-05-31 2008-12-18 Stabilizer mixtures
US12/607,102 US7820744B2 (en) 2000-05-31 2009-10-28 Stabilizer mixtures

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
EP00810482.0 2000-05-31
EP00810482 2000-05-31
EP00810600.7 2000-07-10
EP00810600 2000-07-10
PCT/EP2001/005865 WO2001092398A2 (en) 2000-05-31 2001-05-22 Stabilizer mixtures

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US11/052,714 Continuation US20050143500A1 (en) 2000-05-31 2005-01-19 Stabilizer mixtures

Publications (1)

Publication Number Publication Date
US20030197151A1 true US20030197151A1 (en) 2003-10-23

Family

ID=26073903

Family Applications (5)

Application Number Title Priority Date Filing Date
US10/276,120 Abandoned US20030197151A1 (en) 2000-05-31 2001-05-22 Stabilizer mixtures
US11/052,714 Abandoned US20050143500A1 (en) 2000-05-31 2005-01-19 Stabilizer mixtures
US11/498,351 Abandoned US20060270764A1 (en) 2000-05-31 2006-08-03 Stabilizer mixtures
US12/317,014 Abandoned US20090105379A1 (en) 2000-05-31 2008-12-18 Stabilizer mixtures
US12/607,102 Expired - Fee Related US7820744B2 (en) 2000-05-31 2009-10-28 Stabilizer mixtures

Family Applications After (4)

Application Number Title Priority Date Filing Date
US11/052,714 Abandoned US20050143500A1 (en) 2000-05-31 2005-01-19 Stabilizer mixtures
US11/498,351 Abandoned US20060270764A1 (en) 2000-05-31 2006-08-03 Stabilizer mixtures
US12/317,014 Abandoned US20090105379A1 (en) 2000-05-31 2008-12-18 Stabilizer mixtures
US12/607,102 Expired - Fee Related US7820744B2 (en) 2000-05-31 2009-10-28 Stabilizer mixtures

Country Status (16)

Country Link
US (5) US20030197151A1 (en)
JP (1) JP5498638B2 (en)
KR (1) KR100786239B1 (en)
CN (1) CN1235958C (en)
AU (2) AU6601001A (en)
BE (1) BE1014207A3 (en)
BR (1) BR0111290B1 (en)
CA (1) CA2408093A1 (en)
DE (1) DE10196264T1 (en)
ES (1) ES2199696B1 (en)
FR (1) FR2809740B1 (en)
GB (1) GB2378950B (en)
IT (1) IT1324894B (en)
MX (1) MX286036B (en)
NL (1) NL1018186C2 (en)
WO (1) WO2001092398A2 (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1564253A1 (en) * 2004-02-17 2005-08-17 DSM IP Assets B.V. Unsaturated polyester resins or vinyl ester resin compositions
EP1564254A1 (en) * 2004-02-17 2005-08-17 DSM IP Assets B.V. Unsaturated polyester resing or vinyl ester resin compositions
US20060124904A1 (en) * 2002-04-12 2006-06-15 Francois Gugumus Stabilizer mixtures
US8366822B2 (en) 2011-06-20 2013-02-05 Dow Global Technologies Llc Cementitious tile adhesives and method of applying the same to a tile substrate
US9062143B2 (en) 2008-02-08 2015-06-23 Dow Global Technologies Llc Water-redispersible polymer powder
US20170306133A1 (en) * 2014-12-02 2017-10-26 Nuc Corporation Crosslinkable resin composition and electric wire/cable
WO2018013181A1 (en) 2016-07-13 2018-01-18 Chevron Oronite Company Llc Synergistic lubricating oil composition containing mixture of antioxidants

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI273115B (en) 2000-12-12 2007-02-11 Ciba Sc Holding Ag Improved weatherability of flame retardant polyolefin
ATE388989T1 (en) * 2002-05-30 2008-03-15 Ciba Sc Holding Ag STABILIZED ITEMS
EP1338622A3 (en) * 2003-03-14 2003-09-10 Ciba SC Holding AG Stabilizer mixtures
MY139524A (en) * 2004-06-30 2009-10-30 Ciba Holding Inc Stabilization of polyether polyol, polyester polyol or polyurethane compositions
JP4916313B2 (en) * 2004-07-07 2012-04-11 株式会社Ａｄｅｋａ Vinyl chloride resin composition
JP2009191202A (en) * 2008-02-15 2009-08-27 Nitto Denko Corp Transparent adhesive sheet for flat panel display
CA2763922C (en) * 2009-05-29 2017-05-23 Uponor Innovation Ab Methods and compositions for producing pipe having improved oxidative resistance
JP5379181B2 (en) * 2010-04-20 2013-12-25 ダウ グローバル テクノロジーズ エルエルシー Redispersible polymer powder made from low carboxylated styrene butadiene based latex
US9546261B2 (en) 2011-09-23 2017-01-17 Borealis Ag Stabilizing of organic material with amino-triazine based mannich-compounds
SA116370295B1 (en) * 2015-02-20 2016-12-06 باسف اس اى Light stabilized polyolefin films, tapes and monofilaments
KR102126057B1 (en) * 2017-12-28 2020-06-23 삼성에스디아이 주식회사 Polarizing plate and optical display device comprising the same

Citations (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3640928A (en) * 1968-06-12 1972-02-08 Sankyo Co Stabilization of synthetic polymers
US4110306A (en) * 1975-12-01 1978-08-29 Argus Chemical Corporation Stabilizers for synthetic polymers comprising 2,2,6,6-tetramethyl-4-piperidyl carboxylic acid ester, a triphosphite, and an acid phosphite or salt thereof
US4198334A (en) * 1975-11-07 1980-04-15 Ciba-Geigy Corporation Substituted malonic acid derivatives and their use as stabilizers
US4233412A (en) * 1976-05-11 1980-11-11 Ciba-Geigy Corporation Polymeric light stabilizers for plastics
US4292240A (en) * 1977-09-21 1981-09-29 The B. F. Goodrich Company 2-Keto-1,4-diazacycloalkanes
US4340534A (en) * 1979-10-10 1982-07-20 Hoechst Aktiengesellschaft Ethers based on polyalkyl-1-oxadiazaspirodecanes
US4356307A (en) * 1980-02-20 1982-10-26 Chemische Werke Huls Aktiengesellschaft Cyclic imides, their preparation and use
US4408051A (en) * 1980-12-24 1983-10-04 Sandoz Ltd. 1-Oxa-3,8-diazaspiro[4.5]decanes
US4547538A (en) * 1982-02-19 1985-10-15 The B. F. Goodrich Company Alkylated polyalkylenepolyamines, substituted oxo-piperazinyl-triazines and UV light stabilized compositions
US4619958A (en) * 1982-10-02 1986-10-28 Adeka Argus Chemical Co., Ltd. Mixed 2,2,6,6-tetramethyl piperidinyl carboxylic acid ester and amide light stabilizers and stabilized synthetic polymers
US4689416A (en) * 1985-07-10 1987-08-25 Hoechst Aktiengellschaft Process for the preparation of 1-oxa-3,8-diaza-4-oxo-spiro(4.5)decane compounds
US4692486A (en) * 1981-10-16 1987-09-08 Ciba-Geigy Corporation Synergistic mixture of low-molecular and high-molecular polyalkylpiperidines
US4769457A (en) * 1985-08-28 1988-09-06 Basf Aktiengesellschaft Glycoluril derivatives and their use as stabilizers for polymers
US4863981A (en) * 1986-06-30 1989-09-05 Ciba-Geigy Corporation Synergistic mixture of stabilizers
US4965301A (en) * 1984-12-03 1990-10-23 Phillips Petroleum Company Stabilization of polyolefins
US4976889A (en) * 1987-11-14 1990-12-11 Basf Aktiengesellschaft 4-formylaminopiperidine derivatives, their use as stabilizers and organic material stabilized with the said derivatives
US5026849A (en) * 1989-06-09 1991-06-25 The B. F. Goodrich Company Solventless process for preparing a tri-substituted triazine
US5049604A (en) * 1984-07-24 1991-09-17 Sumitomo Chemical Company, Limited Process for producing piperidine derivative and stabilized resin composition containing said derivative
US5051458A (en) * 1988-05-27 1991-09-24 Enichem Synthesis S.P.A. UV stabilizers for organic polymers
US5071981A (en) * 1990-03-19 1991-12-10 The B. F. Goodrich Company Alkylated oxo-piperanzinyl-triazine
US5182390A (en) * 1990-10-29 1993-01-26 Kyodo Chemical Company Limited Isocyanuric acid derivative useful as a light stabilizer
US5204473A (en) * 1987-09-21 1993-04-20 Ciba-Geigy Corporation O-substituted N-hydroxy hindered amine stabilizers
US5679733A (en) * 1992-06-02 1997-10-21 Clariant Finance (Bvi) Limited Solid Solution of low molecular weight and high molecular weight hals
US5719217A (en) * 1994-10-28 1998-02-17 Ciba Specialty Chemicals Corporation Synergistic stabiliser mixture
US5919399A (en) * 1995-07-21 1999-07-06 Ciba Specialty Chemicals Corporation Synergistic stabilizer mixture
US5965643A (en) * 1995-05-03 1999-10-12 Ciba Specialty Chemicals Corporation Synergistic stabilizer mixture
US5980783A (en) * 1995-04-11 1999-11-09 Ciba Specialty Chemicals Corporation Synergistic stabilizer mixture
US6015849A (en) * 1995-01-23 2000-01-18 Ciba Specialty Chemicals Corporation Synergistic stabilizer mixture
US6020406A (en) * 1995-02-10 2000-02-01 Ciba Specialty Chemicals Corporation Synergistic stabilizer mixture

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4619956A (en) * 1985-05-03 1986-10-28 American Cyanamid Co. Stabilization of high solids coatings with synergistic combinations
IT1243719B (en) 1990-09-18 1994-06-21 Enichem Sintesi STABILIZING MIXTURE FOR PHOTOCROMATIC ACTIVITY COMPOUNDS
CA2127334A1 (en) * 1993-07-02 1995-01-03 Edward A. Bourbonais Synergistic combination of uv light stabilizers for use with organic polymers
GB9607565D0 (en) 1996-04-12 1996-06-12 Clariant Int Ltd Stabilizer composition
GB2354245B (en) 1996-08-22 2001-04-25 Ciba Sc Holding Ag Stabilizer mixtures for polyolefins
JPH10182874A (en) * 1996-12-24 1998-07-07 Ube Ind Ltd Polyamide resin composition
DE19735255B4 (en) * 1997-08-14 2007-08-23 Clariant Produkte (Deutschland) Gmbh Synergistic stabilizer mixture based on polyalkyl-1-oxa-diazaspirodecane compounds and its use
IT1302265B1 (en) * 1998-09-25 2000-09-05 Great Lakes Chemical Italia SYNERGIC STABILIZING MIXTURES

Patent Citations (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3640928A (en) * 1968-06-12 1972-02-08 Sankyo Co Stabilization of synthetic polymers
US4198334A (en) * 1975-11-07 1980-04-15 Ciba-Geigy Corporation Substituted malonic acid derivatives and their use as stabilizers
US4110306A (en) * 1975-12-01 1978-08-29 Argus Chemical Corporation Stabilizers for synthetic polymers comprising 2,2,6,6-tetramethyl-4-piperidyl carboxylic acid ester, a triphosphite, and an acid phosphite or salt thereof
US4233412A (en) * 1976-05-11 1980-11-11 Ciba-Geigy Corporation Polymeric light stabilizers for plastics
US4292240A (en) * 1977-09-21 1981-09-29 The B. F. Goodrich Company 2-Keto-1,4-diazacycloalkanes
US4340534A (en) * 1979-10-10 1982-07-20 Hoechst Aktiengesellschaft Ethers based on polyalkyl-1-oxadiazaspirodecanes
US4356307A (en) * 1980-02-20 1982-10-26 Chemische Werke Huls Aktiengesellschaft Cyclic imides, their preparation and use
US4408051A (en) * 1980-12-24 1983-10-04 Sandoz Ltd. 1-Oxa-3,8-diazaspiro[4.5]decanes
US4692486A (en) * 1981-10-16 1987-09-08 Ciba-Geigy Corporation Synergistic mixture of low-molecular and high-molecular polyalkylpiperidines
US4547538A (en) * 1982-02-19 1985-10-15 The B. F. Goodrich Company Alkylated polyalkylenepolyamines, substituted oxo-piperazinyl-triazines and UV light stabilized compositions
US4619958A (en) * 1982-10-02 1986-10-28 Adeka Argus Chemical Co., Ltd. Mixed 2,2,6,6-tetramethyl piperidinyl carboxylic acid ester and amide light stabilizers and stabilized synthetic polymers
US5049604A (en) * 1984-07-24 1991-09-17 Sumitomo Chemical Company, Limited Process for producing piperidine derivative and stabilized resin composition containing said derivative
US4965301A (en) * 1984-12-03 1990-10-23 Phillips Petroleum Company Stabilization of polyolefins
US4689416A (en) * 1985-07-10 1987-08-25 Hoechst Aktiengellschaft Process for the preparation of 1-oxa-3,8-diaza-4-oxo-spiro(4.5)decane compounds
US4769457A (en) * 1985-08-28 1988-09-06 Basf Aktiengesellschaft Glycoluril derivatives and their use as stabilizers for polymers
US4863981A (en) * 1986-06-30 1989-09-05 Ciba-Geigy Corporation Synergistic mixture of stabilizers
US5204473A (en) * 1987-09-21 1993-04-20 Ciba-Geigy Corporation O-substituted N-hydroxy hindered amine stabilizers
US4976889A (en) * 1987-11-14 1990-12-11 Basf Aktiengesellschaft 4-formylaminopiperidine derivatives, their use as stabilizers and organic material stabilized with the said derivatives
US5051458A (en) * 1988-05-27 1991-09-24 Enichem Synthesis S.P.A. UV stabilizers for organic polymers
US5026849A (en) * 1989-06-09 1991-06-25 The B. F. Goodrich Company Solventless process for preparing a tri-substituted triazine
US5071981A (en) * 1990-03-19 1991-12-10 The B. F. Goodrich Company Alkylated oxo-piperanzinyl-triazine
US5182390A (en) * 1990-10-29 1993-01-26 Kyodo Chemical Company Limited Isocyanuric acid derivative useful as a light stabilizer
US5679733A (en) * 1992-06-02 1997-10-21 Clariant Finance (Bvi) Limited Solid Solution of low molecular weight and high molecular weight hals
US5719217A (en) * 1994-10-28 1998-02-17 Ciba Specialty Chemicals Corporation Synergistic stabiliser mixture
US6015849A (en) * 1995-01-23 2000-01-18 Ciba Specialty Chemicals Corporation Synergistic stabilizer mixture
US6020406A (en) * 1995-02-10 2000-02-01 Ciba Specialty Chemicals Corporation Synergistic stabilizer mixture
US5980783A (en) * 1995-04-11 1999-11-09 Ciba Specialty Chemicals Corporation Synergistic stabilizer mixture
US5965643A (en) * 1995-05-03 1999-10-12 Ciba Specialty Chemicals Corporation Synergistic stabilizer mixture
US5919399A (en) * 1995-07-21 1999-07-06 Ciba Specialty Chemicals Corporation Synergistic stabilizer mixture

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060124904A1 (en) * 2002-04-12 2006-06-15 Francois Gugumus Stabilizer mixtures
US7595008B2 (en) 2002-04-12 2009-09-29 Ciba Specialty Chemicals Corporation Stabilizer mixtures
EP1564253A1 (en) * 2004-02-17 2005-08-17 DSM IP Assets B.V. Unsaturated polyester resins or vinyl ester resin compositions
EP1564254A1 (en) * 2004-02-17 2005-08-17 DSM IP Assets B.V. Unsaturated polyester resing or vinyl ester resin compositions
WO2005078019A1 (en) * 2004-02-17 2005-08-25 Dsm Ip Assets B.V. Unsaturated polyester resins or vinyl ester resin compositions
WO2005078020A1 (en) * 2004-02-17 2005-08-25 Dsm Ip Assets B.V. Unsaturated polyester resins or vinyl resin compositions
US9062143B2 (en) 2008-02-08 2015-06-23 Dow Global Technologies Llc Water-redispersible polymer powder
US8366822B2 (en) 2011-06-20 2013-02-05 Dow Global Technologies Llc Cementitious tile adhesives and method of applying the same to a tile substrate
US20170306133A1 (en) * 2014-12-02 2017-10-26 Nuc Corporation Crosslinkable resin composition and electric wire/cable
WO2018013181A1 (en) 2016-07-13 2018-01-18 Chevron Oronite Company Llc Synergistic lubricating oil composition containing mixture of antioxidants
US10077410B2 (en) 2016-07-13 2018-09-18 Chevron Oronite Company Llc Synergistic lubricating oil composition containing mixture of antioxidants

Also Published As

Publication number Publication date
BR0111290B1 (en) 2011-12-13
US20050143500A1 (en) 2005-06-30
AU6601001A (en) 2001-12-11
MXPA02011696A (en) 2003-03-27
GB2378950B (en) 2004-04-21
GB2378950A (en) 2003-02-26
JP2003535172A (en) 2003-11-25
WO2001092398A2 (en) 2001-12-06
ES2199696A1 (en) 2004-02-16
AU2001266010B2 (en) 2006-06-08
NL1018186C2 (en) 2002-08-06
IT1324894B (en) 2004-12-02
US20060270764A1 (en) 2006-11-30
KR100786239B1 (en) 2007-12-17
GB0228142D0 (en) 2003-01-08
AU2001266010C1 (en) 2001-12-11
ITMI20011135A1 (en) 2002-11-29
BE1014207A3 (en) 2003-06-03
US20090105379A1 (en) 2009-04-23
CN1432041A (en) 2003-07-23
WO2001092398A3 (en) 2002-05-16
FR2809740A1 (en) 2001-12-07
US7820744B2 (en) 2010-10-26
US20100048774A1 (en) 2010-02-25
CA2408093A1 (en) 2001-12-06
ITMI20011135A0 (en) 2001-05-29
FR2809740B1 (en) 2007-02-16
JP5498638B2 (en) 2014-05-21
CN1235958C (en) 2006-01-11
BR0111290A (en) 2003-06-10
ES2199696B1 (en) 2005-03-01
KR20030007683A (en) 2003-01-23
DE10196264T1 (en) 2003-05-15
NL1018186A1 (en) 2001-12-03
MX286036B (en) 2011-04-26

Similar Documents

Publication Publication Date Title
US7820744B2 (en) Stabilizer mixtures
EP1367091B1 (en) Agricultural articles
US7628936B2 (en) Stabilizer mixtures
EP1979406B1 (en) Stabilizer composition for polymers
US6916867B2 (en) Synergistic mixtures of UV-absorbers in polyolefins
US7652081B2 (en) Stabilizer mixtures
US6365651B1 (en) Synergistic stabilizer mixture
US6380286B1 (en) Synergistic stabilizer mixture
US20090111917A1 (en) Stabilized articles
US6545071B1 (en) Stabilizer mixtures
KR20090093983A (en) Multifilament, monofilament, non-woven or tape
US6566427B1 (en) Stabilizer mixtures
AU2001266010A1 (en) Stabilizer mixtures
US6441166B1 (en) Sterically hindered amine compounds
US6328912B1 (en) Tetramethylpiperidyl-containing polysiloxane or polyamine/cyanuric cl/tetramethyl-4-piperidylamine stabilizer
US6403680B1 (en) Block oligomers containing 1-hydrocarbyloxy-2,2,6,6-tetramethyl-4-piperidyl groups as stabilizers for organic materials

Legal Events

Date Code Title Description
AS Assignment

Owner name: CIBA SPECIALTY CHEMICALS CORP., NEW YORK

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:GUGUMUS, FRANCOIS;REEL/FRAME:013994/0796

Effective date: 20020916

STCB Information on status: application discontinuation

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