Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
  • C08K5/3432—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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K2201/00—Specific properties of additives
  • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K

Definitions

• the present invention relates to a stabilizer mixture containing three specific sterically hindered amine compounds, to the use of said mixture for stabilizing an organic material against degradation induced by light, heat or oxidation, and to the material thus stabilized.
• 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. 5,977,221, U.S. Pat. No. 5,980,783, U.S. Pat. No. 6,015,849, U.S. Pat. No. 6,020,406, U.S. Pat. No. 6,174,940, U.S. Pat. No. 6,306,939, EP-A-1,038,912, WO-A-98/51690, WO-A-99/02495, WO-A-01/92392 and WO-A-01/92398.
• the present invention relates in particular to
• a stabilizer mixture containing the components (I), (II) and (III) wherein component (I) is a compound of the formula (B-1), (B-2), (B-4), (B-5), (B-7), (B-8), (B-9) or (B-10),
• component (II) is a compound of the formula (B-0), (B-3) or (B-6), and
• component (III) is a compound of the formula (C-1), (C-2), (C-3), (C-4) or (C-5) or a product (C-6);
• E 1 * has one of the meanings of E 1 .
• E 2 * is C 1 -C 25 alkyl
• 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 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, and if ml is 4, 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
• 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 ;
• the radicals E 23 independently of one another have one of the meanings of E 1 , and 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 when m 2 is 1, E 26 is a group
• 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);
• R 1 , R 3 , R 4 and R 5 independently of one another are hydrogen, C 1 -C 12 alkyl, C 5 -C 12 cycloalkyl, C 1 -C 4 -alkyl-substituted C 5 -C 12 cycloalkyl, phenyl, phenyl which is substituted by —OH and/or C 1 -C 10 alkyl; C 7 -C 9 phenylalkyl, C 7 -C 9 phenylalkyl which is substituted on the phenyl radical by —OH and/or C 1 -C 10 alkyl; or a group of the formula (c-I)
• R 2 is C 2 -C 18 alkylene, C 5 -C 7 cycloalkylene or C 1 -C 4 alkylenedi(C 5 -C 7 cycloalkylene), or
• radicals R 1 , R 2 and R 3 together with the nitrogen atoms to which they are bonded, perform a 5- to 10-membered heterocyclic ring, or
• R 4 and R 5 together with the nitrogen atom to which they are bonded, form a 5- to 10-membered heterocyclic ring,
• R 6 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, and
• b 1 is a number from 2 to 50
• R 7 and R 11 independently of one another are hydrogen or C 1 -C 12 alkyl
• R 8 , R 9 and R 10 independently of one another are C 2 -C 10 alkylene, and
• X 1 , X 2 , X 3 , X 4 , X 5 , X 6 , X 7 and X 8 independently of one another are a group of the formula (c-II),
• R 12 is hydrogen, C 1 -C 12 alkyl, C 5 -C 12 cycloalkyl, C 1 -C 4 alkyl-substituted C 5 -C 12 cycloalkyl, phenyl, —OH— and/or C 1 -C 10 alkyl-substituted phenyl, C 7 -C 9 phenylalkyl, C 7 -C 9 phenylalkyl which is substituted on the phenyl radical by —OH and/or C 1 -C 10 alkyl; or a group of the formula (c-I) as defined above, and
• R 13 has one of the meanings of R 6 ;
• R 14 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,
• R 15 is C 3 -C 10 alkylene
• R 16 has one of the meanings of R 6 .
• b 2 is a number from 2 to 50;
• R 17 and R 21 independently of one another are a direct bond or a —N(X 9 )—CO—X 10 —CO—N(X 11 )— group, where X 9 and X 11 independently of one another are hydrogen, C 1 -C 8 alkyl, C 5 -C 12 cycloalkyl, phenyl, C 7 -C 9 phenylalkyl or a group of the formula (c-I),
• X 10 is a direct bond or C 1 -C 4 alkylene
• R 18 has one of the meanings of R 6 .
• R 19 , R 20 , R 23 and R 24 independently of one another are hydrogen, C 1 -C 30 alkyl, C 5 -C 12 cycloalkyl or phenyl,
• R 22 is hydrogen, C 1 -C 30 alkyl, C 5 -C 12 cycloalkyl, phenyl, C 7 -C 9 phenylalkyl or a group of the formula (c-I), and
• b 3 is a number from 1 to 50;
• R 25 , R 26 , R 27 , R 28 and R 29 independently of one another are a direct bond or
• R 30 has one of the meanings of R 6 .
• b 4 is a number from 1 to 50;
• a product (C-6) obtainable by reacting a product, obtained by reaction of a polyamine of the formula (C-6-1) with cyanuric chloride, with a compound of the formula (C-6-2)
• b′ 5 , b′′ 5 and b′′′ 5 independently of one another are a number from 2 to 12,
• R 31 is hydrogen, C 1 -C 12 alkyl, C 5 -C 12 cycloalkyl, phenyl or C 7 -C 9 phenylalkyl, and
• R 32 has one of the meanings of R 6 .
• alkyl having up to 30 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
• E 1 , E 1 *, E 8 , E 12 , E 13 , E 16 , E 18 , E 22 , E 23 , E 25 , E 29 , R 6 , R 13 , R 16 , R 18 , R 30 and R 32 is C 1 -C 4 alkyl, especially methyl.
• R 31 is preferably butyl.
• 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 and one of the preferred meanings of R 6 is propoxy.
• 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.
• —OH— and/or C 1 -C 10 alkyl-substituted phenyl is for example methylphenyl, dimethylphenyl, trimethylphenyl, tert-butylphenyl or 3,5-di-tert-butyl-4-hydroxyphenyl.
• C 7 -C 9 phenylalkyl examples are benzyl and phenylethyl.
• C 7 -C 9 Phenylalkyl which is substituted on the phenyl radical by —OH and/or by alkyl having up to 10 carbon atoms is for example methylbenzyl, dimethylbenzyl, trimethylbenzyl, tert-butylbenzyl or 3,5-di-tert-butyl-4-hydroxybenzyl.
• 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.
• a 6-membered heterocyclic ring is preferred.
• radicals R 4 and R 5 together with the nitrogen atom to which they are attached, form a 5- to 10-membered heterocyclic ring
• this ring is for example 1-pyrrolidyl, piperidino, morpholino, 1-piperazinyl, 4-methyl-1-piperazinyl, 1-hexahydroazepinyl, 5,5,7-trimethyl-1-homopiperazinyl or 4,5,5,7-tetramethyl-1-homopiperazinyl.
• Morpholino is particularly preferred.
• R 19 and R 23 are phenyl.
• R 26 is preferably a direct bond.
• 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 or 2 to 20.
• b 1 and b 2 are preferably a number from 2 to 25, in particular 2 to 20.
• b 3 and b 4 are preferably a number from 1 to 25, in particluar 1 to 20 or 2 to 20.
• b′ 5 and b′′′ 5 are preferably 3 and b′′ 5 is preferably 2.
• the product (C-6) can be prepared analogously to known processes, for example by reacting a polyamine of formula (C-6-1) with cyanuric chloride in a molar ratio of from 1:2 to 1:4 in the presence of anhydrous lithium carbonate, sodium carbonate or potassium carbonate in an organic solvent such as 1,2-dichloroethane, toluene, xylene, benzene, dioxane or tert-amyl alcohol at a temperature of from ⁇ 20° C. to +10° C., preferably from ⁇ 10° C. to +10° C., in particular from 0° C.
• an organic solvent such as 1,2-dichloroethane, toluene, xylene, benzene, dioxane or tert-amyl alcohol
• the molar ratio of the 2,2,6,6-tetramethyl-4-piperidylamine to polyamine of the formula (C-6-1) employed is for example from 4:1 to 8:1.
• the quantity of the 2,2,6,6-tetramethyl-4-piperidylamine can be added in one portion or in more than one portion at intervals of a few hours.
• the molar ratio of polyamine of the formula (C-6-1) to cyanuric chloride to 2,2,6,6-tetramethyl-4-piperidylamine of the formula (C-6-2) is preferably from 1:3:5 to 1:3:6,
• a further 18 g (0.13 mol) of anhydrous potassium carbonate are added and the mixture is warmed at 60° C. for a further 6 hours.
• the solvent is removed by distillation under a slight vacuum (200 mbar) and replaced by xylene.
• 18.2 g (0.085 mol) of N-(2,2,6,6-tetramethyl-4-piperidyl)butylamine and 5.2 g (0.13 mol) of ground sodium hydroxide are added, the mixture is heated at reflux for 2 hours and, for a further 12 hours, the water formed during the reaction is removed by azeotropic distillation.
• the mixture is filtered.
• the solution is washed with water and dried over Na 2 SO 4 .
• the solvent is evaporated and the residue is dried at 120-130° C. in vacuo (0.1 mbar).
• the desired product is obtained as a colourless resin.
• the product (C-6) can for example be represented by a compound of the formula (C-6- ⁇ ), (C-6- ⁇ ) or (C-6- ⁇ ). It can also be in the form of a mixture of these three compounds.
• b 5 is preferably 2 to 20, in particular 2 to 10.
• Component (I) is preferably 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), 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) or UVINUL 4050H (RTM), in particular TINUVIN 770 (RTM), TINUVIN 765 (RTM), TINUVIN 144 (RTM), TINUVIN 123 (RTM), DIACETAM 5 (RTM), SUMISORB TM 61 (RTM), UVINUL 4049
• RTM LICOVIN 845
• HOSTAVIN N 20 RTM
• HOSTAVIN N 24 RTM
• SANDUVOR 3050 RTM
• Component (III) is preferably CHIMASSORB 944 (RTM), CHIMASSORB 2020 (RTM), CYASORB UV 3346 (RTM), CYASORB UV 3529 (RTM), DASTIB 1082 (RTM), CHIMASSORB 119 (RTM), UVASIL 299 (RTM), UVASIL 125 (RTM), UVASIL 2000 (RTM), UVINUL 5050H (RTM), LICHTSCHUTZSTOFF UV 31 (RTM), LUCHEM HA B 18 (RTM), ADK STAB LA 63 (RTM), ADK STAB LA 68 (RTM) or UVASORB HA 88 (RTM).
• terminal groups which saturate the free valences in the compounds of the formulae (C-1), (C-3), (C-4), (C-5), (C-6- ⁇ ), (C-6- ⁇ ) and (C-6- ⁇ ) depend on the processes used for their preparation.
• the terminal groups can also be modified after the preparation of the compounds.
• X is halogen, it is advantageous to replace this, for example, by —OH or an amino group when the reaction is complete.
• amino groups which may be mentioned are pyrrolidin-1-yl, morpholino, —NH 2 , —N(C 1 -C 8 )alkyl) 2 and —NR(C 1 -C 8 alkyl), in which R is hydrogen or a group of the formula (c-I).
• R 1 , R 2 , R 3 , R 4 , R 5 and b 1 are as defined above and R 4 * has one of the meanings of R 4 and R 5 * has one of the meanings of R 5 .
• the terminal group bonded to the silicon atom can be, for example, (R 14 ) 3 Si—O—, and the terminal group bonded to the oxygen can be, for example, —Si(R 14 ) 3
• the compounds of the formula (C-3) can also be in the form of cyclic compounds if b 2 is a number from 3 to 10, i.e. the free valences shown in the structural formula then form a direct bond.
• the terminal group bonded to the 2,5-dioxopyrrolidine ring is, for example, hydrogen
• the terminal group bonded to the —C(R 23 )(R 24 )— radical is, for example,
• the terminal group bonded to the carbonyl radical is, for example,
• the terminal group bonded to the triazine radical is, for example, Cl or a
• group, and the terminal group bonded to the amino radical is, for example, hydrogen or a
• E 1 , E 1 *, E 8 , E 12 , E 13 , E 16 , E 18 , E 22 , E 23 , E 25 and E 29 are preferably hydrogen, C 1 -C 4 alkyl, C 1 -C 10 alkoxy, cyclohexyloxy, allyl, benzyl or acetyl.
• R 6 , R 13 , R 16 , R 18 , R 30 and R 32 are preferably hydrogen, C 1 -C 4 alkyl, C 1 -C 10 alkoxy, cyclohexyloxy, allyl, benzyl or acetyl.
• E 1 , E 1 *, E 8 , E 12 , E 13 , E 16 , E 18 , E 22 , E 23 , E 25 , E 29 , R 6 , R 13 , R 16 , R 18 , R 30 and R 32 are in particular hydrogen or methyl and E 1 and R 6 additionally are C 1 -C 8 alkoxy.
• m 1 is 2 or 4
• E 2 * is C 12 -C 20 alkyl
• 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.
• R 1 and R 3 independently of one another are a group of the formula (c-I),
• R 2 is C 2 -C 8 alkylene
• R 4 and R 5 independently of one another are hydrogen, C 1 -C 12 alkyl, C 5 -C 8 cycloalkyl or a group of the formula (c-I), or the radicals R 4 and R 5 , together with the nitrogen atom to which they are bonded, form a 5- to 10-membered heterocyclic ring, and
• b 1 is a number from 2 to 25;
• R 7 and R 11 independently of one another are hydrogen or C 1 -C 4 alkyl
• R 8 , R 9 and R 10 independently of one another are C 2 -C 4 alkylene, and
• X 1 , X 2 , X 3 , X 4 , X 5 , X 6 , X 7 and X 8 independently of one another are a group of the formula (c-II),
• R 12 is hydrogen, C 1 -C 4 alkyl, C 5 -C 8 cycloalkyl or a group of the formula (c-I);
• R 14 is C 1 -C 4 alkyl
• R 15 is C 3 -C 6 alkylene
• b 2 is a number from 2 to 25;
• R 17 and R 21 independently of one another are a direct bond or a group —N(X 9 )—CO—X 10 —CO—N(X 11 )—,
• X 9 and X 11 independently of one another are hydrogen or C 1 -C 4 alkyl
• X 10 is a direct bond
• R 19 and R 23 are C 1 -C 25 alkyl or phenyl
• R 20 and R 24 are hydrogen or C 1 -C 4 alkyl
• R 22 is C 1 -C 25 alkyl or a group of the formula (c-I), and
• b 3 is a number from 1 to 25;
• R 25 , R 26 , R 27 , R 28 and R 29 independently of one another are a direct bond or C 1 -C 4 alkylene, and
• b 4 is a number from 1 to 25;
• b′ 5 , b′′ 5 and b′′′ 5 independently of one another are a number from 2 to 4, and
• R 31 is hydrogen, C 1 -C 4 alkyl, C 5 -C 8 cycloalkyl, phenyl or benzyl.
• component (I) is a compound of the formula (B-1-b), (B-1-c), (B-1-d), (B-2-a), (B-4-a), (B-4-b), (B-5), (B-7), (B-8-a), (B-9-a), (B-9-b), (B-9-c) or (B-10-a);
• component (II) is a compound of the formula (B-0-a), (B-3-a), (B-3-b) or (B-6-a);
• component (III) is a compound of the formula (C-1-a), (C-1-b), (C-1-c), (C-1-d), (C-2-a), (C-3-a), (C-4-a), (C-4-b), (C-4-c) or (C-5-a) or a product (C-6-a);
• E 1 and E 1 * are 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 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 ;
• b 1 is a number from 2 to 20 and R 6 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;
• R 13 has one of the meanings of R 6 .
• a product (C-6-a) obtainable by reacting a product, obtained by reaction of a polyamine of the formula (C-6-1-a) with cyanuric chloride, with a compound of the formula (C-6-2-a)
• R 32 has one of the meanings of R 6 .
• Component (II) is preferably a compound of the formula (B-0).
• Stabilizer mixtures of interest are those wherein
• component (I) is a compound of the formula (B-1), (B-4), (B-5), (B-8), (B-9) or (B-10)
• component (II) is a compound of the formula (B-0), (B-3) or (B-6)
• component (III) is a compound of the formula (C-1), (C-2), (C-3), (C-4) or (C-5) or a product (C-6).
• Stabilizer mixtures of particular interest are those wherein component (I) is a compound of the formula (B-1-b), (B-1-c), (B-4-a), (B-4-b), (B-5), (B-8-a), (B-9-b) or (B-10-a);
• component (II) is a compound of the formula (B-0-a), (B-3-a), (B-3-b) or (B-6-a);
• component (III) is a compound of the formula (C-1-a), (C-1-b), (C-1-c), (C-1-d), (C-2-a), (C-3-a), (C-4-a), (C-4-b), (C-4-c) or (C-5-a) or a product (C-6-a).
• component (I) is a compound of the formula (B-1-b) wherein E 1 is hydrogen or methyl and component (II) is a compound of the formula (B-0-a) wherein E 1 * is hydrogen.
• component (I) is a compound of the formula (B-1-b) wherein E 1 is hydrogen or methyl
• component (II) is a compound of the formula (B-0-a) wherein E 1 * is hydrogen
• component (III) is a compound of the formula (C-1-a), (C-1-b) or (C-1-d) wherein R 6 is hydrogen or methyl.
• component (I) is a compound of the formula (B-1-b) wherein E 1 is hydrogen
• component (II) is a compound of the formula (B-0-a) wherein E 1 * is hydrogen
• component (III) is a compound of the formula (C-1-a) wherein R 6 is hydrogen.
• component (I) is a compound of the formula (B-1-b) wherein E 1 is methyl
• component (II) is a compound of the formula (B-6-a) wherein E 18 is methyl
• component (Ill) is a compound of the formula (C-1-d) wherein R 6 is methyl
• component (C-2-a) wherein R 13 is methyl
• R 30 is methyl
• Examples of stabilizer mixtures according to the present invention are the following combinations of commercial products:
• Particularly preferred stabilizer mixtures are Nos. 1 to 11.
• Compound (B-6-a-I) is the compound of the formula (B-6-a) wherein E 18 is methyl.
• 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.
• the commercial product LICOVIN 845 corresponds to the compound of the formula (B-0-a) wherein E 1 * is hydrogen.
• CHIMASSORB 944 corresponds to the compound of the formula (C-1-a) wherein R 6 is hydrogen.
• CHIMASSORB 119 corresponds to the compound of the formula (C-2-a) wherein R 13 is methyl.
• CHIMASSORB 2020 corresponds to the compound of the formula (C-1-b) wherein R 6 is hydrogen.
• RTM The commercial product DASTIB 1082 (RTM) corresponds to the compound of the formula (C-1-c) wherein R 6 is hydrogen.
• UVASIL 299 corresponds to the compound of the formula (C-3-a) wherein R 16 is hydrogen.
• UVASORB HA 88 corresponds in particular to the compound of the formula (C-6- ⁇ -I).
• UVINUL 5050H corresponds to the compound of the formula (C-4-a) wherein R 18 is hydrogen.
• the commercial product ADK STAB LA 63 corresponds to the compound of the formula (C-5-a) wherein R 30 is methyl.
• RTM The commercial product ADK STAB LA 68 (RTM) corresponds to the compound of the formula (C-5-a) wherein R 30 is hydrogen.
• the commercial product LICHTSCHUTZSTOFF UV 31 corresponds to the compound of the formula (C-4-b) wherein R 18 is hydrogen.
• LUCHEM HA B 18 corresponds to the compound of the formula (C-4-c) wherein R 18 is hydrogen.
• a further preferred embodiment of this invention relates to a stabilizer mixture containing additionally
• the pigment (component (X-1)) may be an inorganic or organic pigment.
• inorganic pigments are titanium dioxide, zinc oxide, carbon black, cadmium sulfide, cadmium selenide, chromium oxide, iron oxide, lead oxide and so on.
• organic pigments examples include azo pigments, anthraquinones, phthalocyanines, tetrachloroisoindolinones, quinacridones, isoindolines, perylenes, pyrrolopyrroles (such as Pigment Red 254) and so on.
• a particularly preferred pigment is titanium dioxide, optionally in combination with an organic pigment.
• UV absorber examples include a 2-(2′-hydroxyphenyl)benzotriazole, a 2-hydroxybenzophenone, an ester of substituted or unsubstituted benzoic acid, an acrylate, an oxamide, a 2-(2-hydroxyphenyl)-1,3,5-triazine, a monobenzoate of resorcinol or a formamidine.
• the 2-(2′-hydroxyphenyl)benzotriazole is e.g. 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-chloro-benzotriazole, 2-(3′-tert-butyl-2′-hydroxy-5′-methylphenyl)-5-chloro-benzotriazole, 2-(3′-sec-butyl-5′-tert-butyl-2′-hydroxyphenyl)benzotriazole, 2-(2′-hydroxy-4′-octyl
• the 2-hydroxybenzophenone is for example the 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2′,4′-trihydroxy or 2′-hydroxy-4,4′-dimethoxy derivatives.
• 2-Hydroxy-4-octyloxybenzophenone is preferred.
• the ester of a substituted or unsubstituted benzoic acid is for example 4-tert-butyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis(4-tert-butylbenzoyl) resorcinol, benzoyl resorcinol, 2,4-di-tertbutylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate or 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.
• the acrylate is for example ethyl ⁇ -cyano- ⁇ , ⁇ -diphenylacrylate, isooctyl ⁇ -cyano- ⁇ , ⁇ -di-phenylacrylate, methyl ⁇ -carbomethoxycinnamate, methyl ⁇ -cyano- ⁇ -methyl-p-methoxy-cinnamate, butyl ⁇ -cyano- ⁇ -methyl- ⁇ -methoxy-cinnamate, methyl ⁇ -carbomethoxy-p-methoxycinnamate or N-( ⁇ -carbomethoxy- ⁇ -cyanovinyl)-2-methylindoline.
• the oxamide is 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 or its mixture with 2-ethoxy-2′-ethyl-5,4′-di-tert-butoxanilide or mixtures of ortho- and para-methoxy—disubstituted oxanilides or mixtures of o- and p-ethoxy-disubstituted oxanilides.
• the 2-(2-hydroxyphenyl)-1,3,5-triazine is 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
• the monobenzoate of resorcinol is for example the compound of the formula
• the formamidine is for example the compound of the formula
• the UV absorber is in particular a 2-(2′-hydroxyphenyl)benzotriazole, a 2-hydroxybenzophenone or a hydroxyphenyltriazine.
• a further preferred embodiment of this invention relates to a stabilizer mixture which additionally contains as a further component (XX) an organic salt of Ca, an inorganic salt of Ca, Ca oxide or Ca hydroxide.
• XX an organic salt of Ca
• an organic salt of Ca are Ca-stearate, Ca-laurate, Ca-lactate and Ca-stearoyl-lactate.
• Examples of an inorganic salt of Ca are CaCO 3 , CaCl 2 , CaF 2 , Ca 3 (PO 4 ) 2 , CaHPO 4 , Ca(PO 3 ) 2 , Ca 2 P 2 O 7 , CaSO 4 and CaSio 3 .
• 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, polyvinylcyclohexane, 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
• Polyolefins i.e. the polymers of monoolefins exemplified in the preceding paragraph, preferably polyethylene and polypropylene, can be prepared by different, and especially by the following, methods:
• a catalyst that normally contains one or more than one metal of groups IVb, Vb, VIb or VIII of the Periodic Table.
• These metals usually have one or more than one ligand, typically oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls that may be either ⁇ - or ⁇ -coordinated.
• These metal complexes may be in the free form or fixed on substrates, typically on activated magnesium chloride, titanium(III) chloride, alumina or silicon oxide.
• These catalysts may be soluble or insoluble in the polymerisation medium.
• the catalysts can be used by themselves in the polymerisation or further activators may be used, typically metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes, said metals being elements of groups Ia, IIa and/or IIIa of the Periodic Table.
• the activators may be modified conveniently with further ester, ether, amine or silyl ether groups.
• These catalyst systems are usually termed Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC).
• Copolymers of monoolefins and diolefins with each other or with other vinyl monomers for example ethylene/propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene/but-1-ene copolymers, propylene/isobutylene copolymers, ethylene/but-1-ene copolymers, ethylene/hexene copolymers, ethylene/methylpentene copolymers, ethylene/heptene copolymers, ethylene/octene copolymers, ethylene/vinylcyclohexane copolymers, ethylene/cycloolefin copolymers (e.g.
• ethylene/norbornene like COC ethylene/1-olefins copolymers, where the 1-olefin is generated in-situ; propylene/butadiene copolymers, isobutylene/isoprene copolymers, ethylene/vinylcyclohexene copolymers, ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylate copolymers, ethylene/vinyl acetate copolymers 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 copoly
• Hydrocarbon resins for example C 5 -C 9
• hydrogenated modifications thereof e.g. tackifiers
• mixtures of polyalkylenes and starch
• Homopolymers and copolymers from 1.) -4.) may have any stereostructure including syndiotactic, isotactic, hemi-isotactic or atactic; where atactic polymers are preferred. Stereoblock polymers are also included.
• Homopolymers and copolymers may have any stereostructure including syndiotactic, isotactic, hemi-isotactic or atactic; where atactic polymers are preferred. Stereoblock polymers are also included.
• Copolymers including aforementioned vinyl aromatic monomers and comonomers selected from ethylene, propylene, dienes, nitriles, acids, maleic anhydrides, maleimides, vinyl acetate and vinyl chloride or acrylic derivatives and mixtures thereof, for example styrene/butadiene, styrene/acrylonitrile, styrene/ethylene (interpolymers), 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 copoly
• 6b Hydrogenated aromatic polymers derived from hydrogenation of polymers mentioned under 6.), especially including polycyclohexylethylene (PCHE) prepared by hydrogenating atactic polystyrene, often referred to as polyvinylcyclohexane (PVCH).
• PCHE polycyclohexylethylene
• PVCH polyvinylcyclohexane
• Homopolymers and copolymers may have any stereostructure including syndiotactic, isotactic, hemi-isotactic or atactic; where atactic polymers are preferred. Stereoblock polymers are also included.
• Halogen-containing polymers such as polychloroprene, chlorinated rubbers, chlorinated and brominated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated or sulfochlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers, especially polymers of halogen-containing vinyl compounds, for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, as well as copolymers thereof such as vinyl chloride/vinylidene chloride, vinyl chloride/vinyl acetate or vinylidene chloride/vinyl acetate copolymers.
• halogen-containing polymers such as polychloroprene, chlorinated rubbers, chlorinated and brominated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated
• Copolymers of the monomers mentioned under 9) with each other or with other unsaturated monomers for example acrylonitrile/butadiene copolymers, acrylonitrile/alkyl acrylate copolymers, acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halide copolymers or acrylonitrile/alkyl methacrylate/butadiene terpolymers.
• Polymers derived from unsaturated alcohols and amines or the acyl derivatives or acetals thereof for example polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well as their copolymers with olefins mentioned in 1) above.
• Polyacetals such as polyoxymethylene and those polyoxymethylenes which contain ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.
• Polyamides and copolyamides derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides starting from m-xylene diamine and adipic acid; polyamides prepared from hexamethylenediamine and isophthalic or/and terephthalic acid and with or without an elastomer as modifier, for example poly-2,4,4,-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide; and also block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, e.g. with polyethylene glycol, polypropylene glycol or polytet
• Polyesters derived from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or the corresponding lactones for example polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylolcyclohexane terephthalate, 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, POMWMBS, 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, POMWMBS, P
• 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.
• Another embodiment of the present invention is a composition comprising an organic material subject to degradation induced by light, heat or oxidation and the stabilizer mixture described above, as well as the method for stabilizing the organic material.
• 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 or a polypropylene copolymer are particularly preferred.
• components (I), (II) and (III) and optionally (X-1) and/or (X-2), as well as optionally component (XX) may be added to the organic material to be stabilized either individually or mixed with one another.
• Each of the components (I), (II) and (III) 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 (I):(II) or (I):(III) 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 components (I) plus (II):(III) is preferably 10:1 to 1:10 or 5:1 to 1:5 or 2:1 to 1:2.
• the pigment (component (X-1)) is optionally present in the organic material in an amount of preferably 0.01 to 10%, in particular 0.05 tol %, relative to the weight of the organic material.
• the UV absorber (component (X-2) is optionally present in the organic material in an amount of preferably 0.01 to 1%, in particular 0.05 to 0.5%, relative to the weight of the organic material.
• the total amount of component (X-3) (the pigment in combination with the UV absorber) is preferably 0.01 to 10%, relative to the weight of the organic material.
• the weight ratio of the UV absorber to the pigment is for example 2:1 to 1:10.
• titanium dioxide is preferably present in the organic material in an amount of 0.01 to 5%, relative to the weight of the organic material, and the organic pigment may be present in an amount of, for example, 0.01 to 2%, relative to the weight of the organic material.
• the Ca compound (component (XX)) is optionally present in the organic material in an amount of e.g. 0.005 to 1%, preferably 0.05 to 0.2%.
• the weight ratio of the sterically hindered amines (components (I), (II) and (III)):(X-1) is for example 1:10 to 10:1, preferably 1:5 to 5:1, in particular 1:2 to 2:1.
• the weight ratio of the sterically hindered amines:(X-2) is for example 1:20 to 20:1 or 1:20 to 10:1 or 1:10 to 10:1 or 1:5 to 5:1, preferably 1:2 to 2:1.
• the weight ratio of the sterically hindered amines:(X-3) is for example 1:10 to 10:1, preferably 1:5 to 5:1, in particular 1:2 to 2:1.
• the weight ratio of the sterically hindered amines:(XX) is for example 1:10 to 10:1, preferably 1:5 to 5:1, in particular 1:2 to 2:1.
• 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.
• components (I), (II) and (Ill) and optionally (X-1) and/or (X-2), as well as component (XX) 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 Plastics according to the Present Invention may be used for the Preparation of:
• I-1) Floating devices, marine applications, pontoons, buoys, plastic lumber for decks, piers, boats, kayaks, oars, and beach reinforcements.
• I-5) Devices for space applications, in particular rockets and satellites, e.g. reentry shields.
• I-6) Devices for architecture and design, mining applications, acoustic quietized systems, street refuges, and shelters.
• Electric appliances in particular washing machines, tumblers, ovens (microwave oven), dish-washers, mixers, and irons.
• III-1) Technical articles such as cogwheel (gear), slide fittings, spacers, screws, bolts, handles, and knobs.
• Hygienic articles in particular diapers (babies, adult incontinence), feminine hygiene articles, shower curtains, brushes, mats, tubs, mobile toilets, tooth brushes, and bed pans.
• III-8 Plates (walls, cutting board), extrusion-coating (photographic paper, tetrapack and pipe coating), silos, wood substitute, plastic lumber, wood composites, walls, surfaces, furniture, decorative foil, floor coverings (interior and exterior applications), flooring, duck boards, and tiles.
• IV-1) Plates (walls and cutting board), trays, artificial grass, astroturf, artificial covering for stadium rings (athletics), artificial floor for stadium rings (athletics), and tapes.
• IV-2) Woven fabrics continuous and staple, fibers (carpets/hygienic articles/geotextiles/monofilaments; filters; wipes/curtains (shades)/medical applications), bulk fibers (applications such as gown/protection clothes), nets, ropes, cables, strings, cords, threads, safety seat-belts, clothes, underwear, gloves; boots; rubber boots, intimate apparel, garments, swimwear, sportswear, umbrellas (parasol, sunshade), parachutes, paraglides, sails, “balloon-silk”, camping articles, tents, airbeds, sun beds, bulk bags, and bags.
• IV-3) Membranes, insulation, covers and seals for roofs, tunnels, dumps, ponds, dumps, walls roofing membranes, geomembranes, swimming pools, curtains (shades)/sun-shields, awnings, canopies, wallpaper, food packing and wrapping (flexible and solid), medical packaging (flexible & solid), airbags/safety belts, arm- and head rests, carpets, centre console, dashboard, cockpits, door, overhead console module, door trim, headliners, interior lighting, interior mirrors, parcel shelf, rear luggage cover, seats, steering column, steering wheel, textiles, and trunk trim.
• V) Films (packaging, dump, laminating, agriculture and horticulture, greenhouse, mulch, tunnel, silage), bale wrap, swimming pools, waste bags, wallpaper, stretch film, raffia, desalination film, batteries, and connectors.
• VI-2) Storage systems such as boxes (crates), luggage, chest, household boxes, pallets, shelves, tracks, screw boxes, packs, and cans.
• Extrusion coating photo paper, tetrapack, pipe coating
• household articles of any kind e.g. appliances, thermos bottle/clothes hanger
• fastening systems such as plugs, wire and cable clamps, zippers, closures, locks, and snap-closures.
• Footwear (shoes/shoe-soles), insoles, spats, adhesives, structural adhesives, food boxes (fruit, vegetables, meat, fish), synthetic paper, labels for bottles, couches, artificial joints (human), printing plates (flexographic), printed circuit boards, and display technologies.
• 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-dioctylthiomethyl-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.
• 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, didodecylmercaptoethyl-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.
• Aromatic hydroxybenzyl compounds for example 1,3,5-tris(3,5-di-tert-butyl-4-hydroxy-benzyl)-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, trimethylol propane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicycl
• 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 D-(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.
• mono- or polyhydric alcohols
• 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)-pphenylenediamine, N-isopropyl-N′-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N′-phenyl
• 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′-octyl
• 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,
• Sterically hindered amines for example bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)succinate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, linear or cyclic condensates of N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-tert-octyla
• 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, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,4-dicumylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythrito
• Tris(2,4-di-tert-butylphenyl) phosphite (Irgafos®168, Ciba-Geigy), tris(nonylphenyl) phosphite,
• Hydroxylamines for example N,N-dibenzylhydroxylamine, N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine, N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine, N-hexadecyl-N-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-heptyinitrone, N-lauryl-alpha-undecylnitrone, N-tetradecyl-alpha-tridecylnitrone, N-hexadecyl-alpha-pentadecyinitrone, N-octadecyl-alpha-heptadecyinitrone, N-hexadecyl-alpha-heptadecyinitrone, N-ocatadecyl-alpha-pentadecylnitrone, N-heptadecyl-alpha-hepta-decylnitrone, N-octadecyl-alpha-hexadecylnitrone, nitrone derived from N,
• Thiosynergists for example dilauryl thiodipropionate or distearyl thiodipropionate.
• Peroxide scavengers for example esters of O-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 O-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)
• 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
• Nucleating agents for example inorganic substances, such as talcum, metal oxides, such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of, preferably, alkaline earth metals; organic compounds, such as mono- or polycarboxylic acids and the salts thereof, e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymeric compounds, such as ionic copolymers (ionomers).
• inorganic substances such as talcum, metal oxides, such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of, preferably, alkaline earth metals
• organic compounds such as mono- or polycarboxylic acids and the salts thereof, e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate
• polymeric compounds such as ionic copolymers (
• Fillers and reinforcing agents for example calcium carbonate, silica, 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 (I), (II) and (III) and optionally (X-1) and/or (X-2) and optionally (XX) to the total amount of the conventional additives can be, for example, 100:1 to 1:1000 or 10:1 to 1:100 or 10:1 to 1:10.
• the material thus obtained is compression molded in a laboratory press between two aluminum foils for 6 min. 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 ⁇ 9° C., without water-spraying).

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