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    • 专利摘要:
    A) A1) one or more compounds of the formula (1) A2) at least one compound of one or more of the following formulas (3a) and (3b); B) organic salts of magnesium oxide, magnesium hydroxide, zinc oxide or zinc or magnesium; And C) C1) UV absorber or C2) pigment or C3) UV absorber and a pigment, wherein component B) is an organic salt of magnesium oxide, magnesium hydroxide or zinc or magnesium when the component A) is at least one compound of formula (3a) and (3b). In the formula, R 1 is for example hydrogen or C 1 -C 8 alkyl; R 2 , R 3 , R 5 and R 6 are, for example, hydrogen, C 1 -C 30 alkyl or phenyl; R 4 is, for example, C 1 -C 30 alkyl or 2,2,6,6-tetramethyl-4-piperidyl; And n < 1 > is a number from 1 to 50, n 2 and n 2 * are in the range of 2 to 50; The above stabilizer mixtures are particularly useful for stabilization against photo-induced degradation of polyolefins.
    公开号:KR19980018297A
    申请号:KR1019970036854
    申请日:1997-08-01
    公开日:1998-06-05
    发明作者:프랑소와즈 구구무스
    申请人:한스-피터 위트린；시바 스페셜티 케미칼스 홀딩 인코포레이티드；
    IPC主号:
    专利说明:

    Stabilizer mixture
    The present invention relates to a stabilizer mixture comprising A) any hindered amine compound, B) a magnesium compound or a zinc compound and C) a stabilizer mixture comprising a UV absorber and / or pigment, a stabilizer mixture of said stabilizer mixture for stabilizing the polyolefin from photo- And to polyolefins stabilized by the above method.
    Some stabilizer mixtures have already been described in the prior art such as US-A-4 929 652, US-A-5 037 870, EP-A-290 388, EP-A-468 923 and EP- Lt; / RTI >
    Although there are already many stabilizers, there is a need to further improve the optical stability of the polyolefin.
    More particularly,
    A)
    A1) one or more compounds of the formula (1)
    A2) one or more compounds of the formulas (3a) and (3b):
    B) organic salts of magnesium oxide, magnesium hydroxide, zinc oxide, zinc hydroxide or zinc or magnesium; And
    C)
    C1) UV absorber or
    C2) pigment or
    C3) UV absorber and a pigment, wherein component B) is an organic salt of magnesium oxide, magnesium hydroxide or zinc or magnesium when component A) is at least one compound of formula (3a) and (3b) will be.


    In the formula,
    R 1 is hydrogen, C 1 -C 8 alkyl, -O . , A -OH, C 1 -C 18 alkoxy, C 5 -C 12 cycloalkoxy, -CH 2 CN, C 3 -C 6 alkenyl, C 7 -C 9 phenylalkyl, C 1 -C 4 alkyl on the phenyl radical by a substituted C 7 -C 9 phenylalkyl; Or C 1 -C 4 acyl,
    R 2 , R 3 , R 5 and R 6 independently of one another are hydrogen, C 1 -C 30 alkyl, C 5 -C 12 cycloalkyl or phenyl,
    R 4 is hydrogen, C 1 -C 30 alkyl, C 5 -C 12 cycloalkyl, C 7 -C 9 phenylalkyl, phenyl or a group of formula (2)
    R 7 has one of the meanings of R 1
    n 1 is a number from 1 to 50,
    n 2 and n 2 * are in the range of 2 to 50;
    When most of component A) is at least one compound of formula (3a) and (3b), preferably component B) is an organic salt of zinc or magnesium.
    Examples of alkyl having up to 30 carbon atoms include methyl, ethyl, propyl, isopropyl, n-butyl, secondary butyl, tertiary butyl, 2-ethylbutyl, n-pentyl, Methylbutyl, 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, icosyl, docosyl and triacontyl. Preferred meanings of R 3 and R 6 are C 1 -C 4 alkyl, particularly preferably methyl. Preferred meanings of R 2 and R 5 are C 1 -C 25 alkyl, particularly preferably C 15 -C 25 alkyl, such as C 18 -C 22 alkyl. A preferred meaning of R 4 is C 1 -C 25 alkyl, particularly preferably C 10 -C 20 alkyl, such as octadecyl. Preferred meanings of R 1 and R 7 are C 1 -C 4 alkyl, particularly preferably methyl.
    Examples of C 1 -C 18 alkoxy are methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, pentoxy, isopentoxy, hexoxy, heptoxy, octoxy, decyloxy, Tetradecyloxy, hexadecyloxy, and octadecyloxy. R 1 and R 7 may be, for example, C 6 -C 12 alkoxy, especially heptoxy or octoxy.
    Examples of C 5 -C 12 cycloalkyl include cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cyclododecyl. C 5 -C 8 cycloalkyl is particularly preferably cyclohexyl.
    Examples of C 5 -C 12 cycloalkoxy include cyclopentoxy, cyclohexoxy, cycloheptoxy, cyclooctoxy, cyclodecyloxy and cyclododecyloxy. C 5 -C 8 cycloalkoxy is preferred, especially when cyclopentoxy and cycloalkyl heksok.
    Examples of C 3 -C 6 alkenyl are allyl, 2-methallyl, butenyl, pentenyl and hexenyl.
    Allyl is preferred. Preferably, the number 1 carbon atom is a saturated carbon atom.
    Examples of C 7 -C 9 phenylalkyl substituted by C 1 -C 4 alkyl on an unsubstituted or phenyl radical are benzyl, phenylethyl, methylbenzyl, dimethylbenzyl, trimethylbenzyl or tert-butylbenzyl. Benzyl is preferred.
    C 1 -C 8 acyl is preferably C 1 -C 8 alkanoyl, C 3 -C 8 alkenoyl or benzoyl. Examples include formyl, acetyl, propionyl, butyryl, pentane oil, hexane oil, octane oil, benzoyl, acrylic oil and croton oil. Acetyl is preferred.
    n 1 is preferably a number of 1 to 25, particularly preferably 1 to 20 or 1 to 10.
    n 2 and n 2 * are, independently of each other, preferably 2 to 25, particularly preferably 2 to 20 or 2 to 10.
    R 1 and R 7 independently of one another are preferably hydrogen, C 1 -C 4 alkyl, -OH, C 6 -C 12 alkoxy, C 5 -C 8 cycloalkoxy, allyl, benzyl or acetyl, particularly preferably hydrogen Or methyl.
    A-262 439 (Derwent 89-122 983/17, Chemical Abstracts 111: 58 964u), WO-A-94 / 12 544 (Derwent 94- 177 274/22) and US-A-4 340 534.
    The compounds of formulas (3a) and (3b) can be obtained as a mixture and can be used in the stabilizer mixture as it is fresh. (3a): (3b) is, for example, 20: 1 to 1:20 or 1: 10 to 10: 1.
    Component A) is preferably the trade name UVINUL 5050 H, LICHTSCHUTZSTOFF UV 31 or HOSTAVIN N 30.
    The meaning of the terminal groups in which the free valences are saturated in the compounds of formulas (1), (3a) and (3b) depends on the process used for their preparation. The terminal group can be modified after preparation of the above compound.
    The terminal group bonded to the 2,5-dioxopyrrolidine ring in the compound of formula (1) is, for example, hydrogen and the terminal group bonded to the -C (R 5 ) (R 6 )
    to be.
    The terminal group bonded to nitrogen in the compound of formula (3a) is, for example, hydrogen and the terminal group bonded to the 2-hydroxypropylene radical is, for example,
    .
    The terminal group bonded to the dimethylene radical in the compound of formula (3b) is, for example, -OH, and the terminal group bonded to oxygen may be, for example, hydrogen. The terminal group may also be a polyether radical.
    A preferred embodiment of the present invention relates to a stabilizer mixture wherein component A) is at least one compound of formula (3a) and (3b).
    Preferred stabilizer mixtures include,
    R 2 and R 5 are independently of each other C 1 -C 25 alkyl or phenyl,
    R 3 and R 6 independently of one another are hydrogen or C 1 -C 4 alkyl,
    The R 4 group is a mixture of C 1 -C 25 alkyl or (2).
    Particularly preferred stabilizer mixtures are those wherein the compound of formula (1) is the following compound:
    or
    R 1 in the formula is hydrogen or methyl, and n 1 is the number of 1 to 25.
    Organic salts of zinc and magnesium as defined in component B) is preferably Me is zinc or magnesium and L is the anion of a compound of the formula MeL 2, or of an organic acid enol. The organic acid may be, for example, a sulfonic acid, a sulfinic acid, a phosphonic acid or a phosphinic acid, but preferably a carboxylic acid. The acids may be aliphatic, aromatic, aromatic aliphatic or cycloaliphatic; Linear or branched; Hydroxy or alkoxy substitution; Saturated or unsaturated and preferably contains from 1 to 24 carbon atoms.
    Examples of such carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, caproic acid, 2-ethylcaproic acid, caprylic acid, capric acid, lauric acid, palmitic acid, stearic acid, 4-butylbenzoic acid, toluic acid, 4-dodecylbenzoic acid, phenylacetic acid, naphthylacetic acid, cyclohexanecarboxylic acid, 4-butylcyclohexanecarboxylic acid or cyclohexanecarboxylic acid Hexyl acetic acid. The carboxylic acid may also be an industrial mixture of carboxylic acids, for example an industrial mixture of fatty acids or a mixture of alkylated benzoic acids.
    Examples of the organic acid containing sulfur or phosphorus include methanesulfonic acid, ethanesulfonic acid, , -Dimethylethanesulfonic acid, n-butanesulfonic acid, n-dodecanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, Benzenesulfonic acid or naphthalenesulfonic acid, butylphosphonic acid, phenylphosphonic acid, monomethyl or monoethylphenylphosphonate, monobutylbenzylphosphonate, dibutylphosphinic acid, or Diphenylphosphinic acid.
    When L is an enolate anion, it is preferably an anion of a -Dicarbonyl compound or o-acylphenol. Examples of -dicarbonyl compounds include acetylacetone, benzoyl acetone, dibenzoylmethane, ethyl acetoacetate, butyl acetoacetate, lauryl acetoacetate or -acetylcyclohexanone. Examples of o-acylphenols include 2-acetylphenol, 2-butyroylphenol, 2-acetyl-1-naphthol, 2-benzoylphenol or salicylaldehyde. The enolate is preferably an anion of a -Dicarbonyl compound having 5 to 20 carbon atoms.
    Preferred examples of the component B) include acetic acid-, lauric acid- and stearic acid- magnesium, formic acid-, acetic acid-, enantantanic-, lauric acid- and zinc stearate and zinc acetylacetonate and magnesium acetylacetonate have.
    In a preferred embodiment of the present invention, component B) is preferably an organic acid salt of zinc or magnesium, for example, acetylacetonate or an aliphatic monocarboxylate having 1 to 24 carbon atoms.
    In component C) the UV absorber is preferably selected from the group consisting of 2- (2'-hydroxyphenyl) benzotriazole, 2-hydroxybenzophenone, esters of substituted or unsubstituted benzoic acid, acrylates, oxamides, 2- 2-hydroxyphenyl) -1,3,5-triazine, resorcinol monobenzoate or formamidine.
    2- (2'-hydroxyphenyl) benzotriazole is, for example, 2- (2'-hydroxy-5'-methylphenyl) -benzotriazole, 2- (3 ', 5'- 2'-hydroxyphenyl) benzotriazole, 2- (5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'- (3 ', 5'-di-tert-butyl-2'-hydroxyphenyl) -5-chloro-benzotriazole, 2- -Butyl-2'-hydroxy-5'-methylphenyl) -5-chloro-benzotriazole, 2- (3'- , 2 - (3 ', 5'-di-tert-amyl-2'-hydroxyphenyl) benzotriazole, 2- (3 ', 5'-bis- ( , - dimethylbenzyl) -2'-hydroxyphenyl) benzotriazole, 2- (3'-tert- butyl-2'- (3'-tert-butyl-5 '- [2- (2-ethylhexyloxy) -carbonylethyl] -2'-hydroxyphenyl) -5 (3 '- tert-butyl-2'-hydroxy-5' (2-methoxycarbonylethyl) phenyl) -5- chloro-benzotriazole, (3'-tert-butyl-2'-hydroxy-5'- (2-methoxycarbonyl) phenyl) benzotriazole, (3'-tert-butyl-5 '[2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) benzotriazole , 3'-tert-butyl-2'-hydroxy-5 '(2-iso-octyloxycar (1, 1, 3,3-tetramethylbutyl) -6-benzotriazol-2-ylphenol] or 2- [3 ' - tert-butyl-5 '- (2-methoxycarbonylethyl) -2'-hydroxyphenyl] -2H-benzotriazole with polyethylene glycol 300 (R is 3'- tert -butyl-4'- -5'-2H-benzotriazol-2-yl phenyl).
    Butyl-2'-hydroxy-5'-hydroxy-phenyl) -5-chloro-benzotriazole, 2- (3'- Methylphenyl) -5-chloro-benzotriazole and 2- (3 ', 5'-di-tert-amyl-2'-hydroxyphenyl) -benzotriazole are preferred.
    2-hydroxybenzophenones include, for example, 4-hydroxybenzyloxy, 4,2 ', 4 ' -trihydroxybenzoyloxy, Hydroxy or 4'-dimethoxy derivatives.
    2-hydroxy-4-octyloxybenzophenone is preferred.
    Esters of substituted or unsubstituted benzoic acids are, for example, 4-tert-butyl-phenyl-salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis (4- tert- butylbenzoyl) resorcinol , Benzoyl resorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl- Octadecyl 3,5-tert-butyl-4-hydroxybenzoate or 2-methyl-4,6-di-tert-butylphenyl 3,5-di- tert -butyl- have.
    2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate and hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate are preferred.
    Acrylates include, for example, ethyl -Cyano- , -Diphenylacrylate, isooctyl -Cyano- , -Diphenylacrylate, methyl -Carbomethoxycinnamate, methyl methyl-p-methoxycinnamate, butyl -cyano- -methyl-p-methoxycinnamate, methyl -carbomethoxy-p-methoxycinnamate or N- ( - [beta] -cyanovinyl) -2-methylindoline.
    Oxamides include, for example, 4,4'-dioctyloxyoctanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di- , 2'-didodecyloxy-5,5'-di-tert-butoxanilide, 2-ethoxy-2'-ethyloxanilide, N, N'-bis (3-dimethylaminopropyl) oxamide Ethoxy-5-tert-butyl-2'-ethoxanilide or 2-ethoxy-2'-ethyl-5,4'-di- tert -butoxanilide or a mixture of ortho- and para- -Methoxy-disubstituted oxanilide or mixtures of o- and p-ethoxy-disubstituted oxanilides.
    2- (2-hydroxyphenyl) -1,3,5, -triazine is, for example, 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6- (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- Phenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) (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- (2,4-dimethyl-1,3,5-triazine, 2- [2-hydroxy-4- (2,4-dimethyl) -1,3,5-triazine, 2- [4- (dodecyloxy / tridecyloxy-2-hydroxypropoxy) 2-hydroxy-4- (2-hydroxy-3-dodecyloxy-propyl) -phenyl] -4,6-bis (2,4-di-methylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-hexyloxy) Phenyl-1,3,5-triazine, 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl- (3-butoxy-2-hydroxy-propoxy) phenyl] -1,3,5-triazine or 2- Phenyl) -6-phenyl-1,3,5-triazine.
    (2,4-dimethylphenyl) -1,3,5-triazine and 2- (2-hydroxy-4-hexyloxy) Phenyl) -4,6-diphenyl-1,3,5-triazine.
    The monobenzoate of resorcinol is, for example, a compound of the formula:
    Formamidine is, for example, a compound of the formula:
    The UV absorber in component C) is in particular 2- (2'-hydroxyphenyl) benzotriazole, 2-hydroxybenzophenone or 2- (2-hydroxyphenyl) -1,3,5-triazine.
    Component C) is preferably a UV absorber.
    In component C) the pigment is an inorganic or organic pigment.
    Examples of the inorganic pigments include titanium dioxide, zinc oxide, carbon black, cadmium sulfide, cadmium selenide, chromium oxide, iron oxide, lead oxide and the like.
    Examples of the organic pigments include azo pigments, anthraquinone, phthalocyanine, tetrachloroisoindolinone, quinacridone, isoindoline, perylene, pyrrolopyrrole (for example, Pigment Red 254) and the like.
    As pigments in component C), all of the pigments listed in the Gachter / Muller: Plastics Additives Handbook, 3rd Edition, Hanser Publishers, Munich Vienna New York, pp. 647 to 659, 11.2.1.1 to 11.2.4.2 can be used.
    A particularly preferred pigment is titanium dioxide.
    In another preferred embodiment of the present invention,
    A) at least one compound of the formula (3a) and (3b) wherein n 2 and n 2 * are independently of each other a number from 2 to 10;
    B) magnesium stearate or zinc stearate and
    C)
    ≪ / RTI > compound.
    The stabilizer mixture according to the invention is useful for stabilizing polyolefins.
    Examples of suitable polyolefins are shown below.
    1. Polymers of monoolefins and diolefins such as polypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyisoprene or polybutadiene, as well as cycloolefins High density and high molecular weight polyethylene (HDPE-HMW), high density and ultra high molecular weight polyethylene (HDPE-UHMW), medium density polyethylene (HDPE) (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and branched low density polyethylene (BLDPE).
    The polyolefins, i.e. the polymers of the monoolefins exemplified above, preferably polyethylene and polypropylene, can be prepared by different processes and in particular the following processes:
    a) radical reaction (usually under high pressure and elevated temperature).
    b) a catalytic reaction using a catalyst which typically contains one or more Group IVb, Vb, VIb or Group VII metals of the Periodic Table. The metal usually has one or more ligands capable of coordinating π- or σ-coordination, such as oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenes and / or aryls.
    The metal complex may be in a free form or may be in a form fixed to a substrate such as activated magnesium chloride, titanium (III) chloride, alumina oxide or silicon oxide. The catalyst may be soluble or insoluble in the polymerization medium. The catalyst may be used alone in the polymerization process or may be used with other activators such as metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes, the metals being of Groups Ia, IIa, IIIa of the Periodic Table It is an element. The activator may be advantageously modified by other ester, ether, amine or silyl ether groups. The catalyst system is usually named Phillips, Standard Oil Indiana, Ziegler (- Natta), TNZ (DuPont), Metallocene or Single Site Catalyst (SSC).
    2. Mixtures of the polymers mentioned in 1), for example mixtures of polypropylene with polyisobutylene, polypropylene and polyethylene (such as PP / HDPE, PP / LDPE) and polyethylene of different types (LPDE / HDPE).
    3. Copolymers between monoolefins and diolefins or between vinyl monomers such as ethylene / propylene copolymers, linear low density propylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene / but-1-ene copolymers , Ethylene / butene copolymer, ethylene / butene copolymer, ethylene / hexene copolymer, ethylene / methylpentene copolymer, ethylene / heptene copolymer, ethylene / octene copolymer, propylene / butadiene copolymer, Ethylene / alkyl acrylate copolymers, ethylene / alkyl methacrylate copolymers, ethylene / vinyl acetate copolymers, and copolymers thereof with carbon monoxide or ethylene / acrylic acid copolymers and their salts (for example, Ionomer), a trimer of ethylene and propylene and a diene (e.g., hexadiene, dicyclopentadiene or ethylidene-norbornene); And a mixture of the copolymers with each other and the polymer described above in 1) such as polypropylene / ethylene-propylene copolymer, LDPE / ethylene-vinyl acetate copolymer (EVA), LDPE / ethylene- acrylic acid copolymer (EAA) LLDPE / EVA, LLDPE / EAA and cross or random polyalkylene / carbon monoxide copolymers and mixtures of these with other polymers such as polyamides.
    The present invention further relates to a composition containing a mixture of a polyolefin and a novel stabilizer.
    The polyolefin shown in the above item 1 is preferable. Copolymers of polyethylene or polypropylene as well as polyethylene and polypropylene are particularly preferred.
    The components of the novel stabilizer mixture may be added to the material to be stabilized, alone or in admixture with each other. Component (A) is preferably present in an amount of from 0.01 to 5%, particularly preferably from 0.05 to 1%; Component (B) is preferably present in an amount of from 0.005 to 1%, particularly preferably from 0.025 to 0.2%; Component (C1) is preferably present in an amount of 0.01 to 1%, component (C2) is preferably present in an amount of 0.01 to 10% and component (C3) is preferably present in an amount of 0.01 to 10%. % Is the relative weight percent of the material to be stabilized.
    The ratio of the UV absorber to the pigment in component (C3) is preferably from 2: 1 to 1:10.
    The ratio of component (A) :( B) is preferably 30: 1 to 1:30, such as 20: 1 to 1:20 or 20: 1 to 1:10.
    The ratio of component (A): (C1) is preferably 1:20 to 30: 1, such as 1:10 to 20: 1 or 1: 5 to 20:
    The ratio of component (A): (C2) is preferably 1:30 to 30: 1, such as 1:20 to 20: 1 or 1:10 to 10: 1.
    The ratio of component (A): (C3) is preferably 1:30 to 30: 1, such as 1:20 to 20: 1 or 1:10 to 10: 1.
    The novel stabilizer mixture or the individual components thereof can be incorporated into the polyolefin, for example, by known methods before or during molding, or by dissolving or dispersing the compound in a polyolefin and, if necessary, evaporating the solvent. The novel stabilizer mixture individual components may be incorporated into the material to be stabilized in the form of a powder, granules or masterbatch containing the components, for example, in a concentration of from 2.5 to 25% by weight.
    If desired, the components of the novel stabilizer mixture may be melt blended together before incorporation into the polyolefin.
    The novel stabilizer mixture or components thereof may be added before, during, or during crosslinking.
    The material stabilized in this way can be used in various forms, such as films, fibers, tapes, molding compositions, profiles or as binders for paints, adhesives or putties.
    The stabilized polyolefin of the present invention may additionally contain various additives such as:
    1. Antioxidant
    1.1. Alkylated monophenols such as 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6- Butyl-4-iso-butylphenol, 2,6-di-cyclopentyl-4-methylphenol, 2- (α -Methylcyclohexyl) -4,6-dimethylphenol, 2,6-di-octadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6- -Methoxymethylphenol, linear or branched nonylphenols such as 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6- (1'- methylundec- Phenol, 2,4-dimethyl-6- (1'-methylheptadec-1'-yl) phenol, 2,4-dimethyl- mixture.
    1.2. Alkylthiomethylphenols such as 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl- 2,6-di-dodecylthiomethyl-4-nonylphenol.
    1.3. Hydroquinone and alkylated hydroquinone such as 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5- Di-tert-butyl-4-hydroxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di- 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis (3,5-di-tert-butyl-4-hydroxyphenyl) adipate.
    1.4. Tocopherol , -Tocopherol, -Tocopherol, -Tocopherol and mixtures thereof (vitamin E)
    1.5. Hydroxyated thiodiphenyl ethers such as 2,2'-thiobis (6-tert-butyl-4-methylphenol), 2,2'-thiobis (4-octylphenol), 4,4'- (6-tert-butyl-3-methylphenol), 4,4'-thiobis- (6-tert- butyl-2-methylphenol), 4,4'- -Amylphenol), 4,4'-bis- (2,6-dimethyl-4-hydroxyphenyl) disulfide.
    1.6. Alkylidene bisphenols such as 2,2'-methylenebis (6-tert-butyl-4-methylphenol), 2,2'-methylenebis Methylenebis (4-methyl-6-cyclohexylphenol), 2,2'-methylenebis (4-methyl- Methylphenol), 2,2'-methylenebis (4,6-di-tert-butylphenol), 2,2'-ethylidenebis (4,6- (6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis [6- (a- methylbenzyl) -4-nonylphenol], 2,2'-methylenebis Methylenebis (2,6-di-tert-butylphenol), 4,4'-methylenebis (6-tert-butylphenol) Methylphenol), 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 2,6- Butylbenzyl) -4-methylphenol, 1,1,3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 1,1- -2-methyl-phenyl) -3-n-dodecylmercur (3-tert-butyl-4-hydroxyphenyl) butyrate, ethylene glycol bis [ Dienes such as bis [2- (3'-tert-butyl-2'-hydroxy-5'-methylbenzyl) -6- tert- Bis (3,5-di-tert-butyl-4-hydroxyphenyl) propane, 2,2- Methylphenyl) -4-n-dodecyl mercaptobutane, 1,1,5,5-tetra- (5-tert-butyl-4-hydroxy-2-methylphenyl) pentane.
    1.7. O-, N- and S-benzyl compounds such as 3,5,3 ', 5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl- Dimethyl-benzylmercaptoacetate, tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate, tris (3,5-di- tert -butyl-4-hydroxybenzyl) amine, Bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, isooctyl-3 (3-hydroxy-2,6-dimethylbenzyl) dithioterephthalate, , 5-di-tert-butyl-4-hydroxybenzyl mercaptoacetate.
    1.8. Hydroxybenzylated malonates such as dioctadecyl 2,2-bis (3,5-di-tert-butyl-2-hydroxybenzyl) malonate, di-octadecyl 2- -Dihydroxy-5-methylbenzyl) -malonate, di-dodecyl mercaptoethyl-2,2-bis- (3,5-di- tert -butyl-4-hydroxybenzyl) malonate, bis [4 - (1,1,3,3-tetramethylbutyl) phenyl] -2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate.
    1.9. Aromatic hydroxybenzyl compounds such as 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,4-bis Di-tert-butyl-4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene, 2,4,6-tris (3,5- phenol.
    1.10. Triazine compounds such as 2,4-bis (octylmercapto) -6- (3,5-di- tert -butyl-4-hydroxyanilino) -1,3,5-triazine, Bis (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6-bis Di-tert-butyl-4-hydroxyphenoxy) -1,3,5-triazine, 2,4,6-tris (3,5- 1,3,5-tris- (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris -Butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 2,4,6-tris (3,5- (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) -hexahydro-1,3,5-triazine, 1,3,5- Tris (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate.
    1.11. Benzylphosphonates such as dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl-3,5-di- tert -butyl-4-hydroxybenzylphosphonate, di Di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, 3,5-di - calcium salt of monoethyl ester of tert-butyl-4-hydroxybenzylphosphonic acid.
    1.12. Acylaminophenols such as 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N- (3,5-di-tert-butyl-4-hydroxyphenyl) carbamate.
    1.13. Mono- or polyhydric alcohols such as methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, (Hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thioundecanol, 3-thioheptanoic acid, 3-thiazol-pentamethyl-decanol, trimethyl-hexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-wave -2,6,7- tree-oxabicyclo [2.2.2] octane and β- (3,5- Di-tert-butyl-4-hydroxyphenyl) propionic acid.
    1.14. Mono- or polyhydric alcohols such as methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, (Hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thioundecanol, 3-thioheptanoic acid, 3-thiopentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane and - (5- Butyl-4-hydroxy-3-methylphenyl) propionic acid .
    1.15. Mono- or polyhydric alcohols such as methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, (Hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thioundecanol, 3-thioheptanoic acid, 3-thiazol-pentamethyl-decanol, trimethyl-hexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-wave -2,6,7- tree-oxabicyclo [2.2.2] octane and β- (3,5- Dicyclohexyl-4-hydroxyphenyl) propionic acid .
    1.16. Mono- or polyhydric alcohols such as methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, (Hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thioundecanol, 3-thioheptanoic acid, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane and 3,5- -Butyl-4-hydroxyphenylacetic acid .
    1.17. amides of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid such as N, N'-bis (3,5-di- tert -butyl-4-hydroxyphenylpropionyl) hexa Methylene diamine, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) trimethylenediamine, - hydroxyphenylpropionyl) hydrazine
    1.18. Ascorbic acid (vitamin C)
    1.19. Amine antioxidants such as N, N'-di-isopropyl-p-phenylenediamine, N, N'-di-tert- butylphenylenediamine, N, N'- (1-methyl-3-methylpentyl) -p-phenylenediamine, N, N'-bis (1-methylheptyl) -p-phenylenediamine , N, N'-bis (2-naphthyl) -p-phenylenediamine, N, N'-dicyclohexyl-p-phenylenediamine, Phenyl-p-phenylenediamine, N- (1, 3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, N- (1-methylheptyl) phenyl-p-phenylenediamine, 4- (p-toluenesulfamoyl) -diphenylamine, N, N'-dimethyl-N, N'-di Tert-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N- Phenyl-2-naphthylamine, octylated diphenylamine such as p, p'-di-tert-octyldiphenylamine, 4-n-butyl 4-octadecanoylaminophenol, bis (4-methoxyphenyl) amine, 2, 4-octadecanoylaminophenol, Di-tert-butyl-4-dimethylaminomethylphenol, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, N, N, N ' (Phenylamino) propane, (o-tolyl) biguanide, bis [4- (2-methylphenyl) (1 ', 3'-dimethylbutyl) phenyl] amine, a mixture of tertiary-octylated N-phenyl-1-naphthylamine, mono- and dialkylated tertiary-butyl / tert-octyldiphenylamine, mono- and di Mixtures of alkylated nonyldiphenylamines, mixtures of mono- and dialkylated dodecyldiphenylamines, mixtures of mono- and di-alkylated isopropyl / isohexyldiphenylamines, mixtures of mono- and dialkylated tertiary-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, A mixture of mono- and dialkylated tertiary-butyl / tert-octylphenothiazine, a mixture of mono- and dialkylated tertiary-octyl-phenothiazine, a mixture of N, N, N ', N'- N, N-bis (2,2,6,6-tetramethyl-piperidin-4-yl-hexamethylenediamine, bis , 6-tetramethylpiperidin-4-yl) sebacate, 2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperid- .
    2. UV absorber and light stabilizer
    2.1 Preparation of 2,2'-thio-bis [4- (1,1,3,3-tetra-naphthyl) -1,2,3,4-tetrahydronaphthalene-2-one having optionally additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, Tetramethylbutyl) phenol], nickel dibutyldithiocarbamate, monoalkyl esters of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid (E.g., methyl ester or ethyl ester), nickel complexes of ketoxime (e.g. 2-hydroxy-4-methylphenyl undecylketoxime), 1-phenyl-4-lauroyl- Nickel complexes of 5-hydroxypyrazole.
    2.2 Sterically hindered amines such as 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- , Bis (1,2,2,6,6-pentamethyl-4-piperidyl) n-butyl-3,5-di- tert -butyl-4-hydroxybenzyl malonate, 1- Hydroxyethyl) -2,2,6,6-tetramethyl-4-hydroxypiperidine with succinic acid, N, N'-bis (2,2,6,6-tetramethyl- (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-triazine, Tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butane-tetracarboxylate, 1,1 '- (1,2- Ethanediyl) bis (3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4- (1,2,2,6,6-pentamethylpiperidyl) -2-n-butyl-2- (2-hydroxyphenyl) Tert-butylbenzyl) malonate, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4.5] decane- (1-octyloxy-2,2,6,6-tetramethylpiperidyl) sebacate, bis (1-octyloxy-2,2,6,6-tetramethylpiperidyl) succinate, Condensation of N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine with 4-morpholino-2,6-dichloro-1,3,5-triazine The product, 2-chloro-4,6-bis (4-n-butylamino-2,2,6,6-tetramethylpiperidyl) 2-chloro-4,6-di- (4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl) -1,3,5- The condensation product of triazine with 1,2-bis (3-aminopropylamino) ethane, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4.5 ] Decane-2,4-dione, 3 (2,2,6,6-tetramethyl-4-piperidyl) pyrrolidine-2,5-dione, 3-dodecyl-1- (1,2,2,6, Pentamethyl-4-piperidyl) pyrrolidine-2,5-dione, 4-hexadecyloxy- and 4-stearyloxy-2,2,6,6-tetramethylpiperidine , N, N'-bis- (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-cyclohexylamino-2,6-di- (2,2,6,6-tetramethyl-4-piperidyl) -n-dodecylsuccinimide, N- (1,2,2,6,6-penta 4-piperidyl) -n-dodecylsuccinimide, 2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro [ 4,5] decane, 7,7,9,9-tetramethyl-2-cyclodecyl-1-oxa-3,8-diaza-4-oxospiro [4,5] decane and epichlorohydrin The reaction product.
    3. Metal deactivators such as N, N'-diphenyl oxamide, N-salicylal-N-salicyloyl hydrazine, N, N'-bis (salicyloyl) hydrazine, N, (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1,2,4-triazole, bis (benzylidene) oxalyl dihydrazide, oxanilide , N, N'-bis (salicyloyl) oxalyl dihydrazide, N, N'-diacetyl adipoyl dihydrazide, Bis (salicyloyl) thiopropionyl dihydrazide.
    4. Phosphites and phosphonites such as triphenyl phosphite, diphenyl alkyl phosphite, phenyl dialkyl phosphite, tris (nonylphenyl) phosphite, triaryl phosphite, trioctadecyl phosphite, distearyl (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, Bis (2,4-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis (2,4,6-tris (tert-butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis (2,4-di-tert-butylphenyl) '-Biphenylene diphosphonite, 6-isooctyloxy-2,4,8,10- Tric-butyl-12H-dibenz [d, g] -1,3,2-dioxaphosphosine, 6-fluoro-2,4,8,10-tetra- Dibenz [d, g] -1,3,2-dioxaphosphosine, bis (2,4-di- tert -butyl-6-methylphenyl) methyl phosphite, bis -6-methylphenyl) ethyl phosphite.
    5. N, N-diethylhydroxyamine, N, N-dioctylhydroxyamine, N, N-dilaurylhydroxyamine, N, N N-dihexadecylhydroxyamine, N, N-dioctadecylhydroxyamine, N-hexadecyl-N-octadecylhydroxyamine, N-heptadecyl-N- Octadecylhydroxyamine, N, N-dialkylhydroxyamine derived from hydrogenated resin amine.
    6. Nitrones such as N-benzyl-alpha-phenyl-nitrone, N-ethyl-alpha-methyl-nitrone, N-octyl-alpha-heptyl-nitrone, N-lauryl- Alpha-heptadecyl-nitrone, N-tetradecyl-alpha-tridecyl-nitrone, N-hexadecyl-alpha-pentadecyl-nitrone, N-octadecyl- N-heptadecyl-alpha-heptadecyl-nitrone, N-octadecyl-alpha-hexadecyl-nitrone, hydrogenated resin amine , ≪ / RTI >N'-dialkylhydroxyamines.
    7. Thio-elevating agents , such as dilauryl thiodipropionate or distearyl thiodipropionate.
    8. Release of peroxides , such as esters of beta -thiodipropionic acid, such as lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, dibutyldithio Zinc carbamide, dioctadecyl disulfide, pentaerythritol tetrakis (beta -dodecyl mercapto) propionate.
    9. Basic technical cleaners such as melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of high fatty acids, For example, calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate, potassium palmitate, antimony pyrocatecholate or pyrocatecholate tin.
    10. Nucleating agents , for example inorganic substances such as talc, metal oxides such as titanium dioxide or magnesium oxide, preferably phosphates, carbonates or sulphates of alkaline earth metals; Organic compounds such as mono- or polycarboxylic acids and their salts such as 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; Polymerizable compounds such as ionic copolymers (ionomers).
    11. Fillers and reinforcing agents such as powders of calcium carbonate, silicates, glass fibers, glass bulbs, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood powders and other natural products Or fibers, synthetic fibers.
    12. Other additives such as plasticizers, lubricants, emulsifiers, pigments, flow additives, catalysts, flow control agents, optical brighteners, flame retardants, antistatic agents and blowing agents.
    13. Benzofuranones and indolinones such as those described in US-A-4325863, US-A-4338244, US-A-5175312, US-A-5216052, US-A-5252643, DE-A-4316611 A-4316622, DE-A-4316876, EP-A-0589839 or EP-A-0591102 or 3- [4- (2-acetoxyethoxy) phenyl] Di-tert-butyl-benzofuran-2-one, 5,7-di-tert-butyl-3- [4- (2-stearoyloxyethoxy) phenyl] benzofuran- Di-tert-butyl-3- (4- [2- hydroxyethoxy] phenyl) benzofuran-2-one], 5,7- 3- (4-ethoxyphenyl) benzofuran-2-one, 3- (4-acetoxy-3,5-dimethylphenyl) -5,7- 3- (3,5-Dimethyl-4-pivaloyloxyphenyl) -5,7-di-tert-butyl-benzofuran-2-one.
    The weight ratio of the total amount of components A), B) and C) to conventional additives may be, for example, from 1: 0.1 to 1: 5.
    Furthermore, the present invention relates to the use of novel stabilizer mixtures for the stabilization of polyolefins against photo-induced cracking.
    The following examples further illustrate the present invention. All percentages and parts are by weight unless otherwise indicated.
    Example 1: Optical stabilization in a polypropylene homopolymer film.
    100 parts of an unstabilized polypropylene powder (melt flow rate: ~ 2.4 / 10 min, measured at 230 캜 / 2160 g) was pentaerythrityl-tetrakis-3- (3,5- 0.05 part of tris- (2,4-di-tert-butylphenyl) -phosphite and 0.05 part of the stabilizer mixture indicated in the table below, It was homogenized in the plastograph. The material obtained above was compression-molded between two aluminum foils at 260 ° C for 6 minutes with an experimental press, and a 0.5 mm thick film was obtained in a water-cooled press immediately after cooling to room temperature. The 0.5 mm thick film was cut into 60 mm x 25 mm specimens and exposed to WEATHER-OMETER Ci 65 (black plate temperature 63 ± 2 ° C, without water spray).
    Periodically, the specimens were removed from the exposure apparatus and their carbonyl content was measured with an infrared spectrometer.
    The corresponding exposure time, which corresponds to a carbonyl absorbance of 0.1, is a measure of the efficiency of the stabilizer mixture. The obtained values are summarized in the following table.
    Stabilizer mixtureCarbonyl absorbance 0.1 Intended month (hours) (A) 0.05%, zinc stearate comparison 0.1% and the TiO 2 (Rutile) 0.5%: US-A- 4 929 stabilizer mixture according to the 652 call (XX) 0.05%, Zinc stearate 0.1% and the TiO 2 (rutile ) 0.5%14701230
    Used light stabilizer:
    Light stabilizer (A):
    A mixture of the following compounds (3a) and (3b).
    In the above formula, the average value of n 2 is about 3.9, the average value of n 2 * is 4.2, and the ratio between (3a) and (3b) is about 4: 1.
    Light stabilizer (XX):
    The average value of n in the above formula is 5.1.
    The stabilizer mixture according to the invention is particularly useful for stabilization against the photo-induced degradation of polyolefins and the material stabilized by the mixture can be used in various forms such as films, fibers, tapes, molding compositions, profiles, It can be used as a binder for putty.
    权利要求:
    Claims (14)
    [1" claim-type="Currently amended] A)
    A1) one or more compounds of the formula (1)
    A2) one or more compounds of formulas (3a) and (3b);
    B) organic salts of magnesium oxide, magnesium hydroxide, zinc oxide, zinc hydroxide or zinc or magnesium; And
    C)
    C1) UV absorber or
    C2) pigment or
    C3) UV absorber and a pigment, wherein component B) is an organic salt of magnesium oxide, magnesium hydroxide or zinc or magnesium when the component A) is at least one compound of formula (3a) and (3b).



    In the formula,
    R 1 is hydrogen, C 1 -C 8 alkyl, -O . , A -OH, C 1 -C 18 alkoxy, C 5 -C 12 cycloalkoxy, -CH 2 CN, C 3 -C 6 alkenyl, C 7 -C 9 phenylalkyl, C 1 -C 4 alkyl on the phenyl radical by a substituted C 7 -C 9 phenylalkyl; Or C 1 -C 4 acyl,
    R 2 , R 3 , R 5 and R 6 independently of one another are hydrogen, C 1 -C 30 alkyl, C 5 -C 12 cycloalkyl or phenyl,
    R 4 is hydrogen, C 1 -C 30 alkyl, C 5 -C 12 cycloalkyl, C 7 -C 9 phenylalkyl, phenyl or a group of formula (2)
    R 7 has one of the meanings of R 1 ,
    n 1 is a number from 1 to 50,
    n 2 and n 2 * are in the range of 2 to 50;
    [2" claim-type="Currently amended] The stabilizer mixture according to claim 1, wherein component A) is at least one compound of formula (3a) and (3b).
    [3" claim-type="Currently amended] Wherein R 1 and R 7 are independently of each other hydrogen, C 1 -C 4 alkyl, -OH, C 6 -C 12 alkoxy, C 5 -C 8 cycloalkoxy, allyl, benzyl or acetyl, mixture.
    [4" claim-type="Currently amended] The stabilizer mixture according to claim 1, wherein R 1 and R 7 are independently of each other hydrogen or methyl.
    [5" claim-type="Currently amended] 3. A compound according to claim 1, wherein R 2 and R 5 are independently of each other C 1 -C 25 or phenyl, R 3 and R 6 independently of one another are hydrogen or C 1 -C 4 alkyl and R 4 is C 1 -C 25 Alkyl or a stabilizer mixture which is a group of formula (2).
    [6" claim-type="Currently amended] The stabilizer mixture according to claim 1, wherein the compound of formula (1) is a compound of the formula:


    In the formula, R 1 is hydrogen or methyl yet n 1 is the number of 1 to 25.
    [7" claim-type="Currently amended] The stabilizing admixture according to claim 1, wherein the organic salt of zinc or magnesium is acetylacetonate or an aliphatic monocarboxylate.
    [8" claim-type="Currently amended] The composition of claim 1 wherein the UV absorber is selected from the group consisting of 2- (2'-hydroxyphenyl) benzotriazole, 2-hydroxybenzophenone, esters of substituted or unsubstituted benzoic acid, acrylates, oxamides, 2- Hydroxyphenyl) -1,3,5-triazine, a monobenzoate of resorcinol or formamidine.
    [9" claim-type="Currently amended] 2. The composition of claim 1, wherein the UV absorber is a stabilizer such as a stabilizer such as 2- (2'-hydroxyphenyl) benzotriazole, 2-hydroxybenzophenone or 2- (2-hydroxyphenyl) mixture.
    [10" claim-type="Currently amended] The stabilizing admixture according to claim 1, wherein the pigment is titanium dioxide.
    [11" claim-type="Currently amended] The stabilizing agent mixture according to claim 1, which contains a UV absorber as component C).
    [12" claim-type="Currently amended] The method according to claim 1,
    A) a compound of the formula: or one or more compounds of the formula (3a) and (3b)

    B) magnesium stearate or zinc stearate and
    C)

    Stabilizing agent mixture containing the compound:
    Wherein n 2 and n 2 * are 2 to 10 independently of each other.
    [13" claim-type="Currently amended] A composition comprising a polyolefin and a stabilizer mixture according to claim 1.
    [14" claim-type="Currently amended] 14. The composition of claim 13, wherein the polyolefin is a copolymer of polyethylene or polypropylene or polyethylene or polypropylene.
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    同族专利:
    公开号 | 公开日
    CA2212553C|2007-10-23|
    GB2316409B|2000-09-20|
    GB0018561D0|2000-09-13|
    GB2316409A|1998-02-25|
    NL1006730A1|1998-02-12|
    IT1293824B1|1999-03-10|
    JPH1077462A|1998-03-24|
    DE19733717A1|1998-02-12|
    US20050075424A1|2005-04-07|
    TW464670B|2001-11-21|
    GB2348880B|2000-12-13|
    FR2752241B1|2001-06-29|
    US6566427B1|2003-05-20|
    BE1011447A3|1999-09-07|
    ES2134732A1|1999-10-01|
    NL1006730C2|1999-03-15|
    FR2752241A1|1998-02-13|
    KR100471951B1|2005-08-05|
    CA2212553A1|1998-02-07|
    ITMI971892A1|1998-02-09|
    ES2134732B1|2000-05-16|
    US7026380B2|2006-04-11|
    DE19733717B4|2013-04-18|
    GB9716205D0|1997-10-08|
    GB2348880A|2000-10-18|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    1996-08-07|Priority to EP96810521
    1996-08-07|Priority to DE96810521.3
    1997-08-01|Application filed by 한스-피터 위트린, 시바 스페셜티 케미칼스 홀딩 인코포레이티드
    1998-06-05|Publication of KR19980018297A
    2005-08-05|Application granted
    2005-08-05|Publication of KR100471951B1
    优先权:
    申请号 | 申请日 | 专利标题
    EP96810521|1996-08-07|
    DE96810521.3|1996-08-07|
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