Title of Invention	UV STABILING ADDITIVE COMPOSITION
Abstract	This invention relates to an UV stabilizing additive composition comprising an oetho-hydroxy triazine compound, a hindered hydroxybenzoate compound and optionally a hindered amine compound. This additive composition may be used to stablize materials from UV radiation. This invention also contemplates a method of stabilizing a material by contacting the material with the UV stabilizing additive composition.

Title of Invention

UV STABILING ADDITIVE COMPOSITION

Abstract

This invention relates to an UV stabilizing additive composition comprising an oetho-hydroxy triazine compound, a hindered hydroxybenzoate compound and optionally a hindered amine compound. This additive composition may be used to stablize materials from UV radiation. This invention also contemplates a method of stabilizing a material by contacting the material with the UV stabilizing additive composition.

Full Text	UV STABILIZED THERMOPLASTIC OLEFINS This application claims the benefit under 35 U.S.C. § 119(e) of United States Provisional Application Serial No. 60/343,681, filed December 27, 2001. FIELD OF THE INVENTION This invention relates to an improved UV stabilizing additive composition. More specifically, this invention relates to an UV stabilizing additive composition comprising an ortho-hydroxy triazine compound, a hindered hydroxybenzoate compound and optionally a hindered amine compound. BACKGROUND OF THE INVENTION Exposure to sunlight and other sources of ultraviolet (UV) radiation is known to cause degradation of a wide variety of materials, especially polymeric materials. For example, polymeric materials such as plastics often discolor, lose gloss and/or become brittle as a result of prolonged exposure to UV light due primarily to a reduction in the molecular weight of the polymer. Accordingly, a large body of art has been developed directed towards materials such as UV light absorbers and stabilizers, which are capable of inhibiting such degradation in polymeric articles. U.S. Patent No. 4,670,491 discloses the use of a C12 to C20alkyl esters of 3,5- tertbutyl-4-hydroxybenzoic acid to stabilize a titanium dioxide pigmented olefin composition. U.S. Pat. No. 5,240, 977 discloses the use of a 3,5-disubstituted tert-butyl-4-hydroxybenzate with a triazine based hindered amine light stabilizer (HALS) in a pigmented polyolefin composition. U.S. Pat. No. 3,206,431 discloses the use of alkyl esters of 3,5-di-tert-butyl-4- hydroxybenzoic acid as light stabilizers for polyolefins in combination with a hindered phenol antioxidant. U.S. Pat. Nos. 3,681,431 and 3,285,855 disclose the use of n-octadecyl 3,5-di- tert-butyl-4-hydroxybenzoate as an antioxidant for polyolefins. British Pat. No. 1,336,931 teaches the use of aryl esters of 3,5-di-tert-butyt-4-hydroxybenzoic acid as light stabilizers for polyolefins in combination with a benzophenone and a peroxide decomposer. U.S. Pat. No. 3,502,613 teaches a synergistic combination of an aryl ester of 3,5-di-tert-butyl-4- hydroxybenzoic acid, a chlorobenzotriazole, a phenolic antioxidant, and a thiodipropionate ester as a light stabilizer for polypropylene. U.S. Pat. No. 4,237,042 discloses a light stabilizer composition for polyolefins comprising n-hexadecyl 3,5-di-tert-butyI-4- hydroxybenzoate and a dialkyl pentaerythrityl diphosphite. None of the above documents disclose the use of a hindered hydroxybenzoate compound with an ortho-hydroxy triazine UV absorber erner with on witner-a-hinserea amine compound. SUMMARY OF THE INVENTION This invention relates to an UV stabilizing additive composition comprising an ortho- hydroxy triazine compound, a hindered hydroxybenzoate compound and optionally a hindered amine compound. This additive composition may be used to stabilize materials from UV radiation. This invention also contemplates a method of stabilizing a material by contacting the material with the UV stabilizing additive composition. DETAILED DESCRIPTION OF THE INVENTION This invention relates to an UV stabilizing additive composition comprising an ortho-hydroxy tris-aryl-s-triazine compound; and a hindered hydroxybenzoate compound, and optionally a hindered amine light stabilizing (HALS) compound containing, for example a 2,2,6,6-tetraalkylpiperdine or 2,2,6,6-tetraalkylpiperazinone radical. Preferably, the ortho-hydroxy tris-aryl-s-triazine compound has the following formula I: where A, B and C are each aromatic, at least one of A, B and C is substituted by a hydroxy group ortho to the point of attachment to the triazine ring, and each of R1 through R9 is selected from the group consisting of hydrogen, hydroxy, alkyl, alkoxy, sulfonic, carboxy, halo, haloalkyl and acylamino having from about 1 to about 24 carbon atoms. One embodiment of the tris-aryl-s-triazine is a compound having the formula II: where Ar1 and Ar2 are the same or different and are subsititud of unsudsimured arly glotips; and where R20 and R21 are each independently a hydrogen, C1-C24 alkyl, C1-C24 haloalkyl, C6- C24 aryl, C1-C24 alkenyl, C1-C24 acyl, C1-C24 cycloalkyl, C5-C24 cycloacyl, C7-C24 aralkyl, or C6- C24 aracyl, substituted or unsubstituted biphenylene, substituted or unsubstituted napthalene, OR, NRR", CONRR', OCOR, CN, SR, SO2R, and where R and R' are each independently a hydrogen, C1-C24 alkyl, C1-C24 haloalkyl, C6-C24 aryl, C2-C24 alkenyl, C1-C24 acyl, C1-C24 cycloalkyl, C5-C24 cycloacyl, C7-C24 aralkyl, or C6-C24 aracyl, substituted or unsubstituted biphenylene, or substituted or unsubstituted napthalene. Preferably, in the above formula II Ar1 has the formula Ha: where R22 and R23 are each independently a hydrogen, C1-C24 alkyl, C1-C24 haloalkyl, C6-C24 aryl, C2-C24 alkenyl, C1-C24 acyl, C1-C24 cycloalkyl, C5-C24 cydoacyl, C7-C24 aralkyl, or C6-C24 aracyl, substituted or unsubstituted biphenylene, substituted or unsubstituted napthalene, OR, NRR', CONRR', OCOR, CN, SR, and SO2R, and where R and R' are as defined above. Also preferred in the above formula II is when R20 is hydrogen or a C1-C6 alkyl, R21 is hydrogen and Ar1 and Ar2 maybe the same or different and are benzyl, methylbenzyl, or dimethylbenzyl. Examples of suitable tris-aryl-s-triazine that may be used are 2,4,6-tris(2-hydroxy-4- octyloxyphenyl)-1,3,5-triazine; 2-(2-hydroxy-4-n-octyloxyphenyl)-4,6-bis(2,4-dirnethylphenyl)- 1,3,5-triazine; 2-(2-hydroxy-4-(mixed iso-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-propyloxyphenyl)-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)-1,3l5-triazine;2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)- 1,3,5-triazine;2-[2-hydroxy-4-(2-hydroxy-3-butyloxypropyloxy)phenyl]-4,6-bis(2l4- dimethylphenyl)-1,3,5-triazine; 2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropyloxy)-phenyl]-4,6- bis(2,4-dimethylphenyl)-1,3,5-triazine; 2-[4-dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2- hydroxyphenyl]-4,6-bis(2.4-dimethylphenyl)-1,3,5-triazine;2-[2-hydroxy-4-(2-hydroxy-3- dodecyloxypropoxy)phenyrj-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine; 2-(2-hydroxy-4- hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine; 2-(2-hydroxy-4-methoxyphenyf)-4.6- 1,3,5-triazine; 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyfj-1,3,5-triazine and 2- (2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine. The optional hindered amine compound may be any suitable hindered amine compound such as those containing a 2,2,6,6-tetraalkylpiperdine or 2,2,6,6- tetraalkylpiperazinone radical. One embodiment of a hinderred arms components one that contains at least one group having the following formula III: where R11 is hydrogen, O, OH, C1-C16 alkyl, -CH2CN, C1-C18 alkoxy, C1-C18 hydroxyalkoxy, C6-C12 cycloalkoxy, C6-C12 hydrocydoalkoxy, C3-C6 alkenyl, C6-C18 alkynyl, C7-C9 phenylalkyl, unsubstituted or substituted on the phenyl with 1, 2 or 3 C1-C4 alkyls, or an aliphatic C1-C8 acyl; R12 is hydrogen, C1-C8 alkyl, or benzyl; R13, R14, R15, and R16 are each independently a C6-C18 alkyl, benzyl or phenethyl, or optionally R13 and R14, and/or R15 and R16, taken together with the carbon which they are attached, form a d-do cycloalkyl. Another embodiment of a hindered amine compound is a compound that has formula IV below: where R10 is a morpholino, C1-C8 alkylamine, di(C1-C6) alkylamine, pyrrolidyl, cyclohexylamine or combinations thereof, X and X1 which may be the same or different, and are hydrogen, C1-C20alkyi, or a radical of formula III defined above, R11 to R16 are as defined above, Z is a straight chained or branched C1-C20 alkylene or a straight chained or branched d- C20 alkalene chain interrupted by at least oxy, thio, or —N(Rt7)—, where R17 is hydrogen, d-do alkyl, C5-C10 cycloalkylene C6-C12 arylene, C6-C14 aralkylene or the radical of formula III; n is an integer greater than 1; and Y is a halogen atom, C1-C8 alkylamine, di(C1-C8) alkylamine, pyrrolidyl, morpholino, cyclohexylamine, or where X, X1f and Z are as previously defined. Preferably In the above formula IV, Z is a C2 to C6 alkylene, R10 is a morpholino or cyclohexylamine, X and X, is the radical of formula III. R11 is hydrogen or methyl, R12 is hydrogen, and R13. R14, H16 and R16 are methyl. Another embodinr ent of a hindered amihe is a 2,2,G,6-tetraalkylpiperazinone. One embodiment of a 2,2,6,6-tetraalkylpiperazinone compound is one that contains at least one group of formula IVa: where R11 is as defined above. Examples of suitable hindered amine compounds include, but are not limited to: 1 H-Pyrrole-2,5-dionet '-o;tadecyl-, polymer with (1-methylHthenyl)benzene and 1-{2,2,6,6- tetramethyl-4-piperidinyl)-1 H-pyrrole-2,5-dione; piperazinone, 1,1', 1 "-[1,3,5-tria/:ine-2,4,6- trlyltris[{cyclohexylimino)-1:-ethanediyl]Jtris[3,3,5,5-tetram6!thyl-; piperazinone, 1,1',1"-[1,3,5- triaz/ne-2,4,6-triyltris[(c/ch)hexyfimino)-2,1-ethanediylJ]tris[3,3.4,5,5-pentamethyl-; (he reaction product of 7,7,9,9-tetrarnethy[-2-cydoundecyl-1-ox;3-3,8-diaza-4-oxospiro[4.5]decane and epichlorohydrin; the candensate of N,N'-bis(2,2,616-tetr.3methylpiperidin-4- yl)hexamethylenediamine and 4-cyclohexylamino-2,6-dichlcro-1,3,5-triazine; the condensate of 1,2-bis(3-aminopropylamino)ethane, 2,4,6-trichloro-1,3,5-triazine and 4-butv!amino-2,2,6,6- tetramethylpiperidine; the condensate of N,N'-bis(2,2,6,6-tetramethylpiperidin-4- yl)hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine; the cc ndensate of 2- chloro-4.6-bis(4-n-butylam no-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazine and 1,2-bis(3 aminopropylamino)ethaie; the condensate of 2-chloro-4,6-bis(4-n-butylamino-1,2,2,6,6- pentamethylpiperidyl)-1,3.5-triazine and 1,2-bls-(3-aminopropylamino)ethane; 2-[(2- hydroxyethyl)aminoJ-4l6-bi3[N-(1-cyclohexyloxy-2l2,6,6-tetr£methyIpiperidin-4-yl)butylar i 1,3,5-triazine; propanedioic add, [(4-methoxyphenyl)-methyl3ne]-bis-(1,2,2,6,6-pentamethv'- 4-piperidinyl) ester; tetrakis (2,2,6,6-tetramethylpiperidin-4-yl)-1,2,3,4-butanetetracarboxyla benzenepropanoic add, 3,:5-bis(1,1 -dimethylethyl)-4-hydroxy-, 1 -[2-f3-[3,5-bis(1,1 - dimethylethylH-hydroxyphsnyfJ-i-oxopropoxylethy]-2,2,6,6 tetrarrrethyl-4-piperidinyl ester; N-(1-octyloxy-2,2,6,6-teiramethylpiperidin-4-yl)--N-dociecyioxaiamKae, ms2,2,6,6 tetramethylpiperidin-4-yi) nitrilotriacetate; 1,5-dfoxaspiro{5,5}undecane-3,3- bis(1,2,2,6,6-pentamethy;-4-piperidinyl): 1,5-dioxaspiro{5,5}undecane-3,3-dicarboxylic add, bis(2,2,6,6-tetramethyl-4-piperidinyl); the condensate of 1-(2-hydroxyethyt)-2,2,6,6- tetramethyl-4-hydroxypiperidine and sucdnic acid; the condensate of N,N'-bis(2,2,6,6- tetramethylpiperidin-4-yl)hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5- triazine; 1,2,3,4-butanetetracarboxylic add, l,2,2,6,6-pentamethyl-4-plperidinyl tridecyl ester; tetrakis(2,2,6,6-tetramethylpiperidln-4-yl)-1,2,3,4-butanetetracarboxylate; 1,2.3,4- butanetetracarboxylic add, 2,2,6,6-tetramethyl-4-piperidinyl tridecyl ester; tetrakis(1,2,2,6,6- pentamethylpiperidin-4-yl)-1,2,3,4-butanetetracarboxylate; mbdure of 2,2,4,4-tetramethyl-21- oxo-7-oxa-3.20-diazaspiro(5.1.11.2)-heneicosane-20-propanoic acid-dodecylester and 2,2,4,4-tetramethyl-21-oxo-7-oxa-3.20-diazaspiro(5.1.11.2)-heneicosane-20-propanoic acid- tetradecylester, 1H,4H,5H,8H-2,3a,4a,6,7a,8a-hexaazacydopenta[dff]fluorene-4,8-dione, hexahydro-2,6-bis(2,2,616-tetramethyl-4-piperidinyf)-;polymethyl[propyl-3-oxy(2l,21,6l,61- tetramethyM^'-piperidinytJlsiloxaneipolymethyllpropyl-S-oxytr.^.^.e'.e'-pentamethyM^'- piperidinyl)]siloxane; copolymer of methyimethacrylate with ethyl acrylate and 2,2,6,6- tetramethylpiperidin-4-yi acrylate; copolymer of mixed C^ to C2« alpha-olefins and (2,2,6,6- tetramethylpiperidin-4-yl)succinimide; 1,2,3,4-butanetetracarboxylic acid, polymer with p,p,p\P'-tetramethyl-2,4,8,10-tetraoxaspiro[5.5Jundecane-3,9-diethanol, 1,2,2,6,6- pentamethyl-4-piperidinyl ester; 1,2,3,4-butanetetracarboxylic acid, polymer with p.p.p'.p'- tetramethyl-2,4,8>10-tetraoxaspiro[5.5]undecane-3,9-diethanol, 2,2,6,6-tetramethyl-4- piperidinyl ester copolymer; 1,3-benzenedicarboxamide, N,N'-bis(2,2,6,6-tetramethyl-4- piperidinyl; 1,1'-(1,10-dioxo-1,10-decanediyl)-bis(hexahydro-2,2,4,4,6-pentamethylpyrimidine; ethane diamide. N-(1-acetyl-2,2l6,6-tetramethylpiperidinyl)-N'-dodecyl; formamide, N,N*-1,6- hexanediylbis[N-(2.2,6,6-te1ramethyl-4-piperidinyl); D-glucitol, 1,3:2,4-bis-O-(2,2,6,6- tetramethyl-4-piperidinylidene)-; 2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21 -oxo- dispirot5.1.11.2]heneicosane; propanamide, 2-methyl-N-(2,2,6,6-tetramethyl-4-piperidinyl)-2- t(2,2,6,6-tetramethyl-4-piperidinyl)amino]-; 7-oxa-3,20-diazadispiro[5.1.11.2]henelcosane-20- propanoic acid, 2,2,4,4-tetramethyl-21-oxo-, dodecyl ester; N-(2,2,6.6-tetramethylpiperidin-4- yl)-P-aminopropionic add dodecyl ester, N^^.e.e-tetramethylpiperidin^-ylVN1- aminooxalamide; propanamide, N-(2,2,6,6-tetramethyl-4-piDeridinyl>-3-{(2,2r6,6-tetramethyl- 4-piperidinyl)amino]-; mixture of 4-hexadecyloxy- and 4-stearyloxy-2,2,6,6- tetramethylptperidine; 3-dodecyl-1-(1,2,2,6,6-pentamethylpiperidin-4-y1)pyrrolidine-2,5-dione; 3-dodecyl-1-(1-ethanoyt-2,2,6,6-pentamethylpiperidin-4-yl)pyrrolidine-2,5-dione;bis(2,2,6,6- tetramethylpiperidin-4-yl)sucdnate; bis(1,2,2,6,6-pentamethylpiperidin-4-yl) n-butyl 3,5-di-tert- butyl-4-hydroxybenzylmalonate; tris(2,2,6,6-tetramethylpiperidin-4-yl) nitrilotriacetate; 1,1'- (1,2-ethanediyl)bis(3,3,5,5-tetramethylpiperazinone);4-benzoyl-2,2,6,6-tetramethylptperidine; 4-stearyloxy-2,2,6,6-tetramethylpiperidine; bis(1,2,2,6,6-pletamenyyipi)-2-nwbury (2- hydroxy-3,5-di-tert-butylbenzyi)malonate; 3-n-octyl-7,7,9,9-tetramethyt-1,3,8- tiiazaspiro[4.5)decan-2,4dione;bfs(1-octyloxy-2,2,6,6-tetramethylpipericlyl)sebacate;bis(1- octaloxy-2,2,6,6-tetramethylpiperidyl)sucxinate;8-acety-3-cklecyl-7,7,9,94etrarnethyl-1,3,8- triazaspiro[4.5]decane-2,4-dione;3-dodecyl-1-(2,2,6,6-tetramethylpipericlin-4-yl)pyrrolidin-2,5- dione; 3-odecyl-1-(1-ethanoyl-2,2,6,6-tetramethylpiperidin-4-yl)pyrrolidin-2,5-dione; 3- dodecyl-1-(1,2,2,6.6-pentamethyip«peridin-4-yl)pyrrolidine-2,5-dlone; a mixture of 4- hexadecyloxy- and 4-stearyloxy-2,2,6,6-tetrarnethylpiperidine; 2-undecyl-7,7,9,9-tetramethyl- 1 -oxa-3,8-draza-4-oxospirof4.5]decane; 1,5-dioxaspiro{5,5)undecane-3,3-dicarboxyltc add, bis(2,2,6,6-tetramethyl-4-piperidinyl) and 1,5-d!oxaspiro{5,5>undecane-3,3-dicarboxylic acid, bis(1,2,2,6,6-pentamethyl-4-piperidinyl). It is also contemplated in this application that the hindered amine compound is not optional and the UV stabilizing additive composition would contain ah ortho-hydroxy triazine compound, a hindered hydroxybenzoate compound and a hindered amine compound. the hindered hydroxybenzoate compound of the present invention may be any suitable hindered hydroxybenzoate compound such as those having the formula V: where R17 is a C1-C8 alkyl and R18 is a C1-C24 alkyl, or substituted or unsubstituted C6-C24 aryl. Preferably, R17 is t-butyl and R18 is a C10-C20 alkyl. Examples of suitable hindered hydroxybenzoate compounds include: 2,4-di-tert- butytphenyl 3,5-di-tert-butyl-4-hydroxybenzoate; hexadecyl-3,5-di-tert-butyl-4- hydroxybenzoate;octadecyl-3,5-di-tert-butyl-4-hydroxybenzoate; octyl-3,5-di-tert-butyl-4- hydroxybenzoate; tetradecyl-3,5-di-tert-butyl-4-hydroxybenzoate; behenylyl-3,5-di-tert-butyt-4- hydroxybenzoate; 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate and butyl 3-[3-t-butyl-4-(3,5-di-t-butyl-4-hydroxybenzoyloxy)phenylI propionate. In one embodiment of the present invention, the UV stabilizing additive composition of the present invention may be employed to stabilize materials which are subject to degradation by ultraviolet radiation by contacting the UV stabilizing additive composition with a composition comprising polymeric or other materials, either chemically or physically. Non-limiting examples of materials that may be so stabilized are polyolefins, polyesters, polyethers, polyketones, polyamides, natural and synthetic rubbers, polyurethanes, polystyrenes, high-impact polystyrenes, polyacrylates, polymethacrylates, polyacetals, polyacrylonitriles, polybutadienes, polystyrenes, acrylonitrile-butadiene- styrene, styrene acrylonitrile, acrylate styrene acrylonithie-cellodsilea acelate butyrate, cellulosic polymers, polyimides, polyamideimides, polyetherimides, polyphenylsulfides, polyphenyioxkie, polysutfones, polyethersulfones, polyvinylchlorides, polycarbonates, polyketones, aliphatic polyketones, thermoplastic olefins, aminoresin cross-linked poryacrylates and polyesters, polyisocyanate cross-linked polyesters and polyacrylates, phenol/formaldehyde, urea/formaldehyde and melamine/formaldehyde resins, drying and non-drying alkyd resins, alkyd resins, polyester resins, acrylate resins cross-linked with melamine resins, urea resins, isocyanates, isocyanurates, carbamates, and epoxy resins, cross-linked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic and aromatic glycidyl compounds, which are cross-linked with anhydrides or amines, polysiloxanes, Michael addition polymers, amines, blocked amines with activated unsaturated and methylene compounds, ketimines with activated unsaturated and methylene compounds, polyketimines in combination with unsaturated acrylic polyacetoacefate resins, polyketimines in combination with unsaturated acrylic resins, radiation curable compositions, epoxymelamine resins, organic dyes, cosmetic products, cellulose-based paper formulations, photographic film paper, fibers, waxes, inks, and blends thereof. Preferably, the materials to be stabilized are thermoplastic olefms, acrylonitrile- butadiene-styrene, polyesters, polyvinylchloride, polyamides, polyurethanes, or homo- and copolymers of propylene, isobutylene, butene, methylpentene, hexene, heptene, octene, isoprene, butadiene, hexadiene, dicyclopentadiene, ethylidene cyclopentene and norbornene. More preferably, the materials are polypropylene and thermoplastic olefins. The amount of the triazine compound used in the material to be stabilized is about 0.001 to about 3.0 wt%, preferably about 0.01 to about 1.0 wt% and more preferably 0.1 to about 0.5 wt% based on the total weight of the material to be stabilized. The amount of the hindered hydroxybenzoate compound is the material to be stabilized about 0.001 to about 3.0 wt%, preferably about 0.01 to about 2.0 wt%, more preferably about 0.1 to about 1.0 wt% based on the total weight of the material to be stabilized. The amount of the hindered amine compound in the material to be stabilized is about 0.001 to about 3.0 wt%, preferably about 0.01 to about 2.0 wt%, more preferably about 0.1 to about 1.0 wt% based on the total weight of the material to be stabilized. This application also contemplates a method of preparing the compositions above by contacting the UV stabilizing additive composition with the material to be stabilized. The material to be stabilized and UV stabilizing additive composition are contacted by preferably blending or compounding the components in a kneading apparatus such as a single or twin screw extruder, Banbury mixer, or hot rollers. The processing parameters and the use of such kneading apparatuses are well known to those skilled in the art. As would be apparent to those skilled in the art of !maxing piasne materials, inacetion to the material to be stabilized and UV stabilizing additive composition, the composition of the present invention may include conventional additives including but are not limited to, antioxidants, metal deactivators, hydroxylamines, nitrones, lactones, co-stabilizers, nucleating agents, clarifying agents, neutralizes, metallic stearates, metal oxides, hydrotalcites, fillers and reinforcing agents, plasticizers, lubricants, emulsifiers, pigments, rheological additives, catalysts, level agents, optical brighteners, flame retardant agents, anti-static agents and blowing agents. The present invention will now be illustrated by the following examples. The examples are not intended to limit the scope of the present invention. In conjunction with the general and detailed descriptions above, the examples provide further understanding of the present invention. EXAMPLES Examples 1 to 3. Gloss retention. Delta E. Delta Yt and Breaking Strength in a polypropylene homopolymer composition The UV additives of Examples 1 to 3 were mixed by using a dry blending technique. In addition to the additives, an antioxidant package containing 0.05% by weight Cyanox® 1741 (1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-s-triazine- 2,4,6(1 H,3H,5H)trione) from Cytec Industries Inc. 0.05% by weight Doverphos® 9228 (bis(2,4-dicumylphenyl) pentaerythritol diphosphite) from Dover Chemical Corporation and 0.05% by weight calcium stearate were also mixed with the UV additives. These additives were compounded with a polypropylene homopolymer from Basell (PH350) and extruded using conventional single-screw extrusion parameters. After extrusion, standard 2 x 2 x 0.125 inch plaques were injection molded using an Arburg injection molder. The performance criteria of Gloss retention. Delta E, Delta Yl and Breaking Strength were measured at set exposure intervals (2000 and 3125 hours) using accelerated exposure in a xenon weather-ometer under ASTM-G-155 testing conditions. Prior to gloss and color measurements, the samples were washed with Dl water and wiped. Gloss retention was conducted under ASTM Test Procedure D523 with a 60° angle. Yellow Index (Yl) and Delta E data was obtained using a Macbeth Color Eye Colorimeter using ASTM D2244-79 with 1" view and D65/100 observer. Delta Yl and Delta E is the difference between samples measured before and after the weather-ometer testing. Lower Delta E and Delta Yl means less color and less yellow index change respectively indicating better performance. For breaking strength, 3 tensile bars per each data point were tested on an Instron Engineering Company Tensile Tester (Model TTB). The average tensile breaking strength of the three test samples were measured and normalized to samples that were not UV exposed to give a % breaking strength. The cross-head speed of the tensile tester was 1 inch (0.254 cm.) per minute. The results are shown in Tables 1 to 4 below. The results demonstrate that additive compositions containing a triazine UV. absorber with the hindered hydroxybenzoate perform better than compositions containing the hindered hydroxybenzoate alone. Examples 4 to 8. Gloss retention and Delta E in a plqmented TPO composition The UV additives of Examples 4 to 8 were mixed by using a-dry blending technique. In addition to the additives, an antioxidant package containing 0.05% by weight Cyanox® 1741 (1,3,5-tris-(3,5-di-di-tert-butyl-4-hydroxybenzyl)-s-triazine- 2,4,6(1 H,3H,5H)trione) from Cytec Industries Inc. 0.05% by weight Doverphos® 9228 (bis(2,4-dicumylphenyl) pentaerythritol diphosphite) from Dover Chemical Corporation and 0.05% by weight calcium stearate were also mixed with the UV additives. These additives were compounded with reactor grade TPO polymer from Equistar (MF 1.3, Flex Modulus 25,200 psi) and a gray pigment using a 4% let down ratio via conventional single-screw extrusion parameters. After extrusion, standard 2 x 2 x 0.125 inch plaques were injection molded using an Arburg injection molder. The total amount of UV stabilizer package for each sample was approximately 0.2 wt%, based on the total weight of the sample. The performance criteria of gloss retention were measured at set exposure intervals (2500, 3750 and 5000 kj) using accelerated exposure in a xenon weather-ometer under SAEJ1885 interior automotive testing conditions. Prior to gloss measurement, the samples were washed with DI water and wiped. The results are shown in table 5 below: (The 2500 kj interval samples were not washed and wiped and thus were not included in the results). The results in Table 5 demonstrate that a TPO composition eohtaning a mindereal hydroxybenzoate, hindered amine and triazine UV absorber, (Example 8), provides better gloss retention than the individual components or combination of components. Color change, (Delta E), were also measured for Examples 4 to 8 and are shown below in Table 6. Delta E measurements were obtained using the same procedure in Examples 1 to 3 above. The results show that the hindered hydroxybenzoate/HALS composition (Example 7) had comparable Delta E performance to the composition containing a hindered hydroxybenzoate, hindered amine and triazine UV absorber (Example 8). It was speculated that the pigment in Example 7 was blocking or absorbing some of the UV radiation. This theory was tested in Examples 9 to 11 discussed below. Examples 9 to 11. Percent Gloss retention and Delta E change in a non-plgmented TPO system. Examples 7 and 8 were tested in a non-pigmented system along with a 0.2 wt% composition of Tinuvin® 791. Tinuvin 791 is an UV additive package used in the TPO industry. The samples were prepared similar to Examples 4 to 8 except that a pigment was not used in the samples and Tinuvin 791 had its own proprietary anti-oxidant package. The results for gloss retention and Delta E are shown in Tables 7 and 8 below. The results in Tables 7 and 8 demonstrate the superior performance of the composition containing the hindered hydroxybenzoate, hindered amine and triazine UV absorber in a non-pigmented TPO system. Example 12. Comparison of UV absorbers A composition containing a benzotriazole UV absorber (Tinuvin® 328), a HALS (Chimassorb® 119) and a hindered hydroxybenzoate is compared to Example 8 with respect to gloss retention and Delta E. Example 12 was prepared according to the procedure of Examples 4 to 8 above except it had its own proprietary anti-oxidant package. The results show that the composition containing the triazine UV absorber was superior over the composition containing the benzotriazole UV absorber. Examples 13 to 19. Comparison to commercial TPO W stapllizers The following Examples illustrate that a TPO composition containing a hindered hydroxybenzoate, hindered amine and triazine UV absorber performs better than commercial TPO additives. The procedure of Examples 4 to 8 was used to make the following examples with the exception that the TPO was produced by Basell (Grade AH 387 Bumper grade resin), the samples contained 5% talc and were washed with 01 water and wiped prior to measurement at all intervals. Examples 17 to 19 had their own proprietary anti-oxidant package. The composition percentages are approximations. The results demonstrate that the compositions'coniaining-tne rineeree hydroxybenzoate, hindered amine and triazine UV absorber in Examples 13 to 16 perform better than compositions containing commercial TPO additives. The invention described and claimed herein is not to be limited in scope by the specific embodiments herein disclosed, since these embodiments are intended as illustrations of several aspects of the invention. Any equivalent embodiments are intended to be within the scope of this invention. Indeed, various modifications of the invention in addition to those shown and described herein will become apparent to those skilled in the art from the foregoing description. Such modifications are also intended to fall within the scope of the appended claims. CLAIMS 1. A composition comprising an UV stabilizing composition comprising: (i) an ortho-hydroxy tris-aryl-s-triazine compound; (ii) a hindered hydroxybenzoate compound; and (iii) optionally a hindered amine compound containing a 2,2,6,6- tetraalkylpiperidine or 2,2,6,6-tetraalkylpiperazinone radical. 2. A composition as claimed in claim 1 in which the tris-aryl triazine has the formula wherein A, B and C are each aromatic, at least one of A, 8 and C is substituted by a hydroxy group ortho of the point of attachment to the triazine ring, and each of R, through Rg is selected from the group consisting of hydrogen, hydroxy, alkyl, aikoxy, sulfonic, carboxy, halo, haloalkyl and acylamino. 3. A composition as claimed in claim 2 in which the triazine is selected from 2,4,6- 2,4,6-tris(24hydroxy-4-octloxy)xyphenyl)-1.3,5-trizone: 2-2-)hydroxy-4-n-octykloxyphenyl)-4,6- bls(2.4-dimethylphenyl)-1,3.5-triazlne; 2-(2-hydroxy-4-(mbsed Iso- octoloxyphenyr)-.6-bls(2,4- dimethyphess)1,3,5-triazine; 2-(2,4dihydroxypherryl)-6-bls(2,4-dimethylphenyl)-1,3,5- triazine; 2,44-bls(2-hydroxy-4-propyloxypheny)-6-2,4-dimethyphenyl)-1,3,5-triazine: 2-(2- triazine; 2,44-bls(2-hydroxy-4-propyloxypheny)-6-2,4-dimethyphenyl)-1,3,5-triazine: 2-(2- triazine; 2,44-bls(2-hydroxy-4-propyloxypheny)-6-2,4-dimethyphenyl)-1,3,5-triazine: 2-(2- triazine; 2,44-bls(2-hydroxy-4-propyloxypheny)-6-2,4-dimethyphenyl)-1,3,5-triazine: 2-(2- triazine; 2,44-bls(2-hydroxy-4-propyloxypheny)-6-2,4-dimethyphenyl)-1,3,5-triazine: 2-(2- triazine; 2,44-bls(2-hydroxy-4-propyloxypheny)-6-2,4-dimethyphenyl)-1,3,5-triazine: 2-(2- triazine; 2,44-bls(2-hydroxy-4-propyloxypheny)-6-2,4-dimethyphenyl)-1,3,5-triazine: 2-(2- triazine; 2,44-bls(2-hydroxy-4-propyloxypheny)-6-2,4-dimethyphenyl)-1,3,5-triazine: 2-(2- dimethylphenylV1,3,5-trlazfne; 2-(2-hydroxy-4-hexytoxy)phenyl)-4-6-dipheny -1,3,5-triazine 2- (2-hydroxy-4-metholoxyl) -4,6-diphenyl 1,3,5-triazone: 2,4,6-tris-(2-hydroxy-4-(3-butoxy-2- riydfoxypropoxy)phenyf]1,3,5-triazine; 2-(2-droxyprienyl)-4methoxypheny)-6-phenyl- 1,3,5-triazine. 4. A composition as claimed in any preceding claim in which the hindered hydroxybenzoate compound has the formula V: wherein R17, Is a C1-C6 alky) and R16 Is a C1-C24 alkyl, or substituted or unsubstftuted C6-C24 aryl. 5. A composition as claimed in claim 4 in which the hindered hydroxybenzoate compound is selected from 2,4-di-tert-butylphenyl-3,5-di-tert-butyt-4- hydroxybenzoate hexadecy-3,5-di -tert buty-4- hydroxyt)erizoate; octadecyl-3.5-di-tret-butyt 4-hydraxybenzoate; octy-1-3,5- hydroxybenzoate; behenyiy-3,5.5di-tert -botyl-4-hrydroxybenzoate; 2-methyl-4,6-d-tert- hydroxybenzoate; behenyiy-3,5.5di-tert -botyl-4-hrydroxybenzoate; 2-methyl-4,6-d-tert- rr/droxybenzoyk>xy)phenyl] proplonate. 6. A composition as claimed in any preceding claim comprising an UV stabilizing composition comprising: (i) an orthb-hydroxy trt-ary-s-triazine compound; (8) a hindered hydroxybenzoate compound; and nj) a hinderd amine compound contaning a 2,2,6,6 tetraakylpiperide or 2,2,6,6-tetraakylespiprazinove radical. 7. A composition as claimed in claim 6 in which the hindered amlne compound contains a radical having the formula III: wherein R11 is hydrogen. O, OH, C1-C11 alkyl, -CH2CN. C1-C18 alkoxy, C1-C18 hydroxyakcoxy, C1-C12 cycloaHtoxy, C1-C12 hydrocycdoalkoxy, C1-C6 alkenyl, C1-C18 alkynyl, C1-C18 pnenylakyl. unsubstituted or substituted on the phenyl with 1,2 or 3 C1-C4 alkyl, or an aliphatic C1-C9 acy); R12 Is hydrogen, C1-C6 alkyl , or benzyl; R13, R14, R14, and R14 are each Independently a C1-C18 alkyl-benzyl or phenethyl, or optionally R18 and R14, and/or R15 and R14, taken together with the carbon which they are attached, form a C1-C18 cycloafcyl. 8. A composition as claimed in claim 7 in which the hindered amine compound is selected from 1H-Pyrrole-2,5-dione, 1-octadecyl-, polymer with (1- methyletheny)-benzene and 1-(2,2,6,6-tetrarrtethyl-piperldinyl)-1H-pyrrole-2,5-dione; piperazinone, 1,1:1-(1.3.5-triazine-2,4,6-triyltris(cyclohexylimino)-2,5 [3,3,5,5- tetramethyt-0; piperazlnone, 1,1:1-[1.3,5-triazine-2.4>6-tnVltris[(cyclohexylinmino)-2.1- ethanedlynjtris[3,3,4,5,5-pentamethyl-]; the reaction product of 7,7,9,9-tetramethyi-2- cydoundecyl-1-oxa-3,8-dia2a-4-oxosplro(4.5}decane and epichlorohydrin; the condensate of N,N-bis(2,2,6,6,4etramethyiplperidin-4-yl)hexarnethylenediamine and 4-cyc)ohexylamln0-2,6- dichloro-1,3,5-triazlne; the condensate of 1,2-bls(3-aminopropyJamino)ethane, 2,4,6-trichlon- 1,3,5-triadne and 44>uty1amlno-2,216,6-tetramethyiplpeeridene; the condensate of N.N'- bls(2.2,6,6-tetramethylp}peridin-4-yl)hexamethytenediarnlne and 4-morpholino-2.6-dichtoro- 1,3,5-triazlne; the condensate of 2-chome-4,6-bls(4-n-bulyamino-2.2,6,6- tetramethylpiperidyl)-1,3,5-trlazine and 1,2-bls(3-aminopropylamino)ethane; the condensate tetramethylpiperidyl)-1,3,5-trlazine and 1,2-bls(3-aminopropylamino)ethane; the condensate (3-anwiopropylarrAx3)etnane; 2^(2-bydroxyetriyl)airfnoH.6-bls[^ tetramethylpiperidyl)-1,3,5-trlazine and 1,2-bls(3-aminopropylamino)ethane; the condensate tetramethylpiperidyl)-1,3,5-trlazine and 1,2-bls(3-aminopropylamino)ethane; the condensate tetramethylplphridln-4-yl)-1, 2,3,4-butanetetracartoxylate; benzeneptopanolc acid, 3.5-bls(1.1- dlmethytetriyI)-4-nydroxy -.1[2[3-[3,5-bls 1.1 dimethyl)-4-hydroxylphenyl]-1-- oxopropoxylethyl]-2,2,6,6-tetramethyl-4-piperidiny ester,N(I-octyloxy-2,2,6,6- tetramethylpiperidyl)-1,3,5-trlazine and 1,2-bls(3-aminopropylamino)ethane; the condensate tetramethylpiperidyl)-1,3,5-trlazine and 1,2-bls(3-aminopropylamino)ethane; the condensate tetramethylpiperidyl)-1,3,5-trlazine and 1,2-bls(3-aminopropylamino)ethane; the condensate tetramethylpiperidyl)-1,3,5-trlazine and 1,2-bls(3-aminopropylamino)ethane; the condensate tetramethylpiperidyl)-1,3,5-trlazine and 1,2-bls(3-aminopropylamino)ethane; the condensate yl)hexamethyienediainine and 4-tert-oxylomeyhy -2.6dichloro-1,3,5-triazlne; 1,2.3.4- tetramethylpiperidyl)-1,3,5-trlazine and 1,2-bls(3-aminopropylamino)ethane; the condensate tetraniethylpiperldiiv4-yrvi,213.44)utanetetracarboxylate; 1.2.3,4-butanetetracart>oxyBcacW. tetramethylpiperidyl)-1,3,5-trlazine and 1,2-bls(3-aminopropylamino)ethane; the condensate 1,2.3,4-butanetetracarboxyiate; mixture of 2^,4,4-tetramethy»-21-oxo-7-oxa-3.20- diazaspiro(5.1.11.2)-henek»sane-20-propanote acid-dodecylester and 2,2,4,4-tetramethyi-2i- oxp-7-axa-3.20-dlaza$piro(5.1.11.2>her»elccisar)e-20-propanoJc add-tetradecytesfer; 1K4Hr5H,8H-2.3a.4a,6,7a,8a4iexaaza2,6- tetramethylpiperidyl)-1,3,5-trlazine and 1,2-bls(3-aminopropylamino)ethane; the condensate tetramethylpiperidyl)-1,3,5-trlazine and 1,2-bls(3-aminopropylamino)ethane; the condensate pjperidinyl)jsltoxane; copolymer of methylmethacrylate with ethyl acrytate and 2,2,6,6- tetramethylpiperklln-4-yl acrytete; copolymer of mixed C20 to C24 aipba-oleffns and (2,2,6,6- tetrainethylpiperfdin-4-yr)succinirnkde; 1,2,3,4-butanetetracatboxySc add, polymer with tetramethylpiperidyl)-1,3,5-trlazine and 1,2-bls(3-aminopropylamino)ethane; the condensate pentamethyM-pfperidinyl ester; 1,2.3.4-butanetetracarboxyficadd. polymer with b,b,b,b- tetramethyl-2,4,8,10-tetraoxasplro[5.5)undecane-3,9-liethanol, 2,2,6.6-tetramethyl-4- plperidinyl ester copolymer; 1.3-benzenedicarboxarnide, N,N'-bis(2,2,6.6-tetramethyl-4- piperldinyl;1.1-(1,10-dioxo-1,10-decanedity)-bls(hexahydro-2,2,4,4,6-pentamethylpyrimidine: ethane diamlde, N-(1-acetyl-2.2,6,6-tetramethylpiperidine-N'-dodecyl; formamkte. N.N'-1.6- ethane diamlde, N-(1-acetyl-2.2,6,6-tetramethylpiperidine-N'-dodecyl; formamkte. N.N'-1.6- ethane diamlde, N-(1-acetyl-2.2,6,6-tetramethylpiperidine-N'-dodecyl; formamkte. N.N'-1.6- dspiro{5.1.11.2]heneicosane; propanamkcle, 2-miethy-N-(2.2,6,6-tetramethyl-4-pipericnnyl)-2- [(2,2,6,6-tetramethyl--iperidiinyl)aitiino)-; 7-oxa-3,20-diazadispiro(5.1.11.2]heneicosane-20- propanoic acid. 2,2.4,4-tetramethyl-21-oxo- dodecyl ester;N-2.2,6,6-tetramethylpiperidin-4- y)-b-amlnoproplonlc add dodecyl ester, N-{2.2f6,6-tetramethylplperidin-4-yl>-NI- propanoic acid. 2,2.4,4-tetramethyl-21-oxo- dodecyl ester;N-2.2,6,6-tetramethylpiperidin-4- 4-piperidinyl)amino]-; mixture of 4-hexadecyloxy- and 4-stearyloxy-2,2,6>6- propanoic acid. 2,2.4,4-tetramethyl-21-oxo- dodecyl ester;N-2.2,6,6-tetramethylpiperidin-4- teramethylplperidin-4-l)succlnate; bls(11,2,6.6-pentamethylplperidin-4-yl) n-buty) 3,5-cel-tert propanoic acid. 2,2.4,4-tetramethyl-21-oxo- dodecyl ester;N-2.2,6,6-tetramethylpiperidin-4- (1,2-erthnethal)-(3,3,5,5-tetrafnethytplperazinone):4-benzoyl-2,2,6,6.nitramethylylpiperidine 4-stearytoxy-2,2.6,6-tetramethylplperidlne; bls(1 2,26,6-pentarnethylplperidyl)-2-n-butyl-2-(2- hydroxy-3,5-di-tert-butybenzyi)malonate; 3-n-octyl-7,7,9,9-teiramethyl-1,3,8 teramethylplperidin-4-l)succlnate; bls(11,2,6.6-pentamethylplperidin-4-yl) n-buty) 3,5-cel-tert- teramethylplperidin-4-l)succlnate; bls(11,2,6.6-pentamethylplperidin-4-yl) n-buty) 3,5-cel-tert trlazasplrot4.$]decane-2,4-dione; 3-doclomecyl- (2,2,6,6tetramethyldin-4-pyrmethyltypical-4-yl)pylicone-2,5 done; 3-diodecyl)-1-(1-ethanoyl-2,2,6.6-tetramethy)p-4-))pyrrolidht-2,5-dione;-2,5 dodecyl-1-(1,2,2,8,6-pertamethyiplperklin-4-yl)pyrrolline -4-2,5-dionoa a mixture of 4- teramethylplperidin-4-l)succlnate; bls(11,2,6.6-pentamethylplperidin-4-yl) n-buty) 3,5-cel-tert teramethylplperidin-4-l)succlnate; bls(11,2,6.6-pentamethylplperidin-4-yl) n-buty) 3,5-cel-tert teramethylplperidin-4-l)succlnate; bls(11,2,6.6-pentamethylplperidin-4-yl) n-buty) 3,5-cel-tert bls(1,22,6.6-pentamethyl-4-plperidlny1). 9. A composition as claimed in any preceding clams further comprising a material to be stabilized selected from pdyolefins, polyesters, polyethers, polyketones, polyamides. natural and synthetic rubbers, polyuretharnes, polystyrenes, high-tonpact polystyrenes, polyacrytates. polymethcylates, potyacetals, polyacylonitrilies, polybutaditions. polystyrenes, acrytorrile4butione-styrene, styrene acrytonitnie. apryiate styerne acrytonnitrate, cellusisIc acetate butyrate, cellulose polymens, potyimides, polyamiders. polystyrenes, acrytorrile4butione-styrene, styrene acrytonitnie. apryiate styerne polyvlnylchlorldes, polycarbonates, polyketones, aliphatic polyketone, themoplastic olefine, aminoresin cross-linked polyacrylates and polyesters, pohisoocyanate cross-linked polyesters and polyacrylates, phenoVformakdeehyde, urea/formaldehyde and melamine/formaldehyde resins, drying and non-drying alkyd resins, alkyd resins, polyester resins, acrylate resins cross-linked with melannine resinsn urea resins, isocyanates, isocyanurates, carbamates, and epoxy resins, cross-linked epoxy resins derived from aliphatic, cycloaliphatic, heterocyctlc and aromatic glycydyi compounds, which are cross-linked with anhydrides or amines, polysiloxanes, Michael addition polymers, amines, blocked amines with activated unsaturated and methylene compounds, ketimines with activated unsaturated and methylene compounds, polyketimines in combination with unsaturated acrylic polyacetoacetate Tesins, polyketimines in combination with unsaturated acrylic resins, radiation curable compositions, epoxymelamine resins, organic dyes, cosmetic products, cellulose-based paper formulations, photographic film paper, fibers, waxes, inks, and blends thereof. 10. - A composition as claimed in claim 9 in which the material to be stabilized is selected from thermoplastic olefins, acrylonitrile-butadiene-styrene, polyesters, polyvinylcchloride, polyamides, polyurethanes, or homo- and copolymers of propylene, isobutytene, butene, methylpentene, hexene, heptene. octene, Isoprene, butadiene, hexadiene, dicyctopentadtene, ethyliene cyclopentene and norbomene. 11. A composition as claimed in claim 9 or claim 10 in which the amount of said triazine compound is from 0.01 to 1.0 wt%, the amount of said hindered hydroxbenzoate compound is from 0.1 to 1.0 wt%and the amount of said hindered amine compound is from 0.1 to 1.0 wt%, based on the total weight of said material to be stabilized. 12. A process for preparing a composition as claimed in any one of claims 9 to 12 in which the material to be stablized is contacted with said UV stablizing-composition. This invention relates to an UV stabilizing additive composition comprising an oetho-hydroxy triazine compound, a hindered hydroxybenzoate compound and optionally a hindered amine compound. This additive composition may be used to stablize materials from UV radiation. This invention also contemplates a method of stabilizing a material by contacting the material with the UV stabilizing additive composition.

Full Text

UV STABILIZED THERMOPLASTIC OLEFINS
This application claims the benefit under 35 U.S.C. § 119(e) of United States
Provisional Application Serial No. 60/343,681, filed December 27, 2001.
FIELD OF THE INVENTION
This invention relates to an improved UV stabilizing additive composition. More
specifically, this invention relates to an UV stabilizing additive composition comprising an
ortho-hydroxy triazine compound, a hindered hydroxybenzoate compound and optionally a
hindered amine compound.
BACKGROUND OF THE INVENTION
Exposure to sunlight and other sources of ultraviolet (UV) radiation is known to cause
degradation of a wide variety of materials, especially polymeric materials. For example,
polymeric materials such as plastics often discolor, lose gloss and/or become brittle as a result
of prolonged exposure to UV light due primarily to a reduction in the molecular weight of the
polymer. Accordingly, a large body of art has been developed directed towards materials such
as UV light absorbers and stabilizers, which are capable of inhibiting such degradation in
polymeric articles.
U.S. Patent No. 4,670,491 discloses the use of a C12 to C20alkyl esters of 3,5-
tertbutyl-4-hydroxybenzoic acid to stabilize a titanium dioxide pigmented olefin composition.
U.S. Pat. No. 5,240, 977 discloses the use of a 3,5-disubstituted tert-butyl-4-hydroxybenzate
with a triazine based hindered amine light stabilizer (HALS) in a pigmented polyolefin
composition. U.S. Pat. No. 3,206,431 discloses the use of alkyl esters of 3,5-di-tert-butyl-4-
hydroxybenzoic acid as light stabilizers for polyolefins in combination with a hindered phenol
antioxidant. U.S. Pat. Nos. 3,681,431 and 3,285,855 disclose the use of n-octadecyl 3,5-di-
tert-butyl-4-hydroxybenzoate as an antioxidant for polyolefins. British Pat. No. 1,336,931
teaches the use of aryl esters of 3,5-di-tert-butyt-4-hydroxybenzoic acid as light stabilizers
for polyolefins in combination with a benzophenone and a peroxide decomposer. U.S. Pat.
No. 3,502,613 teaches a synergistic combination of an aryl ester of 3,5-di-tert-butyl-4-
hydroxybenzoic acid, a chlorobenzotriazole, a phenolic antioxidant, and a thiodipropionate
ester as a light stabilizer for polypropylene. U.S. Pat. No. 4,237,042 discloses a light
stabilizer composition for polyolefins comprising n-hexadecyl 3,5-di-tert-butyI-4-
hydroxybenzoate and a dialkyl pentaerythrityl diphosphite.
None of the above documents disclose the use of a hindered hydroxybenzoate
compound with an ortho-hydroxy triazine UV absorber erner with on witner-a-hinserea
amine compound.
SUMMARY OF THE INVENTION
This invention relates to an UV stabilizing additive composition comprising an ortho-
hydroxy triazine compound, a hindered hydroxybenzoate compound and optionally a
hindered amine compound. This additive composition may be used to stabilize materials
from UV radiation. This invention also contemplates a method of stabilizing a material by
contacting the material with the UV stabilizing additive composition.
DETAILED DESCRIPTION OF THE INVENTION
This invention relates to an UV stabilizing additive composition comprising an
ortho-hydroxy tris-aryl-s-triazine compound; and a hindered hydroxybenzoate compound,
and optionally a hindered amine light stabilizing (HALS) compound containing, for
example a 2,2,6,6-tetraalkylpiperdine or 2,2,6,6-tetraalkylpiperazinone radical.
Preferably, the ortho-hydroxy tris-aryl-s-triazine compound has the following formula I:
where A, B and C are each aromatic, at least one of A, B and C is substituted by a hydroxy
group ortho to the point of attachment to the triazine ring, and each of R1 through R9 is
selected from the group consisting of hydrogen, hydroxy, alkyl, alkoxy, sulfonic, carboxy,
halo, haloalkyl and acylamino having from about 1 to about 24 carbon atoms.
One embodiment of the tris-aryl-s-triazine is a compound having the formula II:
where Ar1 and Ar2 are the same or different and are subsititud of unsudsimured arly glotips;
and where R20 and R21 are each independently a hydrogen, C1-C24 alkyl, C1-C24 haloalkyl, C6-
C24 aryl, C1-C24 alkenyl, C1-C24 acyl, C1-C24 cycloalkyl, C5-C24 cycloacyl, C7-C24 aralkyl, or C6-
C24 aracyl, substituted or unsubstituted biphenylene, substituted or unsubstituted napthalene,
OR, NRR", CONRR', OCOR, CN, SR, SO2R, and where R and R' are each independently a
hydrogen, C1-C24 alkyl, C1-C24 haloalkyl, C6-C24 aryl, C2-C24 alkenyl, C1-C24 acyl, C1-C24
cycloalkyl, C5-C24 cycloacyl, C7-C24 aralkyl, or C6-C24 aracyl, substituted or unsubstituted
biphenylene, or substituted or unsubstituted napthalene.
Preferably, in the above formula II Ar1 has the formula Ha:
where R22 and R23 are each independently a hydrogen, C1-C24 alkyl, C1-C24 haloalkyl, C6-C24
aryl, C2-C24 alkenyl, C1-C24 acyl, C1-C24 cycloalkyl, C5-C24 cydoacyl, C7-C24 aralkyl, or C6-C24
aracyl, substituted or unsubstituted biphenylene, substituted or unsubstituted napthalene, OR,
NRR', CONRR', OCOR, CN, SR, and SO2R, and where R and R' are as defined above.
Also preferred in the above formula II is when R20 is hydrogen or a C1-C6 alkyl, R21 is
hydrogen and Ar1 and Ar2 maybe the same or different and are benzyl, methylbenzyl, or
dimethylbenzyl.
Examples of suitable tris-aryl-s-triazine that may be used are 2,4,6-tris(2-hydroxy-4-
octyloxyphenyl)-1,3,5-triazine; 2-(2-hydroxy-4-n-octyloxyphenyl)-4,6-bis(2,4-dirnethylphenyl)-
1,3,5-triazine; 2-(2-hydroxy-4-(mixed iso-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-propyloxyphenyl)-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)-1,3l5-triazine;2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-
1,3,5-triazine;2-[2-hydroxy-4-(2-hydroxy-3-butyloxypropyloxy)phenyl]-4,6-bis(2l4-
dimethylphenyl)-1,3,5-triazine; 2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropyloxy)-phenyl]-4,6-
bis(2,4-dimethylphenyl)-1,3,5-triazine; 2-[4-dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-
hydroxyphenyl]-4,6-bis(2.4-dimethylphenyl)-1,3,5-triazine;2-[2-hydroxy-4-(2-hydroxy-3-
dodecyloxypropoxy)phenyrj-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine; 2-(2-hydroxy-4-
hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine; 2-(2-hydroxy-4-methoxyphenyf)-4.6- 1,3,5-triazine; 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyfj-1,3,5-triazine and 2-
(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine.
The optional hindered amine compound may be any suitable hindered amine
compound such as those containing a 2,2,6,6-tetraalkylpiperdine or 2,2,6,6-
tetraalkylpiperazinone radical. One embodiment of a hinderred arms components one that
contains at least one group having the following formula III:
where R11 is hydrogen, O, OH, C1-C16 alkyl, -CH2CN, C1-C18 alkoxy, C1-C18 hydroxyalkoxy,
C6-C12 cycloalkoxy, C6-C12 hydrocydoalkoxy, C3-C6 alkenyl, C6-C18 alkynyl, C7-C9 phenylalkyl,
unsubstituted or substituted on the phenyl with 1, 2 or 3 C1-C4 alkyls, or an aliphatic C1-C8
acyl; R12 is hydrogen, C1-C8 alkyl, or benzyl; R13, R14, R15, and R16 are each independently a
C6-C18 alkyl, benzyl or phenethyl, or optionally R13 and R14, and/or R15 and R16, taken together
with the carbon which they are attached, form a d-do cycloalkyl.
Another embodiment of a hindered amine compound is a compound that has formula
IV below:
where R10 is a morpholino, C1-C8 alkylamine, di(C1-C6) alkylamine, pyrrolidyl,
cyclohexylamine or combinations thereof,
X and X1 which may be the same or different, and are hydrogen, C1-C20alkyi, or a
radical of formula III defined above,
R11 to R16 are as defined above,
Z is a straight chained or branched C1-C20 alkylene or a straight chained or branched d-
C20 alkalene chain interrupted by at least oxy, thio, or —N(Rt7)—, where R17 is hydrogen,
d-do alkyl, C5-C10 cycloalkylene C6-C12 arylene, C6-C14 aralkylene or the radical of
formula III;
n is an integer greater than 1;
and Y is a halogen atom, C1-C8 alkylamine, di(C1-C8) alkylamine, pyrrolidyl, morpholino,
cyclohexylamine, or
where X, X1f and Z are as previously defined.
Preferably In the above formula IV, Z is a C2 to C6 alkylene, R10 is a morpholino or
cyclohexylamine, X and X, is the radical of formula III. R11 is hydrogen or methyl, R12 is
hydrogen, and R13. R14, H16 and R16 are methyl.
Another embodinr ent of a hindered amihe is a 2,2,G,6-tetraalkylpiperazinone. One
embodiment of a 2,2,6,6-tetraalkylpiperazinone compound is one that contains at least one
group of formula IVa:
where R11 is as defined above.
Examples of suitable hindered amine compounds include, but are not limited to:
1 H-Pyrrole-2,5-dionet '-o;tadecyl-, polymer with (1-methylHthenyl)benzene and 1-{2,2,6,6-
tetramethyl-4-piperidinyl)-1 H-pyrrole-2,5-dione; piperazinone, 1,1', 1 "-[1,3,5-tria/:ine-2,4,6-
trlyltris[{cyclohexylimino)-1:-ethanediyl]Jtris[3,3,5,5-tetram6!thyl-; piperazinone, 1,1',1"-[1,3,5-
triaz/ne-2,4,6-triyltris[(c/ch)hexyfimino)-2,1-ethanediylJ]tris[3,3.4,5,5-pentamethyl-; (he
reaction product of 7,7,9,9-tetrarnethy[-2-cydoundecyl-1-ox;3-3,8-diaza-4-oxospiro[4.5]decane
and epichlorohydrin; the candensate of N,N'-bis(2,2,616-tetr.3methylpiperidin-4-
yl)hexamethylenediamine and 4-cyclohexylamino-2,6-dichlcro-1,3,5-triazine; the condensate
of 1,2-bis(3-aminopropylamino)ethane, 2,4,6-trichloro-1,3,5-triazine and 4-butv!amino-2,2,6,6-
tetramethylpiperidine; the condensate of N,N'-bis(2,2,6,6-tetramethylpiperidin-4-
yl)hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine; the cc ndensate of 2-
chloro-4.6-bis(4-n-butylam no-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazine and 1,2-bis(3
aminopropylamino)ethaie; the condensate of 2-chloro-4,6-bis(4-n-butylamino-1,2,2,6,6-
pentamethylpiperidyl)-1,3.5-triazine and 1,2-bls-(3-aminopropylamino)ethane; 2-[(2-
hydroxyethyl)aminoJ-4l6-bi3[N-(1-cyclohexyloxy-2l2,6,6-tetr£methyIpiperidin-4-yl)butylar i
1,3,5-triazine; propanedioic add, [(4-methoxyphenyl)-methyl3ne]-bis-(1,2,2,6,6-pentamethv'-
4-piperidinyl) ester; tetrakis (2,2,6,6-tetramethylpiperidin-4-yl)-1,2,3,4-butanetetracarboxyla
benzenepropanoic add, 3,:5-bis(1,1 -dimethylethyl)-4-hydroxy-, 1 -[2-f3-[3,5-bis(1,1 -
dimethylethylH-hydroxyphsnyfJ-i-oxopropoxylethy]-2,2,6,6 tetrarrrethyl-4-piperidinyl ester;
N-(1-octyloxy-2,2,6,6-teiramethylpiperidin-4-yl)--N-dociecyioxaiamKae, ms2,2,6,6
tetramethylpiperidin-4-yi) nitrilotriacetate; 1,5-dfoxaspiro{5,5}undecane-3,3- bis(1,2,2,6,6-pentamethy;-4-piperidinyl): 1,5-dioxaspiro{5,5}undecane-3,3-dicarboxylic add,
bis(2,2,6,6-tetramethyl-4-piperidinyl); the condensate of 1-(2-hydroxyethyt)-2,2,6,6-
tetramethyl-4-hydroxypiperidine and sucdnic acid; the condensate of N,N'-bis(2,2,6,6-
tetramethylpiperidin-4-yl)hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-
triazine; 1,2,3,4-butanetetracarboxylic add, l,2,2,6,6-pentamethyl-4-plperidinyl tridecyl ester;
tetrakis(2,2,6,6-tetramethylpiperidln-4-yl)-1,2,3,4-butanetetracarboxylate; 1,2.3,4-
butanetetracarboxylic add, 2,2,6,6-tetramethyl-4-piperidinyl tridecyl ester; tetrakis(1,2,2,6,6-
pentamethylpiperidin-4-yl)-1,2,3,4-butanetetracarboxylate; mbdure of 2,2,4,4-tetramethyl-21-
oxo-7-oxa-3.20-diazaspiro(5.1.11.2)-heneicosane-20-propanoic acid-dodecylester and
2,2,4,4-tetramethyl-21-oxo-7-oxa-3.20-diazaspiro(5.1.11.2)-heneicosane-20-propanoic acid-
tetradecylester, 1H,4H,5H,8H-2,3a,4a,6,7a,8a-hexaazacydopenta[dff]fluorene-4,8-dione,
hexahydro-2,6-bis(2,2,616-tetramethyl-4-piperidinyf)-;polymethyl[propyl-3-oxy(2l,21,6l,61-
tetramethyM^'-piperidinytJlsiloxaneipolymethyllpropyl-S-oxytr.^.^.e'.e'-pentamethyM^'-
piperidinyl)]siloxane; copolymer of methyimethacrylate with ethyl acrylate and 2,2,6,6-
tetramethylpiperidin-4-yi acrylate; copolymer of mixed C^ to C2« alpha-olefins and (2,2,6,6-
tetramethylpiperidin-4-yl)succinimide; 1,2,3,4-butanetetracarboxylic acid, polymer with
p,p,p\P'-tetramethyl-2,4,8,10-tetraoxaspiro[5.5Jundecane-3,9-diethanol, 1,2,2,6,6-
pentamethyl-4-piperidinyl ester; 1,2,3,4-butanetetracarboxylic acid, polymer with p.p.p'.p'-
tetramethyl-2,4,8>10-tetraoxaspiro[5.5]undecane-3,9-diethanol, 2,2,6,6-tetramethyl-4-
piperidinyl ester copolymer; 1,3-benzenedicarboxamide, N,N'-bis(2,2,6,6-tetramethyl-4-
piperidinyl; 1,1'-(1,10-dioxo-1,10-decanediyl)-bis(hexahydro-2,2,4,4,6-pentamethylpyrimidine;
ethane diamide. N-(1-acetyl-2,2l6,6-tetramethylpiperidinyl)-N'-dodecyl; formamide, N,N*-1,6-
hexanediylbis[N-(2.2,6,6-te1ramethyl-4-piperidinyl); D-glucitol, 1,3:2,4-bis-O-(2,2,6,6-
tetramethyl-4-piperidinylidene)-; 2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21 -oxo-
dispirot5.1.11.2]heneicosane; propanamide, 2-methyl-N-(2,2,6,6-tetramethyl-4-piperidinyl)-2-
t(2,2,6,6-tetramethyl-4-piperidinyl)amino]-; 7-oxa-3,20-diazadispiro[5.1.11.2]henelcosane-20-
propanoic acid, 2,2,4,4-tetramethyl-21-oxo-, dodecyl ester; N-(2,2,6.6-tetramethylpiperidin-4-
yl)-P-aminopropionic add dodecyl ester, N^^.e.e-tetramethylpiperidin^-ylVN1-
aminooxalamide; propanamide, N-(2,2,6,6-tetramethyl-4-piDeridinyl>-3-{(2,2r6,6-tetramethyl-
4-piperidinyl)amino]-; mixture of 4-hexadecyloxy- and 4-stearyloxy-2,2,6,6-
tetramethylptperidine; 3-dodecyl-1-(1,2,2,6,6-pentamethylpiperidin-4-y1)pyrrolidine-2,5-dione;
3-dodecyl-1-(1-ethanoyt-2,2,6,6-pentamethylpiperidin-4-yl)pyrrolidine-2,5-dione;bis(2,2,6,6-
tetramethylpiperidin-4-yl)sucdnate; bis(1,2,2,6,6-pentamethylpiperidin-4-yl) n-butyl 3,5-di-tert-
butyl-4-hydroxybenzylmalonate; tris(2,2,6,6-tetramethylpiperidin-4-yl) nitrilotriacetate; 1,1'-
(1,2-ethanediyl)bis(3,3,5,5-tetramethylpiperazinone);4-benzoyl-2,2,6,6-tetramethylptperidine;
4-stearyloxy-2,2,6,6-tetramethylpiperidine; bis(1,2,2,6,6-pletamenyyipi)-2-nwbury (2-
hydroxy-3,5-di-tert-butylbenzyi)malonate; 3-n-octyl-7,7,9,9-tetramethyt-1,3,8-
tiiazaspiro[4.5)decan-2,4dione;bfs(1-octyloxy-2,2,6,6-tetramethylpipericlyl)sebacate;bis(1-
octaloxy-2,2,6,6-tetramethylpiperidyl)sucxinate;8-acety-3-cklecyl-7,7,9,94etrarnethyl-1,3,8-
triazaspiro[4.5]decane-2,4-dione;3-dodecyl-1-(2,2,6,6-tetramethylpipericlin-4-yl)pyrrolidin-2,5-
dione; 3-odecyl-1-(1-ethanoyl-2,2,6,6-tetramethylpiperidin-4-yl)pyrrolidin-2,5-dione; 3-
dodecyl-1-(1,2,2,6.6-pentamethyip«peridin-4-yl)pyrrolidine-2,5-dlone; a mixture of 4-
hexadecyloxy- and 4-stearyloxy-2,2,6,6-tetrarnethylpiperidine; 2-undecyl-7,7,9,9-tetramethyl-
1 -oxa-3,8-draza-4-oxospirof4.5]decane; 1,5-dioxaspiro{5,5)undecane-3,3-dicarboxyltc add,
bis(2,2,6,6-tetramethyl-4-piperidinyl) and 1,5-d!oxaspiro{5,5>undecane-3,3-dicarboxylic acid,
bis(1,2,2,6,6-pentamethyl-4-piperidinyl).
It is also contemplated in this application that the hindered amine compound is not
optional and the UV stabilizing additive composition would contain ah ortho-hydroxy triazine
compound, a hindered hydroxybenzoate compound and a hindered amine compound.
the hindered hydroxybenzoate compound of the present invention may be any
suitable hindered hydroxybenzoate compound such as those having the formula V:
where R17 is a C1-C8 alkyl and R18 is a C1-C24 alkyl, or substituted or unsubstituted C6-C24 aryl.
Preferably, R17 is t-butyl and R18 is a C10-C20 alkyl.
Examples of suitable hindered hydroxybenzoate compounds include: 2,4-di-tert-
butytphenyl 3,5-di-tert-butyl-4-hydroxybenzoate; hexadecyl-3,5-di-tert-butyl-4-
hydroxybenzoate;octadecyl-3,5-di-tert-butyl-4-hydroxybenzoate; octyl-3,5-di-tert-butyl-4-
hydroxybenzoate; tetradecyl-3,5-di-tert-butyl-4-hydroxybenzoate; behenylyl-3,5-di-tert-butyt-4-
hydroxybenzoate; 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate and
butyl 3-[3-t-butyl-4-(3,5-di-t-butyl-4-hydroxybenzoyloxy)phenylI propionate.
In one embodiment of the present invention, the UV stabilizing additive
composition of the present invention may be employed to stabilize materials which are
subject to degradation by ultraviolet radiation by contacting the UV stabilizing additive
composition with a composition comprising polymeric or other materials, either chemically
or physically. Non-limiting examples of materials that may be so stabilized are polyolefins,
polyesters, polyethers, polyketones, polyamides, natural and synthetic rubbers,
polyurethanes, polystyrenes, high-impact polystyrenes, polyacrylates, polymethacrylates,
polyacetals, polyacrylonitriles, polybutadienes, polystyrenes, acrylonitrile-butadiene-
styrene, styrene acrylonitrile, acrylate styrene acrylonithie-cellodsilea acelate butyrate,
cellulosic polymers, polyimides, polyamideimides, polyetherimides, polyphenylsulfides,
polyphenyioxkie, polysutfones, polyethersulfones, polyvinylchlorides, polycarbonates,
polyketones, aliphatic polyketones, thermoplastic olefins, aminoresin cross-linked
poryacrylates and polyesters, polyisocyanate cross-linked polyesters and polyacrylates,
phenol/formaldehyde, urea/formaldehyde and melamine/formaldehyde resins, drying and
non-drying alkyd resins, alkyd resins, polyester resins, acrylate resins cross-linked with
melamine resins, urea resins, isocyanates, isocyanurates, carbamates, and epoxy resins,
cross-linked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic and aromatic
glycidyl compounds, which are cross-linked with anhydrides or amines, polysiloxanes,
Michael addition polymers, amines, blocked amines with activated unsaturated and
methylene compounds, ketimines with activated unsaturated and methylene compounds,
polyketimines in combination with unsaturated acrylic polyacetoacefate resins,
polyketimines in combination with unsaturated acrylic resins, radiation curable
compositions, epoxymelamine resins, organic dyes, cosmetic products, cellulose-based
paper formulations, photographic film paper, fibers, waxes, inks, and blends thereof.
Preferably, the materials to be stabilized are thermoplastic olefms, acrylonitrile-
butadiene-styrene, polyesters, polyvinylchloride, polyamides, polyurethanes, or homo- and
copolymers of propylene, isobutylene, butene, methylpentene, hexene, heptene, octene,
isoprene, butadiene, hexadiene, dicyclopentadiene, ethylidene cyclopentene and
norbornene. More preferably, the materials are polypropylene and thermoplastic olefins.
The amount of the triazine compound used in the material to be stabilized is about
0.001 to about 3.0 wt%, preferably about 0.01 to about 1.0 wt% and more preferably 0.1 to
about 0.5 wt% based on the total weight of the material to be stabilized.
The amount of the hindered hydroxybenzoate compound is the material to be
stabilized about 0.001 to about 3.0 wt%, preferably about 0.01 to about 2.0 wt%, more
preferably about 0.1 to about 1.0 wt% based on the total weight of the material to be
stabilized.
The amount of the hindered amine compound in the material to be stabilized is about
0.001 to about 3.0 wt%, preferably about 0.01 to about 2.0 wt%, more preferably about 0.1 to
about 1.0 wt% based on the total weight of the material to be stabilized.
This application also contemplates a method of preparing the compositions above by
contacting the UV stabilizing additive composition with the material to be stabilized. The
material to be stabilized and UV stabilizing additive composition are contacted by preferably
blending or compounding the components in a kneading apparatus such as a single or twin
screw extruder, Banbury mixer, or hot rollers. The processing parameters and the use of such
kneading apparatuses are well known to those skilled in the art.
As would be apparent to those skilled in the art of !maxing piasne materials, inacetion
to the material to be stabilized and UV stabilizing additive composition, the composition of the
present invention may include conventional additives including but are not limited to,
antioxidants, metal deactivators, hydroxylamines, nitrones, lactones, co-stabilizers, nucleating
agents, clarifying agents, neutralizes, metallic stearates, metal oxides, hydrotalcites, fillers
and reinforcing agents, plasticizers, lubricants, emulsifiers, pigments, rheological additives,
catalysts, level agents, optical brighteners, flame retardant agents, anti-static agents and
blowing agents.
The present invention will now be illustrated by the following examples. The examples
are not intended to limit the scope of the present invention. In conjunction with the general
and detailed descriptions above, the examples provide further understanding of the present
invention.
EXAMPLES
Examples 1 to 3. Gloss retention. Delta E. Delta Yt and Breaking Strength in a
polypropylene homopolymer composition
The UV additives of Examples 1 to 3 were mixed by using a dry blending
technique. In addition to the additives, an antioxidant package containing 0.05% by weight
Cyanox® 1741 (1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-s-triazine-
2,4,6(1 H,3H,5H)trione) from Cytec Industries Inc. 0.05% by weight Doverphos® 9228
(bis(2,4-dicumylphenyl) pentaerythritol diphosphite) from Dover Chemical Corporation and
0.05% by weight calcium stearate were also mixed with the UV additives. These additives
were compounded with a polypropylene homopolymer from Basell (PH350) and extruded
using conventional single-screw extrusion parameters. After extrusion, standard 2 x 2 x
0.125 inch plaques were injection molded using an Arburg injection molder.
The performance criteria of Gloss retention. Delta E, Delta Yl and Breaking
Strength were measured at set exposure intervals (2000 and 3125 hours) using
accelerated exposure in a xenon weather-ometer under ASTM-G-155 testing conditions.
Prior to gloss and color measurements, the samples were washed with Dl water and
wiped.
Gloss retention was conducted under ASTM Test Procedure D523 with a 60°
angle.
Yellow Index (Yl) and Delta E data was obtained using a Macbeth Color Eye
Colorimeter using ASTM D2244-79 with 1" view and D65/100 observer. Delta Yl and Delta
E is the difference between samples measured before and after the weather-ometer
testing. Lower Delta E and Delta Yl means less color and less yellow index change
respectively indicating better performance.
For breaking strength, 3 tensile bars per each data point were tested on an Instron
Engineering Company Tensile Tester (Model TTB). The average tensile breaking strength
of the three test samples were measured and normalized to samples that were not UV
exposed to give a % breaking strength. The cross-head speed of the tensile tester was 1
inch (0.254 cm.) per minute.
The results are shown in Tables 1 to 4 below.
The results demonstrate that additive compositions containing a triazine UV.
absorber with the hindered hydroxybenzoate perform better than compositions containing
the hindered hydroxybenzoate alone.
Examples 4 to 8. Gloss retention and Delta E in a plqmented TPO composition
The UV additives of Examples 4 to 8 were mixed by using a-dry blending
technique. In addition to the additives, an antioxidant package containing 0.05% by weight
Cyanox® 1741 (1,3,5-tris-(3,5-di-di-tert-butyl-4-hydroxybenzyl)-s-triazine-
2,4,6(1 H,3H,5H)trione) from Cytec Industries Inc. 0.05% by weight Doverphos® 9228
(bis(2,4-dicumylphenyl) pentaerythritol diphosphite) from Dover Chemical Corporation and
0.05% by weight calcium stearate were also mixed with the UV additives. These additives
were compounded with reactor grade TPO polymer from Equistar (MF 1.3, Flex Modulus
25,200 psi) and a gray pigment using a 4% let down ratio via conventional single-screw
extrusion parameters. After extrusion, standard 2 x 2 x 0.125 inch plaques were injection
molded using an Arburg injection molder. The total amount of UV stabilizer package for
each sample was approximately 0.2 wt%, based on the total weight of the sample.
The performance criteria of gloss retention were measured at set exposure
intervals (2500, 3750 and 5000 kj) using accelerated exposure in a xenon weather-ometer
under SAEJ1885 interior automotive testing conditions. Prior to gloss measurement, the
samples were washed with DI water and wiped. The results are shown in table 5 below:
(The 2500 kj interval samples were not washed and wiped and thus were not included in
the results).
The results in Table 5 demonstrate that a TPO composition eohtaning a mindereal
hydroxybenzoate, hindered amine and triazine UV absorber, (Example 8), provides better
gloss retention than the individual components or combination of components.
Color change, (Delta E), were also measured for Examples 4 to 8 and are shown
below in Table 6. Delta E measurements were obtained using the same procedure in
Examples 1 to 3 above.
The results show that the hindered hydroxybenzoate/HALS composition (Example
7) had comparable Delta E performance to the composition containing a hindered
hydroxybenzoate, hindered amine and triazine UV absorber (Example 8). It was
speculated that the pigment in Example 7 was blocking or absorbing some of the UV
radiation. This theory was tested in Examples 9 to 11 discussed below.
Examples 9 to 11. Percent Gloss retention and Delta E change in a non-plgmented
TPO system.
Examples 7 and 8 were tested in a non-pigmented system along with a 0.2 wt%
composition of Tinuvin® 791. Tinuvin 791 is an UV additive package used in the TPO
industry. The samples were prepared similar to Examples 4 to 8 except that a pigment
was not used in the samples and Tinuvin 791 had its own proprietary anti-oxidant
package. The results for gloss retention and Delta E are shown in Tables 7 and 8 below.
The results in Tables 7 and 8 demonstrate the superior performance of the
composition containing the hindered hydroxybenzoate, hindered amine and triazine UV
absorber in a non-pigmented TPO system.
Example 12. Comparison of UV absorbers
A composition containing a benzotriazole UV absorber (Tinuvin® 328), a HALS
(Chimassorb® 119) and a hindered hydroxybenzoate is compared to Example 8 with
respect to gloss retention and Delta E. Example 12 was prepared according to the
procedure of Examples 4 to 8 above except it had its own proprietary anti-oxidant
package.
The results show that the composition containing the triazine UV absorber was
superior over the composition containing the benzotriazole UV absorber.
Examples 13 to 19. Comparison to commercial TPO W stapllizers
The following Examples illustrate that a TPO composition containing a hindered
hydroxybenzoate, hindered amine and triazine UV absorber performs better than
commercial TPO additives. The procedure of Examples 4 to 8 was used to make the
following examples with the exception that the TPO was produced by Basell (Grade AH
387 Bumper grade resin), the samples contained 5% talc and were washed with 01 water
and wiped prior to measurement at all intervals. Examples 17 to 19 had their own
proprietary anti-oxidant package. The composition percentages are approximations.
The results demonstrate that the compositions'coniaining-tne rineeree
hydroxybenzoate, hindered amine and triazine UV absorber in Examples 13 to 16 perform
better than compositions containing commercial TPO additives.
The invention described and claimed herein is not to be limited in scope by the
specific embodiments herein disclosed, since these embodiments are intended as
illustrations of several aspects of the invention. Any equivalent embodiments are intended
to be within the scope of this invention. Indeed, various modifications of the invention in
addition to those shown and described herein will become apparent to those skilled in the
art from the foregoing description. Such modifications are also intended to fall within the
scope of the appended claims.
CLAIMS
1. A composition comprising an UV stabilizing composition comprising:
(i) an ortho-hydroxy tris-aryl-s-triazine compound;
(ii) a hindered hydroxybenzoate compound; and
(iii) optionally a hindered amine compound containing a 2,2,6,6-
tetraalkylpiperidine or 2,2,6,6-tetraalkylpiperazinone radical.
2. A composition as claimed in claim 1 in which the tris-aryl triazine has the formula
wherein A, B and C are each aromatic, at least one of A, 8 and C is substituted by a
hydroxy group ortho of the point of attachment to the triazine ring, and each of R, through
Rg is selected from the group consisting of hydrogen, hydroxy, alkyl, aikoxy, sulfonic,
carboxy, halo, haloalkyl and acylamino.
3. A composition as claimed in claim 2 in which the triazine is selected from 2,4,6-
2,4,6-tris(24hydroxy-4-octloxy)xyphenyl)-1.3,5-trizone: 2-2-)hydroxy-4-n-octykloxyphenyl)-4,6-
bls(2.4-dimethylphenyl)-1,3.5-triazlne; 2-(2-hydroxy-4-(mbsed Iso- octoloxyphenyr)-.6-bls(2,4-
dimethyphess)1,3,5-triazine; 2-(2,4dihydroxypherryl)-6-bls(2,4-dimethylphenyl)-1,3,5-
triazine; 2,44-bls(2-hydroxy-4-propyloxypheny)-6-2,4-dimethyphenyl)-1,3,5-triazine: 2-(2-
triazine; 2,44-bls(2-hydroxy-4-propyloxypheny)-6-2,4-dimethyphenyl)-1,3,5-triazine: 2-(2-
triazine; 2,44-bls(2-hydroxy-4-propyloxypheny)-6-2,4-dimethyphenyl)-1,3,5-triazine: 2-(2-
triazine; 2,44-bls(2-hydroxy-4-propyloxypheny)-6-2,4-dimethyphenyl)-1,3,5-triazine: 2-(2-
triazine; 2,44-bls(2-hydroxy-4-propyloxypheny)-6-2,4-dimethyphenyl)-1,3,5-triazine: 2-(2-
triazine; 2,44-bls(2-hydroxy-4-propyloxypheny)-6-2,4-dimethyphenyl)-1,3,5-triazine: 2-(2-
triazine; 2,44-bls(2-hydroxy-4-propyloxypheny)-6-2,4-dimethyphenyl)-1,3,5-triazine: 2-(2-
triazine; 2,44-bls(2-hydroxy-4-propyloxypheny)-6-2,4-dimethyphenyl)-1,3,5-triazine: 2-(2-
dimethylphenylV1,3,5-trlazfne; 2-(2-hydroxy-4-hexytoxy)phenyl)-4-6-dipheny -1,3,5-triazine 2-
(2-hydroxy-4-metholoxyl) -4,6-diphenyl 1,3,5-triazone: 2,4,6-tris-(2-hydroxy-4-(3-butoxy-2-
riydfoxypropoxy)phenyf]1,3,5-triazine; 2-(2-droxyprienyl)-4methoxypheny)-6-phenyl-
1,3,5-triazine.
4. A composition as claimed in any preceding claim in which the hindered
hydroxybenzoate compound has the formula V:
wherein R17, Is a C1-C6 alky) and R16 Is a C1-C24 alkyl, or substituted or unsubstftuted C6-C24
aryl.
5. A composition as claimed in claim 4 in which the hindered hydroxybenzoate
compound is selected from 2,4-di-tert-butylphenyl-3,5-di-tert-butyt-4-
hydroxybenzoate hexadecy-3,5-di -tert buty-4- hydroxyt)erizoate; octadecyl-3.5-di-tret-butyt
4-hydraxybenzoate; octy-1-3,5- hydroxybenzoate; behenyiy-3,5.5di-tert -botyl-4-hrydroxybenzoate; 2-methyl-4,6-d-tert-
hydroxybenzoate; behenyiy-3,5.5di-tert -botyl-4-hrydroxybenzoate; 2-methyl-4,6-d-tert-
rr/droxybenzoyk>xy)phenyl] proplonate.
6. A composition as claimed in any preceding claim comprising an UV stabilizing
composition comprising:
(i) an orthb-hydroxy trt-ary-s-triazine compound;
(8) a hindered hydroxybenzoate compound; and
nj) a hinderd amine compound contaning a 2,2,6,6 tetraakylpiperide or
2,2,6,6-tetraakylespiprazinove radical.
7. A composition as claimed in claim 6 in which the hindered amlne compound
contains a radical having the formula III:
wherein R11 is hydrogen. O, OH, C1-C11 alkyl, -CH2CN. C1-C18 alkoxy, C1-C18 hydroxyakcoxy,
C1-C12 cycloaHtoxy, C1-C12 hydrocycdoalkoxy, C1-C6 alkenyl, C1-C18 alkynyl, C1-C18 pnenylakyl.
unsubstituted or substituted on the phenyl with 1,2 or 3 C1-C4 alkyl, or an aliphatic C1-C9
acy); R12 Is hydrogen, C1-C6 alkyl , or benzyl; R13, R14, R14, and R14 are each Independently a
C1-C18 alkyl-benzyl or phenethyl, or optionally R18 and R14, and/or R15 and R14, taken together
with the carbon which they are attached, form a C1-C18 cycloafcyl.
8. A composition as claimed in claim 7 in which the hindered amine compound is
selected from 1H-Pyrrole-2,5-dione, 1-octadecyl-, polymer with (1-
methyletheny)-benzene and 1-(2,2,6,6-tetrarrtethyl-piperldinyl)-1H-pyrrole-2,5-dione;
piperazinone, 1,1:1-(1.3.5-triazine-2,4,6-triyltris(cyclohexylimino)-2,5 [3,3,5,5-
tetramethyt-0; piperazlnone, 1,1:1-[1.3,5-triazine-2.4>6-tnVltris[(cyclohexylinmino)-2.1-
ethanedlynjtris[3,3,4,5,5-pentamethyl-]; the reaction product of 7,7,9,9-tetramethyi-2-
cydoundecyl-1-oxa-3,8-dia2a-4-oxosplro(4.5}decane and epichlorohydrin; the condensate of
N,N-bis(2,2,6,6,4etramethyiplperidin-4-yl)hexarnethylenediamine and 4-cyc)ohexylamln0-2,6-
dichloro-1,3,5-triazlne; the condensate of 1,2-bls(3-aminopropyJamino)ethane, 2,4,6-trichlon-
1,3,5-triadne and 44>uty1amlno-2,216,6-tetramethyiplpeeridene; the condensate of N.N'-
bls(2.2,6,6-tetramethylp}peridin-4-yl)hexamethytenediarnlne and 4-morpholino-2.6-dichtoro-
1,3,5-triazlne; the condensate of 2-chome-4,6-bls(4-n-bulyamino-2.2,6,6-
tetramethylpiperidyl)-1,3,5-trlazine and 1,2-bls(3-aminopropylamino)ethane; the condensate
tetramethylpiperidyl)-1,3,5-trlazine and 1,2-bls(3-aminopropylamino)ethane; the condensate
(3-anwiopropylarrAx3)etnane; 2^(2-bydroxyetriyl)airfnoH.6-bls[^
tetramethylpiperidyl)-1,3,5-trlazine and 1,2-bls(3-aminopropylamino)ethane; the condensate
tetramethylpiperidyl)-1,3,5-trlazine and 1,2-bls(3-aminopropylamino)ethane; the condensate
tetramethylplphridln-4-yl)-1, 2,3,4-butanetetracartoxylate; benzeneptopanolc acid, 3.5-bls(1.1-
dlmethytetriyI)-4-nydroxy -.1[2[3-[3,5-bls 1.1 dimethyl)-4-hydroxylphenyl]-1--
oxopropoxylethyl]-2,2,6,6-tetramethyl-4-piperidiny ester,N(I-octyloxy-2,2,6,6-
tetramethylpiperidyl)-1,3,5-trlazine and 1,2-bls(3-aminopropylamino)ethane; the condensate
tetramethylpiperidyl)-1,3,5-trlazine and 1,2-bls(3-aminopropylamino)ethane; the condensate
tetramethylpiperidyl)-1,3,5-trlazine and 1,2-bls(3-aminopropylamino)ethane; the condensate
tetramethylpiperidyl)-1,3,5-trlazine and 1,2-bls(3-aminopropylamino)ethane; the condensate
tetramethylpiperidyl)-1,3,5-trlazine and 1,2-bls(3-aminopropylamino)ethane; the condensate
yl)hexamethyienediainine and 4-tert-oxylomeyhy -2.6dichloro-1,3,5-triazlne; 1,2.3.4-
tetramethylpiperidyl)-1,3,5-trlazine and 1,2-bls(3-aminopropylamino)ethane; the condensate
tetraniethylpiperldiiv4-yrvi,213.44)utanetetracarboxylate; 1.2.3,4-butanetetracart>oxyBcacW.
tetramethylpiperidyl)-1,3,5-trlazine and 1,2-bls(3-aminopropylamino)ethane; the condensate
1,2.3,4-butanetetracarboxyiate; mixture of 2^,4,4-tetramethy»-21-oxo-7-oxa-3.20-
diazaspiro(5.1.11.2)-henek»sane-20-propanote acid-dodecylester and 2,2,4,4-tetramethyi-2i-
oxp-7-axa-3.20-dlaza$piro(5.1.11.2>her»elccisar)e-20-propanoJc add-tetradecytesfer;
1K4Hr5H,8H-2.3a.4a,6,7a,8a4iexaaza2,6-
tetramethylpiperidyl)-1,3,5-trlazine and 1,2-bls(3-aminopropylamino)ethane; the condensate
tetramethylpiperidyl)-1,3,5-trlazine and 1,2-bls(3-aminopropylamino)ethane; the condensate
pjperidinyl)jsltoxane; copolymer of methylmethacrylate with ethyl acrytate and 2,2,6,6-
tetramethylpiperklln-4-yl acrytete; copolymer of mixed C20 to C24 aipba-oleffns and (2,2,6,6-
tetrainethylpiperfdin-4-yr)succinirnkde; 1,2,3,4-butanetetracatboxySc add, polymer with
tetramethylpiperidyl)-1,3,5-trlazine and 1,2-bls(3-aminopropylamino)ethane; the condensate
pentamethyM-pfperidinyl ester; 1,2.3.4-butanetetracarboxyficadd. polymer with b,b,b,b-
tetramethyl-2,4,8,10-tetraoxasplro[5.5)undecane-3,9-liethanol, 2,2,6.6-tetramethyl-4-
plperidinyl ester copolymer; 1.3-benzenedicarboxarnide, N,N'-bis(2,2,6.6-tetramethyl-4-
piperldinyl;1.1-(1,10-dioxo-1,10-decanedity)-bls(hexahydro-2,2,4,4,6-pentamethylpyrimidine:
ethane diamlde, N-(1-acetyl-2.2,6,6-tetramethylpiperidine-N'-dodecyl; formamkte. N.N'-1.6-
ethane diamlde, N-(1-acetyl-2.2,6,6-tetramethylpiperidine-N'-dodecyl; formamkte. N.N'-1.6-
ethane diamlde, N-(1-acetyl-2.2,6,6-tetramethylpiperidine-N'-dodecyl; formamkte. N.N'-1.6-
dspiro{5.1.11.2]heneicosane; propanamkcle, 2-miethy-N-(2.2,6,6-tetramethyl-4-pipericnnyl)-2-
[(2,2,6,6-tetramethyl--iperidiinyl)aitiino)-; 7-oxa-3,20-diazadispiro(5.1.11.2]heneicosane-20-
propanoic acid. 2,2.4,4-tetramethyl-21-oxo- dodecyl ester;N-2.2,6,6-tetramethylpiperidin-4-
y)-b-amlnoproplonlc add dodecyl ester, N-{2.2f6,6-tetramethylplperidin-4-yl>-NI-
propanoic acid. 2,2.4,4-tetramethyl-21-oxo- dodecyl ester;N-2.2,6,6-tetramethylpiperidin-4-
4-piperidinyl)amino]-; mixture of 4-hexadecyloxy- and 4-stearyloxy-2,2,6>6-
propanoic acid. 2,2.4,4-tetramethyl-21-oxo- dodecyl ester;N-2.2,6,6-tetramethylpiperidin-4-
teramethylplperidin-4-l)succlnate; bls(11,2,6.6-pentamethylplperidin-4-yl) n-buty) 3,5-cel-tert
propanoic acid. 2,2.4,4-tetramethyl-21-oxo- dodecyl ester;N-2.2,6,6-tetramethylpiperidin-4-
(1,2-erthnethal)-(3,3,5,5-tetrafnethytplperazinone):4-benzoyl-2,2,6,6.nitramethylylpiperidine
4-stearytoxy-2,2.6,6-tetramethylplperidlne; bls(1 2,26,6-pentarnethylplperidyl)-2-n-butyl-2-(2-
hydroxy-3,5-di-tert-butybenzyi)malonate; 3-n-octyl-7,7,9,9-teiramethyl-1,3,8
teramethylplperidin-4-l)succlnate; bls(11,2,6.6-pentamethylplperidin-4-yl) n-buty) 3,5-cel-tert-
teramethylplperidin-4-l)succlnate; bls(11,2,6.6-pentamethylplperidin-4-yl) n-buty) 3,5-cel-tert
trlazasplrot4.$]decane-2,4-dione; 3-doclomecyl- (2,2,6,6tetramethyldin-4-pyrmethyltypical-4-yl)pylicone-2,5
done; 3-diodecyl)-1-(1-ethanoyl-2,2,6.6-tetramethy)p-4-))pyrrolidht-2,5-dione;-2,5
dodecyl-1-(1,2,2,8,6-pertamethyiplperklin-4-yl)pyrrolline -4-2,5-dionoa a mixture of 4-
teramethylplperidin-4-l)succlnate; bls(11,2,6.6-pentamethylplperidin-4-yl) n-buty) 3,5-cel-tert
teramethylplperidin-4-l)succlnate; bls(11,2,6.6-pentamethylplperidin-4-yl) n-buty) 3,5-cel-tert
teramethylplperidin-4-l)succlnate; bls(11,2,6.6-pentamethylplperidin-4-yl) n-buty) 3,5-cel-tert
bls(1,22,6.6-pentamethyl-4-plperidlny1).
9. A composition as claimed in any preceding clams further comprising a material to
be stabilized selected from pdyolefins, polyesters, polyethers, polyketones, polyamides.
natural and synthetic rubbers, polyuretharnes, polystyrenes, high-tonpact polystyrenes,
polyacrytates. polymethcylates, potyacetals, polyacylonitrilies, polybutaditions.
polystyrenes, acrytorrile4butione-styrene, styrene acrytonitnie. apryiate styerne
acrytonnitrate, cellusisIc acetate butyrate, cellulose polymens, potyimides, polyamiders.
polystyrenes, acrytorrile4butione-styrene, styrene acrytonitnie. apryiate styerne
polyvlnylchlorldes, polycarbonates, polyketones, aliphatic polyketone, themoplastic
olefine, aminoresin cross-linked polyacrylates and polyesters, pohisoocyanate cross-linked
polyesters and polyacrylates, phenoVformakdeehyde, urea/formaldehyde and
melamine/formaldehyde resins, drying and non-drying alkyd resins, alkyd resins, polyester
resins, acrylate resins cross-linked with melannine resinsn urea resins, isocyanates,
isocyanurates, carbamates, and epoxy resins, cross-linked epoxy resins derived from
aliphatic, cycloaliphatic, heterocyctlc and aromatic glycydyi compounds, which are
cross-linked with anhydrides or amines, polysiloxanes, Michael addition polymers, amines,
blocked amines with activated unsaturated and methylene compounds, ketimines with
activated unsaturated and methylene compounds, polyketimines in combination with
unsaturated acrylic polyacetoacetate Tesins, polyketimines in combination with
unsaturated acrylic resins, radiation curable compositions, epoxymelamine resins, organic
dyes, cosmetic products, cellulose-based paper formulations, photographic film paper,
fibers, waxes, inks, and blends thereof.
10. - A composition as claimed in claim 9 in which the material to be stabilized is
selected from thermoplastic olefins, acrylonitrile-butadiene-styrene, polyesters, polyvinylcchloride, polyamides,
polyurethanes, or homo- and copolymers of propylene, isobutytene, butene, methylpentene,
hexene, heptene. octene, Isoprene, butadiene, hexadiene, dicyctopentadtene, ethyliene
cyclopentene and norbomene.
11. A composition as claimed in claim 9 or claim 10 in which the amount of said
triazine compound is from 0.01 to 1.0 wt%, the amount of said hindered hydroxbenzoate
compound is from 0.1 to 1.0 wt%and the amount of said hindered amine compound is
from 0.1 to 1.0 wt%, based on the total weight of said material to be stabilized.
12. A process for preparing a composition as claimed in any one of claims 9 to 12 in
which the material to be stablized is contacted with said UV stablizing-composition.
This invention relates to an UV stabilizing additive
composition comprising an oetho-hydroxy triazine compound,
a hindered hydroxybenzoate compound and optionally a hindered
amine compound. This additive composition may be used to
stablize materials from UV radiation. This invention also
contemplates a method of stabilizing a material by contacting
the material with the UV stabilizing additive composition.

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Patent Number

225179

Indian Patent Application Number

00901/KOLNP/2004

PG Journal Number

45/2008

Publication Date

07-Nov-2008

Grant Date

05-Nov-2008

Date of Filing

28-Jun-2004

Name of Patentee

CYTEC TECHNOLOGY CORP.

Applicant Address

300 DELAWARE AVENUE, WILMINGTON, DE 19801

Inventors:

#	Inventor's Name	Inventor's Address
1	STRETANSKI, JOSEPH, A.	165 BUTTERNUT LANE, STAMFORD, CT 06903
2	SANDERS, BRENT, M.	3370 PEPPERMILL DRIVE, WEST LAFAYETTE, IN 47906

PCT International Classification Number

C08K 5/3492

PCT International Application Number

PCT/US02/39493

PCT International Filing date

2002-12-11

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	60/343,681	2001-12-27	U.S.A.