GB2377222A

GB2377222A - Hydroxyphenyl triazine compounds

Info

Publication number: GB2377222A
Application number: GB0217715A
Authority: GB
Inventors: David George Leppard; Francois Gugumus; Michela Bonora
Original assignee: Ciba Spezialitaetenchemie Holding AG; Ciba SC Holding AG
Current assignee: BASF Schweiz AG; Ciba SC Holding AG
Priority date: 2000-07-26
Filing date: 2001-07-19
Publication date: 2003-01-08
Also published as: GB0228224D0; GB2382348B; GB2382348A; GB0217715D0

Abstract

A compound according to the following formula: <EMI ID=1.1 HE=77 WI=87 LX=616 LY=643 TI=CF> <PC>```The compound is especially used to stabilise polymer articles of low thickness and good transparency against the effects of light, oxygen, heat and aggressive chemicals and may be used in selective UV filters for agricultural applications. A number of other hydroxyphenyl triazine compounds are also claimed.

Description

Hvdroxvphenyitriazines The invention relates to some novel stabilizers suitable for the stabilization of polymer articles of low thickness and good transparency against the effects of light, oxygen, heat and agressive chemicals, and effective as a selective UV filters for agricultural applications.

Certain polyolefin articles containing UV absorbers of the type hydroxyphenyl triazine are known from GB-A-2319523, EP-A-704437, EP-A-704560, WO 99/57189.

Present invention pertains to a compound of one of the formulae b, f, g, h or k

wherein X is C13-C24alkylene ; (C1-C18alkylene)-CO-0-D-0-CO- (C1-Ci8alkylene) where D is C2-C12alkylene; CO-(C13-C24alkylene)-CO; C3-C24alkylene interrupted by oxygen, especially (Ci-C3alkylene)-0- (C1-C3al kylene).

They are conveniently prepared in analogy to procedures described in these references, especially to the method given in example 18 of WO 96/28431.

Present hydroxyphenyl triazine UV absorbers show excellent compatibility and persistence in the polyolefin, polyester or polyamide. The same time, these UV absorbers provide efficient

and selective UV shielding for suppressing microbial growth in a protected environment, especially a plant cultivation, while retaining the UV irradiation necessary for bee activity.

Thus, present invention also pertains to the use of a transparent polyolefin film as described above for suppressing microbial growth in a protected cultivation.

Examples for polyolefines to be used for manufacturing the articles of present invention include the following polymers : 1. Polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for instance of cyclopentene or norbornene, polyethylene (which optionally can be crosslinked), for example high density polyethylene (HDPE), high density and high molecular weight polyethylene (HDPE-HMW), high density and ultrahigh molecular weight polyethylene (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), (VLDPE) and (ULDPE).

Polyolefins, I. e. the polymers of monoolefins exemplified in the preceding paragraph, prefe- rably polyethylene and polypropylene, can be prepared by different, and especially by the following, methods: a) radical polymerisation (normally under high pressure and at elevated temperature). b) catalytic polymerisation using a catalyst that normally contains one or more than one metal of groups IVb, Vb, Vlb or Vill of the Periodic Table. These metals usually have one or more than one ligand, typically oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls that may be either 7t-or o-coordinated. These metal complexes may be in the free form or fixed on substrates, typically on activated magnesium chloride, titanium (lis) chloride, alumina or silicon oxide. These catalysts may be soluble or insoluble in the polymerisation medium. The catalysts can be used by themselves in the polymerisation or further activators may be used, typically metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes, said metals being elements of groups la, a and/or ilia of the Periodic Table. The activators may be modified conveniently with further ester, ether, amine or silyl ether groups. These catalyst systems are usually termed Philips, Standard

Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC).

2. Mixtures of the polymers mentioned under 1), for example mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (for example PP/HDPE, PP/LDPE) and mixtures of different types of polyethylene (for example LDPE/HDPE).

3. Polyolefin copolymers : Copolymers of monoolefins and diolefins with each other or with other vinyl monomers, for example ethylene/propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE),

propylene/but-1-ene copolymers, propylene/isobutylene copolymers, ethylene/but-1-ene copolymers, ethylene/hexene copolymers, ethylene/methylpentene copolymers, ethylene/heptene copolymers, ethylene/octene copolymers, propylene/butadiene copolymers, isobutylene/isoprene copolymers, ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylate copolymers, ethylene/vinyl acetate copolymers and their copolymers with carbon monoxide or ethylene/acrylic acid copolymers and their salts (ionomers) as well as terpolymers of ethylene with propylene and a diene such as hexadiene, dicyclopentadiene or ethylidene-norbornene ; and mixtures of such copolymers with one another and with polymers mentioned in 1) above, for example polypropylene/ethylene-propylene copolymers, LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic acid copolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or random polyalkylene/carbon monoxide copolymers and mixtures thereof with other polymers, for example polyamides.

Polyesters to be used for manufacturing the articles of present invention are mainly those derived from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or the corresponding lactones, for example polyethylene terephtalate, polybutylen terephtalate, poly-1, 4-dimethylolcyclohexane terephthalate, polyalkylene naphthalate (PAN) and polyhydroxybenzoates, as well as block copolyether esters derived from hydroxyl-terminated polyethers ; and also polyesters modified with polycarbonates or MBS. Preferred is polyethylene terephtalate (PET).

Polyamides are usually those derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams, for example polyamide 4, polyamide 6,

polyamide 6/6,6/10, 6/9,6/12, 4/6,12/12, polyamide 11, polyamide 12, aromatic polyamides starting from m-xylene diamine and adipic acid; polyamides prepared from hexamethylenediamine and isophthalic or/and terephthalic acid and with or without an ela- stomer as modifier, for example poly-2, 4, 4, -trimethylhexamethylene terephthalamide or poly- m-phenylen isophthalamid ; and also block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers ; or with polyethers, e. g. with polyethylene glycol, polypropylene glycol or polytetramethylene glycol ; as well as polyamides or copolyamides modified with EPDM or ABS ; and polyamides condensed during processing (RIM polyamide systems).

Most preferred are polyolefines such as polyethylene, especially LDPE or LLDPE, or polypropylene.

Preferably, the amount of hydroxyphenyl triazine UV absorber in the transparent polymer article of the invention is from 0.005 to 0.15 %, more preferably from 0.005 to 0.06 %, especially from 0.01 to 0.06 % by weight the polymer substrate.

Examples for additional components which may be combined with the compounds of the invention include the following : 1. Antioxidants 1.1. Alkylated mono phenols, for example 2, 6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4, 6-dimethylphenol, 2, 6-di-tert-butyl-4-ethylphenol, 2, 6-di-tert-butyl-4-n-butylphenol, 2, 6-di-tert-butyl-4-isobutyl phenol, 2, 6-dicyclopentyl-4-methylphenol, 2- (a-methylcyclohexyl) -4, 6-di methyl- phenol, 2, 6-dioctadecyl-4-methylphenol, 2,4, 6-tricyclohexylphenol, 2, 6-di-tert-butyl-4-meth- oxymethylphenol, nonylphenols which are linear or branched in the side chains, for example 2, 6-di-nonyl-4-methylphenol, 2, 4-dimethyl-6- (1'-methylundec-1'-yl) phenol, 2, 4-dimethyl-6- (1'- methylheptadec-1'-yl) phenol, 2, 4-dimethyl-6- (1'-methyltridec-1'-yl) phenol and mixtures thereof.

1.2. Alkylthiomethvlphenols, for example 2, 4-dioctylthiomethyl-6-tert-butylphenol, 2, 4-dioctyl- thiomethyl-6-methylphenol, 2, 4-dioctylthiomethyl-6-ethylphenol, 2, 6-di-dodecylthiomethyl-4nonylphenol.

1.3. Hydroquinones and alkylated hydroquinones, for example 2, 6-di-tert-butyl-4-methoxy- phenol, 2, 5-di-tert-butylhydroquinone, 2, 5-di-tert-amylhydroquinone, 2, 6-diphenyl-4-octade-

cyloxyphenol, 2, 6-di-tert-butylhydroquinone, 2, S-di- tert -butyl-4-hydroxyan isole, 3, 5-di-tert-butyl-4-hyd roxyanisole, 3, S-di- tert -butyl-4-hyd roxyphenyl stearate, bis (3, 5-di-tert-butyl-4-hy- droxyphenyl) adipate.

1.4. Tocopherols, for example α-tocopherol, ss-tocopherol, γ-tocopherol, #-tocopherol and mixtures thereof (vitamin E).

1.5. Hydroxylated thiodiphenyl ethers, for example 2,2'-thiobis (6-tert-butyl-4-methylphenol), 2, 2' -th iobis (4-octylphenol), 4, 4'-thiobis(6-tert-butyl-3-methylphenol), 4, 4'-thiobis (6-tert-butyl-2methylphenol), 4, 4' -thiobis (3, 6-di-sec-amylphenol), 4, 4'-bis (2, 6-dlmethyl-4-hydroxyphenyl) - disulfide.

1.6. Alkylidenebisphenols, for example 2, 2'-methylenebis (6-tert-butyl-4-methylphenol), 2,2'-

methylenebis (6-tert-butyl-4-ethylphenol), 2, 2'-methylenebis [4-methyl-6- (a-methylcyclohexyl)phenol], 2, 2' -methyleneb is (4-methyl-6-cyclohexyl phenol), 2, 2' -methylenebis (6-nonyl-4methylphenol), 2, 2' -methylenebis (4, 6-d !-tert-buty ! phenoi), 2, 2' -ethylidenebis (4, 6-di-tert-butylphenol), 2, 2'-ethylidenebis (6-tert-butyl-4-isobutylphenol), 2, 2'-methylenebis [6- (a-methylbenzyl) -4-nonylphenol], 2, 2' -methylenebis[6- (a, a-dimethylbenzyl) -4-nonylphenol], 4, 4' -methylenebis (2, 6-di-tert-butylphenol), 4, 4'-methylenebis (6-tert-butyl-2-methylphenol), 1, 1-bis (5-terbutyl-4-hydroxy-2-methyl phenyl) butane, 2, 6-bis (3-tert -butyl-S-methyl-2-hyd roxybenzyl) -4methylphenol, 1, 1, 3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 1, 1-bis (5-tert-butyl-4hyd roxy-2-methyl phenyl) -3-n-dodecyl mercaptobutane, ethylene glycol bis[3, 3-bis (3' -tertbutyl-4'-hydroxyphenyl) butyrate], bis (3-tert -butyl-4-hydroxy-S-methyl-phenyl) dicyclopentadiene, bis[2- (3' - te rt -butyl-2'-hyd roxy-S'-methylbenzyl) -6-tert -butyl-4-methyl phenyl]terephthalate, 1, 1-bis- (3, 5-dimethyl-2-hydroxyphenyl) butane, 2, 2-bis (3, S-di-tert-butyl-4-hydroxyphenyl) propane, 2, 2-bis- (5-tert-buty !-4-hydroxy2-methyipheny !)-4-n-dodecytmercaptobutane, 1, 1, 5, 5-tetra (S-tert-butyl-4-hydroxy-2-methylphenyl) pentane 1. 7. 0-, N-and S-benzvl compounds, for example 3, 5, 3', 5'-tetra-tert-butyl-4, 4'-dihydroxydi- benzyl ether, octadecyl-4-hyd roxy-3, S-dimethylbenzylmercaptoacetate, tridecyl-4-hyd roxy- 3, 5-di-tert-butylbenzylmercaptoacetate, tris (3, S-di-tert -butyl-4-hyd roxybenzyl) amine, bis (4-

te rt-b utyl-3-hyd roxy-2, 6-d i m ethyl ben zyl) d ith iote rephthalate, bis (3, 5-di-tert-butyl-4-hydroxybenzyl) sulfide, isooctyl-3, S-di-tert -butyl-4-hydroxybenzyl mercaptoacetate.

1. 8. Hydroxvbenzylated malonate, for example dioctadecyl-2, 2-bis (3, 5-di-tert-butyl-2-hydroxybenzyl) malonate, di-octadecyl-2- (3-tert-butyl-4-hydroxy-5-methylbenzyl) malonate, didodecyl mercaptoethyl-2, 2-bis (3, S-di-tert-butyl-4-hydroxybenzyl) malonate, bis[4- (1, 1, 3, 3-tetramethyl butyl) phenyl]-2, 2-bis (3, S-d i-tert -butyl-4-hyd roxybenzyl) malonate.

1. 9. Aromatic hvdroxvbenzvl compounds, for example 1, 3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl)-2, 4, 6-tri methyl benzene, 1, 4-bis (3, 5-di-tert-butyl-4-hyd roxybenzyl) -2, 3, 5, 6-tetramethylbenzene, 2, 4, 6-tris (3, S-di-tert -butyl-4-hyd roxybenzyl) phenol.

1. 10. Triazine compounds, for example 2, 4-bis ( octylmercapto) -6- (3, 5-di-tert-butyl-4-hydroxyanilino)-1, 3, 5-triazine, 2-octylmercapto-4, 6-bis (3, S-di-tert -butyl-4-hydroxyanilino) -1, 3, 5-triazine, 2-octylmercapto-4, 6-bis (3, S-di-tert-butyl-4-hydroxyphenoxy) -1, 3, 5-triazine, 2, 4, 6-tris- (3, S-di-tert-butyl-4-hydroxyphenoxy) -1, 2, 3-triazine, 1, 3, 5-tris (3, 5-di-tert-butyl-4-hydroxyben- zyl) isocyanurate, 1,3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) isocyanu rate, 2,4, 6-tris- (3, 5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine, 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxy- phenylpropionyl) -hexahydro-1, 3, 5-triazine, 1,3, 5-tris (3, S-dicyclohexyl-4-hydroxybenzyl) isocyanurate.

1.11. Benzvlphosphonates, for example dimethyl-2, 5-di-tert-butyl-4-hydroxybenzylphospho-

nate, diethyl-3, S-di- tert -butyl-4-hyd roxybenzylphosphonate, d ioctadecyI3, S-di-tert -butyl-4-hyd roxybenzyl phosphonate, dioctadecyl-5- tert -butyl-4-hyd roxy-3-methylbenzyl phosphonate, the calcium salt of the monoethyl ester of 3, 5-di-tert-butyl-4-hydroxybenzylphosphonic acid.

1.12. Acy) aminopheno ! s. for example 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N- (3, S-di-tert -butyl-4-hydroxyphenyl) carbamate.

1.13. Esters of ss-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono-or polyhydric alcohols, e. g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1, 6-hexanediol, 1,9nonanediol, ethylene glycol, 1, 2-propanediol, neopentyl glycol, thiodiethylene glycol, diethy- lene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hy-

droxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2, 6, 7-trioxabicyclo [2. 2. 2] octane.

1.14. Esters of ss- (5-tert-butyl-4-hvdroxy-3-methvlphenvl) propionic acid with mono-or polyhydric alcohols, e. g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1, 9-nonanediol, ethylene glycol, 1, 2-propandiol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis- (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethyl- olpropane, 4-hydroxymethyl-1-phospha-2, 6, 7 -trioxabicyclo[2. 2. 2]octane ; 3, 9-bis[2- {3- (3-tert- butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1, 1-dimethylethyl]-2, 4,8, 10-tetraoxaspiro [5. 5]undecane.

1.15. Esters of j3-(3. 5-dicvclohexvl-4-hvdroxvphenvl) propionic acid with mono-or polyhydric alcohols, e. g. with methanol, ethanol, octanol, octadecanol, 1, 6-hexanediol, 1, 9-nonandiol, ethylene glycol, 1, 2-propandiol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hy-

droxymethyl-1-phospha-2, 6, 7 -trioxabicyclo[2. 2. 2]octane.

1. 16. Esters of 3, 5-di-tert-butyl-4-hvdroxyphenvl acetic acid with mono-or polyhydric alco- hols, e. g. with methanol, ethanol, octanol, octadecanol, 1, 6-hexanediol, 1, 9-nonandiol, ethylene glycol, 1, 2-propandiol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurat, N, N'-bis (hydroxyethyl) ox-

amide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2, 6, 7 -trioxabicyclo[2. 2. 2]octane.

1. 17. Amides of 6- (3, 5-di-tert-butvl-4-hydroxvphenvl) proDionic acid e. g. N, N'-bis (3, 5-di-tert- butyl-4-hydroxyphenylpropionyl) hexamethylenediamide, N, N'-bis (3, 5-d i-tert -butyl-4-hydroxy- phenylpropionyl) trimethylenediamide, N, N'-bis (3, 5-di- tert -butyl-4-hydroxyphenylpropionyl) hydrazide, N, N'-bis [2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxamide (Nau- gardXL-1, supplied by Uniroyal).

1.18. Ascorbic acid (vitamin C)

1. 19. Aminic antioxidants, for example N, N'-di-isopropyl-p-phenylenediamine, N, N'-di-sec-butyl-p-phenylenediamine, N, N'-bis (1, 4-dimethylpentyl) -p-phenylenediamine, N, N' -bis (1-ethyl-3methylpentyl)-p-phenylenediamine, N, N'-bis (1-methylheptyl) -p-phenylenediamine, N, N'-dicyclohexyl-p-phenylenediamine, N, N'-diphenyl-p-phenylenediamine, N, N'-b is (2 -naphthyl) -pphenylenediam i ne, N-isopropyl-N'-phenyl-p-phenylenediamine, N- (1, 3-di methylbutyl) -N' -phenyl-p-phenylenediamine, N- (1-methyl heptyl)-N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'phenyl-p-phenylenediami ne, 4- (p- tol uenesulfamoyl) diphenylami ne, N, N'-dimethyl-N, N'-disec-butyl-p-phenylenediamine, diphenylamine, N-allyidiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N- (4-tert-octylphenyl)-1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, for example p, p'-di-tert-octyldiphenylamine, 4n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol, bis (4-methoxyphenyl) amine, 2, 6-di-tert-butyl-4dimethylaminomethylphenol, 2, 4'-diaminodiphenyl methane, 4, 4' -diami nodi phenyl methane, N, N, N', N'- tetramethyl-4, 4'-diaminodiphenylmethane, 1, 2-bis [ (2-methy) pheny)) amino] ethane, 1, 2-bis (phenylamino) propane, (o-tolyl) biguanide, bis[4- (1', 3'-dimethylbutyl) phenyl]amine, tertoctylated N-phenyl-1-naphthylamine, a mixture of mono-and dialkylated tert-butyl/tertoctyidiphenylamines, a mixture of mono-and dialkylated nonyidiphenylamines, a mixture of mono-and dialkylated dodecyldiphenylamines, a mixture of mono-and dialkylated isopropyl/isohexyldiphenylamines, a mixture of mono-and dialkylated tert-butyldiphenylamines, 2, 3-dihydro-3, 3-dimethyl-4H-1, 4-benzothiazine, phenothiazine, a mixture of mono-and dialkylated tert-butyl/tert-octylphenothiazines, a mixture of mono-and dialkylated tert-octylphenothiazines, N-allylphenothiazine, N, N, N', N'-tetraphenyl-1, 4-diaminobut-2-ene, N, N-bis- (2, 2, 6, 6- tetramethyl-piperid-4-yl-hexamethylenediamine, bis (2, 2, 6, 6-tetramethyl piperid-4-yl) sebacate, 2, 2, 6, 6-tetramethylpiperidi n-4-one, 2, 2, 6, 6-tetramethylpiperidin-4-ol.

2. UV absorbers and light stabilisers 2. 1. 2- (2'-Hvdroxvohenvl) benzotriazoles, for example 2- (2'-hydroxy-5'-methylphenyl) benzotriazol e, 2- (3', 5' -d i-tert -butyl-2'-hyd roxyphenyl) benzotriazole, 2- (5' -tert -butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5'- (1, 1, 3, 3-tetramethylbutyl) phenyl) benzotriazole, 2- (3', 5'-ditert -butyl-2'-hyd roxyphenyl) -5-chlorobenzotriazole, 2- (3' -tert -butyl-2'-hyd roxy-5'-methylphenyl) -5-ch lorobenzotriazole, 2- (3' -sec-butyl-5'- tert -butyl-2'-hyd roxyphenyl) benzotriazole, 2- (2'hydroxy-4'-octyloxyphenyl) benzotriazole, 2- (3', 5' -di-tert-amyl-2'-hyd roxyphenyl) benzotriazole, 2- (3', 5'-bis (a, (x-d i m ethyl be nzyl)-2'-hyd roxyphenyl) be nzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-

(2-octyloxycarbonylethyl) phenyl)-5-ch lorobenzotriazole, 2- (3'-tert-butyl-5'- [2- (2-ethylhexyloxy) carbonylethyl]-2' -hydroxyphenyl) -S-ch lorobenzotriazole, 2- (3'- tert -butyl-2'-hyd roxy-S'- (2methoxycarbonylethyl) phenyl) -S-ch lorobenzotriazole, 2- (3'- tert -butyl-2'-hyd roxy-S'- (2-methoxycarbonylethyl) phenyl) benzotriazole, 2- (3' -tert -butyl-2'-hydroxy-S'- (2-octyloxycarbonyl- ethyl) phenyl) benzotriazole, 2- (3'- te rt- butyl-S'. [2- (2-ethyl hexyloxy) carbonylethylj-2'-hyd roxy- phenyl) benzotriazole, 2- (3'-dodecyl-2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3'-tert-butyl- 2'-hydroxy-5'- (2-isooctyloxycarbonylethyl) phenylbenzotriazole, 2, 2'-methylenebis [4-(1, 1,3, 3tetramethylbutyl)-6-benzotriazole-2-ylphenol] ; the transesterification product of 2-[3'-tert-bu-

tyl-S'- (2-methoxycarbonylethyl) -2' -hydroxyphenyl]-2H-benzotriazol e with polyethylene glycol 300 ; [R-CH2CH2COO-CH2CH2+'where R = 3'-tert-butyl-4'-hydroxy-5'-2H-benzotri- 2 azol-2-ylphenyl, 2-[2'-hydroxy-3'- (a, a-dimethylbenzyl) -S'- (1, 1, 3, 3-tetramethylbutyl) phenyljbenzotriazol ; 2-[2'-hydroxy-3'- (1, 1, 3, 3-tetramethylbutyl)-5'- (a, a-dimethylbenzyl) phenyl] ben- zotriazole.

2.2. 2-Hvdroxybenzophenones, for example the 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyl-

oxy, 4-dodecyloxy, 4-benzyloxy, 4, 2', 4'-trihydroxy and 2'-hydroxy-4, 4'-dimethoxy derivatives.

2. 3. Esters of substituted and unsubstituted benzoic acids, for example 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis (4-tert-butylben- zoyl) resorcinol, benzoyl resorcinol, 2, 4-di-tert-butylphenyl 3, 5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3, 5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3, 5-di-tert-butyl-4-hydroxyben- zoate, 2-methyl-4, 6-di-tert-butylphenyl 3, 5-di-tert -butyl-4-hyd roxybenzoate.

2.4. Acrylates, for example ethyl α-cyano-ss,ss-diphenylacrylate, isooctyl α-cyano-ss,ss-diphe-

nylacrylate, methyl a-carbomethoxycinnamate, methyl a-cyano-p-methyl-p-methoxycinnamate, butyl a-cyano-ss-methyl-p-methoxycinnamate, methyl a-carbomethoxy-p-methoxycinnamate and N- (ss-carbomethoxy-ss-cyanovinyl) -2-methylindoline.

2.5. Nickel compounds, for example nickel complexes of 2, 2'-thiobis[4- (1, 1,3, 3-tetramethylbutyl) phenol], such as the 1: 1 or 1: 2 complex, with or without additional ligands such as nbutylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of the monoalkyl esters, e. g. the methyl or ethyl ester, of 4-hydroxy-3, 5-di-tert- butylbenzylphosphonic acid, nickel complexes of ketoximes, e. g. of 2-hydroxy-4-methylphe-

nylundecylketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additional ligands.

2.6. Sterically hindered amines, for example bis (2,2, 6, 6-tetramethyl-4-piperidyl) sebacate, bis (2,2, 6, 6- tetramethyl-4-piperidyl) succi nate, bis (1,2, 2,6, 6-pentamethyl-4-piperidyl) sebacate, bis (1-octyloxy-2, 2,6, 6-tetramethyl-4-piperidyl) sebacate, bis (1,2, 2,6, 6-pentamethyl-4-piperi- dyl) n-butyl-3, 5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of 1- (2-hydroxyethyl) - 2,2, 6, 6-tetramethyl-4-hydroxypiperidine and succinic acid, linear or cyclic condensates of N, N'-bis (2,2, 6, 6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-tert-octylamino-2, 6-di-

chloro-1, 3, 5-triazine, tris (2, 2, 6, 6-tetramethyl-4-piperidyl) nitrilotriacetate, tetrakis (2, 2, 6, 6-tetramethyl-4-piperidyl) -1, 2, 3, 4-butanetetracarboxylate, 1, 1'-(1, 2-ethanediyl)-bis (3, 3, 5, 5-tetramethyl pi perazi none), 4-benzoyl-2, 2, 6, 6-tetramethylpiperidi ne, 4-stearyloxy-2, 2, 6, 6-tetramethylpiperidin, bis (1, 2, 2, 6, 6-pentamethyl piperidyl) -2-n-butyl-2- (2-hyd roxy-3, 5-di- tert -butylbenzyl) malonate, 3-n-octyl-7, 7, 9, 9-tetramethyl-1, 3, 8-triazaspiro [4. 5] decane-2, 4-dione, bis (1-octyloxy-2, 2, 6, 6-tetramethylpiperidyl) sebacate, bis (1-octyloxy-2, 2, 6, 6-tetramethylpiperidyl) succi- nate, linear or cyclic condensates of N, N'-bis (2,2, 6, 6-tetramethyl-4-piperidyl) hexamethylene diamine and 4-morpholino-2, 6-dichloro-1, 3,5-triazine, the condensate of 2-chloro-4, 6-bis (4-nbutylamin-2, 2,6, 6-tetramethylpiperidyl) -1, 3,5-triazine and 1,2-bis (3-aminopropylamino) - ethane, the condensate of 2-chloro-4, 6-di- (4-n-butylamino-1, 2,2, 6, 6-pentamethylpiperidyl) -

1, 3, 5-triazine and 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-dodecyl-1- (2, 2, 6, 6-tetramethyl-4-piperidyl) pyrrolidine-2, 5-dione, 3-dodecyl-1- (1,, 2, 2, 6, 6-pentamethyl-4-piperidyl) pyrrolidine-2, 5-dione a mixture of 4-hexadecyloxy- and 4-stearyloxy-2, 2, 6, 6-tetramethylpiperidine, a condensate of N, N'-bis (2, 2, 6, 6- tetramethyl-4-pipe ridyl) hexamethylenediami ne and 4-cyclohexylami no-2, 6- dichloro-1, 3,5-triazine, a condensate of 1,2-bis (3-aminopropylamino) ethane and 2,4, 6trichlor-1, 3, 5-triazine as well as 4-butylamin-2, 2,6, 6-tetramethylpiperidine (CAS Reg. No.

[136504-96-6]) ; a condensate of 1,6-hexanediamine and 2,4, 6-trichlor-1, 3, 5-triazine as well as N, N-dibutylamin and 4-butylamino-2, 2,6, 6-tetramethylpiperidine (CAS Reg. No. [192268- 64-7]) ; N- (2, 2,6, 6-tetramethyl-4-piperidyl)-n-dodecylsuccinimide, N-(1, 2,2, 6, 6-pentamethyl-4- piperidyl) -n-dodecylsuccinimide, 2-undecyl-7, 7,9, 9-tetramethyl-1-oxa-3, 8-diaza-4-oxo-spiro- [4, 5] decane, a reaction product of 7,7, 9, 9-tetramethyl-2-cycloundecyl-1-oxa-3, 8-diaza-4oxospiro- [4, 5] decane and epichlorohydrin, 1,1-bis (1,2, 2,6, 6-pentamethyl-4-piperidyloxy- carbonyl) -2- ( 4-methoxyphenyl) ethene, N, N'-bis-formyl-N, N'-bis (2,2, 6, 6-tetramethyl-4-piperi- dyl) hexamethylenediamine, a diester of 4-methoxymethylenemalonic acid with 1,2, 2,6, 6-

pentamethyl-4-hyd roxypipe rid i ne, poly [methylpropyl-3-oxy-4- (2, 2,6, 6-tetramethyl-4-piperi- dyl)] siloxane, a reaction product of maleic acid anhydride-ex-olefin copolymer with 2,2, 6,6- tetramethyl-4-am i nopi pe ridi ne or 1,2, 2,6, 6-pentamethyl-4-aminopiperidine.

2.7. Oxamides, for example 4, 4'-dioctyloxyoxanilide, 2, 2'-diethoxyoxanilide, 2, 2'-dioctyloxy- 5, 5'-di-tert-butoxanilide, 2, 2'-didodecyloxy-5, 5'-di-tert-butoxanilide, 2-ethoxy-2'-ethyloxanilide, N, N'-bis (3-dimethylaminopropyl) oxamide, 2-ethoxy-5-tert-butyl-2'-ethoxanilide and its mixture with 2-ethoxy-2'-ethyl-5, 4'-di-tert-butoxanillde, mixtures of o-and p-methoxy-disubstituted oxanilides and mixtures of o-and p-ethoxy-disubstituted oxanilides.

3. Metal deactivators, for example N, N'-diphenyloxamide, N-salicylal-N'-salicyloyl hydrazine, N, N'-bis (salicyloyl) hydrazine, N, N'-bis (3, 5-d Hert -butyl-4-hyd roxyphenylpropionyl) hydrazi ne,

3-salicyloylamino-1, 2, 4-triazole, bis (benzylidene) oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, N, N'-diacetyladipoyl dihydrazide, N, N'-bis (salicyloyl) oxalyl dihydrazide, N, N'-bis (salicyloyl) thiopropionyl dihydrazide.

4. Phosphites and phosphonites, for example triphenyl phosphite, diphenylalkyl phosphites, phenyldialkyl phosphites, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylpentaerythritol diphosphite, tris (2, 4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis (2, 4-di-te rt-butyl-6-methylphenyl) - pentaerythritol diphosphite, bis (2,4, 6-tris (tert-butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis (2, 4-di-tert-butylphenyl) 4, 4'-biphenylen diphosphonite, 6- isooctyloxy-2, 4,8, 10-tetra-tert-butyl-12H-dibenz [d, g]-1, 3,2-dioxaphosphocin, bis (2,4-di-tertbutyl-6-methyl phenyl) methyl phosphite, bis (2, 4-di-tert-butyl-6-methylphenyl) ethyl phosphite, 6-fluor-2, 4,8, 10-tetra-tert-butyl-12-methyl-dibenz [d, g]-1, 3,2-dioxaphosphocin, 2,2', 2"-nitril-

[triethyltris (3, 3', 5, 5'-tetra-tert-butyl-1, 1'-biphenyl-2, 2'-diyl) phosphite], 2-ethylhexyl (3, 3', 5, 5'-tetra-tert-butyl-1, 1'-biphenyl-2, 2'-diyl) phosphite, 5-butyl-5-ethyl-2- (2, 4, 6-tri-tert-butylphenoxy) - 1,3, 2-dioxaphosphirane.

The following phosphites are especially preferred: Tris (2, 4-di-tert-butylphenyl) phosphite (Irgafos168, Ciba-Geigy), tris (nonylphenyl) phosphite,

5. Hydroxylamines, for example N, N-dibenzylhydroxylamine, N, N-diethylhydroxylamine, N, N-

dioctylhydroxylamine, N, N-dilaurylhydroxylamine, N, N-ditetradecylhydroxylamine, N, Ndl hexadecylhydroxylamine, N, N-dioctadecythydroxylamine, N-hexadecyl-N-octadecylhydrox- lamine, N-heptadecyl-N-octadecylhydroxylamine, N, N-dialkylhydroxylamine derived from hydrogenated tallow amine.

6. Nitrones, for example N-benzyl-alpha-phenylnitrone, N-ethyl-alpha-methylnitrone, N-octyl-

al pha-heptyln itrone, N-I au ryl-alpha-u ndecyl nitrone, N-tetradecyl-al pha - tridecyl n itrone, Nhexadecyl-alpha-pentadecylnitrone, N-octadecyl-alpha-heptadecylnitrone, N-hexadecyl-alpha-heptadecylnitrone, N-ocatadecyl-alpha-pentadecylnitrone, N-heptadecyl-alpha-heptadecylnitrone, N-octadecyl-alpha-hexadecylnitrone, nitrone derived from N, N-dialkylhydroxyl- amine derived from hydrogenated tallow amine.

7. Thiosynergists, for example dilauryl thiodipropionate or distearyl thiodipropionate.

8. Peroxide scavengers, for example esters of ss-thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2-mercapto- benzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis (pdodecylmercapto) propionate.

9. Polyamide stabilisers, for example copper salts in combination with iodides and/or phosphorus compounds and salts of divalent manganese.

10. Basic co-stabilisers, for example melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids, for example calcium stearate,

zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitat, antimony pyrocatecholate or zinc pyrocatecholate.

11. Nucleatinq agents, for example inorganic substances, such as talcum, metal oxides, such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of, preferably, alkaline earth metals ; organic compounds, such as mono-or polycarboxylic acids and the salts thereof, e. g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymeric compounds, such as ionic copolymers (ionomers). Especially preferred are 1,3 : 2,4-bis (3', 4'-dimethylbenzylidene) sorbitol, 1,3 : 2,4-di (paramethyldibenzyli- dene) sorbitol, and 1,3 : 2,4-di (benzyliden) sorbitol.

12. Fillers and reinforcing agents, for example calcium carbonate, silicates, glass fibres, glass bulbs, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood flour and flours or fibers of other natural products, synthetic fibers.

13. Other additives, for example plasticisers, lubricants, emulsifiers, pigments, rheology additives, catalysts, flow-control agents, optical brighteners, flameproofing agents, antistatic agents and blowing agents.

14. Benzofuranones and indolinones, for example those disclosed in U. S. 4,325, 863; U. S. 4,338, 244; U. S. 5,175, 312; U. S. 5,216, 052 ; U. S. 5,252, 643; DE-A-4316611 ; DE-A-4316622; DE-A-4316876; EP-A-0589839 or EP-A-0591102 or 3- [4- (2-acetoxyethoxy)-

pheny)]-5, 7 -di-tert-butyl-benzofuran-2-one, S, 7 -di-tert-butyl-3-[ 4- (2-stearoyloxyethoxy) phenyijbenzofuran-2-one, 3, 3' -bis[S, 7 -di-tert-butyl-3- (4-[2-hydroxyethoxy]phenyl) benzofu ran-2one], 5, 7 -di-tert-butyl-3- (4-ethoxyphenyl) benzofuran-2-one, 3- (4-acetoxy-3, S-dimethylphenyl) -S, 7 -di-tert-butyl-benzofuran-2-one, 3- (3, S-dimethyl-4-pivaloyloxyphenyl) -5, 7 -di-tert-butylbenzofuran-2-one, 3- (3, 4-dimethylphenyl)-5, 7-di-tert-butyl-benzofuran-2-one, 3- (2, 3-dimethyl phenyl) -S, 7 -di- tert-butyl-benzofu ran-2-one. Where appropriate, the conventional additives are judiciously employed in amounts up to 10 % by weight, e. g. 0.1-10 % by weight, especially 0.2-5 % by weight, based on the material to be stabilized.

Acid scavengers may be added, especially in order to improve the lifetime of agricultural materials which come in contact with pesticides, e. g. greenhouse films. Components active as acid scavengers include metal oxides and/or hydroxides, e. g. oxides or hydroxides of zinc, magnesium, aluminum, calcium, mixed salts thereof, as well as hydrotalcites or zeolithes as described, for example, in GB-A-2300192, from page 2, line 2, until page 4, line 22.

Where present, the sterically hindered amine is usually contained in an amount of 0. 01-6 % by weight the polyolefin, polyester or polyamide, the weight ratio sterically hindered amine : hydroxyphenyl triazine UV absorber preferably ranging from 2: 1 to 20: 1.

Examples for sterically hindered amines preferably contained in the polyolefin, polyester or polyamide articles of the invention are given in the above list (item 2.6).

More preferred sterically hindered amines include the following compounds: bis (2,2, 6, 6-tetramethyl-4-piperidyl) sebacate; bis (1,2, 2,6, 6-pentamethyl-4-piperidyl) sebacate; the condensate of 1-(2-hydroxyethyl)-2, 2, 6, 6-tetramethyl-4-hydroxypiperidine and succinic acid (CAS-No. 65447-77-0); N, N', N", N"'-Tetrakis (4,6-bis (butyl- (N-methyl-2, 2,6, 6-tetramethylpiperidin-4-yl) amino) triazin-2yl)-4, 7-diazadecane-1, 10-diamine (CAS-No. 106990-43-6) ;

(Chimassorb2020, CAS No. 192268-64-7), where n is mainly from the range 3-5; or mixtures of these compounds.

Best results are obtained with a sterically hindered amine from the class of the hydroxylamine ethers. Sterically hindered hydroxylamine ethers are mainly piperidine

derivatives containing one or more functional groups of the formula

H R-C CHgR' wherein Rand R'independently are hydrogen or methyl, and at R-C CH3 H2

least the chemical bond of the oxygen atom and optionally a further chemical bond is linked to an organic residue while the remaining is/are saturated with hydrogen; or all 3 chemical bonds are linked to an organic residue. Examples for such compounds are described inter alia in US patents Nos. 5204473,5216156, or in GB-A-2347928.

Examples for the most preferred hydroxylamine ethers are compounds of the formula (1 g-1)

in which the index n ranges from 1 to 15, being especially from the range 3-9;

R12 is C2-C12alkylene, C4-C12alkenylene, Cs-C7cycloalkylene, Cs-C7cycloalkylenedi (C1-C4alkylene), C1-C4alkylenedi (Cs-C7cycloalkylene), phenylenedi (C1-C4alkylene) or C4-C12alkylene interrupted by 1, 4-piperazinediyl,-O- or > N-X1 with X1 being C1-C12acyl or (C1-C12alkoxy) carbonyl or having one of the definitions of R14 given below except hydrogen; or R12 is a group of the formula (lb') or (Ic') ;

with m being 2 or 3, X2 being C1-C18alkyl, C5-C12cycloalkyl which is unsubstituted or substituted by 1,2 or 3 C1-C4alkyl ; phenyl which is unsubstituted or substituted by 1,2 or 3 Ci-C4alkyl or C1-C4alkoxy ; C7-C9phenylalkyl which is unsubstituted or substituted on the phenyl by 1,2 or : C1-C4alkyl ; and the radicals X3 being independently of one another Cs-Cigatkyiene ; the radicals B are independently of one another Cl, -OR13, -N(R14)(R15) or a group of the formula (iliad) ;

R13, and R15'which are identical or different, are hydrogen, C1-C18alkyl, C5-C12cycloalkyl which is unsubstituted or substituted by 1,2 or 3 C1-C4alkyl ; C3-C18alkenyl, phenyl which is unsubstituted or substituted by 1,2 or 3 C1-C$alkyl or Cl-C4alkoxy ; C7-Cgphenylalkyl which is unsubstituted or substituted on the phenyl by 1,2 or 3 C1-C4alkyl ; tetrahydrofurfuryl or C2-C4alkyl which is substituted in the 2,3 or 4 position by-OH, Ci-Csaikoxy,

di (C1-C4alkyl) amino or a group of the formula (le') ;

with Y being -0-, -CH2-, -CH2CH2- or > N-CH3, or-N (Ri4) (Ri5) is additionally a group of the formula (le') ; X is -O- or > N-R16 ;

R16 is hydrogen, Ci-Cigaikyi, Cs-CisaJkeny !, Cs-Ciacydoaikyi which is unsubstituted or substituted by 1,2 or 3 C1-C4alkyl ; C7-Cgphenylalkyl which is unsubstituted or substituted on the phenyl by 1,2 or 3 Dialkyl ; tetrahydrofurfuryl, a group of the formula (IIIf),

or C2-C4alkyl which is substituted in the 2,3 or 4 position by -OH, C1-C8alkoxy, di (C1-C4alkyl) amino or a group of the formula (le') ; R11 has one of the definitions given for Rie.

In these compounds, the end group bonded to the triazine residue can be, for example, a group B or-N (Rn)-Ri2-B, such as chlorine or a group

and the end group bonded to the diamino group can be, for example, hydrogen or a di-Bsubstituted triazinyl group, such as a group

It may be convenient to replace the chlorine attached to the triazine by e. g.-OH or an amino group. Suitable amino groups are typically : pyrrolidin-1-yl, morpholino, -NH2, -N (C1-Csalkylh and -NY' (C1-Csalkyl) wherein Y'is hydrogen or a group of the formula

In the above shown oligomeric and polymeric compounds, examples of alkyl are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1, 3-dimethylbutyl, n-hexyl, 1-methylhexyl, n- heptyl, isoheptyl, 1,1, 3, 3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethyl- hexyl, 1,1, 3-trimethylhexyl, 1,1, 3, 3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 1,1, 3,3, 5, 5-hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, eicosyl and docosyl ;

examples of cycloalkyl are cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl ; an example of C7-Cgphenylalkyl is benzyl ; and examples of alkylene are ethylene, propylene, trimethylene, tetramethylene, pentamethylene, 2, 2-dimethyltrimethylene, hexamethylene, trimethylhexamethylene, octamethylene and decamethylen.

Another example for a sterically hindered amine ether advantageously to be used within present polymer articles is the compound of the formula

An example for a highly effective compound of formula (1 g-1) is the compound of the formula (1 g-2)

wherein n'is approximately 3 (example 2 of GB-A-2334717, CAS &num; 247243-62-5, which is the NO-n-propyl derivative of the block oligomer Chimassorbe 2020 CAS &num; 192268-64-7, Ciba Specialty Chemicals Corp.).

The additives of the invention and optional further components may be added to the polymer material individually or mixed with one another. If desired, the individual components can be

mixed with one another for example in the melt (melt blending) before incorporation into the polymer.

The incorporation of the additives of the invention and optional further components into the polymer is carried out by known methods such as dry mixing in the form of a powder, or wet mixing in the form of solutions or suspensions. The additives of the invention and optional further additives may be incorporated, for example, before or after molding or also by applying the dissolved or dispersed addtitve or additive mixture to the polymer material, with or without subsequent evaporation of the solvent. They may be added direct into the processing apparatus (e. g. extruders, internal mixers, etc), e. g. as a dry mixture or powder or as solution or melt.

The incorporation can be carried out in any eatable container equipped with a stirrer, e. g. in a closed apparatus such as a kneader, mixer or stirred vessel. The incorporation is preferably carried out in an extruder or in a kneader. It is immaterial whether processing takes place in an inert atmosphere or in the presence of oxygen.

The additives of the invention and optional further additives can also be added to the polymer in the form of a masterbatch which contains the components in a concentration of, for example, about 2.5 % to about 25 % by weight; in such operations, the polymer can be used in the form of powder, granules, solutions, suspensions or in the form of latices.

The examples which follow describe the invention further without constituting any restriction.

Parts and percentages therein are by weight; an example which mentions room temperature means thereby a temperature in the range 20-25 C. In the case of solvent mixtures such as those for chromatography the parts indicated are by volume. These definitions apply unless specified otherwise.

The following abbreviations are used:

m. p. melting point or melting range NMR nuclear magnetic resonance Tg glass transition temperature; h: hours.

Preparation of Hydroxyphenyl Triazine UV Absorbers h) A suspension of 2, 4-bis (4-methoxyphenyl)-6-[2,4-dihydroxyphenyl]-1, 3,5-triazine (0.0227 mole) in dimethylformamide (30 ml) is heated under nitrogen at 70 0 until a clear brown solution is formed. Anhydrous potassium carbonate (3.77 g, 0.0227 mole) is added and the brown suspension heated at 80 OC for 30 minutes. 2-Ethylhexylbromide (5.70g, 0.0295 mole) is added dropwise over 30 minutes, after which the suspension is heated at 110 C for a further 3 hours. Precipitated salts are filtered off and the filtrate cooled to 0"C. Methanol (20 ml) is added and the precipitated product removed by filtration. After drying under vacuum, compound (h) of the formula

is obtained with mp 105 C.

The compounds shown in the following table are obtained when the above reaction is

repeated using corresponding amounts of other alkylbromides or alkylene-dibromides.

Example R-1 Mp : C b) CH (CH3)- (CH-CH3 OIL

Example X Mp: C f) -(CH2)10- > 250 g) (CH2),,- > 0

Corresponding compounds wherein X is C13-C24alkylene ; (CrC18alkylene) -CO-O-D-O-CO- (Ci-Cisa ! ky ! ene) ; CO- (Ci3-C24alkylene)-CO ; C3-C24alkylene interrupted by oxygen, especially (C1-C3alkylene)-O-(C1-C3alkylene) are obtained using the appropriate alkylene-dibromides or alkylene-dibromides Interrupted by-CO-0-D-O-CO-or oxygen, or dichlorides or dibromides of aliphatic Cis-Caediacids.

Application Examples In some of the application examples, the following sterically hindered amines (HALS) are employed :

compound formula/chemical name (1 g-2) CAS-No. 247243-62-5 (see above) H-2 bis (2,2, 6, 6-tetramethyl-4-piperidyl) sebacate) H-3 condensate of 1- (2-hydroxyethyl) -2, 2,6, 6-tetramethyl-4hydroxypiperidine and succinic acid (CAS-No. 65447-77-0)

H-5 N, N', N", N"'-Tetrakis (4,6-bis (butyl- (N-methyl-2, 2,6, 6- tetramethylpiperidin-4-yl) amino) triazin-2-yl) -4, 7 -diazadecane-1, 10- diamine (CAS-No. 106990-43-6).

Example 2: Hvdroxvphenvl triazine as a UV Filter in a Polyethylene Aqrofilm In order to prepare thin LDPE films and to evaluate the spectral features imparted by the additive and its persistency, the compound of the invention is mixed with LDPE pellets (Riblene FF 29, supplied by Polimeri Europa, Milano, Italy), characterized by a density of 0.921 g/cm3 and a melt flow index (190 C/2. 16Kg) of 0.6) in a turbo mixer in order to give a formulation containing 0.15% by weight of the additive. The mixture is extruded at a maximum temperature of 2000C in a OMC twin-screw extruder. The granules so obtained are blown in a lab scale Formac blow-extruder at a maximum temperature of 210 C to give a film 150m thick. UV-Vis spectra are recorded in the range 200-800 nm by means of a Perkin- Elmer Lambda 20 spectrophotometer, equipped with a RSA-PE-20 Labsphere integrating sphere.

In order to test the photostability of the additive upon exposure to light, a portion of the film is exposed in an Atlas Weather-o-Meter (WOM), model Ci65A (as per ASTM G26-96, irradiance 0.35 W/m2, black panel temperature 633 C).

Example 4 A film containing 0.15% by weight of compound (b) is prepared as described in example 2.

The film displays a strong absorption band in the range 280-360 nm. In particular, transmittance is below 20% in the above mentioned range and below 5% in the range 295- 345 nm.

After 1000 hours of exposure in the WOM (see example 2 for details), the film still retains the spectral features described above.

Example 5 A film containing 0.15% by weight of compound (g) is prepared as described in example 2.

The film displays a strong absorption band in the range 280-360 nm. In particular, transmittance is below 20% in the above mentioned range and below 5% in the range 295- 345 nm. After 1000 hours of exposure in the WOM (see example 2 for details), the film still displays a transmittance below 25% between 280 and 360 nm and below 10% between 295 and 345 nm. Another portion of the film is also exposed in oven at 60 C. After 1000 hours of exposure the film retains about 75% of the initial absorption.

Example 6: A film containing 0.15% by weight of compound (f) is prepared as described in example 2. The film displays a strong absorption band in the range 280-360 nm. In particular, transmittance is below 20% in the above mentioned range and below 5% in the range 295- 345 nm. After 1000 hours of exposure in the WOM (see example 2 for details), the film still displays a transmittance below 25% between 280 and 360 nm and below 15% between 295 and 345 nm.

Claims

WHAT IS CLAIMED IS : 1. A compound of one of the formulae b, f, g, h or k

<Desc/Clms Page number 28>

wherein X is C1S-C24alkylene ; (C1-C1salkylene) -CO-O-D-O-CO- (CrC1salkylene) where D is CTC12alkylene ; CO- (C1S-C24alkylene) -CO ; CS-C24alkylene interrupted by oxygen.
2. A compound of claim 1 of formula (k), wherein X is C13-C18 alkylene or (C1-C3alkylene)-O- (Ci-Csalkylene).