GB2382348A - Transparent polyolefin film comprising hydroxyphenyl triazine UV absorber - Google Patents

Abstract

A polyolefin film having a thickness between 1 and 500 žm and containing 0.005 to 0.30% by weight, based on the polyolefin, of a hydroxyphenyl triazine UV absorber. The film is used for suppressing microbial growth in a protected environment, such as plant cultivation. The film may further contain a sterically hindered amine, which may be a hydroxylamine ether, in an amount of 0.01 to 6% by weight of the polyolefin. The polyolefin is preferably polyethylene or polypropylene. Also claimed is a method for screening solar and/or artificial light radiation to crops in a greenhouse using the film.

Description

Polyolefin Film for Protected Environment The invention relates to a novel

polyolefin film of good transparency having enhanced stability against the effects of light, oxygen, heat and agressive chemicals, which is effective as a selective UV filter for agricultural applications.

Certain polyolefin films 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 transparent polyolefin film stabilized by addition of 0.005-0.30 % by weight the polymer substrate of a hydroxyphenyl triazine UV absorber, characterized in that the film has a thickness between 1 and 500 m.

Preferred films contain as a hydroxyphenyl triazine UV absorber a compound of the formula I N >< N (I)

R /\ i RR24 wherein R. is H or OR7, R2 and Rat independently are H. C,C8alkyl, OR 8 ORs; R4 and Rs independently are H. C,-Cealkyl, OR1o; R6 is H. C,-C,8alkyl, Cs-C42cycloalkyl, C7-C,2phenylalkyl, C7-C,2alkylphenyl, C3-C12alkenyl, halogen, OH, ORg; Rat is H; halogen; C,-C,2alkoxy; C,-C, 2alkyl; C3-C24alkyl interrupted by oxygen and/or substituted by OH; or is NH-CO-R,4 or NH-COO-R,2;

- 2 R7 Rg and R,0 independently are H; C,-C24alkyl; C3-C,2alkenyl; C3C24alkyl interrupted by oxygen and/or substituted by OH; or is C5-C, 2cycloalkyl C7-C'2phenylalkyl C7-

C,2alkylphenyl; CH2CH(OH)CH2OR,,; C,-C,2alkyl substituted by COOR'2 CONR, 3R'4 OCOR,5 OH or halogen; or R7 is a polymeric hydrocarbon residue of 10 to 1000 carbon atoms preferably 20 to 500 carbon atoms; and R7 also embraces a residue of formula 11 X O OH N N (II)

R. 3/q /: N J\ RR2 wherein X is C2-C24alkylene; -CH2CH(OH)CH2-; -CH2CH(OH) CH2O-D-OCH2CH(OH)CH2; (C, -C, 8alkylene)-CO-O-D-O-CO-(C, -C'8alkylene); CO; CO-(C2-C24alkylene)-CO; C3-C24alkylene interrupted by oxygen; D is C2C,2alkylene; C4-Cs0alkylene interrupted by O; phenylene; biphenylene or phenylene-E-phenylene; E is O S SO2; CH2; CO or -C(CH3)2-; R., is H C,-C, 2alkyl; phenyl; phenyl substituted by 1-3 C,-C4alkyl; Cs-C'2cycloalkyl; C7 C,2phenylalkyl; C3-C,2alkenyl; R'2 is H C,-C24alkyl; C3-C12alkenyl; C3C36alkyl interrupted by oxygen and/or substituted by OH; oris Cs-C, 2cycloalkyl C7-C,2phenylalkyl C7-C,2alkylphenyl; phenyl; R,3 and R,4 independently are H C,-C,8alkyl; phenyl; phenyi substituted by 1-3 C,C4alkyl and/or C,-C4alkoxy; Cs-C,2cycloalkyl; C3-C,2alkenyl; R,5 is C,-C, 2alkyl; phenyl; phenyl substituted by 1-3 C,-C4alkyi and/or C,-C4alkoxy; Cs C,2cycloalkyl; C3-C,2alkenyl; C,-C,2alkoxy; or is NR,3R,4.

More preferably in the hydroxyphenyl triazine UV absorber of the formula I R4 and R5 independently are H or methyl; R6 is H; R8 is H; C,-Caalkoxy; C,-C8alkyl;

- 3 R7, Rg independently are H; C,-C,8alkyl; C3-C,2alkenyl; C3-C24alkyl interrupted by oxygen and/or substituted by OH; or is Cs-C,2cycloalkyl, C7-C,2phenylalkyl, CrC,2alkylphenyl; C, C,2alkyl substituted by COORS, OCOR,s, OH; or R7 is a polymeric hydrocarbon residue of 20 to 500 carbon atoms; and R7 also embraces a residue of formula 11, wherein X is C2-C, alkylene; -CH2CH(OH)CH2 -CH2CH(OH)CH2O-D-OCH2CH(OH)CH2;

(C,-C4alkylene)-CO-O-D-O-CO-(C,-C4alkylene); CO; CO-(C2-C 8alkylene)-CO; C3-C, alkylene interrupted by oxygen; D is C2-C,2alkylene; R'2 is H; C,C24alkyl; C3-C,2aikenyl; C3-C24alkyl interrupted by oxygen and/or substituted by OH; or is Cs-C,2cycloalkyl, C7-C,2phenylalkyl, C7-C, 2alkylphenyl; phenyl; R,s is C,-C,2alkyl; Cs-C,2cycloalkyl; C3-C,2alkenyl; especially R. is OR7; R2 and R3 independently are H. methyl, FIR EN. ORg; R4 and Rs and R6 are H; Rig is H; C,-C8alkoxy; C,-C4alkyl; R7, Rg independently are C4-C,8alkyl or Cs-C'2cycloalkyl; and R7 also embraces a residue of fommula 11, wherein X is C -C,aalkylene.

Of utmost importance are compounds of the formula 1, wherein R. is OR7; R2 and R3 each are phenyl; R4, Rs and R6 are hydrogen; and R7 is C4-C, alkyl or Cs-Cl2cycloalkyl or a residue of formula 11, wherein X is C4-C, 2alkylene.

A halogen substitutent is -F. -Cl, -Br or -1, preferably -F. -Cl or-Br and, in particular, -Cl.

Alkylphenyl is alkyl-substituted phenyl; C7-C,4alkylphenyl embraces examples such as methylphenyl (tolyl), dimethylphenyl (xyiyl), trimethylphenyl (mesityl), ethylphenyl, propylphenyl, butylphenyl, dibutylphenyl, pentylphenyl, hexylphenyl, heptylphenyl and octylphenyl. Phenylalkyl is phenyl-substituted alkyl; C7-C',phenyialkyl embraces examples such as benzyl, or-methylbenzyl, (x-ethylbenzyi, cr,adimethylbenzyi phenylethyl, phenylpropyl,

- 4 phenylbutyl and phenylpentyl.

n-alkyl or alkyl-n is an unbranched alkyl radical.

Alkyl interrupted by O. NH, NR,3, etc., can generally comprise one or more nonadjacent heteroatoms. Preferably, a carbon atom of the alkyl chain bonds to not more than 1 heteroatom. R7, Rg and R,o, especially R7, as alkyl substituted by COOR,2 is most preferably CH2-COOR,2. R,2 is most preferably C,-C., alkyl, or C6-C,2cycloalkyl; cycloalkyl is most preferably cyclohexyl or cyclododecyl.

W'thin the scope of the stated definitions, the radicals R4, R5, R5, R, R', R.,, R,2, R', R,4, R,5 as alkyl are branched or unbranched alkyl such as methyl, ethyl, propyl, isopropyl, n-

butyl, sec-butyl, isobutyl, t-butyl, 2 - thylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1,3-

dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3tetramethylbutyl, 1-

methylheptyl, 3-methylheptyl, n-octyl, 2 - thylhexyl, 1,1,3trimethylhexyl, 1,1,3,3-

tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 1,1,3, 3,5,5-

hexernethylhexyl, tr decyl, tetradecyl, pentadecyl, hexedecyl, heptadecyl and octadecyl.

C -C4alkyl is especially methyl, ethyl, isopropyl, n-butyl, 2-butyl, 2methylpropyl or tert-butyl.

Wthin the scope of the stated definitions, R4, Rs, R6, R8, Rg, R.,, R,z, R,3, R,4, R s as alkenyl include allyl, isopropenyl, 2-butenyi, 3-butenyl, isobutenyl, n-penta-2,4-dienyl, 3-methyl-but-2-

enyl. R4, Rs and R6 are most preferably hydrogen. R2 and R3 are most preferably phenyl or ORg, especially phenyl. Rg is most preferably C,C4alkyl.

Examples for highly effective compounds of the formula I are as listed below or in the following tables: 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)1,3,5-triazine, 2-(2-hydroxy4-octyloxyphenyl) 4,6-

bis(2,4 imethylphenyl)-1, 3, 5-triazine, 2-(2,4 ihydroxyphenyl)4,6-bis(2, 4-dimethylphenyl)-

1, 3, 5-triazine, 2,4-bis(2-hydroxy-4-propyloxyphenyl) -(2,4 imethylphenyl)-1,3, 5-triazine, 2-

(2-hydroxy-4-octyiox-yphenyl) -,6-bis(4-methylphenyl)-1, 3,5-triazine, 2(2-hydroxy4

dodecyloxyphenyl)4,6-bis(2,4-dimethylphenyl)-1, 3, 5-triazine, 2-(2hydroxy4-

tridecyloxyphenyl)4,6-bis(2,4-dimethylphenyl)-1, 3, 5-triazine, 2-[2hydroxy4-(2-hydroxy-3-

butyloxypropoxy)phenyl]4,6-bis(2,4-dimethyl)-1,3, 5-triazine, 2-[2hydroxy4-(2-hydroxy-3-

octyloxypropyloxy)ph,enyl]4,6-bis(2,4-dimethyl)- 1, 3, 5-triazine, 2-[4(dodecyloxy tridecylaxy-2-

hydroxypropoxy)-2-hydroxyphenyl]4,6-bis(2,4-dimethylphenyl) 1,3,5triazine, 2-[2-hydroxy4-

(2-hydroxy-3-dodecyloxypropoxy)phenyl] -,6-bis(2,4-dimethylphenyl)-1,3,5triazine, 2-(2-

hydroxy-4-hexyloxy)phenyl4,6-diphenyl-1! 3,5-triazine, 2-(2-hydroxy4methoxyphenyl)-4,6-

diphenyl-1, 3, 5-triazine, 2,4,6-tris[2-hydroxy4-(3-butoxy-2hydroxypropOxy)phenyl]- 1, 3,5-

triazine, 2-(2-hydroxyphenyl) -(4-methoxyphenyl/6-phenyl-1,3,5-triazine, 2{2-hydroxy 4-[3-

(2-ethylhexyl-1 -oxy)-2-hydroxypropyloxy]phenyl} -, 6-bis(2,4dimethylphenyl)-1, 3,5-triazine.

Table 1: Compounds of the formula [ OH No compound R; a) CH2CH(C2Hs) (CH2) 3 cH3 b) CH(CH3)-(CH2)9-CH3 c) n-C6H,3 d) n-C8H'7 e) n-C12H25 In the above definitions; n denotes a straight alkyl chain.

- 6 Table 2: Compounds of the formula (k) O X - 0

OH POOH

N^N N^N

34: compound X f) -(C Hz) 1 2 9) -(CH2).0

or corresponding compounds wherein X is C,3-C24alkylene; (C,-C,aalkylene)CO-O-D-O-CO-

(C'-C,aalkylene); CO-(C,3-C24alkylene)-CO; C3-C24alkylene interrupted by oxygen, especially (C,-C3alkylene)-O-(C,-C3alkylene). Further examples for highly effective compounds of the formula I are the compounds 0 I/-CH3

h) - I'oHcH3 N:N CH3-O; O-CH3

- 7 H2 CH3

j' OH N N }c-o:>R 0 H2 H3C CH3

o'tCH2)s CH3 i) OH N N N Some compounds of formula I are known, e.g. from WO 96/28431, US-5591850, EP-A-

434608; others, e.g. the compounds O- -CH3

CH3 OH (a) N^N (3, N as well as (b), (c (g) and (h) are novel compounds. They are conveniently prepared in analogy to procedures described in these references, especially to the method given in example 18 of WO 96/28431.

- 8 A particular useful application of polymer films, especially polyolefin films of present invention is their use as greenhouse films. Some types of crops are degraded by the UV-components of solar radiation which must be filtered off to obtain high quality and productivity of the crops. Additionally, some microorganisms, e.g. Botrytis Cinerea, as well as some harmful insects, e.g. white flies, aphides, thrips or leafminers, can proliferate under specific UV-irradiation. These pest can be significantly reduced when UV light does not or to less extent reach the plants. [R. Reuveni et al., Development of photoselective PE films for control of foliarpathogens in greenhouse rown crops, Plasticulture No. 102, p 7 (1994J; Y. Antignus et al., The use of UV absorbing plastic sheets to protect crops against insects and spread of virus diseases, CIPA Congress March 1997, pp.23-33]. On the other hand, bee activity, requiring a certain band of UV radiation, needs to be retained in greenhouses in order to ensure fnuctification on flowering plants, e.g. tomato, cucumber, pumpkin etc. Present hydroxyphenyl triazine UV absorbers show excellent compatibility and persistence in the polyolefin. 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 films of present invention include the following polymers.

1. Polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, po-

lybut-1-ene, poly4-methylpent-1-ene, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for instance of cyclopentene or norbomene, polyethylene (which optionally can be crosslinked), for example high density polyethylene (HOPE), high density and high mole-

cular weight polyethylene (HDPE-HMW), high density and ultrahigh molecular weight poly-

ethylene (HDPE-UHMW), medium density polyethylene (MOPE), low density polyethylene (LOPE), linear low density polyethylene (LLDPE), (\ILDPE) 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:

- 9 - a) radical polymerization (normally under high pressure and at elevated temperature).

b) catalytic polymerization using a catalyst that normally contains one or more than one metal of groups IVb, Vb, Vlb or Vlil 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 a- or o-coordinated. These metal complexes may be in the free form or fixed on substrates, typically on activated magnesium chloride, titanium(l11) chloride, alumina or silicon oxide. These catalysts may be soluble or insoluble in the polymensation medium. The catalysts can be used by themselves in the polymerization 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, lla and/or Illa of the Periodic Table. The activators may be modified conveniently with further ester, ether, amine or silyl ether groups. These catalyst systems are usually termed Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC).

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, propyiene/isobutylene copolymers, ethylene/but-1 -ene copolymers, ethylene/hexene copolymers, ethylene/methylpentene copolymers, ethylene/heptene copolymers, ethylene/octane 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-norbomene; 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

- lo -

(EVA), LDPE/ethylene-acrylic acid copolymers (EM), LLDPE/EVA, LLDPEJEM and alter-

nating or random polyalkylenelcarbon monoxide copolymers and mixtures thereof with other polymers, for example polyamides.

Most preferred are polyolefines such as polyethylene, especially LOPE or LLDPE, or polypropylene. Preferably, the amount of hydroxyphenyl triazine UV absorber in the transparent polymer film 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.

The transparent polyolefin film of the invention usually is an agricultural film. Its thickness preferably ranges between 1 and 300 m, especially between 1 and 200 Am. Films, ribbons or tapes of the invention usually are not biaxially oriented. The transparent polyolefin film of the invention often contains one or more further components, e.g. selected from further light stabilizers, processing stabilizers, fillers, clarifiers, modifiers, acid scavengers, pigments, flame retarciants or other additives Known in the art. These components usually do not effectively block light transmission through the present polymer films, which is usually more than 20 %, often more than 50 %, and preferably more than 80 % of white incoming light. For sufficient transparency, present films preferably do not contain crystalline components in an amount that would significantly impair this property; preferably they contain no pigments and no or merely minor amounts, e.g. O - 5 % by weight of the polymer, of fillers or crystalline inorganic components having lower opaquing effect than pigments (e.g. hydrotalcites).

Examples for additional components which may be contained in the polymer films of the invention include the following: 1. Antioxidants 1.1. Alkvlated monophenols, for example 2,6-di-tert-butyl4-methylphenol, 2tert-butyl4,6 i-

methylphenol, 2,6-di-tert-butyl4-ethylphenol, 2,6 i-tert-butyl4-nbutylphenol, 2,6-di-tert-bu-

tyl4-isobutylphenol, 2,6-dicyclopentyl4-methylphenol, 2-(ccmethylcyclohexyl)4,6-dimethyl-

phenol, 2,6-dioctadecyl4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-ditert-butyl4-meth-

oxymethylphenol, nonylphenols which are linear or branched in the side chains, for example 2,6-di-nonyl4-methylphenol, 2,4-dimethyl -(1'methylundec-1'-yl)phenol, 2,4-dimethyl4-(1'

methylheptadec-1'-yi)phenci, 2,4-dimethyl -(1'-methyltridec-1'-yl)phenol and mixtures there-

of. 1.2. AikvithiomethYIphenols, for example 2,4-dioctylthiomethyl-6-tertbutylphenol, 2,4-dioctyl-

thiomethyl -methylphenol, 2,4-dioctylthiomethyi-6-ethylphenol, 2,6-didodecylth iomethyl4-

nonylphenol. 1.3. HYdroquJnones and alkvlated hvdrocuinones, for example 2,6-di-tert-butyl4-methoxy-

phenol, 2,5-di-tert-butylLydroquinone, 2,5-di-tert-amyihydroquinone, 2,6diphenyl4-octade-

cyloxyphenol, 2,6-di-tert-butylhydroquinone, 2, 5-di-tert-butyl4hydroxyanisole, 3,5-di-tert-bu-

tyl4-hydroxyanisole, 3,5-di-tert-butyl4-hydroxyphenyl stearate, bis(3,5di-tert-butyl - -hy-

droxyphenyl) adipate.

1.4. Tocopherols, for example cc-tocopherol, p-tocopherol, y-tocopherol, 8-tocopherol and mixtures thereof (vitamin E).

1.. Hydrox latecl thiodiphenvl ethers, for example 2,2'-thiabis(6-tertbuty'-4-methylphenol', 2, 2'-thiobis(4-octylphenoi), 4,4'-thiobis(6-tertbutyl-3-methylphenol), 4,4'-thichis(6-tert-butyl-2-

methylphenol), 4,4'-thiobis(3,6-di-sec-amylphenol), 4,4'-bis(2,6-dimethyl4-hydroxyphenyi)-

disulfide. 1.6. AlkYlidenebisohenols, for example 2,2'-methylenebis(6tert-butyl4-methylphenol), 2,2'-

methylenebis(6-tert-butyi4-ethylphenol), 2,2'-methylenebis[4-methyl-6-(amethylcyclohexyl)-

phenol], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'methylenebis(6-nonyl4-

methylphenoi), 2,2'-methylenebis(4,6-di-tert-butylphenol), 2,2'ethylidenebis(4,6-di-tert-butyl-

phenol), 2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenoi), 2,2'methylenebis[6-( -methylben-

zyl)4-nonylphenol], 2,2'-methylenebis[6-(a,cr-dimethylbenzyl)4nonylphenol], 4,4'-methy-

lenebis(2,6-di-tert-butylphenol), 4,4'-methyienebis(6-tert-butyl-2methylphenol), 1,1-bis(5-tert-

butyl4-hydroxy-2-methylphenyl)butane, 2,6-bis(3-tert-butyl-5-methyl-2hydroxybenzyl)4-

methylphenol, 1,1,3-tris(5-tert-butyl-4-nydroxy-2-methylphenyl)butane, 1, 1-bis(5-tert-butyl-4-

hydroxy-2-methylphenyi)-3-n-dodecylmercaptobutane, ethylene glycol bis[3, 3-bis(3'-tert-

butyl4'-hydroxyphenyl)butyrate], bis(3-tert-butyl4-hydroxy-5-methylphenyl)dicyclopenta-

diene, bis[2-(3'-tert-butyl-2'-hydroxy-s'-methylbenzyl)-6-tert-butyi4methylphenyl]terephtha-

late, 1,1 -bis-(3,5-dimethyl-2-hydroxyphenyl)butane, 2, 2-bis(3, 5 i-tertbutyl4-hydroxyphe

- 12 nyl)propane, 2,2-bis-(5-tertbutyi4-hydroxy2-methylphenyl)4-ndodecylmercaptobutane, 1,1, 5,5-tetra(5-tert-butyl4-hydroxy-2methylphenyl)pentane 1.7. O-, N- and S-benzvl compounds, for example 3,5, 3',5'-tetra-tert-butyl4,4'-dihydroxydi-

benzyl ether, octadecyl4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tridecyl4-hydroxy-

3, 5-di-tert-butylbenzylmercaptoacetate, tris(3, 5-di-tert-butyl-4hydroxybenzyl)amine, bis(4-

tert-butyi-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate, bis(3,5-ditert-butyl4-hydroxy-

benzyl)sulfide, isooctyl-3,5-di-tert-butyl4-hyd roxybenzylmercaptoacetate.

1.8. Hvdroxvbenzvl ted malonates, for example dioctadecyl-2,2-bis(3,5-ditert-butyl-2-hy-

droxybenzyl)malonate, di-octadecyl-2-(3-tert-butyl4-hydroxy-5methylbenzyl)malonate, di-

dcdecylmercaptoethyl-2, 2-bis(3, 5-di-tert-butyl4-hydroxybenzyl)malonate, bis[4-( 1,1, 3, 3-te-

tramethylbutyl)phenyl]-2,2-bis(3, 5-di-tert-butyl4-hydroxybenzyl)malonate.

1.9. Aromatic hydrox benzvl compounds, for example 1,3,5-tris(3 5-di-tertbutyl4-hydroxy-

benzyl)-2,4,6-trimethylbenzene, 1,4-bis(3,5-di-tert-butyl4-hydroxybenzyl)2, 3,5,6-tetrame-

thylbenzene,,4,6-tris(3,5-d,-'er'.-but;14-hydrcxybenzy!)phcOcl. 1.10. Triazine compounds, for example 2,4-bis(octylmercapto)-6-(3,5-di-tertbutyl4-hydroxy-

anilino)-1, 3, 5-triazine, 2-octylmercapto4,6-bis(3,5-di-tert-butyl4hydroxyanilino)-1,3, 5-tri-

azine, 2-octylmercapto4,6-bis(3, 5-di-tert-butyl4-hydroxyphenoxy)-1,3,5triazine, 2,4,6-tris-

(3, 5-di-tert-butyi4-hydroxyphenoxy)-1,2,3-triazine, 1,3, 5-tris(3,5-ditert-butyl4-hydroxyben-

zyl)isocyanurate, 1,3, 5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyi) isocyanurate, 2,4,6-tns-

(3, 5-di-tert-butyl4-hydroxyphenylethyl)-1, 3, 5-triazine, 1,3,5-tris(3,5 i-tert-butyl4-hydroxy-

phenylpropionyl)-hexahydro-1,3, 5-triazine, 1, 3,5-tris(3,5-dicyclohexyl4hydroxybenzyl)iso-

cyanurate. 1.11. Benzylphosohonates, for example dimethyl-2,5-di-tertbutyl4-hydroxybenzylphospho-

nate, diethyl-3,5-di-tert-butyl4-hydroxybenzylphosphonate, dioctadecyl3,5di-tert-butyl4-hy-

droxybenzylphosphonate, dioctadecyl-5-tert-butyl4-hydroxy-3methylbenzylphosphonate, the calcium salt of the monoethyl ester of 3,5di-tert-butyl4-hydroxybenzylphosphonic acid.

1.12. Acvlaminophenols, for example 4-hydroxylauranilide, 4hydroxystearanilide, octyl N-

(3, 5-di-tert-butyl4-hydroxyphenyl)carbamate.

- 13 1.13. Esters of (3,5-di-tert-butvl4-hydroxyphenvl)Propionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, l,9-

nonanediol, 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, trimethylol-

propane, 4-hydroxymethyl-1 -phospha-2,6,7-trioxabicyclo[2.2. 21octane.

with mono- or poly-

hydric alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanedi-

ol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis-

(hydroxyethyl)oxamide, 3-thie undeca no l, 3-th iapentadeca no l, trimeth ylhexanediol, trimethyl-

olpropane, 4-hydroxymethyl-1 -phospha-2,6, 7-trioxabicyclo[2.2.2]octane; 3, 9-bist243-(3-tert-

butyl4-hydroxy-5-methylphenyl)propionyloxy}1, 1 -dimethylethyl]-2,4,8, 1 0-tetraoxaspiro[5.5]-

undecane. 1.15. Esters:of B-(3,5-dicyclohexYI4-hydroxvphenyl)propionic acid with mono- or polyLydric alcohols, e.g. with methanol, ethanol, octanol, octadecanoi, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1, 2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, tri-

ethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'bis(hydroxyethyl)ox-

amide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hy-

droxymethyl-1 -phospha-2,6,7-trioxabicyclo[2. 2.2loctane.

1.16. Esters of 3.5-di-tert-butvl4-hYdroxYphenvl acetic acid with mono- or polyLydric alco-

hols, e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene giycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)ox-

amide, 3-thieundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hy-

droxymethyl-1 -phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.17. Amides of (3 5-di-tert-butvl4-hYdroxYPhenYl)propionic acid e.g. N, N'-bis(3,5-di-tert-

butyl4-hydroxyphenylpropionyl)hexamethylenediamide, N,N'-bis(3,5-di-tertbuty!-4-hydroxy-

phenylpropionyl)trimethylenediamide, N,N'-bis(3,5 i-tert-butyl4hydroxyphenylpropionyl)hy

- 14 drazide, N,N'-bis[2-(3-[3,5-di-tert-butyl4-hydroxyphenyl] propionyloxy)ethyl]oxamide (Nau-

gard XL-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-bu-

tyl-p-phenylenediamine, N. N'-bis( 1,4 imethylpentyl)-p-phenylenediamine, N. N'-bis( 1 -ethyl-3-

methylpentyl)-p-phenylenediamine, N. N'-bis(1 -methylheptyl)-pphenylenediamine, N. N'-dicy-

clohexyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N,N'-bis(2naphthyl)-p-

phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3dimethylbutyl)-N'-phe-

nyl-p-phenylenediamine, N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'-

phenyi-p-phenylenediamine, 4-(p-toluenesulfamoyl)diphenylamine, N. N'dimethyl-N, N'-di-

sec-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4isopropoxy-

diphenylamine, N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1naphthylamine, N-phe-

nyl-2-naphthylamine, octylated diphenylamine, for example p,p'-di-tertoctyidiphenylamine, 4-

n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4dodecanoyl-

aminophenol, 4-Gctadecanoylamino?henc!, bis( -methcxyphenyl)arnine, 2,6di-tert-buty!4-

dimethylam nomethylphenol, 2,4'-diaminodiphenylmethane, 4,4'diaminodiphenylmethane, N. N. N',N'-tetramethyl4,4'diaminodiphenylmethane, 1,2-bis[(2-methylphenyl)amino]ethane, 1,2bis(phenylamino)propane, (o-tolyl)biguanide, bis[4-(1', 3'-dimethylbutyl) phenyliamine, tert-

octylated N-phenyl-1-napUthylamine, a mixture of mono- and dialkylated tert-butyl/tert-

octyidiphenylamines, a mixture of mono- and dialkylated nonyidiphenylamines, a mixture of mono- and dialkylated dodecyidiphenylamines, a mixture of mono- and dialkylated isopro-

pyl/isohexyidiphenylamines, a mixture of mono- and dialkylated tertbutyidiphenylamines, 2,3-dihydro-3,3-dimethyl4H-1,4-benzothiazine, phenothiazine, a mixture of mono- and dialkylated tert-butyl/tertoctylphenothiazines, a mixture of mono- and dialkylated tert-octyl-

phenothiazines, N-ailylphenothiazine, N. N. N', N'-tetraphenyl-1,4diaminobut-2-ene, N. N-bis-

(2, 2,6,6-tetramethyl-piperid -yl-hexamethylenediamine, bis(2,2,6,6tetramethylpiperid4-yl)-

sebacate, 2,2,6,6-tetramethylpiperidin4-one, 2,2,6,6-tetramethylpiperidin4-ol.

2. UV absorbers ar d linht stabilisers 2.1. 2- y benzotriazoles, for example 2-(2'-hydroxy-5'-methylphenyl)benzc,-

triazole, 2-(3', 5'-di-terr-butyl-2'-hydroxyphenyl)benzotriazole, 2-(5'tert-butyl-2'-hydroxyphe

- 15 nyl)benzotriazolel 2-(2'-hydroxy-5'-(1,1, 3,3-tetramethylbutyl) phenyl)benzotriazole, 2-(3', 5'-di-

tert-butyl-2'-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-2'hydroxy-5'-methylphe-

nyl)-5-chlorobenzotriazole, 2-(3'-secbutyl-5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2-(2'-

hydroxy4'-oclyloxyphenyl)benzotriazole, 2-(3', 5'-di-tert-amyl-2'hydroxyphenyl)benzotriazole, 2-(31 5 -bis(ala-dimethylbenzyi)-2 hydroxyphenyl)benzotriazole' 2-(3'-tert-butyl-2'-hydroxy-5'-

(2-octyloxycarbonylethyl)phenyl)-5-chlorobenzOtriazole, 2-(3'-tert-butyl5'-[2-(2-ethylhexyl-

oxy)carbonylethyl]-2'-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3'-tertbutyl-2'-hydroxy-5'-(2-

methoxycarbonylethyl)phenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-2'hydroxy-5'-(2-meth-

oxycarbonylethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2octyloxycarbonyl-

ethyl)phenyl benzotriazole, 2-(3'-tert-butyl-5'- 2-(2-ethylhexyloxy) carbonylethyl]-2'-hydroxy-

phenyl)benzotriazole, 2-(3'-dodecyl-2'-hydroxy-5'-methylphenyl) benzotriazole, 2-(3'-tert-butyl-

2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)phenylbenzotriazole, 2,2'methyienebis[4-(1, l, 3, 3-

tetramethylbutyl)-6-benzotriazole-2-ylphenolJ; the transesterification product of 2-[3'-tert-bu-

tyl-5'-(2-methoxyCarbonylethyl)-2'-hydroxyphenyl]-2H-benzotriazole with polyethylene glycol 300; [R-CH2CH2 COO-CH2CH2:, where R = 3'-tert-butyl4'hydroxy-5'-2H-benzotri azol- -ylphenyl, 2-[2'-hydroxy-3'-(a,ordimethylbenzyl)-5'-(1,1, 3,3-tetramethylbutyl)phenyll-

benzotriazole; 2-[2'-hydroxy-3'-(1,1,3,3-tetramethylbutyl)-5'-(a, adimethylbenzyl)phenyl]ben-

zotriazole. 2.2. 2-HydroxYbenzonhenones, for example the 4-hydroxy, 4methoxy, 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 4enzoic acids, for example 4tert-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-

butyl4-hydroxybenzo-

ate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5 i-tertbutyl-4-hydroxyben-

zoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hyd roxybenzoate.

2.4. AcrYlates, for example ethyl a-cyano-0,0-diphenylacrylate, isooctyl a-cyano-5, diphe-

nylacrylate, methyl a-carbomethoxycinnamate, methyl a-cyano- methyl-pmethoxycinna-

mate, butyl a-cyano- methyl-p-methoxycinnamate, methyl cr-carbomethoxy-pmethoxycin-

namate and N-(,8-carbomethoxy- cyanovinyl)-2-methylindoline.

- 16 2.5. Nickel compounds, for example nickel complexes of 2,2'thiobis[4-(1,1,3,3-tetramethyl-

butyl)phenol]. such as the 1:1 or 1:2 complex, with or without additional ligands such as n-

butylamine, triethanoiamine or N-cyclohexyidiethanolamine, nickel dibutyidithiocarbamate, 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 2hydroxy-4-methyiphe-

nylundecylketoxime, nickel complexes of 1 -phenyl4-lauroyl-5hydroxypyrazole, with or with-

out additional ligands.

2.6. Stericaliv hindered amines, for example bis(2,2,6,6-tetramethyl4piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)succinate, bis(1, 2,2, 6, 6-pentamethyl4-piperidyl)sebacate, bis(1 -octyloxy-2,2,6, 6tetramethyl4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl4-piperi-

dyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of 1-(2-hydroxyethyl)-

2,2,6,6-tetramethyl4-hydroxypiperidine and succinic acid, linear or cyclic condensates of N,N'-bis(2,2,6,6-tetramethyl4-piperidyl) hexamethylenediamine and 4-tert-octylamino-2,6 i-

chloro-1, 3,5-triazine, tris(2, 2,6,6-tetramethyl4-piperidyl) nitrilotriacetate, tetrakis(2, 2,6,6-tetra-

methyl4-piperidyl)-1,2, 3,4-butanetetracarboxylate, 1,1 '-(1,2-ethanediyl) -bis(3,3, 5, 5-tetrame-

thy'pipcrazir,one), 4-benzoyl-2,2,6,6-tetrameth,'!piperidine, 4steary!oxy-2,2,6,6-teframethyl-

piperidine, bis(1,2,2,6,6-pentamethyipiperidyl)-2-n-butyl-2- 2-hydroxy-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 -octyl-

oxy-2,2,6,6-tetramethylpiperidyl)sebacate, bis(1-octylaxy-2,2,6,6tetramethylpiperidyl)succi-

nate, linear or cyclic condensates of N,N'-bis(2,2,6,6-tetramethyl4piperidyl)hexamethylene-

diamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate of 2chloro4,6-bis(4-n-

butylamino-2,2,6,6-tetramethylpiperidyl)-1, 3, 5-triazine and 1, 2-bis(3aminopropylamino)-

ethane, the condensate of 2-chloro4,6-di-(4-n-butylamino-1,2,2,6,6pentamethylpiperidyl)-

1, 3, 5-triazine and 1, 2-bis(3-aminopropylamino)ethane, 8-acetyl-3dodecyl-7,7, 9, 9-tetrame-

thyl-1,3,8-triazaspiro[4. 5]decane-2,4-dione, 3-dodecyl-1 -(2,2,6,6tetramethyl-4-piperidyi)pyr-

rolidine-2,5-dione, 3-dodecyl-1-( 1,2,2,6,6-pentamethyl4-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-tetramethyl4piperidyl)hexamethylenediamine and 4-cyclohexylamino-2,6-

dichloro-1,3,5-triazine, a condensate of 1,2-bis(3-aminopropylamino) ethane and 2,4,6-

trichloro-1,3,5-triazine as well as 4-butylamino-2,2,6,6tetramethylpiperidine (CAS Reg. No. 1136504-96-6]); a condensate of 1,6hexanediamine and 2,4,6-trichloro-1,3,5-triazine as well as N,Ndibutylamine 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-pentamethyl4

- 1 7 -

piperidyl)-n odecylsuccinimide, 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-1oxa-3,8-diaza-4-

oxospiro-[4,5]decane and epichlorohydrin, 1,1 -bis(1,2, 2,6,6-pentamethyl4-piperidyloxy-

cart onyl)-2-(4-methoxyphenyl)ethene, N. N'-bis-formyl-N, N'-bis(2, 2,6,6tetramethyl-4-piperi-

dyl)hexamethylenediamine, a diester of 4-methoxymethylenemalonic acid with 1,2,2,6,6-

pentamethyl4-hydroxypiperidine, poly[methylpropyl-3-oxy4-(2,2,6,6tetramethyl-4-piperi-

dyl)]siloxane, a reaction product of maleic acid anhydride-cc-olefin copolymer with 2,2,6,6-

tetramethyl4-aminopiperidine or 1,2,2, 6,6-pentamethyl4-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, 2ethoxy-5-tert-butyi-2'-ethoxanilide and its mixture with 2-ethexy-2'ethyl-5,4'-di-tert-butoxanilide, mixtures of o- and p-methoxydisubstituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides.

3. Metal deactivators, for example N,N'-diphenyloxamide, N-salicylal-N'salicyloyl hydrazine, N. I1'-bis(salicy'oyl)hydrazine, N. h "-bis(3,5-ditert-butyl - -hydrox\/pheny!propion\yl)h\ydrazine, 3-salicyloylamino-1,2, 4-triazole, bis(benzylidene)oxalyl dihydrazide, oxanilide, isophthaloyl dibydrazide, sebacoyl bisphenylhydrazide, N,N'-diacetyladipoyl dibydrazide, N,N'-bis(salicyl-

oyl)oxalyl dihydrazide, N. N'-bis(salicyloyl)thiopropionyl dihydrazide.

4. Phosphites and ohosphonites, for example triphenyl phosphite, diphenylalkyl phosphites, phenyidialkyl phosphites, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phos-

phite, distearylpentserythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tertbutylphenyl)penteerythritol diphosphite, bis(2,4-di-

cumylphenyl)pentaerythritol diphosphite, bis(2, 6-di-tert-butyl-4methylphenyl)pentaerythritol diphosphite, diisodecyloxypenteerythritol diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl)-

pentaerythritol diphosphite, bis(2,4,6-tris(tert-butylphenyl) pentaerythritol diphosphite, tristea-

ryl sorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl) 4,4'biphenylene diphosphonite, 6-

isooctyloxy-2,4,8, 1 0-tetra-tert-butyl-1 2H-dibenz[d,g]-1,3,2dioxaphosphocin, bis(2,4-di-tert-

butyl-6-methylphenyl)methyl phosphite, bis(2,4 di-tert-butyl-6methylphenyl)ethyl phosphite, 6-fluoro-2,4, 8,1 0-tetra-tert-butyl-1 2methyl-dibenzld, 9]-1,3,2 ioxaphosphocin, 2,2',2"-nitrilo-

[triethyHris(3,3', 5, 5'-tetra-tert-butyl-1, 1'-biphenyl-2,2'-diyi) phosphite], 2-ethylhexyl(3, 3', 5,5'-te

- 18 tra-tert-butyl-1,1'-biphenyi-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-tertbutylphenyl) phosphite (Irgafos 168, Ciba- Geigy), tris(nonylphenyl) phosphite, (CH3 3C C(CH3 3 (CH3 3C C(CH3), 1

(A) H3C NIP-F t (CH,)3C P-O-CH2CHz N () C (CH3)3 C(CH3)3

*(CH3)3C 3

(CH3)3C C(CH3)3

I P-O-CH2CH(C4Hg)CH2CH3 (C) (CH3)3C-

C(CH3)3

(CH3)3C 'oXo 3C(CH3)3 (D) C(CH3)3 (CH3)3C

C(CH3 3 (CH3)3C

H3C -O-Px X UP o CH3 (E) C(CH3)3 (CH3)3C

- 19 r I H3 -

H3C-C-CH3

() 17C, 0 P X,P O C,, H3' H. C O P-OCHZCH3 (G)

5. Hydroxviamines, for example N,N-dibenzyihydroxylamine, N,Ndiethylhydroxylamine, N,N-

dioctylhydroxylamine, N,N-dilaurylhydroxylamine, N,Nditetradecylhydroxylamine, N,N-

dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine, N-hexadecyi-Noctadecylhydrox-

ylamine, N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylKydroxylamine derived from hydrogenated tallow amine.

6. Nitrones, for example N-benzyl-alpha-phenyinitrone, N-ethyl-alphamethyinitrone, N-octyl-

alpha-heptyinitrone, N-lauryl-alpha-undecyinitrone, N-tetradecyl-alphatridecyinitrone, N-

hexedecyl-a!pha-?entadecyinitrone, N-octadecyl-alpha-heptadecyinitrone, Nhexedecyl-al-

pha-heptadecyinitrone, N-ocatadecyl-alpha-pentadecyinitrone, N-heptadecylalpha-hepta-

decyinitrone, N-octadecyi-a!pha-hexadecyinitrone, nitrone derived from N, N-dialkylhydroxyl-

amine derived from hydrogenated tallow amine.

7. Thiosvneraists, for example dilauryl thiodipropionate or distearyl thiodipropionate 8. PeroxJde scavenners, for example esters of thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2-mercapto-

benzimidazole, zinc dibutyidithiocarbamate, dioctadecyl disuffide, pentaerythritol tetrakis( dodecylmercapto)propionate. 9. Polyamide stabilisers, for example copper salts in combination with iodides and/or phos-

phonus 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,

- 20 zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate, antimony pyrocatecholate or zinc pyrocatecholate.

11. Nucleating agents, for example inorganic substances, such as talcum, metal Oxides, such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of, preferably, alkaline earth metals; organic compounds, such as mono- or polycarboxylic acids and the salts thereof, e. g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymeric compounds, such as ionic copolymers (ionomers). 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(benzylidene)sorbitol.

1 2. 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 plasticizers, lubricants, emulsifiers, pigments, rheology additives, catalysts, flo N-control agents, optical brighteners, flamepronfing 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-A4316611;

DE-A4316622; DE-A4316876; EP-A-0589839 or EP-A-05911 02 or 3-[4-(2acetoxyethoxy)-

phenyl]-5,7-di-tert-butyl-benzofuran-2-one, 5,7-di-tert-butyl-3-l4-(2stearoyloxyethoxy)phe-

nyl]benzofuran-2-one, 3,3'-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy] phenyl)benzofuran-2-

onel, 5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one, 3-(4-acetoxy3,5-dimethylphe-

nyl)-5,7-di-tert-butyl-benzofuran-2-one, 3-(3,5-dimethyl4pivaloyloxyphenyl)-5,7-di-tert-butyl-

benzofuran-2-one, 3-(3,4 imethylphenyl)-5,7-d,-tert-butyl-benzofuran-2one, 3-(2,3-di-

methylphenyl)-5,7-di-tert-butyl-benzofuran-2-one. Where appropriate, the conventional additives are judiciously employed in amounts up to 1 0 % by weight, e.g. 0.1-10 % by weight, especially 0.2-5 % by weight, based on the material to be stabilized.

- 21 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 GE3-A-2300192, from page 2, line 2, until page 4, line 22. Thin-walled films of the invention, especially transparent polyolefin agricultural films, act as a selective UV filter enhancing plant growth and crop while suppressing the undesired activity of microorganisms. Light of the medium or far UV region (e.g. 200-360 nm, especially 300-

340 nm) required by these microorganisms is effectively blocked. The same time, the activity of useful insects such as bees is not affected.

Preferably, the transparent polyolefin film of the invention also contains a sterically hindered amine as further stabilizer in order to obtain optimum light stability of the substrate. The sterically hindered amine is usually contained in an amount of 0.01 - 6 % by weight the polyolefin, the v eight,atio s'erical'y hindered amine: hydroxypher!y! triazine UV absorber preferably ranging from 2: 1 to 20:1.

Examples for sterically hindered amines preferably contained in the polyolefin films of the invention are given in the above list (item 2.6).

More preferred statically hindered amines include the following compounds: bis(2,2, 6,6-tetramethyl4-piperidyl)sebacate; bis(1,2,2,6,6pentamethyl4-pipendyl)sebacate; the condensate of 1-(2-hydroxyethyl)-2,2, 6,6-tetramethyl4-hydroxypiperidine and succinic acid (GAS-No. 65447-77-0); N,N', N", N"'-Tetrakis(4,6-bis(butyl-(N-methyl-2,2,6,6tetramethylpiperidin4-yl)amino)triazin-2 yl)-4,7-diazadecane-1, 1 Odiamine (GAS-No. 10699043-6);

- 22 f N N-(CH2)6 N r' N (CH2)6 N -H H C$CH3

CH3H2CH3 n; H H H H

_ _ N-(CH2)6 N I+N N-(CH2)6 N- -H

N,N L:0 n N _ (Chimassorb$ 2020, CAS No. 192268-64-7), where n is mainly from the range 3-5; or mixtures of these compounds.

Best resuHs 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

- 23 H2 CH \/ / O-No< wherein R and R' independently are hydrogen or methy!, 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 alla in US patents Nos. 5204473, 5216156, Grin GB-A-2347928.

Examples for the most preferred hydroxylamine ethers are compounds of the formula (19-1) B H,C, <CH t 3C N C 3 (19-1)

H2 Cl H2 - CH3 n in which the index n ranges from 1 to 15, being especially from the range 3-9; R,2 is C2-C,2alkylene, C4-C,2aikenylene, Cs-C7cycloalkylene, C5-C7cycloalkylene-

di(C1-C4alkyiene), C,-C4alkylenedi(Cs-C7cycloalkylene), phenylenedi(C'C4alkyiene) or C4-C,2alkylene interrupted by t,4-piperazinediyi, -O- or > N-X1 with X' being C,-C,2acyl or (C -C, alkoxy)carbonyl or having one of the definitions of R,4 given below except hydrogen; or R12 is a group of the formula (lb') or (Ic');

- 24 CH2 CH-CH2 (lbl) f C=0 x2 o o X3 oXo 3 (C') with m being 2 or 3, X2 being C,-C,8alkyl, Cs-C,2cycloalkyl which is unsubst,tuted or substituted by 1, 2 or 3 C,-C4alkyl; phenyl which is unsubstituted or substituted by 1, 2 or 3 C,-C4alkyl or C,-C4alkoxy; C7-Cgphenylalkyl which is unsubstituted or substituted on the phenyl by 1, 2 or 3 C,-C4alkyi; and the radicals X3 being independently of one another C2-C alkylene; the radicals B are independently of one another Cl, -ORE, -N(R,4)(R,s) or a group of the formula (lild); H <CH3

-X <N-O-C-C-C H3 (I lid) H3C CH3

R,3, R,4 and R,5, which are identical or different, are hydrogen, C,-C, aalkyl, Cs-C,2cycloaikyl which is unsubstituted or substituted by 1, 2 or 3 C,-C4alkyl; C3-C,aalkenyl, phenyl which is unsubst tuted or substituted by 1, 2 or 3 C,-C4alkyl or C,-C4alkoxy; CrCgphenylalkyl which is unsubstituted or substi uted on the phenyl by 1, 2 or 3 C,-C4alkyl; tetrabydrofurfuryl or C2-C4alkyl which is substituted in the 2, 3 or 4 position by -Otl, C,-Caalkoxy, di(C,-C4alkyl)amino or a group of the formula (le'); / Y N (lel) \J w th Y being -O-, -CH2-, -CH2CH2- or N-CH3, or -t i(R,4)(R,s) is additionally a group of the formula (le'); X is -Oor >N-R,6;

- 25 R, is hydrogen, C,-C,8alkyl, C3-C,8alkenyl, Cs-C,2cycioaikyl which is unsubstituted or substituted by 1, 2 or 3 C,-C4alkyl; C -Cgphenylalkyl which is unsubstituted or substituted on the phenyl by 1, 2 or 3 C,C4alkyl; tetrahydrofurfuryl, a group of the formula (elf), H/ <CH3

7<N-O-C-C-CH3 Allis H3C CH3

or C2-C4alkyi which is substituted in the 2, 3 or 4 position by -OH, C,Caalkoxy, di(C,-C4alkyl)amino or a group of the formula (le'); R., has one of the definitions given for R,6.

In these compounds, the end group bonded to the tnazine residue can be, for example, a group B or -N(R,,)-R,2-B, such as chlorine or a group - N (CH2)6 N H

H3C::: CH3 H3C CH3;

G., G.,

and the end group bonded to the diamino group can be, for example, hydrogen or a di-B-

substituted tnazinyl group, such as a group N or ' CI CH3 ICH3 NON

AN C-CH2-C-CH3 HN{ 3

CH3 CH3

It may He 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-C8alkyl)2 and -NY'(C,-C8alkyl) wherein Y' is hydrogen or a group of the formula

- 26 H3C CH3

Y N-G11 1 7< H3C CH3

In the above shown oligomeric and polymeric compounds, examples of alkyl are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tertbutyl, 2 ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1,3dimethylbutyl, n-hexyl, 1-methylhexyl, n heptyl, isoheptyl, 1,1,3,3tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethyl hexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, eicosyl and docosyl; examples of cycioalkyl 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-dimethyltrimethyiene, hexamethylene, trimethylhexamethylene, octamethylene and decamethylene. Another example for a sterically hindered amine ether advantageously to be used within present polymer films is the compound of the formula Hl7C8-O-N O 11 (CH2) 8 11 O N-O-C8H'7 3 CH3 H3C

An example for a highly effective compound of formula (19-1) is the compound of the formula (1 9-2)

- 27 CqHg C4 N - N) N (Con Nit,1lN-(CH2\ N:N - N | N.;,N 1 Ng AN No AN l l H3C; CH3 TIC; Coo H3C CH3 ARC CH3HgC4 C4Hg ARC N ARC N CH3 H3C N CH3 ARC N CH3 C -C4 H9C4- H9C4-

CH3 CH3 ARC CH3 CH3 Cal C4Hg ARC N CH3

o CH3 wherein n' is approximately 3 (example 2 of GB-A-2334717, CAS # 247243 2-5, which is the NO-n-propyl derivative of the block oligomer Chimassorb 2020 CAS # 192268 64-7, Ciba Specialty Chemicals Clomp.).

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 treatable 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 extnuder or in a kneader. It is immaterial whether processing takes place in

- 28 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 fomm 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.

- 29 Preparation of HYdroxYphenvl Triazine UV Absorbers Ox\-ECHO CH3 Synthesis of 2,4-bis-biphenyl-6-[2-hydroxy4-(2-ethyl-hexyloxy)phenyl]-1,3, 5-triazine A yellow suspension of 2,4-bis-biphenyl-6-[2,4-dihydroxyphenyl] -1,3,5-triazine (11.2 9, 0.0227 mole) in dimethylformamide (30 ml) is heated under nitrogen at 70 until a clear brow,, solution is fondled. Anhydrous potassium carbonate (3.77 9, 0.0227 mole) is added and the brown suspension heated at 80 C for 30 minutes. 2-Ethylhexylbromide (5. 709, 0.0295 mole) is added dropwise over 30 minutes, after which the suspension is heated at 1 10 C for a further 3 hours. Precipitated salts are filtered off and the filtrate cooled to O C. Methanol (20 ml) is added and the precipitated product removed by filtration. After drying under vacuum, 2,4-bis-biphenyl-6-[2-hydroxy4-(2-ethylhexyloxy-phenyl]-1, 3, 5-triazine (12.8 9) is obtained with mp 70 .

h) When in the above preparation the educt 2,4-bis-biphenyl-6-12,4dihydroxyphenyl]-1,3,5-

triazine is replaced by the equivalent amount of 2,4-bis(4-methoxyphenyl)6-[2,4-

dihydroxyphenyl]-1,3,5-triazine, compound (h) of the formula 0-'AH CH3 OH N^N CH3{>J: O-CH3

- 30 is obtained with mp 105 C, The compounds shown in the following table are obtained when the above reaction (a) is repeated using corresponding amounts of other alkylbromides or alkylene-dibromides.

O,R1 OH IN Example R-1 Mp: C A) CH(CH3)-(CH2)9-CH3 OIL

C) n-C6H,3 178 dJ n aHl7 160 eJ n-C12H25 146 O- X 0

OH HOW

N N N N

3, N art Nit, | Example - X _ _ L -(CH2)lo- > 250 g) -(CHz)12 > 250

- 31 Corresponding compounds wherein X is C,3-C24alkylene; (C,-C, 8alkylene)-CO-O-D-O-CO-

(C'-C,8alkyiene), CO-(C,3-C24alkylene)-CO; C3-C24alkylene interrupted by oxygen, especially (C,-C3alkylene)-O-(C,-C3alkylene) are obtained using the appropriate alkylene-dibromides or alkylene-dibromides interrupted by -CO-O-D-O-CO- or oxygen, or dichlorides or dibromides of aliphatic C,5C26diacids.

I) Preparation of the compound of the formula: a =. <.1 -Or No; N it =.' N j N' 11,,,

' In a manner analogous to Example 16 of WO 96/28431, a white powder is obtained from the starting material: 4-(4,6-bis-biphenyl-4-yl-(1,3,5) triazin-2-yl)-benzene-1,3-diol and allyl bromide. H NMR (300 MHz, CDC13): = 13.3 (s, 1 H), 8.7 - 6.2 (aromatic signals, 21 H), 6.1 (m, 1 H), 5.3 (m, 2H),4.3(m,2H).

m) Preparation of the oligomer of the formula: N'

- 32 30 9 (0.056 mol) of the compound from Example (I) and 30.2 9 (0.320 mol) of norbom-

ylene and 42.3 9 (0.320 mol) of dicyclopentadiene and 0.49 9 (0.6 mmol) of the catalyst bis(tricyclopentylphosphine)dichloro(3-methyi2butenylidene)ruthenium (APT Cat ASMC 716) are added to 300 ml of toinene. The mixture is left to react for 24 hours at 30 . The solution is then concentrated under vacuum and a pale brown solid is obtained.

Visual melting range: 168- 180 C; Mn: 2216; Mw: 4663; PDI: 2.10; Elemental analysis: %C %H %N

theory 87.5 8.4 2.3 found 85.8 8.6 2.1 n) Preparation of the hydrogenated oligomer of the formula: N To a solution of 92 9 (0.050 mol) of the oligomer of Example (m) in 300 ml of xylene,1.0 9 of platinum on carbon (10 % w/w) is added. The mixture is poured into an autoclave and hydrogenated for 24 hours at 65 bar (PH2) and 105 C. The hydrogenated mixture is purified from the catalyst by adding 10 9 of TonsyllO 414 FF at 80-90 C and left under vigorous stirring for 2 hours. After filtering off over a pad of 10 9 of Tonsil the filtrated yel-

low solution is concentrated under vacuum and a pale yellow solid is obtained.

Visual melting range: 55-68 C; Mn: 2197; Mw: 4347; PDI: 1.98; (290 nm, toluene): 34574; Elemental analysis: %C % H % N

- o -

Theory 85.8 10.2 2.2 Found 84.7 10.2 2.0 Application Exams In some of the application examples, the following sterically hindered amides (HALS) are employed: compound forrnula/chernical name C, C4

N - N) N (Cad-N AN N (Cad-N AN - N | ICY at En En En En of C4 I C N C C N C | C N C N l N-C 9 -N C,-N

19-2) c c H3C CF'3 CH3 C4 C H-2 bis(2,2,6,6-tetramethyl4-piperidyl) sebacate) H-3 condensate of 1 -(2-hydroxyethyl)-2,2,6,6-tetramethyi4 hydroxypiperidine and succinic acid (GAS-No. 65447-77-0) H _ _ H I N (CH2) 6 N f- N-(CH2)6 N -H H-$5C $CH3

CH3H2CH3

H-5 N, N', N", N"'-Tetrakis(4, 6bis(butyl-(N-methyl-2, 2, 6,6 tetramethylpiperidin-4-yl)amino)triazin-2-yl), 7-diazadecane- 1,1 G-

diamine (GAS-No. 106990 3-6!

- 34 Example 1: Combination hydroxvphenvl triazine compound (a) with compound (1q-2) In order to evaluate the UV-absorber characteristics of hydroxyphenyl triazine compound (a), when mixed with a commercial thermoplastic material, thin low density polyethylene (LDPE) films are prepared, containing, as a typical formulation, 0. 15% by weight of the above compound (a) and 0.70% of the sterically hindered amine ether (19-2) , used as light stabilizer of the polymeric system in highly demanding environments for agriculture applications. To do so, properly weighted amounts of the compounds are mixed with ground LDPE (Polimeri Europa, supplied by Enichem, Milano, Italy), characterized by a density of 0.921 gicm3 and a melt flow index (190 C/2.16 kg) of 0.6 in a turbo mixer. The mixture is extruded at a maximum temperature of 200 C in a OMC twin-screw extruder. The granules so obtained are blown in a lab scale Format blowextruder at a maximum temperature of 210 C to give a film of 150 Am thickness.

UV-Vis spectrum of the film as-obtained is recorded in the range 200-800 rim by means of a Perkin-cimer lambdas 20 spectrophotometer, equipped with a RSA-PE-20 Labsphere integrating sphere. At 0.15% loading, compound (a) imparts to the film a strong UV absorption feature, with a transmittance value less than 10% between 290 and 360 nm and less than 1% between 300 and 340 nm. The photos/ability of compound (a) is demonstrated by exposing the film sample to UV light in an Atlas Ci 65 Xenon Arc Weather-O-meter (VVOM, 63 C black panel temperature, continues dry cycle, according to ASTM G 26-96).

After 1500 hours of WOM exposure the minimum transmittance displayed by the film is still around 1% at 320 nm.

Compound (a) is fully compatible in LDPE film, no blooming is observed after storage of the film for 6000 hours at room temperature. Same behavior is observed keeping the film for the same amount of time in oven at 60 C. After the same time of exposure in oven, no significant change in the UV-Vis absorption spectrum is observed, meaning there is no loss of additive, because of the high temperature.

WOM exposure of the formulation reported in this example is continuing, in order to evaluate the light stability performance of the polymer containing compound (a). Samples are also being exposed to natural weathering and are subdued to treatments with pesticides, in order to evaluate the resistance to chemicals that can be employed in agriculture.

Example 2: Hydrox y henyl triazine compound (c) as a UV Filter in a Polvethvlene Aqrofilm

- 35 In order to prepare thin LOPE films and to evaluate the spectral features imparted by the additive and its persistency, compound (c) is mixed with LOPE 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 200 C 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 15O1lm thick. UV-Vis spectra are recorded in the range 200-800 rim by means of a Perkin-Elmer Lambda 20 spectrophotometer, equipped with a RSA-PE-20 Labsphere integrating sphere.

Results: 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.

In order to test the photos/ability of the additive upon exposure to light, a portion of the film is exposed in an Atlas Weather-o-Meter (VVOM) , model Ci65A (as per ASTM G26-96, irradiance 0.35 W/m2, black panel temperature 63+3 C). After 1000 hours of exposure the film still displays a transmittance below 40% between 280 and 360 nm and below 25% between 295 and 345 nm.

Example 3

A film containing 0.15% by weight of compound (d) 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.

Another portion of the film is also exposed in a forced circulating air oven at 60 C, in order to evaluate the thermal persistency of the additive in the film. After 1000 hours of exposure the film still retains the initial spectral features.

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 280-36C nm. In particular,

- 36 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 C. 5 / by v/eight 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. Example 10: Absorption band and persistency in LDPE of compound (m) Thin low density polyethylene (LDPE) films are prepared as described in example 2 but without addition of HALS. They are 150pm thick and contain 0.5% of the compound (m). W Vis spectra are recorded as described in example 2. The film displays a strong absorption in the range 280-360 nm. Transmittance values below 3% are detected in the range 290 350 nm.

The persistency of the polymer in LDPE films is determined after exposure of the films at 60 C in a forced circulating air oven and evaluated as described in example 3. No decrease of the absorbance value at the maximum is observed after 3000 hours at 6Q C.

Claims (12)

- 37 WHAT IS CT-AIMED IS:

1. Process for suppressing microbial growth in a protected environment, which process comprises covering the environment with the transparent polyolefin film having a thickness between 1 and 500 Am and containing 0. 005 - 0.30 % by weight, based on the polyolefin, of a hydroxyphenyl triazine UV absorber.

2. Process of claim 1, wherein the protected environment is a plant cultivation.

3. Process according to claim 1, wherein the transparent polyolefin film contains as further stabilizer a sterically hindered amine in an amount of 0.01 - 6 % by weight the polyolefin.

4. Process according to claim 3, wherein the weight ratio sterically hindered amine: hydroxyphenyi triazine UV absorber ranges from 2: 1 to 20:1.

5. Process according to claim 3, wherein the sterically hindered amine belongs to the class of hydroxylam ne ethers.

6. Process according to claim 1, wherein the hydroxyphenyl triazine UV absorber conforms to the formula I R R6 OH NAN (I)

R 3 R< R 4

wherein R. is H or OR7, R2 and R3 independently are H. C,-C8alkyl, OR B, ORs;

- 38 R4 and R5 independently are H. C1-C8alkyl, OR10; R6 is H. C1-C, 8alkyl, C5-C12cycloalkyll C7-C,2phenylalkyl, C7-C12alkylphenyl, C3-C, 2alkenyl, halogen, OH, ORg; R8 is H; halogen; C,-C,2alkoxy; C'-C,2alkyl; C3-C24alkyl interrupted by oxygen and/or substituted by OH; or is NH-COR14 or NH-COO-R12: R7, Rg and R,o independently are H; C,-C24alkyl; C3-C, 2alkenyl; C3-C24alkyl interrupted by oxygen and/or substituted by OH; or is Cs-c12cycloalkyl' C7-C,2phenylalkyl, C7 C,2alkylphenyl; CH2CH(OH)CH2OR, '; C,-C,2alkyl substituted by COORS CONR 3R,4, OCOR,5, OH or halogen; or R7 is a polymeric hydrocarbon residue of 10 to 10G0 carbon atoms; and R7 also embraces a residue of formula 11 X O N N (11)

R 3/ R 2

wherein X is C2-C24alkylene; -CH2CH(OH)CH2-; -CH2CH(OH)CH2O-D-OCH2CH(OH) CH2; (C'-C'aalkylene)-CO-O-D-O-CO-(C, -C, 8alkylene); CO; CO-(C2C24alkylene)-CO; C3-Cz4al,kylene interrupted by oxygen; D is C2-C, 2alkylene; C4-Cs0alkylene interrupted by O; phenylene; biphenylene or phenylene-E-phenylene; E is O. S. SO2; CH2; CO or-C(CH3)2-; R., is H. C,C,2alkyl; phenyl; phenyl substituted by 1-3 C -C4alkyl; Cs-C,2cycloalkyl; C -

C,2phenylalkyl; C3-C, 2alkenyl; R'2 is H; C,-C24alkyl; C3-C,2alkenyl; C3C36alkyl,nterrupted by oxygen andlor subs'ituted by OH; or is CsC'2cycloalkyi, C7-C 2phenylalkyl, C7-C12alkylphenyl; phenyl; R,3 and R,4 independently are H. C,-C,aalkyl; phenyl; phenyl substituted by 1-3 C -C. alkyl and/or C,-C4alkcxy; C5-C,2cycioalkyl; C3-C,2alkenyl;

- 39 R's is C,-C,2alkyl; phenyl; phenyl substituted by 1-3 C,-C4alkyl and/or C,-C4alkoxy; Cs-

C,2cycloalkyl; C3-C, 2a lkenyl; C, -C,2a ikoxy, or is NR, 3R,4.

7. Process according to claim 6, where in formula I R2 and R3 independently are H. methyl, R'3, ORg; R4 and R5 independently are H or methyl, especially H; R6is H; Ret is H; C,-C alkoxy; C,-C8alkyl; R7, Rg independently are H; C,-C,8alkyl; C3-C,2alkenyl; C3-C24alkyl interrupted by oxygen and/or substituted by OH; or is C5-C,2cycloalkyl, C7-C, 2phenylalkyi, Crc'2alkylphenyl; C, C,2alkyl substituted by COOR,2, OCOR,5, OH; or R7 is a polymeric hydrocarbon residue of 20 to 500 carbon atoms; and R7 also embraces a residue of formula 11, wherein X is C2-C,8alkylene, H2 - H(^H)CH2-; -^H2CH(OH)C H2O-)-OCH2CHtOH)GH2; (C,-C4alkylene)-CO-O-DO-CO-(C,-C4alkylene); CO; CO-(C2-C,aalkylene)-CO; C3-C, alkylene intern pted by oxygen; D is C2-C,2alkylene; R'2 is H; C,-C24alkyl; C3-C,2alkenyl; C3-C24alkyl interrupted by oxygen and/or substituted by OH; or is C5-C, 2cycloalkyl, C7-C,2phenylaikyl, C7-C,2aikylphenyl; phenyl; R,5 is C,-C, 2alkyl; C5-C,2cycloalkyl; C3-C,2alkenyl.

8. Process according to claim 1, wherein the polyolefin is polyethylene or polypropylene.

9. Process according to any of claims 1 to 9, wherein the film additionally contains a further component selected from the group consisting of processing stabilizers, fillers, clarifiers, modifiers, acid scavengers, flame retardants and, especially, further light stabilizers.

1 O. Use of a transparent polyolefin film having a thickness between 1 and 500,um, which is stabilized against the effects of light, oxygen, heat and/or agressive chemicals by addition of 0.005 - 0.30 % by weight, based on the polyolefin, of a hydroxyphenyl triazine W absorber, for suppressing microbial grovhh in a protected cultivation.

- 40

11. A method for selectively screening solar andlor artificial light radiation to crops contained inside a green house which comprises covering said green house with a polyolefin film having a thickness between 1 and 500 rum and containing 0.005 - 0.30 % by weight, based on the polyolefin, of a hydroxyphenyl triazine UV absorber.

12. Process according to claim 3, wherein the sterically hindered amine is selected from bis(2,2,6,6-tetramethyl4-piperidyl)sebacate, bis(2,2,6,6tetramethyl4-piperidyl)succinate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl4-piperidyl) n-butyi-3,5-di-tertbutyl4-hydroxybenzylmalonate, the condensate of 1-(2-hydroxyethyl)-2,2,6, 6-tetramethyl4-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-dichloro-1,3, 5-triazine, tris(2,2,6,6-tetramethyl4-piperidyl)nitrilotriacetate, tetrakis(2,2,6,6tetramethyl4-piperidyl)-1,2,3,4-butanetetraca rboxylate, 1,1'-(1,2ethanediyl)-bis(3,3,5, 5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, bis(1, 2,2,6,6-pentamethyipiperidyl)-2-n-butyl-2-(2-hydroxy-3, 5-di-tertbutylbenzyl)malonate, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspirol4.5] decane-2,4-dione, linear or cyclic condensates of N,N'-bis(2,2,6,6tetramethyl4-piperidyl)hexamethylenedi amine and 4-morpholino-2,6dichloro-1,3,5-triazine, the condensate of 2-chloro4,6-bis(4-n-butylamino2,2,6,6-tetramethylpiperidyi)-1,3,5-triazine and 1,2-bis(3aminopropylamino)ethane, the condensate of 2-chloro4,6-di-(4-n-butylamino1,2,2,6,6-pentamethylpiperidyl)-1, 3, 5 triazine and 1,2-bis(3aminopropylamino)ethane, 8-acetyl-3-dodecyl-7,7,9, 9-tetramethyl-1,3,8triazaspiro[4. 5]decane-2,4-dione, 3-dodecyl-1-(2,2, 6,6-tetramethyl4piperidyl)pyrrolidine-2, 5-dione, 3-dodecyl-1-(1,2,2,6,6-pentamethyl-4piperidyl)pyrrolidine-2, 5-dione, a mixture of 4-hexadecyloxy- and 4stearyloxy-2,2,6,6-tetramethylpiperidine, a condensate of N,N'-bis(2,2,6, 6-tetramethyl4-piperidyl)hexamethylenediamine and 4 cyclohexylamino-2,6dichloro-1, 3,5-triazine,

- 41 a condensate of 1,2-bis(3-aminopropylamino)ethane and 2,4,6trichloro-1,3,5-triazine as well as 4-butylamino-2,2,6, 6tetramethylpiperidine; a condensate of 1,6-hexanediamine and 2,4,6trichloro-1,3,5-triazine as well as N,N dibutylamine and 4-butylamino-2,2, 6,6-tetramethylpiperidine; N-(2,2, 6, 6-tetramethyl4-piperidyl)-ndodecylsuccinimide, N-( 1,2,2,6,6-pentamethyl=-piperidyl)-ndodecylsuccinimide, 2-undecyl-7,7,9, 9-tetramethyi-1 -oxa-3,8-diaza4-oxospiro[4,5]decane, a reaction product of 7,7,9,9-tetramethyl-2cycloundecyl-1-oxa-3,8-diaza4-oxospiro [4,53decane and epichlorobydrin, 1, 1-bis(1,2,2,6,6-pentamethyi4-piperidyloxycarbonyl)-2-(4-methoxyphenyl) ethene, N. N'-bis-forrnyl-N, N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexa methylenediamine, a diester of 4-methoxymethylenemalonic acid with 1,2,2, 6,6-pentamethyl -

hydroxypiperidine, poly[methylpropyl-3-oxy4-(2,2,6,6-tetramethyl-4piperidyi)3siloxa ne, a reaction product of maleic acid anhydride-aolefin copolymer with 2,2,6,6-tetramethyl4 aminopiperidine or 1,2,2,6,6pentamethyl 4-aminopiperidine; N. N', N", N"'-Tetrakis(4,6-bis(butyl-(Nmethyl-2,2,6,6-tetramethylpiperidin4-yl)amino)triazin-2 yl)4, 7diazadecane- 1,1 O-diamine; H N H

N-(CHAT N - - IN-(CHAT N--H

H -. NAN

N (43 +3 n

- 42 _ H:_ N-(CH2)6 N 'AN r N-(CH)-N--H l C i,-; 7,11' where n is mainly from the range 3-5; sterically hindered hydroxylamine ethers, and mixtures of these compounds.