US20020083641A1 - Transparent polymer articles of low thickness - Google Patents

Transparent polymer articles of low thickness Download PDF

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Publication number
US20020083641A1
US20020083641A1 US09/912,139 US91213901A US2002083641A1 US 20020083641 A1 US20020083641 A1 US 20020083641A1 US 91213901 A US91213901 A US 91213901A US 2002083641 A1 US2002083641 A1 US 2002083641A1
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Prior art keywords
alkyl
alkylene
tert
butyl
polyolefin
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US09/912,139
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David Leppard
Francois Gugumus
Michela Bonora
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BASF Performance Products LLC
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Ciba Specialty Chemicals Corp
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Assigned to CIBA SPECIALTY CHEMICALS CORP. reassignment CIBA SPECIALTY CHEMICALS CORP. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BONORA, MICHELA, GUGUMUS, FRANCOIS, LEPPARD, DAVID GEORGE
Publication of US20020083641A1 publication Critical patent/US20020083641A1/en
Priority to US10/430,128 priority Critical patent/US7166653B2/en
Priority to US10/894,773 priority patent/US20050059758A1/en
Priority to US11/359,228 priority patent/US7265171B2/en
Priority to US11/827,210 priority patent/US20070259165A1/en
Priority to US12/283,464 priority patent/US20090042006A1/en
Priority to US12/511,380 priority patent/US20090291289A1/en
Priority to US12/748,488 priority patent/US20100178484A1/en
Abandoned legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
    • C07D251/24—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to three ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/298—Physical dimension

Definitions

  • the invention relates to a novel polymer article of low thickness and good transparency having enhanced stability against the effects of light, oxygen, heat and agressive chemicals, which is also effective as a selective UV filter for agricultural applications, and to some novel stabilizers suitable for this application.
  • 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 transparent polyolefin, polyester or polyamide article stabilized by addition of 0.005-0.30% by weight the polymer substrate of a hydroxyphenyl triazine UV absorber, characterized in that the article has a thickness between 1 and 500 ⁇ m.
  • Preferred articles contain as a hydroxyphenyl triazine UV absorber a compound of the formula I
  • R 1 is H or OR 7 ;
  • R 2 and R 3 independently are H, C 1 -C 8 alkyl
  • R 4 and R 5 independently are H, C 1 -C 8 alkyl, OR 10 ;
  • R 6 is H, C 1 -C 8 alkyl, C 5 -C 12 cycloalkyl, C 7 -C 12 phenylalkyl, C 7 -C 12 alkylphenyl, C 3 -C 12 alkenyl, halogen, OH, OR 9 ;
  • R 8 is H; halogen; C 1 -C 12 alkoxy; C 1 -C 12 alkyl; C 3 -C 24 alkyl interrupted by oxygen and/or substituted by OH; or is NH—CO—R 14 or NH—COO—R 12 ;
  • R 7 , R 9 and R 10 independently are H; C 1 -C 24 alkyl; C 3 -C 12 alkenyl; C 3 -C 24 alkyl interrupted by oxygen and/or substituted by OH; or is C 5 -C 12 cycloalkyl, C 7 -C 12 phenylalkyl, C 7 -C 12 alkylphenyl; CH 2 CH(OH)CH 2 OR 11 ; C 1 -C 12 alkyl substituted by COOR 12 , CONR 13 R 14 , OCOR 15 , OH or halogen; or R 7 is a polymeric hydrocarbon residue of 10 to 1000 carbon atoms, preferably 20 to 500 carbon atoms;
  • R 7 also embraces a residue of formula II
  • X is C 2 -C 24 alkylene; —CH 2 CH(OH)CH 2 —; —CH 2 CH(OH)CH 2 O—D—OCH 2 CH(OH)CH 2 ;
  • D is C 2 -C 12 alkylene; C 4 -C 50 alkylene interrupted by O; phenylene; biphenylene or phenylene-E-phenylene;
  • E is O, S, SO 2 ; CH 2 ; CO or —C(CH 3 ) 2 —;
  • R 11 is H, C 1 -C 12 alkyl; phenyl; phenyl substituted by 1-3 C 1 -C 4 alkyl; C 5 -C 12 cycloalkyl; C 7 -C 12 phenylalkyl; C 3 -C 12 alkenyl;
  • R 12 is H; C 1 -C 24 alkyl; C 3 -C 12 alkenyl; C 3 -C 36 alkyl interrupted by oxygen and/or substituted by OH; or is C 5 -C 12 cycloalkyl, C 7 -C 12 phenylalkyl, C 7 -C 12 alkylphenyl; phenyl;
  • R 13 and R 14 independently are H, C 1 -C 18 alkyl; phenyl; phenyl substituted by 1-3 C 1 -C 4 alkyl and/or C 1 -C 4 alkoxy; C 5 -C 12 cycloalkyl; C 3 -C 12 alkenyl;
  • R 15 is C 1 -C 12 alkyl; phenyl; phenyl substituted by 1-3 C 1 -C 4 alkyl and/or C 1 -C 4 alkoxy; C 5 -C 12 cycloalkyl; C 3 -C 12 alkenyl; C 1 -C 12 alkoxy; or is NR 13 R 14 .
  • R 4 and R 5 independently are H or methyl
  • R 6 is H
  • R 8 is H; C 1 -C 8 alkoxy; C 1 -C 8 alkyl;
  • R 7 , R 9 independently are H; C 1 -C 18 alkyl; C 3 -C 12 alkenyl; C 3 -C 24 alkyl interrupted by oxygen and/or substituted by OH; or is C 5 -C 12 cycloalkyl, C 7 -C 12 phenylalkyl, C7-C 12 alkylphenyl; C 1 -C 12 alkyl substituted by COOR 12 , OCOR 15 , OH; or R 7 is a polymeric hydrocarbon residue of 20 to 500 carbon atoms;
  • R 7 also embraces a residue of formula II, wherein X is C 2 -C 18 alkylene; —CH 2 CH(OH)CH 2 —; —CH 2 CH(OH)CH 2 O—D—OCH 2 CH(OH)CH 2 ;
  • C 3 -C 18 alkylene interrupted by oxygen; D is C 2 -C 12 alkylene;
  • R 12 is H; C 1 -C 24 alkyl; C 3 -C 12 alkenyl; C 3 -C 24 alkyl interrupted by oxygen and/or substituted by OH; or is C 5 -C 12 cycloalkyl, C 7 -C 12 phenylalkyl, C 7 -C 12 alkylphenyl; phenyl;
  • R 15 is C 1 -C 12 alkyl; C 5 -C 12 cycloalkyl; C 3 -C 12 alkenyl;
  • R 1 is OR 7 ;
  • R 2 and R 3 independently are H, methyl
  • R 4 and R 5 and R 6 are H;
  • R 8 is H; C 1 -C 8 alkoxy; C 1 -C 4 alkyl;
  • R 7 , R 9 independently are C 4 -C 18 alkyl or C 5 -C 12 cycloalkyl
  • R 7 also embraces a residue of formula II, wherein X is C 4 -C 18 alkylene.
  • R 1 is OR 7 ;
  • R 2 and R 3 each are phenyl;
  • R 4 , R 5 and R 6 are hydrogen;
  • R 7 is C 4 -C 18 alkyl or C 5 -C 12 cycloalkyl or a residue of formula II, wherein X is C 4 -C 12 alkylene.
  • a halogen substitutent is —F, —Cl, —Br or —I, preferably —F, —Cl or —Br and, in particular, —Cl.
  • Alkylphenyl is alkyl-substituted phenyl;
  • C 7 -C 14 alkylphenyl embraces examples such as methylphenyl (tolyl), dimethylphenyl (xylyl), trimethylphenyl (mesityl), ethylphenyl, propylphenyl, butylphenyl, dibutylphenyl, pentylphenyl, hexylphenyl, heptylphenyl and octylphenyl′.
  • Phenylalkyl is phenyl-substituted alkyl;
  • C 7 -C 11 phenylalkyl embraces examples such as benzyl, ⁇ -methylbenzyl, ⁇ -ethylbenzyl, ⁇ , ⁇ -dimethylbenzyl, phenylethyl, phenylpropyl, phenylbutyl and phenylpentyl.
  • n-alkyl or alkyl-n is an unbranched alkyl radical.
  • Alkyl interrupted by O, NH, NR 13 , etc. can generally comprise one or more nonadjacent heteroatoms.
  • R 7 , R 9 and R 10 , especially R 7 , as alkyl substituted by COOR 12 is most preferably CH 2 —COOR 12 .
  • R 12 is most preferably C 1 -C 18 alkyl, or C 6 -C 12 cycloalkyl; cycloalkyl is most preferably cyclohexyl or cyclododecyl.
  • the radicals R 4 , R 5 , R 6 , R 8 , R 9 , R 11 i R 12 , R 13 , R 14 , R 15 as alkyl are branched or unbranched alkyl such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, t-butyl, 2-ethylbutyl, 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-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpenty
  • C 1 -C 4 alkyl is especially methyl, ethyl, isopropyl, n-butyl, 2-butyl, 2-methylpropyl or tert-butyl.
  • R 4 , R 5 , R 6 , R 8 , R 9 , R 11 , R 12 , R 13 , R 14 , R 15 as alkenyl include allyl, isopropenyl, 2-butenyl, 3-butenyl, isobutenyl, n-penta-2,4-dienyl, 3-methyl-but-2-enyl.
  • R4, R 5 and R 6 are most preferably hydrogen.
  • R 2 and R 3 are most preferably phenyl or OR 9 , especially phenyl.
  • R 9 is most preferably C 1 -C 4 alkyl.
  • X is C 13 -C 24 alkylene; (C 1 -C 18 alkylene)—CO—O—D—O—CO—(C 1 -C 18 alkylene); CO—(C 13 -C 24 alkylene)—CO; C 3 -C 24 alkylene interrupted by oxygen, especially (C 1 -C 3 alkylene)-O-(C 1 -C 3 alkylene).
  • 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.
  • some microorganisms such as fungi, e.g.
  • Botrytis cinerea Botryosporium, Cladosporium cucumerium, Endomyces geotrichium, Endomyces fibulinger, Sphaerotheca pannosa, Erysiphe polygoni , Gonatobotrys, Cylindrocapron, Fusarium, Thielaviopsis, Verticillium, and virus, e.g Cucumo-virus, Tombus-virus, etc. as well as some harmful insects, e.g. white flies, aphides, thrips or leafminers, proliferate under preferred specific UV-irradiation. These pests can be significantly reduced when UV light does not or to less extent reach the plants. [R.
  • 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 proliferation in a protected environment, especially a plant cultivation, while retaining the UV irradiation necessary for bee, bumblebee activity. Thus, present invention also pertains to the use of a transparent polyolefin film as described above for suppressing microbial proliferation in a protected cultivation.
  • Examples for polyolefines to be used for manufacturing the articles of present invention include the following polymers:
  • 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).
  • HDPE high density polyethylene
  • HDPE-HMW high density and high molecular weight polyethylene
  • HDPE-UHMW high density and ultrahigh molecular weight polyethylene
  • MDPE medium density polyethylene
  • LDPE low density polyethylene
  • LLDPE linear low density poly
  • Polyolefins i.e. the polymers of monoolefins exemplified in the preceding paragraph, preferably polyethylene and polypropylene, can be prepared by different, and especially by the following, methods:
  • a catalyst that normally contains one or more than one metal of groups IVb, Vb, VIb or VIII of the Periodic Table.
  • These metals usually have one or more than one ligand, typically oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls that may be either ⁇ - or ⁇ -coordinated.
  • These metal complexes may be in the free form or fixed on substrates, typically on activated magnesium chloride, titanium(III) chloride, alumina or silicon oxide.
  • These catalysts may be soluble or insoluble in the polymerisation medium.
  • the catalysts can be used by themselves in the polymerisation or further activators may be used, typically metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes, said metals being elements of groups Ia, IIa and/or lIIa 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).
  • 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/acryl
  • 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 terephthalate, polybutylene terephthalate, poly-1,4-dimethylolcyclohexane terephthalate, polyalkylene naphthalate (PAN) and polyhydroxybenzoates, as well as block copolyether esters derived from hydroxyl-terminated polyethers; and also polyesters modified with polycarbonates or MBS.
  • Preferred is polyethylene terephthalate (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 elastomer as modifier, for example poly-2,4,4,-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide; and also block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, e.g. with polyethylene glycol, polypropylene glycol or polytetramethylene glycol
  • polyolefines such as polyethylene, especially LDPE or LLDPE, or polypropylene.
  • 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.
  • the transparent polyolefin, polyester or polyamide article of the invention usually is a film, fiber, ribbon or stretched tape, especially an agricultural film. Its thickness preferably ranges between 1 and 300 ⁇ m, especially between 1 and 200 ⁇ m. Films, ribbons or tapes of the invention usually are not biaxially oriented.
  • the transparent polyolefin, polyester or polyamide article 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 retardants or other additives known in the art.
  • present articles usually do not effectively block light transmission through the present polymer articles, which is usually more than 20%, often more than 50%, and preferably more than 80% of white incoming light.
  • present articles 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. 0-5% by weight of the polymer, of fillers or crystalline inorganic components having lower opaquing effect than pigments (e.g. hydrotalcites).
  • additional components which may be contained in the polymer articles of the invention include the following:
  • Alkylated monophenols for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-di-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-( ⁇ -methylcyclohexyl)-4,6-dimethyl-phenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols which are linear or branched in the side chains, for example 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6-(1′-methylundec-1′-yl
  • Alkylthiomethylphenols for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctyl-thiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl-4-nonylphenol.
  • Hydroquinones and alkylated hydroquinones for example 2,6-di-tert-butyl-4-methoxy-phenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octade-cyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis(3,5-di-tert-butyl-4-hydroxyphenyl) adipate.
  • 2,6-di-tert-butyl-4-methoxy-phenol 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-dipheny
  • Tocopherols for example ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol and mixtures thereof (vitamin E).
  • Hydroxylated thiodiphenyl ethers for example 2,2′-thiobis(6-tert-butyl-4-methylphenol), 2,2′-thiobis(4-octylphenol), 4,4′-thiobis(6-tert-butyl-3-methylphenol), 4,4′-thiobis(6-tert-butyl-2-methylphenol), 4,4′-thiobis(3,6-di-sec-amylphenol), 4,4′-bis(2,6-dimethyl-4-hydroxyphenyl)-disulfide.
  • 2,2′-thiobis(6-tert-butyl-4-methylphenol 2,2′-thiobis(4-octylphenol), 4,4′-thiobis(6-tert-butyl-3-methylphenol), 4,4′-thiobis(6-tert-butyl-2-methylphenol), 4,4′-thiobis(3,6-di-sec-amylphenol), 4,4′-bis(2,6-
  • Alkylidenebisphenols for example 2,2′-methylenebis(6-tert-butyl-4-methylphenol), 2,2′-methylenebis(6-tert-butyl-4-ethylphenol), 2,2′-methylenebis[4-methyl-6-( ⁇ -methylcyclohexyl)-phenol], 2,2′-methylenebis(4-methyl-6-cyclohexylphenol), 2,2′-methylenebis(6-nonyl-4-methylphenol), 2,2′-methylenebis(4,6-di-tert-butylphenol), 2,2′-ethylidenebis(4,6-di-tert-butyl-phenol), 2,2′-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2′-methylenebis[6-( ⁇ -methylbenzyl)-4-nonylphenol], 2,2′-methylenebis[6-( ⁇ , ⁇ -dimethylbenzyl)
  • O—, N— and S-benzyl compounds for example 3,5,3′,5′-tetra-tert-butyl-4,4′-dihydroxydi-benzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine, bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate, bis(3,5-di-tert-butyl-4-hydroxy-benzyl) sulfide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.
  • 1.8. Hydroxybenzylated malonates for example dioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate, di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate, di-dodecylmercaptoethyl-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, bis[4-( 1 , 1 , 3 , 3 -tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.
  • Hydroxybenzylated malonates for example dioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate, di-octadecyl-2-(3-tert-
  • Aromatic hydroxybenzyl compounds for example 1,3,5-tris(3,5-di-tert-butyl-4-hydroxy-benzyl)-2,4,6-trimethylbenzene, 1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.
  • Triazine compounds for example 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxy-anilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine, 2,4,6-tris-(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, 2,4,
  • Benzylphosphonates for example dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.
  • esters of ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylol-propane, 4-hydroxymethyl-1-phospha-2,6,7-trio
  • esters of ⁇ -(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with mono- or poly-hydric alcohols e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis-(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethy-olpropane, 4-hydroxymethyl-1-phospha-2,6,7
  • esters of ⁇ -(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
  • esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
  • Aminic antioxidants for example N,N′-di-isopropyl-p-phenylenediamine, N,N′-di-sec-butyl-p-phenylenediamine, N,N′-bis(1,4-dimethylpentyl)-p-phenylenediamine, N,N′-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine, N,N′-bis(1-methylheptyl)-p-phenylenediamine, N,N′-dicyclohexyl-p-phenylenediamine, N,N′-diphenyl-p-phenylenediamine, N,N′-bis(2-naphthyl)-p-phenylenediamine, N-isopropyl-N′-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N′-phenyl-N-phenyl
  • 2-(2′-Hydroxyphenyl)benzotriazoles for example 2-(2′-hydroxy-5′-methylphenyl)benzo-triazole, 2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)benzotriazole, 2-(5′-tert-butyl-2′-hydroxyphenyl) benzotriazole, 2-(2′-hydroxy-5′-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole, 2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3′-tert-butyl-2′-hydroxy-5′-methylphenyl) -5-chlorobenzotriazole, 2-(3′-sec-butyl-5′-tert-butyl-2′-hydroxyphenyl)benzotriazole, 2-(2′-hydroxy-4′-oct
  • R 3′-tert-butyl-4′-hydroxy-5′-2H-benzotriazol-2-ylphenyl, 2-[2′-hydroxy-3′-( ⁇ , ⁇ -dimethylbenzyl)-5′-(1,1,3,3-tetramethylbutyl)phenyl]-benzotriazole; 2-[2′-hydroxy-3′-(1,1,3,3-tetramethylbutyl)-5′-( ⁇ , ⁇ -dimethylbenzyl)phenyl]benzotriazole.
  • esters of substituted and unsubstituted benzoic acids for example 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis(4-tert-butylbenzoyl) resorcinol, benzoyl resorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.
  • Nickel compounds for example nickel complexes of 2,2′-thiobis[4-(1,1,3,3-tetramethyl-butyl) phenol], such as the 1:1 or 1:2 complex, with or without additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, 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 2-hydroxy-4-methylphenylundecylketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additional ligands.
  • additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyidithiocarba
  • Sterically hindered amines for example bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)succinate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, linear or cyclic condensates of N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-tert-octyla
  • Oxamides for example 4,4′-dioctyloxyoxanilide, 2,2′-diethoxyoxanilide, 2,2′-dioctyloxy-5,5′-di-tert-butoxanilide, 2,2′-didodecyloxy-5,5′-di-tert-butoxanilide, 2-ethoxy-2′-ethyloxanlide, N,N′-bis(3-dimethylaminopropyl)oxamide, 2-ethoxy-5-tert-butyl-2′-ethoxanilide and its mixture with 2-ethoxy-2′-ethyl-5,4′-di-tert-butoxanilide, mixtures of o- and p-methoxy-disubstituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides.
  • Metal deactivators for example N,N′-diphenyloxamide, N-salicylal-N′-salicyloyl hydrazine, N,N′-bis(salicyloyl)hydrazine, N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine, 3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, N,N′-diacetyladipoyl dihydrazide, N,N′-bis(salicyl oyl)oxalyl dihydrazide, N,N′-bis(salicyloyl)thiopropionyl dihydrazide.
  • N,N′-diphenyloxamide
  • 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-di-cumylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythr
  • Hydroxylamines for example N,N-dibenzylhydroxylamine, N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine, N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydroxylamine, N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derived from hydrogenated tallow amine.
  • Nitrones for example N-benzyl-alpha-phenylnitrone, N-ethyl-alpha-methylnitrone, N-octyl-alpha-heptylnitrone, N-lauryl-alpha-undecyinitrone, N-tetradecyl-alpha-tridecylnitrone, N-hexadecyl-alpha-pentadecylnitrone, N-octadecyl-alpha-heptadecylnitrone, N-hexadecyl-alpha-heptadecylnitrone, N-ocatadecyl-alpha-pentadecylnitrone, N-heptadecyl-alpha-hepta-decylnitrone, N-octadecyl-alpha-hexadecylnitrone, nitrone derived from N,
  • Thiosynerqists for example dilauryl thiodipropionate or distearyl thiodipropionate.
  • Peroxide scavengers 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 dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis( ⁇ -dodecylmercapto)propionate.
  • esters of ⁇ -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( ⁇ -dodecyl
  • Polyamide stabilisers for example copper salts in combination with iodides and/or phosphorus compounds and salts of divalent manganese.
  • Basic co-stabilisers for example melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids, for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palpitate, antimony pyrocatecholate or zinc pyrocatecholate.
  • Basic co-stabilisers for example melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids, for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium
  • Nucleating agents for example inorganic substances, such as talcum, metal oxides, such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of, preferably, alkaline earth metals; organic compounds, such as mono- or polycarboxylic acids and the salts thereof, e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymeric compounds, such as ionic copolymers (ionomers).
  • inorganic substances such as talcum, metal oxides, such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of, preferably, alkaline earth metals
  • organic compounds such as mono- or polycarboxylic acids and the salts thereof, e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate
  • polymeric compounds such as ionic copolymers (
  • Fillers and reinforcing agents for example calcium carbonate, silicates, glass fibres, glass bulbs, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood flour and flours or fibers of other natural products, synthetic fibers.
  • additives for example plasticisers, lubricants, emulsifiers, pigments, rheology additives, catalysts, flow-control agents, optical brighteners, flameproofing agents, antistatic agents and blowing agents.
  • the 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.
  • Thin-walled articles of the invention act as a selective UV filter enhancing plant growth and crop while suppressing the undesired proliferation of microorganisms.
  • Light of the medium or far UV region e.g. 200-360 nm, especially 300-340 nm
  • the activity of useful insects such as bees and bumblebees is not affected.
  • the transparent polyolefin, polyester or polyamide article 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, polyester or polyamide, the weight ratio sterically hindered amine: hydroxyphenyl triazine UV absorber preferably ranging from 2:1 to 20:1.
  • More preferred sterically hindered amines include the following compounds:
  • Sterically hindered hydroxylamine ethers are mainly piperidine derivatives containing one or more functional groups of the formula
  • R and R′independently are hydrogen or methyl, and at 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 U.S. Pat. Nos. 5,204,473, 5,216,156, or in GB-A-2347928.
  • R 12 is C 2 -C 12 alkylene, C 4 -C 12 alkenylene, C 5 -C 7 cycloalkylene, C 5 -C 7 cycloalkylene-di(C 1 -C 4 alkylene), C 1 -C 4 alkylenedi(C 5 -C 7 cycloalkylene), phenylenedi(C 1 -C 4 alkylene) or C 4 -C 12 alkylene interrupted by 1,4-piperazinediyl, —O— or >N—X 1 with X 1 being C 1 -C 12 acyl or (C 1 -C 12 alkoxy)carbonyl or having one of the definitions of R 14 given below except hydrogen; or R 12 is a group of the formula (1b′) or (1c′);
  • X 2 being C 1 -C 18 alkyl, C 5 -C 12 cycloalkyl which is unsubstituted or substituted by 1, 2 or 3 C 1 -C 4 alkyl; phenyl which is unsubstituted or substituted by 1, 2 or 3 C 1 -C 4 alkyl or
  • radicals X 3 being independently of one another C 2 -C 12 alkylene
  • radicals B are independently of one another Cl, —OR 13 , —N(R 14 )(R 15 ) or a group of the formula (IIId);
  • R 13 , R 14 and R 15 which are identical or different, are hydrogen, C 1 -C 8 alkyl, C 5 -C 12 cycloalkyl which is unsubstituted or substituted by 1, 2 or 3 C 1 -C 4 alkyl; C 3 -C 18 alkenyl, phenyl which is unsubstituted or substituted by 1, 2 or 3 C 1 -C 4 alkyl or C 1 -C 4 alkoxy; C 7 -C 9 phenylalkyl which is unsubstituted or substituted on the phenyl by 1, 2 or 3 C 1 -C 4 alkyl; tetrahydrofurfuryl or C 2 -C 4 alkyl which is substituted in the 2, 3 or 4 position by —OH, C 1 -C 8 alkoxy, di(C 1 -C 4 alkyl)amino or a group of the formula (Ie′);
  • X is —O— or >N—R 16 ;
  • R 16 is hydrogen, C 1 -C 18 alkyl, C 3 -C 18 alkenyl, C 5 -C 12 cycloalkyl which is unsubstituted or substitutedby 1, 2 or 3 C 1 -C 4 alkyl; C 7 -C 9 phenylalkyl which is unsubstituted or substituted on the phenyl by 1, 2 or 3 C 1 -C 4 alkyl; tetrahydrofurfuryl, a group of the formula (IIIf),
  • R 11 has one of the definitions given for R 16 .
  • the end group bonded to the triazine residue can be, for example, a group B or —N(R 11 )—R 12 —B, such as chlorine or a group
  • the end group bonded to the diamino group can be, for example, hydrogen or a di-B-substituted triazinyl group, such as a group
  • Suitable amino groups are typically: pyrrolidin-1-yl, morpholino, —NH 2 , —N(C 1 -C 8 alkyl) 2 and —NY′(C 1 -C 8 alkyl) wherein Y′ is hydrogen or a group of the formula
  • alkyl examples are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, 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,
  • examples of cycloalkyl are cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl;
  • C 7 -C 9 phenylalkyl is benzyl
  • alkylene examples include ethylene, propylene, trimethylene, tetramethylene, pentamethylene, 2,2-dimethyltrimethylene, hexamethylene, trimethylhexamethylene, octamethylene and decamethylene.
  • n′ is approximately 3 (example 2 of GB-A-233471 7, CAS #247243-62-5, which is the NO-n-propyl derivative of the block oligomer Chimassorb®2020 CAS #192268-64-7, Ciba Specialty Chemicals Corp.).
  • 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 heatable container equipped with a stirrer, e.g. in a closed apparatus such as a kneader, mixer or stirred vessel.
  • 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.
  • Example X Mp ° C. f) —(CH 2 ) 10 — >250 g) —(CH 2 ) 12 — >250
  • Corresponding compounds wherein X is C 13 -C 24 alkylene; (C 1 -C 18 alkylene)—CO—O—D—O—CO—(C 1 -C 18 alkylene); CO—(C 13 -C 24 alkylene)—CO; C 3 -C 24 alkylene interrupted by oxygen, especially (C 1 -C 3 alkylene)—O—(C 1 -C 3 alkylene) 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 15 -C 26 diacids.
  • HALS sterically hindered amines
  • LDPE thin low density polyethylene
  • 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 of 150 ⁇ m thickness.
  • UV-Vis spectrum of the film as-obtained is 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.
  • 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 photostability of compound (a) is demonstrated by exposing the film sample to UV light in an Atlas Ci 65 Xenon Arc Weather-O-meter® (WOM, 63° C. black panel temperature, continuos 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.
  • WOM Atlas Ci 65 Xenon Arc Weather-O-meter®
  • 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 Hydroxyphenyl triazine compound (c) as a UV Filter in a Polyethylene Agrofilm
  • compound (c) is mixed with LDPE pellets (Riblene FF 29, supplied by Polimeri Europa, Milano, Italy), characterized by a density of 0.921 g/cm 3 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.
  • 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.
  • 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.
  • 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.
  • transmittance is below 20% in the above mentioned range and below 5% in the range 295-345 nm.
  • 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.
  • 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.
  • transmittance is below 20% in the above mentioned range and below 5% in the range 295-345 nm.
  • 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.
  • transmittance is below 20% in the above mentioned range and below 5% in the range 295-345 nm.
  • the film 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.
  • 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.
  • transmittance is below 20% in the above mentioned range and below 5% in the range 295-345 nm.
  • the film 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.
  • the granules obtained on extrusion and granulation are transformed into films at 220-260° C. in a second extruder equipped with a flat sheet die. Samples of 60 ⁇ 25 mm are cut out of these 0.11 mm films and exposed in a WEATHER-OMETER Ci 65 (black panel temperature 63 ⁇ 20° C., without water-spraying).
  • FIG. 1 Low molecular mass HALS H-2 (bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate);
  • FIG. 2 Polymeric HALS H-3 (CAS-No. 65447-77-0, white circles);
  • FIG. 3 non-polymeric high molecular mass HALS H-5.
  • the blend is compounded in an extruder at temperatures of 180-220° C.
  • the granules obtained on extrusion and granulation are transformed into films at 220-260° C. in a second extruder equipped with a flat sheet die.
  • the films are cut into ribbons, which are drawn to achieve a stretch ratio of 1:6.
  • the tapes obtained with this procedure are finally 50 ⁇ m thick and 2.5 mm wide.
  • the tapes are mounted without tension on sample holders and subjected to natural weathering in Florida (45° South, direct, approximately 140 kLy/year). Periodically, the tensile strength of the exposed tapes is measured. The received energy (in kLy) corresponding to a loss of 50% of the initial tensile strength is a measure for the stabilizing efficiency of the light stabilizer.
  • the values obtained with a polymeric HALS and the hydroxyphenyl triazine UV absorber are plotted in FIG. 4.
  • the tapes are mounted without tension on sample holders and exposed in a WEATHER-O-METER Ci 65 (black panel temperature 63 ⁇ 2° C., without water-spraying). Periodically, the tensile strength of the exposed tapes is measured. The exposure time corresponding to a loss of 50% of the initial tensile strength (T50) is a measure for the stabilizing efficiency of the light stabilizer.
  • HALS UV Absorber T50 none none 530 0.1% H-3 none 2150 0.1% H-3 0.1% V-1 2500 0.1% H-3 0.1% V-2 2700 0.1% H-3 0.1% compound j 3800 0.1% H-4 none 3000 0.1% H-4 0.1% V-2 2900 0.1% H-4 0.1% compound j 4150
  • Compound V-1 is 2-(2′-hydroxy-3′-t-butyl-5′-methylphenyl)-5-chlorobenzotriazole.
  • Compound V-2 is of the formula
  • Example 10 Absorption band and persistency in LDPE of compound (m)
  • LDPE thin low density polyethylene

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US09/912,139 2000-07-26 2001-07-24 Transparent polymer articles of low thickness Abandoned US20020083641A1 (en)

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US11/359,228 US7265171B2 (en) 2000-07-26 2006-02-22 Transparent polymer articles of low thickness
US11/827,210 US20070259165A1 (en) 2000-07-26 2007-07-11 Transparent polymer articles of low thickness
US12/283,464 US20090042006A1 (en) 2000-07-26 2008-09-12 Transparent polymer articles of low thickness
US12/511,380 US20090291289A1 (en) 2000-07-26 2009-07-29 Transparent polymer articles of low thickness
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US10/894,773 Abandoned US20050059758A1 (en) 2000-07-26 2004-07-20 Transparent polymer articles of low thickness
US11/359,228 Expired - Lifetime US7265171B2 (en) 2000-07-26 2006-02-22 Transparent polymer articles of low thickness
US11/827,210 Abandoned US20070259165A1 (en) 2000-07-26 2007-07-11 Transparent polymer articles of low thickness
US12/283,464 Abandoned US20090042006A1 (en) 2000-07-26 2008-09-12 Transparent polymer articles of low thickness
US12/511,380 Abandoned US20090291289A1 (en) 2000-07-26 2009-07-29 Transparent polymer articles of low thickness
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US11/359,228 Expired - Lifetime US7265171B2 (en) 2000-07-26 2006-02-22 Transparent polymer articles of low thickness
US11/827,210 Abandoned US20070259165A1 (en) 2000-07-26 2007-07-11 Transparent polymer articles of low thickness
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US20100178484A1 (en) 2010-07-15
CA2352708A1 (fr) 2002-01-26
CN1660823A (zh) 2005-08-31
KR20020010530A (ko) 2002-02-04
SA01220283B1 (ar) 2009-06-01
US20030236327A1 (en) 2003-12-25
NL1018520C2 (nl) 2002-06-21
CA2352708C (fr) 2011-10-18
US20050059758A1 (en) 2005-03-17
FR2812299A1 (fr) 2002-02-01
US20090291289A1 (en) 2009-11-26
GR1004356B (el) 2003-10-07
GB2367824A (en) 2002-04-17
IL144490A0 (en) 2002-05-23
US20070259165A1 (en) 2007-11-08
US20060141207A1 (en) 2006-06-29
FR2812299B1 (fr) 2007-04-27
AU778032B2 (en) 2004-11-11
GB0117537D0 (en) 2001-09-12
ITMI20011606A1 (it) 2003-01-25
AU5596601A (en) 2002-01-31
JP5489383B2 (ja) 2014-05-14
CO5231248A1 (es) 2002-12-27
KR20070081460A (ko) 2007-08-16
GB2367824B (en) 2003-04-30
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ITMI20011606A0 (it) 2001-07-25
ES2208018A1 (es) 2004-06-01
KR100778769B1 (ko) 2007-11-27
US7265171B2 (en) 2007-09-04
US20090042006A1 (en) 2009-02-12
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CN1308314C (zh) 2007-04-04
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DE10135795A1 (de) 2002-04-04

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