Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/10—Homopolymers or copolymers of propene
  • C08L23/12—Polypropene
• • 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
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/0041—Optical brightening agents, organic pigments
• • 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
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/0083—Nucleating agents promoting the crystallisation of the polymer matrix

Definitions

• the present invention is aimed at polypropylene articles with reduced haze, increased temperature of crystallization and excellent clarity.
• U.S. 2007/0185247 discloses polypropylene resin containing low loadings of carbon black together with dibenzylidene sorbitol based clarifying agents.
• the polypropylene articles are taught to have enhanced visual benefits.
• MILLAD NX8000 is a commercial clarifying agent for polypropylene available from Milliken, Spartanburg, North Carolina. It has a bluish tint.
• polypropylene articles with superior optical properties and/or an increased temperature of crystallization may be prepared where they comprise trisamide nucleating agents together with low levels of poiycyclic organic blue, green, magenta, red, yellow, orange or violet pigments.
• a polypropylene article with improved optical properties and/or an increased temperature of crystallization comprising a polypropylene resin and uniformly dispersed therein from about 1 ppm to about 10 ppm of one or more pigments selected from blue, green, magenta, red, yellow, orange and violet poiycyclic organic pigments and from about 50 ppm to about 250 ppm of one or more aromatic trisamide nucleating agents, where the ppm levels are by weight based on the weight of the polypropylene resin.
• Also disclosed is a method for providing a polypropylene article with improved optical properties and/or an increased temperature of crystallization comprises uniformly dispersing into a polypropylene resin from about 1 ppm to about 10 ppm of one or more pigments selected from blue, green, magenta, red, yellow, orange and violet poiycyclic organic pigments and from about 50 ppm to about 250 ppm of one or more aromatic trisamide nucleating agents, where the ppm levels are by weight based on the weight of the polypropylene resin.
• the polypropylene resin is for instance a polypropylene homopolymer.
• Polypropylene homopolymer also covers long chain branched polypropylene.
• Polypropylene can be prepared by different methods. Examples are:
• These metals usually have one or more than one ligand, typically oxides, haiides, alcoholates, esters, ethers, amines, alkyls, alkeny!s 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(lll) chloride, alumina or silicon oxide.
• These catalysts may be soluble or insoluble in the polymerization medium.
• the catalysts can be used by themselves in the polymerization or further activators may be used, typically metal alkyls, metal hydrides, metal alkyl haiides, metal alkyl oxides or metai alkyloxanes, said metals being elements of groups la, Ha and/or Ilia of the Periodic Table.
• the activators may be modified conveniently with further ester, ether, amine or silyl ether groups.
• These catalyst systems are usually termed Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC).
• the polypropylene resin is a polypropylene random copolymer, alternating or segmented copolymer or block copolymer containing one or more comonomers selected from the group consisting of ethylene, C 4 -C 20 -a- olefin, vinylcyciohexane, vinylcyclohexene, C 4 -C 2 oalkandiene, C 5 -C 12 cycloalkandiene and norbornene derivatives; the total mole amount of propylene and the comonomer(s) being 100%.
• Polypropylene copolymer also covers long chain branched polypropylene copolymer.
• C 4 -C 20 -olefins examples include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1- octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and 4-methyi-1-pentene.
• Examples of suitable C 4 -C 20 aikandienes are hexadiene and octadiene.
• Examples of suitable C 5 -C 12 cycioalkandienes are cyclopentadiene, cyclohexadiene and cyclooctadiene.
• Suitable norbornene derivatives are 5-ethylidene-2-norbornene (ENB), dicyciopentadiene (DCP) and methy!ene-domethylene-hexahydronaphthaline (MEN).
• a propylene/ethylene copolymer contains for example 50 to 99.9 %, preferably 80 to 99.9 %, in particular 90 to 99.9 %, by weight of propylene.
• C 9 -C 2 oalkandiene, C 9 -Ci 2 cycloalkandiene or a norbornene derivative such as e.g. 5-ethyfidene-2- norbornene (ENB) or methylene-domethy!ene-hexahydronaphthaline (MEN) contains preferably more than 90 mol %, in particular 90 to 99.9 moi % or 90 to 99 mol %, of propylene.
• the comonomer is a C 4 -C 8 a-olefin such as e.g. 1-butene, 1- pentene, 1-hexene, 1-heptene, 1-octene or 4-methyl-1-pentene
• vinylcyclohexane, vinylcyc!ohexene C 4 -C 8 alkandiene or C 5 -C
• polypropylene resin examples include propylene/isobutylene copolymer, propyiene/butadiene copolymer, propylene/cycloolefin copolymer, terpolymers of propylene with ethylene and a diene such as hexadiene, dicyciopentadiene or ethylidene-norbornene; propylene/1 - olefin copolymers where the 1 -olefin is generated in situ; and propylene/carbon monoxide
• polypropylenes of the present invention are in particular polypropylene homopolymers, polypropylene impact (heterophasic) copolymers, blends thereof and TPO's such as blends of polypropylene homopolymers and impact modifiers such as EPD or ethylene/alpha-o!efin copolymers.
• TPO thermoplastic olefin
• the elastomeric copolymer is for instance ethylene/propylene copolymer (EP ) or ethylene/propylene/non-conjugated diene (EPDM).
• EP ethylene/propylene copolymer
• EPDM ethylene/propylene/non-conjugated diene
• Polypropylene includes for instance reactor (such as metallocene) and visbroken (e.g. peroxides, hydroxylamine esters, thermally broken, etc.) grades.
• reactor such as metallocene
• visbroken e.g. peroxides, hydroxylamine esters, thermally broken, etc.
• aromatic trisamides are for instance of formula I
• R2, R3, R 4 , 5 and R 6l independently of one another, are
• C 7 -C 9 phenylalkyl which is substituted on the phenyl by 1, 2 or 3 radicals selected from the group consisting of C r C 0 alkyi ( C C 10 alkoxy and hydroxy;
• -C 2 oalkyl examples include methyl, ethyl, propyl, isopropyl, n-butyl, sec-buty!, isobutyi, tert-butyl, 2-ethylbutyi, n-pentyl, isopentyl, 1-methylpentyl, 1 ,3-dimethy!butyl, n-hexyl, 1-methyl- hexyl, n-heptyi, isoheptyl, 1,1 ,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2- ethylhexyl, 1 ,1 ,3-trimethylhexyl, 1 ,1 ,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methyl- undecyl, dodecyl, 1,1 ,3,3,5,5-
• C 2 -C 20 alkyl substituted by C Ci 0 alkylamino , diid-C ⁇ alky amino, C Ci 0 aIkyloxy or hydroxy are 3-methylaminopropyi, 2-dimethylaminoethyl, 2-diethylaminoethyl, 3-dimethylaminopropyI, 3-diethylaminopropyl, 2-methoxyethyl, 2-ethoxyethyi, 2-methoxypropyl, 3-methoxypropyl, 2-ethoxypropyl, 3-isopropoxypropyl and hydroxyethyl.
• Preferred examples are 3-dimethylaminopropyl, 3-methoxypropyl and 2-methoxyethyl.
• Examples of C 3 -C 20 a!keny! are aliyl, 2-methallyl, butenyl, pentenyl, hexenyl and oleyl.
• the carbon atom in position 1 is preferably saturated.
• Preferred examples are allyl and oieyl.
• Examples of C 5 -C 12 cycloalkyl are cyclopentyl, cyclohexyl, cycioheptyi, cyclooctyl and cyclododecyl.
• Preferred examples are cyclohexyl, cycioheptyi, cyclooctyl and cyclododecyl.
• C 5 -C 12 cycloalkyl substituted by 1 , 2 or 3 C Cioalkyl are preferred examples of C 5 -C 12 cycloalkyl substituted by 1 , 2 or 3 C Cioalkyl.
• cyc!ohexylmethy! substituted by 1 , 2 or 3 C C 10 a!kyl is 1 -cyclohexylethyl.
• C 5 -C 9 cycloalkenyl is cyclohexenyi.
• Cioalkyl An example of C 5 -C 9 cycloalkenyl substituted by 1 , 2 or 3 C r Cioalkyl is
• phenyl substituted by 1 , 2 or 3 radicals selected from the group consisting of Ci-C 10 alky!, CrC 10 aJkyloxy, hydroxy, halogen, trihalogenmethyl, trihalogenmethoxy, benzoyl, phenylamino, acy!amino and phenyiazo are 4-methylphenyl, 2-ethylphenyl, 4-ethylphenyl, 4- isopropylphenyi, 4-tert-butylphenyl, 4-sec-butylphenyl, 4-isobutylphenyl, 3,5-dimethylphenyi, 3,4-dimethylphenyl, 2,4-dimethylphenyl, 2,6-diethylphenyi, 2-ethyl-6-methyiphenyl, 2,6- diisopropyiphenyl, 4-methoxyphenyl, 4-ethoxyphenyl, 4-hydroxyphenyl, 4-fluorophenyl, 3,5- difluorophen
• Cr-Cgphenylalkyl examples include benzyl and 2-phenylethyl. Benzyl is preferred.
• C 7 -C 9 phenylalkyl which is substituted on the phenyl by 1 , 2 or 3 radicals selected from the group consisting of CrCi 0 alkyl, C C 10 alkoxy and hydroxy are methylbenzyl, dimethylbenzyl, trimethyibenzyl, tert-butylbenzyl, methoxybenzyl and 3,5-di-tert-butyl-4- hydroxy benzyl.
• naphthyl substituted by CrC 10 alkyl is methylnaphthyl.
• Examples of a 5 to 6 membered heterocyclic group are 2-picolyl, (2-furyi)methyl, (2-tetrahydrofuryl)methyl, 2-pyrimidyf, 6-methy!-2-pyridyl, 1 ⁇ -triazol-S-yl and
• aromatic trisamides are for example of formulae Ha, lib or lie
• R 10 , R20 and R 30 , or Y-i , Y 2 and Y 3 , or Z Z 2 and Z 3 independently of one another are
• phenyl unsubstituted or substituted by one or more radicals selected from C C 20 afkyl, C 1 -C 20 alkoxy ) CrC 20 alky!amino, di(C C 20 alkyl)amino, hydroxy and nitro;
• phenyl-C C 20 alkyl unsubstituted or substituted by one or more radicals selected from
• naphthyl-C C 20 alkyl unsubstituted or substituted by one or more C C 20 alkyl; naphthoxymethyi unsubstituted or substituted by one or more Ci-C 20 alky!;
• a 5- to 6-membered heterocyclic radical unsubstituted or substituted by one or more C C 20 aikyl; a C C 20 hydrocarbon radical containing one or more halogen; or
• phenyi-C doaikyl unsubstituted or substituted by one or more radicals selected from
• At least one of the radicals R 10 , R 20 and R 30) or Y 2 and Y 3 , or Z ⁇ Z 2 and Z 3 is branched C 3 -C 20 alkyl, or C 3 -C 2 cycloalkyl unsubstituted or substituted by one or more CrC 20 alkyl.
• At least one of the radicals R 10 , R20 and 3o, or YL Y 2 and Y 3 , or Z Z 2 and Z 3 is branched C 3 -Ci 0 alkyi.
• CrCa.aikyl e.g. branched C 3 -C 2 oalkyl, unsubstituted or substituted by one or more hydroxy, e.g. 1 , 2 or 3 hydroxy
• Branched C 3 - C 10 alkyl is particularly preferred.
• One of the preferred meanings of the radicals Ri 0 , f3 ⁇ 4o and R 30 , or Yi, Y 2 and Y 3 , or Z 1( Z 2 and Z 3 is branched C 3 -C 10 alkyl with a quaternary C atom in position 1 , in particular -C(CH 3 ) 2 -H or -C(CH 3 ) 2 -(C C 7 alkyl).
• C 2 -C 2 oalkenyl unsubstituted or substituted by one or more hydroxy are 9-decenyl, 8-heptadecenyl and 11-hydroxy-8-heptadecenyl.
• C 2 -C 20 alkyl interrupted by oxygen are t-butoxymethyl, t-butoxyethyl, t-butoxypropyi and t-butoxybutyl.
• Examples of C 2 -C 20 alkyl interrupted by sulfur are (H 3 C) 3 C-S-CH 2 ⁇ , (H 3 C) 3 C-S-C 2 H4-, (H 3 C) 3 C-S-C 3 H 6 - and (H 3 C) 3 C-S-C 4 H 8 -.
• C 3 -Ci 2 cycloalkyl unsubstituted or substituted by one or more CrC 20 alkyl e.g. 1 , 2, 3 or 4 C C 4 alkyl
• CrC 20 alkyl e.g. 1 , 2, 3 or 4 C C 4 alkyl
• Examples of C 3 -Ci 2 cycloalkyl unsubstituted or substituted by one or more CrC 20 alkyl, e.g. 1 , 2, 3 or 4 C C 4 alkyl are cyclopropyl, 3-methylcyclopropyl, 2,2,3,3-tetramethylcyclopropyl, cyc!obutyl, cyc!opentyl, cyclohexyl, 1-methylcyclohexyl, 2-methylcyciohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 4-tert-butylcyclohexyl and cycloheptyl.
• phenyl unsubstituted or substituted by one or more radicals selected from Ci-C 20 alkyl, C doalkoxy, C C 2 oalkylamino, di(CrC 20 alkyl)amino, hydroxy and nitro, preferably d-dalkyl, C 1 -C 4 aikoxy, C C 4 aikylamino, diid-CialkylJamino, hydroxy and nitro, are phenyl, 3-methylphenyl, ' 3-methoxyphenyl, 4-methylphenyl, 4-ethy!phenyl, 4-propylphenyl, 4-isopropylphenyl, 4-tert-butylphenyl, 4-isopropoxyphenyl, 2,3-dimethoxyphenyl, 2-nitrophenyl, 3-methyl-6-nitrophenyl, 4-dimethylaminophenyl, 2,3-dimethylphen
• phenyl-C C 20 alkyl unsubstituted or substituted by one or more radicals e.g. 1 , 2 or 3 radicals, selected from C C 20 aikyl, C3-C 2 cycloalkyl, phenyl, C C 20 alkoxy and hydroxy, preferably C C 4 alkyl, C 3 -Cecycioaikyl, phenyl, C r C 4 alkoxy and hydroxy, are benzyl, - cyclohexylbenzyl, diphenylmethyl, 1 -phenylethyl, -hydroxybenzyl, 2-phenylethyi, 2- phenyipropyl, 3-phenylpropyl, 3-methylbenzyS, 3,4-dimethoxybenzyl and 2-(3,4- dimethoxyphenyl)ethyl.
• radicals e.g. 1 , 2 or 3 radicals, selected from C C 20 aikyl, C3-
• phenylethenyl unsubstituted or substituted by one or more C 1 -C 20 alkyi l e.g. 1 , 2 or 3 C C alkyl, is 2 ⁇ (4-methylphenyl)ethenyl.
• bipheny Ci-doalkyl unsubstituted or substituted by one or more C C 2 oalkyl, e.g. 1 , 2 or 3 d-C 4 aikyi, is 4-biphenylmethyl.
• naphthyl unsubstituted or substituted by one or more d-doalkyl e.g. 1 , 2 or 3 C C 4 alkyl
• d-doalkyl e.g. 1 , 2 or 3 C C 4 alkyl
• naphthyl-C C 20 alkyl unsubstituted or substituted by one or more
• Ci-C 20 alkyl e.g. 1 , 2 or 3 C C 4 alkyl
• Ci-C 20 alkyl are 1-naphthylmethyl and 2-naphthyimethyl.
• biphenylenyl, flourenyl or anthryl is 2-biphenylenyl, 9-flourenyl, 1-flourenyl or 9-anthryl, respectively.
• Examples of a 5- to 6-membered heterocyclic radical unsubstituted or substituted by one or more C r C 20 alkyl, e.g. 1, 2 or 3 C ⁇ alkyi, are 3-pyridinyl, 4-pyridtnyl, 2-hydroxypyridin-3-yl, 3-quinolinyl, 4-quinolinyl, 2-furyl, 3-furyl and 1-methyl-2-pyrryl.
• Examples of a C C 20 hydrocarbon radical containing one or more halogen, e.g. 1, 2, 3, 4, 5, or 6 -F, -CI or -I, are l-bromo-2-methylpropyl, dichioromethyl, pentafluoroethyl, 3,5- bis[trifluoromethyl]phenyl, 2,3,5,6-tetrafluoro-p-tolyl, 2,3-dichlorophenyl, 3,4-dichlorophenyl and 2,4-bis[trifiuoromethyl]phenyl.
• Examples of compounds of formula (lie) are:
• the present pigments are polycyciic organic pigments and are selected from the group consisting of blue, green, magenta, red, yellow, orange and violet polycyciic organic pigments.
• the blue pigments are for example of the indanthrone and the copper phthalocyanine classes, for instance Pigment Blue 60, Pigment Blue 15:1 , Pigment Blue 15:3, Pigment Blue 15:4 and Pigment Blue 15:6.
• the green pigments are for example of the copper phthalocyanine class, for instance Pigment Green 7 and Pigment Green 36.
• the magenta pigments are for instance of the quinacridone class, for example 2,9-dichloro quinacridone, Pigment Red 202.
• the red pigments are for instance of the quinacridone class, for instance dimethyl quinacridone, Pigment Red 122, or of the perylene class, for instance Pigment Red 149, Pigment Red 178 and
• Pigment Red 179 or of the diketopyrrolo pyrrole class, for instance Pigment Red 254 and Pigment Red 264.
• the yellow pigments are for instance of the pteridine, isoindo!inone, and isoindoline classes, for example Pigment Yellow 215, Pigment Yelfow 1 0, and Pigment Yellow 139.
• the orange pigments are of the isoindolinone or diketopyrrolopyrrole class, for instance Pigment Orange 61, Pigment Orange 71 , and Pigment Orange 73.
• the violet pigments are for instance of the quinacridone class, for instance pigment violet 9 or of the dioxazine class, for instance pigment violet 23 or pigment violet 37.
• mixtures of pigments may be employed.
• the above described aromatic trisamide compounds are present in concentrations, based on the amount of the polypropylene resin, of from about 50 ppm to about 250 ppm by weight.
• the trisamides are present from about 100 ppm to about 200 ppm by weight.
• the trisamides are present at about 50, 100, 150, 200 or 250 ppm by weight and ranges in between.
• the aromatic trisamides can be added as individual compounds or as mixtures to the polypropylene.
• the above pigments are present in concentrations of from about 1 ppm to about 0 ppm by weight, based on the weight of the polypropylene resin.
• the pigments are present at weight levels of about 1, 2, 3, 4, 5, 6, 7, 8, 9 or about 10 ppm, based on the weight of the polypropylene resin.
• the above pigments are preferably present in concentrations of from about 2 ppm or about 4 ppm to about 10 ppm by weight, based on the weight of polypropylene resin.
• the pigments are for example a mixture of one or more blue pigments and one or more magenta, red or violet pigments.
• ultraviolet light absorbers selected from hydroxyphenylbenzotriazole,
• hydroxyphenyltriazine benzophenone and benzoate UV absorbers, organic phosphorus stabilizers, hydroxylamine stabilizers, benzofuranone stabilizers, amine oxide stabilizers, hindered phenol antioxidants and/or hindered amine light stabilizers.
• the further additives are for instance employed at levels of about 0.1 to about 10% by weight, based on the weight of the polypropylene resin.
• further additives are selected from the organic phosphorus stabilizers, hindered phenol antioxidants, hydroxylamines, hindered amines and benzoate UV absorbers.
• the organic phosphorus stabilizers are for example known phosphite and phosphonite stabilizers and include triphenyl phosphite, diphenyl alkyl phosphites, phenyl diaikyl phosphites, tris(nonylphenyl) phosphite, trilauryi phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, bis(2,4-di-a-cumylpheny!) pentaerythrtitol diphosphite, diisodecyi pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite (D), bis(2,6-di-ter
• Hindered phenolic antioxidants include for example tris(3,5-di-tert ⁇ butyl-4-hydroxybenzyl) isocyanurate, 1 ,3,5-tris-(3 ] 5-di-tert-butyl-4-hydroxybenzyl)-2,4 !
• 6-trimethylbenzene the calcium salt of the monoethyi ester of 3,5-di-tert-butyl-4-hydroxybenzy!phosphonic acid, pentaerythrttol tetrakis [3-(3 1 5-di-tert-butyi-4-hydroxyphenyl) propionate] or octadecyl 3-(3,5-di-tert-butyl-4- hydroxyphenyl) propionate.
• the present stericatly hindered amine stabilizers contain at least one moiety of formula
• G 2l G 3 and G 4 are independently alkyl of 1 to 8 carbon atoms or d and G 2 or G 3 and G 4 together are pentamethylene and G 5 is hydrogen or alkyl of 1 to 8 carbon atoms.
• the hindered amines are disclosed for example in U.S. Pat. Nos. 5,004,770, 5,204,473, 5,096,950, 5,300,544, 5,112,890, 5,124,378, 5,145,893, 5,216,156, 5,844,026, 5,980,783, 6,046,304, 6,117,995, 6,271 ,377, 6,297,299, 6,392,041, 6,376,584, 6,472,456, and 7,030,196.
• the relevant disclosures of these patents are hereby incorporated by reference.
• Suitable hindered amines include for example:
• the oligomeric compound which is the condensation product of 4,4'-hexamethylene- bis(amino-2,2,6,6-tetramethylpiperid!ne) and 2,4-dichloro-6-[(2,2,6,6-tetramethyipiperidin-4- yl)butyiamino]-s-triazine end-capped with 2-ch!oro-4,6-bis(dibutyIamino)-s-triazine,
• the oligomeric compound which is the condensation product of 4,4'-hexamethylene- bis(amino-1 ,2,2,6,6-pentaamethylpiperidine) and 2,4-dichloro-6-[(1 ,2,2,6,6-pentaamethyl- piperidin-4-yl)butylamino]-s-triazine end-capped with 2-chloro-4,6-bis(dibutylamino)-s-triazine,
• the oligomeric compound which is the condensation product of 4,4'-hexamethylene- bis ⁇ amino-1 -propoxy-2,2,6,6-tetramethylpiperidine) and 2,4-dichloro-6-[(1 -propoxy-2,2 ) 6,6-tetra- methylpiperidin-4-yl)butylamino]-s-triazine end-capped with 2-chloro-4,6-bis(dibutylamino)-s- triazine,
• the oligomeric compound which is the condensation product of 4,4'-hexamethylene- bis(amino-1-acyloxy-2,2,6,6-tetramethylpiperidine) and 2,4-dichloro-6-[(1-acy[oxy-2,2,6,6-tetra- methylpiperidin-4-yi)butylamino]-s-triazine end-capped with 2-chIoro- ,6-bis(dibutylamino)-s- triazine and
• Aiso included are the stericalfy hindered N-H, N-methyl, N-methoxy, N-propoxy, N- octyloxy, N-cyclohexyloxy, N-(2-hydroxy-2-methy[propoxy) and N-acyl analogues of any of the above mentioned compounds.
• N-H hindered amine replacing an N-H hindered amine with an N-methyl hindered amine would be employing the N-methyl analogue in place of the N-H.
• Hydroxylamine stabilizers are for example ⁇ , ⁇ -dibenzylhydroxylamine, N,N- diethylhydroxylamine, N.N-dioctylhydroxyiamine, ⁇ , ⁇ -dilaurylhydroxyfamine, N,N- didodecylhydroxylamine, ⁇ , ⁇ -ditetradecylhydroxylamine, ⁇ , ⁇ -dihexadecylhydroxy!amine, N,N- dioctadecy!hydroxylamine, N-hexadecyl-N-tetradecylhydroxylamine, N-hexadecyl-N- heptadecylhydroxylamine, N-hexadecyi-N-octadecylhydroxylamine, N-heptadecyl-N- octadecylhydroxylamine, N-methyl-N-octadecylhydroxylamine or N,N-di(hydrogenated tallow)
• Benzofuranone stabilizers are for example 3-(4-(2-acetoxyethoxy)phenyl)-5,7-di-tert- butyl-benzofuran-2-one, 5,7-di-tert-butyl-3-(4-(2-stearoyloxyethoxy)phenyl)benzofuran-2-one, 3,3'-bis(5,7-di-tert-butyl-3-(4-(2-hydroxyethoxy)phenyS)benzofuran-2-one), 5,7 ⁇ di-tert-butyl-3-(4- ethoxyphenyl)benzofuran-2-one, 3-(4-acetoxy-3,5-dimethy!phenyl)-5,7-di-tert-butyl-benzofuran- 2-one, 3-(3,5-dimethy!-4-pivaloyloxyphenyl)-5,7-di-tert-butyt-benzofuran-2-one, 3-
• Benzoate UV absorbers are for instance esters of substituted and unsubstituted benzoic acids, as for example 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyi 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-iert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl- 4-hydroxybenzoate.
• 4-tert-butylphenyl salicylate phenyl salicylate,
• Hydroxyphenylbenzotriazole, hydroxyphenyltriazine and benzophenone UV absorbers are well known and are disclosed for instance in U.S. Pat. No. 6,444,733, incorporated by reference.
• the addition of the aromatic trisamides, the pigments and further additives to the polypropylene resin can be carried out in all customary mixing machines in which the polymer is melted and mixed with the additives.
• Suitable machines are known to those skilled in the art. They are predominantly mixers, kneaders and extruders.
• the process is preferably carried out in an extruder by introducing the additives during processing.
• processing machines are single-screw extruders, contrarotating and corotating twin-screw extruders, planetary-gear extruders, ring extruders or cokneaders. It is also possible to use processing machines provided with at least one gas removal compartment to which a vacuum can be applied.
• the screw length is 1 - 60 screw diameters, preferably 35-48 screw diameters.
• the rotational speed of the screw is preferably 10 - 600 rotations per minute (rpm), very particularly preferably 25 - 300 rpm.
• the maximum throughput is dependent on the screw diameter, the rotational speed and the driving force.
• the process of the present invention can also be carried out at a level lower than maximum throughput by varying the parameters mentioned or employing weighing machines delivering dosage amounts. if a plurality of components are added, these can be premixed or added individually.
• the polypropylene resins need to be subjected to an elevated temperature for a sufficient period of time during incorporation of additives.
• the temperature is generally above the softening point of the polymers.
• a temperature range lower than 280°C, particularly from about 160°C to 280°G is employed.
• the temperature range from about 200°C to 270° ⁇ is employed.
• Such “melt mixing” or “melt compounding” results in uniform dispersion of the present additives in the polypropylene.
• incorporation of additives into the polypropylene resin can be carried out, for example, by mixing the above-described aromatic trisamides or mixtures thereof and pigments and, if desired, further additives into the polymers using the methods customary in process technology.
• the aromatic trisamides, pigments and further additives can also be added to the polypropylene resin in the form of a masterbatch in which these compounds are present, for example, in a concentration of from about 0.5 to about 30% by weight in a thermoplastic polymer.
• the present invention therefore further provides a concentrate in which the additives of the invention are present in a concentration of from about 0.5 to about 30% by weight in a thermoplastic polymer and which can be added to the polypropylene resin.
• the thermoplastic polymer may be polypropylene or another thermoplastic resin.
• the additized polypropylene resin is normally collected as pellets, which may be stored for a time or employed immediately in a forming process.
• one or more letdown steps may be included.
• the forming processes include injection molding, extrusion blow molding, injection stretch blow molding, thermoforming, compression molding or sheet extrusion.
• the final formed articles are for instance molded parts, sheets, films or fibers.
• the final formed articles are for instance molded parts, sheets, films or fibers.
• bottles, containers, automotive parts, refrigerator parts, trays, computer parts and the like are for instance molded parts, sheets, films or fibers.
• the present polypropylene articles have superior optical properties and/or an increased temperature of crystallization. They exhibit reduced haze and high clarity and/or an increased temperature of crystallization. Optica! properties are measured by light transmission, clarity, haze and degree of yellowness. Light transmission, clarity and haze are measured according to ASTM D1003. Yellowness Index (Yl) is measured in a similar fashion to ASTM E313, iliuminant C 2° observer, reflectance with specular light included. The present articles exhibit for example a haze value of less than 8.0 according to ASTM D1003.
• the present articles are essentially clear and exhibit high transmission of visible light.
• low levels of one or more pigments selected from blue, green, magenta, red, yellow, orange and violet polycyclic organic pigments together with a certain level of one or more aromatic trisamide nucleating agents towards providing polypropylene articles with improved optical properties and/or an increased temperature of crystallization are from about 1 to about 10 ppm and the levels of aromatic trisamides are from about 50 to about 250 ppm, by weight, based on the weight of the polypropylene resin.
• Polypropylene homopolymer with a melt index of 12.0 g/10 min. is compounded with the additives with a twin screw W&P ZSK 25 extruder under a nitrogen blanket at 220°C.
• Each formulation contains 400 ppm IRGANOX 1010 phenolic antioxidant, 800 ppm IRGAPHOS 168 phosphite process stabilizer, 500 ppm calcium stearate and 180 ppm present nucleating agent TA1.
• Additive levels are weight percent based on the weight of the polypropylene.
• the compounded polypropylene is collected as pellets. The pellets are subjected to injection molding with a Boy 50 M, step mold, die temperature of 230°C. Plaques are prepared, 2" by 2", 25 mil, 40 mil and 50 mil thick. The plaques are stored for 3 days at room temperature prior to any testing.
• CROMOPHTAL Blue BCN is pigment blue 15:1.
• CROMOPHTAL Magenta P is pigment red 202.
• Light transmission, clarity and haze are measured according to ASTM D1003 on 40 mil plaques.
• Yl is measured on 50 mil plaques.
• the present formulation has a temperature of crystallization, T c , of 126°C.
• T c temperature of crystallization
• the formuation without pigment has a T c of 122°C.
• Temperature of crystallization is measured by differential scanning calorimetry on a 5 mg sample removed from the center of a 25 mil plaque.
• the present formulation exhibits improved visual apperance, Yi of -1.69.
• the formulation without pigment exhibits a Yl of 4.50.
• Yl is measured on a Datacolor SF600 spectrophotometer using C illuminant and 2° observer.
• the transmission (T), haze (H) and clarity (C) on 40 mil plaques are as follows:
• the transmission (T), haze (H) and clarity (C) on 50 mil plaques are as follows:
• Polypropylene random copolymer with a melt index of 12.0 g/10 min. is compounded with the additives with a twin screw W&P ZSK 25 extruder under a nitrogen blanket at 220°C.
• Each formulation contains 400 ppm IRGANOX 1010 phenolic antioxidant, 800 ppm IRGAPHOS 168 phosphite process stabilizer, 500 ppm calcium stearate and 50 ppm present nucleating agent TA1. Additive levels are weight percent based on the weight of the polypropylene.
• the compounded polypropylene is collected as pellets.
• CROMOPHTAL Blue BCN is pigment blue 15:1.
• CROMOPHTAL Magenta P is pigment red 202.
• Present formulations a-c have elevated temperatures of crystallization, T Cl as compared to the formulation without pigment. Temperature of crystallization is measured by differentia! scanning calorimetry, cooling from the melt at a rate of 20°C/min on a 5 mg sample cut from a pellet.
• Increased temperature of crystallization is commercially important because it translates into faster cooling time resulting in reduced cycle time in molding processes.

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