Title of Invention	USE OF NUCLEATED PROPYLENE BUTENE TERPOLYMERS FOR THE PRODUCTION OF STERILIZABLE BLOWN FILMS
Abstract	Use of a polymer composition comprised of (i) a propylene/butene terpolymer which is comprised of 86.0 - 98.0 wt% of propylene 2.0 - 12.0 wt% of butene and 0.1 - less than 1.0 wt% of ethylene and (ii) 0.001 - 1.0 wt% of one or more phosphorous based and/or polymeric α-nucleating agents for the production of stehlizable water or air quenched blown films which have the following properties: a) a haze according to ASTM D 1003-92 for a 50 µm film of less than 8% before and after steam sterilization at 121˚C for 30 minutes and b) 20° Gloss according to DIN 67 530 for a 50 µm film of at least 55% be fore steam sterilization at 121˚C for 30 minutes.

Title of Invention

USE OF NUCLEATED PROPYLENE BUTENE TERPOLYMERS FOR THE PRODUCTION OF STERILIZABLE BLOWN FILMS

Abstract

Use of a polymer composition comprised of (i) a propylene/butene terpolymer which is comprised of 86.0 - 98.0 wt% of propylene 2.0 - 12.0 wt% of butene and 0.1 - less than 1.0 wt% of ethylene and (ii) 0.001 - 1.0 wt% of one or more phosphorous based and/or polymeric α-nucleating agents for the production of stehlizable water or air quenched blown films which have the following properties: a) a haze according to ASTM D 1003-92 for a 50 µm film of less than 8% before and after steam sterilization at 121˚C for 30 minutes and b) 20° Gloss according to DIN 67 530 for a 50 µm film of at least 55% be fore steam sterilization at 121˚C for 30 minutes.

Full Text	Use of nucleated propylene butene terpolymers for the production of sterilizable blown films The present invention relates to tiie use of nucleated propyl-ene/butene/ethylene terpolymers for the production of sterilizable blown films. Blown films produced from these polymers are sterilizable and have excel¬lent optical properties as well as mechanical properties. Technological background Poiyolefins have gained wide acceptance and usage in numerous com¬mercial applications because of their relatively low costs and desirable properties. Such commercial applications include plastic films such as cast films, blown films, mono- and biaxially oriented films and coating. These plastic films can for example be used for various flexible and rigid packaging, e.g. for food, medicals, flowers, etc. In a continuously increasing part of this marl Polypropylene for films is today almost exclusively used tor cast films. In the cast film process a very quick cooling of the melt is achieved with a chill roll, in order to utilize the potentially good optical and mechanical proF>erties of polypropylene for film applications. Until recently, polypropylene could be used in the blown film process only when it was possible to use water contact cooling in order to achieve the same quick cooling as in the cast fiim process. In a conventional blown film process using air cooling, the polymer melt and the films produced from it are only slowly cooled. This results in insuf¬ficient optical and mechanical parameters because the slow cooling proc¬ess causes an uncontrolled growth of the crystal- and spherulitic structure. Propylene blown films produced with air cooling are both cloudy and brit¬tle. It has therefore been tried to improve the problem of cloudiness respec¬tively haziness and brittleness of polypropylene blown films by using a combination of propylene random copolymers with either inorganic nucle¬ating agent or sorbitol-based nucleating agents, which resulted in im¬provements of optical and mechanical parameters to a very limited extent. So there was the need to look for further improvements for air quenched blown films from propylene polymers. In the examples of WO 2005/026240 blown films, comprising a polypro¬pylene composition containing a propylene homopolymer or propene co¬polymer with 4.8 wt% ethylene, the polypropylene copolymer composition containing 0.2 wt% of a clarifier comprising a phosphate-based a-nucleating agent respectively a sorbitol-based a-nudeating agent, are de¬scribed. In these examples it is shown that the blown film of the propylene ethylene copolymer comprising the phosphate-based a-nucteating agent has better optical properties gloss and haze compared to a blown film of a propylene ethylene copdymer comprising the sorbitol-based a-nucleating agent. The blown film according to example 1 fijrther shows a tensile modulus of about 925 MPa (md) respectively of about 972 MPa (td). WO 02/44252 discloses the use of polymer compositions comprised of a propylene terpolymer and erucic acid amide and/or oleic acid amide as slip agent for films, lil a) a dynamic Coefficient of Friction after storage for 3 days at 23 °C of smaller than 0.30 (measured according to DIN 53 375) b) a blooming behavior, measured in tenns of haze according to ASTM D 1003-92 after storage for 14 days at 40 "C which shows a deterioration of no more than 100 % of the original value which is measured after storage for 4 days at 23 "C. Further it is described that lamination films produced from these polymer compositions show a smaller loss of optical properties compared to films from propylene butene or propylene ethylene random copolymers after sterilization at 121 "C for 30 minutes. The tensile modulus of the films produced with cast film technology is be¬tween 385 and 440 MPa. WO 03/040202 discloses e.g. blown films made from - annongst other polymers -propylene/1-butene copolymers and propylene/ethylene/1-butene terpolymers. These films comprise at least 50 wt% propylene and at least 5 wt% ethyl¬ene and/or one or more unsaturated comonomer and have a haze value of less than about 10 and a 45° gloss of greater than about 65. In the examples, WO 03/040202 describes a base resin for blending stud¬ies for the production of bAovm films using a commercially available Ziegler-Natta propylene (H110-02Z: a Z-N-mini-random PP containing 0.5 wt% ethylene, nucleated with methylene-bis-(4,6-di-t-butylphenyl) phos¬phate sodium salt, available from The Dow Chemical Company). The re¬sulting blown film disclosed as a comparative example showed less favor¬able properties than the blends comprising special PIE copolymers claimed in WO 03/040202. It is therefore an object of the present invention to provide improved water or air quenched blown films, preferably air quenched blown films, pro¬duced from propylene butene terpolymers, which are sterilizable and have improved mechanical properties and excellent optical properties, which are even improved after sterilization. This object was achieved by using a polymer composition comprised of (i) a propylene/butene terpolymer which is comprised of 86.0 - 98.0 wt% of propylene 2.0-12.0 wt% of 1 -butene and 0.1 - less than 1.0 wt% of ethylene and (ii) O.OOt - 1.0 wt% of one or more phosphorous based and/or polymeric Q-nucleating agents for the production of sterilizable water or air quenched blown films which have the following properties: a) a haze according to ASTM D 1003-92 for a 50 pm film of less than 8% before and after steam sterilization at 12rc for 30 minutes and b) 20° Gloss according to DIN 67 530 for a 50 pm film of at least 55% be¬fore steam sterilization at 12rC for 30 minutes and of at least 60% af¬ter steam sterilizatton at 121 'C for 30 minutes. Surprisingly these films combine high stiffness (tensile modulus) and ex¬cellent optical parameters, which are even improved after sterilization. The use of these propylene terpolymer compositions for the production of sterilizable blown films, preferably air quenched blown films, having the above cited desirable advantages is not disclced in the state of the art. According to further embodiments of the present invention ethylene is preferably present at levels less than 1.0 wt%, more preferably less than 0.5 wt% and most preferably betv««en 0.1 and 0.4 wt%. According to further embodiments of the present invention butene is pref¬erably present at levels of more than 5 wt%, more preferably more than 6 wt% and most preferably between 7 and 12 wt%. Additionally the composition can contain other polymers like HOPE, LDPE, LLDPE, VLDPE, ULDPE or other polymers or copolymers containing eth¬ylene and another a-olefin. The polymer composition further contains 0.001 to 1.0 % wt of one or more alpha-nucleating agents. Preferably 0.005 to 0.5 wt%, more prefera¬bly 0.01 to 0.3 wt% of one or more alpha-nucleating agents are added. Smaller amounts of alpha-nucleating agents than 0.001 wt% usually do not give the desired level of effect, while with larger amounts than 1 wt%, although giving the desired effect, the produced blown films are becoming too expensive because of the high priced nucleating agents. The alpha-nucleating agent which may be used for the polymer composi¬tion of the invention include organic alpha-nucleating agents selected from the gnsup of phosphorous based nucleating agents like phosphoric acid esters metal salts represented by fomnula I wherein R1 is oxygen, sulphur or a hydrocarbon group of 1 to 10 carbon atoms; each of R2 and R3 Is hydrogen or a hydrocarbon or a hydrocarbon group of 1 to 10 carbon atoms; R2 and R3 may be the same or different from each other, two of R2, two of R3, or R2 and R3 may be bonded to¬ gether to form a ring, M Is a monovalent to trivalent metal atom; n Is an In¬ teger from 1 to 3 and m Is either 0 or 1, provided that n > m. Prefen-ed examples of the alpha nucleating agents represented by the above fomnula Include sodium-2,2'-methylene-bls(4,6-dl-t-butyl- phenyl)phosphate, sodlum-2,2'-ethylidene-bls(4,6-dl-t-butylphenyl)-phos- phate, llthlum-2,2'-methylene-bls(4,6-di-t-butylphenyl)phosphate, llthium- 2,2'-ethylldene-bis(4,6-dl-t-butylphenyl)pho8phate, sodium-2,2'-ethyli- dene-bis(4-l-propyl-6-t-butylphenyl)phosphate, lifriium-2,2'-methylene- bls(4-methyl-6-t-butylphenyl)phosphate, lithlum-2,2'-methylene-bis(4-ethyl- 6-t-butylphenyl)ph08phate, calclum-bls[2,2'-thtobis(4-methyl-6-t-bytyl- phenyl)-phosphate], calclum-bis[2,2'-tiiiobis{4-ethyl-6-t-butylphenyl)- phosphate], calcium-bis[2,2'-thiobi8(4,6-di-t-butylphenyl)pho8phate], mag- nesium-bls[2,2'-thiobis(4,6-di-t-butylphenyl)ph08phate], magnesium- bis[2,2'-thiobls(4-t-octylphenyl)pho8phate], sodlum-2,2'-butylidene-bis(4,6- dimethylphenyl)phosphate, sodium-2,2'-butylidene-bis(4,6-cli-t-butyl- phenyl)-phosphate, sodium-2,2'-t-octylmethylene-bis{4,6-climethyl-phenyl)-phosphate, sodium-2,2'-t-octylmethylene-bis(4,6-cli-t-butylphenyl)-phos-phate, calcium-bis[2,2 '-methylene-bis(4,6-di-t-butylphenyl )-phosphate], magnesium-bis[2,2 '-methylene-bis(4,6-di-t-butylphenyl)-phosphate], bar-ium-bis[2,2'-methylene-bis(4,6-di-t-butylphenyl>-phosphate], sodium-2,2'-methylene-bis(4-methyl-6-t-butylphenyl)-phosphate, sodium-2,2 'nnethy-lene-bis(4-ethyl-6-t-butylphenyl)phosphate, sodium(4,4'-dimethyl-5,6'-di-t-butyl-2,2'-blphenyl)phosphate, calcium-bis-[(4,4'-dimethyl-6,6'-di-t-butyl-2,2'-biphenyl)phosphate], sodium-2,2'-ethyli-dene-bis(4-m-butyl-6-t-butyl-phenyl)phosphate, sodiunn-2,2'-methylene-bis-(4,6-di-methylphenyl)-phos-phate, sodium-2,2 '-methylene-bis(4,6-di-t-ethyl-phenyl)phosphate, potas-sium-2,2'-ethylidene-bis(4,6-di-t-butylphenyl)-phosphate, calcium-bis[2,2'-ethylidene-bis(4,6-di-t-butylphenyl)-phosphate], magnesium-bis[2,2'-ethyli-dene-bis(4,6-di-t-butylphenyl)-phosphatel, barium-bis[2,2'-ethylidene-bis-(4,6-di-t-butylphenyl)-phosphate], aluminium-hydroxy-bisI2,2'-methylene-bis(4,6-di-t-butyl-phenyl)phosphate], aluminium-tris[2,2'-ethylidene-bis(4,6-di-t-butyl phenyl )-phosphate]. A second group of phosphorous based nucleating agents includes for ex¬ample aluminium-hydroxyl-bis[2,4,8,10-tetrakis(1,1 -dimethylethyl)-6-hydro-xy-12H-dibenzo-[d,g]-dioxa-phoshocin-6-oxidato] and blends with Li-myrlstate or Li-stearate. Of the phosphorous based nucleating agents sodium-2,2'-methylene-bis(4,6-dl-t-t)utylphenyl)phosphate or aluminlum-hydroxy-bis[2,2'-methy-lene-bis(4,6-di-t-butyl-phenyl)-phosphate] or aluminium-hydroxyl-bis-[2,4,8,10-tetrakis(1,1-dimethylethyl)-6-hydroxy-12H-dibenzo-[d,g]-dtoxa-phoshocin-6-oxidato] or blends with Li-myristate or Li-stearate are espe¬cially preferred. Further suitable alpha-nucleating agents are polymeric nucleating agents selected from the group consisting of vinylcycloalkane polynners and vi-nylalkane polymers. Nucleation with these polymeric nucleating agents is either accomplished by a special reactor technique, where the catalyst is prepolymerised with monomers like e.g. vinylcyclohexane (VCH), or by blending the propylene polymer with the vinyl(cyclo)alkane polymer. These methods are described in greater detail in e.g. EP 0 316 187 A2 and WO 99/24479. Suitable alpha-nucleating agents for the propylene-based composition of the invention are in addition nucleating agents, as described for example in Macromolecules 2005,38, 3688-3695. Nucleating agents such as ADK NA-11 (Methylen-bis(4,6-di-t-butylphenyl)phosphate sodium salt) and ADK NA-21 (aluminium hydroxyl-bis[2,4,8,10-tetrakis(1,1-dimethylethyl)-6-hydroxy-12H-dibenzo-[d,g]-dioxa-phoshocin-6-oxidato]) are commercially available from Asahi Denka Kokai and are preferably added to the propylene-based composition of the in¬vention. Among all alpha nucleating agents mentioned above aluminium hydroxyl-bis[2,4,8,10-tetrakls(1,1 -dimethylethyl)-6-hydroxy-12H-dibenzo-[d,g]-dk)xa-phoshocin-6-oxidato] based nucleating agents like ADK NA-21, NA-21 E, NA-21 F. etc., sodium-2,2'-methylene-bis(4,6-di-t-butylphenyl)pho8phate (ADK NA-11), aluminium-hydroxy-bis[2,2'-methyl©ne-bis(4,6-di-t-butyl-phenyl)-phosphate] and polymeric nucleating agents selected from the group consisting of vinylcycloalkane polymers and vinylalkane polymers are particularly preferred. Most particularly prefenned nucleating agents are ADK NA-21 and ADK NA-11. The propylene compositions whicli are used for tlie films according to the invention may contain various additives, which are generally used in pro¬pylene compositions, such as stabilizers, antioxidants, acid neutralizing agents, lubricants, ultraviolet absorbers, antiblocking agents, antistatic agents, antlfogging agents, etc., provided they do not adversely affect the desired properties of the composition. Preferred antioxidants are stericaily hindered phenolic antioxidants, e.g.2- t-butyl-4,6-dimethylphenol, 2,6-di-t-butyl-4-methyl-phenol, 2,6-di-t-butyl-4- isoamylphenol, 2,6-di-t-butyl-4-ethylphenol, 2-t-butyl-4,6-diisopropylphenyl, 2,6-d icydopentyl-4-methylphenol, 2,6-di-t-butyl-4-methoxymethylphenol, 2-t-butyl-4,6-dioctadecylphenol, 2,5-di-t-butylhydroquinone, 2,6-di-t-butyl- 4,4-hexadecyloxyphenol, 2,2'-methylene-bis(6-t-butyl-4-methylphenol), 4,4'-thio-bis-(6-t-butyl-2-methylphenol), 2,2'-thiodiethylenebis-(3,5-di-tert.- butyl-4-hydroxyphenyl)-propionate, octadecyl-3-(3,5-di-t-butyl-4-hroxy- phenyl)propionate, 1.3,5-trimethyl-2,4,6-tris{3',5'-di-t-butyl-4-hydroxy- benzyl)benzene, 2,5,7,8-Tetramethyl-2(4',8',12'-trimethyltrldecyl)- chroman-6-ol and pentaerythrityl-tetraki8-3-(3,5-di-t-butyl-4-hydroxy-phenyl)propionate. Antioxidants which are commercially available are for example from Ciba Speciality Chemicals Irganox 1010, Irganox 1330, Inganox 1076, Irganox 1035, lrganoxE201, etc.. Prefened stabilizers are phosphite based stabilizers, e.g. tris-(2,4-di-t-butylphenyl)-phosphite), Bls(2,4-dl-f-butylphenyl)-pentaerythrityl-di-phos-phite, Bls(2,4-dicumyl-phenyl)pentaerythrltol diphosphite, etc.. Commercially available stabilizers are for example from Clba Speciality Chemicals Irgafos 168, Irgafos 126, etc. or from Dover Chemical Corpora¬tion Doverphos S-9228 CT, etc.. The acid neutralizing agents and/or lubricants are for example carboxylic acid salts, where the metal is selected from the 1' or 2"' group of the peri¬odic table or from transition metals like zinc. Preferred carboxylates are Li-stearate, K-stearate, Li-myristate, Na-myristate, K-myristate, Ca-stearate, Mg-stearate, Ca-12-hydroxy stearate, Mg-12-hydroxy stearate, Ca-myristate, Ca-palmitate, Ca-laurate, Mg-myristate, Mg-palmltate, Mg-laurate and Zn-stearate. Also zeolite structures (hydrotalcite, both natiral and synthetic), magne¬sium oxide or zinc oxide can be used. Preferably a synthetic hydrotalcite (SHT), more preferably Mg4,5Al2(OH) i3(C03) S.SHaO is added. Further it is particularly preferred to use the above polymer compositions for the production of sterilizable blown films, preferably air quenched blown films with a haze according to ASTM D 1003-92 for a 50 pm film of less than 8%, preferably of less than 7, more preferably of less than 6 and most preferably of less than 5 before and after steam sterillzatton at 121°C for 30 minutes. In addition to the above described characteristics, it Is preferred to use the above polymer compositions for the production of sterilizable blown films, preferably air quenched btown films with a 20" gloss according to DIN 67 530 for a 50 Mm film of at least 55%, preferably of at least 58% before ster¬ilization and of at least 60%, preferably of at least 65%, more preferably of at least 70 %, after steam sterilization at 12rc for 30 minutes. The blown films produced from polymer compositions which are used ac¬cording to the present invention have a S.I.T (Seal Initiatton Temperature) of 5130 "C, preferably of S126 "C for a 50 [tm blown film. According to a further embodiment the blown films have the following property: a tensile modulus (md) according ISO 527 of at least 1000 MPa for a 50 \|jm blown film. It is particularly preferred to use the above polymer composition for the production of blown films with a tensile modulus (md) of above 1150 MPa and more preferably above 1200 MPa. According to the invention it Is advantageous to use a polymer composi¬tion comprised of a propylene/butene terpolymer which has a proportion of polymer soluble in cold xylene at 23'C of no more than 5%, preferably of no more than 4.5% and more preferably of no more than 4.0%. The films produced from polymer compositions containing these terpoly-mers meet the solubles requirements which are necessary for applications in food packaging. The films according to the present inventton have a preferred thickness of from 5 to 1500 \in\, more preferably to 1000 Mm and most preferably to 200 pm. The films which are obtainable according to the present invention are ad¬vantageously used for the production of sterillzable films. A further aspect of the inventkn relates to the use of the polymer composi¬tion of the invention for multilayer blown films, where at least one layer is comprised of a propylene blown film according to the inventton. Description of Production of Propylene/Butene Terpoiymer The particular type of polymerization process utilized is not critical to the operation of the present invention and the polymerization processes now regarded as conventional are suitable in the process of the invention. The polymerization process for the production of the polymers according to the invention may be a continuous process or a batch process utilizing known methods. The polymer composition of the invention may be produced by single- or multistage process polymerization of propylene, 1-butane and ethylene such as bulk polymerization, gas phase polymerization, sluny polymeriza¬tion, solution polymerization or combinations thereof. Those processes are well known to one skilled in the art. A preferred process is a combination of bulk slurry loop reactor(s) and gas phase reactor(s). The polymer composition of the inventton can be made either in loop reactors or in a combination of loop and gas phase reactors. One skilled in the art is aware of the various possibilities to produce pro¬pylene CO- and terpolymers and will simply find out a suitable procedure to produce suitable polymers which are used in the present invention. The process is preferably carried out in the presence of a stereospecific catalyst system. All catalysts suitable for the polymerization of propylene with butene and ethylene such as Ziegler Natta catalysts and single-site catalysts, including metallocenes and non-metallocenes, can be used. Any metallocene catalyst capable of catalyzing the fonnation of a propyl-ene/butene co- or terpoiymer can also be used as single-site catalyst. A suitable metallocene catalyst comprises a metallocene/activator reactton product impregnated In a porous support at maximum internal pore vol¬ume. The catalyst complex comprises a ligand which is typically bridged. and a transition metal of group IVa...Vla, and an organoalunninium cam-pound. The catalytic metal compound is typically a metal halide. In a preferred embodiment of the process, the process as discussed above is carried out using a Ziegler-Natta catalyst, in particular a high yield Ziegler-Natta catalyst (so called fourth and fifth generation type to differen¬tiate from low yield, so called second generation Ziegler-Natta catalysts). A suitable Ziegler-Natta catalyst to be employed in accordance with the pre¬sent invention comprises a catalyst componoit (optionally a vinyl-modified catalyst component), a co-catalyst component and at least one electron donor (internal and/or external electron donor, preferably at least one ex¬ternal donor). Preferably, the catalyst component is a TI-Mg-based catalyst component and typically the co-catalyst is an Al-alkyI based compound. Such catalyst systems are described, for example, US 5,234,879, WO 92/19653, WO 92/19653, WO 99/33843, WO 02/60962, etc., and such systems comprising vinyl-modified catalyst components in WO 99/24478 and WO 99/24479. An essential component in those catalysts are solid catalyst components comprising a titanium compound having at least one titanium-halogen bond, an intemal electron donor compound and a magnesium halide in ac¬tive form as a easier for both the titanium component and the donor com¬pound. The catalysts can contain - as intemal electron donor - com¬pounds selected from ethers, ketones, lactones, compounds containing N, P and/or S atoms and esters of mono and dicarboxylic acids. A further essential component of the catalyst is an organoaluminium com¬pound, such as an alkylalumlnium compound. Additionally, an external electron donor is generally used. Preferred exter¬nal donors are the known sllane-based donors, preferably dicydopentyl dimethoxy silane or cyclohexyl methyldimethoxy silane. To obtain the propylene/butene terpolymer, it is preferred to use a polym¬erization process based on a combination of one or more bulk polymeriza¬tion reactor(s) and one or more gas phase reactor(s). Preferably the process comprises also a prepolymerizatton with the cho¬sen catalyst system. Preferably the propylene polymer composition of the invention is produced in loop reactors or in a combination of loop and gas phase reactor. Those processes are well known to one skilled in the art. A slurry reactor designates any reactor, such as a continuous or simple batch stin-ed tank reactor or loop reactor, operating in bulk or slurry and in which the polymer forms in particulate fomn. "Bulk" means a polymeriza¬tion in reaction medium that comprises at least 60 wt-% monomer. Accord¬ing to a prefen-ed embodiment the slun7 reactor comprises a bulk loop re¬actor. It is also possible to use several reactors of each type, e.g. one loop reac¬tor and two or three gas phase reactors or two loops and one gas phase reactor, in series. "Gas phase reactor" means any mechanically mixed or flukl bed reactor. Preferably the gas phase reactor comprises a mechanically agitated fluid bed reactor with gas velocities of at least 0.2 m/sec. The particularly prefen-ed embodiment of the invention comprises carrying out the polymerization in a process comprising loop and gas phase reac¬tors. A preferred multistage process is the above>kJentified slurry-gas phase process, such as developed by Borealis and known as the Borstal tech¬nology. In this respect, reference Is made to the European applications EP 0 887 379 A1 and EP 517 868 A1, incorporated herein by reference. With respect to the above-mentioned preferred slurry-gas phase process, the following generalinformation can be provided with respect to the proc¬ess conditions. Temperature of from 40'C to HO'C, preferably between BOX and lOCC, in particular between ZO'C and 90°C, with a pressure in the range of from 20 to 80 bar, preferably 30 to 60 bar, with the option of adding hydrogen in order to control the molecular weight in a manner known per se. The reaction product of the slunv polymerization, which preferably is car¬ried out in a loop reactor, is then transferred to the subsequent gas phase reactor, wherein the temperature preferably is within the range of from SO'C to 130°C, more preferably 60'C to 100°C, at a pressure in the range of from 5 to 50 bar, preferably 15 to 35 bar, again with the option of adding hydrogen in order to control the molecular weight, with the option of add¬ing hydrogen in order to control the molecular weight in a manner known per se. The residence time can vary in the reactor zones identified above. In one embodiment, the residence time in the sluny reactor, for example a loop reactor, is in the range of from 0.5 to 5 hours, for example 0.5 to 2 hours, while the residence time in the gas phase reactor generally will be from 1 to 8 hours. If desired, the polymerization may be effected In a known manner under supercritical conditions in the slun7, preferably loop reactor, and/or as a condensed nnxje in the gas phase reactor. The polymerizatk>n process enable highly feasible means for producing and further tailoring the propylene polymer composition within the inven¬tion. E.g. the properties of the polymer compositton can be adjusted or controlled in a known manner e.g. with one or more of the following proc- ess parameters: temperature, hydrogen feed, comonomer feed, propylene feed e.g. in the gas phase reactor, catalyst, the type and amount of an ex¬ternal donor (if used), split between components. The precise control of the polymerization conditions and reaction parameters is within the skill of the art. After polymerization in the first and the optional second reactor is finished, through known after-treatment steps including the steps of deactivating the catalyst, removing the catalyst residue and drying, the aimed co- or ter-polymer can be produced. The resulting polymer particles may be pelletized in a conventional com¬pounding extruder with various additives, which are generally used in the thermoplastic polymer compositions, such as stabilizers, antbxidants, acid neutralizing agents, antistatic agents, etc., fovlded they do not adversely affect the desired properties of the composition. Further the polymer material contains at least one a-nucleating agent which is derived from phosphate-based and/or polymeric nucleating agents, which may be added directly in the compounding step or during the processing of films in the way of an external master batch. Applications The propylene/butene terpolymer can be used for all extrusion technolo¬gies. Preferably they are used for technologies for extruded bi- and monoaxially - and non oriented blown films in a film thickness range betwn 5 to 1500 Mm. More preferably they are used for the manufacturing of stiff non-oriented and bi- and monoaxiaily oriented films between 5 and 1000 pm with the blown film technology. Most preferably they are used for the manufacturing of non-oriented blown films in the thicl Description of film production by biown Aim ieclinology The polymer compositions of the invention are capable of being manufac¬tured into water or air quench blown films; preferably air quenched blown films, on typical polyethylene blown film productton equipment. Biown film tectinoiogy witli water contact cooiing ring In this technology for producing polymer films, the molten polymer is ex¬truded through a tubular die fed by a (usually single-screw) extruder and blown up to a tube. The film tube has contact on the exterior side to a wa¬ter cooling ring and is cooled down quickly. The already solidified film tube is flattened afterwards by take-up rolls and taken off to a winder. For a more detailed description see "Polypropylene Handbook", edited by Edward P. Moore, Jr., Hanser Publishers, 1996. Biown fiim teciinoiogy witli air quench In this manufacturing step for air quenched blown films the film is made using at least a 1.5 blow up ratio, preferably at least a 2.0 blow up ratio, more preferably at least a 2.5 blow up ratto. The technique of air quenched blown film extrusion is well known for the productk>n of thin plastic films. In an advantageous process, plastks, such as low, linear low and high doisity polyethylene are extruded through a circular die to form a film. Air is introduced through the center of the die to maintain the film in the form of a bubble which increases the diameter of the film about 1.5 to 6 fold, after which the bubble is collapsed onto rolers. There are a number of variations of such a process within the skill in the art. Most references to blowing polyolefin films disclose processes used for polyethylene, but these are applicable to the polymer compositions of the invention within few modifications within the skill In the art without un¬due experimentation. For instance cooling is often advantageously modified because the art recognizes that polypropylene cools and crystallizes at a rate different from that of polyethylene. Therefore, adjustments to the cooling parameters often produce a more stable bubble at desired output rates. In the fomnation of blown films, the melted polymer composition (melt) en¬ters a ring-shaped die either through the bottom or sWe thereof. The melt is forced through spiral grooves around the surface of a mandrel insWe the die and extruded through the die opening as a thick-walled tube. The tube is expanded into a bubble of desired diameter and correspondingly de¬creased thickness as previously described. Films produced from the polymer compositions according to the Inventton have of very good optical properties, high stiffness, good sealing proper¬ties and good lay flat. In addition they are steam sterilizable at 12rc for 30 min. Refen-ing to the sterilization process, the films according to the invention have higher improved optical properties after stem sterilization compared to films from propylene ethylene random copolymers or terpolymers ac¬cording to the stete of the art, where these properties deteriorate after steam sterilizatton. Therefore these films can be advantageously used in the pharmaceutical area and in food packaging TEST METHODS Polymer properties The melt flow rates were measured with a load of 2.16 kg and at 230°C. The melt flow rate (MFR) is that quantity of polymer in grams which the test apparatus standardized to ISO 1133 extrudes within 10 minutes at a temperature of aSCC under a weight of 2.16 kg. Comonomer contents (ethylene and butene) were measured with Fourier transform infrared spectroscopy (FTIR) calibrated with C-NMR. Xylene solubles were detemnined at 25 °C according to ISO 6427. Blown Film properties Gloss and haze as measures for the optical appearance of the blown film were determined according to DIN 67 530 (gloss) and ASTM D 1003-92 (haze), both on blown film samples with a thickness of 50 pm. The tensile modulus as a measure for the stiffness of the blown films was detemnined according to ISO 527 on blown film samples with a thickness of 50 Mm. Elmendorf was determined according to ISO 6383/2 on blown film sam¬ples with a thickness of 50 pm. Heat sealing initiating temperature (SIT) 1. General The method determines the sealing temperature range of polypropylene blown films. The sealing temperature range is the temperature range, in which the films can be sealed according to the conditions given below. The lower limit (heat sealing initiation temperature (SIT)) is the sealing temperature at which a sealing strength of > 5 N is achieved. The upper limit (sealing end temperature (SET)) is reached, when the films start to crimp. 2. Sample geometry and sample preparation The samples are taken in longitudinal direction of extrusion. The sample size is 25,4 mm x 250 mm, the film thicl 3. Sealing Device For sealing the laboratory sealing device DTC Hot tack tester is used. Prior to the test, the device is checked for the parallel position of the seal¬ing jaws. 4. Sealing parameters The sealing parameters are set to: Sealing force: 0,66 N/mm2 Sealing time: 1 s Sealing jaws: 50 x 5 mm. smooth + Teflon film Heating: both jaws, precision+/-1'C Start temperature: 100 "C Take off speed: 42 mm/sec 5. Sealing procedure - Stripes are folded to 125 x 25,4 mm and put (between the sealing jaws. - The jaws are heated to sealing temperature - Immediately after sealing, the sample is taken out of the device - For each temperati/re, 5 samples are sealed 6. Testing To determine the initial strength, 5 samples are seated at one temperature setting and with DTC Hot tack tester tested for the sealing strength. If the mean value of 5 tests - as described atx)ve - is > 5N, then the heat sealing temperature is reached. If not, the sealing temperature is in¬creased by 2 "C and the test is repeated. After having reached the SIT, the sealing temperature is further increased in steps of 2 °C until the films start to crimp. After a delay time of 30 sec after the sealing tiie film is stretched with a take-off speed of 42 mm/sec to measure the sealing strength in Newton. The SIT is the temperature where the sealing strength of > 5 N is reached. EXAMPLES Example 1 finventionh Pro(;iigti9n 9lH pr9PYl?n$/gthYlgn$/1-\|?Mt9n9 tgnglvmr A process comprising a prspolymerizatton step and a main polymerization step was used to produce the propylene terpolymer. Temperatures, pressures, catalyst-, monomer- and hydrogen feed in the separate polymerization steps as well as the polymer concentration in the main reactor are kept constant. The molar mass of the terpolymer is con¬trolled by adding hydrogen gas. The concentration of hydrogen in the mix¬ture of liquid monomers is continuously measured by gas chromatography. The relevant processing parameters and analytical results of the resulting polymer are listed in tables 1 and 2. The catalyst used was a highly active, stereospeclfic transesterified MgClr supported Ziegler-Natta catalyst. The catalyst is contacted with triethylaluminium (TEAL) as a cocatalyst and cyclohexyl methyldimethoxy silane (donor C) as an external donor to yield a catalyst system and then prepolymerized in a known manner in the presence of propylene in a small reactor (equipped with stin'er and cooling system). The prepolymer (product A) is continuously removed from the prepoly-merization unit and passed into the main reactor system (equipped with stinner and cooling system), where under excess of a liqukj mixture of the monomers propylene and 1-butene, under addition of ethylene, the final terpolymer (B) is fomrred. Further a mixture of monomers (propylene/1- butene/ethylene) and hydrogen (for molar mass control) are fed into the main reactor continuously. The polymer concentration is Icept constant. A part of the reactor content (polymer-Zmonomer excess) is continuously removed from the reactor into a degassing unit to separate the fonned ter-polymer (B) from unreacted monomer mixture by evaporatton. The separated terpolymer (B) was subjected to a steam treatment, to re¬move the unreacted monomers and volatile substances, and then dried. The polymer powder was mixed with 0,18 wt% nucleating agent ADK NA-21 from Asahi Denlta Kokai. Further the following additives were added: 300 ppm Mg4,5Al2(OH) 13(003) 3,5H20 as acid neutralizing agent, 500 ppm Irganox 1010 (Ciba Speciality Ohemicals) as antioxidant and 500 ppm Irgafos 168 (Oiba Speciality Chemicals) as stabilizer This mixture Is then pelletized in a conventional compounding line. The polymer properties can be seen from table 3. PrQ0Mpti9P9ffilfn? The palletized materials have been used for film blowing at a commercial blown-film line Alpine 35. Blown films were produced on a single screw extruder with a barrel diame¬ter of 70 mm and a round-section die of 200 mm with 1 mm die gap in combinaticMi with a monolip cooling ring and internal bubble cooling (IBC). Melt temperature was 210 "0 in the die; the temperature of the cooling air was kept at 15 'C and the blow up ratto (BUR) 3:1. A film thickness of 50 pm was adjusted through the ratio between extruder output, take off speed and BUR. The film properties can be seen from table 3. Comparative example 2 and 3: As comparative examples 2 and 3 commercially available random copoly¬mer grades (Borclear™ RB709CF and Borclear™RB707CF) were used. Table 1: Parameter unit Example 1 TEAI/DonorD [g/g] 5 TEAI/Ti [g/g] 0,82 TEAI/Ti [mol/mol] 1,36 Table 2: Parameter unit Example 1 Prepolymerizatlon reactor / Liquid monomer pliase Feed catalyst compound [g/h] ~ 1,2 Pressure [bar] 34 Temperature ["C] 20 Mean residence time [min] 10 Main reactor/ Liquid monomer phase Pressure [bar] 34 Temperature ["C] 64 Mean residence time catalyst [min] ~90 Polymer concentration in reactor [g/l] -0,52 Feed propylene/1-buten mixture) [kg/h] 127-133 1 -Butene content in monomer feed [Vol%] -20,5 Ethylene feed [kg/h] 0,5 H2-concentration in monomer feed [ppm] 410-420 Polymer productton rate (product B) [kg/h] 27-43 ) total feed of liquid monomer mixture into the reactor system Table 3 Examples Polymer Properties 12 3 (RB709CF) (RB707CF) Ethylene cone. [wt%] 0,3 5,7 4,5 1-Buteneconc. [wt%] 6,9 Nucleator NA-21 [ppm] 1800 1800 1800 Xylene Solubles [wt%] 3,5 7 7 Melt Temperature ['C] 143 135 144 MFR g/IOmin 1,7 1,5 1,5 cone concentration Table 4; Film Properties Examples 1 2 3 (RB709CF) (RB707CF) Hazeb.s) [%] 4,5 3,5 7.1 Hazea.s) [%] 4,8 9,4 8,3 Gloss 20° outside b.s) [%] 59,1 60,1 43,7 Gloss 20° outside a.s) [%] 71,4 13,6 37,2 Gloss 20° inside b.s) [%] 61,0 61,6 44.1 Gloss 20° inside a.s) [%] 72,3 20,5 35.9 ) b.s before sterilization *}a.s after sterilization steam sterilization was perfomned at 121 °C for 30 min Tensile modulus md [MPa] 1250 739 1127 Tensile modulus td [MPa] 1219 718 1127 S.I.T. rC] 122 112 124 Sealing temperature [°C] 115 105 120 These examples show that the values of the optical properties haze and gloss of example 1 improve after the sterilization, wrhereas for examples 2 and 3 they deteriorate. Furthermore the film from example 1 shows a much higher tensile modulus compared to example 2 and a higher tensile modulus compared to example 3. Patent claims 1. Use of a polymer composition comprised of (i) a propylene/butene ter- poiymer which is comprised of 86.0 - 98.0 wt% of propylene 2.0-12.0 wt% of butene and 0.1 - to less than 1.0 wt% of ethylene and (ii) 0.001 - 1.0 wt% of one or more phosphorous based and/or poly¬meric Q-nucleating agents for the production of sterilizable water or air quenched blown films which have the fdiowing properties: a) a haze according to ASTM D 1003-92 for a 50 pm film of less than 8% before and after steam sterilization at 121'C for 30 minutes and b) 20° Gloss according to DIN 67 530 for a 50 pm film of at least 55% before steam sterilization at 121'C for 30 minutes and of at least 60% after steam sterilization at 12rC for 30 minutes. 2. Use according to claim 1, characterized in that the films exhibit the fol¬ lowing property: a tensile modulus (md) according ISO 527 of at least 1000 MPa for a 50 pm film. 3. Use according to any of claims 1 or 2, characterized in that the Q-nucleating agent comprises one or more phosphorous-based alpha-nucleating agents and/or polymeric alpha-nucleating agents selected from the group consisting of vinylcycloalkane polymers and vinylalkane polymers. 4. Use according to claims 3, characterized in ttiat tiie a-nucleating agent is selected from the group of aluminium hydroxyl-bisI2,4,8,10-tetrakis(1,1 -dimethylethyl)-6-hydroxy-12H-dlbenzo[d,g]dioxaphoshocin- 6-oxidato] based nucleating agents, sodium-2,2'-methylene-bis(4,6-di-t-butylphenyl)phosphate, aluminium-hydroxy-bis[2,2'-methylene-bis(4,6-di-t-butylphenyl)-phosphate] and from polymeric nucleating agents se¬lected from the group consisting of vinylcycloalkane polymers and vl-nylalkane polymers. 5. Use according to any of claims 1 to 4, characterized in that said polymer has a portion of polymer soluble in cold xylene (25'C) of no more than 5%. 6. Use according to any of claims 1 to 5, characterized in that the films have a thickness of from 5 to 1500 \|jm. 7. Use according to any of claims 1 to 6 for the production of sterilizable air quenched blown films. 8. Use according to any of claims 1 to 7 for the production of sterilizable films for the pharmaceutical area and for food packaging. 9. Use according to any one of claims 1 to 8 for multilayer blown films, where at least one layer is comprised of a propylene blown film accord¬ing to claim 1. 10. Blown films obtained by a use according to any one of claims 1 to 9. 11. Blown film, wherein the blown film comprises a polymer composition comprised of (i) a propylene/butene terpolymer which is comprised of 86.0 - 98.0 wt% of propylene 2.0 -12.0 wt% of butene and 0.1 - to less than 1.0 wt% of ethylene and (ii) 0.001 - 1.0 wt% of one or more phosphorous based and/or polynneric a-nucleating agents which film has the following properties: a) a haze according to ASTM D 1003-92 for a 50 jjm film of less than 8% before and after steam sterilization at 121'C for 30 minutes and b) 20˚ Gloss according to DIN 67 530 for a 50 µm film of at least 55% before steam sterilization at 12rc for 30 minutes and of at least 60% after steam sterlization at 12 rc for 30 minutes.

Full Text

Use of nucleated propylene butene terpolymers for the production of sterilizable blown films
The present invention relates to tiie use of nucleated propyl-ene/butene/ethylene terpolymers for the production of sterilizable blown films.
Blown films produced from these polymers are sterilizable and have excel¬lent optical properties as well as mechanical properties.
Technological background
Poiyolefins have gained wide acceptance and usage in numerous com¬mercial applications because of their relatively low costs and desirable properties.
Such commercial applications include plastic films such as cast films, blown films, mono- and biaxially oriented films and coating. These plastic films can for example be used for various flexible and rigid packaging, e.g. for food, medicals, flowers, etc.
In a continuously increasing part of this marl Polypropylene for films is today almost exclusively used tor cast films. In the cast film process a very quick cooling of the melt is achieved with a chill roll, in order to utilize the potentially good optical and mechanical proF>erties of polypropylene for film applications. Until recently, polypropylene could be used in the blown film process only when it was possible to use water contact cooling in order to achieve the same quick cooling as in the cast fiim process.

In a conventional blown film process using air cooling, the polymer melt and the films produced from it are only slowly cooled. This results in insuf¬ficient optical and mechanical parameters because the slow cooling proc¬ess causes an uncontrolled growth of the crystal- and spherulitic structure. Propylene blown films produced with air cooling are both cloudy and brit¬tle.
It has therefore been tried to improve the problem of cloudiness respec¬tively haziness and brittleness of polypropylene blown films by using a combination of propylene random copolymers with either inorganic nucle¬ating agent or sorbitol-based nucleating agents, which resulted in im¬provements of optical and mechanical parameters to a very limited extent. So there was the need to look for further improvements for air quenched blown films from propylene polymers.
In the examples of WO 2005/026240 blown films, comprising a polypro¬pylene composition containing a propylene homopolymer or propene co¬polymer with 4.8 wt% ethylene, the polypropylene copolymer composition containing 0.2 wt% of a clarifier comprising a phosphate-based a-nucleating agent respectively a sorbitol-based a-nudeating agent, are de¬scribed.
In these examples it is shown that the blown film of the propylene ethylene copolymer comprising the phosphate-based a-nucteating agent has better optical properties gloss and haze compared to a blown film of a propylene ethylene copdymer comprising the sorbitol-based a-nucleating agent. The blown film according to example 1 fijrther shows a tensile modulus of about 925 MPa (md) respectively of about 972 MPa (td).
WO 02/44252 discloses the use of polymer compositions comprised of a propylene terpolymer and erucic acid amide and/or oleic acid amide as slip agent for films, lil
a) a dynamic Coefficient of Friction after storage for 3 days at 23 °C of smaller than 0.30 (measured according to DIN 53 375)
b) a blooming behavior, measured in tenns of haze according to ASTM D 1003-92 after storage for 14 days at 40 "C which shows a deterioration of no more than 100 % of the original value which is measured after storage for 4 days at 23 "C.
Further it is described that lamination films produced from these polymer compositions show a smaller loss of optical properties compared to films from propylene butene or propylene ethylene random copolymers after sterilization at 121 "C for 30 minutes.
The tensile modulus of the films produced with cast film technology is be¬tween 385 and 440 MPa.
WO 03/040202 discloses e.g. blown films made from - annongst other polymers -propylene/1-butene copolymers and propylene/ethylene/1-butene terpolymers.
These films comprise at least 50 wt% propylene and at least 5 wt% ethyl¬ene and/or one or more unsaturated comonomer and have a haze value of less than about 10 and a 45° gloss of greater than about 65. In the examples, WO 03/040202 describes a base resin for blending stud¬ies for the production of bAovm films using a commercially available Ziegler-Natta propylene (H110-02Z: a Z-N-mini-random PP containing 0.5 wt% ethylene, nucleated with methylene-bis-(4,6-di-t-butylphenyl) phos¬phate sodium salt, available from The Dow Chemical Company). The re¬sulting blown film disclosed as a comparative example showed less favor¬able properties than the blends comprising special PIE copolymers claimed in WO 03/040202.
It is therefore an object of the present invention to provide improved water or air quenched blown films, preferably air quenched blown films, pro¬duced from propylene butene terpolymers, which are sterilizable and have

improved mechanical properties and excellent optical properties, which are even improved after sterilization.
This object was achieved by using a polymer composition comprised of (i) a propylene/butene terpolymer which is comprised of
86.0 - 98.0 wt% of propylene
2.0-12.0 wt% of 1 -butene and
0.1 - less than 1.0 wt% of ethylene and (ii) O.OOt - 1.0 wt% of one or more phosphorous based and/or polymeric
Q-nucleating agents for the production of sterilizable water or air quenched blown films which have the following properties:
a) a haze according to ASTM D 1003-92 for a 50 pm film of less than 8% before and after steam sterilization at 12rc for 30 minutes and
b) 20° Gloss according to DIN 67 530 for a 50 pm film of at least 55% be¬fore steam sterilization at 12rC for 30 minutes and of at least 60% af¬ter steam sterilizatton at 121 'C for 30 minutes.
Surprisingly these films combine high stiffness (tensile modulus) and ex¬cellent optical parameters, which are even improved after sterilization.
The use of these propylene terpolymer compositions for the production of sterilizable blown films, preferably air quenched blown films, having the above cited desirable advantages is not disclced in the state of the art.
According to further embodiments of the present invention ethylene is preferably present at levels less than 1.0 wt%, more preferably less than 0.5 wt% and most preferably betv««en 0.1 and 0.4 wt%.

According to further embodiments of the present invention butene is pref¬erably present at levels of more than 5 wt%, more preferably more than 6 wt% and most preferably between 7 and 12 wt%.
Additionally the composition can contain other polymers like HOPE, LDPE, LLDPE, VLDPE, ULDPE or other polymers or copolymers containing eth¬ylene and another a-olefin.
The polymer composition further contains 0.001 to 1.0 % wt of one or more alpha-nucleating agents. Preferably 0.005 to 0.5 wt%, more prefera¬bly 0.01 to 0.3 wt% of one or more alpha-nucleating agents are added. Smaller amounts of alpha-nucleating agents than 0.001 wt% usually do not give the desired level of effect, while with larger amounts than 1 wt%, although giving the desired effect, the produced blown films are becoming too expensive because of the high priced nucleating agents.
The alpha-nucleating agent which may be used for the polymer composi¬tion of the invention include organic alpha-nucleating agents selected from the gnsup of phosphorous based nucleating agents like phosphoric acid esters metal salts represented by fomnula I

wherein R1 is oxygen, sulphur or a hydrocarbon group of 1 to 10 carbon
atoms; each of R2 and R3 Is hydrogen or a hydrocarbon or a hydrocarbon
group of 1 to 10 carbon atoms; R2 and R3 may be the same or different
from each other, two of R2, two of R3, or R2 and R3 may be bonded to¬
gether to form a ring, M Is a monovalent to trivalent metal atom; n Is an In¬
teger from 1 to 3 and m Is either 0 or 1, provided that n > m.
Prefen-ed examples of the alpha nucleating agents represented by the
above fomnula Include sodium-2,2'-methylene-bls(4,6-dl-t-butyl-
phenyl)phosphate, sodlum-2,2'-ethylidene-bls(4,6-dl-t-butylphenyl)-phos-
phate, llthlum-2,2'-methylene-bls(4,6-di-t-butylphenyl)phosphate, llthium-
2,2'-ethylldene-bis(4,6-dl-t-butylphenyl)pho8phate, sodium-2,2'-ethyli-
dene-bis(4-l-propyl-6-t-butylphenyl)phosphate, lifriium-2,2'-methylene-
bls(4-methyl-6-t-butylphenyl)phosphate, lithlum-2,2'-methylene-bis(4-ethyl-
6-t-butylphenyl)ph08phate, calclum-bls[2,2'-thtobis(4-methyl-6-t-bytyl-
phenyl)-phosphate], calclum-bis[2,2'-tiiiobis{4-ethyl-6-t-butylphenyl)-
phosphate], calcium-bis[2,2'-thiobi8(4,6-di-t-butylphenyl)pho8phate], mag-
nesium-bls[2,2'-thiobis(4,6-di-t-butylphenyl)ph08phate], magnesium-
bis[2,2'-thiobls(4-t-octylphenyl)pho8phate], sodlum-2,2'-butylidene-bis(4,6-

dimethylphenyl)phosphate, sodium-2,2'-butylidene-bis(4,6-cli-t-butyl-
phenyl)-phosphate, sodium-2,2'-t-octylmethylene-bis{4,6-climethyl-phenyl)-phosphate, sodium-2,2'-t-octylmethylene-bis(4,6-cli-t-butylphenyl)-phos-phate, calcium-bis[2,2 '-methylene-bis(4,6-di-t-butylphenyl )-phosphate], magnesium-bis[2,2 '-methylene-bis(4,6-di-t-butylphenyl)-phosphate], bar-ium-bis[2,2'-methylene-bis(4,6-di-t-butylphenyl>-phosphate], sodium-2,2'-methylene-bis(4-methyl-6-t-butylphenyl)-phosphate, sodium-2,2 'nnethy-lene-bis(4-ethyl-6-t-butylphenyl)phosphate, sodium(4,4'-dimethyl-5,6'-di-t-butyl-2,2'-blphenyl)phosphate, calcium-bis-[(4,4'-dimethyl-6,6'-di-t-butyl-2,2'-biphenyl)phosphate], sodium-2,2'-ethyli-dene-bis(4-m-butyl-6-t-butyl-phenyl)phosphate, sodiunn-2,2'-methylene-bis-(4,6-di-methylphenyl)-phos-phate, sodium-2,2 '-methylene-bis(4,6-di-t-ethyl-phenyl)phosphate, potas-sium-2,2'-ethylidene-bis(4,6-di-t-butylphenyl)-phosphate, calcium-bis[2,2'-ethylidene-bis(4,6-di-t-butylphenyl)-phosphate], magnesium-bis[2,2'-ethyli-dene-bis(4,6-di-t-butylphenyl)-phosphatel, barium-bis[2,2'-ethylidene-bis-(4,6-di-t-butylphenyl)-phosphate], aluminium-hydroxy-bisI2,2'-methylene-bis(4,6-di-t-butyl-phenyl)phosphate], aluminium-tris[2,2'-ethylidene-bis(4,6-di-t-butyl phenyl )-phosphate].
A second group of phosphorous based nucleating agents includes for ex¬ample aluminium-hydroxyl-bis[2,4,8,10-tetrakis(1,1 -dimethylethyl)-6-hydro-xy-12H-dibenzo-[d,g]-dioxa-phoshocin-6-oxidato] and blends with Li-myrlstate or Li-stearate.
Of the phosphorous based nucleating agents sodium-2,2'-methylene-bis(4,6-dl-t-t)utylphenyl)phosphate or aluminlum-hydroxy-bis[2,2'-methy-lene-bis(4,6-di-t-butyl-phenyl)-phosphate] or aluminium-hydroxyl-bis-[2,4,8,10-tetrakis(1,1-dimethylethyl)-6-hydroxy-12H-dibenzo-[d,g]-dtoxa-phoshocin-6-oxidato] or blends with Li-myristate or Li-stearate are espe¬cially preferred.

Further suitable alpha-nucleating agents are polymeric nucleating agents selected from the group consisting of vinylcycloalkane polynners and vi-nylalkane polymers. Nucleation with these polymeric nucleating agents is either accomplished by a special reactor technique, where the catalyst is prepolymerised with monomers like e.g. vinylcyclohexane (VCH), or by blending the propylene polymer with the vinyl(cyclo)alkane polymer. These methods are described in greater detail in e.g. EP 0 316 187 A2 and WO 99/24479.
Suitable alpha-nucleating agents for the propylene-based composition of the invention are in addition nucleating agents, as described for example in Macromolecules 2005,38, 3688-3695.
Nucleating agents such as ADK NA-11 (Methylen-bis(4,6-di-t-butylphenyl)phosphate sodium salt) and ADK NA-21 (aluminium hydroxyl-bis[2,4,8,10-tetrakis(1,1-dimethylethyl)-6-hydroxy-12H-dibenzo-[d,g]-dioxa-phoshocin-6-oxidato]) are commercially available from Asahi Denka Kokai and are preferably added to the propylene-based composition of the in¬vention.
Among all alpha nucleating agents mentioned above aluminium hydroxyl-bis[2,4,8,10-tetrakls(1,1 -dimethylethyl)-6-hydroxy-12H-dibenzo-[d,g]-dk)xa-phoshocin-6-oxidato] based nucleating agents like ADK NA-21, NA-21 E, NA-21 F. etc., sodium-2,2'-methylene-bis(4,6-di-t-butylphenyl)pho8phate (ADK NA-11), aluminium-hydroxy-bis[2,2'-methyl©ne-bis(4,6-di-t-butyl-phenyl)-phosphate] and polymeric nucleating agents selected from the group consisting of vinylcycloalkane polymers and vinylalkane polymers are particularly preferred.
Most particularly prefenned nucleating agents are ADK NA-21 and ADK NA-11.

The propylene compositions whicli are used for tlie films according to the invention may contain various additives, which are generally used in pro¬pylene compositions, such as stabilizers, antioxidants, acid neutralizing agents, lubricants, ultraviolet absorbers, antiblocking agents, antistatic agents, antlfogging agents, etc., provided they do not adversely affect the desired properties of the composition.
Preferred antioxidants are stericaily hindered phenolic antioxidants, e.g.2-
t-butyl-4,6-dimethylphenol, 2,6-di-t-butyl-4-methyl-phenol, 2,6-di-t-butyl-4-
isoamylphenol, 2,6-di-t-butyl-4-ethylphenol, 2-t-butyl-4,6-diisopropylphenyl,
2,6-d icydopentyl-4-methylphenol, 2,6-di-t-butyl-4-methoxymethylphenol,
2-t-butyl-4,6-dioctadecylphenol, 2,5-di-t-butylhydroquinone, 2,6-di-t-butyl-
4,4-hexadecyloxyphenol, 2,2'-methylene-bis(6-t-butyl-4-methylphenol),
4,4'-thio-bis-(6-t-butyl-2-methylphenol), 2,2'-thiodiethylenebis-(3,5-di-tert.-
butyl-4-hydroxyphenyl)-propionate, octadecyl-3-(3,5-di-t-butyl-4-hroxy-
phenyl)propionate, 1.3,5-trimethyl-2,4,6-tris{3',5'-di-t-butyl-4-hydroxy-
benzyl)benzene, 2,5,7,8-Tetramethyl-2(4',8',12'-trimethyltrldecyl)-
chroman-6-ol and pentaerythrityl-tetraki8-3-(3,5-di-t-butyl-4-hydroxy-phenyl)propionate.
Antioxidants which are commercially available are for example from Ciba Speciality Chemicals Irganox 1010, Irganox 1330, Inganox 1076, Irganox 1035, lrganoxE201, etc..
Prefened stabilizers are phosphite based stabilizers, e.g. tris-(2,4-di-t-butylphenyl)-phosphite), Bls(2,4-dl-f-butylphenyl)-pentaerythrityl-di-phos-phite, Bls(2,4-dicumyl-phenyl)pentaerythrltol diphosphite, etc.. Commercially available stabilizers are for example from Clba Speciality Chemicals Irgafos 168, Irgafos 126, etc. or from Dover Chemical Corpora¬tion Doverphos S-9228 CT, etc..

The acid neutralizing agents and/or lubricants are for example carboxylic acid salts, where the metal is selected from the 1*' or 2"*' group of the peri¬odic table or from transition metals like zinc. Preferred carboxylates are Li-stearate, K-stearate, Li-myristate, Na-myristate, K-myristate, Ca-stearate, Mg-stearate, Ca-12-hydroxy stearate, Mg-12-hydroxy stearate, Ca-myristate, Ca-palmitate, Ca-laurate, Mg-myristate, Mg-palmltate, Mg-laurate and Zn-stearate.
Also zeolite structures (hydrotalcite, both natiral and synthetic), magne¬sium oxide or zinc oxide can be used.
Preferably a synthetic hydrotalcite (SHT), more preferably Mg4,5Al2(OH) i3(C03) S.SHaO is added.
Further it is particularly preferred to use the above polymer compositions for the production of sterilizable blown films, preferably air quenched blown films with a haze according to ASTM D 1003-92 for a 50 pm film of less than 8%, preferably of less than 7, more preferably of less than 6 and most preferably of less than 5 before and after steam sterillzatton at 121°C for 30 minutes.
In addition to the above described characteristics, it Is preferred to use the above polymer compositions for the production of sterilizable blown films, preferably air quenched btown films with a 20" gloss according to DIN 67 530 for a 50 Mm film of at least 55%, preferably of at least 58% before ster¬ilization and of at least 60%, preferably of at least 65%, more preferably of at least 70 %, after steam sterilization at 12rc for 30 minutes.
The blown films produced from polymer compositions which are used ac¬cording to the present invention have a S.I.T (Seal Initiatton Temperature) of 5130 "C, preferably of S126 "C for a 50 [tm blown film.

According to a further embodiment the blown films have the following
property:
a tensile modulus (md) according ISO 527 of at least 1000 MPa for a 50
|jm blown film.
It is particularly preferred to use the above polymer composition for the
production of blown films with a tensile modulus (md) of above 1150 MPa
and more preferably above 1200 MPa.
According to the invention it Is advantageous to use a polymer composi¬tion comprised of a propylene/butene terpolymer which has a proportion of polymer soluble in cold xylene at 23*'C of no more than 5%, preferably of no more than 4.5% and more preferably of no more than 4.0%.
The films produced from polymer compositions containing these terpoly-mers meet the solubles requirements which are necessary for applications in food packaging.
The films according to the present inventton have a preferred thickness of from 5 to 1500 \in\, more preferably to 1000 Mm and most preferably to 200 pm.
The films which are obtainable according to the present invention are ad¬vantageously used for the production of sterillzable films.
A further aspect of the inventkn relates to the use of the polymer composi¬tion of the invention for multilayer blown films, where at least one layer is comprised of a propylene blown film according to the inventton.

Description of Production of Propylene/Butene Terpoiymer
The particular type of polymerization process utilized is not critical to the operation of the present invention and the polymerization processes now regarded as conventional are suitable in the process of the invention. The polymerization process for the production of the polymers according to the invention may be a continuous process or a batch process utilizing known methods.
The polymer composition of the invention may be produced by single- or multistage process polymerization of propylene, 1-butane and ethylene such as bulk polymerization, gas phase polymerization, sluny polymeriza¬tion, solution polymerization or combinations thereof. Those processes are well known to one skilled in the art.
A preferred process is a combination of bulk slurry loop reactor(s) and gas phase reactor(s). The polymer composition of the inventton can be made either in loop reactors or in a combination of loop and gas phase reactors. One skilled in the art is aware of the various possibilities to produce pro¬pylene CO- and terpolymers and will simply find out a suitable procedure to produce suitable polymers which are used in the present invention.
The process is preferably carried out in the presence of a stereospecific catalyst system.
All catalysts suitable for the polymerization of propylene with butene and ethylene such as Ziegler Natta catalysts and single-site catalysts, including metallocenes and non-metallocenes, can be used.
Any metallocene catalyst capable of catalyzing the fonnation of a propyl-ene/butene co- or terpoiymer can also be used as single-site catalyst. A suitable metallocene catalyst comprises a metallocene/activator reactton product impregnated In a porous support at maximum internal pore vol¬ume. The catalyst complex comprises a ligand which is typically bridged.

and a transition metal of group IVa...Vla, and an organoalunninium cam-pound. The catalytic metal compound is typically a metal halide.
In a preferred embodiment of the process, the process as discussed above is carried out using a Ziegler-Natta catalyst, in particular a high yield Ziegler-Natta catalyst (so called fourth and fifth generation type to differen¬tiate from low yield, so called second generation Ziegler-Natta catalysts). A suitable Ziegler-Natta catalyst to be employed in accordance with the pre¬sent invention comprises a catalyst componoit (optionally a vinyl-modified catalyst component), a co-catalyst component and at least one electron donor (internal and/or external electron donor, preferably at least one ex¬ternal donor). Preferably, the catalyst component is a TI-Mg-based catalyst component and typically the co-catalyst is an Al-alkyI based compound. Such catalyst systems are described, for example, US 5,234,879, WO 92/19653, WO 92/19653, WO 99/33843, WO 02/60962, etc., and such systems comprising vinyl-modified catalyst components in WO 99/24478 and WO 99/24479.
An essential component in those catalysts are solid catalyst components comprising a titanium compound having at least one titanium-halogen bond, an intemal electron donor compound and a magnesium halide in ac¬tive form as a easier for both the titanium component and the donor com¬pound. The catalysts can contain - as intemal electron donor - com¬pounds selected from ethers, ketones, lactones, compounds containing N, P and/or S atoms and esters of mono and dicarboxylic acids. A further essential component of the catalyst is an organoaluminium com¬pound, such as an alkylalumlnium compound.
Additionally, an external electron donor is generally used. Preferred exter¬nal donors are the known sllane-based donors, preferably dicydopentyl dimethoxy silane or cyclohexyl methyldimethoxy silane.

To obtain the propylene/butene terpolymer, it is preferred to use a polym¬erization process based on a combination of one or more bulk polymeriza¬tion reactor(s) and one or more gas phase reactor(s). Preferably the process comprises also a prepolymerizatton with the cho¬sen catalyst system. Preferably the propylene polymer composition of the invention is produced in loop reactors or in a combination of loop and gas phase reactor. Those processes are well known to one skilled in the art.
A slurry reactor designates any reactor, such as a continuous or simple batch stin-ed tank reactor or loop reactor, operating in bulk or slurry and in which the polymer forms in particulate fomn. "Bulk" means a polymeriza¬tion in reaction medium that comprises at least 60 wt-% monomer. Accord¬ing to a prefen-ed embodiment the slun7 reactor comprises a bulk loop re¬actor.
It is also possible to use several reactors of each type, e.g. one loop reac¬tor and two or three gas phase reactors or two loops and one gas phase reactor, in series.
"Gas phase reactor" means any mechanically mixed or flukl bed reactor. Preferably the gas phase reactor comprises a mechanically agitated fluid bed reactor with gas velocities of at least 0.2 m/sec.
The particularly prefen-ed embodiment of the invention comprises carrying out the polymerization in a process comprising loop and gas phase reac¬tors.
A preferred multistage process is the above>kJentified slurry-gas phase process, such as developed by Borealis and known as the Borstal tech¬nology. In this respect, reference Is made to the European applications EP 0 887 379 A1 and EP 517 868 A1, incorporated herein by reference.

With respect to the above-mentioned preferred slurry-gas phase process, the following generalinformation can be provided with respect to the proc¬ess conditions.
Temperature of from 40'C to HO'C, preferably between BOX and lOCC, in particular between ZO'C and 90°C, with a pressure in the range of from 20 to 80 bar, preferably 30 to 60 bar, with the option of adding hydrogen in order to control the molecular weight in a manner known per se.
The reaction product of the slunv polymerization, which preferably is car¬ried out in a loop reactor, is then transferred to the subsequent gas phase reactor, wherein the temperature preferably is within the range of from SO'C to 130°C, more preferably 60'C to 100°C, at a pressure in the range of from 5 to 50 bar, preferably 15 to 35 bar, again with the option of adding hydrogen in order to control the molecular weight, with the option of add¬ing hydrogen in order to control the molecular weight in a manner known per se.
The residence time can vary in the reactor zones identified above. In one embodiment, the residence time in the sluny reactor, for example a loop reactor, is in the range of from 0.5 to 5 hours, for example 0.5 to 2 hours, while the residence time in the gas phase reactor generally will be from 1 to 8 hours.
If desired, the polymerization may be effected In a known manner under supercritical conditions in the slun7, preferably loop reactor, and/or as a condensed nnxje in the gas phase reactor.
The polymerizatk>n process enable highly feasible means for producing and further tailoring the propylene polymer composition within the inven¬tion. E.g. the properties of the polymer compositton can be adjusted or controlled in a known manner e.g. with one or more of the following proc-

ess parameters: temperature, hydrogen feed, comonomer feed, propylene feed e.g. in the gas phase reactor, catalyst, the type and amount of an ex¬ternal donor (if used), split between components. The precise control of the polymerization conditions and reaction parameters is within the skill of the art.
After polymerization in the first and the optional second reactor is finished, through known after-treatment steps including the steps of deactivating the catalyst, removing the catalyst residue and drying, the aimed co- or ter-polymer can be produced.
The resulting polymer particles may be pelletized in a conventional com¬pounding extruder with various additives, which are generally used in the thermoplastic polymer compositions, such as stabilizers, antbxidants, acid neutralizing agents, antistatic agents, etc., fovlded they do not adversely affect the desired properties of the composition.
Further the polymer material contains at least one a-nucleating agent which is derived from phosphate-based and/or polymeric nucleating agents, which may be added directly in the compounding step or during the processing of films in the way of an external master batch.
Applications
The propylene/butene terpolymer can be used for all extrusion technolo¬gies.
Preferably they are used for technologies for extruded bi- and monoaxially - and non oriented blown films in a film thickness range betwn 5 to 1500 Mm.

More preferably they are used for the manufacturing of stiff non-oriented and bi- and monoaxiaily oriented films between 5 and 1000 pm with the blown film technology.
Most preferably they are used for the manufacturing of non-oriented blown films in the thicl Description of film production by biown Aim ieclinology
The polymer compositions of the invention are capable of being manufac¬tured into water or air quench blown films; preferably air quenched blown films, on typical polyethylene blown film productton equipment.
Biown film tectinoiogy witli water contact cooiing ring
In this technology for producing polymer films, the molten polymer is ex¬truded through a tubular die fed by a (usually single-screw) extruder and blown up to a tube. The film tube has contact on the exterior side to a wa¬ter cooling ring and is cooled down quickly. The already solidified film tube is flattened afterwards by take-up rolls and taken off to a winder.
For a more detailed description see "Polypropylene Handbook", edited by Edward P. Moore, Jr., Hanser Publishers, 1996.
Biown fiim teciinoiogy witli air quench
In this manufacturing step for air quenched blown films the film is made using at least a 1.5 blow up ratio, preferably at least a 2.0 blow up ratio, more preferably at least a 2.5 blow up ratto.
The technique of air quenched blown film extrusion is well known for the productk>n of thin plastic films. In an advantageous process, plastks, such as low, linear low and high doisity polyethylene are extruded through a

circular die to form a film. Air is introduced through the center of the die to maintain the film in the form of a bubble which increases the diameter of the film about 1.5 to 6 fold, after which the bubble is collapsed onto rolers. There are a number of variations of such a process within the skill in the art. Most references to blowing polyolefin films disclose processes used for polyethylene, but these are applicable to the polymer compositions of the invention within few modifications within the skill In the art without un¬due experimentation.
For instance cooling is often advantageously modified because the art recognizes that polypropylene cools and crystallizes at a rate different from that of polyethylene.
Therefore, adjustments to the cooling parameters often produce a more stable bubble at desired output rates.
In the fomnation of blown films, the melted polymer composition (melt) en¬ters a ring-shaped die either through the bottom or sWe thereof. The melt is forced through spiral grooves around the surface of a mandrel insWe the die and extruded through the die opening as a thick-walled tube. The tube is expanded into a bubble of desired diameter and correspondingly de¬creased thickness as previously described.
Films produced from the polymer compositions according to the Inventton have of very good optical properties, high stiffness, good sealing proper¬ties and good lay flat. In addition they are steam sterilizable at 12rc for 30 min.
Refen-ing to the sterilization process, the films according to the invention have higher improved optical properties after stem sterilization compared to films from propylene ethylene random copolymers or terpolymers ac¬cording to the stete of the art, where these properties deteriorate after steam sterilizatton.

Therefore these films can be advantageously used in the pharmaceutical area and in food packaging
TEST METHODS
Polymer properties
The melt flow rates were measured with a load of 2.16 kg and at 230°C. The melt flow rate (MFR) is that quantity of polymer in grams which the test apparatus standardized to ISO 1133 extrudes within 10 minutes at a temperature of aSCC under a weight of 2.16 kg.
Comonomer contents (ethylene and butene) were measured with Fourier transform infrared spectroscopy (FTIR) calibrated with C-NMR.
Xylene solubles were detemnined at 25 °C according to ISO 6427.
Blown Film properties
Gloss and haze as measures for the optical appearance of the blown film were determined according to DIN 67 530 (gloss) and ASTM D 1003-92 (haze), both on blown film samples with a thickness of 50 pm.
The tensile modulus as a measure for the stiffness of the blown films was detemnined according to ISO 527 on blown film samples with a thickness of 50 Mm.
Elmendorf was determined according to ISO 6383/2 on blown film sam¬ples with a thickness of 50 pm.

Heat sealing initiating temperature (SIT)
1. General
The method determines the sealing temperature range of polypropylene blown films. The sealing temperature range is the temperature range, in which the films can be sealed according to the conditions given below. The lower limit (heat sealing initiation temperature (SIT)) is the sealing temperature at which a sealing strength of > 5 N is achieved. The upper limit (sealing end temperature (SET)) is reached, when the films start to crimp.
2. Sample geometry and sample preparation
The samples are taken in longitudinal direction of extrusion. The sample size is 25,4 mm x 250 mm, the film thicl 3. Sealing Device
For sealing the laboratory sealing device DTC Hot tack tester is used. Prior to the test, the device is checked for the parallel position of the seal¬ing jaws.
4. Sealing parameters
The sealing parameters are set to:
Sealing force: 0,66 N/mm2
Sealing time: 1 s
Sealing jaws: 50 x 5 mm. smooth + Teflon film
Heating: both jaws, precision+/-1'C
Start temperature: 100 "C
Take off speed: 42 mm/sec

5. Sealing procedure
- Stripes are folded to 125 x 25,4 mm and put (between the sealing jaws.
- The jaws are heated to sealing temperature
- Immediately after sealing, the sample is taken out of the device
- For each temperati/re, 5 samples are sealed
6. Testing
To determine the initial strength, 5 samples are seated at one temperature setting and with DTC Hot tack tester tested for the sealing strength. If the mean value of 5 tests - as described atx)ve - is > 5N, then the heat sealing temperature is reached. If not, the sealing temperature is in¬creased by 2 "C and the test is repeated.
After having reached the SIT, the sealing temperature is further increased in steps of 2 °C until the films start to crimp.
After a delay time of 30 sec after the sealing tiie film is stretched with a take-off speed of 42 mm/sec to measure the sealing strength in Newton. The SIT is the temperature where the sealing strength of > 5 N is reached.

EXAMPLES Example 1 finventionh
Pro(;iigti9n 9lH pr9PYl?n$/gthYlgn$/1-|?Mt9n9 tgnglvmr
A process comprising a prspolymerizatton step and a main polymerization step was used to produce the propylene terpolymer. Temperatures, pressures, catalyst-, monomer- and hydrogen feed in the separate polymerization steps as well as the polymer concentration in the main reactor are kept constant. The molar mass of the terpolymer is con¬trolled by adding hydrogen gas. The concentration of hydrogen in the mix¬ture of liquid monomers is continuously measured by gas chromatography. The relevant processing parameters and analytical results of the resulting polymer are listed in tables 1 and 2.
The catalyst used was a highly active, stereospeclfic transesterified MgClr supported Ziegler-Natta catalyst.
The catalyst is contacted with triethylaluminium (TEAL) as a cocatalyst and cyclohexyl methyldimethoxy silane (donor C) as an external donor to yield a catalyst system and then prepolymerized in a known manner in the presence of propylene in a small reactor (equipped with stin'er and cooling system).
The prepolymer (product A) is continuously removed from the prepoly-merization unit and passed into the main reactor system (equipped with stinner and cooling system), where under excess of a liqukj mixture of the monomers propylene and 1-butene, under addition of ethylene, the final terpolymer (B) is fomrred. Further a mixture of monomers (propylene/1-

butene/ethylene) and hydrogen (for molar mass control) are fed into the main reactor continuously. The polymer concentration is Icept constant.
A part of the reactor content (polymer-Zmonomer excess) is continuously removed from the reactor into a degassing unit to separate the fonned ter-polymer (B) from unreacted monomer mixture by evaporatton.
The separated terpolymer (B) was subjected to a steam treatment, to re¬move the unreacted monomers and volatile substances, and then dried. The polymer powder was mixed with 0,18 wt% nucleating agent ADK NA-21 from Asahi Denlta Kokai. Further the following additives were added: 300 ppm Mg4,5Al2(OH) 13(003) 3,5H20 as acid neutralizing agent, 500 ppm Irganox 1010 (Ciba Speciality Ohemicals) as antioxidant and 500 ppm Irgafos 168 (Oiba Speciality Chemicals) as stabilizer This mixture Is then pelletized in a conventional compounding line. The polymer properties can be seen from table 3.
PrQ0Mpti9P9ffilfn?
The palletized materials have been used for film blowing at a commercial blown-film line Alpine 35.
Blown films were produced on a single screw extruder with a barrel diame¬ter of 70 mm and a round-section die of 200 mm with 1 mm die gap in combinaticMi with a monolip cooling ring and internal bubble cooling (IBC). Melt temperature was 210 "0 in the die; the temperature of the cooling air was kept at 15 'C and the blow up ratto (BUR) 3:1. A film thickness of 50 pm was adjusted through the ratio between extruder output, take off speed and BUR. The film properties can be seen from table 3.

Comparative example 2 and 3:
As comparative examples 2 and 3 commercially available random copoly¬mer grades (Borclear™ RB709CF and Borclear™RB707CF) were used.
Table 1:
Parameter unit Example 1
TEAI/DonorD [g/g] 5
TEAI/Ti [g/g] 0,82
TEAI/Ti [mol/mol] 1,36
Table 2:
Parameter unit Example 1
Prepolymerizatlon reactor / Liquid monomer pliase
Feed catalyst compound [g/h] ~ 1,2
Pressure [bar] 34
Temperature ["C] 20
Mean residence time [min] 10
Main reactor/ Liquid monomer phase
Pressure [bar] 34
Temperature ["C] 64
Mean residence time catalyst [min] ~90
Polymer concentration in reactor [g/l] -0,52
Feed propylene/1-buten mixture*) [kg/h] 127-133
1 -Butene content in monomer feed [Vol%] -20,5
Ethylene feed [kg/h] 0,5
H2-concentration in monomer feed [ppm] 410-420
Polymer productton rate (product B) [kg/h] 27-43
*) total feed of liquid monomer mixture into the reactor system

Table 3 Examples
Polymer Properties 12 3
(RB709CF) (RB707CF)
Ethylene cone. [wt%] 0,3 5,7 4,5
1-Buteneconc. [wt%] 6,9
Nucleator NA-21 [ppm] 1800 1800 1800
Xylene Solubles [wt%] 3,5 7 7
Melt Temperature ['C] 143 135 144
MFR g/IOmin 1,7 1,5 1,5
cone concentration
Table 4;
Film Properties Examples
1 2 3
(RB709CF) (RB707CF)
Hazeb.s*) [%] 4,5 3,5 7.1
Hazea.s*) [%] 4,8 9,4 8,3
Gloss 20° outside b.s*) [%] 59,1 60,1 43,7
Gloss 20° outside a.s*) [%] 71,4 13,6 37,2
Gloss 20° inside b.s*) [%] 61,0 61,6 44.1
Gloss 20° inside a.s*) [%] 72,3 20,5 35.9
*) b.s before sterilization *}a.s after sterilization steam sterilization was perfomned at 121 °C for 30 min
Tensile modulus md [MPa] 1250 739 1127
Tensile modulus td [MPa] 1219 718 1127
S.I.T. rC] 122 112 124
Sealing temperature [°C] 115 105 120

These examples show that the values of the optical properties haze and gloss of example 1 improve after the sterilization, wrhereas for examples 2 and 3 they deteriorate.
Furthermore the film from example 1 shows a much higher tensile modulus compared to example 2 and a higher tensile modulus compared to example 3.

Patent claims
1. Use of a polymer composition comprised of (i) a propylene/butene ter-
poiymer which is comprised of
86.0 - 98.0 wt% of propylene 2.0-12.0 wt% of butene and 0.1 - to less than 1.0 wt% of ethylene and
(ii) 0.001 - 1.0 wt% of one or more phosphorous based and/or poly¬meric Q-nucleating agents for the production of sterilizable water or air quenched blown films which have the fdiowing properties:
a) a haze according to ASTM D 1003-92 for a 50 pm film of less than 8% before and after steam sterilization at 121'C for 30 minutes and
b) 20° Gloss according to DIN 67 530 for a 50 pm film of at least 55% before steam sterilization at 121'C for 30 minutes and of at least 60% after steam sterilization at 12rC for 30 minutes.
2. Use according to claim 1, characterized in that the films exhibit the fol¬
lowing property:
a tensile modulus (md) according ISO 527 of at least 1000 MPa for a 50 pm film.
3. Use according to any of claims 1 or 2, characterized in that the Q-nucleating agent comprises one or more phosphorous-based alpha-nucleating agents and/or polymeric alpha-nucleating agents selected from the group consisting of vinylcycloalkane polymers and vinylalkane polymers.
4. Use according to claims 3, characterized in ttiat tiie a-nucleating agent is selected from the group of aluminium hydroxyl-bisI2,4,8,10-tetrakis(1,1 -dimethylethyl)-6-hydroxy-12H-dlbenzo[d,g]dioxaphoshocin-

6-oxidato] based nucleating agents, sodium-2,2'-methylene-bis(4,6-di-t-butylphenyl)phosphate, aluminium-hydroxy-bis[2,2'-methylene-bis(4,6-di-t-butylphenyl)-phosphate] and from polymeric nucleating agents se¬lected from the group consisting of vinylcycloalkane polymers and vl-nylalkane polymers.
5. Use according to any of claims 1 to 4, characterized in that said polymer has a portion of polymer soluble in cold xylene (25'C) of no more than 5%.
6. Use according to any of claims 1 to 5, characterized in that the films have a thickness of from 5 to 1500 |jm.
7. Use according to any of claims 1 to 6 for the production of sterilizable air quenched blown films.
8. Use according to any of claims 1 to 7 for the production of sterilizable films for the pharmaceutical area and for food packaging.
9. Use according to any one of claims 1 to 8 for multilayer blown films, where at least one layer is comprised of a propylene blown film accord¬ing to claim 1.

10. Blown films obtained by a use according to any one of claims 1 to 9.
11. Blown film, wherein the blown film comprises a polymer composition comprised of (i) a propylene/butene terpolymer which is comprised of 86.0 - 98.0 wt% of propylene
2.0 -12.0 wt% of butene and
0.1 - to less than 1.0 wt% of ethylene

and (ii) 0.001 - 1.0 wt% of one or more phosphorous based and/or
polynneric a-nucleating agents which film has the following properties:
a) a haze according to ASTM D 1003-92 for a 50 jjm film of less than 8% before and after steam sterilization at 121'C for 30 minutes and
b) 20˚ Gloss according to DIN 67 530 for a 50 µm film of at least 55% before steam sterilization at 12rc for 30 minutes and of at least 60% after steam sterlization at 12 rc for 30 minutes.

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Patent Number

268657

Indian Patent Application Number

576/CHENP/2010

PG Journal Number

37/2015

Publication Date

11-Sep-2015

Grant Date

10-Sep-2015

Date of Filing

29-Jan-2010

Name of Patentee

BOREALIS TECHNOLOGY OY

Applicant Address

P.O. BOX 330, FI-06101 PORVOO

Inventors:

#	Inventor's Name	Inventor's Address
1	GREIN, CHRISTELLE	HARRACHSTRASSE 28, LINZ-A-4020
2	GRUNBERGER, MANFRED	ROSENAUERSTRASSE 26, LINZ-A-4040
3	WOLFSBERGER, ANTON	ESCHENWEG 2, GALLNEUKIRCHEN-A-4210
4	NIEDERSUSS, PETER	BLINDENDORF 221, 4312 RIED/RIEDMARK

PCT International Classification Number

C08L23/14

PCT International Application Number

PCT/EP08/59152

PCT International Filing date

2008-07-14

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	07113499.3	2007-07-31	EUROPEAN UNION