JPH09507083A - Composition comprising a blend of an ethylene polymer or copolymer and a sorbitol derivative - Google Patents

Abstract

  (57) [Summary] Films formed from blends of high impact resistance LLDPE and sorbitol derivatives exhibit excellent optical properties, especially excellent haze properties.

Description

Detailed Description of the InventionA block of ethylene polymer or copolymer and sorbitol or sorbitol derivative. Composition comprising lend   The present invention relates to ethylene polymers or copolymers and sorbitol or sorbitol. It relates to a composition comprising a blend with a derivative. The composition of the present invention is a film or It is especially useful as an extruded product.   A nucleating agent was used to change the crystal structure of the thermoplastic polymer or increase the crystallization temperature. It is known to increase the crystallization speed. The polymer composition is in a thermoplasticized state. During extrusion, various articles such as fibers, filaments, films, Tube, or molded into a molded product by compression or injection, and then After that, it can be cooled to harden and crystallize. Increase crystallization temperature By shortening the cycle time by increasing the crystallization rate and And the production speed can be increased.   The present invention     (I) 99.95 to 98.5% by weight of ethylene polymer or ethylene copolymer Coalescing; and     (Ii) 0.05-1.5% by weight sorbitol or sorbitol derivative body A composition comprising an ethylene polymer or copolymer MF R (I_{twenty one}/ I₂) Is 15 to less than 30, M_w/ M_nIs 2.5-3.5 and cloudy There is provided the above composition, wherein the degree is greater than 7.   Advantageously, the sorbitol or sorbitol derivative is a sorbitol This is when it includes a sorbitol derivative that is a ter or ester.   Sorbitol is H₈(COH)₆Has an empirical formula. Sorbitol derivatives are mono It may be a-, di-, tri-, tetra-, penta- or hexa-substituted derivative.   Also advantageous is that the sorbitol derivative has an empirical formula H₈[(COH)_n[(CO)₂ X]_m], In the formula, m is 0, 1, 2 or 3, and n is in the range of 0 to 6, 2m + n Is 6 and X is a group of the following (1) to (3):     (1) alkyl or aryl having 1 to 8 carbon atoms;     (2) R is alkyl or aryl having 1 to 8 carbon atoms, -C (O) R; and     (3) A mixture of (1) and (2) It is time to be selected from the group consisting of   Preferably m is 1-3. In one aspect, m is 2 or 3.   In one aspect, n is 1-6.   Most preferred sorbitol derivative is bis (dimethylbenzylidene) sorbitol Or dimethyl-dibenzylidene sorbitol.   Examples of other sorbitol derivatives that can be used are sorbitol dibenzylidene, sorbitol Tall hexaacetate, sorbitol hexanicotinate, sorbitol mono Benzylidene, sorbitol pentanitrate, sorbitol tricarbonate , Sorbitol tri (o-chlorobenzylidene).   For the preparation of dibenzylidene sorbitol derivatives, see US-A-40161. 18 and US-A-5135975; Njilidene sorbitol is 1 mol sorbitol and 2 mol benzaldeh. It is produced by reacting the amide at an elevated temperature in the presence of an acid catalyst.   Advantageously, an ethylene copolymer is used in the blend and it is A copolymer with at least one alpha olefin containing 3 to 10 carbon atoms It is when it consists of a linear low density polyethylene.   Preferably, the alpha olefin is 1-hexene.   In one embodiment, the composition of the present invention is measured by ASTM D-1003. It constitutes a film having a haze of less than 7, preferably less than 5.   In another preferred embodiment, the composition of the present invention is measured by ASTM D-1003. Extruded articles having a defined haze of less than 7, preferably less than 5.   The film or extruded product of the present invention is more than the conventional film or extruded product. Also have improved optical properties: for example, the haze of conventional LLDPE exceeds 10. I can.   The films and extrudates of the present invention have a haze measured according to ASTM D-1003. In addition to exhibiting improved optical properties such as transparency, which is judged as It shows a crystallization rate and a high crystallization temperature.   The production of the extrudable composition or blend of the present invention is carried out under an inert atmosphere. Molten ethylene by common methods, such as by using a lavender mixer It can be carried out by mixing polymers or copolymers. Sorbitol derivative Is a blend of the resulting sorbitol derivative and an ethylene polymer or copolymer. Can be used in an amount of 0.05 to 1.5% by weight. Preferably sorbito Is a derivative of the obtained sorbitol derivative and ethylene polymer or copolymer. Used in an amount of from 0.05 to 0.5% by weight of the blend; most preferably obtained Of a blend of a sorbitol derivative and an ethylene polymer or copolymer Used in an amount of 0.25% by weight.   The ethylene polymer or copolymer of the present invention is a catalyst containing a transition metal metallocene. It is preferably formed catalytically in the presence of These catalysts have a high density, Medium density and linear low density polyethylene (LLDPE) can be produced; Linear low density polyethylene consists of a copolymer of ethylene and alpha olefin .   The compositions of the present invention can be extruded or injection molded into articles or extruded and extruded. And blow molded into a film. Film is 0.5-5.0 mil (13-130 micron), preferably 0.5-2.0 mil (13-52 micron) Can be manufactured to a thickness of   The polymer component of the composition of the present invention will be described. WO is a preferred polymer component. The linear low density products described in -9414855 are included.   Linear low density products include ethylene and one or more C_Three~ C_TenAlpha olfi It is a copolymer produced by The copolymer is at least 80% by weight ethylene It is preferable to include the position. The comonomer used in the present invention has 3 to 8 carbon atoms. It is preferable to include Suitable alpha olefins include propylene, 1-butene. Ten, 1-pentene, 1-hexene, 1,4-methylpentene, 1-heptene And 1-octene are included. Preferred alpha olefins are 1-butene, 1- Hexene and 1-octene. The most preferred alpha olefin is 1-f It's Ksen.   Therefore, a copolymer having two types of monomer units is used as a copolymer having three types of monomer units. The same can be mentioned as for the original polymer. A particular example of such a polymer is ethylene / 1-butene copolymer, ethylene / 1-hexene copolymer, ethylene / 4-methyl Ru-1-pentene copolymer, ethylene / 1-butene / 1-hexene terpolymer, Ethylene / propylene / 1-hexene terpolymer, and ethylene / propylene / 1-Putene terpolymer.   Hydrogen can be used as a chain transfer agent in the polymerization reaction of the present invention. Catalysts and reactions Gases such as body inerts may also be present in the gas stream.   These products are preferably present in the presence of the following catalysts, preferably in the following slurry or flow: It can be prepared under bed catalyzed polymerization conditions.   With the catalysts below, the copolymer product contains 0.1 to 2 ppm Zr. . The product is granular and has an average particle size of 0.015 to 0.035 inches (0. 38-0.89 mm), sedimented bulk density 15-36 lbs / ft^Three(240 ~ 577 kg / m^Three). The particles can be spherical. 0.902 for low density products g / cm^ThreeIt features a very low density. For use herein, the density is generally 0. . 900 g / cm^ThreeLarger, preferably 0.910 g / cm^ThreeBigger, yo More preferably 0.911 to 0.929 g / cm^Three, Most preferably from 0.915 0.922 g / cm^ThreeIt is.   Importantly, a narrow molecular weight range of MI from 0.01 to 1 (inclusive of 0.01 and 1) A linear low density copolymer of fabric was produced. The low density product of the present invention is 0.01-5. , Generally from 0.1 to 5, preferably from 0.5 to 4, most preferably from 0.8 to 2.0 Indicates MI. For blown films, the MI of the copolymer is preferably 0.5-1. . 5; for cast films, MI is preferably 2-4.   The low density product of the present invention has a melt flow ratio (MFR) of 15 to 30, preferably 15 to 22. In a preferred aspect, the MFR is 15-18. MFR is a ratio I_{twenty one}/ I₂[I_{twenty one}Is measured at 190 ° C according to ASTM D-1238, Condition F , I₂Is measured at 190 ° C. according to ASTM D-1238, Condition E]. .   The melting point of the copolymer product is 95-130 ° C. In addition, hexane extractable The prevalence is very low, generally 0.3-1.0% by weight. M of these products_w / M_nIs 2.5 to 3.5; M_wIs the weight average molecular weight, M_nIs the number average molecular weight Molecular weight distribution measured by GPC (gel permeation chromatography) Is calculated from   The polymer component of the composition of the present invention has a pull as measured by ASTM D1922. The tear strength is well balanced and the longitudinal direction is 50 to 600, preferably 220 to 420 Transverse direction is 200-700, preferably 200-600. This again And the modulus measured by ASTM D882 is high, 1.0 × 10 4 ~ 6.0 × 104 psi (717 KPa), preferably 1.8 to 4.5 × 104 p si (717 KPa); tensile pull down measured by ASTM D882 High yield, 0.7-3.0 × 103 psi (710 KPa), preferably 1.5 ˜2.3 × 10 3 psi (710 KPa).   Films made with the polymeric component of the composition of the present invention are ASTM D-100. Excellent optical properties as determined by examining the haze measured according to 3. That is, it generally exhibits a haze of 7 to 20. Films with inferior haze characteristics are cloudy The degree exceeds 10. The importance of the optical properties of LLDPE depends on the eyes of LLDPE resin. It depends on the intended use. Insufficient optical properties of normal LLDPE (cloudiness Degree> 10 and gloss <50) for applications where the optical properties of the film are important It is generally accepted that use in the strict limit is severe. Improved optical Films and stamps of the invention having properties (preferably including gloss> 70). The field of application of bargains is quite wide.   Films made with the polymeric components of the composition of the present invention are ASTM D-1709, 9 shows dart impact strength as measured by Method A. For example, such a film It shows superior dart impact strength over films made with previously known catalysts. So Of dart impact strength of films such as Dust measured by ASTM D-1709 Is 100 to 2000, preferably 150 to 1500. Most preferred Una film is 0.911 ~ 0.922g / cm^ThreeDensity, above 900, general Has a dart drop impact strength of 800 to 1500 and the product is not damaged. The dart drop impact strength of 2000, for example, is shown up to the measured value.   The above properties of the polymer component of the composition of the present invention are determined under standard processing conditions outlined in the examples , 0.75 "(19mm) Brabender Extruder, 2.5" (64mm) Bra Ampton Film Extruder or 3.5 "(89mm) Gloster Film Extruder This is for a 1 mil (25 micron) film produced in the extruder. Addition By optimizing the working conditions or adding LDPE or a nucleating agent It will be apparent to those skilled in the art that the film properties can be further adjusted by That's a kana.   The above properties of the polymer component were measured by the following test methods: Density ASTM D-1505-Manufacture plaque at 1                       Condition at 100 ° C. for close to equilibrium crystallinity.                       Density measurements are made in a density gradient column; g / cm^Threeage                       To record. Melt Index ASTM D-1238-Condition E (MI), I₂         Measured at 190 ° C-expressed as grams per 10 minutes                       To record. High load ASTM D-1238-Condition F Melt index 10.5 times the weight used in the above melt index test (HLMI), I_{twenty one}    Measured by weight. Melt flow ratio I_{twenty one}/ I₂ (MFR) 12   The catalyst composition used to make the resins and films of the present invention has at least about 2, 000 g polymer / g catalyst or about 1,000 kg polymer / g transition metal activity It may include one transition metal in the form of a metallocene.   The catalyst comprises a support, an aluminoxane and at least one metallocene. Is preferred.   The carrier material is a solid, granular, porous, inorganic or organic material, but an inorganic material, For example, silicon oxide and / or aluminum oxide is preferable. The carrier material is Average particle size of about 1 to about 250 microns, preferably about 10 to about 150 micron It can be used in the form of a dry powder. If necessary, sift the treated carrier material and Indeed, the particles are preferably of average particle size less than 150 microns. This It is highly desirable in forming narrow molecular weight LLDPE to reduce gels. Is Rukoto. The surface area of the carrier is at least about 3 m²/ G, preferably at least About 50m²/ G and about 350m²/ G or less. When the carrier is silica, this It is preferably heated to about 100 to about 850 ° C, most preferably about 250 ° C. To prepare the catalyst composition of the present invention, the support material is at least some of the hydroxyl. It preferably has a sil (OH) group.   In the most preferred embodiment, the support is nitrogenated prior to its use in the first catalytic synthesis step. Fluidized at room temperature and dehydrated by heating at about 250 ° C for about 4 hours to remove surface heat. It is a silica having a droxyl group concentration of about 1.8 molmol / g. Most preferred Such silica has a large surface area, and amorphous silica (surface area = 250-350 m²/ G ; Pore volume 1.65 to 3.0 cm^Three/ G), and W. R. Grace and PQ 988, Devison 952-1836 from the company's Devison Chemistry Department. , Davison 952 or Davison 955. Silica is in the form of spherical particles, for example as obtained by the spray drying method.   All catalyst precursor components are dissolved with alumoxane to form the catalyst, Then react with the carrier. The carrier material is an aluminoxane solution, preferably methyl acetate. It can be reacted with lumoxane by the following method. This class of alumoxane is linear And / or cyclic alkyl alumoxane oligomers, In the case of moxa gorigomers the formula: R- (Al (R) -O)_n-AlR₂And; In the case of a cyclic alumoxane oligomer, the formula: (-Al (R) -O-)_mIs represented by In the above formula, n is 1 to 40, preferably 10 to 20, and m is 3 to 40, preferably Is 3 to 20, R is C₁~ C₈Alkyl group, preferably methyl. Met Lualumoxane (MAO) has a very broad molecular weight distribution and usually around 1000 It is a mixture of oligomers having an average molecular weight. MAO is a solution in toluene Generally held.   In a preferred embodiment of mixing alumoxane to the support, the alumoxane during catalyst synthesis is used. One of the controlling factors for the mixing of xane into the support material is the pore volume of silica. this In a preferred embodiment, the method of impregnating the carrier material comprises alginating a carrier material such as silica. Injecting alumoxane solution without making slurry in moxane solution It is due to. The volume of the alumoxane solution is the carrier without forming a slurry. A volume that is sufficient to fill the pores of the material and does not exceed the pore volume of silica. Therefore and preferably, the highest volume of alumoxane solution is the carrier material sample. Is the total pore volume of, and does not exceed. Alumoxane solution The highest volume is one where silica slurries are not reliably formed. Therefore, the carrier Material pore volume is 1.65 cm^Three/ G, the volume of alumoxane is 1.65. cm^Three/ G carrier material or less. As a result of this condition, the carrier Even if the pores of the I can.   The solvent is heated and / or under pressure with an inert gas such as nitrogen, It can be removed from the alumoxane impregnated pores of the carrier material. If used, this process Conditions to eliminate agglomeration of the impregnated carrier particles and / or cross-linking of the aluminoxane. Or reduce if not eliminated. In this step, the solvent should be above 40 ° C. , Can be removed by evaporation at relatively low temperatures below about 50 ° C . The solvent is at a temperature above about 40 ° C. and above a limited temperature below about 50 ° C. Can be removed by evaporation in a very short heating time Must be used.   In a preferred embodiment, the metallocene is added to the aluminoxane prior to reacting the solution with the support. Solution. The maximum volume of aluminoxane solution containing metallocene is , The total pore volume of the carrier material sample. Providing aluminum represented as Al The alumoxane to the metallocene metal represented as M (eg, Zr) The molar ratio is 50-500, preferably 75-300, most preferably 100- 200. Another advantage of the present invention is that the Al: Zr ratio can be adjusted directly. It is possible. In a preferred embodiment, the alumoxane and metallocene compound is Responsible Prior to reaction with the body, they are mixed together at about 20-80 ° C. for 0.1-6.0 hours. Metallo Solvents for sen and alumoxane include aromatic hydrocarbons, halogenated hydrocarbons, Is a halogenated aromatic hydrocarbon, preferably a suitable solvent such as toluene.   The metallocene compound has the formula Cp_mMA_nB_pWhere Cp is substituted or unsubstituted A cyclopentadienyl group, M is zirconium or hafnium, And B belong to the group containing a halogen atom, hydrogen or an alkyl group. Metallocene In the above formula of the compound, the preferred transition metal atom M is zirconium. Metallo In the above formula of the sen compound, the Cp group is an unsubstituted, mono- or polysubstituted cyclope It is an interdienyl group. The substituent on the cyclopentadienyl group is preferably linear Or branch C₁~ C₆It is an alkyl group. The cyclopentadienyl group is also an index Nyl, tetrahydroindenyl, fluorenyl or partially hydrogenated fluorenyl groups A portion of a bicyclic or tricyclic moiety such as, as well as one of substituted bicyclic or tricyclic moieties It may be a department. When m in the above formula of the metallocene compound is 2, cyclopentene Tadienyl groups are polymethylene or dialkylsilane groups such as -CH₂−, -CH₂-CH₂-, -CR'R "-and -CR'R" -CR'R "-(R 'and And R ″ are short alkyl groups or hydrogen), —Si (CH_Three)₂-, -Si (C H_Three)₂-CH₂-CH₂-Si (CH_Three)₂-And similar bridge groups It may be hung. The A and B substituents in the above formula of the metallocene compound are halogen If they are nitrogen atoms, they belong to the group of fluorine, chlorine, bromine or iodine. Meta The substituents A and B in the above formula of the rosene compound are alkyl groups or aromatic groups , These are preferably linear or branched C₁~ C₈Alkyl groups such as methyl, ethyl Chill, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, It is n-hexyl or n-octyl.   Suitable metallocene compounds include bis (n-butylcyclopentadienyl) metal dimetal Halide, bis (n-butylcyclopentadienyl) metal hydride halide, bi Bis (n-butylcyclopentadienyl) metal monoalkyl monohalide, bis ( n-Butylcyclopentadienyl) metal dialkyl and bis (indenyl) gold Genus dihalides are included and the metal is titanium, zirconium or hafnium. The halide group is preferably chlorine, and the alkyl group is C₁-C₆With an alkyl group is there. Examples of metallocenes are bis (n-butylcyclopentadienyl) zirconium Dichloride, bis (n-butylcyclopentadienyl) hafnium dichloride, Bis (n-butylcyclopentadienyl) zirconium dimethyl, bis (n-butyl) Cylcyclopentadienyl) hafnium dimethyl, bis (n-butylcyclopen) Tadienyl) zirconium hydride chloride, bis (n-butylcyclopentadi) (Enyl) hafnium hydride chloride, bis (pentamethylcyclopentadienyl) Ru) zirconium dichloride, bis (pentamethylcyclopentadienyl) huff Bis (methylcyclopentadienyl) zirconium dichloride Bis (isobutylcyclopentadienyl) zirconium dichloride, bis ( Indenyl) zirconium dichloride, bis (4,5,6,7-tetrahydro- 1-indenyl) zirconium dichloride, and ethylene [bis (4,5,6 , 7-Tetrahydro-1-indenyl)] zirconium dichloride, It is not limited to these. The metallocene compound used in aspects of this technology is crystalline It can be used as a solid, as an aromatic hydrocarbon solution, or in supported form. Wear. A catalyst containing a metallocene compound and an aluminoxane in the form of a particulate material is Flow for phase polymerization and copolymerization of ethylene and higher alpha olefins It can be fed to a moving bed reactor or a slurry reactor.   Do not operate below the sintering temperature to ensure that sintering will not occur. Is desirable. In the production of the ethylene copolymer according to the method of the present invention, the operating temperature is about 60 to 110 ° C is preferred and about 70-90 ° C is most preferred.   The fluidized bed reactor operates at a pressure of about 150-350 psi (1-2.4 MPa). You. Since the higher the pressure, the higher the unit volume heat capacity of the gas, Operating at higher pressures in favors heat transfer.   In the case of film production, the product is a variety of additives commonly added to polymer compositions. , Containing, for example, lubricant, microtalc, stabilizer, antioxidant, compatibilizer, pigment, etc. It may be. Stabilize the product against oxidation with these reagents be able to. For example, 400 to 1200 ppm for adding to resin powder Hindered phenol; 700-2000 ppm phosphite; 250-1000 Additions containing ppm antistatic agent and 250-1000 ppm stearate Agent The package can be used during pelletization. Pelletized polymer General LLDPE blown film extruder such as Turling extruder When applied directly to a foil, for example, the thickness is about 0.5-5 mils (13-130 microns). The film can be manufactured.   The following examples further illustrate the present invention.Example   The following metallocene catalysts were used to produce the samples used in the test, with a bed volume of 4. 0 feet^Three(0.11m^Three) Pilot plant fluidized bed 13 inches (0.33 m) Used in ID reactor. Polymerization is generally at 77.5 ° C and ethylene at 170-2. It was performed at 00 psi (1.2 to 1.4 MPa). Hexene to ethylene gas ratio is 0 . The density was adjusted by changing from 009 to 0.025. The desired melt index Isopentane partial pressure 0-50 psi (0-344 KPa) and oxygen to obtain Addback level 0.0-0.2ppm or carbon dioxide Duck 0 to 10 ppm was used. Flowing gas velocity is 1-2 feet / second (0.3 .About.0.6 m / sec).   The operability of the reactor was good. Resin settling bulk densities are all 31-34 pounds Per foot^Three(497-545 kg / m^Three) And fine particles (less than 120 mesh Was defined as less than 3%).   The resins used in these examples are shown in Table I. 1000ppm irgano X 1076, 2000 ppm Irgafos 168, 5000 ppm AS 990, addition including 500 ppm ZnSt and 0.2% Millad 3940 By melt compounding the agent at 205 ° C using a Brabender extruder , To the resin. Millad 3940 is bis (dimethylbenzylidene) sorbit It is a rule. The crystallization characteristics are based on a differential scanning calorimeter (DSK-2 manufactured by Perkin-Elmer Co. ) Was used. Table II shows the effect of sorbitol derivatives on resin crystallization properties. Show. Acts as a nucleating agent with a sorbitol derivative (Millad's Millad 3940) Then, the PE resin crystallization temperature (T_c) Raise and crystallize half tie Mu (t_1/2) Can be reduced.Results of blown film   The film is a 3/4 "(19 mm) blanket with a 1" (25 mm) annular die It was blow-molded at a melting temperature of 210 ° C. with a extruder. Made this way The optical properties of the produced 1.5 mil (38 micron) film were measured by Millad 394 Shown in Table I, along with the data for the control PE film containing no zero. From the data, By adding a quantity of Millad 3940 to the PE film, the transparency is significantly improved. You can see that it has improved.   The following examples include compositions of the invention that include polymers and copolymers with a narrow molecular weight distribution. The present invention relates to the production of a polymer component of a product.Example 1 [Of WO-9414855]   The raw material used to produce the catalyst was Davison 952-1836 silica 505. g, 698 g of methylaluminoxane in a toluene solution (30 wt% MAO), Bis (n-butylcyclopentadienyl) zirconium dichloride 7.148 g was included.   The catalyst manufacturing process is shown below: 1. Dehydrate 955 silica at 250 ° C. for 4 hours using air for purging . Then it is purged with nitrogen during cooling. 2. Transfer the silica to the mixing vessel. 3. 7.148 g of bis (n-butylcyclopentadienyl) zirconium di Chloride and 698 g of methylalumoxane are added to the bottle. 4. Stir the catalyst solution in the bottle until the metallocene is dissolved in the MAO solution. . 5. MAO and metallocene solution into a mixing vessel containing dehydrated 955 silica Transfer slowly and, at the same time, stir the silica bed vigorously to ensure that the catalyst solution is Disperse well on the floor. 6. After the addition, stirring of the catalyst is continued for 0.5 hours. 7. Start the catalyst drying by purging with nitrogen at 45 ° C. for 5 hours. You. 8. The catalyst is screened to remove particles larger than 150 microns. 9. The analytical values of the catalyst are shown below:           Al = 10% by weight           Zr = 0.2% by weightExample 2 [Of WO-9414855]     Density is 0.918g / cm^ThreeFor low density film with MI, 1 and MFR 17 The following operating conditions were used to produce the polymer in the fluidized bed gas phase reactor:     Fluidization speed 1.7 ft / sec (0.43 m / sec)     Residence time 2.5 hours     Temperature 77.5 ° C     Ethylene 180 psi (1.2 MPa)     Hexen 3.6 psi (25 KPa)     Isopentane 50 psi (345 KPa)     Carbon dioxide 1.1ppm     Ash content 200-300ppm   The catalyst was the catalyst of Example 1.Example 3 [Of WO-9414855]   Density is 0.918g / cm^ThreeFor cast film with MI, 2.5 and MFR of 16 The following operating conditions were used to produce the polymer:     Fluidization speed 1.7 ft / sec (0.43 m / sec)     Residence time 2.5 hours     Temperature 77.5 ° C     Ethylene 180 psi (1.2 MPa)     Hexen 3.6 psi (25 KPa)     Isopentane 38 psi (262 KPa)     Ash 100ppm   The catalyst was the catalyst of Example 1. 1. Resin characteristics   Compared with standard ethylene-hexene copolymer prepared with a commercial Ziegler catalyst Then, the resin produced by using the metallocene of Example 1 by the gas phase method had the following characteristics. Show: (1) narrower molecular weight distribution, (2) more uniform short chain branching distribution, (3) Lower melting point, lower extractables content than (4), and lower haze than (5).   I₂Is 1.0 and the density is 0.918 g / cm^ThreeExamples of important resin properties of these resins in Table II Shown in I: 2. End-use properties   These metallocene LLDPE resins can be easily used with commercially available equipment without adjustment. Can be processed into They also use commercially available Ziegler / Natta catalysts It provides superior properties compared to these resins produced by. Examples are shown in Table IV :

[Procedure of Amendment] Article 184-8 of the Patent Act [Submission date] June 15, 1995 [Correction contents]Substitution sheet 1st page translated text: Original translation 1st page 1st line to 2nd page 1st line replaced.                                 SpecificationComprising a blend of an ethylene polymer or copolymer and a sorbitol derivative Composition   The present invention relates to ethylene polymers or copolymers and sorbitol or sorbitol. It relates to a composition comprising a blend with a derivative. The composition of the present invention is a film or It is especially useful as an extruded product.   A nucleating agent was used to change the crystal structure of the thermoplastic polymer or increase the crystallization temperature. It is known to increase the crystallization speed. The polymer composition is in a thermoplasticized state. During extrusion, various articles such as fibers, filaments, films, Tube, or molded into a molded product by compression or injection, and then After that, it can be cooled to harden and crystallize. Increase crystallization temperature By shortening the cycle time by increasing the crystallization rate and And the production speed can be increased.   The present invention     (I) 99.95 to 98.5% by weight of ethylene polymer or ethylene copolymer Coalescing; and     (Ii) 0.05-1.5% by weight sorbitol or sorbitol derivative body A composition comprising an ethylene polymer or copolymer MF R (I_{twenty one}/ I₂) Is 15 to less than 30, M_w/ M_nIs 2.5-3.5 and cloudy There is provided the above composition, wherein the degree is greater than 7.   Advantageously, the sorbitol or sorbitol derivative is a sorbitol This is when it includes a sorbitol derivative that is a ter or ester.   Sorbitol is H₈(COH)₆Has an empirical formula. Sorbitol derivatives are mono It may be a-, di-, tri-, tetra-, penta- or hexa-substituted derivative.   Also advantageous is that the sorbitol derivative has an empirical formula H₈[(COH)_n[(CO)₂ X]_m], In the formula, m is 0, 1, 2 or 3, and n is in the range of 0 to 6, 2m + n Is 6 and x is a group of the following (1) to (3): [Procedure of Amendment] Article 184-8 of the Patent Act [Submission date] November 17, 1995 [Correction contents]Replacement Sheet Page 16 Translation: Replacement of the original translation with claims 1-9 You.                                The scope of the claims 1. (I) 99.95 to 98.5% by weight of ethylene polymer or ethylene copolymer Polymer; and       (Ii) 0.05-1.5% by weight of sorbitol or sorbitol derivative conductor A composition comprising an ethylene polymer or copolymer MF R (I_{twenty one}/ I₂) Is less than 15 to 30, M_w/ M_nIs 2.5-3.5, and haze Wherein the composition is greater than 7. 2. The sorbitol derivative is an ether or ester of sorbitol. The composition of claim 1. 3. Empirical formula H for sorbitol derivatives₈[(COH)_n[(CO)₂X]_m] Where m is 0, 1, 2 or 3, n is in the range 0-6, 2m + n is equal to 6, And X is the following (1) to (3):     (1) a hydrocarbon group having 1 to 8 carbon atoms which is alkyl or aryl;     (2) R contains 1 to 8 carbon atoms and is alkyl or aryl Is -C (O) R; and     (3) A mixture of (1) and (2) The composition of claim 2, selected from the group consisting of: 4. The composition according to claim 3, wherein m is 1 to 3. 5. The composition according to claim 3, wherein m is 2 or 3. 6. The composition according to claim 3, wherein n is 1 to 6. 7. Sorbitol derivative is bis (dimethylbenzylidene) sorbitol The composition of claim 3. 8. The sorbitol derivative is dimethyl-dibenzylidene sorbitol, The composition according to claim 3. 9. The ethylene copolymer contains ethylene and at least one carbon atom of 3 to 10 carbon atoms. Containing linear low density polyethylene which is a copolymer with alpha olefin The composition according to claim 1, 2 or 3.

────────────────────────────────────────────────── ─── Continuation of front page    (72) Inventor On, Shimei Christine             New Jersey State 07059,             Warren, Glenview Avenue             26 (72) Inventor Sue, Thien-Kui             United States New Jersey 08502,             Bell Mead, Adams Drive 7

Claims (1)

[Claims] 1. A composition comprising (i) 99.95-98.5% by weight of an ethylene polymer or ethylene copolymer; and (ii) 0.05-1.5% by weight of a blend of sorbitol or a sorbitol derivative. And the ethylene polymer or copolymer has a MFR (I ₂₁ / I ₂ ) of 15 to less than 30, a M _w / M _n of 2.5 to 3.5, and a haze of more than 7. . 2. The composition according to claim 1, wherein the sorbitol derivative is an ether or ester of sorbitol. 3. A sorbitol derivative empirical formula _{H 8 [(COH) n [} (CO) 2 X] m], wherein, m is 0, 1, 2 or 3, n is from 0 to 6 range, the 2m + n is 6 Equal and X is the following (1) to (3): (1) Alkyl or aryl having 1 to 8 carbon atoms; (2) R is alkyl or aryl having 1 to 8 carbon atoms -C (O ) R; and (3) The composition according to claim 2, which is selected from the group consisting of a mixture of (1) and (2). 4. The composition according to claim 3, wherein m is 1 to 3. 5. The composition according to claim 3, wherein m is 2 or 3. 6. The composition according to claim 3, wherein n is 1 to 6. 7. The composition according to claim 3, wherein the sorbitol derivative is bis (dimethylbenzylidene) sorbitol. 8. The composition according to claim 3, wherein the sorbitol derivative is dimethyl-dibenzylidene sorbitol. 9. 4. The composition of claim 1, 2 or 3 wherein the ethylene copolymer comprises a linear low density polyethylene which is a copolymer of ethylene and at least one alpha olefin containing 3 to 10 carbon atoms. Stuff. 10. The composition of claim 9, wherein the alpha olefin is 1-hexene. 11. 4. A composition according to claim 1, 2 or 3 which constitutes a film having a haze of less than 7 as measured by ASTM D-1003. 12. 4. A composition according to claim 1, 2 or 3 which constitutes an extrudate having a haze of less than 7 as measured by ASTM D-1003.