CN1351628A - Film with enhanced performance properties - Google Patents

Abstract

Disclosed is a tough and stiff film comprising a blend comprising an alkenyl aromatic polymer and a substantially random interpolymer. The film is particularly suitable for use in applications requiring tough and stiff film, such as a window envelope film or a label. The invention further relates to articles of manufacture comprising such film.

Description

Has the film that improves performance

Technical field

The present invention relates to a kind of toughness, the film of property very, described film comprises the blend of polymeric material.

Background technology

Comprise alkenyl aromatic polymer, as polystyrene, and alpha-olefin/steric hindrance vinyl or vinylidene multipolymer, for example the blend of ethylene-styrene copolymer is well known in the art.Described blend has been proposed to be used in and has comprised some kinds of application, comprises film and porous plastics.

WO95/32095 has disclosed a kind of hot contractile film that comprises the oriented film layer, and described oriented film layer comprises the multipolymer of homogeneous phase alpha-olefin/binyl aromatic hydrocarbons.What also propose in addition is one to comprise foam sheet and be bonded to the laminating material of the film on the foam sheet, and described laminating material can comprise the homogeneous copolymers of Natene and alpha-olefin/binyl aromatic hydrocarbons.

US5,460,818 have described the consistency blend of polymkeric substance of a kind of olefin polymer and monovinylidene aromatic and the expandable compositions that comprises described polymkeric substance blending compound and swelling agent.Described polymkeric substance blending compound can comprise (a) aliphatic alpha-olefin homopolymer or multipolymer, (b) monomeric homopolymer of monovinylidene aromatic or multipolymer and (c) comprise the random substantially multipolymer of aliphatic alpha-olefin and vinylidene aromatic monomer.

WO98/10014 relates to a kind of alpha-olefin/multipolymer of steric hindrance vinylidene monomer and the blend of vinyl aromatic polymer, and by its porous plastics that makes.Concrete disclose is: comprise the porous plastics of general purpose polystyrene and ethene-cinnamic basic random copolymers, foam density from about 40 to about 130kg/m ³

At present, still need to provide the membrane structure that improves use properties, especially needing toughness and enduring in the application of property film.What wish especially is when having good aesthetics, demonstrates the film of very good mechanical properties.The purpose of this invention is to provide a kind of film that makes use properties carry out overall equilbrium, described performance comprises: high toughness, good very property, wear resistance, crack resistance, high elongation limit and good tear-resistant performance and good optical performance.For example,, be used for the packaging film of window frame for being suitable for the film of making the envelope window, greeting card tectum and label, described performance needs.

The envelope of windowing is a kind of envelope that has one or more arbitrary shape openings, and described opening shape is generally rectangle.Described opening can be checked any information, as, be printed on the name and address that is also sealed on the localized area by the window of being formed by the non-opacity plastics film.Known window film is usually by oriented polystyrene, and dispensable a small amount of rubber enhanced polymkeric substance is formed.

Usually, label is adhered on the article or follows article, so that identification or other information are provided.For example, label can be a composition of wrapping material such as window, and this composition does not contact with the inclusion of packing.Preferably, label is printable.For example, with regard to the integrity of article or wrapping material, label can have provide protection.

Window film as label needs high deflection, so that in the high speed printing operation, the envelope preparation is used, and in label preparation and the final use, provides excellent processing and conversion performance.In addition, described film needs high surface gloss (for the outward appearance and printability of excellence), good tensile and toughness, and good scratch resistance or wear resistance.

The purpose of this invention is to provide and a kind ofly make each performance synthesis equilibrated film,, especially be suitable for and make window film or label so that make this film be specially adapted to above-mentioned and relevant application.

Summary of the invention

The present invention relates to a kind of toughness and the film of enduring property, this film comprises the blend of (at least) component (A) and component (B).Wherein the content of component (A) in the gross weight of component A and B from about 45% weight to about 90% weight; In the gross weight of component A and B, the content of component (B) is from about 10% weight to about 55% weight.Component (A) is made up of one or more alkenyl aromatic polymer.Component (B) is made up of one or more random substantially multipolymers, described multipolymer comprises ethene and/or one or more 'alpha '-olefin monomers of polymerized form (i) from about 50 moles of % to 74 mole of %, (ii) from 26 moles of % to one or more vinyl of about 50 moles of % or vinylidene aromatic monomer and/or one or more sterically hindered aliphatic series or cyclic aliphatic vinyl or vinylidene monomer and (iii) from other polymerisable ethylenically unsaturated monomer of about 0-20 mole %.

Blending component and ratio thereof are selected, had high very property and flexible film so that provide.The deflection of film excellence is with modulus (vertical 1% secant modulus) expression, and its value is at least 85,000psi.Toughness is represented with high tensile toughness and ultimate elongation intensity.

The other aspect of the present invention relates to the preparation method of film of the present invention and the purposes of described film.

On the other hand, the invention provides a kind of window envelope with one or more window openings, described window opening is by non-opacity plastic window complete closed, and is made of film of the present invention.

In addition, the present invention also is provided for the label of container, and described label is made by film of the present invention.

The present invention also provides preparation to comprise the article of film of the present invention.

Embodiment

Term " polymeric material " refers to as used herein: by making the available polymerizable compound of one or more monomer polymerizations.Term " polymerizable compound " or " polymkeric substance " comprising: only be commonly used to represent the homopolymer of the polymkeric substance that made by a kind of monomer and term multipolymer as defined herein.

Term " comprises " and means " comprising " as used herein.

Term " film " refers to as used herein: comprise bar, band, and ribbon.

Term " multilayer film " expression as used herein: by two-layer, three layers, four layers, five layers, six layers, seven layers or the more multi-layered film of forming.

Term " foamed thin sheet " refers to as used herein: wherein, structural sheet is that porous plastics and its density are greater than about 300kg/m ³With single or multiple lift structure less than non-foam polymkeric substance.

Term " interpolymer " refers to as used herein: the polymkeric substance that makes by at least two kinds of monomeric polymerizations.Therefore term interpolymer commonly used comprises: be commonly used to represent the term multipolymer of the polymkeric substance that makes by two kinds of different monomers, and by the polymkeric substance that makes more than two kinds of different monomers, as terpolymer.

As definition in the present invention, term in the basic random copolymer of component (B) " random substantially " means: the monomer distribution of described interpolymer can be described by Bernoulli Jacob's statistical model or by the Markovian statistical model of first or second order, determine in the polymkeric substance order as J.C.Randall, carbon-13NMR method (Academic Press, NewYork, 1977, pp.71-78) described in.Preferably, in the block more than 3 unitary vinyl aromatic monomers, basic random copolymer comprises the vinyl aromatic monomer of no more than 15% total amount.More particularly, this interpolymer is characterised in that the degree of isotacticity or the degree of syndiotacticity of height.This means: in the C-13NMR spectrum of basic random copolymer, the peak area that is equivalent to main chain methylene radical and methine carbon should not surpass 75% of main chain methylene radical and methyne total peak area, and wherein said carbon is represented meso divalence sequence or racemize divalence sequence.

The present invention relates to comprise the film of blend, described blend comprises one or more alkenyl aromatic homopolymers, or the multipolymer of alkenyl aromatic homopolymers, but and/or the olefinic unsaturated comonomer of alkenyl aromatic monomer and one or more copolymerization (ethene or linear C ₃-C ₁₂Except the linear alpha-alkene) and the multipolymer of at least a basic random copolymer.

Alkenyl aromatic polymer material (component (A)) can comprise a spot of non-alkenyl aromatic polymer in addition.Alkenyl aromatic polymer material can be only by one or more alkenyl aromatic homopolymers, one or more alkenyl aromatic multipolymers, and the blend of one or more thiazolinyl homopolymer and multipolymer, or the blend of aforementioned substances and non-alkenyl aromatic polymer is formed.Irrelevant with composition, alkenyl aromatic polymer material comprises greater than 50% weight, is preferably greater than the alkenyl aromatic monomeric units of 70% weight.Most preferably, alkenyl aromatic polymer material is made up of alkenyl aromatic monomeric units fully.

Suitable alkenyl aromatic polymers is drawn together: by alkenyl aromatic compound such as vinylbenzene, alpha-methyl styrene, ethyl styrene, vinyl benzene, Vinyl toluene, chloro-styrene, homopolymer and multipolymer that bromstyrol, t-butyl styrene are derived and obtained comprise all isomer of these compounds.Suitable polymers as component (A) also comprises: the alkenyl aromatic polymer with height syndiotaxy configuration.Preferred alkenyl aromatic polymer is a polystyrene.A spot of monoene ethylenically unsaturated compounds such as C _2-6Alkyl acid and ester, ionic derivative, and C _4-6Diene can close with copolymerized.The example of copolymerizable compounds comprises: vinylformic acid, methacrylic acid, ethylacrylic acid, toxilic acid, methylene-succinic acid, vinyl cyanide, maleic anhydride, methyl acrylate, ethyl propenoate, isobutyl acrylate, n-butyl acrylate, methyl methacrylate, vinyl acrylate and divinyl.

Polystyrene commonly used is the highly preferred alkenyl aromatic polymer material that is suitable for the component of doing to define among the present invention (A).Term " polystyrene commonly used " has definition in polymer science and engineering encyclopedia (the 16th volume, 1989,62-71 page or leaf).Described polystyrene is also represented crystal polystyrene or polystyrene homopolymer.

The mono alkenyl aromatic(based)polymer can carry out suitable modification by rubber, so that improve its shock resistance.The example of suitable rubbers is C ₄-C ₆The homopolymer of conjugated diolefine, especially divinyl or isoprene; One or more alkenyl aromatic monomer and one or more C ₄-C ₆The interpolymer of conjugated diolefine; Ethene and propylene, or ethene, propylene and non-conjugated diene, especially 1, the interpolymer of 6-hexadiene or ethylidene norbornene; Vinylformic acid C ₄-C ₆The homopolymer of alkyl ester; Vinylformic acid C ₄-C ₆But comonomer, especially alkenyl aromatic monomer or the methacrylic acid C of alkyl ester and copolymerization ₁-C ₄The interpolymer of alkyl ester.What also comprise in addition is: the graftomer of aforementioned rubber polymer, wherein said graftomer is an alkenyl aromatic polymer.The preferred alkenyl aromatic polymer of using for aforementioned rubber polymer is a vinylbenzene.Most preferred rubber polymer is polyhutadiene or styrene/butadiene copolymers.

The alkenyl aromatic polymer of impact improving in this area be know and can obtain from the market.

Suitable polymers as component (A) also comprises: the alkenyl aromatic polymer with height syndiotaxy configuration.

Preferred alkenyl aromatic polymers as component of the present invention (A) is drawn together: polystyrene, syndyotactic polystyrene, the anti-high impact polystyrene rigidity of modified rubber, poly-(vinyl-toluene) and poly-(alpha-methyl styrene).

Random basically interpolymer at the component (B) of this definition comprises: (i) from about 50 moles of % to 74 mole of % by ethene and/or C ₃-C ₂₀At least a polymer unit of deriving and obtaining of alpha-olefin; (ii) from 26 moles of % to about 50 moles of % by (a) at least a vinyl or vinylidene aromatic monomer, or (b) at least a sterically hindered aliphatic series or cyclic aliphatic vinyl or vinylidene monomer, or (c) combination of at least a aromatic vinyl or the vinylidene monomer polymer unit of deriving and obtaining, (iii) from the polymer unit of deriving and obtaining by one or more alkene unsaturated polymerizable monomers of about 0-20 mole %, by (i) and (ii) derive obtain except.

Suitable alpha-olefin for example comprises: contain 3 to about 20, preferably from 3 to about 12, more preferably from 3 alpha-olefins to about 8 carbon atoms.These alpha-olefins do not contain the aromatics part.

Specially suitable is ethene, propylene, butene-1,4-methyl-1-pentene, hexene-1 or octene-1, or with one or more ethene that combines of propylene, butene-1,4-methyl-1-pentene, hexene-1 or octene-1.

Polymerisable ethylenically unsaturated monomer comprises: norbornylene and C _1-10Alkyl or C _6-10The norbornylene that aryl replaces, the interpolymer of illustrative is an ethylene/styrene/norbornene.

The suitable vinyl or the vinylidene aromatic monomer that can be used for preparing random basically interpolymer comprise: those materials that for example are expressed from the next:

R in the formula ¹Be selected from: hydrogen and contain 1 alkyl group to about 4 carbon atoms is preferably hydrogen or methyl; Each R ²All be independently selected from: hydrogen and contain 1 alkyl group to about 4 carbon atoms is preferably hydrogen or methyl; Ar is phenyl or the phenyl that replaced by 1-5 substituting group, and described substituting group is selected from: halogen, C _1-4Alkyl, and C _1-4Haloalkyl; N preferably from 0-2, most preferably is 0 from 0 to about 4.The vinyl aromatic monomer of illustrative comprises: vinylbenzene, and Vinyl toluene, alpha-methyl styrene, t-butyl styrene, chlorostyrene also comprises all isomer of these compounds in addition.Specially suitable described monomer comprises: vinylbenzene, and the derivative of low alkyl group or halogen replacement.Preferred monomer comprises: vinylbenzene, alpha-methyl styrene, low alkyl group-(C ₁-C ₄) or the derivative that replaces of cinnamic phenyl ring, for example, adjacent-,-and p-methylstyrene, encircle halogenated vinylbenzene, to Vinyl toluene or its mixture.Most preferred aromatic vinyl monomer is a vinylbenzene.

According to term " sterically hindered aliphatic series or cyclic aliphatic vinyl or vinylidene compound ", polymerisable vinyl or vinylidene monomer are corresponding to following formula:

A in the formula ¹Be that the space of 20 carbon atoms at the most is huge, aliphatic series or cyclic aliphatic substituting group, R ¹Be selected from hydrogen and the alkyl group that contains about 4 carbon atoms of 1-, preferred hydrogen or methyl; Each R ²Be independently selected from hydrogen and the alkyl group that contains about 4 carbon atoms of 1-, preferred hydrogen or methyl; Perhaps R ¹And A ¹Form a member ring systems together.Preferred aliphatic series or cyclic aliphatic vinyl or vinylidene compound are: one of the carbon atom that wherein has an olefinic degree of unsaturation is for ternary or tetrasubstituted.Described substituent example comprises: cycloaliphatic group such as cyclohexyl, cyclohexenyl, cyclooctene base, or the derivative of its cycloalkyl or aryl-replacement, the tertiary butyl, or norcamphyl.Most preferred aliphatic series or cyclic aliphatic vinyl or vinylidene compound are the cyclosubstituted derivatives of various isomery vinyl of tetrahydrobenzene and substituted cyclohexene, and 5-ethylidene-2-norbornene.Especially suitable is 1-, 3-and 4-vinyl chloride hexene.Comprise the non-side chain alpha-olefin of simple linearity of the alpha-olefin that for example contains about 20 carbon atoms of 3-, as propylene, butene-1,4-methyl-1-pentene, hexene-1 or octene-1 are not the examples of sterically hindered aliphatic series or cyclic aliphatic vinyl or vinylidene compound.

A kind of preparation method of random substantially interpolymer comprises: in the presence of the catalyzer of one or more metalloceness that combine with various promotors or constraint geometrical configuration, make the mixture of polymerisable monomer carry out polymerization; As EP-A-0,416,815 (people such as James C.Stevens) and US5 described in 703,187 (the Francis J.Timmers), are introduced into as a reference at this.The preferred operations condition that is used for described polyreaction is: pressure is from normal atmosphere to 3000 normal atmosphere, and temperature is from-30 ℃ to 200 ℃.Under the temperature on each monomer autopolymerization temperature, carry out polymerization and remove the homopolymer polymerisate that unreacted monomer may form certain tittle that is produced by radical polymerization.

The suitable catalyst of random substantially interpolymer and preparation method's example are disclosed in: EP-A-514,828; And US5,055,438; 5,057,475; 5,096,867; 5,064,802; 5,132,380; 5,189,192; 5,321,106; 5,347,024; 5,350,723; 5,374,696; 5,399,635; 5,470,993; 5,703,187; With 5,721,185, be introduced into as a reference at this.

Substantially random alpha-olefin aromatic interpolymer also can prepare by the method for describing among the JP07/278230 that uses compound shown in the following general formula:

Cp in the formula ¹And Cp ²Be cyclopentadienyl independently of one another, indenyl, fluorenyl, or the substituent of these groups; R ¹And R ²Represent hydrogen atom independently of one another, halogen atom, C ₁-C ₁₂Alkyl, alkoxyl group, or aryloxy; M is an IV family metal, is preferably Zr or Hf, most preferably is Zr; R ³For being used for making Cp ¹And Cp ²Crosslinked alkylidene group or silane two bases.

Substantially random alpha-olefin aromatic interpolymer also can prepare by the method for the description in the following document: WO95/32095 (people such as John G.Bradfute, W.R.Grace ﹠amp; Co.); WO94/00500 (R.B.Pannell, Exxon Chemicai Patents, Inc.); And plastics technology (the 25th page, in September, 1992), be introduced into as a reference at this.

Also suitable in addition is: the random substantially interpolymer that comprises at least a alpha-olefin/binyl aromatic hydrocarbons/vinyl-arene/alpha-olefin four-tuple that discloses in US application 08/708,869 (asking among the 1996.9.4) that is people such as Francis J.Timmers and WO98/09999.In its C-13NMR spectrum, these interpolymers comprise other signal, and wherein strength ratio peak-peak noise is big three times.These signals appear in the chemical shift range of 43.70-44.25ppm and 38.0-38.5ppm.Specifically, 44.1,43.9 and the 38.2ppm place observe main peak.The NMR experiment of proton test shows: the signal in the 43.7-44.25ppm chemical shift range is a methine carbon, and the signal in the 38.0-38.5ppm scope is a mesomethylene carbon.

It is believed that, these emerging signals be because: at least one alpha-olefin inset, for example comprise before or after ethylene/styrene/styrene/ethylene four-tuple due to the sequence of two statures-tail vinyl aromatic monomer inset, wherein, the styrene monomer inset of described four-tuple only exists in the mode of 1,2 (head-tail).Those of ordinary skills know, for comprising the vinyl aromatic monomer except that vinylbenzene and the described four-tuple of the alpha-olefin except that ethene, ethylene/vinyl base aromatic monomer/vinyl aromatic monomer/ethene will provide similar C-13NMR peak, and just chemical shift is slightly different.

These interpolymers can by approximately-30 ℃ to about 250 ℃ temperature, dispensable but preferred in the presence of active co catalyst in the presence of those catalyzer that are expressed from the next, carry out polymerization and make

In the formula: each Cp is π-the be bonded to cyclopentadienyl of the replacement on the M independently; E is carbon or silicon; M is an IV family metal, is preferably Zr or Hf, most preferably is Zr; Each R is a hydrogen independently, comprise about at the most 30, preferably from 1 to about 20, more preferably from 1 alkyl, silicon alkyl, or alkyl silyl to about 10 carbon or Siliciumatom; Each R ¹Be hydrogen independently, halogen, comprise about at the most 30, preferably from 1 to about 20, more preferably from 1 alkyl,-oxyl, silicon alkyl, alkyl silyl, perhaps two R to about 10 carbon or Siliciumatom ¹Can be C together _1-10The 1,3-butadiene that alkyl replaces; M is 1 or 2.Particularly, the cyclopentadienyl of suitable replacement comprises those materials that following formula is represented:

Each R is a hydrogen independently in the formula, comprise about at the most 30, preferably from 1 to about 20, more preferably from 1 alkyl to about 10 carbon or Siliciumatom, silicon alkyl, or alkyl silyl or two R form the divalent derivative of described group together.Preferably, R is (comprising all suitable isomer) hydrogen, methyl independently, ethyl, propyl group, butyl, amyl group, hexyl, benzyl, two R groups were connected to and formed the condensed ring system together phenyl or silyl or (suitably), as indenyl, fluorenyl, tetrahydroindenyl, tetrahydro-fluorenyl, or octahydro fluorenyl.

Particularly preferred catalyzer for example comprises: racemize-(dimethylsilane two bases)-two-(2-methyl-4-phenyl indenyl) zirconium dichloride, racemize-(dimethylsilane two bases)-two-(2-methyl-4-phenyl indenyl) zirconium 1,4-phenylbenzene-1, the 3-divinyl, racemize-(dimethylsilane two bases)-two-(2-methyl-4-phenyl indenyl) two-C _1-4The alkyl zirconium, racemize-(dimethylsilane two bases)-two-(2-methyl-4-phenyl indenyl) two-C _1-4The alkoxide zirconium, or it makes up arbitrarily.

In addition, also may use the catalyzer of following titanium base constraint geometrical configuration, [N-(1, the 1-dimethyl ethyl)-1,1-dimethyl-1-[(1,2,3,4,5-η)-1,5,6,7-tetrahydrochysene-s-indacen-1-yl] silicon amine root closes (2-)-N] the dimethyl titanium; (1-indenyl) (tertiary butyl amido) dimethylsilane dimethyl titanium; ((the 3-tertiary butyl) (1,2,3,4,5-η)-1-indenyl) (tertiary butyl amido) dimethylsilane dimethyl titanium; ((3-sec.-propyl) (1,2,3,4,5-η)-1-indenyl) (tertiary butyl amido) dimethylsilane dimethyl titanium; Or its arbitrary combination.

The other preparation method of the interpolymer that uses has in the present invention been described in the literature.Longo and Grassi (Makromol.Chem., the 191st volume, 2387-2396 page or leaf [1990]) and people's (journal of applied such as D ' Anniello, the 58th volume, 1701-1706 page or leaf [1995]) reported that the catalyst system based on methylaluminoxane (MAO) and cyclopentadiene titanous chloride (CpTiCl3) is used for preparing the purposes of ethylene-styrene copolymer.Xu and Lin (PolymerPreprints, Am.Chem.Soc., Div.Polym.Chem.) the 35th volume, 686-687 page or leaf [1994]) have reported and have utilized MgCl ₂/ TiCl ₄/ NdCl ₃/ Al (iBu) ₃The copolymerization of catalyzer is so that the random copolymers of preparation vinylbenzene and propylene.People such as Lu (journal of applied, the 53rd volume, 1453-1460 page or leaf [1994]) have described and have utilized TiCl ₄/ NdCl ₃/ MgCl ₂/ Al (Et) ₃Catalyzer, ethene and cinnamic copolymerization.Sernetz and Mulhaupt (Macromol.Chem.Phvs.. the 197th volume, 1071-1083 page or leaf, 1997) have described polymerizing condition to utilizing Me ₂Si (Me ₄Cp) (the n-tertiary butyl) TiCl ₂The influence of/methylaluminoxane Ziegler-Natta catalyst vinylbenzene and ethylene copolymerization.Arai, Toshiaki and Suzuki (Polymer Preprints, Am.Chem.Soc., Div.Polym.Chem.) the 38th volume, 349-350 page or leaf [1997]) and US5,652,315 (are issued to Mitsui ToatsuChemicals, have described ethene and the cinnamic multipolymer produced by the bridge formation metalloscene catalyst in Inc.).The preparation of alpha-olefin/ethene aromatic monomer interpolymer such as propylene/styrene and butylene/styrene is described in as US5,244,996 (being issued to Mitsui PetrochemicalIndustries Ltd) or US5,652, in 315 (also being to be issued to MitsuiPetrochemical Industries Ltd), perhaps be described in as among DE197 11 339Al (Denki Kagaku Kogyo KK).At this, will be used to prepare all disclosed aforesaid methods of interpolymer component and be incorporated herein by reference.In addition, although because therefore high degree of isotacticity is not " random substantially " also,, at people's such as Aria PolymerPreprints (Vol.39, No.1,1998) component (B) that ethene that discloses in and cinnamic random copolymers also can be used as film of the present invention.

In the basic random copolymer of preparation, because the homopolymerization of vinyl aromatic monomer at high temperature may form a certain amount of atactic vinyl-arene homopolymer.In general, the existence of vinyl-arene homopolymer does not have harm for the present invention, and allows.

Most preferred basic random copolymer as component (B) is ethene and cinnamic interpolymer, and ethene, vinylbenzene and at least a interpolymer that contains the alpha-olefin of 3-8 carbon atom.

Preferably, basic random copolymer comprises about 70 moles of % or ethene still less and/or one or more 'alpha '-olefin monomers of copolymerization form.The preferred upper limit is about 60 moles of % or ethene still less and/or one or more 'alpha '-olefin monomers.

Preferably, basic random copolymer comprises: about 30 moles of % of copolymerized form or more one or more vinyl or vinylidene aromatic monomer and/or one or more sterically hindered aliphatic series or cyclic aliphatic vinyl or vinylidene monomer.Preferred lower limit is about 40 moles of % or more one or more vinyl or vinylidene aromatic monomer and/or one or more sterically hindered aliphatic series or cyclic aliphatic vinyl or vinylidene monomer.

Other polymerisable ethylenically unsaturated monomer exist right and wrong enforceable.Preferably, component (B) does not comprise described monomer.

According to ASTM D1238 method A, the melt index (I of condition E ₂) usually from about 0.01 to about 50 gram/minute, preferably from about 0.01 to about 20 grams/10 minutes, more preferably from about 0.1 to about 7 grams/10 minutes, most preferably from about 0.3 to about 5 grams/10 minutes.

The density of basic random copolymer is about 0.930g/cm usually ³Or bigger, preferably from about 0.930 to about 1.045g/cm ³, more preferably from about 0.930 to about 1.040g/cm ³, most preferably from about 0.930 to about 1.030g/cm ³Molecular weight distribution, Mw/Mn, usually from about 1.5 to about 20, preferably from about 1.8 to about 10, more preferably from about 2 to about 5.

Basic random copolymer can be by common grafting, and hydrogenation is functionalized, or modification is carried out in other reaction that those of ordinary skills know.Technology according to determining can easily make polymkeric substance sulfonation or chlorination, so that functional derivative to be provided.Basic random copolymer also can carry out modification by various chainpropagation methods or cross-linking method, and described method is including, but not limited to peroxidation system, silane systems, irradiation system, or trinitride base curing system.Proving absolutely of various crosslinking process is described in US5, in 869,591 and EP-A-778,852, is introduced into as a reference at this.Utilize heat, the dual cure systems that moisture and irradiating step combine can adopt effectively.For example, wish to use peroxide cross-linking agent, use peroxide cross-linking agent, use with silane crosslinker to contain sulfur crosslinking agent with irradiation with silane crosslinker.Basic random copolymer also can carry out modification by various cross-linking methods, described method is including, but not limited to mixing two olefinic constituentss as comonomer in its preparation process, then by aforesaid method with for example comprise the pass through vinyl of sulphur as linking agent carried out other method of sulfurized and carry out crosslinked.

Be suitable for to make above-mentioned basic random copolymer, be preferably thermoplasticly, this means that it can carry out molding or other moulding and reprocessing under its fusing point or the temperature more than the softening temperature at the component (B) of this definition.

The blend that comprises the polymeric material that uses for the present invention can obtain according to methods known in the art, described method including, but not limited to: in extruser or Banbury, do mixed.Dried mixed pellet directly melt-processed becomes final solid-state product.

Preferably, wherein the content of component (A) is about 60% weight or more, is more preferably 70% or more blend.Be about 20% weight or more for component (B) preferred lower limit amount in blend.Be about 40% weight or still less for component (B) preferred upper limit amount in blend, be more preferably 30% or still less.

Membrane according to the invention, its thickness are lower than about 350 microns (μ m), preferably are lower than about 300 μ m, most preferably are lower than about 250 μ m (10 mil).

Membrane according to the invention can comprise one or more additives, and they are including, but not limited to oxidation inhibitor, photostabilizer, processing aid, softening agent, pigment, filler, slip additive, anti, antifogging agent, tackiness agent, tackifier, whipping agent, nucleator, transparent base, flame-retardant additive.

Film provided by the invention does not almost have or does not have free shrink in the time of 90 ℃.This means that in the time of 90 ℃, the free shrink of film is more preferably less than about 10% less than about 20%.Film of the present invention can be single thin film or multilayer film.One or more layers of described film can be the orientation or the foaming.Multilayer film of the present invention can comprise: be contained in one deck of the blend of this definition, two-layer or multilayer.More preferably, membrane according to the invention, its thickness from about 0.5 to about 10 mils.Preferably, the present invention relates to the toughness and the film of property very, as described herein, described film comprises: the main blend of the polymeric material of being made up of component (A) and component (B).Film of the present invention can print.Particularly preferably be, wherein the film that component (A) is made up of one or more polystyrene and component (B) is made up of one or more random substantially ethene-styrene copolymers.

Film of the present invention can obtain according to methods known in the art.Described film can utilize blown film extrusion processes or cast-film extrusion method to prepare, and described method comprises co-extrusion method and extrusion molding coating method.One or more layers of described film can for example foam with conventional whipping agent, so that the preparation foamed thin sheet.One or more layers film laminating can be formed multilayered structure.Passing through stentering, after double-membrane soaking technology or the blown film processes, film can also be orientated.

In one embodiment, film of the present invention is an oriented film.Term " orientation " refers to as used herein: the thermopolymerization goods are stretched so that make molecular chain aligned process at draw direction.When stretching in one direction, this process is called uniaxial orientation; When stretching on two (vertically) directions, this process is called diaxial orientation.Orientation can be uniaxial, is preferably diaxial orientation.Orientation can be finished according to the method for routine, as blown film process, and " double-membrane soaking " membrane process, cast/stretched membrane process or other processing method as known in the art are so that provide orientation.

Preferably, according to oriented film of the present invention, its modulus (secant modulus vertical 2%) is greater than 150,000psi (1034MPa).Preferred oriented film comprises: wherein component (A) is the blend of ethene-styrene copolymer for polystyrene and component (B).Preferably, the content of component (A) from greater than about 50% to less than in about 80% the scope, more preferably, about 70% to about 77% scope, most preferred about 75% weight, the content of component (B) from greater than about 20% to less than about 50%, more preferably, 23% to the scope of about 30% weight, be most preferably 25% weight.Preferably, random substantially ethene-styrene copolymer comprises: about 60% to about 75% weight, the co polystyrene of preferred about 70% weight.Melt index (condition E) preferably from about 0.3 to about 5 restrains/10 minutes.

Oriented film of the present invention is particularly suitable in window envelope and the application corresponding.For window envelope and application corresponding, high-modulus, good cutting property and low mist degree are the performances of wishing.Advantageously, membrane according to the invention combines these performances.Be characterised in that at this oriented film that provides: at film performance, comprise toughness, modulus and wear resistance direction have to expect and change or improve.In addition, when comparing with the polystyrene film of conventional modified rubber, especially with regard to glossiness (higher) and mist degree (lower), the optical property of blend film of the present invention is improved.When representing by heavily stressed relaxation property, described film also demonstrates the dead pleat characteristic of improvement in addition.In addition, tear resistance also will advantageously obtain influence.When with ratio described herein, during with crystallization syndiotactic polystyrene resin (component (A)) blending, ethene-styrene copolymer resin will provide under suitable diaxial orientation condition: have the good optical characteristic and suspect film less than elongation.

On the other hand, the present invention relates to foamed thin sheet.Described film especially is suitable as label or is applicable to the goods that preparation is thermoformable.

For preparation foamed thin sheet structure, can use physics or chemical foaming agent to finish greater than about 300kg/m ³, be preferably greater than about 350kg/m ³, most preferably greater than about 400kg/m ³Foam density.Usually, foam density is less than about 1000kg/m ³, preferably less than about 950kg/m ³, most preferably less than about 900kg/m ³According to ASTM D3576, macropore foamy cell size is from about 0.01 to about 5.0 millimeters, preferably from about 0.02 to 2.0 millimeter, most preferably from 0.02 to about 1.8 millimeters.The cell size of fine-celled foam will be less than 0.1 millimeter.According to ASTM D2856, foam can perforate or closed pore.

According to methods known in the art, as utilize the co-extrusion method, can obtain multilayer film of the present invention, described film comprises one or more foaming layer, and described foaming layer comprises: the component (A) and the blend (B) that are contained in this definition.Two-layer or the three-layer thin-film that preferably has one or two upper layer, and foaming layer is a sandwich layer.Upper layer can comprise or not contain main blend by the polymeric material of forming at the component (A) and the component (B) of this definition.Preferably such film, it comprises foaming layer, and described foaming layer is included in the component (A) and the blend (B) of this definition, and one or two nonfoamed layer makes by the component (A) in this definition, is particularly prepared by polystyrene.In three-decker, preferably, foaming layer is sandwich layer or middle layer.

Label film can be by printing, be cut into certain width, utilizes conventional tackiness agent and industrial known glue, and the film rolling that will have label is glued on the container, for example on the bottle, and constitutes.In addition, film of the present invention can print, and is coated with pressure sensitive adhesive, is laminated on separate paper or the film, and is applied on bottle, container or other surface by the pressure-sensitive technology of routine.

Preferred foamed thin sheet comprises: wherein component (A) is the blend of the basic random copolymer of ethene-vinylbenzene for polystyrene and component (B).Preferably, the content of component (B) from about 25% to about 35% weight.

Described bottle can be vial or PET bottle.When topped or when being attached on the vial, label can also play the purposes of protection.

If bottle is the PET bottle, preferred labels is greater than about 8 grams and at the coiling labels of horizontal tearing force greater than about 25 grams at tearing force longitudinally.According to foamed thin sheet of the present invention, its elongation should be between about 4 to about 5%.

The performance that is used for polymkeric substance of the present invention, blend and film can be measured by following testing method.These methods will be used in an embodiment.

Melt index (MI) will be according to ASTM D-1238, condition E (190 ℃ 2.16kg) are measured.

Secant modulus, elongation limit and ultimate tensile strength will be measured according to ASTM-D-882-91.

Mist degree is measured according to ASTM D-1003.

Glossiness is measured according to ASTM D-2457.

Vinylbenzene is analyzed: in the interpolymer of component (A), the styrene content of interpolymer or multipolymer and the content of random isotactic polystyrene can utilize proton magnetic resonance (PMR) ( ¹H-NMR) measure.All proton N MR samples all sym.-tetrachloroethane- ²D (TCE- ²D) preparation in.This solution comprises the polymkeric substance of 1.6-3.2 weight %.Melt index (MI) is used as beacon to measure the concentration of sample.Therefore, work as I ₂In the time of/10 minutes, use 40 milligrams of interpolymers greater than 2 grams; And work as I ₂In the time of between 1.5 and 2 restrain/10 minutes, use 30 milligrams of interpolymers; Work as I ₂In the time of/10 minutes, use 20 milligrams of interpolymers less than 1.5 grams.Directly interpolymer is weighed, and add in the test tube.Add 0.75 milliliter of TCE-by syringe ²The aliquots containig of D, and with one the sealing the polyethylene lid cover this test tube.In 85 ℃ water-bath, sample is heated, so that make interpolymer softening.In order to mix, utilize hot rifle that the sample of adding a cover is refluxed occasionally.

At 80 ℃, utilize the sample probe, proton N MR spectrum is accumulated on the Varian VXR 300, and at 5.99ppm, to TCE- ²The residual proton of D carries out reference.Between 1 second, change time of lag, and each sample is collected data in triplicate.Following instrument condition is used for analysis to the interpolymer sample: Varian VXR-300, standard ¹H; Sweep length, 5000Hz; Acquisition time, 3.002 seconds; Pulse width, 8 microseconds; Frequency, 300Mhz; Postpone 1 second; Temporary, 16.

About 10 minutes of the bulk analysis time of each sample.

At the beginning, obtain polystyrene sample, STYRON the time of lag of utilizing second ^TM680 (derive from Dow Corning Corporation (Midland, MI)) ¹H NMR spectrum.Be shown below, proton is carried out " mark ": b, branch; α, alpha; O, the neighbour; M; P is right.

Quadrature according to the proton that marks in the structural formula; " A " represents aPS.Integration A _7.1(aromatic hydrocarbons, about 7.1ppm) it is believed that it is three neighbours/contraposition proton; And integration A _6.6(aromatic hydrocarbons, about 6.6ppm) is two metal protons.The aliphatic proton of two marks resonates at the 1.5ppm place; And the proton of single mark resonates at the 1.9ppm place.The aliphatic series district concentrates on about 0.8-2.5ppm and is referred to as A _A1A _7.1: A _6.6: A _A1Theoretical ratio be 3: 2: 3, or 1.5: 1: 1.5, and with the STYRON of several time of lag of 1 second ^TMThe observed ratio of 680 samples is relevant especially.By with suitable integration divided by A _6.6(ratio A _rBe A _7.1/ A _6.6) carrying out ratio calculating, described ratio is used for checking integration and checks the signal at peak.

Zone A _6.6Be appointed as 1.Ratio A l is integration A _A1/ A _6.6The spectrum of all collections all has (o+p): m: (1.5: 1: 1.5 integration ratio of α+b).Aromatic hydrocarbons is 5/3 to the ratio of aliphatic hydrocarbon proton.According to proton that marks in the following formula and b, can predict the aliphatic hydrocarbon ratio of 2-1 respectively.When individually two aliphatic hydrocarbon peaks being carried out integration, also observed this ratio.

For the ethylene/styrene interpolymer, utilize 1 second time of lag ¹H-NMR spectrum, it has definite integration C _7.1, C _6.6, and C _A1, comprise all aromatic hydrocarbons protons of multipolymer and ortho position and the contraposition proton of aPS to cause integration at peak, 7.1ppm place.Similarly, in the spectrum of interpolymer, aliphatic hydrocarbon district C _A1Integration will comprise: derive from the aliphatic hydrocarbon proton of aPS and interpolymer, wherein with every kind of polymkeric substance all without any baseline resoluting signal clearly.At the peak C of 6.6ppm place _6.6Integration can with other aromatic hydrocarbons signal resolution, it is believed that this only be since the aPS homopolymer due to (may be the metal proton).(according to STYRON ^TM680 credible sample compares, and determines peak-to-peak signal (the integration A of random isotactic polystyrene at the 6.6ppm place _6.6)).This is rational hypothesis, owing to when low levels random isotactic polystyrene very, only can observe very weak signal.Therefore, the phenyl protons of multipolymer needn't work to this signal.Utilize this hypothesis, integration A _6.6To become the basis of quantitative measurment aPS (random isotactic polystyrene) content.

Following equation is used for determining mixing in the ethylene/styrene interpolymer sample cinnamic degree:

(C phenyl)=C _7.1+ A _7.1-(1.5 * A _6.6)

(C aliphatic hydrocarbon)=C _A1-15 * A _6.6)

s _c=(C phenyl)/5

e _c=(C aliphatic hydrocarbon-(3 * s _c))/4

E＝e _c/(e _c+s _c)

S _c＝s _c/(e _c+s _c)

Equation is used for calculating ethene and cinnamic molar percentage in the interpolymer. $\mathrm{Wt}\%E=\frac{E^{*}28}{\left(E^{*}28\right)+\left({S_c}^{*}104\right)}\left(100\right)$ With $\mathrm{Wt}\%S=\frac{{S_c}^{*}104}{\left(E^{*}28\right)+\left({S_c}^{*}104\right)}\left(100\right)$

S in the formula _cAnd e _cBe respectively the vinylbenzene in the interpolymer and the proton umber of ethene, S _cBe respectively the molfraction of styrene monomer and vinyl monomer in the interpolymer with E.

The weight percentage of aPS can utilize following equation to calculate in the interpolymer: $\mathrm{Wt}\%\mathrm{aPS}=\frac{(\mathrm{Wt}\%S)*\left(\frac{A_{6.6}/2}{S_c}\right)}{100+\[(\mathrm{Wt}\%S)*\left(\frac{A_{0.66}/2}{S_c}\right)\]}*100$

Cinnamic total content is also determined by quantitative Fourier transform infrared spectroscopy (FTIR).

The following examples are to explanation of the present invention, and do not constitute limitation of the invention.Abbreviation below using in an embodiment: PS represents polystyrene; ESI represents the interpolymer that ethene-vinylbenzene is random substantially; MD represents vertically; CD represents laterally.

Embodiment 1-comprises the oriented film of the random substantially interpolymer blend of polystyrene/ethene-vinylbenzene

Polystyrene is the STYRON that derives from Dow Chemical Company ^TM665.

ESI is according to following acquisition: preparation interpolymer in operate continuously recirculation reactor (36.8 gallons, 140 liters).Reactor 475psig (3, liquid is full of under 275kPa), about 25 minutes of the residence time.Base feed and catalyst/co-catalyst stream.The solvent of supply response device is by two different source supplies.Use has definite speed, from the fresh toluene liquid of surge pump stream, so that be provided for the earial drainage (20 Pounds Per Hours (9.1kg/h)) of reactor sealing.In the suction side of five parallel surge pumps, circulating solvent is mixed with the styrene monomer that does not suppress.These five surge pumps with solvent and vinylbenzene be conducted to be in 650psig (4, in reactor 583kPa).The fresh benzene ethylene stream passes through flowmeter survey, and by independent flowmeter survey global cycle solvent/styrene stream.Ethene be conducted to be in 687psig (4, in reactor 838kPa).By the mass flow meter measurement ethylene stream.Under meter/controller is used in the exit of ethene control valve hydrogen being passed in the ethylene stream.Ethene/hydrogen mixture mixes with solvent/styrene stream in room temperature.When entering reactor cycles, the temperature of whole feedstream is by reducing to 2 ℃ with-10 ℃ of ethylene glycol in the heat exchange of chuck.Independently prepare three kinds of catalyst components in the container at three: add fresh solvent and catalyst concentration/promotor pre-composition, and sneak in its corresponding processing vessel, the surge pump by variable velocity is conducted in the reactor then.Three component catalyst systems enter in the reactor cycles by syringe and static mixer, and enter the suction side of twin-screw pump.Raw material supplying stream is also in downstream, catalyzer injection phase but in the upstream, suction side of twin-screw pump, be conducted in the reactor cycles by syringe and static mixer.

After the under meter of measuring solution density,, catalyzer killer (being mixed with the water of solvent) stops polymerization by being added in the reactor production line.Static mixer in production line provides the dispersion of catalyzer killer and the additive in the reactor overflow.This overflow enters then: provide in the post-reactor well heater of other energy for the flash distillation of solvent removal of solvents.This flash distillation overflow discharge the post-reactor well heater and the pressure at reactor pressure control valve place from 475psig (3, carry out when 275kPa) reducing to 450mmHg (60kPa) absolute pressure.The polymkeric substance of flash distillation is entered in first of devolatilization device of two hot-oil jacket.The volatile matter that flashes off from the first devolatilization device utilizes the heat exchanger of ethylene glycol chuck to carry out condensation, by the suction side of vacuum pump, and drains in solvent and the styrene/ethylene separating tank.When making solvent cycle, solvent and vinylbenzene take out from the bottom of this jar, and ethene is discharged from the top.Ethylene stream utilizes mass flow meter measurement.To add the calculating of gas dissolved in solvent/styrene stream to the measurement of emptying ethene, be used for calculating the turnover ratio of ethene.Utilize toothed gear pump that isolating polymkeric substance and residual solvent in the devolatilization device are pumped in the second devolatilization device.The second devolatilization device moves under 5mmHg (0.7kPa) absolute pressure, so that flash off residual solvent.In the heat exchanger of ethylene glycol, make this solvent condenses, carry out pumping, and drain in the waste treatment jar by another vacuum pump.Utilize toothed gear pump that dry polymeric (being lower than total volatile matter of 1000ppm) is pumped in the underwater pelletizer with 6 casement heads, carry out pelletizing, Rotary drying, and be collected in the case of 1000 pounds (454kg).

The Al catalysts component is commercially available modified methylaluminoxane 3A type (MMAO-3A).

1 type boron promotor is three (pentafluorophenyl group) borine.

Titanium catalyst is (1H-encircles penta [1] phenanthrene-2-yl) dimethyl (tertiary butyl amido)-silane titanium 1, the 4-diphenyl diethylene).

PS and ESI do to mix.

Film C, D and F utilize downward inflation-alignment method production.Die diameter is 2 inches, and melt temperature is about 230 ℃ (linear velocity is 45fpm (13.7m/min)).Blow-up ratio (girth of bubble form film is divided by the girth of die head) is about 12.Film E is the polystyrene window film DWF Clear LD (deriving from Dow Corning Corporation) of commercially available orientation.The performance (MD) of table 1 orientation PS/ESI film (C, D and F) and DWF Clear LD

Film	????F	????C	????D	????E*
					The styrene content of ESI multipolymer (wt%)	????60	????70	????70	????-
????MI	????0.5	????1.0	????1.0	????-
					PS/ESI is than (wt%)	????75/25	????75/25	????50/50	????100/0
Film thickness (micron)	????30.5	????30.5	????38	????33
					Elongation limit (%)	????75	????41	????57	????26
Ultimate tensile strength (MPa)	????53.1	????53.8	????45.5	????82.7
					Toughness (J/cc)	????18.3	????18.6	????21.4	????17.9
2% the second modulus (MPa)	????1724	????1724	????1344	????2758
					Initial mist degree (%)	????7.9	????6	????13	????5
Glossiness in the time of 60 °	????114	????130	????84	????150
					The quantity of kerf	????27	????32	Can't see	???＞150
Haze change (%)	????0.0	????8.5	????1.7	????82.0

* not embodiments of the invention.

In Embodiment C, when comparing with conventional polystyrene homopolymer film sample E, the combination of high glossiness and high-clarity (low haze) has obtained high modulus, high tensile strength and toughness.Sample D has demonstrated increases the ESI amount on most preferred amount, will cause glossiness to descend, reduce tensile strength and reduce the flexible effect.Sample F has demonstrated and has reduced the effect that cinnamic content will cause glossiness reduction and mist degree to increase in the ESI material.Sample D and F have demonstrated uncommon, the beyond thought combination of high tenacity, high-modulus, high tensile and excellent optical property, but do not have most preferred film good.

In window film was used, scratch resistance was crucial.The scratch resistance of film C, D and F is tested and compared with as a reference film E.In this test, measure the haze value and the record of each film.Then, under the vacuum of 10 inches of mercury, make film face toward LF Smithe 527 bronze drums and carry out relative movement, so that on film, produce scratch.Then, measure the mist degree and the record of each film once more.Then, change by the haze value that calculates each measured thin film of scraping test front and back, and the degree of scratch on the MEASUREMENTS OF THIN.When because the change of scraping Film Optics mist degree when causing film that bigger mist degree changes less than the scraping by under the same conditions, this film is thought scrape resistant more.

Film C, D and F demonstrate than film E and significantly improve.The PS/ESI film demonstrates very little mill white and mist degree increases, and these usually can be seen in Clear LD.

Embodiment 2-is by PS/ESI blend toughness that makes and the foamed thin sheet of enduring property

Prepare the not upper layer of polystyrene foamed of polystyrene-based foam core and two with inflation film co-extrusion method.Foam core is not having the ESI resin to prepare with containing under a small amount of ESI.Be added in the upper layer without any ESI.Produce ESI described in embodiment 1, and the multipolymer styrene content is 69% weight, MI is 4.6.Polystyrene is Krasten (KaucukCorp.; Mw:260,000; Mn:104,000; MI:6-8 gram/10 minutes; Mineral oil: 1.5-2%).PS and ESI are in mixing.The total thickness of foamed thin sheet is 130 microns ± 20 microns.The performance of Table II foamed thin sheet

Foamed thin sheet	Tear resistance (MD, g)	Tear resistance (CD, g)	20 ° of glossiness	2% secant modulus (MD, MPa)
					0wt%ESI (Comparative Examples)	????8	????25	????20.1	????850
????10wt％ESI	????8	????42	????27.4	????674
					????20wt％ESI	????8	????40	????38.4	????660
????30wt％ESI	????8	????56	????46.4	????658

The film that utilizes the PS/ESI blend to make is toughness and endures property, and has the tear resistance and the glossiness of improvement.

Embodiment 3-is by PS/ESI blend toughness that makes and the film of enduring property

Utilize the commercial polysterol resin, STYRON ^TM665 (deriving from Dow Chemical Company) and multipolymer styrene content are respectively the ESI material of 60.6,67.5 and 71.3 weight %, prepare film described in Table III.The performance of Table III ESI/ polystyrene film blend and film

The ESI sample	????1	????2	????3
				????wt％ESI	????30	????30	????30
????wt％PS	????70	????70	????70
				????ESI?MI	????0.55	????0.5	????0.9
ESI% multipolymer S	????71.3	????60.6	????67.5

Extrude parameter (1.25 inches (3.2cm) is with the Killion extruding machine of 3 inches (7.6 centimetres) inflation film die heads)

Temperature (F) melt	????478	????478	????484
				Helix speed (rpm)	????50.3	????50.3	????50.3
Spiral Amps	????15	????15	????15
				Nip rolls speed (m/min)	????7.6	????7.7	????7.6
Flat width (cm)	????22.9	????24.3	????24.3

Film performance mean thickness (micron) 38 38 38 optical properties

Mist degree (%)	????8.0	????15.0	????17.0
				45 ° of glossiness	????84	????75	????71

Secant modulus (MPa)

1% secant modulus, MD, (MPa)

????1441

????1193

????1586

Film stretching intensity (2 inch per minute clock)

Ultimate tensile strength, MD (psi)	????36	????24.7	????25.4
				Elongation limit, MD (%)	????4	????3	????6
Tensile toughness, MD, (J/cc)	????1.1	????0.3	????1.2

According to above-mentioned data as can be seen, will cause the glossiness improved than the high copolymer styrene content, the modulus of increase, the tensile strength of improvement and the toughness of increase, this shows that highly preferred styrene content is in the cinnamic scope of 67-72%.

According to ESI and polystyrene (STYRON ^TM678 (deriving from Dow Chemical Company) do to mix thing, as preparation film as described in the Table IV, the polystyrene that wherein has increasing amount.

Table IV:

Extrude parameter (1.25 inches (3.2cm) is with the Killion forcing machine of 3 inches (7.6cm) inflation film die heads)

Temperature (F) melt	????446	????447	????447
				Helix speed (rpm)	????50	????49.7	????49.8
Spiral Amps	????13	????12	????12
				Nip rolls speed (m/min)	????7.7	????6.5	????9.1
Flat width (cm)	????23	????24	????24

Table V:

ESI/ polystyrene blend and film performance

????％ESI	????40	????10
				The % polystyrene	????60	????90	????100
????ESI?MI	????0.95	????0.95	????-
				ESIwt% multipolymer vinylbenzene	????71.5	????71.5	????-

Film performance mean thickness (micron) 84 69 76 optical properties

Mist degree (%)	????24.7	????6.3	????1.5
				45 ° of glossiness	????104	????98	????109

Secant modulus (MPa)

1% secant modulus, MD, (MPa)

????1296

????1696

????1862

Film stretching intensity (2 inch per minute clock)

Ultimate tensile strength, MD (psi)	????46	????43.1	????40.6
				Elongation limit, MD (%)	????15	????3	????2
Tensile toughness, MD, (J/cc)	????4.8	????0.8	????0.4

According to last Table V as can be seen, even the ESI of low levels (10%) also will influence tensile elongation and toughness, and higher content (40%) will cause toughness and the tensile elongation improved, meanwhile, keep high glossiness and the deflection of representing as by miter angle glossiness and 1% secant modulus.

Claims (13)

1. a toughness that comprises the blend that contains component (A) and component (B) and the very film of property, wherein the content of component (A) in the gross weight of component A and B from about 45% weight to about 90% weight; In the gross weight of component A and B, the content of component (B) is from about 10% weight to about 55% weight; Wherein component (A) is made up of one or more alkenyl arene polymkeric substance and component (B) is made up of one or more random substantially multipolymers, described multipolymer comprises ethene and/or one or more 'alpha '-olefin monomers of polymerized form (i) from about 50 moles of % to 74 mole of %, (ii) from 26 moles of % to one or more vinyl of about 50 moles of % or vinylidene aromatic monomer and/or one or more sterically hindered aliphatic series or cyclic aliphatic vinyl or vinylidene monomer and (iii) from other polymerisable ethylenically unsaturated monomer of about 0-20 mole %.

2. according to the film of claim 1, it is a single thin film.

3. according to the film of claim 1, it is multilayer film.

4. according to each film of claim 1-3, it is an oriented film.

5. according to each film of claim 1-3, wherein one deck is foaming layer at least.

6. according to each film of claim 1-5, wherein component (A) is a polystyrene.

7. according to each film of claim 1-6, wherein component (B) is the random substantially interpolymer of ethene-vinylbenzene.

8. according to each film of claim 1-7, it is a printing film.

9. window envelope with one or more window openings, described window opening is by non-opacity plastic window sticking patch complete closed, and described window sticking patch is made of the film of claim 1.

10. label that makes by the film of claim 1.

11. the film according to claim 4, its at vertical 2% secant modulus greater than 150,000psi (1034MPa).

12. the film according to claim 1, its at vertical 1% secant modulus greater than 85,000psi (586MPa).

13. goods that comprise the film of claim 1.