CN1242029A

CN1242029A - Polyolefin compositions with balanced sealant properties and improved modulus and method for same

Info

Publication number: CN1242029A
Application number: CN 97181099
Authority: CN
Inventors: L·伯斯尔斯; J·A·德路特; L·T·卡勒; P-W·S·楚; S·A·得昆德; J·J·范邓; T·T·奥斯瓦德
Original assignee: Dow Chemical Co
Current assignee: Dow Chemical Co
Priority date: 1996-11-13
Filing date: 1997-11-13
Publication date: 2000-01-19

Abstract

This invention pertains to a sealant film composition comprising at least two ethylene polymer component materials. One aspect of the invention relates to a multilayer structure having balanced sealant properties and comprising a sealant layer and a polypropylene layer, wherein the sealant layer comprises and is made from a polymer composition having particular molecular weight characteristics and a second ethylene polymer. A preferred embodiment of the present invention pertains to a medium density polyolefinic film and composition characterized by an excellent balance of a low seal initiation temperature and improved film modulus. The film and composition is comprised of and made from at least one lower density homogeneously branched ethylene polymer and at least one higher density heterogeneously or homogeneously branched ethylene polymer. The invention is particularly useful in those applications requiring fast seal times and good packaging dimensional stability such as, for example, cook-in packaging, hot-fill packaging, flowable material pouches, compression fill packaging, shrink film packaging and barrier shrink film packaging as well as biaxially oriented polypropylene (BOPP) film structures.

Description

Polyolefin compositions and its preparation method with balanced sealant properties and improved modulus

The present invention relates to comprise the sealing film composition of at least two kinds of ethylene polymer component.One aspect of the present invention relates to and has balanced sealant properties and comprise sealing ply and the multilayered structure of polypropylene layer, and wherein sealing ply comprises and by having the specific molecular measure feature and containing second kind of polyvinyl polymer composition preparation.A preferred embodiment of the present invention relates to the middle density polyolefin film and the composition of the equilibrium response with fabulous low sealing initiation temperature and improved film modulus.This film is formed and is prepared by the mutually non-homogeneous or homogeneously branched ethylene polymer of at least a low density homogeneously branched ethylene polymer and at least a higher density with composition.

Can be used for food product pack and food storage field of containers although find ethene polymers already, the polyolefin compositions that manufacturers and packing merchant can not get having film, coating, lamination or the coextrusion form of appropriate balance performance.For example, should have multiple key property in packing and storage field as the best ethylene polymer composition of sealing ply, but as low heat seal and heat be clamminess starting temperature, high hot sticky intensity, wide hot sticky seal temperature scope, good interlaminar bonding performance, high softening-point and low hexane extraction quantity.

Although can't satisfy this requirement at present, the importance of industrial known balanced sealant properties.In other words, low heat seal and hot sticky starting temperature are important for improving sealing speed and reducing used energy.Height hot sticky the wide hot sticky seal temperature scope under the intensity (promptly, wherein hot sticky intensity is more than or equal to about 46g/cm (measuring by Dupont spring method) or more than or equal to the seal temperature scope of about 3.31N/15mm (5.6N/in.) (measuring with mechanical thermal viscosity tester such as Top Wave tightness system)), for the handiness of guaranteeing package integrity properties, tightness system with hang down that to pack breakthrough rate be important.Good interlayer adhesion for guarantee article packing integrity and article packing or container attractive in appearance also be important.When connection with wrapping of piece at high temperature, as when being used for heat and filling, high softening-point or temperature are required.But application requiring low hexane extraction quantity for contact food.

Usually, when attempting to obtain the equilibrated sealing property, strengthen a certain specific resin performance need and sacrifice another key property to some extent.For example, for ethylene/alpha-olefin polymer, generally reach required heat-sealing and hot sticky starting temperature by the co-monomer content that increases resin.On the contrary, high Vicat softening temperature and low n-hexane extraction amount reach by the co-monomer content that reduces resin usually.Therefore, but improve resin-sealed initiation performance and cause reducing pro rata the Vicat softening temperature usually and increase extraction quantity pro rata.

Several important multi-layer packagings and accumulating structure are by polypropylene layer, and particularly the polypropylene of diaxial orientation (BOPP) homopolymer basic unit or sandwich layer are formed.Usually, the BOPP structure use polypropylene copolymer and ter-polymers as sealing material (and/or binder layer) to guarantee the good interlayer adhesion with BOPP basic unit.Although polypropylene copolymer and ter-polymers can provide and the good interlayer adhesion of BOPP basic unit and good hot sticky strength property really, these multipolymers and ter-polymers show inappropriate high heat seal and hot sticky starting temperature inevitably.

Other polyolefine material has been used as the sealing material of multi-layer packaging and accumulating structure.Yet common known polyolefine sealing material can not provide required whole machine balancing performance and/or umformer and the required processing handiness of wrapping machine.

In addition, also do not obtain to be used as in the padding field the best polyolefine resin composition of sealing ply in lamination or compression because key property (be the low-heat sealing initiation temperature and in-the high film modulus) be to repel mutually for common polyolefin compositions.In other words, the composition with required low sealing initiation temperature characteristic has lower film modulus inevitably.On the contrary, provide in-composition of high film modulus has too high sealing initiation temperature feature inevitably.

Based on a plurality of reasons, low sealing initiation temperature and in-Gao (improvement) film modulus is vital performance.Require improved film modulus (film stiffness) to guarantee the good film machinable of film in packing making, filling and/or seal operation.For example, have the film of good machinability even when cutting facility such as blade and blade are not too sharp, also can be evenly and cutting effectively, reduce waste material thus and/or reduce the renewal and renovation of equipment requirement.In in compression is filled, also requiring-the high film modulus to be to guarantee good dimensional stability, membrane structure, plastics tubing etc. upwards erect, to help the filling article that will pack effectively.

For guaranteeing higher package speed, need low sealing initiation temperature.In other words, the temperature that can form the high strength sealing is low more, and time per unit can obtain more packing unit so that the productivity maximum.In addition, lower sealing initiation temperature must lower control of tightness system temperature and the lower sealing energy expenditure of refinement degree.

Although disclose various polyolefin compositionss as sealing material, although and the mixture of being made up of coextrusion or laminate film structures is allegedly satisfactory, known composition (especially when the time) as the single thin film structure do not have usually comprise low sealing initiation temperature and in-optimum balance of high film modulus key property.For example, known TAFMER ^TMResin (being sold by Mitsui Petrochemical) provides the sealing agent with low sealing initiation temperature.Yet, known TAFMER ^TMNo matter resin all can not provide overall required balance quality as the single component sealing material or as the polymer blending constituent materials.Known TAFMER ^TMDuring resin can not provide-the high film modulus.TAFMER ^TMAnother defective of resin is that this resin is quite expensive, and supply is limited always.

With TAFMER ^TMResin is compared, and heterogeneous branched ethylene polymer such as linear low density polyethylene (LLDPE) and ultra-low density polyethylene obtain easily.Yet heterogeneous branched ethylene polymer can not provide optimum required overall performance balance as sealing material, so they are not suitable for use in the BOPP structure especially.For example, heterogeneous branching linear low density polyethylene (LLDPE) sealing ply of these polymer manufacture (and by) is poor especially with the interlayer adhesion of polypropylene layer.In addition, therefore medium-low sealing initiation temperature that heterogeneous branched ethylene polymer is tending towards having and medium to low film modulus is not particularly suitable for wherein requiring the high-speed packaging of good film machinability to operate.

The AFFINITY that homogeneously branched ethylene polymer such as The Dow Chemical Company sell ^TMResin also is suitable as sealing material.Although the homogeneously branched ethylene polymer material shows improved sealing initiation performance usually, yet this type of material has low relatively film modulus inevitably.

People's such as Shibata US4,429,079 discloses a kind of ethylene/alpha-olefin copolymer blend composition, it comprises (A) 95-40wt% ethene and the random copolymers with alpha-olefin of 5 to 10 carbon atoms, (B) mixture of random copolymers of 5 to 60wt% ethene and alpha-olefin with 3 to 10 carbon atoms, described random copolymers (A) has melt index 0.1 to 20g/10min., density 0.910 is to 0.940g/cc, degree of crystallinity (passing through X-ray measuring) 40-70%, 115 to 130 ℃ of fusing points, ethylene content 94 is to 99.5mol%; Described random copolymers (B) has melt index 0.1 to 50g/10min., and density 0.870 is to 0.900g/cc, degree of crystallinity (passing through X-ray measuring) 5-40%, and 40 to 100 ℃ of fusing points, ethylene content 85 is to 95mol%; It is said (A) component polymer by the production of titanium catalyst system, and (B) component polymer is by vanadium catalyst production.These two kinds of catalyst systems all are called Ziegler-Natta type catalyzer, are used for the production of linear ethylene/alpha-olefin polymer.In other words, this polymkeric substance will have the linear molecule main chain, and not have any long chain branching.In addition, (A) component polymer expects that also having heterogeneous branching short chain distributes, and (B) component polymer has homogeneously branched short chain distribution.Film by people's such as Shibata composition production allegedly has good low temperature heat seal performance, heat-seal strength, anti-pin hole, the transparency and shock strength.Yet, people such as Shibata are unexposed have high limit hot sticky intensity (be the film of numerical value 〉=3.11N/mm), the also unexposed film that has medium to high-modulus.In addition, disclosed data analysis shows among the embodiment that people such as Shibata are provided, and the heat seal performance of film increases and to some extent with the density linear change of blend components polymkeric substance.

People's such as Naito US4,981,760 disclose the polyethylene mixture of density 0.900 to 0.930g/cc and melt flow rate (MFR) 0.1 to 100g/10in, this mixture comprises that (I) 60 is to 90 parts by weight of ethylene/alpha-olefin random copolymers, (II) 1 to the 40 weight part density high density polyethylene(HDPE) of 0.945g/cc at least, wherein (I) and amount sum (II) are 100 weight parts, described random copolymers comprises ethene and has the alpha-olefin of 4 to 10 carbon atoms, it is 2.0 to 10mol% that this multipolymer has alpha-olefin content, density 0.895 is to 0.915g/cc, the program temperature differential thermal analysis curve of described multipolymer (multipolymer melts then cooling back determine with dsc method gradually fully) shows endotherm(ic)peak in 75 ° to 100 ℃ scopes, be at least 0.8 at the caloric receptivity at place, described peak and the ratio of total caloric receptivity, the program temperature differential thermal analysis curve of described high density polyethylene(HDPE) (this polymkeric substance melts fully and makes it cool off the back determine with dsc method) is 120 ℃ or higher temperature place demonstration endotherm(ic)peak.It is said that component polymer (1) prepares with vanadium catalyst, film has improved heat seal and heat-blocking.The unexposed density that comprises of people such as Naito is lower than the film processed of the component polymer of 0.945g/cc.In addition, people such as Naito disclose the film that has low heat seal or thermal viscosity starting temperature when the concentration than low-density fraction polymkeric substance (I) quite high (weight part promptly 〉=85), this film expection have lower Vicat softening temperature and; Lower film modulus.

People's such as Hodgson US5,206,075 disclose the multilayer heat-sealable film that comprises basic unit and be laid on the hot sealable layer on these base material one or both sides.As basic unit, people such as Hodgson disclose a kind of blend of following component: (a) density is greater than the olefin polymer of 0.915g/cc; (b) ethene and C ₃-C ₂₀The multipolymer of α-monoolefine, wherein multipolymer (b) has density about 0.88 to about 0.915g/cc, melt index about 0.5 is to about 7.5dg/min, molecular weight distribution is not more than about 3.5, form the Tile Width index greater than about 70%, as hot sealable layer, Hodgson discloses the multipolymer that comprises conduct (b) in the base material.Hodgson is unexposed will be such as blend used in the basic unit (a) as suitable sealing ply, and the preferred olefin polymers (a) that is used as basic unit's component (a) is the multipolymer of propylene and about 1-10mol% ethene.Therefore, this open source literature has limited the purposes of disclosed heat seal mateiral like this, because the document instructs suitable multilayer heat-sealable film must comprise basic unit and the sealing ply with similar alkene chemical property.

The disclosed material of people such as people such as people such as Shibata, Naito and Hodgson and other known sealant material are not at this on the one hand, have defective on the one hand at that exactly.These materials can not provide the balanced sealant properties that comprises low sealing initiation temperature and improved film modulus.These materials are not particularly suitable for being used as sealing material in the BOPP structure yet.Therefore, need have and polyacrylic good interlayer adhesion, low heat seal and hot sticky starting temperature, high hot sticky intensity and wide high hot sticky the polymer composition of seal temperature scope characteristic.Also need to show the film and the film composite that are suitable for lamination, coextrusion and compression packing field of low-heat sealing initiation temperature and medium paramount film modulus respectively.Also need to have the low hexane extraction quantity, promptly be lower than 15wt%, preferably be lower than 10wt%,, most preferably be lower than the polymeric seal composition of 3wt%, like this in the field that this composition can be used for food directly contacts more preferably less than 6wt%.

As first aspect present invention, we find a kind of new multilayered structure that is made of polymer composition, described composition comprises and by at least two kinds of ethylene polymer component preparations, wherein first kind of ethylene polymer component is characterised in that high molecular and the evenly short-chain branched or composition distribution with optimization.This polymer composition provides the improvement sealing ply that is suitable for multi-layer packaging and accumulating structure with balance quality.This balanced sealant properties comprises and polyacrylic good interlayer adhesion, low heat seal and hot sticky starting temperature, wide high hot sticky seal temperature scope, with for given density polymer, higher softening temperature prevents with machine-direction oriented roller adhesion with (for example) or good machinability is provided.This improved sealing agent is particularly suitable for comprising the multilayered structure of polypropylene layer, particularly Biaially oriented polypropylene (BOPP) thin film layer.

As the present invention on the other hand, we also find a kind of film and film composite that is constituted and prepared by at least two kinds of ethylene polymer component, and wherein first kind of ethene polymers has density and be lower than 0.89 gram per centimeter ³(g/cc) feature, second kind of ethene polymers has density 0.94g/cc to 0.97g/cc feature.Newfound film composite provides the multi-layer packaging field that is applicable to of medium paramount film modulus (being improved modulus) such as the sealing film of lamination, coextrusion and coating.Balance between sealing and the modulus properties also allows it in various application, as the compression that wherein can realize more sealing at a high speed and good machining and dimensional stability fill use in as single thin film.

An extensive aspect of the present invention is the sealing film composition, and it comprises and is prepared by following component:

At least one first kind of ethene polymers (by composition total weight) of 5 to 95wt%, it is homogeneously branched substantial linear ethene polymers or homogeneously branched linear tetrafluoroethylene polymer, wherein first kind of polyvinyl being characterised in that has:

I. I ₂Melt index 0.001g/10min to 2g/10min measures according to 190 ℃/2.16kg of ASTM D-1238 condition,

Ii. density 0.85 is measured according to ASTM D-792 to 0.92g/cc,

Iii. molecular weight distribution mw/mn is less than 3.5, according to gel permeation chromatography,

Iv. short-chain branched dispersion index (SCBDI) is greater than 50%, with the temperature rise elution fractionation measure and

At least one second kind of ethene polymers (by composition total weight) of 5 to 95wt%,

It is homogeneously branched ethylene polymer or heterogeneous branching linear tetrafluoroethylene polymer, wherein

Second kind of polyvinyl feature is to have density to be lower than 0.97g/cc, and wherein the feature of composition is to have density 0.89g/cc to 0.95g/cc (measuring according to ASTMD-792) and at least one first kind of polyvinyl I ₂Melt index is lower than at least one second kind of polyvinyl I ₂Melt index.

Second aspect present invention is the multilayered structure that comprises polypropylene layer and sealing ply, and described sealing ply has balance quality, comprises and polyacrylic fabulous interlaminar bonding performance, contains and is prepared by following component

(A) at least one first kind of ethene polymers (by the gross weight of sealing ply) of 5 to 95wt%, it is homogeneously branched substantial linear ethene polymers or homogeneously branched linear tetrafluoroethylene polymer, wherein first kind of polyvinyl being characterised in that has:

I. I ₂Melt index 0.14g/10min measures according to 190 ℃/2.16kg of ASTM D-1238 condition to being lower than 0.67g/10min,

Ii. density 0.85 is measured according to ASTM D-792 to 0.92g/cc,

Iii. I ₁₀/ I ₂Melt flow is measured according to 190 ℃/2.16kg of ASTM D-1238 condition and 190 ℃/10kg of condition than 6 to 12,

Iv. molecular weight distribution M _w/ M _nBe lower than 3.5, according to gel permeation chromatography,

V. the single differential scanning calorimetric DSC melting hump between-30 to 150 ℃,

Vi. short-chain branched dispersion index (SCBDI) is greater than 50%, with the temperature rise elution fractionation measure and

(B) at least one second kind of ethene polymers (by the sealing ply gross weight) of 5 to 95wt%, it is homogeneously branched ethylene polymer or heterogeneous branching linear tetrafluoroethylene polymer, wherein second kind of polyvinyl feature is to have density 0.89g/cc to 0.965g/cc, wherein the feature of sealing ply is to have density 0.89g/cc to 0.93g/cc (measuring according to ASTMD-792), and I ₂The molecular weight of melt index 1g/10min to 5g/10min (measuring according to 190 ℃/2.16kg of ASTM D-1238 condition) and wherein at least one first kind of ethene polymers (A) is higher than the molecular weight of at least one second kind of ethene polymers (B).

Third aspect present invention is to have film or the thin film layer that improves modulus or composition density, and described film or thin film layer comprise and prepared by following component:

(C) at least one first kind of ethene polymers (by the gross weight of film or thin film layer) of 20 to 60wt%, it is homogeneously branched substantial linear ethene polymers or homogeneously branched linear tetrafluoroethylene polymer, wherein first kind of polyvinyl being characterised in that has:

Ii. density is lower than 0.89g/cc, measure according to ASTM D-792,

(D) at least one second kind of ethene polymers (by film or thin film layer gross weight) of 40 to 80wt%, it is homogeneously branched ethylene polymer or heterogeneous branching linear tetrafluoroethylene polymer, wherein second kind of polyvinyl feature is to have density 0.94g/cc to 0.97g/cc, measure according to ASTM D-792

The I of wherein at least one first kind of ethene polymers (C) ₂Melt index is equal to or less than the I of at least one second kind of ethene polymers (D) ₂The feature of melt index and film or thin film layer is to have composition density 0.915g/cc to 0.95g/cc (measuring according to ASTM D-792).

The sealing film that fourth aspect present invention is improved modulus and comprised at least one thin film layer for preparation has, this method comprises the steps:

The polymer composition that is constituted or prepared by following component is provided

(C) at least one first kind of ethene polymers (by the gross weight of film) of 20 to 60wt%, it is homogeneously branched substantial linear ethene polymers or homogeneously branched linear tetrafluoroethylene polymer, wherein first kind of polyvinyl being characterised in that has:

Ii. density is lower than 0.89g/cc, measure according to ASTM D-792,

(D) at least one second kind of ethene polymers (by the film gross weight) of 40 to 80wt%, it is homogeneously branched ethylene polymer or heterogeneous branching linear tetrafluoroethylene polymer, wherein second kind of polyvinyl feature is to have density 0.94g/cc to 0.97g/cc, measures according to ASTM D-792

The I of wherein at least one first kind of ethene polymers (C) ₂Melt index is equal to or less than the I of at least one second kind of ethene polymers (D) ₂The feature of melt index and film is to have composition density 0.915g/cc to 0.95g/cc (measuring according to ASTM D-792);

Extrude the film that this polymer composition forms at least one thin film layer; With

Collection comprises the film of at least one thin film layer.

Fifth aspect present invention is for providing the heat-sealable composition that improves film modulus, and said composition comprises and prepared by following component:

(C) at least one first kind of ethene polymers (by composition total weight) of 20 to 60wt%, it is substantial linear ethene polymers or homogeneously branched linear tetrafluoroethylene polymer, wherein first kind of polyvinyl being characterised in that has:

Ii. density is lower than 0.89g/cc, measure according to ASTM D-792,

Iv. short-chain branched dispersion index (SCBDI) is greater than 50, with the temperature rise elution fractionation measure and

(D) at least one second kind of ethene polymers (by composition total weight) of 40 to 80wt%, it is homogeneously branched ethylene polymer or heterogeneous branching linear tetrafluoroethylene polymer, wherein second kind of polyvinyl feature is to have density 0.94g/cc to 0.97g/cc, measure according to ASTM D-792

The I of wherein at least one first kind of ethene polymers (C) ₂Melt index is equal to or less than the I of at least one second kind of ethene polymers (D) ₂The feature of melt index and composition is to have composition density 0.915g/cc to 0.95g/cc (measuring according to ASTM D-792).

It is shocking, be significantly higher than its corresponding softening temperature feature although have sealing initiation temperature by the sealing ply of heterogeneous branched ethylene polymer preparation, improvement sealing ply of the present invention have can with the Vicat softening temperature of its heat seal starting temperature analogy.In other words, for minimum 1.8N/15mm sealing intensity, sealing ply has and equals or be lower than 4.5 ℃ of its Vicat softening temperatures at least and more be equal to or less than the diaphragm seal starting temperature of (its Vicat softening temperature-6 ℃) surprisingly in specific embodiments.

As another beat all result of the present invention, although the conventional seals film has with respect to its corresponding density (and/or its respective films modulus) and has higher sealing initiation temperature feature, improvement sealing film of the present invention or thin film layer have lower sealing initiation temperature for given film modulus or density.In other words, compare with general thin, film of the present invention obtains higher modulus under identical sealing initiation temperature, or obtains lower sealing initiation temperature under identical density of film or modulus.For the present invention, be not between low sealing initiation temperature and medium-paramount film modulus, carry out simply compromise because resulting performance is not an adduction or according to the desired value of weight fraction simply.

Though the present invention is not limited only to this, the invention provides a kind of film composite, sealing film, sealed thin rete, coating, be used to pack, store, put on display and protect the thermoformed articles or the moulded parts of purpose.These purposes include but not limited to pressure pad, the bag of the article that are used for flowing, stop and shrink and the non-shrinkable film that stops bottle cap, packaging container lid and packaging film sealing ply.

These and other embodiment of the present invention will be discussed in more detail below.

Fig. 1 is analysis temperature rise elution fractionation (ATREF) curve-response diagram of embodiment 1.

Fig. 2 is match gel permeation chromatography (GPC) curve-response diagram of embodiment 1.

Fig. 3 is the I as first kind of polymeric constituent (A) ₂Hot sticky intensity (N/15mm of the unit) figure of the function of melt index (g/10min of unit).

Fig. 4 is the heat seal starting temperature figure as the present invention of the function of homogeneously branched ethylene polymer component (C) weight percent content and contrast film embodiment.

Fig. 5 is the heat seal starting temperature figure as the present invention of composition density function and contrast film embodiment.

Fig. 6 is the heat seal starting temperature figure as the present invention of film modulus function and contrast film embodiment.

Fig. 7 is the film modulus figure as the film of the present invention of composition density function and contrast film.

Term used herein " composition density " refers to the polyvinyl polymer composition density of one-component polymer or the first and the second (measuring according to ASTM D-792). Term " composition density " refers to the solid-state density measurement of pellet, film or mechanograph, is different from the fusant density measured value.

Term " polymer " composition used herein " refer to the blend of component (A) and component (B) or component (C) and component (D). Film of the present invention and composition comprise and by component A and component, and/or by the performance of blend itself such as the polymer composition preparation of composition density definition.

Term " polymer " used herein " refer to the polymeric material of the monomer preparation by the identical or different type of polymerization. Therefore general term " polymer " " comprise term " homopolymers ", " copolymer ", " ter-polymers " and " EVA ".

Term used herein " EVA " refers to the polymer by at least two kinds of dissimilar monomer preparations of polymerization. Therefore general term " EVA " comprises " copolymer " (be generally used for refer to by two kinds of dissimilar monomers preparations polymer) and term " ter-polymers " (be generally used for refer to prepared by three kinds of dissimilar monomers polymer).

(component (A) or (C) be generally and use homogeneous catalyst system is such as the ethene polymers of metallocene catalyst system, vanadium catalyst system or the preparation of constraint geometry catalyst system for the first ethylene polymer component of using among the present invention. The first ethene polymers is in particular at least a homogeneously branched substantial linear ethene polymers or at least a homogeneously branched linear tetrafluoroethylene polymer. The second component polymer is at least a heterogeneous branched ethylene polymer, or at least a homogeneously branched ethylene polymer (ethene polymers that namely prepares with homogeneous catalyst system). Yet, preferred the first ethylene polymer component (A) or (C) be at least a substantial linear ethenyl copolymer, the second ethylene polymer component (B) or (D) be at least a heterogeneous branching linear ethylene EVA. More preferably the first and the second ethenyl copolymer are all used the continuous solution polymerization method, particularly continuously hypotonic solution polymerization preparation.

The substantial linear ethenyl copolymer is preferably used as the first ethylene polymer component (A) or (C) usually, reason is its improved melt extrusion machinability and unique rheological property, such as people such as Lai at US5,272,236 and 5, describe in 278,272, the content of these two parts of patent disclosures is introduced as reference here. Heterogeneous branching ethenyl copolymer is preferably used as the second ethylene polymer component (be component (B) and (D)).

The molecular weight of polyolefin polymer can be easily according to ASTM D-1238, and 190 ℃/2.16kg of condition (was called in the past " condition E ", and was called again I₂) represent with the melt index (MI) measured value. The molecular weight of melt index (MI) and polymer is inversely proportional to. Therefore, molecular weight is higher, and melt index (MI) is lower, although this relation is not linear.

Have balanced sealant properties for the invention provides sealant aspect of (comprising and polyacrylic fabulous interlayer adhesion), the I that the first ethene polymers (A) has₂Melt index (MI) greater than 0.14g/10min to less than 0.67g/10min, preferably greater than or equal to 0.15g/10 min. to being less than or equal to 0.65g/10min., more preferably greater than or equal 0.16g/10min. to being less than or equal to 0.6g/10min., most preferably more than or equal to 0.16g/10min. to being less than or equal to 0.5g/10min..

Component (A) and component (B) can be used I independently₂Melt index (MI) characterizes. Term " characterizes " I that refers to component (A) independently₂Melt index (MI) needn't with the I of component (B)₂Melt index (MI) is identical. The I that the second ethene polymers (B) can have₂Melt index (MI) more than or equal to 0.01g/10min to being less than or equal to 500g/10min, preferably greater than or equal to 0.1g/10min. to being less than or equal to 50g/10min., more preferably greater than or equal 1g/10min. to being less than or equal to 20g/10min., most preferably more than or equal to 1g/10min. to being less than or equal to 10g/10 min..

Overall melt index (MI) based on component (A) and polymer composition (B) is preferably 1 to 5 g/10min., and more preferably 2 to 4g/10min.

Other measured value that be used for to characterize substantial linear ethenyl copolymer and homopolymers relates to the melt index determination value with higher loading, ASTM D-1238 for example, and 190 ℃/10kg of condition (was called in the past " condition N ", was called again I₁₀). Higher loading melt index determination value is called the melt flows ratio with the ratio of low loading measured value, for the I that measures₁₀And I₂Melt index values, the melt flows ratio is expressed as I easily₁₀/I ₂ For the substantial linear ethene polymers for the preparation of film of the present invention, the melt flows ratio represents long chain branching degree, i.e. I₁₀/I ₂The melt flows ratio is higher, and the long chain branching in the polymer is more. Except representing more long chain branching, higher I₁₀/I ₂Ratio also is the sign than high extensional viscosity.

For balanced sealant properties, the long chain branching of HMW, high level and/or high extensional viscosity are normally preferred. We find that corresponding to each performance of these polymer, particularly the molecular weight corresponding to the first ethylene polymer component (A) has optimum range. Although the optimum weight scope of the first ethylene polymer component (A) is by top concrete I₂The melt index range definition, but it is believed that the substantial linear that is used as the first ethylene polymer component (A) among the present invention is polyvinyl and be defined as I₁₀/I ₂The best long chain branching scope of melt flows ratio be greater than 6 to approximately less than 12, particularly greater than 7 to less than 10. Satisfy this specific melt index range, also satisfy above-mentioned I simultaneously₁₀/I ₂The embodiment of scope is particularly preferred embodiment of the present invention.

The first ethylene polymer component (A) consists of 5 to 95wt % of polymer composition usually, and preferred 15 to 75wt%, more preferably 30 to 5wt% (by the gross weights of polymer composition).

The first ethylene polymer component (A) has density range 0.85 to 0.92g/cc, and preferred 0.87 to 0.915g/cc, more preferably from about 0.885 to 0.905g/cc (measuring according to ASTM D-792). The second ethylene polymer component (B) has density range 0.90 to 0.96 g/cc, and preferred 0.91 to 0.95g/cc, more preferably 0.92 to 0.93g/cc (measuring according to ASTM D-792). In addition, the density of preferred at least one the first ethylene polymer component (A) is lower than the density of at least one the second ethylene polymer component (B).

Total body density based on the polymer composition of component (A) and component (B) is preferably 0.90 to 0.92g/cc, and more preferably 0.905 to 0.925g/cc, most preferably 0.91 to 0.92g/cc (measuring according to ASTM D-792).

For the invention provides the sealant aspect that has balance quality and improve modulus, the first ethene polymers (C) has I₂Melt index range 0.001g/10min to 2g/10min, preferred 0.01g/10min. to 1.5g/10min., more preferably 0.01g/10min. to 1.2g/10min., most preferably 0.05g/10min. to 1g/10min.. The second ethene polymers (D) has I₂Melt index range 0.01g/10min to 30g/10min, preferred 0.5g/10min. to 20g/10min., more preferably 1g/10min. to 10g/10min., most preferably from about 1g/10min. to 5g/10min..

Overall melt index (MI) based on the polymer composition of component (C) and component (D) is preferably 0.1 to 50g/10min, and more preferably 0.5 to 20g/10min, most preferably 0.7 to 6 g/10min.

For the invention provides the aspect that has balanced sealant properties and improve modulus, we have found the polyvinyl I of substantial linear₁₀/I ₂Melt flows ratio Ying Gaozhi makes and can extrude the processability maximum, and should be low to moderate and make the heat-blocking can be minimum. Therefore, should take special care to optimize the I of the first ethene polymers (C)₁₀/I ₂Ratio is to guarantee good well balanced between machinability and the required good heat-blocking energy extruded.

Film or composition generally include 20 to 60wt%, preferred 20 to 55wt%, more preferably 25 to 45wt%, most preferably from about at least one the first ethylene polymer component (C) (by film, thin layer or composition total weight) (or by its preparation) of 25 to 40wt%. Simultaneously, film or composition generally include 40 to 80wt%, preferred 45 to 80wt%, and more preferably 55 to 75wt%, most preferably at least one the second ethylene polymer component (D) (by film, thin layer or composition total weight) (or by its preparation) of 60 to 75wt%.

The density that the first ethylene polymer component (C) has is lower than 0.89g/cc, (measures according to ASTM D-792) in 0.85 to 0.89g/cc scope. The second ethylene polymer component (D) has density range 0.94 to 0.97g/cc, and preferred 0.94 to 0.96g/cc, more preferably 0.945 to 0.955g/cc (measuring according to ASTM D-792).

Total body density based on the polymer composition of component (C) and component (D) is preferably 0.92 to 0.95g/cc, and more preferably 0.925 to 0.945g/cc, most preferably 0.925 to 0.94g/cc (measuring according to ASTM D-792).

Suitable ethene polymers as the second ethylene polymer component (B) is homopolymers and the EVA of ethene, comprise substantial linear ethene polymers, homogeneously branched linear tetrafluoroethylene polymer, heterogeneous branching linear tetrafluoroethylene polymer (is LLDPE (LLDPE), medium density polyethylene (MDPE) and high density polyethylene (HDPE) (HDPE), as with those of Ziegler-Natta catalyst system preparation), and blend or mixture.

The substantial linear ethene polymers respectively by The Dow Chemical Company and Dupont Dow Elastomers with trade name AFFINITY^TMAnd ENGAGE^TMResin is sold. Homogeneously branched linear tetrafluoroethylene polymer respectively by Mitsui Chemical Corporation with trade name TAFMER^TMWith Exxon Chemical Corporation with trade name EXACT^TMAnd EXCEED^TMSell. Suitable heterogeneous branching linear tetrafluoroethylene polymer by The Dow Chemical Company with trade name DOWLEX^TMSell. Suitable medium density polyethylene resin and high-density polyethylene resin (such as EVA or the homopolymers of ethene) can from many production firms, comprise with trade name MARLEX^TMResin is bought from The Dow Chemical Company and Phillips Chemical Corporation.

Term " homogeneously branched linear tetrafluoroethylene polymer " refers to the linear ethylene EVA on the conventional meaning, wherein the comonomer random distribution is in given polymer molecule, and wherein basically all polymer molecules have the ratio of identical ethene and comonomer. This term relates to the ethene polymers that has higher short-chain branched profile exponent (SCBDI) or form profile exponent (CDBI). In other words, the SCBDI of this EVA is more than or equal to 50%, preferably greater than or equal to 70%, more preferably greater than or equal 90%. Yet preferred homogeneously branched ethylene polymer is further characterized in that essentially no measurable high density (crystallization) polymer fractions (measuring with temperature rise elution fractionation technology).

SCBDI is defined as the percentage by weight with co-monomer content polymer molecule in 50 % scopes of total copolymerization monomer molar content intermediate value, and the distribute contrast of the comonomer distribution of expecting of the distribution of expression comonomer in polymer and Bernoullian. The SCDBI of EVA can be calculated by temperature rise elution fractionation technology (referred to as " TREF ") easily, as be described in people's polymer science periodicals such as Wild, polymer physics fascicle (Journal of Polymer Science, Poly. Phy. Ed.), Vol. 20, p.441 (1982), or US4,798,081; 5,008,204; Or L.D.Cady, " comonomer type and distribution are on the impact of LLDPE properties of product ", SPE Regional Technology Conference, Quaker Squaker Hilton, Akron, Ohio, 1-2 day in October, 1985, pp. among the 107-119, its disclosed content is all introduced as reference here. Yet preferred TREF technology does not comprise the clear amount in SCDBI calculates. More preferably, the comonomer distribution of EVA and SCDBI be by according to being described in US5, and 292,845 and J.C.Randall, polymer chemistry physics summary (Rev. Macromol. Chem. Phys.), C29, the technology among the pp.201-317 is used¹³C NMR analyzes mensuration.

Except relating to the short-chain branched distribution of homogeneous phase (or narrow), term " homogeneously branched linear tetrafluoroethylene polymer " also refers to the EVA without long chain branching. In other words, this ethenyl copolymer does not exist long chain branching and " linearity " main polymer chain that has on the ordinary meaning. Yet term " homogeneously branched linear tetrafluoroethylene polymer " does not refer to the high pressure branched polyethylene with a plurality of long-chains that those skilled in the art are known. Homogeneously branched linear tetrafluoroethylene polymer can be with the polymerization that evenly (narrow) short-chain branched distribution is provided (for example Elston is at US3, describes in 645,992) preparation. In his polymerization, Elston uses the soluble vanadium catalyst system to prepare these polymer, yet, other people, such as Mitsui Chemical Industries and Exxon Chemical Company, reported and used so-called single site catalyst systems preparation to have the polymer of similar structures. Homogeneously branched linear tetrafluoroethylene polymer can be with hafnium, zirconium or the preparation of vanadium catalyst system in solution, slurry or gas phase process. The people such as Ewen are at US4, have described the method with the metalloscene catalyst preparation in 937,299.

Here use term " heterogeneous branching linear tetrafluoroethylene polymer " to refer to that relating on the ordinary meaning has the linear ethylene EVA of low short-chain branched profile exponent. In other words, this EVA has quite wide short-chain branched distribution. The SCBDI of heterogeneous branching linear tetrafluoroethylene polymer is less than 50%, usually less than 30%.

Heterogeneous branched ethylene polymer is that the linear polymer those skilled in the art are known. Heterogeneous branching linear tetrafluoroethylene polymer with conventional soln, slurry or gas phase polymerization process (depressing high or low) in the presence of the Ziegler-Natta complex metal according to such as people such as Anderson at US4, the method preparation of the description in 076,698. Therefore these conventional Ziegler-Natta linear tetrafluoroethylene polymers are not " homogeneously branched ", do not have any long chain branching, have the linear polymer main chain on the ordinary meaning of term " linearity ".

Usually, homogeneously branched linear tetrafluoroethylene polymer and heterogeneous branched ethylene polymer are ethylene/alpha-olefin interpolymers, and wherein alpha-olefin is at least a C₃-C ₂₀Alpha-olefin (such as propylene, 1-butylene, amylene, 4-methyl-1-pentene, 1-hexene, 1-octene etc.), and preferred this at least a C₃-C ₂₀Alpha-olefin is the 1-octene. Most preferably this ethylene/alpha-olefin interpolymer is ethene and C₃-C ₂₀The copolymer of alpha-olefin, particularly ethene and C₄-C ₆The copolymer of alpha-olefin, the more especially copolymer of ethene/1-octene.

Term used herein " substantial linear ethene polymers " refers to homogeneously branched ethylene polymer (EVA and homopolymers), and it has narrow short-chain branched distribution and contains long-chain branch and be attributable to the short-chain branch that the homogeneous phase comonomer adds. Long-chain branch has the structure identical with main polymer chain and longer than short-chain branch. Substantial linear α-ethene polymers has 0.01-3 long-chain branch/1000 carbon atom. Be preferred for substantial linear polymer of the present invention and have 0.01 long-chain branch/1000 carbon atom to 1 long-chain branch/1000 carbon atom, more preferably 0.05 long-chain branch/1000 carbon atom to 1 long-chain branch/1000 carbon atom.

It is the chain length with at least 7 carbon atoms that this paper defines long chain branching, can not use greater than this length¹³The C nuclear magnetic resoance spectrum is differentiated. Long-chain branch can be the same with the length of its connected main polymer chain long. The length of long-chain branch is obviously long than the short-chain branch that causes because of the adding comonomer.

With¹³C nuclear magnetic resoance spectrum (NMR) can be determined to have long chain branching in Alathon, and available Randall is in polymer chemistry physics summary, C29, and v.2 ﹠ 3, and the method described in the P285-297 is quantitative.

In fact, present¹³The C nuclear magnetic resoance spectrum can not be measured the long-chain branch length that surpasses 6 carbon atoms. Yet, have other known method for the long-chain branch of measuring ethene polymers (comprising ethene/1-octene copolymer body) existence. Two kinds of such methods are that gel permeation chromatography and low-angle laser light scattering detector are used in conjunction (GPC-LALLS) and gel permeation chromatography and differential viscosity detector and are used in conjunction (GPC-DV). These technology in long-chain branch detects application and the theory of foundation be described in detail in the document. For example, referring to Zimm, G.H. and Stockmayer, W.H., Chemical Physics periodical (J. Chem. Phys.), 17,1301 (1949) and Rudin, A., the modern characterizing method (Modern Methods of Polymer Characterization) of polymer, John Wiley ﹠ Sons is among New York (1991) the pp. 103-112.

The A. Willem deGroot of The Dow Chemical Company and P. Steve Chum on October 4th, 1994 in St. Louis, (FACCS) in the meeting, the digital proof GPC-DV that provides is the applicable technology that has long-chain branch in the quantitative analysis substantial linear ethene polymers for the federal analytical chemistry that Missouri holds and spectroscopy meeting (Federation of Analytical Chemistry and Spectroscopy Society). Particularly, deGroot and Chum find, the amount of the long-chain branch that exists in the substantial linear ethene polymers of measuring with the Zimm-Stockmayer equation is finely identical with the result of the long-chain branch amount of measuring with 13C-NMR.

In addition, Degroot and Chum find that the existence of octene does not change the hydrodynamics volume of polyethylene specimen in solution, and therefore, can calculate the molecular weight that belongs to the octene short-chain branch by the octene mol% in the known sample increases. DeGroot and Chum find, belong to the short-chain branch of 1-octene by deduction to the contribution of molecular weight increase, and GPC-DV can be used for the long-chain branch amount in the quantitative substantial linear ethylene/octene.

Degroot and Chum also prove, as the Log (I of Log (GPC weight average molecular weight) function₂Melt index (MI)) to have described the polyvinyl long chain branching situation of substantial linear (but not being long chain branching content) suitable with the long chain branching of those high pressure, high branched low density polyethylene (LDPE) for figure (measuring by GPC-DV), and obviously be different from the ethene polymers of producing with Ziegler type catalyst such as titanium complex and common homogeneous catalyst such as hafnium and vanadium complex.

Be used for substantial linear ethene polymers of the present invention for further being defined in US5,272,236, serial number 07/776,130 (October 15 1991 applying date) and US5,279,272, the class unique compounds in the serial number 07/939,281 (September 2 1992 applying date).

The substantial linear ethene polymers obviously is different from above-mentioned and (for example) Elston at US 3,645, the homogeneously branched linear tetrafluoroethylene polymer of describing in 992. As an important difference, the substantial linear ethene polymers does not have the linear polymer main chain of the common indication of term " linearity " that has in the homogeneously branched linear tetrafluoroethylene polymer. The substantial linear ethene polymers also obviously be different from be commonly referred to heterogeneous branching traditional Z iegler polymeric linear ethenyl copolymer (such as ultra-low density polyethylene, LLDPE or with people such as Anderson at US 4,076, the high density polyethylene (HDPE) of disclosed technology preparation in 698) a base polymer, reason is that the substantial linear ethenyl copolymer is homogeneously branched polymer; In other words, the substantial linear ethene polymers has SCBDI more than or equal to 50wt%, preferably greater than or equal to 70%, more preferably greater than or equal 90%. The substantial linear ethene polymers also is different from heterogeneous branched ethylene polymer class, and reason is high density or the crystalline polymer fraction of the essentially no available temperature rise elution fractionation commercial measurement of substantial linear ethene polymers.

The substantial linear ethene polymers also obviously is different from the base polymer that free radical causes, such as high branching high pressure low density Alathon and ethenyl copolymer, such as ethylene-acrylic acid (EAA) copolymer and ethane-acetic acid ethyenyl ester (EVA) copolymer. In other words, the substantial linear ethene polymers does not have the long chain branching of same degree with the ethene polymers that high pressure, free radical cause, and uses single site catalyst systems, rather than the preparation of free radical peroxide catalyst system.

Metallocene single-point polymerization catalyst (for example Canich is at US5,026,798 or Canich at US5,055, the monocyclopentadienyl transition metal catalyst for olefin polymerization of describing in 438) or the constraint geometry catalyst (for example, the people such as Steven are at US5,064, describe in 802) can be used for preparing the substantial linear ethene polymers, as long as preparation and use and US5,272,236 and US5, the consistent metalloscene catalyst of method of describing in 278,272 gets final product. These polymerizations also are described among the PCT/US92/08812 (October 15 1992 applying date). Yet the substantial linear ethene polymers is preferably used suitable constraint geometry catalyst, particularly for example US application serial number 545,403 (the July 3 nineteen ninety applying date), US5,132,380, US5,064,802, US5,153,157, US5,470,993, US5,453,410, US5,374,696, US5,532,394, US5,494, those constraint geometry catalysts preparations in 874 and US5,189,192.

Suitable co-catalyst used herein includes but not limited to (for example) polymerization or oligomeric aikyiaiurnirsoxan beta, particularly MAO or modified methylaluminoxane are (for example, at US5,041,584, US4,544,762,5,015,749 and/or 5, describe in 041,585) and the compatible non-coordination ion formation compound of inertia. Preferred co-catalyst is the non-coordination boron compound of inertia.

Be preferably those used in continuous solution polymerization method conditions for the preparation of the polyvinyl polymerizing condition of substantial linear among the present invention, although the present patent application is not limited to this. Also can use continuous slurry and gas phase polymerization process, as long as use suitable catalyst and polymerizing condition. For polymerization is applicable to substantial linear ethene polymers of the present invention, can use above mentioned single-point and constraint geometry catalyst; Yet for the substantial linear ethene polymers, polymerization should operate under the polyvinyl condition of formation substantial linear really. Even when using identical catalyst, be not that all polymerizing conditions all make the substantial linear ethene polymers certainly in other words. For example, in an embodiment for the preparation of the polyvinyl polymerization of substantial linear, use continuous polymerization method, rather than the batchwise polymerization method.

In brief, be used for substantial linear ethene polymers of the present invention and have following feature:

(a) melt flow rate (MFR) I₁₀/I ₂≥5.63

(b) by gel permeation chromatography, molecular weight distribution M_w/M _nDefined by following equation:

(M _w/M _n)≤(I ₁₀/I ₂)-4.63

The gas of large at least 50 % of critical shear rate when the critical shear rate when (c) substantial linear ethene polymers surface melt fracture being begun begins than the surperficial melt fracture of linear tetrafluoroethylene polymer is extruded rheological property, wherein the substantial linear ethene polymers comprises identical comonomer with linear tetrafluoroethylene polymer, the I that linear tetrafluoroethylene polymer has₂、M _w/M _nWith density value in polyvinyl up and down 10% scope of substantial linear, under identical melt temperature, uses gas squeezing rheometer mensuration with the corresponding critical shear rate of substantial linear ethene polymers and linear tetrafluoroethylene polymer wherein,

(d) the single means of differential scanning calorimetry DSC melting hump between-30 to 140 ℃, and

(e) short-chain branched profile exponent is greater than about 50%.

The preferred homogeneously branched ethylene polymer that is used for the present invention's (in particular as at least one the first ethene polymers) is homogeneously branched EVA (namely not being homopolymers), and by suitable TREF commercial measurement essentially no measurable " high density " or crystalline polymer fraction. Preferred homogeneously branched ethenyl copolymer is for having the substantial linear ethene polymers of narrow short chain distribution (being high SCBD index). The substantial linear ethene polymers does not contain the polymer fractions that the degree of branching is less than or equal to 2 methyl/1000 carbon atoms. In other words, be characterised in that the substantial linear ethenyl copolymer that is grouped into by the uniform polymeric level does not contain high density or crystalline polymer fraction, will be characterised in that wherein the polymer fractions of being less than or equal to 2 methyl/1000 carbon atoms without short-chain branched or short-chain branched degree thinks " high density " or " crystalline ". Yet, when being homopolymers or when containing considerably less comonomer, this polymer nature is characterized by the polymer fractions with " high density " or " crystallinity " by the method with homogeneously branched ethylene polymer as the second ethylene polymer component (stipulating that its density is 0.94g/cc to 0.97g/cc) and this polymer.

Being used for substantial linear ethenyl copolymer of the present invention is Alathon and ethene and at least a C₃-C ₂₀Alpha-olefin and/or C₄-C ₁₈The EVA of alkadienes. Ethene and C₃-C ₂₀The copolymer of alpha-olefin is particularly preferred. Term discussed above " EVA " is used for expression copolymer or ter-polymers or its analog here, and wherein at least a other comonomer and ethene or copolymerization of propylene prepare EVA.

Be used for comprising (for example) ethylenically unsaturated monomer with the suitable unsaturated comonomer of vinyl polymerization, conjugation or non-conjugated diene hydrocarbon, polyene hydrocarbon etc.The example of suitable comonomer comprises C ₃-C ₂₀Alpha-olefin is as propylene, iso-butylene, 1-butylene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene etc.Preferred comonomer comprises propylene, 1-butylene, 4-methyl-1-pentene and 1-octene, preferred especially 1-octene.Other suitable monomers comprises vinylbenzene, halogen or alkyl-substituted styrene, tetrafluoroethylene, vinyl benzo tetramethylene, 1,4-hexadiene, 1,7-octadiene and cyclenes such as cyclopentenes, tetrahydrobenzene and cyclooctene.

Relating to the critical shear rate of melt fracture and critical shearing stress and other rheological property (PI) measures and carries out with gas squeezing rheometer (GER) as " rheology processing index ".The gas squeezing rheometer is by M.Shida, R.N.Shroff and L.V. Cancio are described in polymer engineering science (Polymer Engineering Science), Vol.17, No.11, p.770 in (1977), and by John Dealy, be described among " molten plastic rheometer (Rheometers for Molten Plastics) " (Van Nostrand Reinhold Co publishes, (1982)) pp.97-99.With the diameter 0.0754mm with 180 ° of inlet angles, 20: 1 die heads of L/D carry out down at about 190 ℃ of temperature, nitrogen pressure 250 to 5500 psig (1.7 to 37.9Mpa) in the GER experiment.For substantial linear ethene polymers used herein, PI is at apparent shear rate 2.15 * 10 by GRE ⁶Dyne/cm ²The apparent viscosity of the material of following measurement (unit: thousand pools).Be used for substantial linear ethene polymers of the present invention and have about 0.01 thousand pool of PI to about 50,000 pools, preferred about 15,000 pools or lower.The polyvinyl PI of substantial linear used herein is less than or equal to its I ₂, M _w/ M _nWith density substantial linear ethene polymers analog value up and down the linear tetrafluoroethylene polymer in 10% scope (as Elston at US3, conventional Ziegler catalyzed copolymerization body or the Linear homogeneous branching interpolymer described in 645,992) PI about 70%.

Apparent shear-stress and apparent shear rate figure are used for determining melt fracture phenomenon and quantitative polyvinyl critical shear rate and critical shearing stress.According to Ramamurthy at rheology periodical (Journal of Rheology), 30 (2), 337-357, description in 1986, when being higher than a certain critical shear rate, can be observed the extrudate irregularity in the rheometer extrudate, this irregularity can be divided into two types: surperficial melt fracture and overall melt fracture.

The surface melt fracture occurs under apparent steady flow condition, and its scope is reduced to more serious " shark skin spot " form from minute surface film gloss.Here when measuring with above-mentioned GER, surperficial melt fracture begins (OSMF) and begins to reduce sign with extrudate gloss, and wherein the surfaceness of extrudate can detect under 40 times of amplifications easily.Critical shear rate when the surperficial melt fracture of substantial linear ethenyl copolymer begins is than having substantially the same I ₂And M _w/ M _nLinear ethylene interpolymer surface melt fracture at least 50 ℃ of % greatly when beginning.

Overall melt fracture occurs under unstable Extrusion Flow condition, and its scope is from extremely random distortion of rule (alternately the rough and smooth, helicoidal surface etc.).For accepting and obtain optimal seal agent performance industrial, surface imperfection (if existence) should be minimum.Be used for substantial linear ethene polymers of the present invention, the critical shearing stress when promptly the density overall melt fracture that is lower than those polymkeric substance of about 0.91g/cc begins is greater than 4 * 10 ⁶Dyn/cm ²When surperficial melt fracture used herein begins (OSMF) and the critical shear rate of overall melt fracture when beginning (OGMF) based on the surfaceness and the change of configuration of the extrudate of extruding by GER.In the present invention, the substantial linear ethene polymers is preferably used its adjacent boundary shearing rate, rather than critical shearing stress characterizes.

Preferred homogeneous ethylene polymkeric substance is made up of the single polymers component and is had a single DSC melting hump as the polyvinyl further feature of all substantial linear.This single melting hump is measured with the differential scanning calorimeter of indium and deionized water calibration.This method adopts the 5-7mg sample size, and " heating for the first time " to 140 ℃, keeps 4min under this temperature, be cooled to-30 ℃ by 10 °/min, keeps 3min under this temperature, and is heated to 140 ℃ (" heating for the second time ") with 10 ℃/min.Heat content and temperature curve when this single melting hump is taken from " heating for the second time ".Total melting heat of polymkeric substance is calculated by area under a curve.

For having the substantial linear ethenyl copolymer of density 0.875g/cc to about 0.91g/cc, according to the sensitivity of equipment, this single melting hump can " shoulder " or " camel " peak occur in low fusing one side, and it constitutes below 12% of the total melting heat of polymkeric substance, be usually less than 9%, more generally be lower than 6%.This peak (artifact) of following is for homogeneously branched polymkeric substance such as EXACT ^TMCan be observed, and follow the melting area monotone variation identification at peak through this based on the slope of single melting hump.This follow the peak appear at 34 ℃, common 27 ℃ of single melting hump fusing point, more generally in 20 ℃ of scopes.Belong to the melting heat of following the peak and can pass through its relevant area under heat content～temperature curve of special integration, measure separately.

Polyvinyl molecular weight distribution is measured on the Waters 150C high temperature chromatogram unit that mixing porous post is housed by gel permeation chromatography (GPC).Chromatographic column is sold by PolymerLaboratories, usually by

particle size

10 ³, 10 ⁴, 10 ⁵With 10 ⁶A piles up.Solvent is 1,2,4-trichlorobenzene, the 0.3wt% solution of the polymer sample to be measured that is used to inject by the preparation of this solvent.Flow velocity is 1.0ml/min, and the unit operation temperature is about 140 ℃, and injection volume is 100 μ l.

Molecular weight distribution determination with respect to main polymer chain is derived by using narrow molecular weight distributions polystyrene standards (available from Polymer Laboratories) and its elution volume.The equivalent molecular weight of polyethylene is measured with the following equation of the suitable Mark-Houwink coefficient of polyethylene and polystyrene (as Williams and Word at the polymer science periodical, polymkeric substance communication, p.621 Vol.6 describes in (1968)) derivation:

M _Polyethylene=a* (M _Polystyrene) ⁶In this equation, a=0.4316, b=1.0.Weight-average molecular weight M _wWith number-average molecular weight M _nIn a conventional manner by formula M _j=(Σ w _i(M _i ^j)) ^jCalculate, wherein wi is a wash-out from the M that has of i fraction of GPC post _iThe weight fraction of molecule, when calculating M _wThe time, j=1 calculates M _nThe time, j=-1.

For being used for substantial linear ethene polymers of the present invention and homogeneously branched linear tetrafluoroethylene polymer, M _w/ M _nBe usually less than 3.5, preferably be lower than 3.0, more preferably less than 2.5, particularly 1.5 to 2.5, especially 1.8 to 2.3.

Known that the substantial linear ethene polymers has fabulous workability, although its molecular weight distribution narrower (be M _w/ M _nRatio is usually less than 3.5).It is shocking, different with homogeneous phase with heterogeneous branching linear tetrafluoroethylene polymer, the polyvinyl melt flow ratio of substantial linear (I ₁₀/ I ₂) can not rely on its molecular weight distribution M basically _w/ M _nAnd change.Therefore, particularly need well when extruding processibility, being used for preferred substantial linear ethene polymers of the present invention is the substantial linear ethene polymers, particularly the substantial linear ethenyl copolymer.

The further feature of the particularly preferred film of the present invention, thin film layer or composition is, have be lower than 15%, preferably be lower than 10%, more preferably less than 6%, most preferably be lower than the composition hexane extraction amount of 3% (by the gross weight of mixture).

The further feature of another particularly preferred film, thin film layer or composition is, has at least 75 ℃ of Vicat softening temperatures, preferably at least 85 ℃, and more preferably at least 90 ℃.

In another preferred embodiment, when the good hot strength of needs, sealing ply generality of the present invention is characterised in that, when minimum sealing intensity 1.8N/15mm, have sealing initiation temperature and be equal to or less than (layer Vicat softening temperature-4.5 ℃), more preferably in specific embodiments, film heat seal starting temperature is equal to or less than (layer Vicat softening temperature-6 ℃), most preferably is lower than (layer Vicat softening temperature-10 ℃).

The present invention is the method for processing individual layer or multilayer film structure on the other hand, or polymer composition of the present invention is processed as the method for film, thin film layer, coating, thermoforming or moulded product.This method comprises lamination and coextrusion technology or its combination, or comprise and only use polymer composition or mixture, and for the processing sealing material can comprise specifically also that blown film, casting films, substrate extrusion coating, injection moulding, blowing, thermoforming, section bar are extruded, pultrusion, compression moulding, rotational moulding or injection blow molding operation or its in conjunction with etc.

Polymer composition of the present invention or mixture can be by any ordinary methods, comprise each dry component hybrid junction molten mixing in mixing roll, or with directly mixing formation in mixing roll (for example Banbury mixing roll, Haake mixing roll, Brabender Banbury mixer or list or twin screw extruder comprise the side arm forcing machine of preparing burden forcing machine and directly using in copolymerization step downstream) of all components.

Polymer composition of the present invention or mixture (and at least one first kind of ethene polymers and at least one second kind of ethene polymers) can use single-point catalyst at the scene at least one reactor, preferred single-point constraint geometry catalyst, at least using single-point catalyst, preferred single-point constraint geometry catalyst in another reactor, or Ziegler-Natta type polymerization catalyst ethene forms.For polymerized in-situ, reactor can be in order or the parallel mode operation.The example of a polymerized in-situ method is disclosed in the PCT patent application 94/01052, and its disclosed content is introduced as reference here.

Polymer composition of the present invention (and at least one first kind of ethene polymers or at least one second kind of ethene polymers) can further form by the following method: by heterogeneous ethene polymers being classified as the mode separated portion (A) of particular polymers fraction from heterogeneous branched ethylene polymer, (B), (C) and/or (D) (or from homogeneously branched ethylene polymer the mode separated portion (A) by the homogeneous ethylene polymkeric substance being classified as polymer fractions or (C)), choose and satisfy component (A), (B), (C) or (D) the suitable fraction of particular requirement, and with the fraction chosen by appropriate amount and at least one first kind of ethylene polymer component (A) or (C) or at least one second kind of ethylene polymer component (B) or (D) mix.This method obviously is not so good as polymerized in-situ method or above-mentioned blender/forcing machine hybrid technology economy, yet can be used for obtaining polymer composition of the present invention or mixture and at least one first kind of ethene polymers and at least one second kind of ethene polymers.

In any case yet preparation polymeric blends, at least one first kind of ethene polymers or at least one second kind of ethene polymers preparation, think said composition or component polymer for based on top to heterogeneous branching and homogeneously branched (being SCBDI) definition and based on the homogeneously branched ethylene polymer or the heterogeneous branched ethylene polymer of whole composition analysis (as ATREF result) rather than hierarchical analysis or manufacturing technology.

Additive is as oxidation inhibitor (hindered phenol IRGANOX for example ^TM1010 or IRGANOX ^TM1076, sell by Ciba Geigy), phosphorous acid ester (IRGAFOS for example ^TM168, sell by Ciba Geigy equally), cling additives (for example PIB), SANDOSTABPEPQ ^TM(being sold by Sandoz), pigment, tinting material, filler, static inhibitor, processing aid etc. also can be included in polymeric blends of the present invention or by in its film that forms.Although it is optional usually, film, coating and the moulded product that is formed by polymeric blends of the present invention also can contain the additive that strengthens antiseized, the demoulding and frictional coefficient characteristic, include but not limited to the titanium dioxide, talcum, lime carbonate and the clay that are untreated and handle, and primary, secondary and replace fatty amide, releasing agent, silicone coating agent etc.Also can add other additive,, and make these polymeric blends can be used for (for example) heavy duty to pack electricity sensitive articles strengthening the antistatic property of the film, coating and the moulded product that form by polymeric blends of the present invention as single quaternary ammonium compound or it and ethylene-acrylic acid (EAA) multipolymer or other functional polymer's blend.

Film of the present invention, thin film layer or composition can further comprise recovery and rejected material and diluted polymer, and add-on should keep balanced seal agent performance and modulus properties.The example of diluted material comprises (for example) elastomerics, rubber and anhydride modified lldpe (for example polybutene and maleic anhydride graft LLDPE and HDPE), and high-pressure polyethylene such as new LDPE (film grade) (LDPE), ethylene/acrylic acid (EAA) interpolymer, Ethylene/vinyl acetate (EVA) interpolymer and ethylene/methacrylic acid ester (EMA) interpolymer, and composition thereof.

Film of the present invention, thin film layer or composition can be found the purposes in various fields.It is believed that suitable applications includes but not limited to the monolayer package film; By the multi-layer packaging structure that other material is formed, for example be used for shrinkable film and the Biaially oriented polypropylene or the diaxial orientation ethene polymers that stop contraction; The packing material that is processed to form by formation/filling/sealer; The peelable seals packaging structure; The cooking food packaging structure; Compression packing thing; Heat-sealable stretch wrap films is as fresh prod packing and fresh lean meat retail packaging; Lining and sack are as cereal food lining, foreign material/shopping bag, heavily loaded commodity packaging and garbage tank lining (sack), packing ring and packaging container lid.

The purposes of individual layer and multi-layered biaxial oriented film structure based on its enhanced strength, transparent, gloss, stiffness, stop and/or shrinkage.Find this biaxially oriented film structure can be used for non-food product and food such as bulk and cut meat, the packing and the storage of ham, poultry, bacon, cheese etc.Use the typical multi-layered biaxial oriented film structure of polymeric film of the present invention, thin film layer or composition can be and comprise sealed thin rete of the present invention, skin (as heterogeneous branching linea low density or ultra-low density polyethylene), and the sandwich layer between sealed thin rete of the present invention and skin (as Biaially oriented polypropylene homopolymer or vinyl chloride-base polymer) is two-layer to seven-layer structure.

The multilayered structure that comprises film of the present invention, thin film layer or composition can comprise that also the tackify tack coat is (for example available from the PRIMACOR of The Dow Chemical Company ^TMEthylene-acrylic acid (EAA) multipolymer).This multilayered structure also can comprise other structural sheets, as the AFFINITY available from The DowChemical Company ^TMPolyolefin plastomers is available from the ENGAGE of Dupont DowElastomer ^TMPolyolefin elastomer is available from the DOWLEX of The Dow ChemicalCompany ^TMLLDPE is available from the ATTANE of The Dow Chemical Company ^TMULDPE, or these polymkeric substance mutually or with any blend of another polymkeric substance such as EVA multipolymer.

The multilayered structure (no matter whether diaxial orientation) that comprises film of the present invention, thin film layer or composition can include but not limited to blocking layer, tack coat and/or structural sheet usually.Various materials can be used for these layers, and wherein some material can be used as more than one deck in identical multilayered structure.Some suitable material comprises: the polymkeric substance (for example polyethylene of maleic anhydride graft) and the paper of paper tinsel, nylon, ethylene/vinyl alcohol (EVOH) multipolymer, polyvinylidene dichloride (PVDC), polyethylene terephthalate (PET), polypropylene (particularly oriented polypropylene (0PP), especially Biaially oriented polypropylene), Ethylene/vinyl acetate (EVA) multipolymer, ethylene/acrylic acid (EAA) multipolymer, ethylene/methacrylic acid (EMAA) multipolymer, ULDPE, LLDPE, HDPE, MDPE, LMDPE, LDPE, ionomer, graft modification.Common multilayered structure of the present invention can comprise 2 to about 7 layers, or required any number of plies or material or the polymkeric substance of intended purpose.

As mentioned above, think that film of the present invention or composition are particularly suitable for compression filling, cooking food packing and vertical formation/filling/sealing applications.The compression packing is usually directed at first by blown film technology processing plastic pipe.Pipe with this flat folded film form is delivered in the filling machine then, in this filling machine (operate continuously), carries out bottom sealing, pack into compressible article in the pipe and compression to reduce volume.After in article are packed pipe into, carry out top seal and pack article thus.Can be textiles by the article of compress mode filling mode packing, such as but not limited to towel and motion sheath.

The boiling wrap food is pre-packing, the then food of boiling.These packings and the food of boiling directly satisfies the needs of consumers, mechanism or consumer's goods retailer.The packing that is used for boiling must structurally can be born and is exposed under cooking time and the temperature condition, is wrapping food simultaneously.The boiling wrap food is generally used for packing ham, turkey, vegetables, finished meat etc.Because high relatively softening temperature of sealing ply of the present invention and hot sticky starting temperature characteristic, the multilayer film structure that therefore comprises sealing ply of the present invention is particularly suitable for boiling and heat and fills and use.

Form/fill/pack used especially packing flowable materials, as milk, wine, powder etc.In formation/filling/seal packing method, the plastic film structures sheet material is added in formation/filling/sealer, form continuous pipe wherein with the mode of sheet material, or by mode with interior/interior sealing agent overlap sealed plastic film by overlapping plastics film and the vertical limit of film being sealed with the inside/outside sealing agent.At the bottom of then at one end will manage transverse sealing formation sack with seal bar.Use the top of seal bar seal box then, and cut film, from pipe, separate the complete box that forms thus through the plastic film calcination or with cutting unit.The method for preparing box with formation/filling/sealer is described in US4 usually, 503,102 and 5,521, in 437, because of the low heat seal of sealing ply of the present invention and high adhesion starting temperature and high hot sticky intensity and wide hot sticky seal temperature scope, comprise therefore that the multilayer film structure of sealing ply of the present invention is particularly suitable for forming/fill/pack application.

The heat seal starting temperature is measured according to ASTMF88-85.2% secant modulus is measured according to ASTMD-882.Density is according to ASTM D-792 measurement and with g/cm ³(g/cc) provide.The observed value that provides among the following embodiment and all density are measured after 24 hours in annealing under the room temperature at sample according to ASTM D-792.

The density of polymeric constituent and weight percent can be by analyzing temperature rise elution fractionation (ATREF) technical measurement.The hardware and the program that are used for the ATREF technology are disclosed already, people's polymer science periodical such as Wild for example, polymer physics fascicle, 20,41 (1982), people US4 such as Hazlitt, 798,081 and people US5 such as Chum, 089,321.

In ATREF analyzed, the film that will analyze or composition were dissolved in suitable hot solvent (for example in the trichlorobenzene), and make its in containing the pillar of inert support by slowly reducing the temperature crystallization.Mode by the eluting solvent that slowly raises (trichlorobenzene) temperature wash-out crystalline polymer sample from pillar obtains the ATREF chromatographic curve then.The ATREF curve is commonly referred to short-chain branched distribution (SCBD), and reason is that its shows how uniform distribution in entire sample of comonomer (for example octene), and promptly along with eluting temperature reduces, co-monomer content increases.

The ATREF curve can illustrate several key structure characteristics of film or composition easily, and for example known homogeneously branched ethylene polymer is as the AFFINITY available from The Dow Chemical Company ^TMResin, available from the ENGAGE of Dupont Dow Elastomer ^TMResin, available from the TAFMER of Mitsui Chemicali Corporation ^TMResin and available from the EXACT of ExxonChemical Company ^TMResin presents unique symmetrical single elution peak (or homogeneous phase SCBD).On the contrary, the known ethene polymers of producing by conventional Ziegler-Natta catalyst system (as The Dow Chemical Company sell DOWLEX ^TMThe LLDPE resin) under visibly different temperature, shows two or heterogeneous SCBD with wide and narrow elution peak.

Because the uniqueness of eluting temperature and ATREF curve shape is corresponding to density polymer, ATREF analyzes and can be used for the specific polymkeric substance of fingerprint recognition.Particularly,, can measure the weight fraction of each component easily by integration ATREF curve for the composition of forming by multicomponent polymeric.In addition, the density of component polymer can wherein be made up of known according to the measurement of ASTM D-792 the ATREF assay determination.For example, for the substantial linear ethene polymers, the working curve of ATREF eluting temperature and density polymer provides the density polymer by following equation definition: ρ=0.83494+9.6133 * 10 ^-4(T _e) T wherein _eATREF eluting temperature for polymkeric substance.Under the main assembly density of given composition, the weight fraction of the component polymer by integration ATREF curve and the density of substantial linear ethylene polymer component can be calculated the density of remaining ingredient polymkeric substance easily.

For further characterize polymers composition, can use poor formula viscometer.The output valve of difference formula viscometer is viscosity-average molecular weight M _v, its expression changes with respect to the molecular weight that elution volume changes.The Mv response can show that any component polymer has the feature of higher molecular weight, or polymeric constituent does not have the molecular weight characteristic that equates basically.

In brief, under the ATREF of given film or composition curve and composition density, can calculate the weight fraction and the density polymer of component polymer.The ATREF analysis is combined with difference formula viscometer (ATREF/DV), provide the information of the relative molecular weight that shows component polymer.ATREF/DV can be used for fingerprint and recognizes film of the present invention or composition.The ATREF curve also shows two difference elution peaks of the density difference that provides between first and second kinds of ethene polymerss of the present invention, and embodiment preferred relates to demonstration the single elution peak of second kind of high ethylene polymer component of first kind of ethylene polymer component and first kind of ethylene polymer component of molecular weight ratio.

The GPC fitting technique can be used for measuring the melt index of each ethylene polymer component.In this technology, the GPC data obtain with above-mentioned Waters 150C high temperature GPC chromatogram.Under given experiment elution volume, can use the working curve that obtains by a series of narrow molecular weight distributions polystyrene standards to calculate molecular weight easily.Before the operation fit procedure, reply GPC data normalization is to guarantee the unit surface under weight fraction and log (MW) GPC curve.

For fitting technique, suppose that homogeneously branched ethylene polymer observes the Bamford-Tompa molecular weight distribution, i.e. equation [1]

w_{i} (M_{i}) = \ln (10) \frac{M_{i}}{M_{n}} \exp ((- \frac{M_{i} (1 + ζ)}{M_{n}})) \times {(\frac{2 + ζ}{ζ})}^{1 / 2} \times I_{1} (\frac{M_{i} ζ^{1 / 2} {(2 + ζ)}^{1 / 2}}{M_{n}}) - - - [1]

Wherein wi is for having molecular weight M _iThe polymer weight mark, M _nBe number-average molecular weight, I ₁(x) be the first kind single order modification Bessel function that defines by following equation [2],

I_{1} (x) = \underset{b}{Σ} \frac{x^{2 b + 1}}{2^{2 b + 1} b! (b + 1)!} - - - [2]

ζ is the customized parameter that molecular weight distribution is broadened shown in the following equation [3]

\frac{M_{w}}{M_{n}} = 2 + ζ - - - [3]

For fitting technique, suppose that heterogeneous branched ethylene polymer (i.e. the polymkeric substance made from the Ziegler-Natta catalyst system) is in accordance with logarithm distribution equation [4]

w_{i} (M_{i}) = \frac{1}{β {(2 π)}^{0.5}} \exp (- \frac{1}{2} {(\frac{\log (M_{i}) - \log (M_{0})}{β})}^{2}) - - - - [4]

Wherein wi is for having molecular weight M _iThe polymer weight mark, M ₀Be the peak molecular weight, β is for characterizing the parameter of Tile Width, and β is assumed to M shown in the following equation [5] ₀Function: β=5.70506-252383Log (M ₀)+0.30024 (Log (M ₀)) ²[5]

The GPC fitting technique relates to four fitting parameters, M _nWith ζ at homogeneously branched ethylene polymer (being generally first kind of ethylene polymer component of the present invention), M ₀Weight fraction at heterogeneous branched ethylene polymer (preferred second kind of ethylene polymer component of the present invention) and homogeneously branched ethylene polymer.The SigmaPlot that provides at Jandel Scientific ^TMInterior non-linear curve fitting sub-routine (v3.03) is used to estimate these parameters.Number-average molecular weight (M in given homogeneously branched ethylene polymer or first kind of ethylene polymer component _n), equation [3], its I ₁₀/ I ₂Under melt flow ratio and its density, its I ₂Melt index can use equation [6] to calculate easily.

I_{2}^{FCPA} = \exp (62.782 - 3.8620 Ln (M_{w}) - 1.7095 Ln ({(\frac{I_{10}}{I_{2}})}^{FCPA}) - 16.310 \times ρ^{FCPA}) - - - [6]

Wherein FCPA represents ethylene polymer component.

Embodiment

Provide following embodiment to be used to illustrate the present invention, and be not used in qualification the present invention.

Be the various sealing materials of evaluation studies, on Bruckner curtain coating tentering frame BOPP film line, make three layers of (ABC) co-extrusion film.(B) layer is for the core of structure or basic unit and remain Shell KF 6100 homopolymer polypropylene with smooth and antistatic mixed additive.This additive compound provides by using 2.5wt% to contain antistatic and Ampacet 400577 masterbatch surface slip agent blend of 15wt% in 30MFI (measuring with the 2.16kg weight at 230 ℃) polypropylene homopolymer carrier resin.Shell KF 6100 homopolymer polypropylene resins have about 3 (the measuring with the 2.16kg weight at 230 ℃) of MFI.

In whole assessment, use for two-layer identical sealing material production (A) and (C) layer as variable sealing top layer.The additive masterbatch that will contain smooth and agglomeration resistance additive adds in the sealing ply, and the SiO of about 1250ppm erucicamide and about 1500ppm is provided ₂ Embodiment 1 and comparative example 2-8 are the various sealing materials of research in this assessment.

In this assessment, use disclosed polymerized in-situ and blending means in for example PCT patent application 94/01052, preparation embodiment 1 and comparative example 6.The detail of producing provides below.

By with how much organometallic complex [((CH of known constraint ₃) ₄C ₅))-(CH ₃) ₂Si-N-(t-C ₄H ₉)] Ti (CH ₃) ₂Be dissolved in Isopar ^TMIn the E hydrocarbon (available from Exxon ChemicalCompany), obtain titanium (Ti) concentration 9.6 * 10 ^-4The clear solution of M.The similar solution (3 * 10 that also prepares activator complexes three (perfluorophenyl) borine ^-3M).Known weight methylaluminoxane (available from Taxas Alkyls, being called MMAO) is dissolved in normal heptane obtains having MMAO concentration 1.06 * 10 ^-2The solution of M.These solution are pumped into independently, just made before adding first polymerization reactor these solution are mixed, and to make constraint geometry catalyst, activator complexes and MMAO mol ratio be 1: 3.5: 7.

Heterogeneous Ziegler type catalyzer is basically according to US4, and 612,300 (embodiment P) add Isopar by order ^TME hydrocarbon, Magnesium Chloride Anhydrous are at Isopar ^TMSlurry in the E hydrocarbon, EtAlCl ₂Solution in normal hexane and Ti (O-iPr) ₄At Isopar ^TMSolution in the E hydrocarbon, the mode that obtains containing magnesium density 0.166 M and 40.0: 12.5: 3.0 slurry of Mg/Al/Ti ratio prepares.With this slurry of a five equilibrium and Et ₃The dilute solution of Al (TEA) pumps into independently, wherein these two kinds of logistics is mixed before just adding second polymerization reactor, obtains final TEA: 6.2: 1 active catalyst of Ti mol ratio.

In the polymerization system of two reactors, ethene is added in first reactor according to scale speed 40lb/hr (18.2kg/hr).Before in adding first reactor, with ethene with comprise Isopar ^TMThe diluent mixture of E hydrocarbon (available from Exxon Chemical Company) and 1-octene merges.For first polymerization reactor, the 1-octene: ethene ratio (constituting fresh and recycle monomer) is 0.28: 1 (molar percentage), thinner: the ethylene feed ratio is 8.23: 1 (weight percent).The homogeneous phase constraint geometry catalyst and the promotor that prepare are above added in first polymerization reactor.The catalyzer, activator and the MMAO scale flow rate that add in first polymerization reactor are respectively 1.64 * 10 ^-5Lb Ti/hr (7.4 * 10 ^-6Kg Ti/hr), 6.21 * 10 ^-4Lb activator/hr (2.82 * 10 ^-4The kg activator/hr) with 6.57 * 10 ^-5Lb MMAO/hr (3.0 * 10 ^-5Kg MMAO/hr).Be aggregated under temperature of reactor 70-160 ℃ and carry out.

The reactor product of first polymerization reactor is transferred in second reactor.Be lower than 4% at the ethylene concentration in the effusive logistics of first polymerization reactor,, show described in 272,236 to have long chain branching as US5.

Ethene is pressed scale speed 120lb/hr (54.5kg/hr) to add in second polymerization reactor.Before in adding second polymerization reactor, with ethene and hydrogen stream and comprise Isopar ^TMThe mixture of E hydrocarbon and 1-octene merges.For second polymerization reactor, the 1-octene: ethylene raw is 0.196: 1 (molar percentage) than (constituting fresh and recycle monomer), thinner: the ethylene feed ratio is 5.91: 1 (weight percent), hydrogen: the ethylene feed ratio is 0.24: 1 (mol ratio).

The heterogeneous Ziegler-Natta catalyst and the promotor that prepare are above added in second polymerization reactor.Catalyzer (Ti) and the concentration of promotor (TEA) in second polymerization reactor are respectively 2.65 * 10 ^-3With 1.65 * 10 ^-3Mole.The catalyzer and the promotor scale flow rate that add in second polymerization reactor are respectively 4.49 * 10 ^-4Lb Ti/hr (2.04 * 10 ^-4Kg Ti/hr) and 9.14 * 10 ^-3Lb TEA/hr (4.15 * 10 ^-3KgTEA/hr).Being aggregated under temperature of reaction 150-220 ℃ in second reactor carried out.The transformation efficiency between first and second reactor and the division of turnout should obtain embodiment 1 that table 1 provides and " weight percent of first kind of ethylene polymer component (A) " in the comparative example 6.In other words, the weight percent of first kind of ethylene polymer component (A) is represented the division of the turnout of first and second polymerization reactor.

In the polymkeric substance that obtains, add conventional catalyst inactivator (1250ppm calcium stearate) and oxidation inhibitor (200ppm IRGANOX ^TM1010, promptly four (methylene radical 3-(3,5-di-t-butyl-4-hydroxyphenylpropionic acid ester) methane is available from Ciba-Geigy and 800ppm SANDOSTAB ^TMPEPQ, promptly 4,4 '-xenyl phosphonous acid four (2,4-di-t-butyl-phenyl) ester, available from SandozChemical) with stabilization of polymer.

Comparative example 2 is pressed trade mark KS4005 by Solvay and is sold for having the polypropylene copolymer of 5MFI (measuring with the 2.16kg weight down at 230 ℃)).Comparative example 3 is pressed trade mark KS300 by Solvay and is sold for having the polypropylene ter-polymers of 5MFI (measuring with the 2.16kg weight down at 230 ℃).Comparative example 4 is that The Dow Chemical Comapny presses trade mark AFFINITY ^TMThe substantial linear ethene polymers that PL 1845 sells.Comparative example 5 is that The Dow Chemical Comapny presses trade mark AFFINITY ^TMThe substantial linear ethene polymers that PL 1850 sells.Comparative example 7 is that The Dow Chemical Comapny presses trade mark DOWLEX ^TMThe heterogeneous branching linear low density polyethylene that 2035E sells.Comparative example 8 is that The Dow Chemical Comapny presses trade mark ATTANE ^TMThe heterogeneous branching ultra-low density polyethylene that SC4103 sells.

The heat seal starting temperature of various sealing plys measures seal with conventional heat seal tester and tonometer after aging 24 hours, the temperature in the time of will reaching sealing intensity 1.8N/15mm is as sealing initiation temperature.With hot sticky temperature range of putting forth effort to surpass 46g/cm (using Dupont spring method) as hot sticky intensity temperature range.

" enough interlaminar bondings " is defined as here and do not observing demixing phenomenon during the coextrusion procedure of processing or during sealing and the seal test.Otherwise, begin layering during " bad interlaminar bonding " is defined as sealing.

In this assessment, layer thickness is (A)=1 micron (μ m), (B)=18 μ m and (C)=1 μ m.To carry out the amount of corona treatment corresponding to layer (C) one side to about 44 dyne.These materials are extruded under 25-30 ℃ of 245 to 275 ℃ of melt temperatures and chill roll temperature.The temperature of machine-direction oriented (MDO) warming mill is 90 to 125 ℃.The longitudinal stretching ratio is 5: 1, laterally is 8: 1.The tentering frame oven temperature is 180 to 160 ℃.

The overall melt index of the density of first kind of ethylene polymer component (A) and weight percent, resultant polymer composition, composition density and Vicat softening temperature, be used to prepare the catalyst body set type of each embodiment, and the heat seal of embodiment, hot sticky in table 1, provide with the interlaminar bonding performance.Table 1

Embodiment	???1	?2*	?3*	?4*	?5*	?6*	?7*	?8*
Embodiment	???1	?2*	?3*	?4*	?5*	?6*	?7*	?8*	Overall MI, g/10min.	???2.7	?N/A	?N/A	?3.5	?3.0	?3.1	?6.0	?3.3
Total body density, g/cc	???0.918	?N/A	?N/A	?0.910	?0.902	?0.919	?0.919	?0.912	Overall MI, g/10min.	???2.7	?N/A	?N/A	?3.5	?3.0	?3.1	?6.0	?3.3
Total body density, g/cc	???0.918	?N/A	?N/A	?0.910	?0.902	?0.919	?0.919	?0.912	Overall Vicat softening temperature, ℃	???102	??--	?--	?90.7	?82.5	?99.5	?105	?95
Component (A) MI, g/10min.	???0.28	?N/A	?N/A	?3.5	?3.0	?0.67	?N/A	?N/A	Overall Vicat softening temperature, ℃	???102	??--	?--	?90.7	?82.5	?99.5	?105	?95
Component (A) MI, g/10min.	???0.28	?N/A	?N/A	?3.5	?3.0	?0.67	?N/A	?N/A	Component (A) density, g/cc	???0.898	?N/A	?N/A	?0.910	?0.902	?0.901	?N/A	?N/A
Component (A) wt%	???41.0	?N/A	?N/A	?100.0	?100.0	?43.5	?N/A	?N/A	Component (A) density, g/cc	???0.898	?N/A	?N/A	?0.910	?0.902	?0.901	?N/A	?N/A
Component (A) wt%	???41.0	?N/A	?N/A	?100.0	?100.0	?43.5	?N/A	?N/A	Catalyst type	??CGC/ZN	?N/A	?N/A	??CGC	?CGC	?CGC/ZN	?ZN	?ZN
Sealing initiation temperature, ℃	????96	?120	?110	??95	?90	?95	?115	?110	Catalyst type	??CGC/ZN	?N/A	?N/A	??CGC	?CGC	?CGC/ZN	?ZN	?ZN
Sealing initiation temperature, ℃	????96	?120	?110	??95	?90	?95	?115	?110	Hot sticky temperature range (@〉46 g/cm), ℃	??35(105 ??-140)	?15(125 ?-140)	?25(115- ?140)	Do not have	Do not have	Do not have	Do not have	Do not have
Interlayer adhesion with the homopolymerization PP core	Well	Well	Well	Well	Well	Well	Difference	Well	Hot sticky temperature range (@〉46 g/cm), ℃	??35(105 ??-140)	?15(125 ?-140)	?25(115- ?140)	Do not have	Do not have	Do not have	Do not have	Do not have

CGC represents to fetter geometry catalyst Z/N and represents that Ziegler-Natta catalyst * is not embodiments of the invention, only is used for the comparison purpose.

In another assessment, with various sealing ply materials and PP homopolymer Shell KF 6100 coextrusion and assess its heat seal and the heat-blocking energy on conventional curtain coating membrane unit.

Curtain coating coextrusion production line is equipped with 76cm Johnson die lip casting film die alive.Total film thickness of each co-extrusion film sample is 3.0 mils (76.2 μ m).Two-layer co-extrusion film structure is made up of 10% sealing agent and 90%PP homopolymer Shell KF 6100.These films are processed with target line speed 55m/min, about 277 ℃ of target polypropylene homopolymer melt temperature, 265 ℃ of target sealing agent melt temperatures and air gap 12.7cm.

The polymer composition of comparative example 9 is AFFINITY ^TMPL1845 (The DowChemical Company provides, and is identical with top comparative example 4).AFFINITY ^TMPL1845 is a single polymers component substantial linear ethene polymers.The polymer composition of

embodiment

11 and 12 polymer composition and Comparative Examples 10 and 13 with two reactors according to embodiment 1 described polymerized in-situ method preparation.The melt index of first kind of ethylene polymer component (A) is measured by above-mentioned GPC approximating method, the ATREF technical measurement that the density of first kind of ethylene polymer component (A) and weight percentage are also described by top embodiment 1.

In this assessment, none sample shows sealing ply and the stratified sign of polypropylene layer during coextrusion or heat seal operation and seal test.

The heat seal starting temperature is defined as the minimum temperature when obtaining 1lb/in (2N/15mm) sealing intensity in this assessment.Heat seal test Topwave hot sticky use 0.5 second residence time and 40psi (0.275Mpa) seal bar pressure to carry out on the tester.Seal increases progressively by sealing film upwards being folded and the mode that itself seals being formed by 5 ℃.The seal that so forms is spurred under 10in/min pinblock speed with the Instron tensiometer at least after making 24 hours.

In this assessment, it is the maximum heat adhesion strength that obtains in 60-120 ℃ that the limit heat adhesion is defined as in common trial stretch equally.Hot sticky test equally with Topwave hot sticky tester under 0.5 second residence time, 0.2 second time of lag and 40psi (0.275Mpa) seal bar pressure, carry out.Hot sticky seal increases progressively by sealing ply is upwards folding and the mode of itself hot sticky sealing is formed by 5 ℃.The detachment rate that imposes on hot sticky the seal of formation like this is 150mm/sec.Set the tester program after postponing in 0.2 second, to spur seal immediately.

Table 2 is generally listed the heat seal that obtains with the coextrusion of 3.0 mils (0.08mm) cast film and hot sticky data.Table 2

Embodiment	The heat seal starting temperature (℃)	Limit heat adhesion strength lb/in	Overall MI dg/min	Total body density dg/min	First kind of ethylene polymer component MI (dg/min)	First kind of ethylene polymer component Mn (g/mo1)	First kind of ethylene polymer component density (dg/min)	First kind of ethylene polymer component umber % (dg/10min)
Embodiment	The heat seal starting temperature (℃)	Limit heat adhesion strength lb/in	Overall MI dg/min	Total body density dg/min	First kind of ethylene polymer component MI (dg/min)	First kind of ethylene polymer component Mn (g/mo1)	First kind of ethylene polymer component density (dg/min)	First kind of ethylene polymer component umber % (dg/10min)	Comparative example 9	??88	??5.6	??3.5	?0.910	??3.5	?29313	??0.910	???100
Comparative example 10	??96	??6.4	??3.1	?0.919	??0.68	?46605	??0.901	???43.5	Comparative example 9	??88	??5.6	??3.5	?0.910	??3.5	?29313	??0.910	???100
Comparative example 10	??96	??6.4	??3.1	?0.919	??0.68	?46605	??0.901	???43.5	Embodiment 11	??93	??7.0	??2.8	?0.917	??0.39	?55305	??0.900	???41.0
Embodiment 12	??97	??7.9	??2.7	?0.919	??0.28	?62905	??0.900	???41.0	Embodiment 11	??93	??7.0	??2.8	?0.917	??0.39	?55305	??0.900	???41.0
Embodiment 12	??97	??7.9	??2.7	?0.919	??0.28	?62905	??0.900	???41.0	Comparative example 13	??96	??6.2	??3.5	?0.917	??0.14	?67159	??0.891	???38.4

Data in the table 2 (with as shown in Figure 3) illustrate, have first kind of ethylene polymer component (A) optimum weight or melt index for reaching the highest hot sticky intensity under constant overall melt index.From these data as can be seen, has I ₂Melt index provides the optimal heat adhesion strength greater than 0.14g/10min to the first kind of ethylene polymer component (A) that is lower than 0.68g/10min.Comparative example 10 and 13 shows, for as curtain coating BOPP film and vertical in form is filled and sealing (VFFS) field, and as the sealing ply in snack food product packing and cereal system food product pack field, comparative example 10 and 13 hot sticky undercapacity.

In the assessment of the various sealing materials of research, preparation is by the mixture of melts of the composition that adopts substantial linear ethenyl copolymer that fetters the production of geometry catalyst system and the heterogeneous branching ethenyl copolymer of producing with the Ziegler-Natta catalyst system to constitute.This mixture of melts comprises

embodiment

14,15,17,18,20 and 21 and comparative example 16,19 and 22-25.By each component polymer that takes by weighing appropriate amount and this mixture of blending that rolls, use conventional single screw rod compounding forcing machine this mixture of melt extrusion under about 350 (177 ℃) melt temperatures then, preparation melt blend.Comparative Examples 26 and 27 is by using such as method of describing in the PCT patent application 94/01052 and the preparation of program polymerized in-situ.

The heat seal starting temperature of embodiment is definite at (embodiment 14,15,17,18,20 and 21 and Comparative Examples 16,19 and 22-27) on the extruding layer laminated structure of being made up of 0.5 mil PET/1 mil LDPE, 5004/2 mil sealing ply or the three-layer co-extruded performance that goes out (comparative example 28) on the blown film structure be made up of 1 mil (0.025mm) nylon 6/1 mil (0.025mm) PRIMACOR 1410/1.5 mil (0.038mm) sealing ply by measuring sealing ply.The heat seal starting temperature of these embodiment is defined as the minimum temperature when obtaining 11b/in (2N/15mm) sealing intensity.Heat seal test Topwave hot sticky use 0.5 second residence time and 40psi (0.275Mpa) seal bar pressure to carry out on the tester.Seal increases progressively by sealing film upwards being folded and the mode that itself seals being formed by 5 ℃.The seal that so forms is spurred under 10in/min (250mm/min) pinblock speed with the Instron tensiometer at least after forming 24 hours.Under study for action the embodiment that lists in the following table 3 is assessed its sealing ply.Nylon 6 is sold by Allied-Signal Company.Polyester film HOSTAPHAN 2DEF is sold by American Hoechst Corporation.PRIMACOR1410 binder polymer and LDPE 5004 resins are sold by The Dow Chemical Company.

Co-extrusion film is processed on the Gluocester blown film device of three forcing machines that diameter 2,2.5 and 2.5in. (5.1,6.4 and 6.4cm) are housed.Die head is for setting 8in. (20.3cm) the coextrusion die head in 70 mils (1.8mm) die head slit.The imbibition ratio remained 2: 1 in all coextrusion.Than discharging speed is 6lb/hr/in. (6.9kg/hr/cm) die head, and melt temperature is 400 to 420 °F (204 to 216 ℃).

With 2.5in. (6.4cm) being housed, the Black-Clawson extrusion coating device processing extruding layer laminated structure of 30: 1 L/D forcing machines.Extruding layer is pressed under the about 550-600 of melt temperature (288-316 ℃) and the about 440 inches/min. of veneer speed (134m/min.) and carries out.For extruding lamination, LDPE 5004 resin extruded veneers on 0.5 mil (0.013mm) polyester film, and are being extruded nip rolls place slippage compressing tablet on the LDPE resin with 2-mil (0.051-mm) sealing material individual layer blown film.This laminar structure with chill roll cooling and collection, is measured its heat seal starting temperature subsequently.

2% vertical (MD) modulus of embodiment is measured by 2 mils (0.051mm) individual layer blown film.The single thin film (and above-mentioned extrude 2 mils (0.051mm) the individual layer blown film that lamination is used as slippage compressing tablet sealing material) that is used for physical test is being equipped with on the Gloucester blown film device of 2.5in (6.4cm) diameter, 24: 1 L/d forcing machines (use the two mix polyethylene screw rods of single helical, set 6in. (15.2cm) die head of 70 mils (1.8mm) die gap) to be processed.All embodiment keep imbibition than 2.5: 1, process 2 mils (0.051mm) film thus, and melt temperature is set at 450 °F (232 ℃) to reach the die head than discharging speed 61b./hr/in. (6.9kg/hr/cm).Following table 3 provides the performance data of the performance data of various example composition and DOWLEX LLDPE resin 2045 (comparative example 28), DOWLEX LLDPE resin 2049 (comparative example 29), DOWLEX LLDPE resin 2038 (comparative example 30).All DOWLEX resins are the heterogeneous branching ethenyl copolymer that The Dow Chemical Company sells.Table 3

Embodiment	14	15	16*	17	18	19*	20	21	22*	23*	24*	25*	26*	27*	28*	29*	30*
Embodiment	14	15	16*	17	18	19*	20	21	22*	23*	24*	25*	26*	27*	28*	29*	30*	First kind of component (A) polymer type	SLEP	SLEP	SLEP	SLEP	SLEP	SLEP	SLEP	SLEP	SLEP	SLEP	SLEP	SLEP	SLEP	SLEP	Do not have	Do not have	Do not have
First kind of component (A) I ₂Melt index, g/10min.	1.0	1.0	1.0	1.0	1.0	1.0	1.0	1.0	1.3	0.79	1.6	N/D	0.3	0.5	N/A	N/A	N/A	First kind of component (A) polymer type	SLEP	SLEP	SLEP	SLEP	SLEP	SLEP	SLEP	SLEP	SLEP	SLEP	SLEP	SLEP	SLEP	SLEP	Do not have	Do not have	Do not have
First kind of component (A) I ₂Melt index, g/10min.	1.0	1.0	1.0	1.0	1.0	1.0	1.0	1.0	1.3	0.79	1.6	N/D	0.3	0.5	N/A	N/A	N/A	First kind of component (A) density, g/cc.	0.885	0.885	0.885	0.885	0.885	0.870	0.870	0.870	0.920	0.895	0.8965	0.918	0.890	0.887	N/A	N/A	N/A
Second kind of component (B) polymer type	Z/N	Z/N	Z/N	Z/N	Z/N	Z/N	Z/N	Z/N	Z/N	Z/N	Z/N	Z/N	Z/N	Z/N	Z/N	Z/N	Z/N	First kind of component (A) density, g/cc.	0.885	0.885	0.885	0.885	0.885	0.870	0.870	0.870	0.920	0.895	0.8965	0.918	0.890	0.887	N/A	N/A	N/A
Second kind of component (B) polymer type	Z/N	Z/N	Z/N	Z/N	Z/N	Z/N	Z/N	Z/N	Z/N	Z/N	Z/N	Z/N	Z/N	Z/N	Z/N	Z/N	Z/N	Second kind of component (B) I ₂Melt index, g/10min.	1.0	1.0	1.0	1.0	1.0	1.0	1.0	1.0	4.0	4.0	0.9	N/D	1.6	0.05	1.0	1.0	1.0
Second kind of component (B) density, g/cc.	0.952	0.952	0.952	0.952	0.952	0.952	0.952	0.952	0.952	0.952	0.952	0.957	0.944	0.942	0.920	0.926	0.935	Second kind of component (B) I ₂Melt index, g/10min.	1.0	1.0	1.0	1.0	1.0	1.0	1.0	1.0	4.0	4.0	0.9	N/D	1.6	0.05	1.0	1.0	1.0
Second kind of component (B) density, g/cc.	0.952	0.952	0.952	0.952	0.952	0.952	0.952	0.952	0.952	0.952	0.952	0.957	0.944	0.942	0.920	0.926	0.935	The wt% of first kind of component (A)	35	25	17	45	55	13.5	25	45	60	21	30	35	30	30	0	0	0
The wt% of second kind of component (B)	65	75	83	55	45	86.5	75	55	40	79	70	65	70	70	100	100	100	The wt% of first kind of component (A)	35	25	17	45	55	13.5	25	45	60	21	30	35	30	30	0	0	0
The wt% of second kind of component (B)	65	75	83	55	45	86.5	75	55	40	79	70	65	70	70	100	100	100	Composition density, g/cc	0.931	0.9381	0.9429	0.9243	0.9163	0.9435	0.9334	0.9162	0.9317	0.9417	0.9365	0.940	0.9276	0.926	0.920	0.926	0.935
Sealing initiation temperature, ℃	106.5	116.8	123.3	85.0	70.9	127.4	106.2	66.6	120.0	124.5	120.0	125.0	115.5	116.0	105.4	N/D	N/D	Composition density, g/cc	0.931	0.9381	0.9429	0.9243	0.9163	0.9435	0.9334	0.9162	0.9317	0.9417	0.9365	0.940	0.9276	0.926	0.920	0.926	0.935
Sealing initiation temperature, ℃	106.5	116.8	123.3	85.0	70.9	127.4	106.2	66.6	120.0	124.5	120.0	125.0	115.5	116.0	105.4	N/D	N/D	The 2%MD secant modulus, psi	48,825	59,221	69,304	38384	28,697	69,951	53,387	31,?714	43,200	70,892	54,580	71.575	45,523	41,887	22,368	34,790	51,894

SLEP represents to use the substantial linear ethene polymers of constraint geometry catalyst system preparation.Z/N represents the heterogeneous ethene polymers with the preparation of Ziegler-Natta catalyst system.N/A represents inapplicable.N/D represents not measure.* not embodiments of the invention, only be used to contrast purpose

Draw many figure by the data that provide in the table 3.Fig. 4 is the heat seal starting temperature figure as the present invention of the function of homogeneously branched ethylene polymer component (C) weight percent and contrast film embodiment.It is shocking, Fig. 4 explanation, substantial linear ethene polymers for about 20 to about 60wt% is as first kind of ethylene polymer component (C), and

embodiment

14,15,17,18,20 and 21 compares with the film comparative example that is made of greater than the homogeneously branched ethylene polymer of 0.89g/cc density and to present lower sealing initiation temperature.More than or equal to 35wt% (by the two-component composition gross weight of preparation film), the sealing initiation temperature of embodiment especially is lower than analogous comparative example for per-cent.

It is shocking that more Fig. 5 illustrates that the sealing initiation temperature of embodiment significantly is lower than the sealing initiation temperature of the comparative example of same composition density.Fig. 6 explanation is compared embodiment and present low sealing initiation temperature under identical film modulus with the film comparative example.In other words, when comparative example presented higher film modulus and higher sealing initiation temperature, the embodiment of the invention had lower sealing initiation temperature under given film modulus.

At last, Fig. 7 explanation although the embodiment of the invention presents lower sealing initiation temperature for given film modulus, is higher than the film modulus of the heterogeneous branched ethylene polymer of single component of equal densities surprisingly when its film modulus under given composition density.Therefore, in brief, Fig. 4-7 explanation, the embodiment of the invention presents and the sealing initiation temperature that equates than low density ethylene polymer, keeps medium film modulus to higher density ethylene polymer simultaneously.Therefore, these digital proofs, the present invention is amazing and unexpectedly overcome between heat seal performance and the film stiffness cancelling out each other traditionally.

Claims

1. sealing film composition is characterized in that comprising and by following component preparation:

By composition total weight, at least one first kind of ethene polymers of 5 to 95wt%, it is homogeneously branched substantial linear ethene polymers or homogeneously branched linear tetrafluoroethylene polymer, wherein first kind of polyvinyl being characterised in that has:

I. melt flow ratio I ₁₀/ I ₂〉=5.63

Ii. I ₂Melt index 0.001g/10min to 2g/10min measures according to 190 ℃/2.16kg of ASTMD-1238 condition,

Iii. density 0.85 is measured according to ASTM D-792 to 0.92g/cc,

Iii. molecular weight distribution M _w/ M _nBe lower than 3.5, according to gel permeation chromatography,

Iv. short-chain branched dispersion index (SCBDI) is surveyed with the temperature rise elution fractionation greater than 50%

The amount and

By composition total weight, at least one second kind of ethene polymers of 5 to 95wt%, it is homogeneously branched ethylene polymer or heterogeneous branching linear tetrafluoroethylene polymer, wherein second kind of polyvinyl feature is to have density to be lower than 0.97g/cc, wherein the feature of composition is to have composition density 0.89g/cc to 0.95g/cc, measure and at least one first kind of polyvinyl I according to ASTM D-792 ₂Melt index is lower than at least one second kind of polyvinyl I ₂Melt index.

2. multilayered structure that comprises polypropylene layer and sealing ply, described sealing ply has balance quality, comprises and polyacrylic fabulous interlaminar bonding performance, it is characterized in that comprising and by following component preparation:

(A) by the gross weight of sealing ply, at least one first kind of ethene polymers of 5 to 95wt%, it is homogeneously branched substantial linear ethene polymers or homogeneously branched linear tetrafluoroethylene polymer, wherein first kind of polyvinyl being characterised in that has:

I. I ₂Melt index, is measured according to 190 ℃/2.16kg of ASTM D-1238 condition to being lower than 0.67g/10min greater than 0.14g/10min,

Ii. density 0.85 is measured according to ASTM D-792 to 0.92g/cc,

Vi. short-chain branched dispersion index (SCBDI) is surveyed with the temperature rise elution fractionation greater than 50%

The amount and

(B) by the sealing ply gross weight, at least one second kind of ethene polymers of 5 to 95wt%, it is homogeneously branched ethylene polymer or heterogeneous branching linear tetrafluoroethylene polymer, wherein second kind of polyvinyl feature is to have density 0.89g/cc to 0.965g/cc, wherein the feature of sealing ply is to have composition density 0.89g/cc to 0.93g/cc, measure according to ASTMD-792, and I ₂Melt index 1g/10min to 5g/10min measures and the molecular weight of wherein at least one first kind of ethene polymers (A) is higher than the molecular weight of at least one second kind of ethene polymers (B) according to 190 ℃/2.16kg of ASTM D-1238 condition.

3. one kind has film or the thin film layer that improves modulus and composition density, and described film or thin film layer are characterised in that and comprise and prepared by following component:

(C) by the gross weight of film or thin film layer, at least one first kind of ethene polymers of 20 to 60wt%, it is homogeneously branched substantial linear ethene polymers or homogeneously branched linear tetrafluoroethylene polymer, wherein first kind of polyvinyl being characterised in that has:

I. I ₂Melt index 0.001g/10min to 2g/10min measures according to 190 ℃/2.16kg of ASTMD-1238 condition,

Ii. density is lower than 0.89g/cc, measure according to ASTM D-792,

The amount and

(D) by film or thin film layer gross weight, at least one second kind of ethene polymers of 40 to 80wt%, it is homogeneously branched ethylene polymer or heterogeneous branching linear tetrafluoroethylene polymer, wherein second kind of polyvinyl feature is to have density 0.94g/cc to 0.97g/cc, measure according to ASTM D-792

The I of wherein at least one first kind of ethylene polymer component (C) ₂Melt index is equal to or less than the I of at least one second kind of ethylene polymer component (D) ₂The feature of melt index and film or thin film layer is to have composition density 0.915g/cc to 0.95g/cc, measures according to ASTM D-792.

4. one kind prepares the method with the sealing film that improves modulus, and this film is characterised in that and comprises at least one thin film layer, the method is characterized in that to comprise the steps:

(C) by the gross weight of film, at least one first kind of ethene polymers of 20 to 60wt%, it is substantial linear ethene polymers or homogeneously branched linear tetrafluoroethylene polymer, wherein first kind of polyvinyl being characterised in that has:

Ii. density is lower than 0.89g/cc, measure according to ASTM D-792,

The amount and

(D) by the film gross weight, at least one second kind of ethene polymers of 40 to 80wt%, it is homogeneously branched ethylene polymer or heterogeneous branching linear tetrafluoroethylene polymer, wherein second kind of polyvinyl feature is to have density 0.94g/cc to 0.97g/cc, measure according to ASTMD-792

The I of wherein at least one first kind of ethylene polymer component (C) ₂Melt index is equal to or less than the I of at least one second kind of ethylene polymer component (D) ₂The feature of melt index and film is to have composition density 0.915g/cc to 0.95g/cc, measures according to ASTM D-792;

Collection comprises the film of at least one thin film layer.

5. one kind provides the heat-sealable composition that improves film modulus, and said composition is characterised in that and comprises and prepared by following component:

(C) by composition total weight, at least one first kind of ethene polymers of 20 to 60wt%, it is substantial linear ethene polymers or homogeneously branched linear tetrafluoroethylene polymer, wherein first kind of polyvinyl being characterised in that has:

Ii. density is lower than 0.89g/cc, measure according to ASTM D-792,

(D) press composition weight meter, at least one second kind of ethene polymers of 40 to 80wt%, it is homogeneously branched ethylene polymer or heterogeneous branching linear tetrafluoroethylene polymer, wherein second kind of polyvinyl feature is to have density 0.94g/cc to 0.97g/cc, measure according to ASTMD-792

The I of wherein at least one first kind of ethylene polymer component (C) ₂Melt index is equal to or less than the I of at least one second kind of ethylene polymer component (D) ₂The feature of melt index and composition is to have composition density 0.915g/cc to 0.95g/cc, measures according to ASTM D-792.

Claim 1-3 any one composition, structure, film or thin film layer, wherein at least one first kind of ethene polymers is the substantial linear ethene polymers with following feature:

I. pass through gel permeation chromatography, molecular weight distribution M _w/ M _nDefine by following equation:

(M _w/M _n)≤(I ₁₀/I ₂)-4.63

The gas of the critical shear rate big at least 50% the when critical shear rate when substantial linear ethene polymers surface melt fracture is begun begins than the surperficial melt fracture of linear tetrafluoroethylene polymer is extruded rheological property, wherein the substantial linear ethene polymers comprises identical comonomer with linear tetrafluoroethylene polymer, the I that linear tetrafluoroethylene polymer has ₂, M _w/ M _nWith density value in polyvinyl up and down 10% scope of substantial linear, measure with corresponding critical shear rate using gas squeezing rheometer under identical melt temperature of substantial linear ethene polymers and linear tetrafluoroethylene polymer wherein.

7. the composition of claim 6, structure, film or thin film layer, wherein the substantial linear ethene polymers has 0.01 to 3 long-chain branch/1000 carbon atom.

8. any one composition, structure, film or thin film layer of claim 1-3, wherein second kind of ethene polymers is heterogeneous branching linear tetrafluoroethylene polymer.

9. any one composition, structure, film or thin film layer of claim 1-3, wherein at least one first kind of ethene polymers or second kind of ethene polymers are ethene and at least a interpolymer that is selected from the alpha-olefin of 1-propylene, 1-butylene, 1-iso-butylene, 1-hexene, 4-methyl-1-pentene, 1-amylene, 1-heptene and 1-octene.

10. any one composition, structure, film or thin film layer of claim 1-3, wherein at least one first kind of ethene polymers or second kind of multipolymer that ethene polymers is ethene and 1-octene.

11. any one composition, structure, film or thin film layer of claim 1-3, wherein polymer composition or layer are by be mixed with first kind of ethene polymers and second kind of ethene polymers at least at least by the method that at least aly is selected from melt extrusion, does mixed, two polymerization reactors of sequential operation and two polymerization reactors of parallel running.

12. the composition of claim 11, structure, film or thin film layer, wherein at least two polymerization reactors are recirculation loop reactor.

13. the multilayer film structure of claim 2, wherein this structure is boiling packing material, hot packing thing, flowable mass packing box, compression packing thing, shrinkable film or stops shrinkable film.

14. the multilayer film structure of claim 2, wherein this structure comprises the diaxial orientation film layer.

15. the multilayer film structure of claim 2, wherein this structure also comprises blocking material or layer.

16. the multilayer film structure of claim 15, wherein blocking material or layer are polyvinylidene chloride copolymer, polyester, polymeric amide, Biaially oriented polypropylene or aluminium foil.

17. the method for claim 4 is wherein extruded by film-blowing process and is finished.

18. the method for claim 4, wherein extrusion step comprises this layer is combined when forming this layer with another layer at least, or combination after forming this layer.