CN101384628A

CN101384628A - Ethylene polymer and products of molding thereof

Info

Publication number: CN101384628A
Application number: CNA2007800055568A
Authority: CN
Inventors: 田崎力; 明石崇弘; 松原真也; 冈本胜彦
Original assignee: Mitsui Chemical Industry Co Ltd; Prime Polymer Co Ltd
Current assignee: Mitsui Chemicals Inc; Mitsui Chemical Industry Co Ltd; Prime Polymer Co Ltd
Priority date: 2006-02-15
Filing date: 2007-02-14
Publication date: 2009-03-11

Abstract

An ethylene/a-olefin copolymer satisfying the following requirements [1] to [5] is excellent in transparency and moldability and can give films or sheets excellent in mechanical strength: [1] the density (d) falls within the range of 890 to 980kg/m<3>, [2] the limiting viscosity ([eta]) as determined at 135 DEG C in decalin falls within the range of 0.5 to 10dl/g, [3] the ratio (Mw/Mn) of weight-average molecular weight (Mw) to number -average molecular weight (Mn) as determined by GPC falls within the range of 2.0 to 50, [4] in the elution temperature-eluted polymer quantity curve as given by cross fractionation chromatography (CFC), the difference between the temperature at which the integrated quantity of polymer eluted reaches 1% by mass and the temperature at which the integrated quantity of polymer eluted reaches 40% by mass is 12 DEG C or below when the total quantity of polymer eluted is taken as 100% by mass, and [5] the content of matter soluble in decane is 0.5% by mass or below.

Description

Ethylene-based polymer and formed body therefrom

Technical field

The present invention relates to ethylene, say in further detail, relate to the ethylene-based polymer that is suitable for formability excellent and the transparency and physical strength excellence with the formed body headed by the film, and the formed body and the film that obtain by this ethylene-based polymer.

Background technology

Vinyl copolymer, according to different forming methods and purposes, also different to the characteristic of its requirement.For example the film that is formed by vinyl copolymer by various forming method moulding, supplies in many-sided purposes.The kind of employed film also relates to multiple according to the content difference, according to the kind or the amount of the monomeric unit that constitutes vinyl copolymer, perhaps according to the manufacture method of vinyl copolymer, the rerum natura of resulting film is also different.

For example, when thinking the high-speed molding blown film, for bubble being rocked or broken, thereby stably carry out high-speed molding,, have to select the big material of fusion tension force (MT, melt tension) for molecular weight as vinyl copolymer.Same characteristic, sagging or broken when preventing slush molding, it also is necessary that the stand out during perhaps with the moulding of T pattern tool is controlled at inferior limit.

By the film of the straight chain shape low density ethylene butene-1 copolymer moulding of using Z-type catalyst to make, the transparency, surface smoothing excellence.But the physical strength of representing with dart impact strength and dust Er Mendaofu tear strength of this film is little, and fusion tension force is little, splits so film takes place in moulding process easily, and is restricted aspect the raising shaping speed.In this case, Japanese kokai publication sho 56-90810 communique or Japanese kokai publication sho 60-106806 communique etc. have proposed by using Ziegler-type catalyst, especially Titanium series catalyst improve gained ethylene-based polymer fusion tension force and swell than (die swell ratios), improve the method for formability.

But, the common ethylene-based polymer that uses Titanium series catalyst to obtain, especially straight chain shape low density ethylene based copolymer, because molecular weight distribution or composition distribute wide, so when making formed bodys such as film, expect that further minimizing can cause the composition that is clamminess, and then micro mist composition of oozing out such as the low molecular weight compositions of film surface attachment.

In addition, the ethylene-based polymer that uses chromium-based catalysts to obtain though the fusion warp tension ratio is higher, expects to have higher thermostability.

On the other hand, use metallocene catalyst, the straight chain shape new LDPE (film grade) of making by vapour phase polymerization is because narrow molecular weight distribution, so its film is considered to the film that is difficult to stick together.Especially use the straight chain shape low density ethylene 1-hexene copolymer of metallocene catalyst manufacturing to carry out the film moulding, physical properties excellent such as the physical strength of gained film, the transparency, heat sealability.

But, compare narrow molecular weight distribution with Z-type catalyst, so the fusion Tension Difference, therefore have following problem: carry out blow molding, bubble stability is poor, carries out extrusion moulding (moulding of T pattern tool), and neck-in gets greatly and waits.With respect to this,, remedy this performance by adding the big high-pressure process new LDPE (film grade) of fusion tension force.

And then resin pressure and resin temperature height during owing to moulding can produce more spawn and pasty substance during film is produced for a long time, so in order to remove these with regard to needing to decompose cleaning die and forcing machine, perhaps import the additive that suppresses these.

Patent documentation 1: Japanese kokai publication sho 56-90810 communique

Patent documentation 2: Japanese kokai publication sho 60-106806 communique

Summary of the invention

The problem that invention will solve

Therefore, wish the vinyl copolymer of the material of a kind of formability of appearance and mechanical characteristics excellence, and the film or the sheet forming body that comprise this vinyl copolymer.

The object of the present invention is to provide the especially ethylene-based polymer of film or thin plate of a kind of formed body that obtains the transparency, formability excellence and physical strength excellence, it specifically is ethylene, and the formed body that comprises this ethylene-based polymer, preferably film or thin plate.(in the following description, sometimes film of the present invention or thin plate are called " ethylene (E) " with ethylene, perhaps are called " multipolymer (E) " simply.)

The technical scheme of dealing with problems

That is to say to the present invention relates to a kind of film or thin plate ethylene (E), it is characterized in that, satisfy following important document [1]～[5] simultaneously,

[1] density (d) is at 890～980kg/m ³In the scope;

[2] limiting viscosity of measuring in 135 ℃, naphthalane ([η]) is in 0.5～10dl/g scope;

[3] ratio (Mw/Mn) of weight-average molecular weight of being measured by GPC (Mw) and number-average molecular weight (Mn) is in 2.0～50 scopes;

[4] in the stripping temperature-stripping composition discharge curve of intersection classification chromatogram (CFC), when becoming component to be designated as 100 quality % whole strippings, the difference of the temperature when temperature when the stripping semi-invariant becomes 1 quality % and semi-invariant become 40 quality % is below 12 ℃;

[5] decane soluble portions amount is below 0.5 quality %.

In addition, the invention still further relates to the described ethylene with following feature: described ethylene (E) contains the following ethylene (A) of 80～20 quality % and the following ethylene (B) of 20～80 quality %.

Here, ethylene (A) contains the multipolymer of the alpha-olefin of ethene and carbonatoms 3～10, its density (d _A) be 910～980kg/m ³, the limiting viscosity of in 135 ℃, naphthalane, measuring ([η] _A) be 0.5～3.0dl/g, satisfy 1.5～5.0 by the weight-average molecular weight (Mw) of GPC mensuration and the ratio (Mw/Mn) of number-average molecular weight (Mn);

Ethylene (B) contains the multipolymer of the alpha-olefin of ethene and carbonatoms 3～10, its density (d _B) be 880～950kg/m ³, the limiting viscosity of in 135 ℃, naphthalane, measuring ([η] _B) be 1.0～10.0dl/g, satisfy 1.5～5.0 by the weight-average molecular weight (Mw) of GPC mensuration and the ratio (Mw/Mn) of number-average molecular weight (Mn);

And the limiting viscosity of ethylene (A) and ethylene (B) satisfies following relational expression (Eq-1).

([η] _B)/([η] _A)>1 ...... (Eq-1)

In addition, the invention still further relates to described ethylene with following feature: described ethylene (E) at 190 ℃ fusion tension force (MT) more than 20mN.

Moreover, the invention still further relates to the film or the thin plate that obtain by ethylene (E), preferred (1) thickness is 10～500 μ m, and (2) dart impact strength film or thin plate more than 100g when being converted into 40 μ m thickness.

And, the invention still further relates to the packing bag, thin plate or the bag that form by described film or thin plate.

And then, the invention still further relates to the duplexer that contains the above film of one deck or thin plate at least, the duplexer of dart impact strength more than 130g when preferably being converted into 40 μ m thickness.

The invention effect

According to ethylene of the present invention (E), can obtain formed body, especially film or the thin plate of the transparency and physical strength excellences such as formability excellence and dart impact strength.

Embodiment

Below, about ethylene of the present invention (E), the mode of the best that is used for carrying out an invention is described in turn, then, the manufacture method of ethylene of the present invention (E) and film or the thin plate that is obtained by this ethylene (E) are described, and various measuring methods, at last embodiment is described.In the present invention, " multipolymer " is defined as comprising the polymkeric substance of the homopolymer that the alkene by single kind obtains.

Ethylene (E)

Ethylene of the present invention (E) is the alpha-olefin of Alathon or ethene and carbonatoms 3～10, propylene for example, 1-butylene, the 1-amylene, the 1-hexene, 4-methyl-1-pentene, the 3-Methyl-1-pentene, the 1-heptene, the 1-octene, alpha-olefins such as 1-decene, preferred propylene, 1-butylene, the 1-hexene, 4-methyl-1-pentene, the multipolymer of 1-octene, be preferably the multipolymer or these mixture of polymers (composition) that contain 10 moles of following alpha-olefins of %, and satisfy following important document [1]～[5]

[1] density (d) is at 890～980kg/m ³In the scope;

[5] decane soluble portions amount is below 0.5 quality %.

Ethylene of the present invention (E) contains usually by the amount below the above-mentioned alpha-olefin derived structural unit 10mol%, preferably contains the amount of 0.2～10mol%.

Satisfy the ethylene (E) of described important document [1]～[5], can obtain the formed bodys such as film of physical strength excellences such as formability and dart impact strength.Below, specify important document [1]～[5].

Important document [1]～[3]

Ethylene of the present invention (E), density (d) is at 890～980kg/m ³In the scope, preferably at 900～975kg/m ³In the scope, more preferably at 929～975kg/m ³In the scope, further preferably at 929～945kg/m ³In the scope.

Ethylene of the present invention (E), the limiting viscosity of measuring in 135 ℃ naphthalane ([η]) is in 0.5～10.0dl/g scope, preferably in 0.5～8.0dl/g scope, more preferably in 0.5～7.0dl/g scope, further preferably in 0.5～5.0dl/g scope, in 1.0～4.0dl/g scope.The ethylene (E1) of limiting viscosity ([η]) in 0.5～5dl/g scope of measuring in 135 ℃, naphthalane is particularly suitable for film or thin plate purposes.

Ethylene of the present invention (E), the weight-average molecular weight of being measured by GPC (Mw) and the ratio (Mw/Mn) of number-average molecular weight (Mn) are in 2.0～50 scopes, preferably in 2.5～30 scopes, more preferably in 3.0～25 scopes.

Density, limiting viscosity and the molecular weight distribution ethylene in above-mentioned scope, the balance excellence of its mechanical characteristics and formability.About these parameter control, can compare etc. by the feed rate that for example changes hydrogen in the polymerizer, ethene, alpha-olefin, be controlled in the above-mentioned rerum natura scope.

Important document [4], [5]

Ethylene of the present invention (E), in the stripping temperature-stripping composition discharge curve of intersection classification chromatogram (CFC), when becoming component to be designated as 100 quality % whole strippings, the difference of the temperature when temperature when the stripping semi-invariant becomes 1 quality % and semi-invariant become 40 quality % is below 12 ℃, preferably below 10 ℃.

Ethylene of the present invention (E), its decane soluble portions amount is below 0.5 quality %.

This ethylene (E) means that the content of high molecular weight components of alpha-olefin copolymer is few, and it is lower and have a short chain ramose composition perhaps not contain molecular weight, this moment formability and physical strength the balance excellence.

The optimal way of ethylene of the present invention (E) except having above-mentioned important document [1]～[5], also has concurrently at 190 ℃ fusion tension force (MT) more than 20mN, preferably more than 30mN, and more preferably such feature more than 35mN.

The optimal way of ethylene of the present invention (E) is that ethylene (E) is made of ethylene (A) 80～20 quality %, preferred 70～30 quality % and ethylene (B) 20～80 quality %, preferred 30～70 quality %.The ethylene of this optimal way (E), formability and fusion tension force excellence, and the transparency of gained formed body and physical strength excellence.

Above-mentioned ethylene (A) contains the multipolymer of the alpha-olefin of ethene and carbonatoms 3～10, density (d _A) be 910～980kg/m ³, be preferably 915～975kg/m ³, 920～975kg/m more preferably ³Scope; The limiting viscosity of in 135 ℃, naphthalane, measuring ([η] _A) be 0.5～3.0dl/g, be preferably 0.5～2.7dl/g, more preferably the scope of 0.7～2.5dl/g; By the weight-average molecular weight (Mw) of GPC mensuration and the ratio (Mw/Mn) of number-average molecular weight (Mn) is 1.5～5.0, is preferably 1.5～4.5, more preferably 2.0～4.0 scope.

Above-mentioned ethylene (B) contains the multipolymer of the alpha-olefin of ethene and carbonatoms 3～10, density (d _B) be 880～950kg/m ³, be preferably 890～945kg/m ³, 895～940kg/m more preferably ³Scope; The limiting viscosity of in 135 ℃, naphthalane, measuring ([η] _B) be 1.0～10.0dl/g, be preferably 1.0～8.0dl/g, more preferably the scope of 1.0～7.0dl/g; By the weight-average molecular weight (Mw) of GPC mensuration and the ratio (Mw/Mn) of number-average molecular weight (Mn) is 1.5～5.0, is preferably 1.5～4.5, more preferably 2.0～4.0 scope.

In addition, the limiting viscosity of ethylene (A) and ethylene (B) satisfies following relational expression.

([η] _B)/([η] _A) surpass 1, be preferably greater than 1 and, more preferably greater than equaling 1.1 and, further be preferably greater than to equal 1.2 and less than 6.0 less than 6.0 less than 6.0.

Ethylene of the present invention (E), when constituting by multipolymer (A) and multipolymer (B) as mentioned above, demonstrate excellent film formability, the transparency, even when constituting by single multipolymer, as long as satisfy above-mentioned important document [1]～[5], just belong in the claim scope of the present invention.This ethylene that constitutes by single multipolymer (E) (below, abbreviate multipolymer (E ') sometimes as) being characterized as of having, particularly when the film moulding, can obtain gelling material and mashed prod etc. less and be exuded to the feature of the few film of the micro mist on film surface.

Specifically, and multipolymer (E ') be in the ethylene (E) of above-mentioned important document [1]～[5], satisfy the multipolymer of following important document [1 ']～[5 '].

Multipolymer (E ') be characterised in that:

[1 '] density (d) is at 910～980kg/m ³, be preferably 920～975kg/m ³, 925～970kg/m more preferably ³Scope in;

The limiting viscosity ([η]) that [2 '] measured in 135 ℃, naphthalane at 0.5～4.0dl/g, is preferably 0.5～3.5dl/g, more preferably in the scope of 0.5～3.0dl/g;

The weight-average molecular weight (Mw) that [3 '] measured by GPC and the ratio (Mw/Mn) of number-average molecular weight (Mn) are preferably 1.5～4.5, more preferably in 2.0～4.0 the scope 1.5～5.0;

[4 '] is in the stripping temperature-stripping composition discharge curve of intersection classification chromatogram (CFC), when becoming component to be designated as 100 quality % whole strippings, the difference of the temperature when temperature when the stripping semi-invariant becomes 5 quality % and semi-invariant become 50 quality % is below 10 ℃, preferably below 9 ℃;

[5 '] more than 5mN, is preferably 5～50mN, more preferably 5～30mN at the fusion tension force (MT) of 190 ℃ of mensuration.

The multipolymer that also has both important document [1 ']～[5 '] like this (E '), gelling material and mashed prod etc. are few when having moulding, are exuded to the few feature of micro mist on film surface.Specifically, the film that is obtained by multipolymer (E ') satisfies following character [a]～[c].

Total mist degree of the film that [a] 40 μ m are thick is below 35%, is preferably below 30%, more preferably below 25%.

[b] is more than the 5kJ/m in the film shock strength of 23 ℃ of mensuration.

The visual assessment value that guide roller portion pollutes during the moulding of [c] film when estimating with 5 grades,, is preferably more than 4 minutes more preferably 5 minutes more than 3 minutes.

When casting system film ethene polymers (partly describing in detail) at embodiment, normally will be contacted with 20～100 ℃ cooling roller by 170～250 ℃ the molten resin that T pattern tool is extruded, be cured and make film.At this moment, have the situation of adhering to powder on film surface or the guide roller.In the present invention, be that by clamping the black felt-cloth between guide roller and the film and making it through behind the certain hour, visual observations is carried out attached to the such method of the powder on the felt-cloth about the evaluation of polluting.

In addition, be, on the guide roller that is in the cooling roller downstream side,, utilize the friction of cast membrane by between roller and the felt-cloth time, make white powder attached on the felt-cloth with the black felt-cloth of certain tension force crimping about the evaluation of blowing the powder amount.In this was estimated, limit stretching 500m edge joint removed black felt-cloth after touch, according to the adhesion amount of white powder, gives visual score respectively by 5 ranks.

5 minutes: do not adhere to white powder fully.

4 minutes: adhered to a small amount of white powder.

3 minutes: white powder was attached on the area of making an appointment with half.

2 minutes: between 3 minutes and 1 minute.

1 minute: white powder was almost attached on the entire area.

Here, 1 minute benchmark just becomes the result of comparative example 7 described later.

In the ethylene of the present invention (E), in the scope of not damaging the object of the invention, also can cooperate additives such as weather-proof stablizer, heat-resisting stabilizing agent, static inhibitor, processibility modifying agent, slipproofing agent, antiblocking agent, antifogging agent, slip(ping)agent, dyestuff, nucleator, softening agent, antiaging agent, hydrochloric acid absorbent, oxidation inhibitor as required; Pigment such as carbon black, titanium oxide, titan yellow, phthalocyanine, isoindolinone, quinacridone compound, condensation azo-compound, ultramarine, cobalt blue; Other polymkeric substance.

As described oxidation inhibitor, particularly, for example can enumerate 2,6-ditertbutylparacresol (BHT), four (methylene radical-3-(3, the 5-di-tert-butyl-hydroxy phenyl) methane (trade(brand)name: IRGANOX1010 propionic ester), the manufacturing of Ciba company), Octadecane base-3-(4 '-hydroxyl-3,5 '-di-tert-butyl-phenyl) propionic ester phenol such as (trade(brand)name: IRGANOX1076, Ciba company makes) is oxidation inhibitor; Two (2, the 4-di-tert-butyl-phenyl) pentaerythritol diphosphites, three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester, 2,4,8,10-tetra-tert-6-(3-(3-methyl-4-hydroxyl-5-tert-butyl-phenyl) propoxy-) dibenzo [d, f] [1,3,2] Delnav suberane phosphorous acid esters such as (trade(brand)names: スミライザ-GP, Sumitomo Chemical Co. Ltd.'s manufacturing) is an oxidation inhibitor etc.

As above-mentioned slip(ping)agent, can enumerate for example higher fatty acid amides, high-grade aliphatic ester etc. particularly; As static inhibitor, can enumerate for example glyceryl ester and sorbitan acid esters, the macrogol ester etc. of the lipid acid of carbonatoms 8～22 particularly; As the processibility modifying agent, can enumerate for example fatty acid metal salt, fluorine resin etc. such as calcium stearate particularly.As antiblocking agent, can enumerate inorganic is antiblocking agent, organic system antiblocking agent, as inorganic be antiblocking agent, can enumerate for example silica, lime carbonate, talcum etc. particularly, as the organic system antiblocking agent, can enumerate for example crosslinked polymethylmethacrylaparticles, the crosslinked powder that gathers (methyl methacrylate-vinylbenzene) multipolymer, cross-linked silicone, crosslinked polystyrene etc. particularly.

These,, suitably add in the scope of 0.01～30 mass parts with respect to ethylene (E) 100 mass parts according to its kind usually with the cooperation ratio of the additive headed by the oxidation inhibitor.

As other polymkeric substance, can enumerate ethylene (E) polyolefin-based resins in addition of use in the present invention etc., can enumerate the high-pressure process new LDPE (film grade) and the straight chain shape new LDPE (film grade) (LLDPE) that are used to improve formability, the transparency etc., be used to vinylite of improveing flowability, intensity and heat seal property etc. etc.These other polymkeric substance can add in the ratio that with respect to ethylene (E) 100 mass parts is 1～30 mass parts.

As above-mentioned other resins that add as required and the blending means of additive, for example can enumerate together, adopt behind the various stirrer melting mixings such as single screw extrusion machine, twin screw extruder, Banbury stirrer, hot-rolling in the film method for processing ethylene of the present invention (E) and other resins or additive; With ethylene of the present invention (E) and other resins or additive, adopt various mixing machines such as Henschel stirrer, rotary mixer to do mixed back and supply in the film method for processing; After perhaps other resins or additive being made at least a masterbatch, adopt various mixing machines such as Henschel stirrer, rotary mixer and ethylene of the present invention (E) to do to mix that the back supplies in the film method for processing etc.

Ethylene of the present invention (E) can be made by blow molding, cast molding, the extruding layer film that obtains such as molded; Ducted body, pipe and special-shaped extrusion moulding bodies such as the container that obtains by extrusion moulding, bottle; The foam that obtains by foaming; The formed body that obtains by injection molding; The formed body that obtains by rotoforming; The formed body that obtains by calendering formation; The formed body that obtains by rolling and forming.And then ethylene of the present invention (E) can be used for fiber, monofilament, non-woven etc.These formed bodys comprise the formed body (duplexer etc.) of the part that contains the part that is made of ethylene of the present invention (E) and be made of other resins.Here, ethylene of the present invention (E) also can use the material that is crosslinked in moulding process.

Especially, ethylene of the present invention (E) by blow molding, cast molding, the extruding layer film that obtains such as molded, had excellent characteristic.

Aforesaid ethylene (E) also can be that its part has been carried out modification by the polar monomer grafting.As this polar monomer, can enumerate hydroxyl ethene unsaturated compound, contain amino ethene unsaturated compound, contain epoxy group(ing) ethene unsaturated compound, aromatic ethenyl compound, unsaturated carboxylic acid or derivatives thereof, vinyl ester compound, vinylchlorid, contain vinyl organosilicon compound etc.

Ethene improved alpha-olefin copolymer can be by obtaining aforesaid ethylene (E) graft polymerization polar monomer.During to the aforesaid polar monomer of ethylene (E) graft polymerization, with respect to the ethylene (E) of 100 mass parts, polar monomer is usually with 1～100 mass parts, and the amount of preferred 50～80 mass parts is used.This graft polymerization is normally carried out in the presence of radical initiator.

As radical initiator, can use organo-peroxide or azo-compound etc.Radical initiator can directly mix with ethylene-based polymer and polar monomer and uses, and also can be dissolved in a small amount of organic solvent the back and use.As this organic solvent, then be not particularly limited so long as can dissolve the organic solvent of radical initiator, can use.

In addition, during to ethylene (E) graft polymerization polar monomer, also can use reducing substances.If the use reducing substances can improve the grafting amount of polar monomer.

As for the graft modification of ethylene (E) by polar monomer, can carry out with known method in the past, for example ethylene (E) is dissolved in the organic solvent, then polar monomer and radical initiator etc. is joined in the solution, at 70～200 ℃, preferably, reacted 0.5～15 hour, carried out in preferred 1～10 hour 80～190 ℃ temperature.

In addition, also can use forcing machine etc., under condition of no solvent, make the reaction of ethylene (E) and polar monomer, make ethene improved alpha-olefin copolymer.This reaction suits usually more than the fusing point of ethylene (E), 120～250 ℃ temperature, carries out usually 0.5～10 minute specifically.

The modification amount of the ethene improved alpha-olefin copolymer that obtains as mentioned above (the grafting amount of polar monomer) is suitably 0.1～50 quality % usually, is preferably 0.2～30 quality %, more preferably 0.2～10 quality %.

If contain above-mentioned ethene improved alpha-olefin copolymer in the ethylene of the present invention (E), then with cementability, the intermiscibility excellence of other resins, in addition, the formed body wettability of the surface that is obtained by ethylene (E) also improves sometimes.

In addition, by crosslinked ethene improved alpha-olefin copolymer of the present invention, can also be applied to overhead wire, overhead pipe aptly.

The manufacture method of ethylene (E)

Ethylene of the present invention (E) for example uses by (A) cyclopentadienyl and fluorenyl by containing the covalently cross-linked bonded transistion metal compound of IVA family atom; (B) can form at least a compound of selecting the compound of ion pair with the transistion metal compound reaction from (B-1) organometallic compound, (B-2) Organoaluminoxy compound with (B-3); The catalyst for olefines polymerizing that carrier (C) forms makes the alpha-olefin of ethene and carbonatoms 3～10 carry out copolymerization and obtains.

(A) transistion metal compound

Transistion metal compound (A) is the general formula (1) of following record and the compound shown in (2).

[Chemical formula 1]

[Chemical formula 2]

In above-mentioned general formula (1), (2), R ⁷, R ⁸, R ⁹, R ¹⁰, R ¹¹, R ¹², R ¹³, R ¹⁴, R ¹⁵, R ¹⁶, R ¹⁷, R ¹⁸, R ¹⁹And R ²⁰Be to be selected from hydrogen atom, alkyl, hydrocarbyl silyl, separately can be identical or different, R ⁷～R ¹⁸Adjacent substituting group also can mutually combine and form ring; A is the bivalent hydrocarbon radical that also can contain the carbonatoms 2～20 of some unsaturated link(age) and/or aromatic nucleus, forms ring structure with Y, and A can contain the plural ring structure that comprises the ring that forms with Y; Y is carbon or silicon; M is the metal that is selected from periodic table of elements IVB family; Q is with identical or different combination selection from halogen, alkyl, anion ligand or available lone electron pair coordinate neutral ligand; J is 1～4 integer.

In the present invention, the especially suitable R that uses in above-mentioned transistion metal compound ⁷～R ¹⁰Be that hydrogen atom, Y are that carbon atom, M are that Zr, j are 2 compounds.

The transistion metal compound that uses in embodiment described later (A) is following formula (3) specifically, but is not limited to this transistion metal compound in the present invention.

[chemical formula 3]

Here, the transistion metal compound shown in the above-mentioned formula (3) is to use 270MHz ¹Structure has been determined in H-NMR (NEC GSH-270) and FD-mass analysis (NEC SX-102A).

(B-1) organometallic compound

As (B-1) organometallic compound that uses as required in the present invention, can enumerate following organo-aluminium compound particularly.

General formula: R ^a _mAl (OR ^b) _nH _pX _q

In the formula, R ^aAnd R ^bCan be identical or different mutually, expression carbonatoms 1～15, preferred 1～4 alkyl; X represents halogen atom; M is that 0＜m≤3, n are that 0≤n＜3, p are that 0≤p＜3, q are the numbers of 0≤q＜3, and m+n+p+q=3.

The aluminum compound that uses in embodiment described later is triisobutyl aluminium or triethyl aluminum.

(B-2) Organoaluminoxy compound

(B-2) Organoaluminoxy compound that uses as required can be known in the past aikyiaiurnirsoxan beta in the present invention, also can be the benzene-insoluble Organoaluminoxy compound of example in the Japanese kokai publication hei 2-78687 communique.

The Organoaluminoxy compound that uses in embodiment described later is MAO (=methylaluminoxane)/toluene solution that commercially available Nippon Aluminum Alkyls Ltd. makes.

(B-3) can react and the compound of formation ion pair with transistion metal compound

As the compound (B-3) that can form ion pair (below be called the ionization ionic compound), can enumerate Lewis acid, ionic compound, borane compound and the carborane compound etc. of record in Japanese kokai publication hei 1-501950 communique, Japanese kokai publication hei 1-502036 communique, Japanese kokai publication hei 3-179005 communique, Japanese kokai publication hei 3-179006 communique, Japanese kokai publication hei 3-207703 communique, Japanese kokai publication hei 3-207704 communique, the US-5321106 communique etc. with described transistion metal compound (A) reaction.And then, can also enumerate heteropoly compound and with the polyvoltine compound.This ionization ionic compound (B-3), can be used alone also can be used in combination two or more.As (B) composition that in embodiment described later, uses, use (B-1) shown in above-mentioned and (B-2) two kinds.

(C) microparticle support

(C) microparticle support that uses as required is inorganic or organic compound in the present invention, is particulate state or particulate solid.Wherein as mineral compound, preferred porous oxide, inorganic halides, clay, clay mineral or ion exchangeable lamellar compound.This porous oxide is different according to kind and its proterties of manufacture method, and the particle diameter of the preferred carrier that uses is 1～300 μ m in the present invention, is preferably 3～200 μ m; Specific surface area is 50～1000m ²/ g is preferably 100～800m ²The scope of/g; Pore volume is 0.3～3.0cm ³The scope of/g.This carrier can preferably burn till the back at 100～800 ℃ and use as required at 80～1000 ℃.The carrier that uses in embodiment described later is that 12 μ m, specific surface area are 800m so long as use median size without specified otherwise ²/ g, pore volume are 1.0cm ³The SiO that the Asahi Glass Co., Ltd of/g makes ₂

The catalyst for olefines polymerizing that the present invention relates to, except transistion metal compound (A), at least a compound of from (B-1) organometallic compound, (B-2) Organoaluminoxy compound, (B-3) ionization ionic compound, selecting (B), as required microparticle support (C), can also contain specific organic compound ingredient described later (D) as required.

(D) organic compound ingredient

In the present invention, (D) organic compound ingredient is to use for the purpose of the rerum natura that improves polymerization and generation polymkeric substance as required.As this organic compound, can enumerate alcohols, phenoloid, carboxylic acid, phosphorus compound and sulfonate etc., but be not limited to this.

Polymerization process

Ethylene of the present invention (E) by using aforesaid catalyst for olefines polymerizing, makes the alpha-olefin of ethene and carbonatoms 3～10 carry out copolymerization as mentioned above and obtains.

When polymerization, make usage, the interpolation order of each composition can be selected arbitrarily, but the following method of example, (P1)～(P10).

(P1), add method in the polymerizer to random order with composition (A) with from (B-1) organometallic compound, (B-2) Organoaluminoxy compound and at least a composition (B) (being designated hereinafter simply as " composition (B) ") (B-3) selected the ionization ionic compound.

(P2) catalyzer that will contact composition (A) and composition (B) in advance adds the method in the polymerizer to.

(P3) will contact the catalyst component and the composition (B) of composition (A) and composition (B) in advance, add method in the polymerizer to random order.At this moment, composition separately (B) can be identical or different.

(P4) will load to catalyst component on the microparticle support (C) and composition (B) to composition (A) and add method in the polymerizer to random order.

(P5) will load to catalyzer on the microparticle support (C) to composition (A) and composition (B) and add method in the polymerizer to.

(P6) will load to catalyst component and composition (B) on the microparticle support (C) to composition (A) and composition (B), add method in the polymerizer to random order.At this moment, composition separately (B) can be identical or different.

(P7) will load to catalyst component on the microparticle support (C) and composition (A) to composition (B) and add method in the polymerizer to random order.

(P8) will load to catalyst component, composition (A) and composition (B) on the microparticle support (C) to composition (B), add method in the polymerizer to random order.At this moment, composition separately (B) can be identical or different.

(P9) catalyst component that will make the last load of microparticle support (C) have the catalyzer of composition (A) and composition (B) to contact with composition (B) in advance adds the method in the polymerizer to.At this moment, composition separately (B) can be identical or different.

(P10) will make microparticle support (C) go up catalyst component that catalyzer that load has composition (A) and composition (B) contacts in advance with composition (B) in advance and composition (B) and add method in the polymerizer to random order.At this moment, composition separately (B) can be identical or different.

In each method of above-mentioned (P1)～(P10), being contacted in advance more than at least two of each catalyst component is also passable.

Above-mentioned microparticle support (C) is gone up load has the solid catalyst component of composition (A) and composition (B) also can prepolymerization alkene.This prepolymerized solid catalyst component constitutes with the polymerization in advance of following ratio: usually with respect to the every 1g of solid catalyst component, polyolefine is 0.1～1000g, is preferably 0.3～500g, is preferably 1～200g especially.

In addition,, also additives such as static inhibitor or stain control agent can be loaded to catalyst for olefines polymerizing, perhaps directly be supplied in the polymerization tank for carrying out the polymeric purpose smoothly.This additive is not particularly limited, for example can enumerate polyalkylene oxide, polyalkylene oxide block copolymer, polyalkylene oxide alkyl oxide, alkyl diethanolamine, N such as polyoxyethylene glycol or polypropylene glycol, N-two (2-hydroxyethyl) alkylamine etc. in conjunction with two or more polyalkylene oxides.The molecular end of these compounds also can by alkylation.

Polymerization process can adopt any means in solution polymerization, suspension polymerization and the gaseous polymerization.

As the unreactive hydrocarbons solvent that in liquid polymerization, uses, can enumerate aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, kerosene particularly; Clicyclic hydrocarbons such as pentamethylene, hexanaphthene, methylcyclopentane; Aromatic hydrocarbonss such as benzene,toluene,xylene; Halohydrocarbon such as vinylchlorid, chlorobenzene, methylene dichloride or their mixture etc. perhaps also can use alkene itself as solvent.

When using aforesaid catalyst for olefines polymerizing to carry out (being total to) polymerization, with respect to 1 liter of reaction volume, composition (A) is usually to become 10 ^-12～10 ^-2Mole, preferred 10 ^-10～10 ^-3The amount of mole is used.

The composition of Shi Yonging (B-1) as required becomes 0.01～100,000 with the mol ratio of the transition metal atoms (M) in composition (B-1) and the composition (A) [(B-1)/M] usually, and preferred 0.05～50,000 amount is used.

The composition of Shi Yonging (B-2) as required becomes 10～500,000 with the mol ratio of the transition metal atoms (M) in aluminium atom in the composition (B-2) and the composition (A) [(B-2)/M] usually, and preferred 20～100,000 amount is used.

The composition of Shi Yonging (B-3) as required becomes 1～10 with the mol ratio of the transition metal atoms (M) in composition (B-3) and the composition (A) [(B-3)/M] usually, and preferred 1～5 amount is used.

The composition of Shi Yonging (D) when composition (B) is composition (B-1), becomes 0.01～10 with mol ratio [(D)/(B-1)] usually as required, and preferred 0.1～5 amount is used; When composition (B) is composition (B-2), become 0.001～2 with mol ratio [(D)/(B-2)] usually, preferred 0.005～1 amount is used; When composition (B) is composition (B-3), become 0.01～10 with mol ratio [(D)/(B-3)] usually, preferred 0.1～5 amount is used.

In addition, use the polymerization temperature of this catalyst for olefines polymerizing, usually at-50～+ 250 ℃, preferred 0～200 ℃, preferred especially 60～170 ℃ scope.Polymerization pressure is usually at normal pressure～100kg/cm ², preferred normal pressure～50kg/cm ²Condition under, polyreaction can be carried out in any means of batch-type (intermittent type), semi continuous, continous way.Polymerization is normally carried out mutually at the slurries that gas phase or polymer particles precipitate in the solvent.And then, make polymerization be divided into two different stages of reaction conditions and carry out.The situation of slurry polymerization or vapour phase polymerization, polymerization temperature are preferably 60～90 ℃, more preferably 65～85 ℃.By in this temperature range polymerization, can obtain forming the narrower ethylene of distribution.Resulting polymers is the particle shape of tens of～thousands of μ m ф degree.

This catalyst for olefines polymerizing is owing to also having high polymerization to the alpha-olefin (for example 1-hexene) with ethylene copolymer, so need try every possible means to make it finishing to be unlikely to generate the multipolymer with too high alpha-olefin content after the regulation polymerization.For example can enumerate, taking out the polymerization tank content from polymerization tank when or promptly [1] makes polymkeric substance and solvent, the isolating method of unreacted alpha-olefin with solvent separation unit; [2] in this content, add rare gas element such as nitrogen, solvent and unreacted alpha-olefin are discharged to the outer method of system forcibly; [3] control is applied to the pressure of this content, and solvent and unreacted alpha-olefin are discharged to the outer method of system forcibly; [4] in this content, add a large amount of solvents, the unreacted alpha-olefin is diluted to the method that substantive polymeric concentration can take place of not thinking; [5] add the method that methyl alcohol etc. makes the deactivated material of catalyst for polymerization; [6] this content is cooled to not thinks and substantive polymeric method of temperature etc. can take place.These methods can be implemented separately, also several combinations can be implemented.

The molecular weight of gained ethylene (E) can perhaps change polymerization temperature and regulate by there is hydrogen in polymerization system.And then, also can regulate according to the difference of used composition (B).

When for example dividing two stages to make ethylene (E), can example make the ethylene (A) of last stage after, make the method for the high ethylene (B) of limiting viscosity at latter stage.This order can be turned around.Polymerizing conditions such as the kind of the comonomer of last stage and latter stage and amount, polymerization temperature, hydrogen concentration can be different separately.

By the polymer particle that polyreaction obtains, also can make particle according to following method.

(1) with ethylene (E) particle with other compositions that add as required, use physical mixed such as forcing machine, kneader after, be cut into the method for prescribed level.

(2) with ethylene (E) with other compositions that add as required, after being dissolved in suitable good solvent (for example hydrocarbon solvents such as hexane, heptane, decane, hexanaphthene, benzene, toluene and dimethylbenzene), remove and desolvate, after using physical mixed such as forcing machine, kneader then, be cut into the method for prescribed level.

Formed body

Formed body of the present invention is the formed body that is obtained by described ethylene (E).Formed body of the present invention, the so-called formed body that obtains by polyolefine such as molding of polyethylene normally can be enumerated ducted body, pipe and special-shaped extrusion moulding bodies such as the container that for example obtains by extrusion moulding, bottle particularly; The foam that obtains by foaming; The formed body that obtains by injection molding; Formed bodys such as thermally molded article each such as vacuum, pressure sky.

Film or thin plate

Film of the present invention or thin plate are film or the thin plates that is obtained by described ethylene (E).

Film of the present invention or sheet forming body preferably possess following characteristic.

(1) thickness is at 10～500 μ m, preferred 10～300 μ m, the more preferably scope of 15～200 μ m;

Dart impact strength when (2) being converted into 40 μ m thickness is more than 100g, and under the situation of the film of 40 μ m, dart impact strength is preferably more than 130g, more preferably more than 160g.

And then by film or the thin plate that ethylene of the present invention (E) or ethylene (E1) obtain, internal haze is below 30%, preferred scope below 25%.

Film of the present invention or thin plate for example can be enumerated heavy film for packaging, compression packing film particularly, make things convenient for plastics bag, standard bag, laminated film, retort shine ministerial levels such as tackling film, milk with wrapping material, bag-in-box, film for agricultural use (awning film, the film that keeps off the rain, multilayer film), industry with goods, materials and equipments (comprising the water proof thin plate), gamma-radiation with film, protective membrane (comprising electronic unit, building materials engineering paper), electronic component packing film, shrinkability film (comprising label), medical film (comprising transfusion wraps), industrial medicine with film, food and stipulate corresponding film etc.Wherein, be particularly useful for not containing the purposes such as nothing interpolation packing film of additives such as thermo-stabilizer or hydrochloric acid absorbent or antiblocking agent or slip(ping)agent or static inhibitor or weather-proof stablizer.

Film of the present invention can be by various known manufacture method manufacturings.As the manufacture method that relates to (operation manufacturing before tensile), can enumerate for example the single or multiple lift blown film method of forming, the single or multiple lift T pattern tool cast membrane method of forming, the molded method of extruding layer (comprising the tandem method, Ni Lemu (ニ-ラ system) method), rolling-molding method, extrusion forming method etc. particularly.Ethylene of the present invention (E), because fusion tension force height, fused film is stable easily when blow molding, so preferred blow molding.In addition, when extrusion mouldings such as blow molding or cast molding, because the fusion warp tension ratio is higher, so the mashed prod when having striped that can suppress to enter in the film and the moulding that reduces the thickness precision and reduce the advantage of the cleaning frequency around the die lip.

Use the film for packaging or the gauge of sheet of film of the present invention, be generally 10～500 μ m, be preferably 10～300 μ m, more preferably 15～200 μ m.

In addition, also film of the present invention or thin plate layer can be pressed onto on the base material and be used as composite membrane.As base material, can enumerate known base material, for example can enumerate vibrin, oriented polypropylene such as polyamide resin, polyethylene terephthalate and polybutylene terephthalate such as glassine paper, paper, cardboard, fabric, aluminium foil, nylon 6 and nylon 66, it is bonding with tackiness agent etc. for example can to enumerate acrylic acid series caking agent, isoprene-isobutylene rubber, urethane adhesive etc. as adhesive linkage.

As the method that will be pressed onto by the rete that ethylene of the present invention (E) obtains on the base material, can enumerate known method, for example can enumerate dry lamination method, wet type laminating, flush coat platen press, hot melt layer platen press etc.

In addition, also can be applied to contain the duplexer of above film of the present invention of one deck at least or thin plate.The formation of duplexer is not particularly limited, according to desired function, can enumerate propylene resin, cyclic polyolefine hydrocarbon system resin, phenylethylene resin series, polymeric amide, polyester, polycarbonate, vinylite (EVA, ionomer), ethenol system resin, vinyl chloride resin etc.For example, want to have the words of block, can enumerate blocks such as polyvinyl alcohol, EVOH, nylon 6, nylon 66, Ni Long11, nylon 611, NYLON610, cyclic polyolefin, polyethylene terephthalate, polybutylene terephthalate and give resin, by stacked ethylene of the present invention (E) and described resin, can give function.In addition, use ethene improved alpha-olefin copolymer by the middle layer of giving resin in ethylene (E) and block this moment, can make the cementability of interlayer become good.When making duplexer, be not particularly limited preferred multilayer blown film moulding or multilayer T pattern tool cast membrane moulding coextrusion.

Below, be described more specifically the present invention based on embodiment, but the present invention is not limited to these embodiment.

Embodiment

The following describes the sample modulation method of employing in an embodiment and the measuring method of various rerum naturas.

Measure modulation with sample

For emboliform ethylene (E) 100 mass parts, cooperation is as three (2 of secondary oxidation inhibitor, the 4-di-tert-butyl-phenyl) phosphoesterase 30 .20 mass parts, as Octadecane base-3-(4 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl) propionic ester 0.20 mass parts of heat-resisting stabilizing agent, as calcium stearate 0.15 mass parts of hydrochloric acid absorbent.The single screw extrusion machine (screw diameter 65mm ф, L/D=28, the mesh #40/#60/#300 * 4/#60/#40), be used as the mensuration sample that use PLACO company to make then with 200 ℃ of design temperatures, resin extruded amount 25kg/hr granulation.

Ethylene content, alpha-olefin Determination on content

By ¹³C-NMR measures the corresponding methyl branch number of average per 1,000 carbon in the ethylene copolymer molecular chain.Mensuration is the Lambda500 type nuclear magnetic resonance device (1H:500MHz) that adopts Jeol Ltd. to make.With cumulative frequency 10,000～30,000 time mensuration.Here, use the peak (29.97ppm) of main chain methylene radical as the chemical shift benchmark.Measure in the quartz glass tube at the commercially available NMR of diameter 10mm, add the superfine orthodichlorobenzene that sample 250～400mg and Wako Pure Chemical Industries, Ltd. make: benzene-d that ISOTEC company makes ₆The mixed solution 2ml of=5:1 (volume ratio) is heated to 120 ℃ of homodisperse, this solution is carried out NMR measure.

Each ownership that absorbs in the NMR spectrum is based on No. 141 NMR-general introductions of chemical field supplementary issue and experiment guide (chemistry

The territory

Print No. 141 NMR-Gross and Shuo と experiment ガイ De) [I] 132 pages～133 pages carry out.

Composition about ethylene is confirmed usually by the following method, promptly, in the sample tube of 10mm ф, the multipolymer uniform dissolution that makes 250～400mg is in the 2ml hexachlorobutadiene, measure 120 ℃ of temperature, measuring frequency 125.7MHz, spectrogram width 250, under the condition determination of 000Hz, 4.4 seconds pulse repetition times, 45 ° of pulses, measure this sample ¹³The C-NMR spectrum.

Intersection classification chromatogram (CFC)

The following mensuration of CFC T-150A type of using oiling company of Mitsubishi to make.Separator column is three ShodexAT-806MS, and elutriant is an orthodichlorobenzene, and sample solution concentration is 0.1～0.3wt/vol%, and injection rate is 0.5ml, and flow velocity is 1.0ml/min.Sample is after 2 hours, to be cooled to 0 ℃ with 10 ℃/hour 145 ℃ of heating, and then keeps coming in 60 minutes coated coupons at 0 ℃.Intensification stripping column capacity is 0.86ml, and the pipe arrangement capacity is 0.06ml.Detector is the infrared spectroscopy instrument MIRAN 1A CVF type (CaF that FOXBORO company makes ₂Sample cell), the setting with 10 seconds absorbancy pattern of answering time detects 3.42 μ m (2924cm ^-1) infrared light.The stripping temperature is to be divided into 35～55 parts with 0 ℃～145 ℃, especially then is divided into scale and is 1 ℃ part near the stripping peak.It all is integer that temperature shows, for example 90 ℃ stripping partly is the composition that is illustrated in 89 ℃～90 ℃ of strippings.Being determined at 0 ℃ does not have coated composition yet and at the molecular weight of the part of each temperature stripping, uses general calibration curve, obtains PE conversion molecular weight.The SEC temperature is 145 ℃, and interior mark injection rate is 0.5ml, and the injection phase is 3.0ml, and the data sampling time is 0.50 second.Here, too much when the composition of stripping in narrow temperature range, and when producing pressure anomaly, just sample solution concentration is set at less than 0.1wt/vol% sometimes.Data processing is to implement by installing incidental analysis program " CFC data processing (1.50 editions) ".Here, intersect classification chromatogram (CFC) if himself can be described as and make condition determination strictly identical, just can obtain high analysis precision, can reproduce result's analytical method, it is average but get after more preferably repeatedly measuring.

Weight-average molecular weight (Mw), number-average molecular weight (Mn) and molecular weight curve

The following mensuration of GPC-150C of using Waters to make.Separator column is TSKgel GMH6-HT and TSKgel GMH6-HTL, column dimension is respectively internal diameter 7.5mm, length 600mm, column temperature is 140 ℃, moving phase is to use orthodichlorobenzene (with the pure pharmaceutical worker of light industry) and as BHT (military field drug company) the 0.025 quality % of oxidation inhibitor, flow with 1.0ml/min, sample solution concentration is 0.1 quality %, and the sample injection rate is 500 μ l, and detector uses differential refractometer.About polystyrene standard, molecular weight is Mw＜1000 and Mw〉4 * 10 ⁶The person uses eastern Cao company goods, 1000≤Mw≤4 * 10 ⁶Person's applying pressure chemistry (Pressure chemical) company's goods.It is to carry out that general correction is scaled vinylbenzene and the value obtained that molecular weight calculates.

Limiting viscosity ([η])

Be to use the value of naphthalane solvent 135 ℃ of mensuration.That is, about 20mg is dissolved in naphthalane 15ml with granulated pellet, measures relative viscosity η in 135 ℃ oil bath _SpAfter in this naphthalane solution, appending naphthalane solvent 5ml dilution, similarly operate and measure relative viscosity η _SpFurther repeat this dilution operation 2 times, obtain concentration (C) is extrapolated to 0 o'clock η _SpThe value of/C, with it as limiting viscosity (with reference to following formula).

[η]＝lim(η _sp/C)(C→0)

Density (d)

Use is set in the hydraulic type thermocompressor that 190 ℃ refreshing rattan metal industry company makes, with 100kg/cm ²The thick thin plate of pressure forming 0.5mm (partition shape at the thick plate of 240 * 240 * 0.5mm, is got 9 45 * 45 * 0.5mm), and another table oil pressure type thermocompressor that uses the refreshing rattan metal industry company that is set in 20 ℃ to make is with 100kg/cm ²Pressure compression, cool off, make to measure and use sample.Hot plate uses the thick SUS plate of 5mm.This pressing plate 120 ℃ of thermal treatments 1 hour, behind 1 hour slow cool to room temperature of rectilinearity, is measured with density gradient tube.

Melting index (MFR)

According to JIS K7210, with 190 ℃, 2.16kg loading mensuration MFR.

Fusion tension force (MT)

Use the smart mechanism of Japan to make the fusion tension tester mensuration fusion tension force (MT) that Co., Ltd. of institute makes.Condition determination is as follows.

＜condition determination〉use nozzle: L=8.000mm, D=2.095mm, mensuration temperature: 190 ℃, resin extruded speed: 15mm/ minute, resin are pulled out speed: 10m/ minute.

The condition determination of film rerum natura

[1] mensuration (unit: g) of dart impact strength (DI)

According to ASTM D1709, measure in following condition.

Condition: test piece is fastening in the air clamp mode, fall hemisphere footpath dart from the position of certain altitude, from chart, read test piece and destroy 50% o'clock loading.The drop number of a level is 10 times, employing method A.

[2] mensuration of mist degree (transparency, unit: %)

According to ASTM D1003, measure total mist degree and internal haze.Here, be, in being filled with the sample cell of hexalin, put into film, use the mist degree tester to implement to measure with mist degree then the samely about internal haze.

[3] film impacts (FI) strength detection

Under 23 ± 2 ℃, the state of relative humidity 50 ± 5%, leave standstill film more than 48 hours after, cut into the size of 100 * 100mm.With the thickness of micrometer or continuous thickness gauge mensuration (n=10) film sample, obtain mean thickness.

Select the smart mechanism of Japan to make the capacity of impact head of film impact test instrument of manufacturing and shape (in the common mensuration, the capacity of impact head is 30kgcm, impact head be shaped as 1/2 inch) per sample.

On the sample bench of film impact test instrument, place test piece, fastening with air clamp.Pendulum is placed on the starting position, pointer is placed on the maximum scale.Remove the bolt of pendulum, give surging force to sample and carry out punching press.Read with the unit of 0.1kgcm from the position of pointer and to destroy required energy.

Sample for n=10 is measured respectively, calculates the film shock strength by following formula.

FI＝E/D

(FI: film shock strength, E: impact fracture energy, D: the thickness of test piece)

The manufacture method of film

[1] blow molding (individual layer)

Use described mensuration sample, carry out the air cooling blow molding, make wall thickness 40～120 μ m, the film of width 320mm according to following condition of molding.

＜film condition of molding 〉

Shaper: the 50mm ф blow molding machine that modern machines company makes

Screw rod: barrier screw

Mould: 100mm ф (diameter), 2.0mm (die lip width)

Ring gasket: 2 breach types

Mold temperature: 200 ℃

Extrusion capacity: 28.8Kg/h

Pull out speed: 20m/min (during wall thickness 40 μ m moulding)

10m/min (during wall thickness 80 μ m moulding)

(6.7m/min during wall thickness 120 μ m moulding)

[2] blow molding (multilayer)

Use described mensuration sample, under following condition of molding, carry out the air cooling blow molding, make the multilayer film of wall thickness 40～120 μ m, width 710mm.

＜film condition of molding 〉

Shaper: three layers of blow molding machine (three of the 50mm ф forcing machines that Alpine company makes)

Screw rod: barrier screw

Mould: 225mm ф (diameter), 3.5mm (die lip width)

Ring gasket: 2 breach types

Mold temperature: 200 ℃

Extrusion capacity: 100kg/hr (outermost layer: 25kg/hr, middle layer: 50kg/hr, innermost layer: 25kg/hr)

Pull out speed: 32m/min (during wall thickness 40 μ m moulding)

10m/min (during wall thickness 130 μ m moulding)

[3] cast molding (individual layer)

During with ethylene (E) or ethylene (E1) casting system film, normally will be contacted with 20～100 ℃ cooling roller, and solidify and make film by 170～250 ℃ the molten resin that T pattern tool is extruded.For example, implement evaluation as described below.

＜film condition of molding 〉

The middle layer of only using high speed multilayer cast molding machine (manufacturing of SHI modern machines Co., Ltd.) is with forcing machine (65mm ф), according to following condition moulding individual layer cast membrane.

Screw rod: L/D=32, T pattern tool: coating hanger type, width 800mm

Mold temperature: C1/C2/C3/C4/C5/AD/J=200/230/230/230/230/230/230 ℃

Extrusion capacity: 70kg/hr

Chill-roll temperature: 40 ℃, film thickness: 40 μ m, pull out speed: 50m/min

Synthesis example 1

The modulation of solid catalyst component (α)

At 3 hours silica 8.5kg of 200 ℃ of dryings, make suspension with the toluene of 33L after, dripped methylaluminoxane solution (Al=1.42mol/L) 82.7L through 30 minutes.Then, be warming up to 115 ℃, with this thermotonus 4 hours through 1.5 hours.Be cooled to 60 ℃ then, remove supernatant liquor by decantation.Clean the solid catalyst component of 3 gained with toluene after, suspend once more and obtain solid catalyst component (α) (cubic capacity 150L) with toluene.

The modulation of supported catalyst

Fully carrying out in the reactor of nitrogen replacement, adding is scaled the described solid catalyst component (α) in the toluene of being suspended in of 19.60mol with aluminium, this suspension is stirred on the limit, stirred 60 minutes after at room temperature (20～25 ℃) add two (p-methylphenyl) methylene radical (cyclopentadiene) (prestox octahydro dibenzo fluorenyl) zirconium dichloride 31.06mmol/L solution 2L (61.12mmol) on the limit.After stopping to stir, decant is removed supernatant liquor, cleans 2 times with normal hexane 40L, with gained supported catalyst furnishing slurries in normal hexane, makes the catalyst suspension of 25L, obtains solid catalyst component (γ).

Modulation by the prepolymerized solid catalyst component of solid catalyst component (γ) (δ)

In the reactor of subsidiary stirrer, after under nitrogen atmosphere, dropping into refining normal hexane 15.8L and above-mentioned solid catalyst component (γ), add triisobutyl aluminium 5mol, stir on one side, carry out prepolymerization to be equivalent to every 1g solids component at the ethene of 4 hours poly amounts of generation 3g on one side.Polymerization temperature remains on 20～25 ℃.After polymerization finishes, stop to stir, decant is removed supernatant liquor then, cleans 4 times with normal hexane 35L, with the 20L normal hexane gained supported catalyst is made catalyst suspension, obtains solid catalyst component (δ).

Embodiment 1

Polymerization

In first polymerization tank, supply with on one side hexane 45L/hr continuously, be scaled the solid catalyst component (δ), triethyl aluminum 4mmol/hr, ethene 8.1kg/hr, 1-hexene 251g/hr, the hydrogen 40N-L/hr that obtain in synthesis example 1 of 0.050mmol/hr with Zr conversion atom, and take out the polymerization tank content continuously so that the fluid level in the polymerization tank remains necessarily, on one side at 75 ℃ of polymerization temperatures, reaction pressure 7.5kg/cm ²Carry out polymerization under G, 2.5 hours the condition of average retention time.The content that takes out continuously from first polymerization tank is with pressing 0.3kg/cm in remaining on ²G, 65 ℃ flash tank are substantially removed unreacting ethylene and hydrogen.

Then, this content is supplied in second polymerization tank continuously with hexane 43L/hr, ethene 5.7kg/hr, hydrogen 4N-L/hr, 1-hexene 892g/hr, at 72 ℃ of polymerization temperatures, reaction pressure 7kg/cm ²Continue polymerization under G, 1.5 hours the condition of average retention time.

Also take out the polymerization tank content continuously so that the fluid level in the polymerization tank remains necessarily in second polymerization tank, remove hexane and unreacted monomer in this content with solvent separation unit, drying obtains polymkeric substance.For the polymerization that prevents from not expect, in the content that from polymerization tank, takes out, supply with methyl alcohol with 2L/hr, make the catalyst for polymerization inactivation.Then, remove hexane and unreacted monomer in this content with solvent separation unit, drying obtains polymkeric substance.

For these polymer particles 100 mass parts, cooperate 6-(3-(3-tertiary butyl-4-hydroxy-5-methyl) propoxy-)-2,4,8,10-tetra-tert benzo [d, f] [1,3,2] Delnav suberane, 0.2 mass parts, calcium stearate 0.1 mass parts as oxidation inhibitor.The single screw extrusion machine (screw diameter 65mm ф, L/D=28) that uses PLACO company to make then is used as the mensuration sample with 200 ℃ of design temperatures, resin extruded amount 25kg/hr granulation.And, use this sample production film, measure rerum natura.At table 1 and table 2 ecbatic.

Embodiment 2

Polymerization

In first polymerization tank, supply with on one side hexane 45L/hr continuously, be scaled the solid catalyst component (δ), triethyl aluminum 20mmol/hr, ethene 8.1kg/hr, 1-hexene 149g/hr, the hydrogen 50N-L/hr that obtain in synthesis example 1 of 0.0110mmol/hr with Zr conversion atom, and take out the polymerization tank content continuously so that the fluid level in the polymerization tank remains necessarily, on one side at 75 ℃ of polymerization temperatures, reaction pressure 7.5kg/cm ²Carry out polymerization under G, 2.5 hours the condition of average retention time.The content that takes out continuously from first polymerization tank is with pressing 0.3kg/cm in remaining on ²G, 65 ℃ flash tank are substantially removed unreacting ethylene and hydrogen.

Then, this content just is supplied in second polymerization tank continuously with hexane 43L/hr, ethene 49kg/hr, hydrogen 3N-L/hr, 1-hexene 204g/hr, at 72 ℃ of polymerization temperatures, reaction pressure 7kg/cm ²Continue polymerization under G, 1.5 hours the condition of average retention time.

For these polymer particles 100 mass parts, cooperate the oxidation inhibitor and the calcium stearate of condition similarly to Example 1, the single screw extrusion machine granulation of using PLACO company to make is used as measuring uses sample.And, use this sample production film, measure rerum natura.At table 1 and table 2 ecbatic.

Embodiment 3

Polymerization

In first polymerization tank, supply with on one side hexane 45L/hr continuously, be scaled the solid catalyst component (δ), triethyl aluminum 20mmol/hr, ethene 6.3kg/hr, 1-hexene 91g/hr, the hydrogen 40N-L/hr that obtain in synthesis example 1 of 0.20mmol/hr with Zr conversion atom, and take out the polymerization tank content continuously so that the fluid level in the polymerization tank remains necessarily, on one side at 75 ℃ of polymerization temperatures, reaction pressure 7.5kg/cm ²Carry out polymerization under G, 2.5 hours the condition of average retention time.The content that takes out continuously from first polymerization tank is with pressing 0.3kg/cm in remaining on ²G, 65 ℃ flash tank are substantially removed unreacting ethylene and hydrogen.

Then, this content is supplied in second polymerization tank continuously with hexane 43L/hr, ethene 9.4kg/hr, hydrogen 4N-L/hr, 1-hexene 495g/hr, at 72 ℃ of polymerization temperatures, reaction pressure 7kg/cm ²Continue polymerization under G, 1.5 hours the condition of average retention time.

Embodiment 4

Polymerization

In first polymerization tank, supply with on one side hexane 45L/hr continuously, be scaled the solid catalyst component (δ), triethyl aluminum 20mmol/hr, ethene 8.1kg/hr, the hydrogen 50N-L/hr that obtain in synthesis example 1 of 0.075mmol/hr with Zr conversion atom, and take out the polymerization tank content continuously so that the fluid level in the polymerization tank remains necessarily, on one side at 75 ℃ of polymerization temperatures, reaction pressure 7.5kg/cm ²Carry out polymerization under G, 2.5 hours the condition of average retention time.The content that takes out continuously from first polymerization tank is with pressing 0.3kg/cm in remaining on ²G, 65 ℃ flash tank are substantially removed unreacting ethylene and hydrogen.

Then, this content is supplied in second polymerization tank continuously with hexane 43L/hr, ethene 10.2kg/hr, hydrogen 35N-L/hr, 1-hexene 1378g/hr, at 72 ℃ of polymerization temperatures, reaction pressure 7kg/cm ²Continue polymerization under G, 1.5 hours the condition of average retention time.

Embodiment 5

Polymerization

In first polymerization tank, supply with on one side hexane 45L/hr continuously, be scaled the solid catalyst component (δ), triethyl aluminum 20mmol/hr, ethene 8.1kg/hr, 1-hexene 155g/hr, the hydrogen 70N-L/hr that obtain in synthesis example 1 of 0.080mmol/hr with Zr conversion atom, and take out the polymerization tank content continuously so that the fluid level in the polymerization tank remains necessarily, on one side at 75.5 ℃ of polymerization temperatures, reaction pressure 7.5kg/cm ²Carry out polymerization under G, 2.5 hours the condition of average retention time.The content that takes out continuously from first polymerization tank is with pressing 0.3kg/cm in remaining on ²G, 65 ℃ flash tank are substantially removed unreacting ethylene and hydrogen.

Then, this content is supplied in second polymerization tank continuously with hexane 43L/hr, ethene 10.2kg/hr, hydrogen 20N-L/hr, 1-hexene 1295g/hr, at 72 ℃ of polymerization temperatures, reaction pressure 7kg/cm ²Continue polymerization under G, 1.5 hours the condition of average retention time.

Embodiment 6

Polymerization

For these polymer particles 100 mass parts, cooperate the oxidation inhibitor and the calcium stearate of condition similarly to Example 1, the single screw extrusion machine granulation of using PLACO company to make is used as measuring uses sample.And, use this sample production film, measure rerum natura.At table 1 and table 3 ecbatic.

Embodiment 7

Polymerization

Then, this content is supplied in second polymerization tank continuously with hexane 43L/hr, ethene 10.2kg/hr, hydrogen 4N-L/hr, 1-hexene 1275g/hr, at 72 ℃ of polymerization temperatures, reaction pressure 7kg/cm ²Continue polymerization under G, 1.5 hours the condition of average retention time.

Embodiment 8

Polymerization

In first polymerization tank, supply with on one side hexane 45L/hr continuously, be scaled the solid catalyst component (δ), triethyl aluminum 20mmol/hr, ethene 8.1kg/hr, the hydrogen 50N-L/hr that obtain in synthesis example 1 of 0.075mmol/hr with Zr conversion atom, and take out the polymerization tank content continuously so that the fluid level in the polymerization tank remains necessarily, on one side at 75.5 ℃ of polymerization temperatures, reaction pressure 7.5kg/cm ²Carry out polymerization under G, 2.5 hours the condition of average retention time.The content that takes out continuously from first polymerization tank is with pressing 0.3kg/cm in remaining on ²G, 65 ℃ flash tank are substantially removed unreacting ethylene and hydrogen.

For these polymer particles 100 mass parts, cooperate the oxidation inhibitor and the calcium stearate of condition similarly to Example 1, the single screw extrusion machine granulation of using PLACO company to make is used as measuring uses sample.And, use this sample production film, measure rerum natura.At table 1 and table 4 ecbatic.

Comparative example 1

(Puriman Polymer Co., Ltd makes, trade(brand)name: GD1588) as the mensuration sample with linear low density polyethylene.At table 1,2 ecbatics.

Comparative example 2

(Puriman Polymer Co., Ltd makes, trade(brand)name: Ha イゼ Star Network ス HZ3300F), make film similarly to Example 1, measure rerum natura to use high density polyethylene(HDPE).At table 1～3 ecbatics.

Comparative example 3

(Puriman Polymer Co., Ltd makes, trade(brand)name: ウ Le トゼ Star Network ス UZ4020L), make film similarly to Example 1, measure rerum natura to use linear low density polyethylene.At table 1～4 ecbatics.

Comparative example 4

(Puriman Polymer Co., Ltd makes, trade(brand)name: モアテ Star Network 0168N), make film similarly to Example 1, measure rerum natura to use linear low density polyethylene.At table 1,2 and 4 ecbatics.

Table 2

Table 3

Table 4

Embodiment 9

Polymerization

In polymerization tank, supply with on one side hexane 45L/hr continuously, be scaled the solid catalyst component (δ), triethyl aluminum 20mmol/hr, ethene 8.1kg/hr, the hydrogen 50N-L/hr that obtain in synthesis example 1 of 0.13mmol/hr with the Zr atom, and take out the polymerization tank content continuously so that the fluid level in the polymerization tank remains necessarily, on one side at 75 ℃ of polymerization temperatures, reaction pressure 8.5kg/cm ²Carry out polymerization under G, 2.5 hours the condition of average retention time.For the polymerization that prevents from not expect, in the content that from polymerization tank, takes out, supply with methyl alcohol with 2L/hr, make the catalyst for polymerization inactivation.Then, remove hexane and unreacted monomer in this content with solvent separation unit, drying obtains polymkeric substance.

For these polymer particles 100 mass parts, cooperate 6-(3-(3-tertiary butyl-4-hydroxy-5-methyl) propoxy-)-2,4,8,10-tetra-tert benzo [d, f] [1,3,2] Delnav suberane, 0.2 mass parts, calcium stearate 0.1 mass parts as oxidation inhibitor.The single screw extrusion machine (screw diameter 65mm ф, L/D=28) that uses PLACO company to make then is used as the mensuration sample with 200 ℃ of design temperatures, resin extruded amount 25kg/hr granulation.And, use this sample production film, measure rerum natura.At the character value of table 5 and table 6 expression polymkeric substance, at table 7 expression film physics value.

Embodiment 10

Polymerization

In polymerization tank, supply with on one side hexane 45L/hr continuously, be scaled the solid catalyst component (δ), triethyl aluminum 20mmol/hr, ethene 8.1kg/hr, the hydrogen 50N-L/hr that obtain in synthesis example 1 of 0.17mmol/hr with the Zr atom, and take out the polymerization tank content continuously so that the fluid level in the polymerization tank remains necessarily, on one side at 75 ℃ of polymerization temperatures, reaction pressure 8.5kg/cm ²Carry out polymerization under G, 2.5 hours the condition of average retention time.For the polymerization that prevents from not expect, in the content that from polymerization tank, takes out, supply with methyl alcohol with 2L/hr, make the catalyst for polymerization inactivation.Then, remove hexane and unreacted monomer in this content with solvent separation unit, drying obtains polymkeric substance.

Then, the single screw extrusion machine granulation made from PLACO company similarly to Example 9 is used as measuring and uses sample.And, use this sample production film, measure rerum natura.At the character value of table 5 and table 6 expression polymkeric substance, at table 7 expression film physics value.

Embodiment 11

Polymerization

In polymerization tank, supply with on one side hexane 45L/hr continuously, be scaled the solid catalyst component (δ), triethyl aluminum 20mmol/hr, ethene 8.1kg/hr, hydrogen 50N-L/hr, the 1-hexene 117g/hr that obtain in synthesis example 1 of 0.15mmol/hr with the Zr atom, and take out the polymerization tank content continuously so that the fluid level in the polymerization tank remains necessarily, on one side at 75 ℃ of polymerization temperatures, reaction pressure 8.5kg/cm ²Carry out polymerization under G, 2.5 hours the condition of average retention time.For the polymerization that prevents from not expect, in the content that from polymerization tank, takes out, supply with methyl alcohol with 2L/hr, make the catalyst for polymerization inactivation.Then, remove hexane and unreacted monomer in this content with solvent separation unit, drying obtains polymkeric substance.

Embodiment 12

Polymerization

In polymerization tank, supply with on one side hexane 45L/hr continuously, be scaled the solid catalyst component (δ), triethyl aluminum 20mmol/hr, ethene 8.1kg/hr, hydrogen 100N-L/hr, the 1-hexene 233g/hr that obtain in synthesis example 1 of 0.10mmol/hr with the Zr atom, and take out the polymerization tank content continuously so that the fluid level in the polymerization tank remains necessarily, on one side at 75 ℃ of polymerization temperatures, reaction pressure 8.5kg/cm ²Carry out polymerization under G, 2.5 hours the condition of average retention time.For the polymerization that prevents from not expect, in the content that from polymerization tank, takes out, supply with methyl alcohol with 2L/hr, make the catalyst for polymerization inactivation.Then, remove hexane and unreacted monomer in this content with solvent separation unit, drying obtains polymkeric substance.

Comparative example 5

(Puriman Polymer Co., Ltd makes, trade(brand)name: Ha イゼ Star Network ス HZ3300F), make film similarly to Example 9, measure rerum natura to use high density polyethylene(HDPE).At the character value of table 5 and table 6 expression polymkeric substance, at table 7 expression film physics value.

Comparative example 6

(Puriman Polymer Co., Ltd makes, trade(brand)name: ウ Le トゼ Star Network ス UZ4020L), make film similarly to Example 9, measure rerum natura to use linear low density polyethylene.At the character value of table 5 and table 6 expression polymkeric substance, at table 7 expression film physics value.

Comparative example 7

(Puriman Polymer Co., Ltd makes, trade(brand)name: Ha イゼ Star Network ス HZ2200J), make film similarly to Example 9, measure rerum natura to use high density polyethylene(HDPE).At the character value of table 5 and table 6 expression polymkeric substance, at table 7 expression film physics value.

Table 5

	[η] dl/g	Density kg/m ³	Mw/Mn —	Alpha-olefin	Alpha-olefin content mol%
	[η] dl/g	Density kg/m ³	Mw/Mn —	Alpha-olefin	Alpha-olefin content mol%	Embodiment 9	1.7	964	3.3	Do not have	0.0
Embodiment 10	1.5	967	3.3	Do not have	0.0	Embodiment 9	1.7	964	3.3	Do not have	0.0
Embodiment 10	1.5	967	3.3	Do not have	0.0	Embodiment 11	1.4	953	3.6	The 1-hexene	0.3
Embodiment 12	1.8	944	3.5	The 1-hexene	0.5	Embodiment 11	1.4	953	3.6	The 1-hexene	0.3
Embodiment 12	1.8	944	3.5	The 1-hexene	0.5	Comparative example 5	2.2	950	5.3	Propylene	0.5
Comparative example 6	2.3	937	2.6	4-methyl-1-pentene	0.7	Comparative example 5	2.2	950	5.3	Propylene	0.5
Comparative example 6	2.3	937	2.6	4-methyl-1-pentene	0.7	Comparative example 7	1.5	964	8.1	Do not have	0.0

Table 6

	The stripping temperature width of stripping quantity 5～50wt% ℃	MT g(mN) ^(notes)	MFR g/10min
		MT g(mN) ^(notes)	MFR g/10min	Embodiment 9	4.3	1(10)	2.3
Embodiment 10	4.1	0.6(5.5)	5.1	Embodiment 9	4.3	1(10)	2.3
Embodiment 10	4.1	0.6(5.5)	5.1	Embodiment 11	5.2	0.6(6)	5.0
Embodiment 12	6.0	2.2(22)	1.5	Embodiment 11	5.2	0.6(6)	5.0
Embodiment 12	6.0	2.2(22)	1.5	Comparative example 5	12.8	3.1(30)	1.1
Comparative example 6	-	2(20)	2.3	Comparative example 5	12.8	3.1(30)	1.1
Comparative example 6	-	2(20)	2.3	Comparative example 7	14.5	1(10)	5.2

Annotate: make the MT of g (gram) unit multiply by the MT that 9.8 value is mN (newton in the least) unit.

Table 7

	Total mist degree %	Film shock strength kJ/m	The evaluation score that powder adheres to ^(notes)
	Total mist degree %	Film shock strength kJ/m	The evaluation score that powder adheres to ^(notes)	Embodiment 9	13	9	4
Embodiment 10	22	8	5	Embodiment 9	13	9	4
Embodiment 10	22	8	5	Embodiment 11	20	7	5
Embodiment 12	10	11	5	Embodiment 11	20	7	5
Embodiment 12	10	11	5	Comparative example 5	6	13	2
Comparative example 6	4	15	3	Comparative example 5	6	13	2
Comparative example 6	4	15	3	Comparative example 7	11	7	1

Annotate: the visual assessment mark

[adhering to manyly], 1＜2＜3＜4＜5[adhered to fewly]

Industrial applicibility

Ethyleneα-olefincopolymer of the present invention (E) can be shaped to molded etc. the film formed body of blow molding, water cooling blow molding, cast molding, extruding layer; The sheet forming body; The blow molding body; The extrusion molding body of pipe and abnormity etc.; Expanded moldings; Injection molded article etc. And then, can be used for fiber, monofilament, non-weaving cloth etc. These formed bodys comprise the formed body (duplexer etc.) that contains the part that comprises ethyleneα-olefincopolymer and comprise the part of other resins. Here, this ethyleneα-olefincopolymer also can use the material that is crosslinked in forming process. Ethyleneα-olefincopolymer of the present invention is used for molded etc. the film formed body of blow molding, cast molding, the extruding layer of above-mentioned formed body, can gives excellent characteristic.

Film of the present invention or thin plate can be applied to aptly heavy film for packaging, compression packing film, make things convenient for polybag, standard bag, laminated film, alembic shine with goods, materials and equipments (comprising the water proof thin plate) gamma-radiation with packaging material, bag-in-box, film for agricultural use (awning film, the film that keeps off the rain, multilayer film), industry and tackle film etc. with film, diaphragm (comprising electronic unit, building materials engineering paper), electronic component packing film, shrinkage film (comprising label), medical film (comprising transfusion wraps), industrial medicine with film, food.

Claims

1. film or thin plate ethylene is characterized in that, satisfy following important document [1]～[5] simultaneously,

[1] density (d) is at 890～980kg/m ³Scope in;

[2] in the scope of limiting viscosity ([η]) of in 135 ℃, naphthalane, measuring at 0.5～10dl/g;

[3] ratio (Mw/Mn) of weight-average molecular weight of being measured by GPC (Mw) and number-average molecular weight (Mn) is in 2.0～50 scope;

[5] decane soluble portions amount is below 0.5 quality %.

2. film according to claim 1 or thin plate ethylene, it is characterized in that, contain the following ethylene (A) of 80～20 quality % and the following ethylene (B) of 20～80 quality %, and satisfy following formula (Eq-1)

Ethylene (A): contain the multipolymer of the alpha-olefin of ethene and carbonatoms 3～10, satisfy density (d _A) be 910～980kg/m ³, the limiting viscosity of in 135 ℃, naphthalane, measuring ([η] _A) be 0.5～3.0dl/g, (Mw/Mn) be 1.5～5.0;

Ethylene (B): contain the multipolymer of the alpha-olefin of ethene and carbonatoms 3～10, satisfy density (d _B) be 880～950kg/m ³, the limiting viscosity of in 135 ℃, naphthalane, measuring ([η] _B) be 1.0～10.0dl/g, (Mw/Mn) be 1.5～5.0;

([η] _B)/([η] _A)>1 ...... (Eq-1)。

3. ethylene according to claim 1 and 2 is characterized in that, at 190 ℃ fusion tension force (MT) more than 20mN.

4. film or the thin plate that obtains by each the described ethylene (E) in the claim 1～3.

5. the packing bag, thin plate or the bag that contain described film of claim 4 or thin plate.

6. the duplexer that contains described film of the above claim 4 of one deck or thin plate at least.