JPH093137A - Graft modified ethylene polymer - Google Patents

Abstract

PURPOSE: To obtain a graft modified ethylene polymer excellent in adhesion to a metal or a polar resin by grafting a polar monomer onto an ethylene polymer having specified physical properties (e.g. melt flow rate). CONSTITUTION: This graft modified ethylene polymer is produced by grafting 0.1-50wt.% polar monomer (e.g. an ethylenically unsatd. monomer having a hydroxyl, amino, or epoxy group, an arom. vinyl, or a vinyl chloride) onto an ethylene homopolymer or ethylene/3-20C α-olefin copolymer having an ethylene content of 50-100wt.%, a density of 0.85-0.98g/cm<3> , a melt flow rate(MFR) which is 0.01-200g/10min at 190 deg.C under a load of 2.16kg and satisfies the relation with the melt tension (MT) as expressed by formula I, an index of mol.wt. distribution Mw/Mn (wherein Mw is the wt. average mol.wt.; and Mn is the number average mol.wt.) of 2.5 or lower, and a temp. (Tm deg.C) at the max. peak in the endothermic curve obtd. with a differential scanning calorimeter satisfying the relation with the density (d) as expressed by formula II.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel graft-modified ethylene-based polymer, and more particularly to a graft-modified ethylene-based polymer excellent in adhesiveness to a metal or polar resin.

[0002]

TECHNICAL BACKGROUND OF THE INVENTION Ethylene homopolymer, ethylene
Ethylene-based polymers such as α-olefin copolymers are molded by various molding methods and are used for various purposes. The ethylene-based polymer may be used for lamination with another resin, a metal foil or the like, blending with another resin, or the like. However, since the ethylene polymer is a so-called non-polar resin having no polar group in the molecule, it has a poor affinity with various polar substances including metals, and it has been difficult to use it for such applications. Therefore, when it is used for applications such as adhesion with a metal or blending with a polar resin, it is necessary to improve the affinity with a polar substance by graft-copolymerizing a polar monomer with an ethylene polymer. there were.

However, even if the ethylene polymer is subjected to graft modification in order to improve the affinity with polar substances, the adhesiveness with metals and the like may not be sufficient, and the adhesiveness with metals and the like is more excellent. The advent of graft-modified ethylene-based polymers is desired.

The present inventors have conducted intensive studies in view of such conventional techniques, and as a result, density, melt flow rate and M
A polar monomer is graft-copolymerized with an ethylene polymer having w / Mn in a specific range and satisfying a certain relationship between the melt tension, the melt flow rate, and the temperature and density at the maximum peak position in the endothermic curve measured by DSC. The present graft-modified ethylene polymer was found to have excellent adhesiveness with metals or polar resins, and the present invention has been completed.

[0005]

OBJECTS OF THE INVENTION It is an object of the present invention to provide a graft-modified ethylene-based polymer having excellent adhesion to a metal or polar resin.

[0006]

The graft-modified ethylene-based polymer according to the present invention is a homopolymer of ethylene or a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms. Induced structural units are 50 to 1
Is in the range of 00% by weight, and (ii) the density is 0.850 to
In the range of 0.980 g / cm ³ , (iii) 190
The melt flow rate at a temperature of 2.16 kg under a temperature of 0.01 to 200 g / 10 min.
Melt tension (MT) at ℃ and melt flow rate (MFR) satisfy the relationship ^represented by MT ≦ 2.2 × MFR ^−0.84 , and (v) Mw / Mn (Mw: weight average) which is an index of molecular weight distribution. The molecular weight, Mn: number average molecular weight) is 2.5 or less, and (vi) the temperature (Tm (° C.)) and the density (d) at the maximum peak position in the endothermic curve measured by a differential scanning calorimeter are , Tm <400 × d-250, and a polar monomer is graft-copolymerized with the ethylene polymer.

In the present invention, the polar monomer is a hydroxyl group-containing ethylenically unsaturated compound, an amino group-containing ethylenically unsaturated compound, an epoxy group-containing ethylenically unsaturated compound,
At least one monomer selected from aromatic vinyl compounds, unsaturated carboxylic acids and derivatives thereof, vinyl ester compounds, and vinyl chloride is desirable, and hydroxyl group-containing ethylenically unsaturated compounds, aromatic vinyl compounds, unsaturated carboxylic acids. And at least one monomer selected from derivatives thereof is particularly desirable. Further, the graft amount of the graft group derived from the polar monomer is preferably in the range of 0.1 to 50% by weight.

[0008]

DETAILED DESCRIPTION OF THE INVENTION The graft-modified ethylene polymer according to the present invention will be specifically described below.

The graft-modified ethylene-based polymer according to the present invention is a homopolymer of ethylene or an ethylene-based polymer which is a random copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms, and a polar monomer. Is graft-copolymerized.

In the ethylene polymer used in the graft-modified ethylene polymer of the present invention, the constitutional unit derived from ethylene is 50 to 100% by weight, preferably 70% by weight.
To 100% by weight, more preferably 80 to 100% by weight, and the structural unit derived from the α-olefin having 3 to 20 carbon atoms is 0 to 50% by weight, preferably 0 to 30% by weight. %, More preferably 0 to 20% by weight.

Here, as the α-olefin having 3 to 20 carbon atoms, propylene, 1-butene, 1-pentene, 1-
Hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-
Examples include octadecene and 1-eicosene.

In such an ethylene polymer, the density
Is 0.850 to 0.980 g / cm ^Three,Preferably
0.870-0.975 g / cm^Three, More preferably
0.900 to 0.970 g / cm^ThreeIn the range of Mel
Tough flow rate is 0.01 ~ 200g / 10min, preferably
Preferably 0.03 to 100 g / 10 minutes, more preferably
It is in the range of 0.05 to 50 g / min.

In such an ethylene polymer, 190
The melt tension [MT (g)] at a temperature of [deg.] C. and the melt flow rate [MFR (g / 10 min)] satisfy the relationship ^represented by MT ≦ 2.2 × MFR ^−0.84 .

Further, the ethylene polymer is Mw / Mn (Mw: weight average molecular weight, Mn: Mn:
The value of (number average molecular weight) is 2.5 or less, preferably 1.8 to
It is in the range of 2.4.

Further, the ethylene polymer has a temperature [Tm (° C.)] and a density [d (g / cm) at the maximum peak position in an endothermic curve measured by a differential scanning calorimeter (DSC).
³ )] satisfies the relationship represented by: Tm <400 × d-250, preferably Tm <450 × d-297, more preferably Tm <500 × d-344, and particularly preferably Tm <550 × d-391. .

Such an ethylene-based polymer has a lower Tm with respect to the density than the ethylene-based polymer polymerized with a conventional titanium-based catalyst. Therefore, when compared at the same density, the heat-sealing property is excellent. ing.

The ethylene polymer used in the present invention is
In addition to having the above characteristics, it is desirable to have the following characteristics. When the n-decane-soluble component amount ratio [W (wt%)] and the density [d (g / cm ³ )] at room temperature are MFR ≦ 10 g / 10 min: W <80 × exp (−100 (d −0.88)) + 0.1 Preferably W <60 × exp (−100 (d−0.8
8)) + 0.1 More preferably, W <40 × exp (−100 (d−0.8
8)) + 0.1 MFR> 10 g / 10 min: W <80 × (MFR-9) ^0.35 × exp (−100 (d−
0.88)) + 0.1 is preferable.

It can be said that the ethylene-based polymer having a n-decane-soluble component amount ratio and density at room temperature satisfying the above relationship has a narrow composition distribution. Further, the ethylene-based polymer has a stress of 2.4 × 10 ⁶ dyne at 190 ° C. of the molten polymer.
/ Flow index that is defined as a shear rate when reaching the cm ² [FI (1 / sec)] and the melt flow rate [M
FR (g / 10 minutes)] and FI <75 × MFR, preferably FI <80 × MFR, and more preferably FI <85 × MFR.

Further, the ethylene polymer preferably has a crystallinity of more than 30%, more preferably 35 to 90%. The ethylene-based polymer as described above is, for example, a transition metal compound of Group IVB of the periodic table containing (a) a ligand having a cyclopentadienyl skeleton,
In the presence of an olefin polymerization catalyst formed from (b) an organoaluminum oxy compound, (c) a carrier, and optionally (d) an organoaluminum compound, ethylene has a density of 0.850 to 0. Homopolymerization should be performed at 980 g / cm ³ , or the copolymer obtained from ethylene and an α-olefin having 3 to 20 carbon atoms should have a density of 0.850 to 0.980 g / cm ^3. It can be produced by copolymerizing with.

The olefin polymerization catalyst and each catalyst component will be described below. (A) A transition metal compound of Group IVB of the periodic table containing a ligand having a cyclopentadienyl skeleton (hereinafter sometimes referred to as “component (a)”) is specifically represented by the following formula (I ) Is a transition metal compound represented by.

ML _x (I) In the formula, M is a transition metal selected from Group IVB of the periodic table, specifically zirconium, titanium or hafnium, preferably zirconium.

X is the valence of the transition metal M and represents the number of L. L is a ligand that coordinates to the transition metal atom M, and at least two of these ligands L are cyclopentadienyl group, methylcyclopentadienyl group or ethylcyclopentadienyl group. A substituted cyclopentadienyl group having at least one group selected from hydrocarbon groups having 3 to 10 carbon atoms as a substituent, and a ligand other than a (substituted) cyclopentadienyl group L is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a halogen atom, a trialkylsilyl group or a hydrogen atom.

The substituted cyclopentadienyl group may have two or more substituents, and the two or more substituents may be the same or different. The substituted cyclopentadienyl group has at least 1 when it has two or more substituents.
Each of the substituents may be a hydrocarbon group having 3 to 10 carbon atoms, and the other substituent is a methyl group, an ethyl group or a hydrocarbon group having 3 to 10 carbon atoms. The (substituted) cyclopentadienyl groups coordinated to M may be the same or different.

Specific examples of the hydrocarbon group having 3 to 10 carbon atoms include an alkyl group, a cycloalkyl group, an aryl group and an aralkyl group. More specifically, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, octyl group, 2-ethylhexyl group,
Examples thereof include alkyl groups such as decyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; aryl groups such as phenyl group and tolyl group; aralkyl groups such as benzyl group and neophyll group.

Of these, alkyl groups are preferable, and n-propyl group and n-butyl group are particularly preferable. In the present invention, the (substituted) cyclopentadienyl group which coordinates to the transition metal is preferably a substituted cyclopentadienyl group, more preferably a cyclopentadienyl group substituted with an alkyl group having 3 or more carbon atoms. A disubstituted cyclopentadienyl group is more preferable, and a 1,3-substituted cyclopentadienyl group is particularly preferable.

In the above formula (I), the ligand L other than the (substituted) cyclopentadienyl group coordinated to the transition metal atom M is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, It is an aryloxy group, a halogen atom, a trialkylsilyl group or a hydrogen atom.

Examples of the hydrocarbon group having 1 to 12 carbon atoms include an alkyl group, a cycloalkyl group, an aryl group and an aralkyl group, and more specifically,
Methyl group, ethyl group, n-propyl group, isopropyl group,
alkyl groups such as n-butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, octyl group, 2-ethylhexyl group and decyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; An aryl group such as a phenyl group and a tolyl group; and an aralkyl group such as a benzyl group and a neophyl group can be exemplified.

Examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, t-butoxy group, pentoxy group, hexoxy group, octoxy group and the like. Can be illustrated.

Examples of the aryloxy group include a phenoxy group and the like. Examples of the halogen atom include fluorine, chlorine, bromine and iodine.

Examples of the trialkylsilyl group include a trimethylsilyl group, a triethylsilyl group and a triphenylsilyl group. Examples of the transition metal compound represented by the general formula (I) include bis (cyclopentadienyl) zirconium dichloride, bis (methylcyclopentadienyl) zirconium dichloride, bis (ethylcyclopentadienyl) zirconium dichloride, and bis. (N-propylcyclopentadienyl)
Zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride, bis (n-hexylcyclopentadienyl) zirconium dichloride, bis (methyl-n-propylcyclopentadienyl) zirconium dichloride, bis (methyl-n- Butylcyclopentadienyl) zirconium dichloride, bis (dimethyl-n
-Butylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dibromide, bis (n-butylcyclopentadienyl)
Zirconium methoxy chloride, bis (n-butylcyclopentadienyl) zirconium ethoxy chloride, bis (n-butylcyclopentadienyl) zirconium butoxycyclolide, bis (n-butylcyclopentadienyl) zirconium ethoxide, bis (n- Butylcyclopentadienyl) zirconium methyl chloride, bis (n-butylcyclopentadienyl) zirconium dimethyl, bis (n-butylcyclopentadienyl) zirconium benzyl chloride, bis (n-butylcyclopentadienyl) zirconium dibenzyl , Bis (n-butylcyclopentadienyl) zirconium phenyl chloride, bis (n-butylcyclopentadienyl) zirconium hydride chloride and the like. In the above example, the di-substituted cyclopentadienyl ring includes 1,2- and 1,3-substituted compounds, and the tri-substituted compound includes 1,2,3- and 1,2,4-substituted compounds. Including. In the present invention, a transition metal compound in which zirconium metal is replaced with titanium metal or hafnium metal in the above zirconium compound can be used.

Among these transition metal compounds represented by the general formula (I), bis (n-propylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride, bis ( 1-
Methyl-3-n-propylcyclopentadienyl) zirconium dichloride and bis (1-methyl-3-n-butylcyclopentadienyl) zirconium dichloride are particularly preferred.

Next, the organoaluminum oxy compound (b) will be described. The organoaluminum oxy compound (b) (hereinafter sometimes referred to as “component (b)”) may be a conventionally known benzene-soluble aluminoxane and is disclosed in JP-A-2-276807. Such a benzene-insoluble organoaluminum oxy compound may be used.

The aluminoxane as described above can be prepared, for example, by the following method. (1) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, ceric chloride hydrate, etc. The method of adding an organoaluminum compound such as trialkylaluminum to the suspension of a hydrocarbon medium, and reacting the adsorbed water or crystal water with the organoaluminum compound.

(2) A method of directly acting water, ice or steam on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran.

(3) A method of reacting an organoaluminum compound such as trialkylaluminum with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene or toluene.

The aluminoxane may contain a small amount of organometallic component. Alternatively, the solvent or unreacted organoaluminum compound may be removed from the recovered aluminoxane solution by distillation, and then redissolved in the solvent.

Specific examples of the organoaluminum compound used when preparing the aluminoxane include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum and tri-n-.
Trialkyl aluminum such as butyl aluminum, triisobutyl aluminum, tri sec-butyl aluminum, tri tert-butyl aluminum, tripentyl aluminum, trihexyl aluminum, trioctyl aluminum, tridecyl aluminum; tricyclohexyl aluminum, tricyclooctyl aluminum, etc. Tricycloalkyl aluminum; Dialkyl aluminum halides such as dimethyl aluminum chloride, diethyl aluminum chloride, diethyl aluminum bromide, diisobutyl aluminum chloride; Dialkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride; Dimethyl aluminum methoxide, diethyl aluminum ethoxy And dialkylaluminum alkoxides such as diethyl aluminum phenoxide and the like.

Of these, trialkylaluminums and trialkylaluminums are particularly preferred. Further, as the organoaluminum compound represented by the general formula _{(i-C 4 H 9)} x Al y (C 5 H 10) z (x, y, z are each a positive number, a is z ≧ 2x) expressed in Isoprenylaluminum may also be used.

The organoaluminum compound as described above is
Used alone or in combination. As the solvent used in the preparation of aluminoxane, benzene, toluene, xylene, cumene, aromatic hydrocarbons such as cymene,
Aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane and methylcyclopentane; petroleum distillates such as gasoline, kerosene and light oil And hydrocarbon solvents such as halides of the above-mentioned aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons, especially chlorinated products and brominated products. In addition, ethers such as ethyl ether and tetrahydrofuran can also be used. Among these solvents, aromatic hydrocarbons are particularly preferred.

The carrier (c) is an inorganic or organic compound and has a particle size of 10 to 300 μm, preferably 20 to 300 μm.
A 200 μm granular or particulate solid is used. Among them, a porous oxide is preferable as the inorganic carrier, and specifically, SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ ,
TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO _{2 and the} like or a mixture thereof, for example, SiO ₂ -MgO, SiO
_2- Al ₂ O ₃ , SiO ₂ -TiO ₂ , SiO ₂ -V ₂ O ₅ , Si
O ₂ —Cr ₂ O ₃ and SiO ₂ —TiO ₂ —MgO can be exemplified. Of these, those containing, as a main component, at least one component selected from the group consisting of SiO ₂ and Al ₂ O ₃ .

The inorganic oxide contains a small amount of Na ₂ C.
O ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ SO ₄ ,
Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (NO ₃ )
₂ , carbonates such as Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O and Li ₂ O, sulfates, nitrates and oxide components may be contained.

Such a carrier (c) has a specific surface area of 50 to 1000 m, although its properties vary depending on its type and production method.
² / g, preferably 100 to 700 m ² / g, and the pore volume is preferably 0.3 to 2.5 cm ³ / g. The carrier is used by firing at 100 to 1000 ° C, preferably 150 to 700 ° C, if necessary.

Further, examples of the carrier that can be used in the present invention include granular or particulate solids of organic compounds having a particle size of 10 to 300 μm. These organic compounds include ethylene, propylene, 1-butene, 4-methyl-1-pentene and the like having 2 to 1 carbon atoms.
Examples thereof include (co) polymers containing α-olefin of 4 as the main component, or polymers or copolymers containing vinylcyclohexane and styrene as the main components.

The olefin polymerization catalyst used in the production of the ethylene-based polymer is formed from the above-mentioned components (a), (b) and (c), and if necessary, (d) an organoaluminum compound. You may use.

Examples of the (d) organoaluminum compound (hereinafter sometimes referred to as "component (d)") which is optionally used include organoaluminum compounds represented by the following general formula (II). can do.

[0046] In ^{_{R a n AlX 3-n ...}} (II) ( wherein, R ^a represents a hydrocarbon group having 1 to 12 carbon atoms, X is a halogen atom or a hydrogen atom, n represents 1
3. ) In the general formula (II), R ^a has 1 to 1 carbon atoms.
A hydrocarbon group such as an alkyl group, a cycloalkyl group or an aryl group, specifically, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an isobutyl group, a pentyl group, a hexyl group, Octyl, cyclopentyl, cyclohexyl, phenyl, tolyl and the like.

Specific examples of such an organoaluminum compound include the following compounds. Trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, tri2-ethylhexylaluminum; alkenylaluminums such as isoprenylaluminum; dimethylaluminum chloride, diethylaluminium chloride, diisopropylaluminum chloride, diisobutyl. Dialkyl aluminum halides such as aluminum chloride and dimethyl aluminum bromide; alkyl aluminum sesquihalides such as methyl aluminum sesquichloride, ethyl aluminum sesquichloride, isopropyl aluminum sesquichloride, butyl aluminum sesquichloride, ethyl aluminum sesquibromide; methyl Aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride, alkyl aluminum dihalides such as ethyl aluminum dibromide; diethylaluminum hydride, and alkyl aluminum hydride such as diisobutyl aluminum hydride.

As the organoaluminum compound (d),
Using a compound represented by the following general formula (III)
You can also R^a _nAlY_3-n ... (III) (wherein, R^aIs R in the above general formula (II)^aSimilar to carbonization
Y represents -OR ^bGroup, -OSiR^c _ThreeGroup, -O
AlR^d _TwoGroup, -NR^e _TwoGroup, -SiR^f _ThreeGroup or -N
(R^g) AlR^h _TwoRepresents a group, n is 1-2, R^b,
R^c, R^dAnd R ^hIs a methyl group, an ethyl group,
Pill group, isobutyl group, cyclohexyl group, phenyl group
And R^eRepresents a hydrogen atom, a methyl group, an ethyl group,
Sopropyl, phenyl, trimethylsilyl, etc.
Yes, R^fAnd R^gIs a methyl group, an ethyl group, etc.
You. ) As such an organoaluminum compound,
The following compounds are used.

[0049] _{^{(1) R a n Al (}} OR b) a compound represented by _3-n, e.g., dimethylaluminum methoxide, diethylaluminum ethoxide and diisobutylaluminum _{^{methoxide, (2) R a n Al}} (OSiR c ₃ ) a compound represented by _3-n ,
For example, Et ₂ Al (OSiMe ₃ ), (iso-Bu) ₂ Al
_{(OSiMe 3), (iso-} Bu) 2 Al (OSiEt 3)
(3) ^a compound represented by R ^a _n Al (OAlR ^d ₂ ) _3-n ,
For example, Et ₂ AlOAlEt ₂ , (iso-Bu) ₂ AlOA
l (iso-Bu) _{2 and the} like; (4) Compound represented by R ^a _n Al (NR ^e ₂ ) _3-n , for example, Me ₂ AlNEt ₂ , Et ₂ AlNHMe, Me ₂ Al
_{NHEt, Et 2 AlN (SiMe 3} ) 2, (iso-Bu) 2
AlN (SiMe ₃ ) ₂ etc .; (5) R ^a _n Al (SiR ^f ₃ ) _3-n represented by compounds such as (iso-Bu) ₂ AlSi Me ₃ etc .; (6) R ^a _n Al (N A compound represented by (R ^g ) AlR ^h ₂ ) _3-n , for example, Et ₂ AlN (Me) AlEt ₂ , (iso
Etc. _{-Bu) 2 AlN (Et) Al} (iso-Bu) 2.

Among the organoaluminum compounds represented by the above general formulas (II) and (III), the general formula R ^a ₃ Al,
R ^a _n Al (OR ^b ) _3-n , R ^a _n Al (OAlR ^d ₂ ) _3-n
Compounds represented by are preferable, and compounds in which R ^a is an isoalkyl group and n = 2 are particularly preferable.

In the present invention, when an ethylene-based polymer is produced, it is prepared by bringing the above-mentioned component (a), component (b) and carrier (c) and, if necessary, component (d) into contact with each other. A catalyst is used.

The catalyst used for producing the ethylene polymer is the above-mentioned component (a), component (b), carrier (c).
Further, it may be a prepolymerization catalyst obtained by prepolymerizing an olefin in the presence of the component (d) if necessary.
The prepolymerization is carried out by introducing an olefin into an inert hydrocarbon solvent in the presence of the components (a), (b), the carrier (c) and, if necessary, the component (d) as described above. Can be.

The ethylene polymer used in the present invention is
In the presence of the above olefin polymerization catalyst or prepolymerization catalyst, ethylene is homopolymerized, or ethylene and α-olefin having 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1
-Tetradecene, 1-hexadecene, 1-octadecene, 1-
It is obtained by copolymerizing with eicosene.

Homopolymerization of ethylene, or ethylene and α
-Copolymerization with olefins is carried out in the gas phase or in the slurry liquid phase. In slurry polymerization, an inert hydrocarbon may be used as a solvent, or an olefin itself may be used as a solvent.

Specific examples of the inert hydrocarbon solvent used in the slurry polymerization include butane, isobutane, pentane, hexane, octane, decane, dodecane, hexadecane, octadecane, and other aliphatic hydrocarbons; cyclopentane, methylcyclopentane. , Cyclohexane,
Alicyclic hydrocarbons such as cyclooctane; aromatic hydrocarbons such as benzene, toluene and xylene; gasoline;
Examples include petroleum fractions such as kerosene and light oil. Among these inert hydrocarbon media, aliphatic hydrocarbons, alicyclic hydrocarbons, petroleum fractions and the like are preferred.

When carrying out the slurry polymerization method or the gas phase polymerization method, the above-mentioned olefin polymerization catalyst or prepolymerization catalyst usually has a concentration of the transition metal atom in the polymerization reaction system of usually 10 ⁻⁸ to 10 ^−. It is desirable to use an amount of ³ gram atom / liter, preferably 10 ⁻⁷ to 10 ⁻⁴ gram atom / liter.

Further, in the main polymerization, in addition to the supported components (b) and (d), the same organoaluminum oxy compound and / or organoaluminum compound (d) as that of the component (b) is further added. May be. On this occasion,
The atomic ratio of the aluminum atom (Al) in the organoaluminum oxy compound and the organoaluminum compound to the transition metal atom (M) derived from the transition metal compound (a) (A
1 / M) is in the range of 5-300, preferably 10-200, more preferably 15-150.

When carrying out the slurry polymerization method, the polymerization temperature is usually in the range of -50 to 100 ° C, preferably 0 to 90 ° C, and when carrying out the gas phase polymerization method, the polymerization temperature is It is usually in the range of 0 to 120 ° C, preferably 20 to 100 ° C.

The polymerization pressure is usually atmospheric pressure to 100 kg /
It is under a pressure condition of cm ² , preferably ² to 50 kg / cm ² , and the polymerization can be carried out in any of batch system, semi-continuous system and continuous system.

It is also possible to carry out the polymerization in two or more stages under different reaction conditions. The graft-modified ethylene polymer of the present invention can be obtained by reacting the above ethylene polymer with a polar monomer as described below in the presence of a radical initiator.

Examples of polar monomers include hydroxyl group-containing ethylenically unsaturated compounds, amino group-containing ethylenically unsaturated compounds, epoxy group-containing ethylenically unsaturated compounds, aromatic vinyl compounds, unsaturated carboxylic acids and their derivatives, vinyl ester compounds. , Vinyl chloride and the like.

Specific examples of the hydroxyl group-containing ethylenically unsaturated compound include hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate and 2-hydroxy.
-3-phenoxy-propyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, pentaerythritol mono (meth) acrylate, trimethylolpropane mono (meth) acrylate, tetramethylol (Meth) acrylic acid esters such as ethane mono (meth) acrylate, butanediol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, and 2- (6-hydroxyhexanoyloxy) ethyl acrylate; 10-undecene-1- All, 1-octen-3-ol, 2-methanol norbornene, hydroxystyrene,
Hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, N-methylolacrylamide, 2- (meth) acryloyloxyethyl acid phosphate,
Glycerin monoallyl ether, allyl alcohol, allyloxyethanol, 2-butene-1,4-diol, glycerin monoalcohol and the like can be mentioned.

The amino group-containing ethylenically unsaturated compound is
A compound having an ethylenic double bond and an amino group,
Examples of such a compound include a vinyl-based monomer having at least one amino group and substituted amino group represented by the following formula.

[0064]

Embedded image

In the formula, R ⁴ represents a hydrogen atom, a methyl group or an ethyl group, and R ⁵ represents a hydrogen atom or a carbon atom number of 1 to 1.
2, preferably an alkyl group having 1 to 8 or a cycloalkyl group having 6 to 12, preferably 6 to 8 carbon atoms. The above alkyl group and cycloalkyl group may further have a substituent.

Specific examples of the amino group-containing ethylenically unsaturated compound include aminoethyl (meth) acrylate, propylaminoethyl (meth) acrylate,
Alkyl ester derivatives of acrylic acid or methacrylic acid such as dimethylaminoethyl methacrylate, aminopropyl (meth) acrylate, phenylaminoethyl methacrylate and cyclohexylaminoethyl methacrylate; N-vinyldiethylamine and N-acetylvinylamine Vinylamine derivatives: allylamine, methacrylamine, N-methylacrylamine, N, N-
Allylamine derivatives such as dimethylacrylamide and N, N-dimethylaminopropylacrylamide; Acrylamide derivatives such as acrylamide and N-methylacrylamide; Aminostyrenes such as p-aminostyrene; 6-Aminohexylsuccinimide, 2- Aminoethyl succinimide or the like is used.

The epoxy group-containing ethylenically unsaturated compound is a monomer having at least one polymerizable unsaturated bond and one or more epoxy groups in one molecule. As such an epoxy group-containing ethylenically unsaturated compound, Specifically, glycidyl acrylate, glycidyl methacrylate, mono and diglycidyl esters of maleic acid, mono and diglycidyl esters of fumaric acid, mono and diglycidyl esters of crotonic acid, mono and diglycidyl esters of tetrahydrophthalic acid, itaconic acid Mono- and glycidyl esters, butenetricarboxylic acid mono- and diglycidyl esters, citraconic acid mono- and diglycidyl esters, endo-cis-bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid (nadic acid mono and ^TM) Glycidyl esters, end - cis - bicyclo [2.2.1] hept-5-ene-2-methyl-2,
3-Dicarboxylic acid (methyl nadic acid ^TM ) mono and diglycidyl ester, allyl succinic acid mono and glycidyl ester and other dicarboxylic acid mono and alkyl glycidyl esters (in the case of monoglycidyl ester, the alkyl group has 1 to 12 carbon atoms) , Alkyl glycidyl ester of p-styrenecarboxylic acid, allyl glycidyl ether, 2-methylallyl glycidyl ether, styrene-p-glycidyl ether, 3,4-epoxy-1-butene, 3,
4-epoxy-3-methyl-1-butene, 3,4-epoxy-1-pentene, 3,4-epoxy-3-methyl-1-pentene, 5,6-epoxy-1-hexene, vinylcyclohexene monoxide And the like.

Examples of the aromatic vinyl compound include compounds represented by the following formula.

[0069]

Embedded image

In the above formula, R ⁶ and R ^{7, which} may be the same or different, each represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, specifically, a methyl group, an ethyl group, Mention may be made of propyl and isopropyl groups. R ⁸ represents a hydrocarbon group having 1 to 3 carbon atoms or a halogen atom, and specific examples thereof include a methyl group, an ethyl group, a propyl group and an isopropyl group, a chlorine atom, a bromine atom and an iodine atom. be able to. Further, n is usually 0 to 5, preferably 1 to
Represents an integer of 5.

Specific examples of such aromatic vinyl compounds include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, p-chlorostyrene, m-chlorostyrene and p-chloromethylstyrene, 4-vinylpyridine, 2-vinylpyridine, 5-ethyl-2-vinylpyridine, 2-methyl-5-vinylpyridine,
Examples thereof include 2-isopropenylpyridine, 2-vinylquinoline, 3-vinylisoquinoline, N-vinylcarbazole, and N-vinylpyrrolidone.

As the unsaturated carboxylic acid, acrylic acid,
Methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, norbornene dicarboxylic acid, bicyclo [2,
2,1] unsaturated carboxylic acids such as hept-2-ene-5,6-dicarboxylic acid, or acid anhydrides or derivatives thereof (eg, acid halides, amides, imides, esters, etc.). Examples of specific compounds include maleenyl chloride, maleenyl imide, maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo [2,2,1] hept-2-ene-5,6-dicarboxylic acid Acid anhydride, dimethyl maleate, monomethyl maleate, diethyl maleate, diethyl fumarate, dimethyl itaconate, diethyl citraconic acid, dimethyl tetrahydrophthalate, bicyclo [2,2,1] hept-2-ene-5,6 -
Dimethyl dicarboxylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate,
Glycidyl (meth) acrylate, aminoethyl methacrylate, aminopropyl methacrylate and the like can be mentioned. Among these, (meth) acrylic acid,
Maleic anhydride, hydroxyethyl (meth) acrylate, glycidyl methacrylate, and aminopropyl methacrylate are preferred.

Examples of vinyl ester compounds are vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate, vinyl versatate, vinyl laurate, vinyl stearate, benzoic acid. Examples thereof include vinyl, vinyl pt-butylbenzoate, vinyl salicylate and vinyl cyclohexanecarboxylate.

The polar monomer is usually used in an amount of 1 to 100 parts by weight based on 100 parts by weight of the ethylene polymer.
It is preferably used in an amount of 5 to 80 parts by weight. Examples of the radical initiator include organic peroxides and azo compounds.

Specific examples of the organic peroxide include dicumyl peroxide, di-t-butyl peroxide and 2,5
-Dimethyl-2,5-bis (t-butylperoxy) hexane, 2,
5-Dimethyl-2,5-bis (t-butylperoxy) hexine-
3,1,3-bis (t-butylperoxyisopropyl) benzene, 1,1-bis (t-butylperoxy) valerate, benzoyl peroxide, t-butylperoxybenzoate, acetyl peroxide, isobutyryl peroxide , Octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide and 2,4-dichlorobenzoyl peroxide, and m-toluyl peroxide. Examples of the azo compound include azoisobutyronitrile and dimethylazoisobutyronitrile.

Such a radical initiator is generally used in an amount of 0.005 with respect to 100 parts by weight of the ethylene polymer.
It is preferably used in an amount of 1 to 10 parts by weight. The radical initiator can be used as it is by mixing with the ethylene polymer and the polar monomer, or can be used by dissolving the radical initiator in a small amount of an organic solvent. As the organic solvent used here, any organic solvent that can dissolve the radical initiator can be used without particular limitation. Such organic solvents include aromatic hydrocarbon solvents such as benzene, toluene and xylene; aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, nonane and decane;
Alicyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane and decahydronaphthalene; chlorinated hydrocarbons such as chlorobenzene, dichlorobenzene, trichlorobenzene, methylene chloride, chloroform, carbon tetrachloride and tetrachloroethylene; methanol, Alcohol solvents such as ethanol, n-propynol, iso-propanol, n-butanol, sec-butanol and tert-butanol; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate and dimethyl phthalate. Examples thereof include ether solvents such as dimethyl ether, diethyl ether, di-n-amyl ether, tetrahydrofuran and dioxyanisole.

In the present invention, a reducing substance may be used when the ethylene polymer is graft-modified. The reducing substance has a function of improving the graft amount in the obtained graft-modified ethylene polymer.

Examples of the reducing substance include iron (II) ion, chromium ion, cobalt ion, nickel ion, palladium ion, sulfite, hydroxylamine and hydrazine, as well as —SH, SO ₃ H, —NHNH ₂ , CO
Examples include compounds containing groups such as CH (OH)-.

Specific examples of such reducing substances include ferrous chloride, potassium dichromate, cobalt chloride,
Cobalt naphthenate, palladium chloride, ethanolamine, diethanolamine, N, N-dimethylaniline, hydrazine, ethylmercaptan, benzenesulfonic acid, p-
And toluene sulfonic acid.

The reducing substance is used in an amount of usually 0.001 to 5 parts by weight, preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the ethylene polymer.
Graft modification of the ethylene-based polymer can be carried out by a conventionally known method, for example, by dissolving the ethylene-based polymer in an organic solvent and then adding a polar monomer and a radical initiator to the solution, preferably at 70 to 200 ° C. 80 to 19
At a temperature of 0 ° C., for 0.5 to 15 hours, preferably 1 to 10
It is performed by reacting for a time.

The organic solvent used for graft-modifying the ethylene polymer can be used without particular limitation as long as it is an organic solvent capable of dissolving the ethylene polymer.

As such an organic solvent, benzene,
Examples thereof include aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents such as pentane, hexane and heptane.

A graft-modified ethylene-based polymer can be produced by kneading and reacting the ethylene-based polymer and the polar monomer in the absence of solvent using an extruder or the like. The reaction temperature is usually equal to or higher than the melting point of the ethylene polymer,
Specifically, it is in the range of 120 to 250 ° C. The reaction time under such temperature conditions is usually 0.5 to 10 minutes.

The graft amount of the graft group derived from the polar monomer in the graft-modified ethylene polymer thus prepared is usually 0.1 to 50% by weight, preferably 0.2 to 30% by weight. Is within the range of.

The graft-modified ethylene-based polymer of the present invention contains a weather resistance stabilizer within a range not impairing the object of the present invention.
Additives such as heat stabilizers, antistatic agents, anti-slip agents, anti-blocking agents, anti-fogging agents, lubricants, pigments, dyes, nucleating agents, plasticizers, anti-aging agents, hydrochloric acid absorbents, and antioxidants are required. It may be blended accordingly. In addition, a small amount of another polymer compound can be blended without departing from the spirit of the present invention.

[0086]

The graft-modified ethylene-based polymer of the present invention has excellent adhesiveness to metals or polar resins.

Next, the measuring methods of the physical properties used in the present invention are shown.
You. (1) Composition of polymer¹³ Determined by C-NMR. That is, 10 mmφ
Approximately 200 mg of polymer sample in a sample tube and 1 ml of hexa
Of the sample uniformly dissolved in chlorobutadiene¹³C-NM
The R spectrum is measured at a measurement temperature of 120 ° C. and a measurement frequency of 25.
05MHz, spectrum width 1500Hz, pulse repetition
Measured under the measuring conditions of time 4.2sec. And pulse width 6μsec.
To be determined. (2) Density Melt flow rate at 190 ° C under 2.16 kg load
Heat the strands obtained during measurement at 120 ° C for 1 hour.
Treated and gradually cooled to room temperature over 1 hour, then density gradient
Measure with a tube. (3) Melt flow rate (MFR) 190 ° C, 2.1 according to ASTM D1238-65T.
It is measured under the condition of 6 kg load. (4) Melt tension (MT) Measure the stress when the molten polymer is stretched at a constant speed.
It is determined by setting. That is, Toyo Seiki
Manufactured by MT measuring machine, resin temperature 190 ℃, extrusion
Speed 15 mm / min, winding speed 10-20 m / min, nose
Diameter 2.09mmφ, nozzle length 8mm
You. (5) Fluidity index (FI) The fluidity index has a shear stress at 190 ° C of 2.
4 × 10⁶dyne / cm ^TwoDefined by the shear rate when reaching
Is done. The flow index is a tree that changes the shear rate.
Extrude the oil from the capillary and measure the stress at that time.
Determined by That is, the same test as MT measurement
Toyo Seiki Seisakusho Co., Ltd.
Used, resin temperature 190 ℃, shear stress range 5 × 10^Four
~ 3 x 10⁶dyne / cm^TwoMeasured in degrees.

The diameter of the nozzle (capillary) is changed as follows according to the MFR (g / 10 minutes) of the resin to be measured. 0.5 mm when MFR> 20 1.0 mm when 20 ≧ MFR> 3 2.0 mm when 3 ≧ MFR> 0.8 3.0 mm when 0.8 ≧ MFR (6) n-decane soluble component amount Rate (W) About 3 g of polymer was added to 450 ml of n-decane, dissolved at 145 ° C., cooled to 23 ° C., the insoluble part in n-decane was removed by filtration, and the soluble part in n-decane was recovered from the filtrate. To do.

W = n-decane soluble part weight / (n-decane insoluble part and soluble part weight) × 100% The smaller the amount of soluble components, the narrower the composition distribution. (7) Maximum peak temperature (Tm) by DSC The measurement was performed using a DSC-7 type device manufactured by Perkin Elmer. Temperature (Tm) at the maximum peak position on the endothermic curve
Packs about 5 mg of sample in an aluminum pan at 20 ° C / min.
After raising the temperature to 0 ° C and holding at 200 ° C for 5 minutes, 20
It is determined from the endothermic curve when the temperature is lowered to room temperature at ° C / min and then the temperature is raised at 10 ° C / min. (8) Molecular weight distribution (Mw / Mn) Mw / Mn is measured as follows using GPC-150C manufactured by Millipore.

The separation column was TSK GNH HT, the column size was 72 mm in diameter and 600 mm in length, the column temperature was 140 ° C., the mobile phase was o-dichlorobenzene (Wako Pure Chemical Industries) and an antioxidant. As BH
T (Takeda Pharmaceutical) 0.025% by weight, 1.0 ml /
The sample concentration is set to 0.1% by weight, the sample injection amount is set to 500 microliters, and a differential refractometer is used as a detector. Standard polystyrene has a molecular weight of Mw <1
For 000 and Mw> 4 × 10 ⁶ , use a product of Tosoh Corporation, and for 1000 <Mw <4 × 10 ⁶ , use a product of Pressure Chemical Company. (9) Crystallinity The crystallinity is determined by X-ray diffraction measurement of a 1.0 mm thick pressed sheet that has been at least 24 hours after molding.

[0091]

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.

[0092]

[Production Example 1] [Preparation of catalyst] Silica dried at 250 ° C for 10 hours 6.
After suspending 3 kg with 100 liters of toluene,
Cooled to 0 ° C. Then, a toluene solution of methylaluminoxane (Al = 0.96 mol / liter) 41
One liter was added dropwise over one hour. At this time, the temperature in the system is set to 0
C. Subsequently, the mixture was reacted at 0 ° C for 60 minutes, then heated to 95 ° C over 1.5 hours, and reacted at that temperature for 4 hours. Then, the temperature was lowered to 60 ° C., and the supernatant was removed by the decantation method. The solid component thus obtained was washed twice with toluene and then resuspended in 125 liters of toluene. To this system, 15 liters of a toluene solution of bis (n-butylcyclopentadienyl) zirconium dichloride (Zr = 42.7 mmol / liter) was appropriately added at 30 ° C. for 30 minutes, and further reacted at 30 ° C. for 2 hours. It was After that, the supernatant is removed and hexane is added to
By washing twice, a solid catalyst containing 6.2 mg of zirconium per gram was obtained.

[Preparation of prepolymerized catalyst] To 300 liters of hexane containing 14 mol of triisobutylaluminum, 8.5 kg of the solid catalyst obtained above was added,
By preliminarily polymerizing ethylene at 35 ° C for 7 hours,
A prepolymerized catalyst in which 3 g of polyethylene was prepolymerized per 1 g of the solid catalyst was obtained.

[Polymerization] Copolymerization of ethylene and 1-hexene was carried out using a continuous fluidized bed gas phase polymerization apparatus at a total pressure of 18 kg / cm ² -G and a polymerization temperature of 80 ° C. 0.15 mmol of the prepolymerized catalyst prepared above in terms of zirconium atom
/ H, triisobutylaluminum 10 mmol / h
And ethylene, 1-hexene, hydrogen and nitrogen were continuously supplied to maintain a constant gas composition during the polymerization (gas composition; 1-hexene / ethylene = 0.
020, hydrogen / ethylene = 6.6 × 10 ⁻⁴ , ethylene concentration = 16%). The yield of the obtained ethylene / 1-hexene copolymer was 5.0 kg / hr. This ethylene
Table 1 shows the physical properties of the 1-hexene copolymer.

[0095]

[Production Example 2] In Production Example 1, the bis (n-butylcyclopentadienyl) zirconium dichloride was used in place of the titanium catalyst component described in JP-B-63-54289, and the methylaluminoxane was replaced with triethyl. An ethylene / 1-hexene copolymer was produced in the same manner as in Production Example 1 except that aluminum was used and the comonomer content was adjusted as shown in Table 1. Table 1 shows the physical properties of the obtained ethylene / 1-hexene copolymer.

[0096]

Example 1 Toluene was used as a reaction solvent, and 825 g of the ethylene / 1-hexene copolymer obtained in Preparation Example 1 was dissolved at 160 ° C. per 5.7 liters of toluene. Next, a toluene solution of maleic anhydride (4.13 g / 250 ml) and a toluene solution of dicumyl peroxide (DPC) (0.33 g / 50) were added to the toluene solution.
ml) was fed gradually from separate conduits over 4 hours.

After the feed yield, the reaction was further continued at 160 ° C. for 30 minutes and then cooled to room temperature to precipitate a polymer. The precipitated polymer was filtered, washed repeatedly with acetone, and dried under reduced pressure at 80 ° C. for 24 hours to obtain a target modified ethylene / 1-hexene copolymer.

The modified ethylene / 1-hexene copolymer was subjected to elemental analysis and the grafted amount of maleic anhydride was measured. As a result, the modified ethylene / 1-hexene copolymer 1 was obtained.
It was found that 2.0 g per 100 g of maleic anhydride was graft-polymerized. Table 1 shows the physical properties of the modified polymer.

A film was prepared from the obtained modified polymer as follows, and the adhesive strength to Al was measured as follows. The results are shown in Table 1. [Production of Film] A 0.1 mm thick aluminum sheet, a polyethylene terephthalate (PET) sheet and a 100 μm thick aluminum sheet obtained by cutting the center into 15 cm × 15 cm squares were laid in this order on a press plate, and the center ( A sample (modified polymer) of 3.3 g was placed on the cut portion. Then, a PET sheet, an aluminum sheet, and a press plate were further stacked in this order.

The sample sandwiched between the above-mentioned press plates was put in a hot press at 200 ° C., preheated for about 7 minutes, and then,
Pressurized (50 kg / cm ^2- to remove air bubbles in the sample
G) The depressurization operation was repeated several times. Then 100 kg /
The pressure was raised to cm ² -G, and pressure heating was performed for 2 minutes. After depressurization, the press plate was taken out of the press machine, transferred to another press machine at which the pressure-bonded part was kept at 0 ° C., pressure-cooled at 100 kg / cm ² -G for 4 minutes, and then depressurized to give a sample. I took it out. The obtained film (modified polymer film) has a uniform thickness of about 150 to
The portion having a thickness of 170 μm was used for measuring the adhesion strength to Al.

[Measurement of Adhesive Strength to Al] The modified polymer film was sandwiched between two 15 cm × 15 cm square aluminum sheets (thickness: 200 μm), and the aluminum sheet was pressed under the same pressing conditions as in the above “Production of film”. And the modified polymer film were stuck together. The obtained laminate was cut into 15 mm wide strips, and the adhesive interface between the aluminum sheet and the modified polymer film was peeled off in the 180 ° direction.
The peel strength was measured.

[0102]

Examples 2 to 4 Modified polymers were obtained in the same manner as in Example 1 except that the modifying monomer used in Example 1 was changed to those listed in Table 1. Example 1 from this modified polymer
A film was prepared in the same manner as above, and the adhesive strength to Al was measured. The results are shown in Table 1.

[0103]

Comparative Example 1 A modified polymer was obtained in the same manner as in Example 1 except that the ethylene-based polymer produced in Production Example 2 was changed to the ethylene / 1-hexene copolymer produced in Production Example 2. Table 1 shows the physical properties of the modified polymer thus obtained.

A film was prepared from this modified polymer in the same manner as in Example 1 and the adhesive strength to Al was measured. The results are shown in Table 1.

[0105]

[Table 1]

Claims (4)

[Claims] 1. A homopolymer of ethylene or a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms, wherein the structural unit derived from (i) ethylene is 50.
-100% by weight, (ii) density 0.850
In the range of up to 0.980 g / cm ³ , (iii) 190
The melt flow rate at a temperature of 2.16 kg under a temperature of 0.01 to 200 g / 10 min.
Melt tension (MT) at ℃ and melt flow rate (MFR) satisfy the relationship ^represented by MT ≦ 2.2 × MFR ^−0.84 , and (v) Mw / Mn (Mw: weight average) which is an index of molecular weight distribution. The molecular weight, Mn: number average molecular weight) is 2.5 or less, and (vi) the temperature (Tm (° C.)) and the density (d) at the maximum peak position in the endothermic curve measured by a differential scanning calorimeter are , A graft-modified ethylene-based polymer in which a polar monomer is graft-copolymerized with an ethylene-based polymer satisfying the relationship of Tm <400 × d-250. 2. The polar monomer, wherein the polar monomer is a hydroxyl group-containing ethylenically unsaturated compound, an amino group-containing ethylenically unsaturated compound, an epoxy group-containing ethylenically unsaturated compound, an aromatic vinyl compound, an unsaturated carboxylic acid and its derivative, a vinyl ester. The graft-modified ethylene-based polymer according to claim 1, which is at least one monomer selected from the group consisting of compounds and vinyl chloride. 3. The graft-modified ethylene-based polymer according to claim 1, wherein the polar monomer is at least one monomer selected from hydroxyl group-containing ethylenically unsaturated compounds, aromatic vinyl compounds, unsaturated carboxylic acids and their derivatives. Coalescing. 4. The graft-modified ethylene polymer according to claim 1, wherein the graft amount of the graft group derived from the polar monomer is in the range of 0.1 to 50% by weight.