JPH093139A - Graft modified ethylene-alpha-olefin copolymer - Google Patents

Abstract

PURPOSE: To obtain a graft modified copolymer which adheres well to a metal or a polar resin by grafting a polar monomer onto an ethylene-α-olefin copolymer having a specified melt flow rate, a degree of crystallization, etc. CONSTITUTION: This graft modified ethylene-α-olefin copolymer is produced by grafting a polar monomer (e.g. an ethylenically unsatd. compd. having a hydroxyl or amino group, etc., or a vinyl compd.) onto an ethylene-α-olefin copolymer having an ethylene content of 35-98wt.%, a density of 0.85-0.98g/cm, a relation of the melt tension(MT) at 190 deg.C with the melt flow rate(MFR) at 190 deg.C under a load of 2.16kg satisfying the relation expressed by formula I, a degree of crystallization of 30% or lower, a value of B in formula II (wherein PE and PO are molar fractions of ethylene units and α-olefin units. respectively; and PEO is the ratio of ethylene-α-olefin chains to the total dyad chains in the copolymer) of 0.9-2, and a ratio of MFR at 190 deg.C under a load of 10kg to that under a load of 2.16kg of 7-50.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel graft-modified ethylene / .alpha.-olefin copolymer, and more specifically, in adhesion with a metal or a polar resin, low temperature adhesiveness and adhesive strength retention under high temperature atmosphere. The present invention relates to a graft-modified ethylene / α-olefin copolymer having an excellent balance with

[0002]

TECHNICAL BACKGROUND OF THE INVENTION Ethylene-based polymers such as ethylene / 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.

By the way, in recent years, improvement in productivity and energy saving have been required in many manufacturing fields, and in the case of adhering a graft-modified ethylene polymer and a metal or the like, from the viewpoint of high speed molding and energy saving, a lower temperature is used. There is a need for graft-modified ethylene-based polymers that can be adhered by. However, conventionally known graft-modified ethylene-based polymers have the following properties in order to improve low-temperature adhesion.
If a material having a lower melting point is used, the adhesive force in a high temperature atmosphere may be extremely reduced. Therefore, if a graft-modified ethylene polymer that has good low-temperature adhesiveness to metals and the like and shows little decrease in adhesive strength in a high-temperature atmosphere appears, its industrial value will be extremely great.

The inventors of the present invention have conducted intensive studies in view of such conventional techniques, and as a result, the density, the crystallinity, the B value and the MFR.
_A graft-modified ethylene / α-olefin copolymer obtained by graft-copolymerizing a polar monomer onto an ethylene / α-olefin copolymer having a specific ratio of ₁₀ / MFR ₂ and a constant melt tension and melt flow rate. The present inventors have completed the present invention by finding that the polymer has an excellent balance between low-temperature adhesiveness and adhesiveness retention in a high-temperature atmosphere in adhesion to a metal or a polar resin.

[0005]

It is an object of the present invention to provide a graft-modified ethylene / α-olefin copolymer having an excellent balance between low-temperature adhesiveness and adhesiveness retention under high-temperature atmosphere in adhesion to metal or polar resin. Is intended.

[0006]

SUMMARY OF THE INVENTION Graft-modified ethylene / α according to the present invention
-The olefin copolymer has ethylene and 3 to 30 carbon atoms.
A copolymer of 20 α-olefins, wherein (i) the constitutional unit derived from ethylene is in the range of 35 to 98% by weight, and (ii) the density is 0.850 to 0.980 g / c.
in the range of m ^3, and (iii) the melt tension at 190 ℃ (MT), 190 ℃ , the relationship and a melt flow rate (MFR) of at 2.16kg load represented by MT> 1.55 × MFR ^-1.09 Satisfying, (iv) the crystallinity is 30% or less, (v) the following formula

[0007]

[Equation 2]

(Wherein P _E represents the mole fraction of ethylene units contained in the copolymer, P _o represents the mole fraction of α-olefin units contained in the copolymer, and P _Eo represents the copolymer weight). All in coalescence
The B value showing the randomness of the copolymerized monomer chain distribution, which is obtained from (the ratio of ethylene / α-olefin chain to the dyad chain) is in the range of 0.9 to 2, and (vi) 1
Melt flow rate at 90 ° C and 10 kg load (M
FR ₁₀ ) and the melt flow rate (MFR ₂ ) at 190 ° C. under a load of 2.16 kg (MFR ₁₀ / MFR
It is characterized in that a polar monomer is graft-copolymerized to an ethylene / α-olefin copolymer having ₂ ) in the range of 7 to 50.

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.

[0010]

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

Graft-modified ethylene / α-according to the present invention
The olefin copolymer has ethylene and 3 to 2 carbon atoms.
A polar monomer is graft-copolymerized to an ethylene / α-olefin copolymer, which is a random copolymer with 0-α-olefin.

In the ethylene / α-olefin copolymer used in the graft-modified ethylene / α-olefin copolymer of the present invention, the constitutional unit derived from ethylene is 3
The constituent unit derived from the α-olefin having 3 to 20 carbon atoms is present in an amount of 5 to 98% by weight, preferably 40 to 95% by weight, more preferably 45 to 93% by weight,
It is desirable to be present in an amount of 2-65 wt%, preferably 5-60 wt%, more preferably 5-55 wt%.

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.

The ethylene / α-olefin copolymer has a density of 0.850 to 0.980 g / cm ³ ,
It is preferably in the range of 0.855 to 0.940 g / cm ³ , and more preferably 0.860 to 0.910 g / cm ³ .

The ethylene / α-olefin copolymer has a melt tension [MT (g)] and a melt flow rate [MFR (g / 10 min)] at 190 ° C. of MT> 1.55 × MFR ^{− 1.09} preferably ^satisfies MT> 1.56 × MFR ^−1.09, more preferably MT> 1.57 × MFR ^−1.09 .

The ethylene / α-olefin copolymer satisfying the above-mentioned relationship between the melt tension and the melt flow rate has a higher melt tension than the conventional ethylene / α-olefin copolymer and has a good moldability. It is good.

The ethylene / α-olefin copolymer used in the present invention has a crystallinity of 30% or less, preferably 0.
˜28%, more preferably 0 to 26%. The ethylene / α-olefin copolymer used in the present invention has the following formula

[0018]

(Equation 3)

(In the formula, P _E represents the mole fraction of ethylene units contained in the copolymer, P _o represents the mole fraction of α-olefin units contained in the copolymer, and P _Eo represents the copolymer weight. All in coalescence
B value showing the randomness of the copolymerized monomer chain distribution, which is obtained from the ratio of ethylene / α-olefin chain to dyad chain) is 0.9 to 2, preferably 0.95.
It is in the range of 1.5.

This parameter B value is calculated by Coleman et al. (B.
C. Cole-man and TGFox, J. Polym. Sci., Al , 3183 (196
3)), the larger the number, the less the block-like chains, the more uniform the distribution of ethylene units and α-olefin units, and the narrower the composition distribution.

The ethylene / α-olefin copolymer used in the present invention has a melt flow rate [MFR ₁₀ (g / 10 min)] of 190 ° C. and a load of 10 kg, and 190
Melt flow rate [M at ℃, 2.16kg load]
FR ₂ (g / 10 minutes)] (MFR ₁₀ / MFR ₂ ) is in the range of 7 to 50, preferably 7 to 45.

Thus, the MFR ₁₀ / MFR ₂ is 7 to 50.
The ethylene / α-olefin copolymer having the range of 1) has extremely good fluidity. The ethylene / α-olefin copolymer as described above is, for example, a bidentate in which two groups selected from (a) a specific indenyl group and a substituted product thereof are bonded via a carbon-containing group or a silicon-containing group. A compound of Group IVB transition metal having a ligand,
In the presence of (b) an organoaluminum oxy compound, optionally a (c) carrier, and (d) an olefin polymerization catalyst formed from an organoaluminum compound, ethylene and an α-olefin having 3 to 20 carbon atoms are added. It can be produced by copolymerization so that the density of the obtained copolymer is 0.850 to 0.980 g / cm ³ .

The olefin polymerization catalyst and each catalyst component will be described below. (A) A transition metal compound of Group IVB of the periodic table having a bidentate ligand in which two groups selected from a specific indenyl group and a substituted form thereof are bonded via a lower alkylene group (hereinafter referred to as “component (It may be described as “a)” is specifically a transition metal compound represented by the following formula (I).

MKL _x-2 (I) In the above general formula (I), M represents a transition metal atom selected from Group IVB of the periodic table, specifically, zirconium, titanium or hafnium, preferably Is zirconium.

X is the valence of the transition metal atom M, and x
-2 shows the number of L. K represents a ligand coordinating to a transition metal atom, and two same or different groups selected from an indenyl group and a partial water additive thereof and a substituted indenyl group and a partial water additive thereof are lower alkylene groups. Is a bidentate ligand bound through a carbon-containing group such as or a silicon-containing group such as dialkylsilylene.

Specific examples of the substituted indenyl group include 4-phenylindenyl group, 2-methyl-4-phenylindenyl group, 2-methyl-4-naphthylindenyl group and 2-methyl-4-anthracenyl group. Indenyl group, 2-methyl-4-phenanthrylindenyl group, 2-ethyl-4-phenylindenyl group, 2
-Ethyl-4-naphthylindenyl group, 2-ethyl-4-anthracenylindenyl group, 2-ethyl-4-phenanthrylindenyl group, 2-propyl-4-phenylindenyl group, 2-
Examples thereof include a propyl-4-naphthylidenyl group, a 2-propyl-4-anthracenylindenyl group, a 2-propyl-4-phenanthrylindenyl group, and the like.

L represents 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. 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, a methyl group, an ethyl group, n-
Alkyl groups such as propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, octyl group, 2-ethylhexyl group, decyl group; cyclopentyl group, cyclohexyl group And cycloalkyl groups; aryl groups such as phenyl group and tolyl group; aralkyl groups such as benzyl group and neophyll group.

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. Halogen atom is 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 rac-dimethylsilylene-bis {1- (4
-Phenylindenyl) zirconium dichloride, rac
-Dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-Dimethylsilylene-bis {1- (2-methyl-4- (β-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-methyl-4- (1-anthracenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-methyl-4- (2-anthracenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-methyl-4- (9-anthracenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-methyl-4- (9-phenanthryl) indenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-methyl-4- (p-fluorophenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4- (pentafluorophenyl))
Indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4- (p-chlorophenyl))
Indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4- (m-chlorophenyl)
Indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4- (o-chlorophenyl)
Indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4- (o, p-dichlorophenyl) phenylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (p-bromophenyl) indenyl)} zirconium dichloride,
rac-Dimethylsilylene-bis {1- (2-methyl-4- (p-tolyl) indenyl)} zirconium dichloride, rac-Dimethylsilylene-bis {1- (2-methyl-4- (m-tolyl) indenyl) } Zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4- (o-tolyl) indenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-methyl-4- (o, o'-dimethylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4- (p-ethylphenyl) indenyl) )} Zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4- (pi-propylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4- ( p-benzylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4- (p-biphenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2- Methyl-4- (m-biphenyl)
Indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4- (p-trimethylsilylphenyl) indenyl)} zirconium dichloride, ra
c-Dimethylsilylene-bis {1- (2-methyl-4- (m-trimethylsilylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl-4-
Phenylindenyl) zirconium dichloride, rac-
Dimethylsilylene-bis {1- (2-ethyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl-4- (β-naphthyl))
Indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl-4- (1-anthracenyl))
Indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl-4- (2-anthracenyl))
Indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl-4- (9-anthracenyl))
Indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl-4- (9-phenanthryl)
Indenyl)} zirconium dichloride, rac-diphenylsilylene-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-phenyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1-
(2-n-Propyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-n-
Propyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-n-
Propyl-4- (β-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-n-
Propyl-4- (1-anthracenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1-
(2-n-Propyl-4- (2-anthracenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-n-propyl-4- (9-anthracenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-n-propyl-4- (9-phenanthryl)
Indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-i-butyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-i-butyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-i-butyl-4- (β-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-i-butyl-4- (1-anthracenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-i-butyl-4- (2-anthracenyl) indenyl) } Zirconium dichloride, rac-dimethylsilylene-bis {1- (2-i-butyl-4- (9-anthracenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-i-butyl-4) -(9-phenanthryl)
Indenyl)} zirconium dichloride, rac-diethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-di- (i-propyl) silylene-bis {1- (2-methyl- 4-phenylindenyl)} zirconium dichloride, rac-di- (n-butyl)
Silylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-dicyclohexylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-methylphenylsilylene -Bis {1- (2-methyl-4-phenylindenyl)}
Zirconium dichloride, rac-diphenylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-di (p-tolyl) silylene-bis {1
-(2-Methyl-4-phenylindenyl)} zirconium dichloride, rac-di (p-chlorophenyl) silylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-methylene-bis {1- (2-Methyl-4-phenylindenyl)} zirconium dichloride, rac-ethylene-bis {1- (2-methyl-4-phenylindenyl)}
Zirconium dichloride, rac-dimethylgermylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-
Methyl-4-phenylindenyl)} zirconium dibromide, rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dimethyl, rac-dimethylsilylene-bis {1- (2-methyl -4-Phenylindenyl)} zirconium methyl chloride, rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium chloride SO ₂ Me, rac-dimethylsilylene-
Bis {1- (2-methyl-4-phenylindenyl)} zirconium chloride OSO ₂ Me, rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} titanium dichloride, rac-dimethylsilylene -Bis {1- (2-methyl-4-phenylindenyl)} hafnium dichloride and the like. 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.

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 in which water, ice or water vapor is allowed to directly act 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 organic metal 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 above-mentioned component (a) and / or component (b) may be supported on the following carrier (c) for use. The carrier (c) is an inorganic or organic compound and has a particle size of 10 to 300 μm, preferably 20 to 200.
Granules or fine particles of solid having a size of μm are used. Of these, porous oxides are preferred as the inorganic carrier, and specifically, SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , Ti.
_{O 2, B 2 O 3,} CaO, ZnO, BaO, ThO 2 and the like or mixtures thereof, for example, SiO ₂ -MgO, SiO ₂ -A
l ₂ O ₃ , SiO ₂ -TiO ₂ , SiO ₂ -V ₂ O ₅ , SiO _2-
Examples thereof include Cr ₂ O ₃ and SiO ₂ —TiO ₂ —MgO. 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 above 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 for producing the ethylene / α-olefin copolymer may further contain (d) an organoaluminum compound in addition to the above-mentioned components.

Examples of the (d) organoaluminum compound (hereinafter sometimes referred to as “component (d)”) which is used as necessary include, for example, the organoaluminum compounds represented by the following general formula (II). can do.

[0045] 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.

Further, as an 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.

(1) A compound represented by R ^a _n Al (OR ^b ) _3-n , such as dimethyl aluminum methoxide, diethyl aluminum ethoxide, diisobutyl aluminum methoxide, etc. (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 the ethylene / α-olefin copolymer is produced, the above-mentioned components (a) and (b), and if necessary, a carrier (c) and a component (d) are brought into contact with each other. The catalyst prepared by

The catalyst used for producing the ethylene / α-olefin copolymer is prepared in the presence of the above-mentioned component (a), component (b), carrier (c) and, if necessary, component (d). It may be a prepolymerization catalyst obtained by prepolymerizing an olefin. 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 / α-olefin copolymer used in the present invention is an ethylene-α-olefin copolymer having 3 to 20 carbon atoms, for example, in the presence of the above-mentioned olefin polymerization catalyst or prepolymerization catalyst. Propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1
-Octene, 1-decene, 1-dodecene, 1-tetradecene, 1
-It is obtained by copolymerizing with hexadecene, 1-octadecene and 1-eicosene.

The copolymerization of ethylene and α-olefin is
It is carried out in the liquid phase in the form of solution or slurry, or in the gas phase. In solution polymerization or slurry polymerization, an inert hydrocarbon may be used as the solvent, or the olefin itself may be used as the solvent.

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

During the polymerization, the olefin weight as described above is used.
The combined catalyst, as the concentration of transition metal atoms in the polymerization reaction system,
Usually 10^-8-10^-3Gram atoms / liter, preferably
10 ^-7-10^-FourUsed in quantities of gram atoms / liter
It is desirable.

When carrying out the solution polymerization or 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 is carried out. The temperature is usually 0 to 120 ° C., preferably 20 to
It is in the range of 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 / α-olefin copolymer of the present invention is obtained by reacting the above ethylene / α-olefin copolymer with a polar monomer as described below in the presence of a radical initiator. You can

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.

Specifically, as the hydroxyl group-containing ethylenically unsaturated compound, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 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.

[0062]

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.

[0067]

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 an aromatic vinyl compound 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 above polar monomer is the above-mentioned ethylene / α-
Usually, 1 is used with respect to 100 parts by weight of the olefin copolymer.
It is used in an amount of ˜100 parts by weight, preferably 5-80 parts by weight.

Examples of the radical initiator include organic peroxides and azo compounds. Specific examples of organic peroxides include dicumyl peroxide,
Di-t-butyl peroxide, 2,5-dimethyl-2,5-bis (t
-Butylperoxy) hexane, 2,5-dimethyl-2,5-bis
(t-butylperoxy) hexyne-3,1,3-bis (t-butylperoxyisopropyl) benzene, 1,1-bis (t-butylperoxy) bararate, benzoyl peroxide, t
-Butylperoxybenzoate, acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide and 2,4-dichlorobenzoyl peroxide,
m-toluyl peroxide and the like.
Examples of the azo compound include azoisobutyronitrile and dimethylazoisobutyronitrile.

It is desirable that such a radical initiator is generally used in an amount of 0.001 to 10 parts by weight based on 100 parts by weight of the ethylene / α-olefin copolymer.

The radical initiator is ethylene.α as it is.
-Although it can be used as a mixture with an olefin copolymer and a polar monomer, this radical initiator can also be used by dissolving it 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; cyclohexane, methylcyclohexane and decahydronaphthalene. Alicyclic hydrocarbon solvents such as; chlorinated hydrocarbons such as chlorobenzene, dichlorobenzene, trichlorobenzene, methylene chloride, chloroform, carbon tetrachloride and tetrachloroethylene; methanol, ethanol, n-propynol, iso-propanol , N-butanol, sec-butanol and tert-butanol alcohol solvents; acetone, methyl ethyl ketone and methyl isobutyl ketone ketone solvents; ethyl acetate and dimethyl phthalate ester solvents; Chirueteru, diethyl ether, di -n- amyl ether, and ether solvents such as tetrahydrofuran and dioxy anisole.

In the present invention, a reducing substance may be used when graft-modifying the ethylene / α-olefin copolymer. The reducing substance has a function of improving the graft amount in the obtained graft-modified ethylene / α-olefin copolymer.

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 above-mentioned reducing substance is the above-mentioned ethylene / α
-Typically, based on 100 parts by weight of the olefin copolymer,
It is used in an amount of 0.001-5 parts by weight, preferably 0.1-3 parts by weight.

Graft modification of the ethylene / α-olefin copolymer can be carried out by a conventionally known method, for example, by dissolving the ethylene / α-olefin copolymer in an organic solvent, and then polar monomer and radical initiator. To the solution, 70-200 ° C, preferably 80-190 ° C
At a temperature of 0.5 to 15 hours, preferably 1 to 10 hours.

The organic solvent used in the graft modification of the ethylene / α-olefin copolymer is ethylene / α
Any organic solvent capable of dissolving the olefin copolymer can be used without particular limitation.

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.

Further, using an extruder or the like, ethylene
a-olefin copolymer and polar monomer without solvent,
A graft-modified ethylene / α-olefin copolymer can be produced by kneading and reacting. The reaction temperature is usually at least the melting point of the ethylene / α-olefin copolymer, specifically 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 / α-olefin copolymer thus prepared is usually 0.1 to 50% by weight, preferably 0.2. Is in the range of up to 30% by weight.

The graft-modified ethylene / α-olefin copolymer of the present invention contains a weather resistance stabilizer, a heat resistance stabilizer, an antistatic agent, an antislip agent, an antiblocking agent, as long as the object of the present invention is not impaired. Antifogging agent, lubricant, pigment,
Additives such as dyes, nucleating agents, plasticizers, anti-aging agents, hydrochloric acid absorbents, and antioxidants may be added as necessary.
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 / α-olefin copolymer of the present invention has an excellent balance between low-temperature adhesiveness and adhesiveness retention in a high-temperature atmosphere when adhering to a metal or polar resin.

Next, the measuring method of the physical properties used in the present invention will be shown. (1) Composition of copolymer Determined by ¹³ C-NMR. That is, ¹³ C-NMR of a sample in which about 200 mg of the copolymer was uniformly dissolved in 1 ml of hexachlorobutadiene in a 10 mmφ sample tube.
Measure the spectrum at a measurement temperature of 120 ° C and a measurement frequency of 25.0.
It is determined by measurement under the measurement conditions of 5 MHz, spectrum width 1500 Hz, pulse repetition time 4.2 sec., And pulse width 6 μsec. (2) Density The strand obtained at the time of melt flow rate (MFR) measurement at 190 ° C. under a load of 2.16 kg is 120 ° C.
For 1 hour, and slowly cooled to room temperature over 1 hour, followed by measurement with a density gradient tube. (4) Melt flow rate (MFR) 190 ° C, 2.1 according to ASTM D1238-65T.
It is measured under the condition of 6 kg load or 10 kg load. (5) Melt tension (MT) It is determined by measuring the stress when the molten polymer is stretched at a constant rate. That is, using an MT measuring machine manufactured by Toyo Seiki Seisakusho, a resin temperature of 190 ° C., an extrusion speed of 15 mm / min, a winding speed of 10 to 20 m / min, a nozzle diameter of 2.09 mmφ, and a nozzle length of 8 mm are used. (6) Crystallinity The crystallinity is determined by X-ray diffraction measurement of a 1.0 mm-thick press sheet that has been at least 24 hours after molding. (7) B value of about 200 mg of the copolymer in a test tube of 10 mmφ 1 m
of a sample uniformly dissolved in 1 liter of hexachlorobutadiene
^{The 13} C-NMR spectrum is usually measured at a measurement temperature of 120
° C, measurement frequency 25.05 MHz, spectrum width 150
It is calculated by obtaining P _E , P _o and P _Eo under the conditions of 0 Hz, filter width 1500 Hz, pulse repetition time 4.2 μsec. And number of integration times 2000 to 5000.

[0088]

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

[0089]

Production Example 1 Using a continuous reactor having an internal volume of 200 liters, a residence time of 1 hour, a polymerization temperature of 80 ° C. and a polymerization pressure of 5.
Copolymerization of ethylene and 1-octene was carried out under the condition of 6 kg / cm ² -G. At this time, hexane, 1-octene,
The supply rates of ethylene and hydrogen are 95.5 liters / hour, 4.5 liters / hour, and 3.4 liters / hour, respectively.
The time was 10 N liter / hour. Polymer is 5.
Obtained at a rate of 0 kg / hr. Obtained ethylene 1-
Table 1 shows the physical properties of the octene copolymer.

As the catalyst, rac-dimethylsilylenebis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride [catalyst component (A)], methylaluminoxane [catalyst component (B)] and triisobutylaluminum are used. [Catalyst component (D)] was used. The catalyst component (A) and the catalyst component (B) are preliminarily contacted with each other in advance, the catalyst component (A) is 0.024 mmol / hour as zirconium, and the catalyst component (B) is 7.2 mmol / hour as aluminum. Time, catalyst component (D) is 1 as aluminum
It was fed to the polymerization system at a rate of 0 mmol / hour.

[0091]

Example 1 Toluene was used as a reaction solvent, and 825 g of the ethylene / 1-octene 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 gradually fed through 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 a whole day and night to obtain a target modified ethylene / 1-octene copolymer.

The modified ethylene / 1-octene copolymer was subjected to elemental analysis and the grafted amount of maleic anhydride was measured. As a result, the modified ethylene / 1-octene 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 heat-sealing start temperature and 40
The peel strength at ° C was measured as follows. The results are shown in Table 1.

[Production of Film] A film having a thickness of 0.
A 1 mm 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, and 3.3 g of a sample (modified) was placed in the center (cut portion). Copolymer). 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 copolymer film) has a uniform thickness of about 150.
The portion having a thickness of 170 μm is used for measuring the heat sealing start temperature and the 40 ° C. peel strength.

[Measurement of heat-sealing start temperature] The modified copolymer film was cut into 25 mm wide strips, and the strips were cut into 2
It was heat-sealed by sandwiching it between two pieces of aluminum foil having a thickness of 5 mm and a thickness of 50 μm. The heat sealing was performed by keeping the lower temperature of the heat sealer constant at 70 ° C. and changing only the temperature of the upper portion of the hot plate in steps of 5 ° C. The pressure during heat sealing was 1 kg / cm ² , and the heat sealing time was 1 second. The obtained laminate was cut into 15 mm wide strips and left overnight in a thermostatic chamber at 25 ° C., after which the heat seal strength was measured.

The heat-sealing strength was determined by carrying out a tensile test of 200 mm / min for the peeling strength of the modified copolymer film heat-sealed at each of the above heat-sealing temperatures.

The peel strength at each heat-sealing temperature in steps of 5 ° C. was determined by the method described above, and a plot of heat-sealing temperature vs. peel strength was connected by a curve. 500g / based on this curve
The heat-sealing temperature at which the peel strength was 15 mm was obtained and used as the heat-sealing start temperature.

[Measurement of Peel Strength at 40 ° C.] The modified polymer film was sandwiched between two 15 cm × 15 cm square aluminum sheets (thickness: 200 μm), and the aluminum sheets were pressed under the same pressing conditions as in the above-mentioned “Production of film”. And the modified polymer film were stuck together. The obtained laminate was cut into 15 mm wide strips, attached to a chamber installed in a thermostat kept at 40 ° C., and allowed to stand for 10 minutes, after which the adhesive interface between the aluminum sheet and the modified polymer film was oriented at 180 °. Then, the peel strength was measured.

[0101]

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 heat-sealing start temperature and 40 ° C. peel strength were measured. The results are shown in Table 1.

[0102]

Comparative Example 1 Example 1 was repeated except that the ethylene / α-olefin copolymer was replaced with an ethylene / 1-butene copolymer polymerized with a conventionally known vanadium catalyst.
A modified polymer was obtained in the same manner as in. Table 1 shows the physical properties of the ethylene / 1-butene copolymer and the modified polymer.

A film was prepared from this modified polymer in the same manner as in Example 1, and the heat-sealing start temperature and 40
C peel strength was measured. The results are shown in Table 1.

[0104]

[Table 1]

Claims (4)

[Claims] 1. Ethylene and α-containing 3 to 20 carbon atoms
A copolymer with an olefin, wherein (i) the structural unit derived from ethylene is in the range of 35 to 98% by weight,
(Ii) The density is in the range of 0.850 to 0.980 g / cm ³ , and (iii) the melt tension (MT) at 190 ° C.
And the melt flow rate (MFR) at 190 ° C. under a load of 2.16 kg satisfy the relationship ^represented by MT> 1.55 × MFR ^−1.09 , (iv) the crystallinity is 30% or less, and (v) The following formula [Formula 1] (In the formula, P _E represents the mole fraction of ethylene units contained in the copolymer, P _o represents the mole fraction of α-olefin units contained in the copolymer, and P _Eo represents the mole fraction of α-olefin units contained in the copolymer. The B value, which indicates the randomness of the copolymerized monomer chain distribution obtained from the ratio of ethylene / α-olefin chains to the total dyad chains) is in the range of 0.9 to 2, and (vi) 190 ° C., 10
melt flow rate (MFR ₁₀ ) under kg load,
The ratio (MFR ₁₀ / MFR ₂ ) to the melt flow rate (MFR ₂ ) at 190 ° C. and a load of 2.16 kg is 7 to 5.
A graft-modified ethylene / α-olefin copolymer, which is obtained by graft-polymerizing a polar monomer to an ethylene / α-olefin copolymerization in the range of 0. 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 / α-olefin copolymer according to claim 1, which is at least one monomer selected from compounds and vinyl chloride. 3. The graft-modified ethylene / α according to claim 1, wherein the polar monomer is at least one monomer selected from a hydroxyl group-containing ethylenically unsaturated compound, an aromatic vinyl compound, an unsaturated carboxylic acid and a derivative thereof.
-Olefin copolymers. 4. The graft-modified ethylene.α 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.
-Olefin copolymers.