JPH0987603A - Adhesive ethylenic copolymer resin composition and laminate using the composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition excellent in heat stability and formability, capable of forming a film layer having excellent transparency and adhesivity to metal and a highly polar material, and useful for a laminate, etc., by compounding a specific (modified) olefinic copolymer and an olefinic elastomer. SOLUTION: This resin composition is obtained by blending (A) 50-95wt.% of a modified copolymer (A2 ) obtained by grafting an unsaturated carboxylic acid (derivative) to an ethylene-α-olefin copolymer (A1 ) or a mixture of the components A1 and A2 and (B) 5-50wt.% of an olefinic elastomer. The copolymer A1 is obtained in the presence of a catalyst composed of a compound of a transition metal of the group IV of the Periodic Table containing a ligand having a pentadienyl skeleton and an organic aluminum oxy-compound, and has a density (d) of 0.900-0.965g/cm<3> and a melt flow rate(MFR) of 0.01-200g/10min at 190 deg.C and at load of 2.16kg. The olefinic elastomer B has a density of 0.850-0.895g/cm<3> , MFR of 0.01-200 g/10min and a degree of crystallization determined by X-ray diffraction method of <30%.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an adhesive ethylene-based copolymer resin composition and a laminate using the composition,
More specifically, an adhesive ethylene copolymer resin composition that exhibits good adhesiveness to polar materials such as ethylene / vinyl alcohol copolymers, polyamides, polyesters, or metals, and a laminate using the composition. Regarding the body

[0002]

TECHNICAL BACKGROUND OF THE INVENTION Ethylene copolymers are molded by various molding methods and used for various purposes.
The ethylene copolymer has different required properties depending on the molding method and the application. For example, when trying to mold blown film at high speed, the fluctuation of bubbles,
Alternatively, in order to carry out high-speed molding without breakage and stably, it is necessary to select a copolymer having a large melt tension relative to the molecular weight as the ethylene-based copolymer. Similar properties are needed to prevent sagging or tearing in blow molding, or to minimize dropout in T die molding. In addition, in such extrusion molding, it is necessary that the stress of the ethylene-based copolymer under extrusion under high shear is small in view of economic aspects such as improvement of quality of the molded article and reduction of power consumption during molding.

By the way, a method for improving the moldability by improving the melt tension and expansion ratio (die swell ratio) of an ethylene polymer obtained by using a Ziegler type catalyst, particularly a titanium-based catalyst, is disclosed in JP-A-56-90810. Japanese Patent Laid-Open No. 60-106806 and the like. However, in general, an ethylene-based polymer obtained by using a titanium-based catalyst, particularly a low-density ethylene-based copolymer, has a wide composition distribution and has a problem that a molded product such as a film is sticky.

Among ethylene polymers produced by using Ziegler type catalysts, ethylene polymers obtained by using chromium catalysts are relatively excellent in melt tension but poor in thermal stability. There are disadvantages. It is considered that this is because the chain end of the ethylene polymer produced using the chromium catalyst is likely to be an unsaturated bond.

Among the Ziegler-type catalyst systems, it is known that the ethylene-based polymer obtained by using a metallocene-based catalyst has a narrow composition distribution and a molded product such as a film has little stickiness. However, for example, JP-A-60-35007 describes that an ethylene-based polymer obtained by using a zirconocene compound composed of a cyclopentadiene derivative as a catalyst contains one terminal unsaturated bond per molecule, Like the ethylene polymer obtained by using the chromium catalyst, the thermal stability is expected to be poor. In addition, this ethylene-based polymer,
Since the molecular weight distribution is narrow, there is concern that the fluidity during extrusion molding may be poor.

Therefore, if an ethylene polymer having excellent melt tension, small stress in the high shear region, good thermal stability, excellent mechanical strength, and narrow composition distribution appears, its industrial use will be improved. The value is extremely large.

As a result of intensive studies in view of such circumstances, the present inventors have found that (a) a transition metal compound of Group IV of the periodic table containing a ligand having a specific cyclopentadienyl skeleton, b) In the presence of an olefin polymerization catalyst containing an organoaluminum oxy compound, ethylene and 3 carbon atoms are present.
It has been found that the linear ethylene / α-olefin copolymer obtained by copolymerizing the α-olefin with about 20 to 20 is excellent in thermal stability and has a narrow composition distribution.

As a result of further research, a modified ethylene / α-olefin copolymer obtained by grafting an unsaturated carboxylic acid or a derivative thereof onto the ethylene / α-olefin copolymer (the above-mentioned unmodified ethylene / α -A modified ethylene-based copolymer resin composition comprising a blend of an olefin copolymer) and a specific olefin-based elastomer is a polar material such as nylon or ethylene-vinyl alcohol copolymer or a metal. The inventors have found that it is extremely effective in improving the adhesiveness with and have completed the present invention.

[0009]

SUMMARY OF THE INVENTION The present invention is intended to solve the problems associated with the prior art as described above, and has good thermal stability, excellent moldability, excellent transparency, and metal or polar properties. Adhesive ethylene-based copolymer resin composition capable of preparing a film layer having excellent adhesion to high-quality materials,
And to provide a laminate using the composition.

[0010]

SUMMARY OF THE INVENTION An adhesive ethylene-based copolymer resin composition according to the present invention comprises a transition metal compound (a) of Group IV of the periodic table containing a ligand having [I] cyclopentadienyl skeleton. A linear ethylene / α-olefin copolymer [A1] prepared using an olefin polymerization catalyst containing an organoaluminum oxy compound (b) and composed of ethylene and an α-olefin having 3 to 20 carbon atoms. ] To 50 to 95% by weight of a modified ethylene / α-olefin copolymer [A2] grafted with an unsaturated carboxylic acid or a derivative thereof, or an unmodified ethylene / α-olefin copolymer [A1] and modified ethylene. .Alpha.-Olefin copolymer [A2] 50 to 95
% By weight, and [II] olefin elastomer [B] 5 to 50% by weight
The ethylene / α-olefin copolymer [A1] has a (i) density (d) of 0.900 to
In the range of 0.965 g / cm ³ , (ii) 190 ° C,
2. Melt flow rate at 16 kg load (MF
R) is in the range of 0.01 to 200 g / 10 minutes, and the olefin elastomer [B] has (i) a density (d) in the range of 0.850 to 0.895 g / cm ³ . (Ii) The melt flow rate (MFR) at 190 ° C. and a load of 2.16 kg is 0.01 to 200 g / 10.
In the range of minutes, (iii) the crystallinity measured by X-ray diffractometry is less than 30%.

A blend of the modified ethylene / α-olefin copolymer [A2] and the olefin elastomer [B], or an unmodified ethylene / α-olefin copolymer [A1] and a modified ethylene / α-olefin. The blended product of the copolymer [A2] and the olefin elastomer [B] has (i) density (d) of 0.870 to 0.960 g.
/ Cm ³ range, (ii) 190 ℃, 2.16kg
Melt flow rate (MFR) under load is 0.0
1 to 100 g / 10 minutes, (iii) the graft amount of a graft group derived from an unsaturated carboxylic acid or its derivative is 0.01 to 5% by weight, and (iv)
The crystallinity measured by the X-ray diffraction method is preferably 15% or more.

The unmodified ethylene / α-olefin copolymer [A1] has (i) a density (d) of 0.90.
It is in the range of 0 to 0.965 g / cm ³ , and (ii) 190
Melt flow rate (M
FR) is in the range of 0.01 to 200 g / 10 minutes,
(Iii) The temperature (Tm (° C.)) at the maximum peak position of the endothermic curve measured by a differential scanning calorimeter (DSC) and the density (d) satisfy the relationship represented by Tm <400 × d-250, (Iv) Melt tension (MT (g)) at 190 ° C. and melt flow rate (M
FR) satisfies the relationship ^represented by MT ≦ 2.2 × MFR ^−0.84 , and (v) the decane-soluble part (W (wt%)) and the density (d) at 23 ° C. are MFR ≦ 1.
When 0 g / 10 minutes, W <80 × exp (−100 (d−0.88)) + 0.1 MFR> 10 g / 10 minutes, W <80 × (MFR-9) ^0.26 × exp (−100 (d-
It is preferably a linear ethylene / α-olefin copolymer satisfying the relationship of 0.88)) + 0.1.

Further, an olefin elastomer [B]
As for the content of the structural unit derived from ethylene is 7
Ethylene / α-olefin copolymers in the range of 5 to 95 mol% are preferred.

The laminate according to the present invention comprises a layer comprising the above adhesive ethylene copolymer resin composition according to the present invention,
It is characterized in that it is composed of a layer made of a polar material or a layer made of a metal.

The polar material is preferably an ethylene / vinyl alcohol copolymer, polyamide or polyester. Such an adhesive ethylene-based copolymer resin composition is excellent in moldability and has strong adhesiveness to nylon, ethylene-vinyl copolymer, polyester or metal.

[0016]

DETAILED DESCRIPTION OF THE INVENTION The adhesive ethylene copolymer resin composition according to the present invention and the laminate using the composition will be specifically described below.

The adhesive ethylene-based copolymer resin composition according to the present invention is a linear ethylene / α-olefin copolymer [A prepared by using a specific olefin polymerization catalyst.
[1]] modified ethylene / α-olefin copolymer [A2] in which an unsaturated carboxylic acid or a derivative thereof is grafted
And a olefin elastomer [B] in a specific ratio, or an unmodified ethylene / α-olefin copolymer [A1] and a modified ethylene / α-olefin copolymer [A2] and an olefin elastomer [ B] in a specific ratio.

Unmodified linear ethylene / α-olefin
Copolymer [A1] The unmodified linear ethylene / α-olefin copolymer [A1] used in the present invention comprises ethylene and 3 to 10 carbon atoms.
It is a random copolymer with 20 α-olefins.

Specific examples of the α-olefin having 3 to 20 carbon atoms used for copolymerization with ethylene include propylene, 1-butene, 1-pentene, 1-hexene and 4-methyl-1-pentene. , 1-octene, 1-decene, 1-dodecene,
1-tetradecene, 1-hexadecene, 1-octadecene, 1-
Eikosen etc. are mentioned.

Ethylene / α-olefin copolymer [A
1] has an ethylene content of 55 to 99% by weight, preferably 65 to 98% by weight, more preferably 70 to 96% by weight.
It is desirable that the content of the α-olefin having 3 to 20 carbon atoms is 1 to 45% by weight, preferably 2 to 35% by weight, more preferably 4 to 30% by weight.

The composition of the ethylene / α-olefin copolymer is usually determined by measuring the ¹³ C-NMR spectrum of a sample prepared by uniformly dissolving about 200 mg of the copolymer in 1 ml of hexachlorobutadiene in a 10 mmφ sample tube at the measurement temperature. 120
° C, measurement frequency 25.05 MHz, spectrum width 150
0Hz, pulse repetition time 4.2sec., Pulse width 6μse
It is determined by measuring under the measurement conditions of c.

Such an ethylene / α-olefin copolymer has the following characteristics (i) to (ii). (I) Density (d) is 0.900 to 0.965 g / cm
³ , preferably 0.905 to 0.935 g / cm ³ , and more preferably 0.905 to 0.930 g / cm ³ .

Regarding the density (d), the strand obtained at the time of measuring the melt flow rate (MFR) at 190 ° C. under a load of 2.16 kg was heat-treated at 120 ° C. for 1 hour and then gradually cooled to room temperature over 1 hour. , Measured with a density gradient tube. (Ii) Melt flow rate (MFR) is 0.01 to 2
It is in the range of 00 g / 10 minutes, but preferably 0.05 to
50 g / 10 minutes, more preferably 0.1-10 g / 10
Desirably within the range of minutes.

The melt flow rate (MFR) is
It was measured according to ASTM D1238-65T under the conditions of 190 ° C. and 2.16 kg load. The unmodified ethylene / α-olefin copolymer [A1] used in the present invention has a density and a melt flow rate in the above ranges and further has the following characteristics (iii) to (v): A linear ethylene / α-olefin copolymer having is preferable. (Iii) The temperature (Tm (° C.)) and the density (d) at the maximum peak position of the endothermic curve measured by a differential scanning calorimeter (DSC) are Tm <400 × d-250, preferably Tm <450 × d. -297 more preferably, Tm <500 × d-344, particularly preferably Tm <550 × d-391.

The temperature (Tm at the maximum peak position of the endothermic curve measured by a differential scanning calorimeter (DSC))
(° C) is 10 ° C /
The temperature is raised to 200 ° C. at a rate of minutes, held at 200 ° C. for 5 minutes, then lowered to room temperature at a rate of 20 ° C./minute, and then 1
It is obtained from the endothermic curve when the temperature is raised at a rate of 0 ° C / min. A DSC-7 type device manufactured by Perkin Elmer was used for the measurement. (Iv) It is preferable that the melt tension (MT (g)) and the melt flow rate (MFR) satisfy the relationship ^represented by MT ≦ 2.2 × MFR ^−0.84 .

Melt tension (MT (g))
Is determined by measuring the stress when the molten polymer is stretched at a constant rate. That is, the produced polymer powder is melted by a usual method and then pelletized to obtain a measurement sample. Using an MT measuring device manufactured by Toyo Seiki Seisakusho, a resin temperature of 190 ° C., an extrusion speed of 15 mm / min, and a winding speed of 10 to 10. 20m / min, nozzle diameter 2.09mmφ,
The nozzle length was 8 mm. When pelletizing,
The ethylene / α-olefin copolymer [A1] was previously mixed with tri (2,4-di-t-butylphenyl) as a secondary antioxidant.
0.05% by weight of phosphate as a heat stabilizer
0.1% by weight of n-octadecyl-3- (4'-hydroxy-3 ', 5'-di-t-butylphenyl) propionate and 0.05% by weight of calcium stearate as a hydrochloric acid absorbent were added. (V) The n-decane-soluble component amount fraction (W (% by weight)) and the density (d) at 23 ° C. (room temperature) are MFR ≦ 10 g /
At 10 minutes, 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 When MFR> 10 g / 10 minutes, W <80 × (MFR-9) ^0.26 × exp (−100 (d−
It is preferable that the relationship represented by 0.88)) + 0.1 is satisfied.

The amount of the soluble component of n-decane (the smaller the soluble component, the narrower the composition distribution) is about 3% of the copolymer.
g was added to 450 ml of n-decane, dissolved at 145 ° C., cooled to room temperature, the n-decane-insoluble portion was removed by filtration, and the n-decane-soluble portion was recovered from the filtrate.

The relationship between the temperature (Tm) at the maximum peak position and the density (d) in the endothermic curve thus measured by the differential scanning calorimeter (DSC), and the n-decane soluble component amount fraction (W) It can be said that the ethylene / α-olefin copolymer [A] having the above relationship between the density and the density (d) has a narrow composition distribution.

Further, the ethylene / α-olefin copolymer [A1] has the number of unsaturated bonds present in the molecule of 0.5 or less per 1000 carbon atoms, and one molecule of the copolymer. It is desirable that the number is 1 or less.

The amount of unsaturated bond was determined by ¹³ C-NMR.
Is used to identify signals other than double bonds, ie, 10
The area intensity of the signal in the range of ˜50 ppm and the signal attributed to the double bond, that is, the signal in the range of 105 to 150 ppm is determined from the integral curve and determined from the ratio.

The B value represented by the following formula is in the range of 1.00≤B, preferably 1.01≤B≤1.50, and more preferably 1.01≤B≤1.30. Is desirable.

B = P _OE / 2P _O · P _E [wherein P _E represents the content mole fraction of the ethylene component in the copolymer, and P _O represents the content mole fraction of the α-olefin component. Shown, P _OE is the α- of the whole dyad chain.
Indicates the mole fraction of olefin / ethylene chain. ] The above B value is an index showing the distribution state of each monomer component in the copolymer chain, and GJRay (Macromolecules, 1
0, 773 (1977)), JCRandall (Macromolecules, 15, 353,
(1982), J. Polymer Science, Polymer Physics Ed., 11 , 2
75 (1973)), K. Kimura (Polymer, 25 , 441 (1984)) and the like, and is calculated by obtaining P _E , P _O and P _OE defined above. The larger the above B value, the less the blocky chain, the more uniform the distribution of ethylene and α-olefin, and the narrower the compositional distribution.

The B value, which is an index of the breadth of the composition distribution, is about 200 mg of copolymer in a 10 mmφ sample tube.
of a sample uniformly dissolved in ml 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
0 Hz, filter width 1500 Hz, pulse repetition time 4.2 seconds, pulse width 7 μsec, integration number 2000-50
It is measured under the measurement condition of 00 times, and from this spectrum, P
_E, P _O, seeking P _OE, was calculated from the above equation.

The ethylene / α-olefin copolymer [A1] used in the present invention is a transition metal compound (a) of Group IV of the periodic table containing a ligand having the following cyclopentadienyl skeleton, an organic compound. In the presence of a catalyst for olefin polymerization formed from an aluminum oxy compound (b), and optionally a carrier (c) and an organoaluminum compound (d), a so-called metallocene catalyst, ethylene and 3 carbon atoms are contained.
It can be prepared by copolymerizing with .about.20 α-olefin so that the resulting copolymer has a density of 0.900 to 0.965 g / cm ³ .

Transition metal compound (a) used in the present invention
Is represented by the following formula [I]. ML _x ... [I] (In the formula [I], M is a transition metal selected from Group IVB of the Periodic Table, L is a ligand coordinated to the transition metal atom M, and Of at least two ligands L
Is a substituted cyclopentadienyl group having at least one group selected from a cyclopentadienyl group, a methylcyclopentadienyl group, an ethylcyclopentadienyl group, or a hydrocarbon group having 3 to 10 carbon atoms. The ligand L other than the (substituted) cyclopentadienyl group 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, and x is It is the valence of the transition metal M. In the above formula [I], M is a transition metal selected from Group IVB of the periodic table, specifically zirconium, titanium or hafnium, preferably zirconium.

L is a ligand that coordinates to the transition metal atom M, and at least two of these ligands L are a cyclopentadienyl group, a methylcyclopentadienyl group,
Ethylcyclopentadienyl group or C1 to C3
A substituted cyclopentadienyl group having at least one kind of substituent selected from hydrocarbon groups of 0, and the ligand L other than the (substituted) cyclopentadienyl group has a carbon number of 1
To 12 hydrocarbon groups, alkoxy groups, aryloxy groups,
It is a trialkylsilyl group, a halogen atom 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. When the substituted cyclopentadienyl group has two or more substituents, at least one substituent may be a hydrocarbon group having 3 to 10 carbon atoms, and other substituents include a methyl group and an ethyl group. A group or a hydrocarbon group having 3 to 10 carbon atoms. Further, 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, an alkyl group is preferable, and an n-propyl group and an n-butyl group are particularly preferable. In the present invention, the (substituted) cyclopentadienyl group coordinated 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, an aryloxy group, It is a trialkylsilyl group, a halogen atom 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 and octoxy group. Can be illustrated.

Examples of the aryloxy group include a phenoxy group and the like. Examples of the trialkylsilyl group include a trimethylsilyl group, a triethylsilyl group, and a triphenylsilyl group.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine. 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 Bis (1-methyl-3-n-propylcyclopentadienyl) zirconium dichloride , Bis (1-methyl -3-n-
Butylcyclopentadienyl) zirconium dichloride and the like.

In the above example, the disubstituted product of the cyclopentadienyl ring includes 1,2- and 1,3-substituted products, and the trisubstituted product is 1,2,3- and 1,2,4-. Including substitutes. Further, 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 Particularly preferred are -methyl-3-n-propylcyclopentadienyl) zirconium dichloride and bis (1-methyl-3-n-butylcyclopentadienyl) zirconium dichloride.

Next, the organoaluminum oxy compound (b) will be described. The organoaluminum oxy compound (b) forming the olefin polymerization catalyst used in the preparation of the unmodified ethylene / α-olefin copolymer [A1] may be a conventionally known benzene-soluble aluminoxane, Also, a benzene-insoluble organoaluminum oxy compound as disclosed in JP-A-2-276807 may be used.

The aluminoxane as described above can be produced, 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. A method of recovering a hydrocarbon solution by adding an organoaluminum compound such as trialkylaluminum to the hydrocarbon medium suspension and reacting the same. (2) A method in which water, ice or steam is directly applied to an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran to recover it as a hydrocarbon solution. (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 by distillation from the recovered solution of the aluminoxane, and then redissolved in the solvent.

Specific examples of the organoaluminum compound used for producing aluminoxane include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum,
Tri-n-butyl aluminum, triisobutyl aluminum, tri sec-butyl aluminum, tri tert-butyl aluminum, tripentyl aluminum, trihexyl aluminum, trioctyl aluminum, tridecyl aluminum and other trialkyl aluminums; tricyclohexyl aluminum, tricyclooctyl Tricycloalkyl aluminum such as aluminum; dimethyl aluminum chloride, diethyl aluminum chloride,
Dialkylaluminum halides such as diethylaluminum bromide and diisobutylaluminum chloride; dialkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride; dialkylaluminum alkoxides such as dimethylaluminum methoxide and diethylaluminum ethoxide; dialkylaluminum aryloxy such as diethylaluminum 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, the z ≧ 2x) represented by Isoprenylaluminum can also be used.

The above organoaluminum compound is
Used alone or in combination. As the solvent used in the production 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 fractions such as gasoline, kerosene and diesel oil In addition, hydrocarbon solvents such as halogen compounds of aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons, especially chlorinated compounds and brominated compounds, can be mentioned. In addition, ethers such as ethyl ether and tetrahydrofuran can also be used. Of these solvents, aromatic hydrocarbons are particularly preferred.

In the benzene-insoluble organoaluminum oxy compound used in the present invention, the Al component soluble in benzene at 60 ° C. is 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of Al atom. , Insoluble or sparingly soluble in benzene.

The solubility of such an organoaluminum oxy compound in benzene is 10 mg of the organoaluminum oxy compound corresponding to 100 mg of Al.
After suspending in 0 ml of benzene and mixing at 60 ° C for 6 hours with stirring, filtration was carried out at 60 ° C using a G-5 glass filter with a jacket, and the solid portion separated on the filter was heated to 60 ° C. It is determined by measuring the abundance (x mmol) of Al atoms present in the entire filtrate after washing 4 times with 50 ml of benzene (x%).

The catalyst used in the present invention is formed from the metallocene-based transition metal compound (a) and the organoaluminum oxy compound (b), and if necessary, the carrier (c) and the organoaluminum compound (d) are added. You may use.

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, porous oxides are preferable as the inorganic carrier, and specifically, SiO ₂ , Al ₂ O ₃ , MgO, ZrO are used.
₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO
₂ or the like or a mixture thereof, such as SiO ₂ —MgO,
SiO ₂ -Al ₂ O ₃ , SiO ₂ -TiO ₂ , SiO ₂ -V ₂ O
₅ , SiO ₂ —Cr ₂ O ₃ , SiO ₂ —TiO ₂ —MgO and the like can be exemplified. Among these, SiO ₂ and Al
It is preferable that the main component is at least one component selected from the group consisting of 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 oxides may be contained.

The carrier (c) has different properties depending on its type and production method, but the carrier preferably used in the present invention has a specific surface area of 50 to 1000 m ² / g, preferably 100 to 700 m ² / g. Yes, pore volume is 0.3
It is desirable that it is ~ ^2.5 cm ² / g. This carrier is optionally 100 to 1000 ° C., preferably 15
It is used by firing at 0 to 700 ° C.

Further, as the carrier (c) which can be used in the present invention, a granular or fine particle solid of an organic compound having a particle size of 10 to 300 μm can be mentioned. As such an organic compound, a (co) polymer produced mainly from an α-olefin having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene, and 4-methyl-1-pentene, or vinylcyclohexane Examples thereof include polymers or copolymers containing styrene as a main component.

As the organoaluminum compound (d),
For example, an organoaluminum compound represented by the following general formula [III] can be exemplified. R ¹ _n AlX _3-n ... [III] (In the formula [III], R ¹ is a hydrocarbon group having 1 to 12 carbon atoms, X is a halogen atom or a hydrogen atom, n
Is 1 to 3. ) In the above general formula [III], R ¹ has 1 to 1 carbon atoms.
2 hydrocarbon groups such as an alkyl group, a cycloalkyl group or an aryl group, specifically, a methyl group,
Examples include ethyl group, n-propyl group, isopropyl group, isobutyl group, pentyl group, hexyl group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group, and tolyl group.

Such an organoaluminum compound (d)
Specifically, the following compounds are used. Trialkyl aluminums such as trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, trioctyl aluminum, and tri-2-ethylhexyl aluminum;
Alkenyl aluminum such as isoprenyl aluminum; dimethyl aluminum chloride, diethyl aluminum chloride, diisopropyl aluminum chloride,
Dialkyl aluminum halides such as diisobutyl aluminum chloride and dimethyl aluminum bromide; alkyl aluminum sesqui chlorides such as methyl aluminum sesquichloride, ethyl aluminum sesquichloride, isopropyl aluminum sesquichloride, butyl aluminum sesquichloride, ethyl aluminum sesquibromide; methyl aluminum dichloride, ethyl aluminum Alkyl aluminum dihalides such as dichloride, isopropyl aluminum dichloride and ethyl aluminum dibromide; alkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride.

As the organoaluminum compound (d), a compound represented by the following general formula [IV] can also be used. R ¹ _n AlY _3-n ... [IV] (In the formula [IV], R ¹ is the same as above, and Y is —OR ²
Group, -OSiR ³ ₃ group, -OAlR ⁴ ₂ group, -NR ⁵ ₂ group, -
SiR ⁶ ₃ group or —N (R ⁷ ) AlR ⁸ ₂ group, n is 1 to
2, R ² , R ³ , R ⁴ and R ⁸ are a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a cyclohexyl group, a phenyl group, etc., and R ⁵ is a hydrogen atom, a methyl group, an ethyl group, isopropyl group. Group, phenyl group, trimethylsilyl group and the like, and R ⁶ and R ⁷ are methyl group, ethyl group and the like. ) As such an organoaluminum compound, the following compounds are specifically used. (1) Compounds represented by R ¹ _n Al (OR ² ) _3-n , such as dimethyl aluminum methoxide, diethyl aluminum ethoxide, diisobutyl aluminum methoxide and the like. (2) A compound represented by R ¹ _n Al (OSiR ³ ₃ ) _3-n , such as Et ₂ Al (OSiMe ₃ ), (iso-Bu) ₂ Al (OSiM
e ₃ ), (iso-Bu) ₂ Al (OSiEt ₃ ), etc. (3) A compound represented by R ¹ _n Al (OAlR ⁴ ₂ ) _3-n , for example, Et ₂ AlOAlEt ₂ , (iso-Bu) ₂ AlOAl (iso-B
u) ₂ etc. (4) Compounds represented by R ¹ _n Al (NR ⁵ ₂ ) _3-n , such as Me ₂ AlNEt ₂ , Et ₂ AlNHMe, Me ₂ AlNHET
_{, Et 2 AlN (SiMe 3)} 2, (iso-Bu) 2 AlN (SiMe 3) 2
Such. (5) A compound represented by R ¹ _n Al (SiR ⁶ ₃ ) _3-n , such as (iso-Bu) ₂ AlSiMe ₃ . (6) A compound represented by R ¹ _n Al (N (R ⁷ ) AlR ⁸ ₂ ) _3-n , such as Et ₂ AlN (Me) AlEt ₂ , (iso-Bu) ₂ Al
N (Et) Al (iso-Bu) _{2 and the} like.

Among the organoaluminum compounds represented by the above general formulas [III] and [IV], the general formula R ¹ ₃ A
l, is preferably a compound represented by _{^{R 1 n Al (OR 2)}} 3-n, R 1 n Al (OAlR 4 2) 3-n, particularly R is isoalkyl group, compounds which are n = 2 is preferable.

The olefin polymerization catalyst used for producing the ethylene / α-olefin copolymer [A1] is a metallocene-based transition metal compound (a), an organoaluminum oxy compound (b), and the above It is prepared by bringing the carrier (c) and the organoaluminum compound (d) into contact with each other.

The order of contacting the components (a) to (d) at this time is arbitrarily selected, but preferably the carrier (c) and the organoaluminum oxy compound (b) are mixed and contacted, and then the transition metal compound ( a) is mixed and brought into contact with the organoaluminum compound (d), if necessary.

The contact of the above components (a) to (d) can be carried out in an inert hydrocarbon solvent, and specific examples of the inert hydrocarbon medium used for preparing the catalyst include propane, butane and pentane. , Hexane, heptane, octane, decane, dodecane, kerosene and other aliphatic hydrocarbons; cyclopentane, cyclohexane, methylcyclopentane and other alicyclic hydrocarbons; benzene, toluene, xylene and other aromatic hydrocarbons; ethylene chloride, Chlorobenzene,
Examples thereof include halogenated hydrocarbons such as dichloromethane and mixtures thereof.

When the transition metal compound (a), the organoaluminum oxy compound (b), the carrier (c), and the organoaluminum compound (d) are mixed and contacted, the transition metal compound (a) is added per 1 g of the carrier (c). , Usually 5 × 10 ^-6 ~
It is used in an amount of 5 × 10 ⁻⁴ mol, preferably 10 ⁻⁵ to 2 × 10 ⁻⁴ mol, and the concentration of the transition metal compound (a) is about 10
^{-4 to} 2 × 10 ^-2 mol / liter, preferably 2 × 10 ^-4
It is in the range of -10 ^-2 mol / liter. The atomic ratio of the aluminum of the organoaluminum oxy compound (b) to the transition metal in the transition metal compound (a) (Al / transition metal) is
Usually it is 10-500, preferably 20-200. The atomic ratio (Al-d) of the aluminum atom (Al-d) of the organoaluminum (d) and the aluminum atom (Al-b) of the organoaluminum oxy compound (b) that are used as necessary.
/ Al-b) is usually 0.02 to 3, preferably 0.05
１．５1.5. The mixing temperature at the time of mixing and contacting these catalyst components is usually −50 to 150 ° C., preferably −20 to 120 ° C., and the contact time is 1 minute to 50 hours,
It is preferably 10 minutes to 25 hours.

The above-mentioned olefin polymerization catalyst is a carrier.
(C) Transition gold derived from the transition metal compound (a) per 1 g
5 x 10 genus atoms^-6~ 5 × 10^-FourGram atom, preferably
Is 10^-Five~ 2 x 10^-FourIt is carried in the amount of gram atom, and also
Organoaluminum oxy compound per 1 g of carrier (c)
Derived from (b) and organoaluminum compound (d)
10 aluminum atoms^-3~ 5 × 10^-2Gram atom, good
2x10 is better^-3~ 2 x 10 ^-2Carried in the amount of gram atom
It is desirable that

Ethylene / α-olefin copolymer [A
The catalyst used in the production of 1] is a transition metal compound (a), an organoaluminum oxy compound (b),
It may be a prepolymerization catalyst obtained by prepolymerizing an olefin in the presence of the carrier (c) and, if necessary, the organoaluminum compound (d).

This preliminary polymerization can be carried out by introducing an olefin into an inert hydrocarbon solvent in the presence of the above-mentioned preliminary polymerization catalyst. As the olefin used in the prepolymerization, ethylene and a carbon atom number of 3 to
20 α-olefins such as propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene,
Examples thereof include 1-octene, 1-decene, 1-dodecene, 1-tetradecene, and the like. Among these, ethylene used in the polymerization or a combination of ethylene and an α-olefin is particularly preferable.

In the prepolymerization, the transition metal compound (a) is usually used in an amount of 10 ⁻⁶ to 2 × 10 ⁻² mol / liter, preferably 5 × 10 ⁻⁵ to 10 ⁻² mol / liter. The transition metal compound (a) is usually 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ mol, preferably 10 ⁻⁵ to 2 per 1 g of the carrier (c).
Used in an amount of × 10 ^-4 mol. The atomic ratio of the aluminum of the organoaluminum oxy compound (b) to the transition metal in the transition metal compound (a) (Al / transition metal) is
Usually it is 10-500, preferably 20-200. The atomic ratio (Al-d / Al-b) between the aluminum atom (Al-d) of the organoaluminum compound (d) and the aluminum atom (Al-b) of the organoaluminum oxy compound (b) that is used as necessary is , Usually 0.02 to 3, preferably 0.05 to 1.5. Prepolymerization temperature is -20
To 80 ° C, preferably 0 to 60 ° C, and the prepolymerization time is 0.5 to 100 hours, preferably about 1 to 50 hours.

The prepolymerization catalyst is prepared, for example, as follows. That is, the carrier (c) is suspended in an inert hydrocarbon. Next, the organoaluminum oxy compound (b) is added to this suspension, and the reaction is performed for a predetermined time. Thereafter, the supernatant is removed and the solid component obtained is resuspended with an inert hydrocarbon. The transition metal compound (a) is added to the system, and after reacting for a predetermined time, the supernatant liquid is removed to obtain a solid catalyst component. Then, the preliminarily polymerized catalyst can be obtained by adding the above-obtained solid catalyst component to an inert hydrocarbon containing the organoaluminum compound (d) and introducing the olefin therein.

The olefin polymer produced by the prepolymerization is
0.1 to 500 g per 1 g of the carrier (c), preferably 0.1.
It is desirable that the amount is 2 to 300 g, and more preferably 0.5 to 200 g. In addition, in the prepolymerization catalyst, the transition metal compound (a) per 1 g of the carrier (c) is about 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ gram atom as a transition metal atom, preferably 10 ⁻⁵ to 2 × 10 ^{−. The} aluminum atom (Al) derived from the organoaluminum oxy compound (b) and the organoaluminum compound (d), which is supported in an amount of ⁴ gram atoms, is
The molar ratio (Al / M) to the transition metal atom (M) derived from the transition metal compound (a) is preferably 5 to 200, and preferably 10 to 150.

The prepolymerization can be carried out batchwise or continuously, and can be carried out under reduced pressure, normal pressure or under pressure. In the pre-polymerization, a pre-polymerization such that the intrinsic viscosity [η] measured in decalin at 135 ° C. in the presence of hydrogen is in the range of 0.2 to 7 dl / g, preferably 0.5 to 5 dl / g. It is desirable to produce a polymer.

Unmodified ethylene / α used in the present invention
The olefin copolymer [A1] is obtained by copolymerizing ethylene with an α-olefin having 3 to 20 carbon atoms in the presence of the above catalyst.

In the present invention, the copolymerization of ethylene and α-olefin is carried out in the gas phase or in the slurry liquid phase. In the 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 the slurry polymerization include aliphatic hydrocarbons such as butane, isobutane, pentane, hexane, octane, decane, dodecane, hexadecane and octadecane; cyclopentane and methyl. Alicyclic hydrocarbons such as cyclopentane, cyclohexane and cyclooctane; aromatic hydrocarbons such as benzene, toluene and xylene; petroleum fractions such as gasoline, 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 catalyst usually has a concentration of transition metal atoms in the polymerization reaction system of usually 10 ^-8 to 10 ^-3 gram atom /
It is desirable to use it in an amount of liter, preferably 10 ⁻⁷ to 10 ⁻⁴ gram atom / liter.

In the main polymerization, an organoaluminumoxy compound and / or an organoaluminum compound (d) similar to the organoaluminum oxy compound (b) may be added. At this time, the atomic ratio (Al / M) between the aluminum atom (Al) derived from the organoaluminum oxy compound and the organoaluminum compound and the transition metal atom (M) derived from the transition metal compound (a) is 5 to 300. ,
Preferably 10-200, more preferably 15-150
Range.

In the present invention, 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 usually 0 to 120 ° C., preferably 20.
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 by 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. Modified ethylene / α-olefin copolymer [A2] The modified ethylene / α-olefin copolymer [A2] used in the present invention is the above-mentioned ethylene / α-olefin copolymer [A1] with an unsaturated carboxylic acid. Alternatively, its derivative is grafted.

Specific examples of the unsaturated carboxylic acid or its derivative include acrylic acid, methacrylic acid, α-ethylacrylic acid, maleic acid, fumaric acid,
Itaconic acid, citraconic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, endocis-bisic [2,2,
1] Unsaturated carboxylic acids such as hept-5-ene-2,3-dicarboxylic acid (Nadic acid ^™ ) and derivatives of these acid halides, amides, imides, acid anhydrides, esters and the like. Of these, unsaturated dicarboxylic acids or acid anhydrides thereof are preferable, and maleic acid, nadic acid ^™ or acid anhydrides thereof are particularly preferable.

This graft modification can be carried out by a conventionally known method, for example, by dissolving the above ethylene / α-olefin copolymer [A1] in an organic solvent, and then adding the unsaturated carboxylic acid or the unsaturated carboxylic acid to the resulting solution. Add a derivative and a radical initiator and the like, and the temperature is 70 to 200 ° C., preferably 8
The reaction is carried out at a temperature of 0 to 190 ° C. for 0.5 to 15 hours, preferably 1 to 10 hours.

This organic solvent can be used without particular limitation as long as it is an organic solvent capable of dissolving the ethylene / α-olefin copolymer [A1]. Examples of such an organic solvent include aromatic hydrocarbon solvents such as benzene, toluene and xylene, and aliphatic hydrocarbon solvents such as pentane, hexane and heptane.

Further, using an extruder or the like, without solvent,
The graft-modified ethylene / α-olefin copolymer [A2] can be prepared by reacting the ethylene / α-olefin copolymer [A1] with an unsaturated carboxylic acid or a derivative thereof. The reaction temperature is usually equal to or higher than the melting point of the ethylene / α-olefin copolymer [A1], specifically, 1
It is in the range of 20 to 250 ° C. The reaction time under such temperature conditions is usually 0.5 to 10 minutes.

In order to efficiently graft-copolymerize the unsaturated carboxylic acid or its derivative as the grafting monomer, whichever conventionally known grafting method is adopted, the reaction is carried out in the presence of a radical initiator. It is preferably carried out.

Examples of such a radical initiator include organic peroxides and organic peresters such as benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-diester. (Peroxide Benzoate) Hexin
-3,1,4-bis (t-butylperoxyisopropyl) benzene, lauroyl peroxide, t-butylperacetate, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3,2,5 -Dimethyl-2,5-di (t-butylperoxy)
Hexane, t-butyl perbenzoate, t-butyl perphenyl acetate, t-butyl perisobutyrate, t-butyl per-sec-octoate, t-butyl perpivalate, cumyl perpivalate and t-butyl perdiethyl acetate. Other azo compounds such as azobisisobutyronitrile and dimethylazoisobutyrate are used. Among these, dicumyl peroxide, di-t
-Butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3,2,5-dimethyl-2,5-di (t-
Dialkyl peroxides such as butylperoxy) hexane and 1,4-bis (t-butylperoxyisopropyl) benzene are preferred.

The radical initiator is usually 0.1% with respect to 100 parts by weight of the ethylene / α-olefin copolymer [A1].
It is used in a proportion of 001 to 1 part by weight. The graft reaction is usually performed at a temperature of 60 to 350 ° C.

The amount of graft groups derived from the unsaturated carboxylic acid or its derivative in the modified ethylene / α-olefin copolymer [A2] prepared as described above is usually 0.01 to 20. % By weight, preferably 0.05 to 10% by weight, more preferably 0.1 to 5
% By weight.

In the present invention, the modified ethylene / α-olefin copolymer [A2] is based on 100% by weight of the total amount of the modified ethylene / α-olefin copolymer [A2] and the olefin elastomer [B]. 50 to 95% by weight, preferably 60 to 90% by weight, and more preferably 65 to 85% by weight. Further, in place of part of the modified ethylene / α-olefin copolymer [A2], the above-mentioned unmodified ethylene / α-olefin copolymer [A1] is blended within a range not impairing the object of the present invention. You can

Olefin-based elastomer [B] Olefin-based elastomer [B] used in the present invention
Is ethylene and / or α- having 3 to 20 carbon atoms.
It is a (co) polymer of olefin and has a density of 0.850-
0.895 g / cm ³ , preferably 0.860 to 0.8
It is in the range of 90 g / cm ³ , 190 ° C, 2.16 kg
Melt flow rate under load (MFR; ASTM D1238
-65T) is 0.01 to 200 g / 10 minutes, preferably 0.01 to 100 g / 10 minutes, and more preferably 0.0.
It is preferably in the range of 5 to 50 g / 10 minutes. Further, such an olefinic elastomer [B] has X
It is desirable that the crystallinity measured by the line diffraction method is less than 30% or that the crystallinity is amorphous.

Examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-
Mention may be made of hexene, 4-methyl-1-pentene, 1-octene, 1-decene and mixtures thereof. Of these, it is particularly preferable to use an α-olefin having 3 to 10 carbon atoms.

The olefin elastomer [B] used in the present invention is a structural unit other than a structural unit derived from an α-olefin, such as a structural unit derived from a diene compound, within a range that does not impair its properties. May be included.

For example, as the constitutional unit which is allowed to be contained in the olefinic elastomer [B] used in the present invention, specifically, 1,4-hexadiene, 1,6-octadiene, 2-methyl- 1,5-hexadiene, 6-methyl-
Structural units derived from chain-like non-conjugated dienes such as 1,5-heptadiene and 7-methyl-1,6-octadiene; cyclohexadiene, dicyclopentadiene, methyltetrahydroindene, 5-vinylnorbornene, 5-ethylidene-2 -Structural units derived from cyclic non-conjugated dienes such as norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene; 2,3- Examples thereof include constitutional units derived from diene compounds such as diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, and 2-propenyl-2,2-norbornadiene.

Such diene components can be used alone or in combination. The content of the structural unit derived from such a diene component is usually 10 mol% or less, preferably 0 to 5 mol%.

As such an olefin elastomer [B], the content of the structural unit derived from ethylene is, for example, 0 to 95 mol%, preferably 30 to 92 mol%, more preferably 50 to 90 mol%,
It is particularly preferably 75 to 95 mol% and has 3 carbon atoms.
The content of α-olefin of 20 to 1 is 1 to 100 mol%, preferably 4 to 70 mol%, more preferably 8 to 50 mol%, particularly preferably 10 to 40 mol%, and the content of diene component is 0. -10 mol, preferably 0-5 mol%,
More preferably 0 to 3 mol%, and particularly preferably 0 to 2.
Copolymers (ethylene copolymers, α-olefin copolymers) of 5 mol% can be mentioned.

The olefinic elastomer [B] used in the present invention can be prepared by a conventionally known method using a Ti-based, V-based, Zr-based catalyst or the like. In the present invention, the olefin elastomer [B] is a modified ethylene / α-olefin copolymer [A2] or an unmodified ethylene / α-olefin copolymer [A1] and a modified ethylene / α-olefin copolymer. It is used in a proportion of 5 to 50% by weight, preferably 10 to 40% by weight, more preferably 15 to 35% by weight, based on 100% by weight of the total amount of the combined [A2] and the olefin elastomer [B].

Adhesive Ethylene Copolymer Resin Composition The adhesive ethylene copolymer resin composition of the present invention comprises
As described above, the modified ethylene / α-olefin copolymer [A1] and the olefin elastomer [B] are blended in a specific ratio, or the unmodified ethylene / α-olefin copolymer [A1]. ] And a modified ethylene / α-olefin copolymer [A2] and an olefin elastomer [B] are blended in a specific ratio.

The blend as described above preferably has (i) density (d) of 0.870 to 0.960 g / cm 3.
³ , more preferably 0.880 to 0.930 g / cm
³ , particularly preferably 0.900 to 0.920 g / cm ³
And (ii) the melt flow rate (MFR) at 190 ° C. under a load of 2.16 kg is preferably 0.
01 to 100 g / 10 minutes, more preferably 0.05 to
50 g / 10 minutes, particularly preferably 0.1 to 20 g / 1
It is in the range of 0 minutes, and (iii) the graft amount of the graft group derived from the unsaturated carboxylic acid or its derivative is preferably 0.01 to 5% by weight, more preferably 0.03.
˜3 wt%, especially 0.05 to 0.5 wt%, (iv)
Crystallinity measured by X-ray diffraction is preferably 15%
As described above, it is desirable to be in the range of 20 to 70%, particularly preferably 30 to 60%.

The adhesive ethylene-based copolymer resin composition according to the present invention may be the above-mentioned blend alone, or may contain a weather stabilizer, a heat stabilizer and an antistatic agent in the blend. Additives such as agents, anti-slip agents, anti-blocking agents, anti-fog agents, lubricants, pigments, dyes, nucleating agents, plasticizers, anti-aging agents, hydrochloric acid absorbents, antioxidants, etc. without impairing the purpose of the present invention. It may be mixed in the range.

Laminate The laminate according to the present invention is composed of a layer made of the above-mentioned adhesive ethylene copolymer resin composition according to the present invention and a layer made of a polar material or a metal.

As the polar material, specifically, ethylene / vinyl alcohol copolymer, polyamide (nylon), polyester and the like are preferably used. The metal is usually a metal foil, specifically, aluminum,
Examples include iron and copper.

Specific examples of the laminate of the present invention include the following. (A) Aspect of a laminate having a multilayer structure composed of an adhesive ethylene-based copolymer resin composition layer and a nylon layer or an ethylene / vinyl alcohol copolymer layer (i) Adhesive ethylene-based copolymer resin composition A laminate having a two-layer structure in which a layer and a nylon layer or an ethylene / vinyl alcohol copolymer layer are respectively used as an inner layer and an outer layer, or an outer layer and an inner layer.

(Ii) Adhesive Ethylene copolymer resin composition layer, nylon layer or ethylene / vinyl alcohol copolymer layer is used as an intermediate layer, and the other two layers are used as an outer layer and an inner layer, respectively. A laminated body having a three-layer structure.

(Iii) The laminate of (i) or (ii) above has adhesiveness with any of the adhesive ethylene-based copolymer resin composition layer, the nylon layer and the ethylene / vinyl alcohol copolymer layer. The polymer layer, for example, the polymer layer laminated on the adhesive ethylene-based copolymer composition layer may be a layer laminated on polypropylene, polyethylene, ethylene / α-olefin copolymer or the like, or a nylon layer. The layer of the polymer is a layer of ethylene / vinyl alcohol copolymer or the like, and the layer of the polymer to be laminated with the ethylene / vinyl alcohol copolymer layer is of a multilayer structure in which layers of nylon, polyester resin or the like are laminated. Laminate.

As the laminated body having the multilayer structure of (iii) above,
Specifically, a laminate having a three-layer structure of polyethylene layer / adhesive ethylene-based copolymer resin composition layer / nylon layer or ethylene / vinyl alcohol copolymer layer, adhesive ethylene-based copolymer resin composition layer / Ethylene / vinyl alcohol copolymer layer / nylon layer three-layer structure laminate, adhesive ethylene-based copolymer resin composition layer / nylon layer / ethylene / vinyl alcohol copolymer layer three-layer structure laminate ,
4-layer laminate of polyethylene layer / adhesive ethylene-based copolymer resin composition layer / nylon layer or ethylene / vinyl alcohol copolymer layer / adhesive ethylene-based copolymer composition layer, polyethylene layer / adhesiveness 4-layer laminated product of ethylene copolymer resin composition layer / ethylene / vinyl alcohol copolymer layer / nylon layer, polyethylene layer / adhesive ethylene copolymer resin composition layer / nylon layer / ethylene vinyl Laminate of four-layer structure of alcohol copolymer layer, polyethylene layer / adhesive ethylene-based copolymer resin composition layer / nylon layer or ethylene / vinyl alcohol copolymer layer / adhesive ethylene-based copolymer resin composition layer/
A 5-layer structure laminate of polyethylene layers, and a multilayer laminate containing an adhesive ethylene-based copolymer resin composition layer / nylon layer or an ethylene / vinyl alcohol copolymer layer as a part of the constituent elements may be mentioned.

Any of the layers constituting these laminates may be uniaxially or biaxially oriented. (B) A mode of a laminate having a multilayer structure composed of an adhesive ethylene-based copolymer resin composition layer and a metal foil (i) A two-layer structure of adhesive ethylene-based copolymer resin composition layer / metal foil Laminate.

(Ii) A laminate having a three-layer structure of polyethylene layer / adhesive ethylene-based copolymer resin composition layer / metal foil. (iii) A laminate having a four-layer structure of polyethylene layer / adhesive ethylene-based copolymer resin composition layer / metal foil / adhesive ethylene-based copolymer resin composition layer.

(Iv) In addition, a laminate having a multi-layer structure containing an adhesive ethylene-based copolymer resin composition layer / metal foil as a part of the constituent elements. As a laminating method for preparing these laminated bodies, a conventionally known laminating method such as a coextrusion laminating method, an extrusion coating method, and a thermal laminating method can be adopted.

[0111]

EFFECT OF THE INVENTION The adhesive ethylene-based copolymer resin composition according to the present invention has good thermal stability, excellent moldability, excellent transparency, and excellent adhesion to metal or highly polar materials. Excellent film layers can be prepared.

Further, the laminate according to the present invention comprises a layer made of the above adhesive ethylene copolymer resin composition and a highly polar material such as polyamide (nylon), ethylene vinyl alcohol copolymer and polyester. The layer has excellent inter-layer adhesion between the layer and the layer made of metal.

[0113]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

[0114]

[Production Example 1] [Production of graft-modified ethylene / 1-hexene copolymer] [Preparation of catalyst component] 5.0 kg of silica dried at 250 ° C for 10 hours was suspended in 80 liters of toluene and then at 0 ° C. Cooled down. Then, a toluene solution of methylaminoxane (Al; 1.33 mol / liter) 28.
7 liters were dropped in 1 hour. At this time, the temperature in the system was kept at 0 ° C. Subsequently, the reaction was carried out at 0 ° C. for 30 minutes, then the temperature was raised to 95 ° C. over 1.5 hours, and the reaction was carried out at that temperature for 20 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 80 liters of toluene. To this system was added 6.6 liters of bis (1,3-n-butylmethylcyclopentadienyl) zirconium dichloride in toluene (Zr; 34.0 mmol / liter) and bis (1,3-dimethylcyclopentadienyl). ) 2.0 l of a toluene solution of zirconium dichloride (Zr; 28.1 mmol / l) was appropriately added at 80 ° C for 30 minutes, and further reacted at 80 ° C for 2 hours. Thereafter, the supernatant was removed and washed twice with hexane to obtain a solid catalyst containing 3.6 mg of zirconium per gram.

[Preparation of Prepolymerized Catalyst] In 85 liters of hexane containing 1.7 mol of triisobutylaluminum, 0.85 kg of the solid catalyst obtained above and 1-
By adding 255 g of hexene and prepolymerizing ethylene at 35 ° C. for 12 hours, 10 g per 1 g of the solid catalyst is obtained.
A prepolymerized catalyst was obtained by prepolymerizing polyethylene.
[Η] of this ethylene polymer was 1.74 dl / g.

[Polymerization] Copolymerization of ethylene and 1-hexene was carried out using a continuous fluidized bed gas phase polymerization apparatus at a total pressure of 20 kg / cm ² -G and a polymerization temperature of 80 ° C. The prepolymerized catalyst prepared above was converted into zirconium atoms at 0.18 mmol / h and triisobutylaluminum at 10 mmol / h.
Ethylene, 1-hexene, hydrogen and nitrogen were continuously supplied in order to maintain a constant gas composition during the polymerization (gas composition; 1-hexene / ethylene =
0.030, hydrogen / ethylene = 5.5 × 10 ⁻⁴ , ethylene concentration = 25%).

The ethylene / 1-hexene copolymer (A-1) thus obtained had a yield of 6.0 kg / hr, a density of 0.923 g / cm ³ and an MFR of 2. 1 g / 10 minutes, the maximum melting point peak (Tm) in DSC was 114.5 ° C, the melt tension (MT) was 2.1 g, and the decane-soluble part (W) at 23 ° C was 0.26. %, The number of unsaturated bonds is 0.09 per 1000 carbon atoms, and is 0.16 per polymer molecule, showing the distribution state of 1-hexene in the copolymer chain. The B value was 1.02.

[Graft modification] Toluene was used as a reaction solvent, and 825 g of ethylene / 1-hexene copolymer (A-1) was dissolved at 160 ° C per 5.7 liters of toluene.

Then, a toluene solution of maleic anhydride (4.13 g / 250 ml) and a toluene solution of dicumyl peroxide (DPC) (0.33 g / 5) were added to this solution.
0 ml) was gradually fed from a separate conduit over 4 hours.

After the end of the supply, 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 the desired graft-modified ethylene / 1-hexene copolymer (MAH-P
E-1) was obtained.

The modified ethylene / 1-hexene copolymer was subjected to elemental analysis and the grafted amount of maleic anhydride was measured. As a result, maleic anhydride corresponding to 0.2 g per 100 g of the modified ethylene / 1-hexene copolymer was obtained. Was found to have undergone graft polymerization. Also, this modified ethylene / 1-hexene copolymer has a density of 0.923 g /
The cm ³ and MFR were 1.0 g / 10 minutes.

[0123]

[Example 1] [Preparation of composition] Modified ethylene-1-obtained in Production Example 1
90 parts by weight of hexene copolymer (MAH-PE-1) and ethylene / propylene copolymer (EPR; density = 0.86)
5 g / cm ³ , MFR = 0.5 g / 10 min, crystallinity =
4% and 10 parts by weight of a structural unit content derived from ethylene = 80 mol%) were melt mixed to obtain a modified ethylene copolymer resin composition.

Next, this composition was tested for adhesive strength with low density polyethylene (LDPE) and ethylene
The adhesive strength with the vinyl alcohol copolymer was measured by the following method. (Evaluation Method for Adhesive Strength with Ethylene / Vinyl Alcohol Copolymer and Low Density Polyethylene) Ethylene / vinyl alcohol copolymer [EVOH; trade name Eval EP-F, manufactured by Kuraray Co., Ltd., MFR: 1.
3 g / 10 minutes (ASTM D 1238, E), density: 1.19 g /
cm ³ , ethylene content: 32 mol%, saponification degree: 100
%], The above modified ethylene-based copolymer composition and low density polyethylene (LDPE) were used to mold a three-layer coextrusion cast film under the following conditions. <Molding conditions> Film layer structure and thickness of each layer: EVOH (outer layer) / composition (middle layer) / LDPE (inner layer) = 20/10/40 μm Molding machine: die diameter 40 mmφ extruder (for outer layer) Set temperature ...・ 220 ° C. Die diameter 30 mmφ extruder (for intermediate layer) Set temperature ・ ・ ・ 220 ° C. Die diameter 40 mmφ extruder (for inner layer) Set temperature ・ ・ ・ 220 ° C. Molding speed: 20 m / min Width from the obtained three-layer film After cutting a 15 mm test piece and peeling off the layer at one end of the test piece, the interlayer adhesion strength between the EVOH layer and the composition layer was measured by a T-type peeling method at a peeling speed of 300 mm / min using an Instron tensile tester. (Peel strength) F _EVOH [g / 15 mm] and interlayer adhesion strength (peel strength) F _LDPE [g / 15 mm] between the LDPE layer and the composition layer were measured.

[0125]

Example 2 In Example 1, the blending amounts of the modified ethylene / 1-hexene copolymer (MAH-PE-1) and the ethylene / propylene copolymer (EPR) were 80 parts by weight and 20 parts by weight, respectively. Except for the above, in the same manner as in Example 1,
A modified ethylene copolymer resin composition was obtained.

The adhesive strength of this composition with low density polyethylene (LDPE) and the adhesive strength with an ethylene / vinyl alcohol copolymer were measured in the same manner as in Example 1.

The results are shown in Table 1.

[0128]

Example 3 In Example 1, the blending amounts of the modified ethylene / 1-hexene copolymer (MAH-PE-1) and the ethylene / propylene copolymer (EPR) were 70 parts by weight and 30 parts by weight, respectively. Except for the above, in the same manner as in Example 1,
A modified ethylene copolymer resin composition was obtained.

The adhesive strength of this composition with low density polyethylene (LDPE) and the adhesive strength with an ethylene / vinyl alcohol copolymer were measured in the same manner as in Example 1.

The results are shown in Table 1.

[0131]

[Production Example 2] [Production of graft-modified ethylene / 1-hexene copolymer]
Ethylene / 1-hexene copolymer (A-1) 1 of Production Example 1
00 parts by weight, maleic anhydride 0.9 parts by weight, and peroxide [trade name Perhexin-25B, NOF Corporation]
0.08 parts by weight and the resulting mixture at 230 ° C.
The modified ethylene / 1-hexene copolymer (MAH-PE-
2) was obtained.

The modified ethylene / 1-hexene copolymer was subjected to elemental analysis and the grafted amount of maleic anhydride was measured. As a result, maleic anhydride corresponding to 1.0 g per 100 g of the modified ethylene / 1-hexene copolymer was obtained. Was found to have undergone graft polymerization. The modified ethylene / 1-hexene copolymer has a density of 0.926 g /
cm ³ , MFR was 0.2 g / 10 minutes.

[0133]

Example 4 15 parts by weight of the modified ethylene / 1-hexene copolymer (MAH-PE-2) obtained in Production Example 2 and the unmodified ethylene / 1-hexene copolymer obtained in Production Example 1 65 parts by weight of the combined (A-1) and the ethylene used in Example 1
20 parts by weight of propylene copolymer (EPR) was melt mixed to obtain a modified ethylene copolymer resin composition.

The adhesive strength of this composition with low density polyethylene (LDPE) and the adhesive strength with an ethylene / vinyl alcohol copolymer were measured in the same manner as in Example 1.

The results are shown in Table 1.

[0136]

Example 5 In Example 4, an ethylene / 1-octene copolymer (EOR; density = 0.870) was used instead of EPR.
g / cm ³ , MFR = 5.8 g / 10 minutes, crystallinity = 0
%, Content of structural units derived from ethylene = 85.2
A modified ethylene-based copolymer resin composition was obtained in the same manner as in Example 4 except that (mol%) was used.

The adhesive strength of this composition with low density polyethylene (LDPE) and the adhesive strength with an ethylene / vinyl alcohol copolymer were measured in the same manner as in Example 1.

The results are shown in Table 1.

[0139]

Example 6 In Example 4, instead of EPR, ethylene / 1-butene copolymer (EBR; density = 0.85 g)
/ Cm ³ , MFR = 6.0 g / 10 minutes, crystallinity = 16
%, The modified ethylene-based copolymer resin composition was obtained in the same manner as in Example 4, except that the constituent unit content derived from ethylene = 90 mol%) was used.

The adhesive strength of this composition with low density polyethylene (LDPE) and the adhesive strength with an ethylene / vinyl alcohol copolymer were measured in the same manner as in Example 1.

The results are shown in Table 1.

[0142]

Comparative Example 1 As in Example 1, except that a modified ethylene / 1-hexene copolymer (MAH-PE-1) was used alone instead of the modified ethylene copolymer resin composition. The same was done.

The results are shown in Table 1.

[0144]

Comparative Example 2 In Example 4, unmodified ethylene 1-
Low-density polyethylene (Ti-PE; density = 0.921 g / cm ³ , MFR =) prepared by using a conventional titanium-based catalyst instead of 65 parts by weight of hexene copolymer (A-1).
The same procedure as in Example 4 was carried out except that 85 parts by weight of (2.1 g / 10 minutes) was used and the ethylene / propylene copolymer (EPR) was not used.

The results are shown in Table 1.

[0146]

[Table 1]

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Claims (6)

[Claims] 1. An olefin polymerization catalyst comprising a transition metal compound (a) of Group IV of the Periodic Table containing [I] a ligand having a cyclopentadienyl skeleton and an organoaluminum oxy compound (b). Modified ethylene prepared by grafting an unsaturated carboxylic acid or a derivative thereof onto a linear ethylene / α-olefin copolymer [A1] prepared from ethylene and an α-olefin having 3 to 20 carbon atoms.・
50 to 95% by weight of α-olefin copolymer [A2] or unmodified ethylene / α-olefin copolymer [A2]
1] and modified ethylene / α-olefin copolymer [A
2] 50 to 95% by weight, and [II] olefin elastomer [B] 5 to 50% by weight
And an ethylene / α-olefin copolymer [A1] is (i)
The density (d) is in the range of 0.900 to 0.965 g / cm ³ , and (ii) the melt flow rate (MFR) at 190 ° C. and a load of 2.16 kg is 0.01 to 200 g / cm ^3.
It is in the range of 10 minutes, and the olefin elastomer [B] has (i) density (d)
Is in the range of 0.850 to 0.895 g / cm ³ ,
(Ii) the melt flow rate (MFR) at 190 ° C. under a load of 2.16 kg is in the range of 0.01 to 200 g / 10 minutes, and (iii) the crystallinity measured by X-ray diffractometry is less than 30%. An adhesive ethylene-based copolymer resin composition characterized by being present. 2. A blend of the modified ethylene / α-olefin copolymer [A2] and the olefin elastomer [B], or an unmodified ethylene / α-olefin copolymer [A1] and modified ethylene / α. -The blend of the olefin copolymer [A2] and the olefin elastomer [B] has a (i) density (d) of 0.870 to 0.960 g.
/ Cm ³ range, (ii) 190 ℃, 2.16kg
Melt flow rate (MFR) under load is 0.0
1 to 100 g / 10 minutes, (iii) the graft amount of a graft group derived from an unsaturated carboxylic acid or its derivative is 0.01 to 5% by weight, and (iv)
The adhesive ethylene-based copolymer resin composition according to claim 1, which has a crystallinity of 15% or more as measured by an X-ray diffraction method. 3. The unmodified ethylene / α-olefin copolymer [A1] has a density (d) (d) of 0.900 to 0.9.
It is in the range of 965 g / cm ³ , and (ii) 190 ° C., 2.
Melt flow rate (MFR) at a load of 16 kg
Is in the range of 0.01 to 200 g / 10 minutes, and (ii
i) Temperature (Tm (° C)) and density (d) at the maximum peak position of the endothermic curve measured by a differential scanning calorimeter (DSC)
Satisfy the relationship expressed by Tm <400 × d-250, and (iv) melt tension (MT (g)) and melt flow rate (M) at 190 ° C.
FR) satisfies the relation MT ≦ 2.2 × MFR ^−0.84 , and (v) the decane-soluble part (W (wt%)) and the density (d) at 23 ° C. are MFR ≦ 10 g / When 10 minutes, W <80 * exp (-100 (d-0.88)) + 0.1 MFR> 10g / 10 minutes, W <80 * (MFR-9) ^0.26 * exp (-100 (d −
0.88)) + 0.1 which is a linear ethylene / α-olefin copolymer, and the adhesive ethylene-based copolymer resin composition according to claim 1 or 2, . 4. The olefin elastomer [B] is
The adhesive ethylene copolymer according to any one of claims 1 to 3, which is an ethylene / α-olefin copolymer having a structural unit content derived from ethylene in the range of 75 to 95 mol%. Polymer resin composition. 5. A laminate comprising a layer made of the adhesive ethylene copolymer resin composition according to claim 1 and a layer made of a polar material or a layer made of a metal. 6. The laminate according to claim 5, wherein the polar material is made of ethylene / vinyl alcohol copolymer, polyamide or polyester.