JP2000044738A - Ethylene polymer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polymer which can be easily degraded with e.g. ultraviolet rays in a natural or artificial environment and is capable of having been controlled in the time necessary to be degraded by incorporating an ethylenic polymer being a polymer of ethylene or of ethylene and α-olefins having the number of carbon atoms in a specified range and an antioxidant in a specified ratio. SOLUTION: The ethylenic polymer is a polymer of ethylene or of ethylene and a 3-20C α-olefin, and the composition contains 0.01-1.0 pts.wt. antioxidant per 100 pts.wt. polymer. The ehtylenic polymer should have an MFR (at 190 deg.C) of 0.01-1,000 g/10 min, a density of 0.85-0.97 g/cm3, and at least 0.15, in total, per 1,000C, unsaturation represented by formulae I to IV and at least 0.1, per 1,000C in total unsaturation represented by formulae III and IV. The unsaturations contained in a specified amount in the molecular chain make the polymer easily photodegradable without detriment to molding characteristics, the mechanical properties of a molding, and the transparency of a film.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an ethylene polymer composition. More particularly, it relates to an ethylene-based polymer composition that is easily photodegradable. The ethylene-based polymer in this composition is easily decomposed by exposure to sunlight or ultraviolet rays. By adding a specific amount of light stabilizer to this, its degradability can be controlled, so it can be used for applications that want to be decomposed and disintegrated after a certain period of time, and after it has been used for various molded products It has the feature that waste disposal is easy.

[0002]

2. Description of the Related Art Plastics are indispensable to daily life due to their moldability, lightness and low cost, and their demand is increasing year by year. However, on the other hand, various problems arise with respect to waste disposal and environmental pollution after use due to reasons such as difficulty in decomposition in the natural world. Under these circumstances, various studies have been made on plastic waste treatment from the development of easily degradable polymers, improvement of incinerators, and research on recycling.

[0003] Among these, easily decomposable polymers include photodegradable polymers, microbial degradable polymers, and natural polymers. Among them, photodegradable plastics are degraded and disintegrated by sunlight in a natural environment. Research and development have been made vigorously because the decomposition by microorganisms becomes easy. For example, a copolymer of ethylene and carbon monoxide, a vinyl ketone copolymer, polybutadiene and the like are examples. Also, there have been proposed many compositions and the like in which a compound having a photosensitizing effect is added and blended as a decomposition accelerator to ordinary plastics. However, in these methods, in order to obtain sufficient photodegradability, the deterioration of the physical properties of the molded article is unavoidable, the cost is increased, and the photosensitizer to be added may be harmful. Problems were inevitable.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to maintain the excellent moldability of plastics and the good physical properties of molded articles, and after use in natural environments or artificial ultraviolet rays. It is intended to provide a readily decomposable ethylene polymer composition which can be easily decomposed by an action, and a period until the decomposition can be controlled, and is easily disposed of. is there.

[0005]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have conducted various studies and found that a specific amount of an antioxidant was blended with an ethylene polymer having a specific molecular structure at a specific ratio. Molded articles made of ethylene-based polymer composition are easy to decompose by light, the period until decomposition can be adjusted, its processability and mechanical properties of molded articles, or the transparency of the film obtained from the polymer The present inventors have found that the physical properties of products such as these show exactly the same performance as conventional materials, and have reached the present invention.

That is, the gist of the present invention is as follows:
Ethylene satisfying (4) or ethylene and 3 carbon atoms
-Polymer obtained by polymerizing a mixture with α-olefins (hereinafter collectively referred to as “ethylene-based polymer”)
And an ethylene-based polymer composition containing 0.01 to 1.0 part by weight of an antioxidant per 100 parts by weight of the ethylene-based polymer. (1) The melt flow rate (MFR) under a load of 2.16 kg at 190 ° C. is 0.01 to 1000 g / 10 min. (2) The density is 0.85 to 0.97 g / cm ³ (3) Chemical formula (1) to The compound has at least 0.15 unsaturated bonds represented by the chemical formula (4) (hereinafter collectively referred to as “internal unsaturated bonds”) per 1000 carbon atoms.

[0007]

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(4) An unsaturated bond represented by the chemical formula (3) or (4) (wherein R represents a hydrocarbon group having 1 or more carbon atoms. Hereinafter, these two types of unsaturated bonds are collectively (Hereinafter referred to as "trisubstituted internal unsaturated bond") in total.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The ethylene polymer used in the ethylene polymer composition of the present invention is a homopolymer of ethylene or a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms, and has a melt flow rate (MFR). ) Is 0.01 g / 1
0 minutes or more and 1000 g / 10 minutes or less, preferably 0.1 g
g / 10 minutes or more and 100 g / 10 minutes or less. MFR
Is too small, the fluidity at the time of melting is insufficient and molding is difficult. On the other hand, if the MFR is too high, the strength of the molded article tends to decrease, which is not preferable.

The density of the polymer of the present invention is 0.85 g /
cm ³ or more and 0.97 g / cm ³ or less, preferably 0.1 g / cm ³ or less.
It is 87 g / cm ³ or more and 0.96 g / cm ³ or less.
In addition, MFR is based on ASTM1238, 190 degreeC,
2.Measured under a load of 16 kg, density is MFR
The strand obtained at the time of measurement is heat-treated at 100 ° C. for 1 hour, further cooled at room temperature for 1 hour, and then measured by a density gradient tube method.

Particularly important in the present invention is the chemical formula
0.15 unsaturated bonds (hereinafter collectively referred to as "internal unsaturated bonds") represented by formulas (1) to (4) per 1000 carbon atoms (hereinafter, this unit is referred to as "pieces / 1000C") Or more, preferably 0.4 or more, and a chemical formula
(3) or an unsaturated bond represented by the chemical formula (4) (hereinafter collectively referred to as "trisubstituted unsaturated bond")
It has 0.1 or more, preferably 0.3 or more per 00 carbon atoms.

By containing a specific amount of an internal unsaturated bond and a trisubstituted unsaturated bond in the molecular chain of the polymer,
The photodecomposition reaction can be facilitated without impairing the practical properties such as the molding properties of the material itself and the mechanical properties and transparency of molded articles such as films. In the present invention, the chemical formula (1)
Number and chemical formula of internal unsaturated bonds represented by chemical formula (4)
The number of trisubstituted unsaturated bonds represented by (3) and the chemical formula (4) is determined by the nuclear magnetic resonance spectrum (1H-NM
R).

That is, the polymer is dissolved in a mixed solvent of o-dichlorobenzene / deuterated benzene (volume ratio: 80/20),
Nuclear magnetic resonance spectrometer (JNM-JNM-
Using GSX270), a nuclear magnetic resonance spectrum (1H-NMR) is measured 10,000 times or more at a temperature of 130 ° C. with a pulse width of 7 μs and a pulse repetition time of 7 seconds, and a resonance curve is obtained by integration. 0 ppm of tetramethylsilane
Each peak on the resonance curve is assigned as follows using the chemical shift as follows.

[0014]

Table 1 Chemical shifts 0.4 to 2.8 ppm: saturated alkyl chains (0.5 carbon atoms per hydrogen atom) Chemical shifts 5.1 to 5.3 ppm: trisubstituted unsaturated bonds (formula (3) , (4)) (two carbon atoms and one unsaturated bond per hydrogen atom) Chemical shift 5.3 to 5.5 ppm: disubstituted unsaturated bond (formula (1), (2)) (hydrogen atom (One carbon atom and 0.5 unsaturated bond per one)

Therefore, when the peak area corresponding to each chemical shift range is, for example, 0.4 to 2.8 ppm of chemical shifts and is expressed as “A (0.4 to 2.8)”, the number of carbon atoms is 1000. The number of internal unsaturated bonds per piece is

[0016]

(Equation 1)

The number of trisubstituted unsaturated bonds is

[0018]

(Equation 2)

[0019] If the number of internal unsaturated bonds is less than 0.15 / 1000C, or if the number of trisubstituted unsaturated bonds is less than 0.1 / 1000C, photolysis of the polymer is an effect of the present invention. And the object of the present invention is not achieved. Further, when the number of internal unsaturated bonds exceeds 50 / 1000C, the melting point of the polymer decreases and the strength of the product becomes insufficient,
Alternatively, the product tends to be colored, which is not preferable.
More preferably, the number of internal unsaturated bonds is 20 / 1000c or less. The method for obtaining the ethylene-based polymer used in the present invention is not particularly limited, but a so-called metallocene-based catalyst comprising a transition metal belonging to Groups 4 to 6 of the periodic table and at least one conjugated 5-membered ring ligand. It can be produced by a catalyst system comprising a compound containing

This catalyst system generally comprises a component [A]: a metallocene-based transition metal compound and a component [B]: an ionic compound capable of reacting with an aluminum oxy compound, a Lewis acid and a metallocene compound to convert it into a cation. And a catalyst comprising at least one compound selected from the group consisting of These components may be supported on an inorganic or organic solid carrier. Further, as a more preferable metallocene-based catalyst, a catalyst system comprising the above-mentioned component [A] and component [C]: an ion-exchange layered silicate is preferably used.

The component [A] (metallocene transition metal compound) is a compound containing a transition metal belonging to Groups 4 to 6 of the periodic table and at least one conjugated five-membered ring ligand. Preferred as such metallocene transition metal compounds are compounds represented by the following general formulas (7), (8), (9) and (10).

[0022]

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However, A and A 'are conjugated five-membered ring ligands (A and A' may be the same or different in the same compound), and Q is two conjugated five-membered ring ligands. Z represents a nitrogen atom, an oxygen atom, a silicon atom, a phosphorus atom or a sulfur atom-containing ligand, a hydrogen atom, a halogen atom or a hydrocarbon group bonded to M, 'Is any position of the conjugated five-membered ring ligand and Z'
Z ′ is a ligand containing a nitrogen atom, oxygen atom, silicon atom, phosphorus atom or sulfur atom or a divalent hydrocarbon group bonded to M and Q ′.
M is a metal atom selected from Groups 4 to 6 of the periodic table, and X and Y are a hydrogen atom, a halogen atom,
A hydrocarbon group, an alkoxy group, an amino group, a phosphorus-containing hydrocarbon group and a silicon-containing hydrocarbon group are respectively shown.

A and A 'are conjugated five-membered ring ligands,
As described above, these may be the same or different in the same compound. Representative examples of the conjugated five-membered ring ligand (A and A ') include a conjugated five-membered ring ligand, that is, a cyclopentadienyl group. This cyclopentadienyl group has 5 hydrogen atoms.
Or a derivative thereof (C ₅ H ₅ ) or a derivative thereof, that is, a compound in which some of the hydrogen atoms are substituted with a substituent. Examples of the substituent include a hydrocarbon group having 1 to 20, preferably 1 to 12 carbon atoms, and the hydrocarbon group is bonded to a cyclopentadienyl group as a monovalent group. May form a ring together with a part of the cyclopentadienyl group as a divalent group. A representative example of the latter is one in which a divalent substituent shares two adjacent carbon atoms of a cyclopentadienyl group to form a fused six-membered ring, that is, an indenyl group or a fluorenyl group.

That is, conjugated five-membered ring ligands (A and A ')
A typical example of is a substituted or unsubstituted cyclopentadienyl
Group, indenyl group or fluorenyl group
it can. As a substituent on the cyclopentadienyl group
Is 1 to 20, preferably 1 to 12 carbon atoms
In addition to hydrocarbon groups, halogen groups (eg, fluorine, salt
, Bromine), alkoxy group (for example, having 1 to 12 carbon atoms)
), Silicon-containing hydrocarbon groups (for example, a silicon atom
"-Si (R¹ ) (R^Two ) (R^Three Carbon source)
A phosphorus-containing hydrocarbon group (e.g.,
Atom to "-P (R ¹ ) (R^Two Carbon atoms in the form
Groups of formulas 1 to 18), nitrogen-containing hydrocarbon groups (for example, nitrogen
The atom is represented by -N (R¹ ) (R^Two ) ”)
1-18) or a boron-containing hydrocarbon group (eg,
For example, if the boron atom is represented by "-B (R¹ ) (R^Two) "
A group having 1 to 18 carbon atoms). When these substituents are
When there are a number, each substituent is the same or different
May be.

Q is a bonding group bridging any position between the two conjugated five-membered ring ligands, and Q 'is a bonding group bridging any position of the conjugated five-membered ligand and Z. Respectively. Q
Examples of Q and Q 'include (a) an alkylene group having 1 to 20 carbon atoms such as a methylene group, an ethylene group, an isopropylene group, a phenylmethylmethylene group, a diphenylmethylene group, a cyclohexylene group, and a (b) silylene group. , A dimethylsilylene group, a phenylmethylsilylene group, a diphenylsilylene group, a disilylene group, a silylene group such as a tetramethyldisilylene group, (c) a hydrocarbon group containing germanium, phosphorus, nitrogen, boron or aluminum (specifically, (CH ₃ ) ₂ Ge group, (C ₆ H ₅ ) ₂ Ge group, (C
H ₃ ) P group, (C ₆ H ₅ ) P group, (C ₄ H ₉ ) N group,
(C ₆ H ₅ ) N group, (CH ₃ ) B group, (C ₄ H ₉ ) B
Group, (C ₆ H ₅ ) B group, (C ₆ H ₅ ) Al group, (CH ₃
O) Al group etc.). Preferred are alkylene and silylene groups.

M is a metal atom selected from Groups 4 to 6 of the periodic table, preferably a Group 4 atom of the periodic table, specifically, titanium, zirconium, hafnium and the like. Particularly, zirconium is preferable. Z is a ligand, hydrogen atom, halogen atom or hydrocarbon group containing a nitrogen atom, oxygen atom, silicon atom, phosphorus atom or sulfur atom bonded to M. Specific examples of preferred Z include oxygen (-O-), sulfur (-S-), and carbon atoms having 1 to 2 carbon atoms.
0, preferably 1 to 10 alkoxy groups, 1 carbon atom
-20, preferably 1-12 thioalkoxy groups, 1-40 carbon atoms, preferably 1-18 silicon-containing hydrocarbon groups, 1-40 carbon atoms, preferably 1-18 nitrogen-containing hydrocarbon groups Having 1 to 40 carbon atoms, preferably 1
~ 18 phosphorus-containing hydrocarbon groups, hydrogen atoms, chlorine, bromine,
It is a hydrocarbon group having 1 to 20 carbon atoms.

X and Y each represent hydrogen, a halogen group, a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms;
C1-20, preferably C1-10 alkoxy, amino, C1-20, preferably 1-1
A phosphorus-containing hydrocarbon group (e.g., diphenylphosphine group or the like) having 2 or 1 to 20 carbon atoms, preferably 1
To 12 silicon-containing hydrocarbon groups (e.g., trimethylsilyl group, bis (trimethylsilyl) methyl group, etc.).
X and Y may be the same or different. Among these, halogen groups and carbon atom groups (particularly those having 1 to 8 carbon atoms)
And an amino group are preferred. Accordingly, among the compounds represented by the general formulas (5) to (8), which are preferable as the component [A] of the olefin polymerization catalyst used in the present invention, particularly preferable ones have the following substituents.

A, A '= cyclopentadienyl group, n-
Butyl-cyclopentadienyl group, dimethyl-cyclopentadienyl group, diethyl-cyclopentadienyl group,
Ethyl-n-butyl-cyclopentadienyl group, ethyl-methyl-cyclopentadienyl group, n-butyl-methyl-cyclopentadienyl group, indenyl group, 2-methyl-indenyl group, 2-methyl-4- Phenylindenyl group, tetrahydroindenyl group, 2-methyl-tetrahydroindenyl group, 2-methyl-benzoindenyl group Q, Q '= ethylene group, dimethylsilylene group, isopropylidene group Z = t-butylamide group, phenyl Amide group, cyclohexylamide group M = Group 4 transition metal X, Y = Chlorine, methyl group, diethylamino group

In the present invention, the component [A] may be a mixture of two or more compounds. Taking the case where M is zirconium as an example, a specific example of this transition metal compound is as follows. (A) a compound represented by the general formula (7), that is, a compound having no group Q and having two conjugated five-membered ring ligands (1) bis (cyclopentadienyl) zirconium dichloride (2) bis ( Methylcyclopentadienyl) zirconium dichloride (3) bis (dimethylcyclopentadienyl) zirconium dichloride (4) bis (trimethylcyclopentadienyl) zirconium dichloride (5) bis (tetramethylcyclopentadienyl) zirconium dichloride (6 ) Bis (pentamethylcyclopentadienyl) zirconium dichloride (7) bis (n-butylcyclopentadienyl) zirconium dichloride (8) bis (tert-butylcyclopentadienyl)
Zirconium dichloride (9) Bis (ethyl-n-butyl-cyclopentadienyl) zirconium dichloride (10) Bis (ethyl-methyl-cyclopentadienyl) zirconium dichloride

(11) bis (n-butyl-methyl-cyclopentadienyl) zirconium dichloride (12) (cyclopentadienyl) (n-butyl-cyclopentadienyl) zirconium dichloride (13) (cyclopentadienyl ) (Ethyl-methyl-
(Cyclopentadienyl) zirconium dichloride (14) (n-butylcyclopentadienyl) (dimethylcyclopentadienyl) zirconium dichloride (15) bis (indenyl) zirconium dichloride (16) bis (tetrahydroindenyl) zirconium dichloride (17 ) Bis (2-methylindenyl) zirconium dichloride (18) bis (2-methyltetrahydroindenyl) zirconium dichloride (19) bis (fluorenyl) zirconium dichloride (20) bis (cyclopentadienyl) zirconium monochloride monohydride

(21) bis (cyclopentadienyl) methyl zirconium monochloride (22) bis (cyclopentadienyl) ethyl zirconium monochloride (23) bis (cyclopentadienyl) phenyl zirconium monochloride (24) bis ( Cyclopentadienyl) zirconium dimethyl (25) bis (cyclopentadienyl) zirconium diphenyl (26) bis (cyclopentadienyl) zirconium dineopentyl (27) bis (cyclopentadienyl) zirconium dihydride (28) ( Cyclopentadienyl) (indenyl) zirconium dichloride (29) (cyclopentadienyl) (fluorenyl) zirconium dichloride

(B) Compound represented by general formula (8) (b-1) Compound having a bonding group Q = alkylene group (1) methylenebis (indenyl) zirconium dichloride (2) ethylenebis (indenyl) zirconium dichloride ( 3) Ethylene bis (indenyl) zirconium monochloride monohydride (4) Ethylene bis (indenyl) methyl zirconium monochloride (5) Ethylene bis (indenyl) zirconium monomethoxy monochloride (6) Ethylene bis (indenyl) zirconium diethoxide ( 7) Ethylene bis (indenyl) zirconium dimethyl (8) Ethylene bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride (9) Ethylene bis (2-methylindenyl) zirconium dichloride (10) Ethyl Nbisu (2-ethyl-indenyl) zirconium dichloride (11) ethylenebis (2,4-dimethyl-indenyl)
Zirconium dichloride (12) Ethylene (2,4-dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl)
Zirconium dichloride (13) Ethylene (2-methyl-4-tert-butylcyclopentadienyl) (3'-tert-butyl-
5'-methylcyclopentadienyl) zirconium dichloride (14) ethylene (2,3,5-trimethylcyclopentadienyl) (2 ', 4', 5'-trimethylcyclopentadienyl) zirconium dichloride (15) ethylene -1,2-bis (4-indenyl) zirconium dichloride (16) ethylene-1,2-bis [4- (2,7-dimethylindenyl)] zirconium dichloride (17) ethylene-1,2-bis (4 -Phenylindenyl) zirconium dichloride (18) isopropylidenebis (indenyl) zirconium dichloride (19) isopropylidene (2,4-dimethylcyclopentadienyl) (3 ', 5'-dimethylpentadienyl) zirconium dichloride (20 ) Ethylene bis (indenyl) zirconium Mumonochloride monohydride

(21) Methylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dichloride (22) Methylene (cyclopentadienyl) (3,4-
Dimethylcyclopentadienyl) zirconium monochloride monohydride (23) methylene (cyclopentadienyl) (3,4-
Dimethylcyclopentadienyl) zirconium dimethyl (24) methylene (cyclopentadienyl) (3,4-
Dimethylcyclopentadienyl) zirconium diphenyl (25) methylene (cyclopentadienyl) (trimethylcyclopentadienyl) zirconium dichloride (26) methylene (cyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride (27) Isopropylidene (cyclopentadienyl)
(3,4-dimethylcyclopentadienyl) zirconium dichloride (28) isopropylidene (cyclopentadienyl)
(2,3,4,5-tetramethylcyclopentadienyl) zirconium dichloride (29) isopropylidene (cyclopentadienyl)
(3-methylindenyl) zirconium dichloride (30) isopropylidene (cyclopentadienyl)
(Fluorenyl) zirconium dichloride

(31) isopropylidene (2-methylcyclopentadienyl) (fluorenyl) zirconium dichloride (32) isopropylidene (3-tert-butylcyclopentadienyl) (fluorenyl) zirconium dichloride (33) isopropylidene (2) , 5-Dimethylcyclopentadienyl) (3 ', 4'-dimethylcyclopentadienyl) zirconium dichloride (34) Isopropylidene (2,5-dimethylcyclopentadienyl) (fluorenyl) zirconium dichloride (35) ethylene ( Cyclopentadienyl) (3,5-
Dimethylpentadienyl) zirconium dichloride (36) Ethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride (37) Ethylene (2,5-dimethylcyclopentadienyl) (fluorenyl) zirconium dichloride (38) Ethylene (2.5) -Diethylcyclopentadienyl) (fluorenyl) zirconium dichloride (39) diphenylmethylene (cyclopentadienyl)
(3,4-diethylcyclopentadienyl) zirconium dichloride (40) diphenylmethylene (cyclopentadienyl)
(3,4-diethylcyclopentadienyl) zirconium dichloride (41) cyclohexylidene (cyclopentadienyl)
(Fluorenyl) zirconium dichloride (42) cyclohexylidene (2,5-dimethylcyclopentadienyl) (3 ', 4'-dimethylcyclopentadienyl) zirconium dichloride

(B-2) Q = silylene group (1) dimethylsilylenebis (indenyl) zirconium dichloride (2) dimethylsilylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride (3) dimethyl Silylene bis (2-methylindenyl)
Zirconium dichloride (4) Dimethylsilylene bis (2,4-dimethylindenyl) zirconium dichloride, (5) Dimethylsilylene bis (2-methyl-4,5,
(6,7-tetrahydroindenyl) zirconium dichloride, (6) dimethylsilylenebis (2,4-dimethylcyclopentadienyl) (3 ′, 5′-dimethylcyclopentadienyl) zirconium dichloride, (7) dimethylsilylenebis (2-methyl-4,5-benzoindenyl) zirconium dichloride (8) dimethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride (9) dimethylsilylenebis (2-methyl-4,4-dimethyl -4,5,6,7-tetrahydro-4-silinedenyl) zirconium dichloride, (10) dimethylsilylenebis [4- (2-phenylindenyl)] zirconium dichloride

(11) dimethylsilylenebis [4- (2
-Tert-butylindenyl)] zirconium dichloride (12) dimethylsilylenebis [4- (2-phenyl-
3-methylindenyl)] zirconium dichloride (13) phenylmethylsilylenebis (indenyl) zirconium dichloride (14) phenylmethylsilylenebis (4,5,6,7
-Tetrahydroindenyl) zirconium dichloride (15) phenylmethylsilylene (2,4-dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl) zirconium dichloride (16) phenylmethylsilylene (2,3 5-Silimethylcyclopentadienyl) (2 ', 4', 5'-trimethylcyclopentadienyl) zirconium dichloride (17) phenylmethylsilylenebis (tetramethylcyclopentadienyl) zirconium dichloride (18) diphenylsilylenebis (Indenyl) zirconium dichloride (19) tetramethyldisilylenebis (indenyl) zirconium dichloride (20) tetramethyldisilylenebis (cyclopentadienyl) zirconium dichloride

(21) Tetramethyldisilylene (3-methylcyclopentadienyl) (indenyl) zirconium dichloride (22) Dimethylsilylene (cyclopentadienyl)
(3,4-dimethylcyclopentadienyl) zirconium dichloride (23) dimethylsilylene (cyclopentadienyl)
(Trimethylcyclopentadienyl) zirconium dichloride (24) dimethylsilylene (cyclopentadienyl)
(Tetralimethylcyclopentadienyl) zirconium dichloride (25) dimethylsilylene (cyclopentadienyl)
(3,4-diethylcyclopentadienyl) zirconium dichloride (26) dimethylsilylene (cyclopentadienyl)
(Triethylcyclopentadienyl) zirconium dichloride (27) dimethylsilylene (cyclopentadienyl)
(Tetraethylcyclopentadienyl) zirconium dichloride (28) dimethylsilylene (cyclopentadienyl)
(Fluorenyl) zirconium dichloride (29) Dimethylsilylene (3-tert-butyl-cyclopentadienyl) (fluorenyl) zirconium dichloride (30) Dimethylsilylene (cyclopentadienyl)
(2,7-di-tert-butylfluorenyl) zirconium dichloride

(31) Dimethylsilylene (cyclopentadienyl) (octahydrofluorenyl) zirconium dichloride (32) Dimethylsilylene (2-methylcyclopentadienyl) (fluorenyl) zirconium dichloride (33) Dimethylsilylene (2, 5-dimethylcyclopentadienyl) (fluorenyl) zirconium dichloride (34) dimethylsilylene (2-ethylcyclopentadienyl) (fluorenyl) zirconium dichloride (35) dimethylsilylene (2,5-diethylcyclopentadienyl) (fluorenyl ) Zirconium dichloride (36) dimethylsilylene (2-methylcyclopentadienyl) (2 ', 7'-di-tert-butylfluorenyl) zirconium dichloride (37) dimethylsilylene (2 5-dimethylcyclopentadienyl) (2 ', 7'-di-tert-butylfluorenyl) zirconium dichloride (38) dimethylsilylene (2-ethylcyclopentadienyl) (2', 7'-di-tert -Butylfluorenyl) zirconium dichloride (39) dimethylsilylene (diethylcyclopentadienyl) (2 ', 7'-di-tert-butylfluorenyl) zirconium dichloride (40) dimethylsilylene (diethylcyclopentadienyl) (Octahydrofluorenyl) zirconium dichloride

(41) Dimethylsilylene (dimethylcyclopentadienyl) (octahydrofluorenyl) zirconium dichloride (42) Dimethylsilylene (ethylcyclopentadienyl) (octahydrofluorenyl) zirconium dichloride (43) Dimethylsilylene (Diethylcyclopentadienyl) (octahydrofluorenyl) zirconium dichloride

(B-3) Q = having a hydrocarbon group containing germanium, phosphorus, nitrogen, boron or aluminum (1) dimethylgermanium bis (indenyl) zirconium dichloride (2) dimethylgermanium (cyclopentadienyl)
(Fluorenyl) zirconium dichloride (3) methyl aluminum bis (indenyl) zirconium dichloride (4) phenyl aluminum bis (indenyl) zirconium dichloride (5) phenylphosphinobis (indenyl) zirconium dichloride (6) ethylboranobis (indenyl) zirconium dichloride (7) ) Phenylaminobis (indenyl) zirconium dichloride (8) Phenylamino (cyclopentadienyl) (fluorenyl) zirconium dichloride

(C) a compound represented by the general formula (9), that is, a compound having no binding group Q 'and having one conjugated five-membered ring ligand (1) pentamethylcyclopentadienyl-bis (Phenyl) aminozirconium dichloride (2) indenyl-bis (phenyl) aminozirconium dichloride (3) pentamethylcyclopentadienyl-bis (trimethylsilyl) aminozirconium dichloride (4) pentamethylcyclopentadienylphenoxyzirconium dichloride (5) Cyclopentadienyl zirconium trichloride (6) pentamethylcyclopentadienyl zirconium trichloride (7) cyclopentadienyl zirconium benzyl dichloride (8) cyclopentadienyl zirconium dichlorohydride (9) cyclopentadie Nil zirconium triethoxide

(D) A compound represented by the general formula (10), that is, a compound having one conjugated five-membered ring ligand bridged by a bonding group Q '. (1) Dimethylsilylene (tetramethylcyclopentadienyl) Phenylamidozirconium dichloride (2) Dimethylsilylene (tetramethylcyclopentadienyl) tert-butylamidozirconium dichloride (3) Dimethylsilylene (indenyl) cyclohexylamidozirconium dichloride (4) Dimethylsilylene (tetrahydroindenyl) decylamidozirconium dichloride 5) Dimethylsilylene (tetrahydroindenyl)
((Trimethylsilyl) amino) zirconium dichloride (6) dimethylgermane (tetramethylcyclopentadienyl) (phenyl) aminozirconium dichloride

(E) Further, compounds obtained by replacing chlorine in the compounds (a) to (d) with bromine, iodine, a hydride group, a methyl group, a phenyl group and the like can also be used. In the above examples, disubstituted cyclopentadienyl ring includes 1,2- and 1,3-substituted, and tri-substituted is 1,2,3- and 1,2,4-substituted. including. Furthermore,
In the present invention, as the component [A], the zirconium compound exemplified in the above (a) to (e), in which the central metal is changed from zirconium to titanium, hafnium, niobium, molybdenum, tungsten or the like, is a metal belonging to Groups 3 to 6 of the periodic table. Can also be used.

Of these, preferred are zirconium compounds, hafnium compounds and titanium compounds. Even more preferred are zirconium compounds. In particular, the number of substituents of the conjugated five-membered ring ligand of the metallocene-based transition metal compound is 2 or less, or the above-mentioned binding group Q or Q 'is not included, that is, the conjugated five-membered ring ligand is The non-crosslinked type is preferable because the number of internal unsaturated bonds, particularly trisubstituted unsaturated bonds, increases.

The compound used as the component [B] in the present invention includes (a) an aluminum oxy compound, (b)
It is at least one compound selected from the group consisting of Lewis acids and (c) ionic compounds capable of reacting with metallocene compounds to convert them into cations. As the aluminum oxy compound, a compound represented by the general formula (R-Al-
O) _n or a cyclic compound represented by the general formula R (R-
A chain compound represented by Al—O) _n AlR ₂ is used. Here, R is usually an alkyl group having 1 to 8 carbon atoms, and n is an integer of about 1 to 20. Such a compound can be obtained by contacting a solution of a trialkylaluminum in an organic solvent (for example, benzene) with water, or by contacting a trialkylaluminum with a salt hydrate such as copper sulfate hydrate.

As the Lewis acid, a Mg-containing Lewis acid, Al
-Containing Lewis acids, B-containing Lewis acids and the like.
Containing Lewis acids are preferred. Specific examples of the B-containing Lewis acid include trifluoroborane, triphenylborane, tris (pentafluorophenyl) borane and the like, and tris (pentafluorophenyl) borane is particularly preferably used. An ionic compound capable of reacting with a metallocene compound to convert it into a cation is a salt composed of a cationic compound and an anionic compound, and cationizing the metallocene compound by reacting with the metallocene compound, And an anion moiety form an ion pair to stabilize the cation.

Among these compounds, ionic compounds containing a boron atom are preferably used, such as triphenylcarbeniumtetrakis (bentafluorophenyl) borate and N, N-dimethylaniliniumtetrakis (pentafluorophenyl). Examples thereof include borate and ferrocenium tetra (pentafluorophenyl) borate, and N, N-dimethylanilinium tetrakispentafluorophenyl borate is particularly preferable. The ion-exchangeable phyllosilicate used as the component [C] in the present invention is a silicate compound having a crystal structure in which planes formed by ionic bonds and the like are stacked in parallel with a weak bonding force, It means that the contained ions are exchangeable. Most ion-exchanged layered silicates occur naturally primarily as a major component of clay minerals, but may be artificially synthesized.

Specific examples of ion-exchangeable layered silicates include, for example, dickite, nacrite, kaolinite, and the like described in “Clay Mineralogy” by Haruo Shiramizu (published by Asakura Shoten (1995)). Anoxite, metahalloysite, kaolin group such as halloysite, serpentine group such as chrysotile, lizardite, antigolite, montmorillonite, zauconite, beidellite, nontronite, saponite, teniolite, hectorite,
Examples include smectites such as stevensite, vermiculites such as vermiculite, mica, illite, sericite, mica such as marine green stone, attapulgite, sepiolite, palygorskite, bentonite, pyrophyllite, talc, and chlorite. These may form a mixed layer. Among these, smectites, vermiculites, and micas such as montmorillonite, zauconite, beidellite, nontronite, saponite, hectorite, stevensite, bentonite, and teniolite are preferred.

It is also preferable to subject this component [C] to a chemical treatment. As the chemical treatment, any of a surface treatment for removing impurities and the like adhering to the surface and a treatment that affects the crystal structure of the clay can be used. Specifically, acid treatment, alkali treatment, salt treatment, organic matter treatment and the like can be mentioned. The acid treatment removes impurities on the surface and increases the surface area by eluting cations such as Al, Fe, and Mg in the crystal structure. Alkali treatment destroys the crystal structure of the clay, resulting in a change in the structure of the clay. In the salt treatment and the organic substance treatment, an ion complex, a molecular complex, an organic derivative, and the like are formed, and the surface area and the interlayer distance can be changed. By utilizing the ion exchange property and replacing the exchangeable ions between the layers with another large bulky ion (often called a pillar), it is also possible to obtain a layered material in which the layers are expanded.

Further, an intercalation for introducing another substance between the layers may be performed. Guest compounds to be intercalated include cationic inorganic compounds such as TiCl ₄ and ZrCl ₄ , Ti (OR) ₄ , Zr (OR)
₄ , PO (OR) ₃ , B (OR) ₃ (R is an alkyl group,
Metal alcoholates such as aryl groups, etc.), [Al ₁₃ O ₄
(OH) ₂₄ ] ⁷⁺ , [Zr ₄ (OH) ₁₄ ] ²⁺ , [Fe ₃ O
(OCOCH ₃ ) ₆ ] ^{+ and the} like. These compounds can be used alone or
More than one kind may be used together. When intercalating these compounds, Si (OR) ₄ ,
A polymer obtained by hydrolyzing a metal alcoholate such as Al (OR) ₃ and Ge (OR) _{4, and} a colloidal inorganic compound such as SiO ₂ can also coexist. In addition, in order to obtain the above-mentioned pillars, there is also a method in which the above hydroxide ions are intercalated between layers and then heated and dehydrated to generate oxides.

Preferred among the above chemical treatments are:
And salt treatment and / or acid treatment. salts
Treatment and / or acid treatment to make this ion exchangeable
The acid strength of the layered silicate can be varied. Also, salt
Processing forms ionic complexes, molecular complexes, organic derivatives, etc.
Surface area and interlayer distance can be changed. In the present invention
Of the ion-exchange layered casing before being treated with salts.
30% or more of the exchangeable cation contained in the phosphate is preferable.
At least 40%, particularly preferably at least 60%,
Ion exchange with cations dissociated from the salts shown
preferable. Salt treatment for such ion exchange
As the salts used in the above, there are atoms of Groups 2 to 14
A cation containing at least one atom selected from the group consisting of
Compounds containing ions are preferred. Specifically, CaC
l_Two , CaSO_Four , CaC_Two O_Four, Ca (NO_Three )_Two ,
Ca_Three (C₆ H_Five O₇ )_Two , MgCl_Two , MgBr_Two ,
MgSO_Four , Mg_Three (PO_Four )_Two , Mg (ClO_Four )
_Two , MgC_Two O_Four , Mg (NO_Three )_Two , Mg (OOCC
H_Three )_Two , MgC_Four H_Four O_Four , Sc (OOCCH_Three )
_Two , Sc_Two (CO_Three )_Three , Sc_Two (C_Two O_Four )_Three , Sc
(NO_Three )_Three , Sc_Two (SO_Four )_Three , ScF_Three , ScC
l_Three , ScBr_Three , ScI_Three , Y (OOCCH_Three)_Three ,
Y (CH_Three COCHCOCH_Three )_Three , Y_Two (CO_Three )
_Three , Y_Two (C_Two O_Four)_Three , Y (NO_Three )_Three , Y (ClO_Four
 )_Three , YPO_Four , Y_Two (SO_Four )_Three , YF _Three , YCl_Three
 , La (OOCCH_Three )_Three , La (CH_Three COCHC
OCH_Three )_Three, La_Two (CO_Three )_Three , La (NO_Three )
_Three , La (ClO_Four )_Three , La_Two (C_TwoO_Four )_Three , La
PO_Four , La_Two (SO_Four )_Three , LaF_Three , LaCl_Three ,
LaBr _Three , LaI_Three , Sm (OOCCH_Three )_Three , Sm
(CH_Three COCHCOCH_Three )_Three, Sm_Two (CO_Three )
_Three , Sm (NO_Three )_Three , Sm (ClO_Four )_Three , Sm_Two 
(C_TwoO_Four )_Three , Sm_Two (SO_Four )_Three , SmF_Three , Sm
Cl_Three , SmI_Three , Yb (OOCCH_Three )_Three , Yb (N
O_Three )_Three , Yb (ClO_Four )_Three , Yb_Two (C_Two O
_Four )_Three, Yb_Two (SO_Four )_Three , YbF_Three , YbCl_Three ,
TiF_Four , TiCl_Four , TiBr_Four , TiI_Four , TiO
Cl_Two , Ti (SO_Four )_Two , Ti (NO_Three )_Four , TiO
(NO_Three )_Two , Ti_Three (PO_Four )_Four , Ti (ClO_Four )
_Four , Ti (CO_Three )_Two , Ti (OCOH)_Four , Ti (O
COCH_Three )_Four , Ti (OCOC_Two H_Five )_Four , Ti (O
COC_Three H₇ )_Four , Ti ((COO)_Two )_Two , Ti (C
H_Two (COO)_Two)_Two , TiBrCl_Three , TiF_Three , T
iCl_Three , TiBr_Three , TiI_Three , Ti (NO_Three )_Three ,
Ti (ClO_Four )_Three , Zr (OOCCH_Three )_Four , Zr
(CO_Three )_Two, Zr (NO_Three )_Four , Zr (SO_Four )_Two ,
ZrF_Four , ZrCl_Four , ZrBr_Four , ZrI_Four , ZrO
Cl_Two , ZrO (NO_Three )_Two , ZrO (ClO_Four )_Two ,
ZrO (SO_Four ), Hf (OOCCH)_Three )_Four , Hf
(CO_Three )_Two , Hf (NO_Three )_Four, Hf (SO_Four )_Two ,
HfOCl_Two , HfF_Four , HfCl_Four , HfBr_Four , H
fI_Four , V (CH_Three COCHCOCH_Three )_Three , VOSO
_Four , VOCl_Three , VCl_Three, VCl_Four , VBr_Three , Nb
(CH_Three COCHCOCH_Three )_Three , Nb_Two (CO_Three)
_Five , Nb (NO_Three )_Five , Nb_Two (SO_Four )_Five , NbF
_Three , NbCl_Five , NbBr_Three , NbI_Five , Ta (OOC
CH_Three )_Five , Ta_Two (CO_Three )_Five , Ta (NO_Three)_Five ,
Ta_Two (SO_Four )_Five , TaF_Five , TaCl_Five , TaBr
_Five , TaI_Five , Cr (CH_Three COCHCOCH_Three )_Three ,
Cr (OOCH)_Two OH, Cr (NO_Three ) _Three , Cr (C
10_Four )_Three , CrPO_Four , Cr_Two (SO_Four )_Three , CrO
_Two Cl_Three , CrF_Three , CrCl_Three , CrBr_Three , CrI
_Three , MoOCl_Four , MoCl_Three , MoCl_Four , MoCl
_Five , MoF₆ , MoI_Two , WCl_Four , WCl₆ , WF
₆ , WBr_Five , Mn (OOCCH_Three )_Three , Mn (CH_Three 
COCHCOCH_Three )_Two , MnCO_Three , Mn (NO_Three )
_Two , MnO, Mn (ClO_Four )_Two , MnF_Two , MnCl
_Two , MnBr_Two , MnI_Two , Fe (OOCCH_Three )_Two ,
Fe (CH_Three COCHCOCH_Three )_Three , FeCO_Three , F
e (NO_Three )_Three , Fe (ClO_Four )_Three , FePO _Four , F
eSO_Four , Fe_Two (SO_Four )_Three , FeF_Three , FeCl
_Three , FeBr_Three , FeI_Two , FeC₆ H_Five O₇ , Fe
(NO_Three )_Two , Co (OOCCH_Three )_Two , Co (CH_Three 
COCHCOCH_Three )_Three , CoCO_Three , Co (NO_Three )
_Two , CoC_Two O _Four , Co (ClO_Four )_Two , Co_Three (PO
_Four )_Two , CoSO_Four , CoF_Two , CoCI_Two , CoBr
_Two , Col_Two , NiCO_Three , Ni (NO_Three )_Two , NiC
_Two O_Four , Ni (ClO_Four )_Two , NiSO_Four , NiCl
_Two , NiBr_Two , Pb (OOCCH _Three )_Two , Pb (O
OCCH_Three )_Four , PbCO_Three , PbCO_Three , Pb (NO
_Three ) _Two, PbHPO_Four , Pb (ClO_Four )_Two , PbF
_Two , PbI_Two , PbSO_Four , PbCl_Two , PbBr_Two ,
CuCl_Two , CuBr_Two , Cu (NO_Three )_Two , CuC_Two
O_Four , Cu (ClO_Four )_Two , CuSO_Four , Cu (OOC
CH_Three )_Two , Zn (OOCCH_Three )_Two , Zn (CH_Three C
OCHCOCH_Three )_Two , Zn (OOCH_Three )_Two , ZnC
O_Three , Zn (NO_Three )_Two , Zn (ClO_Four )_Two , Zn_Three 
(PO_Four )_Two , ZnSO_Four , ZnF_Two , ZnCI_Two , Z
nBr_Two , ZnI_Two , Cd (OOCCH_Three)_Two , Cd
(CH_Three COCHCOCH_Three )_Two , Cd (OCOCH_Two 
CH_Three )_Two , Cd (NO_Three )_Two , Cd (ClO_Four )_Two ,
CdSO_Four , CdF_Two , CdCl_Two , CdBr_Two , Cd
I_Two , AlF_Three , AlCl_Three , AlBr_Three , AlI_Three ,
Al_Two(SO_Four )_Three , Al_Two (C_Two O_Four )_Three , Al (C
H_Three COCHCOCH_Three )_Three , Al (NO_Three )_Three , Al
PO_Four , GeCl_Four , GeBr_Four , GeI_Four , Sn (O
OCCH_Three )_Four , Sn (SO_Four )_Two , SnF_Four , SnC
l_Four , SnBr_Four , SnI_Four Etc. can be exemplified.

Of these, particularly preferred are cations of transition metals of Groups 4, 5, and 6 of the periodic table, ie, T
i ²⁺ , Ti ³⁺ , Ti ⁴⁺ , Zr ²⁺ , Zr ³⁺ , Zr ⁴⁺ , Hf
^{2+, Hf 3+, Hf 4+,} V 2+, V 3+, V 4+, V 5+, N
b ²⁺ , Nb ³⁺ , Nb ⁴⁺ , Nb ⁵⁺ , Ta ²⁺ , Ta ³⁺ , Ta
⁴⁺ , ^{Ta5 +} , ^{Cr2 +} , Cr3 ⁺ , Cr4 ⁺ , Cr5 ⁺ , C
r ⁶⁺ , Mo ²⁺ , Mo ³⁺ , Mo ⁴⁺ , Mo ⁵⁺ , Mo ⁶⁺ ,
Salts containing W ²⁺ , W ³⁺ , W ⁴⁺ , W ⁵⁺ , W ⁶⁺ .
These salts can be used alone or in combination of two or more.
And / or may be used continuously.

As the acid used in the acid treatment, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, oxalic acid and the like are preferable. The salts and acids used in the treatment may be a mixture of two or more. When the salt treatment and the acid treatment are combined, the salt treatment and the acid treatment may be performed simultaneously or before and after. The conditions of the salt treatment and the acid treatment are not particularly limited, but usually, the concentration of the salt and the acid is 0.1 to 30% by weight, the treatment temperature is room temperature to the boiling point, and the treatment time is 5 minutes to 24 hours. It is preferable to perform the selection under conditions that elute at least a part of the substance constituting the ion-exchange layered silicate.
Further, salts and acids are generally used in an aqueous solution,
It is not particularly limited to this.

The particle properties of the component [C] may be controlled by granulation, sizing, fractionation and the like, and the method may be appropriately selected according to the purpose. For example, as the granulation method, spray granulation method, tumbling granulation method, compression granulation method, stirring granulation method, briquetting method, compacting method, extrusion granulation method, fluidized bed granulation method,
Examples include an emulsion granulation method and a submerged granulation method. Particularly preferred granulation methods are spray granulation, tumbling granulation and compression granulation.

The component [C] usually contains adsorbed water and interlayer water. The adsorbed water is water adsorbed on the surface of the ion-exchangeable layered silicate or the crystal fracture surface, and the interlayer water is water existing between the layers of the crystal. When the component [C] is used, these adsorbed water and / or interlayer water are removed by heat treatment such as heat dehydration, heat dehydration under gas flow, heat dehydration under reduced pressure, and azeotropic dehydration with an organic solvent. It is desirable to keep.

The catalyst component consisting of component [A] and component [C] usually exhibits olefin polymerization activity as it is, but in some cases, a more active olefin polymerization catalyst can be obtained by further combining an organoaluminum compound. Can be.

Examples of the organoaluminum compound used here include trialkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, diethylaluminum hydride, diisobutylaluminum hydride and the like. Halogen-containing alkyl aluminum such as alkyl aluminum hydride, diethyl aluminum chloride and diisobutyl aluminum chloride, alkyl aluminum alkoxide such as diethyl aluminum methoxide and diisobutyl aluminum methoxide, and alkyl aluminum amide such as diethyl aluminum (diethyl amide) and diisobutyl aluminum (diethyl amide) No. Of these, trialkylaluminums such as triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, and tri-n-hexylaluminum are preferred.

In order to prepare a catalyst from the components [A] and [C] of the catalyst usable in the present invention and the above-mentioned organoaluminum compound, these components may be brought into contact with each other by any method. . The contact method is not particularly limited, but the contact can be performed in the following contact order.

After contacting the components [A] and [C], an organoaluminum compound is added. After the component [A] is brought into contact with the organoaluminum compound, the component [C] is added. After contacting the component [C] with the organoaluminum compound, the component [A] is added. The three components are contacted simultaneously. Contact is made under an inert gas such as nitrogen, pentane, hexane,
It is preferable to carry out the reaction in an inert hydrocarbon solvent such as heptane, toluene and xylene. The contact temperature is between -20 ° C and the boiling point of the solvent, particularly preferably between room temperature and the boiling point of the solvent.

The amount of each component of the catalyst used is the amount of component [C] 1
The component [A] is 0.0001 to 10 mmol, preferably 0.001 to 5 mmol, and the organoaluminum compound is 0.01 to 10000 mmol, preferably 0.1 to 100 mmol per g. The metallocene compound of the component [A] exhibits polymerization activity of an olefin as it is by combining with the layered silicate of the component [C]. However, these components are brought into contact in the presence of an α-olefin, Alternatively, if necessary, by further combining an organic aluminum compound, a so-called α-
A method of performing prepolymerization with an olefin is also suitably employed. This prepolymerization is usually carried out using ethylene, but if necessary, other olefins, for example, propylene,
1-butene, 4-methyl-1-pentene, 3-methyl-
Α-olefins such as 1-pentene, aromatic vinyl monomers such as styrene and α-methylstyrene, or mixtures thereof can be used.

The organoaluminum compound used in the preliminary polymerization may be the same as or different from the above-mentioned organoaluminum compound. Some of the compounds exemplified above may be used in combination. Usually, the amount of the polymer produced by the prepolymerization is 0.001 to 1000 g, preferably 0.01 to 300 g per 1 g of the component [C].
g, more preferably in the range of 0.1 to 300 g.

The prepolymerization method is not particularly limited, but is usually carried out by slurry polymerization in an inert hydrocarbon solvent.
The inert hydrocarbon solvent used at this time is not particularly limited, but, for example, the hydrocarbon solvent used at the time of the above-mentioned contact is suitably used. Although the temperature of the prepolymerization is not particularly limited, it is preferably carried out at a temperature between -20 ° C and 150 ° C. When prepolymerization is carried out using ethylene, the polymerization average molecular weight of the polyethylene is preferably 30,000 or more, particularly preferably 50,000 or more.

The prepolymerization catalyst may be used as a slurry after the completion of the prepolymerization, or may be used after washing with an inert hydrocarbon solvent such as hexane, heptane, benzene, toluene, xylene or the like, if necessary. May be. In addition, a dried powder may be used. The drying conditions at this time are not particularly limited, but preferably the drying is performed at 0 ° C to 100 ° C under reduced pressure or under a flow of a dry inert gas. At the time of preliminary polymerization or after drying, a solid such as a polymer such as polyethylene or polypropylene, or an inorganic oxide such as silica or alumina may coexist or be brought into contact.

The ethylene polymer used in the composition of the present invention is preferably obtained by polymerizing ethylene or a mixture of ethylene and an α-olefin having 3 to 20 carbon atoms using the above catalyst. As the α-olefin used here, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 3-
Examples include vinylcycloalkanes such as methyl-1-pentene, 4-methyl-1-pentene, and vinylcyclohexane, ethylidene norbornene derivatives, styrene, and styrene derivatives. In the case of copolymerization of ethylene and an α-olefin, the α-olefin is preferably copolymerized in an amount of up to 50% by weight, preferably up to 30% by weight, based on ethylene.

The polymerization reaction is carried out with butane, pentane, hexane,
It is preferable to carry out the reaction by a gas phase reaction in the presence or absence of an inert hydrocarbon such as heptane, toluene and cyclohexane and a solvent such as α-olefin. The gas phase polymerization is carried out in a gaseous monomer substantially free of a solvent or the like. The apparatus used for the gas phase polymerization is not particularly limited, but for example, a fluidized bed, a stirred bed, a stirred fluidized bed equipped with a stirrer / mixer, or the like can be used. Certain unsaturated bonds of the present invention tend to be introduced in relatively high concentrations in gas phase polymerizations.

As the polymerization temperature, generally used conditions are applied as they are. That is, the temperature is 30 ° C to 150 ° C, preferably 50 ° C to 100 ° C. The polymerization pressure is usually 1
５０50 kg / cm ² G. The molecular weight is adjusted by a generally used method, but the molecular weight (MFR) is usually adjusted by the hydrogen concentration in the monomer. As the antioxidant used in the ethylene polymer composition of the present invention, an antioxidant usually used for polyolefins may be used. For example, various antioxidants such as phosphorus-based, phenol-based and ionic-based antioxidants can be suitably used.

Examples of the phosphorus-based antioxidants include triphenyl phosphite, diphenyl phosphite, trinonyl phenyl phosphite, distearyl pentaerythritol diphosphite, and 4,4'-butylidenebis (3-methyl-6-t-butyl). Phenylditridecyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, tetrakis (2
4-di-t-butylphenyl) -4,4'-biphenylenediphosphonite and the like, and particularly those having the structure represented by the formula (5) are preferable.

[0069]

Embedded image

Examples of the phenolic antioxidant include 1,
3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene,
2,2'-methylenebis (4-methyl-6-t-butylphenol), pentaerythrityl-tetrakis [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate], octadecyl-3- (3,5-di-
t-butyl-4-hydroxyphenyl) propionate, tris [β- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl-oxyethyl] isocyanurate and the like. Examples of the sulfur-based antioxidant include tetrakis (laurylmercaptopropionyloxymethylene) methane, dilaurylthiodipropionate, and distearylthiodipropionate, and particularly those having a structure represented by the formula (6). Is preferred.

[0071]

Embedded image

The antioxidants may be used alone or in combination of two or more. However, a combination of a phosphorus-based antioxidant and a phenol-based antioxidant, or a combination of a sulfur-based antioxidant and a phenol-based antioxidant may be used. Combinations of antioxidants are preferred. The compounding ratio of the antioxidant in the ethylene-based polymer composition of the present invention is 0.01 to 1.0 part by weight, preferably 0.1 to 1.0 part by weight, based on 100 parts by weight of the ethylene-based polymer component.
0.5 to 0.5 parts by weight.

If the compounding ratio of the antioxidant is less than the above range, there are problems in that gel is frequently generated during molding and the moldability is deteriorated. In addition, when the ratio exceeds the above range, there is a problem that the molded product is easily discolored. The ethylene-based polymer composition of the present invention may contain an ethylene-based polymer such as low-density polyethylene or a resin other than polyethylene such as polypropylene depending on the purpose.

Further, additional components such as a neutralizing agent, an ultraviolet absorber, a lubricant, an antistatic agent, a nucleating agent, an anti-condensation agent, a photosensitizer, and a molecular weight regulator within a range not significantly impairing the effects of the present invention. Agents, coloring agents, impact modifiers, fillers, flame retardants, adhesion improvers, printability improvers, etc., and conversely, light stabilizers and weather resistance improvers to suppress and control the decomposability. Can also be used in combination. The ethylene polymer composition of the present invention can be produced by blending an antioxidant in a desired blending ratio by adding other blending agents as necessary, and then melt-kneading or dry blending. However, in the case of dry blending, it is preferable to use a master batch method for compounding agents such as antioxidants.

The above-mentioned melt-kneading is generally performed by a kneading machine such as a single-screw extruder, a twin-screw extruder, a Banbury mixer, a roll mixer, a Brabender plastograph, and a kneader.
Usually, it is carried out by kneading at a temperature of 170 to 250 ° C and preferably granulation. It is preferable to use a single-screw extruder or a twin-screw extruder as the kneading / granulating method because the components can be dispersed well. The molded article obtained by molding the ethylene polymer composition of the present invention is easily decomposed by exposure to sunlight or ultraviolet light, and thus can be used for applications in which decomposition and disintegration are appropriately controlled and utilized. Such molded articles include packaging films, agricultural films, sheets, trays, etc., collection of difficult-to-recycle applications, fertilizers, coated fertilizers for the purpose of gradually exerting pesticides, etc. After the elapse of the period, a tape for raising seedlings or the like for reducing the strength so as not to hinder the growth of the plant or facilitating the treatment of the branches and vines after harvesting can be exemplified.

As a molding method, an inflation method,
It is not limited to a normal film forming method such as a T-die method, but can be processed into various containers, pipes, tubes, and the like by extrusion molding, hollow molding, injection molding, and the like. Furthermore, a composite film can be formed by extrusion coating or co-extrusion molding. The composition of the present invention can also be used for applications such as steel pipe coating, electric wire coating, and foam molding.

[0077]

The following examples are provided to illustrate the present invention. Therefore, the present invention is not limited by these embodiments unless departing from the gist thereof. The following catalyst synthesis step and polymerization step were all performed in a purified nitrogen atmosphere. The solvent used was dehydrated and purified with Molecular Sheep 4A. The MFR is measured at 190 ° C. using a load of 2.16 kg in accordance with ASTM1238, and the density is measured by heating the strand obtained at the time of MFR measurement at 100 ° C. for 1 hour.
Further, after allowing to cool at room temperature for 1 hour, the measurement was carried out by a density gradient tube method.

The thermal deterioration characteristics were evaluated as follows. The ethylene polymer composition sample was blown molded at a temperature of 180 ° C. and a blow-up ratio of 2.0 to a thickness of 20 μm.
m, a film having a width of 230 mm was prepared, the external appearance was visually observed, and the thermal deterioration characteristics were evaluated in three steps as follows. ：: almost no gel (unmelted material) is observed ：: some gel is observed ×: very many gels are observed The tensile strength at break is based on JIS K6781, and the dumbbell is obtained from the above-mentioned blown film. The film was punched out using a punching die so that the MD direction of the film was parallel to the tensile direction, and the test piece was measured by performing a tensile test.

The evaluation of photodegradability was performed as follows. From the above blown film, JIS K6781
Using a compliant dumbbell punching blade die, punch the film so that the TD direction of the film is parallel to the tensile direction,
A dumbbell-shaped test piece was obtained. The test piece “Standard Sunshine Weather Meter” WE manufactured by Suga Test Instruments Co., Ltd. was set at a black panel temperature of 63 ° C., a sample spray pressure of 1 kg / cm ² , and a precipitation cycle of 12 minutes / 60 minutes.
An accelerated test was performed using the L-SUN-HC type, and after 150, 250 and 350 hours respectively, the test pieces were taken out,
A tensile test was carried out on the test specimen after the accelerated test and on a test specimen which had not been subjected to a weather meter and stored separately, and the tensile elongation at break was measured. It is determined that the smaller the value of the tensile elongation at break is, the more the photolysis has progressed.

Example 1 (1) [Preparation of Layered Silicate Particles] A commercially available swellable synthetic mica (“Somasif ME-100”, manufactured by Corp Chemical Co., Ltd.) (400 g) was treated with a 6.0% by weight aqueous solution of zinc nitrate. It was dispersed in 1.4 liters and stirred at room temperature for 2 hours. This was filtered and washed with deionized water. Water was added to the obtained solid part to prepare a 25% by weight water slurry, which was subjected to a spray drying treatment to obtain spherical particles.

(2) [Preparation of Catalyst Component and Preliminary Polymerization] In a 10 L reactor equipped with a stirrer, 4.4 liters of normal heptane, previously dried under reduced pressure at 200 ° C. for 2 hours, to obtain a layered product obtained in the above (1). 150 g of silicate particles, further 6
Bis (normalbutylcyclopentadienyl) zirconium dichloride dissolved in 00 ml of toluene 12.0
was added and stirred at room temperature for 10 minutes. Subsequently, 24 mmol of triethylaluminum was added, and the temperature of the system was adjusted to 60 ° C. Next, ethylene gas was introduced and the reaction was carried out for 2 hours. The polyethylene produced during this time is 1010
g.

(3) [Ethylene-butene copolymerization] The prepolymerized catalyst 1 obtained in the above (2) was placed in a gas phase reactor forming a fluidized bed with about 1.5 kg of ethylene polymer particles.
15 mg / hr, triethylaluminum 150 mg /
While intermittently supplying hr, a total pressure of 7 kg / cm ² G, an ethylene-butene mixed gas (butene / ethylene = 5 mol)
%) Was passed, and continuous polymerization was carried out at a reaction temperature of 90 ° C. The average polymerization rate was 230 g / hr, and the MFR, density, internal unsaturated bond, and trisubstituted unsaturated bond of the obtained polymer were as shown in Table 1.

(4) [Pelletization, film forming and evaluation] 5 kg of the polymer obtained in the above (3) was used.
Octadecyl-3-antioxidant per 100 parts by weight
(3,5-di-t-butyl-4-hydroxyphenyl)
0.03 parts by weight of propionate and tetrakis (2,4
-Di-t-butylphenyl) -4,4-biphenylenediphosphonite, and 0.03 parts by weight thereof,
Using a 0L super mixer, the rotation speed is 800 rpm
After mixing for 5 minutes, screw diameter 40mmφ, L / D
26 single screw extruder 200 ° C, screw rotation speed 50r
The mixture was melt-kneaded at pm and pelletized.

A pellet having a screw diameter of 40 mmφ,
Using an inflation film molding machine having a die diameter of 75 mmφ and a die width of 3 mm equipped with an L / D24 extruder, temperature 180 ° C., screw rotation speed 50 rpm, blow-up ratio 2.0, take-up speed 17 m / min, frost line height Molded under the condition of 150 mm in width, 230 mm in width and 30 in thickness
A μm blown film was obtained. The formed film was evaluated and measured for thermal degradation characteristics, tensile strength at break, and photodegradability. The results were as shown in Table 1.

<Example 2> The amount of each antioxidant was 0.1
Pelletizing in the same manner as in Example 1 except that
The molding was carried out, and the obtained blown film was evaluated and measured for thermal degradation characteristics, tensile strength at break, and photodegradability. The results were as shown in Table 1.

<Example 3> (1) [Preparation of catalyst component] The layered silicate particles obtained in Example 1 (1) were used, and bis (normalbutylcyclopentadienyl) zirconium dichloride was used instead. A prepolymerized catalyst was prepared in the same manner as in Example 1 (2) except that dimethylsilylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride was used. (2) [Ethylene-butene copolymerization] The composition of the ethylene-butene mixed gas is defined as butene / ethylene =
Gas phase polymerization was carried out in the same manner as in Example 1 (3) except that the amount was 8 mol%. Table 1 shows the MFR, density, internal unsaturated bond, and trisubstituted unsaturated bond of the obtained polymer.

(3) [Pelletization, Film Forming and Evaluation] Pelletization and molding were carried out in the same manner as in Example 1 except that the amount of the antioxidant was each 0.05 parts by weight. With respect to the blown film, evaluation and measurement of thermal degradation characteristics and tensile strength at break and photodegradability evaluation were performed. The results were as shown in Table 1.

<Comparative Example 1> Pelletization and molding were carried out in the same manner as in Example 1 except that no antioxidant was added to the ethylene polymer obtained in Example 1 and thus mixing was not carried out with a super mixer. The obtained blown film was evaluated and measured for thermal degradation characteristics and tensile strength at break, and evaluated for photodegradability. Table 1 shows the results.
As shown in FIG.

<Comparative Example 2> A linear low-density polyethylene “Novatec LL U” commercially available from Nippon Polychem Co., Ltd.
F230 ”, MFR, density, internal unsaturated bond,
The trisubstituted unsaturated bond was measured and the frost line height was set to 18
Except having set it to 0 mm, it shape | molded similarly to Example 1. With respect to the obtained blown film, evaluation and measurement of thermal degradation characteristics and tensile strength at break and photodegradability evaluation were performed. The results were as shown in Table 1.

Comparative Example 3 The MFR, density, internal unsaturated bond, and trisubstituted unsaturated bond of a polyolefin plastomer “Affinity PL1840” commercially available from Dow Chemical Japan were measured, and the frost line height was 210 mm. The molding was performed in the same manner as in Example 1 except that the take-off speed was set to 19 m / min. With respect to the obtained blown film, evaluation and measurement of thermal deterioration characteristics and tensile strength at break, and photodegradability evaluation were performed. Table 1 shows the results.
As shown in FIG.

<Comparative Example 4> A plastomer "EXACT SLP9016" manufactured by Exxon Chemical was subjected to MF
R, density, internal unsaturated bond and tri-substituted unsaturated bond were measured, the frost line height was 230 mm, and the take-off speed was 19
Molding was carried out in the same manner as in Example 1 except that m / min was used. With respect to the obtained blown film, evaluation and measurement of thermal deterioration characteristics and tensile strength at break, and photodegradability evaluation were performed. The results were as shown in Table 1.

<Evaluation of Results> As is clear from Table 1,
There is a remarkable difference in the appearance of the film between Examples 1 to 3 which are the compositions of the present invention and Comparative Example 1 where no antioxidant is added. In addition, comparing Examples 1 to 3 and Comparative Examples 2 to 4, in Comparative Example using a commercially available ethylene polymer, 35
In the 0 hour accelerated test, it can be seen that the degradation progresses only slowly, while the composition of the present invention degrades by 250 hours.

[0093]

[Table 2]

[0094]

According to the present invention, there can be obtained an ethylene polymer composition having excellent photodegradability in which the main chain is easily cut and decomposed by the action of sunlight or artificial ultraviolet rays.
This ethylene-based polymer composition has basically the same practical properties as general ethylene-based polymer compositions conventionally used as packaging materials and molded articles in terms of moldability and appearance and initial physical properties of the molded article. , And deteriorates rapidly after a specific time, so that the load on waste disposal after use is reduced.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (reference) // C08F 4/642 C08F 4/642 10/02 10/02 F term (reference) 4F071 AA15 AA15X AA20X AA21X AA82 AA88 AC11 AC13 AC15 AE05 AF57 AG02 AH01 AH04 BA01 BB09 BC01 4J002 BB031 BB051 BB101 BB151 EJ017 EJ037 EJ047 EV058 EV068 EW066 EW126 FD076 FD077 FD078 GG01 GQ01 4J028 AA01A AB00A AC01A AC10A AC20A AC28A BA03B BB01B BC12B BC13B BC25B BC26B CA24C CA30C EB02 EB04 EB05 EB08 EB09 EB10 EB18 EB21 FA04 GA07 GA08 GA26 4J100 AA02P AA03Q AA04Q AA07Q AA16Q AA17Q AA18Q AA19Q AA20Q AB02Q AS02R AS03R AU21Q CA05 DA61 FA10

Claims (11)

[Claims] 1. A polymer obtained by polymerizing ethylene satisfying the following (1) to (4) or a mixture of ethylene and an α-olefin having 3 to 20 carbon atoms (hereinafter collectively referred to as an “ethylene polymer”). "), And an ethylene-based polymer composition containing 0.01 to 1.0 part by weight of an antioxidant per 100 parts by weight of the polymer. (1) The melt flow rate (MFR) under a load of 2.16 kg at 190 ° C. is 0.01 to 1000 g / 10 min. (2) The density is 0.85 to 0.97 g / cm ³ (3) Chemical formula (1) to The compound has at least 0.15 unsaturated bonds represented by the chemical formula (4) (hereinafter collectively referred to as “internal unsaturated bonds”) per 1000 carbon atoms. Embedded image (4) An unsaturated bond represented by the chemical formula (3) or (4) (wherein R represents a hydrocarbon group having 1 or more carbon atoms. Hereinafter, these two types of unsaturated bonds are collectively referred to as “tri-substituted” (Hereinafter referred to as "type internal unsaturated bond"). 2. An ethylene polymer having one internal unsaturated bond.
2. The ethylene polymer composition according to claim 1, wherein the ethylene polymer composition has 0.4 or more per 000 carbon atoms and 0.3 or more trisubstituted internal unsaturated bonds. 3. The ethylene polymer composition according to claim 1, wherein the ethylene polymer is polymerized using a catalyst comprising the following components [A] and [B]. Component [A]: Metallocene transition metal compound Component [B]: At least one compound selected from the following group: (A) aluminum oxy compound (B) Lewis acid (C) Reaction with metallocene compound to convert it into a cation Ionic compounds that can be converted 4. The ethylene polymer composition according to claim 1, wherein the ethylene polymer is polymerized using a catalyst comprising the following components [A] and [C]. Component [A]: metallocene transition metal compound Component [C]: ion-exchange layered silicate 5. The ethylene polymer composition according to claim 3, wherein the number of substituents of the conjugated five-membered ring ligand of the metallocene transition metal compound as the component [A] of the catalyst is 2 or less. 6. The antioxidant is a 1: 4 to 4: 1 (weight ratio) mixture of a phosphorus-based antioxidant and a phenol-based antioxidant, or a mixture of a sulfur-based antioxidant and a phenol-based antioxidant. A mixture of 4 to 4: 1 (weight ratio).
6. The ethylene polymer composition according to any one of items 5 to 5. 7. The ethylene polymer composition according to claim 6, wherein the phenolic antioxidant has at least one t-butyl group at the ortho position of the phenolic hydroxyl group in its structure. 8. The ethylene polymer composition according to claim 6, wherein the phosphorus antioxidant has a structure represented by the formula (5). 9. The ethylene polymer composition according to claim 6, wherein the sulfur-based antioxidant has a structure represented by the formula (6). Embedded image (R ¹ , R ² , R ³ , and R ⁴ are all optionally substituted hydrocarbon groups having 1 to 50 carbon atoms and oxygen-containing substituents. May be.) 10. A molded article molded using the ethylene-based polymer composition according to any one of claims 1 to 9. 11. A film formed by using the ethylene-based polymer composition according to claim 1.