JPH10245457A - Ethylenic copolymer composition, and film, sheet or tube composed of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ethylenic copolymer composition, having moderate elongation elasticity and tackiness and excellent in transparency, strength, strain recovery properties, blocking resistance and processability without containing chlorine, and to provide a film composed thereof. SOLUTION: The ethylenic copolymer composition and film consisting of the composition comprises (A) 10-90wt.% copolymer having >=10 and <90% crystallinity and 1-10dL/g intrinsic viscosity [ηA] as a copolymer of ethylene and an aromatic vinyl compound or an α-olefin and (B) 10-90wt.% polymer having >10 and <=90% crystallinity and 0.1-2dL/g intrinsic viscosity [ηB] as an ethylene homopolymer or a copolymer of the ethylene and the aromatic vinyl compound or the α-olefin. The components A and B are polymerized by using a metallocene catalyst and at least either of the components A and B is copolymerized with the aromatic vinyl compound. The crystallinity of the component A/crystallinity of the component B is <1 and [ηA]/[ηB] exceeds 1.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an ethylene copolymer having a relatively low crystallinity and a high molecular weight, and an ethylene polymer or copolymer having a relatively high crystallinity and a low molecular weight. The present invention relates to an ethylene-based copolymer composition containing the composition, and a film, sheet, or tube comprising the composition.

[0002]

2. Description of the Related Art Films and sheets used for agriculture, industrial use, etc., have moderate elongation elasticity and adhesiveness, as well as excellent strength, anti-blocking properties, strain recovery and transparency, and do not fog on the inside. That (anti-fog),
It is required that it lasts (antifogging persistence). Similar performance is also required for tubes used for piping and medical use.

Heretofore, as such a film, sheet or tube, a film made of a polyvinyl chloride polymer has been used. Polyvinyl chloride-based polymers have excellent performance, but due to recent environmental problems, materials containing no chlorine have been demanded.

As a film or sheet containing no chlorine, a film or sheet made of a linear low-density ethylene / α-olefin-based copolymer is known, but its strength, strain recovery, blocking resistance and anti-fogging durability are known. Further improvements are required.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a resin having a suitable elongational elasticity and adhesiveness, as well as transparency, strength and strength.
An object of the present invention is to provide an ethylene copolymer composition having balanced performances such as excellent strain recovery, blocking resistance and processability. Another object of the present invention is to provide a film comprising the above composition, having a suitable elongation elasticity and tackiness, and having excellent performance such as excellent transparency, strength, strain recovery and blocking resistance. Another object of the present invention is to provide a sheet or a tube having a balance of performances, such as a sheet or moderate elongation elasticity and adhesiveness, and excellent transparency, strength and strain recovery.

[0006]

SUMMARY OF THE INVENTION The present invention provides the following ethylene copolymer composition and a film, sheet or tube comprising the same. (1) A: ethylene and an aromatic vinyl compound and / or a carbon atom having 3 to 20 carbon atoms in the presence of the metallocene catalyst (a)
Ethylene copolymer having an intrinsic viscosity [η _A ] of 1 to 10 dl / g when measured in decalin at 135 ° C. B: a homopolymer of ethylene obtained by homopolymerizing ethylene in the presence of the metallocene catalyst (a), or ethylene in the presence of the metallocene catalyst (a). And a copolymer obtained by copolymerizing an aromatic vinyl compound and / or an α-olefin having 3 to 20 carbon atoms with a crystallinity of 10
% To more than 90%, and an ethylene-based copolymer composition containing 10 to 90% by weight of an ethylene-based polymer (B) having an intrinsic viscosity [η _B ] of 0.1 to 2 dl / g measured in decalin at 135 ° C. An aromatic vinyl compound is copolymerized on one or both of the ethylene-based copolymer (A) and the ethylene-based polymer (B), and a crystal of the ethylene-based copolymer (A) The ratio of the degree of polymerization to the degree of crystallinity of the ethylene-based polymer (B) (the degree of crystallinity of the component (A) / the degree of crystallinity of the component (B)) is less than 1; Wherein the ratio ([η _A ] / [η _B ]) of the intrinsic viscosity of (1) to the intrinsic viscosity of the ethylene polymer (B) exceeds 1. (2) The composition according to the above (1), wherein the content of the aromatic vinyl compound in the ethylene copolymer (A) is 1.4 to 10 mol%. (3) The ethylene polymer (B) is a homopolymer of ethylene or an ethylene / α-olefin copolymer,
The composition according to the above (1) or (2), wherein the composition is a high-density polyethylene having a density of more than 0.93 g / cm ³ and 0.97 g / cm ³ or less. (4) The ethylene polymer (B) is a copolymer of ethylene and an aromatic vinyl compound and / or an α-olefin having 3 to 20 carbon atoms, and the content of the aromatic vinyl compound is 0.05 The composition according to the above (1) or (2), wherein the composition is 0.1 to 1.4 mol%. (5) Ethylene polymer (B) is composed of ethylene and C3
A copolymer with 8 of α- olefins, above, wherein the density is a linear low density polyethylene ^{0.86g / cm 3 ~0.93g / cm 3} (1) or (2 ). (6) Antifogging agent (C) based on 100 parts by weight of ethylene copolymer (A) and ethylene polymer (B) in total
(1) characterized by containing 0.5 to 10 parts by weight.
Or the composition according to any one of (5) to (5). (7) The nucleating agent (D) is added to a total of 100 parts by weight of the ethylene copolymer (A) and the ethylene polymer (B).
The composition according to any one of the above (1) to (6), comprising from 0.01 to 10 parts by weight. (8) The composition according to any one of the above (1) to (7), wherein the metallocene catalyst (a) contains a bridge type metallocene compound. (9) The composition according to the above (8), wherein the bridge type metallocene compound is isopropylidenebis (indenyl) zirconium dichloride. (10) A film, sheet or tube comprising the composition according to any one of the above (1) to (9). (11) A heavy-weight packaging film comprising the composition according to any one of (1) to (9) above,
Sheet or tube.

The ethylene copolymer (A) used in the present invention
Is a copolymer obtained by copolymerizing ethylene with an aromatic vinyl compound and / or an α-olefin having 3 to 20 carbon atoms in the presence of the metallocene catalyst (a), and having a crystallinity of 10 % To less than 90%, preferably 10 to 70%
%, More preferably 10 to 45%, particularly preferably 1 to 45%.
5 to 45%, intrinsic viscosity [η _A ] measured in decalin at 135 ° C. is 1 to 10 dl / g, preferably 1.5 to 3 dl / g.
It is a copolymer of 8 dl / g. When the crystallinity is in the above range, a composition excellent in flexibility, transparency and impact resistance can be obtained. When the intrinsic viscosity [η _A ] is in the above range, a composition excellent in processability can be obtained.

Examples of the aromatic vinyl compound include styrene; o-methylstyrene, m-methylstyrene, p-methylstyrene, o, p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene and the like. Mono- or polyalkylstyrene; styrene derivatives containing a functional group such as methoxystyrene, ethoxystyrene, vinylbenzoic acid, methyl vinylbenzoate, vinylbenzyl acetate, hydroxystyrene, o-chlorostyrene, p-chlorostyrene, divinylbenzene; Phenylpropylene, 4-phenylbutene, α-methylstyrene and the like. These can be used alone or in combination of two or more.

As the α-olefin, ethylene, propylene, 1-butene, 1-pentene, 1-hexene,
4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1- Heptadecene, 1-
Α-olefins having 3 to 20 carbon atoms, such as octadecene, 1-nonadecene, and 1-eicodecene. These can be used alone or in combination of two or more.

The ethylene content of the ethylene copolymer (A), that is, the content of structural units derived from ethylene is 7
5 to 98.6 mol%, preferably 80 to 98.6 mol
1% is desirable. Α-olefin content,
That is, the content of the structural unit derived from the α-olefin is desirably 0 to 15 mol%, preferably 0 to 10 mol%.

When a copolymer obtained by copolymerizing an aromatic vinyl compound is used as the ethylene copolymer (A), the content of the aromatic vinyl compound, that is, the content of the structural unit derived from the aromatic vinyl compound is 1. It is desirable to use 4 to 10 mol%, preferably 1.4 to 4 mol% of the copolymer. When the content of the aromatic vinyl compound is in the above range, a composition excellent in balance between antifogging property, strain recovery property and mechanical strength can be obtained.

The ethylene copolymer (A) used in the present invention has a molecular weight distribution (Mw / Mn) represented by a ratio of a weight average molecular weight (Mw) to a number average molecular weight (Mn).
Is 2 to 10, preferably 2.5 to 6, and the temperature (Tm) at the maximum peak position in an endothermic curve measured by a differential scanning calorimeter (DSC) is 115 to 60 ° C, preferably 11
A temperature of 5 to 85 ° C is desirable. Molecular weight distribution (Mw /
When Mn) is in the above range, a composition excellent in processability can be obtained. When the temperature (Tm) at the maximum peak position in the endothermic curve is within the above range, a composition having an excellent balance between heat resistance and transparency can be obtained.

When a copolymer in which an aromatic vinyl compound is copolymerized is used as the ethylene copolymer (A), a chain structure in which two or more structural units derived from the aromatic vinyl compound are continuous (hereinafter referred to as an aromatic compound). The ratio of the structural units that constitute the aromatic vinyl compound / aromatic vinyl compound chain structure (hereinafter sometimes referred to as the aromatic vinyl compound / aromatic vinyl compound chain structure content) is derived from the aromatic vinyl compound. A copolymer of 1% or less, preferably 0.1% or less, based on all structural units to be prepared is preferred. The aromatic vinyl compound / aromatic vinyl compound chain structure content is a value determined from ¹³ C NMR.

The ethylene polymer (B) used in the present invention
Is a method in which ethylene is solely polymerized in the presence of the metallocene catalyst (a).
Ethylene homopolymer or metallo
Ethylene and aromatic vinylation in the presence of sen catalyst (a)
Compound and / or an α-olefin having 3 to 20 carbon atoms
A copolymer having a crystallinity of 1
More than 0% and 90% or less, preferably 30 to 80%,
Preferably 35 to 70%, particularly preferably 40 to 65%.
%, Intrinsic viscosity measured in 135 ° C decalin [η _B]But
0.1 to 2 dl / g, preferably 0.5 to 1.5 dl / g
g of the polymer or copolymer. Crystallinity within the above range
, A composition with a good balance between heat resistance and transparency
Things are obtained. In addition, the intrinsic viscosity [η_BIs in the above range
In this case, a composition having excellent processability is obtained. Above aromatic bi
As the ethyl compound and α-olefin,
The same as those exemplified as the monomer of the copolymer (A)
There are things like

The ethylene content of the ethylene copolymer (B), that is, the content of structural units derived from ethylene is 8
3.6-100 mol%, preferably 88.6-100
mol% is desirable. The content of the α-olefin, that is, the content of the structural unit derived from the α-olefin is desirably 0 to 15 mol%, preferably 0 to 10 mol%.

When a copolymer obtained by copolymerizing an aromatic vinyl compound is used as the ethylene polymer (B), the content of the aromatic vinyl compound, that is, the content of the structural unit derived from the aromatic vinyl compound is 0.05%. ~ 1.4 mol%,
Preferably, 0.07 to 1.2 mol% of the copolymer is used. When the content of the aromatic vinyl compound is in the above range, a composition having excellent heat resistance can be obtained.

As the ethylene polymer (B), high density polyethylene having a density of more than 0.93 g / cm ³ and 0.97 g / cm ³ or less can be preferably used. Here, the high-density polyethylene is a homopolymer of ethylene or a copolymer of ethylene and a small amount of α-olefin of about 5 mol% or less, for example, propylene. Among such high-density polyethylenes, melt flow rate (190 ° C.)
0.01 to 1 g / 10 min, density 0.94 to 0.97
g / cm ³ of high density polyethylene is preferred.

The ethylene polymer (B) is a copolymer of ethylene and an α-olefin having 3 to 8 carbon atoms, and has a linear low density of 0.86 to 0.93 g / cm ^3. Density polyethylene can also be used preferably.

The ethylene polymer (B) used in the present invention includes a weight average molecular weight (Mw) and a number average molecular weight (Mw).
n) with a molecular weight distribution (Mw / Mn) of 2
10, preferably 2.5 to 6, differential scanning calorimeter (DS
The temperature (Tm) at the maximum peak position in the endothermic curve measured by C) is 125 to 115 ° C, preferably 125 to 115 ° C.
A temperature of 120 ° C. is desirable. Molecular weight distribution (Mw / M
When n) is in the above range, a composition having excellent processability can be obtained. When the temperature (Tm) at the maximum peak position in the endothermic curve is within the above range, a composition having an excellent balance between heat resistance and transparency can be obtained.

When a copolymer in which an aromatic vinyl compound is copolymerized is used as the ethylene polymer (B), the aromatic vinyl compound / aromatic vinyl compound chain structure content is derived from the aromatic vinyl compound. A copolymer of 1% or less, preferably 0.1% or less based on all structural units is preferred.

The composition of the present invention is a composition containing the ethylene-based copolymer (A) and the ethylene-based polymer ((B)). At least one of the components is a copolymer of an aromatic vinyl compound. In other words, as the combination of the components (A) and (B), both the components (A) and (B) are ethylene copolymers in which an aromatic vinyl compound is copolymerized. Whether only component (A) is an ethylene copolymer in which an aromatic vinyl compound is copolymerized or only component (B) is an ethylene copolymer in which an aromatic vinyl compound is copolymerized. The combinations are as follows.

The ratio of the crystallinity of the ethylene copolymer (A) to the crystallinity of the ethylene polymer (B) (crystallinity of component (A) / crystallinity of component (B)) , May be abbreviated as a ratio of crystallinity in some cases) of less than 1, preferably 0.9 or less, and the intrinsic viscosity [η] of the component (A).
_A ] and the intrinsic viscosity ([η _B ]) of the component (B) ([η _A ] / [η _B ], hereinafter sometimes abbreviated as the intrinsic viscosity ratio) exceed 1, preferably 1 The component (A) and the component (B) are used in combination so as to be at least 0.5.

The proportions of the components (A) and (B) in the composition of the present invention are 10 to 90% by weight, preferably 30 to 70% by weight, and 10 to 9% by weight of the component (A).
0% by weight, preferably 30 to 70% by weight. In the present invention, an ethylene copolymer (A) having a relatively low crystallinity and a high molecular weight and an ethylene polymer (B) having a relatively high crystallinity and a relatively high crystallinity are blended at the above-mentioned blending ratio. By doing, it has moderate elongation elasticity and adhesiveness, transparency, strength such as impact resistance, strain recovery, blocking resistance,
And excellent workability such as bubble stability during processing.
An ethylene copolymer composition having balanced performance is obtained.

As a preferable composition of the present invention, the ethylene-based copolymer (A) is preferably composed of 90 to 98.
6 mol% and an aromatic vinyl compound such as styrene 1.4 to 1.4 mol%
10 to 40% by weight of an ethylene / aromatic vinyl compound copolymerized with 10 mol% and an ethylene-based polymer (B), which is a homopolymer of ethylene and has a density exceeding 0.93 g / cm ³ and 0 A high-density polyethylene having a density of 0.86 to 0.93 g / cm ³ or less, or a copolymer of 90 to 97 mol% of ethylene and 3 to 10 mol% of α-olefin having 3 to 8 carbon atoms. cm ³
Ethylene copolymer composition containing 90 to 60% by weight of the linear low-density polyethylene. Further, an antifogging agent (C) and / or a nucleating agent (D) may be added to such a composition.
0.01 to 100 parts by weight of components (A) and (B)
Compositions containing from 10 to 10 parts by weight, preferably from 0.3 to 5 parts by weight, are also preferred. Such a composition is excellent in impact resistance, moldability and transparency, so that various films,
It is particularly suitable for packaging of sheets or tubes, especially heavy goods, ie for heavy bags.

Next, a method for producing the ethylene-based copolymer (A) and the ethylene-based polymer (B) will be described. The ethylene-based copolymer (A) and the ethylene-based polymer (B) used in the present invention are obtained by copolymerizing ethylene with an aromatic vinyl compound and / or an α-olefin in the presence of a metallocene catalyst (a) by a known method. It is produced by polymerizing or polymerizing ethylene alone by a known method in the presence of the metallocene catalyst (a).

As the above-mentioned metallocene catalyst (a), metallocene catalysts conventionally used as single-site catalysts and metallocene catalysts similar thereto can be used without limitation. In particular, metallocene compounds of transition metals (transition metal A catalyst comprising the compound (b) and the organic aluminum oxy compound (c) and / or the ionized ionic compound (d) is preferably used.

As the metallocene compound (b), IUP
Family number 1 according to the revised version of the AC Inorganic Chemistry Nomenclature (1989)
A metallocene compound of a transition metal selected from Group 4 of the periodic table (long-period type) of the elements represented by Nos. To 18, specifically, a metallocene compound represented by the following general formula (1). MLx (1) In the formula (1), M is a transition metal selected from Group 4 of the periodic table, specifically, zirconium, titanium or hafnium, and x is the valence of the transition metal.

L is a ligand that coordinates to the transition metal, and at least one of these ligands L is a ligand having a cyclopentadienyl skeleton, and having this cyclopentadienyl skeleton. The ligand may have a substituent.

The ligand having a cyclopentadienyl skeleton includes, for example, cyclopentadienyl group, methylcyclopentadienyl group, ethylcyclopentadienyl group, n- or i-propylcyclopentadienyl group, n-,
i-, sec-, t-, butylcyclopentadienyl group, hexylcyclopentadienyl group, octylcyclopentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, tetramethylcyclopentadienyl Group, pentamethylcyclopentadienyl group, methylethylcyclopentadienyl group, methylpropylcyclopentadienyl group, methylbutylcyclopentadienyl group, methylhexylcyclopentadienyl group, methylbenzylcyclopentadienyl group, Alkyl or cycloalkyl-substituted cyclopentadienyl groups such as ethylbutylcyclopentadienyl group, ethylhexylcyclopentadienyl group, methylcyclohexylcyclopentadienyl group, and further indenyl group, 4,5,6,7-tetrahydroindenyl Group, fluore And a nyl group.

These groups may be substituted with a halogen atom, a trialkylsilyl group or the like. Among these, an alkyl-substituted cyclopentadienyl group is particularly preferred.

In the case where the metallocene compound (b) represented by the formula (1) has two or more groups having a cyclopentadienyl skeleton as the ligand L, a group having two cyclopentadienyl skeletons among them The two are linked via an alkylene group such as ethylene and propylene, a substituted alkylene group such as isopropylidene and diphenylmethylene, a silylene group or a dimethylsilylene group, a diphenylsilylene group, and a substituted silylene group such as a methylphenylsilylene group. Is also good.

L other than the ligand having a cyclopentadienyl skeleton is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a sulfonic acid-containing group (-SO
₃ R ¹ ), a halogen atom or a hydrogen atom (here, R ¹ is an alkyl group, an alkyl group substituted with a halogen atom, an aryl group, or an aryl group substituted with a halogen atom or an alkyl group). Can be

Examples of the hydrocarbon group having 1 to 12 carbon atoms include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group and the like. More specifically, a methyl group, an ethyl group, an n-propyl group and an isopropyl group Groups, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, octyl group, decyl group, alkyl group such as dodecyl group, cyclopentyl group, cycloalkyl group such as cyclohexyl group, Examples include aryl groups such as phenyl and tolyl groups, and aralkyl groups such as benzyl and neophyl.

The alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy,
n-butoxy group, isobutoxy group, sec-butoxy group, t-butoxy group, pentoxy group, hexoxy group, octoxy group and the like. Examples of the aryloxy group include a phenoxy group.

Examples of the sulfonic acid-containing group (—SO ₃ R ¹ ) include a methanesulfonato group, a p-toluenesulfonato group, a trifluoromethanesulfonato group, and a p-chlorobenzenesulfonato group. Examples of the halogen atom include fluorine, chlorine, bromine and iodine.

The metallocene compound (b) represented by the above formula (1) is more specifically represented by the following general formula (2) when the valence of the transition metal is 4, for example. R ² _k R ³ _l R ⁴ _m R ⁵ _n M (2)

In the formula (2), M is a transition metal similar to the transition metal of the formula (1), preferably zirconium or titanium, and R ² is a group (ligand) having a cyclopentadienyl skeleton. , R ³ , R ⁴ and R ⁵ are each independently the same as L except for a group having a cyclopentadienyl skeleton or a ligand having a cyclopentadienyl skeleton in the general formula (1). k is an integer of 1 or more, and k + 1
+ M + n = 4.

In the following, when M is zirconium and the ligand having a cyclopentadienyl skeleton is at least 2
The metallocene compound (b) containing the same is exemplified. Bis (cyclopentadienyl) zirconium monochloride monohydride, bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) methylzirconium monochloride, bis (cyclopentadienyl) zirconium phenoxymonochloride, bis (methyl) (Cyclopentadienyl) zirconium dichloride, bis (ethylcyclopentadienyl) zirconium dichloride, bis (n-
(Propylcyclopentadienyl) zirconium dichloride, bis (isopropylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl)
Zirconium dichloride, bis (cyclopentadienyl)
Zirconium bis (methanesulfonato), bis (cyclopentadienyl) zirconium bis (p-toluenesulfonato), bis (1,3-dimethylcyclopentadienyl) zirconium dichloride, bis (1-methyl-3-ethylcyclo) (Pentadienyl) zirconium dichloride, bis (1-methyl-3
-Propylcyclopentadienyl) zirconium dichloride, bis (methyl-n-propylcyclopentadienyl) zirconium dichloride, bis (methyl-n-butylcyclopentadienyl) zirconium dichloride, and the like.

In the present invention, a metallocene compound (b) in which the 1,3-substituted cyclopentadienyl group is replaced by a 1,2-substituted cyclopentadienyl group can also be used. In the above formula (2), R ² , R ³ , R
^At least two of ⁴ and R ⁵ , that is, R ² and R ³ are groups having a cyclopentadienyl skeleton (ligand);
A bridge type metallocene compound (b) in which at least two groups are bonded via an alkylene group, a substituted alkylene group, a silylene group or a substituted silylene group, etc.
Can also be exemplified. At this time, R ⁴ and R ⁵ are independently the same as L except for the ligand having a cyclopentadienyl skeleton described in the formula (1).

Examples of the bridge type metallocene compound (b) include isopropylidenebis (indenyl) zirconium dichloride, ethylenebis (indenyl) dimethylzirconium, ethylenebis (indenyl) zirconium dichloride, and ethylenebis (indenyl) zirconiumbis (trifluorofluoride). Methanesulfonato), ethylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-
(Methylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (cyclopentadienyl) zirconium dichloride, dimethylsilylenebis (methylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (Trimethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (indenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl-fluorenyl) zirconium dichloride, diphenylsilylenebis (indenyl) zirconium dichloride, methylphenylsilylenebis (indenyl) zirconium dichloride And so on.

In the present invention, it is desirable to use a metallocene compound represented by the following general formula (3) as the bridge type metallocene compound (b).

Embedded image

In the formula (3), M ¹ represents a transition metal atom belonging to Group 4, 5, or 6 of the periodic table, and specifically includes titanium, zirconium, hafnium and the like. R ⁶ and R ⁷ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group, and a sulfur-containing group. , A nitrogen-containing group or a phosphorus-containing group, specifically, a halogen atom such as fluorine, chlorine, bromine and iodine; an alkyl group such as methyl, ethyl, propyl, butyl, hexyl and cyclohexyl, vinyl, propenyl and cyclohexenyl. A hydrocarbon group having 1 to 20 carbon atoms such as an alkenyl group such as benzyl, phenylethyl, phenylpropyl and the like; an arylalkyl group such as phenyl, tolyl, dimethylphenyl, naphthyl and methylnaphthyl; A halogenated hydrocarbon group substituted by a halogen atom;

Monohydrocarbon-substituted silyls such as methylsilyl and phenylsilyl, dihydrocarbon-substituted silyls such as dimethylsilyl and diphenylsilyl, trihydrocarbon-substituted silyls such as trimethylsilyl and triethylsilyl, and silyls of hydrocarbon-substituted silyl such as trimethylsilyl ether Silicon-containing groups such as ethers, silicon-substituted alkyl groups such as trimethylsilylmethyl, and silicon-substituted aryl groups such as trimethylsilylphenyl; alkoxy groups such as hydroxy, methoxy and ethoxy; alloxy groups such as phenoxy and methylphenoxy; phenylmethoxy and phenyl An oxygen-containing group such as an arylalkoxy group such as ethoxy; a sulfur-containing group such as a substituent in which the oxygen of the oxygen-containing group is substituted with sulfur; an amino group, methylamino, dimethylamino or the like; A phosphorus-containing group such as a phosphino group such as dimethyl phosphinothricin; alkylamino group, phenylamino, nitrogen-containing groups such as an arylamino group or an alkyl aryl amino group such as methylphenylamino.

Among them, R ⁶ is preferably a hydrocarbon group, particularly preferably a hydrocarbon group having 1 to 3 carbon atoms such as methyl, ethyl and propyl. Also R ⁷
Is preferably a hydrogen atom or a hydrocarbon group, particularly a hydrogen atom, or methyl, ethyl or propyl having 1 to 1 carbon atoms.
It is preferably a hydrocarbon group of No. 3.

R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms; Among these, a hydrogen atom, a hydrocarbon group or a halogenated hydrocarbon group is preferred. R ⁸ and R ⁹ , R ⁹
At least one pair of R ^10, R ¹⁰ and R ¹¹ together with the carbon atoms to which they are attached, may form a monocyclic aromatic ring.

When there are two or more hydrocarbon groups or halogenated hydrocarbon groups other than the group forming an aromatic ring, these groups may be bonded to each other to form a ring. When R ¹¹ is a substituent other than an aromatic group, it is preferably a hydrogen atom.

Specific examples of the halogen atom, the hydrocarbon group having 1 to 20 carbon atoms, and the halogenated hydrocarbon group having 1 to 20 carbon atoms are the same as those described above for R ⁶ and R ⁷ .

X ¹ and X ² each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group or a sulfur-containing group. Show. A halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms,
Specific examples of the oxygen-containing group include R ⁶ and R ⁷
The same can be exemplified.

The sulfur-containing groups include R ⁶ and R ⁷
And the same groups as above, and methylsulfonate, trifluoromethanesulfonate, phenylsulfonate, benzylsulfonate, p-toluenesulfonate, trimethylbenzenesulfonate, triisobutylbenzenesulfonate, p-chlorobenzenesulfonate Phonate,
Sulfonate groups such as pentafluorobenzenesulfonate, and sulfinate groups such as methylsulfinate, phenylsulfinate, benzenesulfinate, p-toluenesulfinate, trimethylbenzenesulfinate, and pentafluorobenzenesulfinate. Can be illustrated.

Y ¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, 2
Divalent silicon-containing group, divalent germanium-containing group, divalent tin-containing group, -O-, -CO-, -S-, -SO-,-
^{_{SO 2 -, - NR 12 -}} , - P (R 12) -, - P (O) (R 12)
—, —BR ¹² — or —AlR ¹² — (where R ¹² is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms,
A halogenated hydrocarbon group having 1 to 20 carbon atoms).

Specific examples of Y ¹ include methylene,
Alkylene groups such as dimethylmethylene, 1,2-ethylene, dimethyl-1,2-ethylene, 1,3-trimethylene, 1,4-tetramethylene, 1,2-cyclohexylene, 1,4-cyclohexylene, diphenylmethylene Divalent hydrocarbon groups having 1 to 20 carbon atoms, such as arylalkylene groups such as diphenyl-1,2-ethylene, etc .;
A halogenated hydrocarbon group obtained by halogenating a divalent hydrocarbon group from 20 to 20; methylsilylene, dimethylsilylene, diethylsilylene, di (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, Methylphenylsilylene, diphenylsilylene, di (p-tolyl)
Alkylsilylenes such as silylene, di (p-chlorophenyl) silylene, alkylarylsilylene, arylsilylene group, tetramethyl-1,2-disilylene, alkyldisilylene such as tetraphenyl-1,2-disilylene, alkylaryldisilylene, 2 such as an aryldisilylene group
A divalent silicon-containing group; a divalent germanium-containing group obtained by substituting silicon in the divalent silicon-containing group with germanium; a divalent tin-containing group substituent obtained by substituting silicon in the divalent silicon-containing group with tin And R ¹² is a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms similar to those of R ⁶ and R ⁷ .

Among them, a divalent silicon-containing group, a divalent germanium-containing group, and a divalent tin-containing group are preferable, and a divalent silicon-containing group is more preferable. Preferred are silylene, alkylarylsilylene, and arylsilylene.

Specific examples of the metallocene compound (b) represented by the above formula (3) are shown below. rac-dimethylmethylenebis (indenyl) zirconium dichloride, rac-dimethylmethylenebis (2-methyl-1-indenyl) zirconium-dichloride, rac-diphenylmethylenebis (2-methyl-1-indenyl) zirconium-dichloride, rac-ethylene Bis (2-methyl-1-indenyl) zirconium-dichloride, rac-dimethylsilylenebis (2-methyl-1-indenyl) zirconium-dichloride, rac-dimethylsilylenebis (2-methyl-1-indenyl) zirconium-dimethyl, rac-dimethylsilylene-bis (4,7-dimethyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,4,7-trimethyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2 , 4,6-Trimethyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (4-phenyl-1-indene Zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (α-naphthyl) -1-indenyl) Zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (β-naphthyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (1-anthracenyl) -1- (Indenyl) zirconium dichloride and the like.

In the present invention, the metallocene compound (b)
As the metallocene compound represented by the following general formula (4). L ¹ M ² Z ₂ (4) (wherein, M ² is a metal belonging to Group 4 of the periodic table or a lanthanide series, L ¹ is a derivative of a delocalized π-bonded group,
The metal M ² active site has a constrained geometry,
Is independently a hydrogen atom, a halogen atom or 20
The following carbon, silicon or germanium containing hydrocarbon groups, silyl groups or germyl groups. )

Among the metallocene compounds (b) represented by the formula (4), the metallocene compounds represented by the following general formula (5) are preferable.

Embedded image

In the formula (5), M ³ is titanium, zirconium or hafnium, and Z is the same as described above. Cp
Is a cyclopentadienyl group, a substituted cyclopentadienyl group or a derivative thereof, which is π-bonded to M ³ in an η ⁵ bonding mode.

W ¹ is oxygen, sulfur, boron or an element belonging to Group 14 of the periodic table or a group containing these elements, and V ¹ is a ligand containing nitrogen, phosphorus, oxygen or sulfur. W ¹ and V ¹ may form a condensed ring. Also C
p and W ¹ may form a fused ring.

Preferred examples of the group represented by Cp in the general formula (5) include a cyclopentadienyl group, an indenyl group, a fluorenyl group, and a saturated derivative thereof, and these include a metal atom (M ³ ) Form a ring. Each carbon atom in the cyclopentadienyl group may be the same or different group selected from the group consisting of a hydrocarbyl group and a substituted hydrocarbyl group, and one or more carbon atoms may be a halogen atom, a hydrocarbyl-substituted group. Substituted by a metalloid group, and the metalloid is selected from Group 14 of the Periodic Table of the Elements and halogen atoms. Also, one or more substituents may together form a fused ring. Preferred hydrocarbyl and substituted hydrocarbyl groups which can be substituted with at least one hydrogen atom in the cyclopentadienyl group contain 1 to 20 carbon atoms and are straight-chain or branched alkyl groups,
It includes cyclic hydrocarbon groups, alkyl-substituted cyclic hydrocarbon groups, aromatic groups and alkyl-substituted aromatic groups. Preferred organic metalloid groups are group 14 element mono-di- and tri-
Including substituted organic metalloid groups, each of the hydrocarbyl groups contains 1 to 20 carbon atoms. Specific examples of preferred organic metalloid groups include trimethylsilyl,
Examples include triethylsilyl, ethyldimethylsilyl, methyldiethylsilyl, phenyldimethylsilyl, methyldiphenylsilyl, triphenylsilyl, triphenylgermyl, trimethylshearyl, and the like.

Specific examples of Z ^{1 in} the general formula (5) include hydride, halo, alkyl, silyl, germyl, aryl, amide, aryloxy, alkoxy,
Examples include phosphide, sulfide, acyl, pseudo halide such as cyanide, azide, acetylacetonate or a mixture thereof, which may be the same or different.

Among the metallocene compounds (b) represented by the general formula (5), the metallocene compounds represented by the following general formula (6) are preferable.

Embedded image

In the formula (6), M ⁴ is the same as M ³ ,
V ² is -O -, - S -, - NR 17 -, - PR 17 - a either or ^{OR 17, SR 17, N (} R 17) 2 or P (R ^17), ₂
And a neutral two electron donor ligand selected from the group consisting of: Here, R ¹⁷ is a hydrogen atom, or an alkyl, aryl, silyl, halogenated alkyl or aryl halide group having up to 20 atoms other than hydrogen, or two R ¹⁷ or R ¹⁸ described below. A condensed ring may be formed.

In the equation (6), W^TwoIs Si (R¹⁸)_Two, C (R¹⁸)
_Two, Si (R¹⁸)_TwoSi (R¹⁸)_Two, C (R ¹⁸)_TwoC (R¹⁸)_Two, C
R¹⁸= CR¹⁸, C (R¹⁸)_TwoSi (R¹⁸)_Two, Ge (R¹⁸)_Two,
BR¹⁸, B (R¹⁸)_TwoIt is. Where R¹⁸Is R¹⁷Same as
The same. In the formula (6), R¹³~ R¹⁶Are each independently water
An elemental atom or an alkyl having up to 20 non-hydrogen atoms
Kill, aryl, silyl, jarmil, cyano, halo
And combinations thereof (eg alkaryl, aralkyl
, Silyl-substituted alkyl, silyl-substituted aryl, cyano
Alkyl, cyanoaryl, haloalkyl, halosilyl
Or R¹³~ R¹⁶Is an adjacent pair of cyclo
Forming a hydrocarbyl ring fused to a pentadienyl moiety
It may be.

In formula (6), Z ² is in each case a hydride or halo, alkyl, arylsilyl, germyl, aryloxy, alkoxy, amide, silyloxy and up to 20 atoms other than hydrogen. Their combinations (eg alkaryl, aralkyl,
Silyl, substituted alkyl, silyl-substituted aryl, aryloxyalkyl, aryloxyaryl, alkoxyalkyl, alkoxyaryl, amidoalkyl, amidoaryl, siloxyalkyl, siloxyaryl, amidosiloxyalkyl, haloalkyl, haloaryl, etc.) and up to 20 It is a group selected from the group consisting of neutral Lewis bases having atoms other than hydrogen.

In the metallocene compound (b) represented by the general formula (6), when V ² is a neutral two-electron donor ligand, the bond between M ⁴ and V ² is more precisely arranged. This is a bond called a covalent bond. Also, the complexes can exist as dimers or higher oligomers.

A metallocene compound represented by the general formula (6)
In (b), R¹³~ R¹⁶, Z ^Two, R¹⁷Or R¹⁸
Preferably, at least one of the is a donor moiety
Especially V^TwoIs -NR¹⁹-Or -PR¹⁹− (However,
R¹⁹Is alkyl having 1 to 10 carbons or 6 to 10 carbons
Or an phosphide corresponding to
It is preferably a group.

Among the metallocene compounds (b) represented by the general formula (6), an amidosilane or an amidoalkanediyl compound represented by the following general formula (7) is preferable.

Embedded image

In the formula (7), M ⁵ is titanium, zirconium or hafnium bonded to the cyclopentadienyl group in the η ⁵ bonding mode, and R ^{20 to} R ²⁵ are each independently a hydrogen atom or 10 hydrogen atoms. silyl with carbon up to, alkyl, aryl and a group selected from the group consisting of, or adjacent pairs of R ²² to R ²⁵ is to form a hydrocarbyl ring fused to the cyclopentadienyl moiety You may. In formula (7), W ³ is silicon or carbon and Z ³ is in each case hydride, halo,
It is an alkyl, aryl, aryloxy or alkoxy of up to 10 carbons.

In the metallocene compound (b) represented by the general formula (7), R ²⁰ is methyl, ethyl, propyl,
Butyl, pentyl, hexyl (including isomers), norbornyl, benzyl, phenyl, etc., wherein R ^{22 to} R ²⁵ are each independently a hydrogen atom, methyl, ethyl, propyl,
Butyl, pentyl, hexyl (including isomers), norbornyl, benzyl and the like, and Z ³ is chloro, bromo, iodo, methyl, ethyl, propyl, butyl, pentyl, hexyl (including isomers), norbornyl, benzyl And a metallocene compound such as phenyl. R ^{22 to} R ²⁵ form a condensed ring, and the cyclopentadienyl moiety is indenyl, tetrahydroindenyl,
Metallocene compounds such as fluorenyl and octahydrofluorenyl rings are also preferred.

Specific examples of the metallocene compound (b) represented by the general formula (7) include (t-butylamido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silanetitanium dichloride, butylamido) (tetramethyl-eta ⁵ - cyclopentadienyl) -1,2-ethanediyl zirconium dichloride, (t-butylamido) (tetramethyl-eta ⁵ - cyclopentadienyl) -1,2-ethanediyl titanium dichloride , (methylamide) (tetramethyl-eta ⁵ - cyclopentadienyl) -1,2-ethanediyl zirconium dichloride, (methylamide) (tetramethyl-eta ⁵ - cyclopentadienyl) -1,2-ethanediyl titanium dichloride , (ethylamide) (tetramethyl-eta ⁵ - cyclopentadienyl) - methylene titanium dichloride, (t-butylamido) Methyl (tetramethyl-eta ⁵ - cyclopentadienyl) silane zirconium dibenzyl, (benzylamide) dimethyl (tetramethyl-eta ⁵
- cyclopentadienyl) silane titanium dichloride, (phenyl phosphide) dimethyl (tetramethyl- eta ⁵ - and cyclopentadienyl) silane zirconium dibenzyl and the like.

In the present invention, the metallocene compound (b)
The following metallocene compounds can also be used.
Ethylene {2-methyl-4 (9-phenanthryl) -1-indenyl} (9-fluorenyl) zirconium dichloride, ethylene {2-methyl-4 (9-phenanthryl) -1-indenyl} (2,7-
Dimethyl-9-fluorenyl) zirconium dichloride, ethylene {2-methyl-4 (9-phenanthryl) -1-indenyl}
(2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, ethylene (2-methyl-4,5-benzo-1-indenyl) (9
-Fluorenyl) zirconium dichloride, ethylene (2-
Methyl-4,5-benzo-1-indenyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, ethylene (2-methyl-4,5-benzo-1-indenyl) (2,7-di-t -Butyl-9-fluorenyl) zirconium dichloride, ethylene (2-methyl
-α-acenaphth-1-indenyl) (9-fluorenyl) zirconium dichloride, ethylene (2-methyl-α-acenaphth-
1-indenyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, ethylene (2-methyl-α-acenaphth-1-
Indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, dimethylsilylene {2-methyl-4 (9-phenanthryl) -1-indenyl} (9-fluorenyl) zirconium dichloride and the like.

Other examples of the zirconium compound include compounds in which zirconium is replaced with titanium or hafnium. The method for producing the metallocene compound (b) is described in, for example, JP-A-3-163.
No. 088.

In the case of producing an ethylene copolymer (A) or an ethylene polymer (B) in which an aromatic vinyl compound is copolymerized, the metallocene compound (b) is represented by the general formula (4). The metallocene compound is particularly preferred in view of polymerization activity and transparency, rigidity, heat resistance and impact resistance of the molded article. The metallocene compounds (b) described so far may be used alone or in combination of two or more. The metallocene compound (b) used in the present invention may be used after being diluted with a hydrocarbon or a halogenated hydrocarbon.

Next, the organoaluminum oxy compound (c) and the ionized ionic compound (d) used for forming the metallocene catalyst (a) will be described.

The organoaluminum oxy compound (c) used in the present invention may be a conventionally known aluminoxane (c)
Or a benzene-insoluble organic aluminum oxy compound (c) as exemplified in JP-A-2-78687.

Such a conventionally known aluminoxane (c) is specifically represented by the following general formula (8) or (9).

Embedded image [In the formula (8) or (9), R ²⁶ is a hydrocarbon group such as a methyl group, an ethyl group, a propyl group, and a butyl group, preferably a methyl group, an ethyl group, particularly preferably a methyl group; Is an integer of 2 or more, preferably 5 to 40. ]

Here, this aluminoxane (c) is an alkyloxyaluminum unit represented by the formula (OAl (R ²⁷ )) and an alkyloxyaluminum unit represented by the formula (OAl (R ²⁸ )) (where R ²⁷ and R ²⁸ can be exemplified by the same hydrocarbon groups as R ^26, and R ²⁷ and R ²⁸ represent different groups).

The aluminoxane (c) is produced, for example, by the following method and is usually recovered as a solution in a hydrocarbon solvent. (1) Compounds containing water of adsorption or salts containing water of crystallization such as hydrated magnesium chloride, hydrated copper sulfate, hydrated aluminum sulfate, hydrated nickel sulfate, hydrated cerous chloride A method of adding an organoaluminum compound such as trialkylaluminum to an aromatic hydrocarbon solvent in which is suspended and reacting the resulting mixture to recover a solution of the aromatic hydrocarbon solvent. (2) A method in which water (water, ice or steam) is allowed to directly act on an organic aluminum compound such as a trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran to recover the compound as an aromatic hydrocarbon solvent 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 hydrocarbon medium such as decane, benzene or toluene.

Solvents used in the preparation of aluminoxane (c) include, for example, aromatic hydrocarbons such as benzene, toluene, xylene, cumene and cymene; pentane, hexane, heptane, octane, decane, dodecane and hexadecane Hydrocarbons such as cyclopentane, cyclohexane, cyclooctane and methylcyclopentane; ethers such as ethyl ether and tetrahydrofuran; petroleum fractions such as gasoline, kerosene and light oil; Aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbon halides,
Examples thereof include hydrocarbon solvents such as chlorinated products and brominated products. Among these solvents, aromatic hydrocarbons are particularly preferred.

As the ionized ionic compound (d),
Lewis acids, ionic compounds, borane compounds, and carborane compounds can be exemplified. These ionized ionic compounds (d) are disclosed in JP-A-1-501950, JP-A-1-502036, and JP-A-3-17.
No. 9005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, and USP-5321106.

As the Lewis acid used as the ionized ionic compound (d), BR ₃ (where R is the same or different and may have a substituent such as fluorine, methyl, trifluoromethyl, etc.) A phenyl group or fluorine), for example, trifluoroboron, triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl)
Boron, tris (4-fluoromethylphenyl) boron, tris (pentafluorophenyl) boron and the like.

The ionic compound used as the ionized ionic compound (d) is a salt comprising a cationic compound and an anionic compound. The anion functions to cationize the metallocene compound (b) by reacting with the metallocene compound (b), thereby stabilizing the transition metal cation species by forming an ion pair. Examples of such anions include an organic boron compound anion, an organic arsenic compound anion, and an organic aluminum compound anion, and those which are relatively bulky and stabilize transition metal cation species are preferable. Examples of the cation include a metal cation, an organic metal cation, a carbonium cation, a tripium cation, an oxonium cation, a sulfonium cation, a phosphonium cation, and an ammonium cation. More specifically, triphenylcarbenium cation, tributylammonium cation,
N, N-dimethylammonium cation, ferrocenium cation and the like.

Of these, ionic compounds containing a boron compound as an anion are preferred. Specific examples of the ionic compound include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts, dialkylammonium salts, and trialkylammonium salts. Reel phosphonium salts and the like can be mentioned.

Examples of the above trialkyl-substituted ammonium salts include, for example, triethylammonium tetra (phenyl)
Boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl) ammonium tetra (phenyl) boron, trimethylammonium tetra (p-tolyl) boron and the like.

Examples of the N, N-dialkylanilinium salt include, for example, N, N-dimethylanilinium tetra (phenyl)
Boron.

The dialkylammonium salts include:
For example, di (n-propyl) ammonium tetra (pentafluorophenyl) boron, dicyclohexylammonium tetra (phenyl) boron and the like can be mentioned.

Examples of the triarylphosphonium salt include, for example, triphenylphosphonium tetra (phenyl) boron, tri (methylphenyl) phosphonium tetra (phenyl) boron, tri (dimethylphenyl) phosphonium tetra (phenyl) ) Boron and the like.

Further, as the ionic compound, triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis
(Pentafluorophenyl) borate, ferrocenium tetra (pentafluorophenyl) borate and the like can also be mentioned.

Examples of the borane compound used as the ionized ionic compound (d) include the following compounds. Decaborane (14); salts of anions such as bis [tri (n-butyl) ammonium] nonaborate and bis [tri (n-butyl) ammonium] decaborate;
And tri (n-butyl) ammonium bis (dodecahydride dodecaborate) cobaltate (III), bis (tri
(n-butyl) ammonium] salts of metal borane anions such as bis (dodecahydride dodecaborate) nickelate (III).

The carborane compound used as the ionized ionic compound (d) includes 4-carbanonaborane (1
4) salts of anions such as 1,3-dicarbanonaborane (13); and tri (n-butyl) ammonium bis (nonahydride-1,3-dicarbanonaborate) cobaltate (II
I) and salts of metal carborane anions such as tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundecaborate) ferrate (III). The ionized ionic compound (d) as described above may be used in combination of two or more.

The metallocene catalyst (a) used in the present invention comprises:
If necessary, the composition may further contain the following organoaluminum compound (e) in addition to the above components. The organoaluminum compound (e) optionally used in the present invention includes, for example, an organoaluminum compound represented by the following general formula (10).

(R ²⁹ ) _n AlX _3-n (10) In the formula (10), R ²⁹ has 1 to 15 carbon atoms, preferably 1 to 15 carbon atoms.
4 is a hydrocarbon group, X is a halogen atom or a hydrogen atom, and n is 1 to 3.

Examples of such a hydrocarbon group having 1 to 15 carbon atoms include an alkyl group, a cycloalkyl group and an aryl group. Specifically, a methyl group, an ethyl group, an n-propyl group, Examples thereof include an isopropyl group and an isobutyl group.

Specific examples of such an organoaluminum compound include the following compounds. Trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, tri n-butyl aluminum,
Triisobutylaluminum, in trialkylaluminum, formula _{(i-C 4 H 9)} xAly (C 5 H 10) z ( wherein such tri sec- butyl aluminum, x, y, z are each a positive number, z ≧ 2x) represented by alkenyl aluminum such as isoprenyl aluminum, dialkyl aluminum halide such as dimethyl aluminum chloride and diisobutyl aluminum chloride, dialkyl aluminum hydride such as diisobutyl aluminum hydride, dialkyl aluminum alkoxide such as dimethyl aluminum methoxide, and diethyl And dialkylaluminum aryloxides such as aluminum phenoxide.

As the organoaluminum compound (e), a compound represented by the following formula (11) can also be used. (R ³¹ ) _n Al (R ³⁰ ) _3-n (11) (wherein, R ³¹ is the same as R ²⁹ , and R ³⁰ is —OR ³²
Group, -OSi (R ³³⁾ ₃ group, -OAl (R ³⁴⁾ ₂ group, -N (R
³⁵⁾ ₂ group, -Si (R ³⁶⁾ ₃ group or ^{-N (R 37) Al (R} 38) 2
A group, n is ^{1~2, R 32, R 33,} R 34 and R ³⁸ and the like methyl, ethyl, isopropyl, isobutyl, cyclohexyl, phenyl, R ³⁵
Is hydrogen, methyl, ethyl, isopropyl, phenyl, trimethylsilyl, etc., and R ³⁶ and R ³⁷
Represents a methyl group, an ethyl group or the like. )

Such an organoaluminum compound (e)
Specific examples thereof include the following compounds. (C ₂ H ₅ ) ₂ Al (OSi (CH ₃ ) ₃ ), (iso-C ₄ H ₉ ) ₂ A
l (OSi (CH ₃ ) ₃ ), (C ₂ H ₅ ) ₂ Al (OAl (C
_{2 H 5) 2), (} CH 3) 2 Al (N (C 2 H 5) 2), (C 2 H 5) 2 Al
(NH (CH ₃ )), (iso-C ₄ H ₉ ) ₂ Al [N (Si (C
Such as H _{3) 3) 2].}

Metallocene catalyst (a) used in the present invention
May be a solid catalyst in which at least one of the above-mentioned components (b), (c), (d) and (e) is supported on a particulate carrier.

The metallocene catalyst (a) comprises a fine particle carrier, a component (b), a component (c) (or a component (d)) and a polymer or copolymer formed by prepolymerization, and if necessary, a component. And a prepolymerization catalyst comprising (e).

The fine particle carrier used for the solid catalyst and the prepolymerization catalyst is an inorganic or organic compound having a particle size of 10 to 300 μm, preferably 20 to 200 μm.
It is a granular or particulate solid of μm.

Among them, a porous oxide is used as the inorganic carrier.
Preferably, specifically, SiO 2_Two, Al_TwoO_Three, MgO, Z
rO_Two, TiO_Two, B_TwoO_Three, CaO, ZnO, BaO, T
hO _TwoOr mixtures thereof, for example SiO 2_Two-M
gO, SiO_Two-Al_TwoO_Three, SiO_Two-TiO_Two, SiO_Two-
V_TwoO_Five, SiO_Two-Cr_TwoO_Three, SiO_Two-TiO_Two-MgO
And the like. Of these, SiO_TwoAnd
And Al_TwoO_ThreeAt least one member selected from the group consisting of
It is preferable that the main component is a component.

The above inorganic oxide contains a small amount of Na ₂ C
O ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ SO ₄ ,
Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (NO ₃ ) ₂ ,
It may contain carbonate, sulfate, nitrate and oxide components such as Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O and Li ₂ O.

The properties of such a fine particle carrier differ depending on the kind and production method, but the specific surface area is 50 to 1000.
m ² / g, preferably 100~700m ² / g, it is desirable that the pore volume is 0.3~2.5cm ³ / g. The finely divided carrier may be 100 to 1000 as needed.
C., preferably at a temperature of 150 to 700 C.

Further, the fine particle carrier has a particle size of 10
Granular or fine-grained solids of organic compounds having a size of up to 300 μm can be mentioned. Such organic compounds include ethylene, propylene, 1-butene, 4-methyl-1
A (co) polymer formed mainly of an α-olefin having 2 to 14 carbon atoms such as pentene, or a polymer or copolymer formed mainly of vinylcyclohexane or styrene.

The ethylene copolymer (A) used in the present invention
Or an ethylene polymer (B) as a metallocene catalyst (a)
In the case of using ethylene, ethylene and an aromatic vinyl compound and / or an α-olefin are usually copolymerized in a liquid phase by solution polymerization or slurry polymerization in the presence of the metallocene catalyst (a).

Examples of such hydrocarbon solvents include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane and kerosene and halogen derivatives thereof; alicyclic hydrocarbons such as cyclohexane, methylcyclopentane and methylcyclohexane. Hydrogen and its halogen derivatives; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene and chlorobenzene, and their halogen derivatives are used. These solvents may be used in combination.

The ethylene-based copolymer (A) or ethylene-based polymer (B) is prepared by copolymerizing ethylene with an aromatic vinyl compound and / or an α-olefin by gas phase polymerization in the presence of a metallocene catalyst (a). It can also be produced by polymerization. In this case, the metallocene catalyst (a) supported on a fine-particle carrier is particularly preferably used.

Ethylene and the aromatic vinyl compound and / or α-olefin may be copolymerized by either a batch method or a continuous method. When carrying out the copolymerization by a continuous method, the metallocene catalyst (a) is used in the following concentrations.

That is, the concentration of the metallocene compound (b) in the polymerization system is usually 0.00005 to 0.1 mmol / liter (polymerization volume), preferably 0.0001 to 0.1.
05 mmol / liter. The organoaluminum oxy compound (c) is supplied in an amount of 0.1 to 10000, preferably 1 to 5000 in terms of the ratio of aluminum atoms to the metallocene compound (b) (Al / transition metal) in the polymerization system.

The molar ratio of the ionized ionic compound (d) to the metallocene compound (b) in the polymerization system (the ionized ionic compound (d)
/ Metallocene compound (b)) in an amount of 0.1 to 20, preferably 1 to 10.

When the organoaluminum compound (e) is used, it is used in an amount of usually about 0 to 5 mmol / liter (polymerization volume), preferably about 0 to 2 mmol / liter.

In the copolymerization reaction for producing the ethylene copolymer (A) or the ethylene polymer (B), the temperature is usually -30 to + 250 ° C, preferably 0 to 200 ° C, and the pressure exceeds 0. The reaction is carried out under the conditions of ８０80 kg / cm ² (gauge pressure), preferably more than 0 and ５０50 kg / cm ² (gauge pressure).

The reaction time (average residence time when the copolymerization is carried out by a continuous method) varies depending on conditions such as the catalyst concentration and the polymerization temperature, but is usually from 5 minutes to 3 hours, preferably from 10 minutes to 10 minutes. 1.5 hours. At the time of copolymerization, a molecular weight regulator such as hydrogen can be used.

When the monomers are copolymerized as described above, the ethylene-based copolymer (A) or the ethylene-based polymer (B) is usually obtained as a polymerization solution containing the same. This polymerization solution is treated in a conventional manner, and the ethylene copolymer (A)
Alternatively, an ethylene-based polymer (B) is obtained.

The crystallinity of the ethylene copolymer (A) or the ethylene polymer (B) can be determined by, for example, increasing the amount of the α-olefin to be copolymerized with ethylene.
It can be reduced by increasing the olefin copolymerization ratio. The intrinsic viscosity of the ethylene-based copolymer (A) or the ethylene-based polymer (B) can be adjusted, for example, by adjusting the polymerization temperature, the amount of a molecular weight modifier used, and the like.
Can be controlled.

The composition of the present invention may contain an antifogging agent (C) in addition to the ethylene copolymer (A) and the ethylene polymer (B). The antifogging agent (C) is a chemical compounded to prevent moisture in the air from condensing and fogging on the surface of a molded article such as a film or a sheet. There is no particular limitation as long as it has the effect of spreading the water droplets, and those generally used as antifogging agents can be used as they are.

As such an antifogging agent (C), a surfactant is used, for example, sorbitan fatty acid esters such as sorbitan monooleate, sorbitan monolaurate, sorbitan monobehenate and sorbitan monostearate; glycerin monooleate; Glycerin fatty acid esters such as glycerin monostearate; diglycerin monooleate, diglycerin sesquilaurate, diglycerin sesquiolate, tetraglycerin monooleate, tetraglycerin monostearate, hexaglycerin monolaurate, hexaglycerin monooleate, degas Polyglycerol fatty acid esters such as glycerin monooleate and decaglycerin monolaurate; polyoxyalkylene ethers such as polyoxyethylene lauryl ether; lauryldiethanol Fatty amines such as triethanolamine; the like fatty acid amides such as oleic acid amides,
It is not limited to these. These can be used alone or in combination of two or more.

In the composition of the present invention, the compounding amount of the anti-fogging agent (C) is 0.5 to 0.5 parts by weight based on 100 parts by weight of the total of the ethylene copolymer (A) and the ethylene polymer (B). 1
0 parts by weight, preferably 0.5 to 8 parts by weight, more preferably 1 to 5 parts by weight. When the amount of the anti-fogging agent (C) is within the above range, an anti-fogging effect can be obtained, and the anti-fogging agent (C)
Can be obtained without bleeding from the surface of the molded article, excellent in transparency, and also excellent in antifogging durability, mechanical properties and heat resistance.

The reason why excellent antifogging durability can be obtained when the antifogging agent (C) is added to the composition of the present invention is not clear, but an ethylene copolymer obtained by copolymerizing an aromatic vinyl compound is not clear. It is presumed to be due to a synergistic effect of (A) and / or (B) and the antifogging agent (C).

The composition of the present invention may contain a nucleating agent (D). When the nucleating agent (D) is blended, the crystal grains of the components (A) and (B) can be miniaturized, and the crystallization speed can be improved, whereby a composition excellent in transparency, rigidity, heat resistance rigidity and the like can be obtained. In addition to this, high speed molding becomes possible. Even if the nucleating agent (D) is blended, the nucleating agent (D)
However, the occurrence of troubles such as bleed-out and deterioration of the appearance or the inability to perform efficient molding is small.

As the nucleating agent (D), known nucleating agents can be used, for example, rosin nucleating agents, organic phosphoric acid nucleating agents, sorbitol nucleating agents, aromatic carboxylic acid nucleating agents, high melting polymer nucleating agents, And inorganic nucleating agents. Among these, a rosin-based nucleating agent is particularly preferred. When a rosin-based nucleating agent is used, a molded article having a particularly excellent balance of rigidity, transparency and impact resistance can be obtained. The nucleating agent (D) can be used alone or in combination of two or more. The mixing amount of the nucleating agent (D) is desirably 0.01 to 10 parts by weight, preferably 0.3 to 5 parts by weight, based on 100 parts by weight of the components (A) and (B).

The rosin-based nucleating agent (D) is a nucleating agent containing a metal salt of a rosin as a main component and containing 5 to 100% by weight, preferably 10 to 100% by weight of a metal salt of a rosin. A rosin-based nucleating agent contained in a proportion can be used. Here, the rosin metal salt means a reaction product of the rosin and the metal compound.

Examples of the rosins include natural rosins such as gum rosin, tall oil rosin, and wood rosin; disproportionated rosin, hydrogenated rosin, dehydrogenated rosin, polymerized rosin, α,
Various modified rosins such as β-ethylenically unsaturated carboxylic acid modified rosin; and purified products of the above-mentioned natural rosins and purified rosins.

Examples of the unsaturated carboxylic acid used for preparing the α, β-ethylenically unsaturated carboxylic acid-modified rosin include maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, acrylic Acids, methacrylic acid and the like.

The rosins include resin acids such as pimaric acid, sandaracopimaric acid, parastolic acid, isopimaric acid, abietic acid, dehydroabietic acid, neoabietic acid, dihydropimaric acid, dihydroabietic acid and tetrahydroabietic acid. Usually, multiple types are included.

Examples of the metal compound which forms a metal salt by reacting with a rosin include a compound having a metal element such as sodium, potassium and magnesium and forming a salt with the rosin. Specific examples include chlorides, nitrates, acetates, sulfates, carbonates, oxides, hydroxides, and the like of the above metals.

The rosin metal salt is preferably a rosin sodium, potassium or magnesium salt. Further, the rosin is preferably a disproportionated rosin, a hydrogenated rosin, or a dehydrogenated rosin, particularly preferably dehydroabietic acid, dihydroabietic acid, dihydropimaric acid or a derivative thereof.

As more specific rosins, there may be mentioned rosin compounds represented by the following general formula (12).

Embedded image (In the formula, R ¹ , R ² and R ³ may be the same or different, and represent a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group.)

Specific examples of the alkyl group include methyl, ethyl, n-propyl, i-propyl, n-butyl and i-butyl.
Butyl, tert-butyl, pentyl, heptyl, octyl and other alkyl groups having 1 to 8 carbon atoms, such as a hydroxyl group, a carboxyl group, an alkoxy group,
It may have a substituent such as halogen.

Specific examples of the cycloalkyl group include cycloalkyl groups having 5 to 8 carbon atoms such as cyclopentyl, cyclohexyl and cycloheptyl. These groups are substituted with a hydroxyl group, a carboxyl group, an alkoxy group, a halogen atom or the like. It may have a group.

Examples of the aryl group include aryl groups having 6 to 10 carbon atoms such as a phenyl group, a tolyl group, and a naphthyl group. These groups have a substituent such as a hydroxyl group, a carboxyl group, an alkoxy group and a halogen. It may be.

Among the compounds represented by the general formula (12), a compound in which R ¹ , R ² and R ³ are the same or different alkyl groups is preferable, R ¹ is an i-propyl group, and R ² And compounds wherein R ³ is a methyl group are more preferred. The metal salt of such a compound is particularly excellent in improving the crystallization rate.

Specific examples of the compound represented by the general formula (12) include dehydroabietic acid. The compound represented by the general formula (12), for example, dehydroabietic acid is obtained by disproportionation or dehydrogenation of the natural rosin, followed by purification.

The metal salt of the compound represented by the general formula (12) is represented by the following general formula (13).

Embedded image (Wherein M is a metal ion having 1 to 3 valences, R ¹ , R ² and R
³ is the same as in the aforementioned general formula (12). n is an integer of 1 to 3, and is the same integer as the valence of M. )

In the general formula (13), M is a metal ion having 1 to 3 valences, specifically, lithium, sodium,
Monovalent metal ions such as potassium, rubidium and cesium; divalent metal ions such as beryllium, magnesium, calcium, strontium, barium and zinc; and trivalent metal ions such as aluminum. Among these, a monovalent or divalent metal ion is preferable, and a sodium ion, potassium ion or magnesium ion is more preferable.

Among the compounds represented by the general formula (13), a compound in which R ¹ , R ² and R ³ are the same or different alkyl groups, or a compound in which M is a monovalent or divalent metal ion A compound wherein R ¹ is an i-propyl group and R ² and R ³ are methyl groups;
Or M is sodium ion, compounds are more preferably potassium ion or magnesium ion, R ¹
Is an i-propyl group, R ² and R ³ are methyl groups, and M is a potassium ion or a magnesium ion. Such compounds are:
In particular, the effect of improving the crystallization rate is excellent.

Specific examples of the compound represented by the general formula (13) include lithium dehydroabietic acid, sodium dehydroabietic acid, potassium dehydroabietic acid, beryllium dehydroabietic acid, magnesium dehydroabietic acid, calcium dehydroabietic acid, and the like. And metal salts of dehydroabietic acid such as zinc dehydroabietic acid and aluminum dehydroabietic acid.

The compound represented by the general formula (13) can be produced by reacting the compound represented by the general formula (12) with the metal compound by a conventionally known method. For example, when the compound represented by the general formula (13) is a metal salt of dehydroabietic acid, this metal salt can be prepared by combining a dehydroabietic acid represented by the following general formula (14) with the metal compound by a conventionally known method. To produce the compound.

Embedded image

The rosin nucleating agent (D) can be used alone or in combination of two or more. For example, in the case of the compound represented by the general formula (13), two or more compounds in which R ^{1 to} R ³ are the same and M is different may be used in combination, and at least ^one of R ^{1 to} R ³ may be used. Two or more compounds in which one is different and M is the same may be used in combination.

As the rosin-based nucleating agent (D), not all compounds need to be rosin metal salts, and partial metal salts can also be used. That is, when the metal salt of rosin is 5 to
What is contained at a ratio of 100% by weight, preferably 10 to 100% by weight can be used. For example, the compound (metal salt) represented by the general formula (13) is 5 to 100% by weight, preferably 10 to 100% by weight based on the total amount of the compounds represented by the general formulas (12) and (13). % Can be used. In this case, the compound represented by the general formula (12) preferably contains the metal (M) in an amount of 0.05 to 1 equivalent per equivalent of the carboxyl group.

As the organophosphate nucleating agent (D), a compound represented by the following general formula (15) can be exemplified.

Embedded image

(Wherein R¹Is oxygen, sulfur or carbon number
1 to 10 hydrocarbon groups;^Two, R ^ThreeIs hydrogen or charcoal
A hydrocarbon group having a prime number of 1 to 10,^Two, R^ThreeIs the same kind
Or heterogeneous,^TwoEach other, R^ThreeEach other or R
^TwoAnd R^ThreeMay be combined to form a ring, and M is 1 to 3
Is a valent metal atom, and n is an integer of 1 to 3. )

Specific examples of the compound represented by the general formula (15) include sodium-2,2'-methylene-bis (4,6-
(Di-t-butylphenyl) phosphate, sodium-2,
2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate, lithium-2,2'-methylene-bis- (4,6-di-t-butylphenyl) phosphate, lithium-2 , 2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate,
Sodium-2,2'-ethylidene-bis (4-i-propyl-6-t-
Butylphenyl) phosphate, lithium-2,2'-methylene-bis (4-methyl-6-t-butylphenyl) phosphate, lithium-2,2'-methylene-bis (4-ethyl-6-t- Butylphenyl) phosphate, calcium-bis [2,2'-thiobis (4-methyl-6-t-butylphenyl) phosphate], calcium-bis [2,2'-thiobis (4-ethyl-6-t -Butylphenyl) phosphate], calcium-bis [2,2 '
-Thiobis- (4,6-di-t-butylphenyl) phosphate], magnesium-bis [2,2′-thiobis (4,6-di-t-butylphenyl) phosphate], magnesium-bis [2 , 2 '
-Thiobis- (4-t-octylphenyl) phosphate],
Sodium-2,2'-butylidene-bis (4,6-di-methylphenyl) phosphate, sodium-2,2'-butylidene-bis (4,6-di-t-butylphenyl) phosphate, sodium- 2,2'-t-octylmethylene-bis (4,6-di-methylphenyl) phosphate, sodium-2,2'-t-octylmethylene-bis (4,6-di-t-butylphenyl) phosphate Fate, calcium-bis- (2,2'-methylene-bis (4,6-di-t-
Butylphenyl) phosphate), magnesium-bis
[2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate], barium-bis [2,2'-methylene-bis (4,6-di
-t-butylphenyl) phosphate], sodium-2,2 '
-Methylene-bis (4-methyl-6-t-butylphenyl) phosphate, sodium-2,2'-methylene-bis (4-ethyl-6
-t-butylphenyl) phosphate, sodium (4,4'-
Dimethyl-5,6'-di-t-butyl-2,2'-biphenyl) phosphate, calcium-bis [(4,4'-dimethyl-6,6'-di-t-
Butyl-2,2'-biphenyl) phosphate], sodium
-2,2'-ethylidene-bis (4-m-butyl-6-t-butylphenyl) phosphate, sodium-2,2'-methylene-bis
(4,6-di-methylphenyl) phosphate, sodium-
2,2'-methylene-bis (4,6-di-ethylphenyl) phosphate, potassium-2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate, calcium-bis [ 2,2'-
Ethylidene-bis (4,6-di-t-butylphenyl) phosphate], magnesium-bis [2,2'-ethylidene-bis (4,6-
Di-t-butylphenyl) phosphate], barium-bis
[2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate], aluminum-tris [2,2'-methylene-bis (4,6-di-t-butylfell) phosphate ] And aluminum-tris [2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate], and a mixture of two or more thereof. Of these, sodium-2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate is preferred.

As the preferred organic phosphoric acid nucleating agent (D), a compound represented by the following general formula (16) can be exemplified.

Embedded image (In the formula, R ¹ is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, M is a 1 to 3 valent metal atom, and n is an integer of 1 to 3.)

Specific examples of the compound represented by the general formula (16) include sodium-bis (4-t-butylphenyl) phosphate, sodium-bis (4-methylphenyl) phosphate, and sodium-bis (4-methylphenyl) phosphate. (4-ethylphenyl) phosphate, sodium-bis (4-i-propylphenyl) phosphate, sodium-bis (4-t-octylphenyl) phosphate, potassium-bis (4-t-butylphenyl) phosphate , Calcium-bis (4-t-butylphenyl) phosphate, magnesium-bis (4-t
-Butylphenyl) phosphate, lithium-bis (4-t-
(Butylphenyl) phosphate, aluminum-bis (4
(t-butylphenyl) phosphate and a mixture of two or more thereof. Of these, sodium-bis (4-t-butylphenyl) phosphate is preferred.

The sorbitol nucleating agent (D) includes:
The compound represented by the following general formula (17) can be exemplified.

Embedded image (In the formula, each R ¹ is the same or different and is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms.)

Specific examples of the compound represented by the general formula (17) include 1,3,2,4-dibenzylidene sorbitol, 1,3-benzylidene-2,4-p-methylbenzylidene sorbitol, 1,3-benzylidene-2,4-p-ethylbenzylidenesorbitol, 1,3-p-methylbenzylidene-2,4-benzylidenesorbitol, 1,3-p-ethylbenzylidene-2,4
-Benzylidenesorbitol, 1,3-p-methylbenzylidene-2,4-p-ethylbenzylidenesorbitol, 1,3-p-ethylbenzylidene-2,4-p-methylbenzylidenesorbitol, 1,3,2,4- Di (p-methylbenzylidene) sorbitol, 1,3,2,4-di (p-ethylbenzylidene) sorbitol,
1,3,2,4-di (pn-propylbenzylidene) sorbitol,
1,3,2,4-di (pi-propylbenzylidene) sorbitol,
1,3,2,4-di (pn-butylbenzylidene) sorbitol, 1,
3,2,4-di (ps-butylbenzylidene) sorbitol, 1,3,
2,4-di (pt-butylbenzylidene) sorbitol, 1,3,2,
4-di (2 ', 4'-dimethylbenzylidene) sorbitol, 1,3,
2,4-di (p-methoxybenzylidene) sorbitol, 1,3,2,
4-di (p-ethoxybenzylidene) sorbitol, 1,3-benzylidene-2-4-p-chlorobenzylidenesorbitol, 1,3
-p-chlorobenzylidene-2,4-benzylidenesorbitol, 1,3-p-chlorobenzylidene-2,4-p-methylbenzylidenesorbitol, 1,3-p-chlorobenzylidene-2,4-p-
Ethyl benzylidene sorbitol, 1,3-p-methylbenzylidene-2,4-p-chlorobenzylidene sorbitol, 1,3-p
Examples thereof include -ethylbenzylidene-2,4-p-chlorobenzylidene sorbitol, 1,3,2,4-di (p-chlorobenzylidene) sorbitol, and a mixture of two or more thereof. Among these, 1,3,2,4-dibenzylidene sorbitol, 1,
3,2,4-di (p-methylbenzylidene) sorbitol, 1,3,2,
4-di (p-ethylbenzylidene) sorbitol, 1,3-p-chlorobenzylidene-2,4-p-methylbenzylidene sorbitol, 1,3,2,4-di (p-chlorobenzylidene) sorbitol and their two Mixtures of more than one species are preferred.

Other nucleating agents (D) include metal salts of aromatic carboxylic acids and metal salts of aliphatic carboxylic acids, such as aluminum benzoate, aluminum pt-butylbenzoate, sodium adipate, and thiophene. Sodium carboxylate, sodium pyrrole carboxylate and the like can be used. Further, an inorganic compound such as talc can be used.

As the components used in the present invention, those having the above-mentioned physical properties in the above-mentioned general range can be used, but the components having all of the above-mentioned physical properties in the preferable ranges are most preferable. However, components having specific physical property values within a preferred range and other physical property values within a general range can also be used as preferred.

In the composition of the present invention, other resins, tackifiers, weathering stabilizers, and the like, as long as the object of the present invention is not impaired.
Heat stabilizer, antistatic agent, anti-slip agent, anti-blocking agent, lubricant, pigment, dye, plasticizer, anti-aging agent,
Additives such as a hydrochloric acid absorbent and an antioxidant can be added as necessary. Other resins include polypropylene and styrene-based elastomers (SEBS, SBR,
Hydrogenated products).

The composition of the present invention can be produced by using a known method, for example, the following method. 1) A method of mechanically blending or melt-kneading the component (A), the component (B), and other components to be added as required using an extruder, a kneader or the like. 2) Dissolve component (A), component (B), and other components that are added as desired in a suitable good solvent (for example, a hydrocarbon solvent such as hexane, heptane, decane, cyclohexane, benzene, toluene, and xylene). And then removing the solvent. 3) A method in which components (A), (B), and other components to be added as required are separately dissolved in a suitable good solvent, prepared, mixed, and then the solvent is removed. 4) A method in which the above methods 1) to 3) are combined.

In the composition of the present invention, the copolymerization or polymerization is divided into two or more stages having different reaction conditions, and the ethylene-based copolymer (A) and the ethylene-based polymer (B ) May be copolymerized or polymerized, and then the other components optionally added may be mechanically blended or melt-kneaded, or may be dissolved in a solvent and then the solvent may be removed.

The composition of the present invention has moderate elongation elasticity and tackiness, and has balanced performances such as excellent transparency, strength, strain recovery, blocking resistance and processability. I have. When the antifogging agent (C) is blended, excellent antifogging durability can be obtained. Since the composition of the present invention does not contain chlorine, chlorine is not released even during incineration.

The composition of the present invention is widely used as a material for molded articles which are required to have elongational elasticity, tackiness, transparency, strength, strain recovery, blocking resistance, workability, antifogging property or antifogging durability. Although it can be used, the composition of the present invention is excellent in transparency, strength, strain recovery, blocking resistance, processability and anti-fogging durability, and also has a suitable elongation elasticity and has a strain recovery. Since it is improved, it can be suitably used especially as a material for films, sheets and tubes.

Specifically, various film materials such as packaging films such as agricultural films, industrial films, wrap films, stretch films and shrink films; various sheet materials such as packaging sheets; tubes;
It can be suitably used as various tube materials such as hoses and pipes. Among these, a film or sheet for heavy load packaging is particularly preferable. In addition, it can be used as a material for injection molded products such as blow infusion bags, blow bottles, tear-off caps, miscellaneous goods, fibers, and large molded products formed by rotational molding.

The film or sheet of the present invention is a film or sheet comprising the above-mentioned ethylene copolymer composition, and specific examples thereof include agricultural films, industrial films, wrap films, stretch films, shrink films and the like. Various films or sheets, such as a packaging film or a packaging sheet, may be used. These films or sheets can be used as standard bags, heavy-weight packaging materials such as heavy bags, raw paper lump, sugar bags, oil-based packaging bags, water-based packaging bags, various packaging films for food packaging, infusion bags, and agriculture. It can be used as materials for use.

The thickness of the film is usually 5 to 150 μm.
m, and the thickness of the sheet can be usually 150 to 3000 μm. The film or sheet can be molded by a known molding method, for example, inflation molding,
It can be molded by a molding method such as T-die molding and calendar molding. As the inflation molding,
Normal air-cooled inflation molding, air-cooled two-stage cooling inflation molding, high-speed inflation molding, water-cooled inflation molding and the like can be adopted.

The film or sheet formed in this manner has appropriate elongation elasticity and adhesiveness, and is excellent in transparency, strength, strain recovery, blocking resistance and antifogging durability. There is no stickiness on the film surface. Furthermore, there is no bleed-out of the anti-fogging agent (C) and the nucleating agent (D), and the molding processing operation stability is excellent. Will not bleed out.

The film or sheet of the present invention can be used as a single-layer film or sheet, or can be used as a multilayer laminate by laminating it on another film or substrate such as nylon or polyester.

The tube of the present invention is a hollow cylindrical molded product made of the above-mentioned ethylene-based copolymer composition, and specific examples thereof include a shrink tube, a tube for piping, a tube for medical use, a tube for heavy bags, and a hose. , Pipes and the like.

The tube of the present invention has appropriate elongation elasticity and adhesiveness, and is excellent in transparency, strength, strain recovery and anti-fogging durability. It also has excellent kink resistance. Also, there is no sticky surface. Furthermore, there is no bleed-out of the anti-fogging agent (C) and the nucleating agent (D), and the molding processing operation stability is excellent, and the anti-fogging agent (C) and the nucleating agent (D) bleed from the tube after molding. Never go out.

[0160]

As described above, the ethylene copolymer composition of the present invention comprises:
Contains a specific amount of the specific ethylene copolymer (A) and the specific amount of the ethylene polymer (B), so that it has a moderate elongation elasticity and adhesiveness, and has transparency, strength, strain recovery, and blocking resistance. It has well-balanced performance such as excellent workability and workability. When an antifogging agent is added, the effect is maintained for a long period of time, and the antifogging durability is excellent. Since the ethylene copolymer composition of the present invention does not contain chlorine, chlorine is not released even during incineration.

Since the film or sheet of the present invention is composed of the above composition, it has a suitable elongation elasticity and tackiness, and is excellent in transparency, strength, strain recovery and blocking resistance. Has good performance. When an antifogging agent is added, the effect is maintained over a long period of time, and the antifogging durability is excellent.

Further, since the tube of the present invention is composed of the above-mentioned composition, it has a suitable elongation elasticity and adhesiveness.
Moreover, it has well-balanced performance such as excellent transparency, strength, strain recovery, and kink resistance. When an antifogging agent is added, the effect is maintained over a long period of time, and the antifogging durability is excellent.

[0163]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Next, embodiments of the present invention will be described, but the present invention is not limited thereto. In addition, the measuring method of the physical property in each example is as follows.

<< Film Impact >> A film having a thickness of 30 μm was measured by a pendulum type film impact tester (film impact tester) manufactured by Toyo Seiki Seisaku-sho, Ltd. << Strain recovery >> A film was cut into a length of 80 mm and a width of 10 mm, and stress was applied in an atmosphere at 23 ° C.
Were stretched by 100%, left for 10 minutes and released, and the residual strain after 60 minutes was measured.

<< Anti-fogging property and anti-fogging sustainability >>
It was placed on the top of a 200 ml beaker containing 50 ml of 0 ° C. hot water and placed in a 5 ° C. refrigerator for 1 hour, and the antifogging property was evaluated according to the following criteria. After the film was applied to the sunshine weather meter for 200 hours under rainy conditions, the film was placed on the top of a 200 ml beaker containing 50 ml of 70 ° C. hot water,
It was put in a refrigerator at 5 ° C. for 1 hour, and the antifogging durability was evaluated according to the following criteria. ○: The film is not clouded, and the inside of the beaker is clearly seen. ×: The film is clouded, and the inside of the beaker is not clearly seen. << Bubble stability >> Molding is performed by attaching an inflation molding die to the tip of a 30 mm extruder. The stability of bubbles generated at that time was evaluated according to the following criteria. ○: Bubble does not pop and bubble stability is good ×: Bubble pops or fluctuates and stability is poor

Polymerization Example 1 << Production of Ethylene / Styrene Copolymer >> A 5-liter stainless steel equipped with a pressure gauge, a catalyst dropping device and a stirring device.
The reactor was sufficiently purged with nitrogen and toluene 1500 m
and 17.5 ml of styrene, and the mixture was pressurized to 3 kg / cm ² (gauge pressure) with ethylene while stirring, and the temperature inside the system was raised to 50 ° C. Next, 15 mM of methylaluminoxane (10 wt% toluene solution manufactured by Tosoh Akzo Co., Ltd.) and 0.05 mM of (t-butylamide) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silane titanium dichloride (0.01 mM toluene solution) were added to the catalyst dropping device. )
Was charged and dropped into the system by pressurizing with nitrogen. The temperature was maintained at 60 ° C. while continuously supplying ethylene so that the pressure in the system became constant at 5 kg / cm ² (gauge pressure). After 15 minutes, 50 ml of isobutyl alcohol was dropped by a catalyst dropping device to terminate the polymerization.

Next, after depressurizing the system, 1250 ml of isobutyl alcohol and 50 ml of hydrochloric acid water were added to the polymer, and the mixture was heated with stirring at 80 ° C. for 30 minutes. The reaction solution containing isobutyl alcohol was transferred to a separating funnel, and 1250 ml of water was added. It was washed twice and separated into oil and water. Then, the oil layer was added to 15 liters of methanol to precipitate a polymer. The precipitated polymer was vacuum-dried at 130 ° C. for 12 hours to obtain 115 g of an ethylene copolymer A-1 having a styrene content of 2.9 mol% and [η] of 2.01 dl / g.

The amount of styrene and the polymerization temperature are 60 to 70.
An ethylene copolymer B-1 or C-1 was obtained in the same manner as above, except that the temperature was changed to ° C. Table 1 shows the physical properties of the obtained copolymer.

Polymerization Example 2 << Production of Ethylene / α-Olefin Copolymer >> 250 ° C.
Was suspended in 154 liters of toluene, and then cooled to 0 ° C. afterwards,
Methylaminoxan toluene solution (Al = 1.33mo)
(l / liter) 57.5 liter was dropped in 1 hour. At this time, the temperature in the system was kept at 0 ° C. Subsequently, the mixture was reacted at 0 ° C. for 30 minutes, and then heated to 95 ° C. over 1.5 hours.
The reaction was carried out at that temperature for 20 hours. Thereafter, the temperature was lowered to 60 ° C., and the supernatant was removed by a decantation method. The solid component thus obtained was washed twice with toluene and then resuspended in 100 liter of toluene. In this system, a toluene solution of bis (1-methyl-3-n-butylcyclopentadienyl) zirconium dichloride (Zr = 2
7.0 mmol / liter) of 16.8 liter was dropped 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 3.5 mg of zirconium per gram.

To 87 liters of hexane containing 2.5 mol of triisobutylaluminum were added 870 g of the solid catalyst obtained above and 260 g of 1-hexene,
Preliminary polymerization of ethylene was performed at 35 ° C. for 5 hours to obtain a prepolymerized catalyst in which 10 g of polyethylene was prepolymerized per 1 g of the solid catalyst.

Using a continuous fluidized-bed gas-phase polymerization apparatus, a total pressure of 1
8kg / cm^Two(Gauge pressure), polymerization at 75 ° C
And 1-hexene were copolymerized. Prepared above
0.15mmo in terms of zirconium atom
l / h, 10 mmol /
h and continuously supply a constant gas composition during the polymerization.
Ethylene, 1-hexene, hydrogen and nitrogen to maintain
Continuously supplied (gas composition; 1-hexene / ethylene
= 0.034, hydrogen / ethylene = 1.7 × 10 ^-Four, Ethi
Len concentration = 20%). The obtained ethylene copolymer A-
The yield of 2 was 5.8 kg / hr.

An ethylene copolymer B-2 was obtained in the same manner as above except that the amount of 1-hexene was changed. Table 1 shows the physical properties of the obtained copolymer.

Polymerization Example 3 << Production of Ethylene / Styrene Copolymer >> An ethylene / styrene copolymer was prepared in the same manner as in Polymerization Example 1 except that the catalyst was changed to isopropylidenebis (indenyl) zirconium dichloride synthesized by a known method. Combined D-1 was obtained. Table 1 shows the physical properties of the obtained copolymer.

[Table 1]

Example 1 The ethylene copolymers A-1 and B-1 obtained in the polymerization examples
To 100 parts by weight of the ethylene copolymer composition blended at a weight ratio of 0/40, 2 parts by weight of diglycerin sesquilaurylate, 0.3 part by weight of polyoxyethylene lauryl ether and 0.3 part by weight of lauryl diethanolamine were used as antifoggants.
1 part by weight, rosin acid partial metal salt (potassium 1
0.4 parts by weight of 5 mol%, 15 mol% of sodium), 0.1 part by weight of calcium stearate as a stabilizer, 0.1 part by weight of Irganox 1010 (trade name, manufactured by Ciba Geigy), and Irganox 168 (trade name, manufactured by Ciba Geigy) , Trademark) was added and melt-kneaded to form pellets. Using this pellet, 20mmφ · L
Using a single-screw extruder with / D = 26, a 25 mmφ die, a lip width of 0.7 mm, a single slit air ring, an air flow rate of 90 liter / min, an extrusion rate of 9 g / min, a blow ratio of 1.8, and a take-up speed of 2. Under a condition of 4 m / min and a processing temperature of 200 ° C., a film having a thickness of 30 μm was blown. Table 2 shows the evaluation results.

Examples 2-3 A film was formed in the same manner as in Example 1 except that the copolymers shown in Table 2 were used as the ethylene-based copolymer. Table 2 shows the physical properties of the obtained film.

Example 4 A film was formed in the same manner as in Example 1, except that the copolymer shown in Table 3 was used as the ethylene-based copolymer. Table 3 shows the physical properties of the obtained film. The intrinsic viscosity [η] of the blend was 1.72 dl / g.

Comparative Example 1 A film was formed in the same manner as in Example 1 except that ethylene copolymers A-2 and B-2 containing no aromatic vinyl compound were used as the ethylene copolymer. Table 3 shows the physical properties of the obtained film.

Comparative Example 2 A film was formed in the same manner as in Example 1 except that the ethylene copolymer C-3 was used alone. Table 3 shows the physical properties of the obtained film.

[0179]

[Table 2] Note) NB: Not destroyed

[0180]

[Table 3] Note) NB: Not destroyed

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Tetsuhiro Matsumoto 1-2-1, Waki, Waki-cho, Kuga-gun, Yamaguchi Prefecture Inside Mitsui Petrochemical Industry Co., Ltd.

Claims (11)

[Claims] A: Ethylene in the presence of a metallocene catalyst (a), an aromatic vinyl compound and / or C3
And a copolymer having a crystallinity of 10% or more and less than 90%, and an intrinsic viscosity [η _A ] of 1 to 135 ° C. measured in decalin.
10 dl / g ethylene copolymer (A) 10 to 9
0% by weight, and B: an ethylene homopolymer obtained by homopolymerizing ethylene in the presence of the metallocene catalyst (a), or ethylene and an aromatic vinyl compound and / or in the presence of the metallocene catalyst (a). The copolymer obtained by copolymerizing an α-olefin having 3 to 20 carbon atoms has a crystallinity of more than 10% and 90% or less, and has an intrinsic viscosity [η _B ] of 0.3 in decalin at 135 ° C.
Ethylene polymer (B) having a content of 1 to 2 dl / g
An ethylene-based copolymer composition containing 0% by weight, wherein one or both of the ethylene-based copolymer (A) and the ethylene-based polymer (B) are copolymerized with an aromatic vinyl compound, The ratio of the crystallinity of the ethylene copolymer (A) to the crystallinity of the ethylene polymer (B) (crystallinity of component (A) / crystallinity of component (B)) is less than 1. Wherein the ratio ([η _A ] / [η _B ]) of the intrinsic viscosity of the ethylene copolymer (A) to the intrinsic viscosity of the ethylene polymer (B) exceeds 1. -Based copolymer composition. 2. The composition according to claim 1, wherein the content of the aromatic vinyl compound in the ethylene copolymer (A) is 1.4 to 10 mol%. 3. The ethylene-based polymer (B) is a homopolymer of ethylene or an ethylene / α-olefin copolymer and has a density exceeding 0.93 g / cm ³ and 0.97 g / cm ^3.
3. The composition according to claim 1, which is a high-density polyethylene having a size of not more than cm ³ . 4. An ethylene-based polymer (B) comprising ethylene, an aromatic vinyl compound and / or C 3-20.
3. The composition according to claim 1, wherein the composition is a copolymer with an α-olefin having a content of an aromatic vinyl compound of 0.05 to 1.4 mol%. 4. 5. The ethylene-based polymer (B) is a copolymer of ethylene and an α-olefin having 3 to 8 carbon atoms,
Density 0.86 g / cm ³ according to claim 1 or 2 composition, wherein the linear low density polyethylene of ~0.93g / cm ^3. 6. An antifogging agent (C) is contained in an amount of 0.5 to 10 parts by weight based on a total of 100 parts by weight of the ethylene-based copolymer (A) and the ethylene-based polymer (B). The composition according to any one of claims 1 to 5. 7. The nucleating agent (D) is contained in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the total of the ethylene-based copolymer (A) and the ethylene-based polymer (B). Item 7. The composition according to any one of Items 1 to 6. 8. The metallocene catalyst (a) containing a bridge type metallocene compound.
The composition according to any one of the above. 9. The composition according to claim 8, wherein the bridge type metallocene compound is isopropylidenebis (indenyl) zirconium dichloride. 10. A film, sheet or tube comprising the composition according to any one of claims 1 to 9. 11. A film, sheet or tube for heavy-weight packaging, comprising the composition according to claim 1.