JPH11293054A - Polyethylene based resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide polyethylene based resin compositions excellent in molding stability and capable of obtaining films excellent in clarity, gloss, nerve, anti block properties and strength. SOLUTION: Desired polyethylene based resin compositions comprise (A) 99.5-70 wt.% ethylene/α-olefin copolymer having an MFR of 0.1-15 g/10 min and a density of 0.880-0.960 g/cm<3> to be obtained by copolymerizing ethylene and a 3-12C α-olefin in the presence of an olefin polymerization catalyst comprising a metallocene type transition metal compound, an ion exchangeable laminar compound having a water content of not more than 3 wt.% obtained by conducting salt treatment and/or acid treatment excluding silicate salts, and at least one compound selected from inorganic silicate salts as the essential components; (B) 0.5-30 wt.% low density polyethylene having an MFR of 0.1-20 g/10 min and a density of 0.910-0.935 g/cm<3> produced by the high pressure radical method; (C) 0.05-1.0 pt.wt. antioxidant; and (D) 0.01-0.8 pt.wt. anti-blocking agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyethylene resin which is excellent in stability at the time of molding, and which can obtain a film excellent in transparency, gloss, waist, opening property and strength by forming a film. It relates to a composition.

[0002]

2. Description of the Related Art Conventionally, a film obtained by forming an ethylene / α-olefin copolymer into an inflation film has excellent mechanical properties such as tensile strength and impact strength. It is used in large quantities for various purposes. However, a film obtained by molding an ethylene / α-olefin copolymer alone into a blown film has a problem that transparency and opening property are not sufficient in many applications. On the other hand, an ethylene / α-olefin copolymer using a metallocene catalyst is disclosed in
No. 13309 has been proposed. However, the ethylene / α-olefin copolymer produced using this metallocene catalyst also has insufficient stability at the time of molding, and further has a higher transparency and portability than conventional ethylene / α-olefin copolymer films. Although the opening is somewhat improved, it is not yet fully satisfactory. Therefore, in order to obtain excellent opening stability when forming into a film with excellent molding stability, a large amount of low-density polyethylene produced by the high-pressure radical method is blended, and a large amount of an antiblocking agent is added. I needed to.

[0003]

However, such a method in which a high-pressure method low-density polyethylene or an anti-blocking agent is added causes a problem that the strength and transparency of the film are reduced, and when the amount of the anti-blocking agent is reduced, Although the transparency was improved, the opening property was deteriorated and a problem occurred in terms of product quality. Therefore, the present invention provides an ethylene-α-
An object of the present invention is to provide a polyethylene-based resin composition that can provide a film having sufficient transparency and openability without impairing the excellent mechanical properties of the olefin copolymer and that has excellent stability during molding.

[0004]

As a result of various studies to solve the above problems, the present inventors have found that ethylene and α-olefin are copolymerized in the presence of a specific olefin polymerization catalyst. The obtained ethylene / α-olefin copolymer having MFR and density values within a specific range, a low-density polyethylene produced by a high-pressure radical method having MFR and density values within a specific range, and The present inventors have found that the above object can be achieved by blending a specific amount of an antioxidant and a specific amount of an antiblocking agent, thereby completing the present invention. That is, the polyethylene resin composition of the present invention comprises the following components (A) to (D)
It is characterized by consisting of. Component (A): component (a): a metallocene-type transition metal compound, and component (b): a salt treatment and / or obtained by performing the acid treatment, the water content of 3 wt% or less, (b ₁ ): An ion-exchangeable layered compound other than silicate, and (b ₂ ): an inorganic silicate, and at least one compound selected from the group consisting of: An ethylene / α-olefin copolymer having an MFR of 0.1 to 15 g / 10 min and a density of 0.880 to 0.960 g / cm ³ obtained by copolymerizing an α-olefin having 3 to 12 carbon atoms 99.5 Component (B): low density polyethylene having a MFR of 0.1 to 20 g / 10 minutes and a density of 0.910 to 0.935 g / cm ³ produced by the high pressure radical method 0.5 to 30% by weight , Ingredients ( ): Antioxidant 0.05 to 1.0 part by weight component (D): anti-blocking agent from 0.01 to 0.8 parts by weight

[0005]

DETAILED DESCRIPTION OF THE INVENTION [I] Constituents (1) Ethylene / α-olefin copolymer (component (A)) (A) Physical properties Ethylene / α-olefin of component (A) used in the present invention
The olefin copolymer has an MFR of 0.1 to 15 g / 10 min at 190 ° C. under a load of 2.16 kg, preferably 0.5 to 15 g / 10 min.
It is important that it is ７7 g / 10 min. If the MFR is less than the above range, the extrusion load at the time of molding is increased, and the workability is reduced. On the other hand, if the MFR exceeds the above range, not only does the strength as a film decrease, but also the molding stability decreases. The ethylene / α-olefin copolymer of the component (A) used in the present invention has a density of 0.880.
０．９0.960 g / cm ³ , preferably 0.900-0.
It is important that it is 940 g / cm ³ . If the density is less than the above range, the film is insufficiently stiff and the workability is reduced. On the other hand, when the density exceeds the above range, the transparency is excellent as compared with the ordinary ethylene / α-olefin copolymer, but the absolute transparency is still insufficient.

(B) Production Ethylene α-component of component (A) used in the present invention
The olefin copolymer is obtained by subjecting the metallocene transition metal compound of the component (a) and the salt treatment and / or the acid treatment of the component (b) to have a water content of 3% by weight or less, (b) ₁ ) ethylene and carbon in the presence of an olefin polymerization catalyst comprising at least one compound selected from the group consisting of an ion-exchangeable layered compound excluding silicate and (b ₂ ) an inorganic silicate. It is a random copolymer obtained by copolymerizing α-olefins of Formulas 3 to 12.

(A) Raw Material Ethylene used as a raw material in the ethylene / α-olefin copolymer of the component (A) and α-olefin copolymerized with the ethylene have 3 carbon atoms.
To 12, preferably 4 to 10, specifically, for example, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, or a mixture thereof. In addition, a small amount of other α-olefin or polyene may be copolymerized. Here, examples of other olefins include propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 4-methyl-1-pentene and the like. Examples of the polyene include butadiene, isoprene, 1,4-hexadiene, and dicyclopentadiene. The content of the α-olefin is not limited as long as the ethylene / α-olefin copolymer satisfies the characteristics described below.
It is from 1 to 27% by weight, preferably from 0.5 to 18% by weight, particularly preferably from 2 to 13% by weight.

(B) Catalyst for Olefin Polymerization The polymerization method for obtaining the ethylene / α-olefin copolymer is not limited, but the metallocene transition metal compound of component (a) and the component (a) (b) obtained by performing the salt treatment and / or acid treatment, the moisture content of 3 wt% or less, (b ₁₎ ion-exchange layered compound except silicates, and, (b ₂₎ an inorganic silicate It is important that the catalyst is produced using an olefin polymerization catalyst containing at least one compound selected from the group consisting of salts as an essential component.

(I) Metallocene transition metal compound (component (a)) The metallocene transition metal compound of component (a), which is a catalyst component for olefin polymerization, may be substituted with one or two cyclopentane compounds which may be substituted. A dienyl-based ligand, that is, one or two cyclopentadienyl ring-containing ligands which may form a condensed ring by combining substituents,
It is an organometallic compound comprising a transition metal of Groups 4, 5, and 6, or a cationic complex thereof. Preferred as such a metallocene-based transition metal compound is a compound represented by the following general formula [II] or [III]. General formula _{^{[II] (CpR 1 a H}} 5-a) p (CpR 2 b H 5-b) q M
R ³ _r general formula _{^{[III] [(CpR 1 a}} H 5-a) p (CpR 2 b H 5-b) q
^{_{MR 3 r L m] n +}} [ in R ^{4] n-} (above general formula [II] and [III], CpR ¹ _a H
_5-a and CpR ² _b H _{5 -b} shows derivatives of cyclopentadienyl (Cp) group. General formulas [II] and [III]
R ¹ and R ^{2 in the above} are an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing substituent, a phosphorus-containing substituent, a nitrogen-containing substituent, and an oxygen-containing substituent. It may be different.

Specifically, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-
Butyl group, pentyl group, isopentyl group, hexyl group,
Alkyl group such as heptyl group, octyl group, nonyl group, decyl group, phenyl group, p-tolyl group, o-tolyl group, m
-Aryl group such as tolyl group, fluoromethyl group, fluoroethyl group, fluorophenyl group, chloromethyl group, chloroethyl group, chlorophenyl group, bromomethyl group, bromoethyl group, bromophenyl group, iodomethyl group, iodoethyl group, iodophenyl group, etc. Halo-substituted hydrocarbon groups, trimethylsilyl groups, triethylsilyl groups, silicon-containing substituents such as triphenylsilyl groups, methoxy groups, ethoxy groups, propoxy groups, isopropoxy groups, butoxy groups, isobutoxy groups, t-butoxy groups, etc. Examples thereof include an aryloxy group such as an alkoxy group, a phenoxy group, a methylphenoxy group, a pentamethylphenoxy group, a p-tolyloxy group, an m-tolyloxy group, and an o-tolyloxy group. Among them, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, alkyl group having 1 to 4 carbon atoms such as t-butyl group, trimethylsilyl group, methoxy group, alkoxy group such as ethoxy group, And an aryloxy group such as a phenoxy group.

Further, R ¹ and R ² may be bonded to each other to form a crosslinking group. Specifically, methylene group, alkylene group such as ethylene group, ethylidene group, propylidene group, isopropylidene group, phenylmethylidene group, alkylidene group such as diphenylmethylidene group, dimethylsilylene group, diethylsilylene group, Silicon-containing crosslinking groups such as propylsilylene group, diisopropylsilylene group, diphenylsilylene group, methylethylsilylene group, methylphenylsilylene group, methylisopropylsilylene group, methyl-t-butylsilylene group, dimethylgemylene group, diethylgemylene Group, dipropylgemylene group, diisopropylgemylene group, diphenylgemylene group, methylethylgemylene group, methylphenylgemylene group, methylisopropylgemylene group, germanium-containing crosslinking group such as methyl-t-butylgemylene group, etc. Amino group,
Examples include a phosphinyl group.

Further, R ¹ and R ² may be bonded to each other to form a crosslinking group. Specifically, an indenyl group, a tetrahydroindenyl group, a fluorenyl group, an octahydrofluorenyl group and the like are preferably mentioned, and these may be substituted. R ³ is an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, hydrogen, halogen, a silicon-containing substituent, alkoxy, aryloxy, amide, or thioalkoxy, and specifically, a methyl group, Ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, isopentyl group, hexyl group, heptyl group, octyl group, nonyl group,
Alkyl group such as decyl group, phenyl group, p-tolyl group,
o-tolyl group, aryl group such as m-tolyl group, fluoromethyl group, fluoroethyl group, fluorophenyl group, chloromethyl group, chloroethyl group, chlorophenyl group, bromomethyl group, bromoethyl group, bromophenyl group, iodomethyl group, iodoethyl Groups, halo-substituted hydrocarbon groups such as iodophenyl group, halogens such as fluorine, chlorine, bromine and iodine, silicon-containing substituents such as trimethylsilyl group, triethylsilyl group and triphenylsilyl group, methoxy group, ethoxy group and propoxy group Aryloxy such as an alkoxy group such as isopropoxy group, butoxy group, isobutoxy group and t-butoxy group, phenoxy group, methylphenoxy group, pentamethylphenoxy group, p-tolyloxy group, m-tolyloxy group and o-tolyloxy group Group, dimethylamide group, diethyl Amide groups, dipropyl amide group,
Diisopropylamide group, methylthioalkoxy group, ethylthioalkoxy group, propylthioalkoxy group, butylthioalkoxy group, t-butylthioalkoxy group,
And thioalkoxy groups such as phenylthioalkoxy groups. Among these, hydrogen, methyl, ethyl, propyl, isopropyl, butyl, phenyl, halogen such as chlorine, methoxy, ethoxy, propoxy, isopropoxy, dimethylamide, methylthioalkoxy are preferred. Groups,
Among them, hydrogen, a methyl group, and chlorine are particularly preferable.

R ³ may be bonded to R ^1, R ² or Cp. As a specific example of such a ligand, CpH ₄ (CH ₂ ) _n O- (1 ≦ n ≦ 5 ), C
pMe ₄ (CH ₂ ) _n O— (1 ≦ n ≦ 5), CpH
₄ (Me ₂ Si) (t-Bu) N-, CpMe ₄ (Me
₂ Si) (t-Bu) N— and the like (Cp represents a cyclopentadienyl group, Me represents a methyl group, and Bu represents a butyl group). Further, R ³ may combine with each other to form a bidentate ligand. Specific examples of such R ³ include —O
_{CH 2 O -, - OCH 2} CH 2 O -, - O (o-C 6 H
₄ ) O- and the like can be mentioned.

M is an atom belonging to Group 3, 4, 5, or 6 of the periodic table. Specifically, scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium , Erbium, thulium, ytterbium, lutetium, actinium, thorium, protactinium, uranium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, among these, titanium, zirconium, Hafnium is preferably used. These may be mixed and used.

L is an electrically neutral ligand, and m is an integer of 0 or more. Specific examples include ethers such as diethyl ether, tetrahydrofuran and dioxane, nitriles such as acetonitrile, amides such as dimethylformamide, phosphines such as trimethylphosphine, and amines such as trimethylamine. it can. Preferred are tetrahydrofuran, trimethylphosphine and trimethylamine.

[R ⁴ ] is one or more anions that neutralize the cation. Specific examples include tetraphenyl borate, tetra (p-tolyl) borate, carbadodecaborate, dicarboundecaborate, tetrakis (pentafluorophenyl) borate, tetrafluoroborate, and hexafluorophosphate.
a and b are integers of 0-5. Also, p, q, and r are M
Is a non-negative integer satisfying p + q + r = V when the metallocene compound is represented by the general formula [II], and p + q + r when the metallocene compound is represented by the general formula [III]. = Non-negative integer satisfying Vn.
Usually, p and q are integers of 0 to 3, preferably 0 or 1. r is an integer of 0 to 3, preferably 1 or 2, and n is an integer satisfying 0 ≦ n ≦ V. )

The above-mentioned metallocene transition metal compound, specifically, taking zirconium as an example, those corresponding to the general formula [II] include (1) bis (methylcyclopentadienyl) zirconium dichloride and ( 2) bis (ethylcyclopentadienyl) zirconium dichloride, (3) bis (methylcyclopentadienyl) zirconium dimethyl, (4) bis (ethylcyclopentadienyl) zirconium dimethyl, (5) bis (methylcyclopentadi (Enyl) zirconium dihydride, (6) bis (ethylcyclopentadienyl) zirconium dihydride, (7) bis (dimethylcyclopentadienyl) zirconium dichloride, (8) bis (trimethylcyclopentadienyl) zirconium dichloride , (9)
Bis (indenyl) zirconium dichloride, (1
0) bis (dimethylcyclopentadienyl) zirconium dimethyl, (11) bis (indenyl) zirconium dimethyl, (12) bis (trimethylsilylcyclopentadienyl) zirconium dimethyl, (13) bis (trifluoromethylcyclopentadienyl) Zirconium dichloride, (14) isopropylidene-bis (indenyl) zirconium dichloride, (15) isopropylidene-bis (indenyl) zirconium dihydride, (16) pentamethylcyclopentadienyl (cyclopentadienyl) zirconium dichloride, ( 1
7) pentamethylcyclopentadienyl (cyclopentadienyl) zirconium dimethyl, (18) isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, (19) isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dimethyl ,

(20) bis (cyclopentadienyl) zirconium dichloride, (21) bis (cyclopentadienyl) zirconium dimethyl, (22) bis (cyclopentadienyl) zirconium diethyl, (23) methylcyclopentadienyl (Cyclopentadienyl) zirconium dichloride, (24) methylcyclopentadienyl (cyclopentadienyl) zirconium dimethyl, (25) dimethylcyclopentadienyl (cyclopentadienyl) zirconium dichloride, (26) indenyl (cyclopentane (Dienyl) zirconium dichloride, (27) bis (pendamethylcyclopentadienyl) zirconium dichloride, (28) indenyl (cyclopentadienyl) zirconium zirconium dimethyl, (29) Trimethyl cyclopentadienyl (cyclopentadienyl) zirconium dimethyl, (30)
Trifluoromethylcyclopentadienyl (cyclopentadienyl) zirconium dichloride, (31) trifluoromethylcyclopentadienyl (cyclopentadienyl) zirconium dimethyl, (32) bis (cyclopentadienyl) (trimethylsilyl) (methyl ) Zirconium, (33) methylene-bis (cyclopentadienyl) zirconium dichloride, (34) ethylene-
Bis (cyclopentadienyl) zirconium dichloride, (35) dimethylsilyl-bis (cyclopentadienyl) zirconium dimethyl, (36) bis (cyclopentadienyl) zirconium bis (methanesulfonate)
(37) bis (cyclopentadienyl) zirconium trifluoromethanesulfonatochlorite, (38) bis (indenyl) zirconium bis (triple methanesulfonate), (39) ethylenebis (indenyl) zirconium bis (trifluoromethanesulfonate) ),

(40) (Tertiary butylamido) dimethyl (tetramethylcyclopentadienyl) silane dibenzyl zirconium (tertiary butylamido) dimethyl (2,
3,4,5-tetramethylcyclopentadienyl) silane dibenzyl zirconium, (41) indenyl zirconium tris (dimethylamide), (42) (tertiary butylamide) (tetramethylcyclopentadienyl)-
1,2-ethanediylconium dichloride, (43)
(Tertiary butylamide) dimethyl- (tetramethylcyclopentadienyl) silane zirconium dichloride,
(44) (phenyl phosphide) dimethyl (tetramethylcyclopentadienyl) silane zirconium dichloride, (45) bis (1,3-dimethylcyclopentadienyl) zirconium dichloride, (46) bis (1
-Ethyl-3-methylcyclopentadienyl) zirconium dichloride, (47) bis (1-n-propyl-3)
-Methylcyclopentadienyl) zirconium dichloride, (48) bis (1-i-propyl-3-methylcyclopentadienyl) zirconium dichloride, (49)
Bis (1-n-butyl-3-methylcyclopentadienyl) zirconium dichloride,

(50) bis (1-i-butyl-3-methylcyclopentadienyl) zirconium dichloride,
(51) bis (1-cyclohexyl-3-methylcyclopentadienyl) zirconium dichloride, (52) bis (1,3-dimethylcyclopentadienyl) zirconium dimethyl, (53) bis (1-ethyl-3-methylcyclo) (Pentadienyl) zirconium dimethyl, (5
4) bis (1-n-propyl-3-methylcyclopentadienyl) zirconium dimethyl, (55) bis (1-
n-butyl-3-methylcyclopentadienyl) zirconium dimethyl, (56) bis (1,3-dimethylcyclopentadienyl) zirconium bis (diethylamide), (57) bis (1-ethyl-3-methylcyclopentadienyl) ) Zirconium bis (diethylamide),
(58) bis (1-n-butyl-3-methylcyclopentadienyl) zirconium bis (diethylamide) and the like.

Further, those corresponding to the general formula [III] include (1) bis (methylcyclopentadienyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, and (2) bis (ethylcyclopentadiene). (Enyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, (3) bis (methylcyclopentadienyl) zirconium (methyl)
(Tetraphenyl borate) tetrahydrofuran complex,
(4) bis (ethylcyclopentadienyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, (5) bis (methylcyclopentadienyl) zirconium (hydrido) (tetraphenylborate) tetrahydrofuran complex, (6) bis (Dimethylcyclopentadienyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex,
(7) Bis (indenyl) zirconium (chloride)
(Tetraphenyl borate) tetrahydrofuran complex,
(8) bis (dimethylcyclopentadienyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, (9) bis (trimethylcyclopentadienyl) zirconium (hydrido) (tetraphenylborate) tetrahydrofuran complex,

(10) isopropylidene-bis (indenyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, (11) isopropylidene-bis (indenyl) zirconium (methyl) complex
(Tetraphenyl borate) tetrahydrofuran complex,
(12) isopropylidene-bis (indenyl) zirconium (hydride) (tetraphenylborate) tetrahydrofuran complex, (13) pentamethylcyclopentadienyl (cyclopentadienyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, 14) Isopropylidene (cyclopentadienyl) (fluorenyl) zirconium (chloride)
(Tetraphenyl borate) tetrahydrofuran complex,
(15) bis (cyclopentadienyl) (methyl) zirconium (tetraphenylborate) tetrahydrofuran complex, (16) methylcyclopentadienyl (cyclopentadienyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, (17) )
Dimethylcyclopentadienyl (cyclopentadienyl) zirconium (chlorite) (tetraphenylborate) tetrahydrofuran complex, (18) indenyl (cyclopentadienyl) zirconium (chloride)
(Tetraphenyl borate) tetrahydrofuran complex,
(19) trimethylsilylcyclopentadienyl (cyclopentadienyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex,

(20) Bis (cyclopentadienyl)
(Trimethylsilyl) zirconium (tetraphenylborate) tetrahydrofuran complex, (21) bis (cyclopentadienyl) (trimethylsilylmethyl) zirconium (tetraphenylborate) tetrahydrofuran complex, (22) ethylene-bis (cyclopentadienyl) zirconium (chloride) ) (Tetraphenylborate) tetrahydrofuran complex, (23) dimethylsilyl-bis (cyclopentadienyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, (24) ethylene-bis (cyclopentadienyl) zirconium (methyl) (Tetraphenylborate) tetrahydrofuran complex, (25) dimethylsilyl-bis (cyclopentadienyl) zirconium (methyl) (tetraphenylborate Over g) tetrahydrofuran complex, (26) ethylene - bis (cyclopentadienyl)
Zirconium (hydride) (tetraphenylborate)
Tetrahydrofuran complex, (27) bis (cyclopentadienyl) zirconium (methanesulfonato) (tetraphenylborate) tetrahydrofuran complex, and the like. In addition, the same compounds as those described above can also be used for Group 3, 4, 5, and 6 metal compounds such as titanium compounds and hafnium compounds. Further, a mixture of these compounds may be used.

(Ii) Compound of component (b) The compound of component (b), which is a catalyst component for olefin polymerization, is obtained by salt treatment and / or acid treatment.
At least one compound selected from the group consisting of (b ₁ ) an ion-exchange layered compound excluding silicate and a (b ₂ ) inorganic silicate having a water content of 3% by weight or less is used.

(B ₁ ) Ion-exchange layering excluding silicate
An ion-exchange layered compound other than silicate, which has not been subjected to compound salt treatment or acid treatment, is a compound that has a crystal structure in which the planes formed by ionic bonds etc. are stacked in parallel with weak bonding force to each other For example, most clays can be mentioned. Clay is usually composed mainly of clay minerals. These clays, clay minerals, and ion-exchange layered compounds are not limited to natural products,
It may be an artificial compound.

Clay, clay mineral Specific examples of clay and clay mineral include allophane group such as allophane, kaolin group such as dickite, nacrite, kaolinite and anoxite, halloysite group such as metahaloysite and halloysite, chrysotile, and resaltitite. , Serpentine family such as antigorite, montmorillonite, zaukonite, beidellite, nontronite, saponite, hectorite and other smectites, vermiculite and other vermiculite minerals, illite, salicite, mica minerals such as chlorite, attapulgite, sepiolite , Palygorskite, bentonite, kibushi clay, gairome clay, hisingelite, pyrophyllite, ryokudeite group and the like. These may form a mixed layer. Among these, montmorillonite, zaukonite, beidellite, nontronite, saponite,
Smectites such as hectorite, bentonite, teniolite and mica are preferred.

Ion-exchangeable layered compound Further, examples of the ion-exchanged layered compound include ionic crystalline compounds having a layered crystal structure such as hexagonal close-packed type, antimony type, CdCl ₂ type, CdI ₂ type and the like. I can do it. Specific examples of the ion-exchange layered compound having such a crystal structure include α-Zr (HAsO ₄ )
₂ · H ₂ O, α-Zr (HPO ₄ ) ₂ , α-Zr (KP
_{O 4) 2 · 3H 2 O} , α-Ti (HPO 4) 2, α-T
i (HAsO ₄ ) ₂ · H ₂ O, α-Sn (HPO ₄ ) ₂
H ₂ O, γ-Zr (HPO ₄ ) ₂ , γ-Ti (HPO
₄ ) ₂ , and crystalline acidic salts of polyvalent metals such as γ-Ti (NH ₄ PO ₄ ) ₂ .H ₂ O. These may be used as such without any particular treatment, or may be subjected to ball milling, sieving, acid treatment by contact with inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, etc., or organic acids such as formic acid, acetic acid, benzoic acid, etc. It may be used after performing the above processing. Further, they may be used alone or as a mixture of two or more.

(B ₂ ) Examples of the inorganic silicate that has not been subjected to the inorganic silicate salt treatment and the acid treatment include zeolite and diatomaceous earth, and these may be a synthetic product or naturally occurring. Minerals may be used. These may be used as they are without any particular treatment, or may be used after treatments such as ball milling, sieving, and acid treatment. Further, they may be used alone or as a mixture of two or more. At least one compound selected from the group consisting of an ion-exchangeable layered compound excluding silicate and an inorganic silicate, which has not been subjected to salt treatment or acid treatment, used in the present invention, is an exchangeable Group 1 compound. Contains metal cations (usually, for example, Na, K). 1
The cation content of the group metal is desirably 0.1% by weight, preferably 0.5% by weight. At least one compound selected from the group consisting of an ion-exchangeable layered compound other than silicate and an inorganic silicate is subjected to salt treatment and / or
Alternatively, the compound of component (b), which is a catalyst component for olefin polymerization, can be obtained by acid treatment.

Salt treatment and / or acid treatment Salt treatment and / or acid treatment can change the acid strength of a solid. In addition, salt treatment, ion complex,
By forming a molecular complex, an organic derivative or the like, the surface area and the interlayer distance can be changed. That is, utilizing ion exchangeability,
By replacing the exchangeable ions between the layers with another large bulky ion, it is possible to obtain a layered material in which the layers are expanded. In the present invention, the cation of the exchangeable Group 1 metal cation contained in at least one compound selected from the group consisting of an ion-exchangeable layered compound excluding silicate and an inorganic silicate before being treated with salts. It is necessary to exchange 40% or more, preferably 60% or more, of the cations dissociated from the following salts.

Salts The salts used in the salt treatment of the present invention for the purpose of ion exchange are compounds containing a cation containing at least one atom selected from the group consisting of Group 2 to 14 atoms. And preferably a cation containing at least one kind of atom selected from the group consisting of Group 2 to 14 atoms and a halogen atom, at least one kind of anion selected from the group consisting of inorganic acids and organic acids. More preferably, a cation containing at least one atom selected from the group consisting of atoms of groups 2 to 14, and Cl, Br,
I, F, PO ₄ , SO ₄ , NO ₃ , CO ₃ , C ₂ O ₄ ,
ClO ₄ , OCOCH ₃ , CH ₃ COCHCOCH ₃ ,
OCl ₂ , O (NO ₃ ) ₂ , O (ClO ₄ ) ₂ , O (S
O ₄ ), OH, O ₂ Cl ₂ , OCl ₃ , OCOH, OC
It is a compound comprising at least one anion selected from the group consisting of OCH ₂ CH ₃ , C ₂ H ₄ O ₄ and C ₆ H ₅ O ₇ . Specifically, CaCl ₂ , CaSO ₄ ,
Ca (NO ₃ ) ₂ , MgCl ₂ , MgBr ₂ , MgSO
₄ , Mg (PO ₄ ) ₂ , Mg (NO ₃ ) ₂ , Mg (Cl
O ₄ ) ₂ , CrO ₂ Cl ₂ , CrF ₃ , CrCl ₃ , C
rBr ₃ , Cr (NO ₃ ) ₃ , Cr ₂ (SO ₄ ) ₃ , C
o (CH ₃ COCHCOCH ₃ ) ₃ , CoCO ₃ , Co
C ₂ O ₄ , CoF ₂ , NiCO ₃ , NiC ₂ O ₄ , Pb
SO ₄ , Pb (NO ₃ ) ₂ , CuBr ₂ , Cu (OCO
CH ₃ ) ₂ , Zn (CH ₃ COCHCOCH ₃ ) ₂ , Z
n (OCOCH ₃ ) ₂ , Zn (OOCH) ₂ , ZnCO
₃ , Zn (SO ₄ ), Zn (NO ₃ ) ₂ , ZnCl ₂ ,
AlCl ₃ , Al (NO ₃ ) ₃ , GeI ₄ , GeB
r ₄ , Sn (OCOCH ₃ ) ₄ , Pb (ClO ₄ ) ₂ ,
PbI _{2 and the} like. Of these salts, 4, 5,
Alternatively, it is particularly preferable to use a compound of the component (b) which is a catalyst component for olefin polymerization treated with a compound containing a cation of a Group 6 atom. The acid treatment removes impurities on the surface and elutes a part or all of cations such as Al, Fe, and Mg having a crystal structure.

Acid The acid used in the acid treatment is preferably selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid and oxalic acid. The salt and the acid used for the treatment may be two or more. When combining salt treatment and acid treatment, after performing salt treatment,
There are a method of performing an acid treatment, a method of performing a salt treatment after performing the acid treatment, and a method of simultaneously performing the salt treatment and the acid treatment.

Treatment conditions The treatment conditions with salts and acids are not particularly limited.
Usually, the salt and acid concentrations are 0.1 to 30% by weight, the treatment temperature is from room temperature to the boiling point, and the treatment time is from 5 minutes to 24 hours. It is preferable to carry out the reaction under the condition that at least a part of a substance constituting at least one compound selected from the group consisting of salts is eluted. Further, salts and acids are generally used in an aqueous solution. In the present invention, the salt treatment and / or the acid treatment are performed, but the shape may be controlled by pulverization or granulation before, during, or after the treatment. Further, another chemical treatment such as an alkali treatment or an organic substance treatment may be used in combination. As the compound component of component (b) thus obtained, those having a pore volume of at least 20 A in radius measured by mercury porosimetry of 0.1 cc / g or more, particularly preferably 0.3 to 5 cc / g, are preferable. .

At least one compound selected from the group consisting of the ion-exchangeable layered compound other than the silicate and the inorganic silicate usually contains adsorbed water and interlayer water.
In the present invention, the compound water (b) is obtained by removing these adsorbed water and interlayer water. Here, the adsorbed water is clay,
The water adsorbed on the surface of the clay mineral or the ion-exchange layered compound particles or the crystal fracture surface, and the interlayer water is water existing between the layers of the crystal. In the present invention, those obtained by removing these adsorbed water and / or interlayer water by heat treatment are preferably used. There is no particular limitation on the heat treatment method of the adsorbed water and the intercalated water of the clay, the clay mineral and the intercalated water, and methods such as heat dehydration, heat dehydration under a gas flow, heat dehydration under reduced pressure, and azeotropic dehydration with an organic solvent are used. Used. The temperature at the time of heating is 100 ° C. or higher so that interlayer water does not remain.
The temperature is preferably 150 ° C. or higher, but high temperature conditions that cause structural destruction are not preferable. Further, a heat dehydration method for forming a crosslinked structure such as heating under air flow is not preferable because the polymerization activity of the catalyst is reduced. The heating time is 0.
It is 5 hours or more, preferably 1 hour or more. At this time, the water content of the compound of the component (b) after the removal was changed to a temperature of 2
Assuming that the water content when dehydrated for 2 hours under the conditions of 00 ° C. and a pressure of 1 mmHg is 0% by weight, it is necessary that the water content is 3% by weight or less, preferably 1% by weight or less, and the lower limit is 0% by weight or more. is there.

(2) Low-density polyethylene (component (B)) (A) Physical properties The low-density polyethylene produced by the high-pressure radical method of the component (B) used in the present invention has an MFR of 0.1 to 20 g / g. 10 minutes, preferably 0.15 to 10 g
/ 10 minutes. The density is 0.910 to 0.9
35 g / cm ³ , preferably 0.915 to 0.932 g
/ Cm ³ is important. When the MFR of the low-density polyethylene is less than the above range, transparency and gloss may be deteriorated. On the other hand, if the MFR exceeds the above range, sufficient transparency, gloss and molding stability cannot be obtained. If the density of the low-density polyethylene is less than the above range, the stiffness becomes insufficient. On the other hand, when the density exceeds the above range, transparency, gloss and strength become insufficient. Incidentally, the low-density polyethylene produced by the high-pressure radical method is a range of ethylene and other α-olefins, vinyl acetate, polymerizable monomers such as acrylic acid esters, as long as the object of the present invention is not impaired. It may be a copolymer.

(B) Production The low-density polyethylene produced by the high-pressure radical method used in the present invention refers to a polymerization pressure of 1,500 to
3,500 kg / cm ² , polymerization temperature 150-350 ° C
A low-density polyethylene produced by radical polymerization in the presence of a radical generator such as oxygen, air, or an organic peroxide, and is generally commercially available as a high-pressure low-density polyethylene.

(3) Antioxidant (Component (C)) The antioxidant of the component (C) used in the present invention includes:
Known antioxidants for polyolefins may be used, and various antioxidants such as phosphorus-based, phenol-based, and sulfur-based can be used. Phosphorous antioxidants Examples of the above phosphorus antioxidants include triphenyl phosphite, diphenyl phosphite, trinonyl phenyl phosphite, distearyl pentaerythritol diphosphite, 4,4'-butylidenebis (3-methyl- 6-t-butylphenylditridecyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, tetrakis (2 ,
4-di-t-butylphenyl) -4,4'-biphenylenediphosphonite and the like.

Phenolic antioxidants The phenolic antioxidants include, for example, 1,
3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene,
2,2'-methylenebis (4-methyl-6-t-butylphenol), pentaerythrityl-tetrakis [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate], octadecyl-3- (3,5-di-
t-butyl-4-hydroxyphenyl) propionate, tris [β- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl-oxyethyl] isocyanurate, and the like.

Sulfur-based antioxidant Examples of the sulfur-based antioxidant include tetrakis (laurylmercaptopropionyloxymethylene) methane, dilaurylthiodipropionate, distearylthiodipropionate, and the like. . These antioxidants may be used alone or in combination of two or more, but a combination of a phosphorus-based antioxidant and a phenol-based antioxidant, or a combination of a sulfur-based antioxidant and a phenol-based antioxidant Is preferred.

(4) Antiblocking Agent (Component (D)) Examples of the antiblocking agent of component (D) used in the present invention include silicon dioxide, talc, zeolite and the like. More specifically, natural silica, synthetic silica, talc, zeolite A, zeolite Pc, X
Zeolite and the like can be mentioned, and any of them may be subjected to treatment such as acid modification and ion exchange. These anti-blocking agents are manufactured by Mizusawa Chemical Industries, Inc., "Silton JC-
30 "and the like. These anti-blocking agents may be used alone or in combination of two or more kinds, and preferably have an average particle diameter of 10 μm or less.

(5) Other compounding agents (optional component: component (E)) The polyethylene resin composition of the present invention contains the above-mentioned components (such as high-density polyethylene) as long as the effects of the present invention are not significantly impaired. B) Polyethylene resins other than low-density polyethylene and resins other than polyethylene such as polypropylene may be contained, and further, additional components such as a neutralizer, an ultraviolet absorber, a lubricant, an antistatic agent, and weather resistance The composition may further include a property improving agent, a nucleating agent, a dew condensation preventing agent, a molecular weight modifier, a coloring agent, an impact improving agent, a filler, a flame retardant, an adhesion improving agent, a printability improving agent, and the like.

[II] Blending Ratio The blending ratio of the ethylene / α-olefin copolymer of the component (A) contained in the polyethylene resin composition of the present invention is 99.5 to 70% by weight, preferably 97 to 80%. weight%
The blending ratio of the low-density polyethylene produced by the high-pressure radical method of the component (B) is 0.5 to 30% by weight, preferably 3 to 20% by weight. The above component (A)
If the mixing ratio of the ethylene / α-olefin copolymer is less than the above range, a problem arises in that sufficient strength cannot be obtained. In addition, when it exceeds the above range, there arises a problem that sufficient transparency and gloss cannot be obtained. On the other hand, if the compounding ratio of the low-density polyethylene produced by the high-pressure radical method of the component (B) is less than the above range, there arises a problem that sufficient transparency and gloss cannot be obtained. In addition, when it exceeds the above range, there is a problem that sufficient strength cannot be obtained. The ethylene / α-olefin copolymer component of the component (A) and the low-density polyethylene component produced by the high-pressure radical method of the component (B) together constitute 10
0 parts by weight, the amount of the antioxidant of the component (C) is 0.05 to
1.0 part by weight, preferably 0.10 to 0.35 part by weight, and the antiblocking agent of the component (D) is 0.01 to
0.8 parts by weight, preferably 0.1 to 0.5 parts by weight. The compounding ratio of the antioxidant of the component (C) is
If it is less than the above range, a problem arises that gel is frequently generated during molding. In addition, when it exceeds the above range, there is a problem that the film is liable to be discolored. On the other hand, when the compounding ratio of the antiblocking agent of the component (D) is less than the above range, there arises a problem that sufficient mouth opening cannot be obtained. In addition, when it exceeds the above range, there arises a problem that sufficient transparency and gloss cannot be obtained.

[III] Production of polyethylene resin composition (1) Kneading method Ethylene / α-olefin copolymer of component (A),
Component (B), a low-density polyethylene produced by a high-pressure radical method, component (C), an antioxidant, and component (D), an anti-blocking agent, and optionally other components of component (E) The polyethylene resin composition of the present invention can be obtained by blending the above components in the above blending ratio and melt-blending or dry blending. However, in the case of dry blending, the masterbatch method may be used for the antioxidant of component (C), the anti-blocking agent of component (D), and other compounding agents (optional components) of component (E). preferable.

(2) Melt Kneading The above melt kneading is generally performed using a conventional kneader such as a single screw extruder, a twin screw extruder, a Banbury mixer, a roll mixer, a Brabender plastograph, a kneader, and the like.
The polyethylene-based resin composition of the present invention can be obtained by kneading at a temperature of 70 to 250 ° C. and preferably granulation. In this case, it is preferable to select a kneading / roughening method capable of improving the dispersion of each component. Usually, a single-screw extruder or a twin-screw extruder is used to carry out mixing and granulation.

[IV] Molding The polyethylene resin composition of the present invention thus obtained has excellent stability at the time of molding, and a film molded by using it has transparency, gloss, waist, and open mouth. Excellent in properties and strength,
In addition, since these are also excellent in quality balance, standard bags, heavy bags, wrap films, sugar bags, various packaging films such as food packaging, infusion bags, bag-in-boxes,
It is suitable for agricultural materials and the like. Further, the present invention is not limited to ordinary film applications such as blown film molding and T-die film molding, but can also be processed into various containers, pipes, tubes, and the like by extrusion molding, hollow molding, injection molding, and the like. Furthermore, it can be formed into various composite films by extrusion coating or co-extrusion molding on other films, and can also be used for applications such as steel pipe coating, electric wire coating or foam molding.

[0045]

The present invention will be described more specifically with reference to the following examples and comparative examples. [I] Evaluation method (1) MFR JIS K 6760, 190 ° C, 2.16k
It measured under the condition of g load. (2) Density The density was measured according to JIS K6760. (3) Haze Measured according to JIS K7105. (4) Gloss The gloss was measured in accordance with JIS K7105. (5) Tensile modulus According to ISO R1184, measured values in the longitudinal direction are shown. (6) Molding stability During the formation of the blown film, the state of the bubbles was visually observed, and the molding stability was evaluated in three steps as follows. ：: Bubble shaking is hardly recognized. Δ: Bubble shaking or meandering is recognized. X: Bubble shakes or meanders and it is difficult to mold.

(7) Opening property A tubular film sample formed from an inflation film is cut perpendicularly to the axial direction so that the axial length of the tube is 20 cm. A pair of rectangular glass plates with a length of 25 cm and a width of 35 cm is sandwiched, a load of 15 kg is placed on the glass plate, and the temperature is set to 45 ° C. in a gear oven.
After storage for 5 days, the load and the glass plate were removed, the adhered film was peeled off by hand, and the mouth openability was evaluated in three steps as follows. O: Little resistance and peeling possible. △: Resistance when peeling, or whitening or damage is observed on the film surface. X: Considerable resistance, whitening or damage on the film surface when peeled. Is observed or cannot be peeled off.

(8) Memory Effect (ME) Memory effect (ME) is measured according to JIS K72.
Melt indexer and inner diameter 2.095 used in 10
The cylinder temperature was kept at 240 ° C. using an orifice having a diameter of 9.50 mm and a length of 8.000 mm. After filling the device with the sample, only the piston was placed, and after 6 minutes at a constant speed of 3 g / min. Extrude the molten sample,
After one minute, the sample coming out of the orifice was cut at the outlet immediately below the orifice, and then a measuring cylinder containing ethyl alcohol was placed directly under the orifice so that the liquid level of ethyl alcohol was 20 mm from the lower surface of the orifice. Place, take a straight extrudate in ethyl alcohol and measure its diameter to the nearest 0.01 mm. The value obtained by dividing the value by the inner diameter of the orifice 2.095 (mm) is defined as the value of ME.

[II] Examples and Comparative Examples Example 1 (1) Preparation of catalyst component 1 kg of commercially available synthetic mica (ME-100, Corp Chemical Co.) was added to 3.2 kg of demineralized water in which 0.2 kg of zinc sulfate was dissolved.
Was dispersed, stirred at room temperature for 1 hour, and filtered. After washing with demineralized water, the slurry was introduced into a spray drier to obtain spherical granulated particles. Add 200 more of these particles
It dried under reduced pressure at the temperature of 2 degreeC for 2 hours. On the other hand, 4.4 liters of n-heptane and 150 g of the above-mentioned dry granulated particles were introduced into a reactor equipped with an induction stirrer having a capacity of 10 liters. To this
A solution of 12.0 mmol of dimethylsilylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride dissolved in 00 ml of toluene was added and stirred at room temperature for 10 minutes. Subsequently, 72 mmol of triethylaluminum was further added to the stirred mixture, and the temperature of the system was adjusted to 60 ° C. Ethylene gas was introduced therein, and 562 g of ethylene was polymerized over 2 hours while maintaining the temperature at 60 ° C. to obtain a prepolymerized catalyst.

(2) Ethylene / butene copolymerization Gas phase polymerization was carried out using the prepolymerized catalyst obtained in the above “(1) Preparation of catalyst component”. That is, ethylene and 1-
335 mg / hr of the solid catalyst component and 1,256 mg / hr of triethylaluminum were intermittently supplied to a continuous gas phase polymerization reactor in which a mixed gas with butene was circulated. The conditions for the polymerization reaction were a polymerization temperature of 88 ° C. and a polymerization pressure of 20 kg /.
cm ² -G, average residence time was 4.1 hours, and the average polymerization rate of the produced polyethylene was 7.3 kg / hr. The MFR and density of the obtained ethylene / butene copolymer A were measured, and the results are shown in Table 1.

(3) Pelletizing Low-density polyethylene a manufactured by the high-pressure radical method and commercially available from Nippon Polychem shown in Table 2 was added to 92 parts by weight of the above-mentioned ethylene / butene copolymer powder.
8 parts by weight of "Novatec-LD LF280" and 0.1 parts of octadecyl-3- (3,5-di-t-butyl-4-hydrodiphenyl) propionate as an antioxidant.
Parts by weight and tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylenediphosphonite in an amount of 0.1
Parts by weight, 0.0% calcium stearate as a neutralizing agent
5 parts by weight, 0.15 parts by weight of "Silton JC-30" manufactured by Mizusawa Chemical Industry Co., Ltd. as an anti-blocking agent were added, and these were added using a 50 liter super mixer.
After mixing at a rotation speed of 800 rpm / min for 5 minutes, a single screw extruder with a screw diameter of 40 mmφ and L / D = 26 was used for 200 minutes.
The mixture was melt-kneaded at 50 ° C. and a screw rotation speed of 50 rpm to form pellets.

(4) Film Forming The pellets were screwed with a screw diameter of 40 mmφ and L / D = 24.
Die diameter 75mm, die lip width 3m with extruder
m using a blown film molding machine with a temperature of 2
Molded under the conditions of 00 ° C., screw rotation speed 50 rpm, blow-up ratio 2.0, take-up speed 16.5 m / min, frost line height 200 mm, width 230 mm, thickness 3
A blown film of 0 μm was obtained. When molding, evaluate the molding stability, haze of the formed film,
The tensile modulus and the opening property were measured and evaluated. Table 3 shows the results.

Example 2 Using the ethylene / butene copolymer A obtained in “(2) Ethylene / butene copolymerization” of Example 1, high-pressure radical was obtained in “(3) Pelletization” of Example 1 as well. The low-density polyethylene produced by the high-pressure radical method low-density polyethylene b "Novatech-LD LS16
Pelletization and film forming were performed in the same manner as in Example 1 except that the composition was changed to "2". Evaluation of molding stability and measurement of haze, gloss, tensile modulus, and opening property of the formed film were performed and evaluated. did. Table 3 shows the results.

Example 3 (1) Preparation of Catalyst Component 1 k of commercially available synthetic mica (CO-100, ME-100) was added to 3.4 kg of demineralized water in which 0.8 kg of chromium nitrate was dissolved.
g was dispersed, stirred at room temperature for 1 hour, and filtered. After washing with demineralized water, the slurry was introduced into a spray drier to obtain spherical granulated particles. Add 200 more of these particles
It dried under reduced pressure at the temperature of 2 degreeC for 2 hours. On the other hand, 4.4 liters of n-heptane and 150 g of the above-mentioned dry granulated particles were introduced into a reactor equipped with an induction stirrer having a capacity of 10 liters. To this
Bis (n-butylcyclopentadienyl) zirconium dichloride dissolved in 00 ml of toluene 12.0 mm
ol solution and stirred at room temperature for 10 minutes. Following this stirred mixture, further triethylaluminum was added.
5 mmol was added and the temperature of the system was brought to 60 ° C. Ethylene gas was introduced therein, and 562 g of ethylene was polymerized over 2 hours while maintaining the temperature at 60 ° C. to obtain a prepolymerized catalyst.

(2) Ethylene / Butene Copolymerization Gas phase polymerization was carried out using the prepolymerized catalyst obtained in the above “(1) Preparation of catalyst component”. That is, ethylene and 1-
363 mg / hr of the above solid catalyst component and 568 mg / hr of triethylaluminum were intermittently supplied to a continuous gas phase polymerization reactor in which a mixed gas with butene was circulated. The polymerization reaction conditions were as follows: polymerization temperature 83 ° C., polymerization pressure 20 kg / cm.
^2- G, the average residence time was 14 hours, and the average polymerization rate of the produced polyethylene was 4.3 kg / hr. The MFR and density of the obtained ethylene / butene copolymer A were measured, and the results are shown in Table 1.

(3) Pelletization The above-mentioned “(2)” is used as the powder of the ethylene / butene copolymer.
Pelletization was carried out in the same manner as in “(3) Pelletization” of Example 1, except that the ethylene / butene copolymer B obtained in “Ethylene / butene copolymerization” was used.

(4) Film formation In Example 1, "(4) Film formation" except that the pellet obtained in "(3) Pelletization" was used as the pellet.
A film was formed in the same manner as described above, the molding stability was evaluated, and the haze, tensile modulus, and opening property of the formed film were measured and evaluated. Table 3 shows the results.

Comparative Example 1 The ethylene / butene copolymer A obtained in Example 1 was used in the same manner as in Example 1 except that “Silton JC-30” was not added as an antiblocking agent in “(3) Pelletization”. In the same manner as in Example 1, pelletization and film molding were performed, and evaluation of molding stability was performed, and haze, gloss, tensile modulus, and opening property of the formed film were measured and evaluated. Table 3 shows the results.

Comparative Example 2 A linear low-density polyethylene C "Novatec LL F30FG" commercially available from Nippon Polychem Co., Ltd. was used as an ethylene / butene copolymer, and "Silton JC-" was used as an anti-blocking agent during pelletization. Except that "30" was not added, pelletize in the same manner as in "(3) Pelletizing" of Example 1, and perform the same procedure as in "(4) Film forming" of Example 1 to form a film. The stability was evaluated, and the haze, gloss, tensile modulus, and opening property of the formed film were measured and evaluated. Table 3 shows the results. In addition, the MFR of ethylene / butene copolymer C
And density are shown in Table 1.

Comparative Example 3 A linear low-density polyethylene D “Novatec LL UF240” commercially available from Nippon Polychem Co., Ltd. was used as an ethylene / butene copolymer. Without adding polyethylene, "Silton JC-3" was used as an anti-blocking agent.
Except that “0” was not added, the pellet was formed in the same manner as in “(3) Pelletizing” in Example 1, and the film was formed in the same manner as in “(4) Film forming” in Example 1 to form a film. The stability was evaluated, and the haze, gloss, tensile modulus, and opening property of the formed film were measured and evaluated. Table 3 shows the results. Table 1 shows the MFR and density of the ethylene / butene copolymer D.

Comparative Example 4 As an ethylene / α-olefin copolymer, a commercially available linear low-density polyethylene E (α-olefin: 1-hexene, 1-hexene content: 8% by weight) produced using a metallocene catalyst ), Forming a film in the same manner as in “(4) Film forming” of Example 1, evaluating the molding stability, and measuring the haze, gloss, tensile modulus, and opening property of the formed film. Measured and evaluated. Table 3 shows the results. Table 1 shows the MFR and density of the ethylene / butene copolymer D.

[0061]

[Table 1]

[0062]

[Table 2]

[0063]

[Table 3]

[0064]

The polyethylene resin composition of the present invention has excellent molding stability when it is formed into a film, and the formed film has transparency, gloss, waist, openability, and strength. It is excellent.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI // (C08L 23/08 23:06)

Claims (4)

[Claims] 1. A polyethylene resin composition comprising the following components (A) to (D). Component (A): component (a): a metallocene-type transition metal compound, and component (b): a salt treatment and / or obtained by performing the acid treatment, the water content of 3 wt% or less, (b ₁ ): An ion-exchangeable layered compound other than silicate, and (b ₂ ): an inorganic silicate, and at least one compound selected from the group consisting of: An ethylene / α-olefin copolymer having an MFR of 0.1 to 15 g / 10 min and a density of 0.880 to 0.960 g / cm ³ obtained by copolymerizing an α-olefin having 3 to 12 carbon atoms 99.5 Component (B): low density polyethylene having a MFR of 0.1 to 20 g / 10 minutes and a density of 0.910 to 0.935 g / cm ³ produced by the high pressure radical method 0.5 to 30% by weight , Ingredients ( ): Antioxidant 0.05 to 1.0 part by weight component (D): anti-blocking agent from 0.01 to 0.8 parts by weight 2. The polyethylene resin composition according to claim 1, wherein the component (A) (a): the metallocene transition metal compound is a metallocene transition metal compound represented by the following general formula (I). Stuff. R ¹ _i (CpR ² _n ) (CpR ³ _m ) MX ¹ X ² [I] (wherein Cp represents a cyclopentadienyl group, and R ¹ is a covalent bond containing an element belonging to Group 14 of the Long Periodic Table) Group,
i is 0 or 1, R ² and R ³ are a halogen, a silicon-containing group, a hydrocarbon group having 1 to 20 carbon atoms or a halogen-containing hydrocarbon group, an alkoxy group, an aryloxy group, an amino group; the R ² or C ₄ R ³ are bonded to each other when substituted adjacent to the cyclopentadienyl ring
May form a ring of ~C _8, m, n is an integer of 0~5, i + m = 5 and i + n = 5 to meet, M is a transition metal of Group IVb Table long periodic, X ¹ and X ² represent a halogen atom, a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group, an aryloxy group, or an amide group. ) 3. The polyethylene resin composition according to claim 1, wherein the compound (b) of the olefin polymerization catalyst component used in the component (A) is obtained by salt treatment. 4. The polyethylene resin composition according to claim 1, wherein the low density polyethylene used in component (B) has a memory effect (ME) of 1.6 to 2.1.