JP2001045885A - Agricultural film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject film excellent in all of transparency, mechanical strength, antifogging property and setting up operability, slight in problems when incinerated, and having thermal insulation, weatherability and durability of antifogging property. SOLUTION: This agricultural film consists of a layer formed of a polyethylene-based resin composition having specific physical properties and comprising (A) 100 pts.wt. of a copolymer of ethylene and a 3-12C α-olefin, (B) 0.03-1.5 pt(s).wt. of an antiblocking agent and (C) 0.005-0.5 pt.wt., calculated as 4-acryloyloxy-2,2,6,6-tetramethylpiperidine unit, of a copolymer of ethylene and 4-acryloyloxy-2,2,6,6-tetramethylpiperidine.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an agricultural film used for cultivating a house or a tunnel.

[0002]

2. Description of the Related Art In house cultivation and tunnel cultivation for the purpose of forcing cultivation in agriculture, polyvinyl chloride, ethylene / vinyl acetate copolymer, high-pressure low-density polyethylene, ethylene / α-olefin copolymer are generally used as coating materials. Agricultural films composed of polymers and the like are used in large quantities. Among them, polyvinyl chloride films are currently most frequently used because of their excellent heat retention, transparency and strength. However, the polyvinyl chloride film has a problem that it is inferior in dustproof property for preventing adhesion of dust and the like during use, poor in workability in stretching the film, and has a problem that toxic gas is generated during incineration. On the other hand, although the ethylene-vinyl acetate copolymer film has few problems at the time of incineration, it is inferior in transparency, strength, dust-proofing property and spreadability. On the other hand, high-pressure low-density polyethylene films have less problems during incineration, and are superior to ethylene-vinyl acetate copolymer films in terms of dust resistance and spreadability, but are still insufficient, and have low transparency and transparency. The strength is also insufficient.

[0003] Films of an ethylene / α-olefin copolymer have few problems during incineration and are excellent in dustproofness and strength, but those having excellent workability have insufficient transparency and transparency. Sufficient ones have a problem that they are inferior in workability. As a method for achieving both transparency and spreading workability of a film of the ethylene / α-olefin copolymer, JP-A-9-249774 uses an ethylene / α-olefin copolymer polymerized by a single-site catalyst. It has been proposed. However, in this method, although the balance between the transparency and the spreading workability is improved, the transparency is still insufficient. In order to obtain sufficient transparency, a method of blending a high-pressure low-density polyethylene is considered, but in this case, the strength is reduced.

[0004]

The present invention is excellent in all of transparency, strength, dust resistance and spreadability, has few problems during incineration, and has heat retention, weather resistance and, if necessary, anti-fogging durability. An agricultural film provided with:

[0005]

Means for Solving the Problems The inventors of the present invention have conducted various studies to solve the above problems, and as a result, a film made of a polyethylene resin composition having specific components and specific characteristics has been obtained. The inventors have found that the above-mentioned problems can be solved, and have completed the present invention. That is, the present invention provides an agricultural film characterized by comprising a layer formed of a polyethylene resin composition having the following components (A) to (C) and having the following properties (D) to (H). is there. Component (A): 100 parts by weight of a copolymer of ethylene and an α-olefin having 3 to 12 carbon atoms Component (B): Antiblocking agent 0.03 to 1.5
Parts by weight Component (C): ethylene and 4-acryloyloxy-2,
0.005 to 0.5 parts by weight of 2,6,6-tetramethylpiperidine copolymer as 4-acryloyloxy-2,2,6,6-tetramethylpiperidine unit Property (D): Flow ratio (FR) ) Is 7.2 or less. Property (E): MFR is 0.1 to 15 g / 10 min. Property (F): Density is 0.905 to 0.940 g / cm ^3.
Characteristic (G): The hexane-soluble content is 2.5% by weight or less. Characteristic (H): The value of K shown below is 0.15 ≦ K ≦ 4.
0 (1) The resin composition has a flow ratio (FR) of FR ≦ M
When the condition of w / Mn + 4.4 is satisfied, K = MT− (0.196 Mw / Mn−0.197 +
(0.0942Mw / Mn + 0.664) e
^{(-MFR + 0.025Mw / Mn + 0.445) / (
−0.0 417 Mw / Mn + 0.382)} + (0.46
4Mw / Mn-0.128) e ^{(
−MFR + 0.025 Mw / Mn + 0.445) / (0
. 05Mw / Mn + 0. 93)} ) (2) FR of the resin composition is FR> Mw / Mn + 4.4.
When the condition is satisfied, K = MT− (0.196 Mw / Mn−0.197 +
(0.0942Mw / Mn + 0.664) e
^{(-MFR + 0.025Mw / Mn + 0.445) / (
−0.0 417 Mw / Mn + 0.382)} + (0.46
4Mw / Mn-0.128) e ^{(
−MFR + 0.025 Mw / Mn + 0.445) / (0
. 05Mw / Mn + 0. 93)} )-0.097 (FR-
0.9 Mw / Mn) / (Log MFR + 0.39) where MFR is a value measured at 190 ° C. under a load of 2.16 kg, and FR is M measured at 190 ° C. under a load of 10 kg.
And _{I 10} is a FR measurements, 2.16 at 190 ° C.
Ratio to I _2.16 which is the measured value of MFR under kg load (I
₁₀ / _I A _{2.1 6),} MT is 190 ° C., melt tension measured at a tensile speed 4m / min (g), Mw is weight average molecular weight, Mn is the number average molecular weight. E indicates the base of the natural logarithm.

[0006]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. [I] Polyethylene resin composition Resin Composition Constituents The polyethylene resin composition used in the present invention comprises the following components (A), (B), (C), and if necessary, component (I),
Consists of other components.

[0007] Component (A): ethylene and carbon number 3-1
Copolymer with α-olefin of No. 2 A copolymer of ethylene of component (A) and α-olefin of 3 to 12 carbon atoms has properties as a resin composition composed of components (A) to (C) ( Although not limited as long as D) to the property (H) are satisfied, α-olefins having 3 to 12 carbon atoms, preferably 4 to 10 carbon atoms are used. Specifically, for example, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-
Dodecene or a mixture thereof; in addition, a small amount of polyene or the like may be copolymerized. Examples of the polyene include butadiene, isoprene, 1,4-hexadiene, and dicyclopentadiene.

[0008] Ethylene used in the present invention and 3 to 12 carbon atoms
The polymerization method for producing a copolymer with an α-olefin is not limited, and examples thereof include a method using an olefin polymerization catalyst as described below. (B ₁ ) an inorganic silicate obtained by subjecting the component (a) to a metallocene transition metal compound and a salt treatment and / or an acid treatment of the component (b) as an olefin polymerization catalyst;
(B ₂ ) It is important that the catalyst is produced using an olefin polymerization catalyst containing at least one compound selected from the group consisting of ion-exchange layered compounds excluding silicate as an essential component.

(I) Metallocene transition metal compound (component (a)) Component (a), which is a catalyst component for olefin polymerization, is a metallocene transition metal compound represented by the following general formula (I). R ¹ _i (CpR ² _n ) (CpR ³ _m ) MX ¹ X ² (I) (wherein Cp represents a cyclopentadienyl group, and R ¹ contains a Group 14 element in the long period table) A covalent crosslinking group,
i is 0 or 1, R ² and R ³ are 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, and two 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 to 5, satisfy the i + m = 5 and i + n = 5, M is a Group 3, 4, 5 and 6 of Table long periodic A transition metal, X ¹ and X
² represents 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. The metallocene-based transition metal compound represented by the general formula (I) may have one or two optionally substituted cyclopentadienyl-based ligands, that is, a substituent may be bonded to form a condensed ring. Organic compounds comprising one or two cyclopentadienyl ring-containing ligands and a transition metal belonging to Group 3, 4, 5, or 6 of the Long Periodic Table, or a chaotic complex thereof.

The metallocene transition metal compound is
Preferred are those represented by the following general formula (II) or
It is a compound represented by (III). (CpR¹ _aH_5-a)_p(CpR² _bH_5-b)_qMR³ _r ... (II) [(CpR¹ _aH_5-a)_p(CpR² _bH_5-b)_qMR³ _rL_m]^{n +}[R ⁴ ]^n- ... (III)

In the above general formulas (II) and (III),
CpR ¹ _a H _5-a and ^CpR _{2 b H 5-b} show the derivatives of cyclopentadienyl (Cp) group.

In the general formulas (II) and (III), R ¹ ,
R ² is a hydrocarbon group having 1 to 20 carbon atoms which may be substituted, a silicon-containing substituent, a phosphorus-containing substituent, a nitrogen-containing substituent, and an oxygen-containing substituent, each of which may be the same or 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 And other silicon-containing substituents such as trimethylsilyl, triethylsilyl, and triphenylsilyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, t-butoxy, etc. And an aryloxy group such as a p-tolyloxy group, a m-tolyloxy group, an o-tolyloxy group, and the like. Of these, preferred are alkyl groups having 1 to 4 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group and t-butyl group, and alkoxy groups such as trimethylsilyl group, methoxy group and ethoxy group. And aryloxy groups 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, an alkylene group such as an ethylene group, an ethylidene group, a propylidene group, an isopropylidene group, a phenylmethylidene group, an arylidene group such as a diphenylmethylidene group, a dimethylsilylene group, a 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, diproprugemylene 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 or 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 represents an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, hydrogen, halogen, a silicon-containing substituent,
Alkoxy, aryloxy, amide, or thioalkoxy; specifically, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t
Alkyl groups such as butyl group, pentyl group, isopentyl group, hexyl group, heptyl group, octyl group, nonyl group, and decyl group, and aryl groups such as phenyl group, p-tolyl group, o-tolyl group, and m-tolyl group , Fluoromethyl group,
Halo-substituted hydrocarbon groups such as fluoroethyl group, fluorophenyl group, chloromethyl group, chloroethyl group, chlorophenyl group, bromomethyl group, bromoethyl group, bromophenyl group, iodomethyl group, iodoethyl group, iodophenyl group, fluorine, chlorine, Bromine, halogen such as iodine, silicon-containing substituents such as trimethylsilyl, triethylsilyl, and triphenylsilyl, methoxy, ethoxy,
Propoxy group, isopropoxy group, butoxy group, isobutoxy group, alkoxy group such as t-butoxy group, phenoxy group, methylphenoxy group, pentamethylphenoxy group, p-tolyloxy group, m-tolyloxy group, o-tolyloxy group and the like Aryloxy group, dimethylamide group, diethylamide group, dipropylamide group, diisopropylamide group, methylthioalkoxy group, ethylthioalkoxy group, propylthioalkoxy group, butylthioalkoxy group, t-butylthioalkoxy group, phenylthioalkoxy group And the like. Among these, hydrogen, methyl, ethyl, propyl, isopropyl, butyl, phenyl, halogen such as chlorine, methoxy, ethoxy, propoxy, isopropoxy, dimethylamide, methylthioalkoxy are preferred. Groups, among which hydrogen, methyl and chlorine are particularly preferred.

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, or holmium. , Erbium, thulium, ytterbium, lutetium, actinium, thorium, protactinium, uranium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, and tungsten. Of these, titanium, zirconium, and hafnium of Group 4 are 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 cations. Specific examples include tetraphenyl borate, tetra (p-tolyl) borate, carbadodecaborate, dicarboundecaborate, tetrakis (pentafluorophenyl) borate, tetrafluoroborate, and hexafluorophosphate.

A and b are integers from 0 to 5. Also, p,
q and r are non-negative integers satisfying p + q + r = V when the valence of M is V and the metallocene compound is represented by the general formula (II), and the metallocene compound is represented by the general formula (III) Is a non-negative integer satisfying p + q + r = V−n. 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. 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, 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,
(10) 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,
(17) 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 (pentamethylcyclopentadienyl) zirconium dichloride, (28) indenyl (cyclopentadienyl) zirconium dimethyl, (2
9) trimethylcyclopentadienyl (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, (3)
5) dimethylsilyl-bis (cyclopentadienyl) zirconium dimethyl, (36) bis (cyclopentadienyl) zirconium bis (methanesulfonato), (3
7) bis (cyclopentadienyl) zirconium trifluoromethanesulfonatochloride, (38) bis (indenyl) zirconiumbis (trifluoromethanesulfonato), (39) ethylenebis (indenyl) zirconiumbis (trifluoromethanesulfonato),

(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-ethanezirconium dichloride, (43)
(Tert-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, (4
9) 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-methyl) Cyclopentadienyl) 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-methylcyclopenta Dienyl) zirconium bis (diethylamide),
(58) bis (1-n-butyl-3-methylcyclopentadienyl) zirconium bis (diethylamide) and the like.

The compounds corresponding to the general formula (III) include (1) bis (methylcyclopentadienyl) zirconium (chloride) (tetraphenylborate)
Tetrahydrofuran complex, (2) bis (ethylcyclopentadienyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, (3) bis (methylcyclopentadienyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, 4) bis (ethylcyclopentadienyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, (5) bis (methylcyclopentadienyl) zirconium (hydrido) (tetraphenylborate) tetrahydrofuran complex, (6) bis ( Dimethylcyclopentadienyl) zirconium (chloride)
(Tetraphenyl borate) 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)
(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 (chloride) (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 complexes, (27) bis (cyclopentadienyl) zirconium (methanesulfonato) (tetraphenylborate) tetrahydrofuran complexes and the like.
Third, such as titanium compounds and hafnium compounds,
The same compounds as described above can be used for the Group 4, 5, and 6 metal 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 inorganic silicate and (b ₂ ) an ion-exchange layered compound excluding a silicate is used.

(B ₁ ) Inorganic silicate Examples of the inorganic silicate include zeolite, diatomaceous earth, and most clays. Also, clay is usually
It is composed mainly of clay minerals. As these zeolites, diatomaceous earth, clay, and clay minerals, naturally occurring minerals may be used, or artificial synthetic compounds may be used. In addition, these may be used as they are without performing acid treatment,
It may be used after performing treatments such as ball milling, sieving, and acid treatment. Further, they may be used alone or as a mixture of two or more.

Clay, clay mineral Specific examples of clay and clay mineral include allophane group such as allophane; kaolin group such as dickite, nacrite, kaolinite, anoxite, metahaloysite, and halloysite; chrysotile, lizartite, antigorite. Smectites such as serpentine, montmorillonite, zaukonite, beidellite, nontronite, saponite, hectorite, bentonite, teniolite, etc.
Vermiculite minerals such as vermiculite, mica, illite, sericite, mica minerals such as chlorite, attapulgite, sepiolite, palygorskite, kibushi clay,
Geirome clay, hisingelite, pyrophyllite, ryokudeite group and the like can be mentioned. These may form a mixed layer. Among these, smectites such as montmorillonite, zauconite, beidellite, nontronite, saponite, hectorite, bentonite and teniolite, mica minerals such as mica and illite, and vermiculite minerals such as vermiculite are preferred.

(B ₂ ) Ion-exchange layered compounds other than silicates As ion-exchanged layered compounds other than silicates, hexagonal close-packed type, antimony type, CdCl ₂ type, CdI
Examples thereof include an ionic crystalline compound having a layered crystal structure such as type ₂ . 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 (KPO 4) 2} · 3H 2 O, α-Ti (HPO
₄ ) ₂ , α-Ti (HAsO ₄ ) ₂ · H ₂ O, α-Sn
(HPO ₄ ) ₂ · H ₂ O, γ-Zr (HPO ₄ ) ₂ , γ
—Ti (HPO ₄ ) ₂ , γ-Ti (NH ₄ PO ₄ ) _2.
A crystalline acidic salt of a polyvalent metal such as H ₂ O may be mentioned. These may be used without any special treatment,
Ball mill, sectioning, inorganic acid such as hydrochloric acid, sulfuric acid, phosphoric acid, etc.
It may be used after a treatment such as an acid treatment by contact with an organic acid such as formic acid, acetic acid or benzoic acid. Further, they may be used alone or as a mixture of two or more.

At least one compound selected from the group consisting of ion-exchangeable layered compounds other than silicates and inorganic silicates, which has not been subjected to salt treatment or acid treatment, is used in the present invention. Group 1 metal cations (usually, for example, Na and K). The content of the cation of the Group 1 metal is desirably 0.1% by weight, preferably 0.5% by weight. Component (b) which is a catalyst component for olefin polymerization by subjecting at least one compound selected from the group consisting of an ion-exchange layered compound other than silicate and an inorganic silicate to salt treatment and / or acid treatment.
Is obtained.

In the present invention, the solid acid strength can be changed by salt treatment and / or acid treatment. In addition, the salt treatment forms an ion complex, a molecular complex, an organic derivative, and the like, and can change the surface area and the interlayer distance. That is, by using the ion exchange property and replacing the exchangeable ion 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 In the salt treatment of the present invention for the purpose of ion exchange,
The salts used are selected from the group consisting of atoms of groups 2 to 14
Containing a cation containing at least one type of atom
Compound, preferably, from the group consisting of group 2-14 atoms.
A cation containing at least one selected atom;
Selected from the group consisting of gen atoms, inorganic acids and organic acids.
It is a compound consisting of at least one kind of anion.
Preferably, a small group selected from the group consisting of atoms of groups 2 to 14 is used.
A cation containing at least one kind of atom, Cl, Br,
I, F, PO₄, SO₄, NO₃, CO₃, C₂O₄,
ClO₄, OCOCH₃, CH₃COCHCOCH₃,
OCI₂, O (NO₃)₂, O (ClO₄)₂, O (S
O₄), OH, O₂Cl₂, OCI₃, OCOH, OC
OCH₂CH₃, C₂H₄O₄And C₆H₅O₇From
At least one anion selected from the group consisting of
Compound. Specifically, CaCl₂, CaSO₄,
Ca (NO₃)₂, MgCl₂, MgBr₂, MgSO
₄, Mg (PO₄)₂, Mg (NO₃)₂, Mg (Cl
O₄) ₂, Ti (CO₃)₂, Ti (NO₃)₄, Ti
(SO₄)₂, TiF₄, TiCl₄, Zr (CO₃)
₂, Zr (NO₃)₄, Zr (SO₄)₂, ZrC
l₄, VOSO₄, VOCl₃, VCl₃, VCl₄,
VBr₃, CrO₂Cl₂, CrF₃, CrCl₃, C
rBr₃, Cr (NO₃)₃, Cr₂(SO₄)₃, C
o (CH₃COCHCOCH₃)₃, CoCO₃, Co
C₂O₄, CoF₂, NiCO₃, NiC₂O₄, Pb
SO₄, Pb (NO₃)₂, CuBr₂, Cu (OCO
CH₃)₂, Zn (CH₃COCHCOCH₃)₂, Z
n (OCOCH ₃)₂, Zn (OOCH)₂, ZnCO
₃, Zn (SO₄), Zn (NO₃)₂, ZnCl₂,
AlCl₃, Al (NO₃)₃, GeI₄, GeB
r₄, Sn (OCOCH₃)₄, Pb (ClO₄)₂,
PbI₂And the like. Of these salts,
Treated with compounds containing cations of group 5 or 6 atoms
Of component (b), which is the selected catalyst component for olefin polymerization
It is particularly preferred to use a compound. Acid treatment impure surface
In addition to removing substances, the crystal structure of Al, Fe, Mg, etc.
Elute some or all of the ions.

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 conditions that elute at least a part of a substance constituting at least one compound selected from the group consisting of salts. Further, salts and acids are generally used in an aqueous solution. In the present invention, the salt treatment and / or
Alternatively, acid treatment is performed, but shape control may be performed by pulverization, granulation, or the like 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 the component (b) thus obtained,
The pore volume with a radius of 20 ° or more measured by the mercury intrusion method is 0.
It is preferably at least 1 cc / g, particularly preferably 0.3 to 5 cc / g.

The 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.

Component (B): Antiblocking Agent Examples of the antiblocking agent used in the present invention include silicon dioxide, talc, zeolite and the like. More specifically, natural silica, synthetic silica, talc, A-type zeolite, Pc-type zeolite, X-type zeolite and the like,
Any of them may be subjected to treatment such as acid modification and ion exchange. The anti-blocking agent may be used alone or in combination of two or more, but all have an average particle diameter of 10 μm.
The following are preferred. The compounding amount of the antiblocking agent is 0.03 to 1.5 with respect to 100 parts by weight of the component (A).
Parts by weight, preferably 0.08 to 0.5 parts by weight. If the amount is less than the above range, the stretching workability is not sufficient, and if the amount exceeds the above range, the transparency of the film deteriorates.

Component (C): Copolymer of ethylene and 4-acryloyloxy-2,2,6,6-tetramethylpiperidine Ethylene and 4-acryloyloxy-2,2,6,6 used in the present invention The copolymer with tetramethylpiperidine is ethylene and 4-acryloyloxy-2,2,2.
It is obtained by polymerizing 6,6-tetramethylpiperidine by a high-pressure radical polymerization method. For example, Japanese Patent No. 269597
It is obtained by polymerization according to the method described in No. 5. It is necessary that the ethylene copolymer has an MFR (by the measuring method described in JIS K6760) in the range of 0.1 to 200 g / 10 minutes. Preferably, 0.5 to 20 g / 10 minutes,
More preferably, it is 1 to 5 g / 10 minutes. If the MFR is less than 0.1 g / 10 minutes, the compatibility with polyethylene or the like is poor, and when a blend is used, the appearance is deteriorated due to rough skin or bumps. If the MFR exceeds 200 g / 10 min, the copolymer may have a high molecular weight, but bleeding and blooming due to diffusion and loss may occur, and blending with polyethylene or the like may cause a decrease in the strength of the blend. .

With respect to the concentration of 4-acryloyloxy-2,2,6,6-tetramethylpiperidine in the present ethylene copolymer (the concentration is determined by a known nitrogen analysis), Less than 10% by weight of 4-acryloyloxy-2,2,6,6-tetramethylpiperidine, preferably 0.1% by weight, based on the sum of ethylene and 4-acryloyloxy-2,2,6,6-tetramethylpiperidine.
It is 1 to 8% by weight, more preferably 1 to 6% by weight. 4
-When the concentration of acryloyloxy-2,2,6,6-tetramethylpiperidine is less than 0.1% by weight, a high content blend is necessary when blended with polyethylene or the like, and a small amount of In this case, it is difficult to obtain long-term weather resistance. 4-acryloyloxy-2,2,6,6
-When the concentration of tetramethylpiperidine exceeds 10% by weight, a very small amount of a blend is formed in order to obtain proper weather resistance, and uniform dispersion is unlikely. The concentration of 4-acryloyloxy-2,2,6,6-tetramethylpiperidine in polyethylene or the like is 0.005 to 0.5 part by weight, preferably 0.01 to 0.4 part by weight, more preferably 0.01 ~
0.3 parts by weight. If the amount is less than 0.005 parts by weight, the effect of improving the weather resistance is small, and if it exceeds 0.5 parts by weight, the effect of improving the weather resistance is saturated. The specific blend of the ethylene copolymer is based on 100 parts by weight of the component (A).
4-Acryloyloxy-2,2,6,6-tetramethylpiperidine is used at a concentration of 0.005 to 0.5 parts by weight. When the film has a multilayer structure, it is more effective to blend the copolymer not only in one layer but in all layers.

Component (I): Nonionic Surfactant The polyethylene resin composition used in the present invention may optionally contain a nonionic surfactant as Component (I). As the nonionic surfactant used in the present invention, for example, those having a number average molecular weight of less than 1000 are used, glycerin monolaurate, glycerin monopalmitate, glycerin monostearate,
Glycerin-based surfactants such as diglycerin monolaurate, diglycerin monopalmitate, diglycerin monostearate, triglycerin monostearate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monobehenate, sorbitan and alkylene glycol Sorbitan surfactants such as esters of condensates and higher fatty acids; polyethylene glycol surfactants such as polyethylene glycol monopalmitate, polyethylene glycol monostearate, and polyethylene glycol alkyl phenyl ether ether;
Trimethylolpropane-based surfactants such as trimethylolpropane monostearate, pentaerythritol-based surfactants such as pentaerythritol monopalmitate, pentaerythritol monostearate, dipentaerythritol monostearate, lauric acid, palmitic acid, and stearin Examples include amide surfactants such as condensation products of acids and diethanolamine, fluorine surfactants such as perfluoroalkylethylene oxide adducts, and silicon surfactants such as alkylene oxide adducts of organopolysiloxanes. These surfactants may be used alone or as a mixture of two or more.

Of these, glycerin monopalmitate, glycerin monostearate, diglycerin monopalmitate, diglycerin monostearate, sorbitan monopalmitate, sorbitan monostearate, polyoxyethylene sorbitan monopalmitate, and polyoxyethylene sorbitan monopalmitate are preferred. One or a mixture of two or more selected from oxyethylene sorbitan monostearate, palmitic acid, and a condensation product of stearic acid and diethanolamine is used. The amount of the surfactant is determined by the amount of the component (A)
0.05 to 5.0 parts by weight with respect to 100 parts by weight,
Preferably it is 0.5 to 3.0 parts by weight. If the amount is less than the above range, the initial dropping property is not sufficient, and if the amount exceeds the above range, the transparency of the film deteriorates. When the film has a multilayer structure, the surfactant is not limited to one layer, and may be incorporated in all layers.

Other Components In the agricultural film of the present invention, a polyethylene resin such as a low-density polyethylene or a high-density polyethylene by a high-pressure radical method is optionally used as long as the following properties (D) to (H) are satisfied. It may be contained, or a resin other than polyethylene such as polypropylene may be contained.
Further, additional components within a range that does not significantly impair the effects of the present invention, for example, antifogging agents, antioxidants, neutralizing agents, ultraviolet absorbers, warming agents, lubricants, antistatic agents, nucleating agents, anti-condensation agents, A molecular weight modifier, a colorant, an impact modifier, a filler, a flame retardant, an adhesion improver, and a printability improver can be blended.

2. Characteristics of polyethylene resin composition The polyethylene resin composition comprising the components (A) to (C) needs to have the following characteristics (D) to (H). Characteristics (D) It is important that the resin composition comprising the components (A) to (C) has a flow ratio (FR) of 7.2 or less, preferably 7.0 or less. When FR exceeds the above range,
As the transparency of the film decreases, the strength of the film also decreases.

Property (E) MFR of resin composition comprising components (A) to (C)
Is 0.1 to 15 g / 10 min, preferably 0.2 to 5 g
/ 10 minutes, more preferably in the range of 0.5 to 2 g / 10 minutes. When 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, when the MFR exceeds the above range, the molding stability is reduced and the strength of the film is also reduced.

Property (F) The density of the resin composition comprising the components (A) to (C) is as follows:
0.905 to 0.940 g / cm ³ , preferably 0.9
05-0.935 g / cm ³ , more preferably 0.9
It is important that it is in the range of 10 to 0.930 g / cm ³ . If the density is less than the above range, the stretching workability is reduced. On the other hand, if the density exceeds the above range, the transparency and strength of the film decrease.

Property (G) The resin composition comprising the components (A) to (C) has a hexane-soluble content of 2.5% by weight or less, preferably 2.2% by weight.
It is important that the content be 1.8% by weight or less, more preferably 1.8% by weight or less. If the hexane solubles exceed the above range,
The spreading workability decreases.

Property (H) In the resin composition comprising the components (A) to (C), the value of K shown in the following formula is 0.15 ≦ K ≦ 4.0, preferably 0.20 ≦ K ≦ It is important to satisfy 3.0. K
Is less than the above range, the transparency of the film is insufficient. On the other hand, even if the value of K exceeds the above range, the transparency of the film is rather deteriorated. (1) FR of the resin composition is FR ≦ Mw / Mn + 4.4.
When the condition is satisfied, K = MT− (0.196 Mw / Mn−0.197 +
(0.0942Mw / Mn + 0.664) e
^{(-MFR + 0.025Mw / Mn + 0.445) / (
−0.0 417 Mw / Mn + 0.382)} + (0.46
4Mw / Mn-0.128) e ^{(
−MFR + 0.025 Mw / Mn + 0.445) / (0
. 05Mw / Mn + 0. 93)} ) (2) FR of the resin composition is FR> Mw / Mn + 4.4.
When the condition is satisfied, K = MT− (0.196 Mw / Mn−0.197 +
(0.0942Mw / Mn + 0.664) e
^{(-MFR + 0.025Mw / Mn + 0.445) / (
−0.0 417 Mw / Mn + 0.382)} + (0.46
4Mw / Mn-0.128) e ^{(
−MFR + 0.025 Mw / Mn + 0.445) / (0
. 05Mw / Mn + 0. 93)} )-0.097 (FR-
0.9 Mw / Mn) / (Log MFR + 0.39) where MFR is a value measured at 190 ° C. under a load of 2.16 kg, and FR is M measured at 190 ° C. under a load of 10 kg.
And _{I 10} is a FR measurements, 2.16 at 190 ° C.
Ratio to I _2.16 which is the measured value of MFR under kg load (I
₁₀ / _I A _{2.1 6),} MT is 190 ° C., melt tension measured at a tensile speed 4m / min (g), Mw is weight average molecular weight, Mn is the number average molecular weight. E indicates the base of the natural logarithm.

[II] Kneading / granulation The above-mentioned component (A) copolymer of ethylene and α-olefin having 3 to 20 carbon atoms, component (B) antiblocking agent, component (C) ethylene and 4-acryloyl Oxy-
2,2,6,6-tetramethylpiperidine copolymer,
If necessary, the polyethylene resin used in the agricultural film of the present invention by blending the component (I) nonionic surfactant and other compounding agents in the above-mentioned mixing ratio, and melt-kneading or dry-blending. A composition can be obtained. However, when dry blending, component (B) an anti-blocking agent, component (C) ethylene and 4
It is preferable to adopt a masterbatch method for the acryloyloxy-2,2,6,6-tetramethylpiperidine copolymer, the component (I) nonionic surfactant, and other compounding agents. The above-mentioned 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, or a kneader, and usually kneading at a temperature of 170 to 250 ° C.
By granulating, the resin composition used for the agricultural film of the present invention can be obtained. In this case, it is preferable to select a kneading / granulating method capable of improving the dispersion of each component. Usually, kneading / granulating is performed using a single-screw extruder or a twin-screw extruder.

[III] Film Forming The resin composition obtained above was molded by a known molding method,
The agricultural film of the present invention can be obtained by T-die film molding, blown film molding, or the like. The agricultural film of the present invention may have a single-layer structure,
It may have a multilayer structure composed of two or more layers. In the case of a multi-layer film, a multi-layer film can be formed by co-extrusion inflation molding or co-extrusion T-die molding. The thickness of the film is preferably in the range of 15 to 200 μm, and more preferably 30 to 180 μm, and as a multilayer composition ratio in the case of a multilayer film, the thickness of one layer is 5 to 100 μm, preferably 10 to 80 μm
And the further thickness is in the range of 10 to 150 μm, preferably 20 to 120 μm.

[0052]

The present invention will be described more specifically with reference to the following examples and comparative examples. In addition, the evaluation method of physical properties is as follows. (1) MFR: 190 according to JIS-K6760
The measurement was performed under the conditions of a temperature of 2.degree. (2) Density: Measured according to JIS-K6760. (3) FR: 190 ° C. in accordance with JIS-K6760
I _{10 kg,} which is the MFR measured under the condition of a 10 kg load
And MF measured under the conditions of 190 ° C. and 2.16 kg load
R is the ratio of _{2.16 kg} of I, I _{10 kg} / I
_{2.16 kg} was calculated and _designated as FR. (4) MT: Nozzle diameter 2.095 mmφ, nozzle length 8.00 using a Capillograph manufactured by Toyo Seiki Seisaku-sho, Ltd.
mm, an inflow angle of 180 °, a set temperature of 190 ° C, and a piston extrusion speed of 10.0 mm / min and a take-up speed of 4.0 m / min. (5) Mw / Mn: The value of Mw / Mn was determined in accordance with "Gel Permeation Chromatography" published by Takeuchi and published by Maruzen. That is, using standard polystyrene having a known molecular weight (monodisperse polystyrene manufactured by Tosoh Corporation), the value of Mw / Mn was determined by converting into a number average molecular weight Mn and a weight average molecular weight (Mw) by a universal method. The measurement was performed using Waters's ISOC-ALC / GPC, the column used was three AD80M / S's manufactured by Showa Denko, and the sample was dissolved in o-dichlorobenzene and used as a 0.2% by weight solution, and 200 µl was used. The test was performed at 140 ° C. at a flow rate of 1 ml / min. (6) Hexane soluble matter: 190 using a press molding machine.
A pressed sheet having a thickness of 0.1 mm is prepared at a temperature of 10 ° C., and the pressed sheet is cut into a rectangle of 10 mm × 50 mm, collected and weighed to a total of about 5 g. This sample is refluxed and extracted with 200 cc of hexane using a Soxhlet extractor for high temperature for 3 hours. Then, after cooling to room temperature, the extracted portion was dried under reduced pressure and weighed. The value obtained by subtracting the weight after drying under reduced pressure from the original weight was divided by the original weight, and the value obtained by multiplying by 100 was taken as the hexane-soluble component. .

(7) Haze: Measured according to JIS-K7105. (8) Elmendorf tear strength: The measured value in the longitudinal direction was shown in accordance with JIS-Z1702. (9) Blocking (expansion workability): A tubular film sample formed by blowing an inflation film is cut perpendicularly to the axial direction so that the axial length of the tube is 20 cm, and the film sample is cut vertically. Is a rectangular glass plate 2 having a length of 25 cm and a width of 35 cm.
Put a load of 15kg on the glass plate,
After storage in a gear oven set at a temperature of 45 ° C. 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. ：: Peelable with almost no resistance. Δ: There is resistance during peeling, or whitening or damage is observed on the film surface. X: There is considerable resistance, and when peeled off, whitening or damage is observed on the film surface, or the film can be peeled off. (10) Anti-fogging property: 150 cc of water was put into a beaker having a content of 200 cc and having an inclined structure at the upper end face, and the inflation-molded film was stretched around the upper end of the beaker, and then the beaker was placed in a 50 ° C. constant temperature water bath. Soak and store for 20 days with the outside temperature kept at 25 ° C.
After 0 day, the state of the film surface inside the beaker was visually observed, and the antifogging property was evaluated based on the following three levels. ：: No water droplet is observed on the film surface. Δ: Water droplets adhered to 50% of the film surface. ×: Water droplets adhered to the entire film surface. (11) Weather resistance: The weather resistance was evaluated as follows. From the blown film molded as described above, JIS
The film was punched out using a dumbbell punching blade die conforming to -K6781 so that the TD direction of the film was parallel to the tensile direction, to obtain a dumbbell-shaped test piece. A black panel temperature of 63 ° C. and a sample spray pressure of 1 kg /
An acceleration test was performed using a "Standard Sunshine Weather Meter" WEL-SUN-HC model, manufactured by Suga Test Instruments Co., Ltd., set to a cm ² and a precipitation cycle of 12 minutes / 60 minutes. After 500 hours, a test piece was taken out and accelerated. A tensile test was carried out on the test piece after the test and a test piece which was not separately subjected to a weather meter and stored in accordance with JIS-K6781, and the tensile elongation at break was measured. The value of the tensile elongation at break of the test piece after the accelerated test was divided by the value of the tensile elongation at break of the test piece not subjected to the accelerated test, and the value (100) multiplied by 100 was obtained. And It is determined that the greater this value, the better the weather resistance.

Example 1 (1) Chemical treatment of clay mineral 15.0 kg of zinc sulfate heptahydrate was added to 105.0 kg of demineralized water
Was added thereto, and 30.0 kg of synthetic mica (manufactured by Corp Chemical Co., Somasif, ME-100F) was added. After dispersion, the mixture was stirred for 18 hours, and filtered and washed with demineralized water. 4.8 kg of chromium (III) nitrate 9 hydrate was added to 7.5 kg of demineralized water
Was added, and the mixture was stirred at room temperature for 18 hours. At this time, the slurry concentration was adjusted to 20.0% by weight. After being filtered and washed with demineralized water, the solid content was adjusted to 19.0% by weight. Thereto, a synthetic smectite (manufactured by Corp Chemical Co., SWN) was added so as to be 5% by weight with respect to the total solid content in the slurry,
After sufficient dispersion, the slurry was dried and granulated by a spray drier to obtain spherical granulated particles. The obtained powder was further dried continuously at a rate of 3 kg / h (residence time: 10 minutes) using a rotary kiln at a temperature of 260 ° C. under a countercurrent nitrogen flow (nitrogen flow rate: 49 Nm ³ / h). , Collected under dry nitrogen.

(2) Preparation of Catalyst and Prepolymerization 4.0 l of n-heptane and 75.9 g of the particles of the synthetic mica obtained in the above (1) were introduced into a reactor having a capacity of 10 l and equipped with a dielectric stirrer. 7. bis (1-n-butyl-3-methylcyclopentadienyl) zirconium dichloride dissolved in 600 ml of toluene
A solution of 99 mmol was added and stirred at 30 ° C. for 10 minutes. Subsequently, triethylaluminum 107.7 mmo
1 was added to bring the temperature of the system to 60 ° C. After 10 minutes, ethylene gas was introduced, and the reaction was continued for 2.4 hours. The weight of polyethylene produced during this period was 540 g.

(3) Copolymerization of ethylene / 1-hexene Using the prepolymerized catalyst of the above (2), ethylene-hexene
Gas phase polymerization was performed. That is, ethylene and 1-hexene
Mixed gas (1-hexene / ethylene = 3.9%)
As a solid catalyst component in a continuous gas-phase polymerization reactor with water circulation
112 mg / hr, triethylaluminum and diethyl
170 mg / h of aluminum monoethoxide
r, 198 mg / hr were intermittently supplied. Polymerization reaction
Is 83 ° C, ethylene partial pressure 18kg / cm²,average
The residence time was 4.2 hours. Average of polyethylene produced
The polymerization rate was 285 g / hr. Echile obtained
N-hexene copolymer A₁Has an MFR of 1.5 g / 10
Min, density is 0.922 g / cm ³Met.

[0057] (4) Powder 10 pelletizing said ethylene-hexene copolymer _{A 1}
0 parts by weight of octadecyl-3- as an antioxidant
(3,5-di-t-butyl-4-hydroxyphenyl)
0.03 parts by weight of propionate and tetrakis (2,
0.08 part by weight of 4-di-t-butylphenyl) -4,4′-biphenylenediphosphonite, 0.10 part by weight of zinc stearate as a neutralizing agent, and Fuji Talc as an antiblocking agent (B ₁ ) 0.13 parts by weight of talc “MT-7” manufactured by KK, 2.0 parts by weight of diglycerin monostearate as a nonionic surfactant (I ₁ ), ethylene and 4-acryloyl-2,2,6,6 6-tetramethylpiperidine copolymer (XJ100 manufactured by Nippon Polychem Co., Ltd.)
H) was added by 4 parts by weight, and these were mixed at a rotation speed of 800 rpm / min for 5 minutes using a 50 liter supermixer, and then screwed at 200 ° C. with a single screw extruder having a screw diameter of 40 mmφ and L / D26. The mixture was melt-kneaded at several 50 rpm and pelletized. For this pellet, the hexane soluble part, MFR, density, FR, Mw / M
n and MT were measured, and the value of K was calculated.
It was shown to.

(5) Film forming: The pellet obtained in the above (4) was screwed with a screw diameter of 40 mm.
Using a blown film molding machine having a die diameter of 75 mmφ and a die lip width of 3 mm equipped with an extruder of φ, L / D24, temperature 200 ° C., screw rotation speed 50 rpm,
Formed under the conditions of a blow-up ratio of 2.0, a take-up speed of 16.5 m / min, and a frost line height of 200 mm, and a width of 230
mm and a thickness of 30 μm were obtained. The formed film was measured and evaluated for haze, Elmendorf tear strength, blocking, antifogging property and weather resistance. Table 2 shows the results.

[0059] Example 2 Example ethylene-hexene copolymer _{A 1} obtained in 1, as an anti-blocking agent _{(B 2)} in Example 1 (4), in place of talc "MT-7", Takehara 0.16% by weight of talc “HE5” manufactured by Chemical Industry Co., Ltd. was added, and 7: 3 of diglycerin monostearate and glycerin monostearate was used as the nonionic surfactant (I ₂ ) instead of diglycerin monostearate. (Weight ratio) Pelletization and film formation were carried out in the same manner as in Example 1 except that the blended product was added in an amount of 1.0% by weight, and the pellets were dissolved in hexane, MFR, density, FR, Mw / Mn, The MT was measured, the value of K was calculated and the haze, Elmendorf tear strength, blocking,
The antifogging property and weather resistance were measured and evaluated. Tables 1 and 2 show the results.
Shown in

Example 3 (1) Chemical treatment of clay mineral In the same manner as in Example 1 (1), spherical particles of Cr-treated synthetic mica were obtained. However, if the temperature of the rotary kiln is 200
° C.

(2) Preparation of Catalyst and Prepolymerization 4.0 L of heptane was added to a 10 L autoclave dried at 80 ° C. for 2 hours under a stream of dry nitrogen.
The temperature was controlled at 30 ° C. while stirring. 200 in advance
50 g of granulated trivalent chromium ion-exchange type synthetic mica (average particle size: 55 μm) dried under reduced pressure for 2 hours, and 1.62 g (4.0 mmol) of bis (n-butylcyclopentadini) as a metallocene complex. L) Add a toluene solution of zirconium dichloride and add about 0.5 with nitrogen.
After being pressurized to kg / cm ² -G (gauge pressure), it was contacted at that temperature for 10 minutes. After completion of the contact, a solution of triethylaluminum in heptane (triethylaluminum 19
After adding 2.5 mmol), the temperature was raised to 60 ° C., and the mixture was further contacted at that temperature for 10 minutes. After contact, the internal pressure
After purging with nitrogen until the pressure became 0.2 kg / cm ² -G, ethylene was fed at 0.64 l / min.
When the amount of ethylene fed was about eight times the amount of ethylene fed to the synthetic mica charged, the ethylene feed was stopped, and residual polymerization was carried out, and the pressure was 0.1 kg / cm.
^{At the point of 2-} G, the polymerization was stopped by purging the internal ethylene while cooling the autoclave. After purging, the contents were withdrawn from a withdrawal line at the bottom of the autoclave into a flask with a 2 liter internal volume sufficiently purged with nitrogen. After standing and decanting the solvent, under reduced pressure, 70 ° C
For 2 hours. The weight of the catalyst obtained is 402
g, which was 8.0 times the weight of the synthetic mica used as the raw material.

(3) Copolymerization of ethylene-hexene Gas phase polymerization was carried out using the prepolymerized catalyst obtained in the above (2). That is, 61.2 mg of the solid catalyst component was introduced into a continuous gas-phase polymerization reactor in which a mixed gas of ethylene and 1-hexene (1-hexene / ethylene = 2.3%) was circulated.
/ Hr, 120 mg / hr of triethylaluminum and 139 mg / hr of diethylaluminum monoethoxide were intermittently supplied. The conditions for the polymerization reaction were 83 ° C., an ethylene partial pressure of 18 kg / cm ² -G, an average residence time of 4.0 hours, and an average polymerization rate of the produced polyethylene of 302 g / cm ^2.
hr. The obtained ethylene / hexene copolymer A
_{2 has} an MFR of 1.9 g / 10 min and a density of 0.923 g /
cm ³ .

[0063] (4) Powder 10 pelletizing said ethylene-hexene copolymer _{A 2}
0 parts by weight of octadecyl-3- as an antioxidant
(3,5-di-t-butyl-4-hydroxyphenyl)
0.03 parts by weight of propionate and tetrakis (2,
0.08 parts by weight of 4-di-t-butylphenyl) -4,4′-biphenylenediphosphonite, 0.10 part by weight of zinc stearate as a neutralizing agent, and Mizusawa Chemical as an antiblocking agent (B ₃ ) synthetic silica "Silton JC-30" 0.16 parts by weight of the industry Co., nonionic surfactant (I ₂₎ as diglycerin monostearate and glycerin monostearate 7: 3 (weight ratio) mixture 1 0.0 parts by weight, ethylene and 4-acryloyl-2,2,
3, 6 parts by weight of 6,6-tetramethylpiperidine copolymer (XJ100H, manufactured by Nippon Polychem Co., Ltd.) was added, and the mixture was rotated at 80 rpm using a 50-liter super mixer.
After mixing at 0 rpm / min for 5 minutes, screw diameter 40m
The mixture was melt-kneaded with a single screw extruder having a diameter of mφ and L / D26 at 200 ° C. and a screw rotation speed of 50 rpm to form pellets. The hexane-soluble portion, MFR, density, FR, Mw / Mn, and MT of this pellet were measured, and the value of K was calculated. The results are shown in Table 1.

(5) Film forming: The pellet obtained in the above (4) was screwed with a screw diameter of 40 mm.
Using a blown film molding machine having a die diameter of 75 mmφ and a die lip width of 3 mm equipped with an extruder of φ, L / D24, temperature 200 ° C., screw rotation speed 50 rpm,
Formed under the conditions of a blow-up ratio of 2.0, a take-up speed of 16.5 m / min, and a frost line height of 200 mm, and a width of 230
mm and a thickness of 30 μm were obtained. The formed film was measured and evaluated for haze, Elmendorf tear strength, blocking, antifogging property and weather resistance. Table 2 shows the results.

[0065] As Comparative Example 1 Ethylene · alpha-olefin copolymer A _3, Japan, commercially available from Polychem Corporation linear low density polyethylene (alpha-olefin: 1-butene, 1-butene content 7 wt%) " Novatec LL F30FG "
Pelletization and film formation were performed in the same manner as in Example 1. The pellets were dissolved in hexane, MFR, density, F
R, Mw / Mn, and MT were measured, and the value of K was calculated. About the formed film, haze, Elmendorf tear strength, blocking, antifogging property, and weather resistance were measured and evaluated. The results are shown in Tables 1 and 2.

Comparative Example 2 90 parts by weight of a linear low-density polyethylene A ₃ were mixed with a high-pressure low-density polyethylene A commercially available from Nippon Polychem.
₄ Except for using 100 parts by weight of a mixture obtained by adding 10 parts by weight of “Novatec LD LF280”, pelletizing and film forming were performed in the same manner as in Example 1, and hexane soluble matter, MFR, density, FR, Mw / M
The n and MT were measured, the value of K was calculated, and the formed film was measured and evaluated for haze, Elmendorf tear strength, blocking, antifogging property and weather resistance. The results are shown in Tables 1 and 2.

[0067] As Comparative Example 3 Ethylene · alpha-olefin copolymer A _5, a commercially available linear low density polyethylene manufactured using a metallocene catalyst (alpha-olefin: 1-hexene, 1-hexene content 8 wt% ) Was prepared using a roll kneader set at 180 ° C. and the same additives as in Example 1 were added in the same amounts as in Example 1, and pelletized using a sheet pelletizer. A film was formed in the same manner as in (4) above, and the pellets were
The MFR, density, FR, Mw / Mn, and MT were measured, and the value of K was calculated.
Elmendorf tear strength, blocking, antifogging property, and weather resistance were measured and evaluated. The results are shown in Tables 1 and 2.

[0068] Comparative Example 4 Example ethylene-hexene copolymer A ₁ obtained in 1, in Example 1 (3), talc antiblock "M
Except that "T-7" was not added, pelletization and film formation were carried out in the same manner as in Example 1, and the pellets were dissolved in hexane, MFR, density, FR, Mw / Mn, MT
Was measured, the value of K was calculated, and the haze, Elmendorf tear strength, blocking, antifogging property, and weather resistance of the formed film were measured and evaluated. The results are shown in Tables 1 and 2.

[0069] Comparative Example 5 Example Ethylene-hexene copolymer A ₁ obtained in 1, in Example 1 (3), except for not adding diglycerol monostearate nonionic surfactant, Pelletization and film formation were performed in the same manner as in Example 1. The pellets were dissolved in hexane, MFR, density, FR, Mw /
Mn and MT were measured, and the value of K was calculated. The formed film was measured and evaluated for haze, Elmendorf tear strength, blocking, antifogging property, and weather resistance. The results are shown in Tables 1 and 2.

[0070] Comparative Example 6 Example Ethylene-hexene copolymer _{A 1} obtained in 1 of Example 1 (3), ethylene and 4-acryloyloxy-2,2,6,6-tetramethylpiperidine co Except that the polymer was not added, pelletization and film formation were performed in the same manner as in Example 1. For the pellet, the hexane-soluble content, MFR, density, FR, Mw / Mn, and MT were measured, and the value of K was measured. , And for the formed film,
Haze, Elmendorf tear strength, blocking, antifogging property, and weather resistance were measured and evaluated. The results are shown in Tables 1 and 2.

[0071]

[Table 1]

[0072]

[Table 2]

[0073]

According to the present invention, there is provided an agricultural film which is excellent in transparency, strength, dust resistance and spreadability, has few problems during incineration, and has heat retention, weather resistance and anti-fogging durability. can do.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 3/00 C08K 3/00 4J100 C08L 23/08 C08L 23/08 // (C08L 23/08 23:08 ) F-term (Reference) 2B024 DB01 2B029 EB03 EC03 EC19 EC20 4F071 AA15 AA21X AA80 AA82 AA88 AB26 AE22 AF05Y AH01 BC01 4J002 BB072 BB171 DJ006 DJ016 DJ046 FD206 FD317 GA01 4J028 AC01AACACA ACA ACA ACA BAA ACA BA02B BB00A BB01A BB01B BB02B BC15B BC24B CA14C CA15C CA16C CA30C CA36C CA44C CA49C CA54C CA56C DA01 DB10C EB02 EB04 EB05 EB07 EB09 EB10 EB13 EB14 EB16 EB17 4J100 AA02P AA03Q AA04Q AA15Q AA16Q AA17Q AA19Q AA21Q AR22R AS01R AS02R AS03R CA04 CA05 DA04 DA14 DA40 DA43 FA10 JA64

Claims (4)

[Claims] An agricultural film comprising a layer comprising a polyethylene resin composition comprising the following components (A) to (C) and having the following properties (D) to (H). Component (A): 100 parts by weight of a copolymer of ethylene and an α-olefin having 3 to 12 carbon atoms Component (B): Antiblocking agent 0.03 to 1.5
Parts by weight Component (C): ethylene and 4-acryloyloxy-2,
0.005 to 0.5 parts by weight of 2,6,6-tetramethylpiperidine copolymer as 4-acryloyloxy-2,2,6,6-tetramethylpiperidine unit Property (D): Flow ratio (FR) ) Is 7.2 or less. Property (E): MFR is 0.1 to 15 g / 10 min. Property (F): Density is 0.905 to 0.940 g / cm ^3.
Characteristic (G): The hexane-soluble content is 2.5% by weight or less. Characteristic (H): The value of K shown below is 0.15 ≦ K ≦ 4.
0 (1) The resin composition has a flow ratio (FR) of FR ≦ M
When the condition of w / Mn + 4.4 is satisfied, K = MT− (0.196 Mw / Mn−0.197 +
(0.0942Mw / Mn + 0.664) e
^{(-MFR + 0.025Mw / Mn + 0.445) / (
−0.0 417 Mw / Mn + 0.382)} + (0.46
4Mw / Mn-0.128) e ^{(
−MFR + 0.025 Mw / Mn + 0.445) / (0
. 05Mw / Mn + 0. 93)} ) (2) FR of the resin composition is FR> Mw / Mn + 4.4.
When the condition is satisfied, K = MT− (0.196 Mw / Mn−0.197 +
(0.0942Mw / Mn + 0.664) e
^{(-MFR + 0.025Mw / Mn + 0.445) / (
−0.0 417 Mw / Mn + 0.382)} + (0.46
4Mw / Mn-0.128) e ^{(
−MFR + 0.025 Mw / Mn + 0.445) / (0
. 05Mw / Mn + 0. 93)} )-0.097 (FR-
0.9 Mw / Mn) / (Log MFR + 0.39) where MFR is a value measured at 190 ° C. under a load of 2.16 kg, and FR is M measured at 190 ° C. under a load of 10 kg.
And _{I 10} is a FR measurements, 2.16 at 190 ° C.
Ratio to I _2.16 which is the measured value of MFR under kg load (I
₁₀ / _I A _{2.1 6),} MT is 190 ° C., melt tension measured at a tensile speed 4m / min (g), Mw is weight average molecular weight, Mn is the number average molecular weight. E indicates the base of the natural logarithm. 2. In addition to the component (B) and the component (C), based on 100 parts by weight of a copolymer of ethylene and an α-olefin having 3 to 12 carbon atoms, non-ionic The agricultural film according to claim 1, comprising a layer formed from a polyethylene-based resin composition containing 0.05 to 5.0 parts by weight of a surfactant. 3. The agricultural film according to claim 1, wherein the copolymer of ethylene and an α-olefin having 3 to 12 carbon atoms is prepared using the following catalyst. Component (a): a metallocene-based transition metal compound, and Component (b): obtained by performing salt treatment and / or acid treatment, (b ₁ ): an inorganic silicate, and (b ₂ ): a silicate An olefin polymerization catalyst comprising at least one compound selected from the group consisting of ion-exchange layered compounds excluding 4. A copolymer of ethylene and an α-olefin having 3 to 12 carbon atoms, wherein the metallocene transition metal compound represented by the following general formula (I) is a component (a). 2. The agricultural film according to item 1. R ¹ _i (CpR ² _n ) (CpR ³ _m ) MX ¹ X ² (I) (wherein Cp represents a cyclopentadienyl group, and R ¹ contains a Group 14 element in the long period table) A covalent crosslinking group,
i is 0 or 1, R ² and R ³ are 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, and two 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 to 5, satisfy the i + m = 5 and i + n = 5, M is a Group 3, 4, 5 and 6 of Table long periodic A transition metal, X ¹ and X
² represents 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. )