JPH11310648A - Film for agriculture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a film for agriculture which has lasting antifogging property and excellent dust-preventing property and strength by providing a layer made of an ethylene-based copolymer composition having a specific composition. SOLUTION: This film has a layer made of an ethylene-based copolymer composition prepared by mixing (A) 100 parts wt. of an ethylene-4-12C α-olefin copolymer having a density of 0.905-0.935 g/cm<3> and a melt flow rate of 0.1-10 g/10 min, (B) 0.05-5 part(s) wt. of a cloud-preventing agent containing two or more non-ionic surfactants and a polyoxyethylene-containing component at 15-20 wt.%, and (C) 0.01-1 part wt. of a non-ionic fluorine-containing surfactant at 25-62 wt.% of fluorine, component A having a molecular weight distribution of 1.5-5 as measured by GPC, the relation between n-decane-soluble fraction W (wt.%) and density d at 23 deg.C satisfying the equation, the relation between an average value of numbers of branching on higher molecular weight side B1 and an average value of numbers of branching on lower molecular weight side B2 as measured by GPC-IR being B1 >=B2 .

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to agricultural films.

[0002]

BACKGROUND OF THE INVENTION In house cultivation, tunnel cultivation, and mulch cultivation for the purpose of forcing cultivation on agriculture, agricultural films composed of various thermoplastic resins are generally used in large quantities as a covering material. Such agricultural films include, for example, a polyvinyl chloride film, an ethylene / vinyl acetate copolymer film, a polyethylene film, and the like. Among them, the polyvinyl chloride film has a heat retaining property, transparency, toughness (mechanical strength). It is most often used because of its excellent properties.

[0003] However, the polyvinyl chloride film has some problems such as the dust-proofing property and the spreadability being slightly inferior, and the generation of toxic gas at the time of incineration disposal. Here, "heat retention" means the temperature inside the house, tunnel, etc. (air temperature and ground temperature) by absorbing and reflecting the radiation emitted at night from the earth whose temperature has risen by absorbing solar heat during the day and absorbing it at night. Refers to the ability to maintain

[0004] The term "dustproofness" refers to the ability of a film to prevent a decrease in the transparency of a film due to adhesion of dust or the like after a certain period of use. Further, the “stretching workability” indicates whether the film is easy to handle due to stickiness.

On the other hand, a film containing an ethylene / vinyl acetate copolymer as a main component is superior to a polyvinyl chloride film in terms of waste treatment, but is inferior in toughness.
Insufficient spreadability and dust resistance.

When polyethylene is applied to an agricultural film, this film has improved workability and dust-proofing properties as compared with the above-mentioned film containing ethylene / vinyl acetate copolymer as a main component, but it is still in use. Inadequate,
There is a problem that the toughness is inferior to that of the linear ethylene / α-olefin copolymer film.

Further, as an agricultural film in which the heat retaining property of a polyolefin resin film is improved by an additive, there is a coating film obtained by adding silicon oxide to low-density polyethylene or ethylene / vinyl acetate copolymer.

[0008] However, such an agricultural film has improved toughness compared to a polyvinyl chloride film, although the heat insulation of the polyethylene resin film is improved.
Insufficient transparency.

[0009] In order to improve the toughness of such a polyethylene resin film, agricultural films utilizing the toughness of linear low-density polyethylene have recently been devised. For example, JP-A-58-160146 discloses an antifogging method in which a base layer mainly composed of linear low-density polyethylene and a layer made of a polyethylene resin or the like produced by a conventional production method containing a surfactant are laminated. Agricultural multilayer films having good properties have been proposed. Although the toughness of the agricultural multilayer film is improved, the use of a resin or an additive having a higher heat retaining property has not been studied, so that the heat retaining property of the agricultural multilayer film is considerably inferior to that of a polyvinyl chloride film.

In Japanese Patent Laid-Open Publication No. 1-182037,
A multilayer (laminated) film for agriculture has been proposed, in which the outer layer is formed of a polyethylene resin having a linear ethylene / α-olefin copolymer as a main component and an inorganic compound, In addition, the inner layer is formed of a polyethylene resin having an ethylene / vinyl acetate copolymer as a main component, an inorganic compound, and an antifogging agent. JP-A-1-1-1
The agricultural multilayer film described in Japanese Patent No. 82037 is said to have good heat retention, dustproofness, spreading workability, transparency, and weather resistance, and has extremely excellent toughness.

However, the conventional multilayer film for agriculture as described above has room for improvement in antifogging durability, dust resistance, toughness and the like. Therefore, as compared with the above-mentioned conventional agricultural films (single-layer and multilayer films), there is a demand for an agricultural film which has a small degree of deterioration of the anti-fogging continuity over time, and is excellent in dust resistance and toughness. .

[0012]

SUMMARY OF THE INVENTION An object of the present invention is to provide an agricultural film which is less susceptible to aging over time than the conventional agricultural films described above, and which is excellent in dust resistance and toughness. I have.

[0013]

SUMMARY OF THE INVENTION The agricultural film according to the present invention comprises [I]
It is obtained by copolymerizing ethylene and an α-olefin having 4 to 12 carbon atoms, and has a density of 0.905 to 0.935 g / c.
m ³ and the melt flow rate is 0.1 to 10 g / 1.
0 minute ethylene / α-olefin copolymer (A) 1
100 parts by weight, or 100 parts by weight of a mixture of the ethylene / α-olefin copolymer (A) and the high-pressure low-density polyethylene (B) in an amount of 40% by weight or less, and [II] two or more nonionic 0.05 to 5 parts by weight of an antifogging agent (C) comprising a mixture of surfactants, wherein the mixture contains 15 to 50% by weight of a polyoxyethylene group-containing component;
I] Layer formed of ethylene copolymer composition (1) containing 0.01 to 1 part by weight of nonionic fluorine-containing surfactant (D) having a fluorine content of 25 to 65% by weight The ethylene / α-olefin copolymer (A) or a mixture of the ethylene / α-olefin copolymer (A) and the high-pressure low-density polyethylene (B) is obtained by (i) GPC The measured molecular weight distribution (Mw /
Mn: Mw = weight average molecular weight, Mn = number average molecular weight) in the range of 1.5 to 5.0, and (ii) n- at 23 ° C.
The decane soluble component amount fraction (W (% by weight)) and density (d) are: W <80 × exp (−100 (d−0.88)) + 0.
(Iii) When the average value of the number of branches on the high molecular weight side by GPC-IR is B ₁ and the average value of the number of branches on the low molecular weight side is B ₂ , B ₁ ≧ B ₂ It is characterized by having.

The agricultural film according to the present invention may have a single-layer structure or a multilayer structure comprising two or more layers. The preferred agricultural film having a single-layer structure according to the present invention comprises the ethylene / α-olefin copolymer (A), the antifogging agent (C), the nonionic fluorine-containing surfactant (D), and if necessary. And a monolayer film comprising a layer formed of an ethylene copolymer composition (1) containing a high-pressure low-density polyethylene (B), and the film has (i) an Elmendorf tear strength in the MD direction. 90 kg / cm or more, and 90 kg in the TD direction
/ Cm and at least, (ii) dart impact strength in the thickness 100μm is equal to or greater than 450 g, (iii) tensile strength at break is at 350 kg / cm ² or more in the MD direction, and, 350 kg / cm ² in TD direction That is all.

Further, the preferred agricultural film having a multilayered structure according to the present invention is [I] ethylene and C 4-12 carbon atoms.
Of α-olefins having a density of 0.9
An ethylene / α-olefin copolymer (E) having a melt flow rate of 25 to 0.940 g / cm ³ and a melt flow rate of 0.1 to 10 g / 10 minutes, or the ethylene / α-olefin copolymer (E) Outer layer consisting of an ethylene-based copolymer composition (2) containing a mixture of a high-pressure low-density polyethylene (B) in an amount of not more than 40% by weight, [II] ethylene and α- An ethylene / α-olefin copolymer (F) obtained by copolymerizing an olefin and having a density of 0.880 to 0.920 g / cm ³ and a melt flow rate of 0.1 to 10 g / 10 minutes 100 parts by weight or the ethylene / α-olefin copolymer (F)
And a mixture of at least 40% by weight of a high-pressure low-density polyethylene (B) and a mixture of two or more nonionic surfactants, and the mixture contains a polyoxyethylene group-containing polyoxyethylene group. An intermediate layer consisting of an ethylene copolymer composition (3) containing 0.05 to 5 parts by weight of an antifogging agent (C) containing 15 to 50% by weight of a component, and [II]
I] is obtained by copolymerizing ethylene and an α-olefin having 4 to 12 carbon atoms, and has a density of 0.905 to 0.935 g /
cm ³ and the melt flow rate is 0.1 to 10 g /
10 minutes of ethylene / α-olefin copolymer (A)
100 parts by weight or 100 parts by weight of a mixture of the ethylene / α-olefin copolymer (A) and the high-pressure low-density polyethylene (B) in an amount of 40% by weight or less, and two or more nonionic surfactants Of a polyoxyethylene group-containing component in the mixture.
A multilayer film formed by laminating an inner layer comprising an ethylene copolymer composition (1) containing 0.05 to 5 parts by weight of an antifogging agent (C), and the ethylene copolymer Among the compositions (1), (2) and (3), at least the ethylene copolymer composition (1) contains a nonionic fluorine-containing surfactant having a fluorine content of 25 to 65% by weight ( D) is contained in an amount of 0.01 to 1 part by weight, and the ethylene / α-olefin copolymer (E) or the ethylene / α-olefin copolymer (E) forming the outer layer is mixed with a high-pressure low-density polyethylene (E). B) and the density (d _E or d _EB ) of the mixture with ethylene / α-olefin copolymer (A) or ethylene / α-olefin copolymer (A) forming the inner layer and high-pressure low-density polyethylene ( B) Density (d
_A or d _AB ) and d _E or d _EB ≧ d _A or d
A relationship that satisfies _AB .

The resin forming the outer layer, the intermediate layer, and the inner layer has a (i) molecular weight distribution (M
w / Mn: Mw = weight average molecular weight, Mn = number average molecular weight) is in the range of 1.5 to 5.0, and (ii) n-decane soluble component fraction at 23 ° C. (W (weight%)) ) And density (d) are: W <80 × exp (−100 (d−0.88)) + 0.
(Iii) When the average value of the number of branches on the high molecular weight side by GPC-IR is B ₁ and the average value of the number of branches on the low molecular weight side is B ₂ , B ₁ ≧ B ₂ Preferably, there is. Here, resin is ethylene / α
-Refers to an olefin copolymer or a copolymer of an ethylene / α-olefin copolymer and a high-pressure low-density polyethylene.

Further, the agricultural film having a multilayer structure as described above has (i) an Elmendorf tear strength of 90 kg / cm or more in the MD direction and 90 kg / cm in the TD direction.
/ Cm and at least, (ii) dart impact strength in the thickness 100μm is equal to or greater than 900 g, (iii) tensile strength at break is at 350 kg / cm ² or more in the MD direction, and, 350 kg / cm ² in TD direction It is preferable that it is above.

[0018]

DETAILED DESCRIPTION OF THE INVENTION The agricultural film according to the present invention will be specifically described below. The agricultural film according to the present invention comprises an ethylene / α-olefin copolymer (A), an antifogging agent (C), a nonionic fluorine-containing surfactant (D) and, if necessary, a high-pressure low-density polyethylene ( It has a layer formed of the ethylene-based copolymer composition (1) containing B). The agricultural film according to the present invention may be a film having a single-layer structure composed of such layers (single-layer film), or a film having a multilayer structure of two or more layers having such layers ( Multilayer film).

[Ethylene / α-olefin copolymer (A)] The ethylene / α-olefin copolymer (A) constituting the ethylene copolymer composition (1) used in the present invention comprises ethylene and carbon It is a copolymer comprising an α-olefin having 4 to 12 atoms.

The α-olefin having 4 to 12 carbon atoms used for copolymerization with ethylene is, specifically, 1-olefin.
Butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene and the like. Among them, α-olefins having 4 to 10 carbon atoms, particularly α-olefins having 4 to 6 carbon atoms are preferred.

In the present invention, the above-mentioned ethylene / α-olefin copolymer (A) can be used alone or in combination of two or more. The ethylene / α-olefin copolymer (A) used in the present invention has a constitutional unit derived from ethylene of 50% by weight or more and 100% by weight or more.
Less than 55, preferably from 99 to 99% by weight, more preferably from 65 to 98% by weight, particularly preferably from 70 to 96% by weight, wherein the constituent units derived from α-olefins having 4 to 12 carbon atoms comprise 50 or less. Wt% or less, preferably 1-4
Desirably, it is present in an amount of 5% by weight, more preferably 2 to 35% by weight, particularly preferably 4 to 30% by weight.

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

The ethylene / α-olefin copolymer (A) has a density of 0.905 to 0.935 g / cm ³ ,
It is preferably in the range of 0.908 to 0.935 g / cm ³ , more preferably 0.910 to 0.930 g / cm ³ , particularly preferably 0.925 to 0.930 g / cm ³ .

The density is 2.16 at 190 ° C.
The strand obtained at the time of melt flow rate (MFR) measurement under a kg load is heat-treated at 120 ° C. for 1 hour, gradually cooled to room temperature over 1 hour, and measured with a density gradient tube.

The ethylene / α-olefin copolymer (A) has a melt flow rate (MFR; ASTM).
D 1238-65T, 190 ° C, load 2.16 kg)
Is 0.1 to 10 g / 10 min, preferably 0.1 to 5 g
/ 10 min, more preferably in the range of 0.5 to 2 g / 10 min.

The molecular weight distribution (Mw / M) of the ethylene / α-olefin copolymer (A) measured by GPC
n: Mw = weight average molecular weight, Mn = number average molecular weight)
It is in the range of 1.5-5.0, preferably 1.8-3.5, more preferably 2.0-3.0.

The molecular weight distribution (Mw / Mn) was measured as follows using GPC-150C manufactured by Millipore. The separation column is TSK GNH HT,
The column size is 72 mm in diameter and 600 mm in length,
The column temperature was 140 ° C., and the mobile phase used was O-dichlorobenzene (manufactured by Wako Pure Chemical Industries, Ltd.) and 0.025% by weight of BHT (manufactured by Takeda Pharmaceutical Company Limited) as an antioxidant. The sample was moved at 0 ml / min, the sample concentration was 0.1% by weight, the sample injection amount was 500 microliter, and a differential refractometer was used as a detector. Standard polystyrene is
For a molecular weight of Mw <1000 and Mw> 4 × 10 ⁶ , Tosoh Corp.
About ⁶ , the product made by Pressure Chemical Company was used.

Further, the ethylene / α-olefin copolymer (A) has an n-decane soluble component fraction at 23 ° C. (W
(% By weight)) and the density (d) satisfy the relationship shown below.

W <80 × exp (−100 (d−0.8
8)) +0.1 In addition, the amount of n-decane soluble component of the ethylene / α-olefin copolymer (the smaller the soluble component, the narrower the composition distribution)
Is about 3 g of ethylene / α-olefin copolymer.
After adding to 450 ml of n-decane and dissolving at 145 ° C., 23
It cools to ° C, removes an n-decane insoluble part by filtration, and collect | recovers n-decane soluble part from a filtrate.

The ethylene / α-olefin copolymer has a temperature [Tm (° C.)] and a density [d at the maximum peak position of an endothermic curve measured by a differential scanning calorimeter (DSC).
(G / cm ³ )] and the relationship represented by Tm <400 × d-250, preferably Tm <450 × d-297, more preferably Tm <500 × d-344, and particularly preferably Tm <550 × d-391. It is desirable to satisfy

The temperature (Tm) at the maximum peak position of the endothermic curve measured by a differential scanning calorimeter (DSC) is as follows:
Approximately 5mg of sample is packed in aluminum pan and 200 ℃ at 10 ℃
The temperature is kept at 200 ° C. for 5 minutes, then the temperature is lowered to room temperature at 20 ° C./min, and then determined from an endothermic curve when the temperature is raised at 10 ° C./min. Measurements made by PerkinElmer
Use a DSC-7 type device.

As described above, the relationship between the n-decane soluble component amount fraction (W) and the density (d), and the temperature (Tm) at the maximum peak position in the endothermic curve measured by a differential scanning calorimeter (DSC) ) And the density (d) have the above-mentioned relationship, it can be said that the ethylene / α-olefin copolymer has a narrow composition distribution.

Further, the ethylene / α-
The olefin copolymer (A) satisfies B ₁ ≧ B ₂ when the average value of the number of branches on the high molecular weight side by GPC-IR is B ₁ and the average value of the number of branches on the low molecular weight side is B ₂ .

Here, the average value (B ₁ ) of the number of branches on the high molecular weight side by GPC-IR means that the cumulative weight fraction of the elution amount of the high molecular weight fractionated by GPC is 15 to 85%.
The measurement value group of the number of branches measured for each fraction in the range of (ie, the high molecular weight region excluding 15% and the high molecular weight region excluding 15%) was divided into two by the molecular weight at the peak position of the GPC elution curve. It is the average of the values on the high molecular weight side. On the other hand, the average value of the number of branches on the low molecular weight side (B
₂ ) is the average value on the low molecular weight side of the two parts.

The measurement conditions for B ₁ and B ₂ are as follows. Measuring device: Perkin Elmer 1760X Column: TSK gel GMH-HT (7.5mmI.
D. × 600 mm) × 1 Eluent (eluent): o-dichlorobenzene (ODCB) containing 0.05% of MP-J [ex. Wako Pure Chemical Industries, Ltd., ex
tra pure grade] Column temperature: 140 ° C. Sample concentration: 0.1% (weight / volume) Injection volume (inj.volume): 100 microliter detector: MCT Resolution: 8 cm ^-1 The B ₁ and B ₂ is the Ethylene and α in such a relationship
-The olefin copolymer (A) has a narrow composition distribution and a small amount of a low polymer, and thus has a low stickiness. Therefore, when the above-mentioned ethylene / α-olefin copolymer (A) is used, an agricultural film excellent in dustproofness can be obtained.

Further, since the film made of the ethylene / α-olefin copolymer (A) has a very small decrease in light transmittance over time, if such a film is used as an agricultural film, it will last for a long time. It is possible to expand.

The above-mentioned ethylene / α-olefin copolymer (A) is prepared by using a single-site catalyst such as disclosed in
-9724, JP-A-6-136195, JP-A-6-136196, JP-A-6-20757
No. including metallocene catalyst components described in
In the presence of a so-called metallocene-based olefin polymerization catalyst, ethylene and an α-olefin having 4 to 12 carbon atoms are converted into a copolymer having a density of 0.905 to 0.935.
It can be produced by copolymerization to give g / cm ³ .

Such a metallocene catalyst generally contains at least one ligand having a cyclopentadienyl skeleton.
Metallocene catalyst component (a) comprising a transition metal compound of Group IVB of the periodic table, an organoaluminum oxy compound catalyst component (b), a particulate carrier (c), and, if necessary, an organoaluminum compound catalyst component (d ), An ionized ionic compound formed from the catalyst component (e).

The metallocene catalyst component (a) preferably used in the present invention is a transition metal compound of Group IVB of the periodic table having at least one ligand having a cyclopentadienyl skeleton. Examples of such a transition metal compound include a transition metal compound represented by the following general formula [I].

ML ¹ _x ... [I] In the formula, x is the valence of the transition metal atom M. M is a transition metal atom selected from Group IVB of the periodic table, and specifically, zirconium, titanium, and hafnium. Among them, zirconium is preferred.

L ¹ is a ligand that coordinates to the transition metal atom M, and at least one of these ligands L ¹
Is a ligand having a cyclopentadienyl skeleton.
As the ligand L ¹ having a cyclopentadienyl skeleton coordinated to the transition metal atom M as described above, specifically,
Cyclopentadienyl group, methylcyclopentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, tetramethylcyclopentadienyl group, pentamethylcyclopentadienyl group, methylethylcyclopentadienyl group And an alkyl-substituted cyclopentadienyl group such as hexylcyclopentadienyl group, or an indenyl group, a 4,5,6,7-tetrahydroindenyl group or a fluorenyl group. These groups are
It may be substituted with a halogen atom, a trialkylsilyl group or the like.

When the compound represented by the above general formula [I] contains two or more groups having a cyclopentadienyl skeleton, two of the groups having a cyclopentadienyl skeleton are connected to each other by ethylene, propylene or the like. An alkylene group,
It may be bonded through a substituted alkylene group such as isopropylidene diphenylmethylene or the like, or a silylene group or a substituted silylene group such as a dimethylsilylene group, a diphenylsilylene group or a methylphenylsilylene group.

The ligand L ¹ other than the ligand having a cyclopentadienyl skeleton is a hydrocarbon group having 1 to 12 carbon atoms; an alkoxy group such as a methoxy group; an aryloxy group such as a phenoxy group; a trimethylsilyl group; A trialkylsilyl group such as a triphenylsilyl group; SO ₃ R (R is a hydrocarbon group having 1 to 8 carbon atoms which may have a substituent such as halogen), a halogen atom or a hydrogen atom.

Examples of the hydrocarbon group having 1 to 12 carbon atoms include an alkyl group such as a methyl group, a cycloalkyl group such as a cyclopentyl group, an aryl group such as a phenyl group, and an aralkyl group such as a benzyl group.

Specific examples of the ligand represented by SO ₃ R include a P-toluenesulfonato group, a methanesulfonato group, and a trifluoromethanesulfonato group. As the organoaluminum oxy compound catalyst component (b), aluminoxane is preferably used. Specifically, methylaluminoxane, ethylaluminoxane, methylethylaluminoxane having a repeating unit represented by the formula -Al (R) O-, wherein R is an alkyl group, is usually about 3 to 50. Are used.

Such an aluminoxane can be prepared by a conventionally known production method. The particulate carrier (c) used in the preparation of the catalyst for olefin polymerization is an inorganic or organic compound and has a particle size of usually 10 to 300 μm.
And preferably 20 to 200 μm in the form of granules or fine particles.

As the inorganic carrier, a porous oxide is preferable. Specifically, SiO ₂ , Al ₂ O ₃ , MgO, Zr
O ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, S
Examples thereof include nO _{2 and the} like or a mixture thereof. The inorganic oxide contains a small amount of a carbonate such as Na ₂ CO _3, a sulfate such as Al ₂ (SO ₄ ) ₃ , a nitrate such as KNO ₃ , and an oxide such as Li ₂ O. No problem.

Although the properties of such a carrier differ depending on the kind and the production method, the carrier preferably used in the present invention has a specific surface area of 50 to 1000 m ² / g, preferably 1 to 1,000 m ² / g.
00-700 m ² / g, and the pore volume is 0.3-2.
It is preferably 5 cm ³ / g.

The carrier may be used, if necessary, in an amount of from 100 to 100.
It is used by firing at 0 ° C, preferably 150 to 700 ° C. Examples of the organic compound used as the particulate carrier include a (co) polymer formed mainly of an α-olefin having 2 to 14 carbon atoms such as ethylene and 4-methyl-1-pentene, or vinylcyclohexane. And (co) polymers formed mainly of styrene.

Examples of the organoaluminum compound catalyst component (d) optionally used in the preparation of the catalyst for olefin polymerization include trialkylaluminums such as trimethylaluminum, alkenylaluminums such as isoprenylaluminum, and dimethylaluminum. Examples thereof include dialkylaluminum halides such as chloride, alkylaluminum sesquihalides such as methylaluminum sesquichloride, alkylaluminum dihalides such as methylaluminum dichloride, and alkylaluminum hydrides such as diethylaluminum hydride.

Examples of the ionized ionic compound catalyst component (e) include triphenylboron, MgCl ₂ , and Al described in US Pat. No. 5,321,106.
Lewis acids such as ₂ O ₃ and SiO ₂ —Al ₂ O ₃ ; ionic compounds such as triphenylcarbenium tetrakis (pentafluorophenyl) borate; carborane compounds such as dodecaborane and bis-n-butylammonium (1-carbedodeca) borate Is mentioned.

The ethylene / α-olefin copolymer (A) used in the present invention comprises a metallocene catalyst component (a), an organoaluminum oxy compound catalyst component (b), a particulate carrier (c), If necessary, in the presence of an olefin polymerization catalyst containing an organoaluminum compound catalyst component (d) and an ionized ionic compound catalyst component (e), a gas phase or a slurry or solution liquid phase may be used under various conditions. , Ethylene and α- with 4 to 12 carbon atoms
It can be obtained by copolymerizing with an olefin.

In the slurry polymerization method or the solution polymerization method, an inert hydrocarbon may be used as a solvent, or olefin itself may be used as a solvent. When carrying out the polymerization, the above-mentioned metallocene-based olefin polymerization catalyst is usually used in a concentration of 10 ^-8 , based on the concentration of transition metal atoms in the polymerization reaction system.
10 ^-3 gram atom / liter, preferably 10 ^{-7 -1
Preferably,} it is used in an amount of ^0-4 grams atom / liter.

In the polymerization, in addition to the organoaluminum oxy compound catalyst component (b) and the organoaluminum compound catalyst component (d) supported on the carrier, the unsupported organoaluminum oxy compound catalyst component (b) And / or an organoaluminum compound catalyst component (d) may be used. In this case, an aluminum atom (Al) derived from the unsupported organoaluminum oxy compound catalyst component (b) and / or the organoaluminum compound catalyst component (d) and a transition metal atom derived from the metallocene catalyst component (a) ( M) and the atomic ratio [Al
/ M] is in the range of 5 to 300, preferably 10 to 200, and more preferably 15 to 150.

The polymerization temperature in the slurry polymerization method is usually in the range of -50 to 100 ° C, preferably 0 to 90 ° C, and the polymerization temperature in the solution polymerization method is usually -50 to 50 ° C.
0 ° C, preferably in the range of 0 to 400 ° C. Further, the polymerization temperature in the gas phase polymerization method is usually in the range of 0 to 120 ° C, preferably 20 to 100 ° C.

The polymerization pressure is usually from normal pressure to 100 kg /
cm ² , preferably ² to 50 kg / cm ² under pressure, and the polymerization can be carried out in any of a batch system, a semi-continuous system, and a continuous system.

In the present invention, when preparing the ethylene / α-olefin copolymer (A), if necessary,
(1) Multistage polymerization, (2) Multistage polymerization of liquid phase and gas phase, or (3)
Means such as performing polymerization in a gas phase after performing preliminary polymerization in a liquid phase can be employed. In the present invention,
The multi-stage polymerization of the above (1) is preferred.

Examples of the multi-stage polymerization include the following multi-stage polymerization. [1] A metallocene catalyst component comprising at least one compound selected from transition metal compounds of Group IVB of the periodic table containing a ligand having a cyclopentadienyl skeleton represented by the general formula [I]; In the presence of a metallocene catalyst containing an aluminum oxy compound catalyst component, ethylene is copolymerized with an α-olefin having 4 to 12 carbon atoms to produce an ethylene / α-olefin copolymer (A-1). Step [2] In a polymerization vessel different from the polymerization vessel in which the copolymerization reaction is performed, the above-mentioned general formula [I]
A metallocene catalyst component comprising at least one compound selected from transition metal compounds of Group IVB of the Periodic Table containing a ligand having a cyclopentadienyl skeleton represented by the following formula: and an organoaluminum oxy compound catalyst component Ethylene and carbon atoms of 4 to
And α-olefin of 12
And a step of producing an olefin copolymer (A-2). However, the manufacturing conditions in the step [1] are different from the manufacturing conditions in the step [2]. Such production conditions include, for example, the type and amount of the metallocene catalyst component, the type and amount of the organoaluminum oxy compound catalyst component, and the molar ratio of ethylene to α-olefin.

The metallocene catalyst used in the above-mentioned copolymerization step [1] and / or [2] is added to the metallocene catalyst component (a) and the organic aluminum oxy compound catalyst component (b), and the organic aluminum compound catalyst component (d). ), Or a solid catalyst in which the metallocene catalyst component (a) and the organoaluminum oxy compound catalyst component (b) are supported on the particulate carrier (c). These metallocene-based catalysts are prepolymerized catalysts obtained by prepolymerizing an olefin onto a solid catalyst component in which a metallocene catalyst component (a) and an organoaluminum oxy compound catalyst component (b) are supported on a particulate carrier (c). It may be. Further, these metallocene-based catalysts include a catalyst comprising the above-mentioned solid catalyst (solid catalyst component) and an organoaluminum compound catalyst component (d), or the above-mentioned prepolymerization catalyst (preliminary polymerization catalyst component) and an organoaluminum compound catalyst component (d ) May be used.

In this multi-stage polymerization method, the above-mentioned ethylene / α-olefin copolymer (A-1) is first produced using a plurality of polymerization vessels connected in series, and then the ethylene / α-olefin copolymer is produced.
-The ethylene / α-olefin copolymer (A-1) is introduced into a polymerization vessel different from the polymerization vessel used for producing the olefin copolymer (A-1), and the ethylene / α-olefin copolymer (A The ethylene / α-olefin copolymer (A-2) can be produced in the presence of -1).

Further, a plurality of polymerization reactors are connected in parallel, and in each polymerization reactor, ethylene / α-olefin copolymers (A-1) and (A-2) are produced, respectively. Can also be blended.

In the present invention, the ethylene / α-olefin copolymer (A) is used based on 100 parts by weight of the total amount of the ethylene / α-olefin copolymer (A) and the high-pressure low-density polyethylene (B). , 60 to 100 parts by weight, preferably 65 to 99 parts by weight, more preferably 70 to 95 parts by weight.
Used in parts by weight.

[High-Pressure Low-Density Polyethylene (B)] In the present invention, in order to enhance the moldability of the ethylene / α-olefin copolymer (A), the high-pressure low-density polyethylene (B) is converted to ethylene / α-olefin. Olefin copolymer (A)
Can be used as a mixture.

The high-pressure low-density polyethylene (B) constituting the ethylene copolymer composition (1) used in the present invention.
Is the melt flow rate (MFR; ASTM D 123)
8,190 ° C, load 2.16kg) 0.1-100g
/ 10 min, density 0.915 to 0.935 g / cm ³ ,
The swell ratio is preferably 60% or less.

The density of the high-pressure method low-density polyethylene (B) can be determined by the same method as that for measuring the density of the ethylene / α-olefin copolymer (A) described above. The swell ratio is obtained as follows.

The diameter at a position 5 mm from the tip of the strand obtained at the time of measuring the melt flow rate is measured with a micrometer as the diameter (mm) of the sample. Then, the swell ratio is calculated by the following equation.

Swell ratio (%) = [(L ₁ / L ₀ ) −1] × 100 L ₁ : diameter of sample (mm) L ₀ : diameter of orifice (= 2.0955 mm) Polyethylene (B) can be produced by a conventionally known high-pressure method.

In the present invention, the high-pressure low-density polyethylene (B) is used in an amount of 0 to 100 parts by weight based on the total amount of the ethylene / α-olefin copolymer (A) and the high-pressure low-density polyethylene (B). 40 parts by weight, preferably 1
To 35 parts by weight, more preferably 5 to 30 parts by weight. When the high-pressure low-density polyethylene (B) is mixed with the ethylene / α-olefin copolymer (A) at the above ratio, the moldability of the ethylene / α-olefin copolymer (A) can be improved, and The transparency of the film is improved.

[Anti-fogging agent (C)] The anti-fogging agent (C) constituting the ethylene copolymer composition (1) used in the present invention.
Is composed of a mixture of two or more nonionic surfactants, and contains a polyoxyethylene group-containing component in an amount of 15 to 50% by weight, preferably 20 to 45% by weight, more preferably 25 to 40% by weight. % By weight. However, diethanol alkylamine is excluded from the nonionic surfactant used in the present invention. When the polyoxyethylene group-containing component is used in the above ratio, the composition obtained is excellent in moldability, and the film obtained from the composition is excellent in antifogging property and antifogging durability.

This polyoxyethylene group-containing component comprises:
In the formula for the polyoxyethylene group represented by (—CH ₂ CH ₂ O—) _n H, n is 2 to 10, and the balance between hydrophilicity and lipophilicity (hydrophilic-lipophilic bal)
It is preferable that the HLB value as an index of ance) is 5 to 12.

The mixture of two or more nonionic surfactants preferably used as the antifogging agent (C) in the present invention is at least one selected from the group consisting of glycerin fatty acid esters, polyglycerin fatty acid esters and sorbitan fatty acid esters. Species of fatty acid ester (i), ethylene oxide adduct of glycerin fatty acid ester (polyoxyethylene glycerin fatty acid ester), ethylene oxide adduct of polyglycerin fatty acid ester (polyoxyethylene polyglycerin fatty acid ester) and ethylene oxide adduct of sorbitan fatty acid ester (Polyoxyethylene sorbitan fatty acid ester) and at least one polyoxyethylene group-containing component (ii) selected from the group consisting of:

The glycerin fatty acid ester includes
Specifically, glycerin monomyristate, glycerin dimyristate, glycerin monopalmitate, glycerin dipalmitate, glycerin monostearate, glycerin distearate, glycerin monoolate, glycerindiolate, glycerin monolaurate, glycerin dilaurate Glycerin monobehenate, higher fatty acid esters such as glycerin dibehenate, and mixtures of two or more thereof. Among them, glycerin monostearate is particularly preferred.

Specific examples of the polyglycerin fatty acid ester include diglycerin monomyristate, diglycerin dimyristate, diglycerin monopalmitate, diglycerin dipalmitate, diglycerin monostearate, and diglycerin distearate. Diglycerin fatty acid esters such as diglycerin monooleate, diglycerindiolate, diglycerin monolaurate, diglycerin dilaurate, diglycerin monobehenate, diglycerin dibehenate; triglycerin monomyristate, triglycerin dimilli State, triglycerin monopalmitate, triglycerin dipalmitate, triglycerin monostearate, triglycerin distearate, triglycerin monooleate, triglycerindiolate Triglycerol monolaurate,
Examples include higher fatty acid esters such as triglycerin fatty acid esters such as triglycerin dilaurate, triglycerin monobehenate, and triglycerin dibehenate, and mixtures of two or more thereof. Among them, diglycerin monostearate, diglycerin distearate and a mixture thereof are particularly preferred.

The sorbitan fatty acid ester is an ester of a sorbitan mixture and a higher fatty acid. Sorbitan is generally present as a mixture of 1,4-sorbitan, 3,6-sorbitan, 1,5-sorbitan, which is a sorbit monomolecular dehydrate, and 1,4,3,6-sorbide, which is a sorbit bimolecular dehydrate. Manufactured industrially. Higher fatty acids include lauric acid, palmitic acid, stearic acid, oleic acid,
Myristic acid, behenic acid and the like.

As the sorbitan fatty acid ester, specifically, sorbitan monolaurate, sorbitan dilaurate, sorbitan trilaurate, sorbitan monopalmitate, sorbitan dipalmitate, sorbitan tripalmitate, sorbitan monostearate, sorbitan distearate Sorbitan tristearate, sorbitan monooleate, sorbitan dioleate, sorbitan trioleate, sorbitan monomyristate, sorbitan dimyristate, sorbitan trimyristate, sorbitan monobehenate, sorbitan dibehenate, sorbitan tribehenate And higher fatty acid esters such as nates, and mixtures of two or more thereof. Among them, sorbitan monostearate, sorbitan distearate and a mixture thereof are particularly preferred.

Specific examples of the above-mentioned ethylene oxide adduct of glycerin fatty acid ester include the above-mentioned ethylene oxide adduct of glycerin fatty acid ester such as dioxyethylene glycerin myristate (including mono-, di- and triester). Dioxyethylene glycerin palmitate (including mono, di and triester), dioxyethylene glycerin stearate (including mono, di and triester), trioxyethylene glycerin myristate (including mono, di and triester) , Trioxyethylene glycerin palmitate (including mono, di and triester), trioxyethylene glycerin stearate (including mono, di and triester), tetraoxyethylene glycerin myristate (Including mono, di and triesters), tetraoxyethylene glycerin palmitate (including mono, di and triesters), tetraoxyethylene glycerin stearate (including mono, di and triesters), pentaoxyethylene glycerin millimeter State (including mono, di and triester), pentaoxyethylene glycerin palmitate (including mono, di and triester), pentaoxyethylene glycerin stearate (including mono, di and triester), hexaoxyethylene glycerin Myristate (including mono, di and triester), hexaoxyethylene glycerin palmitate (including mono, di and triester), hexaoxyethylene glycerin stearate (mono, di and tries) Heptaoxyethylene glyceryl myristate (including mono, di and triesters), heptaoxyethylene glycerin palmitate (including mono, di and triesters), heptaoxyethylene glycerin stearate (including mono, di and triesters) Triester), octaoxyethylene glycerine myristate (including mono, di and triester), octaoxyethylene glycerin palmitate (including mono, di and triester), octaoxyethylene glycerin stearate (mono and diester) And triesters), nonaoxyethylene glycerine myristate (including mono, di and triesters), nonaoxyethylene glycerin palmitate (including mono, di and triesters), nonaoxyethylene Glycerin stearate (including mono, di and triester), decaoxyethylene glycerine myristate (including mono, di and triester), decaoxyethylene glycerin palmitate (including mono, di and triester), decaoxy Ethylene glycerin stearate (including mono, di and triester) and the like.

As the ethylene oxide adduct of the polyglycerin fatty acid ester, specifically, the ethylene oxide adduct of the polyglycerin fatty acid ester described above, for example, dioxyethylene diglycerin myristate (mono, di, tri and tetra) Esters), dioxyethylene diglycerin palmitate (including mono, di, tri and tetra esters), dioxyethylene diglycerin stearate (including mono, di, tri and tetra esters), dioxyethylene triglycerin Myristate (including mono, di, tri and tetraester), dioxyethylene triglycerin palmitate (including mono, di, tri and tetraester), dioxyethylene triglycerin stearate (mono, di, tri and tetraester) Fine tetra including esters), trioxyethylene diglycerin myristate (mono-, di-,
Trioxyethylene diglycerin palmitate (including mono, di, tri and tetra esters), trioxyethylene diglycerin stearate (including mono, di, tri and tetra esters), tetraoxy Ethylene diglycerin myristate (including mono, di, tri and tetraester),
Tetraoxyethylene diglycerin palmitate (including mono, di, tri and tetraester), tetraoxyethylene diglycerin stearate (including mono, di, tri and tetraester), pentaoxyethylene diglycerin myristate (mono, Di, tri and tetra esters, pentaoxyethylene diglycerin palmitate (including mono, di, tri and tetra esters), pentaoxyethylene diglycerin stearate (including mono, di, tri and tetra esters), Hexaoxyethylene diglycerin myristate (including mono, di, tri and tetraester), hexaoxyethylene diglycerin palmitate (mono,
Di, tri and tetra esters, hexaoxyethylene diglycerin stearate (including mono, di, tri and tetra esters), heptaoxyethylene diglycerin myristate (including mono, di, tri and tetra esters), Heptaoxyethylene diglycerin alumitate (including mono, di, tri and tetraester), heptaoxyethylene diglycerin stearate (including mono, di, tri and tetraester), octaoxyethylene diglycerin myristate (mono,
Di, tri and tetra esters, octaoxyethylene diglycerin palmitate (including mono, di, tri and tetra esters), octaoxyethylene diglycerin stearate (including mono, di, tri and tetra esters), Nonaoxyethylene diglycerin myristate (including mono, di, tri and tetraesters), nonaoxyethylene diglycerin palmitate (including mono, di, tri and tetraesters), nonaoxyethylene diglycerin stearate (mono, The
Tri and tetra esters, decaoxyethylene diglycerine myristate (including mono, di, tri and tetra esters), decaoxy ethylene diglycerin palmitate (including mono, di, tri and tetra esters), decaoxy Ethylene diglycerin stearate (including mono, di, tri and tetra esters) and the like.

Specific examples of the ethylene oxide adduct of the sorbitan fatty acid ester include ethylene oxide adducts of the sorbitan fatty acid ester described above, for example, dioxyethylene sorbitan laurate (including mono, di, tri and tetra esters). ), Dioxyethylene sorbitan palmitate (including mono, di, tri and tetraesters), dioxyethylene sorbitan stearate (including mono, di, tri and tetraesters), dioxyethylene sorbitan oleate (mono, di , Tri and tetra esters, trioxyethylene sorbitan laurate (including mono, di, tri and tetra esters), trioxyethylene sorbitan palmitate (including mono, di, tri and tetra esters), Lioxyethylene sorbitan stearate (including mono, di, tri and tetraester), trioxyethylene sorbitan oleate (including mono, di, tri and tetraester), tetraoxyethylene sorbitan laurate (mono, di, triester) And tetraesters), tetraoxyethylene sorbitan palmitate (including mono, di, tri and tetraesters), tetraoxyethylene sorbitan stearate (including mono, di, tri and tetraesters), tetraoxyethylene sorbitan oleate Ethates (including mono, di, tri and tetraesters), pentaoxyethylene sorbitan laurate (including mono, di, tri and tetraesters), pentaoxyethylene sorbitan palmitate (including mono, di, tri and tetraesters) Pentaoxyethylene sorbitan stearate (including mono, di, tri and tetraester), pentaoxyethylene sorbitan oleate (including mono, di, tri and tetraester), hexaoxyethylene sorbitan laurate (Including mono, di, tri and tetraester), hexaoxyethylene sorbitan palmitate (including mono, di, tri and tetraester), hexaoxyethylene sorbitan stearate (including mono, di, tri and tetraester) , Hexaoxyethylene sorbitan oleate (including mono, di, tri and tetraester), heptaoxyethylene sorbitan laurate (including mono, di, tri and tetraester), heptaoxyethylene sorbitan pal Mitates (including mono, di, tri and tetra esters), heptaoxyethylene sorbitan stearate (including mono, di, tri and tetra esters), heptaoxyethylene sorbitan oleate (including mono, di, tri and tetra esters) ), Octaoxyethylene sorbitan laurate (including mono, di, tri and tetraesters), octaoxyethylene sorbitan palmitate (including mono, di, tri and tetraesters), octaoxyethylene sorbitan stearate (mono and diesters) Octaoxyethylene sorbitan oleate (including mono, di, tri and tetra esters), nonaoxyethylene sorbitan laurate (including mono, di, tri and tetra esters), nonao Siethylene sorbitan palmitate (including mono, di, tri and tetraesters), nonaoxyethylene sorbitan stearate (including mono, di, tri and tetraesters), nonaoxyethylene sorbitan oleate (including mono, di, tri and tetraesters) Including tetraester, decaoxyethylene sorbitan laurate (including mono, di, tri and tetraester), decaoxyethylene sorbitan palmitate (including mono, di, tri and tetraester), decaoxyethylene sorbitan stearate (Including mono, di, tri and tetra esters), decaoxyethylene sorbitan oleate (including mono, di, tri and tetra esters) and the like.

As described above, these polyoxyethylene group-containing components have a polyoxyethylene group represented by (—CH ₂ CH ₂ O—) _n H.
Is preferably 2 to 10, and the HLB value is preferably 5 to 12.

The glycerin fatty acid ester is contained in an amount of 0 to 60 parts by weight, preferably 10 to 50 parts by weight, based on 100 parts by weight of the total amount of the glycerin fatty acid ester, polyglycerin fatty acid ester and sorbitan fatty acid ester. Glycerin fatty acid ester is 0-8
0 parts by weight, preferably 20 to 60 parts by weight, and the sorbitan fatty acid ester is desirably 0 to 50 parts by weight, preferably 10 to 40 parts by weight. The total amount of glycerin fatty acid ester, polyglycerin fatty acid ester and sorbitan fatty acid ester is 50 to 85% by weight based on the whole antifogging agent (C),
Preferably 55 to 80% by weight, more preferably 60 to 80% by weight.
75% by weight.

The polyoxyethylene glycerin fatty acid ester, the polyoxyethylene polyglycerin fatty acid ester and the polyoxyethylene sorbitan fatty acid ester total 100 parts by weight, and the polyoxyethylene glycerin fatty acid ester is 0 to 60 parts by weight. Preferably, the polyoxyethylene polyglycerin fatty acid ester is contained in a proportion of 0 to 80 parts by weight, preferably 20 to 60 parts by weight, and the polyoxyethylene sorbitan fatty acid ester is contained in a proportion of 0 to 50 parts by weight. ~ 5
It is desirably contained in an amount of 0 parts by weight, preferably 10 to 40 parts by weight. Polyoxyethylene glycerin fatty acid ester which is a polyoxyethylene group-containing component,
The total amount of the polyoxyethylene polyglycerin fatty acid ester and the polyoxyethylene sorbitan fatty acid ester is 15 to 50% by weight based on the whole antifogging agent (C),
Preferably 20 to 45% by weight, more preferably 25 to 45% by weight.
40% by weight.

As described above, it is preferable to use different antifogging agents in combination in the proportions within the above range, since the effect of the antifogging properties is maintained for an initial period and for a long period of time. The antifogging agent (C) preferably used in the present invention is, for example, as follows. (1) An antifogging agent comprising glycerin monostearate and polyoxyethylene glycerin monostearate and / or polyoxyethylene glycerin distearate. (2) An antifogging agent comprising diglycerin monostearate and / or diglycerin distearate and polyoxyethylene glycerin monostearate and / or polyoxyethylene glycerin distearate. (3) An antifogging agent comprising sorbitan monostearate and / or sorbitan distearate and polyoxyethylene glycerin monostearate and / or polyoxyethylene glycerin distearate. (4) An antifogging agent comprising glycerin monostearate, diglycerin monostearate and / or diglycerin distearate, and polyoxyethylene glycerin monostearate and / or polyoxyethylene glycerin distearate. (5) An antifogging agent comprising glycerin monostearate, sorbitan monostearate and / or sorbitan distearate, and polyoxyethylene glycerin monostearate and / or polyoxyethylene glycerin distearate. (6) From diglycerin monostearate and / or diglycerin distearate, sorbitan monostearate and / or sorbitan distearate, and polyoxyethylene glycerin monostearate and / or polyoxyethylene glycerin distearate An antifogging agent. (7) glycerin monostearate, diglycerin monostearate and / or diglycerin distearate, sorbitan monostearate and / or sorbitan distearate, and polyoxyethylene glycerin monostearate and / or polyoxyethylene An antifogging agent comprising glycerin distearate. (8) An antifogging agent comprising glycerin monostearate and polyoxyethylene diglycerin monostearate and / or polyoxyethylene diglycerin distearate. (9) An antifogging agent comprising diglycerin monostearate and / or diglycerin distearate and polyoxyethylene diglycerin monostearate and / or polyoxyethylene diglycerin distearate. (10) An antifogging agent comprising sorbitan monostearate and / or sorbitan distearate and polyoxyethylene diglycerin monostearate and / or polyoxyethylene diglycerin distearate. (11) An antifogging agent comprising glycerin monostearate, diglycerin monostearate and / or diglycerin distearate, and polyoxyethylene diglycerin monostearate and / or polyoxyethylene diglycerin distearate. (12) An antifogging agent comprising glycerin monostearate, sorbitan monostearate and / or sorbitan distearate, and polyoxyethylene diglycerin monostearate and / or polyoxyethylene diglycerin distearate. (13) diglycerin monostearate and / or diglycerin distearate, sorbitan monostearate and / or sorbitan distearate, and polyoxyethylene diglycerin monostearate and / or
Or an antifogging agent comprising polyoxyethylene diglycerin distearate. (14) glycerin monostearate, diglycerin monostearate and / or diglycerin distearate, sorbitan monostearate and / or sorbitan distearate, and polyoxyethylene diglycerin monostearate and / or polyoxy An antifogging agent comprising ethylene diglycerin distearate. (15) An antifogging agent comprising glycerin monostearate and polyoxyethylene sorbitan monostearate and / or polyoxyethylene sorbitan distearate. (16) An antifogging agent comprising diglycerin monostearate and / or diglycerin distearate and polyoxyethylene sorbitan monostearate and / or polyoxyethylene sorbitan distearate. (17) An antifogging agent comprising glycerin monostearate, diglycerin monostearate and / or diglycerin distearate, and polyoxyethylene sorbitan monostearate and / or polyoxyethylene sorbitan distearate. (18) An antifogging agent comprising glycerin monostearate, sorbitan monostearate and / or sorbitan distearate, and polyoxyethylene sorbitan monostearate and / or polyoxyethylene sorbitan distearate. (19) Diglycerin monostearate and / or diglycerin distearate, sorbitan monostearate and / or sorbitan distearate, and polyoxyethylene sorbitan monostearate and / or polyoxyethylene sorbitan distearate An antifogging agent. (20) glycerin monostearate, diglycerin monostearate and / or diglycerin distearate, sorbitan monostearate and / or sorbitan distearate, and polyoxyethylene sorbitan monostearate and / or polyoxyethylene An antifogging agent comprising sorbitan distearate.

The antifogging agent (C) is used in an amount of 0.05 to 5 parts by weight, preferably 100 parts by weight, based on the total amount of the ethylene / α-olefin copolymer (A) and the high-pressure low-density polyethylene (B). Is used in a proportion of 0.1 to 4 parts by weight, more preferably 0.5 to 3 parts by weight.

For the purpose of enhancing the retention of the anti-fogging agent (C) in the film and further improving the anti-fogging durability, the modified wax is used as an ethylene / α-olefin copolymer (A).
And total amount of high pressure method low density polyethylene (B) 100
0.1 to 5 parts by weight, preferably 0.5 part by weight,
To 4 parts by weight, more preferably 1 to 3 parts by weight. Specific examples of such a modified wax include a maleic acid-modified polyethylene wax, an acrylic acid-modified polyethylene wax, and an oxidized polyethylene wax.

The modified wax has an acid value of usually 1 to 60 KOH.
mg / g, and the molecular weight (Mv) is usually 1,000 to 50,000.
00. [Nonionic fluorine-containing surfactant (D)] The nonionic fluorine-containing surfactant (D) used in the present invention has a fluorine content of 25 to 65% by weight and 0.001% at 25 ° C. The surface tension of the aqueous solution is usually 42 dyne / c
m or less. In the present invention, an organic fluorine compound having a perfluoroalkyl group is particularly preferred.

As such an organic fluorine compound, for example, a perfluoroalkylethylene oxide adduct,
Alkylene oxide adducts of perfluoroalkyl alcohols such as perfluoroalkylpropylene oxide adducts; and perfluoroalkyl group-containing oligomers such as perfluoroalkyl acrylate oligomers and perfluoroalkyl methacrylate oligomers.

The above perfluoroalkylethylene oxide adduct was obtained, for example, from Daikin Industries, Ltd. under the trade name DS-4.
03 and KC-40 from Asahi Glass Co., Ltd.

The oligomer having a perfluoroalkyl group can be obtained, for example, from S-393 by Asahi Glass Co., Ltd.
It is commercially available under the trade name. Also, a mixture of a perfluoroalkyl ethylene oxide adduct and a perfluoroalkyl-containing oligomer is available from Asahi Glass Co., Ltd.
It is commercially available under the trade name of -14.

Nonionic fluorine-containing surfactant (D)
Is 0.01 to 1 part by weight, preferably 0.05 to 1 part by weight, based on 100 parts by weight of the total amount of the ethylene / α-olefin copolymer (A) and the high-pressure low-density polyethylene (B).
It is used in a ratio of 0.3 parts by weight. Conventionally, when a fluorine compound is blended, the antifogging property of the film is generally deteriorated as compared with a non-blended product. It was found that when the fluorine-containing surfactant (D) was used in the above ratio, the antifogging property was unexpectedly improved, and the antifogging durability (long-term antifogging property) was extremely excellent.

[Other components] In the above-mentioned ethylene copolymer composition (1), if necessary, conventionally known weather resistance stabilizers, antioxidants, inorganic compounds, antistatic agents, heat stabilizers, etc. Can be added in a range that does not impair the purpose of the present invention.

The weathering stabilizers are roughly classified into ultraviolet absorbers and light stabilizers, and they may be used alone or in combination, so that the effect of improving the weathering stability is great.

As the light stabilizer, conventionally known light stabilizers can be used, and among them, hindered amine light stabilizers (HALS; Hindered Amine Light Stabilizers) are preferably used.

The following compounds are specifically used as the hindered amine stabilizer. (1) bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, (2) dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-succinate Tetramethylpiperidine polycondensate, (3) tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, (4) 2,2,6, 6-tetramethyl-4-piperidinyl benzoate, (5) bis- (1,2,6,6-tetramethyl-4
-Piperidinyl) -2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate, (6) bis (N-
Methyl-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, (7) 1,1 ′-(1,2-ethanediyl) bis (3,3,5,
5-tetramethylpiperazinone), (8) (mixed 2,
2,6,6-tetramethyl-4-piperidyl / tridecyl) -1,
2,3,4-butanetetracarboxylate, (9) (mixed 1,2,2,6,6-pentamethyl-4-piperidyl / tridecyl) -1,2,3,4-butanetetracarboxylate, ( 1
0) Mixed {2,2,6,6-tetramethyl-4-piperidyl / β, β, β ′, β′-tetramethyl-3-9- [2,4,8,10-tetraoxaspiro ( 5,5) Undecane] diethyl｝ -1,2,3,4
-Butanetetracarboxylate, (11) mixed {1,2,2,6,6-pentamethyl-4-piperidyl / β, β, β ',
β'-tetramethyl-3-9- [2,4,8,10-tetraoxaspiro (5,5) undecane] diethyl} -1,2,3,4-butanetetracarboxylate, (12) N, N'-bis (3-aminopropyl) ethylenediamine-2-4-bis [N-butyl-N- (1,
2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensate, (13) N, N'-bis (2,
Condensation product of 2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 1,2-dibromoethane, (14) [N-
(2,2,6,6-tetramethyl-4-piperidyl) -2-methyl-2
-(2,2,6,6-tetramethyl-4-piperidyl) imino] propionamide, (15) poly {[6-[(1,1,3,3-tetramethylbutyl) amino] -1,3 , 5-Triazine-2,4-diyl]
[[(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl)
Imino] @ (trade name Kimasorb 944).

These hindered amine light stabilizers include:
They can be used alone or in combination of two or more. The light stabilizer is used in an amount of 0.005 to 5 parts by weight, preferably 0.005 to 5 parts by weight, based on 100 parts by weight of the total amount of the ethylene / α-olefin copolymer (A) and the high-pressure low-density polyethylene (B). 2 parts by weight, more preferably 0.0
It is used in a ratio of 1 to 1 part by weight.

Specific examples of the ultraviolet absorber include salicylic acid-based ultraviolet absorbers such as phenyl salicylate, p-tert-butylphenyl salicylate and p-octylphenyl salicylate; 2,4-dihydroxybenzophenone, 2-hydroxy-4 -Methoxybenzophenone, 2-hydroxy-4
-Octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-methoxy- Benzophenone UV absorbers such as 5-sulfobenzophenone; 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-tert-butylphenyl) benzotriazole, (2'-hydroxy-3 ', 5'
-Di-tert-butylphenyl) benzotriazole, 2-
(2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5- Benzotriazole ultraviolet absorbers such as chlorobenzotriazole and 2- (2'-hydroxy-3 ', 5'-di-tert-amylphenyl) benzotriazole; 2-ethylhexyl-2-cyano-3,
3'-diphenyl acrylate, ethyl-2-cyano-3,3'-
And cyanoacrylate-based ultraviolet absorbers such as diphenylacrylate.

The ultraviolet absorber is used in an amount of 0.005 to 5 parts by weight based on 100 parts by weight of the total of the ethylene / α-olefin copolymer (A) and the high-pressure low-density polyethylene (B).
It is used at a ratio of 0.005 to 2 parts by weight, preferably 0.01 to 1 part by weight.

Inorganic compounds include Mg, which is effective as a heat insulator,
Examples include inorganic oxides, inorganic hydroxides, and hydrotalcites containing at least one atom of Ca, Al and Si.

Specifically, SiO ₂ , Al ₂ O ₃ , Mg
Inorganic oxides such as O and CaO; Al (OH) ₃ , Mg (O
H) ₂ , inorganic hydroxides such as Ca (OH) ₂ ; Formula M 2 ⁺ _{1 -x} Al _x (OH) ₂ (A ⁿ⁻ ) _{x / n} · mH ₂ O wherein M ²⁺ is mg, a divalent metal ion of Ca or Zn, a ^{n-is Cl -, Br -, I -} , NO 3 2-, C
10 ^4- , SO ₄ ^2- , CO ₂ ^2- , SiO ₃ ^2- , HPO
Anions such as ₄ ²⁻ , HBO ₃ ²⁻ , and PO ₄ ²⁻ ;
Is a numerical value satisfying the condition 0 <x <0.5, and m
Is a numerical value satisfying the condition of 0 ≦ m ≦ 2], and hydrotalcites such as a calcined product thereof. Among these, hydrotalcites are preferable, and a fired product of the inorganic composite compound represented by the above formula is particularly preferable.

The above-mentioned inorganic compounds can be used alone or in combination of two or more. The average particle size of the inorganic compound is desirably 10 μm or less, preferably 5 μm or less, and more preferably 3 μm or less.

When the average particle size of the inorganic compound is within the above range, a film having good transparency can be obtained. The inorganic compound is used in an amount of 1 to 20 parts by weight, preferably 1 to 18 parts by weight, more preferably 2 to 100 parts by weight based on 100 parts by weight of the ethylene / α-olefin copolymer (A) and the high-pressure low-density polyethylene (B). It is used in a proportion of up to 15 parts by weight.

When the inorganic compound is used in the above ratio, a film having excellent heat retention can be obtained. The agricultural film according to the present invention has a layer composed of the ethylene copolymer composition (1) as described above.

When the agricultural film according to the present invention is a single-layer film comprising a layer formed of the above-mentioned ethylene copolymer composition (1), the agricultural film usually has a thickness of 30 to 200 μm. Preferably 40 to 180 μm,
More preferably, it is in the range of 50 to 150 μm.

The agricultural film according to the present invention, which is such a single-layer film, has the following physical properties and characteristics. (I) Elmendorf tear strength (JIS Z 1702)
Is 90 kg / c in the MD (film extrusion direction) direction
m or more, preferably 100 kg / cm or more, and 90 kg / cm or more, preferably 100 kg / cm or more in the TD (width direction of the film) direction. (Ii) Dart impact strength at a thickness of 100 μm (JI
SZ 1707) is 450 g or more, preferably 50 g or more.
0 g or more. (Iii) The tensile strength at break (JIS K6781) is M
350 kg / cm ² or more in D direction, preferably 400 k / cm ²
g / cm ² or more and 350 kg / cm in the TD direction.
cm ² or more, preferably 400 kg / cm ² or more.

The agricultural film having a single layer structure according to the present invention as described above can be prepared from the above-mentioned ethylene copolymer composition (1) by, for example, film forming by an inflation method or a T-die method. .

The film formation by the inflation method is carried out by extruding the ethylene copolymer composition (1) through a circular die and expanding it by a predetermined air flow. The resin temperature at the time of extruding the ethylene copolymer composition (1) is 190 to 250 ° C.
It is preferable that

As described above, the agricultural film according to the present invention comprises the above-mentioned ethylene copolymer composition (1).
It may be a multilayer structure having a layer formed by: As the agricultural film having a multilayer structure according to the present invention, for example, a three-layer laminated film including the following outer layer, intermediate layer, and inner layer is particularly preferable.

Outer Layer The outer layer constituting the above three-layer laminated film is made of ethylene α
-An ethylene copolymer composition containing an olefin copolymer (E) and, if necessary, a high-pressure low-density polyethylene (B), an antifogging agent (C), and a nonionic fluorine-containing surfactant (D). It is formed from (2).

[Ethylene / α-olefin copolymer (E)] The ethylene / α-olefin copolymer (E) forming the outer layer of the above three-layer laminated film is composed of ethylene and α-olefin having 4 to 12 carbon atoms. It is a copolymer comprising an olefin, and has a density of 0.925 to 0.940 g / cm ³ , preferably 0.925 to 0.935 g / cm ³ , except that the above-mentioned agricultural monolayer film is formed. It is the same as the ethylene / α-olefin copolymer (A) used in this case.

Such an ethylene / α-olefin copolymer (E) can be prepared by a method similar to the above-mentioned method for producing the ethylene / α-olefin copolymer (A), using a single-site catalyst such as a metallocene olefin polymer. In the presence of a catalyst, ethylene and an α-olefin having 4 to 12 carbon atoms are converted into a copolymer having a density of 0.925 to 0.94.
It can be produced by copolymerizing so as to be 0 g / cm ³ .

In the present invention, the ethylene / α-olefin copolymer (E) is used based on 100 parts by weight of the total amount of the ethylene / α-olefin copolymer (E) and the high-pressure low-density polyethylene (B). , 60 to 100 parts by weight, preferably 65 to 99 parts by weight, more preferably 70 to 95 parts by weight.
Used in parts by weight.

[High-Pressure Low-Density Polyethylene (B)] The high-pressure low-density polyethylene (B) forming the outer layer of the three-layer laminated film is a high-pressure low-density polyethylene used for forming the above-mentioned single-layer agricultural film. Polyethylene (B)
Is the same as

In the present invention, the high-pressure low-density polyethylene (B) may be added, if necessary, to 100 parts by weight of the total amount of the ethylene / α-olefin copolymer (E) and the high-pressure low-density polyethylene (B). On the other hand, 0 to 40 parts by weight, preferably 1 to 35 parts by weight, more preferably 5 to
Used in a proportion of 30 parts by weight.

[Other Components] In the ethylene copolymer composition (2) for forming the outer layer, if necessary, the above-described antifogging agent (C) and nonionic fluorine-containing surfactant (D) ) And conventionally known additives such as a weather resistance stabilizer, an antioxidant, an inorganic compound, an antistatic agent, and a heat stabilizer can be blended within a range not to impair the object of the present invention.

The weathering stabilizers used in forming the outer layer are the same as the weathering stabilizers (UV absorbers and light stabilizers) used as needed in forming the above-mentioned single-layer agricultural film. The light stabilizer is used in an amount of 0.005 to 5 based on 100 parts by weight of the total amount of the ethylene / α-olefin copolymer (E) and the high-pressure low-density polyethylene (B).
It is used at a ratio of 0.005 to 2 parts by weight, preferably 0.01 to 1 part by weight. Also,
The ultraviolet absorber is used in an amount of 0.005 to 5 parts by weight, preferably 0.005 to 2 parts by weight, based on 100 parts by weight of the total of the ethylene / α-olefin copolymer (E) and the high-pressure low-density polyethylene (B). Parts by weight, more preferably 0.01
It is used in a proportion of １1 part by weight.

The antifogging agent (C) used here is the same as the antifogging agent (C) used for forming the above-mentioned monolayer agricultural film. Antifogging agent (C) is ethylene
With respect to 100 parts by weight of the total amount of the α-olefin copolymer (E) and the high-pressure low-density polyethylene (B), 0.0
5 to 5 parts by weight, preferably 0.1 to 4 parts by weight, more preferably 0.5 to 3 parts by weight.

The nonionic fluorine-containing surfactant (D) used for forming the above-mentioned monolayer agricultural film is used as the nonionic fluorine-containing surfactant (D).
Is the same as Nonionic fluorine-containing surfactant (D)
Is 0.01 to 1 part by weight, preferably 0.05 to 1 part by weight, based on 100 parts by weight of the total amount of the ethylene / α-olefin copolymer (E) and the high-pressure low-density polyethylene (B).
It is used in a ratio of 0.3 parts by weight.

The inorganic compound used here is the same as the inorganic compound used as necessary when forming the above-mentioned single-layer agricultural film. Inorganic compounds are
1 to 100 parts by weight of the ethylene / α-olefin copolymer (E) and the high-pressure low-density polyethylene (B)
It is used in a proportion of 20 parts by weight, preferably 1 to 18 parts by weight, more preferably 2 to 15 parts by weight. When the inorganic compound is used at the above ratio when forming the outer layer,
A three-layer laminated film having excellent heat retention can be obtained.

Intermediate Layer The intermediate layer constituting the above three-layer laminated film is made of ethylene.
Ethylene-based copolymer composition containing α-olefin copolymer (F), anti-fogging agent (C), and optionally high-pressure low-density polyethylene (B), and nonionic fluorine-containing surfactant (D) It is formed from the object (3).

[Ethylene / α-olefin copolymer (F)] The ethylene / α-olefin copolymer (F) forming the intermediate layer of the three-layer laminated film is composed of ethylene and α-olefin having 4 to 12 carbon atoms. -An ethylene / α-olefin copolymer, except that the density is 0.880 to 0.920 g / cm ³ , and preferably 0.890 to 0.915 g / cm ³ Same as the polymer (A).

Such an ethylene / α-olefin copolymer (F) can be produced by a method similar to the above-mentioned method for producing the ethylene / α-olefin copolymer (A), using a single-site catalyst such as a metallocene olefin polymer. In the presence of a catalyst, ethylene and an α-olefin having 4 to 12 carbon atoms are converted into a copolymer having a density of 0.880 to 0.92.
It can be produced by copolymerizing so as to be 0 g / cm ³ .

In the present invention, the ethylene / α-olefin copolymer (F) is used based on 100 parts by weight of the total amount of the ethylene / α-olefin copolymer (F) and the high-pressure low-density polyethylene (B). , 60 to 100 parts by weight, preferably 65 to 99 parts by weight, more preferably 70 to 95 parts by weight.
Used in parts by weight.

[High-Pressure Low-Density Polyethylene (B)] The high-pressure low-density polyethylene (B) forming the intermediate layer of the three-layer laminated film is a high-pressure low-density polyethylene used for forming the above-mentioned single-layer agricultural film. Same as the density polyethylene (B).

In the present invention, the high-pressure low-density polyethylene (B) is used in an amount of 0 to 100 parts by weight based on the total amount of the ethylene / α-olefin copolymer (F) and the high-pressure low-density polyethylene (B). 40 parts by weight, preferably 1
To 35 parts by weight, more preferably 5 to 30 parts by weight.

[Anti-fogging agent (C)] The anti-fogging agent (C) added to the ethylene / α-olefin copolymer (F) for forming the intermediate layer and the high-pressure low-density polyethylene (B) is as described above. This is the same as the antifogging agent (C) used for forming the agricultural film having a single-layer structure.

The antifogging agent (C) is used in an amount of preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the total amount of the ethylene / α-olefin copolymer (F) and the high-pressure low-density polyethylene (B). Is used in a proportion of 0.1 to 4 parts by weight, more preferably 0.5 to 3 parts by weight.

[Other Components] In the ethylene copolymer composition (3) for forming an intermediate layer, if necessary, the above-mentioned nonionic fluorine-containing surfactant (D) and a conventionally known weather resistance Additives such as a stabilizer, an antioxidant, an inorganic compound, an antistatic agent, and a heat stabilizer can be blended within a range that does not impair the purpose of the present invention.

The nonionic fluorine-containing surfactant (D) used for forming the above-mentioned monolayer agricultural film is used as the nonionic fluorine-containing surfactant (D).
Is the same as Nonionic fluorine-containing surfactant (D)
Is 0.01 to 1 part by weight, preferably 0.05 to 1 part by weight, based on 100 parts by weight of the total amount of the ethylene / α-olefin copolymer (F) and the high-pressure low-density polyethylene (B).
It is used in a ratio of 0.3 parts by weight.

The weather-resistant stabilizer used in forming the intermediate layer is the same as the weather-resistant stabilizer (ultraviolet absorber, light stabilizer) used as needed in forming the above-mentioned single-layer agricultural film. The light stabilizer is used in an amount of 0.005 to 5 based on 100 parts by weight of the total amount of the ethylene / α-olefin copolymer (F) and the high-pressure low-density polyethylene (B).
It is used at a ratio of 0.005 to 2 parts by weight, preferably 0.01 to 1 part by weight. The ultraviolet absorber is used in an amount of 0.005 to 5 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the total of the ethylene / α-olefin copolymer (F) and the high-pressure low-density polyethylene (B).
005 to 2 parts by weight, more preferably 0.01 to 1 part by weight.

The inorganic compound used in forming the intermediate layer is the same as the inorganic compound used as necessary in forming the above-mentioned single-layer agricultural film.
The inorganic compound is used in an amount of 1 to 20 parts by weight, preferably 1 to 20 parts by weight, based on 100 parts by weight of the total of the ethylene / α-olefin copolymer (F) and the high-pressure low-density polyethylene (B).
To 18 parts by weight, more preferably 2 to 15 parts by weight. When the inorganic compound is used at the above ratio when forming the intermediate layer, a three-layer laminated film excellent in heat retention can be obtained.

Inner Layer The inner layer constituting the above three-layer laminated film comprises the above-mentioned ethylene / α-olefin copolymer (A), antifogging agent (C),
It is formed from an ethylene copolymer composition (1) containing a nonionic fluorine-containing surfactant (D) and, if necessary, a high-pressure low-density polyethylene (B). The composition (1) is as described above.

In the present invention, the density of the resin forming the outer layer (d _E or d _EB ) and the density of the resin forming the inner layer (d _A or d _AB ) are d _E or d _EB ≧ d _A or d _AB is satisfied. Here, the resin is an ethylene / α-olefin copolymer or an ethylene / α-olefin copolymer.
Refers to a copolymer of an olefin copolymer and a high-pressure low-density polyethylene.

Therefore, the transfer of the anti-fogging agent (C) contained in the intermediate layer always predominates toward the inner layer rather than the outer layer, so that the anti-fogging property of the inner layer can be maintained. .

If the density of the ethylene / α-olefin copolymer (A) for forming the inner layer is too low than 0.905 g / cm ³ , the stickiness on the inner surface of the film becomes large,
Sliding with the pipe house is poor, and the workability of spreading tends to be impaired.

It is desirable to use the above-mentioned maleated wax in combination with the antifogging agent (C) from the viewpoint of the antifogging durability. The agricultural film according to the present invention, which is a three-layer laminated film as described above, generally has an outer layer thickness of 3 to 100.
μm, preferably 10-80 μm, more preferably 2 μm
0 to 70 μm, and the thickness of the intermediate layer is 10 to 15 μm.
0 μm, preferably 20 to 120 μm, more preferably 30 to 100 μm, and the thickness of the inner layer is 3 to 1 μm.
00 μm, preferably 10-80 μm, more preferably 20-70 μm, and the total thickness of these layers is 30-200 μm, preferably 50-180 μm
m, more preferably in the range of 70 to 150 μm.

In such a three-layer laminated film,
Ratio of the thicknesses of the outer layer [I], the intermediate layer [II] and the inner layer [III] (outer layer [I] / intermediate layer [II] / inner layer [III])
Is from 0.2 to 4/1 to 10/1, preferably from 0.5 to 2
/ 2 to 6/1.

The agricultural film according to the present invention, which is a three-layer laminated film as described above, has the following physical properties and characteristics. (I) Elmendorf tear strength (JIS Z 1702)
Is 90 kg / cm or more in MD direction, preferably 100 kg / cm or more.
kg / cm or more and 90 kg / c in the TD direction
m, preferably 100 kg / cm or more. (Ii) Dart impact strength at a thickness of 100 μm (JI
S Z 1707) is at least 900 g, preferably 1,0
00 g or more. (Iii) The tensile strength at break (JIS K6781) is M
350 kg / cm ² or more in direction D, preferably 370 k
g / cm ² or more and 350 kg / cm in the TD direction.
cm ² or more, preferably 370 kg / cm ² or more.

The agricultural film according to the present invention having the three-layer structure as described above is obtained by mixing the components such as the polyethylene resin used in each layer and the above-mentioned additives.
It can be prepared by melt-mixing with a Banbury mixer or a roll mill, an extruder or the like, and then laminating an outer layer, an intermediate layer and an inner layer by a coextrusion inflation method or a coextrusion T-die method.

It is to be noted that two or four or more layers
The agricultural film according to the present invention can be prepared according to these preparation methods.

[0139]

According to the present invention, compared to the above-mentioned conventional agricultural films (single-layer and multilayer films), the anti-fogging durability and the dust-proofing and toughness are excellent. A film can be provided. In addition, the agricultural film according to the present invention is lightweight, and has a small amount of low molecular weight components in the polymer used, so that it is less sticky, has excellent spreadability, and has a high degree of fusion between films at high temperatures. It has the advantage of being small. In particular, the agricultural film composed of the above-described three-layer laminated film has a very high antifogging durability (long-term antifogging property) because the resin forming the outer layer has a higher density than the resin forming the inner layer. Is excellent.

Since the agricultural film according to the present invention has the above-mentioned effects, it can be spread over agricultural and horticultural facilities such as houses and tunnels and used for a long time for cultivation of useful crops.

Hereinafter, the present invention will be described with reference to Examples.
The present invention is not limited to these examples. In addition, the evaluation of the agricultural film in an Example and a comparative example was performed as follows. (1) Anti-fog property A pipe house (width 3.6 m, depth 20 m) installed on the site of Mitsui Chemicals Co., Ltd. in Sodegaura-shi, Chiba
0 μm (outer layer / intermediate layer / inner layer = 20 μm / 60 μm / 2
(0 μm) was spread on February 5, 1997.

Thereafter, the state of water droplets adhering to the inner surface of the film at 7:00 to 8:00 in the morning was observed over time. <Five-grade evaluation> 5: No water droplet is observed in a flowing state. 4: Although it is in a dripping state, the flow line remains. 3: Flow streaks and water droplets are mixed. 2: Flow streaks and water droplets are mixed, and there are many water droplets. 1: Fine water droplets adhered to almost the entire surface of the film. Three or more passed the antifogging property, and 1 and 2 failed.

(2) Elmendorf tear strength: JIS
The strength in the vertical and horizontal directions was measured by a method according to Z-1702. (3) Dart Impact Strength Dart impact strength was determined by performing an impact test in accordance with JIS Z 1707 (diameter of dirt tip: 38 mm).

(4) Tensile strength at break The tensile strength at break was measured in accordance with JIS K6781, and in the MD and TD directions of the multilayer film under the following conditions, a constant crosshead moving speed tensile tester (Instron). (Manufactured by K.K.).

[Test conditions] Sample: JIS K6781 Atmospheric temperature: 23 ° C Peeling speed: 500 mm / min

[0146]

[Reference Example 1] Preparation of ethylene / 1-hexene copolymer [Preparation of catalyst for olefin polymerization] 5.0 kg of silica dried at 250 ° C for 10 hours was suspended in 80 liters of toluene, and then cooled to 0 ° C. Cool. Thereafter, 28.7 l of a toluene solution of methylaluminoxane (Al; 1.33 mol / l) was added dropwise over 1 hour. At this time, the temperature in the system was kept at 0 ° C. Subsequently, the reaction was carried out at 0 ° C. for 60 minutes, then the temperature was raised to 95 ° C. over 1.5 hours, and the reaction was carried out at that temperature for 20 hours. Thereafter, the temperature was lowered to 60 ° C., and the supernatant was removed by a decantation method.

The solid component thus obtained was washed twice with toluene and then resuspended in 80 liters of toluene. 7.4 liters of a toluene solution of bis (1,3-n-butylmethylcyclopentadienyl) zirconium dichloride (Zr; 34.0 mmol / l) and bis (1,3-dimethylcyclopentadienyl) were introduced into the system. ) 1.0 L of a toluene solution of zirconium dichloride (Zr; 28.1 mmol / L) was added dropwise at 80 ° C over 30 minutes, and the reaction was further performed at 80 ° C for 2 hours. Thereafter, the supernatant was removed and washed twice with hexane to obtain a solid catalyst containing 3.6 mg of zirconium per gram. [Preparation of prepolymerized catalyst] In 85 l of hexane containing 1.7 mol of triisobutylaluminum, 0.85 kg of the solid catalyst obtained above and 1-hexene 25 were added.
5 g was added and ethylene was prepolymerized at 35 ° C. for 12 hours to obtain a prepolymerized catalyst in which 10 g of polyethylene was prepolymerized per 1 g of the solid catalyst. The intrinsic viscosity [η] of this ethylene polymer was 1.74 dl / g. [Polymerization] Using two continuous fluidized-bed gas-phase polymerization apparatuses connected in series, ethylene and 1-
Copolymerization with hexene was performed to obtain an ethylene / 1-hexene copolymer.

The ethylene / 1-hexene copolymer obtained as described above has a 1-hexene content of 7.5% by weight, a density of 0.928 g / cm ³ and a melt flow rate (MFR). ASTM D 1238-65T, 19
(0 ° C., load 2.16 kg) is 1.63 g / 10 min, and the molecular weight distribution (Mw / Mn) measured by GPC.
Was 3.5.

The copolymer had a temperature [Tm] of one of the maximum peaks of an endothermic curve measured by a differential scanning calorimeter (DSC) of 120 ° C., and a fraction of n-decane soluble component at room temperature. [W] was 0.25% by weight.

The above B ₁ measured by GPC-IR analysis of this copolymer was 12.2 / 1000 C (12.2 per 1,000 carbon atoms), and B ₂ was 9.9 / 1.
000C.

[0151]

Reference Example 2 Copolymerization of ethylene and 1-hexene was carried out in the presence of the prepolymerization catalyst described in Reference Example 1 above using two continuous fluidized bed gas phase polymerization apparatuses connected in series. An ethylene / 1-hexene copolymer was obtained.

The ethylene / 1-hexene copolymer obtained as described above had a 1-hexene content of 11% by weight, a density of 0.915 g / cm ³ and a melt flow rate (MFR; ASTM). D 1238-65T, 19
0 ° C., load 2.16 kg) is 2.19 g / 10 min, and the molecular weight distribution (Mw / Mn) measured by GPC
Was 3.5.

This copolymer had a temperature [Tm] of one of the maximum peaks of an endothermic curve measured by a differential scanning calorimeter (DSC) of 108 ° C., and a fraction of n-decane soluble component at room temperature. [W] was 0.42% by weight.

The above-mentioned B ₁ measured by GPC-IR analysis for this copolymer was 18.6 / 1000C,
₂ was 14.7 / 1000C.

[0155]

Reference Example 3 An ethylene / 1-hexene copolymer as shown in Table 1 was obtained in the same manner as in Reference Example 1.

[0156]

[Table 1]

[0157]

Examples 1 to 8 and Comparative Examples 1 to 6 Using the resins shown in Table 1 and the antifogging agents shown in Table 2, a three-layer film having a thickness of 100 μm was obtained under the conditions shown in Table 3 under the following conditions. Inflation molded. [Inflation molding conditions] Molding machine: 3-layer machine manufactured by Alpine Company Die diameter: 400 mm Molding temperature: 200 ° C Folding width: 1500 mm Thickness: All layers 100 μm (outer layer / intermediate layer / inner layer = 20 μm)
(m / 60 μm / 20 μm) Table 4 shows the physical properties of the film obtained as described above.

[0158]

[Table 2]

[0159]

[Table 3]

(Note 1) Weathering stabilizer: N, N'-bis (3-aminopropyl) ethylenediamine-2-4-bis [N-butyl-N-
(1,2,2,6,6-pentamethyl-4-piperidyl) amino]-
6-Chloro-1,3,5-triazine condensate (Note 2) Hydrotalcite: DHT-4A [Product name:
(Kyowa Chemical Co., Ltd.) (Note 3) Fluorine-containing surfactant: Daikin Industries, Ltd.
Product name, DS-403

[0161]

[Table 4]

[0162]

[Table 5]

As described above, by adding a nonionic fluorine-containing surfactant having a fluorine content in a specific range and a surface tension of an aqueous solution in a specific range, the antifogging level and antifogging property can be improved. Persistence is improved.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08K 5/103 C08K 5/103 C08L 23/08 C08L 23/08 C09K 3/18 C09K 3/18 // (C08L 23/08 23 : 06 71:02 101: 04)

Claims (25)

[Claims] [1] [I] ethylene and α having 4 to 12 carbon atoms
And an ethylene / α-olefin copolymer (A) having a density of 0.905 to 0.935 g / cm ³ and a melt flow rate of 0.1 to 10 g / 10 min. ) 100 parts by weight, or 100 parts by weight of a mixture of the ethylene / α-olefin copolymer (A) and the high-pressure low-density polyethylene (B) in an amount of 40% by weight or less, and [II] 0.05 to 5 parts by weight of an antifogging agent (C) comprising a mixture of ionic surfactants and containing 15 to 50% by weight of a polyoxyethylene group-containing component, and [III] containing fluorine A layer formed of an ethylene copolymer composition (1) containing 0.01 to 1 part by weight of a nonionic fluorine-containing surfactant (D) having an amount of 25 to 65% by weight. The ethylene / α-olefin copolymer (A), Alternatively, a mixture of the ethylene / α-olefin copolymer (A) and the high-pressure low-density polyethylene (B) is obtained by: (Molecular weight) is in the range of 1.5 to 5.0, and (ii) the fraction (W (% by weight) of n-decane soluble component at 23 ° C.) and the density (d) are as follows: W <80 × exp (−100 (d−0.88)) + 0.
(Iii) When the average value of the number of branches on the high molecular weight side by GPC-IR is B ₁ and the average value of the number of branches on the low molecular weight side is B ₂ , B ₁ ≧ B ₂ Agricultural film, characterized in that there is. 2. An ethylene / α-olefin copolymer (A), an antifogging agent (C), a nonionic fluorine-containing surfactant (D) and, if necessary, a high-pressure low-density polyethylene (B). Is a single-layer film composed of a layer formed of an ethylene copolymer composition (1) containing: (i) an Elmendorf tear strength of 9 in the MD direction;
0 kg / cm or more, and 90 kg / cm in the TD direction.
cm or more, (ii) dart impact strength in the thickness 100μm is equal to or greater than 450 g, (iii) tensile strength at break is at 350 kg / cm ² or more in the MD direction, and, 350 kg / cm ² or more in the TD direction The agricultural film according to claim 1, wherein: 3. The ethylene / α-olefin copolymer (A) is a copolymer of ethylene and an α-olefin having 4 to 12 carbon atoms prepared using a metallocene catalyst. The agricultural film according to claim 1 or 2, wherein 4. The polyoxyethylene group-containing component constituting the antifogging agent (C) is a polyoxyethylene group represented by (—CH ₂ CH ₂ O—) _n H, wherein n is 2 to 3. 1
The agricultural film according to any one of claims 1 to 3, wherein the HLB value is 0 and the HLB value is 5 to 12. 5. A mixture of two or more nonionic surfactants constituting said antifogging agent (C), wherein at least one selected from the group consisting of glycerin fatty acid esters, polyglycerin fatty acid esters and sorbitan fatty acid esters. And a mixture of at least one polyoxyethylene group-containing component selected from the group consisting of ethylene oxide adducts of glycerin fatty acid esters, ethylene oxide adducts of polyglycerin fatty acid esters, and ethylene oxide adducts of sorbitan fatty acid esters. The agricultural film according to any one of claims 1 to 4, wherein: 6. The agricultural film according to claim 5, wherein the glycerin fatty acid ester is glycerin monostearate. 7. The agricultural film according to claim 5, wherein the polyglycerin fatty acid ester is diglycerin monostearate and / or diglycerin distearate. 8. The agricultural film according to claim 5, wherein the sorbitan fatty acid ester is sorbitan monostearate and / or sorbitan distearate. 9. The nonionic fluorine-containing surfactant (D) according to claim 1, wherein the surface tension of a 0.001% aqueous solution at 25 ° C. is 42 dyne / cm or less. 2. The agricultural film according to item 1. 10. An ethylene / α-olefin copolymer (A) and an inorganic compound containing at least one atom of Mg, Ca, Al and Si in the ethylene copolymer composition (1). High pressure method low density polyethylene (B)
The agricultural film according to any one of claims 1 to 9, which is contained in an amount of 1 to 20 parts by weight based on 100 parts by weight in total. 11. The agricultural film according to claim 1, having a thickness of 30 to 200 μm. 12. [I] A copolymer obtained by copolymerizing ethylene and an α-olefin having 4 to 12 carbon atoms and having a density of 0.92
An ethylene / α-olefin copolymer (E) having a melt flow rate of 5 to 0.940 g / cm ³ and a melt flow rate of 0.1 to 10 g / 10 minutes, or the ethylene / α-olefin copolymer (E) Outer layer consisting of an ethylene-based copolymer composition (2) containing a mixture of a low-density polyethylene (B) and a high-pressure low-density polyethylene (B) in an amount of 40% by weight or less, [II] ethylene and α- having 4 to 12 carbon atoms. It is obtained by copolymerizing an olefin and has a density of 0.880 to 0.920 g / cm ³ ,
100 parts by weight of an ethylene / α-olefin copolymer (F) having a melt flow rate of 0.1 to 10 g / 10 minutes,
Or the ethylene / α-olefin copolymer (F) and 4
A mixture of 100 parts by weight of a high-pressure low-density polyethylene (B) in an amount of 0% by weight or less and a mixture of two or more nonionic surfactants, and a polyoxyethylene group-containing component in the mixture. Of an ethylene-based copolymer composition (3) containing 0.05 to 5 parts by weight of an antifogging agent (C) containing 15 to 50% by weight of [III] and ethylene and 4 carbon atoms And α-olefins having a density of 0.905 to 0.935 g / cm ³ and a melt flow rate of 0.1 to 10 g / 10 min. 100 parts by weight of the polymer (A) or 100 parts by weight of a mixture of the ethylene / α-olefin copolymer (A) and the high-pressure low-density polyethylene (B) in an amount of 40% by weight or less; From a mixture of nonionic surfactants Ri and into the mixture,
A multilayer comprising an inner layer made of an ethylene copolymer composition (1) containing 0.05 to 5 parts by weight of an antifogging agent (C) containing 15 to 50% by weight of a polyoxyethylene group-containing component. A film, and among the ethylene-based copolymer compositions (1), (2) and (3), at least the ethylene-based copolymer composition (1) has a fluorine content of 2
0.01 to 1 part by weight of a nonionic fluorine-containing surfactant (D) in an amount of 5 to 65% by weight, and the ethylene / α-olefin copolymer (E) or ethylene / Density (d _E or d) of a mixture of α-olefin copolymer (E) and high-pressure low-density polyethylene (B)
_EB ) and the density (d _A ) of the ethylene / α-olefin copolymer (A) or the ethylene / α-olefin copolymer (A) and the high-pressure low-density polyethylene (B) forming the inner layer.
Or d _AB ) and d _E or d _EB ≧ d _A or d _AB
The agricultural film according to claim 1, wherein the relationship is satisfied. 13. An ethylene / α-olefin copolymer (E) or a mixture of an ethylene / α-olefin copolymer (E) and a high-pressure low-density polyethylene (B) for forming the outer layer, and an intermediate layer The ethylene / α-olefin copolymer (F) or a mixture of the ethylene / α-olefin copolymer (F) and the high-pressure low-density polyethylene (B), which forms (i) the molecular weight distribution (G) measured by GPC Mw / Mn: Mw = weight-average molecular weight, Mn = number-average molecular weight) is in the range of 1.5 to 5.0, and (ii) n-decane-soluble component fraction at 23 ° C. (W (% by weight)) ) And density (d) are: W <80 × exp (−100 (d−0.88)) + 0.
(Iii) When the average value of the number of branches on the high molecular weight side by GPC-IR is B ₁ and the average value of the number of branches on the low molecular weight side is B ₂ , B ₁ ≧ B ₂ The agricultural film according to claim 12, wherein: 14. The ethylene / α-olefin copolymers (E) and (F) are copolymers of ethylene and an α-olefin having 4 to 12 carbon atoms prepared using a metallocene catalyst. The agricultural film according to claim 12, wherein the film is provided. 15. The ethylene copolymer composition (2) wherein the antifogging agent (C) is the total amount of the ethylene / α-olefin copolymer (E) and the high-pressure low-density polyethylene (B). The agricultural film according to any one of claims 12 to 14, wherein the amount is 0.05 to 5 parts by weight based on 100 parts by weight. 16. The polyoxyethylene group-containing component constituting the antifogging agent (C) is a polyoxyethylene group represented by (—CH ₂ CH ₂ O—) _n H, wherein n is from 2 to
The agricultural film according to any one of claims 12 to 15, wherein the HLB value is 10 and the HLB value is 5 to 12. 17. A mixture of two or more nonionic surfactants constituting the antifogging agent (C), wherein at least one selected from the group consisting of glycerin fatty acid esters, polyglycerin fatty acid esters and sorbitan fatty acid esters And a mixture of at least one polyoxyethylene group-containing component selected from the group consisting of ethylene oxide adducts of glycerin fatty acid esters, ethylene oxide adducts of polyglycerin fatty acid esters, and ethylene oxide adducts of sorbitan fatty acid esters. The agricultural film according to any one of claims 12 to 16, wherein: 18. The method according to claim 1, wherein the glycerin fatty acid ester is glycerin monostearate.
8. The agricultural film according to 7. 19. The agricultural film according to claim 17, wherein the polyglycerin fatty acid ester is diglycerin monostearate and / or diglycerin distearate. 20. The agricultural film according to claim 17, wherein the sorbitan fatty acid ester is sorbitan monostearate and / or sorbitan distearate. 21. The nonionic fluorine-containing surfactant (D), wherein the surface tension of a 0.001% aqueous solution at 25 ° C. is 42 dyne / cm or less. 2. The agricultural film according to item 1. 22. An ethylene / α-olefin copolymer (E) and an inorganic compound containing at least one atom of Mg, Ca, Al and Si in the ethylene copolymer composition (2). High pressure method low density polyethylene (B)
The agricultural film according to any one of claims 12 to 21, wherein 1 to 20 parts by weight is contained based on 100 parts by weight of the total amount of the above. 23. An ethylene / α-olefin copolymer (F) and an inorganic compound containing at least one atom of Mg, Ca, Al and Si in said ethylene copolymer composition (3). High pressure method low density polyethylene (B)
The agricultural film according to any one of claims 12 to 22, wherein 1 to 20 parts by weight is contained based on 100 parts by weight of the total amount of the above. 24. The thickness ratio of the outer layer [I], the intermediate layer [II] and the inner layer [III] (outer layer [I] / intermediate layer [I]
24] The inner layer [III]) is 0.2 to 4/1 to 10/1, and the total thickness of these layers is 30 to 200 μm. 2. The agricultural film according to item 1. (I) An Elmendorf tear strength of 90 kg / cm or more in the MD direction and 90% in the TD direction.
kg / cm or more, (ii) dart impact strength at a thickness of 100 μm is 900 g or more, (iii) tensile strength at break is 350 kg / cm ² or more in the MD direction, and 350 kg / cm in the TD direction. The agricultural film according to any one of claims 12 to 24, wherein the number is ² or more.