JPH11146733A - Agricultural film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a film excellent in adhesion to an antifogging coating film and a thermoplastic resin and further not only dustproof properties, strength and transparency but also antifogging persistence, weather resistance, etc. SOLUTION: This agricultural film has [I] a thermoplastic resin film layer formed of (C) a resin composed of (A) an ethylene-α-olefin copolymer having 0.880-0.940 g/cm<3> density and 0.01-10 g/10 min melt flow rate(MFR) or (C) the resin composed of a mixture of the component A with (B) a high-pressure- processed low-density polyethylene in an amount of <=40 wt.% and [II] a coating layer formed on at least one surface of the film layer [I] and comprising (D) a surface coating type antifogging agent composition containing a colloidal hydrophilic inorganic compound and a hydrophilic compound. The component A of the resin C or the mixture of the components A with B has 1.5-3.5 Mw/Mn and the fraction of the content soluble in n-decane at 23 deg.C and the density satisfy a specific relationship. When the average value of number of branches on the high-molecular weight side is B1 measured by the gel permeation chromatography-infrared spectrophotometry(GPC-IR) and that on the low- molecular weight side is B2 , 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, transparent materials such as transparent films and transparent glass made of various thermoplastic resins are generally used as covering materials. ing.

However, when the temperature of the surface of the transparent material to be coated falls below the dew point of the environment, dew condensation occurs and the surface of the material becomes cloudy, so that the transparency of the material is lost and the transmittance of sunlight is reduced. In addition to adverse effects such as a decrease in the growth of the crop due to a drop, there is a problem that water droplets attached to the material fall on the crop and cause disease to the crop.

When a transparent film made of a thermoplastic resin is used as a coating material, a composition in which a surfactant (antifog agent) is added to a thermoplastic resin in advance to impart antifogging property to the surface of the transparent film is used. A molded transparent film is generally used. In such a transparent film, antifogging properties are exhibited by bleeding of the surfactant onto the film surface.

However, in such a transparent film made of a thermoplastic resin, when the surfactant bleeding on the surface is washed away by rain or the like, the concentration of the surfactant is reduced, and the antifogging effect is reduced. It is difficult to maintain the fogging effect for more than two years.

Therefore, a method of forming an anti-fogging film on a transparent film for coating has been studied for the purpose of maintaining the anti-fogging effect for a particularly long time, and various attempts have been made.
For example, there has been known a method of forming an antifogging coating mainly containing a polymer of hydroxyethyl methacrylate or polyvinyl alcohol on a transparent film.

However, when a conventional anti-fogging agent is coated on a transparent film, the formed anti-fogging film is extremely easily scratched and easily peeled off from external injuries. There is a problem that the effect of aptitude is lost.

[0008] Usually, lubricants such as fatty acid amide compounds, hydrocarbons and esters are added to the thermoplastic resin in order to reduce friction between the films during or after film processing. Often. When the added lubricant crystallizes on the film surface, friction can be reduced and workability can be improved, but on the other hand, it is known that coatability on the film surface deteriorates. Further, when the molecular weight distribution of the thermoplastic resin itself is large, there is a problem that the low molecular weight component migrates to the film surface and hinders the adhesion to the antifogging coating film.

Therefore, the emergence of an agricultural film which has excellent adhesion between the anti-fogging coating film and the thermoplastic resin, and which is excellent not only in dust resistance, strength and transparency but also in anti-fogging durability and weather resistance. Is desired.

[0010]

SUMMARY OF THE INVENTION The object of the present invention is to solve the problems associated with the prior art as described above. The present invention provides excellent adhesion between an anti-fogging coating film and a thermoplastic resin, and further provides dust resistance, strength and strength.
It is an object of the present invention to provide an agricultural film excellent not only in transparency but also in antifogging durability, weather resistance and the like.

[0011]

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 0.880 to 0.940 g / c.
m ³ and the melt flow rate is 0.01 to 10 g /
10 minutes of ethylene / α-olefin copolymer (A)
Formed from a resin (C) consisting of a resin (C) comprising a mixture of the ethylene / α-olefin copolymer (A) and a high-pressure low-density polyethylene (B) in an amount of 40% by weight or less. A thermoplastic resin film layer and [II] a colloidal hydrophilic inorganic compound (D1) and a hydrophilic organic compound (D2) formed on at least one surface of the thermoplastic resin film layer [I]. An agricultural film comprising a coating layer comprising a surface-coating type anti-fogging agent composition (D), wherein ethylene / α constituting the resin (C) is used.
-The mixture of the olefin copolymer (A) or the ethylene / α-olefin copolymer (A) and the high-pressure low-density polyethylene (B) has (i) a molecular weight distribution (Mw / Mn) measured by GPC. (Ii) n-decane soluble component fraction at 23 ° C. (W
(Weight%)) and density (d (g / cm ³ )): 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 is different from the resin (C) in which the thermoplastic resin film layer [I] is formed on one surface of the thermoplastic resin film layer [I]. One or two or more film layers formed of a thermoplastic resin having the same properties, and the surface coating type anti-fog agent composition is formed on the surface of the thermoplastic resin film layer [I] opposite to the film layer. The coating layer of the product (D) may be formed. That is, the agricultural film according to the present invention has a surface coating type anti-fog agent composition on the surface of the thermoplastic resin film layer [I] of a single-layer film having the thermoplastic resin film layer [I] or a multilayer film having two or more layers. The coating layer [II] of the product (D) is formed.

The ethylene / α-olefin copolymer (A) is a copolymer of ethylene and an α-olefin having 4 to 12 carbon atoms prepared using a single-site catalyst such as a metallocene catalyst or a Brookhardt catalyst. It is preferably a polymer.

The surface coating type anti-fogging composition (D) comprises a layered inorganic compound (D3) and / or a layered inorganic compound (D3) in addition to the colloidal hydrophilic inorganic compound (D1) and the hydrophilic organic compound (D2).
Alternatively, it may contain an organic electrolyte (D4).

In the resin (C), the hindered amine stabilizer (E) is an ethylene / α-olefin copolymer (A) or an ethylene / α-olefin copolymer (A) and a high-pressure low-density polyethylene. Mixture 1 with (B)
It is preferable that 0.005 to 5 parts by weight is contained with respect to 00 parts by weight.

Further, in the resin (C), Mg, Ca,
An inorganic compound (F) containing at least one atom of Al and Si is an ethylene / α-olefin copolymer (A) or an ethylene / α-olefin copolymer (A) and a high-pressure low-density polyethylene (B). Mixture 1)
Preferably, the content is 0.03 to 25 parts by weight based on 00 parts by weight.

The thickness of the thermoplastic resin film layer [I] is preferably 3 to 250 μm.

[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 is a resin (C) comprising the ethylene / α-olefin copolymer (A) or a mixture of the ethylene / α-olefin copolymer (A) and the high-pressure low-density polyethylene (B). A thermoplastic resin film layer [I] formed of a resin (C) comprising: a film having a multilayer structure of two or more layers having such a layer [I]; and a film formed on the surface of the film layer [I]. It has a coating layer [II] (anti-fogging coating film) of the surface coating type anti-fogging composition (D). In the resin (C), additives such as a hindered amine-based stabilizer (E) and an inorganic compound (F) can be blended.

Thermoplastic resin film layer [I] [Ethylene / α-olefin copolymer (A)] The ethylene / α-olefin copolymer (A) constituting the resin (C) used in the present invention is an ethylene / α-olefin copolymer (A). And 4 to 12 carbon atoms
Of α-olefins.

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 0.880 to 0.940 g / cm ³ ,
It is preferably in the range of 0.926 to 0.940 g / cm ³ , and more preferably in the range of 0.926 to 0.936 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 123).
8-65T, 190 ℃, load 2.16kg) is 0.01-10g / 1
It is within a range of 0 minute, preferably 0.1 to 5 g / 10 minutes, and more preferably 0.5 to 2 g / 10 minutes.

The molecular weight distribution of the ethylene / α-olefin copolymer (A) measured by GPC (Mw / M
n: Mw = weight average molecular weight, Mn = number average molecular weight)
It is in the range of 1.5 to 3.5, preferably 2.0 to 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 0.025% by weight of o-dichlorobenzene (manufactured by Wako Pure Chemical Industries, Ltd.) and BHT (manufactured by Takeda Pharmaceutical Co., Ltd.) were used as the mobile phase. 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 density (d (g / cm ³ )) 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 (A) has a temperature [Tm (° C.)] and a density [d (g / g) at the maximum peak position of an endothermic curve measured by a differential scanning calorimeter (DSC). cm ³ )] and Tm <400 × d-250, preferably Tm <450 × d-297, more preferably Tm <500 × d-344, and particularly preferably Tm <550 × d-391. Is desirable.

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 maintained at 200 ° C. for 5 minutes, then lowered to room temperature at 20 ° C./min, and then determined from an endothermic curve when the temperature is raised at 10 ° C./min. The measurement is performed using a DSC-7 type device manufactured by PerkinElmer.

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 BHT [manufactured by Takeda Pharmaceutical Co., Ltd.] [extra pure grade manufactured by Wako Pure Chemical Industries, Ltd.] Column temperature: 140 ° C. Sample concentration: 0.1% (weight / volume) Injection volume (inj.volume): 100 microliter Detector: MCT Resolution: 8 cm ⁻¹ The relationship between B ₁ and B ₂ is as described above. Ethylene α
-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. Here, “dustproofness” refers to a capability of suppressing a decrease in the transparency of a film due to dust adhesion or the like after use for a certain period of time.

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 spread as an agricultural film, it will take a long time. Can be used.

The above-mentioned ethylene / α-olefin copolymer (A) is prepared using a single-site catalyst such as a metallocene catalyst or a Brookhard catalyst as described later.

For example, the ethylene / α-olefin copolymer (A) as described above is disclosed in JP-A-6-9724,
JP-A-6-136195, JP-A-6-13619
No. 6, JP-A-6-207057, etc., in the presence of a so-called metallocene-based olefin polymerization catalyst containing a metallocene catalyst component, ethylene and an α-olefin having 4 to 12 carbon atoms are copolymerized. It can be prepared by polymerizing.

Such a metallocene catalyst generally has 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 which 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.

The nature of such a carrier varies depending on its kind and production method, but the carrier preferably used in the present invention has a specific surface area of 50 to 1000 m ² / g, preferably 1 to 100 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 100 to 100 if necessary.
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 olefin polymerization catalyst 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 , Al ₂ O ₃ , and S described in US Pat. No. 5,321,106.
Lewis acids such as iO ₂ -Al ₂ O ₃ ; ionic compounds such as triphenylcarbenium tetrakis (pentafluorophenyl) borate; and carborane compounds such as dodecaborane and bis-n-butylammonium (1-carbedodeca) borate.

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 an 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 (c) supported on the carrier, the unsupported organoaluminum oxy compound catalyst component (b) and And / or an organoaluminum compound catalyst component (c) may be used. In this case, the unsupported organoaluminum oxy compound catalyst component (b) and / or
Or, the atomic ratio of the aluminum atom (Al) derived from the organoaluminum compound catalyst component (c) to the transition metal atom (M) derived from the metallocene catalyst component (a) [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 -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, in 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 copolymerization step [1] and / or [2] is added to the metallocene catalyst component (a) and the organoaluminum oxy compound catalyst component (b), and the organoaluminum compound catalyst component (d). ) Or a solid catalyst in which the metallocene catalyst component (a) and the organoaluminum catalyst component (b) are supported on the fine-particle 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 catalyst component (b) are supported on a particulate carrier (c). You may. 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.

As described above, the ethylene / α-olefin copolymer (A) can also be prepared by using the following Brookhard type catalyst which is a kind of a single site catalyst.

The Brookhart catalyst comprises a transition metal compound [A] represented by the following formula [A], a Lewis acid or ionized ionic compound [B-1], an organoaluminum oxy compound [B-2] and an alkylboron. And at least one compound [B] selected from the group consisting of acid derivatives [B-3].

[0065]

Embedded image

[In the formula [A], M represents a transition metal selected from Group VIII of the periodic system. X ¹ and X ² are the same or different and each represents a nitrogen atom or a phosphorus atom.

R ¹ and R ² are the same or different and each represents a hydrogen atom or a hydrocarbon group. R ³ is

[0068]

Embedded image

(However, R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R
¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are the same or different and each represent a hydrogen atom or a hydrocarbon group. )
Is shown.

M and n are 1 or 2, respectively, and are numbers satisfying the valences of X ¹ and X ² . R ⁴ and R ⁵ are the same or different and are a hydrogen atom, a halogen atom, a hydrocarbon group, —OR ¹⁷ , —SR ¹⁸ , —N (R ¹⁹ ) ₂
Or —P (R ²⁰ ) ₂ (where R ^{17 to} R ²⁰ each represent a hydrocarbon group or an organic silyl group. Even if R ¹⁹ or R ²⁰ are connected to each other to form a ring, Good). R ⁴ and R ⁵ may be linked to form a ring.

Further, R ¹ , R ² , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R
^{10, R 11, R 12,} R 13, R 14, R 15 and R ^16, two or more of them may be connected to form a ring with each other. In the present invention, the transition metal compound [A]
At least one compound [B] selected from the group consisting of a Lewis acid or ionized ionic compound [B-1], an organoaluminum oxy compound [B-2] and an alkylboronic acid derivative [B-3]; They may be supplied separately to the reaction system, or they may be (A) and one kind of compound [B] selected from [B-1], [B-2] and [B-3] May be contacted in advance and then supplied to the reaction system.

As the transition metal M of Group VIII of the periodic law,
Ni, Pd, and Pt are mentioned. Examples of the hydrocarbon group of R ¹ and R ² include a carbon group having 1 to 2 carbon atoms such as a methyl group and an ethyl group.
About 0 to 2 carbon atoms such as alkyl group and phenyl group
And a substituted aryl group in which a hydrogen atom is partially substituted with the above-mentioned alkyl group.

Specific examples of R ^{6 to} R ¹⁶ include the aforementioned R ¹ ,
The same groups as in R ² can be mentioned. Specific examples of R ^{4 to} R ⁵ include, in addition to the same groups as R ¹ and R ² , —OR ¹⁷ ,
SR ¹⁸ , —N (R ¹⁹ ) ₂ or —P (R ²⁰ ) ₂ (where R ^{17 to} R ²⁰ represent the same groups as R ¹ and R ² ).

As such a coordination compound [A], the following formula:
[A-1]:

[0075]

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In the formula [A-1], M, X ¹ , X ² , R ¹ , R
² , R ⁴ , R ⁵ , R ⁶ , and R ⁷ are the same as described above. ] Is preferable.

The polymerization method of the ethylene / α-olefin copolymer (A) using such a Brookhard catalyst is described in Japanese Patent Application No. 8-7677, which was previously proposed by the present applicant.
No. 4 (application date: March 29, 1996), Japanese Patent Application No. 8
No. 55227 (filing date: March 12, 1996).

[High-pressure low-density polyethylene (B)] A high-pressure low-density polyethylene (B) comprising a mixture of the ethylene / α-olefin copolymer (A) and the high-pressure low-density polyethylene (B) used in the present invention. B) is a melt flow rate (MFR; ASTM D 1238, 190 ° C, load 2.16k)
g) is 0.01 to 100 g / 10 min, preferably 0.2
-10 g / 10 min, more preferably 0.5-5 g / 1
0 minutes, and its density is 0.915-0.
935 g / cm ³ , preferably 0.920 to 0.930
g / cm ³ , more preferably 0.922 to 0.928
g / cm ³ .

Further, high-pressure low-density polyethylene (B)
Is preferably 60% or less, more preferably 50% or less, particularly preferably 45% or less. The density of the high-pressure low-density polyethylene (B) can be determined by the same method as the method 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 melt flow rate measurement is measured with a micrometer as the sample diameter (mm). Then, the swell ratio is calculated by the following equation.

Swell ratio (%) = [(L ₁ / L ₀ ) −1] × 100 L ₁ : sample diameter (mm) L ₀ : orifice diameter (= 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 0 to 100% by weight based on the total amount of the ethylene / α-olefin copolymer (A) and the high-pressure low-density polyethylene (B). 40% by weight, preferably 1
To 35% by weight, more preferably 5 to 30% by weight.

[Hindered amine stabilizer (E)] The hindered amine stabilizer optionally used in the present invention includes all hydrogen atoms bonded to carbon atoms at the 2- and 6-positions of conventionally known piperidine. A compound having a structure in which is substituted with a methyl group is used without particular limitation. Specifically, the following compounds are used. (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) poly {[6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl]
[(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]}, (4) tetrakis (2,2 , 6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, (5) 2,2,6,6-tetramethyl-4-piperidinylbenzoate, (6) Bis- (1,2,6,6-pentamethyl
-4-piperidinyl) -2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate, (7) bis- (N-
Methyl-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, (8) 1,1 ′-(1,2-ethanediyl) bis (3,3,5,
5-tetramethylpiperazinone), (9) (mixed 2,
2,6,6-tetramethyl-4-piperidyl / tridecyl) -1,
2,3,4-butanetetracarboxylate, (10) (mixed 1,2,2,6,6-pentamethyl-4-piperidyl / tridecyl) -1,2,3,4-butanetetracarboxylate, ( 1
1) 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, (12) 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, (13) 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, (14) poly {[6-N-morpholyl-1,3,5-triazine-2 , 4-diyl] [(2,2,6,6-
Tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]｝, (15) N, N'-bis (2,2,6,6- Tetramethyl-4-
Piperidyl) condensate of hexamethylenediamine and 1,2-dibromoethane, (16) [N- (2,2,6,6-tetramethyl-4
-Piperidyl) -2-methyl-2- (2,2,6,6-tetramethyl-
4-piperidyl) imino] propionamide.

Among them, the above (1), (2), (3),
The compounds (4), (8), (10), (11), (14) and (15) are preferably used. These hindered amine-based stabilizers (E) are used alone or in combination as weathering stabilizers.

The hindered amine stabilizer (E) is an ethylene / α-olefin copolymer (A) or an ethylene / α-olefin copolymer.
0.00 parts by weight of a mixture of the α-olefin copolymer (A) and the high-pressure low-density polyethylene (B) is 0.00
5 to 5 parts by weight, preferably 0.005 to 2 parts by weight, more preferably 0.01 to 1 part by weight.

When the hindered amine-based stabilizer (E) is used in the above ratio, the effect of improving stability such as heat resistance and aging resistance is high, the cost of the stabilizer can be reduced, and the resin (C) ), For example, tensile strength is not reduced.

[Inorganic Compound (F)] As the inorganic compound (F) used as required in the present invention, a silica compound containing at least one atom of Mg, Ca, Al and Si, which is effective as a heat insulator, Examples include a magnesium compound and a hydrotalcite compound. Among these, it is desirable to use hydrotalcite compounds.

Examples of the hydrotalcite compounds include the following compounds. (1) hydrotalcite group; general formula Mg ₆ R ² (OH) ₁₆ CO ₃ / 4H ₂ O (R =
(Al, Cr, Fe) hydrated carbonate minerals (natural minerals slightly produced in the Raul region of the USSR, the Sunarm region of Norway, etc.) (2) Synthetic hydrotalcites described below; M 2 ⁺ _1. x Al _x (OH) ₂ (A ⁿ⁻ ) _{x / n} · mH ₂ O (where 0 <x <0.5 and 0 ≦ m ≦ 2) M ²⁺ : Mg, Ca, Zn divalent metal selected from the ions a ^n-: n-valent anion, for example ^{Cl -, Br -, I -} ,
NO ₃ ⁻ , ClO ₄ ⁻ , SO ₄ ²⁻ , CO ₃ ²⁻ , SiO ₃ ²⁻ , H
^{_{PO 4 2-, HBO 3 2-,}} PO 4 3-, Fe (CN) 6 3-, Fe
(CN) ₄ ^4- , CH ₃ COO ⁻ , C ₆ H ₄ (OH) COO ⁻ ,
(OOC-COO) ^{2- and the} like.

The average particle diameter of these hydrotalcite compounds is not particularly limited as long as it does not adversely affect the appearance of the film, the elongation or the formability, and is not particularly limited. Is 5 μm or less, more preferably 3 μm or less.

Further, in order to improve the dispersibility of the above hydrotalcite compound, it is preferable to use it after treating it with a surface treating agent. Examples of surface treatment agents include paraffin, fatty acids, higher alcohols, polyhydric alcohols, thionate-based coupling agents, silane-based coupling agents, and the like.

The inorganic compound (F) such as the above hydrotalcite compound is an ethylene / α-olefin copolymer (A) or an ethylene / α-olefin copolymer (A).
0.03 to 25 parts by weight, preferably 1 to 100 parts by weight, based on 100 parts by weight of a mixture of
20 parts by weight, more preferably 2 to 15 parts by weight.

When the inorganic compound (F) is used in the above ratio, a film having excellent heat retention can be obtained.
Here, "warmth" means absorbing the radiation emitted at night from the earth whose temperature has risen by absorbing solar heat during the day,
It refers to the ability to reflect and maintain the temperature (air temperature and ground temperature) inside agricultural houses, tunnels, and the like.

[Other components] In the above resin (C),
If necessary, conventionally known additives such as an antifog, an ultraviolet absorber, an antioxidant, an antistatic agent, and a heat stabilizer can be blended within a range that does not impair the object of the present invention.

The antifog used in the present invention is a surfactant in which a part or all of a hydrogen atom bonded to a carbon atom of a hydrophobic group of a normal surfactant is replaced by a fluorine atom, and particularly a surfactant. Fluorinated surfactants containing a perfluoroalkyl or perfluoroalkenyl group are preferred.

Representative examples of the fluorine-based surfactant usable in the present invention are as follows. (A) Anionic fluorosurfactant (1) -COOM type _{R f COOM R f SO 2 N} (R ') 2 CH 2 COOM (2) -OSO 3 M type R _f BNR'YOSO ₃ M ₍₃ ) -SO ₃ M type _{R f SO 3 M R f CH} 2 O (CH 2) m SO 3 M

[0096]

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(4) —OPO (OM) ₂ system R _f BNR′YOP (＝ O) (NM) _{2 In} each of the above formulas, R _f and R ′ _f represent a part or all of the hydrogen atoms of the alkyl group. represents a substituted fluoroalkyl group with a fluorine atom, B is -CO -, - CO ₂ -, or -S
R ₂ represents a hydrogen atom or a lower alkyl group, M represents a hydrogen atom, —NH ₄ , an alkali metal atom or an alkaline earth metal atom, and Y represents —CH ₂ —.
Or -C ₂ H ₄ OCH ₂ - represent.

The above fluoroalkyl group is preferably a polyfluoroalkyl group having the following structure. _{CF 3 - (CF 2) l} - l is 2 to 19 integer _{(CF 3) 2 = CF- (} CF 2) m - m is 0 to 17 integer _{HCF 2 - (CF 2) n} - n is 2 19 integer addition of, as the above R _f and R _'f, the other of the fluoroalkyl _{group, CF 2 = CF 2, CF} 3 -CF = CF 2
Or a branched polyfluoroalkyl group synthesized by the oligomerization of C ₃ F ₇ O— (C ₃ F ₆ O) _k CO
-[K is an integer of 0 to 5] and the like. (B) Cationic fluorinated surfactant

[0099]

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In the formula, R _f , B, R ′ _f and Y have the same meaning as described above, R ″ represents a hydrogen atom or a lower alkyl group, HX represents an acid, X represents a halogen atom or Represents acid radical. (C) Amphoteric fluorinated surfactant (1) —N ⁺ (R ′) ₂ —COO ⁻ system R _f BNHYN ⁺ (R ′) ₂ (CH ₂ ) _m COO ^{— wherein} R _f , B, R ′ _f and Y have the same meaning as described above. (D) a non-ionic fluorocarbon surfactant (1) -OH system R _f OH

[0101]

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In the formula, R _f , B, R ′ and Y have the same meaning as described above, and Z represents a hydrogen atom, —C (＝ O) R or —C (＝ O) NHR. R in these groups is
Represents a hydrogen atom or a lower alkyl group.

Preferred examples of the above-mentioned and other types of fluorine-containing surfactants are as follows. (i) C _n F _{2n + 1} COOM In the formula, M is a hydrogen atom, an alkali metal atom or —NH ₄
And n is an integer of 5 to 12, preferably 6 to 10. Examples of the surfactant represented by this formula include the following compounds.

C ₉ F ₁₉ COONa C ₅ F ₁₇ COOLi (ii) C _n F _{2n + 1} CONH (C ₂ H ₄ O) _m H In the formula, n is an integer of 5 to 12, preferably 6 to 10. , M is an integer of 1 to 30, preferably 2 to 20.
Examples of the surfactant represented by this formula include the following compounds.

C ₉ F ₁₉ CONH (C ₂ H ₄ O) ₃ H

[0106]

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In the formula, R is a hydrogen atom or a lower alkyl group, n is 6 to 12, preferably 9, and m is 2 to
30, preferably an integer of 3 to 20.

[0108]

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(Iv) C _n F _{2n + 1} CONHC ₃ H ₆ N ⁺ (CH
_{3) 2 C 2 H 4 COO} - In the formula, n 5 to 12, preferably 6 to 10 integers. Examples of the surfactant represented by this formula include the following compounds.

[0110] _{C 9 F 17 CONHC 3 H 6} N + (CH 3) 2 C 2 H 4 COO - (v) C n F 2n + 1 CONHC 3 H 6 N + (CH 3) 2 · X - wherein X is a halogen acid radical, and n is an integer of 5 to 12, preferably 6 to 10. Examples of the surfactant represented by this formula include the following compounds.

[0111] _{C 8 F 17 CONHC 3 H 6} N + (CH 3) 2 · I - (vi) C n F 2n + 1 (CH 2) m COOM wherein, M is a hydrogen atom, an alkali metal atom or -NH _Four
Wherein n is an integer of 3 to 12, preferably 5 to 10, and m is an integer of 1 to 16, preferably 2 to 10.
Examples of the surfactant represented by this formula include the following compounds.

C ₇ F ₁₅ (CH ₂ ) ₅ COONa C ₈ F ₁₇ (CH ₂ ) ₄ COOK (vii) C _n F _{2n + 1} SO ₂ N (C ₂ H ₅ ) C ₂ H ₄ OPO (O
H) _{2 In the} formula, n is an integer of 5 to 12, preferably 6 to 10. Examples of the surfactant represented by this formula include the following compounds.

C ₈ F ₁₇ SO ₂ N (C ₂ H ₅ ) C ₂ H ₄ OPO (OH) ₂ (viii) C _n F _{2n + 1} SO ₂ N (C ₂ H ₅ ) CH ₂ COOM Is a hydrogen atom, an alkali metal atom or -NH ₄
And n is an integer of 5 to 12, preferably 6 to 10. Examples of the surfactant represented by this formula include the following compounds.

C ₈ F ₁₇ SO ₂ N (C ₂ H ₅ ) CH ₂ COOK (ix) C _n F _{2n + 1} SO ₂ N (C ₂ H ₅ ) C ₂ H ₄ OSO ₃ H In the formula, n is 5 To 12, preferably an integer of 6 to 10. Examples of the surfactant represented by this formula include the following compounds.

C ₈ F ₁₇ SO ₂ N (C ₂ H ₅ ) C ₂ H ₄ OSO ₃ H (x) C _n F _{2n + 1} SO ₂ N (C ₂ H ₅ ) (C ₂ H ₄ O) _m H In the formula, n is an integer of 5 to 12, preferably 6 to 10, and m is an integer of 1 to 30, preferably 2 to 20.
Examples of the surfactant represented by this formula include the following compounds.

C ₈ F ₁₇ SO ₂ N (C ₂ H ₅ ) (C ₂ H ₄ O) ₁₄ H (xi) C _n F _{2n + 1} CON (C ₂ H ₅ ) (C ₂ H ₄ O) _m H In the formula, n is an integer of 5 to 12, preferably 6 to 10, and m is an integer of 1 to 30, preferably 2 to 20.
Examples of the surfactant represented by this formula include the following compounds.

C ₈ F ₁₇ CON (C ₂ H ₅ ) (C ₂ H ₄ O) ₁₄ H (xii) C _n F _{2n + 1} -Y-CH ₂ (OZ) -CH ₂ O-
In _{(C 2 H 4 O) m} -R ' formula, n 5 to 12, preferably 6 to 10 integer, m is 1 to 30, preferably 2 to 20 integer,
Y is _{-CH 2 -, - C 2 H} 4 OCH 2 - represents, Z is a hydrogen atom, -C (= O) R or -C (= O) NHR (where R in these formulas, the hydrogen atom Or a lower alkyl group). Examples of the surfactant represented by this formula include the following compounds.

C ₈ F ₁₇ -CH ₂ -CH ₂ (-OH) -CH ₂ O- (C ₂ H ₄ O) ₁₀ -HC ₈ F ₁₇ -C ₂ H ₄ O-CH ₂ -CH ₂ (-O -CO-CH ₃ ) -CH ₂ O- (C ₂ H ₄ O) ₁₂ -CH ₃ (xiii) C _n F _{2n + 1} -Y-CH ₂ (-OZ) -CH ₂ O- (C ₂ H ₄ O) _m -CH ₂ -CH ₂ (-O
Z) -YC _n F _{2n + 1 In the} formula, n is an integer of 5 to 12, preferably 6 to 10, m is an integer of 1 to 30, preferably 2 to 20,
Y is -CH ₂ - or -C ₂ H ₄ OCH ₂ - represents, Z is a hydrogen atom, -C (= O) R or -C (= O) NHR
(However, R in these formulas is a hydrogen atom or a lower alkyl group). Examples of the surfactant represented by this formula include the following compounds.

C ₈ F ₁₇ -CH ₂ -CH ₂ (-OH) -CH ₂ O- (C ₂ H ₄ O) ₁₀ -CH _2-
CH ₂ (-OH) -CH ₂ -C ₈ F ₁₇ (xiv) C _n F _{2n + 1} SO ₂ N (C ₂ H ₅ ) (C ₂ H ₄ O) _m C ₂ H ₄ N (C ₂ H ₅ ) SO ₂ C _n F
_{In the} formula _{2n + 1} , n is an integer of 5 to 12, preferably 6 to 10, and m is an integer of 1 to 30, preferably 2 to 20.
Examples of the surfactant represented by this formula include the following compounds.

C ₈ F ₁₇ SO ₂ N (C ₂ H ₅ ) (C ₂ H ₄ O) ₁₄ C ₂ H ₄ N (C ₂ H ₅ ) SO ₂ C ₈ F ₁₇

[0121]

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In the formula, n is 5 to 12, preferably 6 to 10
M is an integer of 1 to 30, preferably 2 to 20, and 1 is an integer of 1 to 30, preferably 2 to 20. Examples of the surfactant represented by this formula include the following compounds.

[0123]

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The above-mentioned fluorosurfactants can be used alone or in combination of two or more. The amount of the fluorosurfactant to be added is not critical and can be varied widely depending on the type of the fluorosurfactant to be blended or the type of the resin, but generally, it should be blended. The amount can be at least 0.01 part by weight per 100 parts by weight of the resin (C), and the upper limit of the amount is not strictly limited. Usually, 2.0 parts by weight or less is sufficient because of the possibility.

As the above-mentioned ultraviolet absorber, specifically,
Salicylic acid-based ultraviolet absorbers such as phenyl salicylate, p-tert-butylphenyl salicylate, 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-5
-Benzophenone ultraviolet absorbers such as sulfobenzophenone; 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-tert-butylphenyl) benzotriazole, 2- ( 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, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the resin (C).
005 to 2 parts by weight, more preferably 0.01 to 1 part by weight. When the ultraviolet absorber is used in the above ratio together with the hindered amine compound (E), the effect of improving the weather resistance of the obtained agricultural film becomes larger.

The film for agricultural use according to the present invention is a thermoplastic resin film layer formed of the resin (C) before the film layer of the surface coating type anti-fog composition (D) is formed. In the case of a single layer structure composed of [I], the film layer [I] has a thickness of usually 30 to 250 μm,
Preferably 50 to 180 μm, more preferably 70 to 180 μm
It is in the range of 150 μm.

The thermoplastic resin film layer [I] as described above comprises the above-mentioned ethylene / α-olefin copolymer (A) and, if necessary, a high-pressure low-density polyethylene (B) and a hindered amine-based stabilizer (E). ), Additives such as inorganic compound (F) and antifog, etc. are mixed and melt-mixed with a Banbury mixer or roll mill, extruder, etc.
Then, it can be manufactured by a usual film forming method.

For film formation, an inflation method or a T-die method can be used, and for cooling, an air cooling method or a water cooling method can be adopted. Further, the agricultural film according to the present invention comprises a thermoplastic resin film layer on the surface of the thermoplastic resin film layer [I] on the opposite side of the coating layer [II] of the surface coating type anti-fog composition (D). One or more film layers formed of a thermoplastic resin having a property different from that of the resin (C) forming [I] may be formed. That is, the film before the formation of the coating layer [II] of the surface coating type anti-fogging agent composition (D) may be a multilayer film of two or more layers including the thermoplastic resin film layer [I]. As a preferred form of the multilayer film, for example, a back layer, an intermediate layer laminated thereon, and a surface layer laminated thereon are provided, and at least the back layer is formed of the thermoplastic resin film layer [I]. Three-layer laminated film. The coating layer [II] of the front surface application type antifogging agent composition (D) is formed at least below the back surface layer. The agricultural film according to the present invention is used with the coating layer [II] facing the direction of the crop.

Surface Layer and Back Layer The surface layer and / or the back layer constituting the above three-layer laminated film may be a resin (C) comprising an ethylene / α-olefin copolymer (A) or an ethylene / α-olefin ( It is formed of a resin (C) comprising a mixture of A) and a high-pressure low-density polyethylene (B) of 40% by weight or less. The surface layer may be formed of the resin (C) or a thermoplastic resin other than the resin (C), for example, a high-pressure low-density polyethylene,
It may be formed of an ethylene / vinyl acetate copolymer or the like.

In the present invention, it is desirable that the surface layer is also formed of the above resin (C). The resin (C) is as described above. In the resin (C), if necessary, the above-mentioned conventionally known inorganic compounds (such as hydrotalcite compounds), an antifog agent, an ultraviolet absorber, Additives such as an antioxidant, an antistatic agent, and a heat stabilizer can be blended within a range that does not impair the purpose of the present invention.

Intermediate Layer The intermediate layer constituting the three-layer laminated film is made of ethylene.
at least one member selected from the group consisting of α-olefin copolymer (A), ethylene / vinyl acetate copolymer, high-pressure low-density polyethylene (B), ethylene / (meth) acrylic acid copolymer, and ionomer resin It is preferable to be formed of resin. The resin forming the intermediate layer may be the resin (C), but may be different in properties from the resin forming the front layer and the back layer.

The ethylene / vinyl acetate copolymer has a vinyl acetate content of 3 to 50% by weight, preferably 5 to 50% by weight.
30% by weight, ethylene / (meth)
It is desirable that the acrylic acid copolymer has an ethylene content of 99 to 70% by weight, preferably 98 to 75% by weight. Further, as the ionomer resin, for example, the ethylene / (meth) acrylic acid copolymer may be Na ⁺ , Zn ⁺⁺
And the like, which are crosslinked with metal ions.

In the present invention, the resin (C) comprising 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 used. It is particularly preferred to use

The resin forming the intermediate layer may be composed of the above-described resin alone, or may be composed of two or more resins. Further, shavings such as ears and defective products generated during film forming can be collected and reused for the intermediate layer.

The resin for forming an intermediate layer may include, if necessary, the previously known inorganic compounds (such as hydrotalcite compounds), antifogants, ultraviolet absorbers, antioxidants, antistatic agents, and the like. Additives such as heat stabilizers can be incorporated within a range that does not impair the purpose of the present invention.

The three-layer laminated film composed of the surface layer, the intermediate layer and the back layer as described above has a surface layer usually having a thickness of 3 to 3.
100 μm, preferably 10 to 80 μm, more preferably 15 to 70 μm, and the thickness of the intermediate layer is 10 μm.
To 150 μm, preferably 20 to 120 μm, more preferably 30 to 100 μm, and the thickness of the back layer is 3 to 100 μm, preferably 10 to 80 μm, more preferably 15 to 70 μm, and these The thickness of the entire layer is 30 to 250 μm, preferably 50 to 250 μm.
It is in the range of 180 μm.

In such a three-layer laminated film,
Ratio of the thicknesses of the surface layer, the intermediate layer, and the back layer (the thermoplastic resin film layer [I]) (surface layer / intermediate layer / back layer)
Is 0.2-4 / 0.1-10 / 1, preferably 0.5
２2 / 0.3〜6 / 1.

Such a three-layer laminated film is prepared by mixing the polyethylene resin used in each layer and the above-mentioned additives and other components, and melt-mixing the mixture with a Banbury mixer or a roll mill or an extruder. It can be prepared by laminating a surface layer, an intermediate layer and a back surface layer in order by a molding method or the like.

Coating layer [II] Surface-coated antifogging composition (D) comprising the agricultural film according to the present invention together with the thermoplastic resin film layer [I].
The coating layer [II] is formed on at least one surface of the thermoplastic resin film layer [I].

The surface coating type anti-fogging agent composition (D) used for forming the coating layer [II] comprises a colloidal hydrophilic inorganic compound (D1) and a hydrophilic organic compound (D1) in a dispersion medium described later. D2) are dispersed. The surface coating type anti-fogging agent composition (D) can contain a layered inorganic compound (D3) and / or an organic electrolyte (D4) in addition to these components. The layered inorganic compound (D3) and the organic electrolyte (D4) have a function of further improving the coatability of the surface-coating type antifog composition (D).

The solvent of the surface coating type anti-fog composition [D] is
It is removed from the coating layer [II] in a drying step in forming the coating layer [II]. The concentration of the surface coating type antifogging agent composition [D] in the solvent, that is, the concentration of the active ingredient is usually 0.001 to 10% by weight, preferably 0.1 to 10% by weight.
It is desirably in the range of 1 to 7% by weight, more preferably 0.15 to 5% by weight.

[Colloidal hydrophilic inorganic compound (D1)]
The colloidal hydrophilic inorganic compound (D) used in the present invention
1) Inorganic particles having the property of dispersing an inorganic compound in a colloidal state in a dispersion medium. Specific examples of such a colloidal hydrophilic inorganic compound (D1) include colloidal silica, colloidal alumina, and colloidal Fe.
(OH) ₂ , colloidal Sn (OH) ₄ , colloidal TiO ₂ , colloidal BaSO ₄ and colloidal lithium silicate. Particularly, colloidal silica and colloidal alumina are preferable.

The above-mentioned colloidal hydrophilic inorganic compounds (D1) can be used alone or in combination of two or more. Colloidal hydrophilic inorganic compound (D
1) is used by being added to a dispersion medium. The colloidal hydrophilic inorganic compound (D1) varies depending on the type,
Usually 0.01 to 5 parts by weight, preferably 0.05% by weight, based on 100 parts by weight of the dispersion medium of the surface coating type anti-fogging agent composition (D).
To 4 parts by weight, more preferably 0.1 to 2 parts by weight.

Examples of the dispersion medium of the surface-coating type anti-fog composition (D) include water, methyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, ethylene glycol and xylene. In particular, water is preferred from the viewpoint of environmental safety.

The average particle size of the colloidal particles of the colloidal hydrophilic inorganic compound (D1) dispersed in the dispersion medium of the surface coating type anti-fogging agent composition (D) is usually 5 to 100 nm, preferably 5 to 100 nm. Preferably, it is 80 nm.

The colloidal silica and colloidal alumina preferably used in the present invention will be further described. Colloidal silica is silica particles having the property of dispersing silica in a dispersion. Colloidal silica is
It is commercially available as a dispersion containing alkali metal ions, alkaline earth metal ions or quaternary ammonium ions. The particle size of the silica particles is usually 5 to 100.
nm. Here, silica refers to all silicon compounds called silicic anhydride or simply silicic acid in addition to silicon dioxide represented by the general formula of SiO ₂ , and is not particularly limited.

The colloidal silica is usually added in an amount of 0.1 to 100 parts by weight of the dispersion medium of the surface coating type anti-fogging composition (D).
01 to 1 part by weight, preferably 0.05 to 0.8 part by weight,
More preferably, it is used in a ratio of 0.1 to 0.5 part by weight.

Further, colloidal aluminum is alumina particles having a property that alumina is colloidally dispersed in a dispersion medium. Alumina particles are commercially available as a dispersion containing chlorine ions, nitrate ions or acetate ions. The particle size of the alumina particles is usually in the range of 5 to 200 nm. Here, the term “alumina” includes aluminum hydroxide and the like in addition to aluminum oxide, and is not particularly limited.

The colloidal alumina is usually used in an amount of 100 parts by weight of the dispersion medium of the surface coating type anti-fogging agent composition (D).
0.1 to 5 parts by weight, preferably 0.5 to 4 parts by weight, more preferably 0.5 to 1.5 parts by weight.

[Hydrophilic organic compound (D2)] The hydrophilic organic compound (D2) used in the present invention includes (i) various surfactants such as anionic, cationic and nonionic surfactants, and (ii) a hydroxyl group-containing compound. Vinyl monomer component 60 to 99.9
% By weight and 0.1 to 40% by weight of an acid group-containing vinyl monomer component
Or a partially or completely neutralized product thereof, and (iii) a sulfonic acid group-containing polyester resin.

The anionic surfactant is not particularly limited, but specific examples include sodium caprylate, potassium caprylate, sodium decanoate, sodium caproate, sodium myristate, potassium oleate, sodium stearate, and behenate. 6 to 6 carbon atoms such as potassium phosphate, tetramethylammonium stearate
Metal salts or ammonium salts of carboxylic acids having an alkyl chain of 24; sulfones having an alkyl chain of 6 to 24 carbon atoms, such as sodium octyl sulfonate, sodium dodecyl sulfonate, sodium dodecyl benzene sulfonate, and ammonium dodecyl benzene sulfonate; Metal or ammonium salt of an acid; having 6 to 24 carbon atoms
Metal salts or ammonium salts of phosphate esters having an alkyl chain of the following; metal salts or ammonium salts of borate esters having an alkyl chain having 6 to 24 carbon atoms; sodium perfluorodecanoate, sodium perfluorooctyl sulfonate, etc. Fluorine-based anionic surfactants; silicon-based anionic surfactants having an anionic group in a polydimethylsiloxane group and a metal carboxylate, and the like. Among them, especially those having 6 carbon atoms
Alkali metal salts of carboxylic acids having an alkyl chain of from 10 to 10 are preferred.

The cationic surfactant is not particularly limited, but specific examples thereof include an alkyltrimethylammonium salt, a dialkyldimethylammonium salt and an alkyldimethylethylammonium salt having 12 to 1 carbon atoms.
Ammonium salt having an alkyl chain of 8; ammonium salt having an ester bond such as stearooxymethylpyridinium salt, fatty acid triethanolamine, fatty acid triethanolamine formate; polyoxyethylene alkylamine, N-alkylpropyleneamine, N- Examples thereof include amine derivatives having an alkyl chain having 12 to 18 carbon atoms, such as alkyl polyethylene polyamine.

The nonionic surfactant is not particularly limited, but specific examples thereof include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl naphthyl ether, polyoxyethylene monofatty acid ester, and polyoxyethylene monofatty acid ester. 7 to 7 carbon atoms such as ethylene sorbitan monofatty acid ester
Polyoxyethylene compounds having an alkyl chain of 18; polyhydric alcohol compounds having an alkyl chain having 9 to 17 carbon atoms such as ethylene glycol monofatty acid ester, propylene glycol monofatty acid ester, and sorbitan monofatty acid ester. .

Examples of the copolymer comprising the hydroxyl-containing vinyl monomer component and the acid-containing vinyl monomer component include a polymer having a vinyl alcohol unit and a (meth) acrylic acid unit. Examples include a polymer having a vinyl alcohol derivative unit and a (meth) acrylic acid unit, and a polymer having a hydroxy acrylate unit and a (meth) acrylic acid unit.

Specific examples of the partially or completely neutralized product of the copolymer include polymers such as methyl ester and ethyl ester of the above-mentioned polymer acid groups. The hydrophilic organic compound (D2) varies depending on its kind, but is usually 1 to 50 parts by weight, preferably 2 to 4 parts by weight, per 100 parts by weight of the dispersion medium of the surface-coating type anti-fogging composition (D).
0 parts by weight, more preferably 5 to 30 parts by weight.

[Layered Inorganic Compound (D3)] The layered inorganic compound (D3), which may be optionally added to the surface-coating type anti-fogging composition (D), is formed by stacking unit crystal layers on each other. It is an inorganic compound having a structure, and is not particularly limited as long as it has a particle size of 5 μm or less.
Those which swell and cleave in a solvent are preferably used. Further, when the particle size is 3 μm or less, transparency becomes better, which is preferable.

Specific examples of the layered inorganic compound (D3) include graphite, phosphate-based derivative compounds (zirconium phosphate-based compounds), and chalcogenides [Groups IVB (Ti, Zr, Hf) of the periodic table. , VB (V, Nb,
Ta) and Group VIB (Mo, a dichalcogen product of W), the formula MX _2. Here, X represents chalcogen (S, Se, Te). And clay-based minerals.

The clay-based minerals are of a two-layer structure having an octahedral layer made of aluminum, magnesium or the like as a central metal on the silica tetrahedral layer, and a silica tetrahedral layer formed of aluminum or magnesium. It is classified into a type having a three-layer structure in which an octahedral layer made of magnesium or the like as a central metal is sandwiched from both sides.

Examples of the former type of clay minerals include kaolinite and antigolite minerals. Examples of the latter type of clay mineral include minerals of smectite group, vermiculite group, mica group and the like depending on the number of interlayer cations.

Specific examples of clay minerals include kaolinite, dickite, nacrite, halloysite, antigolite, chrysotile, pyrophyllite, montmorillonite, hectorite, tetrasilyl mica, sodium teniolite, muscovite, Margarite,
Examples include talc, vermiculite, phlogopite, zansophyllite, and mudstone. In particular, a smectite group clay mineral whose aqueous dispersion has a thixotropic viscosity is preferable.

The average particle size of the colloidal particles of the layered inorganic compound (D3) dispersed in the dispersion medium of the surface coating type anti-fogging agent composition (D) is usually 0.1 to 50 nm, preferably 10 to 50 nm.
Desirably, it is 30 nm.

The layered inorganic compound (D3) is different depending on the kind, but the dispersion medium 1 of the surface-coating type anti-fogging agent composition (D) is used.
0.005 parts by weight, usually 0.005 to 0.5 parts by weight,
Preferably, it is used in a proportion of 0.01 to 0.02 parts by weight. When the layered inorganic compound (D3) is used in the above ratio, a surface coating type antifogging agent composition (D) having excellent coatability can be obtained.

[Organic Electrolyte (D4)] The organic electrolyte (D4) which may be optionally added to the surface coating type anti-fogging composition (D) is an organic compound having an ionizable ionic group. There are specifically, sodium benzenesulfonate, sodium p-toluenesulfonate, potassium butylsulfonate, sodium phenylphosphinate and sodium diethylphosphate. Particularly, a benzenesulfonic acid derivative such as sodium benzenesulfonate is preferable.

The organic electrolyte (D4) is usually added to the dispersion medium (100 parts by weight) of the surface-coating type anti-fogging agent composition (D) in view of the effect of the organic electrolyte (D4) and the electric balance.
0001 to 0.010 parts by weight, preferably 0.001 to
It is used in a proportion of 0.005 parts by weight. Organic electrolyte (D
When 4) is used in the above ratio, a surface coating type anti-fog agent composition (D) having excellent coatability can be obtained.

Agricultural Film The agricultural film according to the present invention is a single-layer film comprising one layer of the above-mentioned thermoplastic resin film layer [I] or a multilayer film containing this thermoplastic resin film layer [I];
For example, a coating layer [II] of the surface-coating type anti-fogging agent composition (D) is formed on at least one surface of the above-described three-layer laminated film.

The thickness of the coating layer [II] is usually 0.1 to 10 μm, preferably 0.2 to 5 μm, more preferably 0.5 to 3 μm. The method for coating the surface-coated antifogging agent composition (D) on the single-layer film or the multilayer film may be any of various roll printing methods, dipping methods, spraying methods and the like. In addition, this coating can be performed by an in-line coating method that is performed subsequently after the film is formed, an outline coating method that is performed in a rewinding step after the film is formed and wound, and a method of spray coating the inner surface after the film is stretched. .

When the agricultural film according to the present invention comprises the thermoplastic resin film layer [I] and the coating layer [II] of the surface-applied anti-fog composition (D) formed on the surface thereof, It is desirable that the agricultural film has the following physical properties. (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 450 g or more, preferably 500 g
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.

Further, in the present invention, a coating layer [II] of the surface coating type anti-fogging agent composition (D) is formed on the surface of the thermoplastic resin film layer [I] of the three-layer laminated film as described above. It is desirable that the agricultural film according to the above has the following physical properties. (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.

[0170]

According to the present invention, the adhesion between the anti-fogging coating film and the thermoplastic resin is excellent, and the anti-fogging property, strength and transparency as well as anti-fogging durability and weather resistance are improved. An excellent agricultural film can be provided.

The agricultural film according to the present invention is lightweight,
And because the low molecular weight component in the polymer used is small, there is little stickiness, and it is excellent in spreading workability,
This has the advantage that the fusion of the films at high temperatures is small. Here, the “stretching workability” indicates whether the film is easy to handle due to stickiness.

Since the agricultural film according to the present invention has the above-described 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.

[0173]

EXAMPLES The present invention will be described below with reference to experimental examples, but the present invention is not limited to these experimental examples.

The Elmendorf tear strength, dart impact strength,
The tensile strength at break, transparency (degree of haze), initial anti-fogging property, anti-fogging durability, initial adhesion, and evaluation of adhesion durability were evaluated as follows. (1) Elmendorf tear strength: The strength in the machine direction (MD) and the transverse direction (TD) was measured by a method based on JIS Z 1702. (2) Dart Impact Strength Dart impact strength was determined by performing an impact test in accordance with JIS Z 1707 (dart tip diameter: 38 mm). (3) Tensile strength at break The tensile strength at break is based on JIS K6781, and under the following conditions, MD and TD of the film, constant crosshead moving speed tensile tester (manufactured by Instron).
Is a value obtained by conducting a tensile test using

[Test conditions] Sample: JIS K6781 Atmospheric temperature: 23 ° C Peeling speed: 500 mm / min (4) Transparency As an index of transparency, haze was measured according to JIS K6714. (5) Initial anti-fogging property 70 ml of water was placed in a beaker having a capacity of 100 ml, and the upper surface thereof was covered with a sample film such that the coating layer of the surface-applied anti-fog agent composition was facing down, and the beaker was covered with 50 ml of water. It was immersed in a constant temperature water bath at a room temperature and left in a constant temperature room at a room temperature of 20 ° C. The degree of fogging on the inner surface of the sample film, that is, the film surface on the water surface side was observed after 24 hours, and the initial antifogging property of the film was evaluated based on the following criteria.

Evaluation Criteria:: No water droplets were observed in a flowing state. Δ: Large water droplets partially adhered to the film. ×: Fine water droplets adhere to almost the entire surface of the film. (6) Antifogging persistence The sample film was immersed in warm water at 60 ° C., taken out of the warm water after 40 days and dried, and the antifogging property after 24 hours was observed by the above method (5). The sex was evaluated. (7) Initial Adhesion After inflation molding, the adhesion of the coating film obtained by coating the obtained film surface with an antifogging agent was evaluated by a tape peeling test. 1 from Nichiban Co., Ltd. on the coating film
After adhering about 8 cm of cellophane tape of 8 mm width,
A 180 ° tape peeling test was performed, and the initial adhesion was evaluated based on the following criteria.

Evaluation criteria:: No peeling of the coating film was observed. ×: Peeling of the coating film is observed. (8) Adhesion Persistence The sample film was immersed in warm water at 60 ° C., taken out of the warm water after 40 days and dried, and the adhesion persistence was evaluated by the method of (7) above.

[0178]

[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) was 1.63 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 120 ° C., and a fraction of n-decane soluble component at room temperature. [W] was 0.25% by weight.

[0182] B ₁ above was measured for this copolymer with GPC-IR analysis was 12.2 / 1000 C-(per 1000 carbon atoms 12.2), B ₂ is 9.9 / 1
000C. These physical property data are shown in Table 1 in the section of ethylene / α-olefin copolymer (I).

[0183]

Reference Example 2 An ethylene / 1-hexene copolymer as shown in Table 1 was obtained in the same manner as in Reference Example 1. The physical property data of this copolymer is shown in Table 1 in the section of ethylene / α-olefin copolymer (II).

[0184]

[Table 1]

[0185]

Examples 1 to 14 Using the resins shown in Table 1, under the conditions shown in Table 2, films having a thickness of 100 to 150 μm were blown-molded under the following conditions.

[Inflation molding conditions] Molding machine: manufactured by Alpine Company Die diameter: 400 mm Molding temperature: 200 ° C. Folding width: 1500 mm Thickness: 100 to 150 μm Next, a roll is formed on the surface of the film obtained as described above. An antifogging composition comprising the components shown in Table 3 was applied by a printing method and dried to form a coating film having a thickness of 2 μm.

In the antifogging agent composition, each component of the antifogging agent composition shown in Table 3 was converted to an effective ingredient concentration of 2% by weight under the conditions shown in Table 3. Water was added and stirred and mixed as described above.

With respect to the film obtained as described above, Elmendorf tear strength, dart impact strength,
The tensile strength at break, transparency (cloudiness), initial antifogging property, antifogging durability, initial adhesion and adhesion persistence were tested in accordance with the above methods.

The results are shown in Table 4.

[0190]

COMPARATIVE EXAMPLES 1 AND 3 In Example 1, the resin comprising the ethylene / α-olefin copolymer (II) and the high-pressure low-density polyethylene (III) used in Example 1 was replaced with the high-pressure low-density polyethylene. Except that a resin consisting of polyethylene (III) alone was used, the thickness was 100 μm in the same manner as in Example 1.
m of film was blown. Hereinafter, it carried out similarly to Example 1.

The results are shown in Table 4.

[0192]

Comparative Examples 2 and 4 In Example 1, ethylene-vinyl acetate was used instead of the resin comprising ethylene / α-olefin copolymer (II) and high-pressure low-density polyethylene (III) used in Example 1. Except that a resin consisting of the copolymer (IV) alone was used, a thickness of 10
A 0 μm film was blown molded. Less than,
Performed in the same manner as in Example 1.

The results are shown in Table 4.

[0194]

[Table 2]

[0195]

[Table 3]

[0196]

[Table 4]

[0197]

[Table 5]

[0198]

[Table 6]

[0199]

[Table 7]

[0200]

[Table 8]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI // C08L 23/08 C08L 23/08

Claims (7)

[Claims] [1] [I] ethylene and α having 4 to 12 carbon atoms
And an ethylene / α-olefin copolymer (A) having a density of 0.880 to 0.940 g / cm ³ and a melt flow rate of 0.01 to 10 g / 10 min. Or a resin (C) comprising a mixture of the ethylene / α-olefin copolymer (A) and a high-pressure low-density polyethylene (B) in an amount of 40% by weight or less. A thermoplastic resin film layer and [II] a colloidal hydrophilic inorganic compound (D1) and a hydrophilic organic compound (D2) formed on at least one surface of the thermoplastic resin film layer [I]. An agricultural film comprising a surface coating type anti-fogging agent composition (D) and an ethylene / α-olefin copolymer (A) or ethylene which constitutes the resin (C).・ Α-Oleph The mixture of the vinyl copolymer (A) and the high-pressure low-density polyethylene (B) has the molecular weight distribution (Mw / Mw /
Mn) is in the range of 1.5 to 3.5, and (ii) the fraction (W (% by weight)) and the density (d (g / cm ³ )) of the n-decane soluble component at 23 ° C. 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. The ethylene / α-olefin copolymer (A) is a copolymer of ethylene and an α-olefin having 4 to 12 carbon atoms prepared using a single-site catalyst. The agricultural film according to claim 1, wherein 3. The method according to claim 1, wherein the surface-coating type anti-fogging agent composition (D) comprises a layered inorganic compound (D3) and / or a colloidal hydrophilic inorganic compound (D1) and a hydrophilic organic compound (D2).
The agricultural film according to claim 1 or 2, further comprising an organic electrolyte (D4). 4. The resin (C) comprises a hindered amine-based stabilizer (E) and an ethylene / α-olefin copolymer (A) or an ethylene / α-olefin copolymer (A) in a high pressure method. Mixture 1 with high density polyethylene (B)
The agricultural film according to any one of claims 1 to 3, wherein the amount is 0.005 to 5 parts by weight based on 00 parts by weight. 5. The resin (C) contains an inorganic compound (F) containing at least one atom of Mg, Ca, Al and Si as an ethylene / α-olefin copolymer (A),
2. The composition of claim 1, wherein the content is 0.03 to 25 parts by weight based on 100 parts by weight of the mixture of the ethylene / α-olefin copolymer (A) and the high-pressure low-density polyethylene (B). 5. The agricultural film according to any one of items 1 to 4. 6. The thermoplastic resin film layer [I] has a thickness of 3 to 250 μm.
The agricultural film according to any one of the above. 7. A thermoplastic resin film having a property different from that of the resin (C) forming the thermoplastic resin film layer [I] is formed on one surface of the thermoplastic resin film layer [I]. One or more film layers are formed, and a coating layer of the surface-coating type anti-fogging agent composition (D) is formed on the surface of the thermoplastic resin film layer [I] opposite to the film layer. The agricultural film according to any one of claims 1 to 6, wherein the film is made.