JPH11322965A - Agricultural polyolefinic resin film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prepare an agricultural polyolefinic resin film excellent in transparency, dust-proofing property, anti-fogging property and anti-fogging persistence. SOLUTION: The objective film comprises a film layer comprising 100 pts.wt. of a linear low density polyethylene, obtained by the copolymerization of ethylene and an α-olefin in the presence of a metallocene catalyst, and three ingredients admixed therewith; 0.01-1 pt.wt. of a fluorine-containing compound, 0.1-5 pts.wt. of a nonionic surfactant and 0.05-3 pts.wt. of a fatty acid amide compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an agricultural film. More specifically, the present invention relates to an agricultural polyolefin resin film having excellent transparency, dust resistance, antifogging property and antifogging durability.

[0002]

2. Description of the Related Art In recent years, in order to increase marketability and productivity of agricultural crops by semi-forcing or suppressing cultivation, agricultural vinyl chloride films, polyethylene, ethylene-vinyl acetate copolymers, and polyolefin-based resins have been developed. BACKGROUND ART So-called house cultivation and tunnel cultivation in which useful crops are cultivated under an agricultural covering material such as a special film as a main component are actively performed. Above all, special films mainly composed of polyolefin-based resins do not contain a plasticizer in the film and have a stable chemical structure. In recent years, they have been widely used because they do not generate gas and are inexpensive.

However, among polyolefin-based resins, for example, a method of laminating a branched low-density polyethylene produced by a high-pressure radical method as a base layer as described in Japanese Patent Application Laid-Open No. 63-149147 discloses the transparency of a film. Is not sufficient. On the other hand, for example, Japanese Patent Publication No. 63-65026 proposes a method of laminating linear polyethylene as a substrate layer, but it has not been satisfactory. Then, in recent years, for example,
As a new linear low-density PE disclosed in Japanese Patent No. 52332, a method of laminating a copolymer of ethylene and an α-olefin as a substrate layer using a metallocene catalyst has been proposed. Although the film obtained by this method has improved transparency, when used in a house, the anti-fogging property that prevents fogging due to water droplets condensed on the film surface due to the temperature difference inside and outside the house and the humidity inside the house has long-term performance. There was a problem that it did not lead to maintenance.

[0004]

That is, the gist of the present invention is that 100 parts by weight of a linear low-density polyethylene obtained by copolymerizing ethylene and an α-olefin in the presence of a metallocene catalyst. 0.01 to 1 part by weight of a fluorine-containing compound A, 0.1 to 5 parts by weight of a nonionic surfactant B, and 0.05 to 3 parts by weight of a fatty acid amide compound C And an agricultural polyolefin resin film having a layer formed into a film.

[0005]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
The linear low-density polyethylene (hereinafter, referred to as "metallocene polyethylene") obtained by copolymerizing ethylene and an α-olefin in the presence of the metallocene catalyst in the present invention is disclosed in JP-A-6-9724. JP-A-6-13
No. 6195, JP-A-6-136196, JP-A-6-207057, including a metallocene catalyst component described in JP-A-9-57916, etc., in the presence of a so-called metallocene-based olefin polymerization catalyst, Ethylene is copolymerized with an α-olefin having 3 to 12 carbon atoms such as butene-1,4-methylpentene-1 and octene, and the resulting copolymer has a density of 0.880 to 0.94.
0 g / cm ³ , melt flow rate (MFR) 0.3 to
It was prepared to be 3 g / 10 minutes.

This copolymer is prepared by the method described in (Method A)
9309, JP-A-59-95292, JP-A-60-95292
No. 35005, JP-A-60-35006, JP-A-60-60
JP-A-35007, JP-A-60-35008, JP-A-6-1985
Nos. 0-35009, JP-A-61-130314 and JP-A-3-1630088, European Patent Application Publication No. 420436, U.S. Pat.
No. 38, International Patent Publication WO91 / 04257 and the like, that is, metallocene catalysts, particularly metallocene-alumoxane catalysts, or disclosed in, for example, International Publication WO92 / 01723 and the like. Such a catalyst comprising a metallocene compound and a compound which becomes a stable ion by reacting with the metallocene compound, or further disclosed in JP-A-5-295020 and JP-A-5-252.
Using a catalyst in which a metallocene compound is supported on an inorganic compound, such as described in
The ethylene of the main component and the α-olefin having 4 to 20 carbon atoms of the subcomponent have a density of 0.880 to
This is a method in which copolymerization is performed so as to be 0.930 g / cm ³ . Examples of the polymerization method include a high-pressure ion polymerization method, a solution method, a slurry method, and a gas phase method. Among these, it is preferable to produce by a high pressure ionic polymerization method.

The high-pressure ionic polymerization method is described in JP-A-56-18607 and JP-A-58-25106, and the pressure is at least 100 kg / cm ² , preferably at least 300 kg / cm ^2. It is produced by high-pressure ion polymerization under the reaction conditions of 1500 kg / cm ² and a temperature of 125 ° C. or more, preferably 150 to 200 ° C.
On the other hand, ethylene-α called metallocene polyethylene
As a method for producing an olefin copolymer, for example, (B
Method) JP-A-6-9724, JP-A-6-136195
JP-A-6-136196, JP-A-6-20705
An olefin polymerization catalyst comprising a metallocene catalyst component, an organoaluminum oxy compound catalyst component, a fine particle carrier, and, if necessary, an organoaluminum compound catalyst component and an ionized ionic compound catalyst component described in each of the publications of No. 7 In the presence of, ethylene and α-olefin, specifically α-olefin having 3 to 20 carbon atoms, under various conditions in a gas phase, or a liquid phase in a slurry or a solution, to obtain a copolymer obtained Of 0.900 to 0.9
Although it can be prepared by copolymerization to give a concentration of 30 g / cm ³ , the above method (A) is preferred in that good initial transparency and transparency persistence in a film, which is the main object of the present invention, is obtained. Is more preferred.

The metallocene polyethylene obtained by the method (A) is fractionated by elution at elevated temperature (TREF: Temperatutu).
re Rising Elution Fraction
nation) is determined by a differential elution curve obtained by the measurement according to the present invention. That is, there is one peak of the elution curve obtained by the temperature-rise elution fractionation, and the peak temperature is in the range of 20 to 100 ° C, preferably 40 to 80 ° C. In addition, the substance eluted at a temperature other than the elution temperature of the peak temperature may substantially exist in the elution curve. If there are two or more peaks within the peak temperature of the elution curve, the transparency becomes poor.
If not present, the film will be sticky.

Elution by temperature rise elution fractionation (TREF)
Curve measurement The above-mentioned temperature rise elution fractionation (Temperature Ri)
sing Elution Fractionation
n: TREF) is described in “Journ
al of Applied Polymer Sci
ence. Vol 126, 4, 217-4, 231
(1981) "," Polymer Symposium Proceedings 2P1C09 "
(1988) ”and the like. That is, the target polyethylene is first completely dissolved in a solvent. Then cool down,
Generate a thin polymer layer on the surface of the inert carrier. Such a polymer layer is formed such that an easily crystallizable material is formed on the inner side (a side close to the surface of the inert carrier), and a hardly crystallizable material is formed on the outer side. Next, by elevating the temperature continuously or stepwise, first, at a low temperature, it elutes from an amorphous portion in the target polymer, that is, from a polymer having a large degree of short-chain branching of the polymer. As the elution temperature rises, the one with a low degree of branching gradually elutes, and finally the linear portion without branching elutes, ending the measurement. The concentration of the eluting component at each temperature is continuously detected, and the composition distribution of the polymer can be measured by the peak of a graph (elution curve) drawn by the elution amount and the elution temperature. The ethylene-α-olefin copolymer constituting the outer layer of the laminated film of the present invention has the following physical properties.

Melt flow rate (MFR) MFR measured according to JIS-K7210 is 0.01
-10 g / 10 min, preferably 0.1-5 g / 10 min,
More preferably, it shows a value of 0.3 to 3 g / 10 minutes. If the MFR is larger than this range, the film will meander during molding and will not be stable. On the other hand, if the MFR is smaller than this range, the resin pressure during molding increases and a load is applied to the molding machine. Therefore, it is necessary to reduce the production amount and suppress the increase in pressure, which is not practical.

[0011]density The density measured by JIS-K7112 is 0.880
~ 0.940 g / cm ^Three, Preferably 0.880-0.
930 g / cm^Three, More preferably 0.880 to 0.9
20g / cm^ThreeIt shows the value of. The density is in this range
If it is larger than the surroundings, the transparency deteriorates. Also, if the density is in this range
If it is smaller than the box, the film
Kings occur and the utility becomes poor.

Molecular weight distribution gel permeation chromatography (GPC)
Molecular weight distribution (weight average molecular weight / number average molecular weight) determined by (1) is 1.5 to 3.5, preferably 1.5 to 3.
It indicates a value of 0. If the molecular weight distribution is larger than this range, the mechanical strength decreases, which is not preferable. If the molecular weight distribution is smaller than this range, the film will meander during molding and will not be stable.

[0013] The linear ethylene α- used in the present invention
Polyethylene other than the linear ethylene / α-olefin copolymer (eg, high-pressure low-density polyethylene, medium-density polyethylene, high-density polyethylene, etc.), ethylene / vinyl acetate copolymer, etc. are used in combination with the olefin copolymer. By doing so, film formability and film strength,
Flexibility can be improved. In that case, 100 to 30 parts by weight of the metallocene polyethylene, 0 to 70 parts by weight of the other polyethylene, preferably 99 to 60 parts by weight of the metallocene polyethylene, 1 to 40 parts by weight of the other polyethylene.
It can be used together with parts by weight.

In the present invention, as the fluorine-containing compound A, conventionally used fluorine-based surfactants or copolymerized oligomers can be used. For example,
Examples include compounds represented by the following general formula.

[0015]

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[0016]

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Copolymerization oligomer (1) CF ₃ (CF ₂ ) ₆ (CH ₂ ) ₂ OCOC (CH ₃ ) =
CH ₂ and C ₂ H ₅ OCOCH = CH ₂ and HO (CHCH
O) ₂ OCOCH = CH ₂ and the weight ratio 1:
Copolymerization oligomer having a molecular weight of about 4000, polymerized in a ratio of 0.1: 1.5 Copolymerization oligomer (2) CF ₃ (CF ₂ ) ₇ SO ₂ N (CH ₃ ) (CH ₂ ) ₂ O
COC (CH ₃ ) = CH ₂ and CH ₃ OCOCH = CH ₂
And HO (CHOCHO) ₃ OCOCH ＝ CH ₂ were polymerized at a charge weight ratio of 1: 0.5: 0.5, a copolymerized oligomer having a molecular weight of about 4000, and a copolymerized oligomer (3) CF ₃ (CF ₂ ) ₈ CONH (CH ₂ ) ₂ OCOC (C
H ₃ ) = CH ₂ CH ₃ OCOCH = CH ₂ and HO (CH
(CHO) ₁₀ OCOCH ＝ CH ₂ and a copolymerized oligomer having a molecular weight of about 2000 and a copolymerized oligomer (4) CF ₃ (CF ₂ ) ₈ (CH ₂ ) ₂ OCOCH = CH ₂ and C ₃ H ₇ OCOCH = CH ₂ and HO (CHCHO) ₃ O
COCH = CH ₂ was added at a charge weight ratio of 1: 0.1: 1.
Copolymerized oligomer having a molecular weight of about 2000, which was polymerized at a ratio of

[0018]

Embedded image

And C ₂ H ₅ OCOCH = CH ₂ and HO (C
HCHO) ₃ OCOCH ＝ CH ₃ and a copolymerized oligomer having a molecular weight of about 6000, wherein Rf is a linear or branched polyfluoropolymer, prepared by polymerizing at a charge ratio of 1: 0.2: 1. An alkyl group, R represents an alkyl group, n
Represents a natural number. )

The polyfluoroalkyl group contained in the fluorine-containing compound represented by the above general formula includes a carbon atom having 6 carbon atoms.
~ 12 are particularly preferred. The fluorine-containing compound A used in the present invention can be used alone or in combination of two or more. The amount of the fluorine-containing compound A to be mixed with the polyolefin resin substrate can be changed according to the type of the fluorine-containing compound to be mixed, the type of the base polyolefin resin, and the like. It is 01 to 1 part by weight. If the amount is less than this range, the kneading process of the base polyolefin-based resin becomes non-uniform, and the transparency after film formation is poor. On the other hand, if the amount is more than this range, the amount of jets to the film surface increases, and the transparency is lowered and the antifogging property is adversely affected.

The nonionic surfactant B used in the present invention includes, for example, sorbitan monomyristate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monobehenate and / or sorbitan monostearate.
Sorbitan surfactants such as 1 to 5 moles of alkylene oxide adducts; glycerin monopalmitate, glycerin monostearate, glycerin dipalmitate, glycerin distearate, diglycerin monostearate, diglycerin monobehenate, diglycerol monostearate Glycerin dipalmitate, diglycerin distearate, diglycerin monopalmitate monostearate, triglycerin monostearate, triglycerin distearate, triglycerin tristearate and / or 0.1 to 5
A glycerin-based surfactant such as a molar alkylene oxide adduct; polyethylene glycol monostearate;
Polyethylene glycol surfactants such as polyethylene glycol monopalmitate; trimethylolpropane surfactants such as trimethylolpropane monostearate; pentaerythritol surfactants such as pentaerythritol monopalmitate; alkyl phenol alkylene oxide adducts An ester of a sorbitan / glycerin condensate with a fatty acid, an ester of a sorbitan / alkylene glycol condensate with a fatty acid, alkylenediethanolamines, alkyldiethanolamides, and the like, alone or in combination of two or more. Can be used.

Particularly, surfactants that are advantageous for the present invention include sorbitan and / or glycerin surfactants such as sorbitan monostearate, glycerin monostearate, and diglycerin distearate.
The compounding amount of such an antifogging agent is in the range of 0.1 to 5 parts by weight. When the amount is less than 0.1 part by weight, the antifogging property is not sufficiently exhibited, and when the amount exceeds 5 parts by weight, bleed out is easily caused,
It is not preferable because the transparency and the dust resistance of the film are reduced.

The fatty acid amide compound compounded as the component C, together with the component A at the time of molding, improves the kneading stability and maintains the transparency of the film. For example, stearic acid amide, palmitic acid amide, methylene bis-stearamide, ethylene bis-stearamide,
Oleic acid amide, esylic acid amide, ethylenebislaurylamide and the like can be mentioned. The compounding amount of the component C is 0.05 to 3 based on 100 parts by weight of the base polyolefin resin.
Parts by weight. If the amount is less than 0.05 parts by weight, kneading at the time of molding is not stable, and the transparency of the film is not sufficient.

On the other hand, if the amount exceeds 3 parts by weight, the amount of jet to the surface is increased, and there is a problem that transparency is impaired and expression of antifogging property is impaired. The agricultural polyolefin resin film of the present invention, the following various additives as required, for example, a light stabilizer, an ultraviolet absorber, a stabilizer, an antioxidant, a stabilizing auxiliary, a warming agent, an antistatic agent, An anti-blocking agent, a coloring agent and the like can be added.

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. As the hindered amine-based stabilizer, specifically, the following compounds are used.

Dimethyl succinate-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, poly [{6- (1,1,3,3)
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}], bis (1,2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate
2,2,6,6-pentamethyl-4-piperidyl),
1,5,8,12-tetrakis [4,6-bis {N-
(2,2,6,6-tetramethyl-4-piperidyl) butylamino {-1,3,5-triazin-2-yl]-
1,5,8,12-tetraazadodecane, bis (2,
2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1-n-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,
2,2,6,6-pentamethyl-4-piperidyl) sebacate, 1- [2- {3- (3,5-di-t-butyl-
4-hydroxyphenyl) propionyloxy {ethyl] -4- {3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy} -2,2,6
6-tetramethylpiperidine, 4-benzoyloxy-
2,2,6,6-tetramethylpiperidine, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-
1,3,8-Triazaspiro [4.5] decane-2,4
-Dione, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (2,2,6,6-tetramethyl-4- Piperidyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6
-Pentamethyl-4-piperidyl) di (tridecyl)
-1,2,3,4-butanetetracarboxylate, bis (2,2,6,6-tetramethyl-4-piperidyl)
Di (tridecyl) -1,2,3,4-butanetetracarboxylate, 3,9-bis [1,1-dimethyl-2
-{2,3,4-tris (1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl) butylcarbonyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5.5 ] Undecane, 3,9-bis [1,
1-dimethyl-2- {2,3,4-tris (2,2,
6,6-tetramethyl-4-piperidyloxycarbonyl) butylcarbonyloxydiethyl] -2,4,8,
And 10-tetraoxaspiro [5.5] undecane.

Among them, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1-n-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, Bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxy Rate, tetrakis (2,2,6,6-tetramethyl-4-
Piperidyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-
4-piperidyl) di (tridecyl) -1,2,3,4
-Butanetetracarboxylate, bis (2,2,6,
6-tetramethyl-4-piperidyl) .di (tridecyl) -1,2,3,4-butanetetracarboxylate is preferred, and bis (2,2,6,6) is particularly preferred.
-Tetramethyl-4-piperidyl) sebacate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (2,2,6) 6-tetramethyl-4-
Piperidyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-
4-piperidyl) di (tridecyl) -1,2,3,4
-Butanetetracarboxylate. These hindered amine compounds may be used alone or in combination of two or more.

Examples of the compounds that can be used as an ultraviolet absorber include the following. Benzotriazole UV absorber-2- (2'-hydroxy-
3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-
3'-tert-butyl-5'-methylphenyl) -5
-Chlorobenzotriazole, 2- (2'-hydroxy-3'-tert-amyl-5'-isobutylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-isobutyl-5'-methyl Phenyl)
-5-chlorobenzotriazole, 2- (2'-hydroxy-3'-isobutyl-5'-propylphenyl)-
5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- [ 2'-hydroxy-5 '-(1,1,3,3-tetramethylbutyl)
Phenyl] benzotriazole.

Benzophenone UV absorber-2,2 '
-Dihydroxy-4-methoxybenzophenone, 2,
2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-octo Xybenzophenone,

Salicylic acid-based ultraviolet absorbers-Phenyl salicylate and paraoctylphenyl salicylate ultraviolet absorbers can be used alone or in combination of two or more. Among those exemplified above, benzotriazole-based ultraviolet absorbers and benzophenone-based ultraviolet absorbers are particularly preferred.

Compounds that can be used as stabilizers include
Dibutyltin dilaurate, dibutyltin maleate ester, dioctyltin mercaptide, calcium stearate, barium stearate, zinc stearate,
Examples include calcium laurate, barium ricinoleate, calcium oleate, zinc octoate and the like. These stabilizers can be used alone or in combination of two or more.

Compounds usable as antioxidants include 2,6-di-tert-butyl-4-methylphenol, 2,2'-methylenebis (6-tert-butyl-4-ethylphenol), dilauryl Thiodipropionate and the like can be mentioned. These antioxidants can be used alone or in combination of two or more.

Compounds which can be used as a stabilizing aid include triphenyl phosphite, dioctyl phenyl phosphite, tris (nonylphenyl) phosphite,
Diphenylisodecyl phosphite, trilauryl trithiophosphite, diphenyl acid phosphite,
Dioctyl acid phosphite and the like can be mentioned. These stabilizing aids can be used alone or in combination of two or more.

As the heat insulating agent, Mg, Ca, Al and
Inorganic compounds containing at least one atom of Si are listed.
I can do it. For example, Mg, Ca, A effective as a heat insulator
Inorganic acid containing at least one atom of l and Si
Compounds, inorganic hydroxides, hydrotalcites, etc.
You. Specifically, SiO_Two, Al_TwoO_Three, MgO, Ca
Inorganic oxides such as O; Al (OH)_Three, Mg (O
H)_Two, Ca (OH)_TwoAn inorganic hydroxide such as²⁺
_1-xAlx (OH)_Two(A^n-) X / n · mH_TwoO [wherein
M ²⁺Is a divalent metal ion of Mg, Ca or Zn.
A^n-Is Cl^-, Br^-, I^-, NO_Three ^2-, Cl
O^Four-, SO_Four ^2-, CO_Two ^2-, SiO_Three ^2-, HPO_Four ^2-,
HBO_Three ^2-, PO_Four ^2-And x is 0 <
It is a numerical value satisfying the condition of x <0.5, where m is 0 ≦ m
Is a numerical value satisfying the condition of ≦ 2].
Hydrotalcites such as compounds and their calcined products are listed.
I can do it. Among these, hydrotalcites are preferred.
More preferably, a fired product of the inorganic composite compound represented by the above formula
Is preferred. The above-mentioned inorganic compounds may be used alone or in combination.
These can be used in combination.

Examples of the compound which can be used as an antistatic agent include polyoxyethylene alkylamine, polyglycol ether, sodium p-styrenesulfonate and the like. These antistatic agents can be used alone or in combination of two or more.

The above various additives can be used alone or in combination of two or more. The amount of the various additives is in a range that does not deteriorate the performance of the film, and is usually per 100 parts by weight of the base olefin resin.
It can be selected in a range of 5 parts by weight or less. To compound the base polyolefin resin with the fluorine-containing compound A, the nonionic surfactant B, the fatty acid amide compound C, and various additives, weigh each necessary amount, and use a Banbury mixer or a uniaxial or biaxial It is effective to obtain melt-kneaded pellets by a conventionally known method using a kneading extruder or the like. In order to form the resin composition thus obtained into a film, conventionally known methods such as a melt extrusion molding method (including a T-die method and an inflation method) and a calender molding method are known. According to the method.

Although such a film may be a single layer, a laminated film may be formed in order to exhibit good dustproofness, heat retention, flexibility and strength. In this case, for example, the outer layer,
In a three-layer film having an intermediate layer and an inner layer,
1) Examples of using a layer containing the metallocene polyethylene according to the present invention and components A, B and C for the outer layer, 2) Examples for the intermediate layer, 3) Examples for the inner layer, 4) Examples for the intermediate layer and the inner layer, 5) Examples used for the outer layer and the intermediate layer, 6) examples used for the outer layer and the inner layer, and 7) examples used for the outer layer, the intermediate layer, and the inner layer. In particular, metallocene polyethylene, A, B, and C
The above-mentioned embodiments 3), 4), 6) and 7) in which the components are used for the inner layer are preferred. Incidentally, when the film is actually stretched and used, the outer surface of a house, a tunnel or the like is referred to as an outer layer, the inner surface is referred to as an inner layer, and the intermediate layer is referred to as an intermediate layer.

Examples of the resin constituting the other layer include other polyethylenes such as general linear low-density polyethylene, high-pressure low-density polyethylene, medium-density polyethylene, and high-density polyethylene, and ethylene-α-olefin copolymers. , An ethylene / vinyl acetate copolymer having a vinyl acetate content of 30% by weight or less, and a resin mixture thereof;
Especially linear low density polyethylene, low density polyethylene,
An ethylene / vinyl acetate copolymer is preferred.

In the case of a three-layer structure, at least the inner layer is made of a resin in which three components of a fluorine-containing compound A, a nonionic surfactant B, and a fatty acid amide compound C are essentially blended in order to exhibit the desired performance. Is preferably configured,
Further, other layers may contain these compounding agents.

The film according to the present invention may be transparent, satin-finished or semi-matted, and can be used for covering agricultural houses (greenhouses), tunnels, etc., as well as for mulching and bagging. Can be used. The thickness of the film is preferably in the range of 0.03 to 0.3 mm in terms of strength and cost, and more preferably 0.05 to 0.2 mm.

[0041]

The agricultural polyolefin resin film of the present invention is excellent in all performances such as molding stability, transparency, dustproofness, antifogging durability and the like, and is useful as an agricultural film. Extremely high.

[0042]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist.

Examples 1 to 7 Comparative Examples 1 to 8 As a three-layer inflation molding device, 100
mmφ (Pura Koken Co., Ltd.), the extruder used was 30 mmφ outer and inner layers (Pura Giken Co., Ltd.), and the middle layer was 40 m.
mφ (manufactured by Pla Giken Co., Ltd.) at a molding temperature of 170 ° C., a blow ratio of 2.0, and a take-up speed of 5 m / 2 min. A film was obtained. The following evaluation tests were performed on each of the obtained films. The results are shown in Tables 3-1 to 3-2.

1) Transparency Test The film obtained by the present invention was measured for its straight-line light transmittance at a wavelength of 555 mm by a spectrophotometer (3, manufactured by Hitachi, Ltd.).
30 type) and the value was shown.

2) Low-temperature antifogging property 300 cc of water (15 ° C.) was placed in a 500 cc beaker, covered with a sample film, and then placed in a constant temperature water bath (15 ° C.).
(° C.), the beaker was inclined at 10 ° from the ground surface to be immersed in water from the low part to ２, and left in a constant temperature room at 0 ° C. for a predetermined time to visually observe the state of the film surface. The state of flow of water droplets on the film surface was evaluated according to the following criteria. ：: No droplet (micro water droplet) portion ×: Dropped portion is 10% or less △: Dropped portion is 30% or less ×: Dropped portion exceeds 40%

3) Antifogging durability 300 cc of water (45 ° C.) was placed in a 500 cc beaker, covered with a sample film, and then placed in a constant temperature water bath (45 ° C.).
(° C.), the beaker was tilted at 10 ° from the ground surface and immersed in water from the low part to ２, and left in a constant temperature room at 25 ° C. for a predetermined time to visually observe the state of the film surface. The flow condition of water droplets on the film surface was evaluated according to the same criteria as the low-temperature anti-fog property.

4) Dustproofness The sample film was coated on a pipe house (3m wide, 5m deep, 1.5m high, ridge height 30 °) installed in a test field in Isshi-gun, Mie, from January 1997 to 1997. Year 12
The extension test was performed for 12 months until the month. The film after the test was collected, and the parallel light transmittance at a wavelength of 555 mm was measured with a spectrophotometer (model 330, manufactured by Hitachi, Ltd.). The criteria for the measurement results were as follows. A: Light transmittance of 75% or more. Good: Light transmittance in the range of 65 to 74%. ×: Light transmittance in the range of 55 to 64%. Δ: Light transmittance in the range of 40 to 54%. C: Light transmittance of less than 40%.

[0048]

[Table 1]

[0049]

[Table 2]

MePE kernel 65FI: Ethylene / α-olefin metallocene linear polyethylene manufactured by Nippon Polychem Co., Ltd. (by Method A) LLPE Novatec UF240: Linear polyethylene LPE Novatec LF240 manufactured by Nippon Polychem Co., Ltd .: Nippon Polychem ( Branched polyethylene EVA Novatec LV420: Nippon Polychem Co., Ltd. E
VA DHT-4A: Hydrotalcite UV531 manufactured by Kyowa Chemical Industry Co., Ltd. Benzophenone UV absorber manufactured by Cytec Co., Ltd. Chimassorb 944: Light stabilizer manufactured by Ciba Geigy Co., Ltd.

[0051]

[Table 3]

[0052]

[Table 4]

MePE kernel 65FI: Ethylene / α-olefin metallocene linear polyethylene LLPE Novatec UF240 manufactured by Nippon Polychem Co., Ltd. Linear polyethylene LPE Novatec LF240 manufactured by Nippon Polychem Co., Ltd. Branched product manufactured by Nippon Polychem Co., Ltd. Polyethylene EVA Novatec LV420: E manufactured by Nippon Polychem Co., Ltd.
VA DHT-4A: Hydrotalcite UV531 manufactured by Kyowa Chemical Industry Co., Ltd. Benzophenone ultraviolet absorber manufactured by Cytec Co., Ltd. Chimasorb 944: Hindered amine light stabilizer manufactured by Ciba Geigy Co., Ltd.

[0054]

[Table 5]

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C08L 23/08 C08L 23/08 // (C08L 23/08 101: 04) (72) Inventor Sadao Yamada Nakamura-ku, Nagoya-shi, Aichi No. 2 Oike, Iwatsuka-cho, Nagoya Office of Mitsubishi Chemical MKV Co., Ltd. (72) Inventor Atsushi Obayashi No. 2, Oiketsu, Iwatsuka-cho, Nakamura-ku, Nagoya-shi, Aichi Pref.

Claims (2)

[Claims] 1. A fluorine-containing compound in an amount of 0.01 to 1 part by weight based on 100 parts by weight of a linear low-density polyethylene obtained by copolymerizing ethylene and an α-olefin in the presence of a metallocene catalyst. A, comprising a layer formed by mixing three components of A, 0.1 to 5 parts by weight of a nonionic surfactant B, and 0.05 to 3 parts by weight of a fatty acid amide compound C and forming a film. Agricultural polyolefin resin film. 2. An agricultural polyolefin resin film having a multilayer structure having at least an outer layer, an intermediate layer and an inner layer, wherein at least the inner layer is the layer according to claim 1. Polyolefin resin film.