JP3074061B2 - Agricultural laminated film and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an agricultural laminated film and a method for producing the same. More specifically, the present invention is an agricultural laminate excellent in heat resistance, impact resistance, tear resistance, piercing resistance, cold resistance and high transparency, and particularly excellent in friction resistance and weather resistance of the film surface. The present invention relates to a film and a method for producing the film, and the film of the present invention is used for house cultivation, tunnel cultivation, and mulch cultivation for the purpose of forcing cultivation for agriculture.

[0002]

2. Description of the Related Art Agricultural films conventionally used in house cultivation, tunnel cultivation, and the like include mainly polyvinyl chloride films, high-pressure low-density polyethylene films, and linear low-density polyethylene films. it can.

[0003] A polyvinyl chloride film is excellent in transparency, toughness, durability, heat retention, economy, workability, etc. However, since it contains a plasticizer, if it is used for a long time, it will bleed onto the film surface. However, dust is adsorbed here, lowering the light transmittance and giving a dirty feeling, which is not desirable.
Furthermore, if the polyvinyl chloride film is to be treated by incineration after use, hydrogen chloride gas will be generated, which may cause pollution problems.It is also susceptible to piercing and tearing by the protrusions, and is resistant to friction with house aggregate. It was weak and had poor cold resistance, and often became a problem depending on the use conditions.

A high-pressure low-density polyethylene film, unlike a polyvinyl chloride film, does not generate hydrogen chloride gas when incinerated and does not use a plasticizer, which causes pollution problems, reduced light transmittance, and contamination due to dust. Although there is no advantage, since the crystallinity is about 40%, the light transmittance (transparency) is slightly inferior. In addition, since the film is charged or moisture adheres to the film surface, if an antistatic agent or an antifogging agent is added, it bleeds on the film surface, adsorbs dust, and has a drawback of lowering light transmittance.

[0005] The linear low-density polyethylene film is similar to the high-pressure low-density polyethylene film in the above properties, but is excellent in mechanical strength.
Since the thickness of the film can be reduced and the economic effect is great,
Although it has come to be widely used as an agricultural film, it has a problem in that light transmittance is low due to high crystallinity. In addition, these polyethylene-based films do not have a polar group in the molecule and thus do not have an infrared absorbing ability, and therefore dissipate infrared energy radiated from plants and soil in a greenhouse at night to the outside world, and lack heat insulation. There is.

The applicant of the present invention has improved the disadvantages of a polyvinyl chloride film and a polyethylene film, which have been conventionally used as agricultural films, while improving the disadvantages of the films. No need for plasticizers, no need to use plasticizers, excellent agricultural films with excellent piercing resistance, resistance to rubbing, cold resistance, light transmission (high transparency), mechanical strength, and processability, and methods for producing the same. (Japanese Patent Application No. 3-25752). However, in the invention according to the earlier application, no consideration is given to the friction resistance and the weather resistance for suppressing the bulging of the film surface, and this point is insufficient. If the surface of the film is scuffed, the light transmittance is deteriorated, dust adheres to the sprinkled portion, and the light transmittance is further deteriorated. Further, there is a problem that the weather resistance is deteriorated due to these factors.

[0007]

DISCLOSURE OF THE INVENTION The present invention is directed to use as an agricultural film, while maintaining the excellent properties of the agricultural film according to the above-mentioned application, and further improving the friction resistance and weather resistance of the surface. It is an object of the present invention to provide an agricultural film with further enhanced value and a method for producing the same.

[0008]

The present inventors have developed a laminated film comprising an intermediate layer made of an ultra-low-density ethylene-α-olefin copolymer and both outer layers made of an ethylene-vinyl acetate copolymer (Japanese Patent Application No. It was noticed that the application of cross-linking to the surface of No. 3-25752 would improve the friction resistance of the surface, and an organic peroxide was blended with the ethylene-vinyl acetate copolymer to form a press sheet. When the crosslinked sheet was prepared and heated, the friction resistance of the surface was examined. As a result, good results were obtained without any crushing on the surface. However, in the method of blending an organic peroxide, a laminated sheet cannot be industrially produced in large quantities at low cost. For this reason, cross-linking only the ethylene-vinyl acetate copolymer of the surface layer, and earnestly researched for another method for producing a laminated film in a large amount and at a low cost, the water cross-linking method known per se was determined. The present inventors have found that the above problems can be solved by applying the present invention, and have completed the present invention.

[0009] That is, the present invention provides a density of 0.910 g / m
1 or less, melting point 116 ° C. or more, 1% modulus 1200 k
g / cm ² or less, n-hexane extractables 10% by weight or less,
An intermediate layer made of an ultra-low density ethylene-α-olefin copolymer having a melt index of 0.8 to 10 g / 10 minutes, and a melt index of 0.5 to 5 g / 10 minutes and a vinyl acetate content of 5 to 15% by weight. An unsaturated alkoxysilane and an organic peroxide are added to an ethylene-vinyl acetate copolymer to form a silicone-grafted silicone-grafted ethylene-vinyl acetate copolymer. Wherein the thickness of the intermediate layer is at least 35 to 90 times the thickness of the entire laminated film.
%, And the total thickness of the laminated film is 50 to 200 μm.
It relates to an agricultural laminated film characterized by the following.

[0010] The present invention also relates to a method for producing a composition having a density of 0.910 g / ml.
Below, melting point 116 ° C or higher, 1% modulus 1200 kg
/ Cm ² or less, n-hexane extractables 10% by weight or less, melt index of 0.8 to 10 g / 10 minutes, an intermediate layer made of an ultra-low density ethylene-α-olefin copolymer, and a melt index of 0.5 to Silicone-grafted ethylene-vinyl acetate obtained by adding unsaturated alkoxysilane and an organic peroxide to an ethylene-vinyl acetate copolymer having a vinyl acetate content of 5 to 15% by weight at a rate of 5 g / 10 minutes. The present invention relates to a method for producing a laminated agricultural film, which comprises co-extruding both outer layers made of a copolymer and then performing water crosslinking.

In the present invention, the ultra-low density ethylene-
The α-olefin copolymer is a continuous production method of the following ethylene copolymer: (a) higher α-olefin: ethylene molar ratio in a fluidized bed reaction zone at a temperature of 10 to 80 ° C. and a pressure of 7000 kPa or less. Is 0.35: 1 to 8.0: 1
A gas mixture comprising ethylene and at least one higher α-olefin having 3 to 8 carbon atoms and (b) at least 25 mol% of at least one diluent gas is obtained by the following formula: Mg _m Ti (OR) _n X _p [ED] _q (where R represents an aliphatic or aromatic hydrocarbon group having 1 to 14 carbon atoms or a group COR ′, and R ′ represents an aliphatic having 1 to 14 carbon atoms. Or an aromatic hydrocarbon group;
Is selected from the group consisting of chlorine, bromine, iodine and mixtures thereof, and ED is an organic selected from the group consisting of alkyl esters of aliphatic or aromatic acids, aliphatic ethers, cyclic ethers and aliphatic ketones. Represents an electron donating compound, m is 0.5 to 56, n is 0, 1 or 2, p is 2 to 116, and q is 2 to 85. ) Is continuously contacted with particles of a catalyst system comprising the precursor composition represented by the formula (1), and the precursor composition is diluted with an inert carrier material and the following formula: Al (R ') _d X' _e H _f (Wherein X ′ represents a chlorine atom or a group OR ″, R ′ and R ″ represent a saturated hydrocarbon group having 1 to 14 carbon atoms, e is 0 to 1.5, f is 0 or 1 and d
+ E + f = 3. ) Is completely activated with the organoaluminum compound represented by the formula (1), and the activated compound has a total aluminum: titanium molar ratio of 10:
It is preferably manufactured by using an amount of 1 to 400: 1.

In the present invention, ultra-low density ethylene-α-
Olefin copolymer (hereinafter also referred to as VLDPE)
Is a special polyethylene resin developed by Union Carbide Chemical and Plastics Company of the United States of America, to which the present inventors belong, and to which the present applicant has a technical tie-up, with Nihon Unicar Co., Ltd. This is described in detail in JP-A-59-230011.

The density of the VLDPE used in the present invention is 0.910 g / ml or less, and when it exceeds this, the crystallinity increases and the transparency of the film deteriorates, which is not desirable. Further, the melting point of VLDPE is 116 ° C. or higher, and if it is lower than this, the heat resistance is insufficient and the mechanical strength is also insufficient. The 1% modulus of VLDPE is 12
It is not more than 00 kg / cm ² , and if it exceeds this, the friction resistance is deteriorated. Further, the extractable amount of n-hexane of VLDPE is 10% by weight or less, and if it exceeds this, the low molecular weight polymer bleeds on the surface of the laminated film, and dust adheres to the film, which is not desirable because it impairs light transmittance. Also, VLDPE
Has a melt index of 0.8 to 10 g / 10 min. If the melt index is less than 0.8 g / 10 min, the extrusion characteristics are poor.
If it exceeds 0 g / 10 minutes, the mechanical properties deteriorate, which is not desirable.

The above-mentioned ethylene used in the present invention
The vinyl acetate copolymer (hereinafter also referred to as EVA) has a melt index of 0.5 to 5 g / 10 min.
If it is less than 5 g / 10 min, the extrusion properties are poor, while 5 g / 10 min.
Exceeding the minutes is undesirable because the mechanical properties deteriorate. Also,
The vinyl acetate content is 5 to 15% by weight, and if it is less than 5% by weight, the transparency of the laminated film deteriorates, and if it exceeds 15% by weight, the laminated film is undesirably blocked.

The relationship between the melting point (MP, unit ° C) of the EVA used in the present invention and the vinyl acetate content (VA, unit weight%) is represented by the following equation: MP = 114-1.44VA It is particularly desirable that the distribution (M _w / M _n ) is less than 4, and those in this numerical range have the same vinyl acetate content and a melting point of 2 to 2 compared to EVA outside the above range.
5 ° C higher, excellent in heat resistance and mechanical strength.

The silicone-grafted ethylene-vinyl acetate copolymer used in the present invention is obtained by adding an unsaturated alkoxysilane and an organic peroxide to the above-mentioned ethylene-vinyl acetate copolymer, and melting the copolymer. It is obtained by heating to the above temperature to generate free radicals in the copolymer and performing silicone grafting.

The unsaturated alkoxysilane is represented by the general formula: RR'SiY _{2 wherein} R is an aliphatic unsaturated hydrocarbon group or a hydrocarbonoxy group reactive with a free radical generated in an ethylene-vinyl acetate copolymer. Represents a group, for example a vinyl, allyl, butenyl, cyclohexenyl or cyclopentadienyl group, Y represents an alkoxy group, for example a methoxy, ethoxy or butoxy group, and R ′ is a hydrogen atom, a group Y Or a monovalent hydrocarbon group containing no olefinic unsaturation).
A vinyl group is particularly preferred as the group R. Preferred unsaturated alkoxysilanes are gamma-methacryloyloxypropyltrimethoxysilane, vinyltriethoxysilane and vinyltrimethoxysilane. The amount of the unsaturated alkoxysilane used is preferably 0.5 to 10 parts by weight based on the weight of the ethylene-vinyl acetate copolymer.

Examples of the organic peroxide include dicumyl peroxide, di-t-butyl peroxide, 2,5-
Di (peroxybenzoate) hexin-3 and the like are used. The amount of the organic peroxide to be used is preferably 0.01 to 2.0 parts by weight based on the weight of the ethylene-vinyl acetate copolymer.

In the present invention, a silanol condensation catalyst such as dibutyltin dilaurate, dibutyltin diacetate or dibutyltin dioctane is used as a catalyst for promoting dehydration condensation between silanols of silicone for water crosslinking of the silicone-grafted ethylene-vinyl acetate copolymer. Tate,
Stannous acetate, cobalt naphthenate, ethylamine, dibutylamine and the like are used. The silanol condensation catalyst is usually blended with the silicone-grafted ethylene-vinyl acetate copolymer, but the outer layer of the co-extruded laminated film may be coated or impregnated with a catalyst solution or dispersion. The amount of the silanol condensation catalyst used is 0.00% based on the weight of the silicone-grafted ethylene-vinyl acetate copolymer.
It is about 1 to 10 parts by weight, preferably 0.1 to 5 parts by weight.

The water cross-linking of the laminated film after co-extrusion in the present invention is carried out by bringing the laminated film into contact with moisture, and is usually at room temperature to 200 ° C., usually at room temperature to 100 ° C.
Of water (liquid or vapor) for about 10 seconds to 10 days, usually about 1 minute to 1 day.

The agricultural laminated film of the present invention can be produced by a co-extrusion molding machine using each of the resin compositions to be the intermediate layer and both outer layers. In this case, for example, an inflation method using a circular die, a T A die method or the like can be applied. The reason for adopting a three-layer structure comprising an intermediate layer and both outer layers in the present invention will be described below. First, if VLDPE alone is used to form a film, the extrusion processability is poor, and even if it is extruded, melt fracture occurs, a film with a smooth surface cannot be obtained, and the produced film has severe blocking and is difficult to handle. Met. If the present inventors co-extrude a resin layer on both sides with VLDPE as an intermediate layer, it is difficult to form VLDPE by itself.
Was found to be able to form a film, and this was employed for the intermediate layer. Next, a specific EV is used as the inner and outer layers of the VLDPE intermediate layer.
The reason why A was adopted is that EVA is superior in transparency as compared with high-pressure low-density polyethylene and the like. However,
In the case of EVA, as the vinyl acetate (VA) content increases, the transparency and the cold resistance increase, but the blocking properties and the mechanical properties are deteriorated.

The thickness of the laminated film of the present invention is 50 to 2
If it is 00 μm and less than 50 μm, the mechanical strength is insufficient, and the handling of the film becomes difficult. If it exceeds 200 μm, the quality becomes excessive, and the economical efficiency is poor and undesirable.
Further, the ratio of the intermediate layer to the entire laminated film, that is, the ratio of the thickness is 35 to 90%, and if it is less than 35%, transparency, mechanical properties, cold resistance, friction resistance, economy, etc. are poor. If it exceeds 90%, coextrusion becomes impossible. The thickness of each of the inner and outer layers may be the same or different, but it is important that each occupy at least 5% of the total thickness of the laminated film to enable co-extrusion.

The heat retention of the laminated film of the present invention is slightly inferior to that of the polyvinyl chloride film, but is mainly EVA.
The more the thickness of the inner and outer layers consisting of is increased, the higher the heat retention. When higher heat retention is required, the following inorganic compound particles generally used as a heat insulator: silicon oxide, anhydrous aluminosilicate, phosphate, sulfate, carbonate, magnesium containing hydroxyl group, aluminate Salt and the like are mixed with the raw material resin. Specifically, hydrated silica, anhydrous silica,
Synthetic silica, aluminum oxide, calcium oxide, zirconium oxide, titanium oxide, magnesium oxide, boron oxide, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, lithium hydroxide, calcium phosphate, magnesium phosphate, zinc carbonate, aluminum carbonate, carbonate Calcium, barium carbonate, magnesium carbonate, lithium carbonate, zinc sulfate, aluminum sulfate, potassium sulfate,
Calcium sulfate, zirconium sulfate, barium sulfate, magnesium sulfate, aluminum silicate gel, aluminosilicate gel and the like are blended. The particle size of these heat insulating agents is about 1 to 10 μm, and the compounding amount with respect to the raw material resin is desirably 10% or less. When the amount of the heat insulating agent is increased, the heat insulating property is enhanced, but the light transmittance (transparency) is decreased. Therefore, it is important to mix the heat insulating agent in consideration of the balance between the two. In addition, other additives that impart excellent performance to each layer of the laminated film of the present invention, such as an antifogging agent and a weather resistance improver, may be added without departing from the object of the present invention. . The VLDPE used in the present invention is superior to other polyolefin-based resins in filling properties such as anti-fogging agents, weather resistance improvers, and other inorganic compound granules. Is one of the advantages of the present invention. Further, when the above-mentioned heat retaining agent is used in combination with an anti-fogging agent and a weather resistance improving agent, the durability of the weather resistance effect is further enhanced.

[0024]

Next, the present invention will be described in more detail with reference to examples. Example 1 Raw material A. Intermediate layer: density 0.903 g / ml, melting point 117 ° C.
1% modulus 950 kg / cm ² , n-hexane extractables 2.8% by weight, melt index (MI) 2 g / 1
The ethylene-butene-1 copolymer, which was 0 minutes, was prepared according to
No. 230011, 100 parts by weight of the copolymer, bis (2,2), a hindered light stabilizer,
(2,6,6-tetramethyl-4-piperidyl) sebacate was blended in an amount of 2 parts by weight to prepare a resin composition. B. Both outer layers a. Preparation of Ethylene-Vinyl Acetate Copolymer An ethylene-vinyl acetate copolymer having a MI of 2 g / 10 min, a vinyl acetate (VA) content of 10% by weight, a melting point of 99.6 ° C., and a molecular weight distribution of 3.5 is produced by high pressure polyethylene production. Prepared using equipment. b. Preparation of Silicone-Grafted Ethylene-Vinyl Acetate Copolymer Dicumyl peroxide 0.15 was added to 100 parts by weight of the ethylene-vinyl acetate copolymer granules prepared in a above.
Parts by weight and 2.0 parts by weight of vinyltrimethoxysilane are mixed by a mixer until the granules are completely covered with the silane, and then the mixture is extruded by a 65 mmφ extruder divided into regions according to the temperature setting of the cylinder. Extrusion was performed under the following conditions to obtain a silicone-grafted ethylene-vinyl acetate copolymer. Cylinder supply section 120 ° C Compressing section 150 ° C Measuring section 180 ° C Screw rotation speed 30 rotations / min Discharge rate 30kg / hour c. Preparation of Silanol Condensation Catalyst Masterbatch 1 part by weight of dibutyltin laurate was added to 100 parts by weight of the silicone-grafted ethylene-vinyl acetate copolymer prepared in b above, and a silanol condensation catalyst masterbatch was prepared by the 65 mmφ extruder. did. d. Preparation of Masterbatch for Weather Resistance Improver 20 parts by weight of the light stabilizer described in a above was added to 100 parts by weight of the silicone-grafted ethylene-vinyl acetate copolymer prepared in b above, and weather resistance was obtained with the 65 mmφ extruder. A masterbatch of a property improver was prepared. e. Preparation of Resin Composition for Both Outer Layers 100 parts by weight of the silicone-grafted ethylene-vinyl acetate copolymer prepared in b above, 3 parts by weight of a master batch of a silanol condensation catalyst prepared in c, and a weather resistance improver prepared in d. Mix 10 parts by weight of master batch,
A resin composition for both outer layers was prepared. Production of laminated film a. Co-extrusion Co-extrusion and rapid cooling were performed using the following apparatus and conditions to produce an inflation film.・ Extrusion equipment: Blown film processing equipment manufactured by Placo Co., Ltd. (40 mm × 3 units, L / D28) ・ Circular three-layer die: φ150 mm, die cap 1.5 m
・ Cooling device: with single lip straight and conical color ・ Discharge rate: 60 kg / hr ・ Die temperature: 190 ° C. ・ Blow ratio: 3.0 b. Water crosslinking The laminated film after co-extrusion is placed in a steam room at 60 ° C. for 1 hour.
The mixture was exposed to steam for an additional 2 hours at 100 ° C. for water crosslinking. The gel fraction was 82%. c. The thickness of the manufactured laminated film intermediate layer was 80 μm, and the thickness of both the outer layer and the inner layer was 10 μm. Evaluation and tear strength of laminated film for agricultural use : 125 kg / cm in vertical direction, 146 k in horizontal direction
g / cm, which is sufficiently practical. Haze (measured according to JIS K-6714): 4.7
, And the transparency is sufficient. Heat resistance (tensile strength measured in an environment at an outside air temperature of 80 ° C.): 55 g / cm ² , which is sufficiently practical. The outside air temperature of 80 ° C. is a temperature at which the film near the steel frame of the agricultural house is exposed in the middle of summer. -Anti-blocking property: load 4 kg / 100 cm ² , 5
When measured under the conditions of 0 ° C. and 7 days, 65 g / 100 c
m ^2, which has sufficient anti-blocking properties.・ Abrasion resistance (weakness resistance) and weather resistance: Expose the laminated film on an outdoor exposure table facing the south side and installed at an angle of 45 ° with respect to the plane (installation location: Kawasaki-ku, Kawasaki-shi). After the passage of years, remove a part of the film, place it on a fixed base, put a weight of 30 g with a bottom area of 5 cm ² with a string on it, and move left and right at a speed of 5 cm / sec. After performing a predetermined number of reciprocating friction motions,
The surface condition was observed. After one year of outdoor exposure, the reciprocating frictional motion of the weight was performed 50 times on the laminated film. However, the surface did not flank, and the friction resistance and the durability were sufficient. Further, the appearance and the residual ratio of the breaking strength (see the following formula) of the laminated film were evaluated. Residual strength at break (%) = (rupture strength after stretching) / (rupture strength before stretching) × 100 Evaluation: No change in appearance after one year, and residual strength at break was 9
It was 3%, and the weather resistance and its durability were sufficiently recognized.

Comparative Example A film was obtained in the same manner as in Example 1 except that the ethylene-vinyl acetate copolymer was not crosslinked with water, and a film was evaluated. The results are shown below.・ Tear strength: 108 kg / cm in vertical direction, 122 k in horizontal direction
g / cm, which is considerably lower in strength than that of Example 1. Heat resistance: 43 g / cm ^2, which is also considerably lower than that of Example 1.・ Friction resistance (scratch resistance): Scratch occurs on the surface,
This part was whitened, and this part was clogged with dust, which not only reduced sunlight permeability but also deteriorated weather resistance.

[0026]

As described above in detail, the agricultural laminated film of the present invention comprises a specific ultra-low density ethylene-α-olefin copolymer intermediate layer and a water-crosslinked specific ethylene-vinyl acetate. By having both outer layers made of a copolymer, it has excellent properties of both an ultra-low-density ethylene-α-olefin copolymer and a water-crosslinked ethylene-vinyl acetate copolymer. This is a non-existent agricultural laminated film that has a well-balanced performance, tear strength, transparency, heat resistance, cold resistance, and piercing resistance, especially when both outer layers made of ethylene-vinyl acetate copolymer are water. Since it is cross-linked, it has improved tensile strength, heat resistance, surface friction resistance (scratch resistance), and weather resistance.

Further, according to the present invention, after the materials of each layer are co-extruded, the excellent properties described above are imparted to the laminated film by means of water crosslinking, which can be carried out in a large amount and at low cost. An excellent agricultural laminated film can be obtained at low cost.

Therefore, the present invention provides heat resistance, impact resistance,
Agricultural laminated film excellent in tear resistance, piercing resistance, cold resistance, high transparency, long-lasting frictional effect (scratching effect) and weathering effect on the surface, and low cost, and method for producing the same Was made possible.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) B32B 1/00-35/00 A01G 9/14

Claims (3)

(57) [Claims] 1. Density 0.910 g / ml or less, melting point 11
6 ° C or higher, 1% modulus 1200 kg / cm ² or lower,
Ultra-low density ethylene-α having an extractable amount of n-hexane of 10% by weight or less and a melt index of 0.8 to 10 g / 10 minutes.
An intermediate layer comprising an olefin copolymer, a melt index of 0.5 to 5 g / 10 minutes, and a vinyl acetate content of 5-1.
Both outer layers formed by water-crosslinking a silicone-grafted ethylene-vinyl acetate copolymer obtained by adding an unsaturated alkoxysilane and an organic peroxide to 5% by weight of an ethylene-vinyl acetate copolymer to form a silicone graft. Wherein the thickness of the intermediate layer occupies at least 35 to 90% of the total thickness of the laminated film, and the thickness of the entire laminated film is 50 to 200 μm. For laminated film. 2. A method for continuously producing an ethylene copolymer having an ultra-low density ethylene-α-olefin copolymer as follows: (a) at a temperature of 10 to 80 ° C. and a pressure of 7000 kPa or less in a fluidized bed reaction zone. C.) Ethylene and at least one higher α-olefin having 3 to 8 carbon atoms having a molar ratio of higher α-olefin: ethylene of 0.35: 1 to 8.0: 1, and (b) at least 25 mol At least 1%
The gaseous mixture containing the seeds of the dilution gas, the following formula: Mg _m Ti (OR) in _n X _p [ED] _q (wherein, R, or an aliphatic or aromatic hydrocarbon group having 1 to 14 carbon atoms Represents a group COR ′, wherein R ′ has 1 to 1 carbon atoms.
4 represents an aliphatic or aromatic hydrocarbon group, X is selected from the group consisting of a chlorine atom, a bromine atom, an iodine atom and a mixture thereof, and ED represents an alkyl ester of an aliphatic or aromatic acid, an aliphatic ether, a ring Represents an organic electron donating compound selected from the group consisting of formula ethers and aliphatic ketones, m is 0.5 to 56, n is 0, 1 or 2, p is 2 to 116, and q is 2 to 85. ) Is continuously contacted with particles of a catalyst system comprising the precursor composition represented by the formula (1), and the precursor composition is diluted with an inert carrier material and the following formula: Al (R ') _d X' _e H _f (Wherein X ′ represents a chlorine atom or a group OR ″, R ′ and R ″ represent a saturated hydrocarbon group having 1 to 14 carbon atoms, e is 0 to 1.5, f is 0 or 1, and d + e + f = 3). The activated compound is completely activated, and the molar ratio of all aluminum: titanium in the reaction zone is 1 in the reaction zone.
The agricultural laminated film according to claim 1, which is manufactured by using an amount of 0: 1 to 400: 1. 3. Density 0.910 g / ml or less, melting point 11
6 ° C or higher, 1% modulus 1200 kg / cm ² or lower,
Ultra-low density ethylene-α having an extractable amount of n-hexane of 10% by weight or less and a melt index of 0.8 to 10 g / 10 minutes.
An intermediate layer comprising an olefin copolymer, a melt index of 0.5 to 5 g / 10 minutes, and a vinyl acetate content of 5-1.
Both outer layers consisting of a silicone-grafted ethylene-vinyl acetate copolymer obtained by adding an unsaturated alkoxysilane and an organic peroxide to 5% by weight of an ethylene-vinyl acetate copolymer to form a silicone graft are coextruded. ,next,
A method for producing a laminated film for agricultural use, which comprises water crosslinking.