JP2001062972A - Film for facility gardening - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a film for the facility gardening of good resistance, sprayproof properties and toughness and also superior spread workability on which strength of a fold is hard to be lowered with the passage of time. SOLUTION: A slit is formed along the length direction of a cylindrical film formed by the inflation method, and when the cylindrical film is released and opened from the slit and spread on a facility gardening greenhouse, the inner skin of an inner layer A of the cylindrical film is positioned on the inner face side of the facility gardening greenhouse, while the outer skin of an outer layer C of the cylindrical film is positioned on the outer face side of the facility gardening greenhouse and an intermediate layer B is formed between the inner layer A and the outer layer C on a film of multilayer structure used for the facility gardening, and a main component of a composition constituting the outer layer C of the cylindrical film is an ethylene-α-olefin copolymer (c1) of the 0.88-0.96 g/cm3 density (dc1 or an ethylene homopolymer (c2) of the 0.91-0.93 g/cm3 density (dc2).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a film for greenhouse horticulture. In detail, when a film for greenhouse horticulture is put on a greenhouse for greenhouse (hereinafter referred to as "extension"), it is not necessary to once make a single film (hereinafter referred to as "opening"), and it is excellent in expansion workability. Further, the present invention relates to a film for greenhouse horticulture in which the strength of the film fold is hardly reduced even after a lapse of time.

[0002]

2. Description of the Related Art A polyolefin-based horticultural film formed by an inflation method can produce a wide product of 10 m or more, does not require a width joint, and has no problems such as insufficient fusion at a joint. Are preferably used. In general, the multilayer film by the inflation method, after the thermoplastic resin composition put into several heated extruders is kneaded by the screw of each extruder,
The layers are stacked inside a heated circular die having a circular lip and extruded above the lip.
The cylindrical film in the molten state extruded in this manner is called a bubble. The bubble is cooled by blowing air from the outer periphery of the bubble using an air ring, and is double-folded or gusseted as shown in FIGS. After being formed into a folded tubular film and taken up by a pair of pressure rolls, the film is wound around a paper tube or the like.

[0003] In order to open the crimped cylindrical film so that it can be spread on a greenhouse, a single-opening film provided with a slit portion at a fold at one end as shown in Figs. Or a double-opened film in which a slit portion is provided in the center of the folding width along the longitudinal direction. The method of providing the slit portion includes a method of providing a slit portion immediately after the tubular film is taken up by the pressure roll and winding it around a paper tube or the like, and a method of providing a necessary length from a wound tubular film once wound. There is a method of providing a slit portion when only feeding is performed.

[0004] In the horticultural film by the inflation method, when the width is 3 to 8 m, the state is often double-folded. When the width is more than 6 m and the width is more than 10 m, the handling after the film is formed is simplified. In general, a compact gusset-folded state in which a fold is formed on the outer surface of the blown film is used. These double-fold or gusset-folded horticultural films are:
Once the film is processed into a single film (hereinafter referred to as "single") (hereinafter referred to as "opening process") and then delivered to the greenhouse horticultural producer through a folding process or a drawing process (hereinafter referred to as "case A") ) And double folds or gusset folds and then delivered to the greenhouse horticulture producer through a folding process (hereinafter referred to as “case B”).

In case A, two or three people are required to make the double-folded film into a single film, and two or three people are required to fold the film vertically after the opening step. Effort and time have been spent. These operations have been performed primarily by film processors. In the case B, that is, when the film for greenhouse horticulture is delivered to the greenhouse horticulture producer through the folding process while being double-folded or gusset-folded, the opening process is omitted and the work of the film processor is labor-saving. However, greenhouse horticulture producers can expand the greenhouse horticulture film as a single just before spreading it to the greenhouse, or unfold the greenhouse horticulture film in the longitudinal direction of the greenhouse, and then open the greenhouse. It had to be lifted and extended on top of a horticultural house, and the extension work put a lot of labor and time on the horticultural producers. Improvement of these extension work has been strongly desired with the aging of greenhouse horticultural producers.

On the other hand, polyolefin-based horticultural films are inferior in heat retention, anti-fog properties, toughness, transparency, etc. as compared with agricultural polyvinyl chloride films.
The technique of adding a specific inorganic filler to JP-A-60-104141 for improving the heat retention, and JP-A-58-90960 for improving the antifogging property and toughness.
In the multi-layer film, a linear low-density polyethylene is formed on the outer layer side when the greenhouse is spread on a greenhouse, an ethylene-vinyl acetate copolymer or an olefin-vinyl alcohol copolymer is formed on the intermediate layer, and a linear layer is formed on the inner layer. Techniques using low-density polyethylene or ethylene-vinyl acetate copolymer are disclosed.

In recent years, linear low-density polyethylene, which is an ethylene-α-olefin copolymer using a single-site catalyst instead of a conventional multi-site catalyst, has been developed.
JP-A-09-052332 and JP-A-08-276
No. 542 discloses an ethylene-single-site catalyst.
Agricultural films using α-olefin copolymers have been proposed. These agricultural films use an ethylene-α-olefin copolymer using a single-site catalyst for the inner and outer layers, and the toughness is improved, but the antifogging property and the antifogging property are not sufficiently expressed. However, despite the large amounts of antifogging agent and antifog agent added, the antifogging property and the durability of the antifogging property were insufficient. Also, these agricultural films do not improve the workability of spreading to a greenhouse, and the spreading requires much labor and time.

Furthermore, when these agricultural films are spread on a greenhouse, the strength of the folds decreases with the passage of time, and the folds may break from the folds due to strong winds or the like. Breakage of the horticultural film during crop cultivation may cause damage such as hindering the growth of the crop. Therefore, it has been desired to improve the strength reduction at the fold.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide good anti-fogging properties, anti-fog properties, toughness, excellent workability in spreading,
It is another object of the present invention to provide a greenhouse horticultural film in which the strength of the film fold hardly decreases over time.

[0010]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that the inner skin of the multilayered tubular film formed by the inflation method is an inner layer located on the inner surface side of the greenhouse. An outer layer positioned on the outer surface side of the greenhouse, the outer shell of the tubular film is a multilayer greenhouse gardening film having an intermediate layer between the inner layer and the outer layer, and the main constituent of the composition constituting the outer layer The component is an ethylene-based resin with excellent blocking resistance and toughness.Furthermore, the main component of the composition constituting the inner layer is less likely to cause cracks, etc., which are the cause of tearing, and the anti-fog agent and anti-fog agent are transferred to the inner layer surface. It has been found that a multi-layer film using an ethylene-based resin which is easy to make and a main component of the composition constituting the intermediate layer is an ethylene-based resin having excellent toughness achieves the above-mentioned object. This has led to the completion of the present invention can.

The present invention has the following configuration. (1) The tubular film formed by the inflation method is provided with a slit portion along the length direction, and when the tubular film is opened from the slit portion and spread on a greenhouse, the endothelium of the tubular film is removed. The inner layer (A) located on the inner side of the greenhouse, the outer skin of the tubular film is the outer layer (C) located on the outer side of the greenhouse, and between the inner layer (A) and the outer layer (C). In the middle layer (B)
And a main component of the composition constituting the outer layer (C), which is the outer skin of the tubular film, has a density (d _c1 ) of 0.88 to 0.96 g / cm ^3.
Greenhouse film is ethylene -α- olefin copolymer (c ₁₎ or density (d _c2) 0.91~0.93g / cm ³ of ethylene homopolymer (c _2). (2) An ethylene-α-olefin copolymer (c ₁ ), which is a main component of the composition constituting the outer layer (C) that is the outer shell of the tubular film, is polymerized using a single-site catalyst, and has a density ( The film for greenhouse horticulture according to the above (1), wherein d _c11 ) is an ethylene-α-olefin copolymer (c ₁₁ ) having a ratio of 0.88 to 0.93 g / cm ³ . (3) The ethylene-α-olefin copolymer (c ₁₁ ) which is a main component of the composition constituting the outer layer (C) which is the outer skin of the tubular film is a copolymer having the following properties. 2) The film for facility horticulture according to the above. a) Melt flow ratio I ₁₀ / I ₂ ≧ 5.63 b) Molecular weight distribution Mw / Mn ≦ (I ₁₀ / I ₂ ) −4.63 c) Critical shear stress γ γ> 4 when gross melt fracture begins to occur × 10 ⁶ dyne / cm ² (4) The main component of the composition constituting the inner layer (A) which is the inner layer of the tubular film has a vinyl acetate content of 2 to 15% by weight.
The above-mentioned (1) to ethylene-vinyl acetate copolymers
The film for greenhouse horticulture according to any one of (3). (5) The composition of the inner layer (A), which is the inner layer of the tubular film, is such that the addition ratio X weight% and the BET specific surface area Sm ² / g of the inorganic filler are 1 / S ≦ X ≦ 100 / S. The film for greenhouse horticulture according to any one of the above items (1) to (4), further comprising one or more inorganic fillers satisfying the following. (6) The main component of the composition constituting the intermediate layer (B) is polymerized using a single-site catalyst, has a density (d _b ) of 0.85 to 0.93 g / cm ³ , and has the following properties The film for greenhouse horticulture according to any one of the above (1) to (5), which is an ethylene-α-olefin polymer (b) having the following. a) Melt flow ratio I ₁₀ / I ₂ ≧ 5.63 b) Molecular weight distribution Mw / Mn ≦ (I ₁₀ / I ₂ ) −4.63 c) Critical shear stress γ γ> 4 when gross melt fracture begins to occur × 10 ⁶ dyne / cm ² (7) A slit portion is provided at one location along the length direction of the tubular film at a fold portion at one end of the folded width of the tubular film or at the center of the folded width. The film for greenhouse horticulture according to any one of the above (1) to (6), which is folded in a longitudinal direction.

[0012]

Embodiments of the present invention will be described below. The film for facility horticulture of the present invention is provided with a slit portion along the length direction in a tubular film formed by an inflation method, and when the tubular film is opened from the slit portion and expanded to a facility horticulture house, The inner layer of the tubular film is an inner layer (A) located on the inner surface side of the greenhouse, the outer skin of the tubular film is an outer layer (C) located on the outer surface of the greenhouse, and the inner layer (A). It is a film for greenhouse horticulture having a multilayer structure of three or more layers having an intermediate layer (B) between outer layers (C). In the present invention, the “main component” of the composition refers to a component contained in the composition in an amount of 50% by weight or more.

In the greenhouse horticulture film of the present invention, the main component of the composition constituting the outer layer (C) which is the outer skin of the tubular film is an ethylene-α-olefin copolymer (c ₁ ).
Alternatively, it is an ethylene homopolymer (c ₂ ) having a density (d _c2 ) of 0.91 to 0.93 g / cm ³ . The ethylene-α
The olefin copolymer (c ₁ ) is a random copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms, using a multi-site catalyst such as a Ziegler catalyst or a single-site catalyst such as a metallocene catalyst. polymerized Te, its density (d _c1) is 0.88~0.96g / cm ^3, preferably 0.89~0.93g / cm ^3. When the density (d _c1 ) is less than 0.88 g / cm ³ , the melting point of the ethylene-α-olefin copolymer (c ₁ ) is lowered and the horticultural films are easily fused together by irradiation with sunlight. Tend to be. Further, the density (d _c1 ) is 0.96 g /
If it exceeds cm ³ , the flexibility of the greenhouse horticultural film may be reduced, and the workability at the time of spreading and collection may be reduced.

The α-olefin having 3 to 20 carbon atoms includes propylene, 1-butene, 1-pentene,
-Hexene, 4-methyl-1-pentene, 1-octene, 1
-Decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like, and α in the ethylene-α-olefin copolymer (c ₁ ).
The proportion of polymerized olefin units is from 1 to 45% by weight, preferably from 2 to 35% by weight;

In particular, the ethylene-α-olefin copolymer (c ₁ ) is polymerized using a single-site catalyst and has a density (d _c11 ) of 0.88 to 0.93 g / cm ³ . -If it is an olefin copolymer (c ₁₁ ), it can be formed into a greenhouse horticultural film having excellent toughness and having a less sticky outer layer (C) surface. The density (d _c11 ) of the ethylene-α-olefin copolymer (c ₁₁ ) is 0.88 g
If it is less than / cm ³ , the melting point of the ethylene-α-olefin copolymer (c ₁₁ ) will decrease, and the films for greenhouse horticulture will tend to fuse together by irradiation with sunlight. Also,
If the density (d _c11 ) exceeds 0.93 g / cm ³ , the flexibility of the greenhouse horticultural film may decrease, and the workability at the time of spreading or collection may decrease.

The single-site catalyst used for polymerizing the ethylene-α-olefin copolymer (c ₁₁ ) includes a metallocene of a transition metal of Group IV or V of the Periodic Table of elements such as titanium, zirconium, hafnium and vanadium. A combination of a compound and an organoaluminum compound and / or an ionic compound is used.

The metallocene compound may be a compound obtained by crosslinking at least one cyclopentadienyl group, a substituted cyclopentadienyl group, hydrocarbyl silicon, or the like, and a compound obtained by crosslinking a cyclopentadienyl group to oxygen, nitrogen, and phosphorus atoms. Any known metallocene compound having a compound as a ligand can be used.

Specific examples of these metallocene compounds include dimethylsilyl (2,4-dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl) zirconium dichloride, dimethylsilyl (2,4-dimethyl Silicon-bridged metallocene compounds such as (cyclopentadienyl) (3 ′, 5′-dimethylcyclopentadienyl) hafnium dichloride, ethylenebisindenyl zirconium dichloride, ethylenebisindenylhafnium dichloride, ethylenebis (methylindenyl) zirconium Examples include indenyl crosslinked metallocene compounds such as dichloride and ethylenebis (methylindenyl) hafnium dichloride.

The organoaluminum compound used in combination with the metallocene compound is represented by the general formula-(Al
(R) O) _n- a linear or cyclic polymer (R is a hydrocarbon group having 1 to 10 carbon atoms, including those partially substituted with a halogen atom and / or an RO group. n is the degree of polymerization and is 5 or more, preferably 10 or more), and specific examples include methylalumoxane, ethylalumoxane, and isobutylethylalumoxane, wherein R is each a methyl, ethyl, or isobutyl group. Can be

Further, other organic aluminum compounds include trialkylaluminum, dialkylhalogenoaluminum, sesquialkylhalogenoaluminum, alkenylaluminum, dialkylhydroaluminum, sesquialkylhydroaluminum and the like.

The ionic compound is represented by the general formula [Q] ^{m +} [Y] ^m- (m is an integer of 1 or more), wherein Q is a cation component of the ionic compound, And a cationium ion, a tropylium cation, an ammonium cation, an oxonium cation, a sulfonium cation, and a phosphonium cation. Y is an anionic component of an ionic compound, which is a component that reacts with a metallocene compound to form a stable anion, and includes an organic boron compound anion, an organic aluminum compound anion, an organic gallium compound anion, an organic phosphorus compound anion, and an organic compound. Arsenic compound anions,
Organic antimony compound anions and the like.

As a method for copolymerizing ethylene and an α-olefin using a single-site catalyst, a known polymerization method is used, and examples thereof include a gas phase polymerization method, a slurry polymerization method, and a solution polymerization method.

The ethylene-α-olefin copolymer polymerized by the single-site catalyst has a narrower molecular weight distribution and a higher α-olefin content than that of a multi-site catalyst such as a conventional Ziegler-Natta catalyst. Since they are also polymerized uniformly and have many tie molecules between lamellae, they have low molecular weight components, are excellent in blocking resistance, and are excellent in transparency, impact resistance, and toughness.

The ethylene-α-olefin copolymer (c ₁₁ ) polymerized using a single-site catalyst has a Q value (Mw / Mn) which is a ratio of a weight average molecular weight (Mw) to a number average molecular weight (Mn). Is 1.5 to 3.5. Also, 190
The melt flow rate (hereinafter, referred to as MFR) under a load condition of 2.16 kgf at 0.2 ° C. is 0.2 to 20/10 minutes, and the number of melting peaks by differential scanning calorimetry (DSC) may be two or more. Absent.

Further, when the ethylene-α-olefin copolymer (c ₁₁ ) is the ethylene-α-olefin copolymer (c ₁₂ ) having the following properties, a cylindrical film having a multilayer structure is formed by an inflation method. In doing so, the load applied to the motor of the extruder can be reduced, and a film having excellent surface smoothness can be obtained even at a relatively low extrusion temperature. a) Melt flow ratio I ₁₀ / I ₂ ≧ 5.63 b) Molecular weight distribution Mw / Mn ≦ (I ₁₀ / I ₂ ) −4.63 c) Critical shear stress γ γ> 4 when gross melt fracture begins to occur Even at 10 ⁶ dyne / cm ² , the melt flow ratio I ₁₀ / I ₂ is preferably 5.
63 to 50, more preferably 7 to 30, still more preferably 8 to 20, and the molecular weight distribution Mw / Mn is preferably 1.5 to 2.5, more preferably 1.7 to 2.3.
It is. The critical shear stress γ is preferably 4 × 10
^{It is 6} to 10 × 10 ⁶ dyne / cm ² .

Here, the melt flow ratio I ₁₀ / I ₂ , the molecular weight distribution Mw / Mn and the critical shear stress γ at which gross melt fracture begins to occur are described in JP-A-6-306.
As described in JP-A-121, the melt flow ratio is 190 ° C. 10 based on ASTM D-1238.
expressed as the ratio of the melt index I ₂ measured at a load condition of the melt index I ₁₀ and 190 ° C. 2.16 kg as measured at a load condition of kg. Critical shear stress is measured by a gas extrusion rheometer (GER), and the critical shear stress at which gross melt fracture begins to occur is considered as a regular or irregular strain under unstable flow conditions. , GER, based on the change in surface roughness and shape of the extrudate extruded.

When the ethylene-α-olefin copolymer (c ₁ ) is melted and kneaded with an extruder in order to form a cylindrical film by the inflation method, the motor load of the extruder is increased, and self-heating is caused by kneading. Alternatively, the surface of the cylindrical film may be roughened during the extrusion of the molten resin. In particular, the ethylene-α-olefin copolymer (c ₁₁ ) polymerized using a single-site catalyst tends to have a uniform molecular weight and a narrow molecular weight distribution, and thus tends to cause problems during processing. . In order to solve these problems at the time of processing, methods such as adding low-density polyethylene to the composition constituting the outer layer (C), which is the outer skin of the tubular film, and setting the extrusion temperature higher are taken. However, this is not a preferred method because it leads to a decrease in toughness and the occurrence of thermal degradation.

In addition, the self-heating of the ethylene-α-olefin copolymer (c ₁ ) or the rise in the set temperature at the time of forming the cylindrical film may be caused by not only the temperature of the inner skin of the cylindrical film but also the temperature of the inner skin of the cylindrical film. , The inner surfaces of the tubular film tend to adhere to each other (block), making it difficult for the inner surface to open from the slit. The problem at the time of the processing is that the ethylene-α-olefin copolymer (c ₁₁ )
The use of the α-olefin copolymer (c ₁₂ ) eliminates the problem without lowering the toughness or causing thermal deterioration.

The ethylene-α-olefin copolymer (c ₁₂ ) is prepared by using a constrained geometry catalyst as described in JP-A-6-306121.
lyst), but commercially available products may be used. Commercially available products include Affinity PF1140, PL1880, FM sold by Dow Chemical Japan Co., Ltd.
1570 (both trade names) and Elite 5100, 5400
(All are trade names).

In the greenhouse horticulture film of the present invention, ethylene homopolymer (c ₂ ) used as a main component of the composition constituting the outer layer (C), which is the outer skin of the tubular film
Has a density (d _c2 ) of 0.91 to 0.93 g / cm ³ . As the ethylene homopolymer, a polymer obtained by polymerization using a known high-pressure radical method or the single-site catalyst is used. Ethylene homopolymer (c ₂₎ a density (d _c2) is 0.91 g / cm ³ less than a is ethylene homopolymer (c ₂₎ horticulture film each other by irradiation melting point is lowered sunlight of fusion It tends to be easy to wear. On the other hand, if the density (d _c2 ) exceeds 0.93 g / cm ³ , the flexibility of the greenhouse horticultural film may decrease, and the workability at the time of spreading or collection may decrease.

The composition constituting the outer layer (C), which is the outer skin of the cylindrical film, includes the above-mentioned ethylene-α-olefin copolymer, ethylene homopolymer, different ethylene-α-olefin and different ethylene-α-olefin. 2 ethylene homopolymers
More than one species may be used in combination.

In the greenhouse horticultural film of the present invention, the main component of the composition constituting the inner layer (A) which is the inner layer of the tubular film is a known high-density polyethylene, low-density polyethylene, linear low-density polyethylene, or the like. And thermoplastic resins such as polypropylene resin, polyester resin, and polyamide resin. Among them, ethylene-α-, which is a main component of the composition constituting the outer layer (C) of the tubular film, is exemplified. Inflation molding can be performed by co-extrusion with an olefin copolymer or an ethylene homopolymer, and the resulting facility horticultural film has good performance such as anti-fogging property. Therefore, the vinyl acetate content is 2 to 15% by weight. Certain ethylene-vinyl acetate copolymer (a) is preferably used. When the vinyl acetate content in the ethylene-vinyl acetate copolymer (a) is less than 2% by weight, it is difficult to obtain the antifogging property of the obtained greenhouse horticultural film, especially at low temperatures, and to maintain the antifogging property. Also tends to decrease. If the vinyl acetate content exceeds 15% by weight, the films may adhere to each other or may be stored by the sun rays when left outdoors, and the films may fuse together.

The ethylene-vinyl acetate copolymer (a) is
It is produced by reacting ethylene and vinyl acetate by a known high-pressure radical polymerization process, and has an MFR of 0.1 to 1
0, preferably 0.5 to 5 g / 10 min. If the MFR is too small, the moldability of the film, particularly the extrudability and high-speed stretchability, deteriorate. If the MFR is too large, the moldability of the film, particularly the stability of bubbles in inflation molding, may be reduced.

Further, by using the ethylene-vinyl acetate copolymer (a) as a main component of the composition constituting the inner skin of the tubular film, ethylene-α- In the case of using an olefin copolymer or an ethylene homopolymer, it is possible to prevent a decrease in the strength of the folded portion of the tubular film which occurs with the passage of time. Therefore, in the film for greenhouse horticulture of the present invention, it is preferable to use the ethylene-vinyl acetate copolymer (a) as a main component of the composition constituting the inner layer (A) which is the inner skin of the tubular film. Ethylene-α-olefin copolymer (c ₁ ) or ethylene homopolymer (c ₂ ), preferably ethylene-α-olefin copolymer, as the main component of the composition constituting the outer layer (C) which is the outer skin of the film (C ₁₁ ), more preferably ethylene-
α-olefin copolymer (c ₁₂ ) is used.

In the greenhouse horticulture film of the present invention,
Ethylene-vinyl acetate copolymer (a) as a main component of the composition constituting the inner layer (A) which is the inner layer of the tubular film
By using an ethylene-α-olefin copolymer (c ₁₂ ) as a main component of the composition constituting the outer layer (C) which is the outer skin of the tubular film, the blocking of the tubular film endothelium is reduced, and It has good reactivity and excellent extensibility,
It is possible to obtain a greenhouse horticultural film in which the decrease in the fold strength with time after the spread to the greenhouse is remarkably improved. Also, there is no increase in motor load during molding and there is no rough surface on the surface of the tubular film.

In the present invention, one or more inorganic fillers are added to the composition constituting the inner layer (A), which is the inner skin of the tubular film, in order to prevent blocking between the films. (% By weight) and the BET specific surface area S (m ² / g) of the inorganic filler are 1 / S ≦ X ≦ 1
It is desirable to satisfy the relationship of 00 / S. In addition, BE
The T specific surface area is measured according to JIS Z 8830. When the addition rate X is less than 1 / S, the films are likely to be blocked easily, and the addition rate X is 100 / S.
If it is larger than S, the transparency and the mechanical strength decrease.

As the inorganic filler, silicon oxide,
Silicate compounds such as magnesium silicate, aluminum silicate and calcium silicate; aluminosilicate compounds such as calcium aluminosilicate, sodium aluminosilicate and potassium aluminosilicate; aluminate compounds such as alumina, sodium aluminate, potassium aluminate and calcium aluminate; Examples of the inorganic filler include calcium, hydrotalcites represented by the following formula (1), and lithium-aluminum composite hydroxide salts represented by the following formulas (2) and (3).

[0038]

Embedded image [Al ₂ Li (OH) ₆ ] ₂ (A ⁿ⁻ ) · mH ₂ O—Formula 1 (where m represents a number of 3 or less)

[0039]

Embedded image [Al ₂ (Li _(1-x) · M ²⁺ _x ) (OH) ₆ ] ₂ · (Si _y O _{2y + 1} ² ) _{1 + x} · mH ₂ O-Formula 2 , M ²⁺ is a divalent metal, m is a number in the range of 0 ≦ m <5, x is a number in the range of 0 ≦ x <1, y is 2 ≦ y ≦ 4
Indicates a number in the range. )

[0040]

^{Embedded image} M 2 ⁺ _{1 -x} Al _x (OH) ₂ (A ⁿ⁻ ) _{x / 2} .mH ₂ O-Formula 3 (where M ²⁺ is Mg ²⁺ , Ca ²⁺ , and Zn ^{2 +} represents at least one divalent metal ion selected from among, a ^n-
Is an n-valent anion, x and m are the following conditions, 0 <x <
0.5, 0 ≦ m ≦ 2. )

The inorganic filler can be added, if necessary, not only to the inner layer (A), which is the inner layer of the tubular film, but also to the composition constituting other layers. In that case, one kind selected from the group of the inorganic fillers may be added alone, or two or more kinds may be used in combination.

In the greenhouse horticulture film of the present invention, the main component of the composition constituting the intermediate layer (B) of the tubular film is a known high-density polyethylene, low-density polyethylene, or linear low-density polyethylene. Thermoplastic resins such as polypropylene resin, polyester resin, and polyamide resin, among others, can be cited. Among them, the toughness and surface smoothness of the resulting greenhouse horticultural film, the increase in the motor load of the extruder, and the extrusion temperature In view of the moldability of the film, the density (d _b ) polymerized using a single-site catalyst is 0.85 to 0.85.
0.93 g / cm ³ , a) melt flow ratio I ₁₀ / I ₂ ≧ 5.63 b) molecular weight distribution Mw / Mn ≦ (I ₁₀ / I ₂ ) −4.63 c) when gross melt fracture begins to occur The ethylene-α-olefin copolymer (b) having a critical shear stress γγ> 4 × 10 ⁶ dyne / cm ² is preferably used. The ethylene-α-olefin copolymer (b) is an ethylene-α-olefin copolymer (c ₁₂ )
May be the same as

In the film for greenhouse horticulture of the present invention,
The composition constituting the outer layer (C), the inner layer (A) and the intermediate layer (B) of the tubular film is polymerized with a single-site catalyst or a known multi-site catalyst to improve flexibility, if necessary. Elastic copolymers such as ethylene-diene elastic copolymers, ethylene-propylene elastic copolymers and styrene-butadiene-based elastic copolymers can be added, and further used in ordinary greenhouse horticultural films. Known inorganic or organic warming agents, anti-fogging agents, hindered amine weathering agents, ultraviolet absorbers, anti-fog agents (fluorinated surfactants), antistatic agents, lubricants, anti-blocking agents, antioxidants, heat Stabilizers, antibacterial agents, dyes / colorants, and the like can be added. Further, starch such as corn starch or potato can be adhered to the inner surface of the tubular film to further reduce blocking between the films.

The thickness of the greenhouse horticultural film of the present invention varies depending on the place where the film is used and the service life thereof.
Those having a thickness of about 05 to 0.3 mm are preferably used. Although the thickness of the inner layer and the thickness of the outer layer are not particularly limited,
A range of 5 to 50% of the total layer thickness is preferably used. In addition, the intermediate | middle layer of the film for greenhouse horticulture of this invention may be comprised from one layer, and may be comprised from two or more layers. The film for greenhouse horticulture of the present invention is transparent,
For pears and semi-pears, it may be any, and for mulching other than covering such as greenhouses and tunnels for facility horticulture,
It can also be used for applications such as bagging.

In the facility horticulture film of the present invention, a slit portion is provided along a length direction in a tubular film formed by an inflation method, and the tubular film is opened from the slit portion to be extended to a facility horticulture house. The inner skin of the tubular film is an inner layer (A) located on the inner surface side of the greenhouse, the outer skin of the tubular film is an outer layer (C) located on the outer surface of the greenhouse, and the inner layer ( A multi-layered horticultural film having an intermediate layer (B) between the outer layer (A) and the outer layer (C), and the slit portion is formed at the fold portion at one end of the fold width of the cylindrical film or at the center of the fold width. If it is provided at one place along the length direction and the tubular film is a film folded in the longitudinal direction, it can be easily spread to the greenhouse without the need to open it in advance. Ukoto can. That is, the film for greenhouse horticulture is delivered to the greenhouse horticulture producer in a double fold or gusset fold, and is easily spread to the greenhouse horticulture house.

Hereinafter, a method for spreading the film for greenhouse horticulture of the present invention in a greenhouse horticulture will be described. The double-fold or gusset-folded horticultural film has a single-opening film type in which a slit portion for opening is provided at a fold portion at one end of a folding width and an opening along a longitudinal direction at a central portion of the folding width. There is a double door film type provided,
The extension method of the facility horticulture film of the present invention to the facility horticulture house differs depending on each type.

In the case of the single-opening film type, the greenhouse horticultural film folded in the longitudinal direction is folded (FIG. 1) with respect to the end surface 2 (FIG. 1) of the stretched portion 1 (FIG. 1) of the greenhouse. Is located farther than the slit portion 4 (FIG. 1), and is installed below the wife surface 2 of the house extending portion 1 so that the slit portion 4 is parallel to the wife surface 1. From the cutting portion 5 (FIG. 1) of the house while being extended to the house extending portion 1.

In the case of the double-opening film type, the facility gardening film folded in the longitudinal direction is inserted into the slit portion 4.
(Fig. 2) is the wife's face 2 of the facility horticulture house extension part 1 (Fig. 2).
(FIG. 2), the cutting section 5 (FIG. 2) is installed below the wife surface 2 of the house stretching section 1 so that the cutting section 5 (FIG. 2) is parallel to the wife surface 2 of the facility horticulture house stretching section 1. The film is stretched out from the cutting section 5 of the greenhouse horticultural film to the house stretching section 1.

In any of the above-described one-side opening type and two-way opening type horticultural film expanding methods, in order to reduce friction between the horticultural horticulture house and the horticultural horticultural film, and by using the protrusions of the horticultural horticultural house. In order to prevent the facility horticultural film from being torn, a rotating jig or the like may be installed on the upper part of the wife's face to prevent the facility horticultural film from being torn. In addition, for the purpose of further improving the spreadability of the film for greenhouse horticulture of the present invention, air can be injected from the slit portion and pressed before the cylindrical film is folded in the longitudinal direction, if necessary.

[0050]

The present invention will be described below in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples.

The thermoplastic resins used in the examples and comparative examples are shown below. Elite 5400 manufactured by Dow Chemical Japan Co., Ltd. ・ Think Persite catalyst-based ethylene-α-olefin copolymer resin (S-LLDPE) ・ MFR: 1.0 g / 10 min., Density: 0.916 g / cm ³ affinity PF1140 Dow Chemical Japan (・ Think Persite catalyst ethylene-α-olefin copolymer resin (S-LLDPE) ・ MFR: 1.6g / 10min., Density: 0.895g / cm ³ Yumerit 1520F Ube Industries, Ltd. ・ Think Persite catalyst -Based ethylene-α-olefin copolymer resin (S-LLDPE) ・ MFR: 2.0g / 10min., Density: 0.913g / cm ³ Yumerit 0540F manufactured by Ube Industries, Ltd. ・ Think Persite catalyst-based ethylene-α-olefin copolymer Polymer resin (S-LLDPE)-MFR: 4.0 g / 10 min., Density: 0.904 g / cm ³ NUC3270 manufactured by Nippon Unicar Co., Ltd.-Ethylene divinyl acetate copolymer resin (7.5% divinyl acetate content) (EV
A) · MFR: 2.3 g / 10 min., Density: 0.925 g / cm ³ Ultracene 630 manufactured by Tosoh Corporation · Ethylene divinyl acetate copolymer resin (vinyl acetate content 15%) (EVA) · MFR: 1.5 g 0.936 g / cm ³ Nipolon-L FR151A manufactured by Tosoh Corporation ・ Multi-site catalytic ethylene-α-olefin copolymer resin (M-LLDPE) ・ MFR: 0.9 g / 10 min., Density; 0.924g / cm ³ NUC8505 Nippon Unicar Co., Ltd. ・ High pressure method low density polyethylene (LDPE) ・ MFR 0.8g / 10min., Density 0.923g / cm ³

The characteristics of each of the above thermoplastic resins were measured under the following conditions. a) MFR; 190 ° C. according to JIS K 7210,
It was measured under the condition of 2.16 kgf. b) Density: measured according to JIS K7112.

The evaluation method of the cylindrical film in the examples and comparative examples is as follows. 1) Molding test; equipped with a circular die having a circular die lip clearance of 2.0 mm and a diameter of 50 mm
0.1 mm thickness (thickness ratio, inner layer: middle) at an extrusion temperature (circular die lip temperature) of 160, 170, 180 and 190 ° C. using a three-type three-layer blown film forming tester having three extruders. Layer: outer layer = 1: 3:
1) A cylindrical film having a three-layer structure with a width of 0.6 m was molded, the film forming property was evaluated, and the blocking property of the obtained cylindrical film was evaluated. In addition, a slit part for opening was formed in the fold part of one end of the folding width of the cylindrical film. 1-1) Film-forming property: The surface of the film formed at each extrusion temperature was observed and evaluated according to the following evaluation criteria. ：: good state without melt fracture. Δ: Slight melt fracture is observed. X: A state in which melt fracture is continuously observed and is not practical.

1-2) Blocking resistance: A press-bonded cylindrical film formed at each extrusion temperature and double-wound around a paper tube is opened by hand from the slit portion and adhered (blocking).
The property was evaluated according to the following evaluation criteria. ：: No adhesion between films. Δ: A state in which adhesion between the films is observed, but the films can be easily peeled. ×: A state in which the films are strongly adhered to each other and have difficulty in peeling, and when the film is forcibly peeled, tearing occurs.

2) Change in tensile properties; thickness 0.1 mm, molding width 0.6 m molded at the optimal extrusion temperature in the molding test.
After opening the three-layered tubular film in the arch pipe house with a width of 5 m for one year (April 1998 to April 1999), the fold strength and the tensile strength and elongation other than the fold part were measured. The change in the strength of the fold portion over time was evaluated as compared with that before stretching. For measurement of tensile strength and elongation, refer to JI
Lateral direction (TD) of tubular film according to S K 7127
It was performed about. The measurement of the fold was performed so that the fold was perpendicular to the tensile direction and was located at the center between the test piece reference lines.

3) Low-temperature anti-fog property: Using a water bath having a skylight of 10 degrees in inclination and 3 inches in diameter, fixing a film sample to the skylight of the water bath, and setting an environmental temperature of 2
After leaving for 12 days under the condition of 3 ° C. and water temperature of 45 ° C., it was left for 2 days under the condition of environmental temperature of 5 ° C. and water temperature of 15 ° C., and the antifogging property of the water bath side surface of the sample was visually judged based on five levels. Then, the low-temperature antifogging property was evaluated. The larger the five-stage number, the better the low-temperature antifogging property. <Evaluation criteria for low-temperature antifogging property> Evaluation 5: A uniform water film was formed without adhesion of water droplets. Evaluation 4: Adhesion of water droplets is less than 15%. Evaluation 3: Adhesion of water droplets is less than 40%. Evaluation 2: Adhesion of water droplets is less than 65%. Evaluation 1: Adhesion of water droplets is 65% or more.

7) Antifogging persistence: Using a water bath having a 10-degree tilted, 3-inch diameter skylight, fixing a film sample to the skylight of the water bath, and setting the environmental temperature to 2
It was left standing day and night under the conditions of 3 ° C. and a water temperature of 45 ° C., and the period during which the antifogging property was maintained was visually evaluated. The longer the number of days, the better the antifogging durability.

Examples 1 to 8 and Comparative Examples 1 to 6 Tables 1 and 2 show the composition examples and evaluation results of the three-structure tubular films. Note that the inner layer A, the intermediate layer B, and the outer layer C of the examples in the table are shown.
Indicates an inner layer, an intermediate layer, and an outer layer of a cylindrical film laminated in three layers, respectively, and an inner layer A, an intermediate layer B, and an outer layer C of a comparative example.
Indicates an outer skin, an intermediate layer, and an inner skin of a cylindrical film laminated in three layers. The extrusion temperature at which the tensile properties change is the optimum extrusion temperature in the molding test.

DHT4 described in the formulation examples of Tables 1 and 2
A-2 is Mg- having a BET specific surface area of 13 m ² / g.
Al composite hydroxide salt (manufactured by Kyowa Chemical Industry Co., Ltd.)
Fujirain LS (A) has a BET specific surface area of 11 m ² / g.
Is a composite hydroxide salt (manufactured by Fuji Chemical Industry Co., Ltd.),
Silicon dioxide having an ET specific surface area of 300 m ² / g (manufactured by Fuji Sicilia Corporation). The antifogging agent is diglycerin monostearate: diethanol stearylamine distearate: diethanolamine = 2: 7: 1.
(Weight ratio).

As additives other than those described in Tables 1 and 2, 0.5% by weight of a hindered amine-based weathering agent, 0.05% by weight of an ultraviolet absorber, and 0.1% of a phenolic stabilizer were added to the composition constituting the inner layer A. % By weight, 0.1% by weight of phosphorus-based stabilizer
The composition constituting the intermediate layer B contains 0.5% by weight of a hindered amine-based weathering agent, 0.05% by weight of an ultraviolet absorber, 0.2% by weight of a fluorine-based surfactant, 0.1% by weight of a phenol-based stabilizer, and 0.1% by weight of a phosphorus-based stabilizer. 0.1% by weight of the agent, 0.5% by weight of a hindered amine-based weathering agent, 0.05% by weight of an ultraviolet absorber, 0.2% by weight of a fluorine-based surfactant, 0.1% by weight of a phenol-based stabilizer %, And 0.1% by weight of a phosphorus-based stabilizer.

When Examples 1 to 8 and Comparative Examples 1 to 6 are compared, it takes more time when the inner skin of the tubular film is used as the inner layer on the inner surface side of the house than when the inner skin is used as the outer layer on the outer surface side of the house. The decrease in the strength of the fold portion with the passage of time is small, and the decrease in the strength of the fold portion is further improved by using an ethylene-vinyl acetate copolymer as a main component of the composition constituting the inner layer of the inner surface of the house as the inner skin. Was done. Further, the main component of the composition constituting the inner layer of the inner surface of the house as the inner skin is an ethylene vinyl acetate copolymer, and the main component of the composition constituting the outer layer of the outer surface of the house which is the outer skin of the tubular film is ethylene. When the α-olefin copolymer was used, blocking between films became a problem, but specific ethylene-α-polymerized using a single-site catalyst was used.
By using an olefin copolymer, film forming at low temperature became possible, blocking between films was eliminated, and a film for greenhouse horticulture with good openability and openability was obtained.

Example 9 Using a large-sized three-layer, three-layer blown film production machine having three 90 mmφ extruders, the same composition as in Example 1 at an extrusion temperature of 170 ° C., a thickness of 0.1 mm and a molding width of 4 m.
Was formed into a single-opening film in which a slit portion was provided at a fold portion at one end of a folding width, and was wound around a paper tube to obtain a film for facility horticulture. The film for facility horticulture was fed out from a paper tube by 50 m in length, folded in the longitudinal direction in a double fold state, and transported to a field having a facility horticulture house. Next, the crease 3 (FIG. 1) is farther than the slit portion 4 (FIG. 1) with respect to the wife surface 2 (FIG. 1) of the facility horticulture house extension 1 (FIG. 1) having a width of 4 m and a length of 40 m. Then, it is installed below the wife surface 2 of the facility horticulture house extension part 1 so that the slit portion 4 is parallel to the wife surface 2, and the facility horticulture film is cut from the cutting portion 5 (FIG. 1). We extended it to the top of the horticultural house while stretching it out. At this time, the film could be spread by moving on the ground while holding both ends in the width direction of the film cutting portion for greenhouse horticulture one by one.

COMPARATIVE EXAMPLE 7 Using a large-sized three-layer, three-layer blown film production machine having three 90 mmφ extruders, the same composition as in Comparative Example 1 was used at a molding temperature of 170 ° C., a thickness of 0.1 mm, and a molding width of 4 m.
A three-layered film is formed, and a fold at one end of the folding width is slit to form a single-opening film provided with an opening,
The film was wound into a paper tube and used as a facility horticulture film. The film for facility horticulture was drawn out from a paper tube by 50 m in length, folded in the longitudinal direction in a double fold state, and transported to a field having a house for facility horticulture. Next, at the frontage 4m, length 40
After extending to the ground in the longitudinal direction of the m horticulture house, it was unfolded from the double-folded state to a single (single) state and extended to the top of the house. At this time, it was necessary for two people to climb and work on the top of the greenhouse.

Comparing the ninth embodiment of the present invention with the comparative example 7 of the prior art, in the ninth embodiment, there is no work of feeding out the greenhouse for facility horticulture in the longitudinal direction, and the folded greenhouse horticulture film is directly extended. It is possible to simplify the existing expansion work. In addition, it is safe because it is not necessary to climb the top of the greenhouse, and it can be deployed while staying on the ground.

[0065]

[Table 1]

[0066]

[Table 2]

[0067]

The greenhouse horticultural film of the present invention can prevent the strength of the fold portion from decreasing with the lapse of time by using a double fold or gusset-folded greenhouse horticultural film with a specific configuration. Moreover, since the spreading workability and safety are improved by adopting a specific spreading method, it can be suitably used as a covering material for a facility gardening house and its spreading method.

[Brief description of the drawings]

BRIEF DESCRIPTION OF DRAWINGS FIG. 1 shows a method of spreading a single-opening facility horticulture film to a facility horticulture house.

FIG. 2 shows a method of extending a double-opening horticulture film to a horticulture house.

FIG. 3 shows a single-folding double-fold facility horticultural film.

FIG. 4 shows a double-folded gusset-folded horticultural film.

FIG. 5 is an example of a cross-sectional view of a facility horticulture film according to the present invention.

[Explanation of symbols]

1 ... The section where the film for greenhouse horticulture is installed on the greenhouse for greenhouse. 2. The wife of the greenhouse. 3. The fold of the film for greenhouse horticulture. 4 Slit part of film for greenhouse horticulture. 5 ... Cutting part of film for greenhouse horticulture. 6 ... An outer layer on the outer surface side of the house, which is the outer skin of the tubular film. 7 ... An intermediate layer located between the inner skin and the outer skin of the tubular film. 8 An inner layer on the inner surface side of the house, which is the inner skin of the tubular film.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C08K 3/00 C08K 3/00 4J028 C08L 23/06 C08L 23/06 23/08 23/08 // C08F 4 / 645 C08F 4/645 C08J 5/18 CES C08J 5/18 CES F term (reference) 2B024 DA07 DB01 DB08 2B029 EB04 EC02 EC09 EC19 RA01 RA03 4F071 AA15 AA15X AA20X AA21X AA28X AA82X AB18 AB19 AB21 AF26 BB09 BC01 BC07 4F100 AA01B AK04A AK04B AK22B AK62A AK62C AK68B AL01B BA03 BA06 BA10A BA10B BA16 CA23B GB01 JA06A JA06C JA07A JA07C JA13A JA13C JK01 JK03A JK03C JL05 JL07 JL08A JL08C YY00A YY00B YY00C 4J002 BB03W BB03X BB05W BB06X BB12X BB15W CF00X CL00X DE146 DE186 DE236 DE286 DJ006 DJ016 FD016 FD176 GA01 GF00 4J028 AA01A AB00A AB01A AC02A AC23A BA00A BA01B BB00A BB0 1B BC15B BC16B BC18B BC24B BC25B CA42C CB65C CB81C CB86C CB94C EB02 EB03 EB04 EB05 EB07 EB08 EB09 EB10 EC02 FA02 FA03 FA04 GA06 GA08

Claims (7)

[Claims] 1. A tubular film formed by an inflation method is provided with a slit portion along a length direction, and when the tubular film is opened from the slit portion and spread on a facility gardening house, the tubular film is formed. The inner layer is the inner layer (A) located on the inner surface side of the greenhouse, and the outer layer of the tubular film is the outer layer (C) located on the outer surface of the greenhouse.
And a multi-layered horticultural film having an intermediate layer (B) between the inner layer (A) and the outer layer (C), which constitutes the outer layer (C) which is the outer skin of the tubular film. The main component of the composition has a density (d _c1 ) of 0.88 to 0.96 g.
/ Cm ³ of ethylene -α- olefin copolymer (c ₁₎ or density (d _c2) horticulture film is 0.91～0.93G / cm ³ of ethylene homopolymer (c _2). 2. An ethylene-α-olefin copolymer (c ₁ ) which is a main component of a composition constituting an outer layer (C) which is an outer shell of a cylindrical film is polymerized using a single-site catalyst. Density (d _c11 ) of 0.88 to 0.93 g / cm ³
The greenhouse horticultural film according to claim 1, which is an ethylene-α-olefin copolymer (c ₁₁ ). 3. The ethylene-α-olefin copolymer (c ₁₁ ) which is a main component of the composition constituting the outer layer (C) which is the outer skin of the tubular film is a copolymer having the following properties. Item 7. The film for facility horticulture according to Item 2. a) Melt flow ratio I ₁₀ / I ₂ ≧ 5.63 b) Molecular weight distribution Mw / Mn ≦ (I ₁₀ / I ₂ ) −4.63 c) Critical shear stress γ γ> 4 when gross melt fracture begins to occur × 10 ⁶ dyne / cm ² 4. The composition for forming the inner layer (A), which is the inner layer of the tubular film, has a vinyl acetate content of 2 to 15%.
2. An ethylene-vinyl acetate copolymer of 1% by weight.
4. The film for greenhouse horticulture according to any one of items 3 to 3. 5. The composition constituting the inner layer (A), which is the inner layer of the tubular film, comprises X weight% of additive and B of inorganic filler.
The facility horticulture according to any one of claims 1 to 4, wherein the ET specific surface area Sm ² / g further includes one or more inorganic fillers satisfying a relationship of 1 / S ≦ X ≦ 100 / S. For film. 6. The density (d) in which the main component of the composition constituting the intermediate layer (B) is polymerized using a single-site catalyst.
In _b) is 0.85~0.93g / cm ^3, and horticulture film of an ethylene -α- olefin polymer (b) is according to any one of claims 1 to 5 having the following properties. a) Melt flow ratio I ₁₀ / I ₂ ≧ 5.63 b) Molecular weight distribution Mw / Mn ≦ (I ₁₀ / I ₂ ) −4.63 c) Critical shear stress γ γ> 4 when gross melt fracture begins to occur × 10 ⁶ dyne / cm ² 7. A slit portion is provided at one position along a longitudinal direction of the tubular film at a fold portion or a central portion of the folded width at one end of the tubular film, and the tubular film is folded in the longitudinal direction. The film for greenhouse horticulture according to any one of claims 1 to 6, wherein