JPH09249774A - Agricultural film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an agricultural film used for agricultural houses and tunnel houses or as a mulching or the like, being excellent in optical properties, tensile strength, tearing strength, impact strength, etc., and, unlike a vinyl chloride resin film, not forming any noxious gases when burnt. SOLUTION: This film is made from an ethylene homopolymer or an ethylene/α-olefin copolymer obtained by polymerizing ethylene or copolymerizing ethylene with a 3-20 C α-olefin in the presence of a catalyst comprising a cyclopentadiene compound and a compound of a group IV transition metal in the periodic table and satisfying the following requirements: (i) the density is 0.86-0.96g/cm<3> , (ii) the melt flow rate is 0.01-100g/10min, (iii) the molecular weight distribution (Mw/Mn ratio) is 1.5-5.0, and the compositional distribution parameter Cb is 2.00 or below and optionally other olefin (co)polymers.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an agricultural film made of an ethylene homopolymer or an ethylene / .alpha.-olefin copolymer which satisfies specific requirements and has excellent physical properties such as mechanical strength.

[0002]

2. Description of the Related Art Agricultural greenhouses for greenhouse cultivation, covering films used for tunnel houses, etc., and agricultural films such as mulch films used for covering the surface of the ground by closely spreading, have conventionally been used. Films made of vinyl chloride resin and polyolefin resins such as low-density polyethylene (hereinafter referred to as LDPE) by high-pressure polymerization method, linear low-density polyethylene (hereinafter referred to as LLDPE) obtained by polymerization with Ziegler-based catalyst, and vinyl chloride resin are widely used. Are known. Of these, polyolefin resins are often used as agricultural films because they have good transparency and high water vapor transmission rate, and because they do not generate toxic gas when waste films are incinerated like vinyl chloride resins. However, polyolefin-based films such as LDPE, which have been conventionally used for agriculture, have poor mechanical strength and are not yet satisfactory. That is, it is necessary for the agricultural film to have sufficient tensile strength and tear strength to withstand stretching when the film is stretched on a house or the like, or when the mulch film is closely stretched on the ground surface. In addition, since mulching with a film also has the purpose of preventing soil runoff and soil rebound, from this point as well, although mechanical strength is required, polyolefin film that has been used for agriculture has been used up to now. Does not have sufficient mechanical strength.

[0003]

In view of the above-mentioned circumstances, the present invention has the characteristics of a polyolefin resin as an agricultural film, that is, it is inexpensive, has good transparency, and has a mechanical strength. It is intended to provide an improved agricultural film.

[0004]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that a monolayer film or a laminate with another film using an ethylene homopolymer or an ethylene / α-olefin copolymer satisfying specific parameters. The inventors have found that the film achieves the above object, and completed the present invention.

The first aspect of the present invention is to use ethylene or ethylene and an α-olefin having 3 to 20 carbon atoms in the presence of at least one catalyst containing at least a cyclopentadiene compound and a transition metal compound of Group IV of the periodic table. To provide an agricultural film having an ethylene homopolymer or an ethylene / α-olefin copolymer as an essential constituent resin, which satisfies the following requirements (a) to (d) obtained by (co) polymerizing is there. (A) Density 0.86 to 0.96 g / cm ³ (b) Melt flow rate 0.01 to 100 g / 10
Min (c) molecular weight distribution (Mw / Mn) is 1.5 to 5.0 (d) composition distribution parameter Cb is 2.00 or less

In the second aspect of the present invention, the resin component further comprises an olefinic (co) polymer (B) other than the above-mentioned ethylene homopolymer or ethylene / α-olefin copolymer (A) per 80 resin components. The above-mentioned agricultural film is contained, which is contained by weight% or less. The third aspect of the present invention is an agricultural film comprising a resin or resin composition in which 0.01 to 10 parts by weight of an antifogging agent and / or an antistatic agent are added to 100 parts by weight of the above resin or resin composition. A fourth aspect of the present invention is to provide an agricultural film comprising a film made of the above resin or resin composition and a laminated film containing another film.

Hereinafter, the present invention will be described in more detail. The ethylene homopolymer or ethylene / α-olefin copolymer (A) used in the present invention is ethylene in the presence of at least one catalyst containing at least a cyclopentadiene compound and a transition metal compound of Group IV of the periodic table. Alternatively, the following requirements (a) to (d) obtained by copolymerizing ethylene with an α-olefin having 3 to 20 carbon atoms, and (a) a density of 0.86 to 0.96 g / cm ³ (b) Melt flow rate is 0.01-100g / 10
Min (c) Molecular weight distribution (Mw / Mn) is 1.5 to 5.0 (d) Composition distribution parameter Cb is an ethylene homopolymer or ethylene / α-olefin copolymer satisfying 2.00 or less. Further, one example thereof is one having substantially one peak in the elution temperature-elution amount curve obtained by the continuous temperature rising elution fractionation method (TREF) as shown in FIG. 1, which is cyclopentadiene. A typical metallocene-catalyzed ethylene homopolymer or ethylene / α-olefin copolymerization obtained in the presence of at least one catalyst containing a ligand having an enyl skeleton and a transition metal compound of Group IV of the periodic table Coalescence (A), and another example is a continuous temperature rising elution fractionation method (T
It is a special novel ethylene homopolymer or ethylene / α-olefin copolymer (A2) having a plurality of peaks in the elution temperature-elution amount curve determined by REF).

The α-olefin of the above-mentioned ethylene homopolymer or ethylene / α-olefin copolymer (A) of the present invention has 3 to 20 carbon atoms, preferably 3 to 12 carbon atoms. Is propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-
Octene, 1-decene, 1-dodecene and the like can be mentioned. The content of these α-olefins is desirably selected in a range of usually 30 mol% or less, preferably 20 mol% or less.

The above ethylene homopolymer or ether of the present invention
(A) Density of the ethylene / α-olefin copolymer (A1)
Is 0.86 to 0.96 g / cm^Three, Preferably 0.90
~ 0.94 g / cm^Three, And more preferably 0.91
0.93 g / cm^Three(B) melt flow
Rate (hereinafter referred to as MFR) is 0.01 to 100 g / 1
0 minutes, preferably 0.1 to 50 g / 10 minutes, more preferably
It is preferably in the range of 0.5 to 40 g / 10 minutes. Density
0.86 g / cm^ThreeLess than is too soft and has heat resistance
It becomes poor and the anti-blocking property becomes poor. Ma
0.96 g / cm ^ThreeIf it exceeds, it will be too hard and will tear
Strength and impact drop strength are reduced. MFR is 0.01g
If it is less than / 10 minutes, the workability becomes poor and 100 g / 10
If it exceeds the minute, the strength becomes weak.

Generally, the molecular weight distribution (Mw / M) of ethylene homopolymer or ethylene / α-olefin copolymer
n) is gel permeation chromatography (G
The weight average molecular weight (Mw) and the number average molecular weight (Mn) can be obtained by calculating the ratio (Mw / Mn) of these, and the ethylene homopolymer or ethylene / α-olefin of the present invention can be obtained. The (c) Mw / Mn of the copolymer (A) is in the range of 1.5 to 5.0. In addition, in the typical metallocene-catalyzed ethylene / α-olefin copolymer (A1) shown in FIG.
(C) Mw / Mn is preferably in the range of 1.5 to 4.5, more preferably 1.8 to 3.5. Furthermore, in the special ethylene homopolymer or ethylene / α-olefin copolymer (A2) shown in FIG. 2, (C) Mw / Mn is preferably 1.5 to 4.
5, more preferably 1.8 to 4.0, and most preferably 2.0 to 3.0. Mw above
If / Mn is less than 1.5, the moldability is poor, and if it exceeds 5.0, the impact resistance is poor.

The method for measuring the (d) composition distribution parameter (Cb) of the ethylene homopolymer or ethylene / α-olefin copolymer (A) of the present invention is as follows. That is, orthodichlorobenzene (O 2
DCB) was added to the sample at a concentration of 0.2% by weight.
After heating and dissolving at 5 ° C., the solution is transferred to a column filled with diatomaceous earth (Celite 545), cooled to 25 ° C. at a cooling rate of 0.1 ° C./min, and the copolymer sample is deposited on the Celite surface. . Next, while the ODCB is caused to flow through the column in which this sample is deposited at a constant flow rate, the column temperature is gradually raised to 120 ° C. in steps of 5 ° C. Then, a solution containing an eluted component corresponding to each temperature is collected. Methanol is added to this solution, the sample is precipitated, filtered and dried to obtain an eluted sample at each temperature. The weight fraction and the degree of branching (the number of branches per 1000 carbon atoms) of each sample are measured. The degree of branching is determined by measuring with ¹³ C-NMR.

For each fraction collected at 30 ° C. to 90 ° C. by such a method, the branching degree is corrected as follows. That is, the degree of branching measured against the elution temperature is plotted, and the correlation is approximated to a straight line by the least square method,
Create a calibration curve. The correlation coefficient of this approximation is large enough.
The value obtained from this calibration curve is defined as the degree of branching of each fraction. Note that, for a fraction collected at an elution temperature of 95 ° C. or higher, this correction is not performed because a linear relationship is not always established between the elution temperature and the degree of branching.

Next, the weight fraction w of each fraction
The _i, the amount of change in the degree of branching b _i per the elution temperature 5 ° C. (b _i
Obtaining the relative concentration c _i is divided by -b _i-1), by plotting the relative concentration against the branching degree to obtain a composition distribution curve. This composition distribution curve is divided by a certain width, and the composition distribution parameter Cb is calculated from the following equation.

[0014]

[Equation 1]

Here, c _j and b _j are the relative density and branching degree of the j-th section, respectively. Composition distribution parameter C
b becomes 1.0 when the composition of the sample is uniform, and becomes larger as the composition distribution becomes wider.

Many proposals have been made for a method of expressing the composition distribution of the ethylene / α-olefin copolymer. For example, in Japanese Patent Application Laid-Open No. 60-88016, numerical processing is performed on the assumption that the cumulative weight fraction has a specific distribution (log normal distribution) with respect to the number of branches of each separated sample obtained by solvent separation of the sample. The ratio between the weight average branching degree (Cw) and the number average branching degree (Cn) is determined. The accuracy of this approximation calculation decreases when the number of branches and the cumulative weight fraction of the sample deviate from the lognormal distribution, and when measurement is performed on a commercially available LLDPE, the correlation coefficient R ² is considerably low, and the accuracy of the value is not sufficient. In addition, the method of measuring Cw / Cn and the numerical processing method are the same as those of the present invention.
Although it is different from that of b, if you dare to compare the values, Cw
The value of / Cn is much larger than Cb.

The ethylene homopolymer or ethylene / α-olefin copolymer (A) of the present invention (D) has a composition distribution parameter (Cb) of 2.00 or less, which is a typical metallocene-catalyzed ethylene homopolymer. Alternatively, in the ethylene / α-olefin copolymer (A1), it is preferably 1.01 to 1.2, more preferably 1.02.
It is desirable that it is in the range of 1.18, most preferably 1.03 to 1.17. The special ethylene homopolymer or ethylene / α-olefin copolymer (A
In 2), preferably 1.08 to 2.00, more preferably 1.10 to 1.80, and more preferably 1.
It is preferably in the range of 15 to 1.50. When the composition distribution parameter (Cb) is larger than 2.00, blocking is likely to occur, heat sealability becomes poor, and a low molecular weight or high branching component oozes out on the resin surface to cause problems such as blocking.

The special ethylene homopolymer or ethylene / α-olefin copolymer (A2) (f) of the present invention
The relationship between the amount X (% by weight) of the ODCB-soluble component at 25 ° C. and the density d and MFR is as follows:
When 0.008 log MFR ≧ 0.93 is satisfied, X is less than 2% by weight, preferably less than 1% by weight, d-0.00.
When 8 log MFR <0.93, X <9.8 × 10 ³ × (0.9300−d + 0.008 log MFR) ²
+2.0 Preferably, X <7.4 × 10 ³ × (0.9300−d + 0.008log MFR) ²
+1.0 More preferably, X <5.6 × 10 ³ × (0.9300−d + 0.008log MFR) ²
+0.5 must be satisfied.

The amount of ODCB-soluble matter at 25 ° C. is measured by the following method. 0.5 g of sample is 20 m
Heat at 135 ° C. for 2 hours with 1 ODCB to completely dissolve the sample and cool to 25 ° C. Put this solution at 25 ° C
After overnight standing, filter through a Teflon filter and collect the filtrate. Wave number 2925c of asymmetric stretching vibration of this filtrate
The area of the absorption peak near m ⁻¹ is obtained, and the sample concentration is calculated from the calibration curve prepared in advance. From this value, the ODCB-soluble content at 25 ° C. is determined.

The ODCB-soluble component at 25 ° C. is a highly branched component and a low molecular weight component contained in the ethylene / α-olefin copolymer, and causes hygiene problems and blocking on the inner surface of the molded product. It is desirable that this content is small. The amount of ODCB solubles is affected by the comonomer content and molecular weight. Therefore, the fact that the density and MFR, which are these indexes, and the amount of the ODCB-soluble component satisfy the above relationship indicates that the uneven distribution of the α-olefin contained in the entire copolymer is small.

The special ethylene homopolymer or ethylene / α-olefin copolymer (A2) of the present invention is (e)
In the elution temperature-elution amount curve obtained by the continuous temperature rising elution fractionation method (TREF), there are a plurality of peaks, which are clearly distinguished from the typical metallocene-catalyzed polymer (A1) in FIG. . This multiple peak temperature is 85 ℃
It is particularly preferred that it is present between 1 and 100 ° C. The presence of this peak improves the heat resistance of the film.

The TREF measuring method according to the present invention is as follows. The sample was added to an ODCB containing an antioxidant (for example, butylhydroxytoluene) at a concentration of 0.
The mixture was added so as to have a concentration of 05% by weight and dissolved by heating at 135 ° C. 5 ml of this sample solution is injected into a column filled with glass beads, cooled to 25 ° C. at a cooling rate of 0.1 ° C./min, and the sample is deposited on the surface of the glass beads. Next, the sample is sequentially eluted while the column temperature is raised at a constant rate of 50 ° C./hr while flowing ODCB through the column at a constant flow rate. At this time, the concentration of the sample eluted in the solvent is
The absorption is continuously detected by measuring the absorption of the asymmetric stretching vibration of methylene at a wave number of 2925 cm ^-1 with an infrared detector. From this value, the concentration of the ethylene / α-olefin copolymer in the solution is quantitatively analyzed to determine the relationship between the elution temperature and the elution rate. According to the TREF analysis, a change in the elution rate with respect to a temperature change can be continuously analyzed with a very small amount of sample, so that a relatively fine peak which cannot be detected by the fractionation method can be detected.

The ethylene homopolymer or ethylene / α-olefin copolymer (A1) produced by the typical metallocene catalyst is a transition metal compound of Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton. And in the presence of at least one catalyst containing a cocatalyst, an organoaluminum compound, and a carrier as required, ethylene and a carbon number of 3 to 20
Of α-olefins.

The ethylene homopolymer or ethylene.
The cyclopentadienyl skeleton of a transition metal compound of Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton, which is a catalyst for producing an α-olefin copolymer (A1), is cyclopentadienyl Groups, substituted cyclopentadienyl groups and the like. Examples of the substituted cyclopentadienyl group include a hydrocarbon group having 1 to 10 carbon atoms, a silyl group, a silyl-substituted alkyl group, a silyl-substituted aryl group, a cyano group, a cyanoalkyl group, a cyanoaryl group, a halogen group, a haloalkyl group, and a halosilyl group. And a substituted cyclopentadienyl group having at least one substituent selected from groups and the like. The substituted cyclopentadienyl group may have two or more substituents, and the substituents may be bonded to each other to form a ring.

Examples of the hydrocarbon group having 1 to 10 carbon atoms include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and the like. Specifically, a methyl group, an ethyl group, an n-propyl group, Isopropyl group, n-butyl group,
Alkyl groups such as isobutyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, octyl group, 2-ethylhexyl group, decyl group; cycloalkyl groups such as cyclopentyl group, cycloalkyl group; phenyl group, tolyl group Examples thereof include aryl groups such as groups; and aralkyl groups such as benzyl groups and neophyl groups. Among these, an alkyl group is preferable. Preferred examples of the substituted cyclopentadienyl group include a methylcyclopentadienyl group, an ethylcyclopentadienyl group, an n-hexylcyclopentadienyl group, a 1,3-dimethylcyclopentadienyl group,
3-n-butylmethylcyclopentadienyl group, 1,3
Specific examples thereof include -n-propylmethylethylcyclopentadienyl group. Among these, the substituted cyclopentadienyl group of the present invention is preferably a cyclopentadienyl group substituted with an alkyl group having 3 or more carbon atoms,
A 1,3-substituted cyclopentadienyl group is particularly preferable.
When the substituents, that is, the hydrocarbons are bonded to each other to form one or more rings, examples of the substituted cyclopentadienyl group include an indenyl group and a hydrocarbon group having 1 to 8 carbon atoms (such as an alkyl group). A substituted indenyl group, a naphthyl group, a substituted naphthyl group substituted with a substituent such as a C1-C8 hydrocarbon group (such as an alkyl group), a C1-C8 hydrocarbon group ( Preferred examples thereof include a substituted fluorenyl group substituted by a substituent such as an alkyl group.

Examples of the transition metal of the group IV transition metal compound containing a ligand having a cyclopentadienyl skeleton include zirconium, titanium and hafnium, with zirconium being particularly preferred. The transition metal compound usually has 1 to 3 ligands having a cyclopentadienyl skeleton, and when they have 2 or more ligands, they may be bonded to each other by a bridging group. Examples of the cross-linking group include an alkylene group having 1 to 4 carbon atoms, an alkylsilanediyl group, and a silanediyl group.

As the ligands other than the ligand having a cyclopentadienyl skeleton in the transition metal compound of Group IV of the periodic table, hydrogen and C 1-20 are typical.
(Alkyl group, alkenyl group, aryl group, alkylaryl group, aralkyl group, polyenyl group, etc.), halogen, methalkyl group, metaaryl group and the like.

Specific examples of these are as follows. As dialkyl metallocenes, bis (cyclopentadienyl) titanium dimethyl, bis (cyclopentadienyl) titanium diphenyl, bis (cyclopentadienyl) zirconium dimethyl, bis (cyclopentadienyl) zirconium diphenyl, bis (cyclopentadienyl) ) Hafnium dimethyl, bis (cyclopentadienyl) hafnium diphenyl and the like. Monoalkyl metallocenes include bis (cyclopentadienyl)
Examples include titanium methyl chloride, bis (cyclopentadienyl) titanium phenyl chloride, bis (cyclopentadienyl) zirconium methyl chloride, and bis (cyclopentadienyl) zirconium phenyl chloride. In addition, monocyclopentadienyl titanocene such as pentamethylcyclopentadienyl titanium trichloride, pentaethylcyclopentadienyl titanium trichloride), and bis (pentamethylcyclopentadienyl) titanium diphenyl are exemplified.

Examples of the substituted bis (cyclopentadienyl) titanium compound include bis (indenyl) titanium diphenyl or dichloride, bis (methylcyclopentadienyl) titanium diphenyl or dichloride, dialkyl, trialkyl, tetraalkyl or pentaalkylcyclopenta. Examples of the dienyl titanium compound include bis (1,2-dimethylcyclopentadienyl) titanium diphenyl or dichloride, bis (1,2-diethylcyclopentadienyl) titanium diphenyl or dichloride or other dihalide complex, silicon, amine or Carbon-bonded cyclopentadiene complexes include dimethylsilyldicyclopentadienyl titanium diphenyl or dichloride, methylenedicyclopentadienyl Data iodonium diphenyl or dichloride, and other dihalide complexes.

As the zirconocene compound, pentamethylcyclopentadienyl zirconium trichloride,
Pentaethylcyclopentadienyl zirconium trichloride, bis (pentamethylcyclopentadienyl)
Examples of zirconium diphenyl and alkyl-substituted cyclopentadiene include bis (ethylcyclopentadienyl) zirconium dimethyl, bis (methylcyclopentadienyl) zirconium dimethyl, bis (n-butylcyclopentadienyl) zirconium dimethyl, and haloalkyl or dihalide thereof. Examples of the complex, dialkyl, trialkyl, tetraalkyl or pentaalkylcyclopentadiene include bis (pentamethylcyclopentadienyl) zirconium dimethyl, bis (1,2-dimethylcyclopentadienyl) zirconium dimethyl, and dihalide complexes thereof, silicon And carbon-linked cyclopentadiene complexes such as dimethylsilyldicyclopentadienylzirconium dimethyl or dihalide, methylenedicyclopentene Dienyl zirconium dimethyl or dihalide, such as methylene dicyclopentadienyl zirconium dimethyl or dihalide, and the like.

Still other metallocenes include bis (cyclopentadienyl) hafnium dichloride, bis (cyclopentadienyl) hafnium dimethyl, bis (cyclopentadienyl) vanadium dichloride and the like.

As another example of the transition metal compound of Group IV of the periodic table of the present invention, a ligand having a cyclopentadienyl skeleton represented by the following general formula and other ligands and transition metal atoms are The thing which forms a ring is also mentioned.

[0033]

Embedded image

In the formula, Cp is a ligand having the cyclopentadienyl skeleton, X ₂ is hydrogen, halogen, and a carbon number of 1 to 1.
20 represents an alkyl group, an arylsilyl group, an aryloxy group, an alkoxy group, an amido group, a silyloxy group, etc., and Y represents SiR ₂ , CR ₂ , SiR ₂ SiR ₂ , CR ₂
CR _2, CR = CR, _2-valent group selected from the group consisting of _{SiR 2 CR 2, BR 2,} BR, Z is -O -, - S-,
-NR -, - PR- or _{OR, SR, NR 2, PR} 2
Shows a divalent neutral ligand selected from the group consisting of: Here, R is hydrogen or an alkyl group having 1 to 20 carbon atoms, an aryl group, a silyl group, a halogenated alkyl group, a halogenated aryl group, or Y, Z or 2 from both Y and Z.
One or more R groups form a fused ring system. M represents a transition metal atom of Group IV of the periodic table.

Examples of compounds of formula I include (t
-Butylamide) (tetramethylcyclopentadienyl) -1,2-ethanediylzirconium dichloride, (t-butylamide) (tetramethylcyclopentadienyl) -1,2-ethanediyltitanium dichloride, (methylamide) (tetramethyl Cyclopentadienyl) -1,2-ethanediylzirconium dichloride, (methylamide) (tetramethylcyclopentadienyl) -1,2-ethanediyltitanium dichloride,
(Ethylamide) (tetramethylcyclopentadienyl) methylenetan dichloride, (t-butylamide)
Dimethyl (tetramethylcyclopentadienyl) silane titanium dichloride, (t-butylamido) dimethyl (tetramethylcyclopentadienyl) silanezirconium dibenzyl, (benzylamido) dimethyl (tetramethylcyclopentadienyl) silane titanium dichloride, Phenylphosphido) dimethyl (tetramethylcyclopentadienyl) silanetitanium dichloride.

The cocatalyst referred to in the present invention is one that can effectively use the transition metal compound of Group IV of the periodic table as a polymerization catalyst or one that can balance the ionic charge in the catalytically activated state. Say. Examples of the co-catalyst used in the present invention include benzene-soluble aluminoxane, benzene-insoluble organic aluminum oxy compound, boron compound, lanthanide salts such as lanthanum oxide, and tin oxide of the organic aluminum oxy compound. Of these, aluminoxane is most preferable.

The catalyst is a carrier of an inorganic or organic compound.
May be used. The carrier may be inorganic or
Is preferably a porous oxide of an organic compound.
iO _Two, Al_TwoO_Three, MgO, ZrO_Two, TiO_Two, B
_TwoO_Three, CaO, ZnO, BaO, ThO_TwoEtc. or this
These mixtures include SiO 2_Two-Al_TwoO_Three, Si
O_Two-V_TwoO_Five, SiO_Two-TiO_Two, SiO_Two-Mg
O, SiO_Two−Cr_TwoO_FiveAnd the like.

Examples of the organic aluminum compound include trialkyl aluminum such as triethyl aluminum and triisopropyl aluminum; dialkyl aluminum halide; alkyl aluminum sesquihalide; alkyl aluminum dihalide; alkyl aluminum hydride and organic aluminum alkoxide.

The special ethylene homopolymer of the present invention or
The ethylene / α-olefin copolymer (A2) can be produced by
It is preferably one polymerized with the following catalysts a1 to a5
Is desirable. a1: general formula Me¹R¹ _p(OR^Two)_qX¹ _4-pqRepresented by
Compound (wherein Me ¹Is zirconium, titanium, Huff
And R¹And R^TwoEach have 1 to 2 carbon atoms
A hydrocarbon group of 4, X¹Represents a halogen atom, p and
q satisfies the range of 0 ≦ p <4 and 0 ≦ p + q ≦ 4, respectively.
Is an integer). a2: general formula Me^TwoR^Three _m(OR^Four)_nX^Two _zmnTable
Compound (wherein Me is^TwoIs the I-III family element of the periodic table
Prime, R^ThreeAnd R^FourIs a hydrocarbon having 1 to 24 carbon atoms
Prime group, X^TwoRepresents a halogen atom or a hydrogen atom (however, X
^TwoIs Me when hydrogen is a hydrogen atom^TwoIs a group III element of the periodic table
And z is Me^TwoAnd m and m
And n satisfy the ranges of 0 ≦ m ≦ z and 0 ≦ n ≦ z, respectively.
Is an integer and 0 ≦ m + n ≦ z). a3: an organic cyclic compound having a conjugated double bond. a4: Modified organoaluminum containing Al-O-Al bond
Oxy compound. a5: Inorganic carrier and / or particulate polymer carrier are mutually
The catalyst obtained by contacting with.

Further details will be described below. In the formula of the compound represented by the general formula Me ¹ R ¹ _p (OR ² ) _q X ¹ _4-pq of the catalyst component a1, Me ¹ represents zirconium, titanium or hafnium, and the kinds of these transition metals are limited. However, a plurality of zirconium compounds can be used, but it is particularly preferable that zirconium, which has excellent weather resistance of the copolymer, is contained. R ¹ and R ² are each a hydrocarbon group having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms, and more preferably 1 to 8 carbon atoms. Specifically, alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group and butyl group; alkenyl groups such as vinyl group and allyl group; phenyl group, tolyl group, xylyl group, mesityl group, indenyl group and naphthyl group And an aralkyl group such as a benzyl group, a trityl group, a phenethyl group, a styryl group, a benzhydryl group, a phenylbutyl group, and a neofuyl group. These may have branches. X ¹ is fluorine,
Shows halogen atoms such as iodine, chlorine and bromine. p
And q are integers satisfying the ranges of 0 ≦ p <4 and 0 ≦ p + q ≦ 4, respectively.

Examples of the compound represented by the general formula of the catalyst component a1 include tetramethylzirconium, tetraethylzirconium, tetrabenzylzirconium, tetrapropoxyzirconium, tripropoxymonochlorozirconium, tetrabutoxyzirconium, tetrabutoxytitanium, tetrabutoxyhafnium. And the like. Particularly, Zr (OR) ₄ compounds such as tetrapropoxyzirconium and tetrabutoxyzirconium are preferable, and two or more kinds of these may be mixed and used.

The above catalyst component a2 has the general formula Me ² R
^In the formula of the compound represented by ³ _m (OR ⁴ ) _n X ² _zmn
e ² represents the periodic table I~III group element is lithium, sodium, potassium, magnesium, calcium, zinc, boron, aluminum. R ³ and R ⁴
Is a hydrocarbon group having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms, and more preferably 1 to 8 carbon atoms. Specific examples thereof include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, and butyl group. Alkenyl groups such as vinyl group and allyl group; aryl groups such as phenyl group, tolyl group, xylyl group, mesityl group, indenyl group and naphthyl group; benzyl group, trityl group, phenethyl group, styryl group, benzhydryl group, phenyl An aralkyl group such as a butyl group and a neofuyl group is exemplified. These may have branches. X ² represents a halogen atom or a hydrogen atom such as fluorine, iodine, chlorine and bromine. However, when X ² is a hydrogen atom, Me ² is limited to a group III element of the periodic table exemplified by boron, aluminum and the like. Z represents the valence of Me ² , and m and n are respectively 0 ≦ m ≦ z, 0 ≦ n ≦ z
And satisfies 0 ≦ m + n ≦ z.

Examples of the compound represented by the general formula of the catalyst component a2 include organic lithium compounds such as methyllithium and ethyllithium; organic magnesium compounds such as dimethylmagnesium, diethylmagnesium, methylmagnesium chloride and ethylmagnesium chloride; dimethyl. Organozinc compounds such as zinc and diethylzinc; Organoboron compounds such as trimethylboron and triethylboron; Trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, tridecylaluminum, diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesqui Organic aldehydes such as chloride, diethyl aluminum ethoxide, and diethyl aluminum hydride Derivatives such as iodonium compounds.

The above organic cyclic compound having a conjugated double bond of the catalyst component a3 has one ring having at least two conjugated double bonds, preferably 2 to 4 and more preferably 2 to 3 conjugated double bonds. Or a cyclic hydrocarbon compound having 2 or more and having a total carbon number of 4 to 24, preferably 4 to 12; the cyclic hydrocarbon compound is partially 1 to 6 hydrocarbon residues (typically, A cyclic hydrocarbon compound substituted with an alkyl group having 1 to 12 carbon atoms or an aralkyl group); 2 or more, preferably 2 to 4, and more preferably 2 to conjugated double bonds.
One or more rings having three rings and a total carbon number of 4
An organosilicon compound having a cyclic hydrocarbon group of from 24 to 24, preferably 4 to 12; said cyclic hydrocarbon group being partially substituted by 1 to 6 hydrocarbon residues or an alkali metal salt (sodium or lithium salt) Organosilicon compounds. Particularly preferably, those having a cyclopentadiene structure in any of the molecules are desirable.

Examples of the above-mentioned suitable compounds include cyclopentadiene, indene, azulene or their alkyl, aryl, aralkyl, alkoxy or aryloxy derivatives. Moreover, the compound which these compounds couple | bonded (bridge | crosslink) through the alkylene group (The carbon number is 2-8 normally, Preferably 2-3) is also used suitably.

The organosilicon compound having a cyclic hydrocarbon group can be represented by the following general formula. A _L SiR _4-L wherein A represents the above-mentioned cyclic hydrogen group exemplified by a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, and a substituted indenyl group, and R represents a methyl group, an ethyl group, a propyl group. Alkyl groups such as methoxy, ethoxy, propoxy and butoxy groups; aryl groups such as phenyl groups; aryloxy groups such as phenoxy groups; aralkyl groups such as benzyl groups. And represents a hydrocarbon residue having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms or hydrogen, and L represents 1
≦ L ≦ 4, preferably 1 ≦ L ≦ 3.

Specific examples of the organic cyclic hydrocarbon compound of the above component a3 include cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene, 1,3-dimethylcyclopentadiene, indene, 4-methyl-1-indene, 4,7-. Cyclopolyene or substituted cyclopolyene having 5 to 24 carbon atoms such as dimethylindene, cycloheptatriene, methylcycloheptatriene, cyclooctatetraene, azulene, fluorene and methylfluorene, monocyclopentadienylsilane, biscyclopentadiene Phenylsilane, triscyclopentadienylsilane, monoindenylsilane, bisindenylsilane,
Examples include trisindenylsilane and the like.

The modified organoaluminum oxy compound containing an Al--O--Al bond of the catalyst component a4 is reacted with an alkylaluminum compound and water to obtain a modified organoaluminum oxy compound usually called aluminoxane, The molecule usually contains 1 to 100, preferably 1 to 50 Al-O-Al bonds. The modified organic aluminum oxy compound may be linear or cyclic.

The reaction of organoaluminum with water is usually carried out in an inert hydrocarbon. As the inert hydrocarbon,
Aliphatic, alicyclic and aromatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, benzene, toluene and xylene are preferred. The reaction ratio between water and the organoaluminum compound (water / Al molar ratio) is usually 0.25 / 1 to 1.2.
/ 1, preferably 0.5 / 1 to 1/1.

Inorganic carrier of catalyst component a5 and / or
Particulate polymer carrier means carbonaceous material, metal, metal oxide
Substance, metal chloride, metal carbonate or a mixture thereof
Examples thereof include thermoplastic resins and thermosetting resins. Nothing
Suitable metals that can be used for the equipment carrier include
Examples include iron, aluminum, and nickel. concrete
Has SiO_Two, Al_TwoO_Three, MgO, ZrO_Two, TiO
_Two, B_TwoO_Three, CaO, ZnO, BaO, ThO_TwoToma
Or mixtures thereof; _Two-Al
_TwoO_Three, SiO_Two-V_TwoO_Five, SiO_Two-TiO_Two, S
iO_Two-V_TwoO _Five, SiO_Two-MgO, SiO_Two−Cr
_TwoO_ThreeAnd the like. Among them, SiO_Twoand
Al_TwoO_ThreeAt least one member selected from the group consisting of
Those containing components as main components are preferred. Also, organic compounds
Uses both thermoplastic resin and thermosetting resin
And specifically, polyolefin particles,
Ter, polyamide, polyvinyl chloride, poly (meth) ac
Methyl lylate, polystyrene, polynorbornene, various types
Examples include natural polymers and mixtures thereof.

The above-mentioned inorganic carrier and / or particulate polymer carrier can be used as they are, but preferably, as a pretreatment, these carriers are treated with an organoaluminum compound or a modified organoaluminumoxy compound containing an Al--O--Al bond. It can also be used as the component a5 after being contact-treated with.

Since the ethylene homopolymer or ethylene / α-olefin copolymer (A2) of the present invention has a moderately narrow molecular weight distribution and composition distribution, it has high mechanical strength.
It is a polymer with excellent heat-sealing properties and anti-blocking properties, and also with good heat resistance.

The ethylene homopolymer or ethylene of the present invention
The method for producing the ethylene / α-olefin copolymer (A) is described above.
A gas phase polymerization method in the presence of a catalyst, which is substantially free of a solvent,
Manufactured by slurry polymerization method, solution polymerization method, etc.
Butane, pentane, hexa
And aliphatic hydrocarbons such as heptane, benzene, and toluene
Aromatic hydrocarbons such as benzene and xylene, cyclohexane, and
Exemplified by alicyclic hydrocarbons such as tylcyclohexane
Manufactured in the presence or absence of an inert hydrocarbon solvent
You. The polymerization conditions are not particularly limited, but the polymerization temperature is usually 1
5 to 350 ° C, preferably 20 to 200 ° C, more preferably
It is preferably 50 to 110 ° C, and the polymerization pressure is in the case of low and medium pressure method.
Normal pressure to 70 kg / cm^TwoG, preferably normal pressure to 2
0 kg / cm ^TwoG, usually 1500k for high pressure method
g / cm^TwoG or less is desirable. Polymerization time is low medium pressure method.
Generally 3 minutes to 10 hours, preferably 5 minutes to 5 hours
desirable. In the case of the high pressure method, it is usually 1 minute to 30 minutes, preferably
Is preferably about 2 to 20 minutes. Also, the polymerization is a one-step polymerization.
Method, hydrogen concentration, monomer concentration, polymerization pressure,
Two or more different polymerization conditions such as synthesis temperature and catalyst
The multistage polymerization method is not particularly limited.

The polyolefin resin (B) used in the present invention means polyethylene resin, polypropylene resin, polybutene-1 resin, poly-4-methyl-1-pentene resin, ethylene / propylene copolymer rubber, Includes olefin rubbers such as ethylene / propylene-diene copolymer rubber and ethylene / butene-1 copolymer rubber. Among them, polyeletin resin and polypropylene resin are mechanical strength, economical and versatile. And the like, and a polyethylene resin is particularly preferable. The polypropylene-based resin includes a propylene homopolymer, a propylene-ethylene block copolymer, and a propylene-ethylene random copolymer polymerized by a known technique. Among these, propylene homopolymers and propylene-ethylene random copolymers are preferable because of their excellent transparency. Among the above polyolefin-based resins, ethylene homopolymers and / or ethylene copolymers (ethylene (co) polymers) are preferably used because they have a good balance of transparency, flexibility and strength. The ethylene-based (co) polymer (B) means, first, an ethylene homopolymer or ethylene / α-olefin copolymer different from the component (A),
That is, an ethylene homopolymer or a copolymer of ethylene and an α-olefin having 3 to 12 carbon atoms by a high / medium / low pressure method and other known methods using a conventionally known Ziegler catalyst, Phillips catalyst or the like can be mentioned. . This is because it has a broader molecular weight distribution or composition distribution than the component (A) and has a density of 0.94 g / cm ³ or more (hereinafter referred to as HDPE), and a density of 0.91 to 0.94 g / cm ³ linear low density polyethylene (hereinafter referred to as LLDPE), density 0.86 to 0.9
Ultra low density polyethylene of 1 g / cm ³ (hereinafter VLDPE
And an ethylene / α-olefin copolymer rubber such as an ethylene / propylene copolymer rubber and an ethylene / propylene / diene copolymer rubber having a density of 0.86 to 0.91 g / cm ³ .

The above HDPE has a density of 0.94 to 0.
97 g / cm ³ , preferably 0.95 g / cm ³ or more, ethylene homopolymer or ethylene and carbon number produced by a known process such as a slurry method, a solution method or a gas phase method using a known Ziegler catalyst or the like. 3 to 12 are copolymers with α-olefins and mixtures thereof, and specific α-olefins are propylene, 1
-Butene, 4-methyl-1-pentene, 1-hexene,
Examples thereof include 1-octene and 1-dodecene.
Among these α-olefins, α-olefins having 3 to 8 carbon atoms are particularly preferable. MF of these polymers
R is 0.01 to 30 g / 10 min, preferably 0.02
It is selected in the range of up to 20 g / 10 minutes.

The above LLDPE has a density of 0.91 to 0.91.
0.94 g / cm ³ , preferably 0.91 to 0.93 g
It is an ethylene / α-olefin copolymer in the range of / cm ³ , and the MFR is selected in the range of 0.05 to 30 g / 10 minutes, preferably 0.1 to 20 g / 10 minutes. The molecular weight distribution (Mw / Mn) is not particularly limited, but 3.0 to 13,
It is generally in the range of preferably 3.5 to 8.
The α-olefin of the LLDPE has 3 to 20 carbon atoms,
Preferably it has 4 to 12 carbon atoms, more preferably 6 carbon atoms.
Is an α-olefin in the range of from 12 to 12, specifically, propylene, 1-butene, 4-methyl-1-pentene, 1-
Hexene, 1-octene and the like. When the MFR is less than 0.05 g / 10 minutes, the moldability is deteriorated to 30 g.
If it exceeds / 10 minutes, impact resistance, heat seal strength, etc. may decrease.

The above VLDPE has a density of 0.86.
０．９0.91 g / cm ³ , preferably 0.88 to 0.90
It is an ethylene-α-olefin copolymer in the range of 5 g / cm ³ , and the MFR is selected in the range of 0.01 to 20 g / 10 minutes, preferably 0.1 to 10 g / 10 minutes. The V
LDPE is composed of linear low density polyethylene (LLDPE) and ethylene / α-olefin copolymer rubber (EPR, EP
It is a polyethylene showing an intermediate property of DM) and has a maximum peak temperature (Tm) by a differential scanning calorimetry (DSC).
60 ° C. or higher, preferably 100 ° C. or higher and boiling n-
A resin that is a specific ethylene / α-olefin copolymer having a hexane-insoluble content of 10% by weight or more, and has a high crystalline portion represented by LLDPE and an amorphous portion represented by an ethylene / α-olefin copolymer rubber. In addition, the former characteristics, such as impact resistance and heat resistance, and the latter characteristics, such as rubber elasticity and low temperature impact resistance, coexist in a well-balanced manner.

The ethylene / α-olefin copolymer rubber is, for example, an ethylene / propylene copolymer rubber or ethylene / propylene / diene copolymer rubber having a density of 0.86 to less than 0.91 g / cm ^3. Examples of the ethylene / propylene rubber include a random copolymer (EPM) containing ethylene and propylene as main components, and a diene monomer (dichloropentadiene, ethylidene norbornene, etc.) added as a third component as a main component. And a random copolymer (EPDM).

Further, the ethylene (co) polymer (B) in the present invention has a density of 0.
Examples thereof include ethylene homopolymers (low density polyethylene) of 91 to 0.94 g / cm ³ , ethylene / vinyl ester copolymers, and copolymers of ethylene with α, β-unsaturated carboxylic acids or derivatives thereof.

The low density polyethylene (hereinafter referred to as LDPE) has an MFR selected in the range of 0.05 to 30 g / 10 minutes, preferably 0.1 to 20 g / 10 minutes. Within this range, the melt tension of the composition is in an appropriate range, and film formation and the like are easy. The density of the LDPE is 0.9
1 to 0.94 g / cm ³ , preferably 0.912 to 0.
935 g / cm ³ , more preferably 0.912-0.
It is selected in the range of 930 g / cm ³ . The molecular weight distribution (Mw / Mn) is 3.0 to 12, preferably 4.0.
8.0. The LDPE is produced by a known high-pressure radical polymerization method, and may be any of a tubular method and an autoclave method.

The ethylene / vinyl ester copolymer is produced by a high-pressure radical polymerization method, and contains ethylene as a main component, vinyl propionate, vinyl acetate, vinyl caproate, vinyl caprylate, vinyl laurate, stearic acid. It is a copolymer with vinyl ester monomers such as vinyl and trifluorovinyl acetate. Among them, particularly preferred is vinyl acetate. A copolymer composed of 50 to 99.5% by weight of ethylene, 0.5 to 50% by weight of a vinyl ester, and 0 to 49.5% by weight of another copolymerizable unsaturated monomer is preferable. Further, the vinyl ester content is selected in the range of 3 to 20% by weight, particularly preferably 5 to 15% by weight. The MFR of these copolymers is selected in the range of 0.1 to 20 g / 10 minutes, preferably 0.3 to 10 g / 10 minutes.

Further, as a typical copolymer of the above ethylene and α, β-unsaturated carboxylic acid or its derivative, ethylene / (meth) acrylic acid or its alkyl ester copolymer can be mentioned. As these comonomers, acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, acrylic acid-n- Butyl, methacrylic acid-n-
Butyl, cyclohexyl acrylate, cyclohexyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate,
Glycidyl acrylate, glycidyl methacrylate and the like can be mentioned. Of these, particularly preferred are alkyl esters of (meth) acrylic acid such as methyl and ethyl. In particular, the content of the (meth) acrylate is in the range of 3 to 20% by weight, preferably 5 to 15% by weight. The MFR of these copolymers is 0.1
-30 g / 10 min, preferably 0.2-20 g / 10 min.

The mixing ratio of the component (A) and the component (B) is 100 to 20% by weight of the component (A) and 0 for the component (B).
It is desirable to use (A) component in an amount of 50 to 100% by weight when the film strength is important, but the strength is retained to some extent and the processability is
In consideration of flexibility and texture, it is desirable that the component (B) is blended in an appropriate amount, for example, 10 to 70% by weight. On the other hand, other films used in the laminated film of the present invention include the ethylene / α-olefin copolymer (A) of the present invention, the above ethylene-based (co) polymer (B),
Polypropylene, polybutene-1, poly-4-methyl-
A film made of 1-pentene or the like, which is composed of a single component of these polymers or a mixture of two or more components.

The agricultural film of the present invention can be obtained by molding it into a film by a conventionally known molding method. That is, in the case of a single-layer film, a normal inflation molding method and a T-die molding method, and in the case of a laminated film, a multilayer die is used to join a resin melted by an extruder at a die tip using a multilayer die to form a laminated structure. An ordinary molding method such as a co-extrusion molding method such as a multilayer T-die molding method is applied and is not particularly limited. In addition, the laminated film has a preformed film as a base material, and an extrusion lamination method,
It can also be obtained by a lamination method such as a dry lamination method or a sand lamination method. Although the thickness of the film can be arbitrarily changed according to the intended use, the film for a house has a thickness of 100 to 200 in particular.
μm, which is relatively thick, and mulch film has a thickness of 10
A relatively thin film having a thickness of 50 μm is suitable.

Further, 0.01 to 10 parts by weight of an antifogging agent and / or an antistatic agent is added to 100 parts by weight of the resin component in order to obtain appropriate slipperiness, antistatic property and antifogging property of the agricultural film. It is preferable. Specifically, as the sorbitan fatty acid ester, sorbitan monooleate, sorbitan monolaurate, sorbitan monobehenate,
Sorbitan monostearate, etc .; as glycerin fatty acid ester, glycerin monooleate, glycerin monostearate, glycerin monolaurate, glycerin monobehenate, etc .; as polyglycerin fatty acid ester, diglycerin monolaurate, diglycerin monostearate, diester Glycerin monooleate, tetraglycerin monooleate, tetraglycerin monostearate, hexaglycerin monolaurate, hexaglycerin monooleate, decaglycerin monolaurate, decaglycerin monostearate, decaglycerin monooleate, etc. Fatty acid esters and their ethylene oxide adducts, higher fatty acid amides and their ethylene oxide adducts, higher fatty acid alkanolamides, etc. Including but not limited to. These additives are used alone or as a mixed composition, and the amount of the additive is usually 0.01 to
It is 10% by weight, preferably 0.05 to 5.0% by weight. If the addition amount is less than 0.01% by weight, the effect of modifying the film is not sufficient, and if it exceeds 10% by weight, the amount of protrusion to the film surface is large and the film becomes sticky, resulting in a marked decrease in workability. This is not preferable because problems such as these occur. Agricultural film of the present invention, compared to the agricultural film made of conventional polyolefin-based resin,
Since it is excellent in tensile strength, tear strength and impact strength, it can be easily attached to a house or spread on the ground surface for mulching. In addition, the film does not tear when it hits the soil.

Resin and / or resin set used in the present invention
If necessary, antioxidants, specific waves such as ultraviolet rays may be added to the product.
Ray absorbers that absorb long rays, carbon black, T
iO _TwoSuch as pigments, anti-blocking agents, anti-aging agents, supplements
Various additives such as strong agents, fillers, heat resistance imparting agents, plasticizers, etc.
Can be appropriately mixed.

The agricultural film having the laminated structure of the present invention is composed of a laminate of at least two layers consisting of the film made of the above resin or resin composition and another film. The other film is not particularly limited, but as a film for agriculture, from the viewpoint of transparency, mechanical strength, economy, etc., particularly a polyolefin resin, that is, the above-mentioned other polyolefin (co) polymer (B). Are preferably used, and linear low-density polyethylene having a density of 0.94 g / cm ³ or less and a high-pressure radical method ethylene (co) polymer are particularly preferable. As an example of a concrete laminated body, MLL /
LL, MLL / VL, MLL / EVA, MLL / EE
A, MLL / LL + LD, MLL / VL + LD, MLL
+ LD / EVA, MLL + LL / LL, LL / MLL /
LL, LL + LD / MLL / LL + LD, EVA / ML
L / EVA, LL + LD / MLL + LD / LL + LD,
EVA / LL / MLL + LD, LL / HD + VL / ML
L, LL / HD / MLL, MLL / EVA / MLL, M
LL + LD / EVA / MLL + LD, MLL + LD / E
VA / LL, MLL + LL / EVA / MLL + LL, M
LL + LL / EVA / LD etc. are mentioned. (However,
MLL: ethylene-α-olefin copolymer of the present invention,
LL: conventional linear low density polyethylene, VL: ultra low density polyethylene, HD: high density polyethylene, LD: high pressure radical method low density polyethylene, EVA: ethylene-vinyl acetate copolymer, EEA: ethylene-ethyl acrylate copolymer Represents a polymer, LL + LD represents a mixture. ) The production of these laminates is not particularly limited,
It is manufactured by a conventional method such as a multilayer inflation method or a multilayer T-die method.

[0068]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below based on Examples and Comparative Examples, but the present invention is not limited thereto.

[0069]

[Examples] The test methods in Examples and Comparative Examples are as follows. [Density] According to JIS K6760. [MFR] JIS K6760 compliant. [Haze] According to ASTM D1003. [Tear strength] According to ASTM D1922. [Dirt impact strength] Conforms to JIS Z1702.

(Resin component) (A1): Ethylene / α-olefin copolymer A11: Ethylene / 1-butene copolymer Density = 0.920 g / cm ³ MFR = 0.6 g / 10
min Molecular weight distribution (Mw / Mn) = 2.4 Composition distribution parameter (Cb) = 1.04 TREF peak temperature = 83.5 ° C. (single peak) A12: ethylene / 1-hexene copolymer Density = 0.921 g / Cm ³ MFR = 0.7g / 10
min Molecular weight distribution (Mw / Mn) = 2.4 Composition distribution parameter (Cb) = 1.05 TREF peak temperature = 82.9 ° C. (single peak) Component (A2): ethylene / α-olefin copolymer (A21) ) Ethylene / 1-butene copolymer Density = 0.922 g / cm ³ MFR = 0.5 g / 10
min Molecular weight distribution (Mw / Mn) = 2.6 Composition distribution parameter (Cb) = 1.20 d-0.008log MFR = 0.924 ODCB soluble content (%) = 1.2 <9.8 × 10 ³ × (0.9300- d + 0.00
8logMFR) ² +2.0 TREF peak temperature = 82.5, 94.3 ° C. (plural peaks) (A22) ethylene / 1-hexene copolymer density = 0.923 g / cm ³ MFR = 0.5 g / 10
min Molecular weight distribution (Mw / Mn) = 2.6 Composition distribution parameter (Cb) = 1.22 d-0.008log MFR = 0.925 ODCB soluble content (%) = 1.5 <9.8 × 10 ³ × (0.9300- d + 0.00
8logMFR) ² +2.0 TREF peak temperature = 83.2, 96.5 ° C. (plural peaks) (B1) ethylene-butene-1 copolymer with titanium catalyst Density 0.923 g / cm ³ , MFR 0.5 g / 10 mi
n; Product name: J-LEX LL BF1310, manufactured by Nippon Polyolefin Co., Ltd. (B2) High-pressure radical method polyethylene Density = 0.923 g / cm ³ , MFR = 1.0 g / 10
min; product name: J-LEX LD F22N, manufactured by Nippon Polyolefin Co., Ltd. (B3) ethylene-vinyl acetate copolymer density = 0.929 g / cm ³ , MFR = 0.3 g / 10
min; product name: J-LEX EVA V141, manufactured by Nippon Polyolefin Co., Ltd.

The component (A1) was polymerized by the following method. A stainless steel autoclave equipped with a stirrer was purged with nitrogen and purified toluene was added, then 1-butene or 1-hexene was added, and further bis (n-butylcyclopentadienyl) zirconium dichloride (0.02 mmol as Zr), Methylalumoxane [MAO]
After adding a mixed solution of (MAO / Zr = 500 [molar ratio]), the temperature was raised to 80 ° C. Next, ethylene was added to initiate polymerization. While continuously polymerizing ethylene, polymerization was performed for 1 hour while maintaining the total pressure. In addition, the amount required for each example was produced by repeating these polymerizations.

The component (A2) was polymerized by the following method. (Preparation of solid catalyst) Purified toluene was added to a catalyst preparation device (No. 1) equipped with an electromagnetic induction stirrer under nitrogen, and then dipropoxydichlorozirconium (Zr (OPr) ₂ Cl ₂ ) was added.
28 g and 48 g of methylcyclopentadiene were added,
While maintaining the system at 0 ° C, 45 parts of tridecyl aluminum were added.
g, and after completion of the addition, the reaction system is maintained at 50 ° C.
Stir for 6 hours. This solution is designated as solution A. Next, under nitrogen, purified toluene was added to another catalyst preparation device (No. 2) equipped with a stirrer, and the solution A was added, followed by methylaluminoxane.
A 4 mol toluene solution was added and reacted. This is B
Liquid. Next, under a nitrogen atmosphere, purified toluene was added to a stirrer-equipped preparer (No. 1), and then 1400 g of silica (manufactured by Fuji Devison Co., Ltd., grade # 952, surface area 300 m ² / g) was preliminarily calcined at 400 ° C. for a predetermined time. After the addition, the whole amount of the solution B was added and stirred at room temperature. Then, the solvent was removed by nitrogen blowing to obtain a solid catalyst powder having good fluidity. This is designated as catalyst C.

(Polymerization of Sample) Using a continuous fluidized bed gas phase polymerization apparatus, the polymerization temperature was 70 ° C. and the total pressure was 20 kgf / cm ^2.
G copolymerized ethylene with 1-butene or 1-hexene. The polymerization was carried out by continuously supplying the catalyst C, and the polymerization was carried out while continuously supplying each gas in order to keep the gas composition in the system constant.

[Example 1] Irganox 1010 (manufactured by Ciba-Geigy Co., Ltd.) as an antioxidant in the resin A11
0.05 parts by weight, Irgafoss P-EPQ (manufactured by Ciba Geigy) 0.05 parts by weight, Riquemar AF-82 (manufactured by Riken Vitamin Co., Ltd.) as an anti-fog agent, 1 part by weight, silica (celite) as an anti-blocking agent. After adding 0.3 parts by weight of Super Floss, manufactured by John Manville Co., Ltd., and kneading and pelletizing with an extruder, a film with a thickness of 30 μm is formed by inflation film molding under the following conditions, and haze and tensile rupture are performed. The strength, tensile elongation, Elmendorf tear strength, and dart impact strength were measured. Table 1 shows the results
It was shown to. <Inflation film molding conditions> Molding temperature: 160 to 180 ° C. Blow-up ratio: 2.5 Film thickness: 30 μm

[0075]

[Table 1]

[Examples 2 to 4] Using the resin compositions shown in Table 1, film molding was carried out in the same manner as in Example 1 to evaluate the physical properties of the film. The results are also shown in Table 1. [Example 5] 0.05 part by weight of Irganox 1010 (manufactured by Ciba-Geigy Co., Ltd.) as an antioxidant in Resin A22, Irgafoss P-EPQ (manufactured by Ciba-Geigy Co., Ltd.)
0.05 part by weight was added, and the mixture was kneaded with an extruder and pelletized. Further, as a resin (B2) antifogging agent, Riquemal AF-8
1 part by weight of 2 (manufactured by Riken Vitamin Co., Ltd.) was added, and the mixture was kneaded by an extruder and pelletized. Under the following molding conditions, the intermediate layer is the component (A22) to which the above additive is added, the inner layer is the component (B2) to which the above additive is added, and the outer layer is the component (B2). The outer layer 10 μm / intermediate layer 10 μm / inner layer 10
A μm laminated film was formed. <Multilayer inflation film molding conditions> Multilayer inflation molding apparatus Outer layer, intermediate layer, inner layer 40 mm each extruder, molding temperature: 160 to 180 ° C Blow-up ratio: 2.5 Film thickness: 30 μm [Example 6] The resin composition was used, and the film was formed in the same manner as in Example 5 to evaluate the physical properties of the film. The results are also shown in Table 1.

The films of Examples 1 to 6 are all excellent in haze and film strength and suitable for agricultural films. [Comparative Example 1] Film evaluation was carried out in the same manner as in Example 1 except that (B1) was used as the resin. The results are shown in Table 2. It was inferior in tear strength and dirt impact strength.

[0078]

[Table 2]

Comparative Example 2 Film evaluation was carried out in the same manner as in Example 1 except that (B1) was used as the resin. The results are shown in Table 2. It was inferior in tensile rupture strength, elongation and dirt impact strength. [Comparative Example 3] (A21) and (B1) were used as the resin, and the film evaluation was performed in the same manner as in Example 1 except for the above. The results are shown in Table 2. Since the amount of (A21) was small, the tear strength and the dart impact strength were poor. [Comparative Example 4] Film evaluations were performed in the same manner as in Example 1 except that (A11) and (B2) were used as the resin. The results are shown in Table 2. Since the amount of (A11) was small, the tensile rupture strength, elongation, and dirt impact strength were inferior. [Comparative Example 5] (B1) and (B3) were used as the resin, and the film evaluation was performed in the same manner as in Example 5 except for the above. The results are shown in Table 2. Since the component (A) was not used, the tensile rupture strength was inferior. [Comparative Example 6] (B1) and (B2) were used as the resin, and the film evaluation was performed in the same manner as in Example 5 except for the above. The results are shown in Table 2. Since the component (A) was not used, the tensile rupture strength and the dart impact strength were inferior.

[0080]

INDUSTRIAL APPLICABILITY The agricultural film of the present invention is excellent in film strength and transparency by using an ethylene / α-olefin copolymer satisfying specific requirements, and is a multi-film on a stretch of a house or on the ground surface. It has sufficient tensile strength and tear strength to withstand the expansion when it is closely spread. Further, unlike vinyl chloride resin, it does not generate a toxic gas when the film is incinerated, and is suitably used for agricultural houses, tunnel houses, mulch films and the like.

[Brief description of drawings]

FIG. 1 Elution temperature-elution amount curve peak (single peak) of the ethylene-α-olefin copolymer (A1) of the present invention determined by continuous temperature rising elution fractionation (TREF)

FIG. 2 Elution temperature-elution amount curve peaks (plural peaks) of the ethylene-α-olefin copolymer (A2) of the present invention obtained by continuous temperature rising elution fractionation (TREF)

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical display location B32B 27/18 B32B 27/18 CD C08F 4/64 MFG C08F 4/64 MFG 210/16 MJM 210 / 16 MJM C08J 5/18 CES C08J 5/18 CES

Claims (6)

[Claims] 1. In the presence of (A) at least one catalyst containing at least a cyclopentadiene compound and a transition metal compound of Group IV of the periodic table, ethylene or ethylene and an α-olefin having 3 to 20 carbon atoms ( A film for agriculture, which comprises an ethylene homopolymer or an ethylene / α-olefin copolymer, which is an essential constituent resin, and which satisfies the following requirements (a) to (d) obtained by copolymerization. (A) Density 0.86 to 0.96 g / cm ³ (b) Melt flow rate 0.01 to 100 g / 10
Min (c) molecular weight distribution (Mw / Mn) is 1.5 to 5.0 (d) composition distribution parameter Cb is 2.00 or less 2. The resin component further contains an olefin-based (co) polymer (B) other than the above-mentioned ethylene homopolymer or ethylene / α-olefin copolymer (A) in an amount of 80% by weight or less based on all resin components. The agricultural film according to claim 1. 3. At least one of the ethylene homopolymers or ethylene / α-olefin copolymers (A) containing a ligand having a cyclopentadienyl skeleton and a transition metal compound of Group IV of the periodic table. The following requirements (a) to (e) obtained in the presence of the catalyst (a): a density of 0.86 to 0.96 g / cm ³ (b) a melt flow rate of 0.01 to 100 g / 10
Min (c) molecular weight distribution (Mw / Mn) is 1.5 to 5.0 (d) composition distribution parameter Cb is 1.01 to 1.2 (e) elution temperature by continuous temperature elution fractionation (TREF)- The agricultural film according to claim 1 or 2, characterized in that substantially one peak of the dissolution curve is present. 4. The ethylene homopolymer or ethylene / α-olefin copolymer (A) described below is (a) to
(F) Requirements (a) Density 0.86 to 0.96 g / cm ³ (b) Melt flow rate 0.01 to 100 g / 10
Min (c) molecular weight distribution (Mw / Mn) is 1.5 to 5.0 (d) composition distribution parameter Cb is 1.08 to 2.00 (e) elution temperature by continuous temperature elution fractionation (TREF)- Substantially multiple peaks in the elution volume curve (f) Ortho-dichlorobenzene (ODC) at 25 ° C
B) Soluble content X (wt%), density d and MFR (melt flow rate) satisfy the following relationship: a) d-0.008 log MFR ≧ 0.93 X <2.0 b) d In the case of −0.008 log MFR <0.93 X <9.8 × 10 ³ × (0.9300−d + 0.008 log MFR) ²
4. Satisfies +2.0, Any one of Claims 1-3 characterized by the above-mentioned.
The agricultural film according to the item. 5. An agricultural film comprising 100 parts by weight of the resin or resin composition according to any one of claims 1 to 4 and 0.01 to 10 parts by weight of an antifogging agent and / or an antistatic agent. . 6. An agricultural film comprising a laminated film containing the film according to any one of claims 1 to 5 and another film.