JP2001320986A - Antifogging film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antifogging film excellent in an antifogging property, durability of the antifogging property, not deteriorating the durability with time comparing to a conventional agricultural film, and excellent in durability, transparency, stiffness or the like, usable for an agricultural film or the like. SOLUTION: This antifogging film is a mono layered or multi layered film having a layer composed of an ethylene based polymer composition including a low density linear polyethylene having density of 880-930 kg/m3 obtained by copolymerizing ethylene and a 4-12C α-olefin in the presence of a metallocene based catalyst for polymerization of an olefin, hydrotalcites and an antifogging agent. The composition includes 60-80 pts.wt. of the low-density linear polyethylene, 20-40 pts.wt. of hydrotalcites and 0.5-5 pts.wt. of the antifogging agent per 100 pts.wt. of the sum of the low-density linear polyethylene and hydrotalcites.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an antifogging film having a single-layer or multilayer structure, and more particularly to an antifogging film that can be used for applications such as agricultural films.

[0002]

BACKGROUND OF THE INVENTION In house cultivation, tunnel cultivation, and mulch cultivation for the purpose of forcing cultivation on agriculture, agricultural films composed of various thermoplastic resins are generally used in large quantities as a covering material. Such agricultural films include, for example, a polyvinyl chloride film, an ethylene / vinyl acetate copolymer film, a polyethylene film, and the like. Among them, the polyvinyl chloride film has a heat retaining property, transparency, toughness (mechanical strength). It is most often used because of its excellent properties.

[0003] However, the polyvinyl chloride film has some problems such as the dust-proofing property and the spreadability being slightly inferior, and the generation of toxic gas at the time of incineration disposal. Here, "heat retention" means the temperature inside the house, tunnel, etc. (air temperature and ground temperature) by absorbing and reflecting the radiation emitted at night from the earth whose temperature has risen by absorbing solar heat during the day and absorbing it at night. Refers to the ability to maintain

[0004] The term "dustproofness" refers to the ability of a film to prevent a decrease in the transparency of a film due to adhesion of dust or the like after a certain period of use. Further, the “stretching workability” indicates whether the film is easy to handle due to stickiness.

On the other hand, a film containing an ethylene / vinyl acetate copolymer as a main component is superior to a polyvinyl chloride film in terms of waste treatment, but is inferior in toughness.
Insufficient spreadability and dust resistance.

When polyethylene is applied to an agricultural film, this film has improved workability and dust-proofing properties as compared with the above-mentioned film containing ethylene / vinyl acetate copolymer as a main component, but it is still in use. Inadequate,
There is a problem that the toughness is inferior to that of the linear ethylene / α-olefin copolymer film.

Further, as an agricultural film in which the heat retaining property of a polyolefin resin film is improved by an additive, there is a coating film obtained by adding silicon oxide to low-density polyethylene or ethylene / vinyl acetate copolymer.

[0008] However, such an agricultural film has improved toughness compared to a polyvinyl chloride film, although the heat insulation of the polyethylene resin film is improved.
Insufficient transparency.

[0009] In order to improve the toughness of such a polyethylene resin film, agricultural films utilizing the toughness of linear low-density polyethylene have recently been devised. For example, JP-A-58-160146 discloses an antifogging method in which a base layer mainly composed of linear low-density polyethylene and a layer made of a polyethylene resin or the like produced by a conventional production method containing a surfactant are laminated. Agricultural multilayer films having good properties have been proposed. Although the toughness of the agricultural multilayer film is improved, the use of a resin or an additive having a higher heat retaining property has not been studied, so that the heat retaining property of the agricultural multilayer film is considerably inferior to that of a polyvinyl chloride film.

In Japanese Patent Laid-Open Publication No. 1-182037,
A multilayer (laminated) film for agriculture has been proposed, in which the outer layer is formed of a polyethylene resin having a linear ethylene / α-olefin copolymer as a main component and an inorganic compound, In addition, the inner layer is formed of a polyethylene resin having an ethylene / vinyl acetate copolymer as a main component, an inorganic compound, and an antifogging agent. JP-A-1-1-1
The agricultural multilayer film described in Japanese Patent No. 82037 is said to have good heat retention, dustproofness, spreading workability, transparency, and durability, and has extremely excellent toughness.

However, the conventional agricultural multilayer film as described above has room for improvement in antifogging durability, transparency, toughness and the like. Therefore, compared to the above-mentioned conventional agricultural films (single-layer and multilayer films), the anti-fogging durability is less reduced with time, and furthermore, it is excellent in transparency, toughness, etc., and is used for applications such as agricultural films. The emergence of a possible anti-fog film is desired.

[0012]

The object of the present invention is to reduce the anti-fogging continuity with time and to have excellent transparency, toughness, etc. as compared with the above-mentioned conventional agricultural films, and to be used for applications such as agricultural films. It is intended to provide an antifogging film that can be used.

[0013]

The antifogging film according to the present invention is obtained by copolymerizing ethylene and an α-olefin having 4 to 12 carbon atoms in the presence of a metallocene olefin polymerization catalyst and having a density of 880. Linear low-density polyethylene (A) of up to 930 kg / m ³ and hydrotalcites (B)
And a layer [1] formed from an ethylene-based copolymer composition (1) containing an antifogging agent (C), and a linear low-density composition in the composition (1). The linear low-density polyethylene (A) is contained in an amount of 60 parts by weight or more and less than 80 parts by weight based on 100 parts by weight of the total amount of the polyethylene (A) and the hydrotalcites (B), It is characterized in that the site (B) is contained in an amount of more than 20 parts by weight and 40 parts by weight or less, and the antifogging agent (C) is contained in an amount of 0.5 to 5 parts by weight.

The linear low-density polyethylene (A) is
High-pressure low-density polyethylene (D) in an amount of 40% by weight or less
May be contained. The antifogging film according to the present invention may have a single-layer structure or a multilayer structure of two or more layers.

In the preferred antifogging film having a multilayer structure according to the present invention, one surface of the layer [1] has a density of 925 to 94.
Outer layer of polyethylene (E) of 5 kg / m ³ [2]
Are laminated, and the ratio of the thickness of the layer [1] to the total thickness of the two-layer film is 50%.
That is all.

The particularly preferred multilayer antifogging film according to the present invention has a density of 9 on one surface of the layer [1].
An outer layer [2] made of polyethylene (E) having a thickness of 25 to 945 kg / m ³ is laminated, and the other side of the layer [1] is a polyolefin containing 0.5 to 5% by weight of an antifogging agent (C). 3 formed by laminating an inner layer [3] made of resin (F)
A layer film, wherein the ratio of the thickness of the layer [1] to the entire thickness of the three-layer film is 50% or more.

In the three-layer film, the density (d _E ) of the polyethylene (E) forming the outer layer [2] is as follows:
The density (d _F ) of the polyolefin-based resin (F) forming the inner layer [3] is usually in a relation satisfying d _E ≧ d _F.

As the antifogging agent (C), an antifogging agent (C1) containing 15 to 50% by weight of a polyoxyethylene group-containing component is particularly preferred.

[0019]

DETAILED DESCRIPTION OF THE INVENTION The antifogging film according to the present invention will be specifically described below. The antifogging film according to the present invention comprises a specific linear low density polyethylene copolymer (A), a hydrotalcite (B) and an antifogging agent (C), and if necessary, a high pressure method low density polyethylene ( It has a layer [1] formed from the ethylene copolymer composition (1) containing D).

The antifogging film according to the present invention may be a single-layer film (single-layer film) composed of such a layer [1], or may have such a layer [1]. It may be a film having a multilayer structure of two or more layers (multilayer film).

It is composed of the ethylene copolymer composition (1).
Layer [1] First, each component constituting the ethylene-based copolymer composition (1) used in the present invention will be described.

[Linear Low Density Polyethylene (A)] The linear low density polyethylene (A) constituting the ethylene copolymer composition (1) used in the present invention is a metallocene olefin polymerization catalyst. It is a copolymer of ethylene and an α-olefin having 4 to 12 carbon atoms prepared by using the same.

As the α-olefin having 4 to 12 carbon atoms used for copolymerization with ethylene, specifically, 1-olefin
Butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene and the like. Among them, α-olefins having 4 to 10 carbon atoms, particularly α-olefins having 4 to 6 carbon atoms are preferred.

The above-mentioned linear low-density polyethylene (A) can be used alone or in combination of two or more. The linear low-density polyethylene (A) used in the present invention has a constitutional unit derived from ethylene of 50% by weight or more and less than 100% by weight, preferably 55-99% by weight, more preferably 65-98% by weight, particularly preferably Preferably it is present in an amount of 70 to 96% by weight and has 4 to 12 carbon atoms.
50% by weight or less, preferably 1 to 45% by weight, more preferably 2 to
Desirably it is present in an amount of 35% by weight, particularly preferably 4 to 30% by weight.

The composition of the linear low-density polyethylene (A) is determined by measuring the ¹³ C-NMR spectrum of a sample in which about 200 mg of a copolymer is dissolved uniformly in 1 ml of hexachlorobutadiene in a 10 mmφ sample tube. Temperature 120
° C, measurement frequency 25.05 MHz, spectrum width 150
0 Hz, pulse repetition time 4.2 sec., Pulse width 6 μse
It is determined by measuring under the conditions of c.

The linear low-density polyethylene (A) used in the present invention has a density of 880 to 930 kg / m.
³ , preferably 890-925 kg / m ³ , more preferably 895-920 kg / m ³ , particularly preferably 90
In the range of 0~915kg / m ^3. The density is 1
The strand obtained at the time of melt flow rate (MFR) measurement at a load of 2.16 kg at 90 ° C. is heat-treated at 120 ° C. for 1 hour, and gradually cooled to room temperature over 1 hour.
Measure with a density gradient tube.

The linear low density polyethylene (A) has a melt flow rate (MFR; ASTM D 1).
238-65T, 190 ° C, load 2.16 kg) is usually 0.1 to 10 g / 10 min, preferably 0.1 to 5 g / min.
It is in the range of 10 minutes, more preferably 0.5 to 2 g / 10 minutes.

G of this linear low density polyethylene (A)
The molecular weight distribution (Mw / Mn: Mw = weight average molecular weight, Mn = number average molecular weight) measured by PC is usually 1.5 to
5.0, preferably 1.8 to 3.5, more preferably 2.0 to 3.0.

The molecular weight distribution (Mw / Mn) was measured as follows using GPC-150C manufactured by Millipore. The separation column is TSK GNH HT,
The column size is 72 mm in diameter and 600 mm in length,
The column temperature was 140 ° C., and the mobile phase used was O-dichlorobenzene (manufactured by Wako Pure Chemical Industries, Ltd.) and 0.025% by weight of BHT (manufactured by Takeda Pharmaceutical Company Limited) as an antioxidant. The sample was moved at 0 ml / min, the sample concentration was 0.1% by weight, the sample injection amount was 500 microliter, and a differential refractometer was used as a detector. Standard polystyrene is
For the molecular weights of Mw <1000 and Mw> 4 × 10 ⁶ , use Tosoh Corporation and 1000 ≦ Mw ≦ 4 × 10 6
About ⁶ , the product made by Pressure Chemical Company was used.

Further, linear low-density polyethylene (A)
It is preferable that the n-decane-soluble component amount fraction (W (% by weight)) and the density (d) at 23 ° C. satisfy the following relationship.

W <80 × exp (−100 (d−0.8
8)) + 0.1 Incidentally, the measurement of the n-decane-soluble component amount (the smaller the soluble component amount, the narrower the composition distribution) of the linear low-density polyethylene (A) is, 3 g of n-decane 4
After dissolving at 145 ° C., cooling to 23 ° C., removing the n-decane insoluble portion by filtration, and collecting the n-decane soluble portion from the filtrate.

Further, linear low density polyethylene (A)
Are the temperature [Tm (° C.)] and the density [d at the maximum peak position of an endothermic curve measured by a differential scanning calorimeter (DSC).
(G / cm ³ )] and the relationship represented by Tm <400 × d-250, preferably Tm <450 × d-297, more preferably Tm <500 × d-344, and particularly preferably Tm <550 × d-391. It is desirable to satisfy

The temperature (Tm) at the maximum peak position of the endothermic curve measured by a differential scanning calorimeter (DSC) is as follows:
Approximately 5mg of sample is packed in aluminum pan and 200 ℃ at 10 ℃ / min
The temperature is kept at 200 ° C. for 5 minutes, then the temperature is lowered to room temperature at 20 ° C./min, and then determined from an endothermic curve when the temperature is raised at 10 ° C./min. Measurements made by PerkinElmer
Use a DSC-7 type device.

As described above, the relationship between the fraction (W) of the n-decane soluble component and the density (d), and the temperature (Tm) at the maximum peak position in the endothermic curve measured by the differential scanning calorimeter (DSC) ) And density (d) have the above-mentioned relationship, and linear low-density polyethylene (A)
Can be said to have a narrow composition distribution.

In the linear low-density polyethylene (A) used in the present invention, the average of the number of branches on the high molecular weight side by GPC-IR is B ₁ , and the average of the number of branches on the low molecular weight side is B _2. In this case, it is preferable that B ₁ ≧ B ₂ .

Here, the average value (B ₁ ) of the number of branches on the high molecular weight side by GPC-IR means that the cumulative weight fraction of the elution amount of the high molecular weight fractionated by GPC is 15 to 85%.
The measurement value group of the number of branches measured for each fraction in the range of (ie, the high molecular weight region excluding 15% and the high molecular weight region excluding 15%) was divided into two by the molecular weight at the peak position of the GPC elution curve. It is the average of the values on the high molecular weight side. On the other hand, the average value of the number of branches on the low molecular weight side (B
₂ ) is the average value on the low molecular weight side of the two parts.

The measurement conditions for B ₁ and B ₂ are as follows. Measuring device: Perkin Elmer 1760X Column: TSK gel GMH-HT (7.5mmI.
D. × 600 mm) × 1 Eluent (eluent): o-dichlorobenzene (ODCB) containing 0.05% of MP-J [ex. Wako Pure Chemical Industries, Ltd., ex
tra pure grade] Column temperature: 140 ° C. Sample concentration: 0.1% (weight / volume) Injection volume (inj.volume): 100 microliter detector: MCT Resolution: 8 cm ^-1 The B ₁ and B ₂ is the The linear low-density polyethylene (A) having such a relationship has a narrow composition distribution and a small amount of low polymer, and thus has a low stickiness. Therefore,
When the linear low-density polyethylene (A) as described above is used, an antifogging film excellent in dust resistance can be obtained.

Further, since the linear low density polyethylene (A) film has a very small decrease in light transmittance with time, if such a film is used as an agricultural film, for example, it will be used for a long time. It is possible to expand.

The linear low-density polyethylene (A) as described above is used as a single-site catalyst, for example, as disclosed in JP-A-6-97.
No. 24, JP-A-6-136195, JP-A-6-136195
In the presence of a so-called metallocene-based olefin polymerization catalyst containing a metallocene catalyst component described in JP-A-136196, JP-A-6-207057 and the like, ethylene and an α-olefin having 4 to 12 carbon atoms are converted. The copolymer can be produced by copolymerization so that the density of the obtained copolymer is 880 to 930 kg / m ³ .

Such a metallocene catalyst generally has at least one ligand having a cyclopentadienyl skeleton.
Metallocene catalyst component (a) comprising a transition metal compound of Group IVB of the periodic table, an organoaluminum oxy compound catalyst component (b), a particulate carrier (c), and, if necessary, an organoaluminum compound catalyst component (d ), An ionized ionic compound formed from the catalyst component (e).

The metallocene catalyst component (a) preferably used in the present invention is a transition metal compound of Group IVB of the periodic table having at least one ligand having a cyclopentadienyl skeleton. Examples of such a transition metal compound include a transition metal compound represented by the following general formula [I].

ML ¹ _x ... [I] In the formula, x is the valence of the transition metal atom M. M is a transition metal atom selected from Group IVB of the periodic table, and specifically, zirconium, titanium, and hafnium. Among them, zirconium is preferred.

L ¹ is a ligand that coordinates to the transition metal atom M, and at least one of these ligands L ¹
Is a ligand having a cyclopentadienyl skeleton.
As the ligand L ¹ having a cyclopentadienyl skeleton coordinated to the transition metal atom M as described above, specifically,
Cyclopentadienyl group, methylcyclopentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, tetramethylcyclopentadienyl group, pentamethylcyclopentadienyl group, methylethylcyclopentadienyl group And an alkyl-substituted cyclopentadienyl group such as hexylcyclopentadienyl group, or an indenyl group, a 4,5,6,7-tetrahydroindenyl group or a fluorenyl group. These groups are
It may be substituted with a halogen atom, a trialkylsilyl group or the like.

When the compound represented by the above general formula [I] contains two or more groups having a cyclopentadienyl skeleton, two of the groups having a cyclopentadienyl skeleton are connected to each other by ethylene, propylene or the like. An alkylene group,
It may be bonded through a substituted alkylene group such as isopropylidene diphenylmethylene or the like, or a silylene group or a substituted silylene group such as a dimethylsilylene group, a diphenylsilylene group or a methylphenylsilylene group.

The ligand L ¹ other than the ligand having a cyclopentadienyl skeleton is a hydrocarbon group having 1 to 12 carbon atoms; an alkoxy group such as a methoxy group; an aryloxy group such as a phenoxy group; a trimethylsilyl group; A trialkylsilyl group such as a triphenylsilyl group; SO ₃ R (R is a hydrocarbon group having 1 to 8 carbon atoms which may have a substituent such as halogen), a halogen atom or a hydrogen atom.

Examples of the hydrocarbon group having 1 to 12 carbon atoms include an alkyl group such as a methyl group, a cycloalkyl group such as a cyclopentyl group, an aryl group such as a phenyl group, and an aralkyl group such as a benzyl group.

Specific examples of the ligand represented by SO ₃ R include a P-toluenesulfonato group, a methanesulfonato group, and a trifluoromethanesulfonato group. As the organoaluminum oxy compound catalyst component (b), aluminoxane is preferably used. Specifically, methylaluminoxane, ethylaluminoxane, methylethylaluminoxane having a repeating unit represented by the formula -Al (R) O-, wherein R is an alkyl group, is usually about 3 to 50. Are used.

Such an aluminoxane can be prepared by a conventionally known production method. The particulate carrier (c) used in the preparation of the catalyst for olefin polymerization is an inorganic or organic compound and has a particle size of usually 10 to 300 μm.
And preferably 20 to 200 μm in the form of granules or fine particles.

As the inorganic carrier, a porous oxide is preferable. Specifically, SiO ₂ , Al ₂ O ₃ , MgO, Zr
O ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, S
Examples thereof include nO _{2 and the} like or a mixture thereof. The inorganic oxide contains a small amount of a carbonate such as Na ₂ CO _3, a sulfate such as Al ₂ (SO ₄ ) ₃ , a nitrate such as KNO ₃ , and an oxide such as Li ₂ O. No problem.

Although the properties of such a carrier differ depending on the kind and the production method, the carrier preferably used in the present invention has a specific surface area of 50 to 1000 m ² / g, preferably 1 to 1,000 m ² / g.
00-700 m ² / g, and the pore volume is 0.3-2.
It is preferably 5 cm ³ / g.

The carrier may be 100 to 100 if necessary.
It is used by firing at 0 ° C, preferably 150 to 700 ° C. Examples of the organic compound used as the particulate carrier include a (co) polymer formed mainly of an α-olefin having 2 to 14 carbon atoms such as ethylene and 4-methyl-1-pentene, or vinylcyclohexane. And (co) polymers formed mainly of styrene.

Organoaluminum compound catalyst component (d) optionally used in the preparation of metallocene catalyst
Specific examples thereof include trialkylaluminums such as trimethylaluminum, alkenylaluminums such as isoprenylaluminum, dialkylaluminum halides such as dimethylaluminum chloride, alkylaluminum sesquihalides such as methylaluminum sesquichloride, and alkyls such as methylaluminum dichloride. Examples thereof include alkyl aluminum hydrides such as aluminum dihalide and diethyl aluminum hydride.

Examples of the ionized ionic compound catalyst component (e) include triphenylboron, MgCl ₂ , and Al described in US Pat. No. 5,321,106.
Lewis acids such as ₂ O ₃ and SiO ₂ —Al ₂ O ₃ ; ionic compounds such as triphenylcarbenium tetrakis (pentafluorophenyl) borate; carborane compounds such as dodecaborane and bis-n-butylammonium (1-carbedodeca) borate Is mentioned.

The linear low-density polyethylene (A) used in the present invention comprises the above-mentioned metallocene catalyst component (a), organoaluminum oxy compound catalyst component (b), particulate carrier (c), and Accordingly, in the presence of an olefin polymerization catalyst containing an organoaluminum compound catalyst component (d) and an ionized ionic compound catalyst component (e), ethylene is used under various conditions in a gas phase or a slurry or solution liquid phase. And α- having 4 to 12 carbon atoms
It can be obtained by copolymerizing with an olefin.

In the slurry polymerization method or the solution polymerization method, an inert hydrocarbon may be used as a solvent, or olefin itself may be used as a solvent. When carrying out the polymerization, the above-mentioned metallocene-based olefin polymerization catalyst is usually used in a concentration of 10 ^-8 , based on the concentration of the transition metal atom in the polymerization reaction system.
10 ^-3 gram atom / liter, preferably 10 ^{-7 -1
Preferably,} it is used in an amount of ^0-4 grams atom / liter.

In the polymerization, in addition to the organoaluminum oxy compound catalyst component (b) and the organoaluminum compound catalyst component (d) supported on the carrier, the unsupported organoaluminum oxy compound catalyst component (b) And / or an organoaluminum compound catalyst component (d) may be used. In this case, an aluminum atom (Al) derived from the unsupported organoaluminum oxy compound catalyst component (b) and / or the organoaluminum compound catalyst component (d) and a transition metal atom derived from the metallocene catalyst component (a) ( M) and the atomic ratio [Al
/ M] is in the range of 5 to 300, preferably 10 to 200, and more preferably 15 to 150.

The polymerization temperature in the slurry polymerization method is usually -50 to 100 ° C, preferably 0 to 90 ° C, and the polymerization temperature in the solution polymerization method is usually -50 to 50 ° C.
0 ° C, preferably in the range of 0 to 400 ° C. Further, the polymerization temperature in the gas phase polymerization method is usually in the range of 0 to 120 ° C, preferably 20 to 100 ° C.

The polymerization pressure is usually from normal pressure to 100 kg /
cm ² , preferably ² to 50 kg / cm ² under pressure, and the polymerization can be carried out in any of a batch system, a semi-continuous system, and a continuous system.

In the present invention, when preparing the above-mentioned linear low-density polyethylene (A), if necessary, (1) multi-stage polymerization, (2) multi-stage polymerization of liquid phase and gas phase, or (3) liquid phase For example, performing polymerization in the gas phase after performing the preliminary polymerization in step (1). In the present invention, the multi-stage polymerization of the above (1) is preferred.

As the multi-stage polymerization method, for example, the following multi-stage polymerization method can be mentioned. [1] A metallocene catalyst component comprising at least one compound selected from transition metal compounds of Group IVB of the periodic table containing a ligand having a cyclopentadienyl skeleton represented by the general formula [I]; In the presence of a metallocene catalyst containing an aluminum oxy compound catalyst component, ethylene is copolymerized with an α-olefin having 4 to 12 carbon atoms to produce an ethylene / α-olefin copolymer (A-1). Step [2] In a polymerization vessel different from the polymerization vessel in which the copolymerization reaction is performed, the above-mentioned general formula [I]
A metallocene catalyst component comprising at least one compound selected from transition metal compounds of Group IVB of the Periodic Table containing a ligand having a cyclopentadienyl skeleton represented by the following formula: and an organoaluminum oxy compound catalyst component Ethylene and carbon atoms of 4 to
And α-olefin of 12
And a step of producing an olefin copolymer (A-2). However, the manufacturing conditions in the step [1] are different from the manufacturing conditions in the step [2]. Such production conditions include, for example, the type and amount of the metallocene catalyst component, the type and amount of the organoaluminum oxy compound catalyst component, and the molar ratio of ethylene to α-olefin.

The metallocene catalyst used in the copolymerization step [1] and / or [2] is added to the metallocene catalyst component (a) and the organoaluminum oxy compound catalyst component (b) and the organoaluminum compound catalyst component (d). ), Or a solid catalyst in which the metallocene catalyst component (a) and the organoaluminum oxy compound catalyst component (b) are supported on the particulate carrier (c). These metallocene-based catalysts are prepolymerized catalysts obtained by prepolymerizing an olefin onto a solid catalyst component in which a metallocene catalyst component (a) and an organoaluminum oxy compound catalyst component (b) are supported on a particulate carrier (c). It may be. Further, these metallocene-based catalysts include a catalyst comprising the above-mentioned solid catalyst (solid catalyst component) and an organoaluminum compound catalyst component (d), or the above-mentioned prepolymerization catalyst (preliminary polymerization catalyst component) and an organoaluminum compound catalyst component (d ) May be used.

In this multi-stage polymerization method, the above-mentioned ethylene / α-olefin copolymer (A-1) is first produced using a plurality of polymerization vessels connected in series, and then the ethylene / α-olefin copolymer is produced.
-The ethylene / α-olefin copolymer (A-1) is introduced into a polymerization vessel different from the polymerization vessel used for producing the olefin copolymer (A-1), and the ethylene / α-olefin copolymer (A The ethylene / α-olefin copolymer (A-2) can be produced in the presence of -1).

Further, a plurality of polymerization reactors are connected in parallel, and in each polymerization reactor, ethylene / α-olefin copolymers (A-1) and (A-2) are respectively produced. Can also be blended.

In the present invention, the linear low-density polyethylene (A) is 60 parts by weight based on 100 parts by weight of the total amount of the linear low-density polyethylene (A) and the hydrotalcites (B). Not less than 80 parts by weight, preferably 7
It is used in an amount of 0 part by weight or more and less than 80 parts by weight.

In the present invention, a part of the linear low-density polyethylene (A) can be replaced by a high-pressure low-density polyethylene (D) described later. [Hydrotalcites (B)] Specific examples of the hydrotalcites (B) constituting the ethylene copolymer composition (1) used in the present invention include a compound represented by the formula: M 2 ⁺ _{1 -x} Al ^{_{x (OH) 2 (a n-}} ) in _x / n · mH ₂ O [wherein, M ²⁺ is a divalent metal ion of Mg, Ca or Zn, a ^n-is, Cl ^-, Br ^-, I ^-, NO ₃ ^2-,
ClO ⁴⁻ , SO ₄ ²⁻ , CO ₂ ²⁻ , SiO ₃ ²⁻ , HPO ₄ ²⁻
, HBO ₃ ^2-, an anion of PO ₄ ^2-like, x is,
Is a numerical value satisfying the condition 0 <x <0.5, and m is
The numerical value satisfies the condition of 0 ≦ m ≦ 2], and a fired product thereof.
Among these, a fired product of the inorganic composite compound represented by the above formula is particularly preferred.

Hydrotalcites (B) as described above
Can be used alone or in combination of two or more. It is desirable that the average particle size of the hydrotalcites (B) is 10 μm or less, preferably 5 μm or less, and more preferably 3 μm or less.

When the average particle size of the hydrotalcites (B) is within the above range, a film having excellent transparency can be obtained. The hydrotalcites (B) exceed 20 parts by weight based on 100 parts by weight of the linear low-density polyethylene (A) and the hydrotalcites (B),
And it is used in an amount of not more than 40 parts by weight, preferably more than 20 parts by weight and not more than 30 parts by weight.

When the hydrotalcites (B) are used in the above amounts, a film having excellent antifogging durability and excellent heat retention can be obtained. [Anti-fogging agent (C)] As the anti-fogging agent (C) constituting the ethylene copolymer composition (1) used in the present invention, specifically, sorbitan monostearate, sorbitan distearate, Sorbitan monopalmitate, sorbitan dipalmitate, sorbitan monobehenate, sorbitan dibehenate, sorbitan monolaurate, sorbitan dilaurate and other sorbitan-based surfactants; glycerin monolaurate, glycerin dilaurate, diglycerin monopalmitate, disorbate Glycerin dipalmitate,
Glycerin-based surfactants such as glycerin monostearate, glycerin distearate, diglycerin monostearate, diglycerin distearate, diglycerin monolaurate, diglycerin dilaurate; polyethylene glycol monostearate, polyethylene glycol monopalminate Polyethylene glycol-based surfactants such as trimethylolpropane monostearate; diethanolalkylamines such as lauryldiethanolamine, oleyldiethanolamine, stearyldiethanolamine, lauryldiethanolamide, oleyldiethanolamide, stearyldiethanolamide And diethanol alkylamide surfactants: pentaerythritol monopalmi Over preparative like pentaerythritol surfactant and polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan distearate, sorbitan - such as mono- and distearate diglycerin condensates and the like. These can be used alone or in combination of two or more.

Antifogging agent (C) preferably used in the present invention
Is 15 to 50% by weight of a polyoxyethylene group-containing component.
It is a contained antifogging agent (C1). This anti-fog agent (C1)
Is composed of a mixture of two or more nonionic surfactants, and contains a polyoxyethylene group-containing component in an amount of 15 to 50% by weight, preferably 20 to 45% by weight, more preferably 25 to 40% by weight. % By weight. However, diethanol alkylamine and fatty acid diethanolamide are excluded from the polyoxyethylene group-containing component used in the present invention. When the polyoxyethylene group-containing component is used in the above ratio, the resulting composition has excellent moldability,
The film obtained from the composition is excellent in antifogging property and antifogging durability.

This polyoxyethylene group-containing component comprises:
In the formula for the polyoxyethylene group represented by (—CH ₂ CH ₂ O—) _n H, n is 2 to 10, and the balance between hydrophilicity and lipophilicity (hydrophilic-lipophilic bal)
It is preferable that the HLB value as an index of ance) is 5 to 12.

The mixture of two or more nonionic surfactants preferably used as the antifogging agent (C1) in the present invention comprises:
At least one component (i) selected from the group consisting of glycerin fatty acid ester, polyglycerin fatty acid ester, sorbitan fatty acid ester, diethanolalkylamine and fatty acid diethanolamide, and an ethylene oxide adduct of glycerin fatty acid ester (polyoxyethylene glycerin fatty acid ester ), At least one polyoxyethylene group selected from the group consisting of ethylene oxide adducts of polyglycerin fatty acid esters (polyoxyethylene polyglycerin fatty acid esters) and ethylene oxide adducts of sorbitan fatty acid esters (polyoxyethylene sorbitan fatty acid esters) And component (ii).

The glycerin fatty acid ester includes
Specifically, glycerin monomyristate, glycerin dimyristate, glycerin monopalmitate, glycerin dipalmitate, glycerin monostearate, glycerin distearate, glycerin monoolate, glycerindiolate, glycerin monolaurate, glycerin dilaurate Glycerin monobehenate, higher fatty acid esters such as glycerin dibehenate, and mixtures of two or more thereof. Among them, glycerin monostearate is particularly preferred.

Examples of the polyglycerin fatty acid ester include diglycerin monomyristate, diglycerin dimyristate, diglycerin monopalmitate, diglycerin dipalmitate, diglycerin monostearate, and diglycerin distearate. Diglycerin fatty acid esters such as diglycerin monooleate, diglycerindiolate, diglycerin monolaurate, diglycerin dilaurate, diglycerin monobehenate, diglycerin dibehenate; triglycerin monomyristate, triglycerin dimilli State, triglycerin monopalmitate, triglycerin dipalmitate, triglycerin monostearate, triglycerin distearate, triglycerin monooleate, triglycerindiolate Triglycerol monolaurate,
Examples include higher fatty acid esters such as triglycerin fatty acid esters such as triglycerin dilaurate, triglycerin monobehenate, and triglycerin dibehenate, and mixtures of two or more thereof. Among them, diglycerin monostearate, diglycerin distearate and a mixture thereof are particularly preferred.

The sorbitan fatty acid ester is an ester of a sorbitan mixture and a higher fatty acid. Sorbitan is generally present as a mixture of 1,4-sorbitan, 3,6-sorbitan, 1,5-sorbitan, which is a sorbit monomolecular dehydrate, and 1,4,3,6-sorbide, which is a sorbit bimolecular dehydrate. Manufactured industrially. Higher fatty acids include lauric acid, palmitic acid, stearic acid, oleic acid,
Myristic acid, behenic acid and the like.

As the sorbitan fatty acid ester, specifically, sorbitan monolaurate, sorbitan dilaurate, sorbitan trilaurate, sorbitan monopalmitate, sorbitan dipalmitate, sorbitan tripalmitate, sorbitan monostearate, sorbitan distearate Sorbitan tristearate, sorbitan monooleate, sorbitan dioleate, sorbitan trioleate, sorbitan monomyristate, sorbitan dimyristate, sorbitan trimyristate, sorbitan monobehenate, sorbitan dibehenate, sorbitan tribehenate And higher fatty acid esters such as nates, and mixtures of two or more thereof. Among them, sorbitan monostearate, sorbitan distearate and a mixture thereof are particularly preferred.

Specific examples of the diethanolalkylamine include compounds such as stearyldiethanolamine, lauryldiethanolamine, oleyldiethanolamine, and myristyldiethanolamine.

The fatty acid diethanolamides include
Specific examples thereof include compounds such as stearic acid diethanolamide, lauric acid diethanolamide, myristic acid diethanolamide, and oleic acid diethanolamide.

Examples of the above-mentioned ethylene oxide adduct of glycerin fatty acid ester include the above-mentioned ethylene oxide adduct of glycerin fatty acid ester such as dioxyethylene glycerin myristate (including mono, di and triester). Dioxyethylene glycerin palmitate (including mono, di and triester), dioxyethylene glycerin stearate (including mono, di and triester), trioxyethylene glycerin myristate (including mono, di and triester) , Trioxyethylene glycerin palmitate (including mono, di and triester), trioxyethylene glycerin stearate (including mono, di and triester), tetraoxyethylene glycerin myristate (Including mono, di and triesters), tetraoxyethylene glycerin palmitate (including mono, di and triesters), tetraoxyethylene glycerin stearate (including mono, di and triesters), pentaoxyethylene glycerin millimeter State (including mono, di and triester), pentaoxyethylene glycerin palmitate (including mono, di and triester), pentaoxyethylene glycerin stearate (including mono, di and triester), hexaoxyethylene glycerin Myristate (including mono, di and triester), hexaoxyethylene glycerin palmitate (including mono, di and triester), hexaoxyethylene glycerin stearate (mono, di and tries) Heptaoxyethylene glyceryl myristate (including mono, di and triesters), heptaoxyethylene glycerin palmitate (including mono, di and triesters), heptaoxyethylene glycerin stearate (including mono, di and triesters) Triester), octaoxyethylene glycerine myristate (including mono, di and triester), octaoxyethylene glycerin palmitate (including mono, di and triester), octaoxyethylene glycerin stearate (mono and diester) And triesters), nonaoxyethylene glycerine myristate (including mono, di and triesters), nonaoxyethylene glycerin palmitate (including mono, di and triesters), nonaoxyethylene Glycerin stearate (including mono, di and triester), decaoxyethylene glycerine myristate (including mono, di and triester), decaoxyethylene glycerin palmitate (including mono, di and triester), decaoxy Ethylene glycerin stearate (including mono, di and triester) and the like.

As the ethylene oxide adduct of the polyglycerin fatty acid ester, specifically, the ethylene oxide adduct of the polyglycerin fatty acid ester described above, for example, dioxyethylene diglycerin myristate (mono, di, tri and tetra) Esters), dioxyethylene diglycerin palmitate (including mono, di, tri and tetra esters), dioxyethylene diglycerin stearate (including mono, di, tri and tetra esters), dioxyethylene triglycerin Myristate (including mono, di, tri and tetraester), dioxyethylene triglycerin palmitate (including mono, di, tri and tetraester), dioxyethylene triglycerin stearate (mono, di, tri and tetraester) Fine tetra including esters), trioxyethylene diglycerin myristate (mono-, di-,
Trioxyethylene diglycerin palmitate (including mono, di, tri and tetra esters), trioxyethylene diglycerin stearate (including mono, di, tri and tetra esters), tetraoxy Ethylene diglycerin myristate (including mono, di, tri and tetraester),
Tetraoxyethylene diglycerin palmitate (including mono, di, tri and tetraester), tetraoxyethylene diglycerin stearate (including mono, di, tri and tetraester), pentaoxyethylene diglycerin myristate (mono, Di, tri and tetra esters, pentaoxyethylene diglycerin palmitate (including mono, di, tri and tetra esters), pentaoxyethylene diglycerin stearate (including mono, di, tri and tetra esters), Hexaoxyethylene diglycerin myristate (including mono, di, tri and tetraester), hexaoxyethylene diglycerin palmitate (mono,
Di, tri and tetra esters, hexaoxyethylene diglycerin stearate (including mono, di, tri and tetra esters), heptaoxyethylene diglycerin myristate (including mono, di, tri and tetra esters), Heptaoxyethylene diglycerin alumitate (including mono, di, tri and tetraester), heptaoxyethylene diglycerin stearate (including mono, di, tri and tetraester), octaoxyethylene diglycerin myristate (mono,
Di, tri and tetra esters, octaoxyethylene diglycerin palmitate (including mono, di, tri and tetra esters), octaoxyethylene diglycerin stearate (including mono, di, tri and tetra esters), Nonaoxyethylene diglycerin myristate (including mono, di, tri and tetraesters), nonaoxyethylene diglycerin palmitate (including mono, di, tri and tetraesters), nonaoxyethylene diglycerin stearate (mono, The
Tri and tetra esters, decaoxyethylene diglycerine myristate (including mono, di, tri and tetra esters), decaoxy ethylene diglycerin palmitate (including mono, di, tri and tetra esters), decaoxy Ethylene diglycerin stearate (including mono, di, tri and tetra esters) and the like.

Specific examples of the ethylene oxide adduct of the sorbitan fatty acid ester include ethylene oxide adducts of the sorbitan fatty acid ester described above, for example, dioxyethylene sorbitan laurate (including mono-, di-, tri- and tetraesters). ), Dioxyethylene sorbitan palmitate (including mono, di, tri and tetraesters), dioxyethylene sorbitan stearate (including mono, di, tri and tetraesters), dioxyethylene sorbitan oleate (mono, di , Tri and tetra esters, trioxyethylene sorbitan laurate (including mono, di, tri and tetra esters), trioxyethylene sorbitan palmitate (including mono, di, tri and tetra esters), Lioxyethylene sorbitan stearate (including mono, di, tri and tetraester), trioxyethylene sorbitan oleate (including mono, di, tri and tetraester), tetraoxyethylene sorbitan laurate (mono, di, triester) And tetraesters), tetraoxyethylene sorbitan palmitate (including mono, di, tri and tetraesters), tetraoxyethylene sorbitan stearate (including mono, di, tri and tetraesters), tetraoxyethylene sorbitan oleate Ethates (including mono, di, tri and tetraesters), pentaoxyethylene sorbitan laurate (including mono, di, tri and tetraesters), pentaoxyethylene sorbitan palmitate (including mono, di, tri and tetraesters) Pentaoxyethylene sorbitan stearate (including mono, di, tri and tetraester), pentaoxyethylene sorbitan oleate (including mono, di, tri and tetraester), hexaoxyethylene sorbitan laurate (Including mono, di, tri and tetraester), hexaoxyethylene sorbitan palmitate (including mono, di, tri and tetraester), hexaoxyethylene sorbitan stearate (including mono, di, tri and tetraester) , Hexaoxyethylene sorbitan oleate (including mono, di, tri and tetraester), heptaoxyethylene sorbitan laurate (including mono, di, tri and tetraester), heptaoxyethylene sorbitan pal Mitates (including mono, di, tri and tetra esters), heptaoxyethylene sorbitan stearate (including mono, di, tri and tetra esters), heptaoxyethylene sorbitan oleate (including mono, di, tri and tetra esters) ), Octaoxyethylene sorbitan laurate (including mono, di, tri and tetraesters), octaoxyethylene sorbitan palmitate (including mono, di, tri and tetraesters), octaoxyethylene sorbitan stearate (mono and diesters) Octaoxyethylene sorbitan oleate (including mono, di, tri and tetra esters), nonaoxyethylene sorbitan laurate (including mono, di, tri and tetra esters), nonao Siethylene sorbitan palmitate (including mono, di, tri and tetraesters), nonaoxyethylene sorbitan stearate (including mono, di, tri and tetraesters), nonaoxyethylene sorbitan oleate (including mono, di, tri and tetraesters) Including tetraester, decaoxyethylene sorbitan laurate (including mono, di, tri and tetraester), decaoxyethylene sorbitan palmitate (including mono, di, tri and tetraester), decaoxyethylene sorbitan stearate (Including mono, di, tri and tetra esters), decaoxyethylene sorbitan oleate (including mono, di, tri and tetra esters) and the like.

As described above, these polyoxyethylene group-containing components have a polyoxyethylene group represented by (—CH ₂ CH ₂ O—) _n H.
Is preferably 2 to 10, and the HLB value is preferably 5 to 12.

The glycerin fatty acid ester is used in an amount of 0 to 60 parts by weight, preferably 10 to 50 parts by weight, based on 100 parts by weight of the total amount of the glycerin fatty acid ester, polyglycerin fatty acid ester, sorbitan fatty acid ester, diethanolalkylamine and fatty acid diethanolamide. Parts of polyglycerin fatty acid ester
-80 parts by weight, preferably 20-60 parts by weight, the sorbitan fatty acid ester is 0-50 parts by weight,
It is preferably contained in a proportion of 10 to 40 parts by weight, and the diethanolalkylamine is contained in an amount of 0 to 20 parts by weight, preferably 5 to
It is desirable that the fatty acid diethanolamide be contained in a proportion of 0 to 20 parts by weight, preferably 5 to 10 parts by weight. The total amount of glycerin fatty acid ester, polyglycerin fatty acid ester, sorbitan fatty acid ester, diethanolalkylamine and fatty acid diethanolamide is 50 to 85% by weight, preferably 55 to 80% by weight, based on the whole antifoggant (C). More preferably, it is 60 to 75% by weight.

The polyoxyethylene glycerin fatty acid ester, the polyoxyethylene polyglycerin fatty acid ester and the polyoxyethylene sorbitan fatty acid ester total 100 parts by weight, and the polyoxyethylene glycerin fatty acid ester is 0 to 60 parts by weight. Preferably, the polyoxyethylene polyglycerin fatty acid ester is contained in a proportion of 0 to 80 parts by weight, preferably 20 to 60 parts by weight, and the polyoxyethylene sorbitan fatty acid ester is contained in a proportion of 0 to 50 parts by weight. ~ 5
It is desirably contained in an amount of 0 parts by weight, preferably 10 to 40 parts by weight. Polyoxyethylene glycerin fatty acid ester which is a polyoxyethylene group-containing component,
The total amount of polyoxyethylene polyglycerin fatty acid ester and polyoxyethylene sorbitan fatty acid ester is 15 to 50% by weight, preferably 20 to 45% by weight, more preferably 2 to 50% by weight, based on the whole antifogging agent (C1).
5 to 40% by weight.

As described above, it is preferable to use different antifogging agents in combination in the proportions within the above range, since the effect of the antifogging properties is maintained for an initial period and for a long period of time. The antifogging agent (C1) preferably used in the present invention is, for example, as follows. (1) An antifogging agent comprising glycerin monostearate and polyoxyethylene glycerin monostearate and / or polyoxyethylene glycerin distearate. (2) An antifogging agent comprising diglycerin monostearate and / or diglycerin distearate and polyoxyethylene glycerin monostearate and / or polyoxyethylene glycerin distearate. (3) An antifogging agent comprising sorbitan monostearate and / or sorbitan distearate and polyoxyethylene glycerin monostearate and / or polyoxyethylene glycerin distearate. (4) An antifogging agent comprising glycerin monostearate, diglycerin monostearate and / or diglycerin distearate, and polyoxyethylene glycerin monostearate and / or polyoxyethylene glycerin distearate. (5) An antifogging agent comprising glycerin monostearate, sorbitan monostearate and / or sorbitan distearate, and polyoxyethylene glycerin monostearate and / or polyoxyethylene glycerin distearate. (6) From diglycerin monostearate and / or diglycerin distearate, sorbitan monostearate and / or sorbitan distearate, and polyoxyethylene glycerin monostearate and / or polyoxyethylene glycerin distearate An antifogging agent. (7) glycerin monostearate, diglycerin monostearate and / or diglycerin distearate, sorbitan monostearate and / or sorbitan distearate, and polyoxyethylene glycerin monostearate and / or polyoxyethylene An antifogging agent comprising glycerin distearate. (8) An antifogging agent comprising glycerin monostearate and polyoxyethylene diglycerin monostearate and / or polyoxyethylene diglycerin distearate. (9) An antifogging agent comprising diglycerin monostearate and / or diglycerin distearate and polyoxyethylene diglycerin monostearate and / or polyoxyethylene diglycerin distearate. (10) An antifogging agent comprising sorbitan monostearate and / or sorbitan distearate and polyoxyethylene diglycerin monostearate and / or polyoxyethylene diglycerin distearate. (11) An antifogging agent comprising glycerin monostearate, diglycerin monostearate and / or diglycerin distearate, and polyoxyethylene diglycerin monostearate and / or polyoxyethylene diglycerin distearate. (12) An antifogging agent comprising glycerin monostearate, sorbitan monostearate and / or sorbitan distearate, and polyoxyethylene diglycerin monostearate and / or polyoxyethylene diglycerin distearate. (13) diglycerin monostearate and / or diglycerin distearate, sorbitan monostearate and / or sorbitan distearate, and polyoxyethylene diglycerin monostearate and / or
Or an antifogging agent comprising polyoxyethylene diglycerin distearate. (14) glycerin monostearate, diglycerin monostearate and / or diglycerin distearate, sorbitan monostearate and / or sorbitan distearate, and polyoxyethylene diglycerin monostearate and / or polyoxy An antifogging agent comprising ethylene diglycerin distearate. (15) An antifogging agent comprising glycerin monostearate and polyoxyethylene sorbitan monostearate and / or polyoxyethylene sorbitan distearate. (16) An antifogging agent comprising diglycerin monostearate and / or diglycerin distearate and polyoxyethylene sorbitan monostearate and / or polyoxyethylene sorbitan distearate. (17) An antifogging agent comprising glycerin monostearate, diglycerin monostearate and / or diglycerin distearate, and polyoxyethylene sorbitan monostearate and / or polyoxyethylene sorbitan distearate. (18) An antifogging agent comprising glycerin monostearate, sorbitan monostearate and / or sorbitan distearate, and polyoxyethylene sorbitan monostearate and / or polyoxyethylene sorbitan distearate. (19) Diglycerin monostearate and / or diglycerin distearate, sorbitan monostearate and / or sorbitan distearate, and polyoxyethylene sorbitan monostearate and / or polyoxyethylene sorbitan distearate An antifogging agent. (20) glycerin monostearate, diglycerin monostearate and / or diglycerin distearate, sorbitan monostearate and / or sorbitan distearate, and polyoxyethylene sorbitan monostearate and / or polyoxyethylene An antifogging agent comprising sorbitan distearate. (21) glycerin monostearate, diglycerin monostearate and / or diglycerin distearate, stearyl diethanolamine and / or diethanolamide stearate, and polyoxyethylene diglycerin monostearate and / or polyoxyethylene distearate An antifogging agent comprising glycerin distearate. (22) glycerin monostearate, diglycerin monolaurate and / or diglycerin dilaurate, stearyl diethanolamine and / or diethanolamide stearate, and polyoxyethylene diglycerin monostearate and / or polyoxyethylene diglycerin dilaurate Antifogging agent consisting of stearate. (23) glycerin monostearate, diglycerin monostearate and / or diglycerin distearate, stearyl diethanolamine and / or diethanolamide stearate, and polyoxyethylene sorbitan monostearate and / or polyoxyethylene sorbitan diester Antifogging agent consisting of stearate.

The antifogging agent (C) was used in an amount of 10% in total of the linear low-density polyethylene (A) and the hydrotalcites (B).
0.5 to 5 parts by weight, preferably 0.1 to 5 parts by weight, per 0 parts by weight.
It is used in an amount of 5 to 4 parts by weight, more preferably 0.5 to 3 parts by weight.

For the purpose of increasing the retention of the anti-fogging agent (C) in the film and further improving the anti-fogging durability, the modified wax is replaced with a linear low-density polyethylene (A) and hydrotalcites. 0.1 to 5 parts by weight, preferably 0.5 to 4 parts by weight, based on 100 parts by weight in total with (B)
More preferably, it can be added at a ratio of 1 to 3 parts by weight.

Specific examples of such a modified wax include maleic acid-modified polyethylene wax, acrylic acid-modified polyethylene wax, oxidized polyethylene wax and the like.

The modified wax has an acid value of usually 1 to 60 KOH.
mg / g, and the molecular weight (Mv) is usually 1,000 to 50,000.
00. [High-Pressure Low-Density Polyethylene (D)] The high-pressure low-density polyethylene (D), which may constitute the ethylene copolymer composition (1) used in the present invention, has a melt flow rate (MFR; ASTM D 1238). , 190 ℃, load 2.16kg).
1-100 g / 10 min, density 915-935 kg / m
^{3. The} swell ratio is preferably 60% or less.

The mixing amount of the high-pressure low-density polyethylene (D) is 40% by weight or less based on 100% by weight of the total of the linear low-density polyethylene (A) and the high-pressure low-density polyethylene (D). It is usually desirable that the content be 1 to 40% by weight, preferably 1 to 20% by weight.

The density of the high-pressure low-density polyethylene (D) can be determined by the same method as the method for measuring the density of the linear low-density polyethylene (A) described above. The swell ratio is obtained as follows.

The diameter at a position 5 mm from the tip of the strand obtained at the time of measuring the melt flow rate is measured with a micrometer as the diameter (mm) of the sample. Then, the swell ratio is calculated by the following equation.

Swell ratio (%) = [(L ₁ / L ₀ ) −1] × 100 L ₁ : sample diameter (mm) L ₀ : orifice diameter (= 2.0955 mm) Polyethylene (D) can be produced by a conventionally known high-pressure method.

[Other Components] In the ethylene copolymer composition (1) used in the present invention, if necessary, conventionally known weather resistance stabilizers (ultraviolet absorbers, light stabilizers) and nonionic ones may be used. Additives such as a fluorine-containing surfactant, an antioxidant, an antifog, an antistatic agent, and a heat stabilizer can be blended within a range that does not impair the purpose of the present invention.

The weather stabilizer is roughly classified into an ultraviolet (UV) absorber and a light stabilizer. The light stabilizer is more effective for a thin antifogging film such as an agricultural film, The effect of improvement is great.

As the light stabilizer, conventionally known light stabilizers can be used, and among them, hindered amine light stabilizers (HALS; Hindered Amine Light Stabilizers) are preferably used.

As the hindered amine-based stabilizer, specifically, the following compounds are used. (1) bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, (2) dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-succinate Tetramethylpiperidine polycondensate, (3) tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, (4) 2,2,6, 6-tetramethyl-4-piperidinyl benzoate, (5) bis- (1,2,6,6-tetramethyl-4
-Piperidinyl) -2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate, (6) bis (N-
Methyl-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, (7) 1,1 ′-(1,2-ethanediyl) bis (3,3,
5,5-tetramethylpiperazinone), (8) (mixed
2,2,6,6-tetramethyl-4-piperidyl / tridecyl)-
1,2,3,4-butanetetracarboxylate, (9) (mixed 1,2,2,6,6-pentamethyl-4-piperidyl / tridecyl) -1,2,3,4-butanetetracarboxylate ,
(10) Mixed {2,2,6,6-tetramethyl-4-piperidyl / β, β, β ′, β′-tetramethyl-3-9- [2,4,8,10-tetraoxaspiro (5,5) undecane] diethyl｝ -1,2,
3,4-butanetetracarboxylate, (11) mixed {1,2,2,6,6-pentamethyl-4-piperidyl / β, β,
β ', β'-tetramethyl-3-9- [2,4,8,10-tetraoxaspiro (5,5) undecane] diethyl} -1,2,3,4-butanetetracarboxylate, (12 ) N, N'-Bis (3-aminopropyl) ethylenediamine-2-4-bis [N-butyl-N-
(1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6
-Chloro-1,3,5-triazine condensate, (13) N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 1,2-dibromoethane Condensate, (14)
[N- (2,2,6,6-tetramethyl-4-piperidyl) -2-methyl-2- (2,2,6,6-tetramethyl-4-piperidyl) imino] propionamide, (15) Poly {[6-[(1,1,3,3-tetramethylbutyl) amino] -1,3,5-triazine-2,4-diyl] [[(2,2,6,6-tetramethyl- 4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]｝ (trade name Chimassorb 944), (1
6) 1,5,8,12-tetrakis [4,6-bis (N-butyl-N-1,2,
2,6,6-pentamethyl-4-piperidylamino) -1,3,5-triazin-2-yl] -1,5,8,12-tetraazadodecane.

These hindered amine light stabilizers include:
They can be used alone or in combination of two or more. Such a light stabilizer is used in an amount of 0.005 to 5 parts by weight based on 100 parts by weight of the linear low density polyethylene (A).
It is preferably used in a proportion of 0.005 to 2 parts by weight, more preferably 0.01 to 1 part by weight.

Specific examples of the ultraviolet absorber include salicylic acid ultraviolet absorbers such as phenyl salicylate, p-tert-butylphenyl salicylate, and p-octylphenyl salicylate; 2,4-dihydroxybenzophenone, 2-hydroxy-4 -Methoxybenzophenone, 2-hydroxy-4
-Octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-methoxy- Benzophenone UV absorbers such as 5-sulfobenzophenone; 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-tert-butylphenyl) benzotriazole, (2'-hydroxy-3 ', 5'
-Di-tert-butylphenyl) benzotriazole, 2-
(2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5- Benzotriazole-based absorbents such as chlorobenzotriazole and 2- (2'-hydroxy-3 ', 5'-di-tert-amylphenyl) benzotriazole; 2-ethylhexyl-2-cyano-3,3'-diphenylacrylate And cyanoacrylate-based ultraviolet absorbers such as ethyl-2-cyano-3,3'-diphenylacrylate.

The ultraviolet absorber is used in an amount of 0.005 to 5 parts by weight, preferably 0.005 to 2 parts by weight, more preferably 0.01 to 1 part by weight, per 100 parts by weight of the linear low-density polyethylene (A). Used in parts by weight.

The nonionic fluorine-containing surfactant optionally used in the present invention has a fluorine content of 25 to 65.
%, And the surface tension of a 0.001% aqueous solution at 25 ° C. is usually 42 dyne / cm or less. In the present invention, an organic fluorine compound having a perfluoroalkyl group is particularly preferred.

Examples of such an organic fluorine compound include perfluoroalkylethylene oxide adducts,
Alkylene oxide adducts of perfluoroalkyl alcohols such as perfluoroalkylpropylene oxide adducts; and perfluoroalkyl group-containing oligomers such as perfluoroalkyl acrylate oligomers and perfluoroalkyl methacrylate oligomers.

The above perfluoroalkylethylene oxide adduct was obtained, for example, from Daikin Industries, Ltd. under the trade name DS-4.
03 and KC-40 from Asahi Glass Co., Ltd.

The oligomer having a perfluoroalkyl group can be obtained, for example, from S-393 by Asahi Glass Co., Ltd.
It is commercially available under the trade name. Also, a mixture of a perfluoroalkyl ethylene oxide adduct and a perfluoroalkyl-containing oligomer is available from Asahi Glass Co., Ltd.
It is commercially available under the trade name of -14.

The nonionic fluorine-containing surfactant is used in an amount of 0.01 to 1 part by weight, preferably 0.05 to 0.1 part by weight, based on 100 parts by weight of the total amount of the linear low density polyethylene (A).
Used in an amount of 3 parts by weight. When the nonionic fluorine-containing surfactant is used in the above-described amount, the antifogging property is improved, and a film having excellent antifogging durability (long-term antifogging property) can be obtained.

The anti-fogging film according to the present invention comprises a layer [1] comprising the above ethylene copolymer composition (1).
Having. When the antifogging film according to the present invention is a single-layer film composed of the layer [1] formed of the above-mentioned ethylene-based copolymer composition (1), its thickness varies depending on the use, but for example, for agricultural use. For film, the thickness is usually 20
To 200 μm, preferably 30 to 200 μm, more preferably 40 to 180 μm, and even more preferably 50 to 200 μm.
１５０150 μm.

The antifogging film according to the present invention, which is such a single-layer film, includes (i) an Elmendorf tear strength (JIS Z 1702) of at least 900 N / cm in the MD (extrusion direction of the film). Preferably 1,
000 N / cm or more, and 900 N / cm or more in the TD (width direction of the film) direction, preferably
(Ii) The haze (ASTM D 1003-61) at a thickness of 100 μm is preferably 30% or less, and more preferably 25% or less.

The antifogging film having a single layer structure according to the present invention as described above can be prepared from the above-mentioned ethylene-based copolymer composition (1) by, for example, film forming by an inflation method or a T-die method. it can.

The film formation by the inflation method is carried out by extruding the ethylene copolymer composition (1) through a circular die and expanding it by a predetermined air flow. The resin temperature at the time of extruding the ethylene copolymer composition (1) is 190 to 250 ° C.
It is preferable that

As described above, the anti-fogging film according to the present invention comprises the above-mentioned ethylene copolymer composition (1).
May be a multilayer structure having a layer [1] formed from. As the antifogging film having a multilayer structure according to the present invention,
For example, a two-layer film in which the following outer layer [2] is laminated on one surface of a layer [1] formed from the above ethylene-based copolymer composition (1) is preferable, and the other one surface of the layer [1] is preferable. Particularly, a three-layer film in which an inner layer [3] is further laminated is particularly preferable.

Outer Layer [2] The outer layer [2] constituting the two-layer or three-layer film is
A polyethylene composition (2) containing polyethylene (E) having a density of 925 to 945 kg / m ³ , or, if necessary, hydrotalcites (B) and an antifogging agent (C) in addition to polyethylene (E). Is formed from.

[Polyethylene (E)] The polyethylene (E) used in the present invention has a density of 925 to 945 kg /
If m ^3, it may be any polyethylene. For example, ethylene homopolymer, ethylene / α-olefin copolymer, linear polyethylene and the like can be mentioned.

When the antifogging film according to the present invention is a three-layer film comprising the outer layer [2], the layer [1] (intermediate layer) and the inner layer [3], the polyethylene forming the outer layer [2] density of (E) and (d _E), and the density of the polyolefin resin (F) for forming the inner layer _{[3] (d F),} d E ≧
It is preferable that d _F be satisfied. In a three-layer film satisfying such a relationship, the layer [1] (intermediate layer)
The transfer of the anti-fogging agent (C) contained in the inner layer always predominates toward the inner layer rather than the outer layer, so that the anti-fogging property of the inner layer can be maintained for a long time.

[Hydrotalcites (B)] Hydrotalcites (B) used as optional components in the present invention
Is the same as the hydrotalcites (B) constituting the above-mentioned ethylene copolymer composition (1).

The hydrotalcites (B) are used in an amount of 1 to 15 parts by weight, preferably 2 to 12 parts by weight, more preferably 3 to 10 parts by weight, based on 100 parts by weight of the polyethylene (E). . When the hydrotalcites (B) are used in the above amount, the antifogging durability of the obtained multilayer film can be further improved.

[Anti-fogging agent (C)] The anti-fogging agent (C) used as an optional component in the present invention is the same as the anti-fogging agent (C) constituting the above-mentioned ethylene copolymer composition (1). It is.

The antifogging agent (C) is a polyethylene (E) 10
It is used in an amount of 0.05 to 5 parts by weight, preferably 0.1 to 4 parts by weight, more preferably 0.5 to 3 parts by weight with respect to 0 parts by weight. In order to further increase the anti-fogging durability of the obtained multilayer film, it is preferable to use the anti-fogging agent (C) in the above amount.

[Other Components] In the above polyethylene composition (2), if necessary, conventionally known weathering stabilizers (ultraviolet absorbers, light stabilizers), nonionic fluorine-containing surfactants, antioxidants Additives such as an agent, an antistatic agent and a heat stabilizer can be blended within a range that does not impair the object of the present invention.

The weathering stabilizers are the same as the weathering stabilizers (ultraviolet absorbers, light stabilizers) used as needed when forming the above-mentioned single-layered antifogging film. The light stabilizer is used in an amount of 0.1 to 100 parts by weight of polyethylene (E).
005 to 5 parts by weight, preferably 0.005 to 2 parts by weight,
More preferably, it is used in an amount of 0.01 to 1 part by weight.

The ultraviolet absorber is used in an amount of 0.005 to 5 parts by weight based on 100 parts by weight of polyethylene (E).
It is preferably used in an amount of 0.005 to 2 parts by weight, more preferably 0.01 to 1 part by weight.

The above nonionic fluorine-containing surfactant is as follows:
It is the same as the nonionic fluorine-containing surfactant used in forming the above-described single-layer structure antifogging film. The nonionic fluorine-containing surfactant is polyethylene (E)
It is used in an amount of 0.01 to 1 part by weight, preferably 0.05 to 0.3 part by weight, based on 100 parts by weight.

Inner Layer [3] The inner layer [3] constituting the two-layer or three-layer film is
In addition to the polyolefin resin (F) containing 0.5 to 5% by weight of the antifogging agent (C) or the polyolefin resin (F) containing 0.5 to 5% by weight of the antifogging agent (C), It is formed from a polyolefin-based resin composition (3) containing a hydrotalcite (B) accordingly.

[Polyolefin Resin (F)] Examples of the polyolefin resin (F) used in the present invention include high-pressure low-density polyethylene (HPLDPE),
Examples include ethylene-vinyl acetate copolymer (EVA), linear low-density polyethylene (LLDPE), and linear low-density polyethylene (M-LLDPE) prepared using a metallocene-based olefin polymerization catalyst.

[Hydrotalcites (B)] Hydrotalcites (B) used as optional components in the present invention
Is the same as the hydrotalcites (B) constituting the above-mentioned ethylene copolymer composition (1).

The hydrotalcites (B) are used in an amount of 1 to 15 parts by weight, preferably 1 to 12 parts by weight, more preferably 1 to 15 parts by weight, based on 100 parts by weight of the polyolefin resin (F).
Used in an amount of 10 parts by weight. When the hydrotalcites (B) are used in the above amount, the antifogging durability of the obtained multilayer film can be further improved.

[Anti-fogging agent (C)] The anti-fogging agent (C) used as an optional component in the present invention is the same as the above-mentioned anti-fogging agent (C) constituting the ethylene copolymer composition (1). It is.

The antifogging agent (C) is used in an amount of 0.1% based on 100% by weight of the polyolefin resin (F) and the antifogging agent (C).
It is used in an amount of 5 to 5% by weight, preferably 0.5 to 4% by weight, more preferably 0.5 to 3% by weight. In order to further enhance the antifogging durability of the obtained multilayer fill, it is preferable to use the antifogging agent (C) in the above-mentioned amount.

[Other Components] In the above-mentioned polyolefin resin composition (3), if necessary, a conventionally known weather resistance stabilizer (ultraviolet absorber, light stabilizer), a nonionic fluorine-containing surfactant, Additives such as an antioxidant, an antistatic agent, and a heat stabilizer can be blended within a range that does not impair the purpose of the present invention.

The above-mentioned weathering stabilizers are the same as the weathering stabilizers (ultraviolet absorbers, light stabilizers) used as needed when forming the above-mentioned single-layer structure antifogging film. The light stabilizer is used in an amount of 0.005 to 5 parts by weight, preferably 0.005 to 2 parts by weight, based on 100 parts by weight of the polyolefin resin (F).
Parts by weight, more preferably 0.01 to 1 part by weight.

The ultraviolet absorber is used in an amount of 0.005 to 5 parts by weight, preferably 0.005 to 2 parts by weight, more preferably 0.01 to 1 part by weight, per 100 parts by weight of the polyolefin resin (F). Used in parts amounts.

The above nonionic fluorine-containing surfactant is
It is the same as the nonionic fluorine-containing surfactant used in forming the above-described single-layer structure antifogging film. The nonionic fluorine-containing surfactant is used in an amount of 0.01 to 1 part by weight, based on 100 parts by weight of the polyolefin resin (F).
It is preferably used in an amount of 0.05 to 0.3 parts by weight.

In a two-layer film in which the layer [1] and the outer layer [2] are laminated, the ratio of the thickness of the layer [1] to the total thickness of the two-layer film is 50% or more, preferably 5% or more.
It is desirable to be 5 to 95%, more preferably 60 to 90%.

In a three-layer film in which the outer layer [2], the layer [1] and the inner layer [3] are laminated in this order, the ratio of the thickness of the layer [1] to the total thickness of the three-layer film is as follows. , 50% or more, preferably 55 to 90%, more preferably 60 to 80%.

In the antifogging film according to the present invention, which is a two-layer film as described above, the outer layer [2] usually has a thickness of 1 to 3.
100 μm, preferably 2 to 90 μm, more preferably 3 to 80 μm, and the thickness of the layer [1] is 10 to
190 μm, preferably 12 to 180 μm, more preferably 14 to 170 μm, and the total thickness of these layers is 20 to 200 μm, preferably 30 to 2 μm.
00 μm, more preferably in the range of 40 to 180 μm.

The antifogging film according to the present invention, which is a three-layer film as described above, has a thickness of the outer layer [2] of usually 1 to 90 μm, preferably 2 to 80 μm, more preferably 3 to 70 μm. And the thickness of the layer [1], ie, the intermediate layer, is 10 to 180 μm, preferably 12 to 170 μm.
μm, more preferably 14 to 160 μm, and the thickness of the inner layer [3] is 1 to 90 μm, preferably 2 to 90 μm.
80 μm, more preferably in the range of 3 to 70 μm, and the total thickness of these layers is 20 to 200 μm,
Preferably 30 to 200 μm, more preferably 50 to 200 μm
180 μm, even more preferably in the range of 70 to 150 μm.

In such a three-layer film, the ratio of the thickness of each of the outer layer [I], the intermediate layer [II] and the inner layer [III] (outer layer [I] / intermediate layer [II] / inner layer [III]) Is
It is desirable that the ratio be 1/2/1 to 1/40/1, preferably 1/3/1 to 1/20/1.

The antifogging film according to the present invention, which is a two-layer film as described above, includes (i) an Elmendorf tear strength (JIS Z 1702) of 900 in the MD direction.
N / cm or more, preferably 1,000 N / cm or more, and 900 N / cm or more, preferably 1,000 N / cm or more in the TD direction, and (ii) a thickness of 100 μm.
Haze (ASTM D 1003-61) is 30%
Or less, preferably 25% or less.

The antifogging film according to the present invention, which is a three-layer film as described above, includes (i) an Elmendorf tear strength (JIS Z 1702) of 9 in the MD direction.
(N) thickness 100 N / cm or more, preferably 1,000 N / cm or more, and TD direction 900 N / cm or more, preferably 1,000 N / cm or more.
The haze at μm (ASTM D 1003-61) is 3
It is desirably 0% or less, preferably 25% or less.

The antifogging film according to the present invention having a three-layer structure as described above is prepared by mixing the above-mentioned components constituting each layer, and mixing them with a Banbury mixer or a roll mill.
It can be prepared by melt-mixing with an extruder or the like, and then laminating an outer layer, an intermediate layer and an inner layer by a coextrusion inflation method or a coextrusion T-die method.

It should be noted that two or four or more layers
The antifogging film according to the present invention can be prepared according to these preparation methods.

[0140]

The anti-fogging film according to the present invention is superior in the anti-fogging property and the anti-fogging durability to the conventional agricultural films (single-layer and multi-layer films) described above, and the anti-fogging property of the anti-fogging property is longer. It has a small degree of deterioration and is excellent in durability, transparency, toughness and the like, and can be used for applications such as agricultural films.

Further, the antifogging film according to the present invention is light in weight and has a small amount of low molecular weight components in the polymer used, so that it has a low stickiness, is excellent in spreading workability, and has a high film resistance at high temperatures. Has the advantage of less fusion. In particular, in the antifogging film composed of the above-described three-layer film, the resin forming the outer layer [2] has a higher density than the resin forming the inner layer [3], so that the antifogging durability (long term) (Anti-fogging property) is very excellent.

The antifogging film according to the present invention has the above-mentioned effects, and can be used as an agricultural film, and can be spread on agricultural and horticultural facilities such as houses and tunnels.
It can be used for a long time to cultivate useful crops.

Hereinafter, the present invention will be described with reference to Examples.
The present invention is not limited to these examples. The evaluation of the antifogging films in Examples and Comparative Examples was performed as follows.

(1) Toughness (Elmendorf Tear Strength) Elmendorf tear strength was measured in the machine direction (MD) by a method in accordance with JIS Z-1702.

(2) Anti-fogging property (flowability under low temperature) In a 200 ml beaker, 50 ml of water at 20 ° C was put, and the beaker was covered with a film so that the inner layers of the three-layer film faced the inside of the beaker. Sealed. Next, this beaker was fixed in a constant temperature water bath at 20 ° C. set in a constant temperature bath at 0 ° C. at a tilt of 10 ° with respect to the horizontal, and after 1 hour, the inner surface of the film was observed. It was evaluated by evaluation.

<Five-grade evaluation> 5: The entire inner surface of the film is wet with a uniform water film. 4: There are no water droplets on the inner surface of the film, but flow streaks are observed. 3: Flow streaks and water droplets are mixed on the inner surface of the film. 2: Flow streaks and water droplets are mixed on the inner surface of the film, and there are many water droplets. 1: The entire inner surface of the film is covered with water droplets. 3, 4, and 5 passed the antifogging property, and 1, 2 failed.

(3) Anti-fogging durability (anti-fogging durability under high temperature) In a 200 ml beaker, 50 ml of water at 50 ° C. is placed, and the beaker film is placed inside the beaker so that the inner layers of the three-layer film face each other. And sealed.

Next, this beaker was fixed in a constant temperature water bath at 50 ° C. installed in a room at 23 ° C. at an inclination of 10 ° with respect to the horizontal, and after 70 days, the inner surface of the film was observed. The evaluation was performed on a five-point scale.

<Five-grade evaluation> 5: The entire inner surface of the film is wet with a uniform water film. 4: There are no water droplets on the inner surface of the film, but flow streaks are observed. 3: Flow streaks and water droplets are mixed on the inner surface of the film. 2: Flow streaks and water droplets are mixed on the inner surface of the film, and there are many water droplets. 1: The entire inner surface of the film is covered with water droplets.

3, 4, and 5 passed antifogging durability, and 1,
2 is rejected.

(4) Transparency (Haze) Haze was measured according to ASTM D 1003-61.

[0152]

Reference Example 1 Preparation of Linear Low-Density Polyethylene (I) [Preparation of Catalyst for Olefin Polymerization] 5.0 kg of silica dried at 250 ° C. for 10 hours was suspended in 80 liters of toluene, and then suspended at 0 ° C. Cooled down. Thereafter, 28.7 l of a toluene solution of methylaluminoxane (Al; 1.33 mol / l) was added dropwise over 1 hour. At this time, the temperature in the system was kept at 0 ° C. Subsequently, the reaction was carried out at 0 ° C. for 60 minutes, then the temperature was raised to 95 ° C. over 1.5 hours, and the reaction was carried out at that temperature for 20 hours. Thereafter, the temperature was lowered to 60 ° C., and the supernatant was removed by a decantation method.

The solid component thus obtained was washed twice with toluene and then resuspended in 80 liters of toluene. 7.4 liters of a toluene solution of bis (1,3-n-butylmethylcyclopentadienyl) zirconium dichloride (Zr; 34.0 mmol / l) and bis (1,3-dimethylcyclopentadienyl) were introduced into the system. ) 1.0 L of a toluene solution of zirconium dichloride (Zr; 28.1 mmol / L) was added dropwise at 80 ° C over 30 minutes, and the reaction was further performed at 80 ° C for 2 hours. Thereafter, the supernatant was removed and washed twice with hexane to obtain a solid catalyst containing 3.6 mg of zirconium per gram. [Preparation of prepolymerized catalyst] In 85 liters of hexane containing 1.7 mol of triisobutylaluminum, 0.85 kg of the solid catalyst obtained above and 1-hexene 25 were added.
5 g was added, and ethylene was prepolymerized at 35 ° C. for 12 hours to obtain a prepolymerized catalyst in which 10 g of polyethylene was prepolymerized per 1 g of the solid catalyst. The intrinsic viscosity [η] of this ethylene polymer was 1.74 dl / g. [Polymerization] Using two continuous fluidized-bed gas-phase polymerization apparatuses connected in series, ethylene and 1-
Copolymerization with hexene was performed to obtain a linear low-density polyethylene (I).

The linear low-density polyethylene (I) obtained as described above has a 1-hexene content of 7.5% by weight, a density of 0.928 g / cm ³ and a melt flow rate ( MFR; ASTM D 1238-65T, 1
90 ° C., load 2.16 kg) is 1.63 g / 10 min, and the molecular weight distribution (Mw / Mn) measured by GPC.
Was 3.5.

The linear low-density polyethylene (I) has a temperature [Tm] of one of the maximum peaks of an endothermic curve measured by a differential scanning calorimeter (DSC) of 120 ° C., and n-decane at room temperature. The soluble component amount fraction [W] was 0.25% by weight.

The above B ₁ measured by GPC-IR analysis on this linear low-density polyethylene (I) was 12.2
/ A 1000 C-(per 1000 carbon atoms 12.2), B ₂ was 9.9 / 1000 C-.

[0157]

Reference Example 2 Preparation of Linear Low-Density Polyethylene (II) Using two continuous fluidized-bed gas-phase polymerization apparatuses connected in series, ethylene was used in the presence of the prepolymerized catalyst described in Reference Example 1 above. And 1-hexene were copolymerized to obtain a linear low-density polyethylene (II).

The linear low density polyethylene (II) thus obtained has a 1-hexene content of 11% by weight, a density of 0.915 g / cm ³ and a melt flow rate (MFR; ASTM D 1238-65T, 19
0 ° C., load 2.16 kg) is 2.19 g / 10 min, and the molecular weight distribution (Mw / Mn) measured by GPC
Was 3.5.

The linear low-density polyethylene (I
I) shows that the temperature [Tm] of one of the maximum peaks of the endothermic curve measured by a differential scanning calorimeter (DSC) is 108 ° C., and the n-decane soluble component amount fraction [W] at room temperature is 0.42. % By weight.

The above-mentioned B ₁ of this linear low-density polyethylene (II) measured by GPC-IR analysis was 18.6.
/ Is a 1000C, B ₂ was 14.7 / 1000C.

[0161]

Reference Example 3 Preparation of Linear Low-Density Polyethylene (III) A linear low-density polyethylene (III) as shown in Table 1 was obtained in the same manner as in Reference Example 1.

[0162]

[Table 1]

[0163]

Examples 1 to 3 and Comparative Examples 1 and 2 A three-layer film having a thickness of 100 μm was blown under the conditions shown in Table 2 using the resins shown in Table 1 and the antifogging agents shown below. did. [Inflation molding conditions] Molding machine: 3-layer machine manufactured by Alpine Company Die diameter: 400 mm Molding temperature: 200 ° C. Folding width: 1500 mm Thickness: All layers 100 μm (outer layer / intermediate layer / inner layer = 20 μm / 60 μm / 20 μ)
m) Table 2 shows the physical properties of the film obtained as described above. [Anti-fogging agent] glycerin monostearate 20% by weight,
An antifogging agent comprising 40% by weight of diglycerin monodistearate and 40% by weight of a 3 mol ethylene oxide adduct of sorbitan monodistearate.

[0164]

[Table 2]

The weathering stabilizers in Table 2 were N, N'-bis (3-
Aminopropyl) ethylenediamine-2--4-bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensate The hydrotalcite is DHT-4A [trade name; manufactured by Kyowa Chemical Co., Ltd.], and the fluorine-containing surfactant is DS-4.
03 [trade name; manufactured by Daikin Industries, Ltd.].

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 3/26 C08K 3/26 5/06 5/06 C08L 23/08 C08L 23/08 // (C08L 23 / 08 (C08L 23/08 23:06) 23:06) (72) Inventor Yasuo Tanaka 3 Chigusa Coast, Ichihara-shi, Chiba Mitsui Chemicals, Inc. (72) Inventor Mamoru Takahashi Kuga-gun, Yamaguchi Prefecture 6-1-2 Waki, Wakicho F-term in Mitsui Chemicals, Inc. (reference) 2B024 DB01 DB07 2B029 EB02 EB03 EB16 EC02 EC09 EC17 RA03 4F071 AA18 AA19 AA81 AA82 AB21 AC06 AE22 AF05Y AF56 AH01 BA01 BB06 A01A02A AH02H AK03C AK04B AK06A AK62C AK63A AK66C AL05A BA02 BA03 BA10B BA10C BA15 BA26 CA10 CA10A CA10C CA18 EH20 GB01 JA07A JA13A JA13B JA13C JA20 JA20A JK01 JL00 JN01 YY00A YY00B YB02C D206 FD207 GA01

Claims (7)

[Claims] 1. A copolymer obtained by copolymerizing ethylene and an α-olefin having 4 to 12 carbon atoms in the presence of a metallocene-based olefin polymerization catalyst, and having a density of 880 to 930 kg / m 2.
A linear low density polyethylene (A) which is a ^3, hydrotalcite (B), and a layer formed from anti-fogging agent (C) ethylene copolymer composition comprising the (1) [1 In the composition (1), a linear low-density polyethylene (A)
The linear low-density polyethylene (A) is contained in an amount of not less than 60 parts by weight and less than 80 parts by weight based on 100 parts by weight of the total amount of the hydrotalcites (B) and the hydrotalcites (B). ) Is contained in an amount of more than 20 parts by weight and 40 parts by weight or less, and the antifogging agent (C) is contained in an amount of 0.5 to 5 parts by weight. 2. The linear low-density polyethylene (A) comprises:
High-pressure low-density polyethylene (D) in an amount of 40% by weight or less
The anti-fogging film according to claim 1, comprising: 3. The linear low-density polyethylene (A), or a mixture of the linear low-density polyethylene (A) and the high-pressure low-density polyethylene (D), comprises (i) a molecular weight distribution measured by GPC. Mw / Mn: Mw = weight average molecular weight, Mn = number average molecular weight) is in the range of 1.5 to 5.0, and (ii) n-decane soluble component fraction at 23 ° C. (W
(% By weight)) and the density (d), W <80 × exp (−100 (d−0.88)) + 0.
(Iii) When the average value of the number of branches on the high molecular weight side by GPC-IR is B ₁ and the average value of the number of branches on the low molecular weight side is B ₂ , B ₁ ≧ B ₂ The anti-fogging film according to claim 1 or 2, wherein: 4. A layer having a density of 925 to 9 on one surface of the layer [1].
A two-layer film in which an outer layer [2] made of polyethylene (E) of 45 kg / m ³ is laminated, and the ratio of the thickness of the layer [1] to the total thickness of the two-layer film is 50% or more. An anti-fogging film characterized by the following. 5. A layer having a density of 925 to 9 on one surface of the layer [1].
An outer layer [2] made of 45 kg / m ³ of polyethylene (E) is laminated, and a polyolefin resin containing 0.5 to 5% by weight of an antifogging agent (C) is provided on the other side of the layer [1] ( A three-layer film in which an inner layer [3] made of F) is laminated, wherein the ratio of the thickness of the layer [1] to the total thickness of the three-layer film is 50% or more. the film. Density polyethylene (E) of 6. to form the outer layer [2] and (d _E), an inner layer [3] and the density of the polyolefin resin (F) to form a (d _F) but, d _E ≧ antifogging film according to claim 5, characterized in that a relation to satisfy the d _F. 7. The antifogging agent (C1) according to claim 1, wherein said antifogging agent (C) is a polyoxyethylene group-containing component in an amount of 15 to 50% by weight. Anti-fog film.