JP3907764B2 - Ethylene resin heat-resistant container - Google Patents

Description

【０１１６】
【表２】

【０１１７】
【実施例３】
［フィルムの製造および評価］
実施例１のエチレン・α-オレフィン（Ａ−１）を、モダン社製キャストフィルム成形機により、シリンダー温度１８０〜２２０℃、ダイス温度２２０℃、ロール温度３０℃の条件で、フィルム成形して厚さ２００μｍのフィルムを得た。
【０１１８】
得られたフィルムについて、１１５℃、３０分の耐熱処理した後、ヘイズ、外観およびヤング率を上述した方法で測定ないし評価した。
結果を表３に示す。
【０１１９】
【実施例４】
［フィルムの製造および評価］
実施例３において、実施例１のエチレン・α-オレフィン（Ａ−１）の代わりに実施例２のエチレン・α-オレフィン共重合体（Ａ−２）を用いた以外は、実施例３と同様にして、厚さ２００μｍのフィルムを得た。
【０１２０】
得られたフィルムについて、１１５℃、３０分の耐熱処理した後、ヘイズ、外観およびヤング率を上述した方法で測定ないし評価した。
結果を表３に示す。
【０１２１】
【比較例２】
［フィルムの製造および評価］
実施例３において、実施例１のエチレン・α-オレフィン共重合体（Ａ−１）の代わりに比較例１のエチレン系共重合体（Ａ−３）を用いた以外は、実施例３と同様にして、厚さ２００μｍのフィルムを得た。
【０１２２】
得られたフィルムについて、１１５℃、３０分の耐熱処理した後、ヘイズ、外観およびヤング率を上述した方法で測定ないし評価した。
結果を表３に示す。
【０１２３】
【表３】

【０１２４】
【実施例５】
［フィルムの製造および評価］
実施例１のエチレン・α-オレフィン共重合体（Ａ−１）を、以下のような条件でモダン社製キャストフィルム成形機により、シリンダー温度１８０〜２２０℃、ダイス温度２２０℃、ロール温度３０℃の条件で、フィルム成形して厚さ１００μｍのフィルムを得た。
【０１２５】
得られたフィルムについて、１１５℃、３０分の耐熱処理した後、ヘイズ、外観およびヤング率を上述した方法で測定ないし評価した。
結果を表４に示す。
【０１２６】
【実施例６】
［フィルムの製造および評価］
実施例５において、実施例１のエチレン・α-オレフィン共重合体（Ａ−１）の代わりに実施例２のエチレン・α-オレフィン共重合体（Ａ−２）を用いた以外は、実施例５と同様にして、厚さ１００μｍのフィルムを得た。
【０１２７】
得られたフィルムについて、１１５℃、３０分の耐熱処理したのち、ヘイズ、外観およびヤング率を上述した方法で測定ないし評価した。
結果を表４に示す。
【０１２８】
【比較例３】
［フィルムの製造および評価］
実施例５において、実施例１のエチレン・α-オレフィン共重合体（Ａ−１）の代わりに比較例１のエチレン系共重合体（Ａ−３）を用いた以外は、実施例５と同様にして、厚さ１００μｍのフィルムを得た。
【０１２９】
得られたフィルムについて、１１５℃、３０分の耐熱処理した後、ヘイズ、外観およびヤング率を上述した方法で測定ないし評価した。
結果を表４に示す。
【０１３０】
【表４】

【０１３１】
【実施例７】
［中空成形品の製造および評価］
実施例１のエチレン・α-オレフィン共重合体（Ａ−１）９５重量部と、高密度ポリエチレン［ＨＤＰＥ（ａ）と略す；密度＝０．９４１g/cm³、ＭＦＲ＝２．０g/10分、Ｍｗ／Ｍｎ＝２．４、Ｔｍ＝１２８℃］５重量部とからなるエチレン・α-オレフィン共重合体組成物を用いた以外は、実施例１と同様して中空成形品（ボトル）を得た。
【０１３２】
得られた中空成形品について、１１５℃、３０分の耐熱処理した後、ヘイズ、外観およびヤング率を上述した方法で測定ないし評価した。
結果を表５に示す。
【０１３３】
【実施例８】
実施例７において、実施例１のエチレン・α-オレフィン共重合体（Ａ−１）および高密度ポリエチエン［ＨＤＰＥ（ａ）］の配合量をそれぞれ９０重量部、１０重量部とした以外は実施例７と同様にして、中空成形品を得た。
【０１３４】
得られた中空成形品について、１１５℃、３０分の耐熱処理した後、ヘイズ、外観およびヤング率を上述した方法で測定ないし評価した。
結果を表５に示す。
【０１３５】
【表５】

[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a heating container made of an ethylene-based resin, and more specifically, a heat-resistant container for storing blood, a chemical solution, etc., which has excellent hygiene, flexibility, impact resistance, transparency, heat resistance, and the like, and cooked food It relates to a heat-resistant container in which etc. are put.
[0002]
TECHNICAL BACKGROUND OF THE INVENTION
Currently known medical containers include hard containers made of glass, polyethylene, polypropylene, etc., and soft bags made of polyvinyl chloride containing a plasticizer. However, the above-mentioned rigid container needs to introduce air using a vent needle or an infusion set with a vent when dropping the content liquid such as blood and chemical liquid. There is a risk of contamination. On the other hand, the soft bag, unlike the above-mentioned hard container when dripping the content liquid, does not require the introduction of air, and the bag itself is squeezed by the atmospheric pressure along with the dripping of the content liquid. There are advantages such as convenient transportation and small waste. However, there are problems such as the plasticizer contained in the polyvinyl chloride and the toxicity of the residual monomer.
[0003]
On the other hand, for the purpose of improving flexibility, transparency, hygiene, etc., a medical bag using a polymer such as an ethylene / vinyl acetate copolymer or an elastomer as an intermediate layer has been proposed (Japanese Patent Laid-Open No. 58). -165866). However, in this medical bag, since the heat resistance of the polymer used for the intermediate layer is poor, there is a problem that the bag is wrinkled during heat sterilization. In addition, conventional medical bags made from polyethylene are somewhat insufficient in heat resistance and cannot be sterilized at a high temperature, so the sterilization process takes a long time or is sterilized in a clean atmosphere. The inefficiency in the sterilization process, which must be performed, has become a problem.
[0004]
Therefore, hygiene and flexibility are good, transparency is not lost even if sterilization at 115 ° C or higher shown in the Japanese Pharmacopoeia, and it is excellent in heat resistance so that wrinkles and deformation do not occur. The emergence of such medical containers made of polyethylene, such as medical bags made of multilayer or single-layer films, and medical bottles made of multilayer or single-layers, is desired.
[0005]
By the way, polyolefin resin is generally used for the sealant film of the food laminate packaging material, and a polypropylene film having a high melting point is often used for retort foods from the viewpoint of heat resistance.
[0006]
However, in order to realize long-term storage at low temperatures and in cold regions by making pouches for large-sized commercial containers in recent years, retort food films have been required to have low temperature impact resistance. Transparency is also required from the standpoint that it is better to confirm things.
[0007]
Since the polypropylene film is generally inferior in low-temperature impact resistance, it cannot satisfy the above requirements. As films having improved low-temperature impact resistance, there are films such as ethylene / propylene block copolymers, but these films are inferior in transparency, and therefore cannot be used in fields requiring transparency.
[0008]
On the other hand, the conventional low density polyethylene film has excellent low temperature impact resistance and transparency, and also has excellent low temperature sealing properties, so that it can overcome the drawbacks of the above polypropylene film, but it has poor heat resistance and thus raises the sterilization temperature. There is a problem that can not be. Moreover, when the composition which mix | blended the high density polyethylene with the low density polyethylene is used, although the heat resistance of the film obtained improves, there exists a problem that transparency falls. Furthermore, this film has a problem of a decrease in transparency due to heat sterilization treatment (retort treatment).
[0009]
Therefore, the appearance of a heat-resistant container that has good hygiene, excellent transparency, and does not cause wrinkles or deformation is desired.
[0010]
OBJECT OF THE INVENTION
The present invention is excellent in moldability and is intended to solve the problems associated with the prior art as described above, has good hygiene and flexibility, and is transparent even when sterilized at 115 ° C. or higher. An object of the present invention is to provide a heat-resistant container made of polyethylene which is not lost, yet has excellent heat resistance and does not wrinkle or deform.
[0011]
SUMMARY OF THE INVENTION
The heat-resistant container made of ethylene resin according to the present invention is
A heat-resistant container made of a copolymer of ethylene and an α-olefin having 3 to 12 carbon atoms, and the ethylene / α-olefin copolymer is
(i) Density from 0.918 to 0.940 g / cm^ThreeIn the range of
(ii) The melt flow rate (MFR (g / 10 min)) at 190 ° C. and 2.16 kg load is in the range of 0.1 to 10.0 g / 10 min.
(iii) Amount of decane soluble component at room temperature (W (% by weight)) and density (d (g / cm^Three)) And
W <80 × exp (-100 (d-0.88)) + 0.1
Indicated by
(iv) The shear stress of the molten polymer at 190 ° C. is 2.4 × 10⁶dyne / cm²The fluidity index (FI (1 / second)) defined by the shear rate when arriving at and the melt flow rate (MFR (g / 10 minutes))
FI> 75 × MFR
Indicated by
(v) Melt tension at 190 ° C. (MT (g)) and melt flow rate (MFR (g / 10 min))
5.5 x MFR^-0.65> MT> 2.2 × MFR^-0.84
Satisfy the relationship indicated by
And the heat-resistant container is
(A) The haze after heat sterilization is 30% or less,
(B) The deformation start temperature (Td (° C.)) is 115 ° C. or higher.
[0012]
The ethylene / α-olefin copolymer [A] is:
(a) a transition metal compound of Group IV of the periodic table having a specific substituted cyclopentadienyl group as a ligand;
(b) an organoaluminum oxy compound and
It is preferable that it consists of the copolymer obtained by copolymerizing ethylene and C3-C12 alpha olefin in presence of the olefin polymerization catalyst containing this.
[0013]
The ethylene / α-olefin copolymer [A]: 70 to 95 parts by weight,
High density polyethylene [B]: 5 to 30 parts by weight
A heat-resistant container comprising an ethylene / α-olefin copolymer composition containing
This heat-resistant container
(A) The haze after heat sterilization is 30% or less,
(B) The deformation start temperature (Td (° C.)) is 115 ° C. or higher.
[0014]
The high density polyethylene [B]
(i) Density of 0.940 to 0.970 g / cm^ThreeIn the range of
(ii) The molecular weight distribution (Mw / Mn) measured by GPC is preferably in the range of 1.5 to 4.0.
[0015]
Such a heat-resistant container made of an ethylene resin according to the present invention is suitable as a medical container and a food container.
[0016]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the ethylene resin heat-resistant container according to the present invention will be specifically described.
First, the ethylene / α-olefin copolymer [A] used in the heat-resistant container made of ethylene resin according to the present invention will be described.
[0017]
Ethylene / α-olefin copolymer [A]
The ethylene / α-olefin copolymer [A] used in the present invention is a random copolymer of ethylene and an α-olefin having 3 to 12 carbon atoms.
[0018]
In the ethylene / α-olefin copolymer [A], a structural unit derived from ethylene is present in an amount of 65 to 99% by weight, preferably 70 to 98% by weight, more preferably 75 to 96% by weight, The structural unit derived from the α-olefin having 3 to 12 carbon atoms is present in an amount of 1 to 35% by weight, preferably 2 to 30% by weight, more preferably 4 to 25% by weight.
[0019]
Examples of the α-olefin having 3 to 12 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene and 1-dodecene. It is done.
[0020]
The density of the ethylene / α-olefin copolymer [A] is from 0.918 to 0.940 g / cm.^Three, Preferably 0.920-0.930 g / cm^ThreeIt is in the range.
The melt flow rate (MFR (g / 10 min)) of the ethylene / α-olefin copolymer [A] at 190 ° C. and a load of 2.16 kg is 0.1 to 10.0 g / 10 min, preferably 0.2. It is in the range of ˜10.0 g / 10 min.
[0021]
The ethylene / α-olefin copolymer [A]
Amount of decane-soluble component at room temperature (W (% by weight)) and density (d (g / cm^Three))
W <80 × exp (-100 (d-0.88)) + 0.1
Preferably, the relationship represented by W <60 × exp (-100 (d-0.88)) + 0.1 is satisfied.
[0022]
The ethylene / α-olefin copolymer [A]
The shear stress at 190 ° C of the molten polymer is 2.4 x 10⁶dyne / cm²The fluidity index (FI (1 / second)) defined by the shear rate when arriving at and the melt flow rate (MFR (g / 10 minutes))
FI> 75 × MFR
Preferably, the relationship represented by FI> 80 × MFR is satisfied.
[0023]
Further, such an ethylene / α-olefin copolymer [A] has a melt tension (MT (g)) at 190 ° C. and a melt flow rate (MFR (g / 10 min)),
5.5 x MFR^-0.65> MT> 2.2 × MFR^-0.84
Preferably, 5.0 × MFR^-0.65> MT> 2.5 × MFR^-0.84  The relationship indicated by is satisfied.
[0024]
The ethylene / α-olefin copolymer [A] as described above is suitable for a heat-resistant container.
[0025]
Such an ethylene / α-olefin copolymer [A] is, for example,
(a) a transition metal compound of Group IV of the periodic table containing a cyclopentadienyl skeleton,
(b) an organoaluminum oxy compound,
(c) a carrier,
If necessary
(d) Organoaluminum compound
Can be produced by copolymerizing ethylene and an α-olefin having 3 to 20 carbon atoms in the presence of an olefin polymerization catalyst.
[0026]
The olefin polymerization catalyst and each catalyst component will be described below.
Transition metal compounds (a)
(a) A transition metal compound of Group IV of the Periodic Table containing a cyclopentadienyl skeleton (hereinafter sometimes referred to as “component (a)”) is specifically represented by the following formula [I]: It is a transition metal compound represented.
[0027]
ML¹ _X      ... [I]
(In the formula, M represents a transition metal selected from Group IV of the periodic table, and L¹Represents a ligand coordinated to a transition metal atom, of which at least two ligands L¹Is a substituted cyclopentadienyl group having only 2 to 5 substituents selected from a methyl group and an ethyl group, and a ligand L other than the substituted cyclopentadienyl group¹Is a C1-C12 hydrocarbon group, alkoxy group, aryloxy group, halogen atom, trialkylsilyl group or hydrogen atom, and X represents the valence of the transition metal atom M. )
L¹Represents a ligand coordinated to the transition metal atom M, of which at least two ligands L¹Is a substituted cyclopentadienyl group having only 2 to 5 substituents selected from a methyl group and an ethyl group, and each ligand may be the same or different. This substituted cyclopentadienyl group is a substituted cyclopentadienyl group having 2 or more substituents, and preferably a cyclopentadienyl group having 2 to 3 substituents. And more preferably a 1,3-substituted cyclopentadienyl group. Each substituent may be the same or different.
[0028]
In the above formula [I], a ligand L other than the substituted cyclopentadienyl group coordinated to the transition metal atom M¹Is a C1-C12 hydrocarbon group, alkoxy group, aryloxy group, halogen atom, trialkylsilyl group or hydrogen atom.
[0029]
As such a transition metal compound represented by the general formula [I],
Bis (cyclopentadienyl) zirconium dichloride,
Bis (methylcyclopentadienyl) zirconium dichloride,
Bis (ethylcyclopentadienyl) zirconium dichloride,
Bis (n-propylcyclopentadienyl) zirconium dichloride,
Bis (n-butylcyclopentadienyl) zirconium dichloride,
Bis (n-hexylcyclopentadienyl) zirconium dichloride,
Bis (methyl-n-propylcyclopentadienyl) zirconium dichloride,
Bis (methyl-n-butylcyclopentadienyl) zirconium dichloride,
Bis (dimethyl-n-butylcyclopentadienyl) zirconium dichloride,
Bis (n-butylcyclopentadienyl) zirconium dibromide,
Bis (n-butylcyclopentadienyl) zirconium methoxychloride,
Bis (n-butylcyclopentadienyl) zirconium ethoxy chloride,
Bis (n-butylcyclopentadienyl) zirconium butoxychloride,
Bis (n-butylcyclopentadienyl) zirconium ethoxide,
Bis (n-butylcyclopentadienyl) zirconium methyl chloride,
Bis (n-butylcyclopentadienyl) zirconium dimethyl,
Bis (n-butylcyclopentadienyl) zirconium benzyl chloride,
Bis (n-butylcyclopentadienyl) zirconium dibenzyl,
Bis (n-butylcyclopentadienyl) zirconium phenyl chloride,
Bis (n-butylcyclopentadienyl) zirconium hydride chloride, bis (dimethylcyclopentadienyl) zirconium dichloride,
Bis (diethylcyclopentadienyl) zirconium dichloride,
Bis (methylethylcyclopentadienyl) zirconium dichloride,
Bis (dimethylethylcyclopentadienyl) zirconium dichloride,
Bis (dimethylcyclopentadienyl) zirconium dibromide,
Bis (dimethylcyclopentadienyl) zirconium methoxychloride,
Bis (dimethylcyclopentadienyl) zirconium ethoxy chloride,
Bis (dimethylcyclopentadienyl) zirconium butoxychloride,
Bis (dimethylcyclopentadienyl) zirconium diethoxide,
Bis (dimethylcyclopentadienyl) zirconium methyl chloride,
Bis (dimethylcyclopentadienyl) zirconium dimethyl,
Bis (dimethylcyclopentadienyl) zirconium benzyl chloride,
Bis (dimethylcyclopentadienyl) zirconium dibenzyl,
Bis (dimethylcyclopentadienyl) zirconium phenyl chloride,
Bis (dimethylcyclopentadienyl) zirconium hydride chloride
Etc. In the above examples, the disubstituted product of the cyclopentadienyl ring includes 1,2- and 1,3-substituted products, and the trisubstituted product includes 1,2,3- and 1,2,4-substituted products. Including. In the present invention, a transition metal compound in which zirconium metal is replaced with titanium metal or hafnium metal in the above-described zirconium compound can be used.
[0030]
Of these transition metal compounds represented by the general formula [I],
Bis (n-propylcyclopentadienyl) zirconium dichloride,
Bis (n-butylcyclopentadienyl) zirconium dichloride,
Bis (1-methyl-3-n-propylcyclopentadienyl) zirconium dichloride,
Bis (1-methyl-3-n-butylcyclopentadienyl) zirconium dichloride,
Bis (1,3-dimethylcyclopentadienyl) zirconium dichloride,
Bis (1,3-diethylcyclopentadienyl) zirconium dichloride,
Bis (1-methyl-3-ethylcyclopentadienyl) zirconium dichloride
Is particularly preferred.
[0031]
The transition metal compound used in the present invention may be a mixture of a transition metal compound represented by the above general formula [I] and a transition metal compound represented by the following general formula [II].
[0032]
MKL² _X-2  … [II]
Wherein M represents a transition metal atom selected from Group IVB of the periodic table, and K and L²Represents a ligand coordinated to a transition metal atom. Ligand K is a bidentate ligand in which the same or different indenyl group, substituted indenyl group or its partial hydride is bonded via a lower alkylene group,²Is a C1-C12 hydrocarbon group, alkoxy group, aryloxy group, halogen atom, trialkylsilyl group or hydrogen atom, and X represents the valence of the transition metal atom M. )
As the transition metal compound represented by the general formula [II],
Ethylenebis (indenyl) zirconium dichloride,
Ethylenebis (4-methyl-1-indenyl) zirconium dichloride,
Ethylene bis (4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride
Etc.
[0033]
Selected from the transition metal compound (a-2) represented by the general formula [II] and at least one transition metal compound selected from the transition metal compound (a-1) represented by the general formula [I] The at least one transition metal compound is a molar ratio (a-1) / (a-2) of 99/1 to 50/50, preferably 97/3 to 70/30, more preferably 95/5. It is desirable that the amount used is 75/25, most preferably 90/10 to 80/20.
[0034]
Organoaluminum oxy compounds (b)
Next, the organoaluminum oxy compound (b) will be described.
The organoaluminum oxy compound (b) (hereinafter sometimes referred to as “component (b)”) used in the present invention may be a conventionally known benzene-soluble aluminoxane. It may be a benzene-insoluble organoaluminum oxy compound as disclosed in Japanese Patent No. 276807.
[0035]
The aluminoxane as described above can be prepared, for example, by the following method.
(1) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, and cerium chloride hydrate A method of adding an organoaluminum compound such as trialkylaluminum to the hydrocarbon medium suspension of the reaction and recovering it as a hydrocarbon solution.
[0036]
(2) A method of recovering a hydrocarbon solution by directly applying water, ice or water vapor to an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran.
[0037]
(3) A method in which an organotin oxide such as dimethyltin oxide or dibutyltin oxide is reacted with an organoaluminum compound such as trialkylaluminum in a medium such as decane, benzene, or toluene.
[0038]
The aluminoxane may contain a small amount of an organometallic component. Further, the solvent or the unreacted organoaluminum compound may be removed by distillation from the recovered solution of the above aluminoxane and then redissolved in the solvent.
[0039]
Specific examples of organoaluminum compounds used in the preparation of aluminoxane include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, trisec-butylaluminum, trialkylaluminums such as tert-butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum;
Tricycloalkylaluminum such as tricyclohexylaluminum, tricyclooctylaluminum;
Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride;
Dialkylaluminum hydrides such as diethylaluminum hydride, diisobutylaluminum hydride;
Dialkylaluminum alkoxides such as dimethylaluminum methoxide and diethylaluminum ethoxide;
Examples thereof include dialkylaluminum aryloxides such as diethylaluminum phenoxide.
[0040]
Of these, trialkylaluminum and trialkylaluminum are particularly preferred.
In addition, as this organoaluminum compound, a general formula
(i-C_FourH₉)_xAl_y(C_FiveH_Ten)_z
(X, y, z are positive numbers and z ≧ 2x)
Isoprenylaluminum represented by the formula can also be used.
[0041]
The above organoaluminum compounds are used alone or in combination.
Solvents used in the preparation of aluminoxane include aromatic hydrocarbons such as benzene, toluene, xylene, cumene, and cymene, and aliphatic carbonization such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, and octadecane. Hydrogen, cyclopentane, cyclohexane, cyclooctane, methylcyclopentane and other alicyclic hydrocarbons, petroleum fractions such as gasoline, kerosene and light oil, or halogens of the above aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons Among them, hydrocarbon solvents such as chlorinated products and brominated products are mentioned. In addition, ethers such as ethyl ether and tetrahydrofuran can also be used. Of these solvents, aromatic hydrocarbons are particularly preferred.
[0042]
The benzene-insoluble organoaluminum oxy compound has an Al component dissolved in benzene at 60 ° C. of 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of Al atom, and is insoluble in benzene or Slightly soluble.
[0043]
The solubility of such an organoaluminum oxy compound in benzene is determined by suspending the organoaluminum oxy compound corresponding to 100 milligrams of Al in 100 ml of benzene, mixing at 60 ° C. for 6 hours with stirring, and then attaching a jacket. Using a G-5 glass filter, hot filtration was performed at 60 ° C., and the solid portion separated on the filter was washed four times with 50 ml of benzene at 60 ° C., and the Al atoms present in the total filtrate were removed. It is determined by measuring the abundance (x mmol) (x%).
[0044]
Carrier (c)
The carrier (c) used in the present invention is an inorganic or organic compound, and a granular or particulate solid having a particle size of 10 to 300 μm, preferably 20 to 200 μm is used. Of these, porous oxides are preferred as the inorganic carrier, specifically, SiO.₂, Al₂O_Three, MgO, ZrO₂TiO₂, B₂O_Three, CaO, ZnO, BaO, ThO₂Etc. or mixtures thereof, eg SiO₂-MgO, SiO₂-Al₂O_Three, SiO₂-TiO₂, SiO₂-V₂O_Five, SiO₂-Cr₂O_Three, SiO₂-TiO₂-MgO etc. can be illustrated. Among these, SiO₂And Al₂O_ThreeThe main component is at least one component selected from the group consisting of:
The inorganic oxide contains a small amount of Na.₂CO_Three, K₂CO_Three, CaCO_Three, MgCO_Three, Na₂SO_Four, Al₂(SO_Four)_Three, BaSO_Four, KNO_Three, Mg (NO_Three)₂, Al (NO_Three)_Three, Na₂O, K₂O, Li₂Even if it contains carbonates such as O, sulfates, nitrates and oxide components, there is no problem.
[0045]
Such carrier (c) has different properties depending on the type and production method, but the carrier preferably used in the present invention has a specific surface area of 50 to 1000 m.²/ G, preferably 100-700m²/ G, and the pore volume is 0.3 to 2.5 cm.²/ G is desirable. The carrier is used after calcining at 100 to 1000 ° C., preferably 150 to 700 ° C., if necessary.
[0046]
Furthermore, examples of the carrier that can be used in the present invention include a granular or fine particle solid of an organic compound having a particle size of 10 to 300 μm. These organic compounds include (co) polymers mainly composed of α-olefins having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene and 4-methyl-1-pentene, or vinylcyclohexane and styrene as the main components. And a polymer or copolymer.
[0047]
The olefin polymerization catalyst used in the production of the ethylene / α-olefin copolymer used in the present invention is formed from the above component (a), component (b) and (c) carrier, but if necessary (d ) Organoaluminum compounds may be used.
[0048]
Organoaluminum compound (d)
Examples of the organoaluminum compound (d) used as necessary (hereinafter sometimes referred to as “component (d)”) include, for example, an organoaluminum compound represented by the following general formula [II]. it can.
[0049]
R¹ _nAlX_3-n  … [II]
(Wherein R¹Represents a hydrocarbon group having 1 to 12 carbon atoms, X represents a halogen atom or a hydrogen atom, and n is 1 to 3. )
In the above general formula [II], R¹Is a hydrocarbon group having 1 to 12 carbon atoms, such as an alkyl group, a cycloalkyl group, or an aryl group. Specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an isobutyl group, a pentyl group, and the like. Group, hexyl group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group, tolyl group and the like.
[0050]
Specific examples of such organoaluminum compounds include the following compounds.
Trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, tri-2-ethylhexylaluminum;
Alkenyl aluminum such as isoprenyl aluminum;
Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, dimethylaluminum bromide;
Alkylaluminum sesquichlorides such as methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide;
Alkylaluminum dihalides such as methylaluminum dichloride, ethylaluminum dichloride, isopropylaluminum dichloride, ethylaluminum dibromide;
Alkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride.
[0051]
As the organoaluminum compound (d), a compound represented by the following general formula [III] can also be used.
R¹ _nAlY_3-n  … [III]
(Wherein R¹Is R in the general formula [II].¹And Y represents —OR²-OSiR^Three _ThreeGroup, -OAlR^Four ₂Group, -NR^Five ₂Group, -SiR⁶ _ThreeGroup or -N (R⁷) AlR⁸ ₂Represents a group, n is 1-2, R², R^Three, R^FourAnd R⁸Is a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a cyclohexyl group, a phenyl group or the like;^FiveIs a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, a phenyl group, a trimethylsilyl group, etc., and R⁶And R⁷Is a methyl group, an ethyl group or the like. )
As such an organoaluminum compound, specifically, the following compounds are used.
[0052]
(1) R¹ _nAl (OR²)_3-nA compound represented by, for example,
Dimethylaluminum methoxide, diethylaluminum ethoxide, diisobutylaluminum methoxide, etc.
(2) R¹ _nAl (OSiR^Three _Three)_3-nA compound represented by, for example,
Et₂Al (OSi Me_Three), (Iso-Bu)₂Al (OSiMe_Three), (Iso-Bu)₂Al (OSiEt_Three)Such;
(3) R¹ _nAl (OAR^Four ₂)_3-nA compound represented by, for example,
Et₂AlOAlEt₂, (Iso-Bu)₂AlOAl (iso-Bu)₂Such;
(4) R¹ _nAl (NR^Five ₂)_3-nA compound represented by, for example,
Me₂AlNEt₂, Et₂AlNHMe, Me₂AlNHEt, Et₂AlN (SiMe_Three)₂, (Iso-Bu)₂AlN (SiMe_Three)₂Such;
(5) R¹ _nAl (SiR⁶ _Three)_3-nA compound represented by, for example,
(iso-Bu)₂AlSi Me_Three Such;
(6) R¹ _nAl (N (R⁷) AlR⁸ ₂)_3-nA compound represented by, for example,
Et₂AlN (Me) AlEt₂,
(iso-Bu)₂AlN (Et) Al (iso-Bu)₂Such.
[0053]
Among the organoaluminum compounds represented by the general formulas [II] and [III], the general formula R¹ _ThreeAl, R¹ _nAl (OR²)_3-n, R¹ _nAl (OAR^Four ₂)_3-nIn particular, a compound in which R is an isoalkyl group and n = 2 is preferable.
[0054]
In producing the ethylene / α-olefin copolymer used in the present invention, by contacting the component (a), the component (b) and the carrier (c) as described above, and the component (d) as necessary. The prepared catalyst is used. The order of contact of the components at this time is arbitrarily selected, but preferably the carrier (c) and the component (b) are mixed and contacted, then the component (a) is mixed and contacted, and if necessary, the component ( d) mixed contact.
[0055]
Contact of each of the above components can be carried out in an inert hydrocarbon solvent. Specifically, as the inert hydrocarbon medium used for the preparation of the catalyst, propane, butane, pentane, hexane, heptane, octane, decane, Aliphatic hydrocarbons such as dodecane and kerosene; Alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane; Aromatic hydrocarbons such as benzene, toluene and xylene; Halogenated carbonization such as ethylene chloride, chlorobenzene and dichloromethane Examples thereof include hydrogen or a mixture thereof.
[0056]
In mixing and contacting the component (a), the component (b), the carrier (c) and, if necessary, the component (d), the component (a) is usually 5 × 10 per 1 g of the carrier (c).^-6~ 5x10^-FourMoles, preferably 10^-Five~ 2x10^-FourUsed in molar amounts, the concentration of component (a) is about 10^-Four~ 2x10^-2Mol / liter, preferably 2 × 10^-Four-10^-2The range is mol / liter. The atomic ratio (Al / transition metal) of the component (b) aluminum and the transition metal in the component (a) is usually 10 to 500, preferably 20 to 200. The atomic ratio (Al-d / Al-b) of the aluminum atom (Al-d) of the component (d) and the aluminum atom (Al-b) of the component (b) used as necessary is usually from 0.02 to 3, preferably in the range of 0.05 to 1.5. The mixing temperature when mixing and contacting the component (a), the component (b), the carrier (c) and, if necessary, the component (d) is usually −50 to 150 ° C., preferably −20 to 120 ° C., The contact time is 1 minute to 50 hours, preferably 10 minutes to 25 hours.
[0057]
The olefin polymerization catalyst obtained as described above contains 5 × 10 5 transition metal atoms derived from the component (a) per 1 g of the carrier (c).^-6~ 5x10^-FourGram atoms, preferably 10^-Five~ 2x10^-Four10 grams of aluminum atoms derived from the component (b) and the component (d) per gram of the carrier (c) are supported.^-3~ 5x10^-2Gram atoms, preferably 2 × 10^-3~ 2x10^-2It is preferably supported in the amount of gram atoms.
[0058]
The catalyst used for the production of the ethylene / α-olefin copolymer is prepared by preliminarily preparing the olefin in the presence of the component (a), the component (b), the carrier (c) and, if necessary, the component (d). It may be a prepolymerization catalyst obtained by polymerization. The prepolymerization is performed by introducing an olefin into an inert hydrocarbon solvent in the presence of the component (a), the component (b), the carrier (c) and, if necessary, the component (d). Can do.
[0059]
Examples of the olefin used in the prepolymerization include ethylene and an α-olefin having 3 to 20 carbon atoms such as propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene and 1-octene. 1-decene, 1-dodecene, 1-tetradecene and the like. Among these, ethylene used in the polymerization or a combination of ethylene and α-olefin is particularly preferable.
[0060]
In the prepolymerization, the component (a) is usually 10%.^-6~ 2x10^-2Mol / liter, preferably 5 × 10^-Five-10^-2Used in an amount of mol / liter, component (a) is usually 5 x 10 per gram of carrier (c).^-6~ 5x10^-FourMoles, preferably 10^-Five~ 2x10^-FourUsed in molar amounts. The atomic ratio (Al / transition metal) of the component (b) aluminum and the transition metal in the component (a) is usually 10 to 500, preferably 20 to 200. The atomic ratio (Al-d / Al-b) of the aluminum atom (Al-d) of the component (d) and the aluminum atom (Al-b) of the component (b) used as necessary is usually from 0.02 to 3, preferably in the range of 0.05 to 1.5. The prepolymerization temperature is -20 to 80 ° C, preferably 0 to 60 ° C, and the prepolymerization time is 0.5 to 100 hours, preferably about 1 to 50 hours.
[0061]
The prepolymerization catalyst is prepared, for example, as follows. That is, the support (c) is suspended with an inert hydrocarbon. Next, an organoaluminum oxy compound (component (b)) is added to the suspension and allowed to react for a predetermined time. The supernatant is then removed and the resulting solid component is resuspended with inert hydrocarbons. A transition metal compound (component (a)) is added to the system and reacted for a predetermined time, and then the supernatant is removed to obtain a solid catalyst component. Subsequently, a prepolymerized catalyst is obtained by adding the solid catalyst component obtained above to an inert hydrocarbon containing an organoaluminum compound (component (d)) and introducing an olefin therein.
The olefin polymer produced by the preliminary polymerization is desirably in an amount of 0.1 to 500 g, preferably 0.2 to 300 g, more preferably 0.5 to 200 g, per 1 g of the carrier (c). In addition, in the prepolymerization catalyst, the component (a) per 1 g of the support (c) is about 5 × 10 as transition metal atoms.^-6~ 5x10^-FourGram atoms, preferably 10^-Five~ 2x10^-FourAluminum atoms (Al) supported in the amount of gram atoms and derived from component (b) and component (d) are in a molar ratio (Al / M) to transition metal atoms (M) derived from component (a), It is desirable that it is supported in an amount in the range of 5-200, preferably 10-150.
[0062]
The prepolymerization can be performed either batchwise or continuously, and can be performed under reduced pressure, normal pressure, or increased pressure. In the prepolymerization, the preliminary viscosity [η] measured in decalin at least 135 ° C. in the presence of hydrogen is in the range of 0.2 to 7 dl / g, preferably 0.5 to 5 dl / g. It is desirable to produce a polymer.
[0063]
The ethylene / α-olefin copolymer used in the present invention comprises ethylene and an α-olefin having 3 to 20 carbon atoms such as propylene, 1- 1 in the presence of the olefin polymerization catalyst or the prepolymerization catalyst as described above. Copolymerizes butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene Can be obtained.
[0064]
In the present invention, the copolymerization of ethylene and α-olefin is carried out in the gas phase or in the slurry liquid phase. In slurry polymerization, an inert hydrocarbon may be used as a solvent, or olefin itself may be used as a solvent.
[0065]
Specific examples of the inert hydrocarbon solvent used in the slurry polymerization include aliphatic hydrocarbons such as butane, isobutane, pentane, hexane, octane, decane, dodecane, hexadecane, and octadecane; cyclopentane, methylcyclopentane, cyclohexane, Examples thereof include alicyclic hydrocarbons such as cyclooctane; aromatic hydrocarbons such as benzene, toluene and xylene; petroleum fractions such as gasoline, kerosene and light oil. Of these inert hydrocarbon media, aliphatic hydrocarbons, alicyclic hydrocarbons, petroleum fractions and the like are preferable.
[0066]
When the slurry polymerization method or the gas phase polymerization method is used, the olefin polymerization catalyst or the prepolymerization catalyst as described above is usually 10% as the transition metal atom concentration in the polymerization reaction system.^-8-10^-3Gram atom / liter, preferably 10^-7-10^-FourIt is preferably used in an amount of gram atoms / liter.
[0067]
In the main polymerization, the same organoaluminum oxy compound and / or organoaluminum compound (d) as in component (b) may be added. At this time, the atomic ratio (Al / M) of the aluminum atom (Al) derived from the organoaluminum oxy compound and the organoaluminum compound to the transition metal atom (M) derived from the transition metal compound (a) is 5 to 300. , Preferably 10 to 200, more preferably 15 to 150.
[0068]
When carrying out the slurry polymerization method, the polymerization temperature is usually in the range of −50 to 100 ° C., preferably from 0 to 90 ° C. When carrying out the gas phase polymerization method, the polymerization temperature is usually from 0 to 120 degreeC, Preferably it is the range of 20-100 degreeC.
[0069]
The polymerization pressure is usually normal pressure to 100 kg / cm.², Preferably 2-50 kg / cm²The polymerization can be carried out in any of batch, semi-continuous and continuous systems.
[0070]
Furthermore, the polymerization can be performed in two or more stages having different reaction conditions.
The ethylene / α-olefin copolymer of the present invention includes a weather resistance stabilizer, a heat resistance stabilizer, an antistatic agent, an anti-slip agent, an anti-blocking agent, an antifogging agent, and a lubricant as long as the object of the present invention is not impaired. Additives such as pigments, dyes, nucleating agents, plasticizers, anti-aging agents, hydrochloric acid absorbents and antioxidants may be blended as necessary. Further, other polymer compounds can be blended in small amounts without departing from the spirit of the present invention.
[0071]
Ethylene ・ α - Olefin copolymer composition
Next, the ethylene / α-olefin copolymer composition used in the heat-resistant container made of ethylene resin according to the present invention will be described.
[0072]
The ethylene / α-olefin copolymer composition used in the present invention comprises the ethylene / α-olefin copolymer [A] and high-density polyethylene [B].
Such an ethylene / α-olefin copolymer composition has an ethylene / α-olefin copolymer [A] of 70 to 95 parts by weight, preferably 80 to 95 parts by weight, more preferably 90 to 95 parts by weight. The high-density polyethylene [B] is desirably contained in an amount of 5 to 30 parts by weight, preferably 5 to 20 parts by weight, and more preferably 5 to 10 parts by weight.
[0073]
Such an ethylene / α-olefin copolymer is suitable for a heat-resistant container.
[0074]
Such high-density polyethylene [B] is an ethylene / α-olefin copolymer obtained by copolymerizing ethylene and an α-olefin having 3 to 12 carbon atoms.
[0075]
Specific examples of the α-olefin having 3 to 12 carbon atoms include propylene, 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene. Of these, 1-hexene, 4-methyl-1-pentene, and 1-octene are preferable.
[0076]
In the high-density polyethylene [B] used in the present invention, structural units derived from ethylene are usually present in a proportion of 95 to 99 mol%, preferably 96 to 98 mol%, and α having 3 to 12 carbon atoms. The structural unit derived from the olefin is usually present in a proportion of 1 to 5 mol%, preferably 2 to 4 mol%.
[0077]
The composition of such high-density polyethylene [B] is usually that of a sample in which about 200 mg of high-density polyethylene is uniformly dissolved in 1 ml of hexachlorobutadiene in a 10 mmφ sample tube.¹³The C-NMR spectrum is determined by measurement under measurement conditions of a measurement temperature of 120 ° C., a measurement frequency of 25.05 MHz, a spectrum width of 1500 Hz, a pulse repetition time of 4.2 sec., And a pulse width of 6 μsec.
[0078]
This high density polyethylene [B] has a density of 0.940-0.970 g / cm.^Three, Preferably 0.945 to 0.965 g / cm^ThreeIt is in the range. When high-density polyethylene [B] having a density in the above range is used, an ethylene / α-olefin copolymer that can form a film or bottle that has a high deformation start temperature (Td) and hardly loses transparency. A coalescence composition is obtained. When such a composition is used, the heat sterilization treatment temperature can be increased, and the heat sterilization treatment time can be shortened.
[0079]
The high-density polyethylene [B] has a molecular weight distribution (Mw / Mn) measured by GPC of 1.5 to 5.0, preferably 2.0 to 4.0.
[0080]
Such high-density polyethylene [B] can be produced using a known polymerization method as long as it has the above-described properties. Examples of such high-density polyethylene [B] include conventional titanium-based Ziegler catalysts and those subjected to the aforementioned metallocene catalyst.
[0081]
The ethylene / α-olefin copolymer composition used in the present invention can be produced from the ethylene / α-olefin copolymer [A] and the high-density polyethylene [B] using a known method. it can. Specifically, the following methods are mentioned.
[0082]
(1) A method of mechanically blending an ethylene / α-olefin copolymer, high-density polyethylene, and other components added as necessary, using an extruder, a kneader or the like.
[0083]
(2) A suitable good solvent (for example, hexane, heptane, decane, cyclohexane, benzene, toluene, xylene, etc.) with an ethylene / α-olefin copolymer, high-density polyethylene, and other components added as necessary. In a hydrocarbon solvent), and then the solvent is removed.
[0084]
(3) Prepare a solution in which an ethylene / α-olefin copolymer, high-density polyethylene, and other components added as necessary are separately dissolved in a suitable good solvent, and then mix, then mix the solvent How to remove.
[0085]
(4) A method of combining the above methods (1) to (3).
In addition to the above method, an ethylene / α-olefin copolymer composition can also be produced by the following method.
[0086]
For example, it can be produced by polymerizing ethylene / α-olefin copolymer [A] and high-density polyethylene [B] by dividing polymerization into two or more stages having different reaction conditions using one polymerization vessel. . Specifically, the ethylene / α-olefin copolymer [A] is polymerized in the former stage and the high-density polyethylene [B] is polymerized in the latter stage, or the high-density polyethylene [B] in the former stage, by a two-stage polymerization process. And the ethylene / α-olefin copolymer [A] is polymerized at a later stage.
[0087]
Also, using a plurality of polymerizers, the ethylene / α-olefin copolymer [A] is polymerized in one polymerizer, and then the ethylene / α-olefin copolymer [A] is present in the other polymerizer. The high-density polyethylene [B] is polymerized underneath, or the high-density polyethylene [B] is polymerized in one polymerizer, and then in the presence of the high-density polyethylene [B] in the other polymerizer, ethylene · α It can also be produced by polymerizing the olefin copolymer [A].
[0088]
The ethylene / α-olefin copolymer composition of the present invention includes a weather resistance stabilizer, a heat resistance stabilizer, an antistatic agent, an anti-slip agent, and an antiblocking agent as long as the object of the present invention is not impaired as described above. Additives such as an antifogging agent, a lubricant, a pigment, a dye, a nucleating agent, a plasticizer, an anti-aging agent, a hydrochloric acid absorbent, and an antioxidant may be blended as necessary. Further, other polymer compounds can be blended in small amounts without departing from the spirit of the present invention.
[0089]
Manufacturing of heat-resistant containers
The heat-resistant container made of ethylene resin according to the present invention is a bag made of a multi-layer or single-layer film, or a single-layer or multi-layer bottle, etc., and includes at least one layer of the multi-layer film, at least one layer of the multi-layer bottle, A layer bottle is formed from the ethylene / α-olefin copolymer [A] or the ethylene / α-olefin copolymer composition.
[0090]
The layer other than the ethylene / α-olefin copolymer [A] or the ethylene / α-olefin copolymer composition is not particularly limited, and polypropylene, nylon, polyester, polyvinyl alcohol, or the like may be used.
[0091]
The heat-resistant container made of ethylene resin according to the present invention can be produced by a water-cooled or air-cooled inflation method, a T-die method, a dry lamination method, an extrusion lamination method, a hollow molding method, or the like.
[0092]
As a method for forming a heat-resistant bag, an inflation method and a coextrusion T-die method are preferable from the viewpoint of hygiene and economy, and a hollow molding method is preferable for forming a heat-resistant bottle. The heat-resistant container thus molded may have a thickness in the range of 0.05 to 1.00 mm, preferably 0.1 to 0.7 mm, and more preferably 0.15 to 0.3 mm. If the thickness of the heat-resistant container is 0.05 mm or more, the impact resistance is good and there is no practical problem.
[0093]
The heat-resistant polyethylene container according to the present invention has a haze (ASTM D-1003-61) after heat sterilization of 30% or less, preferably 20 to 0%.
Further, the deformation start temperature (Td (° C.)) of the polyethylene heat-resistant container according to the present invention is 115 ° C. or higher, preferably 116 ° C. or higher.
[0094]
The deformation start temperature (Td (° C.)) is measured as follows. That is, a sample of a bag or bottle made of a molded film is sterilized by hot water at a sterilization temperature x 30 minutes using an Alp RK-4016 type small heat and high pressure steam sterilizer, and the sample taken out from the sterilizer is visually observed. And evaluate the deformation. Starting from a sterilization temperature of 110 ° C., the sterilization temperature setting is increased by 1 ° C. after each sterilization. This operation is repeated, and when the sample taken out from the sterilizer is deformed for the first time, the sterilization temperature is set as the deformation start temperature (Td (° C.)).
[0095]
【The invention's effect】
The heat-resistant container made of ethylene resin according to the present invention has good hygiene and flexibility, does not lose transparency even when sterilized at 115 ° C. or higher, has excellent heat resistance, and is wrinkled or deformed. Never do. In particular, a heat-resistant container formed of a composition comprising the above-mentioned ethylene / α-olefin copolymer [A] and high-density polyethylene [B] is excellent in heat resistance, so that the sterilization temperature can be increased. The sterilization time can be shortened. Furthermore, it is excellent in moldability.
[0096]
Moreover, the heat resistant container made of an ethylene resin according to the present invention exhibits excellent performance as a medical container or a food container.
[0097]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples.
[0098]
The physical properties of the copolymers obtained in the production examples, the hollow molded articles (bottles) and films prepared in Examples and Comparative Examples were evaluated as follows.
(1) Density
The strand obtained at the time of measuring the melt flow rate (MFR) with a load of 2.16 kg at 190 ° C. is heat-treated at 120 ° C. for 1 hour, gradually cooled to room temperature over 1 hour, and then measured with a density gradient tube.
(2) Composition of copolymer
¹³Determined by C-NMR. That is, a sample in which about 200 mg of copolymer powder was uniformly dissolved in 1 ml of hexachlorobutadiene in a 10 mmφ test tube.¹³The C-NMR spectrum is determined by measuring under measurement conditions of a measurement temperature of 120 ° C., a measurement frequency of 25.05 MHz, a spectrum width of 1500 Hz, a pulse repetition time of 4.2 seconds, and a pulse width of 6 μsec.
(3) Melt flow rate (MFR)
It is measured under conditions of 190 ° C. and 2.16 kg load according to ASTM D1238-65T using copolymer pellets.
(4) Molecular weight distribution (Mw / Mn)
It was measured by Waters GPC model ALC-GPC-150C. The measurement conditions are PSK-GMH-HT manufactured by Toyo Soda Co., Ltd. as a column, an orthodichlorobenzene (ODCB) solvent, 140 ° C.
(5) Maximum peak temperature (Tm) by DSC
This was performed using a DSC-7 type apparatus manufactured by PerkinElmer. The temperature (Tm) at the maximum peak position in the endothermic curve is about 5 mg of sample packed in an aluminum pan, heated to 200 ° C. at 10 ° C./minute, held at 200 ° C. for 5 minutes, and then cooled to room temperature at 10 ° C./minute. Then, the temperature is obtained from an endothermic curve when the temperature is raised at 10 ° C./min.
(6) n-decane soluble component ratio (W)
The amount of the n-decane soluble component in the copolymer was measured by adding about 3 g of the copolymer to 450 ml of n-decane, dissolving at 145 ° C., cooling to 23 ° C., and removing the n-decane insoluble part by filtration. This is done by recovering the n-decane soluble part from the filtrate.
[0099]
W = weight of n-decane soluble part / (weight of n-decane insoluble part and soluble part) × 100%
Defined by
(7) Melt tension (MT)
It is determined by measuring the stress when the molten polymer is stretched at a constant speed. That is, using a granulated pellet of a copolymer as a measurement sample, using a MT measuring device manufactured by Toyo Seiki Seisakusho, resin temperature 190 ° C., extrusion temperature 15 mm / min, winding speed 10-20 m / min, nozzle diameter 2.09 mmφ The nozzle length is 8 mm.
(8) Liquidity index (FI)
The flow index (FI) has a shear stress of 2.4 × 10 at 190 ° C.⁶dyne / cm²It is defined by the shear speed when reaching. The flow index (FI) was determined by extruding the resin from the capillary while changing the shear rate and measuring the stress at that time. That is, using the same sample as the MT measurement, using a capillary characteristic tester manufactured by Toyo Seiki Seisakusho, the resin temperature is 190 ° C., and the shear stress range is 5 × 10.^Four~ 3x10⁶dyne / cm²Measured in degree.
[0100]
In addition, it changes by changing the diameter of a nozzle (capillary) as follows by MFR (g / 10min) of resin to measure.
0.5 mm when MFR> 20
1.0 mm when 20 ≧ MFR> 3
2.0 mm when 3 ≧ MFR> 0.8
3.0mm when 0.8 ≧ MFR
(9) Haze (transparency)
The haze as an index of the transparency of a hollow molded article and a film heat-treated at 115 ° C. for 30 minutes was measured according to ASTM D-1003-61.
(10) Appearance
The appearance of the hollow molded product and film heat-treated at 115 ° C for 30 minutes is observed with the naked eye, and the appearance evaluation when the deformation is observed is indicated by x, and the appearance evaluation when the deformation is not observed is indicated by ○. In addition, the appearance evaluation in the case where deformation was observed but the spotted cloudiness occurred was indicated by Δ.
(11) Young's modulus (flexibility)
Young's modulus was measured according to JIS K6781.
(12) Deformation start temperature (Td)
A sample of a bag or bottle made of a film formed from an ethylene / α-olefin copolymer is sterilized with hot water at a sterilization temperature of 30 minutes in an RK-4016 small heat and high pressure steam sterilizer manufactured by Alp, The sample taken out from the sterilizer is visually observed to evaluate its deformation. Starting from a sterilization temperature of 110 ° C., the sterilization temperature setting is increased by 1 ° C. after each sterilization. This operation is repeated, and when the sample taken out from the sterilizer is deformed for the first time, the sterilization temperature is set as the deformation start temperature (Td (° C.)).
[0101]
[Production Example 1]
Ethylene / α-olefin copolymer (A-1)
[Preparation of catalyst]
10 kg of silica dried at 250 ° C. for 10 hours was suspended in 154 liters of toluene, and then cooled to 0 ° C. Thereafter, 57.5 liters of a toluene solution of methylaminooxane (Al = 1.33 mol / liter) was added dropwise over 1 hour. At this time, the temperature in the system was kept at 0 ° C. Subsequently, the mixture was reacted at 0 ° C. for 30 minutes, then heated to 95 ° C. over 1.5 hours, and reacted 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 100 liters of toluene. Into this system, 16.8 liters of a toluene solution of bis (1,3-dimethylcyclopentadienyl) zirconium dichloride (Zr = 27.0 mmol / liter) was appropriately reduced at 80 ° C. over 30 minutes, and further at 80 ° C. The reaction was performed for 2 hours. Thereafter, the supernatant was removed and washed twice with hexane to obtain a solid catalyst containing 3.5 mg of zirconium per gram.
[0102]
[Preparation of prepolymerization catalyst]
By adding 870 g of the solid catalyst obtained above and 260 g of 1-hexene to 87 liters of hexane containing 2.5 mol of triisobutylaluminum, and preliminarily polymerizing ethylene at 35 ° C. for 5 hours, A prepolymerized catalyst in which 10 g of polyethylene was prepolymerized was obtained.
[0103]
[Polymerization]
Using a continuous fluidized bed gas phase polymerization apparatus, total pressure 20kg / cm²-G was copolymerized with ethylene and 1-hexene at a polymerization temperature of 80 ° C. In order to maintain a constant gas composition during the polymerization, the prepolymerized catalyst prepared above was continuously supplied at a rate of 0.33 mmol / hr in terms of zirconium atom and triisobutylaluminum at a rate of 10 mmol / hr. Hexene, hydrogen and nitrogen were continuously supplied (gas composition; 1-hexene / ethylene = 0.023, hydrogen / ethylene = 12.4 × 10^-Four, Ethylene concentration = 70%).
[0104]
The yield of the obtained ethylene / α-olefin copolymer (A-1) is 60 kg / hr, and the density is 0.923 g / cm.^ThreeThe MFR was 1.5 g / 10 min, the temperature at the maximum peak position of the endothermic curve measured by DSC was 115.8 ° C., and the decane soluble part at room temperature was 0.41% by weight.
[0105]
[Example 1]
[Production and evaluation of hollow molded products]
The ethylene / α-olefin copolymer obtained in Production Example 1 was pelletized with an extruder, and a hollow molded product was molded under the following molding conditions.
[0106]
From this ethylene / α-olefin copolymer, a cylinder temperature of 160 to 180 ° C., a die temperature of 180 ° C., a mold temperature of 20 ° C., and a blow pressure of 3 kg / cm using a blow molding machine manufactured by Placo² A hollow molded product (bottle) was molded under the conditions of G.
[0107]
The obtained hollow molded article was heat-treated at 115 ° C. for 30 minutes, and then the haze, appearance, and Young's modulus were measured and evaluated by the methods described above.
The results are shown in Table 2.
[0108]
[Production Example 2]
Ethylene ・ α - Olefin copolymer (A-2)
[Preparation of catalyst]
In Production Example 1, instead of a toluene solution of bis (1,3-dimethylcyclopentadienyl) zirconium dichloride, a toluene solution of bis (1,3-dimethylcyclopentadienyl) zirconium dichloride (Zr; 28.1 mmol) Example 1 except that 3.2 liters and bis (1,3-n-butylmethylcyclopentadienyl) zirconium dichloride in toluene (Zr; 34.0 mmol / liter) 10.7 liters were used. In the same manner as above, a polymerization catalyst was obtained.
[polymerization]
Density and MFR were prepared as shown in Table 1, and an ethylene / α-olefin copolymer (A-2) was obtained in the same manner as in Production Example 1 except that the polymerization catalyst was used. Table 1 shows the physical properties of the obtained ethylene / α-olefin copolymer (A-2).
[0109]
[Example 2]
[Production and evaluation of hollow molded products]
The ethylene / α-olefin copolymer (A-2) obtained in Production Example 2 was pelletized with an extruder, and a hollow molded product was molded and evaluated in the same manner as in Example 1.
[0110]
The results are shown in Table 2.
[0111]
[Comparative Example 1]
Ethylene copolymer (A-3)
[Preparation of catalyst]
In a nitrogen stream, 10 mol of commercially available anhydrous magnesium chloride was suspended in 50 liters of dehydrated and purified hexane, and 60 mol of ethanol was added dropwise over 1 hour with stirring, followed by reaction at room temperature for 1 hour.
[0112]
Next, 27 mol of diethylaluminum chloride was added dropwise to the reaction solution at room temperature, and the mixture was stirred for 1 hour.
Subsequently, 100 mol of titanium tetrachloride was added, and then the system was heated to 70 ° C. and reacted while stirring for 3 hours. The produced solid part was separated by decantation, washed repeatedly with purified hexane, and then made into a hexane suspension.
[polymerization]
Into a 200 liter continuous polymerization reactor, dehydrated and purified solvent hexane was continuously supplied at a rate of 80 liter / hr, and the supported catalyst was converted into titanium at a rate of 1.2 mmol / hr. hr, 1-butene 13.0 kg / hr, hydrogen 100 liter / hr continuously fed, polymerization temperature 145 ° C., total pressure 30 kg / cm² G. The copolymer was polymerized under the conditions that the residence time was 1 hour and the concentration of the copolymer with respect to the solvent hexane was 120 g / l.
[0113]
Table 1 shows the physical properties of the resulting ethylene copolymer (A-3).
[Production and evaluation of hollow molded products]
The said ethylene-type copolymer (A-3) was shape | molded on the same conditions as Example 1, and the hollow molded article was obtained. The obtained hollow molded article was heat-treated at 115 ° C. for 30 minutes, and then the haze, appearance, and Young's modulus were measured or evaluated by the methods described above.
[0114]
The results are shown in Table 2 and Table 5.
[0115]
[Table 1]

[0116]
[Table 2]

[0117]
[Example 3]
[Production and evaluation of film]
The ethylene / α-olefin (A-1) of Example 1 was formed into a film by a cast film molding machine manufactured by Modern Corp. under conditions of a cylinder temperature of 180 to 220 ° C., a die temperature of 220 ° C., and a roll temperature of 30 ° C. A film having a thickness of 200 μm was obtained.
[0118]
The obtained film was heat-treated at 115 ° C. for 30 minutes, and then the haze, appearance, and Young's modulus were measured or evaluated by the methods described above.
The results are shown in Table 3.
[0119]
[Example 4]
[Production and evaluation of film]
Example 3 is the same as Example 3 except that the ethylene / α-olefin copolymer (A-2) of Example 2 was used instead of the ethylene / α-olefin (A-1) of Example 1. Thus, a film having a thickness of 200 μm was obtained.
[0120]
The obtained film was heat-treated at 115 ° C. for 30 minutes, and then the haze, appearance, and Young's modulus were measured or evaluated by the methods described above.
The results are shown in Table 3.
[0121]
[Comparative Example 2]
[Production and evaluation of film]
Example 3 was the same as Example 3 except that the ethylene-based copolymer (A-3) of Comparative Example 1 was used instead of the ethylene / α-olefin copolymer (A-1) of Example 1. Thus, a film having a thickness of 200 μm was obtained.
[0122]
The obtained film was heat-treated at 115 ° C. for 30 minutes, and then the haze, appearance, and Young's modulus were measured or evaluated by the methods described above.
The results are shown in Table 3.
[0123]
[Table 3]

[0124]
[Example 5]
[Production and evaluation of film]
The ethylene / α-olefin copolymer (A-1) of Example 1 was subjected to a cylinder film temperature of 180 to 220 ° C., a die temperature of 220 ° C., and a roll temperature of 30 ° C. using a cast film molding machine manufactured by Modern Corporation under the following conditions. Then, a film having a thickness of 100 μm was obtained by film forming.
[0125]
The obtained film was heat-treated at 115 ° C. for 30 minutes, and then the haze, appearance, and Young's modulus were measured or evaluated by the methods described above.
The results are shown in Table 4.
[0126]
[Example 6]
[Production and evaluation of film]
Example 5 Example 5 except that the ethylene / α-olefin copolymer (A-2) of Example 2 was used instead of the ethylene / α-olefin copolymer (A-1) of Example 1 In the same manner as in No. 5, a film having a thickness of 100 μm was obtained.
[0127]
The obtained film was heat-treated at 115 ° C. for 30 minutes, and then the haze, appearance, and Young's modulus were measured or evaluated by the methods described above.
The results are shown in Table 4.
[0128]
[Comparative Example 3]
[Production and evaluation of film]
Example 5 is the same as Example 5 except that the ethylene-based copolymer (A-3) of Comparative Example 1 was used instead of the ethylene / α-olefin copolymer (A-1) of Example 1. Thus, a film having a thickness of 100 μm was obtained.
[0129]
The obtained film was heat-treated at 115 ° C. for 30 minutes, and then the haze, appearance, and Young's modulus were measured or evaluated by the methods described above.
The results are shown in Table 4.
[0130]
[Table 4]

[0131]
[Example 7]
[Production and evaluation of hollow molded products]
95 parts by weight of the ethylene / α-olefin copolymer (A-1) of Example 1 and high-density polyethylene [abbreviated as HDPE (a); density = 0.941 g / cm^Three, MFR = 2.0 g / 10 min, Mw / Mn = 2.4, Tm = 128 ° C.] Same as Example 1 except that an ethylene / α-olefin copolymer composition consisting of 5 parts by weight was used. As a result, a hollow molded product (bottle) was obtained.
[0132]
The obtained hollow molded article was heat-treated at 115 ° C. for 30 minutes, and then the haze, appearance, and Young's modulus were measured or evaluated by the methods described above.
The results are shown in Table 5.
[0133]
[Example 8]
In Example 7, except that the blending amounts of the ethylene / α-olefin copolymer (A-1) and high-density polyethylene [HDPE (a)] in Example 1 were 90 parts by weight and 10 parts by weight, respectively. In the same manner as in Example 7, a hollow molded product was obtained.
[0134]
The obtained hollow molded article was heat-treated at 115 ° C. for 30 minutes, and then the haze, appearance, and Young's modulus were measured or evaluated by the methods described above.
The results are shown in Table 5.
[0135]
[Table 5]

Claims (5)

Ethylene and 3 to 12 carbon atoms alpha - copolymers of olefins (ethylene · alpha - olefin copolymer [A]): and 70 to 95 parts by weight,
High density polyethylene [B]: 5 to 30 parts by weight
A heat-resistant container comprising an ethylene / α - olefin copolymer composition containing
The ethylene / α-olefin copolymer [A] is:
(i) the density is in the range of 0.918 to 0.940 g / cm ³ ;
(ii) The melt flow rate (MFR (g / 10 min)) at 190 ° C. and 2.16 kg load is in the range of 0.1 to 10.0 g / 10 min.
(iii) The amount of decane-soluble component at room temperature (W (% by weight)) and the density (d (g / cm ³ )) are W <80 × exp (-100 (d-0.88)) + 0.1
Indicated by
(iv) Fluidity index (FI (1 / second)) defined by the shear rate when the shear stress at 190 ° C. of the molten polymer reaches 2.4 × 10 ⁶ dyne / cm ² , and the melt flow rate (MFR (g / 10 min))
FI> 75 × MFR
Indicated by
(v) Melt tension at 190 ° C. (MT (g)) and melt flow rate (MFR (g / 10 min))
5.5 × MFR ^-0.65 >MT> 2.2 × MFR ^-0.84
Satisfy the relationship indicated by
And the heat-resistant container is
(A) The haze (according to ASTM D-1003-61 ) after heat treatment at 115 ° C. for 30 minutes is 30% or less,
(B) A heat-resistant container made of an ethylene-based resin, having a deformation start temperature (Td (° C.)) of 115 ° C. or higher. The ethylene / α-olefin copolymer [A] is:
(a) a transition metal compound of Group IV of the Periodic Table containing a cyclopentadienyl skeleton, and
(b) an organoaluminum oxy-compound and in the presence of an olefin polymerization catalyst comprising, that ethylene and and alpha-olefin having 3 to 12 carbon atoms is an ethylene · alpha-olefin copolymer obtained by copolymerizing The heat resistant container made of ethylene resin according to claim 1, wherein: The high-density polyethylene is
(i) the density is in the range of 0.940 to 0.970 g / cm ³ ;
(ii) The heat resistant container made of an ethylene-based resin according to claim 1, wherein the molecular weight distribution (Mw / Mn) measured by GPC is in the range of 1.5 to 4.0.   The container according to any one of claims 1 to 3, wherein the heat-resistant container is a medical container.   The container according to any one of claims 1 to 3, wherein the heat-resistant container is a food container.