JP2001098028A - Polyethylene resin for medical and medical container - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin for medical containers having an excellent heat resistance, transparency and strength and medical containers prepared by molding this. SOLUTION: A polyethylene resin contains the following component (A) and has all the following properties (B)-(G). Medical containers are prepared by molding the resin. Component (A): A copolymer of ethylene and a 3-12C α-olefin. Property (B): A maximum temperature Tm among the melt peak temperature determined by DSC(differential scanning calorimeter) of >=115 deg.C. Property (C): A FR(flow ratio) of <=7.2. Property (D): A MFR(melt flow rate) of from 0.05 to 15 g/10 min. Property (E): A density of from 0.910 to 0.940 g/cm3. Property (F): A hexane-soluble content of <=3 wt.%. Property (G): A K calculated from the melt tension, the Mw (weight average molecular weight) and the Mn (number average molecular weight) of from 0.15 to 4.0.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyethylene resin for medical containers, particularly a container for storing blood components (particularly, platelets and plasma) represented by a blood bag, a physiological saline solution represented by an infusion bag, and an electrolyte. TECHNICAL FIELD The present invention relates to a liquid medicine container such as a liquid, a dextran preparation, a mannitol preparation, a saccharide preparation, an amino acid preparation, a polyethylene resin suitable for a tube connected thereto, and a container formed by molding the same.

[0002]

2. Description of the Related Art Conventionally, as materials for medical containers, polyvinyl chloride, low-density polyethylene prepared by a high-pressure radical method, ethylene / vinyl acetate copolymer, ethylene / α-olefin copolymer, and the like have been used. However, polyvinyl chloride may cause problems such as the dissolution of plasticizers and the generation of toxic substances in waste treatment.Low-density polyethylene produced by the high-pressure radical method has disadvantages in terms of heat resistance, transparency and strength, and , Ethylene-vinyl acetate copolymer is heat resistant,
There was a problem in strength. Therefore, ethylene / α-olefin copolymers, which have few problems such as elution of plasticizers and generation of toxic substances in waste treatment, and have a relatively excellent balance of heat resistance, transparency and strength, are often used. .

[0003] However, ethylene / α-olefin copolymers having sufficient heat resistance have problems in transparency and strength, while those having excellent transparency and strength have problems in which heat resistance is not sufficient. At present, it is used at the expense of any quality. This ethylene α
JP-A-9-99 discloses a method for improving the balance between heat resistance, transparency and strength of an olefin copolymer film.
No. 035 proposes to use an ethylene / α-olefin copolymer polymerized by a metallocene catalyst. However, in the case of the ethylene / α-olefin copolymer polymerized by the conventional metallocene catalyst, although the strength is improved, the heat resistance and the transparency may not be enough.

[0004]

SUMMARY OF THE INVENTION The present invention provides a resin for a medical container having excellent heat resistance, transparency and strength, and a medical container obtained by molding the same.

[0005]

The present invention has been made as a result of various studies to solve the above problems. That is, the present invention is a polyethylene resin containing the following component (A) and having all of the following properties (B) to (G), and a medical container obtained by molding the same. Component (A): Copolymer of ethylene and α-olefin having 3 to 12 carbon atoms Characteristic (B): Highest temperature Tm of 115 ° C. or higher among melting peak temperatures in DSC measurement Characteristic (C): Characteristic (D): MFR is 0.05 to 15 g / 10 min Characteristic (E): Density is 0.910 to 0.940 g / cm
Properties it is ³ (F): it hexane soluble component is not more than 3 wt% to characteristics (G): K 0.15 as calculated according to the equation
(1) When the condition of FR ≦ Mw / Mn + 4.4 is satisfied, K = MT− (0.196 Mw / Mn−0.197 +
(0.0942Mw / Mn + 0.664) e
^{(-MFR + 0.025Mw / Mn + 0.445) / (-0.0417Mw / Mn + 0.382)} +
(0.464Mw / Mn-0.128) e
^{(−MFR + 0.025Mw / Mn + 0.445) / (0.05Mw / Mn + 0.93)} ) (2) When the condition of FR ≦ Mw / Mn + 4.4 is not satisfied, K = MT− (0.196Mw / Mn−0) .197+
(0.0942Mw / Mn + 0.664) e
^{(-MFR + 0.025Mw / Mn + 0.445) / (-0.0417Mw / Mn + 0.382)} +
(0.464Mw / Mn-0.128) e
^{(-MFR + 0.025Mw / Mn + 0.445) / (0.05Mw / Mn + 0.93)} )-0.
097 (FR-0.9 Mw / Mn) / (Log MFR +
0.39) In the above characteristics and formula, MFR is 190 ° C., 2.16
Melt flow rate measured under kg load (g / 10 min)
Where FR is the ratio of melt flow rate MFR ′ (g / 10 minutes) measured at 190 ° C. under a load of 10 kg to MFR (flow ratio: MFR ′ / MFR), MT is 190 ° C., tensile speed 4 m Melt tension measured in g / min (g)
Where Mw is the weight average molecular weight and Mn is the number average molecular weight. In addition, e indicates the base of natural logarithm, and Log indicates common logarithm.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Constituents The polyethylene resin of the present invention comprises the following component (A) and, if necessary, other components. Component (A) : a copolymer of ethylene and an α-olefin having 3 to 12 carbon atoms The copolymer of ethylene and an α-olefin having 3 to 12 carbon atoms of the component (A) is a component (A) to a component. The resin composition containing (C) is not limited as long as it satisfies the properties (D) to (H). One or more α-olefins having 3 to 12 carbon atoms, preferably 4 to 10 carbon atoms, are used. Specifically, for example, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, or a mixture thereof. A small amount of a polyene or the like may be copolymerized with the copolymer in addition to the α-olefin. Such polyenes include butadiene, isoprene, 1,4-hexadiene,
Dicyclopentadiene and the like can be mentioned.

The polymerization method for obtaining the above-mentioned copolymer of ethylene and an α-olefin having 3 to 12 carbon atoms is not limited, but a copolymer composition having desired properties is obtained. For this purpose, it is important to select an olefin polymerization catalyst.

An olefin polymerization catalyst, that is, a metallocene-based transition metal compound as component (a) and an ion-exchange layered compound other than (b1) inorganic silicate and (b2) inorganic silicate as component (b) An olefin polymerization catalyst comprising, as an essential component, at least one compound selected from the group consisting of a compound having a water content of 3% by weight or less and obtained by performing a salt treatment and / or an acid treatment. This is very important.

Component (a): Metallocene-based transition metal compound The metallocene-based transition metal compound of component (a), which is a catalyst component for olefin polymerization, contains one or two optionally substituted cyclopentadienyl-based compounds. Ligands, that is, 1 to 2 cyclopentadienyl ring-containing ligands which may combine with each other to form a condensed ring, and 3 to 6 of the periodic table
An organometallic compound comprising a transition metal of group III, or a cationic complex thereof. Preferred as such a metallocene-based transition metal compound is a compound represented by the following general formula [1] or [2]. General formula [1] (CpR ¹ _a H _5-a ) _p (CpR ² _b H _5-b ) _q MR ³
_r General formula [2] [(CpR ¹ _a H _5-a ) _p (CpR ² _b H _5-b ) _q MR
_{^{3 r L m] n + [}} R 4] n- ( in the general formula [1] and _{^{[2], CpR 1 a H}} 5-a and CpR ² _b H _5-b are cyclopentadienyl (Cp)
The five hydrogen atoms on the ring are each replaced by a number of R ¹ and b
1 shows a cyclopentadienyl-based ligand substituted with one R ² . a and b are integers of 0-5. R ¹ and R ² are an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing substituent, a germanium-containing substituent, a nitrogen-containing substituent, a phosphorus-containing substituent, and an oxygen-containing substituent, Each may be the same or different. Further, when R ¹ or R ² is other C
It may be bonded to R ¹ or R ² on the p ring or directly to another Cp ring to form a bridging group. Further, two R ¹ or two R ² on the same Cp ring, may form a fused ring bond to each other. R ³ represents an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom, a halogen atom,
They are a silicon-containing substituent, a nitrogen-containing substituent, a phosphorus-containing substituent, and an oxygen-containing substituent, which may be the same or different.
R ³ can be C ¹ via R ¹ or R ² or directly.
It may combine with a p-ring to form a cyclopentadienyl bidentate ligand. Furthermore, the two R ^3, may form a bidentate ligand bonded to each other. M is the third to sixth periodic table
L is an electrically neutral ligand, and m is an integer of 1 or more. [R ⁴ ] is one or more anions that neutralize an n-valent cation, and when two or more, they may be the same or different. p, q, and r are 0
Or, when the valence of M is V, p + q + r = V is satisfied in the general formula [1], and p + q + r = V-n is satisfied in the general formula [2]. N is 1 to V
It is an integer of -1. )

R ¹ and R ² are an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing substituent, a germanium-containing substituent, a nitrogen-containing substituent, a phosphorus-containing substituent, and an oxygen-containing substituent. And each may be the same or different. Specific examples of the optionally substituted hydrocarbon group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group and an isopentyl group. , Hexyl group, heptyl group, octyl group, nonyl group, alkyl group such as decyl group, phenyl group, p-tolyl group, o-tolyl group, aryl group such as m-tolyl group, fluoromethyl group, fluoroethyl group, Fluorophenyl group, chloromethyl group, chloroethyl group,
Chlorophenyl group, bromomethyl group, bromoethyl group,
Bromophenyl group, iodomethyl group, iodoethyl group,
Examples include halo-substituted hydrocarbon groups such as iodophenyl groups. Further, as a silicon-containing substituent, a trimethylsilyl group, a triethylsilyl group, a triphenylsilyl group, and the like, and as a nitrogen-containing substituent, a dimethylamide group,
Diethylamide group, dipropylamide group, diisopropylamide group, etc., as a phosphorus-containing substituent, methyl phosphide group, ethyl phosphide group, phenyl phosphide group, etc., as an oxygen-containing substituent, methoxy group, ethoxy group, propoxy group, Alkoxy groups such as isopropoxy group, butoxy group, isobutoxy group, t-butoxy group, phenoxy group, methylphenoxy group, pentamethylphenoxy group, p-tolyloxy group, m-tolyloxy group, o-
Examples include an aryloxy group such as a tolyloxy group, a methylthioalkoxy group, an ethylthioalkoxy group, a propylthioalkoxy group, a butylthioalkoxy group, a t-butylthioalkoxy group, and a thioalkoxy group such as a phenylthioalkoxy group. Among them, preferred R ¹ and R ² are an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group and a t-butyl group, a trimethylsilyl group, and a methoxy group. And an alkoxy group such as an ethoxy group, and an aryloxy group such as a phenoxy group.

Further, R ¹ and R ² represent R ¹ on another Cp ring.
Alternatively, the crosslinking group may be formed by bonding to R ² or directly to another Cp ring. Specific examples of the formed crosslinking group include an alkylene group such as a methylene group and an ethylene group, an alkylidene group such as an ethylidene group, a propylidene group, an isopropylidene group, a phenylmethylidene group and a diphenylmethylidene group, and dimethylsilylene. Group, silicon-containing crosslinking group such as diethylsilylene group, dipropylsilylene group, diisopropylsilylene group, diphenylsilylene group, methylethylsilylene group, methylphenylsilylene group, methylisopropylsilylene group, methyl-t-butylsilylene group, dimethyl Gemylene group, diethylgemylene group, dipropylgemylene group, diisopropylgemylene group, diphenylgemylene group, methylethylgemylene group,
Germanium-containing crosslinking groups such as methylphenylgemylene group, methylisopropylgemylene group, methyl-t-butylgemylene group, nitrogen-containing crosslinking groups such as methylimino group and ethylimino group, methylphosphinylene group, ethylphosphinylene group And other phosphorus-containing substituents. In addition, 2 bonded through these crosslinking groups
One Cp ring forms a bidentate ligand of the transition metal atom.
Furthermore, two of the same Cp ring of R ¹ or two R ²
May combine with each other to form a condensed ring. Specific examples of the condensed ring group to be formed preferably include an indenyl group, a tetrahydroindenyl group, a fluorenyl group, and an octahydrofluorenyl group, and these may be substituted.

R ³ is an optionally substituted C 1 -C 1
20 hydrocarbon groups, hydrogen atoms, halogen atoms, silicon-containing substituents, phosphorus-containing substituents, nitrogen-containing substituents, and oxygen-containing substituents, which may be the same or different. Specifically, examples of the optionally substituted hydrocarbon group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group and an isopentyl group. , Hexyl group, heptyl group, octyl group, nonyl group, alkyl group such as decyl group, phenyl group, p-tolyl group, o-tolyl group, aryl group such as m-tolyl group, fluoromethyl group, fluoroethyl group, Fluorophenyl group, chloromethyl group, chloroethyl group,
Chlorophenyl group, bromomethyl group, bromoethyl group,
Bromophenyl group, iodomethyl group, iodoethyl group,
Examples include halo-substituted hydrocarbon groups such as iodophenyl groups. Further, as the halogen atom, a fluorine atom,
Chlorine atom, bromine atom, iodine atom, as a silicon-containing substituent, trimethylsilyl group, triethylsilyl group, triphenylsilyl group and the like; as a nitrogen-containing substituent, a dimethylamide group, a diethylamide group, a dipropylamide group, Amide groups such as diisopropylamide group, phosphorus-containing substituents include methyl phosphide group, ethyl phosphide group, phenyl phosphide group, and the like, and oxygen-containing substituent groups include methoxy group, ethoxy group, propoxy group, isopropoxy group, and butoxy group. Group, isobutoxy group, alkoxy group such as t-butoxy group, phenoxy group, methylphenoxy group, pentamethylphenoxy group, p-tolyloxy group,
aryloxy groups such as m-tolyloxy group and o-tolyloxy group; thioalkoxy groups such as methylthioalkoxy group, ethylthioalkoxy group, propylthioalkoxy group, butylthioalkoxy group, t-butylthioalkoxy group and phenylthioalkoxy group Can be mentioned. Among these, a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a phenyl group, a halogen atom such as a chlorine atom, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group,
Examples thereof include a dimethylamide group and a methylthioalkoxy group. Among them, a hydrogen atom, a methyl group and a chlorine atom are particularly preferable.

Further, R^Three Is R¹ Or R^Two Through
Cyclope bonded to Cp ring or directly bonded to Cp ring
A pentadienyl bidentate ligand may be formed. like this
-CpH as a specific example of a simple ligand_Four (CH_Two )_n O-
(1 ≦ n ≦ 5), -CpMe _Four (CH_Two )_n O- (l ≦
n ≦ 5), -CpH_Four (Me_Two Si) (t-Bu) N
-, -CpMe_Four (Me_Two Si) (t-Bu) N- etc.
(Cp is a cyclopentadienyl group, Me is a methyl group, B
u represents a butyl group. ). Two more
R^Three May combine with each other to form a bidentate ligand. This
R like^Three As a specific example of -OCH_Two O-, -O
CH_Two CH_Two O-, -O (o-C₆ H_Four ) O- and the like
Can be

M is a transition metal atom of Groups 3 to 6 of the periodic table, and specifically, scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium of group 3 of the periodic table. Holmium, erbium, thulium, ytterbium, lutetium, actinium, thorium, protoactinium, uranium; group 4 titanium, zirconium, hafnium; group 5 vanadium, niobium, tantalum; group 6 chromium, molybdenum, and tungsten; Of these, titanium from group 4
Zirconium and hafnium are preferably used. These may be used as a mixture.

L is an electrically neutral ligand, and m is an integer of 1 or more. Electrically neutral ligands, specifically, ethers such as diethyl ether, tetrahydrofuran, dioxane, nitriles such as acetonitrile, amides such as dimethylformamide,
Examples include phosphines such as trimethylphosphine and amines such as trimethylamine. Preferred are tetrahydrofuran, trimethylphosphine and trimethylamine.

[R ⁴ ] is 1 which neutralizes an n-valent cation.
The number of anions is two or more, and in the case of two or more anions, they may be the same or different. Such anions are specifically tetraphenylborate, tetra (p-tolyl) borate, carbadodecaborate, dicarboundecaborate, tetrakis (pentafluorophenyl) borate, tetrafluoroborate, hexafluorophosphate. a and b are integers of 0-5. p, q, r
Is 0 or a positive integer, and when the valence number of M is V,
In the metallocene compound of the general formula [1], p + q + r =
V and the metallocene compound of the general formula [2]
p + q + r = V−n is satisfied. Usually, p and q are integers of 0 to 3, preferably 0 or 1. r is an integer of 0 to 3, preferably 1 or 2. N is an integer satisfying 0 ≦ n ≦ V. )

The above-mentioned metallocene-based transition metal compound, specifically, taking zirconium as an example, those corresponding to the general formula [1] include (1) bis (methylcyclopentadienyl) zirconium dichloride, (2) bis (ethylcyclopentadienyl) zirconium dichloride, (3) bis (methylcyclopentadienyl) zirconium dimethyl, (4) bis (ethylcyclopentadienyl) zirconium dimethyl, (5) bis (methylcyclopenta Dienyl) zirconium dihydride, (6)
Bis (ethylcyclopentadienyl) zirconium dihydride, (7) bis (dimethylcyclopentadienyl)
Zirconium dichloride, (8) bis (trimethylcyclopentadienyl) zirconium dichloride,
(9) bis (indenyl) zirconium dichloride,
(10) bis (dimethylcyclopentadienyl) zirconium dimethyl, (11) bis (indenyl) zirconium dimethyl, (12) bis (trimethylsilylcyclopentadienyl) zirconium dimethyl, (13) bis (trifluoromethylcyclopentadienyl) ) Zirconium dichloride, (14) isopropylidene-bis (indenyl) zirconium dichloride, (15) isopropylidene-bis (indenyl) zirconium dihydride, (16) pentamethylcyclopentadienyl (cyclopentadienyl) zirconium dichloride,
(17) pentamethylcyclopentadienyl (cyclopentadienyl) zirconium dimethyl, (18) isopropylidene- (cyclopentadienyl) (fluorenyl) zirconium dichloride, (19) isopropylidene- (cyclopentadienyl) (fluorenyl) ) Zirconium dimethyl,

(20) bis (cyclopentadienyl) zirconium dichloride, (21) bis (cyclopentadienyl) zirconium dimethyl, (22) bis (cyclopentadienyl) zirconium diethyl, (23) methylcyclopentadienyl (Cyclopentadienyl) zirconium dichloride, (24) methylcyclopentadienyl (cyclopentadienyl) zirconium dimethyl, (25) dimethylcyclopentadienyl (cyclopentadienyl) zirconium dichloride, (26) indenyl (cyclopentane (Dienyl) zirconium dichloride, (27) bis (pentamethylcyclopentadienyl) zirconium dichloride, (28) indenyl (cyclopentadienyl) zirconium zirconium dimethyl, (29) Trimethyl cyclopentadienyl (cyclopentadienyl) zirconium dimethyl, (30)
Trifluoromethylcyclopentadienyl (cyclopentadienyl) zirconium dichloride, (31) trifluoromethylcyclopentadienyl (cyclopentadienyl) zirconium dimethyl, (32) bis (cyclopentadienyl) (trimethylsilyl) (methyl ) Zirconium, (33) methylene-bis (cyclopentadienyl) zirconium dichloride, (34) ethylene-
Bis (cyclopentadienyl) zirconium dichloride, (35) dimethylsilylene-bis (cyclopentadienyl) zirconiumdimethyl (36) bis (cyclopentadienyl) zirconiumbis (methanesulfonato), (37) bis (cyclopentane Dienyl) zirconium trifluoromethanesulfonatochloride, (3
8) bis (indenyl) zirconium bis (triple methanesulfonate), (39) ethylene-bis (indenyl) zirconium bis (trifluoromethanesulfonate),

(40) dimethylsilylene- (tert-butylamide) (tetramethylcyclopentadienyl) zirconium dibenzyl, (41) indenyl zirconium tris (dimethylamide), (42) ethylene- (third
Tert-butylamide) (tetramethylcyclopentadienyl) zirconium dichloride, (43) dimethylsilylene- (tert-butylamide) (tetramethylcyclopentadienyl) zirconium dichloride, (44) dimethylsilylene- (phenylphosphide) (tetra Methylcyclopentadienyl) zirconium dichloride,
(45) bis (l, 3-dimethylcyclopentadienyl) zirconium dichloride, (46) bis (1-ethyl-3-methylcyclopentagenenyl) zirconium dichloride, (47) bis (1-n-propyl-3) −
(48) bis (1-i-propyl-3-methylcyclopentadienyl) zirconium dichloride, (4) methylcyclopentadienyl) zirconium dichloride,
9) bis (1-n-butyl-3-methylcyclopentadienyl) zirconium dichloride,

(50) bis (1-i-butyl-3-methylcyclopentadienyl) zirconium dichloride,
(51) bis (1-cyclohexyl-3-methylcyclopentadienyl) zirconium dichloride, (52)
Bis (1,3-dimethylcyclopentadienyl) zirconium dimethyl, (53) bis (1-ethyl-3-methylcyclopentadienyl) zirconium dimethyl, (5
4) bis (ln-propyl-3-methylcyclopentadienyl) zirconium dimethyl, (55) bis (1-
n-butyl-3-methylcyclopentadienyl) zirconium dimethyl, (56) bis (1,3-dimethylcyclopentadienyl) zirconium bis (diethylamide), (57) bis (1-ethyl-3-methylcyclopenta Dienyl) zirconium bis (diethylamide),
(58) bis (1-n-butyl-3-methylcyclopentadienyl) zirconium bis (diethylamide) and the like.

The compounds corresponding to the general formula [2] include (1) bis (methylcyclopentadienyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, and (2) bis (ethylcyclopentadienyl). ) Zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, (3) bis (methylcyclopentadienyl) zirconium (methyl)
(Tetraphenyl borate) tetrahydrofuran complex,
(4) bis (ethylcyclopentadienyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, (5) bis (methylcyclopentadienyl) zirconium (hydrido) (tetraphenylborate) tetrahydrofuran complex, (6) bis (Dimethylcyclopentadienyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex,
(7) Bis (indenyl) zirconium (chloride)
(Tetraphenyl borate) tetrahydrofuran complex,
(8) bis (dimethylcyclopentadienyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, (9) bis (trimethylcyclopentadienyl) zirconium (hydrido) (tetraphenylborate) tetrahydrofuran complex,

(10) isopropylidene-bis (indenyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, (11) isopropylidene-bis (indenyl) zirconium (methyl) complex
(Tetraphenyl borate) tetrahydrofuran complex,
(12) isopropylidene-bis (indenyl) zirconium (hydride) (tetraphenylborate) tetrahydrofuran complex, (13) pentamethylcyclopentadienyl (cyclopentadienyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, 14) isopropylidene- (cyclopentadienyl) (fluorenyl) zirconium (chloride)
(Tetraphenyl borate) tetrahydrofuran complex,
(15) bis (cyclopentadienyl) (methyl) zirconium (tetraphenylborate) tetrahydrofuran complex, (16) methylcyclopentadienyl (cyclopentadienyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, (17) )
Dimethylcyclopentadienyl (cyclopentadienyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, (18) indenyl (cyclopentadienyl) zirconium (chloride)
(Tetraphenyl borate) tetrahydrofuran complex,
(19) trimethylsilylcyclopentadienyl (cyclopentadienyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex,

(20) Bis (cyclopentadienyl)
(Trimethylsilyl) zirconium (tetraphenylborate) tetrahydrofuran complex, (21) bis (cyclopentadienyl) (trimethylsilylmethyl) zirconium (tetraphenylborate) tetrahydrofuran complex, (22) ethylene-bis (cyclopentadienyl) zirconium (chloride) ) (Tetraphenylborate) tetrahydrofuran complex, (23) dimethylsilylene-bis (cyclopentadienyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, (24) ethylene-bis (cyclopentadienyl) zirconium (methyl) (Tetraphenylborate) tetrahydrofuran complex, (25) dimethylsilylene-bis (cyclopentadienyl) zirconium (methyl) (tetraphenyl Borate) tetrahydrofuran complex, (26) ethylene - bis (cyclopentadienyl)
Zirconium (hydride) (tetraphenylborate)
Tetrahydrofuran complex, (27) bis (cyclopentadienyl) zirconium (methanesulfonato) (tetraphenylborate) tetrahydrofuran complex, and the like. Further, a mixture of these compounds may be used. Further, third compounds such as titanium compounds and hafnium compounds;
The same compounds as described above can be used for the Group 4, 5, and 6 metal compounds.

Component (b): Component (b), which is a catalyst component for olefin polymerization, includes (b1) an inorganic silicate and (b)
2) At least one compound selected from the group consisting of ion-exchange layered compounds excluding inorganic silicate is used.

(B1) Inorganic silicate Examples of the inorganic silicate include zeolite, diatomaceous earth, and most clays. Clay is usually composed mainly of clay minerals. As these zeolites, diatomaceous earth, clay and clay minerals, naturally occurring minerals may be used or artificially synthesized ones. These are also
It may be used as it is without performing any particular treatment, or may be used after treatment such as ball milling, sieving, and acid treatment. Further, they may be used alone or as a mixture of two or more.

Clay, clay mineral Specific examples of clay and clay mineral include allophane family such as allophane, dickite, nacrite, kaolinite,
Kaolin group such as anoxite, metahalloysite, halloysite, serpentine group such as chrysotile, lizartite, antigorite, montmorillonite, zaukonite,
Smectites such as beidellite, nontronite, saponite, hectorite, bentonite, and teniolite; vermiculite and other vermiculite minerals; Geirome clay, hisingelite, pyrophyllite, ryokudeite group and the like can be mentioned. These may form a mixed layer. Among these, smectites such as montmorillonite, zauconite, beidellite, nontronite, saponite, hectorite, bentonite and teniolite, mica minerals such as mica and illite, and vermiculite minerals such as vermiculite are preferred.

(B2) Ion exchange layer excluding inorganic silicate
Ion-exchange layered compounds excluding inorganic silicates include hexagonal close-packed type, antimony type, CdCl ₂ type,
Examples thereof include ionic crystalline compounds having a layered crystal structure, such as dI ₂ type, in which planes formed by ionic bonds and the like are stacked in parallel with weak bonding force to each other. Specific examples of the ion-exchangeable layered compound having such a crystal structure include α-Zr (HAsO ₄ ) ₂ .H ₂
O, α-Zr (HPO ₄ ) ₂ , α-Zr (KPO ₄ ) ₂
3H ₂ O, α-Ti (HPO ₄ ) ₂ , α-Ti (HA
sO ₄ ) ₂ · H ₂ O, α-Sn (HPO ₄ ) ₂ · H ₂
O, γ-Zr (HPO ₄ ) ₂ , γ-Ti (HPO ₄ )
₂ , crystalline acidic salts of polyvalent metals such as γ-Ti (NH ₄ PO ₄ ) ₂ .H ₂ O. These may be used as they are without any particular treatment, or may be used after treatments such as ball milling, sieving, and acid treatment. Further, they may be used alone or as a mixture of two or more.

Salt treatment and / or acid treatment In a preferred embodiment of the present invention, at least one kind selected from the group consisting of the above-mentioned (b1) inorganic silicate and (b2) an ion-exchange layered compound other than the inorganic silicate. By subjecting the compound to salt treatment and / or acid treatment, a compound of component (b), which is one of the catalyst components for olefin polymerization, can be obtained. These treatments improve the performance of the film, especially transparency. In the state where neither the salt treatment nor the acid treatment has been performed, at least one compound selected from the group consisting of inorganic silicates and ion-exchangeable layered compounds excluding inorganic silicates is usually replaced by a periodic rule. Table 1 Contains cations of Group 1 metals (usually, for example, Na, K). The content of the cation of the Group 1 metal of the periodic table is 0.1.
It is desirably 1% by weight, preferably 0.5% by weight.

The acid strength of the solid can be changed by salt treatment and / or acid treatment. In addition, the salt treatment forms an ion complex, a molecular complex, an organic derivative, and the like, and can change the surface area and the interlayer distance. That is, by using the ion exchange property and replacing the exchangeable ion between the layers with another large bulky ion, a layered material in which the layers are expanded can be obtained. In that case, before being treated with salts, an exchangeable periodic table group 1 metal containing at least one compound selected from the group consisting of inorganic silicates and ion-exchangeable layered compounds other than inorganic silicates is used. It is necessary to exchange 40% or more, preferably 60% or more of cations with cations dissociated from the following salts.

Salts In such salt treatment for the purpose of ion exchange,
As on, salts containing atoms of groups 2 to 14 of the periodic table
Used. Preferably, an atom of group 2-14 of the periodic table
Cations, including halogen atoms, inorganic acids and organic acids
From at least one anion selected from the group consisting of
And more preferably, salts 2-1 to 2 of the periodic table.
Cations containing Group 4 atoms, Cl, Br, I, F, P
O_Four , SO_Four , NO_Three , CO_Three , C_Two O_Four , ClO_Four ,
OCOCH_Three , CH_Three COCHCOCH_Three , OCI_Two,
O (NO_Three )_Two , O (ClO_Four )_Two , O (SO_Four ), O
H, O_Two Cl_Two , OCI_Three , OCOH, OCOCH_Two C
H_Three , C_Two H_Four O_Four And C ₆ H_Five O₇ Selected from the group consisting of
Salts consisting of at least one anion
You. Specifically, CaCl_Two , CaSO_Four , Ca (NO
_Three )_Two , MgCl_Two , MgBr_Two , MgSO_Four , Mg_Three 
(PO_Four )_Two , Mg (NO_Three )_Two , Mg (ClO_Four)
_Two , Ti (OCOCH_Three )_Four , Ti (CO_Three )_Two , Ti
(NO_Three )_Four , Ti (SO_Four )_Two , TiF_Four , TiCl
_Four , Zr (CO_Three )_Two , Zr (NO_Three )_Four , Zr (SO
_Four )_Two , ZrCl_Four , VOSO_Four , VOCl_Three , VCl
_Three , VCl_Four , VBr_Three , CrO_Two Cl_Two , CrF_Three ,
CrCl_Three , CrBr_Three , Cr (NO_Three)_Three , Cr_Two 
(SO_Four )_Three , Co (CH_Three COCHCOCH_Three )_Three ,
CoCO_Three, CoC_Two O_Four , CoF_Two , NiCO_Three , N
iC_Two O_Four , CuBr_Two , Cu (OCOCH_Three )_Two , Z
n (CH_Three COCHCOCH_Three )_Two , Zn (OCOCH
_Three ) _Two , Zn (OOCH)_Two , ZnCO_Three , Zn (SO
_Four ), Zn (NO_Three )_Two , ZnCl_Two , AlCl_Three , A
l (NO_Three )_Three , GeI_Four , GeBr_Four , Sn (OCO
CH_Three )_Four , PbSO_Four , Pb (NO_Three )_Two , Pb (C
10_Four )_Two , PbI_TwoAnd the like. these
Inside, CrO_Two Cl_Two , CrF_Three , CrCl _Three , Cr
Br_Three , Cr (NO_Three )_Three , Cr_Two (SO_Four )_Three, Ti
(NO_Three )_Four , Ti (SO_Four )_Two , TiF_Four , TiCl
_Four , Zr (CO_Three )_Two , Zr (NO_Three ) _Four , Zr (SO
_Four )_Two , ZrCl_Four Etc., as cations, Periodic Table 4
Salts containing Group 6 to 6 atoms are particularly preferred.

Acid The acid treatment removes impurities on the surface,
Part or all of cations such as l, Fe, and Mg are eluted. The acid used in the acid treatment is preferably hydrochloric acid, sulfuric acid,
It is selected from inorganic acids such as nitric acid and phosphoric acid, and organic acids such as formic acid, acetic acid, oxalic acid and benzoic acid.

The salts and / or acids used for the salt treatment and / or the acid treatment may be of two or more kinds. When the salt treatment and the acid treatment are combined, there are a method of performing the salt treatment and then performing the acid treatment, a method of performing the acid treatment and then performing the salt treatment, and a method of simultaneously performing the salt treatment and the acid treatment.

Treatment Conditions The treatment conditions for the salt treatment and / or the acid treatment are not particularly limited, but usually, the salt and acid concentrations are 0.1 to 30% by weight, the treatment temperature is from room temperature to the boiling point, and the treatment time is 5. Elution of at least a part of a substance constituting at least one compound selected from the group consisting of inorganic silicates and ion-exchangeable layered compounds excluding inorganic silicates by selecting conditions of 5 minutes to 24 hours It is preferable to carry out under the following conditions. Further, salts and acids are generally used in an aqueous solution. In the salt treatment and / or the acid treatment, the shape may be controlled by pulverization or granulation before, during, or after the treatment. Further, another chemical treatment such as an alkali treatment or an organic substance treatment may be used in combination. The compound component of component (b) thus obtained has a pore volume of not less than 0.1 cm ³ / g, particularly from 0.3 to ⁵ cm ³ / g, having a radius of 20 ° or more measured by a mercury intrusion method.
g are preferred.

Heat Treatment At least one compound selected from the group consisting of these inorganic silicates and ion-exchangeable layered compounds other than inorganic silicates usually contains adsorbed water and interlayer water. In the present invention, these adsorbed water and interlayer water are removed (b)
A compound component is obtained. Here, the adsorbed water is water adsorbed on the surface of a clay, a clay mineral, or an ion-exchange layered compound particle or a crystal fracture surface, and the interlayer water is water existing between crystal layers. In the present invention, it is desirable to use one from which these moistures have been removed by heat treatment. The heat treatment method for removing the adsorbed water and interlayer water of the clay, clay mineral and interlayer water is not particularly limited, and includes thermal dehydration, thermal dehydration under gas flow, thermal dehydration under reduced pressure, and azeotropic distillation with an organic solvent. A method such as dehydration is used. The heating temperature is selected from a temperature of 100 ° C. or higher, preferably 150 ° C. or higher so that no interlayer water remains. However, high temperature conditions that cause structural destruction are not preferable. Heat dehydration methods such as heating under air flow to form a crosslinked structure are not preferred because the polymerization activity of the catalyst decreases. The heating time is at least 0.5 hour, preferably at least 1 hour. At this time, the moisture content of the compound of the component (b) after the heat treatment, that is, the temperature of 200
It is important that the percentage of the weight of the residual water relative to the weight after dehydration for 2 hours at a temperature of 1 ° C. and a pressure of 1 mmHg (this is assumed to be 0% by weight of water) is 3% by weight or less, and it is preferable. Is 1% by weight or less and 0% by weight or more.

Other components : The polyethylene-based resin of the present invention contains component (A), and as long as it satisfies all of the properties (B) to (G), low-density polyethylene and high-density polyethylene by a high-pressure radical method. Or a resin other than polyethylene, such as polypropylene. Further, within the range not significantly impairing the effects of the present invention, the polyethylene-based resin may contain any additional components, for example, an antioxidant, a neutralizing agent,
Anti-blocking agent, ultraviolet absorber, warming agent, lubricant,
An antifogging agent, an antistatic agent, a nucleating agent, an anti-condensation agent, a molecular weight modifier, a colorant, an impact modifier, a filler, a flame retardant, an adhesion improver, a printability improver, and the like can also be blended.

Kneading / granulation The above-mentioned component (A), a copolymer of ethylene and an α-olefin having 3 to 12 carbon atoms, and if necessary, other compounding agents, are mixed with the above-mentioned properties (B) to (G). The polyethylene resin composition used in the medical container of the present invention can be obtained by blending at a predetermined blending ratio that satisfies all the conditions, and melt-kneading or dry blending. However, when dry blending, from the viewpoint of uniform dispersion of the compounding agent,
It is preferable to adopt a master batch method. The above melt kneading is generally performed by a single screw extruder, a twin screw extruder, a Banbury mixer, a roll mixer, a Brabender plastograph,
Using a usual kneader such as a kneader, usually 170 to 25
By kneading at a temperature of 0 ° C. and preferably granulation,
The polyethylene resin composition used for the medical container of the present invention can be obtained. In this case, it is preferable to select a kneading / granulating method capable of improving the dispersion of the components, and usually kneading / granulating using a single-screw extruder or a twin-screw extruder.
Granulation is performed.

2. Characteristics It is necessary that the polyethylene resin composition containing the above-mentioned component (A) thus obtained has all of the predetermined characteristics (B) to (G) for the following reasons. In addition, the definition of each characteristic is as having performed in Claim 1, and the detail of a measuring method is described in an Example section.

Property (B): Tm The highest temperature Tm of the melting peak temperature in the DSC measurement of the polyethylene resin composition is 115 ° C. or higher. When Tm is less than the above range, heat resistance becomes insufficient.

Property (C): FR The polyethylene resin composition has an FR of 7.2 or less, preferably 7.0 or less. If the FR exceeds the above range, the transparency of the molded article is reduced and the strength of the molded article is also decreased.

Property (D): MFR The MFR of the polyethylene resin composition is 0.05 to 15 g.
/ 10 min, preferably 0.2 to 5 g / 10 min, more preferably 0.5 to 3 g / 10 min. MF
If R is less than the above range, the extrusion load at the time of molding becomes high, and the workability decreases. On the other hand, when the MFR exceeds the above range, the molding stability is reduced and the strength of the molded product is also reduced.

Property (E): Density The density of the polyethylene resin composition is 0.910 to 0.9.
40 g / cm ³ , preferably 0.910 to 0.935 g
/ Cm ³ , more preferably 0.910 to 0.930 g
/ Cm ³ range. When the density is less than the above range, heat resistance becomes insufficient. On the other hand, when the density exceeds the above range, the transparency and strength of the molded product are reduced.

Property (F): Hexane-soluble content The hexane-soluble content of the polyethylene resin composition is 3.0% by weight or less, preferably 2.5% by weight or less, more preferably 2.0% by weight or less. There is. When the hexane-soluble component exceeds the above range, the transparency of the molded article decreases.

Property (G): K For the polyethylene resin composition, the above-mentioned value of K satisfies 0.15 to 4.0, preferably 0.20 to 3.0. When the value of K is less than the above range, the transparency of the molded product is insufficient. On the other hand, even if the value of K exceeds the above range, the transparency of the molded product is rather deteriorated.

Molding The medical composition of the present invention can be obtained by molding the resin composition thus obtained by a known molding method, T-die film molding, blown film molding, sheet molding or the like. The medical container of the present invention may have a single-layer structure or a multi-layer structure composed of two or more layers. In the case of a multilayer film, a multilayer film or sheet can be formed by coextrusion inflation molding or coextrusion T-die molding. The thickness of the molded product is 50 to 1000 μm, preferably 60 to 80 μm.
It is preferably in the range of 0 μm, and as a multilayer composition ratio in the case of a multilayer film or sheet, the thickness of one layer is in the range of 5 to 500 μm, preferably 10 to 300 μm, and the thickness of the other layer is 45 to 50 μm. It is in the range of 500 μm, preferably 50-500 μm.

[0045]

The present invention will be more specifically described below with reference to examples and comparative examples. The measurement methods and measurement conditions used in the examples are as follows. (1) Tm SSC5200 thermal analysis system (SSC5200 disk station, RDC22, manufactured by Seiko Denshi Kogyo KK)
JIS K7 using a robot DSC module
In accordance with No. 121, the measurement was performed as follows. 5mg
After keeping the sample at 170 ° C. for 5 minutes,
After cooling to -10 ° C at a rate of 10 ° C / min and keeping at -10 ° C for 1 minute, the sample was heated to 170 ° C at a rate of 10 ° C / min to record the endothermic behavior during melting. The temperature of the highest peak among the melting peaks obtained here was defined as Tm.

(2) FR Melt flow rate MFR 'was measured at 190 ° C. under a load of 10 kg in accordance with JIS K6760.
/ MFR was calculated and set to FR. (3) MFR (g / 10 minutes) According to JIS K6760, 190 ° C, 2.16 kg
It was measured under load conditions. (4) Density (g / cm ³ ) Measured according to JIS K6760.

(5) Hexane-soluble matter (% by weight) Using a press molding machine, a 0.1 mm-thick press sheet is prepared at 190 ° C. and the press sheet is 10 mm × 50 mm.
Cut into rectangles of mm, collect and weigh about 5 g in total. This sample is hexane 200cm
³ at an elevated temperature for a Soxhlet apparatus for 3 hours reflux extraction. Then, after cooling to room temperature, the extraction residue was dried under reduced pressure, weighed, the weight after drying under reduced pressure was subtracted from the original weight, divided by the original weight, and the value obtained by multiplying by 100 was the hexane-soluble matter. did.

(6) Mw / Mn Mw / Mn was determined in accordance with “Gel Permeation Chromatography” published by Maruzen, Takeuchi. That is, using standard polystyrene of known molecular weight (monodisperse polystyrene manufactured by Tosoh Corporation), the number average molecular weight Mn and weight average molecular weight Mw are converted into Mw by the universal method, and Mw
/ Mn was determined. Measurements were made by Waters ISOC
-Using ALC / GPC, column is AD8 manufactured by Showa Denko
3 samples of 0M / S were used, and the sample was dissolved in o-dichlorobenzene to use 200 μl as a 0.2% by weight solution.
The test was performed at 140 ° C. at a flow rate of 1 ml / min. (7) MT (g) Using a Capillograph manufactured by Toyo Seiki Seisaku-sho, a nozzle diameter of 2.095 mmφ, a nozzle length of 8.00 mm, an inflow angle of 180 °, a set temperature of 190 ° C, and a piston extrusion speed of 1
The measurement was performed under the conditions of 0.0 mm / min and a take-up speed of 4.0 m / min.

(8) Haze (%) Measured according to JIS K7105. (9) Dart impact strength (g) Measured in accordance with JIS K7124 method A.

(10) Heat resistance The same film used for measuring the haze and the dart impact strength was cut into a size of 150 mm × 250 mm,
The sheets are stacked and heat sealed at about 5 mm from the end of each side with a heat sealer having a seal bar having a width of 2 mm. Cut one corner of the bag thus completed, inject 800 ml of mineral water from there, and heat seal it with the above heat sealer so that air is not left in the bag as much as possible. . This bag is put in a retort-type high-pressure steam sterilizer, at a temperature of 110 ° C. and a gauge pressure of 1.8.
After treating for 40 minutes under the condition of kg / cm ² ,
The bag was allowed to stand for 8 hours, the surface condition of the bag was observed, and the heat resistance was evaluated in three steps as follows. ：: Abata-shaped defects, wrinkles, and whitening are scarcely observed on the bag surface. Δ: Some avatar-shaped defects, wrinkles, and whitening are observed on the bag surface. ×: Abata-shaped defects, wrinkles, and whitening on the entire bag surface. (11) Water vapor permeability test Mineral water 80 prepared in the same manner as in (10)
Using a bag containing 0 ml, the weight loss was determined in accordance with the Japanese Pharmacopoeia General Test Method "Test Method for Plastic Containers for Infusion". (12) Residue on ignition Using the bag obtained in (10), the test was carried out according to the Japanese Pharmacopoeia General Test Method "Test Method for Plastic Container for Infusion".

Example 1 (1) Chemical treatment of clay mineral 15.0 kg of zinc sulfate heptahydrate was added to 105.0 kg of demineralized water
And 30.0 kg of synthetic mica (manufactured by Corp Chemicals, Somasif, ME-100F) was added thereto, stirred for 18 hours after dispersion, and filtered and washed with demineralized water. An aqueous solution in which 4.8 kg of chromium (III) nitrate 9 hydrate was dissolved in 7.5 kg of deionized water was added, and the mixture was stirred at room temperature for 18 hours. At this time, the slurry concentration was adjusted to 20.0% by weight. After filtration and washing with demineralized water, the solid content
It was adjusted to be 9.0% by weight. Synthetic smectite (manufactured by Corp Chemical Co., SWN) was added to the slurry so as to be 5% by weight based on the total solid content, and the slurry was sufficiently dispersed. The slurry was dried and granulated by a spray dryer. ,
Spherical particles were obtained. The obtained powder was further dried continuously using a rotary kiln at a temperature of 200 ° C. under a countercurrent nitrogen flow (nitrogen flow rate of 49 Nm ³ / hr) at a rate of 3 kg / hr (residence time: 10 minutes) and dried. Collected under nitrogen.

(2) Preparation of Catalyst and Prepolymerization 75.9 g of the synthetic mica particles obtained in the above (1) were mixed with n
-Along with 4.0 l of heptane, it was introduced into a 10 l reactor with induction stirrer. To this was added bis (n-butylcyclopentadienyl) zirconium dichloride 6.01 dissolved in 600 ml of toluene.
The solution of mmol was added and stirred at 30 ° C for 10 minutes.
Subsequently, 71.8 mmol of triethylaluminum was added, and the temperature of the system was set to 40 ° C. Ten minutes later, ethylene gas was introduced, and the reaction was continued for 3.85 hours. The amount of polyethylene produced during this period was 548 g.

(3) Copolymerization of ethylene / 1-hexene Gas phase polymerization was carried out using the prepolymerized catalyst obtained in the above (2). That is, 11.7 mg of the solid catalyst component was added to a continuous gas-phase polymerization reactor in which a mixed gas of ethylene and 1-hexene (1-hexene / ethylene = 2.9%) was circulated.
hr, triethylaluminum and diethylaluminum monoethoxide, 89 mg / hr and 42 mg / hr, respectively
Was supplied intermittently. The polymerization reaction conditions were 83 ° C., an ethylene partial pressure of 18 kg / cm ² , and an average residence time of 4.2 hours. The average polymerization rate of the produced polyethylene is 285 kg
/ Hr. The MFR of the obtained ethylene-hexene copolymer A was 1.4 g / 10 minutes, and the density was 0.927 g /
cm ³ .

(4) Pelletization With respect to 100 parts by weight of the powder of the ethylene / hexene copolymer A obtained in the above (3), octadecyl-3- (3,5-di-t-butyl-) was used as an antioxidant. 0.05 parts by weight of 4-hydroxyphenyl) propionate and tetrakis (2,4-di-t-butylphenyl) -4,4′-
0.05 parts by weight of biphenylenediphosphonite and 0.05 parts by weight of calcium stearate as a neutralizing agent were added, and these were added using a 50-liter super mixer.
After mixing at a rotation speed of 800 rpm for 5 minutes, the mixture was melt-kneaded with a single screw extruder having a screw diameter of 40 mmφ and L / D26 at 200 ° C. and a screw rotation speed of 50 rpm to form pellets. For this pellet, Tm, FR, MFR, density, hexane-soluble matter, Mw / Mn, and MT were measured, and the value of K was calculated. The results are shown in Table 1.

(5) Film forming: The pellet obtained in the above (4) was screwed with a screw diameter of 40 mm.
Using a blown film molding machine with a die diameter of 75 mm and a die lip width of 3 mm equipped with an extruder of φ, L / D24, temperature 180 ° C., screw rotation speed 60 rpm,
Molded under the conditions of a blow-up ratio of 2.0, a take-up speed of 12 m / min, and a frost line height of 160 mm, and a width of 230 m
m, a blown film having a thickness of 60 μm was obtained.
For molded films, haze, dirt impact strength,
Heat resistance, water vapor permeability test, and residue on ignition were measured and evaluated. The results were as shown in Table 1.

Example 2 An ethylene / hexene copolymer B was obtained in the same manner as in Examples 1 (1) to (3) except that the following changes were made in (3) of Example 1. Changes: 1-hexene / ethylene = 4.4%, polymerization temperature 83 ° C., ethylene partial pressure 18 kg / cm ² , average residence time 4.9 hours, average polymerization rate of produced polyethylene 245
g / hr Further, in (4) of Example 1, the frost line height was set to 1
Pelletization and film forming were carried out in the same manner as in Examples 1 (4) and (5) except that the diameter was changed to 70 mm. The pellets were Tm, FR, MFR, density, hexane soluble matter, M
The w / Mn and MT were measured, and the value of K was calculated. For the formed film, haze, dart impact strength, heat resistance,
The water vapor permeability test and the residue on ignition were measured and evaluated. The results were as shown in Table 1.

Example 3 An ethylene / hexene copolymer C was obtained in the same manner as in Examples 1 (1) to (3) except that the following changes were made in (3) of Example 1. Changes: 1-hexene / ethylene = 2.2%, polymerization temperature 83 ° C., ethylene partial pressure 18 kg / cm ² , average residence time 4.0 hours, average polymerization rate 302 of produced polyethylene
g / hr Further, pelletization and film formation were performed in the same manner as in Examples 1 (4) and (5).
MFR, density, hexane-soluble matter, Mw / Mn, MT were measured, and the value of K was calculated. For the formed film, haze, dart impact strength, heat resistance, water vapor permeability test,
Residue on ignition was measured and evaluated. The results were as shown in Table 1.

COMPARATIVE EXAMPLE 1 Commercially available linear low-density polyethylene (α-olefin: 1-hexene, 1-hexene content 13% by weight) produced using a metallocene catalyst as ethylene / α-olefin copolymer D Example 1 (4), (5) except that
Pelletizing and film forming in the same manner as described above, and for pellets, Tm, FR, MFR, density, hexane soluble component,
Mw / Mn and MT were measured, and the value of K was calculated. The formed film was measured and evaluated for haze, dart impact strength, heat resistance, water vapor permeability test, and residue on ignition. The results were as shown in Table 1.

Comparative Example 2 Commercially available linear low-density polyethylene (α-olefin: 1-hexene, 1-hexene content: 8% by weight) produced using a metallocene catalyst as the ethylene / α-olefin copolymer E Except for using, the pelletization and film forming were carried out in the same manner as in Examples 1 (4) and (5). The pellets were Tm, FR, MFR, density, hexane soluble, M
The w / Mn and MT were measured, the value of K was calculated, and the haze, dart impact strength, heat resistance,
The water vapor permeability test and the residue on ignition were measured and evaluated. The results were as shown in Table 1.

Comparative Example 3 Commercially available linear low-density polyethylene (α-olefin: 1-octene, 1-octene content: 2% by weight) produced using a metallocene catalyst was used as the ethylene / α-olefin copolymer F. Pelletization and film formation were carried out in the same manner as in Examples 1 (4) and (5) except that Tm, FR, MFR, density, hexane soluble matter, M
The w / Mn and MT were measured, the value of K was calculated, and the haze, dart impact strength, heat resistance,
The water vapor permeability test and the residue on ignition were measured and evaluated. The results were as shown in Table 1.

Comparative Example 4 Linear low-density polyethylene (α) commercially available from Nippon Polychem Co., Ltd. as ethylene / α-olefin copolymer G
-Olefin: 1-hexene, 1-hexene content 5% by weight) Except for using "Novatech C6 SF941",
Pelletization and film formation were performed in the same manner as in Examples 1 (4) and (5).
Measure density, hexane solubles, Mw / Mn, MT
Is calculated, the haze is about the formed film,
Dart impact strength, heat resistance, water vapor permeability test, and residue on ignition were measured and evaluated. The results were as shown in Table 1.

[0062]

[Table 1]

[0063]

According to the present invention, it is possible to provide a medical container resin excellent in heat resistance, transparency and strength, and a medical container obtained by molding the same.

Continuing on the front page F-term (reference) 4F071 AA15X AA20X AA21X AA81 AA82 AA84 AA88 AF05Y AF14 AF30 AF45 AG02 AH05 BA01 BB06 BC01 4J028 AA01A AB00A AB01A AC01A AC10A AC28A AC31A AC39AAC14BA01BACB ACB BAB ACB CA16C CA30C CA36C CA44C CA49C CA54C CA56C CB53C CB55C DA01 DB08C DB10C EC03 FA04 GA05 GA06 GA07 GA08 GA09 GA19 4J100 AA02P AA03Q AA04Q AA15Q AA16Q AA17Q AA19Q AA21Q CA04 DA41 DA21 DA22 DA24 DA24

Claims (4)

[Claims] 1. A polyethylene resin for a medical container, comprising the following component (A) and having all of the following properties (B) to (G). Component (A): Copolymer of ethylene and α-olefin having 3 to 12 carbon atoms Characteristic (B): Highest temperature Tm of 115 ° C. or higher among melting peak temperatures in DSC measurement Characteristic (C): Characteristic (D): MFR is 0.05 to 15 g / 10 min Characteristic (E): Density is 0.910 to 0.940 g / cm
Properties it is ³ (F): it hexane soluble component is not more than 3 wt% to characteristics (G): K 0.15 as calculated according to the equation
(1) When the condition of FR ≦ Mw / Mn + 4.4 is satisfied, K = MT− (0.196 Mw / Mn−0.197 +
(0.0942Mw / Mn + 0.664) e
^{(-MFR + 0.025Mw / Mn + 0.445) / (-0.0417Mw / Mn + 0.382)} +
(0.464Mw / Mn-0.128) e
^{(−MFR + 0.025Mw / Mn + 0.445) / (0.05Mw / Mn + 0.93)} ) (2) When the condition of FR ≦ Mw / Mn + 4.4 is not satisfied, K = MT− (0.196Mw / Mn−0) .197+
(0.0942Mw / Mn + 0.664) e
^{(-MFR + 0.025Mw / Mn + 0.445) / (-0.0417Mw / Mn + 0.382)} +
(0.464Mw / Mn-0.128) e
^{(-MFR + 0.025Mw / Mn + 0.445) / (0.05Mw / Mn + 0.93)} )-0.
097 (FR-0.9 Mw / Mn) / (Log MFR +
0.39) In the above characteristics and formula, MFR is 190 ° C., 2.16
Melt flow rate measured under kg load (g / 10 min)
Where FR is the ratio of melt flow rate MFR ′ (g / 10 minutes) measured at 190 ° C. under a load of 10 kg to MFR (flow ratio: MFR ′ / MFR), MT is 190 ° C., tensile speed 4 m Melt tension measured in g / min (g)
Where Mw is the weight average molecular weight and Mn is the number average molecular weight. In addition, e indicates the base of natural logarithm, and Log indicates common logarithm. 2. A copolymer of ethylene and an α-olefin having 3 to 12 carbon atoms prepared using an olefin polymerization catalyst containing the following components (a) and (b). The polyethylene-based resin according to claim 1, wherein: Component (a): Metallocene transition metal compound Component (b): At least one compound selected from the group consisting of the following (b1) and (b2): (b1): inorganic silicate (b2): inorganic silicate Excluding ion-exchange layered compounds 3. The polyethylene resin according to claim 1, wherein the component (a) is a metallocene transition metal compound represented by the following general formula [1] or [2]. General formula [1] (CpR ¹ _a H _5-a ) _p (CpR ² _b H _5-b ) _q MR ³
_r General formula [2] [(CpR ¹ _a H _5-a ) _p (CpR ² _b H _5-b ) _q MR
_{^{3 r L m] n + [}} R 4] n- ( in the general formula [1] and _{^{[2], CpR 1 a H}} 5-a and CpR ² _b H _5-b are cyclopentadienyl (Cp)
The five hydrogen atoms on the ring are each replaced by a number of R ¹ and b
1 shows a cyclopentadienyl-based ligand substituted with one R ² . a and b are integers of 0-5. R ¹ and R ² are an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing substituent, a germanium-containing substituent, a nitrogen-containing substituent, a phosphorus-containing substituent, and an oxygen-containing substituent, Each may be the same or different. Further, when R ¹ or R ² is other C
It may be bonded to R ¹ or R ² on the p ring or directly to another Cp ring to form a bridging group. Further, two R ¹ or two R ² on the same Cp ring, may form a fused ring bond to each other. R ³ represents an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom, a halogen atom,
They are a silicon-containing substituent, a nitrogen-containing substituent, a phosphorus-containing substituent, and an oxygen-containing substituent, which may be the same or different.
R ³ can be C ¹ via R ¹ or R ² or directly.
It may combine with a p-ring to form a cyclopentadienyl bidentate ligand. Furthermore, the two R ^3, may form a bidentate ligand bonded to each other. M is the third to sixth periodic table
L is an electrically neutral ligand, and m is an integer of 1 or more. [R ⁴ ] is one or more anions that neutralize an n-valent cation, and when two or more, they may be the same or different. p, q, and r are 0
Or, when the valence of M is V, p + q + r = V is satisfied in the general formula [1], and p + q + r = V-n is satisfied in the general formula [2]. N is 1 to V
It is an integer of -1. ) 4. A medical container comprising the polyethylene resin according to claim 1.