JPH11152378A - Ethylene-alpha-olefin copolymer composition for medical use and molded article made thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an ethylene-α-olefin copolymer compsn. which gives a molded article having good external appearance, low in fine particle elution, and improved in clarity after sterilization, by compounding an ethylene-α-olefin copolymer having specified physical properties with hydrotalcite. SOLUTION: 100 pts.wt. of the ethylene-α-olefin copolymer produced in the presence of a single-site catalyst and having a density of 0.880-0.960 g/cm<3> , pref. 0.890-0.950 g/cm<3> , an MFR2.16 (190 deg.C, 2.16 kg load) of 0.1-20 g/10 min, pref. 0.55-20 g/10 min, a ratio of MFR10.0 (190 deg.C, 10 kg load)/MFR2.16 of 1-20, pref. 3-10, a mol.wt. distribution (Mw/Mn) of 2.0-6.0, pref. 2.5-4.0, and a swell ratio (190 deg.C) lower than 1.35, pref. lower than 1.30, is compounded with 0.01-0.3 pt.wt. of a hydrotalcite to give the ethylene-α-olefin copolymer compsn. for medical use of which the amt. of fine particles dissolving out is 15 or lower and the total light transmission after heat treatment of 40 min is 70% or higher.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a medical ethylene-α-olefin copolymer composition used for medical containers such as infusion bags and medical bottles, and a molded article using this composition.

[0002]

2. Description of the Related Art Polyolefin resins are widely used as materials for medical containers and the like because they are lighter in weight, easier to dispose of, have better chemical resistance, and have superior mechanical properties as compared with conventional glass containers. Used. However, there has been a demand for a polyolefin-based resin having excellent transparency after the sterilization step and further excellent elution of fine particles.

Japanese Patent Application Laid-Open No. 7-96589 discloses that a multilayer film and container excellent in heat resistance, blocking resistance, tensile strength, flexibility and transparency are suitable for use in medical and other applications. 5 consisting of a copolymer
In the layer film, the density of the resin constituting each layer is, in order from the outer layer, the first layer: 0.935 to 0.950 g / c
m ³ , second layer: 0.920 g / cm ³ or less, third layer: 0.9
25 to 0.950 g / cm ³ , fourth layer: 0.920 g / cm ³
Hereinafter, a multilayer film characterized by having a fifth layer of 0.925 to 0.940 g / cm ³ is disclosed.

Further, Japanese Patent Application Laid-Open No. 7-300123 discloses that when used in a single layer, the barrier properties are enhanced without lowering the impact resistance, and when used in a multilayer, The impact resistance can be improved without lowering the barrier properties, and in particular, since it has excellent barrier properties against methanol-containing gasoline, it is used as a material for fuel containers and fuel transfer pipes of automobiles and the like using these gasoline as fuel. A useful ethylene-vinyl alcohol copolymer (a), a boronic acid group, a borinic acid group, at least one functional group selected from a boronic acid group and a boron-containing group that can be converted to a borinic acid group in the presence of water. A single-layer or multi-layer container having a resin composition layer comprising a polyolefin (b) is disclosed.

Further, Japanese Patent Application Laid-Open No. 8-81600 discloses that it has excellent impact resistance and has good oxygen gas barrier properties even when sterilized under conditions where heat and moisture act simultaneously, such as boil sterilization and retort sterilization. And an ethylene-vinyl alcohol-based copolymer (a) having an excellent appearance after sterilization,
Polyolefin (b) having at least one functional group selected from a boronic acid group, a borinic acid group, a boric acid-containing group which can be added to a boronic acid group and a boric acid group in the presence of water, and an inorganic filler (d). And weight of (a) /
The weight of (b) is 10/90 to 99/1, and the weight of (d) / the total weight of (a) and (b) is 0.1 / 99.9 to
A 50/50 resin composition is disclosed.

Further, Japanese Patent Application Laid-Open No. 9-99035 discloses that a layer composed of a metallocene-catalyzed linear low-density polyethylene having a density of 0.920 g / cm ³ or less, which is excellent in transparency and flexibility which can be sterilized by high pressure steam, is used as an inner layer. Alternatively, a medical container characterized by being formed of a multilayer sheet constituting an intermediate layer is disclosed.

Further, Japanese Patent Application Laid-Open No. 9-176400 discloses
Is thermally degraded during molding such as injection molding, extrusion molding, and hollow molding.
Prevents roll contamination and smoke generation during molding and generates heat
Mechanical strength while maintaining properties such as easy incineration with a small amount
(A) (a) Cyclopentadienyl skeleton excellent in degree, etc.
Group IV transition metal compound containing a ligand having
Ethylene and carbon number in the presence of a catalyst containing at least one
Obtained by copolymerizing 3 to 20 α-olefins.
(B) Density 0.86 to 0.96 g / cm ^Three,
(C) melt flow rate 0.01 to 50 g / 10 minutes,
(D) Molecular weight distribution Mw / Mn 1.5-5.0, (e) set
Etch in which the distribution parameter Cb is 1.01 to 1.2
100 parts by weight of a len copolymer, (B) filler 10 to 400
Parts by weight, (C) 0.01 to 2.0 parts by weight of an antioxidant.
Filler-containing ethylene / α-olefin copolymer composition
Is disclosed.

[0008]

DISCLOSURE OF THE INVENTION The present invention provides a medical container such as an injection cylinder, a syringe, an infusion bag, a medical bottle, and the like, which has a good appearance, excellent transparency after a sterilization treatment step, and low elution of fine particles. Medical use ethylene-α
-It is an object to provide an olefin copolymer composition and a molded product using the composition.

[0009]

According to the present invention, 100 parts by weight of an ethylene-α-olefin copolymer produced from a single-site catalyst having the following property (A) and 0.01 parts by weight or more of hydrotalcite are used. The present invention relates to a medical ethylene-α-olefin copolymer composition comprising less than 3 parts by weight.

(A) Ethylene-α-olefin copolymer: (A-1) Density (d) = 0.880 to 0.960 (g /
^{cm 3) (A-2)} 190 ℃, melt flow rate at 2.16Kg load _{(MFR 2. 16) = 0.1~200 (} g / 1
0 min) (A-3) 190 ℃ , melt flow rate in 10.0Kg load (MFR _{10 .0)} and 190 ° C., 2.16 Kg
Ratio to melt flow rate (MFR _2.16 ) under load (MFR _10.0 ) / (MFR _2.16 ) = 1 to 20 (A-4) Molecular weight distribution (Mw / Mn) = 2.0 to 6.0

More preferably, the present invention relates to the above ethylene-α-olefin copolymer composition for medical use, wherein the dissolution property of fine particles is 15 or less.

Further, preferably, the present invention relates to
The present invention relates to the above medical ethylene-α-olefin copolymer composition, which has a total light transmittance of 70% or more after heat treatment at 40 ° C. for 40 minutes.

Further, the present invention relates to a molded article using the above-mentioned medical ethylene-α-olefin copolymer composition.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention relates to 100 parts by weight of an ethylene-α-olefin copolymer produced from a single-site catalyst having the following property (A) and 0.01 to 0.3 parts by weight of hydrotalcite. Parts, preferably less than 0.1 part.
01 to 0.25 parts by weight, more preferably 0.03 to
The present invention relates to a medical ethylene-α-olefin copolymer composition comprising 0.25 parts by weight, particularly preferably 0.05 to 0.2 part by weight.

(A) Ethylene-α-olefin copolymer: (A-1) Density (d) = 0.880 to 0.960 (g /
cm ^3), preferably .890-.950 (g / c
m ³ ), more preferably 0.900 to 0.945 (g
/ Cm ³ ), particularly preferably 0.910 to 0.935
^{(G / cm 3) (A} -2) 190 ℃, melt flow rate at 2.16Kg load _{(MFR 2. 16) = 0.1~200 (} g / 1
0), preferably 0.5 to 20 (g / 10 minutes), more preferably 0.5 to 10 (g / 10 minutes), particularly preferably 1 to 7 (g / 10 minutes) (A-3). 190 ° C., a melt flow rate of 10.0Kg load (MFR _{10 .0)} and 190 ° C., 2.16 Kg
Ratio to the melt flow rate (MFR _2.16 ) under load (MFR _10.0 ) / (MFR _2.16 ) = 1 to 20, preferably 3 to 10, more preferably 4 to 7, particularly preferably 4.5 to 6.5 ( A-4) Molecular weight distribution (Mw / Mn) = 2.0 to 6.0;
Preferably, it is 2.5-4.0, more preferably 2.6-.
3.5, particularly preferably 2.6-3.3

Further, the ethylene-α-olefin copolymer (A) preferably has the following characteristics. (A-5) The swell ratio (SR) at 190 ° C. is SR
<1.35, further SR <1.30, especially 1.00 <S
R <1.30.

The ethylene-α-olefin copolymer (A) is produced by copolymerizing ethylene with an α-olefin having 3 to 10 carbon atoms in the presence of a single-site catalyst.

Examples of the α-olefin having 3 to 10 carbon atoms include propylene, butene-1, pentene-1, hexene-1, 4-methylpentene-1, and octene-1.

The repeating unit derived from α-olefin in the copolymer of ethylene and α-olefin is as follows:
Usually, it is preferably in the range of 10 mol% or less, more preferably in the range of 0.1 to 5 mol%, and particularly preferably in the range of 0.1 to 5 mol%.
-4% by mole. α-olefin is
The ethylene-α-olefin copolymer may be used alone or in combination of two or more.

As the single-site catalyst, a combination of a metallocene compound of a transition metal of Group IV or V of the periodic table with an organoaluminum compound and / or an ionic compound is used.

As the transition metal of Group IV or V of the periodic table, titanium (Ti), zirconium (Zr), hafnium (Hf), vanadium (V) and the like are preferable.

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

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

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

Further, examples of other organic aluminum compounds include trialkylaluminum, dialkylhalogenoaluminum, sesquialkylhalogenoaluminum, alkenylaluminum, dialkylhydroaluminum, and sesquialkylhydroaluminum.

The ionic compound is represented by the general formula: C ⁺ .A
^- , C ⁺ is an oxidizing cation of an organic compound, an organometallic compound, or an inorganic compound, or a Bronsted acid comprising a Lewis base and a proton, and reacts with an anion of a metallocene ligand to form a metallocene cation. Can be generated. Specific examples thereof are disclosed in
JP-A-5-253711, JP-A-4-305585, JP-A-5-507756 and JP-A-5-502906 can be used.

In particular, an ionic compound of a tetrakis (pentafluorophenyl) borate anion and a triphenylcarbonium cation or a dialkylanilinium cation is preferred. These ionic compounds can be used in combination with the aforementioned organic aluminum compounds.

As a method for copolymerizing ethylene and an α-olefin with the above-mentioned single-site catalyst, various well-known methods can be employed, such as fluidized-bed gas-phase polymerization in an inert gas or stirring gas-phase polymerization. Polymerization, slurry polymerization in an inert solvent, bulk polymerization using a monomer as a solvent, and the like.

With respect to 100 parts by weight of the ethylene-α-olefin copolymer (A), high-pressure low-density polyethylene, high-density polyethylene, the above-mentioned single-site catalyst were used for the purpose of improving moldability, transparency and gloss. Manufactured in (A)
Ethylene-α excluding ethylene-α-olefin copolymer
-A polyethylene-based polymer such as an olefin copolymer may be added preferably in an amount of 30 parts by weight or less, more preferably 25 parts by weight or less, particularly 20 parts by weight or less.

Examples of the polyethylene polymer include a homopolymer and an ethylene-α-olefin copolymer of ethylene and a small amount of α-olefin. For example, the Phillips method obtained by polymerization using a catalyst such as chromium oxide supported on ethylene and alumina or silica-alumina, the standard method obtained by polymerization using a catalyst such as molybdenum oxide supported on alumina, Examples thereof include polyethylene and an ethylene-α-olefin copolymer obtained by polymerization using a Ziegler catalyst comprising a transition metal compound and an organometallic compound.

As the high-pressure low-density polyethylene, those produced by high-pressure radical polymerization can be used.

As the high-pressure low-density polyethylene,
In addition to the ethylene homopolymer, a copolymer with another monomer such as an ethylene-vinyl acetate copolymer can be used. When using an ethylene-vinyl acetate copolymer, the repeating unit derived from vinyl acetate in the copolymer,
Usually, it is preferred that it is 20 wt% or less.

The above-mentioned (A) the ethylene-α-olefin copolymer, the medical ethylene-α-olefin copolymer composition, or the molded product using this composition may be used according to the intended use.
Higher fatty acids, higher fatty amides such as erucamide, oleic amide, ethylene bisoleic amide, ethylene bis erucamide, lubricants and slip agents such as metal soap and glycerin ester, natural silica, synthetic silica, talc and zeolite , PMMA fine particles, aluminosilicate, anti-blocking agent such as diatomaceous earth, phenol-based, phosphorus-based, antioxidant such as BHT, ultraviolet absorber such as benzophenone, benzotriazole, HALS,
Aluminum hydroxide, magnesium hydroxide, phosphorus-based, halogen-based flame retardants, silica, calcium carbonate, barium sulfate, mica, carbon black and other inorganic and organic fillers, azo-based, phthalocyanine-based, quinacridone-based, iron oxide, A pigment such as ultramarine blue, an antistatic agent, a surfactant and the like can be added.

With respect to 100 parts by weight of the ethylene-α-olefin copolymer (A), 0.05 to 1 part by weight of the antiblocking agent and 0.05 to 0.1 part by weight of the slipping agent.
It is preferable to add 5 parts by weight.

The medical ethylene-α-olefin copolymer composition of the present invention can be prepared by a method such as extrusion molding, T-die molding, inflation molding, blow molding, or injection molding. A molded article such as a medical molded article such as a medical container or an injection cylinder, for example, a medical molded article can be manufactured.

The molded article produced from the medical ethylene-α-olefin copolymer composition of the present invention can be used for treatment, infusion,
When contacting a drug solution for injection, medical use, etc., for replenishment, etc., the elution of fine particles into the drug solution is smaller than that of the composition,
Excellent transparency after sterilization treatment such as heat treatment for 0 minutes, for example, as a fine particle dissolution, preferably 15 or less, more preferably 12 or less, particularly preferably 10 or less, 110 ° C. The total light transmittance after the heat treatment for 40 minutes is preferably 70% or more, more preferably 72% or more, and particularly preferably 74% or more.

The ethylene-α-olefin copolymer composition for medical use of the present invention and its molded product can be used for paper such as kraft paper, metallic thin films such as aluminum foil and copper foil, low-density polyethylene, high-density polyethylene, Medical ethylene of the invention
Except for the α-olefin copolymer composition, polyolefins such as ethylene-α-olefin copolymers, polyvinyl chloride, polyvinylidene chloride, polyamides, polymers such as polysulfone and two or more multilayer films and multilayer containers It can be used as a multilayer molded product.

[0038]

The present invention will be described below with reference to examples and comparative examples, but the present invention is not limited to these examples. The characteristic values were measured as follows.

(A) Method for Measuring Properties of Ethylene-α-Olefin Copolymer [1] Density: 190 according to JIS K7112
A strand obtained at the time of MFR measurement at a load of 2.16 kg at 100 ° C. was heat-treated at 100 ° C. for 1 hour, and a sample cooled slowly to room temperature over 1 hour was measured using a density gradient tube. [2] Melt flow rate (MFR _2.16 ): JIS
In accordance with K7210, 19
It was determined by measuring the weight of the resin extruded in a strand shape for 10 minutes at a load of 2.16 kg at 0 ° C. [3] Melt flow rate ratio (MFR _10.0 / MFR
_2.16 ): 10.0K in the same manner as in the above method [2].
It is a value obtained by dividing the resin weight (MFR _10.0 ) obtained by the g load by the resin weight (MFR _2.16 ) obtained in the above [2].

[4] Molecular weight distribution: The molecular weight distribution (Mw / Mn) of the ethylene-α-olefin copolymer composition was measured by gel permeation chromatography (GPC). The measurement method is shown below. (1) Measuring device: WATERS 150CV was used. (2) Measurement sample: The polymer was dissolved in a solvent (o-dichlorobenzene) at a temperature of 145 ° C and a concentration of 1 mg / ml. (3) Measurement of molecular weight distribution: Measurement sample of (2) above.
4 ml was injected into two GPC columns AT-806MS, and the solvent was o-dichlorobenzene at a temperature of 145 ° C. and 1.0 g.
Performed at a flow rate of ml / min. The measurement by GPC was performed for 35 minutes. The polymer concentration in the solution separated by the GPC column was measured with a differential refractometer (RI). The molecular weight is
It was converted by a polystyrene standard. (4) Data processing: Data processing is performed in VAX-STATI
ON3100 was used. G obtained by the above measurement (3)
When a baseline is drawn on the PC chromatogram, the area is integrated using data processing software attached to the apparatus, and the number average molecular weight (Mn), weight average molecular weight (Mw), Mw / Mn
Is automatically calculated. The GPC chromatogram was measured on the screen of the apparatus at a size of 125 mm per 20 minutes of measurement time on the horizontal axis and 13 mm per 20 with the total integrated elution amount set at 100 on the vertical axis. [5] Swell ratio:
Using Toyo Seiki Capillograph 1C, temperature 190 ° C,
Diameter 2.09mmφ, length 8.03mm (with taper)
Of the molten strand 7 mm below the nozzle when the resin is extruded with the orifice at a speed of 10 mm / min (D
s) was measured with a laser and divided by the orifice diameter (Do) (Ds / Do).

The properties of the ethylene-α-olefin copolymer used are shown in Table 1.

[0042]

[Table 1]

(Examples 1 to 3 and Comparative Examples 1 to 4) Preparation of film from medical ethylene-α-olefin copolymer composition After blending ethylene-α-olefin copolymer composition shown in Table 2, venting Using a single screw extruder with
The mixture was melt-kneaded at a temperature of 0 ° C. to produce pellets comprising the ethylene-α-olefin copolymer composition. Using a water-cooled inflation molding apparatus with a 40 mmφ extruder, the pellets were 250 μm thick at a temperature of 200 ° C.
m of film were produced. The obtained film was evaluated for a molded article of a medical ethylene-α-olefin copolymer, and the results are shown in Table 2.

Evaluation method of molded article of ethylene-α-olefin copolymer for medical use Various evaluations were performed using the above-mentioned film having a thickness of 250 μm. (1) Fine particle dissolving property: A film of 200 cm 2 was cut into small pieces and washed with distilled water. Cleaning film and pure water 200m
was placed in an autoclave and heated at 110 ° C. for 40 minutes. Particles of 2 μm or more contained in pure water in the autoclave after the heat treatment were measured with a Coulter counter. The number of particles contained in 1 ml of pure water was defined as the particle elution property. (2) Total light transmittance (%): The total light transmittance was measured as the transparency evaluation before and after the heat treatment of the film. (3) Film appearance: The appearance of the film was visually evaluated. The evaluation was based on a four-point scale ranging from very good to poor, depending on the number and size of the bumps (gels) in a given area of the film. ◎: very good, ○: good, Δ: slightly bad, ×: bad

[0045]

[Table 2]

[0046]

Industrial Applicability The medical ethylene-α-olefin copolymer composition of the present invention and a molded article using this composition are as follows:
It has good appearance, good transparency after the sterilization process, and small elution of fine particles in the drug solution even when it comes into contact with the drug solution.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08J 5/00 CES C08J 7/00 301 7/00 301 A61J 1/00 331A

Claims (4)

[Claims] 1. A medical treatment comprising 100 parts by weight of an ethylene-α-olefin copolymer produced from a single-site catalyst having the following property (A) and 0.01 to less than 0.3 parts by weight of hydrotalcite. Ethylene-α-olefin copolymer composition for use. (A) Ethylene-α-olefin copolymer: (A-1) Density (d) = 0.880 to 0.960 (g /
^{cm 3) (A-2)} 190 ℃, melt flow rate at 2.16Kg load _{(MFR 2. 16) = 0.1~200 (} g / 1
0 min) (A-3) 190 ℃ , melt flow rate in 10.0Kg load (MFR _{10 .0)} and 190 ° C., 2.16 Kg
Ratio to melt flow rate (MFR _2.16 ) under load (MFR _10.0 ) / (MFR _2.16 ) = 1 to 20 (A-4) Molecular weight distribution (Mw / Mn) = 2.0 to 6.0 2. The medical ethylene-α-olefin copolymer composition according to claim 1, wherein the fine particle dissolution property is 15 or less. 3. The total light transmittance after heating at 110 ° C. for 40 minutes is 70% or more.
3. The medical ethylene-α-olefin copolymer composition according to item 2. 4. The medical ethylene-α according to claim 1, wherein
-A molded article using the olefin copolymer composition.