WO2015053334A1 - ポリエチレン樹脂組成物、それよりなる積層体およびこの積層体を用いた医療容器 - Google Patents
ポリエチレン樹脂組成物、それよりなる積層体およびこの積層体を用いた医療容器 Download PDFInfo
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- WO2015053334A1 WO2015053334A1 PCT/JP2014/076984 JP2014076984W WO2015053334A1 WO 2015053334 A1 WO2015053334 A1 WO 2015053334A1 JP 2014076984 W JP2014076984 W JP 2014076984W WO 2015053334 A1 WO2015053334 A1 WO 2015053334A1
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- density polyethylene
- molecular weight
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- linear low
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Classifications
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- C—CHEMISTRY; METALLURGY
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- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
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- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61J—CONTAINERS SPECIALLY ADAPTED FOR MEDICAL OR PHARMACEUTICAL PURPOSES; DEVICES OR METHODS SPECIALLY ADAPTED FOR BRINGING PHARMACEUTICAL PRODUCTS INTO PARTICULAR PHYSICAL OR ADMINISTERING FORMS; DEVICES FOR ADMINISTERING FOOD OR MEDICINES ORALLY; BABY COMFORTERS; DEVICES FOR RECEIVING SPITTLE
- A61J1/00—Containers specially adapted for medical or pharmaceutical purposes
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- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/40—Applications of laminates for particular packaging purposes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
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- B32B2307/40—Properties of the layers or laminate having particular optical properties
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- B32B2439/00—Containers; Receptacles
- B32B2439/80—Medical packaging
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to a polyethylene resin composition, a laminate comprising the same, and a medical container using the laminate. More specifically, chemicals such as infusion bags and plastic ampoules are less susceptible to container deformation and transparency loss due to sterilization, have excellent barrier properties against the permeation of water vapor, oxygen, etc., and have little elution of fine particles into the chemicals.
- the present invention relates to a polyethylene resin composition suitable for a medical container filled with blood or the like, a laminate comprising the same, and a medical container using the laminate.
- plastic containers that have excellent impact properties, are flexible, and can be easily discharged are used.
- a soft vinyl chloride resin an ethylene-vinyl acetate copolymer resin, a polypropylene resin, and a polyethylene resin such as a high-pressure low-density polyethylene, a linear low-density polyethylene, and a high-density polyethylene are used.
- soft vinyl chloride resin has problems in terms of hygiene, such as the plasticizer eluting into the chemical solution, ethylene-vinyl acetate copolymer resin is inferior in heat resistance, and polypropylene resin is flexible and clean (low particle size) Has become an issue. Also, in the case of polyethylene resins, there is a problem that if the density is lowered in order to satisfy transparency and flexibility, heat resistance, gas barrier properties and the like are lowered, and further cleanliness is deteriorated.
- the object of the present invention is excellent in heat resistance, flexibility, barrier properties and cleanliness (low particle property) which are disadvantages of conventional plastic containers, and does not deform after sterilization treatment at 121 ° C., and has high transparency.
- the present inventors have found that the above problem can be solved by laminating an outer layer, an inner layer and an intermediate layer made of a polyethylene resin composition containing a specific amount of a polyethylene resin having specific physical properties.
- the present invention has been completed.
- High density polyethylene satisfying the following characteristics (a) to (b): 20 to 80% by weight, linear low density polyethylene (B1) satisfying the following characteristics (c) to (d): 0 to 50% by weight and 5 to 40% by weight of an ethylene polymer (C) satisfying the following characteristics (e) to (h) (total of (A), (B1) and (C) is 100% by weight)
- a polyethylene resin composition characterized by the above.
- the density is from 945 to 970 kg / m 3 .
- MFR is 0.1 to 15.0 g / 10 min.
- C The density is 890 to 915 kg / m 3 .
- MFR is 0.1 to 15.0 g / 10 min.
- E The density is from 930 to 960 kg / m 3 .
- F MFR is 0.1 to 15.0 g / 10 min.
- G Two peaks are shown in the molecular weight measurement by gel permeation chromatography, and the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is in the range of 2.0 to 7.0. It is.
- H 0.15 or more long-chain branches per 1000 carbons of the main chain in a fraction having Mn of 100,000 or more when molecular weight fractionation is performed.
- a medical container comprising a container for storing a chemical solution, wherein at least the container is made of the laminate according to any one of [7] to [10].
- the container for storing the chemical solution is formed by forming a laminate formed into a film shape into a bag shape by hot plate molding.
- the container for storing the chemical solution is formed by forming the laminate into a bottle shape by blow molding.
- the blending ratio of the high density polyethylene (A), the linear low density polyethylene (B1), and the ethylene polymer (C) is 20 to 80% by weight, preferably 25 to 75% by weight of the high density polyethylene (A). More preferably 30 to 70% by weight, linear low density polyethylene (B1) is 0 to 50% by weight, preferably 5 to 45% by weight, more preferably 10 to 40% by weight, and the ethylene polymer (C) is 5 to 40% by weight, preferably 10 to 30% by weight.
- the high density polyethylene (A) is less than 20% by weight, the heat resistance is insufficient, and when it exceeds 80% by weight, the transparency is lowered, which is not preferable.
- linear low density polyethylene (B1) exceeds 50 weight%, since heat resistance is insufficient, it is unpreferable.
- the ethylene polymer (C) is less than 5% by weight, the melt tension is insufficient and the molding stability is lowered.
- it exceeds 40% by weight the heat resistance is insufficient and the smoothness of the obtained laminate surface is poor. It is not preferable because it deteriorates.
- the blending ratio of the high-density polyethylene (A), the linear low-density polyethylene (B1), and the ethylene polymer (C) may be the same or different between the outer layer and the inner layer as long as it is within the above range. It doesn't matter.
- the level after sterilization is higher than when the ethylene polymer (C) is not blended. It becomes possible to maintain the transparency of. The reason why such an effect appears is not necessarily clear, but it has been confirmed that the size of spherulites formed during cooling crystallization is significantly reduced by blending the ethylene-based polymer (C). Thus, it is considered that the ethylene polymer (C) has an effect of inhibiting spherulite growth in the molding process and the sterilization process.
- the blending ratio of the high-density polyethylene (A) and the linear low-density polyethylene (B1) used for the intermediate layer is 10 to 40% by weight, preferably 15 to 35% by weight, more preferably 20% for the high-density polyethylene (A).
- linear low density polyethylene (B1) is 60-90 wt%, preferably 65-85 wt%, more preferably 70-80 wt%.
- the high-density polyethylene (A) is less than 10% by weight (that is, when the linear low-density polyethylene (B1) exceeds 90% by weight), the heat resistance is lowered, and the container is sterilized at 121 ° C. This is not preferable because deformation and a decrease in transparency occur.
- the high-density polyethylene (A) exceeds 40% by weight (that is, when the linear low-density polyethylene (B1) is less than 60% by weight), the flexibility and transparency of the obtained laminate are reduced. It is not preferable.
- the linear low density polyethylene satisfying the following characteristics (m) to (n) with respect to 100 parts by weight of the total amount of the high density polyethylene (A) and the linear low density polyethylene (B1) used for the intermediate layer.
- (B2) is blended in the range of 5 to 30 parts by weight, the transparency can be further enhanced while maintaining the heat resistance, which is more preferable.
- (M) The density is 920 to 945 kg / m 3 .
- (N) MFR is 0.1 to 15.0 g / 10 min.
- High density polyethylene (A) is an ethylene homopolymer or a copolymer of ethylene and ⁇ -olefin.
- the high density polyethylene (A) has a melt flow rate (hereinafter referred to as MFR) measured at 190 ° C. and a load of 2.16 kg in accordance with JIS K6922-1 between 0.1 and 15.0 g / 10 min. It is preferably 0.5 to 10.0 g / 10 minutes, more preferably 1.0 to 5.0 g / 10 minutes.
- MFR melt flow rate
- An MFR of less than 0.1 g / 10 minutes is not preferable because the load on the extruder increases during molding and surface roughness occurs during molding.
- MFR exceeds 15.0 g / 10min, since melt tension becomes small and shaping
- High density polyethylene according to the present invention is, JIS density conforming to K6922-1 is 945 ⁇ 970kg / m 3, preferably 950 ⁇ 965kg / m 3. Density is insufficient equal heat resistance deformation of the container caused by the 121 ° C. sterilization If it is less than 945 kg / m 3, if it exceeds 970 kg / m 3, transparency is not preferable because flexibility is degraded.
- the high-density polyethylene (A) according to the present invention can be produced by a production method such as a slurry method, a solution method, or a gas phase method.
- a Ziegler catalyst generally comprising a solid catalyst component containing magnesium and titanium and an organoaluminum compound, an organic transition metal compound containing a cyclopentadienyl derivative, and A metallocene catalyst, a vanadium catalyst, or the like composed of a compound that forms an ionic complex by reacting with an organic metal compound and / or an organometallic compound can be used, and ethylene is homopolymerized or ethylene and ⁇ -olefin are copolymerized with the catalyst. Can be manufactured.
- the high-density polyethylene (A) having the above characteristics is blended with a linear low-density polyethylene (B1) and an ethylene-based polymer (C) described later, thereby improving the transparency of the obtained medical container and sterilizing treatment.
- the high-density polyethylene (A) has the following characteristics (i) to (j), the post-transparency maintenance effect is exhibited, but the medical container of the present invention is clean (low particulate) and after sterilization This is particularly preferable because of further improving the transparency.
- the high density polyethylene (A) having the characteristics (i) to (j) can be produced by using the metallocene catalyst.
- the high density polyethylene (A) according to the present invention may be a commercially available product.
- Nisoron Hard 5700 manufactured by Tosoh Corporation (trade name)
- Nipolon Hard 8500 manufactured by Tosoh Corporation (trade name).
- Tosoh Corporation (trade name) Nipolon Hard 8022.
- the high-density polyethylene (A) according to the present invention can be produced by the following method.
- a cyclopentadienyl derivative can be produced by a method described in Japanese Patent Application Laid-Open No. 2009-275059, Japanese Patent Application Laid-Open No. 2013-81494, etc., using a production method such as a slurry method, a solution method, or a gas phase method.
- the ⁇ -olefin may be generally referred to as an ⁇ -olefin, and ⁇ -olefin having 3 to 12 carbon atoms such as propylene, butene-1, hexene-1, octene-1, 4-methyl-1-pentene, etc. Preferably it is an olefin.
- the copolymer of ethylene and ⁇ -olefin include an ethylene / hexene-1 copolymer, an ethylene / butene-1 copolymer, and an ethylene / octene-1 copolymer.
- Linear low density polyethylene (B1) The linear low density polyethylene (B1) used in the present invention is a copolymer of ethylene and ⁇ -olefin.
- the linear low density polyethylene (B1) has an MFR measured at 190 ° C. under a load of 2.16 kg in accordance with JIS K6922-1, 0.1 to 15.0 g / 10 min, preferably 0.8. It is 5 to 10.0 g / 10 minutes, more preferably 1.0 to 5.0 g / 10 minutes.
- An MFR of less than 0.1 g / 10 minutes is not preferable because the extrusion load during molding increases and surface roughness occurs during molding.
- MFR exceeds 15.0 g / 10min, since melt tension becomes small and shaping
- Linear low density polyethylene according to the present invention (B1) is, JIS density conforming to K6922-1 is 890 ⁇ 915kg / m 3, preferably 895 ⁇ 910kg / m 3. Density heat resistance is insufficient with less than 890 kg / m 3, when it exceeds 915 kg / m 3, transparency is not preferable because flexibility is degraded.
- the linear low density polyethylene (B1) according to the present invention can be produced by a production method such as a high pressure method, a solution method, or a gas phase method.
- a Ziegler catalyst generally comprising a solid catalyst component containing magnesium and titanium and an organoaluminum compound, and an organic transition metal compound containing a cyclopentadienyl derivative And a metallocene catalyst, a vanadium-based catalyst, or the like composed of a compound and / or an organometallic compound that reacts with this to form an ionic complex, and by copolymerizing ethylene and an ⁇ -olefin by the catalyst. It can be manufactured.
- the linear low-density polyethylene (B1) having the above characteristics is blended with the above-described high-density polyethylene (A) and an ethylene polymer (C) described later, thereby improving the transparency of the obtained medical container and
- the linear low density polyethylene (B) has the following properties (k) to (l), although the transparency maintenance effect after sterilization is expressed, the cleanliness (low particle property) of the medical container of the present invention ) And transparency after sterilization is further improved, which is particularly preferable.
- Such a linear low density polyethylene (B1) having the characteristics (k) to (l) can be produced by using the metallocene catalyst.
- the linear low density polyethylene (B1) related to the present invention may be a commercially available product.
- Nisoron-Z HF212R manufactured by Tosoh Corporation (trade name), manufactured by Tosoh Corporation ( (Product name) Nipolon-Z HF210K, Tosoh Corporation (trade name) Nipolon-Z ZF220, and the like.
- the linear low density polyethylene (B1) according to the present invention can be produced by the following method.
- a cyclopentadienyl derivative can be produced by a method described in Japanese Patent Application Laid-Open No. 2009-275059, Japanese Patent Application Laid-Open No. 2013-81494, etc., using a production method such as a high pressure method, a solution method, or a gas phase method. It is possible to use a method of copolymerizing ethylene and an ⁇ -olefin using a metallocene catalyst comprising an organic transition metal compound containing an organic compound and a compound that reacts with the compound to form an ionic complex and / or an organometallic compound.
- the ⁇ -olefin may be generally referred to as an ⁇ -olefin, and ⁇ -olefin having 3 to 12 carbon atoms such as propylene, butene-1, hexene-1, octene-1, 4-methyl-1-pentene, etc. Preferably it is an olefin.
- the copolymer of ethylene and ⁇ -olefin include an ethylene / hexene-1 copolymer, an ethylene / butene-1 copolymer, and an ethylene / octene-1 copolymer.
- Ethylene polymer (C) The ethylene polymer (C) according to the present invention has an MFR measured at 190 ° C.
- a load of 2.16 kg in accordance with JIS K6922-1 0.1 to 15.0 g / 10 min, preferably 0.5 to The amount is 10.0 g / 10 minutes, more preferably 1.0 to 5.0 g / 10 minutes.
- An MFR of less than 0.1 g / 10 minutes is not preferable because the extrusion load during molding increases and surface roughness occurs during molding. Moreover, when MFR exceeds 15.0 g / 10min, since melt tension becomes small and the processing stability at the time of shaping
- the ethylene polymer (C) according to the present invention has a density according to JIS K6922-1 in the range of 930 to 960 kg / m 3 , preferably 935 to 955 kg / m 3 , particularly preferably 940 to 950 kg / m 3 . 3 range.
- the density is less than 930 kg / m 3 , the heat resistance is insufficient, and when it exceeds 960 kg / m 3 , the transparency and flexibility are undesirably lowered.
- the ethylene polymer (C) according to the present invention exhibits two peaks in molecular weight measurement by gel permeation chromatography (hereinafter referred to as GPC).
- GPC gel permeation chromatography
- the peak top molecular weight (Mp) is obtained by dividing the molecular weight distribution curve obtained by GPC measurement into two peaks by the method described later, and evaluating the top molecular weight of the high molecular weight side peak and the low molecular weight side peak. The case of 100,000 or more was assumed to have two Mp. When it was less than 100,000, the top molecular weight of the actually measured molecular weight distribution curve was defined as one Mp.
- the molecular weight distribution curve was divided as follows.
- the standard deviation is 0.30 with respect to LogM of the molecular weight distribution curve in which the weight ratio is plotted against LogM which is the logarithm of molecular weight obtained by GPC measurement, and an arbitrary average value (molecular weight at the peak top position)
- a composite curve is created by adding together two logarithmic distribution curves having) at an arbitrary ratio. Further, the average value and the ratio are obtained so that the deviation sum of squares of the weight ratio with respect to the same molecular weight (M) value of the actually measured molecular weight distribution curve and the composite curve becomes a minimum value.
- the minimum value of the deviation sum of squares was set to 0.5% or less with respect to the deviation sum of squares when the ratios of the respective peaks were all zero.
- Mp molecular weight at the peak top of each logarithmic distribution curve obtained by dividing into two lognormal distribution curves
- the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 2.0 to 7.0, preferably 2.5 to 6. 5, more preferably 3.0 to 6.0.
- Mw / Mn is less than 2.0, not only the extrusion load at the time of molding is large, but also the appearance (surface skin) of the obtained medical container is deteriorated.
- Mw / Mn exceeds 7.0, not only the strength of the obtained medical container is lowered, but also when used as a medical container, there is a possibility that fine particles in the filled chemical solution increase.
- the ethylene-based polymer (C) according to the present invention preferably has a number average molecular weight (Mn) measured by GPC of 15,000 or more, more preferably 15,000 to 100,000, particularly 15,000 to 50,000 is preferred. When Mn is 15,000 or more, the strength of the obtained medical container is increased.
- the number of long-chain branches of the fraction having Mn of 100,000 or more obtained by molecular weight fractionation is 0.15 or more per 1000 carbons of the main chain.
- the number of long-chain branches in the fraction with Mn of 100,000 or more is less than 0.15 per 1000 carbons of the main chain, even if it is used as one component for obtaining the polyethylene resin composition of the present invention, it is remarkably transparent The effect of improving the property and maintaining the transparency after sterilization cannot be obtained.
- the proportion of the fraction having Mn of 100,000 or more obtained by molecular weight fractionation is preferably less than 40% of the entire ethylene polymer (C).
- the proportion of the fraction of Mn obtained by molecular weight fractionation is 100,000 or more is less than 40% of the entire ethylene polymer (C)
- the extrusion load during molding is small, and the appearance of the obtained medical container ( Surface skin) is good.
- the molding stability at the time of producing the laminate is improved and obtained. It has been found that the medical container is excellent in gas barrier properties and cleanness (low particle size) and maintains a high level of transparency even after sterilization at 121 ° C.
- Examples of the ethylene-based polymer (C) related to the present invention include Japanese Unexamined Patent Publication No. 2012-126862, Japanese Unexamined Patent Publication No. 2012-126863, Japanese Unexamined Patent Publication No. 2012-158654, and Japanese Unexamined Patent Publication No. 2012. -158656, Japanese Unexamined Patent Publication No. 2013-28703, and the like.
- As commercial products (trade name) TOSOH-HMS CK37, CK47 (above, manufactured by Tosoh Corporation) and the like can be used.
- Linear low density polyethylene (B2) The linear low density polyethylene (B2) used in the present invention is a copolymer of ethylene and ⁇ -olefin.
- the linear low density polyethylene (B2) according to the present invention has an MFR measured at 190 ° C. under a load of 2.16 kg in accordance with JIS K6922-1, 0.1 to 15.0 g / 10 min, preferably 0.8. It is 5 to 10.0 g / 10 minutes, more preferably 1.0 to 5.0 g / 10 minutes.
- the linear low density polyethylene (B2) according to the present invention has a density according to JIS K6922-1 of 920 to 945 kg / m 3 , preferably 925 to 940 kg / m 3 .
- the linear low density polyethylene (B2) according to the present invention can be produced by a production method such as a high pressure method, a solution method, a gas phase method, etc., for example, a solid catalyst component containing magnesium and titanium and an organic material.
- a production method such as a high pressure method, a solution method, a gas phase method, etc.
- a solid catalyst component containing magnesium and titanium and an organic material for example, a solid catalyst component containing magnesium and titanium and an organic material.
- Ziegler catalyst composed of aluminum compounds, organic transition metal compounds containing cyclopentadienyl derivatives, and compounds that react with this to form ionic complexes and / or metallocene catalysts composed of organometallic compounds, vanadium catalysts, etc. It can be produced by copolymerizing ethylene and ⁇ -olefin.
- the ⁇ -olefin may be generally referred to as an ⁇ -olefin, and ⁇ -olefin having 3 to 12 carbon atoms such as propylene, butene-1, hexene-1, octene-1, 4-methyl-1-pentene, etc. Preferably it is an olefin.
- the copolymer of ethylene and ⁇ -olefin include an ethylene / hexene-1 copolymer, an ethylene / butene-1 copolymer, and an ethylene / octene-1 copolymer.
- the linear low density polyethylene (B2) related to the present invention may be a commercially available product, for example, Tosoh Co., Ltd. (trade name) Nipolon-Z ZF220, Tosoh Corp. (product) Name) Nipolon-Z ZF230, Tosoh Corporation (trade name) Nipolon-L F14, and the like.
- the polyethylene resin composition of the present invention is a conventionally known high-density polyethylene (A), linear low-density polyethylene (B1), (B2), and ethylene polymer (C).
- a method of mixing with a Henschel mixer, V-blender, ribbon blender, tumbler blender or the like, or a mixture obtained by such a method is further melted with a single screw extruder, twin screw extruder, kneader, Banbury mixer, etc. After kneading, it can be obtained by granulating.
- the resin composition used for the production of the outer layer and the inner layer constituting the laminate of the present invention has good molding stability when the MFR is in the range of 1.0 to 5.0 and the density is in the range of 925 to 950 kg / m 3.
- the balance between the flexibility after sterilization at 121 ° C. and the film appearance is particularly excellent, which is more preferable.
- the resin composition used for the production of the intermediate layer constituting the laminate of the present invention has a molding stability when the MFR is in the range of 1.0 to 5.0 and the density is in the range of 910 to 925 kg / m 3. It is more preferable because the balance between flexibility and transparency after sterilization is particularly excellent.
- additives generally used for example, an antioxidant, a neutralizing agent, an antistatic agent, a lubricant, an antiblocking agent, an antifogging, are used as long as the effects of the present invention are not significantly impaired.
- An agent, an organic or inorganic pigment, an ultraviolet absorber, a dispersant and the like can be appropriately blended as necessary.
- the method of blending the above-mentioned additives into the resin composition according to the present invention is not particularly limited. For example, a method of directly adding in the pellet granulation step after polymerization, or a high-concentration master batch in advance. The method of producing and dry blending this at the time of shaping
- the polyethylene resin composition of the present invention includes other thermoplastics such as high-pressure low-density polyethylene, ethylene-propylene copolymer rubber, poly-1-butene and the like within a range that does not impair the effects of the present invention.
- a resin can also be blended and used.
- Laminate The laminate of the present invention has an outer layer, an inner layer, and an intermediate layer disposed between them, and the outer layer and the inner layer satisfy the following characteristics (a) to (b): A) 20 to 80% by weight, linear low density polyethylene (B1) satisfying the following characteristics (c) to (d) 0 to 50% by weight and ethylene-based weight satisfying the following characteristics (e) to (h) A resin composition containing 5 to 40% by weight of the combined (C) (the total of (A), (B1) and (C) is 100% by weight), and the intermediate layer has at least the following characteristics (a) to (b): High density polyethylene (A) satisfying 10 to 40% by weight, linear low density polyethylene (B1) satisfying the following characteristics (c) to (d): 60 to 90% by weight (total of (A) and (B1) Is 100% by weight).
- MFR is 0.1 to 15.0 g / 10 min.
- the laminated body of the present invention is not particularly limited as long as it has an outer layer, an intermediate layer, and an inner layer (the inner layer is a heat seal layer) in this order.
- the number of layers is most preferably the three layers consisting of the outer layer / intermediate layer / inner layer, but is not limited to this, and the outer layer / intermediate layer / center in which the outer layer / intermediate layer / inner layer further comprises a layer.
- Other layers can be appropriately provided as necessary between the layer configuration of layer / intermediate layer / inner layer, or between the outer layer and the intermediate layer, or between the intermediate layer and the inner layer. Examples of such other layers include an adhesive layer, a gas barrier layer, and an ultraviolet absorbing layer.
- a six-layer structure of outer layer / adhesive layer / gas barrier layer / adhesive layer / intermediate layer / inner layer may be employed.
- a new layer can be provided further outside the outer layer.
- examples of the adhesive constituting the adhesive layer include polyurethane-based adhesives, vinyl acetate adhesives, hot-melt adhesives, or adhesive resins such as maleic anhydride-modified polyolefin and ionomer resins.
- adhesive resins such as maleic anhydride-modified polyolefin and ionomer resins.
- the total thickness of the laminate in the present invention is not particularly limited and can be appropriately determined as necessary, but is preferably 0.01 to 1 mm, more preferably 0.1 to 0.5 mm.
- the thickness ratio of each layer is not particularly limited, but the outer layer and inner layer whose density has been increased in order to prevent deformation and fusion due to sterilization, etc. have been reduced, and the thickness of the intermediate layer which has been reduced in density has been increased in order to increase transparency. This is preferable because the balance between transparency and heat resistance is improved.
- the laminate of the present invention is used by replacing one or two of the outer layer, intermediate layer and inner layer with another resin such as an ethylene-vinyl acetate copolymer resin or a polypropylene resin, depending on the purpose. It is also possible.
- the polypropylene resin has sterilization heat resistance at 121 ° C. which is one of the objects of the present invention, it can be used as a medical container that requires sterilization treatment.
- Polypropylene resins generally used for medical container materials include polypropylene homopolymers, propylene- ⁇ -olefin random copolymers, propylene- ⁇ -olefin block copolymers, and mixtures thereof.
- thermoplastic elastomer examples include ethylene- ⁇ -olefin copolymer elastomers such as ethylene-propylene copolymer and ethylene-butene 1 copolymer, and styrene thermoplastic elastomers such as SEBS, SBS, and SEPS.
- the method for producing the laminate of the present invention is not particularly limited, and examples thereof include a method for forming a multilayer film or sheet by a water-cooled or air-cooled coextrusion multilayer inflation method, a coextrusion multilayer T-die method, a dry lamination method, an extrusion lamination method, and the like. It is done.
- the water-cooled coextrusion multilayer inflation method or the coextrusion multilayer T-die method is preferably used.
- the water-cooled coextrusion multilayer inflation method there are many advantages in terms of transparency, hygiene, and the like.
- the medical container of the present invention is a medical container provided with a storage portion for storing a chemical solution, and at least the storage portion is made of the laminate.
- the laminate is formed into a film by a water-cooled or air-cooled co-extrusion multilayer inflation method, a co-extrusion multilayer T-die method, a dry lamination method, an extrusion lamination method, etc.
- the bag-shaped accommodation part can be formed by heat-sealing the peripheral part.
- the obtained film is overlap
- the port portion that serves as the chemical liquid inlet may be formed by heat sealing at the same time as the housing portion is formed, or the housing portion and the port portion may be formed in separate steps.
- the laminated body can be formed into a bottle shape by a multilayer blow molding method or the like to form an accommodating portion.
- the formation of the port part includes a method of using a mold for integral molding with the accommodating part, a method of heat-sealing the port part to the accommodating part, a method of integrating the accommodating part at the same time by insert blow molding, and the like. It is done.
- the polyethylene medical container of the present invention can be used for all medical purposes, for example, blood bags, platelet storage bags, infusion (medical solution) bags, medical multi-chamber containers, artificial dialysis bags, eye drops containers, injections.
- Examples include liquid ampules.
- the laminate of the present invention is excellent in transparency, flexibility, barrier properties and cleanliness (low particle size), and can maintain transparency even after sterilization treatment at 121 ° C., and therefore requires high transparency.
- Weight average molecular weight (Mw), number average molecular weight (Mn), ratio of weight average molecular weight to number average molecular weight (Mw / Mn) and peak top molecular weight (Mp) were measured by GPC.
- the column temperature was set to 140 ° C. using a GPC device (trade name: HLC-8121GPC / HT, manufactured by Tosoh Corporation) and a column (trade name: TSKgel GMHhr-H (20) HT, manufactured by Tosoh Corporation).
- the measurement was performed using 1,2,4-trichlorobenzene as the eluent.
- a measurement sample was prepared at a concentration of 1.0 mg / ml, and 0.3 ml was injected and measured.
- the calibration curve of molecular weight was calibrated using a polystyrene sample having a known molecular weight.
- Mw and Mn were calculated
- ⁇ Molecular weight fractionation> For molecular weight fractionation, a glass bead packed column (diameter: 21 mm, length: 60 cm) is used as the column, the column temperature is set to 130 ° C., and 1 g of sample dissolved in 30 mL of xylene is injected. Next, distillate is removed by using a xylene / 2-ethoxyethanol ratio of 5/5 as a developing solvent. Thereafter, using xylene as a developing solvent, the components remaining in the column are distilled off to obtain a polymer solution. A component having Mn of 100,000 or more was recovered by adding 5-fold amount of methanol to the obtained polymer solution to precipitate the polymer, filtering and drying.
- ⁇ Long chain branching> The number of long chain branches was determined by 13C-NMR using a JNM-GSX400 type nuclear magnetic resonance apparatus manufactured by JEOL Ltd.
- the solvent is benzene-d6 / orthodichlorobenzene (volume ratio 30/70).
- the number per 1,000 main chain methylene carbons (chemical shift: 30 ppm) was determined from the average value of the peaks of ⁇ -carbon (34.6 ppm) and ⁇ -carbon (27.3 ppm).
- n-heptane ⁇ Extracted amount of n-heptane> About 10 g of a 200 mesh pass crushed sample is precisely weighed, 400 ml of n-heptane is added, extraction is performed at 50 ° C. for 2 hours, the solvent is evaporated from the extract, and the weight of the extract obtained by drying and solidifying is measured. It was calculated by determining the percentage with respect to the initial weight.
- ⁇ Density> The density was measured by a density gradient tube method in accordance with JIS K6922-1.
- ⁇ MFR> MFR (melt flow rate) was measured according to JIS K6922-1.
- the sample for melt tension measurement was prepared by adding a heat-resistant stabilizer (Ciba Specialty Chemicals, Irganox 1010TM; 1,500 ppm, Irgafos 168TM; 1,500 ppm) to an internal mixer (Toyo Seiki Seisakusho, The product kneaded for 30 minutes at 190 ° C. and 30 rpm in a nitrogen stream was used.
- a heat-resistant stabilizer Ciba Specialty Chemicals, Irganox 1010TM; 1,500 ppm, Irgafos 168TM; 1,500 ppm
- a capillary viscometer (Toyo Seiki Seisakusho, trade name Capillograph) with a barrel diameter of 9.55 mm is attached with a die with a length of 8 mm and a diameter of 2.095 mm so that the inflow angle is 90 °. It was measured.
- the temperature was set to 160 ° C.
- the piston lowering speed was set to 10 mm / min
- the stretch ratio was set to 47
- the load (mN) required for take-up was the melt tension.
- the load (mN) required for taking-up at the highest draw ratio that did not break was taken as the melt tension.
- the reaction solution was cooled to 45 ° C. and allowed to stand for 2 hours, and then the supernatant was removed by a gradient method.
- 1.78 kg (0.09 mol) of a 1% by weight hexane solution of triisobutylaluminum was added and reacted at 45 ° C. for 30 minutes.
- the supernatant was removed by a gradient method, 0.45 kg (0.45 mol) of a 20 wt% solution of hexane in triisobutylaluminum was added, and the whole amount was re-diluted with hexane.
- (A) -2 Preparation of modified clay
- a modified clay compound was prepared in the same manner as in (A) -1.
- [Preparation of polymerization catalyst] A polymerization catalyst was prepared in the same manner as (A) -1.
- [Production of (A) -2] Polymerization obtained in the section of “Preparation of polymerization catalyst” in a polymerization vessel having an internal volume of 300 L, hexane 135 kg / hour, ethylene 20.0 kg / hour, butene-1 0.4 kg / hour, hydrogen 8 NL / hour The catalyst was fed continuously. Further, the co-catalyst was continuously fed so that the concentration of triisobutylaluminum in the liquid was 0.93 mmol / kg hexane.
- the polymerization temperature was controlled at 85 ° C.
- Table 1 shows the results of the basic characteristic evaluation of (A) -2.
- (B1) -2 Preparation of modified clay
- a modified clay compound was prepared in the same manner as (B1) -1.
- [Preparation of polymerization catalyst] A polymerization catalyst was prepared in the same manner as (B1) -1.
- [Production of (B1) -2] Using a tank reactor equipped for high-temperature and high-pressure polymerization, ethylene and 1-hexene were continuously injected into the reactor so that the total pressure was 90 MPa, the 1-hexene concentration was 18 mol%, and the hydrogen concentration was 5 mol%. Was set to be.
- the reactor was stirred at 1,500 rpm, and the polymerization catalyst obtained as described above was continuously supplied from the supply port of the reactor, and the polymerization reaction was carried out while maintaining the average temperature at 200 ° C.
- Table 2 shows the basic characteristic evaluation results of (B1) -2.
- (B1) -3 Preparation of modified clay
- a modified clay compound was prepared in the same manner as (B1) -1.
- [Preparation of polymerization catalyst] A polymerization catalyst was prepared in the same manner as (B1) -1.
- [Production of (B1) -3] Using a tank reactor equipped for high-temperature and high-pressure polymerization, ethylene and 1-hexene were continuously injected into the reactor so that the total pressure was 90 MPa, the 1-hexene concentration was 20 mol%, and the hydrogen concentration was 15 mol%. Was set to be.
- the reactor was stirred at 1,500 rpm, and the polymerization catalyst obtained as described above was continuously supplied from the supply port of the reactor, and the polymerization reaction was carried out while maintaining the average temperature at 200 ° C.
- Table 2 shows the basic characteristic evaluation results of (B1) -3.
- (B1) -4 Preparation of modified clay] A modified clay compound was prepared in the same manner as (B1) -1. [Preparation of polymerization catalyst] A polymerization catalyst was prepared in the same manner as (B1) -1. [Production of (B1) -4] Using a tank reactor equipped for high-temperature and high-pressure polymerization, ethylene and 1-hexene were continuously injected into the reactor so that the total pressure was 90 MPa, the 1-hexene concentration was 23 mol%, and the hydrogen concentration was 1 mol%. Was set to be.
- the reactor was stirred at 1,500 rpm, and the polymerization catalyst obtained as described above was continuously supplied from the supply port of the reactor, and the polymerization reaction was carried out while maintaining the average temperature at 200 ° C.
- Table 2 shows the basic characteristic evaluation results of (B1) -4.
- (B2) -1 Preparation of modified clay
- a modified clay compound was prepared in the same manner as (B1) -1.
- [Preparation of polymerization catalyst] To a 20 L stainless steel container under a nitrogen atmosphere, add 2.5 L of heptane, a heptane solution of triethylaluminum (diluted 20 wt%), 4.5 mol (3.6 L) per aluminum atom, and 300 g of the modified clay compound obtained above. Stir for 1 hour. Diphenylmethylene (cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride was added thereto at 10 mmol per zirconium atom and stirred for 12 hours.
- Diphenylmethylene (cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride was added thereto at 10 mmol per zirconium atom and stirred for 12 hours
- a catalyst was prepared by adding 8.7 L of an aliphatic saturated hydrocarbon solvent (trade name IP Solvent 2835, manufactured by Idemitsu Petrochemical Co., Ltd.) to the obtained suspension system. (Zirconium concentration 0.67 mmol / L).
- IP Solvent 2835 an aliphatic saturated hydrocarbon solvent
- (B2) -1) Using a tank reactor equipped for high-temperature and high-pressure polymerization, ethylene and 1-hexene were continuously injected into the reactor so that the total pressure was 90 MPa, the 1-hexene concentration was 20 mol%, and the hydrogen concentration was 4 mol%. Was set to be.
- the reactor was stirred at 1,500 rpm, the polymerization catalyst obtained by the above was continuously supplied from the supply port of the reactor, and average temperature was maintained at 200 degreeC, and the polymerization reaction was performed.
- Table 2 shows the basic characteristic evaluation results of (B2) -1.
- (B2) -2 Preparation of modified clay
- a modified clay compound was prepared in the same manner as (B1) -1.
- [Preparation of polymerization catalyst] A polymerization catalyst was prepared in the same manner as (B2) -1.
- the reactor was stirred at 1,500 rpm, the polymerization catalyst obtained by the above was continuously supplied from the supply port of the reactor, and average temperature was maintained at 200 degreeC, and the polymerization reaction was performed.
- Table 2 shows the basic characteristic evaluation results of (B2) -2.
- (B2) -3 A blend obtained by blending the linear low density polyethylene (B2) -1 and (B2) -2 at 50/50 (parts by weight) was designated as (B2) -3.
- a melt kneaded product obtained by kneading (B2) -3 with an internal mixer (trade name: Labo Plast Mill, manufactured by Toyo Seiki Seisakusho, Ltd.) at 170 ° C. for 15 minutes at a rotation speed of 30 rpm is MFR 3.
- the density was 1 g / 10 min and the density was 926 kg / m 3 .
- Table 2 shows the results of evaluating the basic characteristics of the melt-kneaded product.
- Ethylene polymer (C) -1 [Preparation of modified clay] Into a 1 L flask was placed 300 mL of industrial alcohol (Japan Alcohol Sales (trade name) Echinen F-3) and 300 mL of distilled water, 17.5 g of concentrated hydrochloric acid and dimethylbehenylamine (Lion Corporation (trade name) Armin DM22D). ) 49.4 g (140 mmol) was added and heated to 45 ° C. to disperse 100 g of synthetic hectorite (Rockwood Additives (trade name) Laponite RDS) and then heated to 60 ° C. to maintain the temperature. The mixture was stirred for 1 hour.
- industrial alcohol Japanese Alcohol Sales (trade name) Echinen F-3)
- 17.5 g of concentrated hydrochloric acid and dimethylbehenylamine Lion Corporation (trade name) Armin DM22D).
- 49.4 g 140 mmol was added and heated to 45 ° C. to disperse 100 g
- the slurry was separated by filtration, washed twice with 600 mL of water at 60 ° C., and dried in an oven at 85 ° C. for 12 hours to obtain 132 g of organically modified clay.
- This organically modified clay was crushed by a jet mill to have a median diameter of 15 ⁇ m.
- the obtained polymer had an MFR of 1.6 g / 10 min and a density of 930 kg / m 3 .
- the number average molecular weight was 17,600, the weight average molecular weight was 86,700, and peaks were observed at the molecular weights of 30,500 and 155,300.
- (C) -2 Preparation of modified clay
- industrial alcohol trade name: Echinen F-3, manufactured by Nippon Alcohol Sales Co., Ltd.
- 300 mL of distilled water 18.8 g of concentrated hydrochloric acid and dimethylhexacosylamine (Me 2 N (C 26 H 53 ) 49.1 g (120 mmol) was added and heated to 45 ° C. to disperse 100 g of synthetic hectorite (Rockwood Additives (trade name) Laponite RDS) and then heated to 60 ° C. The mixture was stirred for 1 hour while maintaining the temperature.
- synthetic hectorite Rockwood Additives (trade name) Laponite RDS
- the slurry was filtered, washed twice with 600 mL of water at 60 ° C., and dried in an oven at 85 ° C. for 12 hours to obtain 140 g of organically modified clay.
- This organically modified clay was crushed by a jet mill to have a median diameter of 14 ⁇ m.
- the obtained polymer had an MFR of 4.0 g / 10 min and a density of 941 kg / m 3 .
- the number average molecular weight was 21,200, the weight average molecular weight was 74,000, and peaks were observed at the molecular weights 41,500 and 217,100.
- the slurry was filtered, washed twice with 600 mL of water at 60 ° C., and dried in an oven at 85 ° C. for 12 hours to obtain 122 g of organically modified clay.
- This organically modified clay was crushed by a jet mill to have a median diameter of 15 ⁇ m.
- the obtained polymer had an MFR of 11.5 g / 10 min and a density of 954 kg / m 3 .
- the number average molecular weight was 16,200, the weight average molecular weight was 58,400, and peaks were observed at molecular weights of 28,200 and 181,000.
- This slurry was filtered, washed twice with 600 mL of water at 60 ° C., and dried in an oven at 85 ° C. for 12 hours to obtain 145 g of organically modified clay.
- This organically modified clay was crushed by a jet mill to have a median diameter of 15 ⁇ m.
- the obtained polymer had an MFR of 0.8 g / 10 min and a density of 928 kg / m 3 .
- the number average molecular weight was 17,900, the weight average molecular weight was 99,300, and peaks were observed at molecular weights of 28,100 and 229,100.
- the slurry was filtered, washed twice with 600 mL of water at 60 ° C., and dried in an oven at 85 ° C. for 12 hours to obtain 122 g of organically modified clay.
- This organically modified clay was crushed by a jet mill to have a median diameter of 15 ⁇ m.
- the obtained polymer had an MFR of 0.08 g / 10 min and a density of 926 kg / m 3 .
- the number average molecular weight was 21,900, the weight average molecular weight was 127,000, and peaks were observed at molecular weights of 31,300 and 247,800.
- diphenylmethylene (1-cyclopentadienyl) (2,7-di-tert-butyl-9-fluorenyl) zirconium dichloride 0.1165 g in hexane 10 mL suspension in 20% triisobutylaluminum hexane solution (0 .71M)
- the solution prepared by adding 5 ml was added and stirred at room temperature for 6 hours.
- the supernatant was removed by standing, and after washing twice with 200 mL of hexane, 200 mL of hexane was added to obtain a catalyst suspension (solid weight: 12.0% by weight).
- the number average molecular weight was 9,100, the weight average molecular weight was 77,100, and peaks were observed at molecular weights of 10,400 and 168,400.
- the number of long chain branches contained in the fraction of Mn 100,000 or more when molecular weight fractionation was 0.24 per 1000 carbons of the main chain. Further, the fraction of Mn of 100,000 or more when molecular weight fractionation was 15.7% by weight of the total polymer.
- the melt tension was 210 mN. The evaluation results are shown in Table 3.
- Laminate and sealed container The laminates and medical containers used in Examples and Comparative Examples were produced by the following method and sterilized.
- ⁇ Manufacture of laminates and medical containers> Using a three-layer water-cooled inflation molding machine (manufactured by Placo), a three-layer film having a film width of 135 mm and a film thickness of 250 ⁇ m was formed at a cylinder temperature of 180 ° C., a water bath temperature of 15 ° C., and a take-up speed of 4 m / min. The thickness of each layer was outer layer / intermediate layer / inner layer 20 ⁇ m / 210 ⁇ m / 20 ⁇ m.
- ⁇ Sterilization treatment> The medical container was sterilized at a temperature of 121 ° C. for 20 minutes using a steam sterilizer (manufactured by Nisaka Manufacturing Co., Ltd.). Various properties of the laminates and medical containers used in Examples and Comparative Examples were evaluated by the following methods.
- ⁇ Transparency> A test piece having a width of 10 mm and a length of 50 mm was cut out from the three-layer film and the medical container after sterilization, and the wavelength was measured in pure water using an ultraviolet-visible spectrophotometer (Model V-530 manufactured by JASCO Corporation). The light transmittance at 450 nm was measured. A case where a light transmittance of 70% or more was maintained after sterilization was regarded as a guideline for a medical container having good transparency.
- Example 1 Using the resin compositions shown in Table 4 and Table 5, a three-layer film was formed by a water-cooled inflation molding machine, and the molding stability, surface smoothness and transparency of the film were evaluated. Next, the obtained film is heat-sealed to produce a medical container filled with ultrapure water, and autoclaved at 121 ° C., and the sterilized film appearance, transparency, flexibility, moisture permeability and cleanness Evaluated. The results are shown in Table 6.
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Abstract
Description
[1]下記特性(a)~(b)を満足する高密度ポリエチレン(A)20~80重量%、下記特性(c)~(d)を満足する直鎖状低密度ポリエチレン(B1)0~50重量%および下記特性(e)~(h)を満足するエチレン系重合体(C)5~40重量%((A)、(B1)及び(C)の合計は100重量%)を含むことを特徴とするポリエチレン樹脂組成物。
(a)密度が945~970kg/m3である。
(b)MFRが0.1~15.0g/10分である。
(c)密度が890~915kg/m3である。
(d)MFRが0.1~15.0g/10分である。
(e)密度が930~960kg/m3である。
(f)MFRが0.1~15.0g/10分である。
(g)ゲル・パーミエーション・クロマトグラフィーによる分子量測定において2つのピークを示し、重量平均分子量(Mw)と数平均分子量(Mn)の比(Mw/Mn)が2.0~7.0の範囲である。
(h)分子量分別した際のMnが10万以上のフラクション中に長鎖分岐を主鎖1000炭素数あたり0.15個以上有する。
[2]高密度ポリエチレン(A)が、前記特性(a)~(b)に加えて下記特性(i)~(j)を満足することを特徴とする上記[1]に記載のポリエチレン樹脂組成物。
(i)ゲル・パーミエーション・クロマトグラフィーにより求められる重量平均分子量(Mw)と数平均分子量(Mn)の比(Mw/Mn)が3.0以下である。
(j)日本薬局方に規定の強熱残分試験法による残分が0.02重量%以下である。
[3]直鎖状低密度ポリエチレン(B1)が、前記特性(c)~(d)に加えて下記特性(k)~(l)を満足することを特徴とする上記[1]または[2]に記載のポリエチレン樹脂組成物。
(k)ゲル・パーミエーション・クロマトグラフィーにより求められる重量平均分子量(Mw)と数平均分子量(Mn)の比(Mw/Mn)が3.0以下である。
(l)50℃におけるn-ヘプタン抽出量が1.5重量%以下である。
[4]エチレン系重合体(C)のMw/Mnが3.0~6.0の範囲であり、Mnが15,000以上であることを特徴とする上記[1]~[3]のいずれかに記載のポリエチレン樹脂組成物。
[5]エチレン系重合体(C)の分子量分別した際のMnが10万以上である成分の割合がエチレン系重合体(C)全体の40%未満であることを特徴とする上記[1]~[4]のいずれかに記載のポリエチレン樹脂組成物。
[6]高密度ポリエチレン(A)20~70重量%、直鎖状低密度ポリエチレン(B1)10~50重量%およびエチレン系重合体(C)5~40重量%であることを特徴とする上記[1]~[5]のいずれかに記載のポリエチレン樹脂組成物。
[7]外層と内層とそれらの間に配置された中間層とを有する積層体であって、外層および内層が上記[1]~[6]のいずれかに記載のポリエチレン樹脂組成物からなり、中間層が少なくとも前記特性(a)~(b)を満足する高密度ポリエチレン(A)10~40重量%、前記特性(c)~(d)を満足する直鎖状低密度ポリエチレン(B1)60~90重量%((A)及び(B1)の合計は100重量%)を含む樹脂組成物からなることを特徴とする積層体。
[8]中間層に用いる高密度ポリエチレン(A)が、前記特性(a)、(b)、(i)および(j)を満足することを特徴とする上記[7]に記載の積層体。
[9]中間層に用いる直鎖状低密度ポリエチレン(B1)が、前記特性(c)、(d)、(k)および(l)を満足することを特徴とする上記[7]に記載の積層体。
[10]中間層が、前記高密度ポリエチレン(A)と直鎖状低密度ポリエチレン(B1)の合計量100重量部に対して、下記特性(m)~(n)を満足する直鎖状低密度ポリエチレン(B2)5~30重量部を含む樹脂組成物からなることを特徴とする上記[7]~[9]のいずれかに記載の積層体。
(m)密度が920~945kg/m3である。
(n)MFRが0.1~15.0g/10分である。
[11]薬液を収容する収容部を備えた医療容器であって、少なくとも前記収容部は、上記[7]~[10]のいずれかに記載の積層体からなることを特徴とする医療容器。
[12]薬液を収容する収容部が、フィルム状に成形した積層体を熱板成形により袋状に成形したものであることを特徴とする上記[11]に記載の医療容器。
[13]薬液を収容する収容部が、ブロー成形により、積層体をボトル状に成形したものであることを特徴とする上記[11]に記載の医療容器。
[14]121℃での滅菌処理後も容器の変形がなく、かつ純水中、波長450nmで測定した光線透過率が70%以上となることを特徴とする上記[11]~[13]のいずれかに記載の医療容器。
(m)密度が920~945kg/m3である。
(n)MFRが0.1~15.0g/10分である。
[1]高密度ポリエチレン(A)
本発明に用いる高密度ポリエチレン(A)は、エチレン単独重合体、またはエチレンとα-オレフィンの共重合体である。
(i)ゲル・パーミエーション・クロマトグラフィーにより求められる重量平均分子量(Mw)と数平均分子量(Mn)の比(Mw/Mn)が3.0以下。
(j)日本薬局方に規定の強熱残分試験法による残分が0.02重量%以下。
[2]直鎖状低密度ポリエチレン(B1)
本発明に用いる直鎖状低密度ポリエチレン(B1)は、エチレンとα-オレフィンの共重合体である。
(k)ゲル・パーミエーション・クロマトグラフィーにより求められる重量平均分子量(Mw)と数平均分子量(Mn)の比(Mw/Mn)が3.0以下。
(l)50℃におけるn-ヘプタン抽出量が1.5wt%以下。
[3]エチレン系重合体(C)
本発明に関わるエチレン系重合体(C)は、JIS K6922-1に準拠し、190℃、荷重2.16kgで測定したMFRが0.1~15.0g/10分、好ましくは0.5~10.0g/10分、より好ましくは1.0~5.0g/10分である。MFRが0.1g/10分未満だと、成形加工時の押出負荷が大きくなると共に、成形時に表面荒れが発生するため好ましくない。また、MFRが15.0g/10分を超える場合、溶融張力が小さくなり、成形時の加工安定性が低下するため好ましくない。
い。
Mw/Mnが7.0を超えると得られた医療容器の強度が低下するばかりか、医療容器として使用した際に、充填した薬液中の微粒子が増加する恐れがある。
[4]直鎖状低密度ポリエチレン(B2)
本発明に用いる直鎖状低密度ポリエチレン(B2)は、エチレンとα-オレフィンの共重合体である。
[5]ポリエチレン樹脂組成物
本発明のポリエチレン樹脂組成物は、前述の高密度ポリエチレン(A)、直鎖状低密度ポリエチレン(B1)、(B2)およびエチレン系重合体(C)を、従来公知の方法、例えばヘンシェルミキサー、V-ブレンダー、リボンブレンダー、タンブラーブレンダー等で混合する方法、あるいはこのような方法で得られた混合物をさらに一軸押出機、二軸押出機、ニーダー、バンバリーミキサー等で溶融混練した後、造粒することによって得ることができる。
[6]積層体
本発明の積層体は、外層と内層とそれらの間に配置された中間層とを有し、外層および内層が下記特性(a)~(b)を満足する高密度ポリエチレン(A)20~80重量%、下記特性(c)~(d)を満足する直鎖状低密度ポリエチレン(B1)0~50重量%および下記特性(e)~(h)を満足するエチレン系重合体(C)5~40重量%((A)、(B1)及び(C)の合計は100重量%)を含む樹脂組成物からなり、中間層が少なくとも下記特性(a)~(b)を満足する高密度ポリエチレン(A)10~40重量%、下記特性(c)~(d)を満足する直鎖状低密度ポリエチレン(B1)60~90重量%((A)及び(B1)の合計は100重量%)を含む樹脂組成物からなるものである。
(a)密度が945~970kg/m3である。
(b)MFRが0.1~15.0g/10分である。
(c)密度が890~915kg/m3である。
(d)MFRが0.1~15.0g/10分である。
(e)密度が930~960kg/m3である。
(f)MFRが0.1~15.0g/10分である。
(g)ゲル・パーミエーション・クロマトグラフィーによる分子量測定において2つのピークを示し、重量平均分子量(Mw)と数平均分子量(Mn)の比(Mw/Mn)が2.0~7.0の範囲である。
(h)分子量分別した際のMnが10万以上のフラクション中に長鎖分岐を主鎖1000炭素数あたり0.15個以上有する。
[7]医療容器
本発明の医療容器は、薬液を収容する収容部を備えた医療容器であって、少なくとも収容部が前記積層体からなるものである。前記積層体を、水冷式または空冷式共押出多層インフレーション法、共押出多層Tダイ法、ドライラミネーション法、押出ラミネーション法等によりフィルム状に成形した場合は、得られたフィルムを2枚重ね合わせて、周辺部をヒートシールすることで、袋状の収容部を成形することができる。また、得られたフィルムを真空成形、圧空成形などの熱板成形により、収容部となる凹部を成形した後、凹部同士が対向するように重ね合わせて、周辺部をヒートシールすることで収容部を成形することもできる。この際、薬液の注出入口となるポート部は、前記収容部の成形時に同時にヒートシールして形成させてもよいし、収容部の形成とポート部の形成を別工程で行なうことも可能である。前記積層体を、多層ブロー成形法等によりボトル状に成形して、収容部を形成させることも可能である。多層ブロー成形では、積層体からなるパリソンを押出し、金型でパリソンを挟み込んだ後、パリソン中に清浄エアーを吹き込むことで収容部を形成させることができる。また、ポート部の形成は、収容部との一体成形用金型を使用する方法、ポート部を収容部にヒートシールする方法、インサートブロー成形により収容部の成形と同時に一体化する方法等が挙げられる。
A.樹脂
実施例、比較例に用いた樹脂の諸性質は下記の方法により評価した。
重量平均分子量(Mw)、数平均分子量(Mn)、重量平均分子量と数平均分子量の比(Mw/Mn)およびピークトップ分子量(Mp)は、GPCによって測定した。GPC装置(東ソー(株)製(商品名)HLC-8121GPC/HT)およびカラム(東ソー(株)製(商品名)TSKgel GMHhr-H(20)HT)を用い、カラム温度を140℃に設定し、溶離液として1,2,4-トリクロロベンゼンを用いて測定した。測定試料は1.0mg/mlの濃度で調製し、0.3ml注入して測定した。分子量の検量線は、分子量既知のポリスチレン試料を用いて校正した。なお、MwおよびMnは直鎖状ポリエチレン換算の値として求めた。
分子量分別は、カラムとしてガラスビーズ充填カラム(直径:21mm、長さ:60cm)を用い、カラム温度を130℃に設定して、サンプル1gをキシレン30mLに溶解させたものを注入する。次に、キシレン/2-エトキシエタノールの比率が5/5のものを展開溶媒として用い、留出物を除去する。その後、キシレンを展開溶媒として用い、カラム中に残った成分を留出させ、ポリマー溶液を得る。得られたポリマー溶液に5倍量のメタノールを添加しポリマー分を沈殿させ、ろ過および乾燥することにより、Mnが10万以上である成分を回収した。
長鎖分岐数は、日本電子(株)製JNM-GSX400型核磁気共鳴装置を用いて、13C-NMRによってヘキシル基以上の分岐数を測定した。溶媒はベンゼン-d6/オルトジクロロベンゼン(体積比30/70)である。主鎖メチレン炭素(化学シフト:30ppm)1,000個当たりの個数として、α-炭素(34.6ppm)およびβ-炭素(27.3ppm)のピークの平均値から求めた。
日本薬局方に規定の強熱残分試験法に準拠し、試料50gを精秤した後、白金皿に入れてガスバーナーにより燃焼させ、さらに電気炉で650℃、1時間の条件で完全灰化させたときの残留物の重量を秤量し、初期重量に対する百分率を求めることによって算出した。
200メッシュパスの粉砕試料約10gを精秤し、400mlのn-ヘプタンを加えて50℃で2時間抽出を行い、抽出液から溶媒を蒸発させて、乾燥固化させて得た抽出物の重量の初期重量に対する百分率を求めることによって算出した。
密度は、JIS K6922-1に準拠して密度勾配管法で測定した。
MFR(メルトフローレート)は、JIS K6922-1に準拠して測定を行った。
溶融張力の測定用試料は、サンプルに耐熱安定剤(チバスペシャリティケミカルズ社製、イルガノックス1010TM;1,500ppm、イルガフォス168TM;1,500ppm)を添加したものを、インターナルミキサー(東洋精機製作所製、商品名ラボプラストミル)を用いて、窒素気流下、190℃、回転数30rpmで30分間混練したものを用いた。
(1)高密度ポリエチレン
(A)-1
[変性粘土の調製]
脱イオン水4.8L、エタノール3.2Lの混合溶媒に、ジメチルベヘニルアミン;(C22H45)(CH3)2N 354gと37%塩酸83.3mLを加え、ジメチルベヘニルアミン塩酸塩溶液を調製した。この溶液に合成ヘクトライト1,000gを加え終夜撹拌し、得られた反応液をろ過した後、固体分を水で十分洗浄した。固体分を乾燥させたところ、1,180gの有機変性粘土化合物を得た。赤外線水分計で測定した含液量は0.8%であった。次に、この有機変性粘土化合物を粉砕し、平均粒径を6.0μmに調製した。
[重合触媒の調製]
5Lのフラスコに、[変性粘土化合物の調製]の項で得た有機変性粘土化合物450g、ヘキサン1.4kgを加え、その後トリイソブチルアルミニウムのヘキサン20重量%溶液1.78kg(1.8モル)、ビス(n-ブチル-シクロペンタジエニル)ジルコニウムジクロライド7.32g(18ミリモル)を加え、60℃に加熱して1時間撹拌した。反応溶液を45℃に冷却し、2時間静置した後に傾斜法で上澄液を除去した。次に、トリイソブチルアルミニウムのヘキサン1重量%溶液1.78kg(0.09モル)を添加し、45℃で30分間反応させた。反応溶液を45℃で2時間静置した後に傾斜法で上澄液を除去し、トリイソブチルアルミニウムのヘキサン20重量%溶液0.45kg(0.45モル)を加え、ヘキサンで再希釈して全量を4.5Lとし重合触媒を調製した。
[(A)-1の製造]
内容量300Lの重合器に、ヘキサンを135kg/時、エチレンを20.0kg/時、ブテン-1を0.3kg/時、水素5NL/時および[重合触媒の調製]の項で得られた重合触媒を連続的に供給した。また、助触媒として液中のトリイソブチルアルミニウムの濃度を0.93ミリモル/kgヘキサンとなるように、それぞれ連続的に供給した。重合温度は85℃に制御した。得られた高密度ポリエチレン((A)-1)はMFR=1.0g/10分、密度952kg/m3であった。(A)-1の基本特性評価結果を表1に示す。
[変性粘土の調製]
(A)-1と同様の方法により変性粘土化合物を調製した。
[重合触媒の調製]
(A)-1と同様の方法により重合触媒を調製した。
[(A)-2の製造]
内容量300Lの重合器に、ヘキサンを135kg/時、エチレンを20.0kg/時、ブテン-1を0.4kg/時、水素8NL/時および[重合触媒の調製]の項で得られた重合触媒を連続的に供給した。また、助触媒として液中のトリイソブチルアルミニウムの濃度を0.93ミリモル/kgヘキサンとなるように、それぞれ連続的に供給した。重合温度は85℃に制御した。得られた高密度ポリエチレン((A)-2)はMFR=3.0g/10分、密度945kg/m3であった。(A)-2の基本特性評価結果を表1に示す。
(B1)-1
[変性粘土の調製]
水1,500mlに37%塩酸30mlおよびN,N-ジメチル-ベヘニルアミンを106g加え、N,N-ジメチル-ベヘニルアンモニウム塩酸塩水溶液を調製した。平均粒径7.8μmのモンモリロナイト300g(クニミネ工業製、商品名クニピアFをジェット粉砕機で粉砕することによって調製した)を上記塩酸塩水溶液に加え、6時間反応させた。反応終了後、反応溶液を濾過し、得られたケーキを6時間減圧乾燥し、変性粘土化合物370gを得た。
[重合触媒の調製]
窒素雰囲気下の20Lステンレス容器にヘプタン3.3L、トリエチルアルミニウムのヘプタン溶液(20重量%希釈品)をアルミニウム原子当たり1.13mol(0.9L)および上記で得られた変性粘土化合物50gを加えて1時間撹拌した。そこへジフェニルメチレン(4-フェニル-インデニル)(2,7-ジ-t-ブチル-9-フルオレニル)ジルコニウムジクロライドをジルコニウム原子当たり1.25mmol加えて12時間撹拌した.得られた懸濁系に脂肪族系飽和炭化水素溶媒(出光石油化学製、商品名IPソルベント2835)5.8Lを加えることにより、触媒を調製した。(ジルコニウム濃度0.125mmol/L)
[(B1)-1の製造]
高温高圧重合用に装備された槽型反応器を用い、エチレンおよび1-ヘキセンを連続的に反応器に圧入して、全圧を90MPa、1-ヘキセン濃度を18mol%、水素濃度を7mol%になるように設定した。そして反応器を1,500rpmで撹拌し、上記により得られた重合触媒を反応器の供給口より連続的に供給し、平均温度を200℃に保ち重合反応をいった。得られた直鎖状低密度ポリエチレン((B1)-1)はMFR=3.5g/10分、密度910kg/m3であった。(B1)-1の基本特性評価結果を表2に示す。
[変性粘土の調製]
(B1)-1と同様の方法により変性粘土化合物を調製した。
[重合触媒の調製]
(B1)-1と同様の方法により重合触媒を調製した。
[(B1)-2の製造]
高温高圧重合用に装備された槽型反応器を用い、エチレンおよび1-ヘキセンを連続的に反応器に圧入して、全圧を90MPa、1-ヘキセン濃度を18mol%、水素濃度を5mol%になるように設定した。そして反応器を1,500rpmで撹拌し、上記により得られた重合触媒を反応器の供給口より連続的に供給し、平均温度を200℃に保ち重合反応をいった。得られた直鎖状低密度ポリエチレン((B1)-2)はMFR=2.0g/10分、密度907kg/m3であった。(B1)-2の基本特性評価結果を表2に示す。
[変性粘土の調製]
(B1)-1と同様の方法により変性粘土化合物を調製した。
[重合触媒の調製]
(B1)-1と同様の方法により重合触媒を調製した。
[(B1)-3の製造]
高温高圧重合用に装備された槽型反応器を用い、エチレンおよび1-ヘキセンを連続的に反応器に圧入して、全圧を90MPa、1-ヘキセン濃度を20mol%、水素濃度を15mol%になるように設定した。そして反応器を1,500rpmで撹拌し、上記により得られた重合触媒を反応器の供給口より連続的に供給し、平均温度を200℃に保ち重合反応をいった。得られた直鎖状低密度ポリエチレン((B1)-3)はMFR=12.0g/10分、密度907kg/m3であった。(B1)-3の基本特性評価結果を表2に示す。
[変性粘土の調製]
(B1)-1と同様の方法により変性粘土化合物を調製した。
[重合触媒の調製]
(B1)-1と同様の方法により重合触媒を調製した。
[(B1)-4の製造]
高温高圧重合用に装備された槽型反応器を用い、エチレンおよび1-ヘキセンを連続的に反応器に圧入して、全圧を90MPa、1-ヘキセン濃度を23mol%、水素濃度を1mol%になるように設定した。そして反応器を1,500rpmで撹拌し、上記により得られた重合触媒を反応器の供給口より連続的に供給し、平均温度を200℃に保ち重合反応をいった。得られた直鎖状低密度ポリエチレン((B1)-4)はMFR=0.8g/10分、密度900kg/m3であった。(B1)-4の基本特性評価結果を表2に示す。
[変性粘土の調製]
(B1)-1と同様の方法により変性粘土化合物を調製した。
[重合触媒の調製]
窒素雰囲気下の20Lステンレス容器にヘプタン2.5L、トリエチルアルミニウムのヘプタン溶液(20重量%希釈品)をアルミニウム原子当たり4.5mol(3.6L)および上記で得られた変性粘土化合物300gを加えて1時間撹拌した。そこへジフェニルメチレン(シクロペンタジエニル)(2,7-ジ-t-ブチル-9-フルオレニル)ジルコニウムジクロライドをジルコニウム原子当たり10mmol加えて12時間撹拌した.得られた懸濁系に脂肪族系飽和炭化水素溶媒(出光石油化学製、商品名IPソルベント2835)8.7Lを加えることにより、触媒を調製した。(ジルコニウム濃度0.67mmol/L)。
[(B2)-1の製造]
高温高圧重合用に装備された槽型反応器を用い、エチレンおよび1-ヘキセンを連続的に反応器に圧入して、全圧を90MPa、1-ヘキセン濃度を20mol%、水素濃度を4mol%になるように設定した。そして反応器を1,500rpmで撹拌し、上記により得られた重合触媒を反応器の供給口より連続的に供給し、平均温度を200℃に保ち重合反応を行なった。得られた直鎖状低密度ポリエチレン((B2)-1)はMFR=2.5g/10分、密度921kg/m3であった。(B2)-1の基本特性評価結果を表2に示す。
[変性粘土の調製]
(B1)-1と同様の方法により変性粘土化合物を調製した。
[重合触媒の調製]
(B2)-1と同様の方法により重合触媒を調製した。
[(B2)-2の製造]
高温高圧重合用に装備された槽型反応器を用い、エチレンおよび1-ヘキセンを連続的に反応器に圧入して、全圧を90MPa、1-ヘキセン濃度を10mol%、水素濃度を5mol%になるように設定した。そして反応器を1,500rpmで撹拌し、上記により得られた重合触媒を反応器の供給口より連続的に供給し、平均温度を200℃に保ち重合反応を行なった。得られた直鎖状低密度ポリエチレン((B2)-2)はMFR=3.6g/10分、密度931kg/m3であった。(B2)-2の基本特性評価結果を表2に示す。
前記直鎖状低密度ポリエチレン(B2)-1と(B2)-2を50/50(重量部/重量部)で配合したブレンド物を(B2)-3とした。尚、(B2)-3をインターナルミキサー(東洋精機製作所製、商品名ラボプラストミル)を用いて、窒素気流下、170℃、回転数30rpmで15分間混練した溶融混練物はMFR=3.1g/10分、密度926kg/m3であった。この溶融混練物の基本特性評価結果を表2に示す。
(B2)-4:下記市販品を用いた。
東ソー(株)製、(商品名)ニポロン-Z ZF230(MFR=2.0g/10分、密度=920kg/m3)(B2)-4の基本特性評価結果を表2に示す。
(C)-1
[変性粘土の調製]
1Lのフラスコに工業用アルコール(日本アルコール販売社製(商品名)エキネンF-3)300mL及び蒸留水300mLを入れ、濃塩酸17.5g及びジメチルベヘニルアミン(ライオン株式会社製(商品名)アーミンDM22D)49.4g(140mmol)を添加し、45℃に加熱して合成ヘクトライト(Rockwood Additives社製(商品名)ラポナイトRDS)を100g分散させた後、60℃に昇温させてその温度を保持したまま1時間攪拌した。このスラリーを濾別後、60℃の水600mLで2回洗浄し、85℃の乾燥機内で12時間乾燥させることにより132gの有機変性粘土を得た。この有機変性粘土はジェットミル粉砕して、メジアン径を15μmとした。
[重合触媒の調製]
温度計と還流管が装着された300mLのフラスコを窒素置換した後に[変性粘土の調製]で得られた有機変性粘土25.0gとヘキサンを108mL入れ、次いでジメチルシリレン(シクロペンタジエニル)(2,4,7-トリメチルインデニル)ジルコニウムジクロリドを0.4406g、及び20%トリイソブチルアルミニウム142mLを添加して60℃で3時間攪拌した。45℃まで冷却した後に上澄み液を抜き取り、200mLのヘキサンにて5回洗浄後、ヘキサンを200ml加えて触媒懸濁液を得た(固形重量分:12.4重量%)。
[(C)-1の製造]
2Lのオートクレーブにヘキサンを1.2L、20%トリイソブチルアルミニウムを1.0mL、[重合触媒の調製]で得られた触媒懸濁液を52mg(固形分6.4mg相当)加え、70℃に昇温後、1-ブテンを17.6g加え、分圧が0.80MPaになるようにエチレン/水素混合ガスを連続的に供給した(エチレン/水素混合ガス中の水素の濃度:590ppm)。90分経過後に脱圧し、スラリーを濾別後、乾燥することで61.8gのポリマーを得た。得られたポリマーのMFRは1.6g/10分、密度は930kg/m3であった。また、数平均分子量は17,600、重量平均分子量は86,700であり、分子量30,500および155,300の位置にピークが観測された。また、分子量分別した際のMn10万以上のフラクション中に含まれる長鎖分岐数は、主鎖1000炭素数あたり0.27個であった。また、分子量分別した際のMn10万以上のフラクションの割合は、全ポリマーの20.1重量%であった。また、溶融張力は75mNであった。評価結果を表3に示す。
[変性粘土の調製]
1Lのフラスコに工業用アルコール(日本アルコール販売社製(商品名)エキネンF-3)300mL及び蒸留水300mLを入れ、濃塩酸18.8g及びジメチルヘキサコシルアミン(Me2N(C26H53)、常法によって合成)49.1g(120mmol)を添加し、45℃に加熱して合成ヘクトライト(Rockwood Additives社製(商品名)ラポナイトRDS)を100g分散させた後、60℃に昇温させてその温度を保持したまま1時間攪拌した。このスラリーを濾別後、60℃の水600mLで2回洗浄し、85℃の乾燥機内で12時間乾燥させることにより140gの有機変性粘土を得た。この有機変性粘土はジェットミル粉砕して、メジアン径を14μmとした。
[重合触媒の調製]
温度計と還流管が装着された300mLのフラスコを窒素置換した後に[変性粘土の調製]で得られた有機変性粘土25.0gとヘキサンを108mL入れ、次いでジメチルシリレン(シクロペンタジエニル)(2、4,7-トリメチル-1-インデニル)ジルコニウムジクロリドを0.4406g、及び20%トリイソブチルアルミニウム142mLを添加して60℃で3時間攪拌した。45℃まで冷却した後に上澄み液を抜き取り、200mLのヘキサンにて5回洗浄後、ヘキサンを200ml加えて触媒懸濁液を得た(固形重量分:12.0重量%)
[(C)-2の製造]
2Lのオートクレーブにヘキサンを1.2L、20%トリイソブチルアルミニウムを1.0mL、[重合触媒の調製]で得られた触媒懸濁液を75mg(固形分9.0mg相当)加え、80℃に昇温後、1-ブテンを8.3g加え、分圧が0.85MPaになるようにエチレン/水素混合ガスを連続的に供給した(エチレン/水素混合ガス中の水素の濃度:850ppm)。90分経過後に脱圧し、スラリーを濾別後、乾燥することで58.5gのポリマーを得た。得られたポリマーのMFRは4.0g/10分、密度は941kg/m3であった。また、数平均分子量は21,200、重量平均分子量は74,000であり、分子量41,500および217,100の位置にピークが観測された。また、分子量分別した際のMn10万以上のフラクション中に含まれる長鎖分岐数は、主鎖1000炭素数あたり0.18個であった。また、分子量分別した際のMn10万以上のフラクションの割合は、全ポリマーの14.8重量%であった。また、溶融張力は49mNであった。評価結果を表3に示す。
[変性粘土の調製]
1Lのフラスコに工業用アルコール(日本アルコール販売社製(商品名)エキネンF-3)300mL及び蒸留水300mLを入れ、濃塩酸15.0g及びジメチルベヘニルアミン(ライオン株式会社製(商品名)アーミンDM22D)42.4g(120mmol)を添加し、45℃に加熱して合成ヘクトライト(Rockwood Additives社製(商品名)ラポナイトRDS)を100g分散させた後、60℃に昇温させてその温度を保持したまま1時間攪拌した。このスラリーを濾別後、60℃の水600mLで2回洗浄し、85℃の乾燥機内で12時間乾燥させることにより122gの有機変性粘土を得た。この有機変性粘土はジェットミル粉砕して、メジアン径を15μmとした。
[重合触媒の調製]
温度計と還流管が装着された300mLのフラスコを窒素置換した後に[変性粘土の調製]で得られた有機変性粘土25.0gとヘキサンを108mL入れ、次いでジメチルシリレン(シクロペンタジエニル)(2,4,7-トリメチル-1-インデニル)ジルコニウムジクロリドを0.4406g、及び20%トリイソブチルアルミニウム142mLを添加して60℃で3時間攪拌した。45℃まで冷却した後に上澄み液を抜き取り、200mLのヘキサンにて5回洗浄後、ヘキサンを200ml加えて触媒懸濁液を得た(固形重量分:11.5重量%)。
[(C)-3の製造]
2Lのオートクレーブにヘキサンを1.2L、20%トリイソブチルアルミニウムを1.0mL、[重合触媒の調製]で得られた触媒懸濁液を70mg(固形分8.4mg相当)加え、80℃に昇温後、1-ブテンを2.4g加え、分圧が0.90MPaになるようにエチレン/水素混合ガスを連続的に供給した(エチレン/水素混合ガス中の水素の濃度:720ppm)。90分経過後に脱圧し、スラリーを濾別後、乾燥することで63.0gのポリマーを得た。得られたポリマーのMFRは11.5g/10分、密度は954kg/m3であった。また、数平均分子量は16,200、重量平均分子量は58,400であり、分子量28,200および181,000の位置にピークが観測された。また、分子量分別した際のMn10万以上のフラクション中に含まれる長鎖分岐数は、主鎖1000炭素数あたり0.16個であった。また、分子量分別した際のMn10万以上のフラクションの割合は、全ポリマーの6.8重量%であった。また、溶融張力は38mNであった。評価結果を表3に示す。
[変性粘土の調製]
1Lのフラスコに工業用アルコール(日本アルコール販売社製(商品名)エキネンF-3)300mL及び蒸留水300mLを入れ、濃塩酸20.0g及びジメチルベヘニルアミン(ライオン株式会社製(商品名)アーミンDM22D)56.5g(160mmol)を添加し、45℃に加熱して合成ヘクトライト(Rockwood Additives社製(商品名)ラポナイトRDS)を100g分散させた後、60℃に昇温させてその温度を保持したまま1時間攪拌した。このスラリーを濾別後、60℃の水600mLで2回洗浄し、85℃の乾燥機内で12時間乾燥させることにより145gの有機変性粘土を得た。この有機変性粘土はジェットミル粉砕して、メジアン径を15μmとした。
[重合触媒の調製]
温度計と還流管が装着された300mLのフラスコを窒素置換した後に(1)で得られた有機変性粘土25.0gとヘキサンを108mL入れ、次いでジメチルシリレン(シクロペンタジエニル)(2,4,7-トリメチル-1-インデニル)ジルコニウムジクロリドを0.4406g、及び20%トリイソブチルアルミニウム142mLを添加して60℃で3時間攪拌した。45℃まで冷却した後に上澄み液を抜き取り、200mLのヘキサンにて5回洗浄後、ヘキサンを200ml加えて触媒懸濁液を得た(固形重量分:11.2重量%)。
[(C)-4の製造]
2Lのオートクレーブにヘキサンを1.2L、20%トリイソブチルアルミニウムを1.0mL、[重合触媒の調製]で得られた触媒懸濁液を74mg(固形分8.3mg相当)加え、65℃に昇温後、1-ブテンを17.5g加え、分圧が0.75MPaになるようにエチレン/水素混合ガスを連続的に供給した(エチレン/水素混合ガス中の水素の濃度:570ppm)。90分経過後に脱圧し、スラリーを濾別後、乾燥することで51.5gのポリマーを得た。得られたポリマーのMFRは0.8g/10分、密度は928kg/m3であった。また、数平均分子量は17,900、重量平均分子量は99,300であり、分子量28,100および229,100の位置にピークが観測された。また、分子量分別した際のMn10万以上のフラクション中に含まれる長鎖分岐数は、主鎖1000炭素数あたり0.26個であった。また、分子量分別した際のMn10万以上のフラクションの割合は、全ポリマーの25.4重量%であった。また、溶融張力は90mNであった。評価結果を表3に示す。
[変性粘土の調製]
1Lのフラスコに工業用アルコール(日本アルコール販売社製(商品名)エキネンF-3)300mL及び蒸留水300mLを入れ、濃塩酸15.0g及びジメチルベヘニルアミン(ライオン株式会社製(商品名)アーミンDM22D)42.4g(120mmol)を添加し、45℃に加熱して合成ヘクトライト(Rockwood Additives社製(商品名)ラポナイトRDS)を100g分散させた後、60℃に昇温させてその温度を保持したまま1時間攪拌した。このスラリーを濾別後、60℃の水600mLで2回洗浄し、85℃の乾燥機内で12時間乾燥させることにより122gの有機変性粘土を得た。この有機変性粘土はジェットミル粉砕して、メジアン径を15μmとした。
[重合触媒の調製]
温度計と還流管が装着された300mLのフラスコを窒素置換した後に[変性粘土の調製]で得られた有機変性粘土25.0gとヘキサンを108mL入れ、次いでジメチルシリレン(シクロペンタジエニル)(2,4,7-トリメチル-1-インデニル)ジルコニウムジクロリドを0.4406g、及び20%トリイソブチルアルミニウム142mLを添加して60℃で3時間攪拌した。45℃まで冷却した後に上澄み液を抜き取り、200mLのヘキサンにて5回洗浄後、ヘキサンを200ml加えて触媒懸濁液を得た(固形重量分:11.5重量%)。
[(C)-5の製造]
2Lのオートクレーブにヘキサンを1.2L、20%トリイソブチルアルミニウムを1.0mL、[重合触媒の調製]で得られた触媒懸濁液を90mg(固形分10.4mg相当)加え、65℃に昇温後、1-ブテンを17.5g加え、分圧が0.75MPaになるようにエチレン/水素混合ガスを連続的に供給した(エチレン/水素混合ガス中の水素の濃度:550ppm)。90分経過後に脱圧し、スラリーを濾別後、乾燥することで61.4gのポリマーを得た。得られたポリマーのMFRは0.08g/10分、密度は926kg/m3であった。また、数平均分子量は21,900、重量平均分子量は127,000であり、分子量31,300および247,800の位置にピークが観測された。また、分子量分別した際のMn10万以上のフラクション中に含まれる長鎖分岐数は、主鎖1000炭素数あたり0.32個であった。また、分子量分別した際のMn10万以上のフラクションの割合は、全ポリマーの36.9重量%であった。また、溶融張力は140mNであった。評価結果を表3に示す。
[変性粘土の調製]
1Lのフラスコに工業用アルコール(日本アルコール販売社製(商品名)エキネンF-3)300mL及び蒸留水300mLを入れ、濃塩酸15.0g及びジメチルベヘニルアミン(ライオン株式会社製(商品名)アーミンDM22D)42.4g(120mmol)を添加し、45℃に加熱して合成ヘクトライト(Rockwood Additives社製(商品名)ラポナイトRDS)を100g分散させた後、60℃に昇温させてその温度を保持したまま1時間攪拌した。このスラリーを濾別後、60℃の水600mLで2回洗浄し、85℃の乾燥機内で12時間乾燥させることにより122gの有機変性粘土を得た。この有機変性粘土はジェットミル粉砕して、メジアン径を15μmとした。
[重合触媒の調製]
温度計と還流管が装着された300mLのフラスコを窒素置換した後に[変性粘土の調製]で得られた有機変性粘土25.0gをヘキサン165mLに懸濁させ、ジメチルシランジイルビス(シクロペンタジエニル)ジルコニウムジクロリド0.3485gおよびトリエチルアルミニウムのヘキサン溶液(1.18M)85mLを添加して60℃で3時間撹拌した。静置して室温まで冷却後に上澄み液を抜き取り、1%トリイソブチルアルミニウムのヘキサン溶液200mLにて2回洗浄した。洗浄後の上澄み液を抜き出し、5%トリイソブチルアルミニウムのヘキサン溶液にて全体を250mLとした。次いで、別途ジフェニルメチレン(1-シクロペンタジエニル)(2,7-ジ-tert-ブチル-9-フルオレニル)ジルコニウムジクロライド0.1165gのヘキサン10mL懸濁液に20%トリイソブチルアルミニウムのヘキサン溶液(0.71M)5mlを加えることにより調製した溶液を添加して、室温で6時間撹拌した。静置して上澄み液を除去、ヘキサン200mLにて2回洗浄後、ヘキサンを200mL加えて触媒懸濁液を得た(固形重量分:12.0重量%)。
[(C)-6の製造]
2Lのオートクレーブにヘキサンを1.2L、20%トリイソブチルアルミニウムを1.0mL、[重合触媒の調製]で得られた触媒懸濁液を125mg(固形分15.0mg相当)加え、85℃に昇温後、1-ブテンを2.4g加え、分圧が0.90MPaになるようにエチレンを連続的に供給した。90分経過後に脱圧し、スラリーを濾別後、乾燥することで45.0gのポリマーを得た。得られたポリマーのMFRは4.4g/10分であり、密度は951kg/m3であった。数平均分子量は9,100、重量平均分子量は77,100であり、分子量10,400および168,400の位置にピークが観測された。また、分子量分別した際のMn10万以上のフラクション中に含まれる長鎖分岐数は、主鎖1000炭素数あたり0.24個であった。また、分子量分別した際のMn10万以上のフラクションの割合は、全ポリマーの15.7重量%であった。また、溶融張力210mNであった。評価結果を表3に示す。
実施例、比較例に用いた積層体および医療容器は下記の方法により製造し、滅菌処理を行なった。
<積層体および医療容器の製造>
三層水冷インフレーション成形機(プラコー社製)を用いて、シリンダ温度180℃、水槽温度15℃、引取速度4m/分でフィルム幅135mm、フィルム厚み250μmの三層フィルムを成形した。尚、各層の厚みは外層/中間層/内層=20μm/210μm/20μmとした。次いで、前記三層フィルムから長さ195mmのサンプルを切出し、一方の端をヒートシールして袋状にした後、超純水を300ml充填し、ヘッドスペースを50ml設けてヒートシールして医療容器を作製した。
前記医療容器を、蒸気滅菌装置((株)日阪製作所製)を用いて、温度121℃で20分間滅菌処理を行なった。
実施例、比較例に用いた積層体および医療容器の諸性質は下記の方法により評価した。
三層水冷インフレーション成形機による、成膜時のフィルム(バブル)の安定性を目視により観察、評価した。
○:バブル安定性良好
×:バブル変動大
<フィルムの表面平滑性>
前記成形フィルムの表面状態を目視により観察、評価した。
○:表面平滑性良好
×:表面荒れ大
<フィルム外観>
滅菌処理後のフィルム表面のシワ、変形および内層間の融着等を目視により評価し、シワ、変形が見られない場合を4点、若干のシワ、変形が見られる場合を3点、顕著なシワ、変形が見られる場合を2点、内層同士が融着した場合を1点とした。
前記三層フィルムおよび滅菌処理後の医療容器から、幅10mm×長さ50mmの試験片を切出し、紫外可視分光光度計(日本分光株式会社製 型式V-530)を用いて、純水中で波長450nmにおける光線透過率を測定した。滅菌処理後に70%以上の光線透過率が維持される場合を透明性が良好な医療容器の目安とした。
JIS K 7161に準拠して、前記滅菌処理後の医療容器から試験片を打抜き、引張試験機(型式 オートグラフ DCS-500、島津製作所製)を用いて5%弾性率を測定した。弾性率の値が200MPa以下の場合を柔軟性良好、200MPaを超える場合を柔軟性不良とした。
○:柔軟性良好
×:柔軟性不良
<透湿度>
JIS K 7129 A法(感湿センサー法)に準拠して、水蒸気透過度計(型式 L80-5000、Lyssy社製)により前記滅菌処理後の医療容器から切出した試験片の透湿度を測定した。透湿度が1.0g/(m2・24h)以下の場合をバリアー性が良好な医療容器の目安とした。
1μm以上の微粒子数が0個/10mlであることが確認された超純水を、前記「医療容器の製造」の項に記載した方法で製造した医療容器に充填密封した後、121℃で20分間の熱水滅菌処理を実施し、1日放置後、HIAC/ROYCO社製微粒子カウンター「M-3000・4100・HR-60HA」を用いて1μm以上の微粒子数を測定した。尚、これらの操作は、すべてクラス1000のクリーンルーム中で行った。微粒子数が10個/ml以下である場合をクリーン性が良好な医療容器の目安とした。
表4および表5に示す樹脂組成物を用いて、水冷インフレーション成形機により三層フィルムを成形し、成形安定性およびフィルムの表面平滑性、透明性を評価した。次いで、得られたフィルムをヒートシールし、超純水を充填した医療容器を作製して、121℃で高圧蒸気滅菌を行い、滅菌後のフィルム外観、透明性、柔軟性、透湿度およびクリーン性を評価した。結果を表6に示す。
各層に用いる樹脂組成物を表4および表5に示すように変更した以外は、実施例1と同様にして三層フィルムおよび医療容器を作製し、評価を行った。結果を表6および表7に示す。
Claims (14)
- 下記特性(a)~(b)を満足する高密度ポリエチレン(A)20~80重量%、下記特性(c)~(d)を満足する直鎖状低密度ポリエチレン(B1)0~50重量%および下記特性(e)~(h)を満足するエチレン系重合体(C)5~40重量%((A)、(B1)及び(C)の合計は100重量%)を含むことを特徴とするポリエチレン樹脂組成物。
(a)密度が945~970kg/m3である。
(b)MFRが0.1~15.0g/10分である。
(c)密度が890~915kg/m3である。
(d)MFRが0.1~15.0g/10分である。
(e)密度が930~960kg/m3である。
(f)MFRが0.1~15.0g/10分である。
(g)ゲル・パーミエーション・クロマトグラフィーによる分子量測定において2つのピークを示し、重量平均分子量(Mw)と数平均分子量(Mn)の比(Mw/Mn)が2.0~7.0の範囲である。
(h)分子量分別した際のMnが10万以上のフラクション中に長鎖分岐を主鎖1000炭素数あたり0.15個以上有する。 - 高密度ポリエチレン(A)が、前記特性(a)~(b)に加えて下記特性(i)~(j)を満足することを特徴とする請求項1に記載のポリエチレン樹脂組成物。
(i)ゲル・パーミエーション・クロマトグラフィーにより求められる重量平均分子量(Mw)と数平均分子量(Mn)の比(Mw/Mn)が3.0以下である。
(j)日本薬局方に規定の強熱残分試験法による残分が0.02重量%以下である。 - 直鎖状低密度ポリエチレン(B1)が、前記特性(c)~(d)に加えて下記特性(k)~(l)を満足することを特徴とする請求項1または2に記載のポリエチレン樹脂組成物。
(k)ゲル・パーミエーション・クロマトグラフィーにより求められる重量平均分子量(Mw)と数平均分子量(Mn)の比(Mw/Mn)が3.0以下である。
(l)50℃におけるn-ヘプタン抽出量が1.5重量%以下である。 - エチレン系重合体(C)のMw/Mnが3.0~6.0の範囲であり、Mnが15,000以上であることを特徴とする請求項1~3のいずれかに記載のポリエチレン樹脂組成物。
- エチレン系重合体(C)の分子量分別した際のMnが10万以上である成分の割合がエチレン系重合体(C)全体の40%未満であることを特徴とする請求項1~4のいずれかに記載のポリエチレン樹脂組成物。
- 高密度ポリエチレン(A)20~70重量%、直鎖状低密度ポリエチレン(B1)10~50重量%およびエチレン系重合体(C)5~40重量%であることを特徴とする請求項1~5のいずれかに記載のポリエチレン樹脂組成物。
- 外層と内層とそれらの間に配置された中間層とを有する積層体であって、外層および内層が請求項1~6のいずれかに記載のポリエチレン樹脂組成物からなり、中間層が少なくとも前記特性(a)~(b)を満足する高密度ポリエチレン(A)10~40重量%、前記特性(c)~(d)を満足する直鎖状低密度ポリエチレン(B1)60~90重量%((A)及び(B1)の合計は100重量%)を含む樹脂組成物からなることを特徴とする積層体。
- 中間層に用いる高密度ポリエチレン(A)が、前記特性(a)、(b)、(i)および(j)を満足することを特徴とする請求項7に記載の積層体。
- 中間層に用いる直鎖状低密度ポリエチレン(B1)が、前記特性(c)、(d)、(k)および(l)を満足することを特徴とする請求項7に記載の積層体。
- 中間層が、前記高密度ポリエチレン(A)と直鎖状低密度ポリエチレン(B1)の合計量100重量部に対して、下記特性(m)~(n)を満足する直鎖状低密度ポリエチレン(B2)5~30重量部を含む樹脂組成物からなることを特徴とする請求項7~9のいずれかに記載の積層体。
(m)密度が920~945kg/m3である。
(n)MFRが0.1~15.0g/10分である。 - 薬液を収容する収容部を備えた医療容器であって、少なくとも前記収容部は、請求項7~10のいずれかに記載の積層体からなることを特徴とする医療容器。
- 薬液を収容する収容部が、フィルム状に成形した積層体を熱板成形により袋状に成形したものであることを特徴とする請求項11に記載の医療容器。
- 薬液を収容する収容部が、ブロー成形により、積層体をボトル状に成形したものであることを特徴とする請求項11に記載の医療容器。
- 121℃での滅菌処理後も容器の変形がなく、かつ純水中、波長450nmで測定した光線透過率が70%以上となることを特徴とする請求項11~13のいずれかに記載の医療容器。
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