JP6295588B2 - Polyethylene resin composition and medical container comprising the same - Google Patents

Description

  The present invention relates to a polyethylene medical container excellent in transparency, flexibility, barrier properties, and cleanliness (low particle size). More specifically, there is little loss of transparency due to sterilization, excellent barrier properties against permeation of water vapor, oxygen, etc., and there is little elution of fine particles into the drug solution, so drug solutions such as infusion bags and plastic ampules, blood, etc. It is related with the medical container made from polyethylene suitable for filling of.

  For medical containers filled with chemicals, blood, etc., transparency for confirming changes due to contamination of foreign substances and chemical composition, heat resistance that can withstand sterilization, flexibility for easy discharge of chemicals, containers Gas barrier properties for suppressing deterioration of quality and deterioration of chemicals due to intrusion of water vapor or oxygen into the inside, and reduction of fine particle elution from the container (low particle property) are required.

  Conventionally, glass containers have been used as medical containers that satisfy such performance, but there are problems such as damage to the containers due to impact and dropping, contamination due to intrusion of outside air into the containers at the time of drug administration, etc. Plastic containers that have excellent impact properties, are flexible, and can be easily discharged are used. As the plastic container, a soft vinyl chloride resin, an ethylene-vinyl acetate copolymer resin, a polypropylene resin, and a polyethylene resin such as a high pressure method low density polyethylene, a linear low density polyethylene, and a high density polyethylene are used. However, 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.

  In recent years, linear polyethylene manufactured with a single-site catalyst having excellent transparency has been developed, and a method (see Patent Documents 1 to 3) for solving the above-mentioned problem by laminating films made of these raw materials has been proposed. ing. However, the transparency is still insufficient in these methods, and the problem that transparency is reduced by sterilization has not been solved.

JP-A-8-309939 Japanese Patent Laid-Open No. 7-125738 JP-A-8-244791

  The object of the present invention is a polyethylene medical that is excellent in transparency, flexibility, barrier properties and cleanliness (low particle size), which are disadvantages of conventional plastic medical containers, and that maintains high transparency even after sterilization. To provide a container.

  As a result of intensive studies, the present inventors have found that the above problem can be solved by blending a specific amount of an ethylene-based polymer having specific physical properties with a linear low density polyethylene into a medical container. The present invention has been completed.

That is, the present invention provides a high-density polyethylene (A) 10 to 50% by weight satisfying the following characteristics (a) to (b), and a linear low-density polyethylene (B) satisfying the following characteristics (c) to (d). 1) to 50% by weight of ethylene polymer (C) satisfying 20 to 70% by weight and the following characteristics (e) to (h) (total of (A), (B) and (C) is 100% by weight) And a medical container comprising the same.
(A) A density is 935-970 kg / m < ³ >.
(B) MFR is 0.1 to 15 g / 10 min.
(C) The density is 890 to 920 kg / m ³ .
(D) MFR is 0.1 to 15 g / 10 min.
(E) The density is 920-960 kg / m ³ .
(F) MFR is 0.1 to 15 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.

  The blending ratio of the high density polyethylene (A), the linear low density polyethylene (B) and the ethylene polymer (C) used in the present invention is 10 to 50% by weight of the high density polyethylene (A), preferably 15 to 45 wt%, more preferably 20-40 wt%, linear low density polyethylene (B) 20-70 wt%, preferably 25-65 wt%, more preferably 30-60 wt%, ethylene polymer (C) is 1 to 50% by weight, preferably 5 to 45% by weight, more preferably 10 to 40% by weight.

  When the high-density polyethylene (A) is less than 10% by weight, the heat resistance is insufficient, and when it exceeds 50% by weight, the transparency and flexibility are undesirably lowered. If the linear low density polyethylene (B) is less than 20% by weight, the transparency and flexibility are lowered, and if it exceeds 70% by weight, the heat resistance is lowered, which is not preferable. If the ethylene polymer (C) is less than 1% by weight, the melt tension becomes insufficient and the molding stability is lowered, which is not preferable.

  When the ethylene polymer (C) is blended within the above range, the transparency of the medical container is greatly improved as compared with the case where the ethylene polymer (C) is not blended, and the level after sterilization is high. It becomes possible to maintain the transparency of.

  The reason why such an effect is manifested is not necessarily clear, but it is confirmed that the size of spherulites formed during cooling crystallization is remarkably reduced by blending the ethylene polymer (C). The ethylene polymer (C) is considered to have an effect of inhibiting spherulite growth in the molding process and the sterilization process.

  Thereby, in this invention, the medical container which maintained the high level transparency after the sterilization process can be obtained.

Below, the polyethylene resin composition of this invention and the medical container which consists of it are demonstrated.
[1] High density polyethylene (A)
The high density polyethylene (A) used in the polyethylene resin composition of the present invention is an ethylene homopolymer or a copolymer of ethylene and an α-olefin.

  The high-density polyethylene (A) has a melt flow rate (hereinafter referred to as 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 minutes, preferably 0.5 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 load on the extruder increases during molding and surface roughness occurs during molding. Moreover, when MFR exceeds 15.0 g / 10min, since melt tension becomes small and shaping | molding stability falls, it is unpreferable.

The high density polyethylene (A) has a density according to JIS K6922-1 of 935 to 970 kg / m ³ , preferably 940 to 965 kg / m ³ . When the density is less than 935 kg / m ³ , the heat resistance is insufficient, and when it exceeds 970 kg / m ³ , the transparency and flexibility are undesirably lowered.

  The α-olefin may be generally referred to as α-olefin, and α-olefin having 3 to 12 carbon atoms such as propylene, butene-1, hexene-1, octene-1, and 4-methyl-1-pentene. Preferably it is an olefin. Examples of the copolymer of ethylene and α-olefin include an ethylene / hexene-1 copolymer, an ethylene / butene-1 copolymer, and an ethylene / octene-1 copolymer.

  The high-density polyethylene (A) can be produced by a production method such as a slurry method, a solution method, or a gas phase method. When producing the high-density polyethylene (A), 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 It is possible to use a metallocene catalyst, a vanadium-based catalyst, or the like composed of a compound and / or an organometallic compound that reacts with an ionic complex to homopolymerize ethylene or copolymerize ethylene and α-olefin. Can be manufactured.

The high density polyethylene (A) having the above characteristics is blended with a linear low density polyethylene (B) and an ethylene polymer (C), which will be described later, to improve the transparency of the obtained medical container and sterilization treatment. Although the subsequent transparency maintenance effect is expressed, when the high-density polyethylene (A) has the following properties (i) to (j), the cleanliness (low particle size) of the medical container of the present invention is further improved. Therefore, it is particularly preferable. High density polyethylene (A) having such properties (i) to (j) can be produced by using the metallocene catalyst.
(I) The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) determined by gel permeation chromatography is 3.0 or less.
(J) Residue by an ignition residue test method prescribed in the Japanese Pharmacopoeia is 0.02% by weight or less.
As said high-density polyethylene (A), what was obtained as a commercial item may be used, for example, Tosoh Co., Ltd. (brand name) Nipolon Hard 5110, Tosoh Corporation (brand name) Nipolon Hard 8500, Tosoh (Product name) Nipolon Hard 2400, etc. may be mentioned.

Moreover, it can manufacture with the following method. For example, a method of polymerizing ethylene or copolymerizing ethylene and an α-olefin having 3 to 8 carbon atoms in the presence of a polymerization catalyst described in JP2013-81494A can be used.
[2] Linear low density polyethylene (B)
The linear low density polyethylene (B) used in the present invention is a copolymer of ethylene and α-olefin. The linear low density polyethylene (B) has an MFR measured at 190 ° C. under a load of 2.16 kg in accordance with JIS K6922-1 and is 0.1 to 15.0 g / 10 min, preferably 0.5 to 10 0.0 g / 10 min, more preferably 1.0 to 5.0 g / 10 min. 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 shaping | molding stability falls, it is unpreferable.

It said linear low density polyethylene (B) is, JIS density conforming to K6922-1 is 890~920kg / ^{m 3,} preferably 900~915kg / ^{m 3.} When the density is less than 890 kg / m ³ , the heat resistance is insufficient, and when it exceeds 920 kg / m ³ , the transparency and flexibility are undesirably lowered.

  The α-olefin may be generally referred to as α-olefin, and α-olefin having 3 to 12 carbon atoms such as propylene, butene-1, hexene-1, octene-1, and 4-methyl-1-pentene. Preferably it is an olefin. Examples of the copolymer of ethylene and α-olefin include an ethylene / hexene-1 copolymer, an ethylene / butene-1 copolymer, and an ethylene / octene-1 copolymer.

  The linear low density polyethylene (B) can be produced by a production method such as a high pressure method, a solution method, or a gas phase method. When the linear low density polyethylene (B) is produced, a solid catalyst component generally containing magnesium and titanium, a Ziegler catalyst comprising an organoaluminum compound, and an organic transition metal compound containing a cyclopentadienyl derivative And a metallocene catalyst, a vanadium-based catalyst, or the like comprising a compound and / or an organometallic compound that reacts with this to form an ionic complex, and by copolymerizing ethylene and an α-olefin by the catalyst. It can be manufactured.

The linear low-density polyethylene (B) 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 Although the transparency maintenance effect after sterilization is expressed, when the linear low-density polyethylene (B) has the following properties (k) to (l), the cleanliness (low particle property) of the medical container of the present invention ) Is particularly preferable since it further improves. Such a linear low density polyethylene (B) having the characteristics (k) to (l) can be produced by using the metallocene catalyst.
(K) The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) determined by gel permeation chromatography is 3.0 or less.
(L) The amount of n-heptane extracted at 50 ° C. is 1.5 wt% or less.
As said linear low density polyethylene (B), what was obtained as a commercial item may be used, for example, Tosoh Co., Ltd. (brand name) Nipolon-Z ZF220, Tosoh Corporation (brand name) ) Nipolon-Z ZF230, Tosoh Corporation (trade name) Nipolon-LF14, and the like.

In addition, for example, a method of copolymerizing ethylene and an α-olefin having 3 to 8 carbon atoms in the presence of a polymerization catalyst described in JP2013-81494A can be used.
[3] Ethylene polymer (C)
The ethylene-based polymer (C) related 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 0.5 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. Moreover, when MFR exceeds 15.0 g / 10min, since melt tension becomes small and the processing stability at the time of shaping | molding falls, it is unpreferable.

Ethylene polymer according to the present invention (C) is in the range density conforming to JIS K6922-1 of 920~960kg / ^{m 3,} preferably 925~955kg / ^{m 3,} particularly preferably 930~950kg / m ³ range. When the density is less than 920 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). 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. When the average value and the ratio giving the minimum value of the deviation sum of squares were obtained, the molecular weight at the peak top of each logarithmic distribution curve obtained by dividing into two lognormal distribution curves was defined as Mp.

  Even when an ethylene polymer having one peak in molecular weight measurement by GPC is used as one component for obtaining the polyethylene resin composition of the present invention, an ethylene polymer (C) having two peaks is blended Thus, a medical container having high transparency and maintaining transparency even after sterilization treatment cannot be obtained.

  The ethylene polymer (C) according to the present invention has a weight average molecular weight (Mw) to number average molecular weight (Mn) ratio (Mw / Mn) of 2.0 to 7.0, preferably 2.5 to 6. 5, More preferably, it is 3.0-6.0. When 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. When Mw / Mn exceeds 7.0, the strength of the obtained medical container is decreased, and when the molded body is used as a medical container, there is a possibility that fine particles in the filled chemical solution may increase.

  The ethylene 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, especially 15,000 to 50,000 is preferred. When Mn is 15,000 or more, the strength of the obtained medical container is increased.

  In the ethylene-based polymer (C) according to the present invention, 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. When 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.

  Moreover, it is preferable that the ratio of the fraction whose Mn obtained by molecular weight fractionation is 100,000 or more is less than 40% of the whole ethylene polymer (C). When 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.

  As described above, as a resin material for producing the polyethylene medical container of the present invention, heat resistance is improved by blending the ethylene polymer (C) with the high density polyethylene (A) and the linear low density polyethylene (B). Transparency can be greatly increased without lowering. Surprisingly, it has been found that a medical container produced by blending the ethylene polymer (C) has greatly improved gas barrier properties and clean properties (low particle size).

Examples of the ethylene polymer (C) related to the polyethylene medical container of the present invention include JP 2012-126862 A, JP 2012-126863 A, JP 2012-158654 A, and JP 2012-158656 A. It can obtain by the method as described in gazette, Unexamined-Japanese-Patent No. 2013-28703, etc. Moreover, (trade name) TOSOH-HMS CK37, CK47 (above, Tosoh Co., Ltd. product) etc. can be used as a commercial item.
[4] Polyethylene resin composition The polyethylene resin composition of the present invention is obtained by subjecting high-density polyethylene (A), linear low-density polyethylene (B), and ethylene polymer (C) to a conventionally known method such as a Henschel mixer. , V-blender, ribbon blender, tumbler blender, etc., or a mixture obtained by such a method is further melt-kneaded with a single screw extruder, twin screw extruder, kneader, Banbury mixer, etc., and granulated Can be obtained.

The polyethylene resin composition of the present invention preferably has a density in the range of 915 to 930 kg / m ³ because the balance between flexibility and transparency of the medical container after sterilization is particularly excellent.

  In the polyethylene resin composition of the present invention, known additives usually used, for example, an antioxidant, an antistatic agent, a lubricant, an antiblocking agent, an antifogging agent, an organic system, are used as long as the effects of the present invention are not significantly impaired. Alternatively, inorganic pigments, ultraviolet absorbers, dispersants, and the like can be appropriately blended as necessary. The method of blending the above-mentioned additives into the resin material 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 is prepared in advance. For example, a method of dry blending at the time of molding may be used.

In addition, the polyethylene resin composition of the present invention includes other thermoplastics such as high-pressure low-density polyethylene, ethylene-propylene copolymer rubber, and poly-1-butene within a range that does not impair the effects of the present invention. A resin can also be blended and used.
[5] Medical container The polyethylene medical container of the present invention is a medical container provided with a storage part for storing a chemical solution, and at least the storage part is a linear low density polyethylene (A), an ethylene polymer (B). And a resin composition containing an ethylene polymer (C).

  When the resin composition is formed into a film by water-cooled inflation molding, air-cooled inflation molding, cast molding, or the like, two sheets of the obtained films are overlapped and the peripheral portion is heat-sealed to form a bag The housing portion can be formed. Moreover, after forming the recessed part used as an accommodating part by hot plate shaping | molding, such as vacuum forming and pressure forming, the obtained film is overlap | superposed so that recessed parts may oppose, and an accommodating part is heat-sealed by a peripheral part Can also be molded. At this time, 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. .

  It is also possible to form the container by forming the compound into a bottle by blow molding or the like. In blow molding, a parison composed of a blend of the linear low density polyethylene (A), the ethylene polymer (B) and the ethylene polymer (C) is extruded, and the parison is sandwiched between molds, The container can be formed by blowing clean air into the container. In addition, 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 thickness of the medical container produced using the polyethylene resin composition of 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. ~ 0.5 mm.

  The method for producing the medical container of the present invention is not particularly limited, and examples thereof include a water-cooled or air-cooled inflation molding method, a cast molding method, a blow molding method, and an injection blow molding method. Among these, the use of the water-cooled inflation molding method has many advantages in terms of transparency and hygiene.

  In addition, when a simultaneous filling blow molding method in which a container is filled with a chemical solution at the same time as molding by blow molding, there are many advantages in terms of hygiene, productivity, and the like.

  The medical container produced by the polyethylene composition of the present invention is excellent in transparency, flexibility, barrier properties and cleanliness (low particle size), and can maintain transparency even after sterilization treatment, so high transparency is required. It can be suitably used for medical containers such as medical infusion bags and plastic ampules.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
A. Resins Various properties of the resins used in Examples and Comparative Examples were evaluated by the following methods.

<Molecular weight, molecular weight distribution>
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-8121 GPC / 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 an 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. In addition, Mw and Mn were calculated | required as a value of linear polyethylene conversion.

<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 nuclear magnetic resonance apparatus manufactured by JEOL Ltd., and the number of branches equal to or greater than the hexyl group. 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 α-carbon (34.6 ppm) and β-carbon (27.3 ppm).

<Remaining ignition heat>
In accordance with the Japanese Pharmacopoeia stipulated by the ignition residue test method, weigh accurately 50 g of the sample, put it in a platinum dish and burn it with a gas burner, and then complete ashing in an electric furnace at 650 ° C. for 1 hour The weight of the residue was measured, and the percentage was calculated by calculating the percentage with respect to the initial weight.

<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 K6760 (1995).

<MFR>
MFR (melt flow rate) was measured by a method according to ASTM D1238 Condition E.

<Melting tension>
The sample for melt tension measurement was prepared by adding a heat-resistant stabilizer (Ciba Specialty Chemicals, Irganox 1010TM; 1,500 ppm, Irgaphos 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.

  To measure the melt tension, 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, and the load (mN) required for take-up was the melt tension. When the maximum draw ratio was less than 47, the load (mN) required for taking-up at the highest draw ratio that did not break was taken as the melt tension.

In Examples and Comparative Examples, resin materials produced by the following method and commercially available products were used.
(1) High density polyethylene HD-1
[Preparation of modified clay]
To a mixed solvent of 4.8 L of deionized water and 3.2 L of ethanol, 354 g of dimethylbehenylamine; (C ₂₂ H ₄₅ ) (CH ₃ ) ₂ N and 83.3 mL of 37% hydrochloric acid are added, and the dimethylbehenylamine hydrochloride solution is added. Prepared. To this solution, 1,000 g of synthetic hectorite was added and stirred overnight. The resulting reaction solution was filtered, and the solid was sufficiently washed with water. When the solid content was dried, 1,180 g of an organically modified clay compound was obtained. The liquid content measured with an infrared moisture meter was 0.8%. Next, this organically modified clay compound was pulverized to prepare an average particle size of 6.0 μm.
[Preparation of polymerization catalyst]
To a 5 L flask, 450 g of the organically modified clay compound obtained in [Preparation of modified clay] and 1.4 kg of hexane were added, and then 1.78 kg (1.8 mol) of a 20 wt% solution of triisobutylaluminum in hexane, bis 7.32 g (18 mmol) of (n-butyl-cyclopentadienyl) zirconium dichloride was added, heated to 60 ° C. and stirred for 1 hour. 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. Next, 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. After allowing the reaction solution to stand at 45 ° C. for 2 hours, 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. Was 4.5 L to prepare a polymerization catalyst.
[Production of HD-1]
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. The obtained high-density polyethylene (HD-1) had MFR = 3.0 g / 10 minutes and a density of 945 kg / m ³ . Table 1 shows the results of evaluation of basic characteristics of HD-1.

HD-2
[Preparation of modified clay]
A modified clay compound was prepared by the same method as HD-1.
[Preparation of polymerization catalyst]
A polymerization catalyst was prepared by the same method as HD-1.
[Production of HD-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 0.3 kg / hour, hydrogen 5 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. The obtained high density polyethylene (HD-2) had MFR = 1.0 g / 10 min and a density of 952 kg / m ³ . Table 1 shows the basic characteristic evaluation results of HD-2.

HD-3
Table 1 shows the results of basic characteristics evaluation of Tosoh Corporation, (trade name) Nipolon Hard 2400 (MFR = 8.0 g / 10 min, density = 953 kg / m ³ ) HD-3.

HD-4
Table 1 shows the results of evaluation of basic properties of Tosoh Corporation, (trade name) Nipolon Hard 8500 (MFR = 0.35 g / 10 min, density = 949 kg / m ³ ) HD-4.
(2) Linear low density polyethylene LL-1 [Preparation of modified clay]
To 1,500 ml of water, 30 ml of 37% hydrochloric acid and 106 g of N, N-dimethyl-behenylamine were added to prepare an aqueous solution of N, N-dimethyl-behenylammonium hydrochloride. 300 g of montmorillonite having an average particle size of 7.8 μm (manufactured by Kunimine Kogyo Co., Ltd., prepared by pulverizing trade name Kunipia F with a jet pulverizer) was added to the above hydrochloride aqueous solution and reacted for 6 hours. After completion of the reaction, the reaction solution was filtered, and the resulting cake was dried under reduced pressure for 6 hours to obtain 370 g of a modified clay compound.
[Preparation of polymerization catalyst]
To a 20 L stainless steel container under a nitrogen atmosphere, add 3.3 L of heptane, a heptane solution of triethylaluminum (diluted 20 wt%) 1.13 mol (0.9 L) per aluminum atom, and 50 g of the modified clay compound obtained above. Stir for hours. Thereto was added 1.25 mmol of diphenylmethylene (4-phenyl-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride per zirconium atom, and the mixture was stirred for 12 hours. A catalyst was prepared by adding 5.8 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 0.125 mmol / L)
[Manufacture of LL-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 18 mol%, and the hydrogen concentration was 7 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. The obtained linear low density polyethylene (LL-1) had MFR = 3.5 g / 10 min and a density of 910 kg / m ³ . Table 2 shows the results of basic characteristic evaluation of LL-1.

LL-2
[Preparation of modified clay]
A modified clay compound was prepared in the same manner as LL-1.
[Preparation of polymerization catalyst]
A polymerization catalyst was prepared by the same method as LL-1.
[Manufacture of LL-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. The obtained linear low-density polyethylene (LL-2) had an MFR = 2.0 g / 10 min and a density of 907 kg / m ³ . Table 2 shows the basic characteristic evaluation results of LL-2.

LL-3
[Preparation of modified clay]
A modified clay compound was prepared in the same manner as LL-1.
[Preparation of polymerization catalyst]
A polymerization catalyst was prepared by the same method as LL-1.
[Manufacture of LL-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 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. The obtained linear low density polyethylene (LL-3) had MFR = 0.8 g / 10 minutes and a density of 900 kg / m ³ . Table 2 shows the basic characteristic evaluation results of LL-3.

LL-4
[Preparation of modified clay]
A modified clay compound was prepared in the same manner as LL-1.
[Preparation of polymerization catalyst]
A polymerization catalyst was prepared by the same method as LL-1.
[Manufacture of LL-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 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. The obtained linear low-density polyethylene (LL-4) had MFR = 12.0 g / 10 min and a density of 907 kg / m ³ . Table 2 shows the results of basic characteristic evaluation of LL-4.

LL-5
Table 2 shows the basic characteristic evaluation results of (trade name) Nipolon-Z ZF230 (MFR = 2.0 g / 10 min, density = 920 kg / m ³ ) LL-5 manufactured by Tosoh Corporation.
(3) Ethylene polymer PE-1
[Preparation of modified clay]
Into a 1 L flask is 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. 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 μm.
[Preparation of polymerization catalyst]
A 300 mL flask equipped with a thermometer and a reflux tube was purged with nitrogen, and 25.0 g of the organically modified clay obtained in [Preparation of modified clay] and 108 mL of hexane were added, and then dimethylsilylene (cyclopentadienyl) (2 , 4,7-Trimethylindenyl) zirconium dichloride was added in an amount of 0.4406 g and 142 mL of 20% triisobutylaluminum, followed by stirring at 60 ° C. for 3 hours. After cooling to 45 ° C., the supernatant was extracted, washed 5 times with 200 mL of hexane, and then 200 mL of hexane was added to obtain a catalyst suspension. (Solid weight: 12.4 wt%)
[Production of PE-1]
To a 2 L autoclave, add 1.2 L of hexane, 1.0 mL of 20% triisobutylaluminum, and 52 mg of the catalyst suspension obtained in [Preparation of polymerization catalyst] (corresponding to 6.4 mg solid content), and the temperature is raised to 70 ° C. After warming, 17.6 g of 1-butene was added, and an ethylene / hydrogen mixed gas was continuously supplied so that the partial pressure was 0.80 MPa (concentration of hydrogen in the ethylene / hydrogen mixed gas: 590 ppm). After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain 61.8 g of polymer. 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. Further, the number of long chain branches contained in the fraction of Mn 100,000 or more when molecular weight fractionation was 0.27 per 1000 carbons of the main chain. Moreover, the ratio of the fraction of Mn 100,000 or more when molecular weight fractionation was 20.1 wt% of the total polymer. The melt tension was 75 mN. Table 3 shows the results of evaluation of basic characteristics of PE-1.

PE-2
[Preparation of modified clay]
Into a 1 L flask, 300 mL of industrial alcohol (trade name: Echinen F-3, manufactured by Nippon Alcohol Sales Co., Ltd.) and 300 mL of distilled water were added. 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. 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 μm.
[Preparation of polymerization catalyst]
A 300 mL flask equipped with a thermometer and a reflux tube was purged with nitrogen, and 25.0 g of the organically modified clay obtained in [Preparation of modified clay] and 108 mL of hexane were added, and then dimethylsilylene (cyclopentadienyl) (2 , 4,7-trimethyl-1-indenyl) zirconium dichloride and 0.4406 g of 20% triisobutylaluminum were added and stirred at 60 ° C. for 3 hours. After cooling to 45 ° C., the supernatant was extracted, washed 5 times with 200 mL of hexane, and then 200 mL of hexane was added to obtain a catalyst suspension. (Solid weight: 12.0wt%)
[Production of PE-2]
To a 2 L autoclave, add 1.2 L of hexane, 1.0 mL of 20% triisobutylaluminum, and 75 mg of the catalyst suspension obtained in [Preparation of polymerization catalyst] (corresponding to a solid content of 9.0 mg). After warming, 8.3 g of 1-butene was added, and an ethylene / hydrogen mixed gas was continuously supplied so that the partial pressure became 0.85 MPa (concentration of hydrogen in the ethylene / hydrogen mixed gas: 850 ppm). After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain 58.5 g of polymer. 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. Further, the number of long chain branches contained in the fraction of Mn 100,000 or more when molecular weight fractionation was 0.18 per 1000 carbons of the main chain. Moreover, the ratio of the fraction of Mn of 100,000 or more when molecular weight fractionation was 14.8 wt% of the total polymer. The melt tension was 49 mN. Table 3 shows the results of basic characteristic evaluation of PE-2.

PE-3
[Preparation of modified clay]
Into a 1 L flask, put 300 mL of industrial alcohol (Japan Alcohol Sales (trade name) Echinen F-3) and 300 mL of distilled water, 20.0 g of concentrated hydrochloric acid and dimethylbehenylamine (Lion Corporation (trade name) Armin DM22D). ) 56.5 g (160 mmol) was added, 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. 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 μm.
[Preparation of polymerization catalyst]
After a 300 mL flask equipped with a thermometer and a reflux tube was purged with nitrogen, 25.0 g of the organically modified clay obtained in (1) and 108 mL of hexane were added, and then dimethylsilylene (cyclopentadienyl) (2, 4, 4 0.4406 g of 7-trimethyl-1-indenyl) zirconium dichloride and 142 mL of 20% triisobutylaluminum were added and stirred at 60 ° C. for 3 hours. After cooling to 45 ° C., the supernatant was extracted, washed 5 times with 200 mL of hexane, and then 200 mL of hexane was added to obtain a catalyst suspension. (Solid weight: 11.2 wt%)
[Production of PE-3]
To a 2 L autoclave, add 1.2 L of hexane, 1.0 mL of 20% triisobutylaluminum, and 74 mg (equivalent to 8.3 mg of solid content) of the catalyst suspension obtained in [Preparation of polymerization catalyst], and raise the temperature to 65 ° C. After warming, 17.5 g of 1-butene was added, and an ethylene / hydrogen mixed gas was continuously supplied so that the partial pressure was 0.75 MPa (hydrogen concentration in the ethylene / hydrogen mixed gas: 570 ppm). After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain 51.5 g of polymer. 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. Further, the number of long chain branches contained in the fraction of Mn 100,000 or more when molecular weight fractionation was 0.26 per 1000 carbons of the main chain. Moreover, the ratio of the fraction of Mn 100,000 or more when molecular weight fractionation was 25.4 wt% of the total polymer. The melt tension was 90 mN. Table 3 shows the results of evaluation of basic characteristics of PE-3.

PE-4
[Preparation of modified clay]
Into a 1 L flask is placed 300 mL of industrial alcohol (Japan Alcohol Sales (trade name) Echinen F-3) and 300 mL of distilled water, 15.0 g of concentrated hydrochloric acid and dimethylbehenylamine (Lion Corporation (trade name) Armin DM22D). ) 42.4 g (120 mmol) was added, 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. 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 μm.
[Preparation of polymerization catalyst]
A 300 mL flask equipped with a thermometer and a reflux tube was purged with nitrogen, and 25.0 g of the organically modified clay obtained in [Preparation of modified clay] and 108 mL of hexane were added, and then dimethylsilylene (cyclopentadienyl) (2 , 4,7-trimethyl-1-indenyl) zirconium dichloride and 0.4406 g of 20% triisobutylaluminum were added and stirred at 60 ° C. for 3 hours. After cooling to 45 ° C., the supernatant was extracted, washed 5 times with 200 mL of hexane, and then 200 mL of hexane was added to obtain a catalyst suspension. (Solid weight: 11.5 wt%)
[Production of PE-4]
To a 2 L autoclave, add 1.2 L of hexane, 1.0 mL of 20% triisobutylaluminum, and 70 mg (equivalent to 8.4 mg of solid content) of the catalyst suspension obtained in [Preparation of polymerization catalyst] and raise the temperature to 80 ° C. After warming, 2.4 g of 1-butene was added, and an ethylene / hydrogen mixed gas was continuously supplied so that the partial pressure became 0.90 MPa (concentration of hydrogen in the ethylene / hydrogen mixed gas: 720 ppm). After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain 63.0 g of polymer. 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. Further, the number of long chain branches contained in the fraction of Mn 100,000 or more when molecular weight fractionation was 0.16 per 1000 carbons of the main chain. Moreover, the ratio of the fraction of Mn 100,000 or more when molecular weight fractionation was 6.8 wt% of the total polymer. The melt tension was 38 mN. Table 3 shows the basic characteristic evaluation results of PE-4.

PE-5
[Preparation of modified clay]
Into a 1 L flask is placed 300 mL of industrial alcohol (Japan Alcohol Sales (trade name) Echinen F-3) and 300 mL of distilled water, 15.0 g of concentrated hydrochloric acid and dimethylbehenylamine (Lion Corporation (trade name) Armin DM22D). ) 42.4 g (120 mmol) was added, 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. 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 μm.
[Preparation of polymerization catalyst]
A 300 mL flask equipped with a thermometer and a reflux tube was purged with nitrogen, and 25.0 g of the organically modified clay obtained in [Preparation of modified clay] and 108 mL of hexane were added, and then dimethylsilylene (cyclopentadienyl) (2 , 4,7-trimethyl-1-indenyl) zirconium dichloride and 0.4406 g of 20% triisobutylaluminum were added and stirred at 60 ° C. for 3 hours. After cooling to 45 ° C., the supernatant was extracted, washed 5 times with 200 mL of hexane, and then 200 mL of hexane was added to obtain a catalyst suspension. (Solid weight: 11.5 wt%)
[Production of PE-5]
To a 2 L autoclave, add 1.2 L of hexane, 1.0 mL of 20% triisobutylaluminum, and 70 mg (equivalent to 8.4 mg of solid content) of the catalyst suspension obtained in [Preparation of polymerization catalyst] and raise the temperature to 80 ° C. After warming, 2.4 g of 1-butene was added, and an ethylene / hydrogen mixed gas was continuously supplied so that the partial pressure became 0.90 MPa (concentration of hydrogen in the ethylene / hydrogen mixed gas: 750 ppm). After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain 63.0 g of polymer. The obtained polymer had an MFR of 15.5 g / 10 min and a density of 954 kg / m ³ . Moreover, the number average molecular weight was 15,500, the weight average molecular weight was 52,700, and peaks were observed at positions of molecular weights 27,900 and 179,000. Further, the number of long chain branches contained in the fraction of Mn 100,000 or more when molecular weight fractionation was 0.16 per 1000 carbons of the main chain. Moreover, the ratio of the fraction of Mn 100,000 or more when molecular weight fractionation was 6.5 wt% of the total polymer. The melt tension was 35 mN. Table 3 shows the results of evaluation of basic characteristics of PE-5.

PE-6
[Preparation of modified clay]
Into a 1 L flask is placed 300 mL of industrial alcohol (Japan Alcohol Sales (trade name) Echinen F-3) and 300 mL of distilled water, 15.0 g of concentrated hydrochloric acid and dimethylbehenylamine (Lion Corporation (trade name) Armin DM22D). ) 42.4 g (120 mmol) was added, 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. 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 μm.
[Preparation of polymerization catalyst]
A 300 mL flask equipped with a thermometer and a reflux tube was purged with nitrogen, and 25.0 g of the organically modified clay obtained in [Preparation of modified clay] and 108 mL of hexane were added, and then dimethylmethylene (cyclopentadienyl) (2 , 7-di-t-butyl-9-fluorenyl) zirconium dichloride / 0.5447 g and 142 mL of 20% triisobutylaluminum were added and stirred at 60 ° C. for 3 hours. After cooling to 45 ° C., the supernatant was extracted, washed 5 times with 200 mL of hexane, and then 200 mL of hexane was added to obtain a catalyst suspension. (Solid weight: 10.9 wt%)
[Production of PE-6]
Add 1.2 L of hexane, 1.0 mL of 20% triisobutylaluminum to a 2 L autoclave, and 86 mg (equivalent to 9.4 mg of solid content) of the catalyst suspension obtained in [Preparation of polymerization catalyst], and the temperature is raised to 65 ° C. After warming, 17.5 g of 1-butene was added, and an ethylene / hydrogen mixed gas was continuously supplied so that the partial pressure became 0.75 MPa (concentration of hydrogen in the ethylene / hydrogen mixed gas: 610 ppm). After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain 17.9 g of polymer. The obtained polymer had an MFR of 5.0 g / 10 min and a density of 910 kg / m ³ . The number average molecular weight was 28,000, the weight average molecular weight was 82,300, and peaks were observed at the positions of molecular weights 42,500 and 260,900. Further, the number of long chain branches contained in the fraction of Mn 100,000 or more when molecular weight fractionation was 0.40 per 1000 carbons of the main chain. Moreover, the ratio of the fraction of Mn 100,000 or more when molecular weight fractionation was 39.8 wt% of the total polymer. The melt tension was 45 mN. Table 3 shows the results of evaluation of basic characteristics of PE-6.

PE-7
[Preparation of modified clay]
Into a 1 L flask is placed 300 mL of industrial alcohol (Japan Alcohol Sales (trade name) Echinen F-3) and 300 mL of distilled water, 15.0 g of concentrated hydrochloric acid and dimethylbehenylamine (Lion Corporation (trade name) Armin DM22D). ) 42.4 g (120 mmol) was added, 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. 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 μm.
[Preparation of polymerization catalyst]
After substituting a 300 mL flask equipped with a thermometer and a reflux tube with nitrogen, 25.0 g of the organically modified clay obtained in [Preparation of modified clay] was suspended in 165 mL of hexane, and dimethylsilanediylbis (cyclopentadienyl) was suspended. ) 0.3485 g of zirconium dichloride and 85 mL of a hexane solution of triethylaluminum (1.18 M) were added and stirred at 60 ° C. for 3 hours. After allowing to stand and cooling to room temperature, the supernatant was taken out and washed twice with 200 mL of a 1% triisobutylaluminum hexane solution. The supernatant liquid after washing was extracted and the whole was made up to 250 mL with a 5% triisobutylaluminum hexane solution. Subsequently, a 20% triisobutylaluminum hexane solution (0%) was added to a suspension of diphenylmethylene (1-cyclopentadienyl) (2,7-di-tert-butyl-9-fluorenyl) zirconium dichloride 0.1165 g in hexane 10 mL. .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: 12.0wt%)
[Production of PE-7]
To a 2 L autoclave, add 1.2 L of hexane, 1.0 mL of 20% triisobutylaluminum, and 125 mg (corresponding to a solid content of 15.0 mg) of the catalyst suspension obtained in [Preparation of polymerization catalyst]. After warming, 2.4 g of 1-butene was added, and ethylene was continuously supplied so that the partial pressure became 0.90 MPa. After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain 45.0 g of polymer. The obtained polymer had an MFR of 4.4 g / 10 min and a density of 951 kg / m ³ . 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. Moreover, 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. Moreover, the ratio of the fraction of Mn of 100,000 or more when molecular weight fractionation was 15.7 wt% of the total polymer. The melt tension was 210 mN. Table 3 shows the results of evaluation of basic characteristics of PE-7.

Ｂ．単層フィルムおよび医療容器
実施例、比較例に用いた単層フィルム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。

B. Single-layer film and medical container The single-layer film and medical container used in Examples and Comparative Examples were produced by the following method and sterilized.

<Manufacture of monolayer film and medical container>
A single-layer film having a film width of 135 mm and a film thickness of 250 μm was formed at a cylinder temperature of 180 ° C., a water bath temperature of 15 ° C., and a take-off speed of 4 m / min using a single-layer water-cooled inflation molding machine (manufactured by Placo). Next, a sample having a length of 195 mm was cut out from the single-layer film, heat sealed at one end, filled with 300 ml of ultrapure water, 50 ml of headspace was provided, and heat sealed to form a medical container. Produced.

<Sterilization treatment>
The medical container was sterilized at a temperature of 115 ° C. for 30 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.

<Molding stability>
The stability of the film (bubble) at the time of film formation was visually observed and evaluated by a single-layer water-cooled inflation molding machine.

○: Bubble stability is good ×: Bubble fluctuation is large <Surface smoothness of film>
The surface state of the molded film was visually observed and evaluated.

○: Excellent surface smoothness ×: Large surface roughness <Film appearance>
The film surface after sterilization is visually evaluated for wrinkles, deformation, film fusion, etc., and 4 points when wrinkles and deformation are not observed, 3 points when slight wrinkles and deformation are observed, 3 points. Two points were given when wrinkles and deformation were observed, and one point was given when the inner layers were fused together.

<Transparency>
A test piece having a width of 10 mm and a length of 50 mm was cut out from the single-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.

<Flexibility of film>
In accordance with JIS K 7161, a test piece was punched out from the sterilized medical container, and a 5% elastic modulus was measured using a tensile tester (model Autograph DCS-500, manufactured by Shimadzu Corporation). When the value of the elastic modulus was 200 MPa or less, the flexibility was good, and when it exceeded 200 MPa, the flexibility was poor.

○: Good flexibility ×: Poor flexibility <Moisture permeability>
In accordance with JIS K 7129 A method (humidity sensitive sensor method), the moisture permeability of a test piece cut out from the sterilized medical container was measured with a water vapor permeability meter (model L80-5000, manufactured by Lyssy). A case where the moisture permeability is 1.0 g / (m ² · 24 h) or less was used as a standard for a medical container having good barrier properties.

<Cleanness (number of fine particles)>
Ultrapure water whose number of fine particles of 1 μm or more was confirmed to be 0/10 ml was filled and sealed in a medical container manufactured by the method described in the above-mentioned “Manufacture of medical container”, and then 30 ° C. at 115 ° C. After carrying out a hot water sterilization treatment for 1 minute and leaving it to stand for 1 day, the number of fine particles of 1 μm or more was measured using a fine particle counter “M-3000 · 4100 · HR-60HA” manufactured by HIAC / ROYCO. These operations were all performed in a class 1000 clean room. A case where the number of fine particles was 10 / ml or less was used as a guideline for a medical container with good cleanliness.

Example 1
Using the resin materials shown in Table 4, a single-layer film was formed by a water-cooled inflation molding machine, and the molding stability, the surface state of the film and the transparency were evaluated. The film thickness was 250 μm. Next, the obtained film is heat-sealed to prepare a medical container filled with ultrapure water, and autoclaved at 115 ° C. for 30 minutes. After sterilization, the film appearance, transparency, flexibility, moisture permeability and Cleanliness (number of fine particles) was evaluated. The results are shown in Table 4.

Examples 2-6, Comparative Examples 1-7
A single layer film and a medical container were prepared and evaluated in the same manner as in Example 1 except that the resin material was changed as shown in Tables 4 and 5. The results are shown in Table 4 and Table 5.

Comparative Example 8
Ethylene polymer (C) is a commercially available low density polyethylene from PE-2 [manufactured by Tosoh Corporation, (trade name) Petrocene 339, (MFR = 3.0 g / 10 min, density = 924 kg / m ³ )] ( A single-layer film and a medical container were produced and evaluated in the same manner as in Example 2 except that it was changed to S-1). The results are shown in Table 5. The characteristics of S-1 are shown in Table 3.

Comparative Example 9
Ethylene polymer (C) is commercially available high density polyethylene from PE-2 [S-2: manufactured by Nippon Polyolefin Co., Ltd., (trade name) RS1000, (MFR = 0.1 g / 10 min, density = 953 kg / m) ³ )] (hereinafter referred to as S-2) A single layer film and a medical container were prepared and evaluated in the same manner as in Example 2 except that the evaluation was performed. The results are shown in Table 5. The characteristics of S-2 are shown in Table 3.

Comparative Example 10
Ethylene polymer (C) is commercially available high density polyethylene from PE-2 [S-3: manufactured by Nippon Polyethylene Co., Ltd., (trade name) KBX47D, (MFR = 0.04 g / 10 min, density = 946 kg / m) ³ )] (hereinafter referred to as S-3) A single-layer film and a medical container were prepared and evaluated in the same manner as in Example 2. The results are shown in Table 5. The characteristics of S-3 are shown in Table 3.

Claims (5)

A medical container comprising a storage portion for storing liquid medicine, at least the housing part high-density polyethylene (A) 10 to 50% by weight satisfy the following Symbol properties (a) ~ (b), the following characteristics (c ) To (d) satisfying 20 to 70% by weight of the linear low density polyethylene (B) and the ethylene polymer (C) satisfying the following characteristics (e) to (h) (1 to 50% by weight ((A ), (B) and (C) are 100% by weight in total).
(A) A density is 935-970 kg / m < ³ >.
(B) MFR is 0.1 to 15 g / 10 min.
(C) The density is 890 to 920 kg / m ³ .
(D) MFR is 0.1 to 15 g / 10 min.
(E) The density is 920-960 kg / m ³ .
(F) MFR is 0.1 to 15 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. The medical container according to claim 1, wherein the container for storing the chemical solution is a film-shaped molded body formed into a bag shape by hot plate molding. The medical container according to claim 1 or 2, wherein the container for storing the chemical liquid is formed into a bottle shape by blow molding. The Mw / Mn of the ethylene-based polymer (C) is in the range of 3.0 to 6.0, and the Mn is 15,000 or more and 100,000 or less. The medical container described. The ratio of the component whose Mn is 100,000 or more when molecular weight fractionation of the ethylene-based polymer (C) is less than 40% of the entire ethylene-based polymer (C). Medical container according to crab.