Resin composition and film comprising it
11407884 · 2022-08-09
Assignee
Inventors
Cpc classification
C08L23/0815
CHEMISTRY; METALLURGY
C08L65/00
CHEMISTRY; METALLURGY
C08L23/0815
CHEMISTRY; METALLURGY
C08L45/00
CHEMISTRY; METALLURGY
International classification
C08L45/00
CHEMISTRY; METALLURGY
Abstract
To provide a resin composition comprising a cyclic polyolefin and an ethylene polymer, having excellent impact resistance and having high transparency maintained. A resin composition comprising from 5 to 95 parts by weight of a cyclic polyolefin (A) and from 5 to 95 parts by weight of an ethylene polymer (B) which satisfies the following requirements (a) to (d) (the total amount of (A) and (B) is 100 parts by weight): (a) the density is from 930 to 960 kg/m.sup.3; (b) MFR is from 0.1 to 15.0 g/10 min; (c) in molecular weight measurement by gel permeation chromatography, two peaks are observed, and the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is within a range of from 3.0 to 7.0; and (d) a fraction having Mn of at least 100,000 as obtained by molecular weight fractionation, has at least 0.15 long-chain branches per 1,000 carbon atoms of the main chain.
Claims
1. A resin composition comprising from 5 to 95 parts by weight of a cyclic polyolefin (A) and from 5 to 95 parts by weight of an ethylene polymer (B) which satisfies the following requirements (a) to (d) (the total amount of (A) and (B) is 100 parts by weight): (a) the density as measured by density gradient tube method in accordance with JIS K6922-1 is from 930 to 960 kg/m.sup.3; (b) the melt mass flow rate as measured in accordance with JIS K6922-1 at 190° C. under a load of 21.18 N is from 1 to 15 g/10 min; (c) in molecular weight measurement by gel permeation chromatography, two peaks are observed, and the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is within a range of from 3.0 to 7.0; and (d) a fraction having Mn of at least 100,000 as obtained by molecular weight fractionation, has at least 0.15 long-chain branches having at least 6 carbon atoms per 1,000 carbon atoms of the main chain.
2. The resin composition according to claim 1, which comprises from 10 to 90 parts by weight of the cyclic polyolefin resin (A) and from 10 to 90 parts by weight of the ethylene polymer (B).
3. The resin composition according to claim 1, which comprises from 20 to 40 parts by weight of the cyclic polyolefin (A) and from 60 to 80 parts by weight of the ethylene polymer (B).
4. The resin composition according to claim 1, wherein of the ethylene polymer (B), Mw/Mn is within a range of from 3.0 to 6.0, and Mn is at least 15,000.
5. The resin composition according to claim 1, wherein the proportion of a component having Mn of at least 100,000 as obtained by molecular weight fractionation of the ethylene polymer (B), is less than 40% of the entire ethylene polymer (B).
6. The resin composition according to claim 1, which further contains from 20 to 300 parts by weight of a high density polyethylene (C) which satisfies the following requirements (e) to (g) per 100 parts by weight of the cyclic polyolefin resin (A) and the ethylene polymer (B): (e) the density as measured by density gradient tube method in accordance with JIS K6922-1 is from 940 to 970 kg/m.sup.3; (f) the melt mass flow rate as measured in accordance with JIS K6922-1 at 190° C. under a load of 21.18 N is from 0.1 to 15 g/10 min; (g) a fraction having Mn of at least 100,000 as obtained by molecular weight fractionation has at most 0.14 long-chain branches having at least 6 carbon atoms per 1,000 carbon atoms of the main chain.
7. The resin composition according to claim 6, which contains from 80 to 150 parts by weight of the high density polyethylene (C) per 100 parts by weight of the cyclic polyolefin resin (A) and the ethylene polymer (B).
8. A resin composition comprising from 20 to 40 parts by weight of a cyclic polyolefin (A) and from 60 to 80 parts by weight of a high density polyethylene (C) which satisfies the following requirements (e) to (g) (the total amount of (A) and (C) is 100 parts by weight): (e) the density as measured by density gradient tube method in accordance with JIS K6922-1 is from 940 to 970 kg/m.sup.3; (f) the melt mass flow rate as measured in accordance with JIS K6922-1 at 190° C. under a load of 21.18 N is from 1 to 15 g/10 min; (g) a fraction having Mn of at least 100,000 as obtained by molecular weight fractionation has at most 0.14 long-chain branches having at least 6 carbon atoms per 1,000 carbon atoms of the main chain.
9. The resin composition according to claim 8, which comprises from 30 to 40 parts by weight of the cyclic polyolefin resin (A) and from 60 to 70 parts by weight of the high density polyethylene (C).
10. The resin composition according to claim 6, wherein of the high density polyethylene (C), Mw/Mn is within a range of from 2.0 to 3.5, and Mn is at least 25,000.
11. A film comprising the resin composition according to claim 1.
12. A film using the film as defined in claim 11 for a sealant layer.
Description
BRIEF DESCRIPTION OF DRAWINGS
(1)
(2)
REFERENCE SYMBOLS
(3) 10: Multi-chamber container prepared from a cylindrical blown film 11: Easily releasable sealed portion 12: Periphery strongly sealed portion 13: Chamber partitioned by easily releasable sealed portion EXAMPLES
(4) Now, the present invention will be described in further detail with reference to Examples. However, it should be understood that the present invention is by no means restricted to such specific Examples.
(5) A: Resin
(6) Various physical properties of the resin used in Examples and Comparative Examples were evaluated by the following method.
(7) <Molecular Weight, Molecular Weight Distribution>
(8) The weight average molecular weight (Mw), the number average molecular weight (Mn), the ratio (Mw/Mn) of the weight average molecular weight to the number average molecular weight and the peak top molecular weight (Mp) were measured by GPC, using a GPC apparatus (manufactured by TOSOH CORPORATION, HLC-8121GPC/HT (trade name)) and a column (manufactured by TOSOH CORPORATION, TSKgel GMHhr-H(20)HT (trade name)), at a column temperature set at 140° C., using 1,2,4-trichlorobenzene as an eluent. The measurement sample was prepared at a concentration of 1.0 mg/ml, and 0.3 ml of the measurement sample was injected for measurement. The analytical curve of the molecular weight was calibrated using a polystyrene sample having a known molecular weight. Mw and Mn were obtained as values as calculated as linear polyethylene.
(9) <Molecular Weight Fractionation>
(10) For molecular weight fractionation, using as a column a column (diameter 21 mm, length: 60 nm) packed with glass beads, at a column temperature set at 130° C., a solution of 1 g of a sample dissolved in 30 mL of xylene was injected. Then, using a mixture of xylene/2-ethoxyethanol in a proportion of 5:5 as a developing solvent, distillates were removed. Then, using xylene as a developing solvent, components remaining in the column were distilled off to obtain a polymer solution. The obtained polymer solution was mixed with methanol in an amount 5 times the polymer solution to precipitate polymer content, which was subjected to filtration and dried to obtain a component having Mn of at least 100,000.
(11) <Long-Chain Branch>
(12) To obtain the number of long-chain branches, the number of branches of a hexyl group and longer was measured by 13C-NMR using JNM-GSX400 nuclear magnetic resonance spectrometer manufactured by JEOL Ltd. The solvent was benzene-d6/orthodichlorobenzene (volume ratio: 30/70). The number per 1,000 carbon atoms (chemical shift: 30 ppm) of the main chain methylene carbon, was obtained from the average values of peaks of α-carbon (34.6 ppm) and β-carbon (27.3 ppm).
(13) <Density>
(14) The density was measured by density gradient tube method in accordance with JIS K6922-1.
(15) <MFR>
(16) MFR was measured in accordance with JIS K6922-1.
(17) <Melt Tension>
(18) As a sample for measuring the melt tension, a sample having a heat stabilizer (Irganox 1010™, 1,500 ppm, Irgafos 168™, 1,500 ppm, manufactured by Ciba Specialty Chemicals) added was kneaded by an internal mixer (manufactured by Toyo Seiki Seisaku-Sho, Ltd., trade name: LABO PLASTOMILL) in a stream of nitrogen at 190° C. at a number of revolutions of 30 rpm for 30 minutes.
(19) To measure the melt tension, to a capillary viscometer (manufactured by Toyo Seiki Seisaku-Sho, Ltd., trade name: CAPILOGRAPH) having a barrel diameter of 9.55 mm, a die having a length of 8 mm and a diameter of 2.095 mm was set so that the entrance angle would be 90° for measurement. The temperature was set at 160° C., the piston descending speed was 10 mm/min, the draw ratio was set at 47, and the load (mN) required for drawing was taken as the melt tension. In a case where the maximum draw ratio was less than 47, the load (mN) required for drawing at the maximum draw ratio at which breaking did not occur was taken as the melt tension.
(20) In Examples and Comparative Examples, resins prepared by the following methods and commercial products were used.
(21) (1) Cyclic Polyolefin
(22) The following commercial products were used.
(23) (A)-1: Manufactured by Mitsui Chemicals, Inc., APEL APL6509T (trade name) ([MFR (ASTM D1238 (260° C., 21.18 N))]: 30 g/10 min)
(24) (A)-2: Manufactured by Zeon Corporation, Zeonor 1020R (trade name) ([MFR (ISO 1133 (280° C., 21.1 N))]: 20 g/10 min)
(25) (A)-3: Manufactured by TOPAS Advanced Polymers, TOPAS 9506F-04 (trade name) ([MVR (ISO 1133 (230° C., 21.18 N))]: 6 g/10 min)
(26) (A)-4: Manufactured by TOPAS Advanced Polymers, TOPAS 8007F-04 (trade name) ([MVR (ISO 1133 (230° C., 21.18 N))]: 12 g/10 min)
(27) (2) Ethylene Polymer
(28) One obtained by any of the following production methods or a commercial product was used.
(29) (B)-1: Obtained by the Following Production Method.
(30) [Preparation of Modified Clay]
(31) Into a 1 L flask, 300 mL of industrial alcohol (manufactured by Japan Alcohol Trading CO., LTD., EKINEN F-3 (trade name)) and 300 mL of distilled water were put, 18.8 g of concentrated hydrochloric acid and 49.1 g (120 mmol) of dimethylhexacosylamine (Me.sub.2N(C.sub.26H.sub.53), prepared by conventional method) were added, followed by heating at 45° C., 100 g of synthetic Hectorite (manufactured by Rockwood Additives Ltd., LAPONITE RDS (trade name)) was dispersed, and the dispersion was heated to 60° C. and stirred for one hour while the temperature was maintained. The slurry was subjected to filtration, the residue was washed with 600 mL of water of 60° C. twice and dried in a dryer at 85° C. for 12 hours to obtain 140 g of organic modified clay. The organic modified clay was pulverized by a jet mill to a median diameter of 14 μm.
(32) [Preparation of Polymer Catalyst]
(33) A 300 mL flask equipped with a thermometer and a reflux condenser was replaced with nitrogen, and 25.0 g of the organic modified clay obtained in [Preparation of modified clay] and 108 mL of hexane were put, and then 0.4406 g of dimethylsilylene(cyclopentadienyl)(2,4,7-trimethyl-1-indenyl)zirconium dichloride and 142 mL of 20% triisobutylaluminum were added, followed by stirring at 60° C. for 3 hours. The mixture was cooled to 45° C., the supernatant was withdrawn, and the residue was washed with 200 mL of hexane five times and mixed with 200 ml of hexane to obtain a catalyst suspension (solid content by weight: 12.0 wt %).
(34) [Production of (B)-1]
(35) Into a 2 L autoclave, 1.2 L of hexane, 1.0 mL of 20% triisobutylaluminum and 75 mg (corresponding to solid content 9.0 mg) of the catalyst suspension obtained in [Preparation of polymerization catalyst] were added, followed by heating to 80° C., 8.3 g of 1-butene was added, and an ethylene/hydrogen mixed gas was continuously supplied (concentration of hydrogen in ethylene/hydrogen mixed gas: 850 ppm) so that the partial pressure would be 0.85 MPa. 90 minutes later, the pressure was lowered, and the slurry was subjected to filtration, and the residue was dried to obtain 58.5 g of polymer. Of the polymer, MFR was 4.0 g/10 min, and the density was 941 kg/m.sup.3. Further, the number average molecular weight was 21,200, the weight average molecular weight was 74,000, and peaks were observed at positions of molecular weights of 41,500 and 217,100. Further, the number of long-chain branches contained in a fraction having Mn of at least 100,000 as obtained by molecular weight fractionation was 0.18 per 1,000 carbon atoms of the main chain. Further, the proportion of the fraction having Mn of at least 100,000 as obtained by molecular weight fractionation was 14.8 wt % of the entire polymer. Further, the melt tension was 49 mN. The evaluation results are shown in Table 1.
(36) (B)-2: Obtained by the Following Production Method.
(37) [Preparation of Modified Clay]
(38) Into a 1 L flask, 300 mL of industrial alcohol (manufactured by Japan Alcohol Trading CO., LTD., EKINEN F-3 (trade name)) and 300 mL of distilled water were put, 17.5 g of concentrated hydrochloric acid and 49.4 g (140 mmol) of dimethylbehenylamine (manufactured by Lion Corporation, FARMIN DM22D (trade name)) were added, followed by heating to 45° C., 100 g of synthetic Hectorite (manufactured by Rockwood Additives Ltd., LAPONITE RDS (trade name)) was dispersed, and the dispersion was heated to 60° C. and stirred for one hour while the temperature was maintained. The slurry was subjected to filtration, the residue was washed with 600 mL of water of 60° C. twice and dried in a dryer at 85° C. for 12 hours to obtain 132 g of organic modified clay. The organic modified clay was pulverized by a jet mill to a median diameter of 15 μm.
(39) [Preparation of Polymerization Catalyst]
(40) A 300 mL flask equipped with a thermometer and a reflux condenser was replaced with nitrogen, 25.0 g of the organic modified clay obtained in [Preparation of modified clay] and 108 mL of hexane were put, and then 0.4406 g of dimethylsilylene(cyclopentadienyl)(2,4,7-trimethylindenyl)zirconium dichloride and 142 mL of 20% triisobutylaluminum were added, followed by stirring at 60° C. for 3 hours. The mixture was cooled to 45° C., the supernatant was withdrawn, and the residue was washed with 200 mL of hexane five times and mixed with 200 ml of hexane to obtain a catalyst suspension (solid content by weight: 12.4 wt %).
(41) [Production of (B)-2]
(42) Into a 2 L autoclave, 1.2 L of hexane, 1.0 mL of 20% triisobutylaluminum and 52 mg (corresponding to solid content 6.4 mg) of the catalyst suspension obtained in [Preparation of polymerization catalyst] were added, followed by heating to 70° C., 17.6 g of 1-butene was added, and an ethylene/hydrogen mixed gas was continuously supplied (concentration of hydrogen in ethylene/hydrogen mixed gas: 590 ppm) so that the partial pressure would be 0.80 MPa. 90 minutes later, the pressure was lowered, and the slurry was subjected to filtration, and the residue was dried to obtain 61.8 g of polymer. Of the polymer, MFR was 1.6 g/10 min, and the density was 930 kg/m.sup.3. Further, the number average molecular weight was 17,600, the weight average molecular weight was 86,700, and peaks were observed at positions of molecular weights of 30,500 and 155,300. Further, the number of long-chain branches contained in a fraction having Mn of at least 100,000 as obtained by molecular weight fractionation was 0.27 per 1,000 carbon atoms of the main chain. Further, the proportion of the fraction having Mn of at least 100,000 as obtained by molecular weight fractionation was 20.1 wt % of the entire polymer. Further, the melt tension was 75 mN. The evaluation results are shown in Table 1.
(43) (B)-3: Obtained by the Following Production Method.
(44) [Preparation of Modified Clay]
(45) Into a 1 L flask, 300 mL of industrial alcohol (manufactured by Japan Alcohol Trading Co., Ltd., EKINEN F-3 (trade name)) and 300 mL of distilled water were put, 15.0 g of concentrated hydrochloric acid and 42.4 g (120 mmol) of dimethylbehenylamine (manufactured by Lion Corporation, FARMIN DM22D (trade name)) were added, followed by heating to 45° C., 100 g of synthetic Hectorite (manufactured by Rockwood Additives Ltd., LAPONITE RDS (trade name)) was dispersed, and the dispersion was heated to 60° C. and stirred for one hour while the temperature was maintained. The slurry was subjected to filtration, the residue was washed with 600 mL of water of 60° C. twice and dried in a dryer at 85° C. for 12 hours to obtain 122 g of organic modified clay. The organic modified clay was pulverized by a jet mill to a median diameter of 15 μm.
(46) [Preparation of Polymerization Catalyst]
(47) A 300 mL flask equipped with a thermometer and a reflux condenser was replaced with nitrogen, 25.0 g of the organic modified clay obtained in [Preparation of modified clay] and 108 mL of hexane were put, and then 0.4406 g of dimethylsilylene(cyclopentadienyl)(2,4,7-trimethyl-1-indenyl)zirconium dichloride and 142 mL of 20% triisobutylaluminum were added, followed by stirring at 60° C. for 3 hours. The mixture was cooled to 45° C., the supernatant was withdrawn, and the residue was washed with 200 mL of hexane five times and mixed with 200 ml of hexane to obtain a catalyst suspension (solid content by weight: 11.5 wt %).
(48) [Production of (B)-3]
(49) Into a 2 L autoclave, 1.2 L of hexane, 1.0 mL of 20% triisobutylaluminum and 70 mg (corresponding to solid content 8.4 mg) of the catalyst suspension obtained in [Preparation of polymerization catalyst] were added, followed by heating to 80° C., 2.4 g of 1-butene was added, and an ethylene/hydrogen mixed gas was continuously supplied (concentration of hydrogen in ethylene/hydrogen mixed gas: 720 ppm) so that the partial pressure would be 0.90 MPa. 90 minutes later, the pressure was lowered, and the slurry was subjected to filtration, and the residue was dried to obtain 63.0 g of polymer. Of the polymer, MFR was 11.5 g/10 min, and the density was 954 kg/m.sup.3. Further, the number average molecular weight was 16,200, the weight average molecular weight was 58,400, and peaks were observed at positions of molecular weights of 28,200 and 181,000. Further, the number of long-chain branches contained in a fraction having Mn of at least 100,000 as obtained by molecular weight fractionation was 0.16 per 1,000 carbon atoms of the main chain. Further, the proportion of the fraction having Mn of at least 100,000 as obtained by molecular weight fractionation was 6.8 wt % of the entire polymer. Further, the melt tension was 38 mN. The evaluation results are shown in Table 1.
(50) (B)-4: Obtained by the Following Production Method.
(51) [Preparation of Modified Clay]
(52) Into a 1 L flask, 300 mL of industrial alcohol (manufactured by Japan Alcohol Trading Co., Ltd., EKINEN F-3 (trade name)) and 300 mL of distilled water were put, 20.0 g of concentrated hydrochloric acid and 56.5 g (160 mmol) of dimethylbehenylamine (manufactured by Lion Corporation, FARMIN DM22D (trade name)) were added, followed by heating to 45° C., 100 g of synthetic Hectorite (manufactured by Rockwood Additives Ltd., LAPONITE RDS (trade name)) was dispersed, and the dispersion was heated to 60° C. and stirred for one hour while the temperature was maintained. The slurry was subjected to filtration, the residue was washed with 600 mL of water of 60° C. twice and dried in a dryer at 85° C. for 12 hours to obtain 145 g of organic modified day. The organic modified clay was pulverized by a jet mill to a median diameter of 15 μm.
(53) [Preparation of Polymerization Catalyst]
(54) A 300 mL flask equipped with a thermometer and a reflux condenser was replaced with nitrogen, 25.0 g of the organic modified clay obtained in (1) and 108 mL of hexane were put, and then 0.4406 g of dimethylsilylene(cyclopentadienyl)(2,4,7-trimethyl-1-indenyl)zirconium dichloride and 142 mL of 20% triisobutylaluminum were added, followed by stirring at 60° C. for 3 hours. The mixture was cooled to 45° C., the supernatant was withdrawn, and the residue was washed with 200 mL of hexane five times and mixed with 200 ml of hexane to obtain a catalyst suspension (solid content by weight: 11.2 wt %).
(55) [Production of (B)-4]
(56) Into a 2 L autoclave, 1.2 L of hexane, 1.0 mL of 20% triisobutylaluminum and 74 mg (corresponding to solid content 8.3 mg) of the catalyst suspension obtained in [Preparation of polymerization catalyst] were added, followed by heating to 65° C., 17.5 g of 1-butene was added, and an ethylene/hydrogen mixed gas was continuously supplied (concentration of hydrogen in ethylene/hydrogen mixed gas: 570 ppm) so that the partial pressure would be 0.75 MPa. 90 minutes later, the pressure was lowered, and the slurry was subjected to filtration, and the residue was dried to obtain 51.5 g of polymer. Of the polymer, MFR was 0.8 g/10 min, and the density was 928 kg/m.sup.3. Further, the number average molecular weight was 17,900, the weight average molecular weight was 99,300, and peaks were observed at positions of molecular weights of 28,100 and 229,100. Further, the number of long-chain branches contained in a fraction having Mn of at least 100,000 as obtained by molecular weight fractionation was 0.26 per 1,000 carbon atoms of the main chain. Further, the proportion of the fraction having Mn of at least 100,000 as obtained by molecular weight fractionation was 25.4 wt % of the entire polymer. Further, the melt tension was 90 mN. The evaluation results are shown in Table 1.
(57) (B)-5: Obtained by the Following Production Method.
(58) [Preparation of Modified Clay]
(59) Into a 1 L flask, 300 mL of industrial alcohol (manufactured by Japan Alcohol Trading Co., Ltd., EKINEN F-3 (trade name)) and 300 mL of distilled water were put, 15.0 g of concentrated hydrochloric acid and 42.4 g (120 mmol) of dimethylbehenylamine (manufactured by Lion Corporation, FARMIN DM22D (trade name)) were added, followed by heating to 45° C., 100 g of synthetic Hectorite (manufactured by Rockwood Additives Ltd., LAPONITE RDS (trade name)) was dispersed, and the dispersion was heated to 60° C. and stirred for one hour while the temperature was maintained. The slurry was subjected to filtration, the residue was washed with 600 mL of water of 60° C. twice and dried in a dryer at 85° C. for 12 hours to obtain 122 g of organic modified clay. The organic modified clay was pulverized by a jet mill to a median diameter of 15 μm.
(60) [Preparation of Polymerization Catalyst]
(61) A 300 mL flask equipped with a thermometer and a reflux condenser was replaced with nitrogen, 25.0 g of the organic modified clay obtained in [Preparation of modified clay] and 108 mL of hexane were put, and then 0.4406 g of dimethylsilylene(cyclopentadienyl)(2,4,7-trimethyl-1-indenyl)zirconium dichloride and 142 mL of 20% triisobutylaluminum were added, followed by stirring at 60° C. for 3 hours. The mixture was cooled to 45° C., the supernatant was withdrawn, and the residue was washed with 200 mL of hexane five times and mixed with 200 ml of hexane to obtain a catalyst suspension (solid content by weight: 11.5 wt %).
(62) [Production of (B)-5]
(63) Into a 2 L autoclave, 1.2 L of hexane, 1.0 mL of 20% triisobutylaluminum and 90 mg (corresponding to solid content 10.4 mg) of the catalyst suspension obtained in [Preparation of polymerization catalyst] were added, followed by heating to 65° C., 17.5 g of 1-butene was added, and an ethylene/hydrogen mixed gas was continuously supplied (concentration of hydrogen in ethylene/hydrogen mixed gas: 550 ppm) so that the partial pressure would be 0.75 MPa. 90 minutes later, the pressure was lowered, and the slurry was subjected to filtration, and the residue was dried to obtain 61.4 g of polymer. Of the polymer, MFR was 0.08 g/10 min, and the density was 926 kg/m.sup.3. Further, the number average molecular weight was 21,900, the weight average molecular weight was 127,000, and peaks were observed at positions of molecular weights of 31,300 and 247,800. Further, the number of long-chain branches contained in a fraction having Mn of at least 100,000 as obtained by molecular weight fractionation was 0.32 per 1,000 carbon atoms of the main chain. Further, the proportion of the fraction having Mn of at least 100,000 as obtained by molecular weight fractionation was 36.9 wt % of the entire polymer. Further, the melt tension was 140 mN. The evaluation results are shown in Table 1.
(64) (B)-6: Obtained by the Following Production Method.
(65) [Preparation of Modified Clay]
(66) Into a 1 L flask, 300 mL of industrial alcohol (manufactured by Japan Alcohol Trading Co., Ltd., EKINEN F-3 (trade name)) and 300 mL of distilled water were put, 15.0 g of concentrated hydrochloric acid and 42.4 g (120 mmol) of dimethylbehenylamine (manufactured by Lion Corporation, FARMIN DM22D (trade name)) were added, followed by heating to 45° C., 100 g of synthetic Hectorite (manufactured by Rockwood Additives Ltd., LAPONITE RDS (trade name)) was dispersed, and the dispersion was heated to 60° C. and stirred for one hour while the temperature was maintained. The slurry was subjected to filtration, and the residue was washed with 600 mL of water of 60° C. twice and dried in a dryer at 85° C. for 12 hours to obtain 122 g of organic modified clay. The organic modified clay was pulverized by a jet mill to a median diameter of 15 μm.
(67) [Preparation of Polymerization Catalyst]
(68) A 300 mL flask equipped with a thermometer and a reflux condenser was replaced with nitrogen, 25.0 g of the organic modified clay obtained in [Preparation of modified clay] was suspended in 165 mL of hexane, 0.3485 g of dimethylsilanediylbis(cyclopentadienyl)zirconium dichloride and 85 mL of a hexane solution (1.18 M) of triethylaluminum were added, followed by stirring at 60° C. for 3 hours. The mixture was left at rest and cooled to room temperature, the supernatant was withdrawn, and the residue was washed with 200 mL of a hexane solution of 1% triisobutylaluminum twice. The supernatant after washing was withdrawn, and the residue was mixed with a hexane solution of 5% triisobutylaluminum to the entire amount of 250 mL. Further, a solution prepared by adding 5 ml of a hexane solution (0.71 M) of 20% triisobutylaluminum to a suspension of 0.1165 g of diphenylmethylene(1-cyclopentadienyl)(2,7-di-tert-butyl-9-fluorenyl)zirconium dichloride in 10 mL of hexane, was added, followed by stirring at room temperature for 6 hours. The mixture was left at rest, the supernatant was removed, and the residue was washed with 200 mL of hexane twice, and mixed with 200 mL of hexane to obtain a catalyst suspension (solid content by weight: 12.0 wt %).
(69) [Production of (B)-6]
(70) Into a 2 L autoclave, 1.2 L of hexane, 1.0 mL of 20% triisobutylaluminum and 125 mg (corresponding to solid content 15.0 mg) of the catalyst suspension obtained in [Preparation of polymerization catalyst] were added, followed by heating to 85° C., 2.4 g of 1-butene was added, and ethylene was continuously supplied so that the partial pressure would be 0.90 MPa. 90 minutes later, the pressure was lowered, and the slurry was subjected to filtration, and the residue was dried to obtain 45.0 g of polymer. Of the polymer, MFR was 4.4 g/10 min, and the density was 951 kg/m.sup.3. Further, the number average molecular weight was 9,100, the weight average molecular weight was 77,100, and peaks were observed at positions of molecular weights of 10,400 and 168,400. Further, the number of long-chain branches contained in a fraction having Mn of at least 100,000 as obtained by molecular weight fractionation was 0.24 per 1,000 carbon atoms of the main chain. Further, the proportion of the fraction having Mn of at least 100,000 as obtained by molecular weight fractionation was 15.7 wt % of the entire polymer. Further, the melt tension was 210 mN. The evaluation results are shown in Table 1.
(71) (S)-1: The Following Commercial Product was Used.
(72) Manufactured by TOSOH CORPORATION, PETROTHENE 219 (trade name) (MFR: 3.0 g/10 min, density: 934 kg/m.sup.3) The results of evaluation of basic properties of (S)-1 are shown in Table 1.
(73) TABLE-US-00001 TABLE 1 Ethylene polymer Unit (B)-1 (B)-2 (B)-3 (B)-4 (B)-5 (B)-6 (S)-1 MFR g/10 min 4.0 1.6 11.5 0.8 0.08 4.4 3.0 Density kg/m.sup.3 941 930 954 928 926 951 934 Mn — 21,200 17,600 16,200 17,900 21,900 9,100 18,300 Mw — 74,000 86,700 58,400 99,300 127,000 77,100 66,600 Mw/Mn — 3.5 4.9 3.6 5.6 5.8 8.5 3.6 Molecular — 41,500 30,500 28,200 28,100 31,300 10,400 39,800 weight peak — 217,100 155,300 181,000 229,100 247,800 168,400 — Number of long-chain Number/1,000 0.18 0.27 0.16 0.26 0.32 0.24 5.30 branches in component carbon atoms having Mn of at least 100,000 Proportion of component wt % 14.8 20.1 6.8 25.4 36.9 15.7 17.8 having Mn of at least 100,000 MS mN 49 75 38 90 140 210 90
(3) High Density Polyethylene
(74) Ones obtained by the following production methods or a commercial product was used.
(75) (C)-1: Obtained by the Following Production Method.
(76) [Preparation of Modified Clay]
(77) Into a mixed solvent of 4.8 L of deionized water and 3.2 L of ethanol, 354 g of dimethylbehenylamine ((C.sub.22H.sub.45)(CH.sub.3).sub.2N) and 83.3 mL of 37% hydrochloric acid were added to prepare a dimethylbehenylamine hydrochloride solution. To the solution, 1,000 g of synthetic Hectorite was added, followed by stirring overnight, the obtained reaction liquid was subjected to filtration, and the solid content was sufficiently washed with water. The solid content was dried to obtain 1,180 g of organic modified clay. The liquid content measured by an infrared moisture meter was 0.8%. Then, the organic modified clay was pulverized to have an average particle size of 6.0 μm.
(78) [Preparation of Polymerization Catalyst]
(79) In a 5 L flask, 450 g of the organic modified clay obtained in [Preparation of modified clay] and 1.4 kg of hexane were added, and 1.78 kg (1.8 mol) of a hexane 20 wt % solution of triisobutylaluminum and 7.32 g (18 mmol) of bis(n-butyl-cyclopentadienyl)zirconium dichloride were added, followed by stirring for one hour with heating to 60° C. The reaction solution was cooled to 45° C., and left at rest for 2 hours, and the supernatant was removed by gradient method. Then, 1.78 kg (0.09 mol) of a hexane 1 wt % solution of triisobutylaluminum was added, followed by reaction at 45° C. for 30 minutes. The reaction solution was left at rest at 45° C. for 2 hours, and the supernatant was removed by gradient method, and 0.45 kg (0.45 mol) of a hexane 20 wt % solution of triisobutylaluminum was added, and the mixture was diluted again with hexane to adjust the entire amount to be 4.5 L to prepare a polymerization catalyst.
(80) [Production of (C)-1]
(81) Into a polymerization vessel having an internal capacity of 300 L, hexane at 135 kg/hour, ethylene at 20.0 kg/hour, butene-1 at 0.3 kg/hour, hydrogen at 5 NL/hour and the polymerization catalyst obtained in [Preparation of polymerization catalyst] were continuously supplied. Further, triisobutylaluminum as a promoter was continuously supplied so that its concentration in the liquid would be 0.93 mmol/kg hexane. The polymerization temperature was controlled to be 85° C. The obtained high density polyethylene ((C)-1) had MFR of 1.0 g/10 min and a density of 952 kg/m.sup.3. The results of evaluation of basic properties of (C)-1 are shown in Table 2.
(82) (C)-2: Obtained by the Following Production Method.
(83) [Preparation of Modified Clay]
(84) Modified clay was prepared in the same manner as of (C)-1.
(85) [Preparation of Polymerization Catalyst]
(86) A polymerization catalyst was prepared in the same manner as of (C)-1.
(87) [Production of (C)-2]
(88) Into a polymerization vessel having an internal capacity of 300 L, hexane at 135 kg/hour, ethylene at 20.0 kg/hour, butene-1 at 0.4 kg/hour, hydrogen at 8 NL/hour and the polymerization catalyst obtained in [Preparation of polymerization catalyst] were continuously supplied. Further, triisobutylaluminum as a promoter was continuously supplied so that its concentration in the liquid would be 0.93 mmol/kg hexane. The polymerization temperature was controlled to be 85° C. The obtained high density polyethylene ((C)-2) had MFR of 3.0 g/10 min and a density of 945 kg/m.sup.3. The results of evaluation of basic properties of (C)-2 are shown in Table 2.
(89) (P)-1: The following commercial product was used. The results of evaluation of basic properties of (P)-1 are shown in Table 2.
(90) Manufactured by TOSOH CORPORATION, Nipolon Hard 5700 (trade name) (MFR: 1.0 g/10 min, density: 954 kg/m.sup.3)
(91) TABLE-US-00002 TABLE 2 High density polyethylene Unit (C)-2 (C)-1 (P)-1 MFR g/10 min 3.0 1.0 1.0 Density kg/m.sup.3 945 952 954 Mn — 32,000 42,000 22,000 Mw — 83,000 109,000 118,000 Mw/Mn — 2.6 2.6 5.4 Number of Number/1,000 At most At most At most long-chain carbon atoms 0.09 0.09 0.09 branches in component having Mn of at least 100,000
(4) Linear Low Density Polyethylene
(92) The following commercial product was used.
(93) (Q)-1: Manufactured by TOSOH CORPORATION, Nipolon-Z HF213K (trade name) (MFR: 2.0 g/10 min, density: 905 kg/m.sup.3)
(94) (5) Polypropylene
(95) The following commercial product was used.
(96) (R)-1: Manufactured by Japan Polypropylene Corporation NOVATEC (registered trademark) PP FW4B (trade name) (MFR: 6.5 g/10 min (230° C.), density: 900 kg/m.sup.3)
Examples 1 to 12 and Comparative Examples 1 to 13
(97) A film was produced by the following method using the resin composition as identified in Table 3 or 4, and evaluated.
(98) <Production of Film>
(99) Pellets of the resin composition were heat-compressed by a compression molding machine AWFA. 50 (manufactured by Sinto Metal Industries, Ltd.) at a heating temperature of 200° C. under a heating pressure of 10 kgf/cm.sup.2 for a heating time of 10 minutes and solidified at a cooling temperature of 30° C. under a cooling pressure of 10 kgf/cm.sup.2 for a cooling time of 4 minutes to produce a 200 μm film for evaluation.
(100) <Evaluation of Film>
(101) Various properties of the films in Examples 1 to 12 and Comparative Examples 1 to 13 were evaluated by the following methods. The results are shown in Tables 5, 6, 7 and 8.
(102) <Transparency>
(103) A test specimen of 10 mm×50 mm was cut out from the above film, and the light transmittance at a wavelength of 450 nm was measured in pure water using an ultraviolet/visible spectrophotometer (manufactured by JASCO Corporation, model V-530). A sample having a light transmittance of at least 45% was evaluated as having high transparency.
(104) <Low-Temperature Impact Strength>
(105) The impact strength was measured in accordance with JIS K7160 method B at a temperature of at most −20° C. A sample having an impact strength of at least 30 kJ/m.sup.2 was evaluated as having high impact resistance.
(106) TABLE-US-00003 TABLE 3 X-1 X-2 X-3 X-4 X-5 X-6 X-7 X-8 X-9 X-10 X-11 X-12 Cyclic Resin No. (A)-1 (A)-1 (A)-1 (A)-1 (A)-1 (A)-1 (A)-1 (A)-2 (A)-3 (A)-4 (A)-1 (A)-1 polyolefin (A) Ethylene Resin No. (B)-1 (B)-1 (B)-1 (B)-1 (B)-1 (B)-1 (B)-1 (B)-1 (B)-1 (B)-1 (B)-2 (B)-3 polymer (B) Density 941 941 941 941 941 941 941 941 941 941 930 954 MFR 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 1.6 11.5 High density Resin No. — — — (C)-1 (C)-1 (C)-1 (C)-1 — — — — — polyethylene Density — — — 952 952 952 952 — — — — — (C) MFR — — — 1.0 1.0 1.0 1.0 — — — — — Composition Parts by 75/25 50/50 25/75 93/7 80/20 57/43 17/83 50/50 50/50 50/50 50/50 50/50 (A)/(B) weight Amount of (C) Parts by 0 0 0 23 60 127 250 0 0 0 0 0 weight
(107) TABLE-US-00004 TABLE 4 Y-1 Y-2 Y-3 Y-4 Y-5 Y-6 Y-7 Y-8 Y-9 Y-10 Y-11 Y-12 Y-13 Cyclic Resin No. (A)-1 (A)-2 (A)-3 (A)-4 (A)-1 (A)-1 (A)-1 (A)-1 (A)-1 (A)-1 (A)-1 (A)-1 (A)-1 polyolefin (A) Ethylene Resin No. — — — — — — — — — (B)-4 (B)-5 (B)-6 (S)-1 polymer (B) Density — — — — — — — — — 928 926 951 934 MFR — — — — — — — — — 0.08 0.1 4.4 3.0 High density Resin No. — — — — (C)-2 (C)-2 — — — — — — — polyethylene Density — — — — 945 945 — — — — — — — (C) MFR — — — — 3.0 3.0 — — — — — — — Linear Resin No. — — — — — — (Q)-1 (Q)-1 (Q)-1 — — — — low density Density — — — — — — 905 905 905 — — — — polyethylene MFR — — — — — — 2.0 2.0 2.0 — — — — (Q) Composition Parts by 100/0 100/0 100/0 100/0 100/0 100/0 100/0 100/0 100/0 50/50 50/50 50/50 50/50 (A)/(B) weight Amount of (C) Parts by 0 0 0 0 100 300 0 0 0 0 0 0 0 weight Amount of (Q) Parts by 0 0 0 0 0 0 33 100 300 0 0 0 0 weight
(108) TABLE-US-00005 TABLE 5 Example Example Example Example Example Example Unit 1 2 3 4 5 6 Resin — X-1 X-2 X-3 X-4 X-5 X-6 composition Low- kJ/m.sup.2 31 61 95 58 134 187 temperature impact strength Light % 69 64 46 70 57 49 transmittance
(109) TABLE-US-00006 TABLE 6 Example Example Example Example Example Example Unit 7 8 9 10 11 12 Resin — X-7 X-8 X-9 X-10 X-11 X-12 composition Low- kJ/m.sup.2 214 58 63 59 131 51 temperature impact strength Light % 45 70 68 69 63 68 transmittance
(110) TABLE-US-00007 TABLE 7 Comp. Comp. Comp. Comp. Comp. Comp. Example Example Example Example Example Example Unit 1 2 3 4 5 6 Resin — Y-1 Y-2 Y-3 Y-4 Y-5 Y-6 composition Low- kJ/m.sup.2 3 1 4 2 109 170 temperature impact strength Light % 97 96 95 95 44 30 transmittance
(111) TABLE-US-00008 TABLE 8 Comparative Comparative Comparative Comparative Comparative Comparative Comparative Unit Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Resin — Y-7 Y-8 Y-9 Y-10 Y-11 Y-12 Y-13 composition Low- kJ/m.sup.2 66 289 721 130 142 48 85 temperature impact strength Light % 9 6 8 44 39 43 22 transmittance
Examples 13 to 22 and Comparative Examples 14 to 20
(112) Using the resin composition as identified in Table 9 or 10, a film and a container were produced and evaluated by the following method. The results are shown in Tables 11 and 12.
(113) <Preparation of Film and Container>
(114) Using a water cooling three-layer co-extrusion blown film making machine (manufactured by Placo Co., Ltd.), a three-layer film having a film width of 135 mm and a film thickness of 250 μm was produced at an outer layer and intermediate layer cylinder temperature of 180° C., at an inner layer cylinder temperature of 230° C., at a water bath temperature of 15° C., at a drawing rate of 4 m/min. The thicknesses of the respective layers were such that outer layer/intermediate layer/inner layer. 20 μm/210 μm/20 μm. The resin composition of the present invention was used for the inner layer, a linear low density polyethylene Nipolon-P FY12 (trade name) (MFR: 1.5 g/10 min, density: 916 kg/m.sup.3) manufactured by TOSOH CORPORATION was used for the intermediate layer, and a high density polyethylene Nipolon-P FY13 (trade name) (MFR: 1.1 g/10 min, density: 950 kg/m.sup.3) manufactured by TOSOH CORPORATION was used for the outer layer. Then, a sample having a length of 200 mm was cut out from the three-layer film, one edge was heat-sealed to form a bag, which was filled with 300 ml of ultrapure water, and the opening was heat-sealed with 50 ml of a head space to prepare a container for sterilization.
(115) <Sterilization>
(116) The container was subjected to sterilization using a high temperature high pressure retort sterilizer (manufactured by HISAKA WORKS, LTD.) at a temperature of 121° C. for 20 minutes.
(117) <Evaluation of Film Properties>
(118) The film properties were evaluated by the following method.
(119) <Transparency>
(120) A test specimen of 10 mm×50 mm was cut out from each of the three-layer film and the container after sterilization, and the light transmittance at a wavelength of 450 nm was measured in pure water using an ultraviolet/visible spectrophotometer (manufactured by JASCO Corporation, model V-530). A container having a light transmittance of at least 70% maintained after sterilization was evaluated as having favorable transparency.
(121) <Outer Appearance>
(122) Wrinkles on the film surface, deformation, fusion between inner layers, etc. after sterilization were visually evaluated, and a film with no wrinkle nor deformation observed counts 4 point, a film with slight wrinkle or deformation observed counts 3 points, a film with remarkable wrinkle or deformation observed counts 2 points, and a film with fusion of the inner layers observed counts 1 point.
(123) <Sealing Stability after Sterilization>
(124) The shape of the easily releasable sealed part after sterilization was visually evaluated.
(125) ◯: No change in the sealed layer shape
(126) Δ: Sealed layer partly peeled (such as a decrease of sealing width)
(127) x: Sealed layer peeled, and chambers connected
(128) <Sealing Strength after Sterilization>
(129) The heat-sealed portion was cut into a strip having a width of 15 mm vertical to the sealing direction, 180° peeling was conducted at a rate of 200 mm/min, and the maximum value obtained at the time of peeling was taken as the peel strength (test was conducted with n=5, and the average was calculated). A case where the sealing strength after sterilization was at least 35 N/15 mm is evaluated as having strong sealing property so that peeling or the like at the heat sealed portion at the periphery of the container would not occur.
(130) <Sealing Temperature Width after Sterilization>
(131) The blown film (cylindrical) having the inner layers, that is, the sealant layers faced each other, was heat-sealed under a sealing pressure of 2 kg/cm.sup.2 for a sealing time of 2 seconds at a sealing temperature changed at 1 to 2° C. intervals, to prepare samples. Then, each sample was subjected to sterilization at 121° C. for 20 minutes, and the sealing strength was measured by the method disclosed in the above <Sealing strength> to prepare a graph (heat sealing curve) as shown in
Comparative Example 21
(132) A film was prepared in the same manner as in Example 13 except that the inner layer resin composition was changed to (C)-3, and various properties of the film and the container were evaluated. The results are shown in Table 12.
(133) TABLE-US-00009 TABLE 9 X-13 X-14 X-15 X-16 X-17 X-18 X-19 X-20 X-21 X-22 Cyclic Resin No. (A)-1 (A)-1 (A)-2 (A)-3 (A)-4 (A)-1 (A)-1 (A)-1 (A)-1 (A)-1 polyolefin (A) Ethylene Resin No. (B)-1 (B)-1 (B)-1 (B)-1 (B)-1 (B)-2 (B)-3 (B)-1 (B)-1 (B)-1 polymer (B) Density 941 941 941 941 941 930 954 941 941 941 MFR 4.0 4.0 4.0 4.0 4.0 1.6 11.5 4.0 4.0 4.0 High density Resin No. — — — — — — — (C)-1 (C)-1 (C)-1 polyethylene Density — — — — — — — 952 952 952 (C) MFR — — — — — — — 1.0 1.0 1.0 Composition Parts by 30/70 20/80 20/80 40/60 30/70 40/60 20/80 73/28 65/35 50/50 (A)/(B) weight Amount of Parts by 0 0 0 0 0 0 0 82 115 150 (C) weight
(134) TABLE-US-00010 TABLE 10 Y-14 Y-15 Y-16 Y-17 Y-18 Y-19 Y-20 Cyclic Resin No. (A)-1 (A)-1 (A)-1 (A)-1 — (A)-1 (A)-1 polyolefin (A) Ethylene Resin No. (B)-1 — — — — (B)-1 (B)-1 polymer (B) Density 941 — — — — 941 941 MFR 4.0 — — — — 4.0 4.0 High density Resin No. — — — — (C)-2 (C)-1 (0-1 polyethylene Density — — — — 945 952 952 (C) MFR — — — — 3.0 1.0 1.0 Linear Resin No. — (Q)-1 (Q)-1 (Q)-1 — — — low density Density — 905 905 905 — — — polyethylene MFR — 2.0 2.0 2.0 — — — (Q) Polypropylene Resin No. — — — — (R)-1 — — (R) Density — — — — 900 — — MFR — — — — 6.5 — — Composition Parts by 55/45 100/0 100/0 100/0 0/0 76/24 70/30 (A)/(B) weight Amount of (C) Parts by 0 0 0 0 80 70 200 weight Amount of (Q) Parts by 0 43 67 100 0 0 0 weight Amount of (R) Parts by 0 0 0 0 20 0 0 weight
(135) TABLE-US-00011 TABLE 11 Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Unit 13 14 15 16 17 18 19 20 21 22 Inner layer resin — X-13 X-14 X-15 X-16 X-17 X-18 X-19 X-20 X-21 X-22 composition Film Light Before % 84 86 87 85 83 84 83 81 85 84 physical transmittance sterilization properties After % 77 77 78 76 75 75 74 70 76 76 sterilization Outer appearance — 4 4 4 4 4 4 4 4 4 4 after sterilization Sealing stability — ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ after sterilization Sealing strength N/15 42 54 54 35 40 38 55 39 54 56 after sterilization mm Sealing temperature width ° C. 30 7 6 12 25 15 10 40 10 7 after sterilization
(136) TABLE-US-00012 TABLE 12 Comp. Comp. Comp. Comp. Comp. Comp. Comp. Comp. Unit Ex. 14 Ex. 15 Ex. 16 Ex. 17 Ex. 18 Ex. 19 Ex. 20 Ex. 21 Inner layer resin — Y-14 Y-15 Y-16 Y-17 Y-18 Y-19 Y-20 (C)-3 composition Film Transparency Before % 81 78 74 76 80 82 86 84 physical sterilization properties After % 70 65 61 56 68 71 75 75 sterilization Outer appearance — 4 1 1 1 4 4 4 4 after sterilization Sealing stability — ◯ —.sup.2) —.sup.2) —.sup.2) ◯ Δ ◯ ◯ after sterilization Sealing strength N/15 7 40 51 50 58 20 61 65 after sterilization mm Sealing temperature width ° C. .sup. >50 .sup.1) —.sup.3) —.sup.3) —.sup.3) 10.0 .sup. >50 .sup.1) 5 5 after sterilization .sup.1) In the measured heat sealing temperature region, the heat sealing strength did not reach 20 N/15 mm. .sup.2)The sealed peripheries fused by sterilization, and the sealing stability could not be evaluated. .sup.3)The sealed portions fused by sterilization and the heat sealing strength increased and as a result, a sample showing a strength of from 5 to 20 N/15 mm could not be obtained.
Examples 23 to 28 and Comparative Examples 22 to 24
(137) Using the resin compositions as identified in Tables 13 and 14, a film was produced in the same manner as in Example 1 and evaluated. The results are shown in Tables 15 and 16.
(138) TABLE-US-00013 TABLE 13 X-23 X-24 X-25 X-26 X-27 X-28 Cyclic Resin No. (A)-2 (A)-3 (A)-4 (A)-1 (A)-2 (A)-4 polyolefin (A) High density Resin No. (C)-2 (C)-2 (C)-2 (C)-1 (C)-2 (C)-2 polyethylene Density 945 945 945 952 945 945 (C) MFR 3.0 3.0 3.0 1.0 3.0 3.0 Composition Parts by 40/60 30/70 20/80 30/70 30/70 30/70 (A)/(C) weight
(139) TABLE-US-00014 TABLE 14 Y-21 Y-22 Y-23 Cyclic polyolefin (A) Resin No. (A)-1 (A)-1 (A)-1 High density Resin No. (C)-2 (P)-1 — polyethylene (C) Density 945 954 — MFR 3.0 1.0 — Linear low density Resin No. — — (Q)-1 polyethylene (Q) Density — — 905 MFR — — 2.0 Composition Parts by 10/90/0 75/25/0 75/0/25 (A)/(C)/(Q) weight
(140) TABLE-US-00015 TABLE 15 Example Example Example Example Example Example Unit 23 24 25 26 27 28 Resin — X-23 X-24 X-25 X-26 X-27 X-28 composition Low- kJ/m.sup.2 130 159 199 168 162 175 temperature impact strength Light % 42 41 40 55 41 44 transmittance
(141) TABLE-US-00016 TABLE 16 Comparative Comparative Comparative Unit Example 22 Example 23 Example 24 Resin composition — Y-21 Y-22 Y-23 Low-temperature kJ/m.sup.2 205 57 66 impact strength Light transmittance % 35 38 9
Examples 29 to 35 and Comparative Examples 25 to 31
(142) Using the resin composition as identified in Table 17 or 18, a film and a medical container were produced in the same manner as in Example 13 and evaluated. The results are shown in Tables 19 and 20.
(143) TABLE-US-00017 TABLE 17 X-29 X-30 X-31 X-32 X-33 Cyclic Resin No. (A)-1 (A)-1 (A)-1 (A)-2 (A)-3 polyolefin (A) High density Resin No. (C)-2 (C)-2 (C)-2 (C)-2 (C)-2 polyethylene Density 945 945 945 945 945 (C) MFR 3.0 3.0 3.0 3.0 3.0 Composition Parts by 40/60 30/70 20/80 40/60 40/60 (A)/(C) weight
(144) TABLE-US-00018 TABLE 18 Y-25 Y-26 Y-27 Y-28 Y-29 Y-30 Cyclic Resin No. (A)-1 (A)-1 (A)-1 (A)-1 (A)-1 — polyolefin (A) High density Resin No. (C)-2 (C)-2 — — — (C)-2 polyethylene Density 945 945 — — — 945 (C) MFR 3.0 3.0 — — — 3.0 Linear Resin No. — — (Q)-1 (Q)-1 (Q)-1 — low density Density — — 905 905 905 — polyethylene MFR — — 2.0 2.0 2.0 — (Q) Polypropylene Resin No. — — — — — (R)-1 (R) Density — — — — — 900.0 MFR — — — — — 6.5 Composition Parts by 50/50 10/90 100/0 100/0 100/0 0/100 (A)/(C) weight Amount of (Q) Parts by 0 0 43 67 100 0 weight Amount of (R) Parts by 0 0 0 0 0 25 weight
(145) TABLE-US-00019 TABLE 19 Example Example Example Example Example Example Example Unit 29 30 31 32 33 34 35 Inner layer resin — X-29 X-30 X-31 X-32 X-33 X-26 X-28 composition Film Light Before % 83 83 83 83 87 84 84 physical transmittance sterilization properties After % 75 74 73 75 78 76 73 sterilization Outer appearance — 4 4 4 4 4 4 4 after sterilization Sealing stability — ◯ ◯ ◯ ◯ ◯ ◯ ◯ after sterilization Sealing strength N/15 48 50 55 35 36 40 52 after sterilization mm Sealing temperature width ° C. 9 8 6 35 40 11 9 after sterilization
(146) TABLE-US-00020 TABLE 20 Comp. Comp. Comp. Comp. Comp. Comp. Comp. Unit Ex. 25 Ex. 26 Ex. 27 Ex. 28 Ex. 29 Ex. 30 Ex. 31 Inner layer resin — Y-25 Y-26 Y-27 Y-28 Y-29 Y-30 (P)-1 composition Film Transparency Before % 82 85 78 74 76 80 84 physical sterilization properties After % 73 74 65 61 56 68 75 sterilization Outer appearance — 4 4 1 1 1 4 4 after sterilization Sealing stability — ◯ ◯ —.sup.2) —.sup.2) —.sup.2) ◯ ◯ after sterilization Sealing strength N/15 15 60 40 51 50 58 65 after sterilization mm Sealing temperature width ° C. —.sup.1) 4 —.sup.3) —.sup.3) —.sup.3) 10.0 5 after sterilization .sup.1)In the measured heat sealing temperature region, the heat sealing strength did not reach 20 N/15 mm. .sup.2)The sealed peripheries fused by sterilization, and the sealing stability could not be evaluated. .sup.3)The sealed portions fused by sterilization and the heat sealing strength increased and as a result, a sample showing a strength of from 5 to 20 N/15 mm could not be obtained.
(147) The present invention was described in detail with reference to specific embodiments. However, it is obvious for those skilled in the art that various changes and modifications are possible without departing from the intention and the scope of the present invention.