Resin composition

Abstract: A resin composition comprising (A) 99 - 40 parts by weight of a 4-methyl-1-pentene based polymer, (B) 0 - 30 parts by weight of a butene based liquid polymer having a kinematic viscosity of 2 - 5000 cSt at 100°C, and (C) 1 - 30 parts by weight of a butene-1 based solid polymer, with the sum of (A) + (B) + (C) being 100 parts by weight, has excellent heat resistance, flexibility and impact resistance.

Description: This invention relates to a resin composition, more particularly, to a resin composition that has improved heat resistance, flexibility and impact resistance. In food and other industries, there has been a strong demand for materials which are provided with well-balanced heat resistance, flexibility and impact resistance. It is well known that 4-methyl-1-pentene based polymers have excellent heat resistance, and have a melting point in the range of from 220 to 240°C. Molded articles fabricated from such 4-methyl-1-pentene polymers, however, have poor flexibility and impact resistance in spite of their excellent heat resistance. EP-A-139,892, DE-A-3,307,946 and FR-A-2,396,782 disclose compositions comprising a 4-methyl-1-pentene polymer and other polyolefins containing 1-butene. The present invention seeks to provide a resin composition that retains the high heat resistance of the 4-methyl-1-pentene based polymers and which also excels in flexibility and impact resistance. The present inventors have conducted intensive studies and found that a resin composition comprising a 4-methyl-l-pentene based polymer, a butene based liquid polymer and a butene-1 based solid polymer in specified proportions exhibited not only high heat resistance but also good flexibility and high impact resistance and, hence, was free from bleeding. The present invention attains the aforementioned object by providing a resin composition comprising: (A) 99 to 40 parts by weight of a 4-methyl-1-pentene based polymer; (B) 3 to 30 parts by weight of a butene based liquid polymer having a kinematic viscosity of 2 to 5000 10 -6 m 2 /s (2 to 5000 cSt) at 100°C; and (C) 1 to 30 parts by weight of a butene-1 based solid polymer, with the sum of (A) + (B) + (C) being 100 parts by weight. Fig. 1 is a diagram showing conceptually a method of measuring the tack of films prepared in Examples 1 - 5 and Comparative Example 1; and Fig. 2 is a diagram showing the test piece used to measure the heat-resisting temperature of films prepared in Examples 1 - 5 and Comparative Example 1. The resin composition of the present invention is described below in more detail. Component (A), or 4-methyl-1-pentene based polymer, which is the first essential component of the resin composition of the present invention, is a polymer containing 4-methyl-1-pentene as a principal ingredient. Examples are a homopolymer of 4-methyl-1-pentene, as well as copolymers of 4-methyl-1-pentene and other α-olefins. Examples of α-olefins other than 4-methyl-1-pentene are α-olefins having 2 - 20 carbon atoms including ethylene, propylene, 1-butene, 1-heptene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicocene. These α-olefins may be contained in the 4-methyl-1-pentene based polymer either singly or in admixture. When these α-olefins are to be contained in the 4-methyl-1-pentene based polymer, their content should be typically in the range of from about 1 to 10 wt%. The intrinsic viscosity [η] of the 4-methyl-1-pentene base polymer as measured in the solvent decalin at 135°C is typically in the range of from about 1.0 to about 3.0, preferably from about 2.0 to about 2.5. Component (B), or butene based liquid polymer, which is the second component of the resin composition of the present invention, is a polymer containing isobutylene as a principal ingredient. Examples are a homopolymer of isobutylene, as well as copolymers that contain a major amount of isobutylene and a minor amount, say, no more than 40 mol%, of other α-olefins. Examples of α-olefins other than isobutylene include 1-butene, 2-butene and butadiene. These α-olefins may be contained in the butene based liquid polymer either singly or in admixture. The butene based liquid polymer has a kinematic viscosity of 2 to 5000 10 -6 m 2 /s (2 to 5000 cSt) at 100°C; preferably, this polymer has a kinematic viscosity of 50 to 1000 10 -6 m 2 /s (50 to 1000 cSt) since it contributes to the production of a resin composition having excellent moldability and quality. Component (C), or butene-1 based solid polymer, which is the third essential component of the resin composition of the present invention, is a crystalline polymer containing butene-1 as a principal ingredient. Examples are a homopolymer of butene-1, as well as copolymers of butene-1 and other α-olefins. Examples of α-olefins other than butene-1 include ethylene and propylene. These α-olefins may be contained in the butene-1 based solid polymer either singly or in admixture. When these α-olefins are to be contained in the butene-1 based solid polymer, their content is typically less than 30 mol%, more preferably with less than 20 mol%. The butene-1 based solid polymer as component (C) can be prepared by polymerizing butene-1 either alone or in combination with other α-olefins in the presence of a Ziegler catalyst. The butene-1 based solid polymer (C) typically has about 20 - 60% crystallinity, which preferably ranges from about 30 to 50% to ensure substantial effectiveness in providing improved flexibility. The butene-1 based solid polymer (C) generally has a melt flow rate of 0.01 - 50 g/10 min, preferably 0.05 - 20 g/10 min, to provide a resin composition having satisfactory mechanical strength and good compatibility between the butene-1 based solid polymer (C) and the 4-methyl-1-pentene based polymer (A). The value of melt flow rate as specified in the present invention is measured in accordance with ASTM D 1238E. The resin composition of the present invention is produced by molding a resin composition which comprises the above-described polymers (A), (B) and (C). In order to ensure the production of resin composition which excels in heat resistance, flexibility, and impact resistance and which is substantially free from the bleeding of the butene based liquid polymer (B), the relative proportions of the three components (A), (B) and (C) in the resin composition are such that the component (B) is present in an amount of 3 to 30 parts by weight for 99 to 40 parts by weight of the component (A), and the component (C) is present in an amount of 1 to 30 parts by weight for 99 to 40 parts by weight of the component (A). Preferably, each of the components (B) and (C) is present in an amount of 3 to 15 parts by weight for 94 to 70 parts by weight of the component (A). In whichever proportions, the sum of (A) + (B) + (C) is 100 parts by weight. The resin composition of the present invention may optionally contain one or more compounding ingredients selected from antioxidants, colorants, UV absorbers, inorganic fillers, antistatics,antihaze agents and heat stabilizers. The method of producing the resin composition of the present invention is in no way limited. In a typical case, the components (A), (B) and (C) of the resin composition, as well as any of the compounding ingredients listed above which may be added as required, are supplied separately into an extruder in predetermined proportions; alternatively, the individual components and ingredients are preliminarily mixed, and the mixture is supplied into the extruder; in the extruder, the mixture is melted and kneaded to prepare the resin composition, followed by extrusion through a suitable molding die such as a T-die or tube die for shaping into a film, or by injection molding. The heating temperature in the extruder or injection molding machine is typically from 240 to 300°C. The resin composition of the present invention has excellent heat resistance, flexibility, and impact resistance, and therefore, it may be utilized in various applications wherein both heat resistance and flexibility are greatly required, for example, wrapping films, containers, and various other packages used in microwave ovens, as well as products subjected to high-temperature sterilization such as a retortable food package or Ringer solution transfusion bag. The following Examples and Comparative Examples further illustrate the present invention. Example 1 Ninety parts by weight of poly4-methyl-l-pentene (MX021 of Mitsui Petrochemical Industries, Ltd.), 5 parts by weight of liquid polybutene (B) (HV300 of Nippon Petrochemicals Co., Ltd.; kinematic viscosity, 630 10 -6 m 2 /s (630 cSt) at 100°C) and 5 parts by weight of polybutene-1 (C-1) (Beaulon M2181 of Mitsui Petrochemical Industries, Ltd.; melt flow rate, 1.0 g/10 min; density, 0.900 g/cm 3 ; m.p. 71°C) were mixed in a Henschel mixer to prepare a resin composition. The resin composition was then supplied into an extruder, in which it was melted and kneaded at a molding temperature of 290°C. The melt was extruded through a T-die to yield an overwrap film 12 µm thick and 300 mm wide. The yield strength, breaking strength, elongation, modulus, tear strength, haze, gloss, tack and heat-resisting temperature of the overwrap film thus produced were measured by the methods described below and the results are shown in Table 1. Yield strength, breaking strength and elongation Measured in accordance with ASTM D 882. Tear strength Measured in accordance with ASTM D 1922 (Elmendorf tear test). Haze Measured in accordance with ASTM D 1003. Gloss Measured at 60° in accordance with ASTM D 523. Tack Two films 8 cm wide by 10 cm long that had been aged at 40°C for 1 week after molding were placed in superposition and passed between press rolls at a nip pressure of 0.2 kg/cm 2 , thereby preparing a test piece in which the two films were held in intimate contact with each other in all areas except for a width of 2 cm from one side of the film. Then, the test piece was set up as shown in Fig. 1 in which the test piece is indicated by 1; and end portion 2 of one film 1a on the side of the test piece 1 where the two films were not held in intimate contact with each other was secured by means of double-coated tape to an end portion 5 of support 4 fixed on a table 3. Furthermore, a load 7 was put on an end portion 6 of the other film 1b on the same side of the test piece 1 (where the two films were not held in intimate contact with each other) in an atmosphere of 23°C x 50% RH. The load was successively replaced by heavier ones until the superposed films 1a and 1b of the test piece 1 separated from each other, whereupon the load 7 to started to move. The weight (in grams/8 cm) of the load applied at that time was measured as the tack of the film. Heat-resisting temperature As shown in Fig. 2, a heat-resistant overwrap film 11 measuring 3 cm wide by 14 cm long was provided and sheets of flat-grained paper 13a and 13b and each measuring 3 cm wide by 2.5 cm long were superposed on an upper end 12a and a lower end 12b, respectively, of the overwrap film 11 and the corresponding members were bonded together with double-coated adhesive tape to prepare a test piece. The upper end 12a of this test piece was secured to a jig and a load weighing 10 g was applied to the lower end 12b. Immediately after this setup operation, the test piece was put into an air oven and heated with the temperature raised in 5°C increments at 1-h intervals until the sample broke. The maximum temperature which the sample could withstand without break was designated as the "heat-resisting temperature" of the sample. Example 2 A heat-resistant overwrap film was prepared by repeating the procedure of Example 1, except that poly4-methyl-1-pentene, liquid polybutene and polybutene-1 (C-1) were mixed in relative proportions of 85, 5 and 10 parts by weight, respectively. The film was measured for its yield strength, breaking strength, elongation, modulus, tear strength, haze, gloss, tack and heat-resisting temperature. The results are shown in Table 1. Example 3 A heat-resistant overwrap film was prepared by repeating the procedure of Example 1, except that polybutene-1 (C-1) was replaced by polybutene-1 (C-2) (Beaulon M3080 of Mitsui Petrochemical Industries, Ltd.; melt flow rate, 0.2 g/10 min; density, 0.890 g/cm 3 ; m.p. 98°C). The film was measured for its yield strength, breaking strength, elongation, modulus, tear strength, haze, gloss, tack and heat-resisting temperature. The results are shown in Table 1. Example 4 A heat-resistant overwrap film was prepared by repeating the procedure of Example 1, except that poly4-methyl-1-pentene, liquid polybutene and polybutene-1 (C-2) which replaced polybutene-1 (C-1) were mixed in relative proportions of 85, 5 and 10 parts by weight, respectively. The film was measured for its yield strength, breaking strength, elongation, modulus, tear strength, haze, gloss, tack and heat-resisting temperature. The results are shown in Table 1. Example 5 A heat-resistant overwrap film was prepared by repeating the procedure of Example 1, except that poly4-methyl-1-pentene, liquid polybutene and polybutene-1 (C-2) which replaced polybutene-1 (C-1) were mixed in relative proportions of 85, 7 and 8 parts by weight, respectively. The film was measured for its yield strength, breaking strength, elongation, modulus, tear strength, haze, gloss, tack and heat-resisting temperature. The results are shown in Table 1. Comparative Example 1 A heat-resistant overwrap film was prepared by repeating the procedure of Example 1, except that the resin composition from which the film was molded was replaced by a composition consisting of 90 parts by weight of poly4-methyl-1-pentene and 10 parts by weight of liquid polybutene. The film was measured for its yield strength, breaking strength, elongation, modulus, tear strength, haze, gloss, tack and heat-resisting temperature. The results are shown in Table 1. Example 6 Seventy parts by weight of poly4-methyl-l-pentene (MX021 of Mitsui Petrochemical Industries, Ltd.), 15 parts by weight of liquid polybutene (B) (HV300 of Nippon Petrochemicals Co., Ltd.; kinematic viscosity, 630 10 -6 m 2 /s (630 cSt) at 100°C) and 15 parts by weight of polybutene-1 (C-1) (Beaulon M2181 of Mitsui Petrochemical Industries, Ltd.; melt flow rate, 1.0 g/10 min; density, 0.900 g/cm 3 ; m.p. 71°C) were mixed in a Henschel mixer to prepare a resin composition. The resin composition was then supplied into an extruder, in which it was melted and kneaded at a molding temperature of 290°C. The melt was extruded through a T-die to yield a film 200 µm thick and 300 mm wide. The yield strength, modulus, tear strength, haze, impact strength, bleeding property and heat resistance of the film thus produced were measured by the methods described below and the results are shown in Table 2. Yield strength and modulus Measured in accordance with ASTM D 882. Tear strength Measured in accordance with ASTM D 1992 (Elmendorf tear test). Haze Measured in accordance with ASTM D 1003. Bleeding property A test piece 50 mm wide by 50 mm long was prepared by cutting the 200 µm thick film. After heating in an air-oven at 80°C for 2 hrs, the test piece was evaluated by feel with the following criteria. o non-slimy or non-sticky x slimy or sticky Heat resistance The resin composition was supplied into a injection molding machine, and the feed was molded at 295°C to prepare a test piece 50 mm thick, 50 mm high and having a diameter of 46 mm. After heating in an air-oven at 160°C for 30 minutes, the shape of the test piece was evaluated by visual inspection with the following criteria. o there was neither change in shape nor fusion. x there were changes in shape or fusion. Impact strength Measured in accordance with ASTM D 3420. Example 7 A heat-resistant overwrap film and injection molded piece were prepared by repeating the procedure of Example 6, except that polybutene-1 (C-1) was replaced by polybutene-1 (C-2) (Beaulon M3080 of Mitsui Petrochemical Industries, Ltd.; melt flow rate, 0.2 g/10 min; density, 0.890 g/cm 3 ; m.p. 98°C). The film was measured for its yield strength, modulus, tear strength, haze, impact strength, bleeding property and heat resistance. The results are shown in Table 2. Example 8 A film and injection molded piece were prepared by repeating the procedure of Example 6, except that poly4-methyl-1-pentene, liquid polybutene and polybutene-1 (C-1) were mixed in relative proportions of 60, 20 and 20 parts by weight, respectively. The film and molded piece were measured for yield strength, modulus, tear strength, haze, impact strength and heat resistance. The results are shown in Table 2. Comparative Example 2 A film and injection molded piece were prepared by repeating the procedure of Example 6, except that the resin composition from which the film was molded was replaced by 100 parts by weight of poly4-methyl-1-pentene. The film and piece were measured for yield strength, modulus, tear strength, haze, impact strength, bleeding property and heat resistance. The results are shown in Table 2. Comparative Example 3 A film and injection molded piece were prepared by repeating the procedure of Example 6, except that the resin composition from which the film was molded was replaced by 70 parts by weight of poly4-methyl-1-pentene and 30 parts by weight of liquid polybutene. The film and piece were evaluated for yield strength, modulus, tear strength, haze, impact strength, bleeding property and heat resistance. The results are shown in Table 2. Comparative Example 4 A film and injection molded piece were prepared by repeating the procedure of Example 6, except that poly4-methyl-1-pentene and polybutene-1 (C-1) were mixed in relative proportions of 70 and 30 parts by weight, respectively. The film and molded piece were evaluated for yield strength, modulus, tear strength, haze, impact strength, bleeding property and heat resistance. The results are shown in Table 2. The resin composition of the present invention excels in flexibility and impact resistance, as well as heat resistance since it has a high heat-resisting temperature of 160°C. Hence, the resin composition of this invention can be used in the high-temperature range where conventional flexible materials have been entirely unsuitable for use. Principally for this anticipated expansion of use, the resin composition of the present invention will offer great benefits in practice.

Claims: A resin composition comprising: (A) 99 to 40 parts by weight of a 4-methyl-1-pentene based polymer; (B) 3 to 30 parts by weight of a butene based liquid polymer having a kinematic viscosity of 2 to 5000 10 -6 m 2 /s (2 to 5000 cSt) at 100°C; and (C) 1 to 30 parts by weight of a butene-1 based solid polymer, with the sum of (A) + (B) + (C) being 100 parts by weight. A resin composition according to claim 1 which comprises 94 to 70 parts by weight of (A) and 3 to 15 parts by weight of each of (B) and (C), the sum of (A) + (B) + (C) being 100 parts by weight.

Inventors: IMUTA SHINICHI, KATO TATSUO, KOBAYASHI MASAMI, NAGASE YASUSHI, IMUTA, SHINICHI, KATO, TATSUO, KOBAYASHI, MASAMI, NAGASE, YASUSHI, Imuta, Shinichi, c/o Mitsui Petrochem. Ind., Ltd., Kato, Tatsuo, c/o MITSUI PETROCHEM. IND., LTD., Kobayashi, Masami, c/o Chugoku Resin Co., Ltd., Nagase, Yasushi, c/o CHUGOKU RESIN CO., LTD.
Applicants: MITSUI PETROCHEMICAL IND, MITSUI PETROCHEMICAL INDUSTRIES, LTD.
Application year: 1993
Main classification: C08L23
IPC codes: C08L23, C08J5