Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/10—Homopolymers or copolymers of propene
  • C08L23/12—Polypropene
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
  • B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/04—Homopolymers or copolymers of ethene
  • C08L23/08—Copolymers of ethene
  • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms
  • C08L23/0815—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms with aliphatic 1-olefins containing one carbon-to-carbon double bond
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K2201/00—Specific properties of additives
  • C08K2201/019—Specific properties of additives the composition being defined by the absence of a certain additive
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2201/00—Properties
  • C08L2201/10—Transparent films; Clear coatings; Transparent materials

Definitions

• the present invention relates to an injection-molded article made of a propylene-based polymer composition that has good transparency, rigidity, and excellent impact strength.
• Polyolefins (olefin polymers) represented by polyethylene and polypropylene require little energy for production, are lightweight, and have excellent recyclability. Reuse, Recycle) is gaining more attention. Polyolefins are used in various fields such as daily necessities, kitchen utensils, home electric appliances, machine parts, electrical parts, and automobile parts.
• polypropylene is excellent in transparency, rigidity, and heat resistance, but is inferior to polyethylene in cold resistance and impact resistance. Therefore, many methods have been proposed to improve the impact resistance of polypropylene.
• a propylene resin composition of a propylene block copolymer and an ethylene/ ⁇ -olefin copolymer having a density in the range of 900 to 919 kg/m 3 is used as a method for improving the impact strength of polypropylene without impairing its transparency and rigidity. It has been proposed to make things (Patent Document 1).
• An object of the present invention is to obtain an injection-molded article having good transparency and rigidity and excellent impact strength, in other words, an injection-molded article made of a propylene-based polymer composition having an excellent balance of transparency, impact strength, and rigidity. be.
• the present invention relates to the following [1] to [8].
• the melt flow rate measured at a temperature of 230° C. and a load of 2.16 kg according to JIS K6921 is in the range of 1 to 50 g/10 minutes.
• Requirement (a-ii) The content of ⁇ -olefins other than propylene determined by infrared spectroscopy is 1% by mass or less (including 0).
• Requirement (b-i) The melt flow rate measured at a temperature of 190° C. and a load of 2.16 kg according to JIS K6921 is in the range of 0.1 to 15 g/10 minutes.
• the injection molded article of the present invention has good transparency and rigidity, and excellent impact strength, so it can be suitably used for food containers, beverage containers, containers, daily necessities, and the like.
• the propylene-based polymer (A), one of them, is a propylene polymer that satisfies the following requirements (ai) and requirements (a-ii).
• melt flow rate (MFR 230 ) measured at a temperature of 230° C. and a load of 2.16 kg according to JIS K6921 is in the range of 1 to 50 g/10 minutes, preferably 1 to 30 g/10 minutes.
• the propylene-based polymer (A) satisfying the above range of MFR 230 is well compatible with the following ethylene/ ⁇ -olefin copolymer (B) according to the present invention. If the MFR 230 exceeds the above range, the impact strength of the resulting molded article may be low. It is likely to become difficult.
• the propylene-based polymer composition containing the propylene-based polymer (A) satisfying the above range has good injection moldability, and the resulting molded article has good mechanical properties and good transparency.
• Requirements (a-ii) The ⁇ -olefin content other than propylene determined by infrared spectroscopy is 1% by mass or less (including 0), preferably 0.5% by mass or less (including 0), more preferably a propylene homopolymer. .
• the ⁇ -olefin other than propylene is at least one ⁇ -olefin selected from ethylene and ⁇ -olefins having 4 to 8 carbon atoms.
• the propylene-based polymer composition containing the propylene-based polymer (A) satisfying the above range has good injection moldability, and the resulting molded article has good mechanical properties and good transparency.
• the propylene-based polymer (A) according to the present invention can be produced by various known production methods, specifically, in the presence of a known olefin polymerization catalyst when the propylene-based polymer (A) contains only propylene. , can be obtained by homopolymerizing propylene, or by polymerizing with 1% by mass or less of an ⁇ -olefin.
• Specific examples of olefin polymerization catalysts include titanium-based catalysts and metallocene-based catalysts. Titanium-based catalysts are particularly preferred.
• Melt flow rate (MFR 190 ) measured at a temperature of 190° C. and a load of 2.16 kg according to JIS K6921 is 0.1 to 15 g/10 minutes, preferably 1 to 10 g/10 minutes, more preferably 1 to 5 g/10 minutes.
• the ethylene/ ⁇ -olefin copolymer (B) satisfying the above range is well compatible with the propylene-based polymer (A) of the present invention.
• an ethylene/ ⁇ -olefin copolymer (B) having an MFR 190 in the range of 1 to 5 g/10 minutes is used, the impact resistance of the resulting molded article is improved.
• the impact strength of the resulting molded article may be low. It is likely to become difficult.
• the propylene-based polymer composition containing the ethylene/ ⁇ -olefin copolymer (B) satisfying the above range has good injection moldability, and the resulting molded article has good mechanical properties and good transparency. be.
• the density measured according to JIS K6922 is in the range of 900-920 kg/m 3 , preferably 903-915 kg/m 3 .
• the molded article obtained from the propylene-based polymer composition containing the ethylene/ ⁇ -olefin copolymer (B) satisfying the above range greatly exceeds the impact strength of the molded article obtained from the propylene-based polymer (A) alone. It has excellent impact strength, does not significantly reduce transparency and rigidity, and has an excellent balance of transparency, impact strength, and rigidity.
• the ethylene/ ⁇ -olefin copolymer (B) is a copolymer whose main component is a structural unit derived from ethylene.
• the ⁇ -olefin is preferably at least one ⁇ -olefin selected from the group consisting of ⁇ -olefins having 3 to 8 carbon atoms, more preferably propylene, 1-butene, 1-hexene and 1-octene. At least one ⁇ -olefin selected from the group consisting of Among them, 1-hexene is particularly preferred.
• the ethylene/ ⁇ -olefin copolymer (B) according to the present invention usually has a content of structural units derived from ethylene in the range of 83 to 93 mol%, preferably 86 to 90 mol%.
• the propylene-based polymer composition for forming the injection-molded article (hereinafter sometimes abbreviated as "molded article") of the present invention contains the propylene-based polymer (A) in an amount of 60 to 90% by mass, preferably 70% by mass. to 90% by mass, more preferably 70 to 80% by mass, and 10 to 40% by mass, preferably 10 to 30% by mass, more preferably 10 to 20% by mass of the ethylene/ ⁇ -olefin copolymer (B)
• the total amount of (A) and (B) is 100% by mass.
• ] is a composition containing in the range of
• the propylene-based polymer composition according to the present invention generally has an MFR 230 of 1 to 50 g/10 minutes, preferably 3 to 30 g/10 minutes, more preferably 5 to 20 g/10 minutes.
• the propylene-based polymer composition according to the present invention contains, in addition to the propylene-based polymer (A) and the ethylene/ ⁇ -olefin copolymer (B), an appropriate neutralizing agent within a range that does not impair the object of the present invention.
• the propylene-based polymer composition according to the present invention preferably does not contain a nucleating agent (nucleating agent).
• nucleating agent nucleating agent
• Injection-molded products made from compositions containing nucleating agents increase both transparency and rigidity. easier.
• An injection-molded article made of the propylene-based polymer composition according to the present invention greatly exceeds the impact strength of a molded article obtained from the propylene-based polymer (A) alone, is excellent in impact strength, and does not significantly reduce transparency and rigidity. excellent balance of transparency, impact strength, and rigidity.
• the propylene-based polymer composition according to the present invention is prepared by mixing the propylene-based polymer (A) and the ethylene/ ⁇ -olefin copolymer (B) with a dry blend, a Henschel mixer, a Banbury mixer, or the like, or after mixing, A propylene-based polymer composition can be obtained by melt-kneading with a single-screw extruder, twin-screw extruder, high-speed twin-screw extruder, or the like.
• the injection-molded article of the present invention is a molded article obtained by injection-molding the propylene-based polymer composition of the present invention.
• the injection molded article of the present invention is produced by using a known injection molding machine, heating and melting the propylene-based polymer composition of the present invention, injecting it into a mold, cooling and solidifying it, and removing it from the mold. can be manufactured by
• the propylene-based polymer composition is put into the hopper of an injection molding machine, fed into a cylinder heated to about 200° C. to 250° C., kneaded, plasticized and melted. state.
• the mold is passed through a nozzle at high pressure and high speed (maximum pressure 700 to 1500 kg/cm 3 ) with cooling water or hot water at a temperature of 5 to 50°C, preferably 10 to 40°C. Inject into the mold. It can be carried out by cooling and solidifying the injected propylene-based polymer composition by cooling from the mold, opening the mold with a mold clamping mechanism, and obtaining an injection-molded article.
• the propylene-based polymer composition is put into the hopper of an injection molding machine, and the resin is fed into a cylinder heated to about 200° C. to 250° C., kneaded and plasticized to a molten state. to The mold is passed from the nozzle at high pressure and high speed (maximum pressure 700 to 1500 kg/cm 3 ), and the temperature is adjusted to 5 to 80°C, preferably 10 to 60°C, with cooling water or warm water. Injection molded into a mold where it cools for 1.0-3.0 seconds to form a preform, then immediately opens the mold and is stretch oriented in the machine direction using stretch rods and then in the transverse direction by blow molding. and stretch orientation to obtain an injection molded product.
• the injection-molded article of the present invention includes food containers, beverage containers, containers, daily necessities, and the like. More specifically, it can be widely used as food containers (dessert cups) for solids such as jelly, pudding and yogurt, containers for chemicals, containers for industrial liquids, and the like.
• the thickness of the container body is in the range of 0.3 to 2.0 mm.
• the propylene-based resin composition of the present invention has sufficient impact strength even when it is thinned in this way, and does not break into fragments during the manufacturing process.
• the injection molded product of the present invention has a good balance of impact resistance, transparency, and rigidity even in these products.
• Ethylene/ ⁇ -olefin copolymer (B) The following ethylene/ ⁇ -olefin copolymer was used as the ethylene/ ⁇ -olefin copolymer (B).
• Ethylene/1-hexene copolymer (B-2) Ethylene/1-hexene copolymer (B-2) having an MFR 190 of 3.8 g/10 min and a density of 918 kg/m 3 : Evolue SP2040 manufactured by Prime Polymer Co., Ltd. was used.
• (2-3) Ethylene/1-hexene copolymer (B-3) Ethylene/1-hexene copolymer (B-3) having an MFR 190 of 1 g/10 min and a density of 915 kg/m 3 : Evolue SP0510 (trade name, manufactured by Prime Polymer Co., Ltd.) was used.
• Ethylene/1-hexene copolymer (B-4) Ethylene/1-hexene copolymer (B-4) having an MFR 190 of 2 g/10 min and a density of 913 kg/m 3 : Evolue SP1520 manufactured by Prime Polymer Co., Ltd. was used.
• (2-5) Ethylene/1-hexene copolymer (B-5) Ethylene/1-hexene copolymer (B-5) having an MFR 190 of 10 g/10 min and a density of 911 kg/m 3 : Evolue SP1071C manufactured by Prime Polymer Co., Ltd. was used.
• Ethylene/ ⁇ -olefin copolymer (C) As the ethylene/ ⁇ -olefin copolymer, the following ethylene/ ⁇ -olefin copolymer was used. (3-1) Ethylene/ ⁇ -olefin copolymer (C-1) Ethylene/propylene copolymer (C-1) having an MFR 190 of 1.5 g/10 min and a density of 862 kg/m 3 : VISTAMAXX 6102FL manufactured by ExxonMobil was used.
• Ethylene/ ⁇ -olefin copolymer (C-2) Ethylene/propylene copolymer (C-2) having an MFR 190 of 4 g/10 min and a density of 879 kg/m 3 : VISTAMAXX 3980FL manufactured by ExxonMobil was used.
• the physical properties of the injection molded articles obtained in Examples and Comparative Examples were measured by the following methods.
• (1) Transparency Haze was measured in accordance with JIS K7136 for the central portion of the injection molded body.
• the total haze is the sum of the internal haze and the external haze.
• (2) High-speed surface impact test (high-rate impact) Using an injection molded body consisting of a flat plate of 200 mm ⁇ 200 mm ⁇ 2.0 mm, place a test piece for measurement on a support with a hole with an inner diameter of 40 mm ⁇ , fix it using a sample holder with an inner diameter of 76 mm ⁇ , and then hit it with a hemispherical impact.
• a striker having a diameter of 12.7 mm ⁇ with a surface was used to hit the test piece at an impact speed of 1 m/sec, and the puncture energy (J) was determined according to JIS K7211-2. The average value of the puncture energy of each of the four test pieces for measurement was taken as the plane impact strength (high rate impact).
• the tensile modulus of a dumbbell test piece was measured according to JIS K7161 and K7162-1.
• Example 1 A propylene polymer composition obtained by mixing 90% by mass of the propylene polymer (A-1) and 10% by mass of the ethylene/1-hexene copolymer (B-1) was injected into an injection molding machine (Fanuc Co., Ltd.).
• a FANUC ROBOSHOT ⁇ 100C manufactured by the company was used under the conditions of a molten resin temperature of 200°C, a mold temperature of 40°C, an average injection speed of 35 mm/sec, a holding pressure time of 10 seconds, and a total cycle time of 45 seconds.
• An injection-molded object for high-speed surface impact test and transparency (haze) measurement consisting of a flat plate of 0 mm, and an injection-molded object consisting of a tensile modulus test piece (dumbbell test piece conforming to JIS K7161 and K7162-1). made.
• Example 1 shows the results.
• Example 2 to 11 instead of the propylene-based polymer composition used in Example 1, propylene of the propylene-based polymer (A-1) described in Table 1 and the ethylene/1-hexene copolymer (B-1), etc.
• An injection-molded article was produced in the same manner as in Example 1, except that the polymer composition was used.
• Example 1 An injection-molded article was produced in the same manner as in Example 1, except that the propylene-based polymer (A-1) was used alone instead of the propylene-based polymer composition used in Example 1.
• the injection-molded articles obtained in Examples 1 to 11 have better haze than the injection-molded articles obtained in Comparative Example 1 consisting of the propylene-based polymer (A) alone. is becoming Also, impact strength at 23°C, impact strength at 0°C, and impact strength at -20°C are improved.
• the injection-molded articles made of the propylene-based polymer composition containing the ethylene/ ⁇ -olefin copolymer having a density of 862 kg/m 3 obtained in Comparative Examples 2 to 5 had a deteriorated haze of -20. No improvement in impact strength at °C.
• the haze of the injection-molded articles made of the propylene-based polymer composition containing the ethylene/ ⁇ -olefin copolymer having a density of 879 kg/m 3 obtained in Comparative Examples 6 to 8 did not worsen. C. and -20.degree. C. impact strength show no improvement.

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• 2022
  • 2022-04-27 JP JP2023523376A patent/JP7690579B2/ja active Active
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