Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F210/02—Ethene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • 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
• • 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
  • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers

Definitions

• the present invention relates to a polypropylene resin composition. More specifically, the present invention relates to a polypropylene resin composition which is excellent in impact resistance and heat adhesiveness, and in particular, has a low appearance of orange peel after retort sterilization, and is suitable for retort food packaging applications.
• a polypropylene resin composition comprising a polymerized ethylene-propylene block copolymer.
• Retort food packaging which is sterilized after packaging and stored at room temperature or low temperature for a long time, is a packaging technology that is easy to handle and occupies less volume than conventional glass or metal cans, and has a low cost of packaging materials. .
• Retort containers which are sterilized mainly at 120 ⁇ 135 o C, are used in multiple layers by adhering polypropylene, polyester, nylon film, and metal foil, and depending on the application, polyester / nylon / metal foil / polypropylene or polyester / metal foil It is made of a configuration such as polypropylene.
• polypropylene is generally used as an ethylene-propylene block copolymer, and is processed into an unstretched film (CPP film) so as to be located on the innermost side of the heat-adhesive layer.
• Japanese Patent 2012-184302A blends linear low density-polyethylene (LLDPE) using metallocene catalysts to suppress orange peel generation, but the thermal bond strength is lowered by blending LLDPE, so Japanese Patent 2013-087275A adds when forming CPP film Blending rubber components with high-density-polyethylene (HDPE) to suppress orange peel generation, but there is a problem of uneven dispersion and cost increase due to blending a large amount of rubber components and HDPE, and it is difficult to control the dispersed phase depending on the processing equipment. There are disadvantages.
• LLDPE linear low density-polyethylene
• HDPE high-density-polyethylene
• An object of the present invention is to provide a polypropylene resin composition for films capable of high temperature sterilization, excellent impact resistance and thermal adhesion characteristics, and excellent appearance after sterilization, that is, to suppress the generation of orange peel.
• Still another object of the present invention is to provide a film capable of high temperature sterilization, excellent impact resistance and heat adhesion property, and no orange peel after sterilization.
• the present invention comprises an ethylene propylene block copolymer in which 65 to 82% by weight of propylene homopolymer and 18 to 35% by weight of ethylene propylene rubber are polymerized in stages in the reactor, the ethylene propylene rubber
• the ethylene content of 25 to 50% by weight, and the intrinsic viscosity of the solvent extract (solvent decalin, 135 °C) of the ethylene propylene rubber provides a polypropylene resin composition, characterized in that 1 to 2.5dl / g.
• the present invention provides a film made of the polypropylene resin composition according to the present invention.
• the polypropylene resin composition according to the present invention can be used in a heat-adhesive layer of a retort package composed of multiple layers, and exhibits excellent impact resistance and heat-adhesive properties and suppresses the generation of orange peel after sterilization. It is expected to be suitable for.
• (a) 65-82% by weight of propylene homopolymer and (b) 18-35% by weight of ethylene propylene rubber comprises ethylene propylene block copolymer polymerized step by step in the reactor, Provides a polypropylene resin composition characterized in that the ethylene content of the ethylene propylene rubber is 25 to 50% by weight, and the intrinsic viscosity of the solvent extract (solvent decalin, 135 ° C) of the ethylene propylene rubber is 1 to 2.5 dl / g. .
• the polypropylene resin composition according to the present invention the polypropylene resin has a heat resistance suitable for high temperature sterilization, excellent impact resistance and heat adhesive properties, can be provided a CPP film having an excellent appearance is suppressed orange peel after sterilization. have.
• Component (a) propylene homopolymer
• Propylene homopolymer in component (a) is polymerized by injecting propylene alone in a polymerization reactor.
• the polymerization method of the polymer is a conventional method known in the art, and is not particularly limited in the present invention.
• the component (a) is 65 to 82% by weight in the ethylene-propylene block copolymer. If the content of component (a) is less than 65% by weight, the degree of crystallinity is lowered, resulting in lower heat resistance and lower thermal bond strength. In addition, when the content exceeds 82% by weight, impact resistance is lowered, and orange peel occurs after sterilization, which is not preferable.
• the component (b) is polymerized continuously in the presence of the component (a) in a polymerization reactor which is subsequently polymerized after the component (a).
• the polymerization method of the rubber copolymer is a conventional method known in the art, and is not particularly limited in the present invention.
• Component (b) is polymerized continuously in the reactor after component (a) polymerization, and the components of component (a) and component (b) are identical in propylene chain and are uniformly dispersed by the affinity of the two phases, It can minimize the deterioration of thermal adhesive properties, improve the impact strength and suppress the orange peel after sterilization.
• Component (b) is polymerized at 18 to 35% by weight relative to the ethylene-propylene block copolymer.
• Intrinsic viscosity (decalin solvent) of the solvent extract in the component (b) is preferably 1 ⁇ 2.5dl / g.
• the intrinsic viscosity is less than 1 dl / g, the size of the rubber component is small and the molecular weight of the rubber component is small, the impact characteristic is lowered.
• the intrinsic viscosity exceeds 2.5dl / g, the size of the rubber component increases and agglomeration occurs, the dispersibility is reduced, orange peel is generated after sterilization.
• partial breakage of the pouch film may occur after sterilization.
• the ratio of the intrinsic viscosity of the solvent insoluble in the ethylene propylene block copolymer and the intrinsic viscosity of the solvent extract in the ethylene propylene block copolymer is ⁇ (Intrinsic Viscosity of Solvent Extract) / (Intrinsic Viscosity of Solvent Insoluble) ⁇ 0.6 to 1.4 are preferred. If the ratio of intrinsic viscosity is less than 0.6, the size of the rubber component is reduced and the impact characteristic is lowered. If the intrinsic viscosity ratio is greater than 1.4, agglomeration of the rubber component is generated and dispersibility is reduced.
• the ethylene content in the component (b) is preferably 25 to 50% by weight. If the ethylene content is less than 20% by weight, the elasticity of the rubber is reduced and the impact resistance is lowered. If the ethylene content is more than 50% by weight, the compatibility of the component (a) and the component (b) is lowered to increase the size of the rubber phase, so that the dispersibility It lowers and an orange peel arises.
• the melt index of the polypropylene resin is preferably 1 ⁇ 10g / 10 minutes (ASTM D 1238, 230 °C). If the melt index is less than 1g / 10 minutes, the flowability of the molten resin is lowered, the extrusion load is increased during film formation of the CPP film, and the productivity is greatly reduced. If the melt index is more than 10g / 10 minutes, the melt viscosity discharged from the die is increased. This lowers the thickness uniformity in forming the CPP film and lowers the mechanical strength due to the low molecular weight, which is undesirable.
• the polypropylene resin composition according to the present invention may further include additives and solvents known in the art within the scope of not impairing the object of the present invention.
• additives and solvents known in the art within the scope of not impairing the object of the present invention.
• antioxidants, nucleating agents, heat stabilizers, weather stabilizers, antistatic agents, lubricants, slip agents, flame retardants, pigments, dyes and the like can be used, preferably antioxidants and ultraviolet rays to impart heat and weather stability An absorbent etc. can be added.
• the additives can be appropriately adjusted by those skilled in the art without departing from the object of the present invention.
• the components constituting the resin composition may be selected and mixed according to a desired order without any particular order limitation, and specifically, kneader, for example, by the required amount of each component and other additives as described above. It may be prepared by a method of kneading raw materials introduced by using the apparatus after the addition to a kneading machine such as a roll, a Banbury mixer, or a single screw twin screw extruder, but is not limited thereto. no.
• the present invention provides a film made of the polypropylene resin composition.
• the film may be applied to a protective film, a decor sheet, a retort pouch, or the like of an electronic product requiring high precision, such as a liquid crystal display.
• a protective film such as a decor sheet, a retort pouch, or the like of an electronic product requiring high precision, such as a liquid crystal display.
• it can be preferably applied to a retort pouch.
• Ethylene content was measured using an infrared absorption spectrum (FT-IR) using a 720, 730 cm -1 characteristic peak.
• FT-IR infrared absorption spectrum
• Intrinsic viscosity was measured using a viscometer under 135 ° C decalin solution.
• Intrinsic viscosity ratio was calculated as follows.
• the solvent extract of ethylene propylene rubber component (b) shows the component soluble at 150 degreeC using the decalin solvent.
• a 70 ⁇ m film was taken with a width of 15 mm and a length of 100 mm and measured at a tensile speed of 300 m / min in UTM.
• 70 ⁇ m films were measured according to the ASTM D4226 method.
• Polypropylene film 70 ⁇ m
• aluminum foil 9 ⁇ m
• Nylon 15 ⁇ m
• PET 12 ⁇ m
• the adhesive film before and after sterilization was cut to a width of 15 mm to measure peel strength of the film.
• the appearance of the pouch was evaluated to evaluate the occurrence of orange peel.
• the polypropylene resin according to the present invention exhibited excellent mechanical properties such as high Izod impact strength and heat deformation temperature, high film impact strength, and good thermal adhesive strength after sterilization. In addition, orange peel does not occur in appearance, it was shown to have excellent characteristics.
• Comparative Example 1 has a good thermal adhesive strength, but the content of component (b) is low, the polling dart impact strength is greatly reduced, a large amount of orange peel after sterilization was poor appearance.
• Comparative Examples 2 and 3 have good Izod impact strength and polling dart impact strength due to the content of component (b), but orange peel occurred after sterilization due to high intrinsic viscosity and intrinsic viscosity ratio of solvent extract.
• Comparative Example 2 had a high ethylene content of component (b), and the change of thermal adhesive strength before and after sterilization was severe.
• Comparative Example 4 was unsuitable for commercial application of the thermal adhesive strength of less than 5kgf after sterilization due to the high content of component (b).

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
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• Engineering & Computer Science (AREA)
• Manufacturing & Machinery (AREA)
• Materials Engineering (AREA)
• Compositions Of Macromolecular Compounds (AREA)
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• 2014
  • 2014-11-12 KR KR1020140157223A patent/KR101598715B1/ko active IP Right Grant
• 2015
  • 2015-04-28 WO PCT/KR2015/004206 patent/WO2016076490A1/ko active Application Filing
  • 2015-04-28 CN CN201580055808.2A patent/CN106795344B/zh active Active

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