WO2023132306A1 - Film non orienté, film d'étanchéité et film d'étanchéité multicouche - Google Patents

Film non orienté, film d'étanchéité et film d'étanchéité multicouche Download PDF

Info

Publication number
WO2023132306A1
WO2023132306A1 PCT/JP2022/048281 JP2022048281W WO2023132306A1 WO 2023132306 A1 WO2023132306 A1 WO 2023132306A1 JP 2022048281 W JP2022048281 W JP 2022048281W WO 2023132306 A1 WO2023132306 A1 WO 2023132306A1
Authority
WO
WIPO (PCT)
Prior art keywords
propylene
based polymer
mass
molecular weight
film
Prior art date
Application number
PCT/JP2022/048281
Other languages
English (en)
Japanese (ja)
Inventor
知也 村上
篤太郎 木村
博貴 志水
淳 尾留川
友章 水川
凪 ▲高▼井
Original Assignee
株式会社プライムポリマー
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 株式会社プライムポリマー filed Critical 株式会社プライムポリマー
Publication of WO2023132306A1 publication Critical patent/WO2023132306A1/fr

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/06—Propene
    • 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

Definitions

  • the present invention relates to non-stretched films, sealant films and multilayer sealant films.
  • Propylene-based polymers are widely used as materials for various molded articles (see, for example, Patent Documents 1 to 4), and the required properties differ depending on the molding method and application.
  • films made of propylene-based polymers are widely used as packaging films for foods and miscellaneous goods, taking advantage of their excellent mechanical properties such as rigidity and optical properties such as gloss.
  • Unstretched polypropylene films are known to have an excellent balance of rigidity and heat resistance.
  • Patent Document 8 discloses an unstretched polypropylene film using a specific propylene-based polymer and having particularly excellent rigidity.
  • the object of the first aspect of the present invention is to provide an unstretched polypropylene film that is excellent in well-balanced rigidity and low-temperature heat-sealing performance (hereinafter referred to as "first object").
  • a second aspect of the present invention is to provide a non-stretched polypropylene film having excellent rigidity and capable of being heat-sealed at a low temperature (hereinafter referred to as a "second problem"). ).
  • a first aspect of the present invention relates to, for example, the following [1].
  • a propylene-based polymer (A) containing Melt flow rate (230 ° C., 2.16 kg load) is 0.1 to 30 g / 10 minutes, and intrinsic viscosity [ ⁇ ] measured in tetralin solvent at 135 ° C.
  • the content of the propylene-based polymer (A) is 1 to 10 parts by mass with respect to a total of 100 parts by mass of the propylene-based polymer (A) and the propylene/ ⁇ -olefin copolymer (B1)
  • An unstretched film comprising a propylene-based polymer composition (X1) containing 90 to 99 parts by mass of the propylene/ ⁇ -olefin copolymer (B1).
  • a second aspect of the present invention relates to, for example, the following [2].
  • the content of the propylene-based polymer (A) is 1 to 18 parts by mass with respect to a total of 100 parts by mass of the propylene-based polymer (A) and the propylene/ ⁇ -olefin copolymer (B2),
  • An unstretched film comprising a propylene-based polymer composition (X2) containing 82 to 99 parts by mass of the propylene/ ⁇ -olefin copolymer (B2).
  • the first and second aspects of the present invention further relate to [3] to [6] below.
  • the area ratio of the high molecular weight region having a molecular weight of 1,500,000 or more in the total area of the region surrounded by the molecular weight distribution curve measured by gel permeation chromatography (GPC) is 7% or more.
  • the propylene-based polymer (A) has two peaks in the molecular weight distribution curve measured by GPC, and the ratio (MH/ML) of the peak molecular weight MH on the high molecular weight side and the peak molecular weight ML on the low molecular weight side is The unstretched film according to any one of [1] to [4], which is 50 or more.
  • the first aspect of the present invention further relates to [7] below.
  • the second aspect of the present invention further relates to [8] below.
  • the unstretched film of the first aspect of the present invention is excellent in well-balanced rigidity and low-temperature heat-sealing performance (that is, a low seal initiation temperature, which will be described later).
  • the non-stretched film of the second aspect of the present invention has excellent rigidity and excellent sealing performance (that is, it has a low sealing initiation temperature, which will be described later).
  • the unstretched film of the first aspect of the present invention is a propylene-based polymer composition (X1 ).
  • non-stretched film of the second aspect of the present invention is a propylene-based polymer composition containing a propylene-based polymer (A) and a propylene/ ⁇ -olefin copolymer (B2) described below. (X2).
  • propylene/ ⁇ -olefin copolymer (B1) and the propylene/ ⁇ -olefin copolymer (B2) are collectively referred to as "propylene/ ⁇ -olefin copolymer It is also described as “union (B)”.
  • propylene-based polymer composition (X1) when there is no particular need to distinguish between the propylene-based polymer composition (X1) and the propylene-based polymer composition (X2), they may be collectively referred to as "propylene-based polymer composition (X)." Describe.
  • the propylene polymer (A) contains 20 to 50% by mass of the propylene polymer (a1) having a limiting viscosity [ ⁇ ] of 10 to 12 dl/g measured in a tetralin solvent at 135°C, and 135 °C, 50 to 80% by mass of the propylene polymer (a2) having an intrinsic viscosity [ ⁇ ] measured in a tetralin solvent in the range of 0.5 to 1.5 dl/g [however, the propylene polymer (a1 ) and the propylene-based polymer (a2) is 100% by mass. ⁇ include.
  • intrinsic viscosity [ ⁇ ] measured in a tetralin solvent at 135°C is also simply referred to as "intrinsic viscosity [ ⁇ ]".
  • the mass fractions of the propylene-based polymer (a1) and the propylene-based polymer (a2) are based on the total amount of (a1) and (a2).
  • the intrinsic viscosity [ ⁇ ] of the propylene-based polymer (a1) is in the range of 10-12 dl/g, preferably in the range of 10.5-11.5 dl/g.
  • the mass fraction of the propylene-based polymer (a1) in the propylene-based polymer (A) is in the range of 20 to 50% by mass, preferably 20 to 45% by mass, more preferably 20 to 40% by mass, More preferably, it is in the range of 22-40% by mass.
  • propylene-based polymer (a1) examples include propylene homopolymers and copolymers of propylene and ⁇ -olefins having 2 to 8 carbon atoms (excluding propylene).
  • ⁇ -olefins having 2 to 8 carbon atoms include ethylene, 1-butene, 1-hexene, 1-octene and 4-methyl-1-pentene. Ethylene is preferred as these ⁇ -olefins.
  • One or more ⁇ -olefins can be used.
  • the content of structural units derived from propylene is usually 90% by mass or more, preferably 95% by mass or more, more preferably 98% by mass or more. and the content of structural units derived from ⁇ -olefins having 2 to 8 carbon atoms (excluding propylene) is usually 10% by mass or less, preferably 5% by mass or less, more preferably 2% by mass or less. is.
  • the content ratio can be measured by 13 C-NMR.
  • the intrinsic viscosity [ ⁇ ] of the propylene-based polymer (a1) is within the range of 10 to 12 dl/g, it is preferable from the viewpoint of suppressing the number of fish eyes (FE) in the film obtained from the polymer composition.
  • the intrinsic viscosity [ ⁇ ] of the propylene-based polymer (a1) exceeds 12 dl/g, the film formability tends to deteriorate and the film surface appearance tends to deteriorate. Further, when the intrinsic viscosity [ ⁇ ] of the propylene-based polymer (a1) is less than 10 dl/g, the resulting film tends to have insufficient rigidity, heat resistance and gas barrier properties.
  • the mass fraction of the propylene-based polymer (a1) is less than 20% by mass, the resulting polymer composition tends to have insufficient melt tension, and the resulting film tends to have insufficient rigidity, heat resistance and gas barrier properties. If it exceeds 50% by mass, it tends to cause poor appearance during film molding.
  • the propylene-based polymer (a1) can be used alone or in combination of two or more.
  • the intrinsic viscosity [ ⁇ ] of the propylene-based polymer (a2) is in the range of 0.5 to 1.5 dl/g, preferably 0.6 to 1.5 dl/g, more preferably 0.8 to 1.5 dl/g. It is in the range of 5 dl/g.
  • the mass fraction of the propylene-based polymer (a2) in the propylene-based polymer (A) is in the range of 50 to 80% by mass, preferably 55 to 80% by mass, more preferably 60 to 80% by mass, More preferably, it is in the range of 60-78% by mass.
  • propylene-based polymer (a2) examples include propylene homopolymers and copolymers of propylene and ⁇ -olefins having 2 to 8 carbon atoms (excluding propylene).
  • ⁇ -olefins having 2 to 8 carbon atoms include ethylene, 1-butene, 1-hexene, 1-octene and 4-methyl-1-pentene. Ethylene is preferred as these ⁇ -olefins.
  • One or more ⁇ -olefins can be used.
  • the content of structural units derived from propylene is usually 90% by mass or more, preferably 93% by mass or more, more preferably 94% by mass or more. and the content of structural units derived from ⁇ -olefins having 2 to 8 carbon atoms (excluding propylene) is usually 10% by mass or less, preferably 7% by mass or less, more preferably 6% by mass or less. is.
  • the content ratio can be measured by 13 C-NMR.
  • the intrinsic viscosity [ ⁇ ] of the propylene-based polymer (a2) is less than 0.5 dl/g, the melt tension of the resulting polymer composition will be insufficient, and the resulting film will tend to have poor fisheyes. If the intrinsic viscosity [ ⁇ ] exceeds 1.5 dl/g, the viscosity tends to be high and the film formability tends to deteriorate.
  • the mass fraction of the propylene-based polymer (a2) is less than 50% by mass, it tends to cause poor appearance during film molding. In addition, the rigidity, heat resistance and gas barrier properties of the resulting film tend to be insufficient.
  • the propylene-based polymer (a2) can be used alone or in combination of two or more.
  • Additives such as an antioxidant, a neutralizer, a flame retardant, and a crystal nucleating agent can be added to the propylene-based polymer (A), if necessary. Additives can be used alone or in combination of two or more. The proportion of the additive is not particularly limited and can be adjusted as appropriate.
  • the propylene-based polymer (A) preferably has a melt flow rate (MFR) of 0.01 to 5 g/10 minutes, more preferably 0.05 to 4 g/10 minutes, measured at 230°C under a load of 2.16 kg. , more preferably in the range of 0.1 to 3 g/10 minutes.
  • MFR melt flow rate
  • the propylene-based polymer (A) preferably has a melt tension (MT) measured at 230°C in the range of 5 to 30 g, more preferably 7 to 25 g, and even more preferably 10 to 20 g.
  • MT melt tension
  • Melt tension (MT) can be measured with the following equipment and conditions.
  • the area ratio of the high molecular weight region of 10,000 or more (corresponding to the mass ratio of the high molecular weight component having a molecular weight of 1,500,000 or more) is preferably 7% or more, more preferably 10% or more, and still more preferably 12% or more.
  • the upper limit of the area ratio is, for example, 30%, preferably 25%.
  • the area ratio of the high-molecular-weight region occupies a specific ratio or more means that the propylene-based polymer (A) contains a high-molecular-weight component having a molecular weight of 1,500,000 or more. At least part of this high molecular weight component is a high molecular weight component having an intrinsic viscosity [ ⁇ ] of 10 to 12 dl/g. Therefore, if the ratio of the high molecular weight component is within the above range, the melt tension of the polymer composition will be more excellent.
  • the propylene-based polymer (A) preferably has two peaks in the molecular weight distribution curve measured by GPC.
  • the ratio (MH/ML) of the peak molecular weight MH on the high molecular weight side to the peak molecular weight ML on the low molecular weight side is preferably 50 or more, more preferably 70 or more, and even more preferably 90 or more.
  • the upper limit of the ratio (MH/ML) is, for example, 500, preferably 300.
  • the fact that the molecular weight distribution curve has two peaks and MH/ML is a specific value or more indicates that the polymer has a high content of high molecular weight components and a high intrinsic viscosity [ ⁇ ]. Therefore, the propylene-based polymer (A) having such an aspect contributes to improvement of melt tension and improvement of rigidity and heat resistance when formed into a film.
  • the propylene-based polymer (A) preferably has a peak molecular weight ML on the low molecular weight side of the molecular weight distribution curve measured by GPC of 100,000 or less, more preferably 80,000 or less, from the viewpoint of viscosity and film formability. More preferably, it is 50,000 or less.
  • Examples of the method for producing the propylene-based polymer (A) include various known production methods, such as those described in [0038] to [0075] of International Publication No. 2021/025142.
  • the propylene/ ⁇ -olefin copolymer (B1) has a melt flow rate (MFR) of 0.1 to 30 g/10 minutes measured under a load of 2.16 kg at 230°C, and measured in a tetralin solvent at 135°C.
  • MFR melt flow rate
  • the intrinsic viscosity [ ⁇ ] of more than 1.5 dl / g and 5.0 dl / g or less, and a copolymer containing 5.5 mol% or more of structural units derived from ⁇ -olefins (excluding propylene) It is a polymer.
  • the propylene/ ⁇ -olefin copolymer (B2) has a melt flow rate (MFR) of 0.1 to 30 g/10 minutes measured under a load of 2.16 kg at 230°C, and measured in a tetralin solvent at 135°C. has a limiting viscosity [ ⁇ ] of more than 1.5 dl/g and 5.0 dl/g or less, and a structural unit derived from an ⁇ -olefin (excluding propylene) is 1 mol% or more and 5.5 mol% It is a copolymer containing less than
  • the intrinsic viscosity [ ⁇ ] of the propylene/ ⁇ -olefin copolymer (B) is more than 1.5 dl/g and 5.0 dl/g or less, preferably more than 1.5 dl/g and 4.5 dl/g or less. , more preferably more than 1.5 dl/g and less than or equal to 4.0 dl/g, more preferably more than 1.5 dl/g and less than or equal to 2.5 dl/g.
  • the melt flow rate (MFR) of the propylene/ ⁇ -olefin copolymer (B) measured at 230°C under a load of 2.16 kg is 0.1 to 30 g/10 minutes, preferably 0.3 to 10 g. /10 minutes, more preferably 0.5 to 10 g/10 minutes.
  • MFR melt flow rate
  • the melting point (Tm) of the propylene/ ⁇ -olefin copolymer (B1) is , preferably 120 to 170°C, more preferably 125 to 170°C, still more preferably 125 to 135°C.
  • the melting point (Tm) is preferably within the above range from the viewpoint of moldability and heat resistance.
  • the melting point (Tm) of the propylene/ ⁇ -olefin copolymer (B2) is , preferably 120 to 170°C, more preferably 125 to 170°C, even more preferably 130 to 170°C, and particularly preferably 130 to 155°C.
  • the melting point (Tm) is preferably within the above range from the viewpoint of moldability and heat resistance.
  • the molecular weight distribution (Mw/Mn) of the propylene/ ⁇ -olefin copolymer (B) measured by gel permeation chromatography (GPC) is preferably at least 4.0, more preferably from 4.0 to 6.5, more preferably 4.0 to 6.0.
  • Mn is the number average molecular weight
  • Mw is the weight average molecular weight.
  • propylene/ ⁇ -olefin copolymer (B) examples include propylene/ ⁇ -olefin random copolymers, block-type propylene copolymers (propylene homopolymers or propylene/ ⁇ -olefin random copolymers, mixture with amorphous or low-crystalline propylene/ ⁇ -olefin random copolymer) and random block polypropylene.
  • ⁇ -olefins examples include ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 4-methyl-1-pentene, 3-methyl-1-pentene and the like. and ⁇ -olefins having 2 to 12 carbon atoms. Among these ⁇ -olefins, ethylene, 1-butene, 1-hexene, 1-octene and 4-methyl-1-pentene are preferred. One or more ⁇ -olefins can be used.
  • the content of structural units derived from ⁇ -olefins is determined by the content of structural units derived from propylene and the structure derived from ⁇ -olefins. Assuming that the total amount of units is 100 mol %, it is 5.5 mol % or more, preferably 5.5 to 9.0 mol %, more preferably 5.5 to 7.0 mol %.
  • the content of structural units derived from ⁇ -olefins (excluding propylene) is 1 mol% in the case of the propylene/ ⁇ -olefin copolymer (B2). 5.5 mol % or more, preferably 1.5 to 4.5 mol %, more preferably 2.0 to 4.0 mol %.
  • the content ratio can be measured by 13 C-NMR.
  • the propylene/ ⁇ -olefin copolymer (B) can be produced by copolymerizing propylene with another ⁇ -olefin using a catalyst, and a commercially available polypropylene resin can be used.
  • a catalyst for example, a solid catalyst component containing magnesium, titanium and halogen as essential components, and an organometallic compound catalyst such as an organoaluminum compound, described in [0050] to [0075] of International Publication No. 2021/025142.
  • the propylene-based polymer (A) and the propylene/ ⁇ -olefin copolymer (B) may each contain structural units derived from at least one biomass-derived monomer (propylene).
  • the same kind of monomers constituting the polymer may be only biomass-derived monomers, may be only fossil fuel-derived monomers, or may be both biomass-derived monomers and fossil fuel-derived monomers.
  • Biomass-derived monomers are monomers derived from any renewable natural raw materials and their residues, such as plant-derived or animal-derived, including fungi, yeast, algae and bacteria, and have 1 C isotope as carbon. It contains about ⁇ 10 ⁇ 12 , and the biomass carbon concentration (pMC) measured according to ASTM D6866 is about 100 (pMC).
  • pMC biomass carbon concentration
  • a biomass-derived monomer (propylene) can be obtained, for example, by a conventionally known method.
  • the propylene-based polymer (A) or the propylene/ ⁇ -olefin copolymer (B) contains structural units derived from biomass-derived monomers from the viewpoint of reducing the environmental load. If the polymer production conditions such as the polymerization catalyst and the polymerization temperature are the same, even if the raw olefin is a propylene-based polymer containing a biomass-derived olefin or a propylene/ ⁇ -olefin copolymer, the 14 C isotope is reduced to 1.
  • the molecular structure other than the ratio of about ⁇ 10 -12 is equivalent to that of a propylene-based polymer or a propylene/ ⁇ -olefin copolymer composed of fossil fuel-derived monomers. Therefore, these performances are said to be unchanged.
  • the propylene-based polymer (A) and the propylene/ ⁇ -olefin copolymer (B) may contain structural units derived from at least one chemically recycled monomer (propylene).
  • the same kind of monomers constituting the polymer may be only chemically recycled monomers, or may include chemically recycled monomers and fossil fuel-derived monomers and/or biomass-derived monomers.
  • a chemically recycled monomer (propylene) can be obtained, for example, by a conventionally known method.
  • the propylene-based polymer (A) and the propylene/ ⁇ -olefin copolymer (B) contain structural units derived from monomers derived from chemical recycling from the viewpoint of reducing the environmental load (mainly reducing waste). Even if the raw material monomer contains a monomer derived from chemical recycling, the monomer derived from chemical recycling is a monomer obtained by depolymerizing or thermally decomposing a polymer such as waste plastic into a monomer unit such as ethylene, or using the monomer as a raw material.
  • the molecular structure is a propylene-based polymer or a propylene/ ⁇ -olefin copolymer consisting of a fossil fuel-derived monomer. is equivalent to Therefore, these performances are said to be unchanged.
  • the propylene-based polymer composition (X) contains a weather stabilizer, a heat stabilizer, an antistatic agent, a slip agent, an antiblocking agent, an antifogging agent, a nucleating agent, Decomposing agent, pigment, dye, plasticizer, hydrochloric acid absorbent, antioxidant, cross-linking agent, cross-linking accelerator, reinforcing agent, filler, softener, processing aid, activator, moisture absorbent, adhesive, flame retardant, Additives such as release agents may be included. Additives can be used alone or in combination of two or more.
  • the propylene-based polymer composition (X) can be produced by adopting any known method.
  • the content of the propylene-based polymer (A) with respect to a total of 100 parts by mass of the propylene-based polymer (A) and the propylene/ ⁇ -olefin copolymer (B1) is 1 to 10 parts by mass, preferably 3 to 10 parts by mass, more preferably 4 to 10 parts by mass, and the content of the propylene/ ⁇ -olefin copolymer (B1) is 90 to 99 parts by mass. , preferably 90 to 97 parts by mass, more preferably 90 to 96 parts by mass.
  • the unstretched film according to the present invention in which the contents of the propylene-based polymer (A) and the propylene/ ⁇ -olefin copolymer (B) are within the above range, has excellent rigidity and heat-sealing performance in a well-balanced manner. It also looks great when sealed.
  • the content of the propylene/ ⁇ -olefin copolymer (B1) is less than 90 parts by mass, the sealing performance of the film tends to deteriorate, that is, the heat sealing temperature tends to increase, and when the film is heat sealed, may deteriorate the appearance of
  • the content of the propylene/ ⁇ -olefin copolymer (B1) exceeds 99 parts by mass, the rigidity of the film tends to deteriorate, that is, the tensile modulus tends to decrease.
  • the content of the propylene-based polymer (A) with respect to a total of 100 parts by mass of the propylene-based polymer (A) and the propylene/ ⁇ -olefin copolymer (B2) is 1 to 18 parts by mass, preferably 3 to 10 parts by mass, more preferably 4 to 10 parts by mass, and the content of the propylene/ ⁇ -olefin copolymer (B2) is 82 to 99 parts by mass. , preferably 90 to 97 parts by mass, more preferably 90 to 96 parts by mass.
  • the content of the propylene/ ⁇ -olefin copolymer (B2) is less than 82 parts by mass, the sealing performance of the film tends to deteriorate, that is, the heat sealing temperature tends to increase.
  • the content of the propylene/ ⁇ -olefin copolymer (B2) exceeds 99 parts by mass, the rigidity of the film tends to deteriorate, that is, the tensile modulus tends to decrease.
  • a propylene-based polymer containing a propylene-based polymer (a1) and a propylene-based polymer (a2) obtained by batchwise multistage polymerization is used. It is preferable to prepare the propylene-based polymer composition (X) by mixing the coalescence (A) and the propylene/ ⁇ -olefin copolymer (B).
  • the molecular weight distribution (Mw/Mn) of the propylene-based polymer composition (X) measured by gel permeation chromatography (GPC) is preferably 5.0 or more, more preferably 5.5 or more, and still more preferably. is 6.0 or more, and the upper limit is not particularly limited, but is 25, for example.
  • the propylene-based polymer (a2), the propylene/ ⁇ -olefin copolymer (B), and the propylene-based polymer (a1) having a higher molecular weight than these are used.
  • the composition (X) has a large molecular weight distribution. Therefore, it is presumed that the degree of orientation in the MD direction of the molding increases during film molding of the propylene-based polymer composition (X), and the orientation increases the crystallization of the propylene-based polymer. And it is thought that a film having excellent gas barrier properties can be obtained.
  • the melt flow rate (MFR) of the propylene-based polymer composition (X) measured at 230° C. under a load of 2.16 kg is usually 1 to 20 g/10 min, preferably 2 to 15 g/10 min, more It is preferably 3 to 10 g/10 minutes.
  • the unstretched film of the present invention is formed from the propylene-based polymer composition (X).
  • the unstretched film of the present invention exhibits higher rigidity, heat resistance and gas barrier properties than conventional unstretched polypropylene films.
  • the unstretched film is used, for example, as a packaging material for foods, beverages, industrial parts, miscellaneous goods, toys, daily necessities, office supplies, medical supplies, and the like.
  • the thickness of the unstretched film of the present invention is usually less than 200 ⁇ m, preferably 10-150 ⁇ m, more preferably 15-100 ⁇ m. Since the unstretched film of the present invention is excellent in rigidity, it can be easily made into a thin film.
  • the degree of axial orientation of the PP (110) plane specified by wide-angle X-ray diffraction measurement is preferably 0.85 or more, more preferably is greater than or equal to 0.88.
  • the upper limit of the degree of axial orientation may be, for example, 0.91.
  • the value of the degree of axial orientation can be increased or decreased by changing the intrinsic viscosity [ ⁇ ] of the propylene-based polymer (a1), for example, by changing the film forming speed.
  • film manufacturing methods include extrusion molding methods such as the T-die method and inflation method, compression molding methods, calendar molding methods, and casting methods.
  • Film molding can be performed, for example, as follows.
  • the above components constituting the propylene-based polymer composition (X) may be directly added to a hopper or the like of a film forming machine, or may be mixed using a ribbon blender, Banbury mixer, Henschel mixer, super mixer or the like. may be mixed in advance, or further melt-kneaded using a kneader such as a single-screw or twin-screw extruder or a roll to obtain the propylene-based polymer composition (X), followed by film forming.
  • a kneader such as a single-screw or twin-screw extruder or a roll
  • T-die method A specific example of film production will be described by the T-die method.
  • the above components are put into an extruder, and usually melt-kneaded at a temperature of 180 to 280 ° C., preferably 200 to 270 ° C., and then T-die.
  • a film is extruded through a die lip, and the molten film is cooled and taken up by a take-up device such as a nip roll to obtain a film.
  • Cooling methods for molten films include, for example, air knife method or air chamber method using rolls and air cooling, polishing roll method, swing roll method, narrow pressure cooling method such as belt casting method, contact with refrigerant such as water cooling method, etc. cooling method.
  • the obtained non-stretched film can be subjected to film treatment methods used for ordinary film molding, such as corona discharge treatment and liquid agent coating treatment.
  • the sealant film of the present invention has the unstretched film of the first aspect of the present invention as a surface layer.
  • the sealant film of the present invention consists of a laminate having a sealant film main body and a surface layer in this order.
  • Methods for producing the sealant film include a coextrusion method and an extrusion coating method.
  • the sealant film main body and surface layer may each be a single layer or multiple layers.
  • the multilayer sealant film of the present invention has the unstretched film of the second aspect of the present invention as an intermediate layer.
  • the multilayer sealant film of the present invention consists of a laminate having an outer layer, an intermediate layer and a sealant layer in this order.
  • Methods for producing the multilayer sealant film include co-extrusion and extrusion coating.
  • the outer layer, intermediate layer and sealant layer may each be a single layer or multiple layers.
  • Examples of materials for the sealant layer include materials used for conventional sealant layers, such as ethylene-based resins.
  • the sealant film main body and the outer layer include a base material layer.
  • the base layer is made of a material with relatively high rigidity and strength.
  • the materials include polyamide resins such as nylon 11 and nylon 12, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyolefin resins such as polyethylene resin and polypropylene resin, polyvinylidene chloride resin, and ethylene-vinyl acetate copolymer.
  • thermoplastic resin selected from the group consisting of saponified products, polycarbonate resins, polystyrene resins, and acrylic resins (which may be stretched films), metal foils, metal vapor deposition films, inorganic oxide vapor deposition At least one selected from ceramic deposited films such as films, paper, nonwoven fabrics, and laminates thereof may be used.
  • the thickness of the base material layer is usually about 5 to 50 ⁇ m.
  • sealant film main body and the outer layer examples include, in addition to the base layer, a barrier layer for gases such as water vapor and oxygen, a sound absorbing layer, a light shielding layer, an adhesive layer, an adhesive layer, a colored layer, a conductive layer, and a reproduction layer.
  • a resin-containing layer (these layers listed in addition to the base material layer are also collectively referred to as "another layer").
  • examples of materials for forming the other layers include olefin polymer compositions other than the propylene polymer composition (X1) and gas barrier resin compositions. , and adhesive resin compositions.
  • examples of materials for forming the other layers include olefin-based polymer compositions other than the propylene-based polymer composition (X2) and gas-barrier resin compositions. products, and adhesive resin compositions.
  • the sealant film of the present invention has the unstretched film of the first aspect of the present invention as a surface layer, heat sealing at a low temperature, specifically lower than 140 ° C., preferably 135 ° C. or lower, It enables sealing at the sealing initiation temperature described later and has a high tensile modulus. Moreover, the appearance when heat-sealed is also excellent.
  • the multilayer sealant film of the present invention has the unstretched film of the second aspect of the present invention as an intermediate layer. Therefore, the intermediate layer contributes to heat sealing at a lower temperature than when a propylene homopolymer is used for the intermediate layer. Also, the multi-layer sealant film of the present invention has a higher tensile modulus than when a conventional propylene/ ⁇ -olefin copolymer is used.
  • the unstretched film, sealant film and multi-layer sealant film of the present invention are suitable for various food packaging fields such as fresh foods such as vegetables and fish meat, dried foods such as snacks and noodles, water foods such as soups and pickles; It is used as a packaging film in a wide range of packaging fields, such as packaging for various forms of medical products such as powders and liquids, medical peripheral materials, etc.; packaging for various electrical equipment such as cassette tapes and electrical parts. can do.
  • Intrinsic viscosity [ ⁇ ] The intrinsic viscosity [ ⁇ ] (dl/g) was measured at 135°C in a tetralin solvent.
  • the intrinsic viscosity [ ⁇ ] 2 of the propylene-based polymer (corresponding to the propylene-based polymer (a2)) obtained in the second stage is a value calculated from the following formula.
  • [ ⁇ ] 2 ([ ⁇ ] total x 100 - [ ⁇ ] 1 x W 1 )/W 2 [ ⁇ ] total : Intrinsic viscosity of the entire propylene-based polymer [ ⁇ ] 1 : Intrinsic viscosity of the propylene-based polymer obtained in the first stage W 1 : Mass of the propylene-based polymer obtained in the first stage Fraction (%) W 2 : mass fraction (%) of the propylene-based polymer obtained in the second stage
  • Melt flow rate (MFR) (g/10 minutes) was measured according to JIS-K7210 at a temperature of 230°C and a load of 2.16 kgf (21.2 N).
  • the ratio of the high molecular weight region having a molecular weight of 1,500,000 or more is the region surrounded by the molecular weight distribution curve (specifically, the molecular weight distribution curve and the horizontal axis) measured by gel permeation chromatography (GPC) using the following equipment and conditions. It is the area ratio of the high molecular weight region having a molecular weight of 1,500,000 or more to the total area of .
  • the horizontal axis is molecular weight (logarithmic value) and the vertical axis is dw/dLog(M) [w: integrated mass fraction, M: molecular weight].
  • the peak molecular weight MH on the high molecular weight side and the peak molecular weight ML on the low molecular weight side of the molecular weight distribution curve were obtained to calculate MH/ML.
  • the crystalline melting point was determined according to JIS-K7121 using a differential scanning calorimeter (DSC, manufactured by PerkinElmer (Diamond DSC)) under the following measurement conditions.
  • the apex of the endothermic peak in the fourth step was defined as the crystalline melting point (Tm) when the measurement was performed under the following measurement conditions.
  • Tm crystalline melting point
  • Measurement condition Measurement environment: Nitrogen gas atmosphere Sample amount: 5 mg Sample shape: Press film (molded at 230°C, thickness 400 ⁇ m) Sample pan: Aluminum sample pan with a flat bottom First step: The temperature is raised from 30°C to 200°C at 320°C/min and held for 10 minutes.
  • Second step Lower the temperature to 30°C at 20°C/min.
  • Fourth step Raise the temperature to 200°C at 20°C/min.
  • the intrinsic viscosity [ ⁇ ] of the propylene-based polymer (a1-1) polymerized under the same conditions as in the first stage was 11 dl/g.
  • Table 1 summarizes the physical properties of the polymer obtained in Production Example 1.
  • antioxidants Irganox 1010 (manufactured by BASF) 2000 ppm, Irgaphos 168 (manufactured by BASF) 2000 ppm, Sandstab P-EPQ (manufactured by Clariant Japan) ) 1000 ppm and 1000 ppm of calcium stearate as a neutralizing agent were added and melt-kneaded with a twin-screw extruder to obtain pellet-like propylene/ethylene/1-butene random copolymer (B-1).
  • composition analysis value (gas chromatographic analysis) of the gas portion in the polymerization apparatus is ethylene concentration of 2.0 mol%, 1-butene concentration of 0 mol%, and hydrogen concentration of 5.5 mol%.
  • a propylene/ethylene random copolymer (B-2) in the form of pellets was obtained in the same manner as in Production Example 2, except that the amounts of ethylene, 1-butene and hydrogen supplied were adjusted as described above.
  • composition analysis value (gas chromatography analysis) of the gas portion in the polymerization apparatus is ethylene concentration of 1.3 mol%, 1-butene concentration of 0 mol%, and hydrogen concentration of 3.5 mol%.
  • a propylene/ethylene random copolymer (B-5) in the form of pellets was obtained in the same manner as in Production Example 2, except that the amounts of ethylene, 1-butene and hydrogen supplied were adjusted as in the above.
  • Table 2 summarizes the physical properties of the polymers obtained in Production Examples 2 to 7.
  • Example 1-1 5 parts by mass of the propylene-based polymer (A-1) obtained in Production Example 1, and 95 parts by mass of the propylene/ethylene/1-butene random copolymer (B-1) obtained in Production Example 2.
  • a 25 ⁇ m thick non-stretched film was produced under the following molding conditions using a non-stretched film forming machine consisting of an extruder (one unit) with a screw diameter of 75 mm and a single-layer die with a width of 600 mm.
  • Example 1-2 Comparative Examples 1-1 to 1-6
  • a non-stretched film was produced in the same manner as in Example 1-1, except that the formulation was changed as shown in Table 3.
  • Example 2-1 From 5 parts by mass of the propylene-based polymer (A-1) obtained in Production Example 1 and 95 parts by mass of the propylene/ethylene random copolymer (B-3) obtained in Production Example 4, a screw diameter of 75 mm was prepared.
  • Example 2-2 to 2-5 Comparative Examples 2-1 to 2-8
  • a non-stretched film was produced in the same manner as in Example 2-1, except that the formulation was changed as shown in Table 4.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Le problème décrit par la présente invention est de fournir : un film de polypropylène coulé qui présente un excellent équilibre entre rigidité et aptitude au thermoscellage à basse température ; ou un film de polypropylène coulé qui présente une excellente rigidité et peut être thermoscellé à basse température. La solution selon l'invention concerne un film non orienté comprenant une composition de polymère de propylène qui comprend un rapport prédéfini d'un polymère de propylène prédéfini (A) et d'un copolymère de propylène/α-oléfine (B) qui présente un MFR compris entre 0,1 et 30 g/10 min et une viscosité limite [η] supérieure à 1,5 dl/g et pouvant aller jusqu'à 5,0 dl/g comme mesuré dans un solvant formé de tétraline à 135 °C, et qui contient une quantité prédéfinie d'un motif structural dérivé d'une α-oléfine (à l'exclusion du propylène).
PCT/JP2022/048281 2022-01-06 2022-12-27 Film non orienté, film d'étanchéité et film d'étanchéité multicouche WO2023132306A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2022001081 2022-01-06
JP2022001080 2022-01-06
JP2022-001080 2022-01-06
JP2022-001081 2022-01-06

Publications (1)

Publication Number Publication Date
WO2023132306A1 true WO2023132306A1 (fr) 2023-07-13

Family

ID=87073650

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2022/048281 WO2023132306A1 (fr) 2022-01-06 2022-12-27 Film non orienté, film d'étanchéité et film d'étanchéité multicouche

Country Status (1)

Country Link
WO (1) WO2023132306A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019137847A (ja) * 2018-02-09 2019-08-22 株式会社プライムポリマー プロピレン系重合体組成物およびその発泡成形体
JP2019167499A (ja) * 2018-03-26 2019-10-03 株式会社プライムポリマー プロピレン系重合体、プロピレン系樹脂組成物および成形体
WO2021025142A1 (fr) * 2019-08-08 2021-02-11 株式会社プライムポリマー Composition de polymère à base de propylène, film non étiré et stratifié
JP2021024641A (ja) * 2019-08-08 2021-02-22 三井化学株式会社 延伸容器

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019137847A (ja) * 2018-02-09 2019-08-22 株式会社プライムポリマー プロピレン系重合体組成物およびその発泡成形体
JP2019167499A (ja) * 2018-03-26 2019-10-03 株式会社プライムポリマー プロピレン系重合体、プロピレン系樹脂組成物および成形体
WO2021025142A1 (fr) * 2019-08-08 2021-02-11 株式会社プライムポリマー Composition de polymère à base de propylène, film non étiré et stratifié
JP2021024641A (ja) * 2019-08-08 2021-02-22 三井化学株式会社 延伸容器

Similar Documents

Publication Publication Date Title
US9511567B2 (en) Multilayered polyolefin-based films
JP4844091B2 (ja) プロピレン系樹脂組成物およびそのフィルム
JP2002052669A (ja) 積層体およびこれを用いたパウチ
JP2008208362A (ja) プロピレン系共重合体材料、それからなるフィルム、およびプロピレン系共重合体材料の製造方法
WO2019176403A1 (fr) Composition de résine et films monocouches et multicouches
US8258227B2 (en) Laminating resin composition and multilayer structure
JP4163112B2 (ja) ポリオレフィン系樹脂材料およびそれを用いた積層体ならびにその製造方法、それらの成形体
JP7308954B2 (ja) プロピレン系重合体組成物、無延伸フィルムおよび積層体
JP5227031B2 (ja) ポリプロピレン系単層フィルムおよびその用途
WO2023132306A1 (fr) Film non orienté, film d'étanchéité et film d'étanchéité multicouche
JP7257522B2 (ja) 非発泡シートおよび容器
WO2022196239A1 (fr) Film de polyéthylène étiré pour stratification
JP7397642B2 (ja) ポリプロピレン系多層延伸フィルムおよびその製造方法
JP2017105174A (ja) 多層フィルム
JP5786608B2 (ja) 積層フィルム
JP4034598B2 (ja) プロピレン系樹脂積層体
WO2024070720A1 (fr) Film multicouche
JPH11245351A (ja) ポリオレフィン系積層フィルム
JP3440798B2 (ja) レトルト食品包装用フィルム
JP2002052668A (ja) パウチ
WO2023090201A1 (fr) Film non étiré comprenant une composition polymère de propylène
EP1923407A1 (fr) Feuille étirée dans deux directions ayant une meilleure aptitude au fa onnage
WO2024068314A1 (fr) Film asymétrique, orienté dans le sens machine, de polyéthylène formé par extrusion à plat, pourvu de propriétés d'étanchéité et stratifié comprenant un tel film
WO2022201741A1 (fr) Composition polymère à base d'oléfine et film
JP5919768B2 (ja) 耐ブロッキング性に優れたフィルム

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22918889

Country of ref document: EP

Kind code of ref document: A1