WO2023026991A1 - ポリプロピレン系多孔性フィルムおよびこれを含む積層フィルム - Google Patents
ポリプロピレン系多孔性フィルムおよびこれを含む積層フィルム Download PDFInfo
- Publication number
- WO2023026991A1 WO2023026991A1 PCT/JP2022/031423 JP2022031423W WO2023026991A1 WO 2023026991 A1 WO2023026991 A1 WO 2023026991A1 JP 2022031423 W JP2022031423 W JP 2022031423W WO 2023026991 A1 WO2023026991 A1 WO 2023026991A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polypropylene
- porous film
- mass
- based porous
- strength
- Prior art date
Links
- -1 Polypropylene Polymers 0.000 title claims abstract description 97
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 80
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 80
- 229920000092 linear low density polyethylene Polymers 0.000 claims abstract description 21
- 239000004707 linear low-density polyethylene Substances 0.000 claims abstract description 21
- 230000035699 permeability Effects 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000011256 inorganic filler Substances 0.000 claims abstract description 13
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 13
- 239000011342 resin composition Substances 0.000 claims abstract description 10
- 239000012779 reinforcing material Substances 0.000 claims description 18
- 239000004698 Polyethylene Substances 0.000 claims description 16
- 229920000573 polyethylene Polymers 0.000 claims description 16
- 239000004745 nonwoven fabric Substances 0.000 claims description 11
- 229920005672 polyolefin resin Polymers 0.000 claims description 2
- 229920005989 resin Polymers 0.000 abstract description 12
- 239000011347 resin Substances 0.000 abstract description 12
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- 238000003475 lamination Methods 0.000 description 20
- 238000000034 method Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 239000002245 particle Substances 0.000 description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 7
- 239000005977 Ethylene Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229920001903 high density polyethylene Polymers 0.000 description 3
- 239000004700 high-density polyethylene Substances 0.000 description 3
- 229920001684 low density polyethylene Polymers 0.000 description 3
- 239000004702 low-density polyethylene Substances 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 239000002274 desiccant Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000012760 heat stabilizer Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229920001384 propylene homopolymer Polymers 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005267 amalgamation Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
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
-
- 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
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
- B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/417—Polyolefins
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/44—Fibrous material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/494—Tensile strength
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to a novel polypropylene-based porous film. More specifically, the present invention provides a polypropylene-based porous film having high air permeability while maintaining high strength by using polypropylene as a raw material, and achieving sufficient lamination strength with a reinforcing material.
- a porous film in which microporosity is formed by stretching a sheet of a resin composition in which a large amount of filler is added to polypropylene or polyethylene has both air permeability and water impermeability. used for the purpose.
- polypropylene-based porous films are used for packaging materials such as battery separators, dehumidifiers, and desiccants because they have higher strength, for example, higher water pressure resistance than polyethylene-based porous films.
- the porous film is used as a breathable reinforcing material such as a polyethylene nonwoven fabric (at least the surface of which is made of polyethylene fibers) in order to provide higher strength and improve texture.
- a polyethylene nonwoven fabric at least the surface of which is made of polyethylene fibers
- Non-woven fabric may be used as a laminated product.
- the polypropylene-based porous film has a problem that it is difficult to laminate with high strength due to its poor adhesion to the breathable reinforcing material.
- Patent Documents 2 to 4 disclose polypropylene-based porous films containing high-density polyethylene. Although the strength of the polypropylene-based porous film is improved by blending high-density polyethylene, the adhesiveness to the reinforcing material is poor, making it difficult to laminate with high strength.
- JP-A-54-54558 Japanese Patent Application Laid-Open No. 2009-185093 JP-A-5-331306 JP-A-2002-249622
- an object of the present invention is to provide a polypropylene-based porous film that achieves sufficient lamination strength with a reinforcing material while maintaining high strength and high air permeability using polypropylene as a raw material.
- the amount of polyethylene blended in the polypropylene is limited to a specific amount lower than the conventional blend, while maintaining high strength with polypropylene as a material.
- the present inventors have succeeded in obtaining a polypropylene-based porous film having high air permeability and sufficient strength in terms of lamination strength with a reinforcing material, and have proposed the present invention.
- 230 to 230 parts of an inorganic filler is added to 100 parts by mass of a polyolefin resin containing linear low-density polyethylene (hereinafter referred to as LLDPE) in polypropylene at a ratio of 3% by mass or more and less than 10% by mass.
- LLDPE linear low-density polyethylene
- MD machine direction
- TD transverse direction
- a polypropylene-based porous film characterized by being able to achieve a tensile strength of 5 N/15 mm or more.
- polypropylene-based porous film it is possible to achieve a laminate strength of 1.0 N/15 mm or more to the polyethylene-based nonwoven fabric.
- the present invention provides a laminated polypropylene porous film in which a reinforcing material having air permeability is laminated with high lamination strength on at least one side of the polypropylene porous film.
- the polypropylene-based porous film of the present invention has high air permeability while maintaining high strength due to the use of polypropylene, and furthermore, it is possible to obtain a porous film that is sufficiently satisfactory in lamination with a reinforcing material. can.
- the polypropylene-based porous film of the present invention is made of a resin composition containing 230 to 400 parts by mass of an inorganic filler with respect to 100 parts by mass of a mixed resin containing polypropylene and LLDPE at a ratio of 3% by mass or more and less than 10% by mass. .
- the ratio of LLDPE in the components of the mixed resin constituting the polypropylene-based porous film of the present invention was conventionally considered to be the ratio necessary to ensure lamination properties.
- the greatest feature is that sufficient lamination properties can be obtained without the use of , and that the loss of strength of the porous film can be prevented as compared with the case of using branched low-density polyethylene.
- known polypropylene is used without any particular limitation.
- examples include homopolymers of propylene, random propylene copolymers containing 5% by mass or less of other olefins such as ethylene, and propylene block copolymers containing 10% by mass or less of other olefins such as ethylene. Amalgamation etc. are mentioned. Among them, propylene homopolymers and propylene-based block copolymers are particularly preferably used.
- propylene homopolymer include isotactic polypropylene, syndiotactic polypropylene, atactic polypropylene, etc., preferably isotactic polypropylene.
- the propylene-based copolymer is not limited to a binary copolymer, and may be a terpolymer.
- the catalyst used may be Ziegler type, metallocene type or the like.
- the weight-average molecular weight (Mw) of polypropylene is preferably 1,000,000 or less, preferably 700,000 or less, in terms of facilitating melt-kneading and, as a result, improving fish-eye defects when formed into a film. More preferably, it is 600,000 or less.
- the weight average molecular weight (Mw) of polypropylene is the one measured by the GPC method (converted to polystyrene).
- the polypropylene preferably has a melt flow rate (MFR) of 0.1 to 15 g/10 minutes, particularly 0.1 to 8 g/10 minutes.
- melt flow rate is a value measured by A method at 190°C according to JIS K 7210.
- the LLDPE is a copolymer of ethylene and an olefin having 4 to 8 carbon atoms, preferably a copolymer of ethylene and butene-1, hexene-1, 4-methylpentene-1, etc. Among them, a copolymer of ethylene and butene-1 is most preferred.
- the content of olefin units other than ethylene contained in LLDPE is preferably 1 to 30 mol %. Two or more olefins other than ethylene may be contained in the LLDPE.
- the LLDPE preferably has a melt flow rate (MFR) of 1 to 20 g/10 minutes, particularly 1 to 8 g/10 minutes, and more preferably 1 to 5 g/10 minutes.
- MFR melt flow rate
- the LLDPE preferably has a density of 0.900 to 0.950 g/cm 3 , particularly 0.910 to 0.940 g/cm 3 , more preferably 0.915 to 0.938 g/cm 3 . be.
- the resin component contains the LLDPE in the polypropylene at a ratio of 3% by mass or more and less than 10% by mass, preferably 4 to 8% by mass. That is, when the proportion of LLDPE is 10% by mass or more, the strength of the porous polypropylene film is lowered, and the object of the present invention cannot be achieved. In addition, the proportion of LLDPE must be 3% by mass or more in order to maintain practical lamination strength.
- inorganic filler known inorganic fillers conventionally used in the production of porous films can be used without particular limitation.
- Calcium carbonate is the most commonly used inorganic filler and is most preferably used in the present invention.
- the particle size of the inorganic filler is not particularly limited, but considering the balance of properties of the obtained polypropylene-based porous film, the average particle size (D 50 ) is 1 to 30 ⁇ m, preferably 1 to 30 ⁇ m. 10 ⁇ m is preferred.
- the average particle size was calculated by measuring the particle size distribution using a laser diffraction particle size distribution measurement method.
- a laser diffraction particle size distribution apparatus LA-950 manufactured by Horiba Ltd. is used as a measuring apparatus.
- ethanol is used as a dispersion medium and a sample is added to measure the particle size distribution to measure the average particle size (D 50 ). was calculated.
- the inorganic filler is blended in a proportion of 230 to 400 parts by mass, preferably 250 to 350 parts by mass, with respect to 100 parts by mass of the mixed resin. If the proportion of the inorganic filler is less than 230 parts by mass, sufficient porosity cannot be imparted to the polypropylene-based porous film. On the other hand, if it exceeds 400 parts by mass, it becomes difficult to impart sufficient strength to the polypropylene-based porous film.
- the polypropylene-based porous film of the present invention has a permeability of 80 seconds/100 ml or less, particularly 50 seconds/100 ml or less, and a water pressure resistance of 50 kPa or more, particularly 70 kPa or more, depending on the composition of the resin component and the inorganic filler. Excellent wettability and achieves high strength.
- the air permeability is a value measured by the Oken type testing machine method according to JIS P 8117
- the water pressure resistance is a value measured by a water pressure resistance measuring instrument according to JIS L 1092.
- the film in addition to the air permeability and water pressure resistance, the film has a tensile strength of 15 N/15 mm or more in the machine direction (MD) and a tensile strength of 5 N in the transverse direction (TD). /15 mm or more can be achieved.
- the polypropylene-based porous film of the present invention exhibits high lamination strength when laminated with a breathable reinforcing material. Specifically, it has a high lamination strength of 1.0 N/15 mm or more, particularly 1.5 N/15 mm or more in the lamination test described below.
- the thickness of the film is generally 10-300 ⁇ m, particularly 50-200 ⁇ m.
- the polypropylene-based porous film of the present invention can be laminated with a known breathable reinforcing material within a range that does not significantly impair the above properties.
- the reinforcing material may be laminated on one side or both sides of the polypropylene-based porous film.
- a resin having a melting point of 180° C. or less preferably a non-woven fabric or a perforated film having polyethylene present at least on its surface is used.
- a nonwoven fabric having a core/sheath structure, the sheath resin being polyethylene, and the core resin being polyester, is preferably used.
- polyethylene constituting the sheath includes HDPE, VLD (Very Low Density) PE, LLDPE, and the like.
- the thickness of the reinforcing material is not particularly limited, it is preferably 80 to 350 ⁇ m, more preferably 90 to 250 ⁇ m.
- the laminated polypropylene-based porous film laminated with the reinforcing material exhibits high lamination strength as described above.
- the laminated polypropylene-based porous film can further improve the tensile strength of the film while maintaining excellent performance such as air permeability of 80 seconds/100 ml or less and water pressure resistance of 50 kPa or more, and reliability in various applications. make it possible to raise it further.
- the laminated polypropylene-based porous film it is generally possible to improve the tensile strength by 10% or more relative to the single layer of the polypropylene-based porous film, depending on the type of reinforcing material.
- the polypropylene-based porous film and laminated polypropylene-based porous film of the present invention can be suitably used in applications such as packaging materials such as battery separators, dehumidifiers, and desiccants by making use of the above properties.
- the method for producing the polypropylene-based porous film of the present invention is not particularly limited.
- a resin composition containing 230 to 400 parts by mass, preferably 230 to 350 parts by mass of the inorganic filler is formed into a film with respect to 100 parts by mass of the mixed resin contained at a ratio of 250 to 250 parts by mass in the machine direction (MD).
- the polypropylene, LLDPE, and inorganic filler used are those described above.
- the method of forming the resin composition into a film is not particularly limited, but a method of extruding from a T-die or an annular die is common.
- the resin composition extruded into a film shape is stretched by a known stretching method according to each shape described above.
- a film-like material extruded from a T-die is stretched in the longitudinal direction by rolls and stretched in the transverse direction by a tenter.
- the film-like material extruded from the annular die is stretched longitudinally and laterally at the same time by being taken up by rolls via a mandrel.
- the stretching temperature of the film material is preferably 90 to 120°C.
- the stretched film may be heat-set as necessary.
- the heat treatment temperature is preferably above the softening point of the resin and below the melting point.
- pellets were supplied to an extruder at 190° C. and inflation-molded with an annular die to obtain a film-like material.
- the above-mentioned film material is further uniaxially stretched in the longitudinal direction (stretch ratio: 265%) between stretching rolls heated to 105°C, and biaxially stretched in the transverse direction through a mandrel heated to 110°C.
- a biaxially stretched film was obtained by stretching (stretch ratio: 175%).
- a heat setting treatment was performed with a heat set roll heated to 90° C., and a polypropylene-based porous film was obtained by winding it into a film shape with a winder.
- Table 2 shows the results of evaluating the thickness, air permeability, water pressure resistance, tensile strength in the machine direction (MD) and transverse direction (TD) of the obtained polypropylene-based porous film.
- a non-woven fabric manufactured by Unitika Ltd., trade name: Elves T0203WDO
- Elves T0203WDO a non-woven fabric made of polyester core and polyethylene sheath
- a laminated polypropylene-based porous film was obtained by thermocompression bonding at a rate of 30 m/min between a hot roll at 140° C. and a nip roll with a nip pressure of 2.75 kg/cm 2 .
- Table 3 shows the results of evaluating the air permeability, water pressure resistance, tensile strength in the machine direction (MD) and transverse direction (TD), and lamination strength of the obtained laminated polypropylene porous film.
- Examples 2-5 A polypropylene-based porous film and a laminated polypropylene-based porous film were produced and evaluated in the same manner as in Example 1, except that the formulation of the composition was changed as shown in Table 1. The results are shown in Tables 2 and 3, respectively. Indicated. All of the porous films maintained high strength while having good air permeability, and the lamination properties were also sufficiently satisfactory.
- Comparative Examples 1-4 A polypropylene-based porous film and a laminated polypropylene-based porous film were produced and evaluated in the same manner as in Example 1, except that the formulation of the composition was changed as shown in Table 1. The results are shown in Tables 2 and 3, respectively. Indicated.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Laminated Bodies (AREA)
Abstract
Description
本発明のポリプロピレン系多孔性フィルムは、ポリプロピレンにLLDPEを3質量%以上10質量%未満の比率で含む混合樹脂100質量部に対して、無機充填剤230~400質量部を含む樹脂組成物からなる。
試料のポリプロピレン系多孔性フィルムと、不織布とを140℃に加熱した熱ロールを使用し、ニップ圧2.75kg/cm2、30m/minの速度で熱圧着して、積層ポリプロピレン系多孔性フィルムを作成した。不織布としては、ポリエステルの芯とポリエチレンの鞘よりなる繊維の不織布(ユニチカ(株)製、商品名:エルベス T0203WDO)を用いた。得られた積層ポリプロピレン系多孔性フィルムを巾15mm、長さ150mmに切り取り試験片を作製し、多孔性シートと補強材シートの間の剥離部分をJIS K 7127に準じて、チャック間距離50mm、引張速度200mm/minで引張り、剥離強度を測定し、得られた測定値をラミネート強度とした。
また、上記積層ポリプロピレン系多孔性フィルムは、通気度80秒/100ml以下、耐水圧50kPa以上という優れた性能を維持しながら、フィルムの引張強度をより向上せしめることができ、各種用途における信頼性を一層高めることを可能とする。因みに、前記積層ポリプロピレン系多孔性フィルムによれば、補強材の種類にもよるが、一般に、前記ポリプロピレン系多孔性フィルム単層の引張強度に対して10%以上向上させることが可能である。
本発明のポリプロピレン系多孔性フィルムの製造方法は特に制限されないが、代表的な製造方法を例示すれば、前記ポリプロピレンに前記LLDPEを3質量%以上10質量%未満、好ましくは、4~8質量%の比率で含む混合樹脂100質量部に対して、前記無機充填剤230~400質量部、好ましくは230~350質量部を含む樹脂組成物をフィルム状に成形し、機械方向(MD)に250~350%、好ましくは、250~300%、横断方向(TD)に150~300%、好ましくは、150~250%の倍率で2軸延伸する方法が挙げられる。
試料フィルムより50mm×50mmの試験片を採取し、JIS P 8117に準じて、王研式透気度試験装置により測定した。
試料フィルムより150mm×150mmの試験片を採取し、JIS L 1092のA法(低水圧法)に準じて、耐水圧試験装置に取り付け、試験片の一方の面に水圧を加えていき、試験片の他方の面の3か所から水が出たときの水圧を読み取った。
試料フィルムより巾15mm、長さ150mmの試験片を、機械方向(MD)および横断方向(TD)にそれぞれ採取し、JIS K 7127に準じて、チャック間距離50mm、引張速度200mm/minで引張り、最大まで伸びたときの強度(応力)を機械方向(MD)および横断方向(TD)にそれぞれ測定した。
試料フィルムより巾15mm、長さ150mmに切り取り試験片を作製し、剥離部分をJIS K 7127に準じて、チャック間距離50mm、引張速度200mm/minで引張り、剥離強度を測定した。
A:直鎖状低密度ポリエチレン[日本ポリエチレン(株)製、商品名:UF240、密度:0.920 g/cm3、MFR:2.0 g/10min]
B:直鎖状低密度ポリエチレン[ダウケミカル(株)製、商品名:ダウレックス2036P、密度:0.935 g/cm3、MFR:2.5 g/10min]
C:分岐状低密度ポリエチレン[住友化学(株)製、商品名:スミカセンL705、密度:0.919 g/cm3、MFR:7.0 g/10min]
D:ポリプロピレン[サンアロマー(株)製、商品名:PL-400A、密度:0.900 g/cm3、MFR:0.8 g/10min]
E:炭酸カルシウム[(株)カルファイン製、商品名:ASK-8]
F:添加剤[二酸化チタン(CCTiO2製、商品名:RCL-69)50質量部、ヒンダードフェノール系熱安定剤(ケミプロ化成(株)製、商品名:KEMINOX179)20質量部、チオエーテル系熱安定剤(ADKEA(株)製、商品名:AO-412S)30質量部]
実施例1
表1に示す直鎖状低密度ポリエチレンAが4質量部、直鎖状低密度ポリエチレンBが4質量部、ポリプロピレンDが92質量部からなる混合樹脂100質量部に、炭酸カルシウムEを250質量部、さらに添加剤Fを1.4質量部含む樹脂組成物を混合し、190℃の二軸押出機でペレット状に加工した。次に、上記ペレットを190℃の押出機に供給し、環状ダイによりインフレーション成形することでフィルム状物を得た。前記フィルム状物をさらに105℃に加熱された延伸ロールとの間で縦方向に一軸延伸(延伸倍率:265%)し、加えて110℃に加熱されたマンドレルを介して横方向にも二軸延伸(延伸倍率:175%)することで二軸延伸フィルムを得た。その後、90℃に加熱した熱セットロールで熱固定処理を行い、巻取機でフィルム状に巻き取ることでポリプロピレン系多孔性フィルムを得た。
組成物の配合を表1に示すように変更した以外は実施例1と同様にポリプロピレン系多孔性フィルム、積層ポリプロピレン系多孔性フィルムを製造して評価を行い、結果を表2、表3にそれぞれ示した。いずれの多孔性フィルムも良好な通気度を有しながら高い強度を維持しており、またラミネート性においても十分満足できる結果であった。
組成物の配合を表1に示すように変更した以外は実施例1と同様にポリプロピレン系多孔性フィルム、積層ポリプロピレン系多孔性フィルムを製造して評価を行い、結果を表2、表3にそれぞれ示した。
Claims (4)
- ポリプロピレンに直鎖状低密度ポリエチレンを3質量%以上10質量%未満の比率で含むポリオレフィン樹脂100質量部に対して、無機充填剤230~400質量部を含む樹脂組成物からなり、通気度80秒/100ml以下、耐水圧50kPa以上、機械方向の引張強度が15N/15mm以上、横断方向の引張強度が5N/15mm以上であることを特徴とするポリプロピレン系多孔性フィルム。
- ポリエチレン系不織布に対するラミネート強度が1.0N/15mm以上である請求項1に記載のポリプロピレン系多孔性フィルム。
- 請求項1または2に記載のポリプロピレン系多孔性フィルムの少なくとも片面に通気性を有する補強材が積層された積層ポリプロピレン系多孔性フィルム。
- 前記通気性を有する補強材が、ポリエチレン系不織布である請求項3に記載の積層ポリプロピレン系多孔性フィルム。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202280051534.XA CN117693549A (zh) | 2021-08-25 | 2022-08-19 | 聚丙烯系多孔性膜和包含该聚丙烯系多孔性膜的层叠膜 |
JP2022567759A JP7204069B1 (ja) | 2021-08-25 | 2022-08-19 | ポリプロピレン系多孔性フィルムおよびこれを含む積層フィルム |
KR1020247001362A KR20240046705A (ko) | 2021-08-25 | 2022-08-19 | 폴리프로필렌계 다공성 필름 및 이를 포함하는 적층 필름 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2021136757 | 2021-08-25 | ||
JP2021-136757 | 2021-08-25 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2023026991A1 true WO2023026991A1 (ja) | 2023-03-02 |
Family
ID=85322315
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2022/031423 WO2023026991A1 (ja) | 2021-08-25 | 2022-08-19 | ポリプロピレン系多孔性フィルムおよびこれを含む積層フィルム |
Country Status (2)
Country | Link |
---|---|
TW (1) | TW202317382A (ja) |
WO (1) | WO2023026991A1 (ja) |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002249622A (ja) * | 2001-02-22 | 2002-09-06 | Mitsui Chemicals Inc | 多孔性フィルムおよびその製造方法 |
JP2002307627A (ja) * | 2001-04-10 | 2002-10-23 | Mitsui Chemicals Inc | 通気性積層シートの製造方法 |
JP2004174768A (ja) * | 2002-11-25 | 2004-06-24 | Mitsubishi Plastics Ind Ltd | 透湿性シート及びそれを用いた糞尿堆積物被覆材 |
JP2012136035A (ja) * | 2012-04-02 | 2012-07-19 | Mitsubishi Plastics Inc | 積層多孔性フィルム、それを利用した電池用セパレータおよび電池 |
JP2017105031A (ja) * | 2015-12-08 | 2017-06-15 | 三菱樹脂株式会社 | 透湿性積層体 |
-
2022
- 2022-08-19 WO PCT/JP2022/031423 patent/WO2023026991A1/ja active Application Filing
- 2022-08-23 TW TW111131645A patent/TW202317382A/zh unknown
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002249622A (ja) * | 2001-02-22 | 2002-09-06 | Mitsui Chemicals Inc | 多孔性フィルムおよびその製造方法 |
JP2002307627A (ja) * | 2001-04-10 | 2002-10-23 | Mitsui Chemicals Inc | 通気性積層シートの製造方法 |
JP2004174768A (ja) * | 2002-11-25 | 2004-06-24 | Mitsubishi Plastics Ind Ltd | 透湿性シート及びそれを用いた糞尿堆積物被覆材 |
JP2012136035A (ja) * | 2012-04-02 | 2012-07-19 | Mitsubishi Plastics Inc | 積層多孔性フィルム、それを利用した電池用セパレータおよび電池 |
JP2017105031A (ja) * | 2015-12-08 | 2017-06-15 | 三菱樹脂株式会社 | 透湿性積層体 |
Also Published As
Publication number | Publication date |
---|---|
TW202317382A (zh) | 2023-05-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0921943B1 (en) | Breathable film/nwf-laminates having high wvtr prepared from melt embossed polyolefin/filler precursor films | |
JP5567535B2 (ja) | 多孔性ポリプロピレンフィルム | |
US8431234B2 (en) | Biaxially oriented polypropylene film with heat sealable matte layer | |
TWI687475B (zh) | 多孔質膜及收納袋 | |
USH1955H1 (en) | Polyolefin/filler films having increased WVTR and method for making | |
JPWO2018180164A1 (ja) | 二軸配向ポリプロピレンフィルム | |
US9669607B2 (en) | Biaxially oriented polypropylene film with low moisture vapor transmission rate | |
DE112004001741B4 (de) | Gestreckte Folie | |
JP2023010777A (ja) | 食品用包装フィルムおよび食品用包装体 | |
JP2024099658A (ja) | 二軸配向ポリプロピレン系樹脂フィルム及びそれを用いた包装体 | |
JP2020152424A (ja) | ヒートシール用フィルムおよび収納袋 | |
JP7204069B1 (ja) | ポリプロピレン系多孔性フィルムおよびこれを含む積層フィルム | |
US9238315B2 (en) | Rigid film having high puncture resistance and tear propagation resistance | |
WO2023026991A1 (ja) | ポリプロピレン系多孔性フィルムおよびこれを含む積層フィルム | |
JP2014181250A (ja) | 微多孔フィルム、及びそれを用いたリチウムイオン電池用セパレータ | |
JP4540858B2 (ja) | 多孔性フィルム及びその製造方法 | |
JP5705605B2 (ja) | ポリプロピレン系樹脂多孔シート及びポリプロピレン系樹脂多孔シートの製造方法 | |
JP2004345327A (ja) | 積層体 | |
JP4143215B2 (ja) | 延伸フィルム用ポリプロピレン組成物 | |
JPS60180818A (ja) | ポリエチレンを基礎とするポリマーコンパウンドからのインフレートフイルムの製造法 | |
JPS6174820A (ja) | ポリエチレン延伸フイルム | |
JP2007001102A (ja) | 多層熱収縮性ポリオレフィンフィルム | |
WO2024157762A1 (ja) | 無延伸ポリオレフィン系樹脂フィルム、積層体、及び包装体 | |
JPH10249945A (ja) | 微多孔フィルムの製法及び多層フィルム | |
JPH11349907A (ja) | 粘着テープ及びその製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
ENP | Entry into the national phase |
Ref document number: 2022567759 Country of ref document: JP Kind code of ref document: A |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 22861279 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 202280051534.X Country of ref document: CN |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2401000923 Country of ref document: TH |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 22861279 Country of ref document: EP Kind code of ref document: A1 |