WO2012063914A1 - ポリオレフィン複合フィルム - Google Patents
ポリオレフィン複合フィルム Download PDFInfo
- Publication number
- WO2012063914A1 WO2012063914A1 PCT/JP2011/075984 JP2011075984W WO2012063914A1 WO 2012063914 A1 WO2012063914 A1 WO 2012063914A1 JP 2011075984 W JP2011075984 W JP 2011075984W WO 2012063914 A1 WO2012063914 A1 WO 2012063914A1
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- WIPO (PCT)
- Prior art keywords
- propylene
- mol
- units derived
- composite film
- olefin
- Prior art date
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Classifications
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- 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
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- 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
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/40—Applications of laminates for particular packaging purposes
-
- 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
-
- 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
- B32B2250/00—Layers arrangement
- B32B2250/03—3 layers
-
- 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
- B32B2250/00—Layers arrangement
- B32B2250/24—All layers being polymeric
-
- 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
- B32B2250/00—Layers arrangement
- B32B2250/24—All layers being polymeric
- B32B2250/242—All polymers belonging to those covered by group B32B27/32
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- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/31—Heat sealable
-
- 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
- B32B2439/00—Containers; Receptacles
- B32B2439/70—Food packaging
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
- C08L2203/162—Applications used for films sealable films
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- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
- Y10T428/2495—Thickness [relative or absolute]
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- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31909—Next to second addition polymer from unsaturated monomers
- Y10T428/31913—Monoolefin polymer
Definitions
- the present invention relates to a polyolefin composite film, and relates to a polyolefin composite film excellent in low-temperature heat sealability, heat seal strength, and transparency.
- a propylene polymer having a melting point of 150 ° C. or higher: 1 to 50% by weight and a propylene copolymer having a melting point of 100 ° C. or higher and lower than 150 ° C .: 10 to 90% by weight %
- a stretched film obtained by laminating a polypropylene resin composition comprising 1 to 80% by weight as a heat-fusible layer Patent Document 1: International Published WO 2007/015415 pamphlet), a propylene / ⁇ -olefin random copolymer having a melting point of 120 to 140 ° C. on both sides of a biaxially stretched film mainly composed of a propylene polymer, and a propylene / ⁇ -olefin random copolymer having a melting point of 80 to less than 120 ° C.
- Patent Document 2 Japanese Patent Application Laid-Open No. 2003-170554
- a coating layer made of a propylene polymer composition is laminated.
- a propylene homopolymer is provided between a biaxially stretched polypropylene film as a base material layer and a surface layer comprising a composition containing two or more types of propylene copolymers having different melting points.
- Heat-sealable laminated polypropylene-based resin film having an intermediate layer composed of a composition of propylene / ⁇ -olefin copolymer Patent Document 3: JP-A-2005-104151, Patent Document 4: JP-A-2005
- the present invention provides a polyolefin composite film excellent in low-temperature heat sealability, heat seal strength, and transparency.
- the present invention A polyolefin composite film having at least one surface layer [i], a core layer [ii], and an intermediate layer [iii] in direct contact with both the surface layer [i] and the core layer [ii],
- the surface layer [i] A propylene / ⁇ -olefin random copolymer containing 50 to 97 mol% of units derived from propylene and 3 to 50 mol% of units derived from an ⁇ -olefin having 2 to 10 carbon atoms (excluding propylene) ( A), And / or 50 to 95 mol% of units derived from 1-butene, 50 to 5 mol% of units derived from ⁇ -olefins having 2 to 10 carbon atoms (excluding 1-butene), ⁇ -olefins (1 1-butene / ⁇ -olefin copolymer (E) containing 50 to 5 mol% of units derived from (excluding -butene) 0-50% by weight, And Propylene series containing
- the core layer [ii] A crystalline polypropylene containing 97 to 100 mol% of units derived from propylene, 0 to 3 mol% of ⁇ -olefin (excluding propylene) having 2 to 10 carbon atoms, and a melting point of 150 to 170 ° C.
- the intermediate layer [iii] A crystalline polypropylene containing 97 to 100 mol% of units derived from propylene, 0 to 3 mol% of ⁇ -olefin (excluding propylene) having 2 to 10 carbon atoms, and a melting point of 150 to 170 ° C. C) 50 to 95% by weight, And 50 to 100 mol% of units derived from propylene, 0 to 50 mol% of units derived from an ⁇ -olefin having 2 to 10 carbon atoms (excluding propylene), and a melting point of 120 to 170 ° C.
- the polyolefin composite film in the case of “another aspect” in the present invention is At least one surface layer [i] and a core layer [ii] and an intermediate layer [iii] in direct contact with both the surface layer [i] and the core layer [ii],
- the surface layer [i] A propylene / ⁇ -olefin random copolymer containing 50 to 97 mol% of units derived from propylene and 3 to 50 mol% of units derived from an ⁇ -olefin having 2 to 10 carbon atoms (excluding propylene) ( A) 15 to 100% by weight, as well as, Propylene series containing 50 to 100 mol% of units derived from propylene, 0 to 50 mol% of units derived from ⁇ -olefins (excluding propylene) having 2 to 10 carbon atoms, and having a melting point of 120 to 170 ° C
- the polymer (B) consists of 0 to 85% by weight,
- Units derived from propylene are contained in an amount of 50 mol% to less than 97 mol%, and units derived from an ⁇ -olefin having 2 to 10 carbon atoms (excluding propylene) are contained in an amount of 50 mol% or less and exceeding 3 mol%.
- the melting point measured by a differential scanning calorimeter (DSC) is less than 140 ° C.
- the intermediate layer [iii] A crystalline polypropylene containing 97 to 100 mol% of units derived from propylene, 0 to 3 mol% of ⁇ -olefin (excluding propylene) having 2 to 10 carbon atoms, and a melting point of 150 to 170 ° C. C) 50 to 95% by weight, A unit derived from propylene is contained in an amount of 50 mol% to less than 97 mol%, and a unit derived from an ⁇ -olefin having 2 to 10 carbon atoms (excluding propylene) is contained in an amount of 50 mol% or less and exceeding 3 mol%.
- a propylene polymer (D) whose melting point measured by a differential scanning calorimeter (DSC) is less than 140 ° C. or whose melting point is not observed.
- the total of (C), (D) and (E) is 100% by weight.
- the propylene / ⁇ -olefin random copolymer (A) has a melting point of 110 ° C. or lower or no melting point is observed.
- the melting point of the propylene polymer (B) is 120 to 140 ° C.
- the melting point of the 1-butene / ⁇ -olefin copolymer (E) is 60 to 110 ° C. It is. *
- preferred embodiments of the present invention include: Propylene / ⁇ -olefin random copolymer (A) (1) The intrinsic viscosity measured in decalin at 135 ° C. is 0.1 to 5 dl / g, (2) The molecular weight distribution (Mw / Mn) obtained by gel permeation chromatography (GPC) is 1.5 or more and 3 or less, (3) A polyolefin composite film characterized by being a propylene / 1-butene random copolymer having a parameter B value indicating the randomness of the copolymer monomer chain distribution of 0.9 to 1.5.
- Another preferred embodiment of the present invention is characterized in that the polyolefin composite film is unstretched.
- Another preferred embodiment of the present invention is characterized in that the polyolefin composite film is biaxially stretched.
- the ratio of the total thickness of the surface layer to the total thickness of the polyolefin composite film is 2 to 10%.
- Another preferred embodiment of the present invention is characterized in that the ratio of the total thickness of the intermediate layer to the total thickness of the polyolefin composite film is 2 to 10%.
- polyolefin composite film has a five-layer structure consisting of the order of surface layer / intermediate layer / core layer / intermediate layer / surface layer.
- Another preferred embodiment of the present invention is characterized in that the total thickness of the polyolefin composite film is 10 to 35 micrometers ( ⁇ m).
- Another preferred embodiment of the present invention is characterized in that the tensile elastic modulus in the longitudinal or lateral stretching direction of the polyolefin composite film falls within a range of 1.9 to 5.0 GPa.
- the polyolefin composite film of the present invention is excellent in low-temperature heat sealability, heat seal strength, and transparency, and can be used for a wide range of applications as a packaging film for foods, industrial materials, and the like.
- the propylene / ⁇ -olefin random copolymer (A) forming the surface layer [i] of the polyolefin composite film of the present invention contains 50 to 97 mol%, preferably 50 to 95 mol% of units derived from propylene. And a propylene / ⁇ -olefin random copolymer (A) containing 3 to 50 mol%, preferably 5 to 50 mol% of units derived from an ⁇ -olefin having 2 to 10 carbon atoms (excluding propylene) ( The sum of units derived from propylene and units derived from ⁇ -olefin is 100 mol%).
- One or more ⁇ -olefins may be used as necessary.
- the propylene / ⁇ -olefin random copolymer (A) more preferably contains 60 mol% or more of units derived from propylene, and contains 80 mol% or less, and an ⁇ having 2 to 10 carbon atoms.
- -Olefin in particular, those containing at least 20 mol% and at most 40 mol% of units derived from an ⁇ -olefin selected from ethylene and 1-butene.
- the propylene / ⁇ -olefin copolymer (A) according to the present invention preferably has a melting point of 140 ° C. or lower, or no melting point is observed, and further has a melting point of 110 ° C. or lower, or a melting point is observed. Preferably not.
- the resulting polyolefin composite film may be inferior in low-temperature heat sealability.
- propylene / ⁇ -olefin copolymer (A) As the propylene / ⁇ -olefin copolymer (A) according to the present invention, one kind or two or more kinds of polymers may be used as necessary.
- propylene / ⁇ -olefin copolymer (A) examples include propylene / ethylene copolymer, propylene / 1-butene copolymer, propylene / ethylene / 1-butene copolymer. Coalescence is illustrated.
- the propylene / ⁇ -olefin random copolymer (A) As the propylene / ⁇ -olefin random copolymer (A) according to the present invention, (1) The intrinsic viscosity [ ⁇ ] measured in decalin at 135 ° C. is 0.1 to 5 dl / g, (2) The molecular weight distribution (Mw / Mn) obtained by gel permeation chromatography (GPC) is 1.5 or more and 3 or less, (3) Parameter B value indicating the randomness of the copolymerization monomer chain distribution is 0.9 to 1.5, preferably 1.0 to 1.4, A propylene / 1-butene random copolymer is preferred.
- B P 12 / (2P 1 ⁇ P 2 )
- P 1 and P 2 are the first monomer and second monomer content fractions, respectively
- P 12 is the ratio of (first monomer)-(second monomer) linkage in all the bimolecular linkages.
- the MFR (melt flow rate; ASTM 12 D-1238 load 2160 g, temperature 230 ° C) of the propylene / ⁇ -olefin random copolymer (A) according to the present invention is not particularly limited as long as it can be made into a film. It is in the range of 5 to 20 g / 10 minutes, preferably 2 to 10 g / 10 minutes.
- the 1-butene / ⁇ -olefin copolymer (E) forming the surface layer [i] and the intermediate layer [iii] of the polyolefin composite film of the present invention contains 50 to 95 mol% of units derived from 1-butene.
- One or more ⁇ -olefins may be used as necessary.
- the 1-butene / ⁇ -olefin random copolymer (E) according to the present invention preferably has a melting point in the range of 60 to 110 ° C.
- the resulting polyolefin composite film may be inferior in low-temperature heat sealability, while a 1-butene / ⁇ -olefin copolymer having a melting point of less than 60 ° C. may be used.
- a 1-butene / ⁇ -olefin copolymer having a melting point of less than 60 ° C. may be used.
- the resulting polyolefin composite film may have a sticky surface.
- 1-butene / ⁇ -olefin random copolymer (E) As the 1-butene / ⁇ -olefin random copolymer (E) according to the present invention, one kind or two or more kinds of polymers may be used as necessary.
- 1-butene / ⁇ -olefin random copolymer (E) examples include, for example, 1-butene / ethylene copolymer, 1-butene / propylene copolymer, 1-butene / Examples include ethylene / propylene copolymers.
- the MFR (melt flow rate; ASTM D-1238 load 2160 g, temperature 230 ° C.) of the 1-butene / ⁇ -olefin random copolymer (E) according to the present invention is not particularly limited as long as it can be made into a film. Usually, it is in the range of 1 to 20 g / 10 min, preferably 5 to 15 g / 10 min.
- the propylene polymer (B) forming the surface layer [i] and the intermediate layer [ii] of the polyolefin composite film of the present invention contains 50 to 100 mol%, preferably 85 to 97 mol% of units derived from propylene. And 0 to 50 mol%, preferably 3 to 15 mol%, of units derived from an ⁇ -olefin having 2 to 10 carbon atoms (excluding propylene), and has a melting point of 120 to 170 ° C., preferably 120 to 140
- the propylene polymer (B) at 0 ° C. the total of units derived from propylene and units derived from ⁇ -olefin is 100 mol%).
- One or more ⁇ -olefins may be used as necessary.
- propylene polymer (B) As the propylene polymer (B) according to the present invention, one kind or two or more kinds of polymers may be used as necessary.
- the polyolefin composite film obtained therefrom may have an insufficient balance between low-temperature heat sealability and seal strength.
- propylene polymer (B) examples include blocks such as propylene / ethylene copolymer, propylene / ethylene / 1-butene copolymer, propylene / 1-butene copolymer, and the like. Examples include copolymers and random copolymers.
- the MFR (melt flow rate; ASTM 12 D-1238 load 2160 g, temperature 230 ° C) of the propylene polymer (B) according to the present invention is not particularly limited as long as it can be made into a film, but usually 0.5 to 20 g / It is in the range of 10 minutes, preferably 2-10 g / 10 minutes.
- the unit derived from propylene is 97 to 100 mol%, preferably 98 to 100 mol. 0 to 3 mol%, preferably 0 to 2 mol% of a unit derived from an ⁇ -olefin having 2 to 10 carbon atoms (excluding propylene) and having a melting point of 150 to Crystalline polypropylene (C) at 170 ° C., preferably 155 to 165 ° C.
- the sum of units derived from propylene and units derived from ⁇ -olefin is 100 mol%).
- the crystalline polypropylene (C) contains a unit derived from an ⁇ -olefin, one or more kinds may be used as necessary.
- the resulting polyolefin composite film tends not to have sufficient rigidity and heat resistance.
- the crystalline polypropylene (C) according to the present invention may use one kind or two or more kinds of polymers as necessary.
- crystalline polypropylene (C) examples include propylene homopolymers, propylene / ethylene copolymers, copolymers of propylene and ⁇ -olefins such as propylene / 1-butene copolymer. And propylene / ethylene / 1-butene copolymer, and propylene homopolymer is preferred.
- the MFR (melt flow rate; ASTM D-1238 ⁇ load 2160 g, temperature 230 ° C.) of the crystalline polypropylene (C) according to the present invention is not particularly limited as long as it can be made into a film, but usually 0.5 to 20 g / 10 Min, preferably in the range of 2-10 g / 10 min.
- ⁇ Propylene polymer (D)> the propylene / ⁇ -olefin random copolymer (A) forming the components of the core layer [ii] and the intermediate layer [iii] of the polyolefin composite film is converted into a propylene-based polymer (D). There is a case.
- This propylene polymer (D) contains units derived from propylene in an amount of 50 mol% or more and less than 97 mol%, preferably 60 mol% or more and less than 80 mol%, and an ⁇ -olefin having 2 to 10 carbon atoms (including propylene). At least one unit derived from (excludes) is contained in an amount of 50 mol% or less and more than 3 mol%, preferably 40 mol% or less and more than 20 mol%, and measured by a differential scanning calorimeter (DSC). It is a polymer having a melting point of less than 140 ° C. or no melting point is observed, preferably 110 ° C. or less or no melting point is observed. One or more ⁇ -olefins may be used as necessary.
- propylene polymer (D) As the propylene polymer (D) according to the present invention, one kind or two or more kinds of polymers may be used as necessary.
- the resulting polyolefin composite film may be inferior in low-temperature heat sealability and / or heat seal strength.
- propylene polymer (D) examples include a propylene / ethylene copolymer, a propylene / 1-butene copolymer, and a block copolymer of propylene / ethylene / 1-butene copolymer.
- a polymer and a random copolymer are exemplified.
- the MFR (melt flow rate; ASTM D-1238 load 2160 g, temperature 230 ° C.) of the propylene polymer (D) according to the present invention is not particularly limited as long as it can be made into a film, but usually 0.5 to 20 g. / 10 minutes, preferably in the range of 2 to 10 g / 10 minutes.
- the polyolefin composite film of the present invention comprises at least one surface layer [i], a core layer [ii], and an intermediate layer [iii] in direct contact with both the surface layer [i] and the core layer [ii] It is a composite film.
- the term “core layer” simply means a layer serving as a core material. However, it is not necessarily used to mean the center between the surface layer and the intermediate layer.
- the surface layer [i] of the polyolefin composite film of the present invention comprises 0 to 50 weight percent of the propylene / ⁇ -olefin random copolymer (A) and / or the 1-butene / ⁇ -olefin copolymer (E). %, Preferably 0 to 30% by weight, more preferably 3 to 30% by weight, and 50 to 100% by weight of the propylene polymer (B), preferably 70 to 100% by weight, more preferably 70 to 97% by weight. % (However, the total of (A), (E) and (B) in the surface layer is 100% by weight).
- the surface layer [i] includes a case where the propylene / ⁇ -olefin random copolymer (A) and / or the 1-butene / ⁇ -olefin copolymer (E) is not blended. .
- it contains the propylene / ⁇ -olefin random copolymer (A) and / or the 1-butene / ⁇ -olefin copolymer (E), and preferably 3 to 30% by weight is contained.
- the core layer [ii] of the polyolefin composite film of the present invention contains 70 to 100% by weight of the crystalline polypropylene (C) and 0 to 30% by weight of the propylene / ⁇ -olefin copolymer (A) [provided that The total of (A) and (C) is 100% by weight. ] Propylene polymer composition (Y).
- the heat seal strength is higher than when the propylene / ⁇ -olefin copolymer (A) and the crystalline polypropylene (C) are used in combination.
- the improvement effect that becomes stronger is great.
- the intermediate layer [iii] in the polyolefin composite film of the present invention is composed of 50 to 95% by weight, preferably 70 to 95% by weight of the crystalline polypropylene (C), and the propylene polymer (B), the propylene / ⁇ -
- the olefin random copolymer (A) and / or the 1-butene / ⁇ -olefin random copolymer (E) is 50 to 5% by weight, preferably 30 to 5% by weight [however, in the intermediate layer ( C), (B), (A) and (E) are 100% by weight in total].
- the meaning of “and / or” means the propylene polymer (B), the propylene / ⁇ -olefin random copolymer (A), and 1-butene / ⁇ -.
- the olefin random copolymer (E) it is an expression including any of the case where two components are used in combination, and the case where all three components are used.
- the heat seal strength of the resulting polyolefin composite film may be inferior.
- the heat seal strength of the resulting polyolefin composite film may be inferior.
- polyolefin composite film in the case of “another aspect” of the present invention is as follows.
- the surface layer [i] uses the propylene / ⁇ -olefin random copolymer (A) in a proportion of 15 to 100 wt% and the propylene polymer (B) 85 to 0 wt%.
- the propylene / ⁇ -olefin random copolymer (A) in a proportion of 15 to 100 wt% and the propylene polymer (B) 85 to 0 wt%.
- the core layer [ii] The crystalline polypropylene (C) is 70 to 100% by weight and the propylene polymer (D) is 0 to 30% by weight.
- the core layer [ii] contains a recycled product of the core layer [ii] as well as a recycled product of the polymer constituting the surface layer [i] and the intermediate layer [iii] as long as it falls within the above range. You may do it.
- the core layer [ii] comprises 70 to 100% by weight of the crystalline polypropylene (C), preferably 80 to 100% by weight, particularly preferably 85 to 100% by weight, and the propylene polymer (D) 0 to 30% by weight. %, Preferably 0 to 20% by weight, particularly preferably 0 to 15% by weight [in each case, the total of (C) and (D) is 100% by weight. ].
- the intermediate layer [iii] Composition (A) 50 comprising 50 to 95% by weight of the crystalline polypropylene (C) and the propylene polymer (D) and / or the 1-butene / ⁇ -olefin random copolymer (E) [The total amount of (C) and (D) and / or (E)] is 100% by weight. ].
- the crystalline polypropylene (C) used for the intermediate layer [iii] may be different from the crystalline polypropylene (C) used for the core layer [ii] as long as it is within the above specified range. Good.
- the propylene-based polymer (D) that may be used for the intermediate layer [iii] is within the range specified above, and more preferably within the preferable range, the propylene-based polymer (used for the core layer [ii] ( It may be different from D) or may be the same.
- the 1-butene / ⁇ -olefin copolymer (E) that may be used in the intermediate layer [iii] includes 1-butene / ethylene copolymer, 1-butene / propylene copolymer, Examples include butene / ethylene / propylene copolymers. These may be used alone or in combination of two or more.
- the intermediate layer [iii] is composed of the above (C) and the above (D), or the above (C) and the above (E). ) And (D) and (E).
- (A) comprises 50 to 95% by weight
- (D) and / or (E) comprises 50 to 5% by weight, among which (A) comprises 60 to 90% by weight, (D) and / or 40 to 10% by weight is preferable [the total of (D) and / or (E) together with (A) is 100% by weight. ].
- Each polymer constituting the intermediate layer preferably includes a polymer defined as a surface layer within the above range, but it is not always necessary to use the same polymer as that used for the surface layer. May be included. The above has been described by paying attention to the polyolefin composite film in the case of another embodiment of the present invention.
- the propylene / ⁇ -olefin random copolymer (A), the 1-butene / ⁇ -olefin copolymer (E), the propylene polymer (B), and the crystallinity forming the polyolefin composite film of the present invention are provided.
- the polyolefin composite film of the present invention comprises a surface layer [i], a core layer [ii], and an intermediate layer [iii] so that the intermediate layer [iii] is directly on both the surface layer [i] and the core layer [ii]. Configured to touch.
- Specific examples of the polyolefin composite film of the present invention include, for example, a three-layer film made of [i] // [iii] // [ii], [i] // [iii] // [ii] // [iii ]
- a five-layer film composed of // [i] can be exemplified, but is not particularly limited as long as it has a configuration of [i] // [iii] // [ii].
- the surface layers [i] on both sides of the five-layer film or the like made of [i] // [iii] // [ii] // [iii] // [i] do not necessarily have the same thickness. It is desirable to have substantially the same thickness.
- the intermediate layers [iii] on both sides are not necessarily required to have the same thickness, but are desirably substantially the same thickness.
- each layer of the polyolefin composite film of the present invention can be appropriately determined according to the application.
- the thickness of the surface layer [i] is 0.5 to 10 ⁇ m, preferably 1 to 5 ⁇ m
- the core layer [ii] is usually 8 to 60 ⁇ m, preferably 10 to 50 ⁇ m, more preferably 15 to 45 ⁇ m
- the thickness of the intermediate layer [iii] is usually 0.5 to 10 ⁇ m, preferably 1 to 5 ⁇ m.
- the total thickness of the polyolefin composite film is usually 9 to 100 ⁇ m, and preferably 10 to 35 ⁇ m.
- the thickness of the intermediate layer is less than 0.5 ⁇ m, sufficient heat seal strength may not be obtained depending on the application.
- the thickness of the surface layer [i] is 1 to 20%, particularly 2 to 10%, particularly 3 to 8% of the thickness of the core layer [ii].
- the thickness of the intermediate layer [iii] is preferably 1 to 20%, more preferably 2 to 10%, and most preferably 3 to 8%.
- regulations are the thickness of each surface layer [i] and intermediate
- the polyolefin composite film of the present invention is excellent in both strength and heat seal strength.
- the polyolefin composite film of the present invention may be an unstretched film or a uniaxially or biaxially stretched film.
- the polyolefin composite film of the present invention may be laminated with another base material depending on the application.
- the base material include polyethylene terephthalate, a film made of polyester typified by polyethylene naphthalate, a polycarbonate film, a polyamide film made of nylon 6, nylon 66, etc., an ethylene / vinyl alcohol copolymer film, a polyvinyl alcohol film, It is composed of a film made of a thermoplastic resin such as a polyvinyl chloride film, a polyvinylidene chloride film, and a film made of polyolefin such as polypropylene, aluminum foil, paper or the like.
- the substrate made of such a thermoplastic resin film may be an unstretched film or a uniaxially or biaxially stretched film. Of course, the substrate may be a single layer or two or more layers.
- the thermoplastic resin film may be a film on which an inorganic substance such as aluminum, zinc, silica, or the oxide thereof is deposited.
- the polyolefin composite film of the present invention can be produced by a known method. For example, there is a method of producing a composite film by coextrusion molding by a T-die method or an inflation method using a number of extruders corresponding to the type of resin composition of the layer to be laminated. Moreover, after coextrusion, it is also stretched in at least one direction to form a stretched film. These stretching methods include uniaxial stretching, sequential biaxial stretching, simultaneous biaxial stretching, and the like. The stretching ratio in biaxial stretching is usually about 3 to 12 times in the longitudinal direction and about 3 to 12 times in the transverse direction.
- the polyolefin composite film of the present invention is a biaxially stretched film, excellent low-temperature heat sealing performance can be exhibited while maintaining the strength of the polyolefin composite film.
- the biaxially stretched polyolefin composite film of the present invention has not only a tensile elastic modulus (MD, TD) of less than 3 GPa but also a tensile elastic modulus (MD, TD) of 3 GPa or more. It exhibits excellent low-temperature heat properties together with its excellent strength.
- the tensile modulus of elasticity in the machine direction (MD) or transverse (TD) direction of the polyolefin composite film of the present invention is preferably 1.9 to 5.0 GPa, and more preferably 1.9 to 4.5 GPa. Furthermore, it is desirable that the length is in the above range in both the longitudinal (MD) and lateral (TD) stretching directions.
- the composite film of the present invention is further stacked so that the surface layers overlap each other, and the heat seal strength (upper part of the heat seal bar) related to the 180 ° peel strength when heat sealing is performed by the method described later.
- the heat seal strength (upper part of the heat seal bar) related to the 180 ° peel strength when heat sealing is performed by the method described later. Is preferably 7.5 N / 15 mm or more, more preferably 7.5 N / 15 mm to 75 N / 15 mm, and particularly preferably 9 N / 15 mm to 75 N / 15 mm. is there.
- the polyolefin composite film of the present invention is subjected to surface treatment, for example, corona treatment, plasma treatment, flame treatment, and the like as long as the purpose of the present invention is not impaired.
- the test specimen (fluororesin sheet / composite film / composite film / fluororesin sheet) was sandwiched between the heat seal bars and heat sealed at a pressure of 0.2 MPa for 1.0 second.
- the fluororesin sheet was removed, and the heat-sealed composite film part was left at room temperature of about 23 ° C. for 2 days.
- a slit having a width of 15 mm was inserted so as to include the heat seal portion of the composite film, and the unsealed portion was chucked by a tensile tester (“IM-20ST, manufactured by INTERSCO”).
- IM-20ST tensile tester
- the heat seal start temperature was defined as the temperature at the top of the seal bar at which the heat seal strength measured by the above method was 2 N / 15 mm, as the heat seal start temperature (° C.).
- Propylene / ⁇ -olefin random copolymer (A) (1-1) PBR Propylene content: 75 mol%, 1-butene content: 25 mol%, melting point: 77 ° C., MFR (230 ° C.): 7 g / 10 min, intrinsic viscosity [ ⁇ ]: 1.8 dl / g, Mw / Mn: A propylene / 1-butene random copolymer (PBR) having 2.0 and a B value of 1.0 was used.
- the polymers are supplied to the respective extruders in the proportions shown in the surface layer, core layer and intermediate layer shown in Table 1, And the extrusion amount of each extruder so that the thickness of the skin layer // intermediate layer // core layer // intermediate layer // skin layer is 1/1/2/1/1 to 230 ° C.
- An unstretched film having a thickness of 1000 ⁇ m was obtained by co-extrusion molding.
- thermo seal strength For the polyolefin composite film, “heat seal strength” and “heat seal start temperature” were measured. The results are shown in Table 1.
- the polyolefin composite film of the present invention exhibits high heat seal strength.
- the polyolefin composite film of the present invention has an excellent performance with a heat seal strength of 7.5 N / 15 mm or more at a temperature of 140 ° C. and excellent transparency, and various packaging for food, industrial materials, etc. It can be widely used as a material.
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Abstract
Description
少なくとも1層の表面層[i]と、コア層[ii]、及び表面層[i]とコア層[ii]の両方に直接接する中間層[iii]を有するポリオレフィン複合フィルムであって、
表面層[i]は、
プロピレンから導かれる単位を50~97モル%含有し、炭素数2~10のα-オレフィン(プロピレンを除く)から導かれる単位を3~50モル%含有するプロピレン・α-オレフィンランダム共重合体(A)、
及び/または、
1-ブテンから導かれる単位を50~95モル%含有し、炭素数2~10のα-オレフィン(1-ブテンを除く)から導かれる単位を50~5モル%含有し、α―オレフィン(1-ブテンを除く)から導かれる単位を50~5モル%含有する1-ブテン・α-オレフィン共重合体(E)が、
0~50重量%、
であると共に、
プロピレンから導かれる単位を50~100モル%含有し、炭素数2~10のα-オレフィン(プロピレンを除く)から導かれる単位を0~50モル%含有し、融点が120~170℃のプロピレン系重合体(B)50~100重量%
からなり、
〔但し、表面層における(A)、(E)及び(B)の合計を100重量部とする。〕
コア層[ii]は、
プロピレンから導かれる単位を97~100モル%含有し、炭素数が2~10のα-オレフィン(プロピレンを除く)を0~3モル%含有し、融点が150~170℃である結晶性ポリプロピレン(C)70~100重量%、
及び、
プロピレンから導かれる単位を50~97モル%含有し、炭素数2~10のα-オレフィン(プロピレンを除く)から導かれる単位を3~50モル%含有するプロピレン・α-オレフィンランダム共重合体(A)0~30重量%からなり、
〔但し、コア層にける(C)及び(A)の合計を100重量部とする。〕
中間層[iii]は、
プロピレンから導かれる単位を97~100モル%含有し、炭素数が2~10のα-オレフィン(プロピレンを除く)を0~3モル%含有し、融点が150~170℃である結晶性ポリプロピレン(C)50~95重量%、
と共に
プロピレンから導かれる単位を50~100モル%含有し、炭素数2~10のα―オレフィン(プロピレンを除く)から導かれる単位を0~50モル%含有し、融点が120~170℃のプロピレン系重合体(B)、
プロピレンから導かれる単位を50~97モル%含有し、炭素数2~10のα―オレフィン(プロピレンを除く)から導かれる単位を3~50モル%含有するプロピレン・α-オレフィンランダム共重合体(A)、
及び/または、
1-ブテンから導かれる単位を50~95モル%含有し、α―オレフィン(1-ブテンを除く)から導かれる単位を50~5モル%含有する1-ブテン・α-オレフィンランダム共重合体(E)が、
50~5重量%、
〔但し、中間層における(C)、(B)、(A)及び(E)の合計を100重量%とする〕
とからなるプロピレン系樹脂組成物
からなることを特徴とするポリオレフィン複合フィルムに関する。
少なくとも1層の表面層[i]と、コア層[ii]及び表面層[i]とコア層[ii]の両方に直接接する中間層[iii]からなり、
表面層[i]は、
プロピレンから導かれる単位を50~97モル%含有し、炭素数2~10のα―オレフィン(プロピレンを除く)から導かれる単位を3~50モル%含有するプロピレン・α-オレフィンランダム共重合体(A)15~100重量%、
及び、
プロピレンから導かれる単位を50~100モル%含有し、炭素数2~10のα―オレフィン(プロピレンを除く)から導かれる単位を0~50モル%含有し、融点が120~170℃のプロピレン系重合体(B)0~85重量%からなり、
コア層[ii]は、
プロピレンから導かれる単位を97~100モル%含有し、炭素数が2~10のα―オレフィン(プロピレンを除く)を0~3モル%含有し、融点が150~170℃である結晶性ポリプロピレン(C)70~100重量%、
及び、
プロピレンから導かれる単位を50モル%以上97モル%未満含有し、炭素数2~10のα―オレフィン(プロピレンを除く)から導かれる単位を50モル%以下であり3モル%を越えて含有し、示差走査熱量計(DSC)で測定される融点が140℃未満または融点が観測されないプロピレン系重合体(D)0~30重量%からなり、
中間層[iii]は、
プロピレンから導かれる単位を97~100モル%含有し、炭素数が2~10のα―オレフィン(プロピレンを除く)を0~3モル%含有し、融点が150~170℃である結晶性ポリプロピレン(C)50~95重量%、
と共に
プロピレンから導かれる単位を50モル%以上97モル%未満含有し、炭素数2~10のα―オレフィン(プロピレンを除く)から導かれる単位を50モル%以下であり3モル%を越えて含有し、示差走査熱量計(DSC)で測定される融点が140℃未満または融点が観測されないプロピレン系重合体(D)
及び/または、
1-ブテンから導かれる単位を50~95モル%含有し、α―オレフィン(1-ブテンを除く)から導かれる単位を50~5モル%含有する1-ブテン・α-オレフィンランダム共重合体(E)、
が50~5重量%
〔但し、(C)、(D)及び、(E)の合計を100重量%とする。〕
とからなるプロピレン系樹脂組成物からなることを特徴とするポリオレフィン複合フィルムに関する。
プロピレン・α-オレフィンランダム共重合体(A)が、
(1)135℃、デカリン中で測定される極限粘度が0.1~5dl/gであり、
(2)ゲルパーミエイションクロマトグラフィー(GPC)により求められる分子量分布(Mw/Mn)が1.5以上3以下であり、
(3)共重合モノマー連鎖分布のランダム性を示すパラメータB値が0.9~1.5であるプロピレン・1-ブテンランダム共重合体であることを特徴とするポリオレフィン複合フィルムである。
本発明のポリオレフィン複合フィルムの表面層[i]を形成するプロピレン・α-オレフィンランダム共重合体(A)は、プロピレンから導かれる単位を50~97モル%、好ましくは50~95モル%含有し、炭素数2から10のα―オレフィン(プロピレンを除く)から導かれる単位を3~50モル%、好ましくは5~50モル%含有するプロピレン・α-オレフィンランダム共重合体(A)である(プロピレンから導かれる単位とα-オレフィンから導かれる単位の合計を100モル%とする)。上記α-オレフィンは必要に応じて1種または2種以上を用いてもよい。
(1)135℃、デカリン中で測定される極限粘度[η]が0.1~5dl/gであり、
(2)ゲルパーミエイションクロマトグラフィー(GPC)により求められる分子量分布(Mw/Mn)が1.5以上3以下であり、
(3)共重合モノマー連鎖分布のランダム性を示すパラメータB値が0.9~1.5、好ましくは1.0~1.4、
であるプロピレン・1-ブテンランダム共重合体が好適である。
B=P12/(2P1 ・P2 )
ここで、P1 、P2 はそれぞれ第1モノマー、第2モノマー含量分率であり、P12は全二分子中連鎖中の(第1モノマー)-(第2モノマー)連鎖の割合である。
本発明のポリオレフィン複合フィルムの表面層[i]、及び中間層[iii]を形成する1-ブテン・α―オレフィン共重合体(E)は、1-ブテンから導かれる単位を50~95モル%、好ましくは60~95モル%、特に好ましくは70~95モル%含有し、かつα―オレフィン(1-ブテンを除く)から導かれる単位を50~5モル%、好ましくは40~5モル%、特に好ましくは30~5モル%含有する1-ブテン・α-オレフィンランダム共重合体(E)である(1-ブテンから導かれる単位とα-オレフィンから導かれる単位の合計を100モル%とする)。上記α-オレフィンは必要に応じて1種または2種以上を用いてもよい。
(1’’)135℃、デカリン中で測定される極限粘度[η]が0.1~5dl/gであり、
(2’’)ゲルパーミエイションクロマトグラフィー(GPC)により求められる分子量分布(Mw/Mn)が2~6であり、
(3’’)共重合モノマー連鎖分布のランダム性を示すパラメータB値が0.9~1.5、好ましくは0.9~1.4、
である1-ブテン・α―オレフィン共重合体が好適である。
本発明のポリオレフィン複合フィルムの表面層[i]、中間層[ii]を形成するプロピレン系重合体(B)は、プロピレンから導かれる単位を50~100モル%、好ましくは85~97モル%含有し、炭素数2~10のα-オレフィン(プロピレンを除く)から導かれる単位を0~50モル%、好ましくは3~15モル%含有し、その融点が120~170℃、好ましくは120~140℃のプロピレン系重合体(B)である(プロピレンから導かれる単位とα―オレフィンから導かれる単位の合計を100モル%とする)。上記α-オレフィンは必要に応じて1種または2種以上を用いてもよい。
本発明のポリオレフィン複合フィルムのコア層[ii]、及び中間層[iii]の成分を形成する結晶性ポリプロピレン(C)は、プロピレンから導かれる単位を97~100モル%、好ましくは98~100モル%含有し、炭素数が2~10のα-オレフィン(プロピレンを除く)から導かれる単位を少なくとも1種類の単位を0~3モル%、好ましくは0~2モル%含有し、融点が150~170℃、好ましくは155~165℃である結晶性ポリプロピレン(C)である(プロピレンから導かれる単位とα-オレフィンから導かれる単位の合計を100モル%とする)。結晶性ポリプロピレン(C)がα-オレフィンから導かれる単位を含む場合は、必要に応じて1種または2種以上を用いてもよい。
本発明の1つの態様として、ポリオレフィン複合フィルムのコア層[ii]、及び中間層[iii]の成分を形成するプロピレン・α-オレフィンランダム共重合体(A)がプロピレン系重合体(D)となる場合がある。
(1’)135℃、デカリン中で測定される極限粘度[η]が0.1~5dl/gであり、
(2’)ゲルパーミエイションクロマトグラフィー(GPC)により求められる分子量分布(Mw/Mn)が1.5~4であり、
(3’)共重合モノマー連鎖分布のランダム性を示すパラメータB値が0.7~1.5であるプロピレン系重合体(D)が好適である。
本発明のポリオレフィン複合フィルムは、少なくとも1層の表面層[i]と、コア層[ii]、及び表面層[i]とコア層[ii]の両方に直接接する中間層[iii]を有するポリオレフィン複合フィルムである。
本発明のポリオレフィン複合フィルムの表面層[i]は、前記プロピレン・α-オレフィンランダム共重合体(A)、及び/または前記1-ブテン・α-オレフィン共重合体(E)を0~50重量%、好ましくは0~30重量%、さらに好ましくは3~30重量%、並びに前記プロピレン系重合体(B)を50~100重量%、好ましくは70~100重量%、さらに好ましくは70~97重量%含む(但し、表面層における(A)、(E)及び(B)の合計を100重量%とする。)オレフィン系重合体組成物(X)からなる。
本発明のポリオレフィン複合フィルムのコア層[ii]は、前記結晶性ポリプロピレン(C)70~100重量%、及び、プロピレン・α-オレフィン共重合体(A)を0~30重量%含む〔但し、(A)及び(C)の合計で100重量%とする。〕プロピレン系重合体組成物(Y)からなる。
〈中間層[iii]〉
本発明のポリオレフィン複合フィルムにおける中間層[iii]は、前記結晶性ポリプロピレン(C)50~95重量%、好ましくは70~95重量%、と共に前記プロピレン系重合体(B)、前記プロピレン・α-オレフィンランダム共重合体(A)、及び/または、前記1-ブテン・α-オレフィンランダム共重合体(E)が、50~5重量%、好ましくは30~5重量%〔但し、中間層における(C)、(B)、(A)及び(E)の合計を100重量%とする〕とからなるプロピレン系樹脂組成物からなる。
前記結晶性ポリプロピレン(C)70~100重量%、及び、前記プロピレン系重合体(D)0~30重量%からなる。
前記結晶性ポリプロピレン(C)50~95重量%と共に、前記プロピレン系重合体(D)、及び/または、前記1-ブテン・α-オレフィンランダム共重合体(E)かなる組成物(イ)50~5重量%からなる〔(C)と(D)及び、または(E)からなる組成物(イ)との合計で100重量%とする。〕。
以上が本発明の他の態様の場合のポリオレフィン複合フィルムに注目して説明したものである。
測定する対象であるポリオレフィン複合フィルムの表面層同士が重なるように複合フィルムを重ね、重ねた複合フィルムの両面を厚さ50μmのフッ素樹脂シート(フッ素樹脂(デュポン社製 商品名:テフロン(登録商標))からなるシート)で挟んだ試験体を作製した。次いで、ヒートシールテスター(テスター産業株式会社製TB-701B型)のヒートシールバーを幅5mm×長さ300mmに設置し、シールバー下側を70℃に設定し、シールバー上部の温度を変化させ、ヒートシールバー部分に、該試験体(フッ素樹脂シート/複合フィルム/複合フィルム/フッ素樹脂シート)を挟み、0.2MPaの圧力で1.0秒間ヒートシールを行った。フッ素樹脂シートを外し、ヒートシールされた複合フィルム部分を約23℃の室温下で2日間放置した。複合フィルムのヒートシール部分を含むように15mm幅のスリットを入れ、シールされていない部分を引張試験機(「INTESCO社製 IM-20ST」)にチャックした。300mm/分の速度で複合フィルムの180°剥離強度を測定した。上記操作を5回行い、その平均値をヒートシール強度とした。
190℃に設定した油圧式熱プレス成形機を用いて、5分予熱した後2分間加圧し、すぐに20℃に設定した冷却槽で4分間冷却し、3mm厚のプレスシートを作成した。これを試験前に23℃±2℃で10日間保管した後、示差走査熱量計(DSC)により-40℃まで冷却してから昇温速度10℃/分で200℃迄昇温し、発熱・吸熱曲線を求め、最大吸熱ピーク位置の温度を融点とした。
ヒートシール開始温度は、上記の方法で測定したヒートシール強度が2N/15mmになるシールバー上部の温度をヒートシール開始温度(℃)とした。
JIS K7127に準じた方法で、フィルムの縦方向(MD)及び横方向(TD)について、それぞれ5回測定し、その平均値を弾性率とした。
(1-1)PBR
プロピレン含有量:75モル%、1-ブテン含有量:25モル%、融点:77℃、MFR(230℃):7g/10分、極限粘度[η]:1.8dl/g、Mw/Mn:2.0、及び、B値:1.0のプロピレン・1-ブテンランダム共重合体(PBR)を用いた。
プロピレン含有量:69モル%、エチレン含有量:31モル%、融点:96℃、MFR(230℃):8g/10分、極限粘度[η]:1.7dl/g、Mw/Mn:2.7、B値:0.7のプロピレン・エチレンランダム共重合体(PER)を用いた。
1-ブテン含有量:20モル%、エチレン含有量:14モル%、融点は観測されず、極限粘度[η] :1.8dl/g、MFR(230℃):7g/10分、Mw/Mn:2.0、B値:1.0のプロピレン・1-ブテン・エチレンランダム共重合体(PBER)を用いた。
(2-1)r-PP
エチレン含有量:2.2モル%、1-ブテン含有量:1.5モル%、融点:138℃、及び、MFR(230℃):7g/10分のプロピレン・エチレン・1-ブテンランダム共重合体(r-PP)を用いた。
エチレン含有量:9.5モル%、1-ブテン含有量:3.9モル%、融点:131℃、及びMFR(230℃):6g/10分のプロピレン・エチレン・1-ブテンランダム共重合体(Ter-PP)を用いた。
(3-1)h-PP
融点:160℃、MFR(230℃):3g/10分のプロピレン単独重合体(h-PP)を用いた。
(4-1)BER
1-ブテン含有量:95モル%、エチレン含有量:5モル%、融点:100℃、MFR(230℃)9g/10分、極限粘度[η] :1.8dl/g、Mw/Mn:3.4、B値:1.0の1-ブテン・エチレンランダム共重合体(BER)を用いた。
1-ブテン含有量:75モル%、プロピレン含有量:25モル%、融点:77℃、MFR(230℃):9g/10分、極限粘度[η]:1.7dl/g、Mw/Mn:4.9、B値:0.9の1-ブテン・プロピレンランダム共重合体(BPR)を用いた。
〔ポリオレフィン複合フィルムの成形〕
上記各重合体を用いて表1に示すように、表面層、コア層及び中間層からなる3種5層の複合フィルム(表面層//中間層//コア層//中間層//表面層)を以下のようにして成形した。
Claims (12)
- 少なくとも1層の表面層[i]と、コア層[ii]、及び表面層[i]とコア層[ii]の両方に直接接する中間層[iii]を有するポリオレフィン複合フィルムであって、
表面層[i]は、
プロピレンから導かれる単位を50~97モル%含有し、炭素数2~10のα-オレフィン(プロピレンを除く)から導かれる単位を3~50モル%含有するプロピレン・α-オレフィンランダム共重合体(A)、
及び/または、
1-ブテンから導かれる単位を50~95モル%含有し、炭素数2~10のα―オレフィン(1-ブテンを除く)から導かれる単位を50~5モル%含有する1-ブテン・α―オレフィン共重合体(E)が、
0~50重量%、
であると共に、
プロピレンから導かれる単位を50~100モル%含有し、炭素数2~10のα-オレフィン(プロピレンを除く)から導かれる単位を0~50モル%含有し、融点が120~170℃のプロピレン系重合体(B)50~100重量% からなり、
〔但し、表面層における(A)、(E)及び(B)の合計を100重量部とする。〕
コア層[ii]は、
プロピレンから導かれる単位を97~100モル%含有し、炭素数が2~10のα-オレフィン(プロピレンを除く)を0~3モル%含有し、融点が150~170℃である結晶性ポリプロピレン(C)70~100重量%、
及び、
プロピレンから導かれる単位を50~97モル%含有し、炭素数2~10のα-オレフィン(プロピレンを除く)から導かれる単位を3~50モル%含有するプロピレン・α-オレフィンランダム共重合体(A)0~30重量%からなり、
〔但し、コア層にける(C)及び(A)の合計を100重量部とする。〕
中間層[iii]は、
プロピレンから導かれる単位を97~100モル%含有し、炭素数が2~10のα-オレフィン(プロピレンを除く)を0~3モル%含有し、融点が150~170℃である結晶性ポリプロピレン(C)50~95重量%、
と共に、
プロピレンから導かれる単位を50~100モル%含有し、炭素数2~10のα-オレフィン(プロピレンを除く)から導かれる単位を0~50モル%含有し、融点が120~170℃のプロピレン系重合体(B)、
プロピレンから導かれる単位を50~97モル%含有し、炭素数2~10のα-オレフィン(プロピレンを除く)から導かれる単位を3~50モル%含有するプロピレン・α-オレフィンランダム共重合体(A)、
及び/または、
1-ブテンから導かれる単位を50~95モル%含有し、α-オレフィン(1-ブテンを除く)から導かれる単位を50~5モル%含有する1-ブテン・α-オレフィンランダム共重合体(E)が50~5重量%、
〔但し、中間層における(C)、(B)、(A)及び(E)の合計を100重量%とする〕
とからなるプロピレン系樹脂組成物、
からなることを特徴とするポリオレフィン複合フィルム。 - 少なくとも1層の表面層[i]と、コア層[ii]及び表面層[i]とコア層[ii]の両方に直接接する中間層[iii]からなり、
表面層[i]は、
プロピレンから導かれる単位を50~97モル%含有し、炭素数2~10のα-オレフィン(プロピレンを除く)から導かれる単位を3~50モル%含有するプロピレン・α-オレフィンランダム共重合体(A)15~100重量%、
及び、
プロピレンから導かれる単位を50~100モル%含有し、炭素数2~10のα-オレフィン(プロピレンを除く)から導かれる単位を0~50モル%含有し、融点が120~170℃のプロピレン系重合体(B)0~85重量%からなり、
コア層[ii]は、
プロピレンから導かれる単位を97~100モル%含有し、炭素数が2~10のα-オレフィン(プロピレンを除く)を0~3モル%含有し、融点が150~170℃である結晶性ポリプロピレン(C)70~100重量%、
及び、
プロピレンから導かれる単位を50モル%以上97モル%未満含有し、炭素数2~10のα-オレフィン(プロピレンを除く)から導かれる単位を50モル%以下であり3モル%を越えて含有し、示差走査熱量計(DSC)で測定される融点が140℃未満または融点が観測されないプロピレン系重合体(D)0~30重量%からなり、
中間層[iii]は、
プロピレンから導かれる単位を97~100モル%含有し、炭素数が2~10のα-オレフィン(プロピレンを除く)を0~3モル%含有し、融点が150~170℃である結晶性ポリプロピレン(C)50~95重量%、
と
プロピレンから導かれる単位を50モル%以上97モル%未満含有し、炭素数2~10のα-オレフィン(プロピレンを除く)から導かれる単位を50モル%以下であり3モル%を越えて含有し、示差走査熱量計(DSC)で測定される融点が140℃未満または融点が観測されないプロピレン系重合体(D)、
及び/または、
1-ブテンから導かれる単位を50~95モル%含有し、α-オレフィン(1-ブテンを除く)から導かれる単位を50~5モル%含有する1-ブテン・α-オレフィンランダム共重合体(E)、
が50~5重量%、
〔但し、(C)、(D)及び(E)の合計を100重量%とする。〕
とからなるプロピレン系樹脂組成物からなることを特徴とするポリオレフィン複合フィルム。 - プロピレン・α-オレフィンランダム共重合体(A)の融点が110℃以下または融点が観測されないことを特徴とする請求項1または請求項2のいずれかに記載のポリオレフィン複合フィルム。
- プロピレン系重合体(B)の融点が120から140℃であり、1-ブテン・α-オレフィン共重合体(E)の融点が60から110℃であることを特徴とする請求項1から請求項3のいずれかに記載のポリオレフィン複合フィルム。
- プロピレン・α-オレフィンランダム共重合体(A)が、
(1)135℃、デカリン中で測定される極限粘度が0.1~5dl/gであり、
(2)ゲルパーミエイションクロマトグラフィー(GPC)により求められる分子量分布(Mw/Mn)が1.5以上3以下であり、
(3)共重合モノマー連鎖分布のランダム性を示すパラメータB値が0.9~1.5であるプロピレン・1-ブテンランダム共重合体であることを特徴とする請求項1~4のいずれかに記載のポリオレフィン複合フィルム。 - 未延伸であることを特徴とする請求項1~5のいずれかに記載のポリオレフィン複合フィルム。
- 二軸延伸されていることを特徴とする請求項1~5のいずれかに記載のポリオレフィン複合フィルム。
- ポリオレフィン複合フィルムの全体の厚さにおける表面層の全体の厚さの割合が、2~10%であることを特徴とする請求項1~7のいずれかに記載のポリオレフィン複合フィルム。
- ポリオレフィン複合フィルムの全体の厚さにおける中間層の全体の厚さの割合が、2~10%であることを特徴とする請求項1~8のいずれかに記載のポリオレフィン複合フィルム。
- ポリオレフィン複合フィルムが、表面層/中間層/コア層/中間層/表面層の順からなる5層の構造を有することを特徴とする請求項1~9のいずれかに記載のポリオレフィン複合フィルム。
- ポリオレフィン複合フィルムの全体の厚さが10~35μmであることを特徴とする請求項1~10のいずれかに記載のポリオレフィン複合フィルム。
- ポリオレフィン複合フィルムの縦、又は横の延伸方向の引張弾性率が、1.9~5.0GPaの範囲に入ることを特徴とする請求項1から請求項11のいずれかに記載のポリオレフィン複合フィルム。
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BR112013010919A2 (pt) | 2016-08-23 |
EP2639062B1 (en) | 2019-05-22 |
KR20130093643A (ko) | 2013-08-22 |
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