Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/10—Homopolymers or copolymers of propene
  • C08L23/14—Copolymers of 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
  • 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
• • 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
  • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
• • 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
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
  • B32B27/327—Layered products comprising a layer of synthetic resin comprising polyolefins comprising polyolefins obtained by a metallocene or single-site catalyst
• • 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
  • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
• • 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
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/04—Interconnection of layers
  • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
• • 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
  • C08L23/04—Homopolymers or copolymers of ethene
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
  • C09J7/22—Plastics; Metallised plastics
  • C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • C09J7/241—Polyolefin, e.g.rubber
  • C09J7/243—Ethylene or propylene polymers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
  • C09J7/35—Heat-activated
• • 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
  • B32B2250/02—2 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
  • B32B2250/03—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
• • 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
  • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
  • B32B2264/10—Inorganic particles
• • 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
  • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
• • 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
• • 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
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
  • B32B2307/514—Oriented
• • 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
  • B32B2307/70—Other properties
  • B32B2307/732—Dimensional properties
  • B32B2307/737—Dimensions, e.g. volume or area
  • B32B2307/7375—Linear, e.g. length, distance or width
  • B32B2307/7376—Thickness
• • 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
  • B32B2307/70—Other properties
  • B32B2307/746—Slipping, anti-blocking, low friction
• • 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
  • B32B2307/70—Other properties
  • B32B2307/748—Releasability
• • 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
  • B32B2439/02—Open containers
  • B32B2439/06—Bags, sacks, sachets
• • 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
  • B32B2553/00—Packaging equipment or accessories not otherwise provided for

Definitions

• the present invention relates to a non-stretched film, a laminate, and a package including a sealant layer and a base layer.
• a heat-sealable packaging film is composed of multiple layers of film.
• non-stretched films tend to be used in multi-layer films, for example, for packages that require high sealing strength for liquids or retort packages.
• polypropylene (PP) film and polyethylene (PE) film are widely used as films for heat-sealing packaging. is considered important from the perspective of
• Patent Documents 1 and 2 describe a laminate having excellent low-temperature heat-sealability, including a sealant film containing a polypropylene resin, a propylene/ ⁇ -olefin copolymer, and a 1-butene/ ⁇ -olefin copolymer. It is
• the present invention has been made in view of the above, and an object of the present invention is to provide a non-stretched film capable of constituting a laminate having excellent low-temperature heat-sealing property and heat-sealing strength in a well-balanced manner.
• the present invention relates to, for example, the following [1] to [10].
• the content of the copolymer (B) is equal to or greater than the content of the copolymer (C);
• the total content of the copolymer (B) and the copolymer (C) is 25 to 80% by mass
• the propylene-based polymer (A) has a melting point (Tm) of 120° C.
• the copolymer (B) has a Tm measured by DSC of less than 120 ° C. or no Tm is observed by DSC, contains 51 to 99 mol% of 1-butene-derived structural units, and has 2 carbon atoms. 1 to 49 mol% of ⁇ -olefin-derived structural units having 5 to 20 carbon atoms (provided that the total of the 1-butene-derived structural units and the ⁇ -olefin-derived structural units is 100 mol) %.); The copolymer (C) has a Tm measured by DSC of less than 120 ° C.
• the copolymer (C) contains at least one propylene/ ⁇ -olefin copolymer selected from the group consisting of a propylene/ethylene copolymer (C1) and a propylene/1-butene copolymer (C2). , the unstretched film according to [1].
• the substrate layer contains the propylene-based polymer (A) (which may be the same as or different from the propylene-based polymer (A) contained in the sealant layer), [1] or [ 2].
• [5] A laminate comprising the unstretched film and stretched film according to any one of [1] to [4].
• the maximum value of heat seal strength in the temperature range of 70 ° C. or higher and 120 ° C. or lower is 8 N / 15 mm or more
• the maximum value of heat seal strength in the temperature range of 70 ° C. or higher and 200 ° C. or lower is 15 N / 15 mm or more
• Any of [5] to [7], wherein the peeling form of the heat-sealed portion when the heat-seal strength shows 30 N / 15 mm or more in the heat-seal strength measurement in the temperature range of 70 ° C. or higher and 200 ° C. or lower is edge breakage.
• the laminate according to any one of the above.
• the unstretched film of the present invention a specific propylene-based polymer, a 1-butene/ ⁇ -olefin copolymer, and a propylene/ ⁇ -olefin copolymer are added in a predetermined ratio to the sealant layer constituting the unstretched film.
• the laminate using the non-stretched film is excellent in low-temperature heat-sealing property and heat-sealing strength in a well-balanced manner.
• the laminate using the non-stretched film of the present invention tends to be excellent in peeling appearance and excellent in blocking resistance.
• the unstretched film of the present invention has a sealant layer and a substrate layer. That is, the unstretched film of the present invention has a structure in which a sealant layer and a substrate layer are laminated.
• the sealant layer is a layer that imparts thermal adhesiveness to the laminate having the unstretched film and the stretched film, and the base layer is a layer that holds the sealant layer.
• the sealant layer is made of a resin composition containing the following (A) to (C) in a predetermined ratio.
• a propylene-based polymer hereinafter also referred to as “(co)polymer (A)” having a melting point (Tm) of 120° C. or higher and 170° C. or lower as measured by differential scanning calorimetry (DSC).
• (B) a melting point measured by DSC of less than 120°C, or no melting point observed by DSC, containing 51 to 99 mol% of 1-butene-derived structural units, and having 2 to 3 carbon atoms or a number of carbon atoms; Contains 1 to 49 mol% of structural units derived from 5 to 20 ⁇ -olefins (provided that structural units derived from 1-butene and ⁇ -olefins having 2 to 3 carbon atoms or 5 to 20 carbon atoms The total amount with units is 100 mol%.) 1-butene/ ⁇ -olefin copolymer (hereinafter also referred to as “copolymer (B)”) (C) a melting point measured by DSC of less than 120°C, or no melting point observed by DSC, containing 51 to 95 mol% of propylene-derived structural units and having 2 carbon atoms or 4 to 20 carbon atoms; Containing 5 to 49 mol% of ⁇ -olefin-derived structural units (
• propylene-based polymer (A) examples include propylene homopolymers, random copolymers of propylene and an ⁇ -olefin having 2 carbon atoms or 4 to 20 carbon atoms, propylene and 2 carbon atoms or Examples include block copolymers with ⁇ -olefins having 4 to 20 carbon atoms, preferably homopolymers of propylene, or random copolymers of propylene and ⁇ -olefins having 2 or 4 to 20 carbon atoms. It is a polymer.
• the (co)polymer (A) may be one kind of (co)polymer or two or more kinds of (co)polymers.
• the resin composition constituting the sealant layer of the present invention it is particularly preferable to use a propylene homopolymer from the viewpoint of imparting heat resistance and rigidity to the sealant layer. From the viewpoint of being able to provide the above, it is particularly preferable to use a random copolymer of propylene and an ⁇ -olefin having 2 carbon atoms or 4 to 20 carbon atoms.
• Examples of ⁇ -olefins having 2 carbon atoms or 4 to 20 carbon atoms to be copolymerized with propylene include ethylene, 1-butene, 1-pentene, 3-methyl-1-butene, 4-methyl-1-pentene, 1 -hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like.
• the ⁇ -olefin may be used alone or in combination of two or more.
• the (co)polymer (A) is propylene Preferably 91 to 99.9 mol%, more preferably 92 to 99.8 mol%, still more preferably 93 to 99.7 mol% of the constituent units derived from, having 2 carbon atoms or 4 to 20 carbon atoms 0.1 to 9 mol%, preferably 0.2 to 8 mol%, more preferably 0.3 to 7 mol% of the ⁇ -olefin-derived structural unit (provided that the propylene-derived structural unit and the ⁇ -The sum of the olefin-derived structural units is 100 mol%.).
• the (co)polymer (A) has a melting point (Tm) measured by Differential Scanning Calorimetry (DSC) of 120° C. or higher and 170° C. or lower, preferably 125° C. or higher and 165° C. or lower. is.
• Tm melting point measured by Differential Scanning Calorimetry
• DSC Differential Scanning Calorimetry
• the (co)polymer (A) having a melting point within the above range the moldability of the sealant layer can be improved, and heat resistance and transparency can be imparted to the sealant layer.
• the heat of fusion ( ⁇ H) obtained simultaneously with the melting point by DSC is preferably 50 mJ/mg or more.
• the melting point (Tm) of the (co)polymer (A) was measured using a differential scanning calorimeter (for example, DSCPyris1 or DSC7 manufactured by PerkinElmer) under a nitrogen atmosphere (20 mL/min) with a sample of about 5 mg at 200°C. C. and held for 10 minutes, cooled to 30.degree. C. at 10.degree. C./min, held for 5 minutes, and then heated to 200.degree. It is the melting point (Tm) of the polymer. If multiple peaks are detected, the peak detected on the highest temperature side is adopted.
• a differential scanning calorimeter for example, DSCPyris1 or DSC7 manufactured by PerkinElmer
• melt flow rate (MFR) of the (co)polymer (A) is measured according to ASTM D1238 under conditions of 230° C. and a load of 2.16 kg, preferably 0.01 to 40 g/10 min. It is preferably 0.1 to 10 g/10 min.
• the (co)polymer (A) is obtained by polymerizing a monomer by a known polymerization method such as a gas phase method, a bulk method, or a slurry method in the presence of a known catalyst such as a Ziegler-Natta catalyst or a metallocene catalyst. It can be manufactured by As a method of making the melting point 120 ° C. or higher and 170 ° C. or lower, as an example, the polymerization conditions such as the amount of monomer feed are controlled, and in the case of polymerization with a Ziegler-Natta catalyst, the comonomer content is less than 20 mol%. In the case of polymerization with a catalyst, there is a method of controlling the comonomer content to less than 10 mol %, and by this method a polymer having the target melting point can be obtained.
• a known polymerization method such as a gas phase method, a bulk method, or a slurry method in the presence of a known catalyst such as a
• the copolymer (B) may be one kind of copolymer or two or more kinds of copolymers.
• the use of a 1-butene/ ⁇ -olefin copolymer improves the low-temperature sealability and blocking resistance of the laminate.
• Examples of ⁇ -olefins having 2 to 3 carbon atoms or 5 to 20 carbon atoms to be copolymerized with 1-butene include ethylene, propylene, 1-pentene, 3-methyl-1-butene and 4-methyl-1-pentene. , 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, etc.
• ethylene, propylene, 1 - Pentene is preferred, ethylene and propylene are more preferred, and propylene is even more preferred.
• the ⁇ -olefin may be used alone or in combination of two or more.
• the copolymer (B) contains 51 to 99 mol%, preferably 60 to 97 mol%, more preferably 70 to 95 mol% of structural units derived from 1-butene, and has 2 to 3 carbon atoms or carbon Contain 1 to 49 mol%, preferably 3 to 40 mol%, more preferably 5 to 30 mol% of a structural unit derived from an ⁇ -olefin having 5 to 20 atoms (provided that the structural unit derived from 1-butene and the above The sum of the constituent units derived from ⁇ -olefin is 100 mol%.). By setting it as the said range, it is excellent in handleability and becomes easy to heat-seal even if it is a comparatively low temperature.
• the copolymer (B) has a melting point measured by DSC of less than 120° C. or no melting point observed by DSC, preferably 50° C. or higher and 115° C. or lower, more preferably 60° C. or higher and 110° C. or higher. °C or less, more preferably 65°C or more and 110°C or less.
• the melting point (Tm) of the copolymer (B) was determined by using a differential scanning calorimeter (eg, DSC manufactured by Seiko Instruments Inc.), filling about 10 mg of a sample in an aluminum pan for measurement, and heating at 100 ° C./min to 200. C. and held for 5 minutes, then cooled to -100.degree. C. at 10.degree. C./min and then heated to 200.degree. C. at 10.degree. Let it be the melting point (Tm). If multiple peaks are detected, the peak detected on the highest temperature side is adopted.
• a differential scanning calorimeter eg, DSC manufactured by Seiko Instruments Inc.
• the melt flow rate (MFR) of the copolymer (B) measured under conditions of 230° C. and a load of 2.16 kg according to ASTM D1238 is preferably 0.1 to 30 g/10 min, more preferably is 0.5 to 20 g/10 min, more preferably 1.0 to 10 g/10 min.
• the melt flow rate (MFR) measured under the conditions of 190°C and a load of 2.16 kg in accordance with ASTM D1238 is preferably 0.5. 1 to 30 g/10 min, more preferably 0.5 to 20 g/10 min, still more preferably 1.0 to 10 g/10 min.
• the copolymer (B) is obtained by polymerizing a monomer by a known polymerization method such as a gas phase method, a bulk method, or a slurry method in the presence of a known catalyst such as a Ziegler-Natta catalyst or a metallocene catalyst. can be manufactured.
• a known polymerization method such as a gas phase method, a bulk method, or a slurry method in the presence of a known catalyst such as a Ziegler-Natta catalyst or a metallocene catalyst.
• a known catalyst such as a Ziegler-Natta catalyst or a metallocene catalyst.
• the comonomer content is adjusted to 20 mol % or more and 50 mol % or less.
• a method of controlling the comonomer content to 10 mol % or more and 50 mol % or less can be used, and a copolymer having a target melting point can be obtained by this method.
• the copolymer (C) may be one kind of copolymer or two or more kinds of copolymers.
• the use of a propylene/ ⁇ -olefin copolymer is inexpensive and improves the heat seal strength, but the low temperature sealability and blocking resistance are not sufficient. Therefore, by using it in combination with a relatively expensive 1-butene/ ⁇ -olefin copolymer, the laminate has excellent heat seal strength, low temperature sealability and blocking resistance, and various physical properties and production costs can be reduced. It becomes easy to achieve compatibility with
• Examples of ⁇ -olefins having 2 carbon atoms or 4 to 20 carbon atoms to be copolymerized with propylene include ethylene, 1-butene, 1-pentene, 3-methyl-1-butene, 4-methyl-1-pentene, 1 -hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like.
• the ⁇ -olefin may be used alone or in combination of two or more.
• the copolymer (C) selected from the ⁇ -olefins is specifically a propylene/ethylene copolymer (C1), a propylene/1-butene copolymer (C2), or a propylene/1-pentene copolymer. , propylene/1-hexene copolymer, propylene/3-methyl-1-butene random copolymer, and propylene/4-methyl-1-pentene random copolymer.
• the copolymer (C) contains at least one propylene/ ⁇ -olefin copolymer selected from the group consisting of a propylene/ethylene copolymer (C1) and a propylene/1-butene copolymer (C2). More preferably, it contains a propylene/1-butene copolymer (C2) because it tends to have excellent blocking power.
• the copolymer (C) contains 51 to 99 mol%, preferably 60 to 95 mol%, more preferably 70 to 90 mol% of structural units derived from propylene, and has 2 carbon atoms or 4 to 4 carbon atoms. Contain 1 to 49 mol%, preferably 5 to 40 mol%, more preferably 10 to 30 mol% of 20 ⁇ -olefin-derived structural units (provided that propylene-derived structural units and the ⁇ -olefin-derived structural units The sum with the unit is 100 mol%.). When the content is within the above range, heat sealing is easy and good surface properties are obtained even at a relatively low temperature.
• the copolymer (C) has a melting point measured by DSC of less than 120°C or no melting point observed by DSC. °C or less, more preferably 65°C or more and 95°C or less. By using the copolymer (C) having a melting point within the above range, heat-sealing is easy and good surface properties can be obtained even at a relatively low temperature.
• the melting point (Tm) of the copolymer (C) can be determined, for example, by the same method as the method for measuring the melting point of the copolymer (B) described above.
• the melt flow rate (MFR) of the copolymer (C) measured under conditions of 230° C. and a load of 2.16 kg according to ASTM D1238 is preferably 0.1 to 30 g/10 min, more preferably is 0.5 to 20 g/10 min, more preferably 1.0 to 10 g/10 min.
• the melt flow rate (MFR) measured under the conditions of 190°C and a load of 2.16 kg in accordance with ASTM D1238 is preferably 0.5. 1 to 30 g/10 min, more preferably 0.5 to 20 g/10 min, still more preferably 1.0 to 10 g/10 min.
• the copolymer (C) is obtained by polymerizing a monomer by a known polymerization method such as a gas phase method, a bulk method, or a slurry method in the presence of a known catalyst such as a Ziegler-Natta catalyst or a metallocene catalyst. can be manufactured.
• a known polymerization method such as a gas phase method, a bulk method, or a slurry method in the presence of a known catalyst such as a Ziegler-Natta catalyst or a metallocene catalyst.
• a known catalyst such as a Ziegler-Natta catalyst or a metallocene catalyst.
• the comonomer content is adjusted to 20 mol % or more and 50 mol % or less.
• a method of controlling the comonomer content to 10 mol % or more and 50 mol % or less can be used, and a copolymer having a target melting point can be obtained by this method.
• the resin composition constituting the sealant layer in the present invention contains (co)polymer (A), copolymer (B) and copolymer (C).
• the (co)polymer (A) is 20 to 75% by weight, preferably 23 to 70% by weight, more preferably 25 to 65% by weight, and the copolymer (B) is 20 to 75% by weight.
• copolymer (C) % 75% by weight, preferably 23 to 70% by weight, more preferably 25 to 65% by weight, and 5 to 40% by weight, preferably 7 to 37% by weight, more preferably 10 to 35% by weight of the copolymer (C) % (However, the total content of (co)polymer (A), copolymer (B) and copolymer (C) is 100% by mass.).
• the content of the (co)polymer (A) and the copolymer (B) satisfies the above range, and the content of the (co)polymer (A) is the copolymer (B) is more preferably at least the content of
• the content of the (co)polymer (A) is equal to or greater than the content of the copolymer (B)
• the heat-sealed portion of the laminate tends to be peeled off at the edges, which will be described later.
• the content of the copolymer (B) is equal to or greater than the content of the copolymer (C), and the total content of the copolymer (B) and the copolymer (C) is 25 to 80 % by mass, preferably 30 to 77 mass %, more preferably 35 to 75 mass %.
• the content of each component contained in the resin composition is within the above range, a laminate having excellent low-temperature sealability and sufficient heat seal strength can be produced.
• the sealant layer contains a resin other than the (co)polymers (A) to (C), a tackifier, a weather stabilizer, a heat stabilizer, an antistatic agent, and a slip agent, as long as the objects of the present invention are not impaired. , anti-blocking agents, lubricants, pigments, dyes, plasticizers, anti-aging agents, hydrochloric acid absorbents, antioxidants and the like may be included as necessary.
• the sealant layer may consist of one layer or may consist of a plurality of layers.
• the (co)polymers (A) to (C) used in the resin composition constituting the sealant layer, and the (co)polymers used in the resin composition constituting the base material layer described later are each at least one or more biomass-derived monomers (biomass-derived propylene, biomass-derived ethylene, biomass-derived ⁇ -olefin having 4 to 20 carbon atoms). may contain The same kind of monomers constituting the polymer may be only biomass-derived monomers, may be only fossil fuel-derived monomers, or may contain both biomass-derived monomers and fossil fuel-derived monomers.
• the resin composition constituting the base material layer is polypropylene.
• the polypropylene include homopolymers of propylene and copolymers containing propylene as a main monomer. In the case of a copolymer, it may be a random copolymer or a block copolymer.
• Monomers to be copolymerized with propylene include ⁇ -olefins having 2 carbon atoms or 4 to 20 carbon atoms, diene compounds, and the like.
• the polypropylene contains 85 to 100 mol%, preferably 90 to 99.5 mol%, structural units derived from propylene, and 0 to 15 mol%, preferably 0.5 to 10 mol%, structural units derived from other monomers. Contain mol % (however, the total of structural units derived from propylene and structural units derived from other monomers is 100 mol %).
• Examples of ⁇ -olefins having 2 carbon atoms or 4 to 20 carbon atoms to be copolymerized with propylene include ethylene, 1-butene, 1-pentene, 3-methyl-1-butene, 4-methyl-1-pentene, 1 -hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene and the like.
• the ⁇ -olefin may be used alone or in combination of two or more.
• the melt flow rate (MFR) of the polypropylene is measured according to ASTM D1238 under conditions of 230° C. and a load of 2.16 kg, preferably 0.01 to 400 g/10 min, more preferably 0.1 to 100 g/10 min. and a melting point (Tm) of preferably 115 to 175°C, more preferably 120 to 170°C.
• polypropylene examples include propylene homocopolymer, propylene/ethylene random copolymer, propylene/1-butene random copolymer, propylene/1-butene/ethylene random copolymer, propylene/1- Hexene random copolymers, propylene/3-methyl-1-butene random copolymers, propylene/4-methyl-1-pentene random copolymers and the like can be mentioned.
• the polypropylene can be used singly or in combination of two or more.
• the polypropylene can be produced by polymerizing a monomer by a known polymerization method such as a gas phase method, a bulk method, or a slurry method in the presence of a known catalyst such as a Ziegler-Natta catalyst or a metallocene catalyst. .
• the polypropylene contained in the resin composition constituting the base material layer is preferably the propylene-based polymer (A) contained in the resin composition constituting the sealant layer.
• the type of the (co)polymer (A) is used in the resin composition constituting the sealant layer ( It may be the same as or different from the co)polymer (A).
• the base material layer contains a resin other than polypropylene, a tackifier, a weather stabilizer, a heat stabilizer, an antistatic agent, a slip agent, an antiblocking agent, a lubricant, a pigment, a dye, a Additives such as plasticizers, anti-aging agents, hydrochloric acid absorbents, and antioxidants may be included.
• the substrate layer may consist of one layer or may consist of a plurality of layers.
• the unstretched film of the present invention is obtained by laminating a sealant layer and a substrate layer. For example, using two extruders to which a T-die is connected, the resin composition constituting the sealant layer described above and the resin composition constituting the base layer are supplied to the respective extruders, and co-extruded. It can be produced by
• the thickness of the sealant layer is usually 3-30 ⁇ m, preferably 5-25 ⁇ m, and the thickness of the base layer is usually 10-100 ⁇ m, preferably 20-75 ⁇ m. When there are a plurality of sealant layers and substrate layers, the thickness of each sealant layer is preferably within the above range.
• the thickness of the entire unstretched film of the present invention is usually 13-130 ⁇ m, preferably 25-100 ⁇ m.
• the laminate of the present invention has the unstretched film and stretched film described above.
• Examples of the aspect of the laminate include, but are not limited to, structures such as unstretched film/stretched film and unstretched film/stretched film/stretched film.
• an adhesive layer may optionally be provided between the unstretched film and the stretched film.
• the substrate layer contained in the unstretched film is adjacent to the stretched film or in contact with the stretched film via an adhesive layer.
• ⁇ Stretched film> Conventionally known films can be employed as the film constituting the stretched film according to the application. Specific examples thereof include polyester films such as polyethylene terephthalate and polyethylene naphthalate, polyethylene carbonate films, polyamide films such as nylon 6 and nylon 66, ethylene-vinyl alcohol copolymer films, polyvinylidene chloride films, and polypropylene. films made of polyolefins such as The stretched film composed of the above films may be used singly or in combination of two or more. Moreover, the film may be a film in which an inorganic substance such as aluminum, zinc, silica, or an oxide thereof is vapor-deposited.
• a stretched PET film obtained by stretching a film formed from polyethylene terephthalate (PET) and a stretched PP film obtained by stretching a film formed from polypropylene (PP).
• PET polyethylene terephthalate
• PP polypropylene
• a stretching method a known method for producing a stretched film can be used. Specific examples include roll stretching, tenter stretching, tubular stretching, and the like.
• the draw ratio is usually 1.5 to 20 times, preferably 2 to 15 times.
• the thickness of the stretched film is usually 10 to 50 ⁇ m, preferably 15 to 45 ⁇ m. When there are a plurality of stretched films, the thickness of each stretched film is preferably within the above range.
• the thickness of the laminate of the present invention as a whole is usually 30-150 ⁇ m, preferably 40-115 ⁇ m.
• the laminate of the present invention has excellent low-temperature sealability and sufficient heat seal strength. This heat seal strength is obtained by superimposing the sealant layer surfaces of two identical laminates, setting the temperature of the lower seal bar to 70 ° C., and the temperature of the upper seal bar to 70 ° C., 80 ° C., 90 ° C., 100 ° C.
• Excellent low-temperature sealability means the maximum value of the heat seal strength of the laminate in the temperature range of 70 ° C. or higher and 120 ° C. or lower. is 8 N/15 mm or more, preferably 9 N/15 mm or more, and more preferably 10 N/15 mm or more.
• the upper limit of the maximum heat seal strength in the temperature range of 70°C or higher and 120°C or lower is usually 50 N/15 mm.
• the maximum value of the heat seal strength of the laminate in the temperature range of 70° C. or higher and 120° C. or lower is 8 N/15 mm or more, heat sealing at a low temperature is possible and high-speed filling is also possible.
• Having sufficient heat seal strength means the maximum value of the heat seal strength of the laminate in the temperature range of 70 ° C. or higher and 200 ° C. or lower, that is, in the measurement of the heat seal strength described above, the temperature of the upper seal bar is set to 70 to 70 ° C.
• the maximum value of the heat seal strength of each test piece produced by changing within the range of 200 ° C. is preferably 15 N / 15 mm or more, more preferably 20 N / 15 mm or more, further preferably 25 N / 15 mm or more. and particularly preferably 30 N/15 mm or more.
• the upper limit of the maximum heat seal strength in the temperature range of 70°C or higher and 200°C or lower is usually 100 N/15 mm.
• the maximum value of the heat seal strength of the laminate in the temperature range of 70° C. or higher and 200° C. or lower is 15 N/15 mm or more, the adhesion of the sealed portion is excellent and heavy objects can be filled.
• the two laminated bodies that are sealed are peeled in the form of edge breakage, cohesive peeling, or the like, or film breakage, tearing of the film, etc. .
• the heat seal strength shows a value of 30 N/15 mm or more for the first time in the heat seal strength measurement in the temperature range of 70 ° C. or higher and 200 ° C. or lower, that is, the heat seal strength in the heat seal strength measurement described above Among the test pieces with a temperature of 30 N / 15 nm or more, in the test piece with the lowest temperature of the upper seal bar at the time of test piece preparation, the heat-sealed part of the laminate peeled off, and the peeled shape was edge cut.
• the heat seal strength shows a value of 30 N/15 mm or more for the first time in the heat seal strength measurement in the temperature range of 70 ° C. or higher and 200 ° C. or lower, that is, the heat seal strength in the heat seal strength measurement described above Among the test pieces with a temperature of 30 N / 15
• the laminate of the present invention may also be excellent in blocking resistance.
• the blocking force is within the above range, blocking during storage can be effectively prevented.
• a method for measuring the blocking force is described in detail in Examples.
• the laminate of the present invention may be produced by laminating a non-stretched film and a stretched film by dry lamination, non-solvent lamination, sand lamination, or the like, or by laminating a non-stretched film and a stretched film by melt extrusion lamination.
• a method of laminating by dry lamination or melt extrusion lamination is preferable.
• the laminate of the present invention may further have at least one functional layer selected from a print layer, a barrier layer and an embossed layer in order to impart a specific function to the sealant layer, base layer and stretched film.
• the functional layer is adjacent to or adheres to at least one layer or film selected from the sealant layer, base layer and stretched film. It is preferable that they are in contact with each other through the agent layer.
• a resin film on which an inorganic compound or an inorganic oxide is vapor-deposited, a metal foil, a coating film of a resin having a special function, a resin film on which a pattern is printed, or the like can be used.
• the resin film used it is possible to use a resin film similar to the resin film used for the base film, and furthermore, similar plastic compounding agents and additives may be used to improve other performance. It can also be added in an arbitrary amount depending on the purpose within a range that does not give adverse effects.
• the resin film for example, one or two or more resins selected from the same group of resins as the resin for the base film are used, and extrusion method, cast molding method, T-die method, cutting method, inflation method, etc. It can be produced by a conventionally used film-forming method, or by a multi-layer co-extrusion film-forming method using two or more resins. Furthermore, from the viewpoint of film strength, dimensional stability, and heat resistance, the film can be stretched uniaxially or biaxially using, for example, a tenter method or a tubular method.
• a laminate further comprising a barrier layer can be obtained by forming the barrier layer as one layer in the sealant layer, base layer or stretched film by metal deposition, coating or co-extrusion, and It can be produced by a method similar to the method for producing a laminate including the step of laminating a stretched film.
• the laminate of the present invention has excellent low-temperature sealability and high heat-seal strength. Furthermore, it tends to be excellent in blocking resistance and peeling appearance of the heat-sealed portion.
• a package can be obtained from the laminate of the present invention.
• a package formed from the laminate of the present invention is excellent in low-temperature sealability.
• the package formed by the laminate of the present invention obtained in this way has the same heat seal strength as the conventional product when molded at the conventional heat seal temperature (for example, over 100 ° C. to 160 ° C.). more can be maintained.
• the sealant layers of the laminate are opposed to each other, or the sealant layers of the laminate are opposed to another film, and then at least part of the periphery is heated from the outer surface side so that the desired container shape is obtained.
• a package can be produced by sealing. Also, by heat-sealing the entire periphery, a hermetically sealed package can be produced. When this package forming process is combined with the content filling step, the bottom and sides of the package are heat-sealed, the content is filled, and then the top is heat-sealed to form the content-filled package. can be manufactured.
• This package can be used in an automatic packaging device for solids, powders, or liquid materials such as snacks and bread.
• the laminate or a sheet comprising the laminate may be used as a cup-shaped container formed in advance by vacuum forming, pressure forming, etc., a container obtained by injection molding, or a container formed from a paper base material.
• a container in which the contents are packaged is obtained by filling the contents, covering the laminate with the laminate of the present invention as a lid material, and heat-sealing the top or side of the container.
• This container is suitable for packaging instant noodles, miso, jelly, pudding, snacks, and the like.
• the laminate or package When the laminate or package has a monomaterial structure, it can be effectively used as a recycled product.
• a molded article that is a recycled product of the laminate or package makes it possible to reduce the amount of newly polymerized plastic used, and is an article that can contribute to the reduction of environmental load.
• A Propylene-based polymer rPP
• A-1 random polypropylene (MFR (230°C, 2.16 kg load, conforming to ASTM D1238): 7 g/10 min, melting point: 138°C, propylene content: 95 mol%, ethylene content: 2 mol%, 1-butene content: 3 mol%)
• B 1-butene/ ⁇ -olefin copolymer
• BPR (B-1) 1-butene/propylene copolymer (MFR (230°C, 2.16 kg load, according to ASTM D1238): 9 g/10 min, MFR (190° C., 2.16 kg load, according to ASTM D1238): 4 g/10 min, melting point: 100° C., 1-butene content: 87 mol %, propylene content: 13 mol %)
• the melting point, heat seal strength, and blocking force of each (co)polymer were measured by the following measurement methods.
• the temperature of the upper seal bar at the time of manufacturing the test body when the heat seal strength first showed 30 N / 15 mm or more was the temperature when manufacturing the test body in which edge breakage or cohesive peeling occurred in the evaluation of peel appearance described later.
• the heat seal strength was not measured for the specimens that were above the temperature of the top seal bar.
• the upper limit of the temperature of the upper seal bar in this test was set to 180°C, and the heat seal strength was not measured for the test pieces whose heat seal strength did not exceed 30 N/15 mm up to 180°C.
• the low-temperature sealability of the laminate was evaluated according to the following criteria. ⁇ : The maximum value of heat seal strength in the temperature range of 70 ° C. or higher and 120 ° C. or lower is 8 N / 15 mm or more ⁇ : The maximum value of heat seal strength in the temperature range of 70 ° C. or higher and 120 ° C. or lower is less than 8 N / 15 mm
• the maximum heat seal strength of the laminate was evaluated according to the following criteria. ⁇ : The maximum value of heat seal strength in the temperature range of 70 ° C. or higher and 200 ° C. or lower is 30 N / 15 mm or more ⁇ : The maximum value of heat seal strength in the temperature range of 70 ° C. or higher and 200 ° C. or lower is less than 30 N / 15 mm
• the laminate is made into a strip with a width of 200 mm, the sealant surfaces of the two strip-shaped laminates are overlapped, placed in an air oven at 50 ° C., and a load of 20 kg is applied from above the overlapped laminate for 3 days. bottom. After that, the laminate was taken out from the air oven, and the strength when the two strip-shaped laminates were peeled off at a rate of 200 mm/min in the direction of 180° to the laminate surface was measured, and the numerical value was defined as the blocking force. .
• Blocking force The blocking force of the laminate was evaluated according to the following criteria. ⁇ : Blocking force is less than 10 N/m ⁇ : Blocking force is 10 N/m or more
• Example 1 60 parts by mass of rPP (A-1), 30 parts by mass of BPR (B-1) and 10 parts by mass of BPR (C2-1) were blended to prepare a resin composition for producing a sealant layer. Furthermore, 1000 ppm of erucic acid amide as a slip agent and 1200 ppm of silica (particle size: 3 ⁇ m) as an anti-blocking agent were added to the resin composition and blended.
• the resin composition for producing the sealant layer to which the additive is added and the rPP (A-1) for producing the base layer are supplied to each extruder. Then, the die and resin temperature are set to 230 ° C., the extrusion rate of each extruder is adjusted, and a non-stretched base layer with a thickness of 50 ⁇ m and a non-stretched sealant layer with a thickness of 20 ⁇ m are formed by co-extrusion molding. A laminated unstretched film was produced.
• a 25 ⁇ m-thick stretched PET film (manufactured by Toray Industries, Inc.) was laminated on the substrate layer surface of the obtained non-stretched film via an adhesive layer by a dry lamination method to produce a laminate.
• the low-temperature sealability, maximum heat seal strength, peel appearance, and blocking force were determined by the above-described measurement methods. Table 1 shows the results.
• Examples 2 to 12, Comparative Examples 1 to 4 Laminate in the same manner as in Example 1 except that the composition of the resin composition for producing the sealant layer was changed to the composition shown in Table 1, or the stretched PP film (manufactured by Mitsui Chemicals Tohcello) was used as the stretched film. manufactured. Using each of these laminates, low-temperature sealability, maximum heat seal strength, peel appearance, and blocking force were determined by the above-described measurement methods. Table 1 shows the results.

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• 2023
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