Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • 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
  • B32B7/02—Physical, chemical or physicochemical properties
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  • 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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  • 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
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  • 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
  • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
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  • 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
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  • 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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  • 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
  • B32B7/02—Physical, chemical or physicochemical properties
  • B32B7/022—Mechanical properties
• • 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
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/20—Carboxylic acid amides
• • 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
  • 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
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  • 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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  • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
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  • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
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• • B—PERFORMING OPERATIONS; TRANSPORTING
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• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B32B2307/00—Properties of the layers or laminate
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• • B—PERFORMING OPERATIONS; TRANSPORTING
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• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B32B2307/00—Properties of the layers or laminate
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  • B32B2307/746—Slipping, anti-blocking, low friction
• • B—PERFORMING OPERATIONS; TRANSPORTING
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• • B—PERFORMING OPERATIONS; TRANSPORTING
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• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B32B2323/16—EPDM, i.e. ethylene propylene diene monomer
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B32B2439/00—Containers; Receptacles
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• • B—PERFORMING OPERATIONS; TRANSPORTING
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• • B—PERFORMING OPERATIONS; TRANSPORTING
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• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B32B2439/80—Medical packaging

Definitions

• the present invention relates to a laminated sealant film having excellent bag-making properties, low-temperature bag-making properties, and excellent sealing strength.
• Packaging materials have been developed to suit the contents of many products such as food, beverages, pharmaceuticals, and chemicals. Packaging materials are used in various forms such as pillow packaging, gusset packaging, and three-side seal packaging, and sealant films used in packaging materials also have functions required according to their uses.
• the sealant film is better if it can be heat-sealed at a lower temperature, but it is particularly suitable for automatically forming pillow packaging bags, gusset packaging bags, or 3-sided seal packaging bags while packaging the contents, reducing electricity costs. It also reduces the risk of burns and improves workability. It also leads to faster packaging and bag-making speeds and less loss of packaging materials. In addition, the finish of the packaging bag is also improved. However, the sealant film is originally required to have various functions such as smooth packaging and bag-making process, sealing performance of the resulting packaging bag, and good sealing strength.
• the seal strength is sufficient even if the resin of the sealant film is in a molten state immediately after heat sealing, and it is a heavy item. It is required that the sealed portion does not peel off even with the impact caused by the pressure generated when the contents are filled into the bag.
• the sealing strength is sufficient even if the resin of the sealant film is in a molten state, and the high-pressure (nitrogen flush) gas seal when filling the bag with gas. is required not to peel off.
• No conventional sealant film satisfies all requirements for bag-making properties, low-temperature bag-making properties, and heat-sealing strength (see, for example, Patent Documents 1 to 5, etc.).
• An object of the present invention is to provide a sealant film containing a propylene-based resin and a polyethylene-based resin, which has excellent low-temperature bag-making properties and heat seal strength.
• the present invention was able to obtain a laminated sealant film having excellent low-temperature bag-making properties and seal strength by controlling the raw material composition of each layer of the laminated sealant film. . That is, the laminated sealant film according to the present invention has the following constitution.
• a laminated sealant film that satisfies all of the following 1) to 8).
• a laminated sealant film comprising at least a laminate layer and a seal layer.
• the laminate layer is made of a resin composition containing a polypropylene-based resin as a main component.
• the seal layer is made of a resin composition containing a mixture of polypropylene-based resin and polyethylene-based resin as a main component.
• the polyethylene-based resin constituting the seal layer contains 90% by weight or more of linear polyethylene resin.
• the melting point difference between the polypropylene-based resin and the linear polyethylene resin of the sealing layer is 15°C or more.
• the ratio of the melt flow rate of the polypropylene-based resin to the melt flow rate of the linear polyethylene resin of the seal layer is 0.5 or more and 2.0 or less.
• the melt flow rate of the polypropylene resin and linear polyethylene resin of the seal layer is 9 g/10 minutes or less.
• the laminated sealant film of the present invention has excellent low-temperature bag-making properties, it is suitable as a packaging material for many products such as foods, beverages, pharmaceuticals, and chemicals. In particular, it is suitable for automatically forming a pillow packaging bag, a gusset packaging bag, or a three-sided seal packaging bag while packaging the contents.
• the laminated sealant film of the present invention includes at least a laminate layer and a seal layer. Laminate layers and seal layers are discussed in more detail below.
• the seal layer in the present invention is made of a resin composition containing a mixture of polypropylene-based resin and polyethylene-based resin as a main component.
• the "main component” means that the ratio of the mixture of polypropylene resin and polyethylene resin in the resin composition is 90% by mass or more, but it is more preferably 95% by weight or more. It is more preferably 97% by weight or more, and even more preferably 99% by weight or more.
• the polypropylene-based resin in the sealing layer is a resin containing propylene as a main component.
• examples include random copolymers and block copolymers with ⁇ -olefins such as pentene-1 and octene-1.
• the "main component” means that the proportion of propylene in the polypropylene resin is 90% by mass or more, more preferably 95% by weight or more, further preferably 97% by weight or more, and 99% by weight or more. is even more preferable.
• the polypropylene resin constituting the seal layer preferably has a melt flow rate of 0.1 g/10 minutes or more and 9 g/10 minutes or less, and 0.5 g/10 minutes or more and 8 g/10 minutes or less. is more preferable, and 1 g/10 minutes or more and 7 g/10 minutes or less is even more preferable.
• the polypropylene resin constituting the seal layer preferably has a melting point of 120° C. or higher, more preferably 125° C. or higher and 150° C. or lower, and even more preferably 130° C. or higher and 140° C. or lower. .
• the polypropylene-based resin is contained in an amount of 1% by weight or more and 90% by weight or less, more preferably 5% by weight or more and 90% by weight or less, based on 100% by weight of the mixture of the polypropylene-based resin and the polyethylene-based resin that constitute the sealing layer. preferable.
• the polypropylene-based resin is 1% by weight or more, the slipperiness is excellent, and the achieved heat-sealing strength is less likely to vary.
• the polyethylene-based resin in the seal layer is mainly composed of linear low-density polyethylene.
• linear low-density polyethylene for example, at least one ethylene homopolymer selected from the group consisting of high-pressure low-density polyethylene, medium-density polyethylene and high-density polyethylene can be used.
• ethylene other ⁇ -olefins such as propylene, butene-1, pentene-1, hexene-1, 3-methylbutene-1, 4-methylpentene-1, octene-1, vinyl acetate, (meth ) Random or block copolymers obtained by copolymerizing monomers such as acrylic acid and (meth)acrylic acid esters, or mixtures thereof can be used. They may be crystalline, poorly crystalline or amorphous.
• the polyethylene resin constituting the seal layer has a melt flow rate of 0.1 to 9 g/10 minutes, preferably 0.5 to 8 g/10 minutes, more preferably 1 to 7 g/10 minutes.
• the polyethylene resin constituting the seal layer has a melting point of 100 to 140°C, preferably 105 to 135°C, more preferably 110 to 130°C.
• the polyethylene resin constituting the seal layer preferably contains linear polyethylene resin in an amount of 90% by weight or more, more preferably 95% by weight or more, still more preferably 97% by weight or more, and even more preferably 99% by weight or more. .
• the difference in melting point between the polypropylene-based resin and the polyethylene-based resin constituting the seal layer is preferably 15°C or higher, more preferably 16°C or higher, even more preferably 17°C or higher, even more preferably 18°C or higher, and 19°C. The above are particularly preferred.
• the arithmetic mean melting point of the polypropylene-based resin and the polyethylene-based resin constituting the sealing layer is preferably 100°C or higher, more preferably 112°C or higher, even more preferably 115°C or higher, even more preferably 116°C or higher, and 121 °C or higher is particularly preferred.
• the boiling suitability as a packaging material is further improved.
• the suitability for retort is further improved, and when the temperature is 121°C or higher, the suitability for high retort is further improved.
• Antiblocking agents in the resin composition in the seal layer include inorganic particles such as synthetic silica, diatomaceous earth, talc and mica, and organic particles such as silicone particles, acrylic particles, nylon particles and polyethylene particles.
• the average particle size of the particles used in the present invention is preferably 2 ⁇ m or more, more preferably 3 ⁇ m or more, and even more preferably 5 ⁇ m or more.
• the average particle size is preferably 20 ⁇ m or less, more preferably 15 ⁇ m or less, and even more preferably 10 ⁇ m or less.
• the content of the particles in the resin composition in the seal layer is preferably 0.1% by weight or more, more preferably 0.3% by weight or more, and more preferably 0.4% by weight or more relative to the seal layer of the film. More preferred. Also, it is preferably 2% by weight or less, more preferably 1.5% by weight or less, and even more preferably 1.0% by weight or less. If the amount of particles added is less than 0.1% by weight, it becomes difficult to make the surface roughness Ra of at least one surface layer 0.1 ⁇ m or more, making it difficult to obtain antiblocking properties and slipperiness. On the other hand, if the amount of particles added is more than 2% by weight, the number of protrusions on the surface increases, resulting in poor appearance and poor scratch resistance.
• the resin composition in the sealing layer preferably contains 0.01 to 2.0% by weight, more preferably 0.05 to 1.5% by weight, more preferably 0.1 to 1.0% by weight of fatty acid amide as an organic lubricant. 0% by weight is particularly preferred. If the fatty acid amide content is less than 0.01%, blocking between films will be strong, and the handleability of the film will not be satisfied. At 2.0% or more, the seal strength decreases.
• fatty acid amides include erucic acid amide, ethylenebisoleic acid amide, and behenic acid amide, and these may be used in combination.
• the melt flow rate ratio of the raw material resins mixed in the sealing layer is preferably 0.5 or more and 2.0 or less, more preferably 0.8 or more and 1.8 or less, and 1.0 or more and 1.6 or less. More preferred. When the melt flow rate ratio is within this range, it is difficult to cause layer misalignment and appearance defects called mela and unevenness.
• the laminate layer in the present invention is made of a resin composition containing a polypropylene-based resin as a main component.
• the "main component” means that the proportion of the polypropylene resin in the resin composition is 90% by mass or more, more preferably 95% by weight or more, further preferably 97% by weight or more, and 99% by weight. % or more is even more preferable.
• the polypropylene-based resin in the laminate layer is a resin containing propylene as a main component, such as propylene homopolymer, propylene and ethylene, butene-1, pentene-1, hexene-1,3-methylbutene-1,4-methyl Examples include random copolymers and block copolymers with ⁇ -olefins such as pentene-1 and octene-1.
• random copolymers of propylene and ⁇ -olefins such as ethylene, butene-1, pentene-1, hexene-1, 3-methylbutene-1, 4-methylpentene-1, and octene-1, and/or Block copolymers are preferred.
• the "main component” means that the proportion of propylene in the polypropylene resin is 90% by mass or more, more preferably 95% by weight or more, further preferably 97% by weight or more, and 99% by weight or more. is even more preferable.
• the polypropylene resin constituting the laminate layer preferably has a melt flow rate (JIS K7112) of 0.1 g/10 minutes or more and 9 g/10 minutes or less, and 0.5 g/10 minutes or more and 8 g/10 minutes. It is more preferably 1 g/10 minutes or more and 7 g/10 minutes or less.
• the polypropylene resin constituting the laminate layer preferably has a melting point (JIS K7121) of 120° C. or higher and 160° C. or lower, more preferably 125° C. or higher and 155° C. or lower, and 130° C. or higher and 150° C. The following are even more preferable.
• the polypropylene-based resin that constitutes the laminate layer is a resin containing propylene as a main component.
• -Random copolymers and block copolymers with ⁇ -olefins such as methylpentene-1 and octene-1.
• random copolymers of propylene and ethylene and/or butene-1 are preferred.
• the resin composition of the laminate layer is a polypropylene-based resin, and at least one ethylene homopolymer selected from the group consisting of, for example, high-pressure low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, and high-density polyethylene.
• ethylene other ⁇ -olefins such as propylene, butene-1, pentene-1, hexene-1, 3-methylbutene-1, 4-methylpentene-1, octene-1, vinyl acetate, (meth ) Random or block copolymers obtained by copolymerizing monomers such as acrylic acid and (meth)acrylic acid esters, or mixtures thereof can be used. They may be crystalline, poorly crystalline or amorphous.
• the polyethylene resin constituting the laminate layer preferably has a melt flow rate (JIS K7112) of 0.1 g/10 minutes or more and 9 g/10 minutes or less, and 0.5 g/10 minutes or more and 8 g/10 minutes. It is more preferably 1 g/10 minutes or more and 7 g/10 minutes or less.
• the polyethylene resin constituting the laminate layer preferably has a melting point (JIS K7121) of 100°C or higher and 140°C or lower, more preferably 105°C or higher and 135°C or lower, and 110°C or higher and 130°C. It is even more preferable to have the following.
• the melting point of the polyethylene-based resin may show two or more melting endothermic peaks, and the peak with the largest melting endothermic amount was taken as the main peak.
• Anti-blocking agents in the resin composition in the laminate layer include synthetic silica, diatomaceous earth, inorganic particles such as talc and mica, and organic particles such as silicone particles, acrylic particles, nylon particles and polyethylene particles.
• the average particle size of the particles used in the present invention is preferably 2 ⁇ m or more, more preferably 3 ⁇ m or more, and even more preferably 5 ⁇ m or more.
• the average particle size is preferably 20 ⁇ m or less, more preferably 15 ⁇ m or less, and even more preferably 10 ⁇ m or less.
• the content of the particles in the resin composition in the laminate layer is preferably 0.1% by weight or more, more preferably 0.3% by weight or more, and more preferably 0.4% by weight or more relative to the seal layer of the film. More preferred. Also, it is preferably 2% by weight or less, more preferably 1.5% by weight or less, and even more preferably 1.0% by weight or less. If the amount of particles added is less than 0.1% by weight, it becomes difficult to make the surface roughness Ra of at least one surface layer 0.1 ⁇ m or more, making it difficult to obtain antiblocking properties and slipperiness. On the other hand, if the amount of particles added is more than 2% by weight, the number of protrusions on the surface increases, resulting in poor appearance and poor scratch resistance.
• the resin composition in the laminate layer preferably contains 0.01 to 2.0% by weight of fatty acid amide, which is an organic lubricant, more preferably 0.05 to 1.5% by weight, and 0.1 to 1% by weight. 0% by weight is particularly preferred. If the fatty acid amide content is less than 0.01%, blocking between films will be strong, and the handleability of the film will not be satisfied. At 2.0% or more, the seal strength decreases.
• fatty acid amides include erucic acid amide, ethylenebisoleic acid amide, and behenic acid amide, and these may be used in combination.
• the melt flow rate ratio of the raw material resins mixed in the sealing layer is preferably 0.5 or more and 2.0 or less, more preferably 0.8 or more and 1.8 or less, and 1.0 or more and 1.6 or less. More preferred. When the melt flow rate ratio is within this range, it is difficult to cause layer misalignment and appearance defects called mela and unevenness.
• the laminated sealant film of the present invention may include an intermediate layer between the laminate layer and the seal layer.
• the intermediate layer in the present invention is made of a resin composition containing a polypropylene-based resin as a main component.
• the "main component” means that the proportion of the polypropylene resin in the resin composition is 90% by mass or more, more preferably 95% by weight or more, further preferably 97% by weight or more, and 99% by weight. % or more is even more preferable.
• the polypropylene-based resin in the intermediate layer is a resin containing propylene as a main component.
• examples include random copolymers and block copolymers with ⁇ -olefins such as pentene-1 and octene-1.
• random copolymers of propylene and ⁇ -olefins such as ethylene, butene-1, pentene-1, hexene-1, 3-methylbutene-1, 4-methylpentene-1 and octene-1 are preferred.
• the "main component” means that the proportion of propylene in the polypropylene resin is 90% by mass or more, more preferably 95% by weight or more, further preferably 97% by weight or more, and 99% by weight or more. is even more preferable.
• the polypropylene resin constituting the intermediate layer preferably has a melt flow rate of 0.1 g/10 minutes or more and 9 g/10 minutes or less, and 0.5 g/10 minutes or more and 8 g/10 minutes or less. is more preferable, and 1 g/10 minutes or more and 7 g/10 minutes or less is even more preferable.
• the polypropylene resin constituting the intermediate layer preferably has a melting point of 120° C. or higher and 160° C. or lower, more preferably 125° C. or higher and 150° C. or lower, and preferably 130° C. or higher and 140° C. Even more preferable.
• the polypropylene-based resin constituting the intermediate layer is a resin containing propylene as a main component.
• -Random copolymers and block copolymers with ⁇ -olefins such as methylpentene-1 and octene-1.
• random copolymers of propylene and ethylene and/or butene-1 are preferred.
• the resin composition of the intermediate layer is a polypropylene-based resin, and at least one ethylene homopolymer selected from the group consisting of high-pressure low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, and high-density polyethylene.
• ethylene other ⁇ -olefins such as propylene, butene-1, pentene-1, hexene-1, 3-methylbutene-1, 4-methylpentene-1, octene-1, vinyl acetate, (meth )
• Random or block copolymers obtained by copolymerizing monomers such as acrylic acid and (meth)acrylic acid esters, or mixtures thereof can be used. They may be crystalline, poorly crystalline or amorphous.
• the polyethylene resin constituting the intermediate layer preferably has a melt flow rate of 0.1 g/10 minutes or more and 9 g/10 minutes or less, and 0.5 g/10 minutes or more and 8 g/10 minutes or less. is more preferable, and 1 g/10 minutes or more and 7 g/10 minutes or less is even more preferable.
• the polyethylene resin constituting the intermediate layer preferably has a melting point of 100° C. or higher and 140° C. or lower, more preferably 105° C. or higher and 135° C. or lower, and 110° C. or higher and 130° C. or lower. is even more preferable.
• the resin composition in the intermediate layer may contain an anti-blocking agent, including synthetic silica, diatomaceous earth, inorganic particles such as talc and mica, and organic particles such as silicone particles, acrylic particles, nylon particles and polyethylene particles.
• the average particle size of the particles used in the present invention is preferably 2 ⁇ m or more, more preferably 3 ⁇ m or more, and even more preferably 5 ⁇ m or more.
• the average particle size is preferably 20 ⁇ m or less, more preferably 15 ⁇ m or less, and even more preferably 10 ⁇ m or less.
• the content of the particles in the resin composition in the intermediate layer is preferably 0.1% by weight or more, more preferably 0.3% by weight or more, and more preferably 0.4% by weight or more relative to the sealing layer of the film. More preferred. Also, it is preferably 2% by weight or less, more preferably 1.5% by weight or less, and even more preferably 1.0% by weight or less.
• the resin composition in the intermediate layer preferably contains 0.01 to 2.0% by weight, more preferably 0.05 to 1.5% by weight, more preferably 0.1 to 1.0% by weight of fatty acid amide as an organic lubricant. 0% by weight is particularly preferred. If the fatty acid amide content is less than 0.01%, blocking between films will be strong, and the handleability of the film will not be satisfied. At 2.0% or more, the seal strength decreases.
• fatty acid amides include erucic acid amide, ethylenebisoleic acid amide, and behenic acid amide, and these may be used in combination.
• the melt flow rate ratio of the raw material resins mixed in the sealing layer is preferably 0.5 or more and 2.0 or less, more preferably 0.8 or more and 1.8 or less, and 1.0 or more and 1.6 or less. More preferred. When the melt flow rate ratio is within this range, it is difficult to cause layer misalignment and appearance defects called mela and unevenness.
• the layer structure of the laminated sealant film of the present invention includes laminate layer/seal layer, laminate layer/intermediate layer/seal layer, and laminate layer/intermediate layer 1/intermediate layer 2/seal layer. It is preferable to provide an intermediate layer between the laminate layer and the seal layer in terms of preventing separation between the laminate layer and the seal layer and facilitating the use of recycled raw materials. In order to prevent separation between layers, it is preferable to use a raw material composition that is intermediate between the laminate layer and the sealing layer.
• the ratio of the melt flow rates of the raw material resins of adjacent layers is preferably 0.5 to 2.0. When the melt flow rate ratio is within this range, it is difficult to cause layer slippage and appearance defects called mela and unevenness.
• the main peak of the melting point of the laminated sealant film of the present invention is preferably 121° C. or higher, more preferably 130° C. or higher, even more preferably 140° C. or higher, and 150° C. or higher. Even more preferably, it is particularly preferably 160° C. or higher. When the main peak of the melting point of the film is 121° C. or higher, the suitability for high retort is further improved.
• the resin composition of the laminate layer and the sealing layer is blended with the above-described resin raw materials and various additives as necessary in a mixer such as a Henschel mixer, a Banbury mixer, a tumbler mixer, etc., and then extruded with a single- or twin-screw extruder.
• a mixer such as a Henschel mixer, a Banbury mixer, a tumbler mixer, etc.
• extruded with a single- or twin-screw extruder can be used for film forming in the form of pellets, but it is also possible to blend the above components and supply them to a film forming machine.
• the mixed resin composition is melted, for example, at a resin temperature of 110 to 300° C., melt-extruded into a sheet through a T-shaped die, cast on a cooling roll, and cooled to solidify to obtain an unstretched sheet.
• a multi-layering device such as a multi-layer feed block, static mixer, multi-manifold die, etc. can be used for multi-layering.
• resins sent out from different flow paths using two or more extruders are laminated in multiple layers using a multi-layer feed block or a multi-manifold die. Examples include a method of extruding a melt-kneaded laminated resin composition sheet into a film by a T-die method or an inflation method, but the T-die method is particularly desirable in that the melting temperature of the resin can be increased.
• the lower limit of the chill roll temperature is preferably 10°C. If it is less than the above, not only the effect of suppressing crystallization may be saturated, but also problems such as dew condensation occur, which is not preferable.
• the upper limit of the cooling roll temperature is preferably 70°C or less. If the above is exceeded, crystallization proceeds and the transparency deteriorates, which is not preferable.
• the temperature of the cooling roll is set within the above range, it is preferable to lower the humidity of the environment around the cooling roll in order to prevent dew condensation.
• the thickness of the unstretched sheet is preferably in the range of 3 ⁇ m or more and 200 ⁇ m or less.
• the thickness of the film is preferably 5 ⁇ m or more and 100 ⁇ m or less, more preferably 10 ⁇ m or more and 80 ⁇ m or less.
• the "longitudinal direction" in the laminated sealant film of the present invention is the direction corresponding to the flow direction in the film manufacturing process, and the “width direction” is the direction perpendicular to the flow direction in the film manufacturing process.
• “longitudinal direction” may be abbreviated as “MD direction” and “width direction” as “TD direction”.
• the laminated sealant film of the present invention is required to have general homogeneity and excellent appearance.
• the thickness variation is small, there are few fish eyes, foreign substances, streaks and scratches, there are few color unevenness and wrinkles, and there are no pinholes.
• the number of detected foreign substances of less than 2 mm square is less than 100 per 10000 m 2 , and more preferably that foreign substances of 1 mm square or larger are not detected.
• the haze of the laminated sealant film of the present invention is preferably 10% or less, more preferably 9% or less, even more preferably 8% or less, still more preferably 7% or less, and particularly preferably 5% or less. If the haze exceeds 10%, the film often has streaks and scratches, and it becomes difficult to visually recognize the contents.
• the haze of the laminated sealant film of the present invention is preferably 1% or more, more preferably 2% or more, and even more preferably 3% or more. When the haze is 1% or more, the blocking strength is less likely to decrease.
• the coefficient of static friction of the laminated sealant film of the present invention is preferably 2.0 or less, more preferably 1.0 or less, even more preferably 0.5 or less between the sealing surfaces when the load is 0.5 kgf. When the coefficient of static friction is 2.0 or more, the slipping property between the films becomes insufficient, and the handleability as a packaging material is not satisfied.
• the static friction coefficient of the laminated sealant film of the present invention is preferably 2.0 or less, more preferably 1.0 or less, even more preferably 0.5 or less between the sealing surfaces when the load is 1.5 kgf. When the coefficient of static friction is 2.0 or more, the slipping property between the films becomes insufficient, and the handleability as a packaging material is not satisfied.
• the dynamic friction coefficient of the laminated sealant film of the present invention is preferably 2.0 or less, more preferably 1.0 or less, and even more preferably 0.5 or less between the sealing surfaces when the load is 0.5 kgf. When the coefficient of dynamic friction is 2.0 or more, the slipping property between the films becomes insufficient, and the handleability as a packaging material is not satisfied.
• the dynamic friction coefficient of the laminated sealant film of the present invention is preferably 2.0 or less, more preferably 1.0 or less, even more preferably 0.5 or less between the sealing surfaces when the load is 1.5 kgf. When the coefficient of dynamic friction is 2.0 or less, the sliding property between the films is sufficient, and the handleability as a packaging material is likely to be satisfied.
• the scratch resistance is better as the amount of change in haze before and after treatment is smaller.
• the amount of change is preferably 3% or less, more preferably 2% or less, and particularly preferably 1% or less.
• the haze after the friction test between the sealing surface and the laminate surface of the laminated sealant film of the present invention is preferably 10% or less, more preferably 8% or less, even more preferably 6% or less, and particularly preferably 5% or less. .
• the blocking value of the laminated sealant film of the present invention is preferably 500 N/15 mm or less. When the blocking value is 500 N/15 mm or less, the bag making process is easier.
• the blocking value is preferably 200 N/15 mm or less, more preferably 100 N/15 mm or less.
• the longitudinal tensile modulus of the laminated sealant film of the present invention is preferably 200 MPa or more, more preferably 250 MPa or more, even more preferably 300 MPa or more, still more preferably 330 MPa or more, and particularly preferably 345 MPa or more.
• the tensile elastic modulus in the width direction of the laminated sealant film of the present invention is preferably 200 MPa or more in the longitudinal direction, more preferably 250 MPa or more, still more preferably 300 MPa or more, still more preferably 300 MPa or more, even more preferably 330 MPa or more, and 345 MPa or more. Especially preferred. When the tensile modulus is 200 MPa or more, the bag making process is easier.
• the ultimate heat seal strength of the laminated sealant film of the present invention is preferably 10 N/15 mm or more, more preferably 12 N/15 mm or more, still more preferably 14 N/15 mm or more, and particularly preferably 16 N/15 mm or more. In the case of general packaging bags, etc., where the mass of the contents is large and rather strong heat seal strength is required, 15 N/15 mm or more is required.
• the fluctuation rate of the ultimate heat seal strength of the laminated sealant film of the present invention is preferably 20% or less, more preferably 19% or less, still more preferably 17% or less, and particularly preferably 16% or less. 20% or less, it is considered that one of the measures is to make it difficult to cause peeling between the seal layer and the laminate layer of the laminated sealant film.
• the state between the seal layer and the laminate layer can be confirmed by observing the cross section of the test piece after measuring the ultimate heat seal strength with a microscope.
• the heat sealing temperature is preferably 60° C. or higher and 180° C. or lower, more preferably 70° C. or higher and 170° C. or lower, and even more preferably 80° C. or higher and 160° C. or lower.
• the lower limit of the heat sealing temperature is a temperature that is 20°C or more lower than the lowest melting point of the polyethylene resin and/or polypropylene resin of the seal layer, and the highest melting point of the polyethylene resin and/or polypropylene resin of the laminate layer. It is preferable to set the upper limit to a temperature that is 10° C. or more higher than the temperature.
• the low-temperature sealing effect of the heat sealing temperature is evaluated by the degree of decrease in the heat sealing temperature based on the heat sealing temperature in Comparative Example 1 described later.
• the low-temperature sealability of the heat sealing temperature is preferably 5°C or higher, more preferably 10°C or higher, still more preferably 15°C or higher, even more preferably 22°C or higher, particularly preferably 25°C or higher, and most preferably 27°C or higher.
• hot tack As for the hot tack property of the laminated sealant film of the present invention, it is desired that the tack peel distance is 20 mm or less at a lower temperature. Here, even if the resin of the sealant film is in a molten state, the fact that the sealing strength between the sealant films is sufficient is called good hot tack.
• the low-temperature sealing effect of hot tack is evaluated by the degree of decrease in heat sealing temperature with reference to the hot tack temperature in Comparative Example 1 described later.
• the hot-tack low-temperature sealability is preferably 5° C. or higher, more preferably 10° C. or higher, still more preferably 15° C. or higher, even more preferably 18° C. or higher, and particularly preferably 20° C. or higher.
• the bag breaking strength of the laminated sealant film of the present invention is evaluated with a bag produced from the laminated sealant film.
• high bursting strength such as a container for retort sterilization, it is preferably 20 kPa or more, more preferably 23 Pa or more, and even more preferably 27 Pa or more.
• the low-temperature sealing effect of the bag-breaking strength is evaluated by the degree of decrease in the temperature at which the bag-breaking strength becomes 0 kPa based on the temperature at which the bag-breaking strength becomes 0 kPa in Comparative Example 1 described later.
• the low-temperature sealing effect of the bag-breaking strength is preferably 5°C or higher, more preferably 10°C or higher, still more preferably 15°C or higher, and even more preferably 18°C or higher.
• the melting point of the resin was measured using a thermal differential scanning calorimeter (DSC60, Seiko Instruments Inc.) in accordance with JIS K7121. Specifically, about 5 mg of the sample is packed in an aluminum pan, heated from room temperature to 200 ° C. at a heating rate of 10 ° C./min, held at 200 ° C. for 3 minutes, cooled to 23 ° C., and heated to 23 ° C. After being held at 200° C. for 3 minutes, the maximum melting endothermic peak temperature when the temperature was raised to 200° C. was taken as the melting point. When there were two or more melting endothermic peaks, the highest melting endothermic peak was taken as the melting point.
• melt flow rate In accordance with JIS K7112, using a thermal flow evaluation device (Shimadzu Corporation, capillary rheometer, CFT-500D), polypropylene resin was measured at a temperature of 230 ° C., polyethylene resin such as L-LDPE was measured at a temperature of 190 ° C. .
• Inorganic particles or polyethylene particles are dispersed in deionized water sold at a predetermined rotation speed (about 5000 rpm) using a high-speed stirrer, and the dispersion is added to Isoton (physiological saline) and further dispersed with an ultrasonic disperser. After dispersion, the particle size distribution was determined by the call counter method and calculated as the volume average particle size.
• the refractive index used was 1.30 for physiological saline, 1.457 for synthetic silica and diatomaceous earth, and 1.54 for polyethylene.
• Inspection items for film appearance include fisheyes, foreign matter, streaks, and scratches. Fish eyes, foreign matter, streaks, scratches, and the like were evaluated using a defect detector (Hutech Co., Ltd., MaxEye.X Series). Evaluation criteria are as follows. In the case of ⁇ , it can be used without problems. In the case of ⁇ , it is necessary to confirm the purpose of use, but in many cases it can be used without problems. In the case of x, the application may be limited and the measurement conditions may be used. O: No fish eyes, foreign matter, streaks, or scratches of 1 mm square or more were detected.
• ⁇ The number of detected fisheyes, foreign matter, streaks, and flawed foreign matter having a size of 1 mm square or more and less than 2 mm square was less than 100 per 10,000 m 2 .
• x 100 or more fisheyes, foreign matter, streaks, or scratched foreign matter of 1 mm square or more and less than 2 mm square, or foreign matter of 2 mm square or more was detected per 10,000 m 2 . Note that the color of the foreign matter does not matter here.
• the sample blocked by this pressure treatment and an aluminum rod with a diameter of 6 mm are mounted on an autograph (manufactured by Shimadzu Corporation, model: UA-3122), and the aluminum rod peels off the blocking portion at a speed of 200 mm / min. measured the force of time. In this case, it is assumed that the aluminum rod and the peeling surface are horizontal. The same sample was measured four times, and the average value was shown.
• tensile modulus It was measured under the following conditions according to JIS K7127. The tensile elastic modulus in the film machine direction (MD) and the film transverse direction (TD) was measured three times at a sample length of 100 mm, a sample width of 15 mm, a distance between chucks of 20 mm, and a speed of 200 mm / min. directional tensile modulus.
• a laminate with a biaxially oriented polypropylene film (Pyrene (registered trademark), P2161, 20 ⁇ m, manufactured by Toyobo Co., Ltd.) was prepared as follows.
• a dry laminating adhesive (TM569, CAT-10L, Toyo-Morton Co., Ltd.) was applied to the corona surface of the biaxially oriented polypropylene film so that the solid content was 3 g/m2, and the solvent was removed by volatilization in an oven at 80°C. After that, the corona surface of the laminated sealant film and the adhesive coated surface were nipped on a temperature control roll at 60° C. for lamination. This laminated laminated sealant film was allowed to stand at 40° C. for 2 days.
• test sealer (semi-automatic mouth sealer, TYB-300, manufactured by Seibu Kikai Co., Ltd.) was used to seal the laminated laminated sealant film with the laminated sealant surfaces facing each other, using a seal bar with a width of 10 mm. 2 MPa, sealing time 1.0 second, heat sealing temperatures of 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, and 160°C. After that, it was allowed to cool.
• the samples obtained with these test sealers are cut into strips so that the heat seal width is 15 mm, set in a tensile tester (manufactured by Instron, universal material testing machine, 5980 series), and set at 200 mm / min. At the speed, the maximum value of the strength peeled off the sealant surface was measured. A total of three measurements were performed for each temperature, and the average value was taken as the heat seal strength at the above heat seal temperature. The ultimate heat-sealing strength was taken as the highest value among these heat-sealing strengths.
• Variation rate of ultimate heat seal strength (maximum attained heat-seal strength/minimum attained heat-seal strength)/average attained heat-seal strength x 100 (%) (1)
• heat seal temperature It was measured under the following conditions according to JIS Z1707.
• a test sealer (semi-automatic mouth sealer, TYB-300, manufactured by Seibu Kikai Co., Ltd.) was used to seal the laminated laminated sealant film with the laminated sealant surfaces facing each other, using a seal bar with a width of 10 mm. 2 MPa, sealing time 1.0 second, heat sealing temperatures of 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, and 160°C. After that, it was allowed to cool.
• the samples obtained with these test sealers are cut into strips so that the heat seal width is 15 mm, set in a tensile tester (manufactured by Instron, universal material testing machine, 5980 series), and set at 200 mm / min. At the speed, the maximum value of the strength peeled off the sealant surface was measured. A total of three measurements were performed for each temperature, and the average value was taken as the heat seal strength at the above heat seal temperature, and the temperature at which the heat seal strength was 10 N/15 mm was taken as the heat seal temperature.
• Example 1 Low temperature sealing effect of heat sealing temperature
• Comparative Example 7 Low temperature sealing effect of heat sealing temperature
• the low-temperature sealing effect of the heat sealing temperature is evaluated by the difference (° C.) of the heat sealing temperature based on the heat sealing temperature in Comparative Example 1 described later.
• hot tack temperature The sealant surfaces of the laminated laminates are placed facing each other, and the temperature is 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, and 160°C. After heat-sealing for 1 second at a pressure of cm 2 , a load of 46 g was applied, and the peeled distance of the sealed portion was measured.
• HEAT SEAL TESTER, TP-701-B manufactured by Tester Sangyo Co., Ltd. was used as the hot tack temperature.
• Example 1 Low temperature sealing effect at hot tack temperature
• the low temperature sealing effect of the hot tack temperature is evaluated by the hot tack temperature difference (° C.) based on the hot tack temperature in Comparative Example 1 described later.
• the low-temperature sealability of the bag-breaking strength is evaluated by the difference (° C.) between the temperature at which the bag-breaking strength is 0 kPa and the temperature at which the bag-breaking strength is 0 kPa in Comparative Example 1 described later.
• PP-1 FL6745A (manufactured by Sumitomo Chemical Co., Ltd., Noblen (registered trademark), propylene/ethylene/butene random copolymer, melting point 132° C., melt flow rate 6.0 g/10 min)
• PP-2 F744NP (manufactured by Prime Polymer Co., Ltd., Prime Polypro (registered trademark), ethylene/propylene random copolymer, melting point 133° C., melt flow rate 7.0 g/10 min)
• PP-3 FS2011DG3 (manufactured by Sumitomo Chemical Co., Ltd., Noblen (registered trademark), propylene random copolymer, melting point 158° C., melt flow rate 2.5 g/10 min)
• PP-4 WF893R9 (manufactured by Sumitomo Chemical Co., Ltd., Noblen (registered trademark), propylene random copolymer, melting point 137
• PE-1 FV401 (manufactured by Sumitomo Chemical Co., Ltd., Sumikasen (registered trademark) E, linear low-density polyethylene resin, melting point 112° C., melt flow rate 3.8 g/10 min)
• PE-2 FV402 (manufactured by Sumitomo Chemical Co., Ltd., Sumikasen (registered trademark) E, linear low-density polyethylene resin, melting point 115° C., melt flow rate 3.8 g/10 min)
• PE-3 FV403 (manufactured by Sumitomo Chemical Co., Ltd., Sumikasen (registered trademark) E, linear low-density polyethylene resin, melting point 117° C., melt flow rate 3.8 g/10 min)
• PE-4 FV405 (manufactured by Sumitomo Chemical Co., Ltd., Sumikasen (registered trademark) E, linear low-density polyethylene resin, melting point
• Synthetic silica KMP130-2 (average particle size 2 ⁇ m, Shin-Etsu Chemical Co., Ltd.)
• Diatomaceous earth Dicalite WF (average particle size 4 ⁇ m, manufactured by Grefco. Inc.)
• Ultra-high molecular weight polyethylene particles PM200 (average particle size 10 ⁇ m, manufactured by Mitsui Chemicals, Inc.)
• Erucamide brand name Diamid L-200 (melting point 81°C, manufactured by Mitsubishi Chemical Corporation)
• Behenic acid amide brand name D1007 (melting point 110°C, manufactured by Tokyo Chemical Industry Co., Ltd.)
• Ultra-high molecular weight polyethylene particles (Mipelon PM200, manufactured by Mitsui Chemicals, Inc., average particle size 10 ⁇ m), A masterbatch containing 10% by weight of ultra-high molecular weight polyethylene particles was prepared.
• Behenic acid amide masterbatch Noblen (registered trademark) FL6745 manufactured by Sumitomo Chemical Co., Ltd. was mixed with behenic acid amide to prepare a masterbatch containing 2% by weight of behenic acid amide.
• Examples 1 to 6 The laminate layer and the intermediate layer were made from FL6745A.
• the sealing layer is made from the resins and additives shown in Table 1 as raw materials, using three extruders, each melted at 240 ° C., filtered through a sintered filter with a filtration accuracy of 60 ⁇ m, and co-extruded into a sheet form from a T die. .
• the thickness ratio of the laminate layer, the intermediate layer and the seal layer was 25:50:25 vol.
• the laminated sealant films obtained in Examples 1 to 6 had excellent low-temperature sealing properties and hot tack properties, exhibited stable blocking resistance and coefficient of friction, and had good appearance and scratch resistance. Needless to say, there was no problem in film-forming processability, and sufficient bursting strength was obtained. In particular, Example 4 was particularly excellent in scratch resistance.
• Examples 7 to 11 FL8115 was used for the laminate layer, and FL6745A was used for the intermediate layer.
• the sealing layer is made from the resins and additives shown in Table 2 as raw materials, using three extruders, each melted at 240 ° C., filtered through a sintered filter with a filtration accuracy of 60 ⁇ m, and co-extruded into a sheet form from a T die. .
• the thickness ratio of the laminate layer, the intermediate layer and the seal layer was 25:50:25 vol.
• the laminated sealant films obtained in Examples 7 to 11 had excellent low-temperature sealing properties and hot tack properties, exhibited stable blocking resistance and coefficient of friction, and had good appearance and scratch resistance. Needless to say, there was no problem in film-forming processability, and sufficient bursting strength was obtained.
• Example 12 FL8115 was used as a raw material for the laminate layer and the intermediate layer.
• the sealing layer is made from the resins and additives shown in Table 2 as raw materials, using three extruders, each melted at 240 ° C., filtered through a sintered filter with a filtration accuracy of 60 ⁇ m, and co-extruded into a sheet form from a T die. .
• the thickness ratio of the laminate layer, the intermediate layer and the seal layer was 20:60:20 vol.
• the laminated sealant film obtained in Example 12 had excellent low-temperature sealing properties and hot tack properties, exhibited stable blocking resistance and coefficient of friction, and had good appearance and scratch resistance. Needless to say, there was no problem in film-forming processability, and sufficient bursting strength was obtained.
• Comparative Examples 1 to 10 A polypropylene resin film was obtained in the same manner as in Example 1 using the resins and additives shown in Tables 3 and 4 as raw materials. Evaluation results are shown in Tables 3 and 4.
• the film obtained in Comparative Example 1 is inferior in heat sealing temperature, hot tackiness, and low-temperature sealability in terms of bag breaking strength.
• the film obtained in Comparative Example 2 is inferior in heat sealing temperature, hot tackiness, and low-temperature sealability in terms of bag breaking strength.
• the film obtained in Comparative Example 3 is inferior in slipperiness and varies in heat-sealing temperature, resulting in insufficient bag-making properties.
• the film obtained in Comparative Example 4 is inferior in low-temperature sealability of bag breaking strength.
• the film obtained in Comparative Example 5 is inferior in low-temperature sealability of bag breaking strength.
• the film obtained in Comparative Example 6 is inferior in appearance.
• the film obtained in Comparative Example 7 is inferior in appearance and low-temperature sealability such as bag breaking strength.
• the film obtained in Comparative Example 8 is inferior in ultimate heat seal strength, blocking resistance and scratch resistance.
• the films obtained in Comparative Examples 9 and 10 are inferior in ultimate heat seal strength, blocking resistance, scratch resistance, and low-temperature sealability of bag strength.
• the laminated sealant film of the present invention has excellent low-temperature bag-making properties, it is suitable as a packaging material for many products such as foods, beverages, pharmaceuticals, and chemicals.
• it can be suitably used as an automatic bag-making process such as a pillow packaging bag, a gusset packaging bag, or a three-sided seal packaging bag while packaging the contents.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
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• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Physics & Mathematics (AREA)
• Thermal Sciences (AREA)
• Laminated Bodies (AREA)
• Wrappers (AREA)

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• 2022
  • 2022-10-21 EP EP22892549.1A patent/EP4431277A4/en active Pending
  • 2022-10-21 WO PCT/JP2022/039338 patent/WO2023085049A1/ja not_active Ceased
  • 2022-10-21 TW TW111139950A patent/TW202330282A/zh unknown
  • 2022-10-21 KR KR1020247011703A patent/KR20240101786A/ko active Pending
  • 2022-10-21 JP JP2023559534A patent/JPWO2023085049A1/ja active Pending
  • 2022-10-21 US US18/708,490 patent/US20250010591A1/en not_active Abandoned

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