WO2023166995A1 - Multilayer film for ultrasonic sealing and package - Google Patents
Multilayer film for ultrasonic sealing and package Download PDFInfo
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- WO2023166995A1 WO2023166995A1 PCT/JP2023/005348 JP2023005348W WO2023166995A1 WO 2023166995 A1 WO2023166995 A1 WO 2023166995A1 JP 2023005348 W JP2023005348 W JP 2023005348W WO 2023166995 A1 WO2023166995 A1 WO 2023166995A1
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- multilayer film
- ultrasonic
- layer
- ultrasonic sealing
- sealing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
Definitions
- the present invention relates to a multilayer film for ultrasonic sealing and a package.
- mono-materials single materials
- multi-layer laminate structure of different materials e.g., oriented polyethylene terephthalate OPET/non-oriented polypropylene CPP multi-layer film
- biaxially oriented polyethylene/non-oriented polyethylene sealant are used to support monomaterials. Film is required.
- the laminated film proposed above which is suitable for ultrasonic sealing, includes an ethylene resin layer and a polypropylene resin layer, and cannot be used as a monomaterial. Therefore, there is a demand for a multilayer film resin structure that can be used as a monomaterial, has sufficient rigidity, and is suitable for ultrasonic sealing.
- the present invention provides a multi-layer ultrasonic seal that can be used as a monomaterial, has sufficient rigidity, can be ultrasonically welded, and has a narrow seal width and uniform and stable ultrasonic seal strength.
- the purpose is to provide a film.
- the present invention is based on the above findings by the present inventors, and means for solving the above problems are as follows. i.e. ⁇ 1> a thermoplastic resin layer containing a thermoplastic resin; a seal layer containing a linear low-density polyethylene resin and an ⁇ -olefin resin; The ⁇ -olefin resin contains a butene-based ⁇ -olefin resin,
- the multilayer film for ultrasonic sealing is characterized in that it can be sealed by ultrasonic waves.
- ⁇ 3> The multilayer film for ultrasonic sealing according to ⁇ 1>, wherein the linear chain low-density polyethylene in the seal layer has a density of 0.900 kg/m 3 or more and 0.940 kg/m 3 or less.
- ⁇ 4> The multilayer film for ultrasonic sealing according to ⁇ 1>, wherein the sealing layer contains the butene-based ⁇ -olefin resin in an amount of 10% by mass or more and 50% by mass or less.
- ⁇ 5> The multilayer film for ultrasonic sealing according to ⁇ 1>, wherein the seal layer has a thickness of 15% or more.
- ⁇ 6> The multilayer film for ultrasonic sealing according to ⁇ 1>, having a total thickness of 40 ⁇ m or more.
- thermoplastic resin contains at least one of polyethylene and polypropylene.
- the above-mentioned problems in the past can be solved, the above-mentioned objects can be achieved, it can be used as a monomaterial, ultrasonic welding is possible, it has sufficient rigidity, and the seal width is narrow. It is possible to provide a multilayer film for ultrasonic sealing that can have uniform and stable ultrasonic sealing strength.
- FIG. 1 is a schematic cross-sectional view showing an example of the multilayer film for ultrasonic sealing of the present invention.
- FIG. 2 is a schematic cross-sectional view showing another example of the multilayer film for ultrasonic sealing of the present invention.
- FIG. 3A is a schematic cross-sectional view (No. 1) showing an example of an ultrasonic sealing device used for ultrasonic welding of the multilayer film for ultrasonic sealing of the present invention.
- FIG. 3B is a schematic cross-sectional view (No. 2) showing an example of an ultrasonic sealing device used for ultrasonic welding of the multilayer film for ultrasonic sealing of the present invention.
- FIG. 3C is a schematic cross-sectional view (No. 3) showing an example of an ultrasonic sealing device used for ultrasonic welding of the multilayer film for ultrasonic sealing of the present invention.
- the ultrasonic sealing multilayer film of the present invention has at least a thermoplastic resin layer and a sealing layer, and is ultrasonically sealable.
- the thermoplastic resin layer contains a thermoplastic resin as a main resin component.
- the thermoplastic resin layer may be a single layer or multiple layers.
- Said thermoplastic layer may be a surface layer on which printing of the packaging film can be provided.
- thermoplastic resin is not particularly limited and can be appropriately selected from known thermoplastic resins depending on the intended purpose. Examples thereof include olefin resins, styrene resins, ester resins and acrylic resins. Among these, the olefin resin is preferable because it can be made into a monomaterial.
- the olefin resin examples include homopolymers of olefin monomers (polyethylene homopolymer, polypropylene homopolymer, etc.); copolymers containing olefin monomers as main components (propylene-ethylene block copolymers, propylene-ethylene random copolymer, ethylene-1-butene copolymer, propylene-1-butene copolymer, etc.). These may be used individually by 1 type, and may use 2 or more types together. Among these, ethylene homopolymers, propylene homopolymers, propylene-ethylene block copolymers, and propylene-ethylene random copolymers containing at least one of polyethylene and polypropylene are preferred.
- the content of the olefin monomer in the olefin resin is preferably 50 mol % to 100 mol %, more preferably 70 mol % to 100 mol %.
- a cyclic olefin resin can also be used as the thermoplastic resin.
- the cyclic olefin-based resins include norbornene-based polymers, vinyl alicyclic hydrocarbon polymers, and cyclic conjugated diene polymers. Among these, norbornene-based polymers are preferred.
- norbornene-based polymers include ring-opening polymers (COP) of norbornene-based monomers, and norbornene-based copolymers (COC) obtained by copolymerizing norbornene-based monomers with olefins such as ethylene. Hydrogenates of COP and COC are also particularly preferred.
- the weight average molecular weight of the cyclic olefin resin is preferably 5,000 to 500,000, more preferably 7,000 to 300,000.
- the norbornene-based polymer and the norbornene-based monomer as a raw material are alicyclic monomers having a norbornene ring.
- Examples of such norbornene-based monomers include norbornene, tetracyclododecene, ethylidenenorbornene, vinylnorbornene, ethylidetetracyclododecene, dicyclopentadiene, dimethanotetrahydrofluorene, phenylnorbornene, methoxycarbonylnorbornene, methoxy carbonyltetracyclododecene and the like.
- These norbornene-based monomers may be used alone or in combination of two or more.
- the norbornene-based copolymer is obtained by copolymerizing the norbornene-based monomer with a copolymerizable olefin.
- cycloolefins such as cyclobutene, cyclopentene and cyclohexene; non-conjugated dienes such as 1,4-hexadiene;
- the content of the cyclic olefin resin contained in the thermoplastic resin layer is 15 to 35 mass%, preferably 20 to 30 mass% of the resin component contained in the thermoplastic resin layer. Suitable easy tearability and straight cutability can be realized without impairing the properties.
- the cyclic olefin resin used in the thermoplastic resin layer has a glass transition temperature of 100° C. or lower, preferably 90° C. or lower, more preferably 80° C. or lower.
- the lower limit is not particularly limited, it is preferably 50°C or higher, more preferably 60°C or higher, and even more preferably 70°C or higher.
- cyclic olefin-based resin examples include ring-opening polymers (COP) of norbornene-based monomers, such as “ZEONOR” manufactured by Nippon Zeon Co., Ltd.
- COP ring-opening polymers
- Norbornene-based copolymers ( COC) includes, for example, "APEL” manufactured by Mitsui Chemicals, Inc., and "TOPAS” manufactured by Polyplastics.
- the melt flow rate (MFR) of the thermoplastic resin is not particularly limited and can be appropriately selected according to the purpose. 50.0 g/10 minutes is preferred, 3.0 g/10 minutes to 45.0 g/10 minutes is more preferred, and 3.0 g/10 minutes to 12.0 g/10 minutes is even more preferred.
- the melt flow rate (MFR) is a value measured at 190° C. under a load of 2.16 kg (21.18 N) according to JISK7210.
- the melt flow rate (MFR) of the cyclic olefin resin is preferably 0.2 to 30 g/10 minutes (230°C, 21.18N), more preferably 3 to 17 g/10 minutes (230°C, 21.18N). Preferably, 5 to 15 g/10 minutes (230° C., 21.18 N) is more preferable. When the MFR is within this range, it is preferable in that good film formability can be obtained in various multilayer film forming methods.
- the density of the thermoplastic resin is not particularly limited and can be appropriately selected according to the purpose . 93 g/cm 3 is more preferred.
- the melting point of the thermoplastic resin is not particularly limited and can be appropriately selected according to the purpose.
- the melting point can be measured using a differential scanning calorimeter (DSC) (for example, DSC7020 manufactured by Hitachi High-Tech Science Co., Ltd.).
- DSC differential scanning calorimeter
- the seal layer contains a linear low-density polyethylene resin and an ⁇ -olefin resin as main resin components.
- the linear low density polyethylene is a copolymer of ethylene and ⁇ -olefin polymerized using a multi-site catalyst such as a Ziegler-Natta catalyst or a single-site catalyst such as a metallocene catalyst. It is a coalescence.
- a multi-site catalyst such as a Ziegler-Natta catalyst or a single-site catalyst such as a metallocene catalyst. It is a coalescence.
- resins that satisfy the linear low-density polyethylene resins that satisfy the specifications of ⁇ -olefin resins, which will be described later, may also be included. Treat as density polyethylene resin.
- the linear low-density polyethylene resin is not particularly limited and can be appropriately selected according to the purpose.
- Examples thereof include copolymers obtained by copolymerizing ⁇ -olefins such as pentene monomers and 1-octene.
- a copolymer obtained by copolymerizing at least one of 1-hexene and 1-octene with an ethylene monomer as a main component is preferable. These may be used individually by 1 type, and may use 2 or more types together.
- the content of the ethylene monomer in the linear low-density polyethylene resin is preferably 20 mol % to 95 mol %, more preferably 30 mol % to 95 mol %.
- the melt flow rate (MFR) of the linear low-density polyethylene resin is not particularly limited and can be appropriately selected according to the purpose. 0 g/10 minutes to 50.0 g/10 minutes is preferable, 3.0 g/10 minutes to 45.0 g/10 minutes is more preferable, and 3.0 g/10 minutes to 12.0 g/10 minutes is even more preferable.
- the density of the linear low-density polyethylene resin is not particularly limited and can be appropriately selected according to the purpose. 3 to 0.935 g/cm 3 is more preferable.
- the melting point of the linear low-density polyethylene resin is not particularly limited and can be appropriately selected according to the purpose. °C is more preferred.
- the content of the linear low-density polyethylene resin is preferably 40% by mass or more and 95% by mass or less, preferably 50% by mass or more and 90% by mass or less, relative to the total amount of the resin components contained in the seal layer. 60% by mass or more and 80% by mass or less is more preferable.
- the content is 40% by mass or more and 95% by mass or less, it is advantageous in terms of exhibiting ultrasonic sealing properties. Further, when the content is 40% by mass or more and 95% by mass or less, it is particularly advantageous in terms of ensuring uniform and stable ultrasonic sealing performance over the entire sealing length.
- the ⁇ -olefin resin contains at least a butene-based ⁇ -olefin resin and, if necessary, other ⁇ -olefin resins other than the butene-based ⁇ -olefin resin.
- butene-based ⁇ -olefin resin-- refers to a copolymer containing 50 mol % or more of butene-1 monomer or a butene-1 monomer homopolymer.
- the butene-based ⁇ -olefin resin is not particularly limited and can be appropriately selected according to the purpose.
- -1-butene copolymer, propylene-1-butene copolymer containing 50 mol% or more of butene-1 monomer, ethylene-propylene-1-butene copolymer containing 50 mol% or more of butene-1 monomer A coalescence etc. are mentioned.
- propylene-1-butene copolymers containing 50 mol % or more of butene-1 monomer are preferred. These may be used individually by 1 type, and may use 2 or more types together.
- the content of the butene-1 monomer in the butene-based ⁇ -olefin resin is preferably 50 mol% to 95 mol%, preferably 60 mol%. It is more preferably to 95 mol %, even more preferably 70 mol % to 95 mol %.
- the melt flow rate (MFR) of the butene-based ⁇ -olefin resin is not particularly limited and can be appropriately selected according to the purpose. 10 minutes to 50.0 g/10 minutes is preferred, 3.0 g/10 minutes to 45.0 g/10 minutes is more preferred, and 3.0 g/10 minutes to 12.0 g/10 minutes is even more preferred.
- the density of the butene-based ⁇ -olefin resin is not particularly limited and can be appropriately selected according to the purpose . 0.92 g/cm 3 is more preferred.
- the melting point of the butene-based ⁇ -olefin resin is not particularly limited and can be appropriately selected according to the purpose. More preferred.
- the content of the butene-based ⁇ -olefin resin is preferably 5% by mass or more and 60% by mass or less, more preferably 10% by mass or more and 50% by mass or less, based on the total amount of the resin components contained in the seal layer. It is more preferably 50% by mass or less, and particularly preferably 20% by mass or more and 50% by mass or less.
- the content is 5% by mass or more and 60% by mass or less, it is advantageous in terms of exhibiting ultrasonic sealing properties. Further, when the content is 20% by mass or more and 50% by mass or less, it is particularly advantageous in terms of ensuring uniform and stable ultrasonic sealing performance over the entire sealing length.
- the mass ratio (b2/b1) of the butene-based ⁇ -olefin resin (b2) to the linear low-density polyethylene (b1) in the sealing layer is not particularly limited and can be appropriately selected according to the purpose. , preferably 5/95 to 60/40, more preferably 10/90 to 50/50, still more preferably 20/80 to 50/50, and particularly preferably 30/70 to 40/60.
- the other ⁇ -olefin resin is not particularly limited as long as it contains an ⁇ -olefin and the content of the 1-butene monomer is less than 50 mol%, and can be appropriately selected according to the purpose.
- Examples include ethylene polymers containing olefins, propylene polymers containing ⁇ -olefins, ethylene-propylene copolymers containing ⁇ -olefins, ethylene-1-butene copolymers, propylene-1-butene copolymers, and the like.
- ⁇ -olefins include 1-butene, 1-hexene, 4-methylpentene, 1-octene and the like.
- copolymers containing 50 mol% or more of butene-1 monomer correspond to butene-based ⁇ -olefin resins, and copolymers containing less than 50 mol% of butene-1 monomer are other ⁇ It corresponds to olefin resin.
- copolymers of ethylene and ⁇ -olefins polymerized using multi-site catalysts such as Ziegler-Natta catalysts or single-site catalysts such as metallocene catalysts linear low-density polyethylene is used instead of ⁇ -olefin resins. Applicable.
- these may be used individually by 1 type, and may use 2 or more types together.
- the content of the ⁇ -olefin monomer in the ⁇ -olefin resin is not particularly limited and can be appropriately selected according to the purpose.
- the melt flow rate (MFR) of the other ⁇ -olefin resin is not particularly limited and can be appropriately selected according to the purpose. 10 minutes to 50.0 g/10 minutes is preferred, 2.0 g/10 minutes to 45.0 g/10 minutes is more preferred, and 2.0 g/10 minutes to 10.0 g/10 minutes is even more preferred.
- the density of the other ⁇ -olefin resin is not particularly limited and can be appropriately selected according to the purpose . 0.90 g/cm 3 is more preferred.
- the melting point of the other ⁇ -olefin resin is not particularly limited and can be appropriately selected according to the purpose, but is preferably 40°C to 120°C, more preferably 50°C to 100°C.
- a cyclic olefin resin may also be used in the seal layer of the present invention.
- the cyclic olefin-based resin the same cyclic olefin-based resin that can be used in the thermoplastic resin layer can be used.
- the seal layer may contain other olefinic resins.
- Other olefin-based resins include various ethylene-based resins and propylene-based resins.
- the resin of the thermoplastic resin layer and the seal layer contains other ingredients such as antioxidants, ultraviolet absorbers, antistatic agents, and lubricants (antiblocking agents, slip agents) commonly used in polyolefins. may be blended as appropriate.
- the thermoplastic resin layer in the multilayer film for ultrasonic sealing may be a single layer or a plurality of layers.
- the plurality of thermoplastic resin layers may have the same composition or different compositions.
- the multilayer film for ultrasonic sealing is a multilayer film laminated in the order of thermoplastic resin layer/seal layer.
- the thermoplastic resin layer has a base layer that serves as a surface layer of the multilayer film for ultrasonic sealing and an intermediate layer (one to multiple layers).
- the multilayer film for ultrasonic sealing is a multilayer film laminated in the order of base layer (thermoplastic resin layer)/intermediate layer (thermoplastic resin layer)/seal layer.
- the intermediate layer is also preferably a cyclic olefin resin layer.
- the said cyclic olefin resin layer refers to the layer which contains 60 mass % or more of cyclic olefin resins among the resin components of the said layer.
- the multilayer film for ultrasonic sealing may be a coextrusion multilayer film in which each layer is extruded and laminated together, or may be a laminate film in which some layers are adhered and laminated.
- the adhesion method for laminating the additional base material layer is not particularly limited and can be appropriately selected according to the purpose. Examples thereof include dry lamination, wet lamination, non-solvent lamination and extrusion lamination.
- the ultrasonic sealing multilayer film is preferably a non-stretched film. Since the sealant film for ultrasonic sealing can be obtained as a substantially unstretched multilayer film by the above coextrusion production method, secondary forming such as deep drawing forming by vacuum forming is also possible. In addition, when the multilayer film for ultrasonic sealing is a laminate film laminated by bonding some layers, the resin film may be a stretched resin film in which some layers are laminated, but a non-stretched resin Films are preferably used.
- the multilayer film for ultrasonic sealing is basically transparent and has a smooth surface.
- the mixed resin layer on both sides or one side of the multilayer film for ultrasonic sealing may be subjected to a corona discharge treatment to impart printability.
- both sides or one side of the multilayer film for ultrasonic sealing may be embossed to give an aperture pattern such as a satin finish.
- the total thickness of the multilayer film for ultrasonic sealing is not particularly limited and can be appropriately selected according to the purpose. The above is more preferable. Moreover, it is preferably 30 ⁇ m or more and 100 ⁇ m or less, and more preferably 40 ⁇ m or more and 90 ⁇ m or less.
- the average thickness of a single layer or each layer of the thermoplastic resin layer is not particularly limited and can be appropriately selected according to the purpose.
- the total average thickness of each layer is not particularly limited and can be appropriately selected according to the purpose.
- the thickness of the thermoplastic resin layer is not particularly limited and can be appropriately selected according to the purpose. (%) is preferably 90% or less, more preferably 20% to 90%, even more preferably 50% to 80%.
- the average thickness of the sealing layer is not particularly limited and can be appropriately selected depending on the intended purpose.
- the thickness of the seal layer is not particularly limited and can be appropriately selected according to the purpose. 10% or more is preferred, 15% or more is more preferred, and 20% or more is even more preferred. Moreover, it is preferably 10% or more and 50% or less, more preferably 15% or more and 50% or less, and still more preferably 20% or more and 50% or less. When the thickness is 10% or more, it is advantageous in that uniform and stable ultrasonic sealing performance is ensured over the entire sealing length.
- the thickness ratio thereof is preferably 5% or more and 30% or less, more preferably 5% or more and 20%, with respect to the total thickness of the multilayer film. The following is more preferable, and 8% or more and 18% or less is even more preferable.
- the thickness ratio of the cyclic olefin-based resin layer is within the range, the rigidity and seal strength can be improved, and when the multilayer film is used as a laminate film, it is easily made into a monomaterial film, which is preferable.
- the said cyclic olefin resin layer exists in multiple numbers, it is preferable in the total thickness ratio being the said range.
- the heat of fusion measured by differential scanning calorimetry (DSC) in the multilayer film for ultrasonic sealing is preferably 60 mJ/mg or more, more preferably 65 mJ/mg or more, from the viewpoint of uniform weldability by ultrasonic sealing. , more preferably 75 mJ/mg or more. Also, it is preferably 60 mJ/mg or more and 115 mJ/mg or less, more preferably 60 mJ/mg or more and 110 mJ/mg or less, and even more preferably 60 mJ/mg or more and 100 mJ/mg or less.
- the amount of heat of fusion measured by differential scanning calorimetry is the amount of heat of fusion in the first temperature rise, and is measured in the following procedure using, for example, a differential scanning calorimeter (manufactured by Hitachi High-Tech Science Co., Ltd., DSC7020). be able to.
- a differential scanning calorimeter manufactured by Hitachi High-Tech Science Co., Ltd., DSC7020.
- an analysis program for a differential scanning calorimeter is used to select the DSC curve at the time of the first temperature increase, and the heat of fusion [mJ/mg] of the target sample at the first temperature increase can be obtained. can.
- the heat of fusion measured by differential scanning calorimetry (DSC) in the multilayer film for ultrasonic sealing is preferably 55 mJ/mg or more, and preferably 60 mJ. /mg or more, and more preferably 70 mJ/mg or more. If the amount of heat of fusion when the cyclic olefin resin layer is provided as the thermoplastic resin layer is within the above range, uniform welding is facilitated in the case of ultrasonic sealing, and perforation or the like is less likely to occur during welding. .
- the heat of fusion measured by differential scanning calorimetry (DSC) in the multilayer film for ultrasonic sealing of the present invention is 70 mJ / mg or more, or when a cyclic olefin resin layer is provided as the thermoplastic resin layer, the heat of fusion is If it is 55 mJ/mg or more, it becomes easier to perform uniform welding in the case of ultrasonic sealing, and the reason why perforation or the like is less likely to occur during welding is not clear, but the inventors speculate as follows. there is That is, polyethylene has relatively low rigidity, and the vibrational energy generated by ultrasonic waves during ultrasonic sealing tends to be attenuated, and high energy must be applied for uniform sealing. A multilayer film having a relatively high heat of fusion in the above range achieves a uniform seal, so even when the vibration energy of ultrasonic waves during ultrasonic sealing is high, a good sealing result can be obtained without perforation or the like. can.
- the rigidity of the multilayer film for ultrasonic sealing can be evaluated by 1% tangent modulus.
- 1% tangent modulus means the tangent modulus at 1% strain.
- the 1% tangential modulus in the multilayer film for ultrasonic sealing is preferably 190 MPa or more, more preferably 200 MPa or more, and even more preferably 210 MPa or more.
- the method for measuring the 1% tangential modulus is not particularly limited and can be appropriately selected according to the purpose. 1% tangential modulus (unit: MPa) at 23° C. using a Tensilon tensile tester (device name: RTC-1210A, manufactured by A&D Co., Ltd.).
- the rigidity of the multilayer film for ultrasonic sealing of the present invention can be selected according to the application by adjusting the resin composition of the multilayer film.
- the resin composition of the multilayer film For example, when using the ultrasonic sealing multilayer film for applications that require flexibility such as horizontal pillow packaging, by using a polyethylene resin such as linear low density polyethylene for the thermoplastic resin layer, the The 1% tangential modulus in the multilayer film for ultrasonic sealing can be adjusted to 190 MPa or more and about 300 MPa.
- the ultrasonic sealing multilayer film when using the ultrasonic sealing multilayer film for applications that require rigidity such as standing pouches and vertical pillow packaging, by using a cyclic olefin resin for the thermoplastic resin layer, the ultrasonic sealing multilayer
- the 1% tangential modulus of the film can be adjusted to 300 MPa or more and about 900 MPa.
- the ultrasonic sealing method is not particularly limited, and a known ultrasonic sealing method, a method using a known ultrasonic sealing device, or the like can be appropriately selected according to the purpose.
- the “ultrasonic seal” is a combination of an “ultrasonic horn” that transmits vibration energy by ultrasonic waves and a fixing jig “anvil” using ultrasonic vibration amplitude that converts electrical energy into mechanical energy. It is a technology in which a film to be joined is sandwiched in between, and frictional energy is generated uniformly at the interfaces of the film materials, resulting in instantaneous fusion and welding.
- the terms “ultrasonic sealing”, “ultrasonic welding”, “ultrasonic fusion welding”, and “ultrasonic fusion bonding” can be synonymous with each other.
- the ultrasonic horn may be arranged vertically above the object to be welded and the anvil, or horizontally with respect to the object to be welded and the anvil.
- Ultrasonic horns vibrate with ultrasonic waves, typically between 20 kHz and 40 kHz, to transfer energy under pressure, typically in the form of frictional heat, to the joints to be joined. Due to the frictional heat and pressure, a portion of at least one of the objects to be joined softens or melts, thereby joining the objects to be joined together.
- the "bonding object” is not particularly limited as long as it contains at least the multilayer film for ultrasonic sealing of the present invention, and can be appropriately selected according to the purpose.
- Two multilayer films may be arranged so that the seal layers are in contact with each other, and a series (one sheet) of the multilayer film for ultrasonic sealing may be folded so that the seal layers are in contact with each other.
- the ultrasonic sealing multilayer film and the thermoplastic resin film are arranged such that the sealing layer of the ultrasonic sealing multilayer film is in contact with the thermoplastic resin film.
- a laminate to be described later can be obtained by ultrasonically sealing the portions where the seal layers are in contact with each other and the portions where the seal layers are in contact with the thermoplastic resin film to form joints.
- the ultrasonic waves in the ultrasonic seal are not particularly limited, and elastic vibration waves (sound waves) having a high frequency that cannot be heard by the human ear can be appropriately selected according to the purpose.
- the frequency of the ultrasonic waves is preferably 16 kHz or higher, more preferably 20 kHz or higher, and particularly preferably 20 kHz or higher and 40 kHz or lower.
- Conditions such as pressure, amplitude, welding time, hold time, etc. in the ultrasonic sealing vary depending on the type of object to be welded and the combination of frequency and conditions, and cannot be univocally defined, but there are no particular restrictions. can be selected as appropriate depending on the purpose.
- the pressure means the pressing pressure of the ultrasonic horn against the object to be joined in the ultrasonic sealing device, and is expressed in units such as [Pa] (pascal), [MPa] (megapascal), and the like.
- the pressure is preferably 0.15 [MPa] to 0.3 [MPa], more preferably 0.25 [MPa] to 0.3 [MPa].
- the amplitude means the magnitude of ultrasonic vibration.
- the amplitude is preferably 20 ⁇ m or more and 50 ⁇ m or less, and more preferably 35 ⁇ m or more and 50 ⁇ m or less in order to have a uniform and stable seal strength.
- the welding time indicates the oscillation time of ultrasonic waves, and means the time during which the ultrasonic horn contacts and welds the object to be welded.
- the welding time is preferably 0.2 seconds or more and 1 second or less, more preferably 0.5 seconds or more and 1 second or less.
- the hold time means the holding time of the ultrasonic oscillator and the hardening time of the welded portion.
- the hold time is preferably 0.2 seconds or more and 1.0 seconds or less, more preferably 0.5 seconds or more and 1.0 seconds or less.
- Suitable examples of the ultrasonic sealing device include a continuous ultrasonic sealing type device, a device having a rotary ultrasonic horn, and the like.
- Such continuous ultrasonic sealing type devices are commonly known as "continuous ultrasonic fusion bonds".
- Continuous ultrasonic fusion bonding can generally be fed substantially continuously into an ultrasonic sealing device, and is used to substantially continuously seal objects to be bonded.
- the ultrasonic horn is usually fixed and the object to be welded moves underneath it.
- One type of continuous ultrasonic fusion bond uses a stationary horn and a rotating anvil face. During continuous ultrasonic fusion bonding, the object to be welded is pulled between the ultrasonic horn and the rotating anvil.
- the ultrasonic horn typically extends longitudinally toward the object to be joined, and vibrations are transmitted axially along the ultrasonic horn to the material.
- the ultrasonic horn In the device with a rotating ultrasonic horn, the ultrasonic horn is of rotary type, cylindrical and rotates about its longitudinal axis.
- the input vibration is in the axial direction of the ultrasonic horn and the output vibration is in the radial direction of the ultrasonic horn.
- the ultrasonic horn is placed in close proximity to the anvil, and the anvil is typically also rotatable such that the object to be welded passes between the cylindrical surfaces at a linear velocity substantially equal to the tangential velocity of the cylindrical surfaces. .
- ultrasonic seals examples include JP-A-2008-526552, JP-A-2010-195044, JP-A-2013-231249, JP-A-2015-16294, and US Pat. No. 5,976,316. and the disclosure of which is incorporated herein by reference.
- the multilayer film of the present invention can also be laminated with another substrate to form a laminate having the multilayer film of the present invention.
- the laminate has another substrate and the multilayer film of the present invention laminated with the other substrate.
- the other substrate that can be used is not particularly limited, but from the viewpoint of easily expressing the effects of the present invention, a thermoplastic resin film having high rigidity and high gloss, especially two It is preferable to use an axially stretched resin film.
- substrates such as aluminum foil, paper, and coated paper can be used singly or in combination.
- the adhesion method for laminating the multilayer film of the present invention to the other substrate is not particularly limited and can be appropriately selected according to the purpose. Examples include dry lamination, wet lamination, non-solvent lamination, and extrusion lamination. etc.
- biaxially oriented resin film examples include biaxially oriented polyester (BOPET), biaxially oriented polyethylene (BOPE), biaxially oriented polypropylene (BOPP), biaxially oriented polyamide (BOPA), and ethylene vinyl alcohol copolymer.
- BOPET biaxially oriented polyester
- BOPE biaxially oriented polyethylene
- BOPP biaxially oriented polypropylene
- BOPA biaxially oriented polyamide
- ethylene vinyl alcohol copolymer examples include coextrusion biaxially oriented polypropylene with a core layer of coalescence (EVOH), biaxially oriented ethylene vinyl alcohol copolymer (BOEVOH), and coextruded biaxially oriented polypropylene coated with polyvinylidene chloride (PVDC). These may be used singly, or two or more of them may be used in combination or in combination.
- the package of the present invention includes at least the multilayer film for ultrasonic sealing of the present invention, and is a laminate obtained by arranging two sheets of the multilayer film for ultrasonic sealing so that the respective sealing layers are in contact with each other and sealing them by ultrasonic waves. It may be a laminate obtained by folding and arranging a series (one sheet) of the multilayer film for ultrasonic sealing so that the sealing layers are in contact with each other, and then sealing by ultrasonic waves, or A laminate obtained by arranging the multilayer film for ultrasonic sealing and a thermoplastic resin film so that the seal layer of the multilayer film for ultrasonic sealing is in contact with the thermoplastic resin film and sealing them by ultrasonic waves, good too.
- the packaging body can be suitably used as various packaging bodies such as food packaging bodies for western confectionery, snacks, bread, Japanese confectionery, and seasonings.
- the package body can be made of a monomaterial, and can be sealed by an ultrasonic seal capable of heating only the sealing surface, so that the width of the seal can be narrowed and the amount of material can be reduced.
- thermoplastic resin film The material of the thermoplastic resin film is not particularly limited and can be appropriately selected from known thermoplastic resins according to the purpose, but olefin resins are preferable from the viewpoint of monomaterialization.
- olefin resin any of the olefin resins described in the thermoplastic resin layer can be appropriately employed.
- the ultrasonic sealing multilayer film 10 of the present invention is, for example, a multilayer film composed of a thermoplastic resin layer 1 and a sealing layer 2 and having two layers laminated, as shown in FIG.
- the multilayer film 10 for ultrasonic sealing of the present invention may have a plurality of thermoplastic resin layers, a thermoplastic resin layer (base layer) 1a, a thermoplastic resin layer ( It may be a multi-layer film consisting of an intermediate layer) 1b and a seal layer 2 and laminated in the order of base layer/intermediate layer/seal layer.
- the intermediate layer is one layer in FIG. 2, the intermediate layer may be plural layers.
- FIG. 3A to 3C are schematic cross-sectional views showing an example of an ultrasonic sealing device used for ultrasonic welding of the multilayer film for ultrasonic sealing of the present invention.
- the ultrasonic sealing device 100 has an anvil 110 and an ultrasonic horn 120 facing the outer peripheral surface of the anvil 110 . Seal projections are formed in a predetermined seal pattern on the outer peripheral surface of the anvil 110, and the ultrasonic horn 120 moves in the direction of the arrow in FIG. You can hold the joint target.
- the object to be joined passed between the anvil 110 and the ultrasonic horn 120 may be, for example, two layers of the ultrasonic sealing multilayer film 10 (FIG. 3A).
- the plastic resin film may be doubled (not shown), and the metal rod 130 is hooked and tension is applied in the direction of the arrow in FIG. It may be a multilayer film 10 for ultrasonic sealing (Fig. 3B).
- a portion of the object to be joined sandwiched between the seal projection on the outer peripheral surface of the anvil 110 and the ultrasonic horn 120 is melt-sealed by frictional heat generated by ultrasonic vibration transmitted from the ultrasonic horn 120, thereby ultrasonically sealing.
- a laminate 50 containing at least the multi-layer film 10 is produced (see FIG. 3C).
- the ultrasonic sealing device transmits vibration energy to the object to be welded from the tip of an ultrasonic horn in contact with the object to be welded, and welds the object to be welded by frictional heat. It is almost the same as the shape of the contact surface with the tip of the ultrasonic horn.
- the seal projections on the outer peripheral surface of the anvil 110 have a shape of 200 mm ⁇ 2 mm, thereby manufacturing the welded laminate 50 with a seal length of 200 mm ⁇ seal width of 2 mm. .
- Example 1 ⁇ Preparation of multilayer film for ultrasonic sealing> Resins and resin mixtures for forming each layer using the following resins as resin components for forming each layer of the substrate layer (A), the intermediate layer (B), the intermediate layer (C) and the seal layer (D). adjusted.
- Base layer (A) 100 parts of linear low-density polyethylene resin (density 0.933 g/cm 3 , MFR 3.6 g/10 min, melting point 123° C.) (hereinafter referred to as LLDPE (2)).
- Middle layer (B) 100 parts of LLDPE (2).
- Middle layer (C) 100 parts of LLDPE (2).
- Sealing layer (B) 60 parts of linear low-density polyethylene resin (density of 0.920 g/cm 3 , MFR of 4.3 g/10 minutes, melting point of 112° C.) (hereinafter referred to as LLDPE (1)), and 1- Butene-propylene copolymer (density 0.900 g/cm 3 , MFR 9.0 g/10 min, melting point 100° C., content of 1-butene-derived component: 60 mol % to 95 mol %) (hereinafter referred to as BPR (1) ) and 40 parts.
- LLDPE (1) linear low-density polyethylene resin
- BPR (1) 1- Butene-propylene copolymer
- the average thickness ratio of each layer is 20%: 36%: 20%: 24%, coextruded from a T die at an extrusion temperature of 250 ° C., cooled with a water-cooled metal cooling roll at 40 ° C., and the total thickness
- the obtained multilayer film for ultrasonic sealing was cut into 210 mm ⁇ 600 mm, and two thermoplastic resin films (biaxially oriented polypropylene, P2161, manufactured by Toyobo Co., Ltd.) cut into the same size were stacked so that the sealing layer was in contact.
- a total of three sides, two long sides and one short side, were ultrasonically sealed using the same apparatus and conditions as in the evaluation of "ultrasonic sealability" described later, except that the package of Example 1 was was made.
- the DSC curve at the time of the first heating was selected using a differential scanning calorimeter analysis program, and the heat of fusion [mJ/mg] of the target sample at the first heating was determined.
- 1% tangential modulus (unit: MPa) at 23 ° C. in the extrusion direction during film production was measured using a Tensilon tensile tester (device name: : RTC-1210A, manufactured by A&D Co., Ltd.). Stiffness was evaluated based on the 1% tangent modulus.
- 1% tangential modulus means a tangential elastic modulus (Tangent Modulus) when a strain of 1% is applied, and in the present invention, it is preferably 190 MPa or more, more preferably 200 MPa or more, and further preferably 210 MPa or more. .
- Example 2 In Example 1, as shown in Table 1, BPR (1) in the sealing layer (D) was a 1-butene-propylene copolymer (density 0.900 g/cm 3 , MFR 9.0 g/10 minutes, melting point 58°C, Content of 1-butene-derived component: 60 mol% to 95 mol%) (hereinafter referred to as BPR (2)) for ultrasonic sealing in the same manner as in Example 1 A multilayer film was produced and evaluated. Table 1 shows the results.
- BPR (2) 1-butene-propylene copolymer
- Examples 3-4) In Example 2, as shown in Table 1, except that the amount ratio of LLDPE (1) and BPR (2) in the seal layer (D) was changed, Examples 3 and 4 were prepared in the same manner as in Example 2. A multilayer film for ultrasonic sealing was produced and evaluated. Table 1 shows the results.
- Example 5 In Example 2, as shown in Table 1, LLDPE (1) in the sealing layer (D) was replaced with LLDPE (2) and linear low-density polyethylene resin (density 0.940 g/cm 3 , MFR 4.3 g/10 minutes, Melting point 124° C.) (hereinafter referred to as LLDPE (3)). . Table 1 shows the results.
- Base layer (A) A mixture of 60 parts of LLDPE (1) and 40 parts of high-density polyethylene (960 g/cm 3 , MFR 7.5 g/10 min, melting point 131° C.) (hereinafter referred to as HDPE).
- Middle layer (B) a mixture of 70 parts LLDPE (1) and 30 parts HDPE.
- Middle layer (C) 100 parts of LLDPE (1).
- Seal layer (B) a mixture of 60 parts LLDPE (1) and 40 parts BPR (2).
- a resin mixture forming each layer is supplied to each of three extruders, and each layer of a laminated film formed of a base layer (A)/intermediate layer (B)/intermediate layer (C)/seal layer (D).
- the average thickness ratio of 20%: 36%: 20%: 24% is co-extruded from a T die at an extrusion temperature of 250 ° C., cooled with a water-cooled metal cooling roll at 40 ° C., and the total thickness is 40 ⁇ m.
- the multilayer film for ultrasonic sealing of Example 7, which is a laminated film of was molded.
- the obtained multilayer film for ultrasonic sealing of Example 7 was evaluated in the same manner as in Example 1. Table 2 shows the results.
- Example 8 In Example 7, as shown in Table 2, the ratio of the average thickness of each layer of the laminated film formed of base layer (A)/intermediate layer (B)/intermediate layer (C)/seal layer (D) was , 20%:36%:28%:16%, a multilayer film for ultrasonic sealing of Example 8 was produced and evaluated in the same manner as in Example 7. Table 2 shows the results.
- Example 9-10 In Example 2, as shown in Table 2, 60 parts by mass of LLDPE (1) in the seal layer (D) was changed to 40 parts by mass and 95 parts by mass, respectively, 40 parts by mass of BPR (2) was changed to 60 parts by mass, and The multilayer films for ultrasonic sealing of Examples 9 and 10 were produced and evaluated in the same manner as in Example 2, except that each was changed to 5 parts by mass. Table 2 shows the results.
- Example 11-12 In Example 2, as shown in Table 2, the LLDPE (1) in the seal layer (D) was replaced with a linear low-density polyethylene resin (density 0.903 g/cm 3 , MFR 3.0 g/10 minutes, melting point 98°C). (hereinafter referred to as LLDPE (4)), and linear low-density polyethylene resin (density 0.944 g/cm 3 , MFR 4.0 g/10 min, melting point 128° C.) (hereinafter referred to as LLDPE (5)). ), the multilayer films for ultrasonic sealing of Examples 11 and 12 were produced and evaluated in the same manner as in Example 2, except that each was changed to ). Table 2 shows the results.
- LLDPE (4) linear low-density polyethylene resin
- LLDPE (5) linear low-density polyethylene resin
- Example 13 In Example 2, as shown in Table 3, the ratio of the average thickness of each layer of the laminated film formed of base layer (A)/intermediate layer (B)/intermediate layer (C)/seal layer (D) was , 20%:46%:20%:14%. Table 3 shows the results.
- Example 14 In Example 2, as shown in Table 3, a multilayer film for ultrasonic sealing of Example 14 was produced in the same manner as in Example 2, except that the total thickness of the multilayer film for ultrasonic sealing was changed from 40 ⁇ m to 35 ⁇ m. , conducted an evaluation. Table 3 shows the results.
- Examples 15-23 Ultrasonic sealing multilayer films of Examples 15 to 20 were produced and evaluated in the same manner as in Example 1 except that the composition and the layer ratio of each layer were changed to those shown in Tables 4 and 5. The results are shown in Tables 4 and 5.
- Example 1 In Example 1, as shown in Table 6, comparison was made in the same manner as in Example 1, except that the butene-based olefin resin was not included in the seal layer (D) and 60 parts of LLDPE (1) was changed to 100 parts. A multilayer film for ultrasonic sealing of Example 1 was produced and evaluated. Table 6 shows the results.
- PBR (1) polypropylene-1-butene copolymer (density 0.900 g/cm 3 , MFR 7.0 g/10 min, melting point 98°C, propylene-derived component content: 85 mol%)
- PBR (2) Polypropylene-1-butene copolymer (density 0.900 g/cm 3 , MFR 7.0 g/10 min, melting point 75°C, propylene-derived component content: 74 mol%)
- EBR (1) polyethylene-1-butene copolymer (density 0.893 g/cm 3 , MFR 6.7 g/10 min, melting point 77° C., ethylene-derived component content: 70 mol % to 92 mol %)
- EBR (2) polyethylene-1-butene copolymer (density 0.885 g/cm 3 , MFR 6.7 g/10 min, melting point 66° C., content of ethylene-derived component: 76 mol % to 90 mol %,
- Comparative Example 6 (Comparative Example 6)
- Example 1 As shown in Table 6, a multilayer film for ultrasonic sealing of Comparative Example 6 was produced in the same manner as in Example 1, except that LLDPE (1) was changed to HDPE in the sealing layer (D). and evaluated. Table 6 shows the results.
- the rigidity of the multilayer film for ultrasonic sealing was increased from 190 MPa to about 300 MPa. It was possible to obtain a multilayer film for ultrasonic sealing which could be adjusted and which is useful for flexible packaging applications. Further, in Examples 15 to 19 and Example 23, in which a cyclic olefin resin was used as part of the thermoplastic resin layer, the rigidity of the multilayer film for ultrasonic sealing can be adjusted to 300 MPa or more and about 900 MPa. A multi-layer film for ultrasonic sealing useful for applications requiring rigidity such as standing pouches was obtained.
- the MFR, density, melting point, and compound name of each resin used in the examples are shown below.
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Abstract
Description
本発明は、超音波シール用多層フィルム、及び包装体に関する。 The present invention relates to a multilayer film for ultrasonic sealing and a package.
洋菓子、スナック等の食品用包装フィルムにおいて、リサイクルを促進して環境負荷を低減するため、モノマテリアル(単一素材)化が進んでいる。従来の異素材の多層ラミネート構成(例えば、延伸ポリエチレンテレフタレートOPET/無延伸ポリプロピレンCPPの多層フィルム)に対し、モノマテリアル化に対応するためには、二軸延伸ポリエチレン/無延伸ポリエチレンシーラントのような多層フィルムが求められている。 The use of mono-materials (single materials) is progressing in order to promote recycling and reduce the environmental impact of food packaging films such as Western confectionery and snacks. In contrast to the conventional multi-layer laminate structure of different materials (e.g., oriented polyethylene terephthalate OPET/non-oriented polypropylene CPP multi-layer film), multi-layers such as biaxially oriented polyethylene/non-oriented polyethylene sealant are used to support monomaterials. Film is required.
しかしながら、従来のモノマテリアル化に対応した二軸延伸ポリエチレン/無延伸ポリエチレンシーラントからなる多層フィルムでは、素材間の耐熱性が異なるため、多層フィルムの表面が耐熱低下し、包装適性の低下が懸念されるという問題点がある。 However, with multilayer films made of biaxially oriented polyethylene and non-oriented polyethylene sealant, which are compatible with conventional mono-materialization, the heat resistance of the materials differs, so there is concern that the surface of the multilayer film will deteriorate in heat resistance and reduce packaging suitability. There is a problem that
一方、シール面のみ加熱可能な超音波を用い、超音波シール可能な多層フィルムが検討されている。これまでに、超音波溶接によっても強固に溶接することができる積層フィルムとして、一軸延伸ポリプロピレンフィルムから成る外層と、バリア層及び樹脂中間層と、線状低密度ポリエチレンであってもよいヤング率が高いシーラント層とを含有する積層フィルムが提案されている(例えば、特許文献1参照)。 On the other hand, a multilayer film that can be ultrasonically sealed using ultrasonic waves that can heat only the sealing surface is being studied. So far, as a laminated film that can be strongly welded even by ultrasonic welding, an outer layer made of a uniaxially oriented polypropylene film, a barrier layer and a resin intermediate layer, and a linear low density polyethylene may be used. Laminated films containing high sealant layers have been proposed (see, for example, Patent Document 1).
しかしながら、ポリエチレンを用いてモノマテリアル化に対応した多層フィルムでは、素材間の耐熱性が異なるため、超音波シールした場合に均一かつ安定なシール強度を得ることが困難であった。加えて、洋菓子、スナック等の食品用包装に用いられるピロー包装等の包装適性を得るために、フィルムの剛性も両立する必要がある。しかし、超音波シールに適した前記提案の積層フィルムでは、エチレン系樹脂層とポリプロピレン系樹脂層を含み、モノマテリアル化に対応できていない。したがって、モノマテリアル化に対応でき、十分な剛性を有し、かつ超音波シールに適した多層フィルムの樹脂構成が求められている。 However, with a multilayer film that uses polyethylene to support monomaterialization, it is difficult to obtain a uniform and stable seal strength when ultrasonically sealed due to differences in heat resistance between materials. In addition, in order to obtain packaging aptitude such as pillow packaging used for packaging foods such as western confectionery and snacks, it is necessary for the film to have both rigidity. However, the laminated film proposed above, which is suitable for ultrasonic sealing, includes an ethylene resin layer and a polypropylene resin layer, and cannot be used as a monomaterial. Therefore, there is a demand for a multilayer film resin structure that can be used as a monomaterial, has sufficient rigidity, and is suitable for ultrasonic sealing.
本発明は、前記従来における諸問題を解決し、以下の目的を達成することを課題とする。すなわち、本発明は、モノマテリアル化に対応でき、十分な剛性を有し、超音波溶接が可能であり、シール幅が狭く均一かつ安定な超音波シール強度を有することができる超音波シール用多層フィルムを提供することを目的とする。 The object of the present invention is to solve the above-mentioned conventional problems and to achieve the following objectives. That is, the present invention provides a multi-layer ultrasonic seal that can be used as a monomaterial, has sufficient rigidity, can be ultrasonically welded, and has a narrow seal width and uniform and stable ultrasonic seal strength. The purpose is to provide a film.
本発明は、本発明者らによる前記知見に基づくものであり、前記課題を解決するための手段としては、以下の通りである。すなわち、
<1> 熱可塑性樹脂を含有する熱可塑性樹脂層と、
直鎖状低密度ポリエチレン樹脂及びαオレフィン樹脂を含有するシール層と、を少なくとも有し、
前記αオレフィン樹脂が、ブテン系αオレフィン樹脂を含有し、
超音波によりシール可能であることを特徴とする超音波シール用多層フィルムである。
<2> 前記シール層における前記直鎖状低密度ポリエチレンの含有量が、50質量%以上90質量%以下である前記<1>に記載の超音波シール用多層フィルムである。
<3> 前記シール層における前記直状鎖低密度ポリエチレンの密度が、0.900kg/m3以上0.940kg/m3以下である前記<1>に記載の超音波シール用多層フィルムである。
<4> 前記シール層における前記ブテン系αオレフィン樹脂の含有が、10質量%以上50質量%以下である前記<1>に記載の超音波シール用多層フィルムである。
<5> 前記シール層の厚みが、15%以上である前記<1>に記載の超音波シール用多層フィルムである。
<6> 総厚みが40μm以上である前記<1>に記載の超音波シール用多層フィルムである。
<7> 示差走査熱量測定によって測定される融解熱量が60mJ/mg以上である前記<1>に記載の超音波シール用多層フィルムである。
<8> 前記熱可塑性樹脂が、ポリエチレン、及びポリプロピレンの少なくともいずれかを含有する前記<1>に記載の超音波シール用多層フィルムである。
<9> 前記<1>から<8>のいずれかに記載の超音波シール用多層フィルムと、熱可塑性樹脂フィルムとを超音波によりシールした包装体である。
The present invention is based on the above findings by the present inventors, and means for solving the above problems are as follows. i.e.
<1> a thermoplastic resin layer containing a thermoplastic resin;
a seal layer containing a linear low-density polyethylene resin and an α-olefin resin;
The α-olefin resin contains a butene-based α-olefin resin,
The multilayer film for ultrasonic sealing is characterized in that it can be sealed by ultrasonic waves.
<2> The multilayer film for ultrasonic sealing according to <1>, wherein the content of the linear low-density polyethylene in the seal layer is 50% by mass or more and 90% by mass or less.
<3> The multilayer film for ultrasonic sealing according to <1>, wherein the linear chain low-density polyethylene in the seal layer has a density of 0.900 kg/m 3 or more and 0.940 kg/m 3 or less.
<4> The multilayer film for ultrasonic sealing according to <1>, wherein the sealing layer contains the butene-based α-olefin resin in an amount of 10% by mass or more and 50% by mass or less.
<5> The multilayer film for ultrasonic sealing according to <1>, wherein the seal layer has a thickness of 15% or more.
<6> The multilayer film for ultrasonic sealing according to <1>, having a total thickness of 40 μm or more.
<7> The multilayer film for ultrasonic sealing according to <1>, having a heat of fusion of 60 mJ/mg or more as measured by differential scanning calorimetry.
<8> The multilayer film for ultrasonic sealing according to <1>, wherein the thermoplastic resin contains at least one of polyethylene and polypropylene.
<9> A package obtained by ultrasonically sealing the multilayer film for ultrasonic sealing according to any one of <1> to <8> and a thermoplastic resin film.
本発明によれば、従来における前記諸問題を解決し、前記目的を達成することができ、モノマテリアル化に対応でき、超音波溶接が可能であり、十分な剛性を有し、シール幅が狭く均一かつ安定な超音波シール強度を有することができる超音波シール用多層フィルムを提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the above-mentioned problems in the past can be solved, the above-mentioned objects can be achieved, it can be used as a monomaterial, ultrasonic welding is possible, it has sufficient rigidity, and the seal width is narrow. It is possible to provide a multilayer film for ultrasonic sealing that can have uniform and stable ultrasonic sealing strength.
(超音波シール用多層フィルム)
本発明の超音波シール用多層フィルムは、熱可塑性樹脂層と、シール層とを少なくとも有し、超音波によりシール可能である超音波シール用多層フィルムである。
(multilayer film for ultrasonic sealing)
The ultrasonic sealing multilayer film of the present invention has at least a thermoplastic resin layer and a sealing layer, and is ultrasonically sealable.
<熱可塑性樹脂層>
前記熱可塑性樹脂層は、熱可塑性樹脂を主たる樹脂成分として含有する。
前記熱可塑性樹脂層は、単層であってもよく、複数の層であってもよい。
前記熱可塑性樹脂層は、包装用フィルムの印刷を設けることができる表面層であってもよい。
<Thermoplastic resin layer>
The thermoplastic resin layer contains a thermoplastic resin as a main resin component.
The thermoplastic resin layer may be a single layer or multiple layers.
Said thermoplastic layer may be a surface layer on which printing of the packaging film can be provided.
-熱可塑性樹脂-
前記熱可塑性樹脂としては、特に制限はなく目的に応じて公知の熱可塑性樹脂を適宜選択することができ、例えば、オレフィン樹脂、スチレン樹脂、エステル樹脂、アクリル樹脂等が挙げられる。これらの中でも、モノマテリアル化できる点から、オレフィン樹脂が好ましい。
前記オレフィン樹脂としては、例えば、オレフィン単量体の単重合体(ポリエチレン単重合体、ポリプロピレン単重合体等);オレフィン単量体を主成分とした共重合体(プロピレン-エチレンブロック共重合体、プロピレン-エチレンランダム共重合体、エチレン-1-ブテン共重合体、プロピレン-1-ブテン共重合体等)等が挙げられる。これらは、1種単独で使用してもよく、2種類以上を併用してもよい。これらの中でも、ポリエチレン、及びポリプロピレンの少なくともいずれかを含有する、エチレン単重合体、プロピレン単重合体、プロピレン-エチレンブロック共重合体、プロピレン-エチレンランダム共重合体が好ましい。
前記オレフィン樹脂中のオレフィン単量体の含有量としては、50モル%~100モル%が好ましく、70モル%~100モル%がより好ましい。
-Thermoplastic resin-
The thermoplastic resin is not particularly limited and can be appropriately selected from known thermoplastic resins depending on the intended purpose. Examples thereof include olefin resins, styrene resins, ester resins and acrylic resins. Among these, the olefin resin is preferable because it can be made into a monomaterial.
Examples of the olefin resin include homopolymers of olefin monomers (polyethylene homopolymer, polypropylene homopolymer, etc.); copolymers containing olefin monomers as main components (propylene-ethylene block copolymers, propylene-ethylene random copolymer, ethylene-1-butene copolymer, propylene-1-butene copolymer, etc.). These may be used individually by 1 type, and may use 2 or more types together. Among these, ethylene homopolymers, propylene homopolymers, propylene-ethylene block copolymers, and propylene-ethylene random copolymers containing at least one of polyethylene and polypropylene are preferred.
The content of the olefin monomer in the olefin resin is preferably 50 mol % to 100 mol %, more preferably 70 mol % to 100 mol %.
上記熱可塑性樹脂としては、環状オレフィン系樹脂を使用することもできる。
当該環状オレフィン系樹脂としては、例えば、ノルボルネン系重合体、ビニル脂環式炭化水素重合体、環状共役ジエン重合体等が挙げられる。
これらの中でも、ノルボルネン系重合体が好ましい。
また、ノルボルネン系重合体としては、ノルボルネン系単量体の開環重合体(COP)、ノルボルネン系単量体とエチレン等のオレフィンを共重合したノルボルネン系共重合体(COC)等が挙げられる。
また、COP及びCOCの水素添加物も、特に好ましい。
また、環状オレフィン系樹脂の重量平均分子量は、5,000~500,000が好ましく、より好ましくは7,000~300,000である。
A cyclic olefin resin can also be used as the thermoplastic resin.
Examples of the cyclic olefin-based resins include norbornene-based polymers, vinyl alicyclic hydrocarbon polymers, and cyclic conjugated diene polymers.
Among these, norbornene-based polymers are preferred.
Examples of norbornene-based polymers include ring-opening polymers (COP) of norbornene-based monomers, and norbornene-based copolymers (COC) obtained by copolymerizing norbornene-based monomers with olefins such as ethylene.
Hydrogenates of COP and COC are also particularly preferred.
The weight average molecular weight of the cyclic olefin resin is preferably 5,000 to 500,000, more preferably 7,000 to 300,000.
前記ノルボルネン系重合体と原料となるノルボルネン系単量体は、ノルボルネン環を有する脂環族系単量体である。
このようなノルボルネン系単量体としては、例えば、ノルボルネン、テトラシクロドデセン、エチリデンノルボルネン、ビニルノルボルネン、エチリデテトラシクロドデセン、ジシクロペンタジエン、ジメタノテトラヒドロフルオレン、フェニルノルボルネン、メトキシカルボニルノルボルネン、メトキシカルボニルテトラシクロドデセン等が挙げられる。
これらのノルボルネン系単量体は、単独で用いても、2種以上を併用しても良い。
The norbornene-based polymer and the norbornene-based monomer as a raw material are alicyclic monomers having a norbornene ring.
Examples of such norbornene-based monomers include norbornene, tetracyclododecene, ethylidenenorbornene, vinylnorbornene, ethylidetetracyclododecene, dicyclopentadiene, dimethanotetrahydrofluorene, phenylnorbornene, methoxycarbonylnorbornene, methoxy carbonyltetracyclododecene and the like.
These norbornene-based monomers may be used alone or in combination of two or more.
前記ノルボルネン系共重合体は、前記ノルボルネン系単量体と共重合可能なオレフィンとを共重合したものであり、このようなオレフィンとしては、例えば、エチレン、プロピレン、1 ブテン等の炭素原子数2~20個を有するオレフィン;シクロブテン、シクロペンテン、シクロヘキセン等のシクロオレフィン;1,4 ヘキサジエン等の非共役ジエン等が挙げられる。 The norbornene-based copolymer is obtained by copolymerizing the norbornene-based monomer with a copolymerizable olefin. cycloolefins such as cyclobutene, cyclopentene and cyclohexene; non-conjugated dienes such as 1,4-hexadiene;
上記熱可塑性樹脂層中に含まれる環状オレフィン系樹脂の含有量は、当該熱可塑性樹脂層に含まれる樹脂成分中の15~35質量%、好ましくは20~30質量%とすることで、耐衝撃性を損なうことなく、好適な易引き裂き性や直進カット性を実現できる。 The content of the cyclic olefin resin contained in the thermoplastic resin layer is 15 to 35 mass%, preferably 20 to 30 mass% of the resin component contained in the thermoplastic resin layer. Suitable easy tearability and straight cutability can be realized without impairing the properties.
また、上記熱可塑性樹脂層中に使用する環状オレフィン系樹脂は、そのガラス転移温度が100℃以下であり、好ましくは90℃以下、より好ましくは80℃以下である。
また、下限は特に制限されないが、50℃以上であることが好ましく、60℃以上であることがより好ましく、70℃以上であることがさらに好ましい。
当該環状オレフィン系樹脂として当該ガラス転移温度のものを使用することで、良好な耐熱性や剛性を得やすく、また、落下等に対する耐破袋性を向上させやすくなる。
また、良好な相溶性を得やすくなり、外観ムラを抑制しやすくなる。
当該ガラス転移温度は、DSCにより測定して得られる値である。
The cyclic olefin resin used in the thermoplastic resin layer has a glass transition temperature of 100° C. or lower, preferably 90° C. or lower, more preferably 80° C. or lower.
Although the lower limit is not particularly limited, it is preferably 50°C or higher, more preferably 60°C or higher, and even more preferably 70°C or higher.
By using the cyclic olefin-based resin having the glass transition temperature, it is easy to obtain good heat resistance and rigidity, and it is easy to improve the bag breakage resistance against dropping and the like.
Moreover, it becomes easy to obtain favorable compatibility and it becomes easy to suppress appearance unevenness.
The glass transition temperature is a value obtained by measuring with DSC.
上記環状オレフィン系樹脂として使用できる市販品として、ノルボルネン系モノマーの開環重合体(COP)としては、例えば、日本ゼオン株式会社製「ゼオノア(ZEONOR)」等が挙げられ、ノルボルネン系共重合体(COC)としては、例えば、三井化学株式会社製「アペル」、ポリプラスチックス社製「トパス(TOPAS)」等が挙げられる。 Examples of commercially available products that can be used as the cyclic olefin-based resin include ring-opening polymers (COP) of norbornene-based monomers, such as "ZEONOR" manufactured by Nippon Zeon Co., Ltd. Norbornene-based copolymers ( COC) includes, for example, "APEL" manufactured by Mitsui Chemicals, Inc., and "TOPAS" manufactured by Polyplastics.
前記熱可塑性樹脂のメルトフローレート(MFR)としては、特に制限はなく目的に応じて適宜選択することができるが、温度190℃、及び荷重2.16kgの測定条件において、1.0g/10分間~50.0g/10分間が好ましく、3.0g/10分間~45.0g/10分間がより好ましく、3.0g/10分間~12.0g/10分間が更に好ましい。
ここで、前記メルトフローレート(MFR)は、JISK7210に準拠して、190℃、荷重2.16kg(21.18N)で測定した値である。
The melt flow rate (MFR) of the thermoplastic resin is not particularly limited and can be appropriately selected according to the purpose. 50.0 g/10 minutes is preferred, 3.0 g/10 minutes to 45.0 g/10 minutes is more preferred, and 3.0 g/10 minutes to 12.0 g/10 minutes is even more preferred.
Here, the melt flow rate (MFR) is a value measured at 190° C. under a load of 2.16 kg (21.18 N) according to JISK7210.
上記環状オレフィン系樹脂のメルトフローレート(MFR)としては、0.2~30g/10分(230℃、21.18N)が好ましく、3~17g/10分(230℃、21.18N)がより好ましく、5~15g/10分(230℃、21.18N)がさらに好ましい。MFRがこの範囲であると、各種の多層成膜法において良好な成膜性が得られる点で好ましい。 The melt flow rate (MFR) of the cyclic olefin resin is preferably 0.2 to 30 g/10 minutes (230°C, 21.18N), more preferably 3 to 17 g/10 minutes (230°C, 21.18N). Preferably, 5 to 15 g/10 minutes (230° C., 21.18 N) is more preferable. When the MFR is within this range, it is preferable in that good film formability can be obtained in various multilayer film forming methods.
前記熱可塑性樹脂の密度としては、特に制限はなく目的に応じて適宜選択することができるが、0.89g/cm3~0.96g/cm3が好ましく、0.89g/cm3~0.93g/cm3がより好ましい。 The density of the thermoplastic resin is not particularly limited and can be appropriately selected according to the purpose . 93 g/cm 3 is more preferred.
前記熱可塑性樹脂の融点としては、特に制限はなく目的に応じて適宜選択することができるが、110℃~170℃が好ましく、120℃~160℃がより好ましい。前記融点は、示差走査熱量計(DSC)(例えば、株式会社日立ハイテクサイエンス製、DSC7020)を用いて測定することができる。 The melting point of the thermoplastic resin is not particularly limited and can be appropriately selected according to the purpose. The melting point can be measured using a differential scanning calorimeter (DSC) (for example, DSC7020 manufactured by Hitachi High-Tech Science Co., Ltd.).
<シール層>
前記シール層は、直鎖状低密度ポリエチレン樹脂及びαオレフィン樹脂を主たる樹脂成分として含有する。
<Seal layer>
The seal layer contains a linear low-density polyethylene resin and an α-olefin resin as main resin components.
-直鎖状低密度ポリエチレン樹脂-
前記直鎖状低密度ポリエチレン樹脂(Linear Low Density Polyethylene,LLDPE)とは、チーグラーナッタ触媒等のマルチサイト触媒又はメタロセン触媒等のシングルサイト触媒を使用して重合した、エチレンとαオレフィンとの共重合体である。
なお、前記直鎖状低密度ポリエチレンの規定を満たす樹脂の中には、後述するαオレフィン樹脂の規定を満たす樹脂も含まれ得るが、本発明においては、そのような樹脂も前記直鎖状低密度ポリエチレン樹脂として扱う。
前記直鎖状低密度ポリエチレン樹脂としては、特に制限はなく目的に応じて適宜選択することができ、例えば、主成分のエチレン単量体に1-ブテン単量体、1-ヘキセン、4-メチルペンテン単量体、1-オクテン等のαオレフィンを共重合させた共重合体等が挙げられる。これらの中でも、主成分のエチレン単量体に1-ヘキセン、及び1-オクテンの少なくともいずれかを共重合させた共重合体が好ましい。これらは、1種単独で使用してもよく、2種類以上を併用してもよい。
前記直鎖状低密度ポリエチレン樹脂中のエチレン単量体の含有量としては、20モル%~95モル%が好ましく、30モル%~95モル%がより好ましい。
-Linear low-density polyethylene resin-
The linear low density polyethylene (LLDPE) is a copolymer of ethylene and α-olefin polymerized using a multi-site catalyst such as a Ziegler-Natta catalyst or a single-site catalyst such as a metallocene catalyst. It is a coalescence.
Among the resins that satisfy the linear low-density polyethylene, resins that satisfy the specifications of α-olefin resins, which will be described later, may also be included. Treat as density polyethylene resin.
The linear low-density polyethylene resin is not particularly limited and can be appropriately selected according to the purpose. Examples thereof include copolymers obtained by copolymerizing α-olefins such as pentene monomers and 1-octene. Among these, a copolymer obtained by copolymerizing at least one of 1-hexene and 1-octene with an ethylene monomer as a main component is preferable. These may be used individually by 1 type, and may use 2 or more types together.
The content of the ethylene monomer in the linear low-density polyethylene resin is preferably 20 mol % to 95 mol %, more preferably 30 mol % to 95 mol %.
前記直鎖状低密度ポリエチレン樹脂のメルトフローレート(MFR)としては、特に制限はなく目的に応じて適宜選択することができるが、温度190℃、及び荷重2.16kgの測定条件において、1.0g/10分間~50.0g/10分間が好ましく、3.0g/10分間~45.0g/10分間がより好ましく、3.0g/10分間~12.0g/10分間が更に好ましい。 The melt flow rate (MFR) of the linear low-density polyethylene resin is not particularly limited and can be appropriately selected according to the purpose. 0 g/10 minutes to 50.0 g/10 minutes is preferable, 3.0 g/10 minutes to 45.0 g/10 minutes is more preferable, and 3.0 g/10 minutes to 12.0 g/10 minutes is even more preferable.
前記直鎖状低密度ポリエチレン樹脂の密度としては、特に制限はなく目的に応じて適宜選択することができるが、0.900g/cm3~0.940g/cm3が好ましく、0.903g/cm3~0.935g/cm3がより好ましい。 The density of the linear low-density polyethylene resin is not particularly limited and can be appropriately selected according to the purpose. 3 to 0.935 g/cm 3 is more preferable.
前記直鎖状低密度ポリエチレン樹脂の融点としては、特に制限はなく目的に応じて適宜選択することができるが、50℃~130℃が好ましく、50℃~125℃がより好ましく、60℃~125℃が更に好ましい。 The melting point of the linear low-density polyethylene resin is not particularly limited and can be appropriately selected according to the purpose. °C is more preferred.
前記直鎖状低密度ポリエチレン樹脂の含有量としては、前記シール層に含まれる樹脂成分の総量に対して、40質量%以上95質量%以下が好ましく、50質量%以上90質量%以下が好ましく、60質量%以上80質量%以下がより好ましい。
前記含有量が40質量%以上95質量%以下であると、超音波シール性が発現する点で有利である。また、前記含有量が40質量%以上95質量%以下であると、シール長の全長で均一かつ安定な超音波シール性が担保される点で特に有利である。
The content of the linear low-density polyethylene resin is preferably 40% by mass or more and 95% by mass or less, preferably 50% by mass or more and 90% by mass or less, relative to the total amount of the resin components contained in the seal layer. 60% by mass or more and 80% by mass or less is more preferable.
When the content is 40% by mass or more and 95% by mass or less, it is advantageous in terms of exhibiting ultrasonic sealing properties. Further, when the content is 40% by mass or more and 95% by mass or less, it is particularly advantageous in terms of ensuring uniform and stable ultrasonic sealing performance over the entire sealing length.
-αオレフィン樹脂-
前記αオレフィン樹脂は、少なくともブテン系αオレフィン樹脂を含有し、更に必要に応じて、ブテン系αオレフィン樹脂以外の、その他のαオレフィン樹脂を含有する。
-α olefin resin-
The α-olefin resin contains at least a butene-based α-olefin resin and, if necessary, other α-olefin resins other than the butene-based α-olefin resin.
--ブテン系αオレフィン樹脂--
ブテン系αオレフィン樹脂は、ブテン-1単量体を50モル%以上含む共重合体又はブテン-1単量体の単重合体を指す。当該ブテン系αオレフィン樹脂としては、特に制限はなく目的に応じて適宜選択することができ、例えば、ブテン-1単量体の単重合体、ブテン-1単量体を50モル%以上含むエチレン-1-ブテン共重合体、ブテン-1単量体を50モル%以上含むプロピレン-1-ブテン共重合体、ブテン-1単量体を50モル%以上含むエチレン-プロピレン-1-ブテン共重合体等が挙げられる。これらの中でも、ブテン-1単量体を50モル%以上含むプロピレン-1-ブテン共重合体が好ましい。これらは、1種単独で使用してもよく、2種類以上を併用してもよい。
当該ブテン系αオレフィン樹脂が共重合体である場合、当該ブテン系αオレフィン樹脂中のブテン-1単量体の含有量としては、50モル%~95モル%であることが好ましく、60モル%~95モル%であることがより好ましく、70モル%~95モル%であることがさらに好ましい。
--butene-based α-olefin resin--
The butene-based α-olefin resin refers to a copolymer containing 50 mol % or more of butene-1 monomer or a butene-1 monomer homopolymer. The butene-based α-olefin resin is not particularly limited and can be appropriately selected according to the purpose. -1-butene copolymer, propylene-1-butene copolymer containing 50 mol% or more of butene-1 monomer, ethylene-propylene-1-butene copolymer containing 50 mol% or more of butene-1 monomer A coalescence etc. are mentioned. Among these, propylene-1-butene copolymers containing 50 mol % or more of butene-1 monomer are preferred. These may be used individually by 1 type, and may use 2 or more types together.
When the butene-based α-olefin resin is a copolymer, the content of the butene-1 monomer in the butene-based α-olefin resin is preferably 50 mol% to 95 mol%, preferably 60 mol%. It is more preferably to 95 mol %, even more preferably 70 mol % to 95 mol %.
前記ブテン系αオレフィン樹脂のメルトフローレート(MFR)としては、特に制限はなく目的に応じて適宜選択することができるが、温度190℃、及び荷重2.16kgの測定条件において、1.0g/10分間~50.0g/10分間が好ましく、3.0g/10分間~45.0g/10分間がより好ましく、3.0g/10分間~12.0g/10分間が更に好ましい。 The melt flow rate (MFR) of the butene-based α-olefin resin is not particularly limited and can be appropriately selected according to the purpose. 10 minutes to 50.0 g/10 minutes is preferred, 3.0 g/10 minutes to 45.0 g/10 minutes is more preferred, and 3.0 g/10 minutes to 12.0 g/10 minutes is even more preferred.
前記ブテン系αオレフィン樹脂の密度としては、特に制限はなく目的に応じて適宜選択することができるが、0.87g/cm3~0.96g/cm3が好ましく、0.88g/cm3~0.92g/cm3がより好ましい。 The density of the butene-based α-olefin resin is not particularly limited and can be appropriately selected according to the purpose . 0.92 g/cm 3 is more preferred.
前記ブテン系αオレフィン樹脂の融点としては、特に制限はなく目的に応じて適宜選択することができるが、50℃~120℃が好ましく、50℃~110℃がより好ましく、50℃~80℃が更に好ましい。 The melting point of the butene-based α-olefin resin is not particularly limited and can be appropriately selected according to the purpose. More preferred.
前記ブテン系αオレフィン樹脂の含有量としては、前記シール層に含まれる樹脂成分の総量に対して、5質量%以上60質量%以下が好ましく、10質量%以上50質量%以下がより好ましく、15質量%以上50質量%以下が更に好ましく、20質量%以上50質量%以下が特に好ましい。
前記含有量が5質量%以上60質量%以下であると、超音波シール性が発現する点で有利である。また、前記含有量が20質量%以上50質量%以下であると、シール長の全長で均一かつ安定な超音波シール性が担保される点で特に有利である。
The content of the butene-based α-olefin resin is preferably 5% by mass or more and 60% by mass or less, more preferably 10% by mass or more and 50% by mass or less, based on the total amount of the resin components contained in the seal layer. It is more preferably 50% by mass or less, and particularly preferably 20% by mass or more and 50% by mass or less.
When the content is 5% by mass or more and 60% by mass or less, it is advantageous in terms of exhibiting ultrasonic sealing properties. Further, when the content is 20% by mass or more and 50% by mass or less, it is particularly advantageous in terms of ensuring uniform and stable ultrasonic sealing performance over the entire sealing length.
前記シール層における前記直鎖状低密度ポリエチレン(b1)に対する前記ブテン系αオレフィン樹脂(b2)の質量比(b2/b1)としては、特に制限はなく目的に応じて適宜選択することができるが、5/95~60/40が好ましく、10/90~50/50がより好ましく、20/80~50/50が更に好ましく、30/70~40/60が特に好ましい。 The mass ratio (b2/b1) of the butene-based α-olefin resin (b2) to the linear low-density polyethylene (b1) in the sealing layer is not particularly limited and can be appropriately selected according to the purpose. , preferably 5/95 to 60/40, more preferably 10/90 to 50/50, still more preferably 20/80 to 50/50, and particularly preferably 30/70 to 40/60.
--その他のαオレフィン樹脂--
前記その他のαオレフィン樹脂としては、αオレフィンを含み、1-ブテン単量体の含有量が50モル%未満であれば、特に制限はなく目的に応じて適宜選択することができ、例えば、αオレフィンを含むエチレン重合体、αオレフィンを含むプロピレン重合体、αオレフィンを含むエチレン-プロピレン共重合体、エチレン-1-ブテン共重合体、プロピレン-1-ブテン共重合体等が挙げられる。αオレフィンとしては、1-ブテン、1-ヘキセン、4-メチルペンテン、1-オクテン等が挙げられる。これらのうち、ブテン-1単量体を50モル%以上含む共重合体は、ブテン系αオレフィン樹脂に該当し、ブテン-1単量体を50モル%未満含む共重合体は、その他のαオレフィン樹脂に該当する。また、チーグラーナッタ触媒等のマルチサイト触媒又はメタロセン触媒等のシングルサイト触媒を使用して重合した、エチレンとαオレフィンとの共重合体については、αオレフィン樹脂ではなく、直鎖状低密度ポリエチレンに該当する。
また、これらは、1種単独で使用してもよく、2種類以上を併用してもよい。
前記αオレフィン樹脂中のαオレフィン単量体の含有量としては、特に制限はなく目的に応じて適宜選択することができる。
--Other α-olefin resins--
The other α-olefin resin is not particularly limited as long as it contains an α-olefin and the content of the 1-butene monomer is less than 50 mol%, and can be appropriately selected according to the purpose. Examples include ethylene polymers containing olefins, propylene polymers containing α-olefins, ethylene-propylene copolymers containing α-olefins, ethylene-1-butene copolymers, propylene-1-butene copolymers, and the like. α-olefins include 1-butene, 1-hexene, 4-methylpentene, 1-octene and the like. Among these, copolymers containing 50 mol% or more of butene-1 monomer correspond to butene-based α-olefin resins, and copolymers containing less than 50 mol% of butene-1 monomer are other α It corresponds to olefin resin. In addition, for copolymers of ethylene and α-olefins polymerized using multi-site catalysts such as Ziegler-Natta catalysts or single-site catalysts such as metallocene catalysts, linear low-density polyethylene is used instead of α-olefin resins. Applicable.
Moreover, these may be used individually by 1 type, and may use 2 or more types together.
The content of the α-olefin monomer in the α-olefin resin is not particularly limited and can be appropriately selected according to the purpose.
前記その他のαオレフィン樹脂のメルトフローレート(MFR)としては、特に制限はなく目的に応じて適宜選択することができるが、温度190℃、及び荷重2.16kgの測定条件において、1.0g/10分間~50.0g/10分間が好ましく、2.0g/10分間~45.0g/10分間がより好ましく、2.0g/10分間~10.0g/10分間が更に好ましい。 The melt flow rate (MFR) of the other α-olefin resin is not particularly limited and can be appropriately selected according to the purpose. 10 minutes to 50.0 g/10 minutes is preferred, 2.0 g/10 minutes to 45.0 g/10 minutes is more preferred, and 2.0 g/10 minutes to 10.0 g/10 minutes is even more preferred.
前記その他のαオレフィン樹脂の密度としては、特に制限はなく目的に応じて適宜選択することができるが、0.85g/cm3~0.96g/cm3が好ましく、0.87g/cm3~0.90g/cm3がより好ましい。 The density of the other α-olefin resin is not particularly limited and can be appropriately selected according to the purpose . 0.90 g/cm 3 is more preferred.
前記その他のαオレフィン樹脂の融点としては、特に制限はなく目的に応じて適宜選択することができるが、40℃~120℃が好ましく、50℃~100℃がより好ましい。 The melting point of the other α-olefin resin is not particularly limited and can be appropriately selected according to the purpose, but is preferably 40°C to 120°C, more preferably 50°C to 100°C.
本発明のシール層には、さらに環状オレフィン系樹脂を使用してもよい。当該環状オレフィン系樹脂としては、熱可塑性樹脂層にて使用できる環状オレフィン系樹脂と同様のものを使用できる。 A cyclic olefin resin may also be used in the seal layer of the present invention. As the cyclic olefin-based resin, the same cyclic olefin-based resin that can be used in the thermoplastic resin layer can be used.
<その他の成分>
前記シール層はその他のオレフィン系樹脂を含んでいてもよい。その他のオレフィン系樹脂としては、各種のエチレン系樹脂やプロピレン系樹脂等が挙げられる。
前記熱可塑性樹脂層、及び前記シール層の樹脂には、その他の成分として、ポリオレフィンに汎用される酸化防止剤、紫外線吸収剤、帯電防止剤、滑剤(ブロッキング防止剤、スリップ剤)等の配合剤を適宜配合してもよい。
<Other ingredients>
The seal layer may contain other olefinic resins. Other olefin-based resins include various ethylene-based resins and propylene-based resins.
The resin of the thermoplastic resin layer and the seal layer contains other ingredients such as antioxidants, ultraviolet absorbers, antistatic agents, and lubricants (antiblocking agents, slip agents) commonly used in polyolefins. may be blended as appropriate.
[超音波シール用多層フィルムの層構成]
前記超音波シール用多層フィルムにおける前記熱可塑性樹脂層は、単層であってもよく、複数の層であってもよい。複数の前記熱可塑性樹脂層は、互いに同じ組成であってもよく、異なる組成であってもよい。
前記熱可塑性樹脂層が単層である場合、前記超音波シール用多層フィルムは、熱可塑性樹脂層/シール層の順で積層される多層フィルムである。
前記熱可塑性樹脂層が複数の層である場合、前記熱可塑性樹脂層は、前記超音波シール用多層フィルムの表面層となる基材層と、(1層~複数層の)中間層とを有し、前記超音波シール用多層フィルムは、基材層(熱可塑性樹脂層)/中間層(熱可塑性樹脂層)/シール層の順で積層される多層フィルムである。
[Layer structure of multilayer film for ultrasonic sealing]
The thermoplastic resin layer in the multilayer film for ultrasonic sealing may be a single layer or a plurality of layers. The plurality of thermoplastic resin layers may have the same composition or different compositions.
When the thermoplastic resin layer is a single layer, the multilayer film for ultrasonic sealing is a multilayer film laminated in the order of thermoplastic resin layer/seal layer.
When the thermoplastic resin layer is a plurality of layers, the thermoplastic resin layer has a base layer that serves as a surface layer of the multilayer film for ultrasonic sealing and an intermediate layer (one to multiple layers). The multilayer film for ultrasonic sealing is a multilayer film laminated in the order of base layer (thermoplastic resin layer)/intermediate layer (thermoplastic resin layer)/seal layer.
上記熱可塑性樹脂層が複数の層であり、中間層がある場合、中間層は環状オレフィン系樹脂層であることも好ましい。当該環状オレフィン系樹脂層とは、環状オレフィン系樹脂を当該層の樹脂成分のうち60質量%以上含む層を指す。
このような層を中間層に使用することで、多層フィルムとしての剛性が向上するほか、接着剤成分の内部への移行を妨げることができ、さらに超音波の伝搬性が良好であるため超音波シール強度も向上する。
When the thermoplastic resin layer is a plurality of layers and there is an intermediate layer, the intermediate layer is also preferably a cyclic olefin resin layer. The said cyclic olefin resin layer refers to the layer which contains 60 mass % or more of cyclic olefin resins among the resin components of the said layer.
By using such a layer as an intermediate layer, in addition to improving the rigidity of the multilayer film, it is possible to prevent the migration of the adhesive component into the interior, and because it has good ultrasonic wave propagation properties, The seal strength is also improved.
前記超音波シール用多層フィルムは、各層が共に押し出されて積層される共押出多層フィルムであってもよく、一部の層を接着して積層されるラミネートフィルムであってもよい。
前記追加基材層をラミネートする際の接着方法としては、特に制限はなく目的に応じて適宜選択することができ、例えば、ドライラミネーション、ウエットラミネーション、ノンソルベントラミネーション、押出ラミネーション等が挙げられる。
The multilayer film for ultrasonic sealing may be a coextrusion multilayer film in which each layer is extruded and laminated together, or may be a laminate film in which some layers are adhered and laminated.
The adhesion method for laminating the additional base material layer is not particularly limited and can be appropriately selected according to the purpose. Examples thereof include dry lamination, wet lamination, non-solvent lamination and extrusion lamination.
前記超音波シール用多層フィルムは、無延伸のフィルムであることが好ましい。当該超音波シール用シーラントフィルムは、上記の共押出による製造方法によって、実質的に無延伸の多層フィルムとして得られるため、真空成形による深絞り成形等の二次成形も可能となる。また、当該超音波シール用多層フィルムが一部の層を接着して積層されるラミネートフィルムである場合は、当該一部の層が延伸された樹脂フィルムであってもよいが、無延伸の樹脂フィルムを用いることが好ましい。 The ultrasonic sealing multilayer film is preferably a non-stretched film. Since the sealant film for ultrasonic sealing can be obtained as a substantially unstretched multilayer film by the above coextrusion production method, secondary forming such as deep drawing forming by vacuum forming is also possible. In addition, when the multilayer film for ultrasonic sealing is a laminate film laminated by bonding some layers, the resin film may be a stretched resin film in which some layers are laminated, but a non-stretched resin Films are preferably used.
前記超音波シール用多層フィルムは、基本的には透明で、表面平滑である。前記超音波シール用多層フィルムの両面又は片面の混合樹脂層にコロナ放電処理して印刷特性を持たせてもよい。また、前記超音波シール用多層フィルムの両面又は片面にエンボス処理して梨地等の絞模様を付与してもよい。 The multilayer film for ultrasonic sealing is basically transparent and has a smooth surface. The mixed resin layer on both sides or one side of the multilayer film for ultrasonic sealing may be subjected to a corona discharge treatment to impart printability. In addition, both sides or one side of the multilayer film for ultrasonic sealing may be embossed to give an aperture pattern such as a satin finish.
前記超音波シール用多層フィルムの総厚みとしては、特に制限はなく目的に応じて適宜選択することができるが、均一かつ安定な超音波シール強度が担保される点で、30μm以上が好ましく、40μm以上がより好ましい。また、30μm以上100μm以下が好ましく、40μm以上90μm以下がより好ましい。 The total thickness of the multilayer film for ultrasonic sealing is not particularly limited and can be appropriately selected according to the purpose. The above is more preferable. Moreover, it is preferably 30 μm or more and 100 μm or less, and more preferably 40 μm or more and 90 μm or less.
前記熱可塑性樹脂層の単層又は各層の平均厚みとしては、特に制限はなく目的に応じて適宜選択することができるが、5μm~30μmが好ましく、10μm~20μmがより好ましい。
前記熱可塑性樹脂層が複数の層である場合の各層の平均厚みの合計としては、特に制限はなく目的に応じて適宜選択することができるが、15μm~90μmが好ましく、30μm~80μmがより好ましい。
前記熱可塑性樹脂層の層みは、特に制限はなく目的に応じて適宜選択することができるが、前記熱可塑性樹脂層、及び前記シール層の合計厚みに対する前記熱可塑性樹脂層の平均厚みの比率(%)として、90%以下が好ましく、20%~90%がより好ましく、50%~80%が更に好ましい。
The average thickness of a single layer or each layer of the thermoplastic resin layer is not particularly limited and can be appropriately selected according to the purpose.
When the thermoplastic resin layer is a plurality of layers, the total average thickness of each layer is not particularly limited and can be appropriately selected according to the purpose. .
The thickness of the thermoplastic resin layer is not particularly limited and can be appropriately selected according to the purpose. (%) is preferably 90% or less, more preferably 20% to 90%, even more preferably 50% to 80%.
前記シール層の平均厚みとしては、特に制限はなく目的に応じて適宜選択することができるが、3μm~30μmが好ましく、5μm~25μmがより好ましく、9μm~20μmが更に好ましい。
前記シール層の層みは、特に制限はなく目的に応じて適宜選択することができるが、前記熱可塑性樹脂層及び前記シール層の合計厚みに対する前記シール層の平均厚みの比率(%)として、10%以上が好ましく、15%以上がより好ましく、20%以上が更に好ましい。また、10%以上50%以下が好ましく、15%以上50%以下がより好ましく、20%以上50%以下が更に好ましい。
前記厚みが10%以上であると、シール長の全長で均一かつ安定な超音波シール性が担保される点で有利である。
The average thickness of the sealing layer is not particularly limited and can be appropriately selected depending on the intended purpose.
The thickness of the seal layer is not particularly limited and can be appropriately selected according to the purpose. 10% or more is preferred, 15% or more is more preferred, and 20% or more is even more preferred. Moreover, it is preferably 10% or more and 50% or less, more preferably 15% or more and 50% or less, and still more preferably 20% or more and 50% or less.
When the thickness is 10% or more, it is advantageous in that uniform and stable ultrasonic sealing performance is ensured over the entire sealing length.
また、上記熱可塑性樹脂層の一部又は全部が上記環状オレフィン系樹脂層である場合、その厚み比率は上記多層フィルムの総厚みに対して5%以上30%以下が好ましく、5%以上20%以下がより好ましく、8%以上18%以下がさらに好ましい。当該環状オレフィン系樹脂層の厚み比率が当該範囲であると、剛性とシール強度を向上することができ、かつ当該多層フィルムをラミネートフィルムとした場合にモノマテリアルフィルムとしやすいため好ましい。当該環状オレフィン系樹脂層が複数存在する場合は、その合計の厚み比率が当該範囲であると好ましい。 Further, when part or all of the thermoplastic resin layer is the cyclic olefin resin layer, the thickness ratio thereof is preferably 5% or more and 30% or less, more preferably 5% or more and 20%, with respect to the total thickness of the multilayer film. The following is more preferable, and 8% or more and 18% or less is even more preferable. When the thickness ratio of the cyclic olefin-based resin layer is within the range, the rigidity and seal strength can be improved, and when the multilayer film is used as a laminate film, it is easily made into a monomaterial film, which is preferable. When the said cyclic olefin resin layer exists in multiple numbers, it is preferable in the total thickness ratio being the said range.
[融解熱量]
前記超音波シール用多層フィルムにおける示差走査熱量測定(DSC)によって測定される融解熱量としては、超音波シールによる均一な溶着性の点で、60mJ/mg以上が好ましく、65mJ/mg以上がより好ましく、75mJ/mg以上が更に好ましい。また、60mJ/mg以上115mJ/mg以下が好ましく、60mJ/mg以上110mJ/mg以下がより好ましく、60mJ/mg以上100mJ/mg以下が更に好ましい。
示差走査熱量測定(DSC)によって測定される融解熱量は、昇温1回目の融解熱量であり、例えば、示差走査熱量計(株式会社日立ハイテクサイエンス製、DSC7020)を用いて以下の手順で測定することができる。
まず、対象試料である超音波シール用多層フィルムの約5.0mgをアルミニウム製の試料容器に入れ、試料容器をホルダーユニットに載せ、電気炉中にセットする。次いで、窒素雰囲気下、30℃から昇温速度10℃/分にて200℃まで加熱(昇温1回目)し、示差走査熱量計を用いてDSC曲線を計測する。
得られたDSC曲線から、示差走査熱量計の解析プログラムを用いて、1回目の昇温時におけるDSC曲線を選択し、対象試料の昇温1回目における融解熱量[mJ/mg]を求めることができる。
[Heat of fusion]
The heat of fusion measured by differential scanning calorimetry (DSC) in the multilayer film for ultrasonic sealing is preferably 60 mJ/mg or more, more preferably 65 mJ/mg or more, from the viewpoint of uniform weldability by ultrasonic sealing. , more preferably 75 mJ/mg or more. Also, it is preferably 60 mJ/mg or more and 115 mJ/mg or less, more preferably 60 mJ/mg or more and 110 mJ/mg or less, and even more preferably 60 mJ/mg or more and 100 mJ/mg or less.
The amount of heat of fusion measured by differential scanning calorimetry (DSC) is the amount of heat of fusion in the first temperature rise, and is measured in the following procedure using, for example, a differential scanning calorimeter (manufactured by Hitachi High-Tech Science Co., Ltd., DSC7020). be able to.
First, about 5.0 mg of a multilayer film for ultrasonic sealing, which is a target sample, is placed in an aluminum sample container, the sample container is placed on a holder unit, and set in an electric furnace. Next, in a nitrogen atmosphere, the sample is heated from 30° C. to 200° C. at a temperature increase rate of 10° C./min (first temperature increase), and the DSC curve is measured using a differential scanning calorimeter.
From the obtained DSC curve, an analysis program for a differential scanning calorimeter is used to select the DSC curve at the time of the first temperature increase, and the heat of fusion [mJ/mg] of the target sample at the first temperature increase can be obtained. can.
上記熱可塑性樹脂層として環状オレフィン系樹脂層を設ける場合、前記超音波シール用多層フィルムにおける示差走査熱量測定(DSC)によって測定される融解熱量としては、55mJ/mg以上であることが好ましく、60mJ/mg以上であることがより好ましく、70mJ/mg以上であることがさらに好ましい。上記熱可塑性樹脂層として環状オレフィン系樹脂層を設ける場合の当該融解熱量が上記範囲であると、超音波シールする場合に均一な溶着を行いやすくなり、また溶着の際に穿孔等が生じにくくなる。 When a cyclic olefin resin layer is provided as the thermoplastic resin layer, the heat of fusion measured by differential scanning calorimetry (DSC) in the multilayer film for ultrasonic sealing is preferably 55 mJ/mg or more, and preferably 60 mJ. /mg or more, and more preferably 70 mJ/mg or more. If the amount of heat of fusion when the cyclic olefin resin layer is provided as the thermoplastic resin layer is within the above range, uniform welding is facilitated in the case of ultrasonic sealing, and perforation or the like is less likely to occur during welding. .
本発明の超音波シール用多層フィルムにおける示差走査熱量測定(DSC)によって測定される融解熱量が70mJ/mg以上である、あるいは熱可塑性樹脂層として環状オレフィン系樹脂層を設ける場合の当該融解熱量が55mJ/mg以上であると超音波シールする場合に均一な溶着を行いやすくなり、また溶着の際に穿孔等が生じにくくなる理由は定かではないが、発明者らは以下のように推測している。すなわち、ポリエチレンは比較的剛性が低く、超音波シールする際の超音波による振動エネルギーが減衰しやすく、均一にシールするには高エネルギーを掛ける必要がある。融解熱量の比較的高い上記範囲の多層フィルムは、均一にシールするため超音波シールする際の超音波による振動エネルギーが高い場合であっても、穿孔等が生じず良好なシール結果を得ることができる。 The heat of fusion measured by differential scanning calorimetry (DSC) in the multilayer film for ultrasonic sealing of the present invention is 70 mJ / mg or more, or when a cyclic olefin resin layer is provided as the thermoplastic resin layer, the heat of fusion is If it is 55 mJ/mg or more, it becomes easier to perform uniform welding in the case of ultrasonic sealing, and the reason why perforation or the like is less likely to occur during welding is not clear, but the inventors speculate as follows. there is That is, polyethylene has relatively low rigidity, and the vibrational energy generated by ultrasonic waves during ultrasonic sealing tends to be attenuated, and high energy must be applied for uniform sealing. A multilayer film having a relatively high heat of fusion in the above range achieves a uniform seal, so even when the vibration energy of ultrasonic waves during ultrasonic sealing is high, a good sealing result can be obtained without perforation or the like. can.
[剛性]
前記超音波シール用多層フィルムにおける剛性は、1%接線モジュラスにより評価できる。
「1%接線モジュラス」は、1%のひずみを与えたときの接線弾性係数(Tangent Modulus)を意味する。
前記超音波シール用多層フィルムにおける1%接線モジュラスとしては、190MPa以上が好ましく、200MPa以上がより好ましく、210MPa以上が更に好ましい。
前記1%接線モジュラスの測定方法としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、超音波シール用多層フィルムについて、ASTM D-882に基づき、フィルム製造時の押出方向の23℃における1%接線モジュラス(単位:MPa)を、テンシロン引張試験機(装置名:RTC-1210A、株式会社エー・アンド・デー製)を用いて測定する方法が挙げられる。
[rigidity]
The rigidity of the multilayer film for ultrasonic sealing can be evaluated by 1% tangent modulus.
"1% tangent modulus" means the tangent modulus at 1% strain.
The 1% tangential modulus in the multilayer film for ultrasonic sealing is preferably 190 MPa or more, more preferably 200 MPa or more, and even more preferably 210 MPa or more.
The method for measuring the 1% tangential modulus is not particularly limited and can be appropriately selected according to the purpose. 1% tangential modulus (unit: MPa) at 23° C. using a Tensilon tensile tester (device name: RTC-1210A, manufactured by A&D Co., Ltd.).
本発明の超音波シール用多層フィルムの剛性は、多層フィルムの樹脂構成を調整することにより、用途に応じて選択することができる。例えば、横ピロー包装等の柔軟性の求められる用途に当該超音波シール用多層フィルムを使用する場合は、上記熱可塑性樹脂層に直鎖状低密度ポリエチレン等のポリエチレン系樹脂を用いることで、当該超音波シール用多層フィルムにおける1%接線モジュラスを190MPa以上300MPa程度に調整することができる。一方、スタンディングパウチや縦ピロー包装といった剛性の求められる用途に当該超音波シール用多層フィルムを使用する場合は、上記熱可塑性樹脂層に環状オレフィン系樹脂を使用することで、当該超音波シール用多層フィルムにおける1%接線モジュラスを300MPa以上900MPa程度に調整することができる。
The rigidity of the multilayer film for ultrasonic sealing of the present invention can be selected according to the application by adjusting the resin composition of the multilayer film. For example, when using the ultrasonic sealing multilayer film for applications that require flexibility such as horizontal pillow packaging, by using a polyethylene resin such as linear low density polyethylene for the thermoplastic resin layer, the
[超音波シール]
前記超音波によりシールする方法としては、特に制限はなく目的に応じて、公知の超音波シール方法や、公知の超音波シール装置を用いた方法等を適宜選択することができる。
ここで、「超音波シール」とは、電気エネルギーを機械的エネルギーに変換した超音波振動振幅を利用して、超音波によって振動エネルギーを送り出す「超音波ホーン」と固定治具「アンビル」との間に接合対象となるフィルムを挟み、フィルム材料の界面に均一に摩擦エネルギーを発生させ、瞬時に溶融溶着する技術である。用語「超音波シール」、「超音波溶接」、「超音波溶融溶着」、及び「超音波融着接合」は、互いに同義であり得る。
[Ultrasonic seal]
The ultrasonic sealing method is not particularly limited, and a known ultrasonic sealing method, a method using a known ultrasonic sealing device, or the like can be appropriately selected according to the purpose.
Here, the "ultrasonic seal" is a combination of an "ultrasonic horn" that transmits vibration energy by ultrasonic waves and a fixing jig "anvil" using ultrasonic vibration amplitude that converts electrical energy into mechanical energy. It is a technology in which a film to be joined is sandwiched in between, and frictional energy is generated uniformly at the interfaces of the film materials, resulting in instantaneous fusion and welding. The terms "ultrasonic sealing", "ultrasonic welding", "ultrasonic fusion welding", and "ultrasonic fusion bonding" can be synonymous with each other.
超音波ホーンは、接合対象及びアンビルの上方に垂直に配置されてもよく、接合対象及びアンビルに対して水平方向に配置されてもよい。超音波ホーンは、通常20kHz~40kHzの超音波で振動して、圧力下、通常摩擦熱の形態でエネルギーを、接合対象の接合部に伝達する。摩擦熱及び圧力のために、接合対象のうちの少なくとも1つの一部が軟化するか又は融解し、それにより接合対象が互いに接合される。 The ultrasonic horn may be arranged vertically above the object to be welded and the anvil, or horizontally with respect to the object to be welded and the anvil. Ultrasonic horns vibrate with ultrasonic waves, typically between 20 kHz and 40 kHz, to transfer energy under pressure, typically in the form of frictional heat, to the joints to be joined. Due to the frictional heat and pressure, a portion of at least one of the objects to be joined softens or melts, thereby joining the objects to be joined together.
ここで、前記「接合対象」としては、本発明においては、本発明の超音波シール用多層フィルムを少なくとも含む限り、特に制限はなく目的に応じて適宜選択することができ、前記超音波シール用多層フィルム2枚を各々の前記シール層が互いに接するように配置したものであってもよく、一続き(1枚)の前記超音波シール用多層フィルムを前記シール層が互いに接するように折畳んで配置したものであってもよく、或いは、前記超音波シール用多層フィルムと熱可塑性樹脂フィルムとを、前記超音波シール用多層フィルムの前記シール層が前記熱可塑性樹脂フィルムに接するように配置したものであってもよい。
シール層が互いに接した部分やシール層が熱可塑性樹脂フィルムに接した部分を超音波シールして接合部を形成することにより、後述する積層体が得られる。
Here, in the present invention, the "bonding object" is not particularly limited as long as it contains at least the multilayer film for ultrasonic sealing of the present invention, and can be appropriately selected according to the purpose. Two multilayer films may be arranged so that the seal layers are in contact with each other, and a series (one sheet) of the multilayer film for ultrasonic sealing may be folded so that the seal layers are in contact with each other. Alternatively, the ultrasonic sealing multilayer film and the thermoplastic resin film are arranged such that the sealing layer of the ultrasonic sealing multilayer film is in contact with the thermoplastic resin film. may be
A laminate to be described later can be obtained by ultrasonically sealing the portions where the seal layers are in contact with each other and the portions where the seal layers are in contact with the thermoplastic resin film to form joints.
前記超音波シールにおける超音波としては、特に制限はなく目的に応じて、人間の耳には聞こえない高い振動数をもつ弾性振動波(音波)を適宜選択することができる。前記超音波の周波数としては、16kHz以上が好ましく、20kHz以上がより好ましく、20kHz以上40kHz以下が特に好ましい。 The ultrasonic waves in the ultrasonic seal are not particularly limited, and elastic vibration waves (sound waves) having a high frequency that cannot be heard by the human ear can be appropriately selected according to the purpose. The frequency of the ultrasonic waves is preferably 16 kHz or higher, more preferably 20 kHz or higher, and particularly preferably 20 kHz or higher and 40 kHz or lower.
前記超音波シールにおける圧力、振幅、溶着時間、ホールド時間等の条件としては、用いる接合対象の種類、及び周波数や条件の組合せに応じて変化し、一義的に規定できるものではないが、特に制限はなく目的に応じて、適宜選択することができる。
前記圧力は、超音波シール装置において、接合対象に対する超音波ホーンによる押しつけ圧力を意味し、単位[Pa](パスカル)、[MPa](メガパスカル)等で表される。前記圧力としては、0.15[MPa]~0.3[MPa]が好ましく、0.25[MPa]~0.3[MPa]がより好ましい。
前記振幅は、超音波振動の大きさを意味する。前記振幅としては、20μm以上50μm以下が好ましく、均一かつ安定なシール強度を有することにより、35μm以上50μm以下がより好ましい。
前記溶着時間は、超音波の発振時間を示し、超音波ホーンが接合対象に接触して溶着する時間を意味する。前記溶着時間としては、0.2秒間以上1秒間以下が好ましく、0.5秒間以上1秒間以下がより好ましい。
前記ホールド時間は、超音波発振機の保持時間かつ溶着部の硬化時間を意味する。前記ホールド時間としては、0.2秒間以上1.0秒間以下が好ましく、0.5秒間以上1.0秒間以下がより好ましい。
Conditions such as pressure, amplitude, welding time, hold time, etc. in the ultrasonic sealing vary depending on the type of object to be welded and the combination of frequency and conditions, and cannot be univocally defined, but there are no particular restrictions. can be selected as appropriate depending on the purpose.
The pressure means the pressing pressure of the ultrasonic horn against the object to be joined in the ultrasonic sealing device, and is expressed in units such as [Pa] (pascal), [MPa] (megapascal), and the like. The pressure is preferably 0.15 [MPa] to 0.3 [MPa], more preferably 0.25 [MPa] to 0.3 [MPa].
The amplitude means the magnitude of ultrasonic vibration. The amplitude is preferably 20 μm or more and 50 μm or less, and more preferably 35 μm or more and 50 μm or less in order to have a uniform and stable seal strength.
The welding time indicates the oscillation time of ultrasonic waves, and means the time during which the ultrasonic horn contacts and welds the object to be welded. The welding time is preferably 0.2 seconds or more and 1 second or less, more preferably 0.5 seconds or more and 1 second or less.
The hold time means the holding time of the ultrasonic oscillator and the hardening time of the welded portion. The hold time is preferably 0.2 seconds or more and 1.0 seconds or less, more preferably 0.5 seconds or more and 1.0 seconds or less.
前記超音波シール装置としては、例えば、連続超音波シールタイプの装置、回転式超音波ホーンを有する装置等が好適に挙げられる。
前記連続超音波シールタイプの装置は、一般に「連続超音波融着接合」として知られている。連続超音波融着接合は、通常、略連続的に超音波シール装置内に供給することができ、略連続的に接合対象を封止するために使用される。連続超音波融着接合では、超音波ホーンは通常固定されており、接合対象がその真下を移動する。一種の連続超音波融着接合は、固定されたホーンと回転アンビル面とを使用する。連続超音波融着接合中、接合対象は、超音波ホーンと回転アンビルとの間に引っ張られる。超音波ホーンは、通常、接合対象に向かって長手方向に延在し、振動は超音波ホーンに沿って軸方向に材料まで伝達する。
Suitable examples of the ultrasonic sealing device include a continuous ultrasonic sealing type device, a device having a rotary ultrasonic horn, and the like.
Such continuous ultrasonic sealing type devices are commonly known as "continuous ultrasonic fusion bonds". Continuous ultrasonic fusion bonding can generally be fed substantially continuously into an ultrasonic sealing device, and is used to substantially continuously seal objects to be bonded. In continuous ultrasonic fusion bonding, the ultrasonic horn is usually fixed and the object to be welded moves underneath it. One type of continuous ultrasonic fusion bond uses a stationary horn and a rotating anvil face. During continuous ultrasonic fusion bonding, the object to be welded is pulled between the ultrasonic horn and the rotating anvil. The ultrasonic horn typically extends longitudinally toward the object to be joined, and vibrations are transmitted axially along the ultrasonic horn to the material.
前記回転式超音波ホーンを有する装置では、超音波ホーンは回転タイプであり、円柱状であって長手方向軸を中心に回転する。入力振動は、超音波ホーンの軸方向にあり、出力振動は超音波ホーンの放射方向にある。超音波ホーンはアンビルに近接して配置され、通常アンビルもまた、接合対象が円柱状面の間を、円柱状面の接線速度に実質的に等しい線速度で通過するように回転することができる。 In the device with a rotating ultrasonic horn, the ultrasonic horn is of rotary type, cylindrical and rotates about its longitudinal axis. The input vibration is in the axial direction of the ultrasonic horn and the output vibration is in the radial direction of the ultrasonic horn. The ultrasonic horn is placed in close proximity to the anvil, and the anvil is typically also rotatable such that the object to be welded passes between the cylindrical surfaces at a linear velocity substantially equal to the tangential velocity of the cylindrical surfaces. .
超音波シールとしては、例えば、特開2008-526552号公報、特開2010-195044号公報、特開2013-231249号公報、特開2015-16294号公報、米国特許第5976316号明細書等に記載されており、その開示内容は参照により本明細書に援用される。 Examples of ultrasonic seals include JP-A-2008-526552, JP-A-2010-195044, JP-A-2013-231249, JP-A-2015-16294, and US Pat. No. 5,976,316. and the disclosure of which is incorporated herein by reference.
(積層体)
本発明の多層フィルムは、他の基材と貼りあわせて、本発明の多層フィルムを有する積層体とすることもできる。
前記積層体は、他の基材と、前記他の基材と貼合してなる本発明の多層フィルムと、を有する。
このとき、使用することができる他の基材としては、特に限定されるものではないが、本発明の効果を容易に発現させる観点から、高剛性、高光沢を有する熱可塑性樹脂フィルム、特に二軸延伸された樹脂フィルムを用いることが好ましい。また透明性を必要としない用途の場合は、アルミ箔、紙、コーティング紙等の基材を単独あるいは組み合わせて使用することもできる。
前記他の基材を本発明の多層フィルムをラミネートする際の接着方法としては、特に制限はなく目的に応じて適宜選択することができ、例えば、ドライラミネーション、ウエットラミネーション、ノンソルベントラミネーション、押出ラミネーション等が挙げられる。
(Laminate)
The multilayer film of the present invention can also be laminated with another substrate to form a laminate having the multilayer film of the present invention.
The laminate has another substrate and the multilayer film of the present invention laminated with the other substrate.
At this time, the other substrate that can be used is not particularly limited, but from the viewpoint of easily expressing the effects of the present invention, a thermoplastic resin film having high rigidity and high gloss, especially two It is preferable to use an axially stretched resin film. For applications that do not require transparency, substrates such as aluminum foil, paper, and coated paper can be used singly or in combination.
The adhesion method for laminating the multilayer film of the present invention to the other substrate is not particularly limited and can be appropriately selected according to the purpose. Examples include dry lamination, wet lamination, non-solvent lamination, and extrusion lamination. etc.
前記二軸延伸された樹脂フィルムとしては、例えば、二軸延伸ポリエステル(BOPET)、二軸延伸ポリエチレン(BOPE)、二軸延伸ポリプロピレン(BOPP)、二軸延伸ポリアミド(BOPA)、エチレンビニルアルコール共重合体(EVOH)を中心層とした共押出二軸延伸ポリプロピレン、二軸延伸エチレンビニルアルコール共重合体(BOEVOH)、ポリ塩化ビニリデン(PVDC)をコートした共押出二軸延伸ポリプロピレン等が挙げられる。これらは、1種単独で使用してもよく、2種類以上を併用乃至複合化して使用してもよい。 Examples of the biaxially oriented resin film include biaxially oriented polyester (BOPET), biaxially oriented polyethylene (BOPE), biaxially oriented polypropylene (BOPP), biaxially oriented polyamide (BOPA), and ethylene vinyl alcohol copolymer. Examples include coextrusion biaxially oriented polypropylene with a core layer of coalescence (EVOH), biaxially oriented ethylene vinyl alcohol copolymer (BOEVOH), and coextruded biaxially oriented polypropylene coated with polyvinylidene chloride (PVDC). These may be used singly, or two or more of them may be used in combination or in combination.
(包装体)
本発明の包装体は、本発明の超音波シール用多層フィルムを少なくとも含み、前記超音波シール用多層フィルム2枚を各々の前記シール層が互いに接するように配置して超音波によりシールした積層体であってもよく、一続き(1枚)の前記超音波シール用多層フィルムを前記シール層が互いに接するように折畳んで配置して超音波によりシールした積層体であってもよく、或いは、前記超音波シール用多層フィルムと、熱可塑性樹脂フィルムとを、前記超音波シール用多層フィルムの前記シール層が前記熱可塑性樹脂フィルムに接するように配置して超音波によりシールした積層体であってもよい。
前記包装体は、洋菓子、スナック、パン、和菓子、調味料等の食品用包装体等の各種包装体として好適に利用できる。
前記包装体は、モノマテリアル化に対応でき、シール面のみ加熱可能な超音波シールによりシールできるためシール幅を狭くでき、材料の省量化を図ることができる。
(package)
The package of the present invention includes at least the multilayer film for ultrasonic sealing of the present invention, and is a laminate obtained by arranging two sheets of the multilayer film for ultrasonic sealing so that the respective sealing layers are in contact with each other and sealing them by ultrasonic waves. It may be a laminate obtained by folding and arranging a series (one sheet) of the multilayer film for ultrasonic sealing so that the sealing layers are in contact with each other, and then sealing by ultrasonic waves, or A laminate obtained by arranging the multilayer film for ultrasonic sealing and a thermoplastic resin film so that the seal layer of the multilayer film for ultrasonic sealing is in contact with the thermoplastic resin film and sealing them by ultrasonic waves, good too.
The packaging body can be suitably used as various packaging bodies such as food packaging bodies for western confectionery, snacks, bread, Japanese confectionery, and seasonings.
The package body can be made of a monomaterial, and can be sealed by an ultrasonic seal capable of heating only the sealing surface, so that the width of the seal can be narrowed and the amount of material can be reduced.
<熱可塑性樹脂フィルム>
前記熱可塑性樹脂フィルムの材料としては、特に制限はなく目的に応じて、公知の熱可塑性樹脂を適宜選択することができるが、モノマテリアル化の観点から、オレフィン樹脂が好ましい。
前記オレフィン樹脂としては、前記熱可塑性樹脂層において説明したオレフィン樹脂を適宜採用することができる。
<Thermoplastic resin film>
The material of the thermoplastic resin film is not particularly limited and can be appropriately selected from known thermoplastic resins according to the purpose, but olefin resins are preferable from the viewpoint of monomaterialization.
As the olefin resin, any of the olefin resins described in the thermoplastic resin layer can be appropriately employed.
本発明の超音波シール用多層フィルム10は、例えば、図1に示すように、熱可塑性樹脂層1、及びシール層2からなり、2層が積層された多層フィルムである。
また、図2に示すように、本発明の超音波シール用多層フィルム10は、複数の熱可塑性樹脂層を有してもよく、熱可塑性樹脂層(基材層)1a、熱可塑性樹脂層(中間層)1b、及びシール層2からなり、基材層/中間層/シール層の順で積層される多層フィルムであってもよい。なお、図2では中間層が1層であるが、中間層が複数層であってもよい。
The ultrasonic
Further, as shown in FIG. 2, the
図3A~Cは、本発明の超音波シール用多層フィルムの超音波溶接に用いる超音波シール装置の一例を示す概略断面図である。超音波シール装置100は、アンビル110と、このアンビル110の外周面と対向する超音波ホーン120とを有する。アンビル110の外周面に所定のシールパターンでシール突起が形成されており、超音波ホーン120は、図3A中の矢印方向に可動して、超音波ホーン120とアンビル110のシール突起との間に接合対象をホールドすることができる。
アンビル110と超音波ホーン120との間に通される接合対象は、例えば、2枚重ねの超音波シール用多層フィルム10であってもよく(図3A)、超音波シール用多層フィルム10と熱可塑性樹脂フィルムとを2枚重ねにしたものであってもよく(不図示)、金属棒130に引っ掛けて図3B中の矢印方向に張力をかけ、2枚重ねになるように折り畳んだ1枚の超音波シール用多層フィルム10であってもよい(図3B)。接合対象のうち、アンビル110の外周面のシール突起と超音波ホーン120との間に挟まれる部分を、超音波ホーン120から伝達される超音波振動による摩擦熱で溶融シールして、超音波シール用多層フィルム10を少なくとも含む積層体50を製造する(図3C参照)。超音波シール装置は、接合対象に接する超音波ホーンの先端から接合対象に振動エネルギーを伝えて、接合対象を摩擦熱で溶着するものであり、溶着形状は、アンビル110の外周面のシール突起と超音波ホーン先端との接触面の形状とほぼ同じとなる。図3Aの超音波シール装置では、アンビル110の外周面のシール突起は、200mm×2mmの形状を有し、これにより、シール長200mm×シール幅2mmで溶着した積層体50を製造することができる。
3A to 3C are schematic cross-sectional views showing an example of an ultrasonic sealing device used for ultrasonic welding of the multilayer film for ultrasonic sealing of the present invention. The ultrasonic sealing device 100 has an
The object to be joined passed between the
以下、実施例に基づいて本発明をより具体的に説明するが、本発明は以下の実施例に制限されるものではない。なお、特に明記しない限り、「部」は「質量部」を指し、「%」は「質量%」を指す。 The present invention will be described in more detail below based on examples, but the present invention is not limited to the following examples. In addition, unless otherwise specified, "part" refers to "mass part" and "%" refers to "mass%".
(実施例1)
<超音波シール用多層フィルムの作製>
基材層(A)、中間層(B)、中間層(C)及びシール層(D)の各層を形成する樹脂成分として、各々下記の樹脂を使用して、各層を形成する樹脂及び樹脂混合物を調整した。
基材層(A):直鎖状低密度ポリエチレン樹脂(密度0.933g/cm3、MFR3.6g/10分、融点123℃)(以下、LLDPE(2)と称する。)100部。
中間層(B):LLDPE(2)100部。
中間層(C):LLDPE(2)100部。
シール層(B):直鎖状低密度ポリエチレン樹脂(密度0.920g/cm3、MFR4.3g/10分、融点112℃)(以下、LLDPE(1)と称する。)60部と、1-ブテン-プロピレン共重合体(密度0.900g/cm3、MFR9.0g/10分、融点100℃、1-ブテン由来成分の含有量:60モル%~95モル%)(以下、BPR(1)と称する。)40部との混合物。
(Example 1)
<Preparation of multilayer film for ultrasonic sealing>
Resins and resin mixtures for forming each layer using the following resins as resin components for forming each layer of the substrate layer (A), the intermediate layer (B), the intermediate layer (C) and the seal layer (D). adjusted.
Base layer (A): 100 parts of linear low-density polyethylene resin (density 0.933 g/cm 3 , MFR 3.6 g/10 min, melting point 123° C.) (hereinafter referred to as LLDPE (2)).
Middle layer (B): 100 parts of LLDPE (2).
Middle layer (C): 100 parts of LLDPE (2).
Sealing layer (B): 60 parts of linear low-density polyethylene resin (density of 0.920 g/cm 3 , MFR of 4.3 g/10 minutes, melting point of 112° C.) (hereinafter referred to as LLDPE (1)), and 1- Butene-propylene copolymer (density 0.900 g/cm 3 , MFR 9.0 g/10 min, melting point 100° C., content of 1-butene-derived component: 60 mol % to 95 mol %) (hereinafter referred to as BPR (1) ) and 40 parts.
各層を形成する樹脂及び樹脂混合物を3台の押出機に各々供給し、基材層(A)/中間層(B)/中間層(C)/シール層(D)にて形成される積層フィルムの各層の平均厚みの比率が、20%:36%:20%:24%となるように、押出温度250℃でTダイから共押出して、40℃の水冷金属冷却ロールで冷却し、総厚みが40μmの積層フィルムである実施例1の超音波シール用多層フィルムを成形した。 A laminated film formed of a substrate layer (A)/intermediate layer (B)/intermediate layer (C)/seal layer (D) by supplying resins and resin mixtures forming each layer to three extruders, respectively. The average thickness ratio of each layer is 20%: 36%: 20%: 24%, coextruded from a T die at an extrusion temperature of 250 ° C., cooled with a water-cooled metal cooling roll at 40 ° C., and the total thickness A multilayer film for ultrasonic sealing of Example 1, which is a laminated film having a thickness of 40 μm, was molded.
<包装体の作製>
得られた超音波シール用多層フィルムを210mm×600mmにカットし、同じサイズにカットした熱可塑性樹脂フィルム(二軸延伸ポリプロピレン、P2161、東洋紡株式会社製)に対しシール層が接するように2枚重ねにしたこと以外は、後述する「超音波シール性」の評価と同様の装置及び条件により、長辺2辺と短辺1辺の計3辺を超音波シールして、実施例1の包装体を作製した。
<Production of package>
The obtained multilayer film for ultrasonic sealing was cut into 210 mm × 600 mm, and two thermoplastic resin films (biaxially oriented polypropylene, P2161, manufactured by Toyobo Co., Ltd.) cut into the same size were stacked so that the sealing layer was in contact. A total of three sides, two long sides and one short side, were ultrasonically sealed using the same apparatus and conditions as in the evaluation of "ultrasonic sealability" described later, except that the package of Example 1 was was made.
<評価>
<<超音波シール性>>
得られた超音波シール用多層フィルムを210mm×600mmにカットし、シール層を金属棒に引っ掛けて2枚重ねになるように折り畳んで2枚重ねにし、図3に示す超音波シール装置のアンビル上に張るよう設置した。超音波シール装置として、超音波プラスチックウェルダーW3080(日本アビオニックス製、周波数:20kHz)を用いた。パラメータ(圧力=0.3MPa、振幅=50μm、溶着時間=1秒、ホールド時間=1秒)を設定し、スイッチを入れ、超音波シール用多層フィルムの210mm長の一辺をシール長200mm×シール幅2mmで超音波シールした。
シール長210mmを目視で観察した後、剥離を行い、下記の評価基準で超音波シール性を評価した。結果を表1に示す。
[評価基準]
〇:シール全長に対し、80%以上が溶着した。
△〇:シール全長に対し、50%以上80%未満が溶着した(実用可能レベルである)。
△:シール全長に対し、一部(50%未満)が溶着した。
×:シール全長で溶着しないか0.5N/210mm以下で軽く剥離できた。
<Evaluation>
<<Ultrasonic sealability>>
The obtained multilayer film for ultrasonic sealing was cut into a size of 210 mm x 600 mm, and the sealing layer was hooked on a metal rod, folded into two layers, and placed on the anvil of the ultrasonic sealing device shown in FIG. It was set up so that it would stretch on the As an ultrasonic sealing device, an ultrasonic plastic welder W3080 (manufactured by Nippon Avionics, frequency: 20 kHz) was used. Set the parameters (pressure = 0.3 MPa, amplitude = 50 μm, welding time = 1 second, hold time = 1 second), turn on the switch, and set one side of the multilayer film for ultrasonic sealing with a length of 210 mm to a seal length of 200 mm × seal width. Ultrasonic sealed at 2 mm.
After a seal length of 210 mm was visually observed, peeling was performed, and the ultrasonic sealability was evaluated according to the following evaluation criteria. Table 1 shows the results.
[Evaluation criteria]
Good: 80% or more of the full length of the seal was welded.
△○: 50% or more and less than 80% of the total length of the seal was welded (practical level).
Δ: A portion (less than 50%) of the full length of the seal was welded.
x: The seal was not welded over the entire length of the seal, or was easily peeled off at 0.5 N/210 mm or less.
<<シール強度の測定>>
得られた実施例1の超音波シール用多層フィルムを幅210mmにカットし、シール層が互いに接するように2枚重ねにし、超音波プラスチックウェルダーW3080(日本アビオニックス製、周波数:20kHz)を用いて、圧力=0.3MPa、振幅=50μm、溶着時間=0.5秒、ホールド時間=1秒の条件で超音波シールした。超音波シールした積層体を幅15mmにカットし、23℃、50%RHの恒温室において引張試験機(株式会社エー・アンド・ディー製)を用いて、300mm/分間の速度で90度剥離することによりシール強度[N/15mm]を測定した。結果を表1に示す。
<<Measurement of seal strength>>
The obtained multilayer film for ultrasonic sealing of Example 1 was cut into a width of 210 mm, and two layers were stacked so that the sealing layers were in contact with each other. , pressure = 0.3 MPa, amplitude = 50 µm, welding time = 0.5 seconds, and hold time = 1 second. Cut the ultrasonically sealed laminate into a width of 15 mm, and peel it at 90 degrees at a speed of 300 mm / min using a tensile tester (manufactured by A&D Co., Ltd.) in a constant temperature room at 23 ° C. and 50% RH. The seal strength [N/15 mm] was measured by Table 1 shows the results.
<<融解熱量の測定>>
得られた実施例1の超音波シール用多層フィルムについて、示差走査熱量測定(DSC)によって測定される昇温1回目の融解熱量を、以下の手順で測定した。結果を表1に示す。
示差走査熱量測定(DSC)の昇温1回目の融解熱量は、示差走査熱量計(株式会社日立ハイテクサイエンス製、DSC7020)を用いて測定した。
まず、対象試料である超音波シール用多層フィルムの約5.0mgをアルミニウム製の試料容器に入れ、試料容器をホルダーユニットに載せ、電気炉中にセットする。次いで、窒素雰囲気下、30℃から昇温速度10℃/分にて200℃まで加熱(昇温1回目)し、示差走査熱量計を用いてDSC曲線を計測する。
得られたDSC曲線から、示差走査熱量計の解析プログラムを用いて、1回目の昇温時におけるDSC曲線を選択し、対象試料の昇温1回目における融解熱量[mJ/mg]を求めた。
<<Measurement of heat of fusion>>
For the obtained multilayer film for ultrasonic sealing of Example 1, the heat of fusion in the first temperature rise measured by differential scanning calorimetry (DSC) was measured by the following procedure. Table 1 shows the results.
The heat of fusion in the first temperature rise in differential scanning calorimetry (DSC) was measured using a differential scanning calorimeter (DSC7020, manufactured by Hitachi High-Tech Science Co., Ltd.).
First, about 5.0 mg of a multilayer film for ultrasonic sealing, which is a target sample, is placed in an aluminum sample container, the sample container is placed on a holder unit, and set in an electric furnace. Next, in a nitrogen atmosphere, the sample is heated from 30° C. to 200° C. at a temperature increase rate of 10° C./min (first temperature increase), and the DSC curve is measured using a differential scanning calorimeter.
From the obtained DSC curve, the DSC curve at the time of the first heating was selected using a differential scanning calorimeter analysis program, and the heat of fusion [mJ/mg] of the target sample at the first heating was determined.
<<剛性の測定>>
得られた実施例1の超音波シール用多層フィルムについて、ASTM D-882に基づき、フィルム製造時の押出方向の23℃における1%接線モジュラス(単位:MPa)を、テンシロン引張試験機(装置名:RTC-1210A、株式会社エー・アンド・デー製)を用いて測定した。
前記1%接線モジュラスに基づき、剛性を評価した。なお、「1%接線モジュラス」は1%のひずみを与えたときの接線弾性係数(Tangent Modulus)を意味し、本発明においては、190MPa以上が好ましく、200MPa以上がより好ましく、210MPa以上が更に好ましい。
<<Measurement of stiffness>>
For the obtained multilayer film for ultrasonic sealing of Example 1, 1% tangential modulus (unit: MPa) at 23 ° C. in the extrusion direction during film production was measured using a Tensilon tensile tester (device name: : RTC-1210A, manufactured by A&D Co., Ltd.).
Stiffness was evaluated based on the 1% tangent modulus. In addition, "1% tangential modulus" means a tangential elastic modulus (Tangent Modulus) when a strain of 1% is applied, and in the present invention, it is preferably 190 MPa or more, more preferably 200 MPa or more, and further preferably 210 MPa or more. .
(実施例2)
実施例1において、表1に示す通り、シール層(D)におけるBPR(1)を1-ブテン-プロピレン共重合体(密度0.900g/cm3、MFR9.0g/10分、融点58℃、1-ブテン由来成分の含有量:60モル%~95モル%)(以下、BPR(2)と称する。)に変更したこと以外は、実施例1と同様にして実施例2の超音波シール用多層フィルムを作製し、評価を実施した。結果を表1に示す。
(Example 2)
In Example 1, as shown in Table 1, BPR (1) in the sealing layer (D) was a 1-butene-propylene copolymer (density 0.900 g/cm 3 , MFR 9.0 g/10 minutes, melting point 58°C, Content of 1-butene-derived component: 60 mol% to 95 mol%) (hereinafter referred to as BPR (2)) for ultrasonic sealing in the same manner as in Example 1 A multilayer film was produced and evaluated. Table 1 shows the results.
(実施例3~4)
実施例2において、表1に示す通り、シール層(D)におけるLLDPE(1)とBPR(2)との量比を変更したこと以外は、実施例2と同様にして実施例3~4の超音波シール用多層フィルムを作製し、評価を実施した。結果を表1に示す。
(Examples 3-4)
In Example 2, as shown in Table 1, except that the amount ratio of LLDPE (1) and BPR (2) in the seal layer (D) was changed, Examples 3 and 4 were prepared in the same manner as in Example 2. A multilayer film for ultrasonic sealing was produced and evaluated. Table 1 shows the results.
(実施例5~6)
実施例2において、表1に示す通り、シール層(D)におけるLLDPE(1)をLLDPE(2)及び直鎖状低密度ポリエチレン樹脂(密度0.940g/cm3、MFR4.3g/10分、融点124℃)(以下、LLDPE(3)と称する。)にそれぞれ変更したこと以外は、実施例2と同様にして実施例5~6の超音波シール用多層フィルムを作製し、評価を実施した。結果を表1に示す。
(Examples 5-6)
In Example 2, as shown in Table 1, LLDPE (1) in the sealing layer (D) was replaced with LLDPE (2) and linear low-density polyethylene resin (density 0.940 g/cm 3 , MFR 4.3 g/10 minutes, Melting point 124° C.) (hereinafter referred to as LLDPE (3)). . Table 1 shows the results.
(実施例7)
<超音波シール用多層フィルムの作製>
基材層(A)、中間層(B)、中間層(C)及びシール層(D)の各層を形成する樹脂成分として、各々下記の樹脂を使用して、各層を形成する樹脂混合物を調整した。
基材層(A):LLDPE(1)60部と、高密度ポリエチレン(960g/cm3、MFR7.5g/10分、融点131℃)(以下、HDPEと称する)40部との混合物。
中間層(B):LLDPE(1)70部と、HDPE 30部との混合物。
中間層(C):LLDPE(1)100部。
シール層(B):LLDPE(1)60部と、BPR(2)40部との混合物。
(Example 7)
<Preparation of multilayer film for ultrasonic sealing>
The following resins are used as resin components for forming each layer of the substrate layer (A), the intermediate layer (B), the intermediate layer (C), and the seal layer (D), and the resin mixture forming each layer is prepared. did.
Base layer (A): A mixture of 60 parts of LLDPE (1) and 40 parts of high-density polyethylene (960 g/cm 3 , MFR 7.5 g/10 min, melting point 131° C.) (hereinafter referred to as HDPE).
Middle layer (B): a mixture of 70 parts LLDPE (1) and 30 parts HDPE.
Middle layer (C): 100 parts of LLDPE (1).
Seal layer (B): a mixture of 60 parts LLDPE (1) and 40 parts BPR (2).
各層を形成する樹脂混合物を3台の押出機に各々供給し、基材層(A)/中間層(B)/中間層(C)/シール層(D)にて形成される積層フィルムの各層の平均厚みの比率が、20%:36%:20%:24%となるように、押出温度250℃でTダイから共押出して、40℃の水冷金属冷却ロールで冷却し、総厚みが40μmの積層フィルムである実施例7の超音波シール用多層フィルムを成形した。
得られた実施例7の超音波シール用多層フィルムについて、実施例1と同様にして評価を実施した。結果を表2に示す。
A resin mixture forming each layer is supplied to each of three extruders, and each layer of a laminated film formed of a base layer (A)/intermediate layer (B)/intermediate layer (C)/seal layer (D). The average thickness ratio of 20%: 36%: 20%: 24% is co-extruded from a T die at an extrusion temperature of 250 ° C., cooled with a water-cooled metal cooling roll at 40 ° C., and the total thickness is 40 μm. The multilayer film for ultrasonic sealing of Example 7, which is a laminated film of , was molded.
The obtained multilayer film for ultrasonic sealing of Example 7 was evaluated in the same manner as in Example 1. Table 2 shows the results.
(実施例8)
実施例7において、表2に示す通り、基材層(A)/中間層(B)/中間層(C)/シール層(D)にて形成される積層フィルムの各層の平均厚みの比率を、20%:36%:28%:16%に変更したこと以外は、実施例7と同様にして実施例8の超音波シール用多層フィルムを作製し、評価を実施した。結果を表2に示す。
(Example 8)
In Example 7, as shown in Table 2, the ratio of the average thickness of each layer of the laminated film formed of base layer (A)/intermediate layer (B)/intermediate layer (C)/seal layer (D) was , 20%:36%:28%:16%, a multilayer film for ultrasonic sealing of Example 8 was produced and evaluated in the same manner as in Example 7. Table 2 shows the results.
(実施例9~10)
実施例2において、表2に示す通り、シール層(D)におけるLLDPE(1)60質量部を40質量部、及び95質量部にそれぞれ変更し、BPR(2)40部を60質量部、及び5質量部にそれぞれ変更したこと以外は、実施例2と同様にして実施例9~10の超音波シール用多層フィルムを作製し、評価を実施した。結果を表2に示す。
(Examples 9-10)
In Example 2, as shown in Table 2, 60 parts by mass of LLDPE (1) in the seal layer (D) was changed to 40 parts by mass and 95 parts by mass, respectively, 40 parts by mass of BPR (2) was changed to 60 parts by mass, and The multilayer films for ultrasonic sealing of Examples 9 and 10 were produced and evaluated in the same manner as in Example 2, except that each was changed to 5 parts by mass. Table 2 shows the results.
(実施例11~12)
実施例2において、表2に示す通り、シール層(D)におけるLLDPE(1)を、直鎖状低密度ポリエチレン樹脂(密度0.903g/cm3、MFR3.0g/10分、融点98℃)(以下、LLDPE(4)と称する。)、及び直鎖状低密度ポリエチレン樹脂(密度0.944g/cm3、MFR4.0g/10分、融点128℃)(以下、LLDPE(5)と称する。)にそれぞれ変更したこと以外は、実施例2と同様にして実施例11~12の超音波シール用多層フィルムを作製し、評価を実施した。結果を表2に示す。
(Examples 11-12)
In Example 2, as shown in Table 2, the LLDPE (1) in the seal layer (D) was replaced with a linear low-density polyethylene resin (density 0.903 g/cm 3 , MFR 3.0 g/10 minutes, melting point 98°C). (hereinafter referred to as LLDPE (4)), and linear low-density polyethylene resin (density 0.944 g/cm 3 , MFR 4.0 g/10 min, melting point 128° C.) (hereinafter referred to as LLDPE (5)). ), the multilayer films for ultrasonic sealing of Examples 11 and 12 were produced and evaluated in the same manner as in Example 2, except that each was changed to ). Table 2 shows the results.
(実施例13)
実施例2において、表3に示す通り、基材層(A)/中間層(B)/中間層(C)/シール層(D)にて形成される積層フィルムの各層の平均厚みの比率を、20%:46%:20%:14%に変更したこと以外は、実施例2と同様にして実施例13の超音波シール用多層フィルムを作製し、評価を実施した。結果を表3に示す。
(Example 13)
In Example 2, as shown in Table 3, the ratio of the average thickness of each layer of the laminated film formed of base layer (A)/intermediate layer (B)/intermediate layer (C)/seal layer (D) was , 20%:46%:20%:14%. Table 3 shows the results.
(実施例14)
実施例2において、表3に示す通り、超音波シール用多層フィルムの総厚み40μmを35μmに変更したこと以外は、実施例2と同様にして実施例14の超音波シール用多層フィルムを作製し、評価を実施した。結果を表3に示す。
(Example 14)
In Example 2, as shown in Table 3, a multilayer film for ultrasonic sealing of Example 14 was produced in the same manner as in Example 2, except that the total thickness of the multilayer film for ultrasonic sealing was changed from 40 μm to 35 μm. , conducted an evaluation. Table 3 shows the results.
(実施例15~23)
表4及び表5に示す組成及び各層の層比率に変更した以外は実施例1と同様にして、実施例15~20の超音波シール用多層フィルムを作製し、評価を実施した。結果を表4及び表5に示す。
(Examples 15-23)
Ultrasonic sealing multilayer films of Examples 15 to 20 were produced and evaluated in the same manner as in Example 1 except that the composition and the layer ratio of each layer were changed to those shown in Tables 4 and 5. The results are shown in Tables 4 and 5.
(比較例1)
実施例1において、表6に示す通り、シール層(D)において、ブテン系オレフィン樹脂を含まず、LLDPE(1)60部を100部に変更したこと以外は、実施例1と同様にして比較例1の超音波シール用多層フィルムを作製し、評価を実施した。結果を表6に示す。
(Comparative example 1)
In Example 1, as shown in Table 6, comparison was made in the same manner as in Example 1, except that the butene-based olefin resin was not included in the seal layer (D) and 60 parts of LLDPE (1) was changed to 100 parts. A multilayer film for ultrasonic sealing of Example 1 was produced and evaluated. Table 6 shows the results.
(比較例2~5)
実施例1において、表6に示す通り、シール層(D)において、BPR(1)を、下記PBR(1)、PBR(2)、EBR(1)、及びEBR(2)にそれぞれ変更したこと以外は、実施例1と同様にして比較例2~5の超音波シール用多層フィルムを作製し、評価を実施した。結果を表6に示す。
・PBR(1):ポリプロピレン-1-ブテン共重合体(密度0.900g/cm3、MFR7.0g/10分、融点98℃、プロピレン由来成分の含有量:85モル%)
・PBR(2):ポリプロピレン-1-ブテン共重合体(密度0.900g/cm3、MFR7.0g/10分、融点75℃、プロピレン由来成分の含有量:74モル%)
・EBR(1):ポリエチレン-1-ブテン共重合体(密度0.893g/cm3、MFR6.7g/10分、融点77℃、エチレン由来成分の含有量:70モル%~92モル%)
・EBR(2):ポリエチレン-1-ブテン共重合体(密度0.885g/cm3、MFR6.7g/10分、融点66℃、エチレン由来成分の含有量:76モル%~90モル%、1-ブテン由来成分の含有量:18モル%)
(Comparative Examples 2-5)
In Example 1, as shown in Table 6, in the sealing layer (D), BPR(1) was changed to PBR(1), PBR(2), EBR(1), and EBR(2) below. Except for this, multilayer films for ultrasonic sealing of Comparative Examples 2 to 5 were produced in the same manner as in Example 1 and evaluated. Table 6 shows the results.
- PBR (1): polypropylene-1-butene copolymer (density 0.900 g/cm 3 , MFR 7.0 g/10 min, melting point 98°C, propylene-derived component content: 85 mol%)
PBR (2): Polypropylene-1-butene copolymer (density 0.900 g/cm 3 , MFR 7.0 g/10 min, melting point 75°C, propylene-derived component content: 74 mol%)
EBR (1): polyethylene-1-butene copolymer (density 0.893 g/cm 3 , MFR 6.7 g/10 min, melting point 77° C., ethylene-derived component content: 70 mol % to 92 mol %)
EBR (2): polyethylene-1-butene copolymer (density 0.885 g/cm 3 , MFR 6.7 g/10 min, melting point 66° C., content of ethylene-derived component: 76 mol % to 90 mol %, 1 - butene-derived component content: 18 mol%)
(比較例6)
実施例1において、表6に示す通り、シール層(D)において、LLDPE(1)をHDPEに変更したこと以外は、実施例1と同様にして比較例6の超音波シール用多層フィルムを作製し、評価を実施した。結果を表6に示す。
(Comparative Example 6)
In Example 1, as shown in Table 6, a multilayer film for ultrasonic sealing of Comparative Example 6 was produced in the same manner as in Example 1, except that LLDPE (1) was changed to HDPE in the sealing layer (D). and evaluated. Table 6 shows the results.
表1~6の結果から、シール層が直鎖状低密度ポリエチレン及びブテン系αオレフィン樹脂を含有することにより、超音波シール性が担保されることがわかった。また、シール層におけるブテン系αオレフィン樹脂の含有量が、5質量%以上でシール強度に劣るものの実用可能レベルの超音波シール性を示し、20質量%以上でシール長の全長で超音波シール性が担保されることがわかった。超音波シール用多層フィルムの総厚み40μmでは、総厚みに対するシール層の厚み14%以上でシール長の全長で超音波シール性が担保されることがわかった。全ての実施例において、200MPa以上の優れた剛性が得られることがわかった。 From the results in Tables 1 to 6, it was found that the ultrasonic sealability was ensured by the sealing layer containing linear low-density polyethylene and butene-based α-olefin resin. In addition, when the content of the butene-based α-olefin resin in the sealing layer is 5% by mass or more, the seal strength is inferior, but the ultrasonic sealing performance is at a practical level, and when the content is 20% by mass or more, the ultrasonic sealing performance is obtained over the entire sealing length. was found to be guaranteed. It was found that when the total thickness of the multilayer film for ultrasonic sealing is 40 μm, the ultrasonic sealing performance is ensured over the entire sealing length when the thickness of the sealing layer is 14% or more of the total thickness. It was found that excellent rigidity of 200 MPa or more was obtained in all the examples.
さらに、上記熱可塑性樹脂層に直鎖状低密度ポリエチレン等のポリエチレン系樹脂を用いた実施例1~14及び実施例20~22は、当該超音波シール用多層フィルムにおける剛性を190MPa以上300MPa程度に調整することができ、軟包装用途に有用な超音波シール用多層フィルムを得ることができた。また、上記熱可塑性樹脂層の一部に環状オレフィン系樹脂を使用した実施例15~19及び実施例23は、当該超音波シール用多層フィルムにおける剛性を300MPa以上900MPa程度に調整することができ、スタンディングパウチ等の剛性の求められる用途に有用な超音波シール用多層フィルムを得ることができた。 Furthermore, in Examples 1 to 14 and Examples 20 to 22 in which a polyethylene-based resin such as linear low-density polyethylene was used for the thermoplastic resin layer, the rigidity of the multilayer film for ultrasonic sealing was increased from 190 MPa to about 300 MPa. It was possible to obtain a multilayer film for ultrasonic sealing which could be adjusted and which is useful for flexible packaging applications. Further, in Examples 15 to 19 and Example 23, in which a cyclic olefin resin was used as part of the thermoplastic resin layer, the rigidity of the multilayer film for ultrasonic sealing can be adjusted to 300 MPa or more and about 900 MPa. A multi-layer film for ultrasonic sealing useful for applications requiring rigidity such as standing pouches was obtained.
以下に、実施例において用いた各樹脂のMFR、密度、融点、及び化合物名を示す。 The MFR, density, melting point, and compound name of each resin used in the examples are shown below.
1 熱可塑性樹脂層
1a 熱可塑性樹脂層(基材層)
1b 熱可塑性樹脂層(中間層)
2 シール層
10 超音波シール用多層フィルム
50 積層体
100 超音波シール装置
110 アンビル
120 超音波ホーン
130 金属棒
1 thermoplastic resin layer 1a thermoplastic resin layer (base material layer)
1b Thermoplastic resin layer (intermediate layer)
2 sealing
Claims (9)
直鎖状低密度ポリエチレン樹脂及びαオレフィン樹脂を含有するシール層と、を少なくとも有し、
前記αオレフィン樹脂が、ブテン系αオレフィン樹脂を含有し、
超音波によりシール可能であることを特徴とする超音波シール用多層フィルム。 a thermoplastic resin layer containing a thermoplastic resin;
a seal layer containing a linear low-density polyethylene resin and an α-olefin resin;
The α-olefin resin contains a butene-based α-olefin resin,
A multilayer film for ultrasonic sealing, characterized in that it can be sealed by ultrasonic waves.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1191800A (en) * | 1997-09-11 | 1999-04-06 | Kishimoto Akira | Easy openable pouch |
| JP2002210899A (en) * | 2000-11-17 | 2002-07-31 | Tohcello Co Ltd | Multi-layer polyolefin film and package |
| JP2003340992A (en) * | 2002-05-24 | 2003-12-02 | Idemitsu Unitech Co Ltd | Laminated film for heat sealing, packaging bag |
| JP2005319583A (en) * | 2001-09-28 | 2005-11-17 | Showa Denko Plastic Products Co Ltd | Laminated film, sealant film and package |
| JP2007245612A (en) * | 2006-03-17 | 2007-09-27 | Dainippon Ink & Chem Inc | Coextruded multilayer film and packaging material using the film |
| JP2011207520A (en) * | 2010-03-30 | 2011-10-20 | Daicel Chemical Industries Ltd | Multi-layered sheet for filter tow bale packing |
| JP2014105015A (en) * | 2012-11-29 | 2014-06-09 | Toppan Printing Co Ltd | Lid member and packaging container |
| JP2015013408A (en) * | 2013-07-04 | 2015-01-22 | 凸版印刷株式会社 | Paper cup flange mold |
| JP2020200063A (en) * | 2019-06-07 | 2020-12-17 | 凸版印刷株式会社 | Pillow packaging bag |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11207520A (en) * | 1998-01-20 | 1999-08-03 | Amitec Corp | Running circular saw |
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2023
- 2023-02-16 JP JP2023544089A patent/JPWO2023166995A1/ja active Pending
- 2023-02-16 TW TW112105562A patent/TW202344405A/en unknown
- 2023-02-16 WO PCT/JP2023/005348 patent/WO2023166995A1/en not_active Ceased
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1191800A (en) * | 1997-09-11 | 1999-04-06 | Kishimoto Akira | Easy openable pouch |
| JP2002210899A (en) * | 2000-11-17 | 2002-07-31 | Tohcello Co Ltd | Multi-layer polyolefin film and package |
| JP2005319583A (en) * | 2001-09-28 | 2005-11-17 | Showa Denko Plastic Products Co Ltd | Laminated film, sealant film and package |
| JP2003340992A (en) * | 2002-05-24 | 2003-12-02 | Idemitsu Unitech Co Ltd | Laminated film for heat sealing, packaging bag |
| JP2007245612A (en) * | 2006-03-17 | 2007-09-27 | Dainippon Ink & Chem Inc | Coextruded multilayer film and packaging material using the film |
| JP2011207520A (en) * | 2010-03-30 | 2011-10-20 | Daicel Chemical Industries Ltd | Multi-layered sheet for filter tow bale packing |
| JP2014105015A (en) * | 2012-11-29 | 2014-06-09 | Toppan Printing Co Ltd | Lid member and packaging container |
| JP2015013408A (en) * | 2013-07-04 | 2015-01-22 | 凸版印刷株式会社 | Paper cup flange mold |
| JP2020200063A (en) * | 2019-06-07 | 2020-12-17 | 凸版印刷株式会社 | Pillow packaging bag |
Also Published As
| Publication number | Publication date |
|---|---|
| TW202344405A (en) | 2023-11-16 |
| JPWO2023166995A1 (en) | 2023-09-07 |
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