WO2024135533A1 - 積層体及び包装袋 - Google Patents

積層体及び包装袋 Download PDF

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Publication number
WO2024135533A1
WO2024135533A1 PCT/JP2023/044864 JP2023044864W WO2024135533A1 WO 2024135533 A1 WO2024135533 A1 WO 2024135533A1 JP 2023044864 W JP2023044864 W JP 2023044864W WO 2024135533 A1 WO2024135533 A1 WO 2024135533A1
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WIPO (PCT)
Prior art keywords
layer
laminate
sealant
seal
heat
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2023/044864
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English (en)
French (fr)
Japanese (ja)
Inventor
靖方 小野
悠 荻原
幹典 山田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toppan Holdings Inc
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Toppan Holdings Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toppan Holdings Inc filed Critical Toppan Holdings Inc
Priority to EP23906897.6A priority Critical patent/EP4640432A4/en
Priority to CN202380085226.3A priority patent/CN120344395A/zh
Priority to JP2024529796A priority patent/JPWO2024135533A1/ja
Publication of WO2024135533A1 publication Critical patent/WO2024135533A1/ja
Priority to JP2025028107A priority patent/JP2025084828A/ja
Priority to US19/236,642 priority patent/US20250303678A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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Definitions

  • This disclosure relates to laminates and packaging bags.
  • a laminate that comprises a biaxially oriented PET (polyethylene terephthalate) film with excellent heat resistance and toughness as a base film and a polyolefin film such as polyethylene or polypropylene as a sealant layer (see, for example, Patent Document 1).
  • the outermost layer is the part that receives the most heat in the heat sealing process when making bags, so a film that is difficult to heat seal is used for it; however, when high temperatures are applied to fuse the sealant, which is the innermost layer, in the heat sealing process, the outermost layer deforms due to heat shrinkage, causing problems such as bag distortion, reduced transportability, and reduced workability when sealing the contents.
  • the range (tolerance) of heat sealing temperatures that can suppress heat shrinkage of the laminate while ensuring sufficient seal strength is narrow, and even a slight deviation in the heat sealing temperature from the specified value can easily cause a decrease in seal strength or heat shrinkage, resulting in a problem that mass production of packaging bags is easily reduced.
  • This disclosure has been made in consideration of the above circumstances, and aims to provide a laminate using polypropylene for the innermost and outermost layers, which can widen the heat sealing temperature tolerance, and a packaging bag using the same.
  • the present disclosure provides a laminate using polypropylene for the innermost and outermost layers, which allows for a wide range of heat sealing temperatures, and a packaging bag using the same.
  • FIG. 1 is a schematic cross-sectional view showing a laminate according to one embodiment.
  • FIG. 1 is a schematic cross-sectional view showing a laminate according to one embodiment.
  • the laminate 100 shown in FIG. 1 includes a base layer 11, an intermediate layer 12, and a sealant layer 13 in this order.
  • the base layer 11 and the intermediate layer 12, and the intermediate layer 12 and the sealant layer 13 may be bonded by an adhesive layer S, respectively.
  • the base layer, the intermediate layer, and the sealant layer all include polypropylene.
  • the base layer, the intermediate layer, and the sealant layer may include a polypropylene film.
  • the laminate includes an inorganic oxide layer and a gas barrier coating layer on the surface of the base layer 11 on the intermediate layer 12 side or at least one surface of the intermediate layer 12.
  • the base layer 11 is disposed on one outermost surface of the laminate 100, and the sealant layer 13 is disposed on the other outermost surface of the laminate 100.
  • the base layer 11 is also called the outermost layer of the laminate 100 (the layer on the opposite side to the content side when the laminate is made into a packaging bag).
  • the sealant layer 13 is also referred to as the innermost layer of the laminate 100 (the layer on the content side when made into a packaging bag).
  • the base layer is a layer that serves as a support and contains polypropylene.
  • the base layer may contain a polypropylene film or may be made of a polypropylene film.
  • the polypropylene film may be an acid-modified polypropylene film obtained by graft-modifying polypropylene with an unsaturated carboxylic acid, an acid anhydride of an unsaturated carboxylic acid, an ester of an unsaturated carboxylic acid, or the like.
  • a polypropylene-based resin such as homopolypropylene resin (PP), propylene-ethylene random copolymer, propylene-ethylene block copolymer, or propylene- ⁇ -olefin copolymer can be used.
  • PP homopolypropylene resin
  • propylene-ethylene random copolymer propylene-ethylene random copolymer
  • propylene-ethylene block copolymer propylene- ⁇ -olefin copolymer
  • the polypropylene constituting the base layer is preferably homopolypropylene.
  • the polypropylene film constituting the base layer may contain various additives such as flame retardants, slip agents, antiblocking agents, antioxidants, light stabilizers, tackifiers, and antistatic agents.
  • the polypropylene film constituting the base layer is preferably a stretched film from the viewpoints of impact resistance, heat resistance, water resistance, dimensional stability, etc. This makes it possible to prevent the base layer from thermally fusing during the heat sealing process during bag manufacturing.
  • the laminate can be more suitably used for applications that require retort processing or boiling processing.
  • Any method can be used as long as it can provide a dimensionally stable film, such as stretching by inflation, uniaxial stretching, or biaxial stretching.
  • the thickness of the substrate layer is not particularly limited. Depending on the application, the thickness can be 6 to 200 ⁇ m, but from the viewpoint of reducing materials to reduce the environmental impact, and from the viewpoint of obtaining excellent heat resistance, impact resistance, and excellent gas barrier properties, the thickness may be 9 to 50 ⁇ m, 12 to 38 ⁇ m, or 18 to 30 ⁇ m.
  • the substrate layer may be pretreated with various pretreatments such as corona treatment, plasma treatment, and flame treatment, as long as the barrier performance is not impaired, or a coating layer such as an easy-adhesion layer may be provided on the laminated surface.
  • the substrate layer is required to have a surface softening temperature T 1 (° C.) measured by local thermal analysis (LTA) that satisfies the following condition. T1 >200°C
  • T 1 a surface softening temperature measured by local thermal analysis (LTA)
  • LTA local thermal analysis
  • T1 >200°C
  • T 1 may be 201°C or more, 203°C or more, or 205°C or more.
  • the upper limit of T 1 is not particularly limited, but may be, for example, 220°C or less.
  • the softening temperature of the substrate surface may be 200°C or more and 220°C or less, 201°C or more and 220°C or less, 203°C or more and 220°C or less, or 205°C or more and 220°C or less.
  • the softening temperature of the substrate layer surface can be adjusted, for example, by the crystallinity, molecular weight, and blending ratio of the copolymer.
  • the softening temperature can also be measured by differential scanning calorimetry (DSC), but the softening temperature measured by DSC includes information on not only the surface of the substrate layer or sealant layer, but also other layers such as the intermediate layer, etc.
  • DSC differential scanning calorimetry
  • the melting point (melting peak temperature) of the substrate layer measured by differential scanning calorimetry (DSC) may be more than 161°C, may be 163°C or more, or may be 165°C or more.
  • a melting point of more than 161°C tends to provide a desired surface softening temperature (more than 200°C).
  • the upper limit of the melting point is not particularly limited, but may be, for example, 180°C or less.
  • the melting point of the substrate layer may be more than 161°C and 180°C or less, may be 163°C or more and 180°C or less, or may be 165°C or more and 180°C or less.
  • the melting point of the substrate layer can be adjusted, for example, by the crystallinity, molecular weight, and blending ratio of the copolymer.
  • the melting point of the substrate layer can be measured using a differential scanning calorimeter (for example, Hitachi High-Tech Science Corporation, product name: DSC7000X) at a heating rate of 10°C/min.
  • the softening temperature is the temperature at which a material such as a resin exhibits softening behavior.
  • the softening temperature is evaluated by local thermal analysis (LTA) using an atomic force microscope. Heating is performed by applying a voltage to a cantilever with a heater.
  • LTA local thermal analysis
  • a cantilever is placed at a specific point on the sample surface with a constant force (contact pressure). The cantilever is heated while keeping the contact pressure constant, and the temperature at which the height position (Z displacement) of the cantilever becomes maximum due to the change in hardness of the sample surface before and after heating is calculated as the softening temperature.
  • the height position changes due to the vertical rise of the cantilever caused by thermal expansion of the sample surface, and the vertical fall of the cantilever caused by softening of the sample surface. That is, just before the cantilever position falls, the sample reaches its softening temperature. Therefore, by converting the applied voltage of the heater of the cantilever when the height position of the cantilever is maximized into temperature, the softening temperature in the nanoscale area locally and near the surface can be calculated. You can find out.
  • the equipment used is an atomic force microscope (AFM) manufactured by Oxford Instruments, MFP-3D-SA (product name), with a local thermal analysis option, Ztherm.
  • AFM atomic force microscope
  • MFP-3D-SA product name
  • Ztherm a local thermal analysis option
  • AC mode tapping mode
  • contact mode is used for softening temperature measurement.
  • the cantilever used is the AN2-200 (product name) manufactured by Anasys Instruments, with a spring constant of 0.5 to 3.5 N/m.
  • the voltage application rate (heating rate) of the cantilever when measuring the softening temperature is 0.5 V/sec.
  • Ztherm the contact pressure of the cantilever (change in the deflection of the cantilever) is controlled to a constant value for measurement.
  • the deflection of the cantilever changes with the applied voltage even without contacting the sample, so the deflection of the cantilever due to the applied voltage must be subtracted before controlling the contact pressure.
  • Ztherm has a detrend correction function that obtains the change in the deflection of the cantilever with respect to the applied voltage, and applies the maximum voltage used for measurement to the cantilever without the cantilever touching the sample surface, and performs detrend correction.
  • detrend correction is performed at the maximum voltage used for measurement and a voltage application rate (heating rate) of 0.5 V/sec before measuring the softening temperature, and then measurement is performed.
  • the contact pressure is set to 0.5 V.
  • the set value for the downward displacement of the cantilever to stop the measurement is 50 nm.
  • the softening point is determined as the point where the vertical height (Z displacement) of the cantilever is at its maximum, and the applied voltage is read at this point.
  • a calibration curve of applied voltage and melting point is created.
  • samples whose melting points (peak melting temperature) have already been measured using a differential scanning calorimeter (DSC) are used, and the softening temperature is measured at different measurement positions for each calibration sample.
  • a calibration curve is created by approximating the average applied voltage at the softening point and the melting point (peak melting temperature) with a cubic function using the least squares method, and this is used as the calibration curve.
  • the calibration samples are polycaprolactone pellets (melting point: 60°C), low-density polyethylene pellets (melting point: 112°C), polypropylene pellets (melting point: 166°C), and biaxially stretched polyethylene terephthalate film (melting point: 255°C), and cross-sectional samples created in an environment below the glass transition temperature are used for each.
  • An ultramicrotome and cryosystem are used to prepare cross-sectional samples, and cross-sections are cut at -80°C for polycaprolactone, -140°C for low-density polyethylene, -40°C for polypropylene, and room temperature of 25°C for polyethylene terephthalate.
  • the applied voltage at the softening point is converted to temperature and used as the softening temperature.
  • an adhesive layer may be provided on the surface of the substrate layer on which the inorganic oxide layer is laminated.
  • the adhesive layer is provided on the substrate layer, and can provide two effects: improving the adhesive performance between the substrate layer and the inorganic oxide layer, and improving the smoothness of the substrate layer surface.
  • the improved smoothness makes it easier to form the inorganic oxide layer uniformly without defects, and makes it easier to exhibit high barrier properties.
  • the adhesive layer can be formed using an anchor coat agent.
  • Anchor coating agents include, for example, polyester-based polyurethane resins and polyether-based polyurethane resins. From the viewpoints of heat resistance and interlayer adhesive strength, polyester-based polyurethane resins are preferred as anchor coating agents.
  • the thickness of the adhesive layer is not particularly limited, but is preferably in the range of 0.01 to 5 ⁇ m, more preferably in the range of 0.03 to 3 ⁇ m, and particularly preferably in the range of 0.05 to 2 ⁇ m. If the thickness of the adhesive layer is equal to or greater than the lower limit above, more sufficient interlayer adhesive strength tends to be obtained, while if the thickness is equal to or less than the upper limit above, the desired gas barrier properties tend to be easily achieved.
  • any known coating method can be used without any particular restrictions as a method for coating the adhesive layer on the substrate layer, and examples of such methods include immersion (dipping) methods, and methods using a spray, coater, printer, brush, etc.
  • examples of the types of coaters and printers used in these methods and the coating methods thereof include gravure coaters such as direct gravure method, reverse gravure method, kiss reverse gravure method, and offset gravure method, reverse roll coaters, microgravure coaters, coaters combined with chamber doctor, air knife coaters, dip coaters, bar coaters, comma coaters, die coaters, etc.
  • the coating amount of the adhesion layer is preferably 0.01 to 5 g/ m2 , more preferably 0.03 to 3 g/ m2 , in terms of the mass per m2 after the anchor coating agent is applied and dried. If the mass per m2 after the anchor coating agent is applied and dried is equal to or greater than the above lower limit, the film formation tends to be sufficient, whereas if it is equal to or less than the above upper limit, the film tends to dry sufficiently and the solvent tends not to remain.
  • the method for drying the adhesive layer is not particularly limited, but examples include natural drying, drying in an oven set at a predetermined temperature, and using a dryer attached to the coater, such as an arch dryer, floating dryer, drum dryer, or infrared dryer. Furthermore, the drying conditions can be appropriately selected depending on the drying method. For example, in the method of drying in an oven, it is preferable to dry at a temperature of 60 to 100°C for about 1 second to 2 minutes.
  • a polyvinyl alcohol resin can be used as the adhesive layer.
  • the polyvinyl alcohol resin may be any resin that has vinyl alcohol units formed by saponifying vinyl ester units, such as polyvinyl alcohol (PVA) and ethylene-vinyl alcohol copolymer (EVOH).
  • methods for forming the adhesion layer include coating with a polyvinyl alcohol resin solution and multi-layer extrusion.
  • the inorganic oxide layer contributes to improving the gas barrier property.
  • examples of inorganic oxides contained in the inorganic oxide layer include aluminum oxide, silicon oxide, magnesium oxide, and tin oxide.
  • the inorganic oxide may be selected from the group consisting of aluminum oxide, silicon oxide, and magnesium oxide.
  • the inorganic oxide layer is a layer using silicon oxide.
  • the O/Si ratio of the inorganic oxide layer is preferably 1.7 or more.
  • the O/Si ratio is 1.7 or more, the content of metal Si is suppressed, and good transparency is easily obtained.
  • the O/Si ratio is preferably 2.0 or less.
  • the crystallinity of SiO is high, and the inorganic oxide layer can be prevented from becoming too hard, and good tensile resistance can be obtained. This makes it possible to suppress the occurrence of cracks in the inorganic oxide layer when laminating the gas barrier coating layer.
  • the base material layer or intermediate layer may shrink due to heat during boiling or retort treatment, but when the O/Si ratio is 2.0 or less, the inorganic oxide layer easily follows the above shrinkage, and the deterioration of the barrier property can be suppressed.
  • the O/Si ratio of the inorganic oxide layer is preferably 1.75 to 1.9, and more preferably 1.8 to 1.85.
  • the O/Si ratio of the inorganic oxide layer can be determined by X-ray photoelectron spectroscopy (XPS).
  • XPS X-ray photoelectron spectroscopy
  • the measurement device is an X-ray photoelectron spectrometer (manufactured by JEOL Ltd., product name: JPS-90MXV), the X-ray source is non-monochromated MgK ⁇ (1253.6 eV), and the measurement can be performed with an X-ray output of 100 W (10 kV-10 mA).
  • XPS X-ray photoelectron spectrometer
  • the thickness of the inorganic oxide layer is preferably 10 nm or more and 50 nm or less.
  • a thickness of 10 nm or more can provide sufficient water vapor barrier properties.
  • a thickness of 50 nm or less can suppress the occurrence of cracks due to deformation caused by internal stress in the thin film, and suppress the deterioration of water vapor barrier properties.
  • a thickness of more than 50 nm is also undesirable from an economic standpoint, since costs are likely to increase due to an increase in the amount of material used and a longer film formation time. From the same standpoint as above, it is more preferable that the thickness of the inorganic oxide layer is 20 nm or more and 40 nm or less.
  • the inorganic oxide layer can be formed, for example, by vacuum deposition.
  • vacuum deposition physical vapor deposition or chemical vapor deposition can be used.
  • physical vapor deposition include, but are not limited to, vacuum deposition, sputtering, and ion plating.
  • chemical vapor deposition include, but are not limited to, thermal CVD, plasma CVD, and photo CVD.
  • the resistive heating vacuum deposition method the EB (Electron Beam) heating vacuum deposition method, the induction heating vacuum deposition method, the sputtering method, the reactive sputtering method, the dual magnetron sputtering method, the plasma enhanced chemical vapor deposition method (PECVD method), etc. are particularly preferably used.
  • the vacuum deposition method is currently the most superior.
  • the heating means for the vacuum deposition method it is preferable to use any of the following methods: the electron beam heating method, the resistive heating method, or the induction heating method.
  • the gas barrier coating layer protects the inorganic oxide layer, contributes to improving the gas barrier property, and exerts high gas barrier property by a synergistic effect with the inorganic oxide layer.
  • the gas barrier coating layer may be a layer formed using a composition for forming a gas barrier coating layer containing at least one selected from the group consisting of a hydroxyl group-containing polymer compound, a metal alkoxide, a silane coupling agent, and a hydrolyzate thereof.
  • the gas barrier coating layer can be formed using a composition for forming a gas barrier coating layer (hereinafter also referred to as a coating agent) containing as a main component an aqueous solution or a water/alcohol mixed solution containing at least one selected from the group consisting of a hydroxyl-containing polymer compound, a metal alkoxide, a silane coupling agent, and their hydrolysates.
  • a coating agent for a gas barrier coating layer
  • a coating agent containing as a main component an aqueous solution or a water/alcohol mixed solution containing at least one selected from the group consisting of a hydroxyl-containing polymer compound, a metal alkoxide, a silane coupling agent, and their hydrolysates.
  • the coating agent preferably contains at least a silane coupling agent or a hydrolysate thereof, more preferably contains at least one selected from the group consisting of a hydroxyl-containing polymer compound, a metal alkoxide, and their hydrolysates, and a silane coupling agent or a hydrolysate thereof, and even more preferably contains a hydroxyl-containing polymer compound or a hydrolysate thereof, a metal alkoxide or a hydrolysate thereof, and a silane coupling agent or a hydrolysate thereof.
  • the coating agent can be prepared, for example, by mixing a metal alkoxide and a silane coupling agent directly or after a treatment such as hydrolysis, with a solution in which a hydroxyl-containing polymer compound, which is a water-soluble polymer, is dissolved in an aqueous (water or water/alcohol mixed) solvent.
  • Hydroxyl-containing polymeric compounds used in coating agents include polyvinyl alcohol, polyvinylpyrrolidone, starch, methyl cellulose, carboxymethyl cellulose, sodium alginate, etc.
  • polyvinyl alcohol (PVA) is preferred when used as a coating agent for the gas barrier coating layer, as it has particularly excellent gas barrier properties.
  • metal alkoxides examples include tetraethoxysilane [Si(OC 2 H 5 ) 4 ], triisopropoxyaluminum [Al(O-2′-C 3 H 7 ) 3 ], etc. Tetraethoxysilane and triisopropoxyaluminum are preferred because they are relatively stable in aqueous solvents after hydrolysis.
  • Silane coupling agents include vinyltrimethoxysilane, ⁇ -chloropropylmethyldimethoxysilane, ⁇ -chloropropyltrimethoxysilane, glycidoxypropyltrimethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -methacryloxypropylmethyldimethoxysilane, etc.
  • the silane coupling agent may be a polymer of these.
  • additives such as isocyanate compounds, dispersants, stabilizers, viscosity adjusters, and colorants to the coating agent as needed, as long as the gas barrier properties are not impaired.
  • Acid catalysts, alkali catalysts, photopolymerization initiators, etc. may be added to the coating agent as needed.
  • the thickness of the gas barrier coating layer is preferably 50 to 1000 nm, and more preferably 100 to 500 nm, from the viewpoint of obtaining excellent gas barrier properties while keeping the polypropylene content in the laminate at 90% by mass or more. If the thickness of the gas barrier coating layer is 50 nm or more, more sufficient gas barrier properties tend to be obtained, and if it is 1000 nm or less, sufficient flexibility tends to be maintained.
  • the coating agent for forming the gas barrier coating layer can be applied by, for example, dipping, roll coating, gravure coating, reverse gravure coating, air knife coating, comma coating, die coating, screen printing, spray coating, gravure offset, etc.
  • the coating film obtained by applying this coating agent can be dried by, for example, hot air drying, hot roll drying, high frequency irradiation, infrared irradiation, UV irradiation, or a combination of these.
  • the temperature at which the coating film is dried can be, for example, 50 to 150°C, and preferably 70 to 100°C. By keeping the drying temperature within the above range, the occurrence of cracks in the inorganic oxide layer and the gas barrier coating layer can be further suppressed, and excellent barrier properties can be achieved.
  • Intermediate layer 12 The configuration of the intermediate layer can be appropriately referred to the above description of the configuration of the base layer.
  • the above-mentioned adhesion layer, inorganic oxide layer, and gas barrier coating layer may be provided on at least one surface of the intermediate layer.
  • the thickness of the intermediate layer is not particularly limited, but may be the same as that of the base layer, and the ratio of the thicknesses of these layers (thickness of base layer/thickness of intermediate layer) may be 1.00 or more, may be greater than 1.00, may be 1.25 or more, or may be 1.50 or more.
  • the base layer is the part that comes into direct contact with or is in close proximity to the heat seal bar during heat sealing, and is the part that is particularly exposed to heat among the layers of the laminate, so it is prone to thermal shrinkage during heat sealing. Therefore, by making the base layer thicker than the intermediate layer, the thermal shrinkage of the base layer can be suppressed.
  • the laminate may include a printing layer.
  • the printing layer can be provided on at least one surface of the base layer or at least one surface of the intermediate layer.
  • the printing layer is provided at a position visible from the outside of the laminate for the purpose of displaying information about the contents, identifying the contents, improving concealment, or improving the design of the packaging bag.
  • the printing method and printing ink are not particularly limited, and are appropriately selected from known printing methods and printing inks in consideration of printability on the film, design such as color tone, adhesion, safety as a food container, etc. Examples of printing methods that can be used include gravure printing, offset printing, gravure offset printing, flexographic printing, and inkjet printing. Among them, gravure printing can be preferably used from the viewpoints of productivity and high definition of the pattern.
  • the surface of the layer on which the printed layer is to be formed may be subjected to various pretreatments such as corona treatment, plasma treatment, and frame treatment, or a coating layer such as an easy-adhesion layer may be formed.
  • pretreatments such as corona treatment, plasma treatment, and frame treatment
  • a coating layer such as an easy-adhesion layer may be formed.
  • the surface of the layer on which the printed layer is to be formed include the surface of the base layer or intermediate layer, and the surface of a gas barrier coating layer.
  • the base layer and the intermediate layer can be laminated via the adhesive layer.
  • polyester-isocyanate resin, urethane resin, polyether resin, etc. can be used as the adhesive material.
  • a two-component curing urethane adhesive that is resistant to retort can be preferably used.
  • the crosslink density is higher than when a one-component curing urethane adhesive is used, so that high adhesion is easily obtained even after retort treatment.
  • a solventless two-component curing urethane adhesive may be used as the two-component curing urethane adhesive. From the viewpoint of environmental consideration, the adhesive does not need to contain 3-glycidyloxypropyltrimethoxysilane (GPTMS).
  • the thickness of the adhesive layer is not particularly limited, but may be, for example, 0.5 to 5 ⁇ m, or 0.3 to 7 ⁇ m. If the thickness of the adhesive layer is 0.5 ⁇ m or more, it is easy to improve the adhesion between the base layer and the intermediate layer, and if it is 5 ⁇ m or less, it is easy to improve the barrier properties and recyclability of the laminate.
  • the sealant layer is a layer that imparts heat-sealing properties to the laminate, and contains polypropylene.
  • the sealant layer may contain a polypropylene film or may be made of a polypropylene film.
  • the polypropylene film may be an acid-modified polypropylene film obtained by graft-modifying polypropylene with an unsaturated carboxylic acid, an acid anhydride of an unsaturated carboxylic acid, an ester of an unsaturated carboxylic acid, or the like.
  • a polypropylene-based resin such as homopolypropylene resin (PP), propylene-ethylene random copolymer, propylene-ethylene block copolymer, or propylene- ⁇ -olefin copolymer can be used.
  • PP homopolypropylene resin
  • propylene-ethylene random copolymer propylene-ethylene random copolymer
  • propylene-ethylene block copolymer propylene- ⁇ -olefin copolymer
  • the polypropylene film that constitutes the sealant layer is preferably a non-oriented film in order to improve the sealing properties by heat sealing.
  • the polypropylene film that constitutes the sealant layer may contain various additives such as flame retardants, slip agents, antiblocking agents, antioxidants, light stabilizers, tackifiers, and antistatic agents.
  • the thickness of the sealant layer is determined by the weight of the contents and the shape of the packaging bag, but may be approximately 30 to 150 ⁇ m, 40 to 100 ⁇ m, or 50 to 80 ⁇ m.
  • the sealant layer can be formed by any of the known lamination methods, including the dry lamination method in which the film-like sealant layer made of the above-mentioned polypropylene is laminated with an adhesive such as a one-component curing or two-component curing urethane adhesive, the non-solvent lamination method in which the film-like sealant layer is laminated with a solvent-free adhesive, and the extrusion lamination method in which the above-mentioned polypropylene is heated and melted, extruded into a curtain shape, and laminated.
  • a solvent-free two-component curing urethane adhesive may be used as the solvent-free adhesive.
  • the amount of residual solvent in the laminate can be reduced because the adhesive component does not contain organic solvents. Furthermore, when a laminate having a base layer made of oriented polypropylene and an intermediate layer made of oriented polypropylene is produced using the dry lamination method, the drying temperature must be lowered to prevent thermal shrinkage of the laminate compared to laminates using polyester-based materials. In this case, the solvent in the adhesive may not be sufficiently volatilized and removed, remaining in the laminate and leaving an odor due to the residual solvent. By using a solvent-free adhesive, the amount of residual solvent can be further reduced.
  • the adhesive layer can be made thinner than when the dry lamination method is used. This allows the polypropylene content in the entire laminate to be further increased. Furthermore, by making the adhesive layer thinner, heat conduction from the heat seal bar is improved when heat sealing is performed, making it possible to reduce the sealing time and sealing temperature, and suppressing the occurrence of wrinkles and other problems associated with heat sealing. Such a laminate is suitable for producing mono-material packaging bags.
  • the sealant layer and intermediate layer can be laminated via the adhesive layer S described above.
  • the sealant layer and intermediate layer are bonded together by applying an adhesive to the intermediate layer and then laminating the sealant layer. If the adhesive is a solvent-free two-component curing urethane adhesive, the intermediate layer is not subjected to thermal stress when the solvent dries. Therefore, the inorganic oxide layer and gas barrier coating layer are less likely to be destroyed due to dimensional changes in the intermediate layer, and the barrier properties are less likely to deteriorate.
  • the sealant layer is required to have a surface softening temperature T 2 (° C.) measured by local thermal analysis (LTA) that satisfies the following condition.
  • T2 ⁇ 150°C
  • T2 may be 148°C or less, or 147°C or less.
  • T2 may be 80°C or more, or 100°C or more.
  • the softening temperature T2 of the sealant layer surface may be 80°C or more and less than 150°C, 80°C or more and 148°C or less, 80°C or more and 147°C or less, 100°C or more and less than 150°C, 100°C or more and 148°C or less, or 100°C or more and 147°C or less.
  • the softening temperature of the sealant layer surface can be adjusted, for example, by the crystallinity, molecular weight, and blending ratio of the copolymer. The method for measuring the softening temperature is as described above.
  • T2 may satisfy the following condition. T2 ⁇ 135° C.
  • the difference (T 1 -T 2 ) between the softening temperature T 1 of the substrate layer surface and the softening temperature T 2 of the sealant layer surface satisfies the following condition. (T 1 - T 2 )>53°C
  • T1 - T2 is greater than 53°C, it is possible to widen the heat sealing temperature tolerance at which thermal shrinkage of the laminate can be suppressed while ensuring sufficient seal strength. From the viewpoint of further enhancing the above effect, T1 - T2 may be 55°C or more, 58°C or more, or 60°C or more.
  • the laminate may contain 90% or more by mass of polypropylene based on the total amount of the laminate. This allows the laminate to be said to be a packaging material made of a single material (mono-material), and has excellent recyclability. From the viewpoint of further improving recyclability, the polypropylene content in the laminate may be 95% or more by mass based on the total amount of the laminate.
  • the resulting seal strength be 20N/15mm or more, and more preferably 25N/15mm or more.
  • the heat shrinkage rate of the resulting seal be less than 3%, and more preferably 2.8% or less.
  • the laminate is heat sealed with the sealant layers facing each other using a heat sealer made of metal on the upper side and silicone rubber on the lower side under conditions of a lower seal actual temperature of 90° C., a sealing pressure of 0.3 MPa, a heating time of 1 second, and varying the upper seal actual temperature, where T L is the lowest upper seal actual temperature at which the seal strength of the resulting seal reaches 20 N/15 mm, and T H is the highest upper seal actual temperature at which the heat shrinkage rate of the resulting seal can be maintained at less than 3%, preferably T H -T L is 15° C. or higher, more preferably 20° C. or higher. By satisfying the above conditions, the heat seal tolerance of the laminate can be widened.
  • the laminate according to this embodiment has a wide heat seal temperature tolerance that can suppress thermal shrinkage of the laminate while ensuring sufficient seal strength. This makes it possible to suppress deterioration of packaging quality, such as bag-making distortion and reduced barrier properties, during heat sealing, and a decrease in mass production of packaging bags.
  • the packaging bag is made by making the above-mentioned laminate into a bag, and is not particularly limited in shape, but may be, for example, one laminate folded in half with the sealant layers facing each other and then heat-sealed on three sides to form a bag shape, or two laminates stacked with the sealant layers facing each other and then heat-sealed on four sides to form a bag shape, or two laminates stacked with the sealant layers facing each other and sealed with a base material between them to form a self-supporting standing pouch.
  • the packaging bag contains food, medicine, and other contents, and can be subjected to heat sterilization treatment such as retort treatment or boiling treatment.
  • Retort processing is a method of sterilizing microorganisms such as mold, yeast, and bacteria under pressure, generally for the preservation of food, medicine, etc.
  • the packaging bag containing the food is sterilized under pressure at 105-140°C, 0.15-0.30 MPa for 10-120 minutes.
  • steam type which uses heated steam
  • hot water type which uses pressurized heated water. The appropriate type is used depending on the sterilization conditions of the food, etc. that will be contained.
  • Boiling is a method of sterilizing food, medicine, etc. by moist heat to preserve it. Normally, depending on the contents, the packaging bag containing the food is sterilized by moist heat at 60-100°C, atmospheric pressure, and 10-120 minutes.
  • Boiling is usually performed using a hot water bath at 100°C or less.
  • a hot water bath at 100°C or less.
  • the packaging bags described above are less likely to deform during manufacturing, making them easier to transport and easier to work with when filling them with contents.
  • Acrylic polyol and tolylene diisocyanate were mixed so that the number of NCO groups in tolylene diisocyanate was equal to the number of OH groups in the acrylic polyol, and the mixture was diluted with ethyl acetate so that the total solid content (total amount of acrylic polyol and tolylene diisocyanate) was 5 mass%.
  • ⁇ -(3,4 epoxycyclohexyl)trimethoxysilane was further added to the diluted mixture so that the amount was 5 parts by mass relative to 100 parts by mass of the total amount of acrylic polyol and tolylene diisocyanate, and these were mixed to prepare a composition for forming an adhesion layer (anchor coating agent).
  • composition for forming a gas barrier coating layer was prepared by mixing the following liquids A, B and C in a mass ratio of 65/25/10, respectively.
  • Liquid A A hydrolysis solution with a solid content of 5 mass % ( SiO2 equivalent) obtained by adding 72.1 g of 0.1N hydrochloric acid to 17.9 g of tetraethoxysilane (Si( OC2H5 ) 4 ) and 10 g of methanol and hydrolyzing the mixture by stirring for 30 minutes.
  • Liquid B a 5% by mass water/methanol solution of polyvinyl alcohol (the mass ratio of water:methanol was 95:5).
  • Liquid C A hydrolysis solution obtained by diluting 1,3,5-tris(3-trialkoxysilylpropyl)isocyanurate with a mixed liquid of water/isopropyl alcohol (water:isopropyl alcohol mass ratio 1:1) to a solid content of 5 mass%.
  • Example 1 The above-mentioned adhesive layer forming composition was applied by gravure roll coating to the corona-treated surface of a stretched polypropylene film (thickness 20 ⁇ m) having one side subjected to corona treatment as an intermediate layer, and dried and cured at 60 ° C. to form an adhesive layer made of a polyester-based polyurethane resin with a coating amount of 0.1 g / m 2.
  • a transparent inorganic oxide layer (silica deposition layer) made of silicon oxide having a thickness of 30 nm was formed by a vacuum deposition apparatus using an electron beam heating method.
  • the deposition material type was adjusted to form a deposition layer with an O / Si ratio of 1.8.
  • the O / Si ratio was measured with an X-ray photoelectron spectrometer (manufactured by JEOL Ltd., product name: JPS-90MXV) using a non-monochromated MgK ⁇ (1253.6 eV) X-ray source at an X-ray output of 100 W (10 kV-10 mA). Quantitative analysis to determine the O/Si ratio was performed using relative sensitivity factors of 2.28 for O1s and 0.9 for Si2p, respectively.
  • the composition for forming the gas barrier coating layer was applied onto the inorganic oxide layer by gravure roll coating, and then heated and dried in an oven under conditions of a tension of 20 N/m and a drying temperature of 120°C to form a gas barrier coating layer with a thickness of 0.3 ⁇ m. This resulted in a gas barrier film having a laminated structure of intermediate layer/adhesive layer/inorganic oxide layer/gas barrier coating layer.
  • a stretched polypropylene film (thickness 20 ⁇ m) as a base layer was laminated on the gas barrier coating layer of the gas barrier film by a dry lamination method via a two-component curing adhesive (manufactured by Mitsui Chemicals, Inc., product name: base agent A525/hardener A52).
  • a corona treatment was applied to the non-corona treated surface of the intermediate layer, and a non-stretched polypropylene film (thickness 60 ⁇ m) as a sealant layer was laminated on the intermediate layer by a dry lamination method via a two-component curing adhesive (manufactured by Mitsui Chemicals, Inc., product name: base agent A525/hardener A52).
  • the thickness of each adhesive layer was 3 ⁇ m.
  • a stretched polypropylene film having a melting point and surface softening temperature shown in Table 1 below was used as the base layer.
  • Examples 2 to 9 and 11, and Comparative Examples 1 to 2 A laminate was produced in the same manner as in Example 1, except that a stretched polypropylene film having a melting point and a surface softening temperature shown in Table 1 below was used as the base layer, and a non-stretched polypropylene film having a surface softening temperature shown in Table 1 below was used as the sealant layer.
  • Example 10 A gas barrier film having a laminated structure of intermediate layer/adhesive layer/inorganic oxide layer/gas barrier coating layer was obtained in the same manner as in Example 1. Next, a stretched polypropylene film (thickness 20 ⁇ m) as a base layer was laminated on the gas barrier coating layer of the gas barrier film through a solvent-free two-component curing urethane adhesive (manufactured by Toyo-Morton Co., Ltd., product name: TSN-4864A/TSN-4864B3) by a non-solvent lamination method. The solvent-free adhesive was applied using a roll coater.
  • a solvent-free two-component curing urethane adhesive manufactured by Toyo-Morton Co., Ltd., product name: TSN-4864A/TSN-4864B3
  • a corona treatment was applied to the non-corona treated surface of the intermediate layer, and a non-stretched polypropylene film (thickness 60 ⁇ m) as a sealant layer was laminated on the intermediate layer through a solvent-free two-component curing urethane adhesive (manufactured by Toyo-Morton Co., Ltd., product name: TSN-4864A/TSN-4864B3) by a non-solvent lamination method.
  • the solvent-free adhesive was applied using a roll coater.
  • the melting point of the base material layer was measured by the following method.
  • the base material layer was cut from the laminates produced in the examples and comparative examples to obtain measurement samples.
  • the melting point (melting peak temperature) of the measurement samples was measured by differential scanning calorimetry (DSC) at a heating rate of 10°C/min.
  • the differential scanning calorimeter used was DSC7000X (product name) manufactured by Hitachi High-Tech Science Corporation.
  • the softening temperatures of the substrate layer surface and the sealant layer surface were measured by the following method using local thermal analysis (LTA) with an atomic force microscope.
  • LTA local thermal analysis
  • the laminates produced in the Examples and Comparative Examples were used, and the sealant layer side was corona-treated and then fixed to a metal disk with an epoxy adhesive, and when measuring the softening temperature of the sealant layer surface, the substrate layer side was corona-treated and then fixed to a metal disk with an epoxy adhesive to prepare a measurement sample.
  • the corona treatment was carried out using a corona treatment machine (product name: CT-0212) manufactured by Kasuga Electric Co., Ltd., under the condition of 0.20 kW.
  • the atomic force microscope was an MFP-3D-SA (product name) manufactured by Oxford Instruments Ltd., with a local thermal analysis option of the Ztherm system, and the cantilever was an AN2-200 (product name) manufactured by Anasys Instruments Ltd. with a spring constant of 0.5 to 3.5 N/m, and the softening temperature was measured on the surface of each measurement sample.
  • the sample surface was heated after detrend correction with the cantilever contact pressure (change in cantilever deflection) set to 0.2 V, the voltage application rate (heating rate) set to 0.5 V/sec, and the maximum applied voltage set to 6.0 V, the sample surface expanded and the cantilever position rose.
  • the sample surface was further heated, it softened, and the measurement was terminated when the cantilever position dropped 30 nm. If the Z displacement did not drop 30 nm from the change point and reached the maximum applied voltage, the maximum applied voltage during detrend correction and measurement was increased by 0.5 V and the measurement was performed again.
  • the voltage applied at the point where the cantilever's vertical height (Z displacement) was maximum was taken as the voltage applied at the softening point, and the voltage value was read.
  • a calibration curve was created to calculate the softening temperature of the sample.
  • Four types of calibration samples were used: polycaprolactone (melting point: 60°C), low-density polyethylene (LDPE, melting point: 112°C), polypropylene (PP, melting point: 166°C), and polyethylene terephthalate (PET, melting point: 255°C).
  • the maximum applied voltage during detrend correction was 3.5 V for polycaprolactone, 5.5 V for low-density polyethylene, 6.7 V for polypropylene, and 7.9 V for polyethylene terephthalate.
  • the cantilever contact pressure (change in cantilever deflection) was 0.2 V, and the voltage application rate (heat rise rate) was 0.5 V/sec.
  • the calibration sample was measured 20 times at different measurement positions, and a calibration curve was created by approximating the average applied voltage at the softening point and the melting point with a cubic function using the least squares method.
  • the applied voltage at the softening points of the substrate layer surface and sealant layer surface was converted to temperature and used as the softening temperature.
  • the softening temperatures of 12 or more points within a 10 ⁇ m field of view were measured, and the average value was calculated to determine the surface softening temperature of each measurement sample.
  • ⁇ Preparation of heat seal sample> The laminates obtained in the examples and comparative examples were cut to 60 mm x 120 mm so that the MD direction was the longitudinal direction.
  • the cut laminate was folded in half at the longitudinal center so that the sealant layers faced each other, and one side on the opposite side to the folded part (at a position 3 mm or more away from the end) was heat sealed over a width of 10 mm using a heat sealer (model number: TP-701-B) manufactured by Tester Sangyo Co., Ltd.
  • the heat sealing conditions were as follows. After that, the folded part was cut with scissors so that the overlapped laminates had approximately equal lengths on the top and bottom, and the top and bottom laminates were separated. This resulted in a heat-sealed sample.
  • Upper seal bar A 10 mm wide metal seal bar (aluminum alloy 2000 series (Al--Cu)) was used, and the actual seal temperature was varied from 130° C. to 165° C. in 5° C. increments.
  • Lower seal bar A seal bar made of silicone rubber having a width of 50 mm was used, and the seal temperature was fixed at 90°C in actual temperature. Sealing pressure: 0.3MPa Heating time: 1.0 seconds
  • the heat seal sample was cut with a cutter to a width of 15 mm x length of 60 mm to obtain a rectangular seal strength measurement sample.
  • the width direction of the seal strength measurement sample is perpendicular to the width direction of the seal portion.
  • the obtained seal strength measurement sample was subjected to a peel test of the seal portion under normal conditions (23 ° C., 50% RH) using a Tensilon universal testing machine (manufactured by Shimadzu Corporation, product name: AGS-100NX) with a chuck distance of 10 mm and a peel speed of 100 m / min.
  • the seal strength at each actual seal temperature is shown in Table 2.
  • T L (°C).
  • ⁇ Distortion evaluation> The presence or absence of distortion (heat wrinkles) in the sealed portion of the heat-sealed sample at the actual upper seal temperature of 160° C. was visually observed and evaluated according to the following criteria. A rating of B or higher is at a level that is acceptable for practical use. The results are shown in Table 3. A: No distortion (heat wrinkles) was observed in either the sealed portion or the non-sealed portion adjacent to the sealed portion. B: Some distortion (heat wrinkles) is observed in the sealed portion, but no distortion (heat wrinkles) is observed in the non-sealed portion adjacent to the sealed portion. C: Distortion (heat wrinkles) was observed in both the sealed portion and the non-sealed portion near the sealed portion.
  • T H -T L The difference (T H -T L ) between the maximum upper seal actual temperature T H at which the heat shrinkage rate of the sealed portion can be maintained at less than 3% and the minimum upper seal actual temperature T L at which the seal strength of the sealed portion reaches 20 N / 15 mm or more was taken as the heat seal tolerance of the laminate and was evaluated according to the following criteria.
  • a rating of B or higher is at a level that is acceptable for practical use.
  • the results are shown in Table 3.
  • B T H -T L is 15°C or higher and lower than 20°C
  • T H -T L is 10°C or higher and lower than 15°C
  • T H -T L is lower than 10°C

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Laminated Bodies (AREA)
  • Wrappers (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
PCT/JP2023/044864 2022-12-22 2023-12-14 積層体及び包装袋 Ceased WO2024135533A1 (ja)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP23906897.6A EP4640432A4 (en) 2022-12-22 2023-12-14 LAMINATE AND PACKAGING BAG
CN202380085226.3A CN120344395A (zh) 2022-12-22 2023-12-14 层叠体以及包装袋
JP2024529796A JPWO2024135533A1 (https=) 2022-12-22 2023-12-14
JP2025028107A JP2025084828A (ja) 2022-12-22 2025-02-25 積層体
US19/236,642 US20250303678A1 (en) 2022-12-22 2025-06-12 Laminate and packaging bag

Applications Claiming Priority (2)

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JP2022-205631 2022-12-22
JP2022205631 2022-12-22

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WO2024135533A1 true WO2024135533A1 (ja) 2024-06-27

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000085073A (ja) * 1998-09-17 2000-03-28 Idemitsu Petrochem Co Ltd ポリプロピレン系多層フィルム
JP2004035730A (ja) * 2002-07-03 2004-02-05 Japan Polychem Corp 樹脂組成物及びそれを成形して成るフィルム
JP2004043545A (ja) * 2002-07-09 2004-02-12 Mitsui Chemicals Inc シーラント用樹脂組成物、およびこれから得られる易ヒートシール性シーラントフィルム
JP2005307112A (ja) * 2004-04-26 2005-11-04 Mitsui Chemicals Inc シーラント用樹脂組成物、およびこれから得られる易ヒートシール性シーラントフィルム
WO2021220935A1 (ja) * 2020-04-28 2021-11-04 凸版印刷株式会社 ガスバリアフィルム
JP7377425B2 (ja) * 2021-11-29 2023-11-10 Ｔｏｐｐａｎホールディングス株式会社 バリアフィルム、積層体及び包装袋

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7088138B2 (ja) * 2019-07-29 2022-06-21 凸版印刷株式会社 積層体及び包装袋
JP7238912B2 (ja) * 2020-03-31 2023-03-14 大日本印刷株式会社 積層体、レトルト用またはボイル用パウチ

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000085073A (ja) * 1998-09-17 2000-03-28 Idemitsu Petrochem Co Ltd ポリプロピレン系多層フィルム
JP2004035730A (ja) * 2002-07-03 2004-02-05 Japan Polychem Corp 樹脂組成物及びそれを成形して成るフィルム
JP2004043545A (ja) * 2002-07-09 2004-02-12 Mitsui Chemicals Inc シーラント用樹脂組成物、およびこれから得られる易ヒートシール性シーラントフィルム
JP2005307112A (ja) * 2004-04-26 2005-11-04 Mitsui Chemicals Inc シーラント用樹脂組成物、およびこれから得られる易ヒートシール性シーラントフィルム
WO2021220935A1 (ja) * 2020-04-28 2021-11-04 凸版印刷株式会社 ガスバリアフィルム
JP7377425B2 (ja) * 2021-11-29 2023-11-10 Ｔｏｐｐａｎホールディングス株式会社 バリアフィルム、積層体及び包装袋

Non-Patent Citations (1)

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Title
See also references of EP4640432A4 *

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EP4640432A4 (en) 2026-04-01
EP4640432A1 (en) 2025-10-29
JPWO2024135533A1 (https=) 2024-06-27
US20250303678A1 (en) 2025-10-02
JP2025084828A (ja) 2025-06-03

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