WO2022196211A1 - 包装材、包装袋及び包装体 - Google Patents

包装材、包装袋及び包装体 Download PDF

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Publication number
WO2022196211A1
WO2022196211A1 PCT/JP2022/005688 JP2022005688W WO2022196211A1 WO 2022196211 A1 WO2022196211 A1 WO 2022196211A1 JP 2022005688 W JP2022005688 W JP 2022005688W WO 2022196211 A1 WO2022196211 A1 WO 2022196211A1
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WO
WIPO (PCT)
Prior art keywords
layer
polyolefin
packaging material
packaging
copolymer
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/JP2022/005688
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English (en)
French (fr)
Japanese (ja)
Inventor
歩実 田中
健 西川
美季 福上
信哉 落合
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 Inc
Original Assignee
Toppan 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 Inc filed Critical Toppan Inc
Priority to EP22770970.6A priority Critical patent/EP4276032A4/en
Priority to CN202280011287.0A priority patent/CN116802125A/zh
Priority to JP2023506877A priority patent/JPWO2022196211A1/ja
Priority to US18/280,858 priority patent/US20240149559A1/en
Publication of WO2022196211A1 publication Critical patent/WO2022196211A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal 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
    • B32B15/085—Layered products comprising a layer of metal comprising metal 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 comprising polyolefins
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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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    • B32B7/04—Interconnection of layers
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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Definitions

  • the present disclosure relates to packaging materials, packaging bags, and packages. Specifically, the present disclosure relates to a packaging material for packaging contents containing fats and oils, capable of suppressing seepage of fats and oils, and capable of material recycling. The present disclosure also relates to a packaging bag and a packaging body using the packaging material that is recyclable.
  • a laminate film in which a polyvinyl alcohol-based resin layer is formed on a biaxially-stretched polypropylene-based resin, and a non-stretched polypropylene film is laminated thereon (for example, Patent Document 1).
  • a packaging bag made mainly of polyolefin such as polyethylene or polypropylene is filled with contents containing oils and fats and sealed
  • a packaging bag made of a laminated body of Ny/LLDPE or PET/Ny/CPP can be used. Oil is more likely to seep out than in the case of filling. Therefore, there is a problem that such packaging bags are difficult to use for packaging contents containing oils and fats.
  • the present disclosure has been made in view of the above circumstances, and aims to provide a packaging material that uses polyolefin as a main material and is suitable for packaging contents containing fats and oils. Another object of the present disclosure is to provide a packaging bag and a package using the packaging material.
  • the inventors investigated a polyolefin-based packaging material that is recyclable and less prone to exudation of oils and fats. As a result, at least a first polyolefin layer having a predetermined layer configuration, an inorganic deposition layer, and a barrier layer obtained by laminating a predetermined barrier coating layer are laminated on a second polyolefin layer having heat-sealing properties.
  • the present inventors have found that the above-mentioned objects can be achieved with a material, and have completed the packaging material of the present disclosure.
  • the packaging material is a packaging material for packaging contents containing fats and oils, and comprises a barrier layer including a first polyolefin layer, an inorganic vapor deposition layer, and a barrier coating layer; and a second polyolefin layer having sealing properties, the first polyolefin layer comprising a homopolymer layer and a copolymer layer.
  • the solubility parameter is a value defined by regular solution theory, and it is empirically known that the smaller the difference between the SP values of two components, the greater the solubility.
  • SP value of polypropylene and polyethylene is 8.0 (cal/cm 3 ) 1/2 .
  • SP value of oleic acid which is the main component of canola oil, is 8.2 (cal/cm 3 ) 1/2 .
  • the inorganic vapor deposition layer may contain at least one of aluminum oxide and silicon oxide.
  • the first polyolefin layer may include a homopolymer layer on the content side.
  • the first polyolefin layer may include a pair of copolymer layers and a homopolymer layer between the copolymer layers.
  • the packaging material may further comprise a printing layer on the opposite side of the barrier layer to the second polyolefin layer.
  • a packaging bag according to one aspect of the present disclosure is formed from the above packaging material.
  • a package according to one aspect of the present disclosure includes the above-described packaging bag and a content containing fat and oil packaged in the packaging bag.
  • a packaging material that uses polyolefin as a main material and is suitable for packaging contents containing fats and oils is provided. It can be said that the packaging material is excellent in suppressing the exudation of oils and fats. According to the packaging material, it is possible to sufficiently suppress the exudation of fats and oils even when heat treatment such as boiling treatment and retort treatment that promotes exudation of fats and oils is performed. Moreover, in the packaging material, it is possible to maintain good adhesion between the layers (especially between the first polyolefin layer and other layers) constituting the packaging material. Furthermore, according to the present disclosure, a packaging bag and a package using the packaging material are provided.
  • FIG. 1 is a cross-sectional view showing one aspect of the packaging material according to the present disclosure.
  • FIG. 2 is a cross-sectional view showing another aspect of the packaging material according to the present disclosure.
  • FIG. 3 is a cross-sectional view showing another aspect of the packaging material according to the present disclosure.
  • the packaging material of the present disclosure is a material for packaging contents containing fats and oils.
  • the packaging material of the present disclosure can be referred to as a packaging material for packaging oil- and fat-containing contents.
  • Fats and oils are substances in which glycerin and fatty acids are combined. Examples of oils include vegetable oils such as canola oil, rapeseed oil, olive oil, sesame oil, palm oil, and cottonseed oil, animal oils such as het (beef tallow), lard (lard), fish oil, and mixtures thereof. Fats and oils may be solid or liquid at room temperature. Contents containing these fats and oils include curries, pasta sauces, processed meat products, and the like.
  • the packaging material of the present disclosure comprises a first polyolefin layer, a barrier layer including an inorganic deposition layer and a barrier coating layer, and a second polyolefin layer having heat-sealing properties.
  • the barrier layer may be a laminate in which the first polyolefin layer, the inorganic deposition layer and the barrier coating layer are laminated in this order. It may be arranged facing the layer side, or the first polyolefin layer of the barrier layer may be arranged facing the second polyolefin layer side.
  • FIG. 1 is a cross-sectional view showing one aspect of the packaging material according to the present disclosure.
  • the packaging material 10 includes a homopolymer layer 1a and a copolymer layer 1b as a first polyolefin layer 1, an inorganic deposition layer 2, a barrier coating layer 3, and a second polyolefin layer 4 having heat sealability. Prepare in this order.
  • the inorganic vapor deposition layer 2 is formed on one surface of the first polyolefin layer 1 in FIG.
  • the second polyolefin layer 4 may be laminated to the barrier coating layer 3 via an adhesive layer (not shown).
  • the barrier coating layer 3 is arranged facing the content side (second polyolefin layer 4 side), and the first polyolefin layer 1 is arranged farther than the content.
  • the positions of the homopolymer layer 1a and the copolymer layer 1b may be interchanged.
  • the adhesion between layers is superior, and the gas barrier properties after boiling treatment and retort treatment are further improved.
  • FIG. 2 is a cross-sectional view showing another aspect of the packaging material according to the present disclosure.
  • the packaging material 20 includes a printed layer 5, a barrier coating layer 3, an inorganic deposition layer 2, a copolymer layer 1b and a homopolymer layer 1a as a first polyolefin layer 1, and a second polyolefin layer 1a having heat-sealing properties.
  • a polyolefin layer 4 is provided in this order.
  • the printed layer 5 is arranged so that the printed surface 5a faces the inner surface of the packaging material.
  • the inorganic vapor deposition layer 2 is formed on one surface of the first polyolefin layer 1 in FIG.
  • the second polyolefin layer 4 may be laminated to the first polyolefin layer 1 via an adhesive layer (not shown), and the printed layer 5 may be laminated to the barrier coating layer via an adhesive layer (not shown). 3 may be stacked.
  • the first polyolefin layer 1 is arranged facing the content side, and the barrier coating layer 3 is arranged farther than the content.
  • the gas barrier properties after boiling treatment and retort treatment can be improved.
  • the positions of the homopolymer layer 1a and the copolymer layer 1b may be interchanged. Compared to the case where the coalesced layer 1a faces the barrier coating layer 3 side, the oil and fat exudation suppression property is excellent, and the interlayer adhesion and the gas barrier property after boiling treatment and retort treatment are further improved.
  • FIG. 3 is a cross-sectional view showing one aspect of the packaging material according to the present disclosure.
  • the packaging material 30 includes a printed layer 5, a pair of copolymer layers 1b as the first polyolefin layer 1, a homopolymer layer 1a between the layers, an inorganic deposition layer 2, a barrier coating layer 3, and a heat-sealing layer. is provided in this order.
  • the inorganic vapor deposition layer 2 is formed on one surface of the first polyolefin layer 1 in FIG.
  • the second polyolefin layer 4 may be laminated to the barrier coating layer 3 via an adhesive layer (not shown), and the printed layer 5 may be laminated to the first polyolefin layer 3 via an adhesive layer (not shown). of polyolefin layers may be laminated.
  • the barrier coating layer 3 is arranged facing the content side (second polyolefin layer 4 side), and the same effect as in FIG. 1 can be obtained.
  • the first polyolefin layer 1 since the first polyolefin layer 1 has the copolymer layer 1b on both sides thereof, it has excellent interlayer adhesion with adjacent layers and excellent gas barrier properties after boiling and retorting.
  • the first polyolefin layer serves as a substrate (polyolefin film) for forming an inorganic deposition layer.
  • the first polyolefin layer includes a homopolymer layer and a copolymer layer.
  • the homopolymer layer can be called a core layer
  • the copolymer layer can be called a skin layer.
  • the homopolymer layer (homopolymer layer) easily suppresses the permeation and exudation of oils and fats.
  • Examples of the polyolefin that constitutes the homopolymer layer include polyethylene and polypropylene.
  • high-density polyethylene can be mentioned when considering vapor deposition processing, printing processing, bag-making processing, filling suitability, etc. Further, in order to improve physical properties such as flexibility, the homopolymer layer is formed by, for example, co-extrusion, high density polyethylene (HDPE)/medium density polyethylene (MDPE)/low density polyethylene (LDPE). /medium density polyethylene (MDPE)/high density polyethylene (HDPE).
  • Polypropylene includes oriented polypropylene (OPP). When used as a base film for packaging, homopolymer polypropylene is preferred.
  • OPP oriented polypropylene
  • the copolymer layer (copolymer layer or terpolymer layer) easily improves the adhesion and sealing properties between the layers that make up the packaging material.
  • the copolymer layer is also a polyolefin layer, and from the viewpoint of sufficiently exhibiting the above functions as a copolymer layer, the total amount of the copolymer layer is based on the amount of monomer units based on olefin.
  • the content is preferably over 50% by mass, more preferably 75% by mass or more, and even more preferably 90% by mass or more.
  • Examples of the copolymer constituting the copolymer layer include ethylene-based resins such as ethylene-vinyl acetate copolymer (EVA), ethylene- ⁇ -olefin copolymer, ethylene-(meth)acrylic acid copolymer; Copolymers such as polypropylene resins such as ethylene random copolymers, propylene-ethylene block copolymers, and propylene- ⁇ -olefin copolymers are included.
  • EVA ethylene-vinyl acetate copolymer
  • ethylene- ⁇ -olefin copolymer ethylene-(meth)acrylic acid copolymer
  • Copolymers such as polypropylene resins such as ethylene random copolymers, propylene-ethylene block copolymers, and propylene- ⁇ -olefin copolymers are included.
  • a copolymer having a monomer unit based on the monomer constituting the copolymer and a monomer unit based on a monomer other than the monomer can be
  • the first polyolefin layer is formed by co-extrusion of a homopolymer layer (homopolymer layer) as a core layer and a copolymer layer (copolymer or terpolymer layer) as a skin layer.
  • a homopolymer layer homopolymer layer
  • a copolymer layer copolymer or terpolymer layer
  • a skin layer can do.
  • homopolymer OPP when used as the homopolymer layer, copolymer or terpolymer OPP may be used as the copolymer layer from the viewpoint of interlayer adhesion.
  • the first polyolefin layer includes a homopolymer layer on the content side. That is, the first polyolefin layer preferably includes a homopolymer layer on the second polyolefin layer (heat seal layer) side. From the viewpoint of easily ensuring gas barrier properties after boiling treatment or retorting treatment, the first polyolefin layer preferably includes a copolymer layer on the content side. That is, the first polyolefin layer preferably includes a copolymer layer on the second polyolefin layer (heat seal layer) side.
  • the first polyolefin layer preferably includes a pair of copolymer layers and a homopolymer layer between the copolymer layers.
  • Each layer constituting the pair of copolymer layers may be composed of the same material or may be composed of different materials.
  • the polyolefin films as the homopolymer layer and the copolymer layer that constitute the first polyolefin layer may be stretched films or non-stretched films.
  • the polyolefin film may be a stretched film.
  • the packaging material can be more suitably used for hot filling, boiling treatment, retort treatment, and other hot water treatments.
  • the stretching method is not particularly limited, and any method such as inflation stretching, uniaxial stretching, or biaxial stretching may be used as long as a film with stable dimensions can be supplied.
  • the thickness of the first polyolefin layer is not particularly limited.
  • the thickness may be 6 to 200 ⁇ m depending on the application, but may be 9 to 50 ⁇ m or 12 to 38 ⁇ m from the viewpoint of obtaining excellent impact resistance and gas barrier properties.
  • the thickness of the copolymer layer (individual layers if more than one) can be from 0.5 to 3 ⁇ m, and can be from 0.6 to 2.5 ⁇ m. When the thickness of the copolymer layer is 0.5 ⁇ m or more, smoothness and impact resistance are likely to be improved, and when it is 3 ⁇ m or less, heat resistance and oil resistance are likely to be improved. If there are multiple layers of copolymer, the individual layers may have the same or different thickness. The thickness of the homopolymer layer may be appropriately adjusted so that the thickness of the first polyolefin layer preferably falls within the above range.
  • Various pretreatments such as corona treatment, plasma treatment, and flame treatment may be applied to the first polyolefin layer to improve the adhesion with the inorganic deposition layer, as long as the barrier performance is not impaired.
  • An adhesion layer may be provided on the surface of the first polyolefin layer on which the inorganic deposition layer is laminated.
  • the adhesion layer can provide two effects: improvement in adhesion performance between the first polyolefin layer and the inorganic deposition layer, and improvement in smoothness of the surface of the polyolefin layer. By improving the smoothness, it becomes easier to form an inorganic deposition layer uniformly without defects, and it is easy to develop a high barrier property.
  • the thickness of the adhesion layer is not particularly limited, it may be 0.01 to 5 ⁇ m, may be 0.03 to 3 ⁇ m, or may be in the range of 0.04 to 2 ⁇ m. When the thickness of the adhesion layer is at least the above lower limit, there is a tendency to obtain more sufficient interlayer adhesive strength.
  • the adhesion layer can be formed using an anchor coating agent.
  • anchor coating agents include polyester-based polyurethane resins, polyether-based polyurethane resins, acrylic-based polyurethane resins, and the like.
  • the anchor coating agent may be an acrylic polyurethane resin.
  • any known coating method can be used without particular limitation, and examples thereof include an immersion method (dipping method); a method using a spray, coater, printer, brush, or the like. mentioned.
  • the types of coaters and printing machines used in these methods and their coating methods include gravure coaters such as direct gravure, reverse gravure, kiss reverse gravure, and offset gravure, reverse roll coaters, and micro gravure.
  • a coater, a coater combined with a chamber doctor, an air knife coater, a dip coater, a bar coater, a comma coater, a die coater and the like can be used.
  • the coating amount of the adhesion layer (mass per 1 m 2 after the anchor coating agent is applied and dried) can be 0.01 to 5 g/m 2 , preferably 0.03 to 3 g/m 2 . may When the coating amount is at least the above lower limit, film formation tends to be sufficient.
  • the method for drying the adhesion layer is not particularly limited, but a method by natural drying, a method of drying in an oven set to a predetermined temperature, a dryer attached to the coater (e.g. arch dryer, floating dryer, drum dryer, infrared A method using a dryer, etc.) can be mentioned.
  • the drying conditions can be appropriately selected depending on the drying method. For example, in the method of drying in an oven, drying can be performed at a temperature of 60 to 100° C. for about 1 second to 2 minutes.
  • the anchor coating agent may contain a silane coupling agent from the viewpoint of improving the adhesion between the substrate layer and the inorganic deposition layer.
  • a silane coupling agent containing any organic functional group can be used, and in particular, a silane coupling agent having a functional group that reacts with the hydroxyl group of a polyol or the isocyanate group of an isocyanate compound can be used.
  • silane coupling agents include those containing isocyanate groups such as ⁇ -isocyanatopropyltriethoxysilane and ⁇ -isocyanatopropyltrimethoxysilane; those containing mercapto groups such as ⁇ -mercaptopropyltriethoxysilane; Those containing an amino group such as propyltriethoxysilane, ⁇ -aminopropyltrimethoxysilane, N- ⁇ -(aminoethyl)- ⁇ -aminopropyltriethoxysilane, ⁇ -phenylaminopropyltrimethoxysilane; ⁇ -glycides those containing epoxy groups such as xypropyltrimethoxysilane and ⁇ -(3,4-epoxycyclohexyl)ethyltrimethoxysilane; those containing vinyl groups such as vinyltrimethoxysilane and vinyltris( ⁇ -methoxyethoxy)
  • the amount of the silane coupling agent can be 0.1 to 100 parts by mass, and may be 1 to 50 parts by mass, with respect to 100 parts by mass of the resin (main agent) constituting the adhesion layer.
  • the inorganic deposition layer has the function of suppressing the seepage of oils and fats contained in the contents of the package from the surface of the first polyolefin layer.
  • constituent materials of the inorganic deposition layer include inorganic oxides such as aluminum oxide, silicon oxide, magnesium oxide, and tin oxide. Therefore, the inorganic deposition layer can also be called an inorganic oxide layer.
  • the inorganic oxide may be selected from the group consisting of aluminum oxide, silicon oxide and magnesium oxide.
  • the inorganic oxide may be selected from aluminum oxide and silicon oxide.
  • the inorganic oxide may be silicon oxide from the viewpoint of excellent tensile stretchability during processing.
  • the O/Al ratio may be 1.4 or more.
  • the content of metallic Al is suppressed, and good transparency can be easily obtained.
  • the O/Al ratio may be 1.7 or less.
  • the inorganic deposition layer is prevented from becoming too hard, and not only is it easy to ensure oil and fat exudation suppression properties, but also it is easy to obtain good tensile resistance.
  • the first polyolefin layer may shrink due to heat during hot water treatment such as hot filling of the packaging bag, boiling treatment, retort treatment, etc.
  • the vapor deposition layer easily follows the shrinkage, and it is easy to suppress the deterioration of the barrier property, oil and fat exudation suppression property, and the like. From the viewpoint of sufficiently obtaining these effects, the O/Al ratio of the aluminum oxide layer can be 1.4 or more and 1.7 or less, and may be 1.5 or more and 1.55 or less.
  • the O/Si ratio may be 1.7 or more.
  • the content of metal Si is suppressed, and good transparency can be easily obtained.
  • the O/Si ratio may be 2.0 or less.
  • the inorganic vapor deposition layer is prevented from becoming too hard, and not only is it easy to ensure oil and fat exudation suppression properties, but also it is easy to obtain good tensile resistance.
  • the first polyolefin layer may shrink due to heat during hot water treatment such as hot filling of the packaging bag, boiling treatment, retort treatment, etc.
  • the vapor deposition layer easily follows the shrinkage, and it is easy to suppress the deterioration of the barrier property, oil and fat exudation suppression property, and the like. From the viewpoint of sufficiently obtaining these effects, the O/Si ratio of the silicon oxide layer can be 1.75 or more and 1.9 or less, and may be 1.8 or more and 1.85 or less.
  • the O/Al ratio and O/Si ratio of the inorganic deposition layer can be obtained by X-ray photoelectron spectroscopy (XPS).
  • XPS X-ray photoelectron spectroscopy
  • the X-ray source is non-monochromatic MgK ⁇ (1253.6 eV), and 100 W (10 kV-10 mA). can be measured at an X-ray output of .
  • the thickness of the inorganic deposition layer may be 5 nm or more and 60 nm or less. When the thickness is 5 nm or more, it is easy to obtain sufficient oil and fat exudation suppression properties and gas barrier properties. Further, when the thickness is 60 nm or less, the generation of cracks due to deformation due to internal stress of the layer is suppressed, and deterioration of oil and fat exudation suppression properties and gas barrier properties can be easily suppressed. Note that if the thickness exceeds 60 nm, the cost tends to increase due to an increase in the amount of material used, an increase in the layer formation time, and the like. From the above viewpoint, the thickness of the inorganic deposition layer may be 10 nm or more and 50 nm or less.
  • the inorganic deposition layer can be formed, for example, by a vacuum film forming method.
  • Vacuum deposition methods include physical vapor deposition and chemical vapor deposition. Examples of the physical vapor deposition method include a vacuum deposition method, a sputtering method, an ion plating method, and the like, but are not limited to these. Examples of chemical vapor deposition methods include thermal CVD, plasma CVD, and optical CVD, but are not limited to these.
  • Vacuum deposition methods include resistance heating vacuum deposition, EB (Electron Beam) heating vacuum deposition, induction heating vacuum deposition, sputtering, reactive sputtering, dual magnetron sputtering, and plasma chemical vapor deposition. method (PECVD method) and the like. Considering productivity, the vacuum deposition method is the best at present.
  • a heating means for the vacuum vapor deposition method any one of an electron beam heating method, a resistance heating method, and an induction heating method can be used.
  • the barrier coating layer imparts gas barrier properties to the packaging material and also has a function of protecting the inorganic deposition layer.
  • the barrier coating layer can also be called an overcoat layer.
  • the barrier coating layer may contain a water-soluble polymer. More specifically, the barrier coating layer may be formed from a liquid composition containing a water-soluble polymer, and may be said to be a heat-dried product (heat-cured product) of the composition.
  • a water-soluble polymer refers to a polymer that can be dissolved in water.
  • water-soluble polymers examples include polyvinyl alcohol resins and modified products thereof, and polyacrylic acid. These can be used individually or in combination of 2 or more types. By using a polyvinyl alcohol resin or a modified product thereof as the water-soluble polymer, it is easy to impart excellent gas barrier properties and oil and fat exudation suppression properties to the packaging material.
  • the water-soluble polymer may be cured with a curing agent.
  • a curing agent is not particularly limited, a metal alkoxide or a silane coupling agent can be used from the viewpoint of maintaining excellent laminate strength even after retorting.
  • metal alkoxides include compounds represented by the following general formula (I).
  • R 1 and R 2 are each independently a monovalent organic group having 1 to 8 carbon atoms, and may be an alkyl group such as methyl or ethyl.
  • M represents an n-valent metal atom such as Si, Ti, Al, Zr.
  • m is an integer from 1 to n.
  • metal alkoxides include tetraethoxysilane [Si(OC 2 H 5 ) 4 ] and triisopropoxyaluminum [Al(O-sec-C 4 H 9 ) 3 ]. These metal alkoxides are relatively stable in aqueous solvents after hydrolysis.
  • Silane coupling agents include, for example, compounds represented by the following general formula (II). Si(OR 1 ) p (R 2 ) 3-p R 3 (II)
  • R 1 represents an alkyl group such as a methyl group or an ethyl group
  • R 2 represents an alkyl group, an aralkyl group, an aryl group, an alkenyl group, an acryloxy group, an alkyl group substituted with a methacryloxy group, or the like.
  • R 3 is a monovalent organic functional group
  • p is an integer of 1-3.
  • R 1s or R 2s may be the same or different.
  • Examples of monovalent organic functional groups represented by R 3 include monovalent organic functional groups containing a vinyl group, an epoxy group, a mercapto group, an amino group, or an isocyanate group.
  • Silane coupling agents include, for example, silane coupling agents having a vinyl group such as vinyltrimethoxysilane and vinyltriethoxysilane; - Silane coupling agents having epoxy groups such as glycidoxypropylmethyldimethoxysilane and 3-glycidoxypropylethyldiethoxysilane; mercapto groups such as 3-mercaptopropyltrimethoxysilane and 3-mercaptopropylmethyldimethoxysilane; silane coupling agents having an amino group such as 3-aminopropyltrimethoxysilane and 3-aminopropyltriethoxysilane; and silane coupling agents having an isocyanate group such as 3-isocyanatopropyltriethoxysilane. mentioned. These silane coupling agents may be used alone or in combination of two or more.
  • the barrier coating layer may be formed from a liquid composition containing a water-dispersible polymer in addition to or instead of the water-soluble polymer, and may be said to be a heat-dried product of the composition.
  • a water-dispersible polymer refers to a polymer dispersed in water. Examples of water-dispersible polymers include polyurethane dispersions obtained by dispersing polyurethane resin in water.
  • the barrier coating layer uses a liquid composition (hereinafter also referred to as an overcoat agent) obtained by adding a raw material containing a water-soluble polymer and, if necessary, a curing agent to water or a water/alcohol mixture.
  • a liquid composition obtained by adding a raw material containing a water-dispersible polymer, optionally a water-soluble polymer, and optionally a curing agent to water or a water/alcohol mixture. may be formed using
  • the amount of hydrolyzate of tetraethoxysilane (SiO 2 ) in the overcoat agent is from the viewpoint of suppressing oil and fat exudation, adhesion to the inorganic deposition layer, and maintaining gas barrier properties.
  • the amount of water-soluble polymer or water-dispersible polymer can be 0/100 to 80/20 in mass ratio, may be 3/97 to 75/25, 30/70 to 50/ It may be 50.
  • the amount of the silane coupling agent in the overcoating agent is 0 to 20% by mass based on the total solid content of the overcoating agent, from the viewpoint of oil and fat exudation suppression, adhesion to the inorganic deposition layer, and maintenance of gas barrier properties. can be from 0 to 15% by weight.
  • the overcoat agent may contain known additives such as dispersants, stabilizers, viscosity modifiers, colorants, metal oxide particles, etc., to the extent that they do not impair the oil and fat exudation suppression properties and gas barrier properties.
  • the overcoat agent can be applied by, for example, a dipping method, a roll coating method, a gravure coating method, a reverse gravure coating method, an air knife coating method, a comma coating method, a die coating method, a screen printing method, a spray coating method, or a gravure offset method. can be done.
  • a coating film formed by applying an overcoat agent can be dried by, for example, hot air drying, hot roll drying, high frequency irradiation, infrared irradiation, UV irradiation, or a combination thereof.
  • the temperature for drying the coating film can be, for example, 50 to 150°C, and may be 70 to 100°C. By setting the drying temperature within the above range, the occurrence of cracks in the inorganic deposition layer and the barrier coating layer can be easily suppressed, and excellent barrier properties can be exhibited.
  • the thickness of the barrier coating layer is preferably 50-1000 nm, more preferably 100-500 nm.
  • the thickness of the barrier coating layer is 50 nm or more, there is a tendency that sufficient gas barrier properties can be obtained while protecting the inorganic deposition layer, and when it is 1000 nm or less, there is a tendency that sufficient flexibility can be maintained. be.
  • the second polyolefin layer is composed of a material having a melting point lower than that of the constituent material of the first polyolefin layer, and has heat-sealing properties. Therefore, the second polyolefin layer can also be called a sealant layer.
  • the second polyolefin layer may be an unstretched film (eg, CPP).
  • the first polyolefin layer and the second polyolefin layer may contain different materials, but may contain the same material from the viewpoint of ease of re-forming after melting of the resin material.
  • including the same material means, for example, that both layers include an ethylene-based resin or that both layers include a propylene-based resin.
  • the second polyolefin layer includes low-density polyethylene resin (LDPE), medium-density polyethylene resin (MDPE), linear low-density polyethylene (LLDPE), ethylene-acetic acid.
  • LDPE low-density polyethylene resin
  • MDPE medium-density polyethylene resin
  • LLDPE linear low-density polyethylene
  • EVA Vinyl copolymers
  • ethylene- ⁇ -olefin copolymers ethylene-based resins such as ethylene-(meth)acrylic acid copolymers
  • blended resins of polyethylene and polybutene can be used.
  • the barrier layer side is made of high density polyethylene (HDPE) or medium density polyethylene (MDPE) and the heat seal side is made of low density polyethylene (LDPE) coextruded.
  • the second polyolefin layer can be used as the second polyolefin layer.
  • the second polyolefin layer may be homopolypropylene resin (PP), propylene-ethylene random copolymer, propylene-ethylene block copolymer, propylene- ⁇ -olefin copolymer.
  • PP homopolypropylene resin
  • propylene-ethylene random copolymer propylene-ethylene random copolymer
  • propylene-ethylene block copolymer propylene- ⁇ -olefin copolymer
  • a propylene-based resin such as coalescing can be used.
  • additives such as flame retardants, slip agents, antiblocking agents, antioxidants, light stabilizers, and tackifiers may be added to the polyolefin film that constitutes the second polyolefin layer.
  • the thickness of the second polyolefin layer is determined by the mass of the contents, the shape of the packaging bag, etc., and can be, for example, 30 to 150 ⁇ m.
  • a printing layer can be provided on the side of the barrier layer opposite the second polyolefin layer.
  • the printing layer has a printing surface on the printing substrate, and the printing surface (ink layer) of the printing layer faces the barrier layer.
  • the printing substrate may be a polyolefin layer, and the polyolefin constituting the polyolefin layer may be the polyolefin exemplified for the first polyolefin layer.
  • the printed layer is provided at a position that can be seen from the outside of the packaging bag for the purpose of displaying information about the contents, identifying the contents, or improving the design.
  • the printing method and printing ink for forming the printing layer are not particularly limited, and from known printing methods and printing inks, printability, design properties such as color tone, adhesion, safety as a food container, etc. are considered. selected as appropriate.
  • As the printing method for example, a gravure printing method, an offset printing method, a gravure offset printing method, a flexographic printing method, an inkjet printing method, or the like can be used.
  • the gravure printing method can be preferably used from the viewpoint of productivity and high definition of the pattern.
  • the barrier layer and the second polyolefin layer may be laminated via an adhesive layer.
  • the barrier layer and the print layer may be laminated via an adhesive layer.
  • Means for laminating each layer include a dry lamination method in which an adhesive such as a one-component curing type or two-component curing type urethane adhesive is used, a non-solvent dry lamination method in which a non-solvent adhesive is used, polyethylene or polypropylene.
  • a known lamination method such as an extrusion lamination method in which a polyolefin resin such as polyolefin resin is heated and melted, extruded in a curtain shape, and laminated together can be employed.
  • the films (the first polyolefin layer, the second polyolefin layer, and the printed layer) that make up the packaging material can all be polyolefin films.
  • a packaging material can be said to be a (mono-material) material made of a single material with excellent recyclability.
  • the total mass of components other than polyolefin components should be 10% by mass or less with respect to the total mass of the packaging material. may be 7.5% by mass or less, and may be 5.0% by mass or less.
  • a packaging bag can be obtained by heat-sealing the second polyolefin layers of the packaging material obtained in this manner so that they face each other.
  • the package can be obtained by filling the thus-obtained packaging bag with a content containing fats and oils and sealing the bag.
  • a packaging material for packaging contents containing oils and fats comprising a first polyolefin layer, a barrier layer including an inorganic deposition layer and a barrier coating layer, and a second polyolefin layer having heat-sealing properties.
  • packaging materials comprising a first polyolefin layer, a barrier layer including an inorganic deposition layer and a barrier coating layer, and a second polyolefin layer having heat-sealing properties.
  • packaging materials comprising a first polyolefin layer, a barrier layer including an inorganic deposition layer and a barrier coating layer, and a second polyolefin layer having heat-sealing properties.
  • packaging materials comprising a first polyolefin layer, a barrier layer including an inorganic deposition layer and a barrier coating layer, and a second polyolefin layer having heat-sealing properties.
  • the above packaging material, wherein the inorganic vapor deposition layer contains at least one of aluminum oxide and silicon oxide.
  • the above packaging material wherein the first polyolefin layer and the second polyolefin layer are made of polyethylene.
  • the above packaging material, wherein the first polyolefin layer and the second polyolefin layer are made of polypropylene.
  • a packaging bag formed from the packaging material described above. A package comprising the above packaging bag and a content containing oil and fat packaged in the packaging bag.
  • Acrylic polyol and tolylene diisocyanate are mixed so that the number of NCO groups of tolylene diisocyanate is equal to the number of OH groups of acrylic polyol, and the total solid content (total amount of acrylic polyol and tolylene diisocyanate ) was diluted with ethyl acetate to 5% by mass.
  • ⁇ -(3,4 epoxycyclohexyl)ethyltrimethoxysilane was further added so as to be 5 parts by mass with respect to the total amount of 100 parts by mass of the acrylic polyol and tolylene diisocyanate.
  • An anchor coating agent was prepared by mixing.
  • the prepared anchor coating agent was applied onto the substrate layer by a gravure coating method and dried to form an adhesion layer having a thickness of 40 nm (other than Experimental Example 18).
  • a 2- ⁇ m-thick adhesive layer (adhesive layer) was formed using a two-component curing urethane adhesive (A525/A52) manufactured by Mitsui Chemicals, Inc. instead of the anchor coating agent.
  • AlOx layer aluminum oxide vapor deposition layer
  • SiOx layer silicon oxide vapor deposition layer
  • Both layer thicknesses were set to 50 nm.
  • the O/Al ratio of the aluminum oxide deposited layer was 1.52, and the O/Si ratio of the silicon oxide deposited layer was 1.81.
  • PVA layer A polyvinyl alcohol (PVA) aqueous solution using PVA124 manufactured by Kuraray Co., Ltd. was used as a coating liquid.
  • PVA/TEOS layer Tetraethoxysilane (TEOS), methanol, and 0.1N hydrochloric acid were mixed in a mass ratio of 45/15/40 to hydrolyze TEOS, and a 5% aqueous solution of PVA124 was mixed.
  • PAA/DA/ZnO layer PAA solution in which AC-10LP (polyacrylic acid (PAA), weight average molecular weight 50,000) manufactured by Toagosei Co., Ltd. is dissolved in isopropanol (IPA) so that the content is 10% by mass. Then, Disparon DA-375 (polyether phosphate ester (DA)) manufactured by Kusumoto Kasei Co., Ltd. was dissolved in IPA so that the content was 10% by mass, and FINEX-30 manufactured by Sakai Chemical Industry Co., Ltd.
  • AC-10LP polyacrylic acid (PAA), weight average molecular weight 50,000) manufactured by Toagosei Co., Ltd. is dissolved in isopropanol (IPA) so that the content is 10% by mass.
  • Disparon DA-375 polyether phosphate ester (DA)
  • IPA isopropanol
  • FINEX-30 manufactured by Sakai Chemical Industry Co., Ltd.
  • PU layer An aqueous solution using Takelac WPB-341 (polyurethane dispersion (PU)) manufactured by Mitsui Chemicals, Inc. was used as a coating liquid.
  • PU/PVA layer An aqueous solution containing Takelac WPB-341 and PVA124 in a mass ratio of solids of 65/35 was used as a coating liquid.
  • PVA/PAA layer An aqueous solution containing PVA124 and a polyacrylic acid-based resin at a solid content ratio of 97/3 by mass was used as a coating liquid.
  • a two-component curable urethane adhesive (A525/A52) manufactured by Mitsui Chemicals, Inc. was used for lamination of the barrier layer and the printed layer and lamination of the barrier layer and the heat seal layer.
  • Heat seal layer second polyolefin layer
  • LLDPE film TUX MC-S manufactured by Mitsui Chemicals Tohcello Co., Ltd.
  • CPP film Torayfan ZK207, thickness 60 ⁇ m, manufactured by Toray Advanced Film Co., Ltd.
  • Print layer Printing was performed on an OPP film (manufactured by Mitsui Chemicals Tohcello Co., Ltd., U-1, thickness 20 ⁇ m) by gravure printing (grid printing) using ink (manufactured by Sakata Inks, Bellcolor R White 120).
  • packaging materials having the configurations shown in Table 1 were obtained.
  • the printed surface of the printed layer faced the substrate layer.
  • OMR oxygen permeability
  • the oxygen permeability (OTR) of the packaging material obtained in each example was measured using an oxygen permeability measuring device (manufactured by MOCON, trade name: OX-TRAN2/20) at a temperature of 30 ° C. and a relative humidity of 70%. was measured in accordance with JIS K-7126-2.
  • the oxygen permeability was measured after the packaging material was produced, after the gelbo flex test described later, after the boiling treatment, and after the retort treatment. Table 2 shows the results.
  • the water vapor transmission rate (WVTR) of the packaging material obtained in each example was measured using a water vapor transmission rate measuring device (manufactured by MOCON, trade name: PERMATRAN 3/31) at a temperature of 40 ° C. and a relative humidity of 90%. Measured according to JIS K-7129. The water vapor transmission rate was measured after the packaging material was produced, after the gelbo flex test described later, after the boiling treatment, and after the retort treatment. Table 2 shows the results.
  • the packaging material according to the present disclosure has excellent exudation suppression properties for oils and fats, and can suitably package contents containing oils and fats.
  • the packaging material according to the present disclosure can have a polyolefin content of 90% by mass or more in the total amount of the packaging material, and material recycling is possible.
  • SYMBOLS 1... First polyolefin layer, 1a... Homopolymer layer, 1b... Copolymer layer, 2... Inorganic deposition layer, 3... Barrier coating layer, 4... Second polyolefin layer, 5... Printing layer, 10, 20, 30... Packaging materials.

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JPWO2024071355A1 (https=) * 2022-09-28 2024-04-04
WO2024219469A1 (ja) * 2023-04-20 2024-10-24 Ｔｏｐｐａｎホールディングス株式会社 バリアフィルム、積層体、包装容器及び包装製品
EP4424510A4 (en) * 2021-11-29 2025-02-19 Toppan Holdings Inc. BARRIER FILM, LAMINATE AND PACKAGING BAGS

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