WO2023042767A1 - Corps stratifié barrière contre les gaz et sac d'emballage - Google Patents

Corps stratifié barrière contre les gaz et sac d'emballage Download PDF

Info

Publication number
WO2023042767A1
WO2023042767A1 PCT/JP2022/033931 JP2022033931W WO2023042767A1 WO 2023042767 A1 WO2023042767 A1 WO 2023042767A1 JP 2022033931 W JP2022033931 W JP 2022033931W WO 2023042767 A1 WO2023042767 A1 WO 2023042767A1
Authority
WO
WIPO (PCT)
Prior art keywords
gas barrier
barrier laminate
layer
vapor deposition
polyolefin
Prior art date
Application number
PCT/JP2022/033931
Other languages
English (en)
Japanese (ja)
Inventor
裕美子 小島
純一 神永
良樹 越山
里佳 石井
寛之 若林
Original Assignee
凸版印刷株式会社
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 凸版印刷株式会社 filed Critical 凸版印刷株式会社
Publication of WO2023042767A1 publication Critical patent/WO2023042767A1/fr

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • 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
    • B32B15/12—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 paper or cardboard
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/10—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 paper or cardboard
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/40—Applications of laminates for particular packaging purposes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/80—Packaging reuse or recycling, e.g. of multilayer packaging

Definitions

  • the present disclosure relates to gas barrier laminates and packaging bags.
  • Packaging materials are required to have permeation-preventing properties (gas barrier properties) against water vapor and the like, which cause deterioration of contents.
  • Patent Document 1 discloses a packaging material having a paper substrate layer, a dry lamination adhesive layer, and a specific sealant layer laminated adjacently on the dry lamination adhesive layer.
  • Paper has the characteristic of being easy to process because it has crease-retaining properties (also called dead-holding properties).
  • crease-retaining properties also called dead-holding properties.
  • cracks occur in the layers and the gas barrier properties are lowered. It turned out that there was room for improvement.
  • the present disclosure includes a gas barrier laminate that has crease retention characteristic of paper, has sufficient water vapor barrier properties even after being folded, and contributes to a reduction in the amount of plastic material used, and the same. Provide packaging bags.
  • a gas barrier laminate includes a paper substrate, a vapor deposition layer, and a sealant layer in this order.
  • X divided by Y is 0.6 to 2.5.
  • the gas barrier laminate may further include an anchor coat layer between the paper substrate and the vapor deposition layer.
  • the anchor coat layer may contain at least one of a polyvinyl alcohol-based resin and a polyolefin having a polar group.
  • the anchor coat layer contains the polyolefin having the polar group, and the polyolefin having the polar group is at least one selected from the group consisting of a carboxyl group, a salt of a carboxyl group, a carboxylic acid anhydride group, and a carboxylic acid ester. may have
  • the anchor coat layer may contain the polyolefin having the polar group, and the polyolefin having the polar group may be a copolymer of acrylic acid ester and maleic anhydride.
  • the anchor coat layer may contain the polyolefin having the polar group, and the polyolefin having the polar group may be an ethylene-vinyl acetate copolymer.
  • the anchor coat layer may contain the polyolefin having the polar group, and the polyolefin having the polar group may be an ethylene-glycidyl methacrylate copolymer.
  • the anchor coat layer may contain the polyvinyl alcohol-based resin.
  • the gas barrier laminate may further comprise an adhesive layer between at least one of the vapor deposition layer and the sealant layer and between the paper substrate and the vapor deposition layer.
  • the adhesive layer is a cured product of a resin composition containing an epoxy resin and an epoxy resin curing agent, and the epoxy resin curing agent is meta-xylylenediamine or para-xylylenediamine, and is represented by the following formula (1). It may be a reaction product with an unsaturated carboxylic acid and/or a derivative thereof.
  • R 1 represents an alkyl group having 1 to 8 carbon atoms, an aralkyl group having 1 to 8 carbon atoms, or an aryl group.
  • the adhesive layer may be a cured product of a resin composition containing a polyol having two or more hydroxyl groups in one molecule and an isocyanate compound having two or more isocyanate groups in one molecule.
  • the weight of the paper substrate may be 50% by mass or more based on the entire gas barrier laminate.
  • a packaging bag according to another aspect of the present disclosure includes the gas barrier laminate.
  • the packaging bag may have folds.
  • a gas barrier laminate that has the characteristic crease retention of paper, has sufficient water vapor barrier properties even after being folded, and contributes to a reduction in the amount of plastic material used, and the same.
  • a packaging bag is provided containing.
  • FIG. 1 is a schematic cross-sectional view showing a gas barrier laminate according to an embodiment of the present disclosure
  • FIG. FIG. 4 is a schematic cross-sectional view showing a gas barrier laminate according to another embodiment of the present disclosure
  • FIG. 4 is a schematic cross-sectional view showing a gas barrier laminate according to still another embodiment of the present disclosure
  • 1 is a perspective view of a packaging bag according to an embodiment of the present disclosure
  • FIG. 1 is a schematic cross-sectional view showing a gas barrier laminate according to one embodiment.
  • a gas barrier laminate 10 according to one embodiment includes a paper substrate 1, an anchor coat layer 2, a deposition layer 3, an adhesive layer 4, and a sealant layer 5 in this order.
  • the distance from the main surface of the vapor deposition layer 3 on the side of the paper substrate 1 to the main surface of the paper substrate 1 opposite to the vapor deposition layer 3 is X
  • the distance from the main surface of the vapor deposition layer 3 on the sealant layer 5 side to the sealant layer 5 Assuming that the distance to the main surface on the side opposite to the deposited layer 3 is Y, the value X/Y obtained by dividing X by Y is 0.6 to 2.5.
  • the gas barrier laminate 10 When X/Y is 0.6 to 2.5, the gas barrier laminate 10 has excellent gas barrier properties.
  • the inventors consider the mechanism by which such effects are exhibited as follows. That is, when the gas barrier laminate is folded, a compressive force is applied to the inner side of the fold, and a tensile force is applied to the outer side of the fold. Ordinarily, when the gas barrier laminate is bent, cracks occur in the deposited layer, which tends to crack due to compressive force or tensile force. However, by setting X/Y within the above range, the compressive force and the tensile force applied to the vapor deposition layer are offset, so that the vapor deposition layer tends to be difficult to crack. As a result, the gas barrier laminate 10 has excellent gas barrier properties.
  • X/Y is 0.6 or more, and the gas barrier property is further improved. Therefore, it is preferably 1.0 or more, more preferably 1.5 or more, and 2.5 or less. It is preferably 2.2 or less, more preferably 2.0 or less, because the properties are further improved.
  • the paper base material 1 is not particularly limited, and may be appropriately selected according to the use of the packaging bag to which the gas barrier laminate 10 is applied. There is no particular limitation as long as the paper is mainly composed of plant-derived pulp. Specific examples of the paper substrate 1 include woodfree paper, special woodfree paper, coated paper, art paper, cast coated paper, imitation paper, kraft paper, and glassine paper. The thickness of the paper substrate 1 may be, for example, 30 ⁇ m or more and 100 ⁇ m or less, or 30 ⁇ m or more and 70 ⁇ m or less.
  • the paper substrate 1 may be provided with a coat layer at least on the side in contact with the anchor coat layer 2 described later.
  • a coat layer By providing a coat layer, it is possible to prevent the anchor coat layer from soaking into the paper, and it can also play the role of a filler that fills in the unevenness of the paper, making it possible to form the anchor coat layer uniformly without defects. can.
  • the gas barrier laminate 10 is even more excellent in gas barrier properties.
  • various copolymers such as styrene/butadiene, styrene/acrylic, ethylene/vinyl acetate, polyvinyl alcohol resin, cellulose resin, paraffin (WAX), etc. are used as binder resins.
  • fillers such as clay, kaolin, calcium carbonate, talc, and mica.
  • the thickness of the coat layer may be, for example, 1-10 ⁇ m, or 3-8 ⁇ m.
  • the weight of the paper substrate 1 is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more, based on the entire gas barrier laminate. If the weight of paper is 50% by mass or more based on the entire gas barrier laminate, the amount of plastic material used can be sufficiently reduced, and the gas barrier laminate as a whole can be said to be made of paper and recycled. Excellent in nature.
  • the anchor coat layer 2 is provided on the surface of the paper base material 1 to improve the adhesion between the paper base material 1 and the vapor deposition layer 3 described later and to improve the gas barrier properties of the gas barrier laminate. is.
  • the anchor coat layer 2 is not particularly limited, it preferably contains a polyvinyl alcohol-based resin and a polyolefin having a polar group because it is more excellent in gas barrier properties (particularly, water vapor barrier properties). Since it is more excellent, it is preferable to contain a polyvinyl alcohol-based resin.
  • polyolefin having a polar group By including polyolefin having a polar group in the anchor coat layer 2, it is possible to form a dense film due to the crystallinity of polyolefin, and the water vapor barrier property is exhibited. Due to the crystallinity of the polyolefin, water vapor barrier properties are exhibited, and the presence of polar groups allows adhesion with the deposition layer 3 to be exhibited.
  • the polyolefin having a polar group may have at least one selected from a carboxyl group, a salt of a carboxyl group, a carboxylic acid anhydride group and a carboxylic acid ester.
  • Polyolefins having polar groups include copolymers of ethylene and propylene with unsaturated carboxylic acids (unsaturated compounds with carboxyl groups such as acrylic acid, methacrylic acid, and maleic anhydride), unsaturated carboxylic acid esters, and carboxylic acid esters.
  • unsaturated carboxylic acids unsaturated compounds with carboxyl groups such as acrylic acid, methacrylic acid, and maleic anhydride
  • unsaturated carboxylic acid esters unsaturated carboxylic acid esters
  • carboxylic acid esters unsaturated carboxylic acid esters
  • a salt obtained by neutralizing an acid with a basic compound may be used, or a copolymer obtained by copolymerizing vinyl acetate, an epoxy-based compound, a chlorine-based compound, a urethane-based compound, a polyamide-based compound, or the like may be used.
  • polyolefins having polar groups include copolymers of acrylic acid esters and maleic anhydride, ethylene-vinyl acetate copolymers, and ethylene-glycidyl methacrylate copolymers.
  • Polyvinyl alcohol resins include, for example, completely saponified polyvinyl alcohol resins, partially saponified polyvinyl alcohol resins, modified polyvinyl alcohol resins, ethylene-vinyl alcohol copolymer resins, and the like.
  • the degree of polymerization of the polyvinyl alcohol resin is preferably 300 or more and 1700 or less. If the degree of polymerization is 300 or more, the gas barrier property and bending resistance of the gas barrier laminate will be good. get better.
  • the anchor coat layer 2 contains a polyvinyl alcohol-based resin, it is excellent in flexibility and can suppress cracking of the vapor deposition layer described later after bending (after bending), thereby suppressing deterioration of the gas barrier properties, and the vapor deposition layer and the anchor coat layer 2 can be improved.
  • the anchor coat layer 2 may contain other components in addition to the above polyolefin and polyvinyl alcohol resin.
  • Other components include, for example, polyolefins other than the above polyolefins, polyacrylics, polyesters, polyurethanes, polyethyleneimine, polylactic acid, polyamides, starch and its derivatives, and resins such as cellulose derivatives, silane coupling agents, organic titanates, Additives such as glycerin, glycols, casein and waxes may be mentioned.
  • the total content of polyolefin and polyvinyl alcohol resin in the anchor coat layer 2 may be, for example, 50% by mass or more, 70% by mass or more, 90% by mass or more, or 100% by mass. It's okay.
  • the thickness of the anchor coat layer 2 may be, for example, 1 ⁇ m or more, 2 ⁇ m or more, 20 ⁇ m or less, 10 ⁇ m or less, or 5 ⁇ m or less. If the thickness of the anchor coat layer 2 is 1 ⁇ m or more, the unevenness of the paper substrate 1 can be efficiently filled, and the vapor deposition layer 3 described later can be uniformly laminated. Moreover, if the thickness of the anchor coat layer 2 is 20 ⁇ m or less, the deposition layer 3 can be uniformly laminated while suppressing the cost.
  • Examples of the solvent contained in the coating liquid of the anchor coat layer 2 include water, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-propyl alcohol, n-butyl alcohol, n-pentyl alcohol, dimethylsulfoxide, dimethylformamide, and dimethylacetamide. , toluene, hexane, heptane, cyclohexane, acetone, methyl ethyl ketone, diethyl ether, dioxane, tetrahydrofuran, ethyl acetate, butyl acetate. These solvents may be used singly or in combination of two or more.
  • methyl alcohol, ethyl alcohol, isopropyl alcohol, toluene, ethyl acetate, methyl ethyl ketone, and water are preferred from the viewpoint of properties.
  • methyl alcohol, ethyl alcohol, isopropyl alcohol, and water are preferable.
  • the method of providing the anchor coat layer 2 is not particularly limited.
  • the anchor coat layer 2 contains at least one of the polyolefin and polyvinyl alcohol resins described above
  • a coating liquid containing at least one of the polyolefin and polyvinyl alcohol resins described above and a solvent is applied onto the paper substrate. It can be obtained by drying.
  • the polyolefin in the coating liquid preferably has a large particle size so that the contact area becomes small.
  • the particle size may specifically be 1 nm or more, 0.1 ⁇ m or more, or 1 ⁇ m or less, 0.7 ⁇ m or less, or 0.5 ⁇ m or less.
  • the deposited layer 3 is a layer deposited with a metal or an inorganic compound.
  • the deposited layer may be obtained by vapor deposition of aluminum, or may contain aluminum oxide (AlO x ), silicon oxide (SiO x ), or the like.
  • the thickness of the vapor deposition layer 3 may be appropriately set depending on the intended use, but may preferably be 10 nm or more, 30 nm or more, 50 nm or more, and may be 300 nm or less, 100 nm or less, and 80 nm or less.
  • the thickness of the deposition layer 3 is 10 nm or more, the continuity of the deposition layer 3 can be easily made sufficient, and when the thickness is 300 nm or less, the occurrence of curling and cracking can be sufficiently suppressed, and sufficient gas barrier performance and flexibility can be obtained. easy to achieve.
  • Film formation means include known methods such as a vacuum deposition method, a sputtering method, and a chemical vapor deposition method (CVD method), but the vacuum deposition method is preferred because of its high film formation speed and high productivity.
  • vacuum evaporation methods electron beam heating is particularly effective because the film formation rate can be easily controlled by adjusting the irradiation area and electron beam current, and the temperature of the vapor deposition material can be raised and lowered in a short period of time. be.
  • the adhesive layer 4 is provided on the surface of the vapor deposition layer 3 so as to be in contact with the vapor deposition layer 3 .
  • various materials can be used as long as they adhere the deposition layer 3 and the sealant layer 5 together. is mentioned.
  • a urethane-based adhesive is a resin composition containing a polyol having two or more hydroxyl groups in one molecule and an isocyanate compound having two or more isocyanate groups in one molecule.
  • a urethane bond is generated by curing the urethane adhesive.
  • the urethane-based adhesive is preferably of a two-liquid curing type.
  • the urethane-based adhesive may have gas barrier properties.
  • Methods for imparting gas barrier properties to urethane-based adhesives include, for example, a method of using a polyol having a skeleton having gas barrier properties, a method of incorporating a phosphoric acid-modified compound into the resin composition, and a method of adding a plate-like inorganic compound to the resin composition.
  • a method of containing a compound is included. These methods can be used singly or in combination of two or more methods.
  • the main skeleton is polyester or polyester polyurethane, and the polyester contains a structure derived from an ortho-oriented aromatic dicarboxylic acid or its anhydride.
  • the polyester portion of the main skeleton may be obtained by a polycondensation reaction between a polyhydric carboxylic acid and a polyhydric alcohol.
  • polyvalent carboxylic acids examples include aliphatic polyvalent carboxylic acids and aromatic polyvalent carboxylic acids.
  • Aliphatic polycarboxylic acids include, for example, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid.
  • aromatic polycarboxylic acids examples include orthophthalic acid, terephthalic acid, isophthalic acid, pyromellitic acid, trimellitic acid, 1,2-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, and 2,3-naphthalenedicarboxylic acid.
  • Polyvalent carboxylic acid can be used alone or in combination of two or more.
  • an ortho-oriented aromatic dicarboxylic acid or its anhydride is preferable.
  • the content of the ortho-oriented aromatic dicarboxylic acid or its anhydride is preferably 70 to 100% by mass based on the total amount of the polyvalent carboxylic acid component constituting the polyester.
  • ortho-oriented aromatic dicarboxylic acids examples include orthophthalic acid, 1,2-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, and anhydrides of these dicarboxylic acids.
  • Polyhydric alcohols include aliphatic polyhydric alcohols and aromatic polyhydric phenols.
  • aliphatic polyhydric alcohols include ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, cyclohexanedimethanol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, and 1,6-hexane.
  • Aromatic polyhydric phenols include, for example, hydroquinone, resorcinol, catechol, naphthalenediol, biphenol, bisphenol A, hisphenol F, tetramethylbiphenol, ethylene oxide extensions thereof, and hydrogenated alicyclics.
  • the isocyanate compound may be aromatic having an aromatic ring, may be aliphatic having no aromatic ring, may be a low-molecular-weight compound or a high-molecular-weight compound, and may be a diisocyanate having two isocyanate groups. compound or three or more polyisocyanate compounds.
  • the isocyanate compound may be a blocked isocyanate compound obtained by addition reaction of an isocyanate blocking agent.
  • the isocyanate compound is preferably a polyisocyanate compound. Since the isocyanate compound imparts oxygen barrier properties to the adhesive layer 4, those having an aromatic ring are preferred, and an isocyanate compound containing a meta-xylene skeleton is particularly preferred.
  • isocyanate compounds include tetramethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, meta-xylylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, and trimers of these isocyanate compounds. be done.
  • isocyanate compounds include, for example, ethylene glycol, propylene glycol, metaxylylene alcohol, 1,3-bishydroxyethylbenzene, 1,4-bishydroxyethylbenzene, trimethylolpropane, glycerol, pentaerythritol, erythritol, sorbitol, ethylenediamine, Low-molecular-weight active hydrogen compounds such as monoethanolamine, diethanolamine, triethanolamine, and meta-xylylenediamine, their alkylene oxide adducts, various polyester resins, polyether polyols, high-molecular-weight active hydrogen compounds such as polyamides, and isocyanate compounds It may be an adduct, burette, or allophanate obtained by reacting with.
  • An epoxy adhesive is a resin composition containing an epoxy resin and an epoxy resin curing agent.
  • Epoxy resins may have saturated or unsaturated bonds, and may be aliphatic compounds, alicyclic compounds, aromatic compounds, or heterocyclic compounds.
  • the epoxy resin is preferably an epoxy resin containing an aromatic ring or an alicyclic structure in its molecule in order to exhibit higher gas barrier properties.
  • epoxy resins examples include epoxy resins having glycidylamino groups derived from metaxylylenediamine, epoxy resins having glycidylamino groups derived from 1,3-bis(aminomethyl)cyclohexane, and epoxy resins derived from diaminodiphenylmethane.
  • epoxy resins having glycidylamino groups epoxy resins having glycidylamino groups and/or glycidyloxy groups derived from para-aminophenol, epoxy resins having glycidyloxy groups derived from bisphenol A, glycidyl derived from bisphenol F
  • Epoxy resins having an oxy group epoxy resins having a glycidyloxy group derived from phenol novolak, and epoxy resins having a glycidyloxy group derived from resorcinol can be mentioned. You may use an epoxy resin individually by 1 type or in combination of 2 or more types.
  • the epoxy resin is preferably an epoxy resin having a glycidylamino group derived from metaxylylenediamine and an epoxy resin having a glycidyloxy group derived from bisphenol F. Epoxy resins having a glycidylamino group are more preferred.
  • the epoxy resin curing agent may be a reaction product of meta-xylylenediamine or para-xylylenediamine and an unsaturated carboxylic acid represented by the following formula (1) and/or its derivative.
  • R 1 represents an alkyl group having 1 to 8 carbon atoms, an aralkyl group having 1 to 8 carbon atoms, or an aryl group.
  • the gas barrier property is further improved by using meta-xylylenediamine or para-xylylenediamine as the precursor of the epoxy resin curing agent.
  • Meta-xylylenediamine or para-xylylenediamine is preferably meta-xylylenediamine from the viewpoint of gas barrier properties.
  • Meta-xylylenediamine or para-xylylenediamine may be used alone or in combination of two or more.
  • the unsaturated carboxylic acids represented by the above formula (1) and/or derivatives thereof include crotonic acid, 2-pentenoic acid, 2-hexenoic acid, 4-methyl-2-pentenoic acid, 2-heptenoic acid, 4-methyl -2-hexenoic acid, 5-methyl-2-hexenoic acid, 4,4-dimethyl-2-pentenoic acid, 4-phenyl-2-butenoic acid, cinnamic acid, o-methylcinnamic acid, m-methylcinnamic acid, Unsaturated carboxylic acids such as p-methylcinnamic acid, 2-octenoic acid, 2-nonenoic acid, 2-decenoic acid, 2-undecenoic acid, and derivatives thereof (e.g., esters, amides, acid anhydrides, acid chlorides, and derivatives thereof (e.g., esters, amides, acid anhydrides, acid chlorides, and derivatives thereof (e.g., esters
  • the unsaturated carboxylic acid represented by the above formula (1) and/or its derivative further improves the gas barrier property and adhesiveness, so that R 1 in the above formula (1) is a hydrocarbon group having 1 to 3 carbon atoms or a phenyl
  • R 1 in the above formula (1) is a hydrocarbon group having 1 to 3 carbon atoms or a phenyl
  • At least one selected from the group consisting of unsaturated carboxylic acids and derivatives thereof is preferred, at least one selected from the group consisting of crotonic acid and crotonic acid derivatives is more preferred, and the group consisting of crotonic acid and crotonic acid esters At least one selected from is more preferable.
  • the crotonate an alkyl ester having 1 to 3 carbon atoms is more preferred, and methyl crotonate is even more preferred.
  • the adhesive layer 4 may be formed using a one-component curing or two-component curing adhesive (dry lamination method), or may be formed using a non-solvent adhesive (non-solvent dry lamination method ), or may be formed by extruding a molten resin onto the surface of the deposition layer 3 (extrusion lamination method).
  • the thickness of the adhesive layer 4 is preferably 0.01 ⁇ m or more, more preferably 3 ⁇ m or more, so that the amount of plastic material used can be further reduced. Therefore, it is preferably 10 ⁇ m or less.
  • the sealant layer 5 is provided on the surface of the adhesive layer 4 so as to be in contact with the adhesive layer 4 .
  • Materials for the sealant layer 5 include thermoplastic resins such as polyolefin resins, polyester resins, and biodegradable resins such as polylactic acid and polybutylene succinate, and polyolefin resins are generally used.
  • polyolefin resins include low-density polyethylene resin (LDPE), medium-density polyethylene resin (MDPE), linear low-density polyethylene resin (LLDPE), ethylene-vinyl acetate copolymer (EVA), ethylene- ⁇ Olefin copolymers, ethylene-based resins such as ethylene-(meth)acrylic acid copolymers, homopolypropylene resins (PP), propylene-ethylene random copolymers, propylene-ethylene block copolymers, propylene- ⁇ olefin copolymers Polypropylene-based resins such as coalesced, or mixtures thereof and the like can be used.
  • LDPE low-density polyethylene resin
  • MDPE medium-density polyethylene resin
  • LLDPE linear low-density polyethylene resin
  • EVA ethylene-vinyl acetate copolymer
  • ethylene- ⁇ Olefin copolymers ethylene-based resins such as ethylene-(
  • the thickness of the sealant layer is preferably 5 ⁇ m or more because the seal strength is improved, and is preferably 50 ⁇ m or less because the amount of plastic material used is further reduced.
  • gas barrier laminates according to other embodiments may include an adhesive layer instead of the anchor coat layer.
  • the gas barrier laminate according to another embodiment may have a film substrate between the vapor deposition layer and the adhesive layer.
  • the gas barrier laminate 30 shown in FIG. in this order.
  • Examples of materials for the film base layer include polyethylene terephthalate (PET) film.
  • PET polyethylene terephthalate
  • a gas barrier laminate 40 shown in FIG. 3 includes a paper substrate 1, an adhesive layer 4, a deposition layer 3, and a sealant layer 5 in this order.
  • FIG. 4 is a perspective view showing a gusset bag 20 made of the gas barrier laminate 10.
  • FIG. A packaging bag is manufactured by sealing the upper opening of the gusset bag 20 .
  • the gusset bag 20 has portions (folded portions B1, B2) where the gas barrier laminate 10 is folded.
  • the bent portion B1 is a portion where the gas barrier laminate 10 is valley-folded when viewed from the innermost layer side
  • the bent portion B2 is a portion where the gas barrier laminate 10 is mountain-folded when viewed from the innermost layer side.
  • the packaging bag may be formed into a bag shape by folding one sheet of the gas barrier laminate in two so that the sealant layers 5 face each other, then appropriately folding it into a desired shape and heat-sealing it.
  • two gas barrier laminates may be stacked such that the sealant layers 5 face each other, and then heat-sealed to form a bag shape.
  • the heat seal strength may be 2N or more, or 10N or more. Although the upper limit of the heat seal strength is not particularly limited, it may be 20 N or less, for example.
  • the packaging bag can contain contents such as food and medicine. In particular, it is suitable for storing sweets and the like as food.
  • the packaging bag according to this embodiment can maintain a high gas barrier property even if it has a shape having a folded portion.
  • a gusset bag is given as an example of a packaging bag, but the gas barrier laminate according to the present embodiment may be used to produce, for example, a pillow bag, a three-sided seal bag, or a standing pouch. .
  • Example 1 A coating solution containing a salt of a carboxyl group (trade name: Chemipearl S100 , An ionomer type, particle size: ⁇ 0.1 ⁇ m, solvent: water, IPA, manufactured by Mitsui Chemicals) was applied with a bar coater and dried in an oven to form an anchor coat layer (thickness: 3 ⁇ m). AL vapor deposition was performed on the anchor coat layer to form an AL vapor deposition layer (thickness: 50 nm).
  • a salt of a carboxyl group trade name: Chemipearl S100 , An ionomer type, particle size: ⁇ 0.1 ⁇ m, solvent: water, IPA, manufactured by Mitsui Chemicals
  • LLDPE linear low-density polyethylene
  • TUX-MCS linear low-density polyethylene
  • an adhesive trade name: Takelac A525/Takenate
  • the thickness of the adhesive layer was 5 ⁇ m.
  • the weight of paper in the gas barrier laminate was 53% by mass.
  • Example 2 Bondine HX-8290 (trade name, manufactured by Arkema), which is a copolymer of acrylic acid ester and maleic anhydride, was neutralized with triethylamine in a water/IPA mixed solvent to prepare a polyolefin aqueous dispersion. Part or all of maleic anhydride is ring-opened in an aqueous solvent to form a carboxylic acid, but after drying, part or all of it is again dehydrated and cyclized.
  • a gas barrier laminate was obtained in the same manner as in Example 1, except that the anchor coat layer was formed using a polyolefin aqueous dispersion instead of the coating liquid containing a salt of a carboxyl group. The weight of paper in the gas barrier laminate was 53% by mass.
  • Example 3 The procedure was the same as in Example 1, except that an ethylene-glycidyl methacrylate copolymer (trade name: Sepolsion G515, manufactured by Sumitomo Seika Chemical Co., Ltd.) was used instead of the coating solution containing a carboxyl group salt to form the anchor coat layer. to obtain a gas barrier laminate.
  • the weight of paper in the gas barrier laminate was 53% by mass.
  • Example 4 Except that the anchor coat layer was formed using a coating liquid made of ethylene-vinyl acetate copolymer (trade name: Chemipearl V300, manufactured by Mitsui Chemicals, Inc.) instead of the coating liquid containing a carboxyl group salt.
  • a gas barrier laminate was obtained in the same manner as in Example 1. The weight of paper in the gas barrier laminate was 53% by mass.
  • Example 5 A gas barrier laminate was obtained in the same manner as in Example 1, except that silica was used instead of AL for the deposited layer. The weight of paper in the gas barrier laminate was 53% by mass.
  • Example 6 Except that the adhesive layer was formed using Maxieve M-100/C-93 (trade name, manufactured by Mitsubishi Gas Chemical Company, Inc., an epoxy adhesive with gas barrier properties) instead of Takelac A525/Takenate A52.
  • a gas barrier laminate was obtained in the same manner as in Example 1. The weight of paper in the gas barrier laminate was 53% by mass.
  • Example 7 In the same manner as in Example 1, except that the adhesive layer was formed using PASLIM VM001/108CP (trade name, manufactured by DIC Corporation, a urethane-based adhesive having gas barrier properties) instead of Takelac A525/Takenate A52. A gas barrier laminate was obtained. The weight of paper in the gas barrier laminate was 53% by mass.
  • PASLIM VM001/108CP trade name, manufactured by DIC Corporation, a urethane-based adhesive having gas barrier properties
  • Example 8 An anchor coat layer was formed on the surface of the paper in the same manner as in Example 1, and an AL deposition layer was formed on the anchor coat layer.
  • a linear low-density polyethylene (LLDPE) film (trade name: TUX-MCS, manufactured by Mitsui Chemicals Tohcello, Inc., thickness: 30 ⁇ m) as a sealant layer is applied with NSRD011/NSRD006 (trade name, DIC Corporation).
  • LLDPE linear low-density polyethylene
  • NSRD011/NSRD006 trade name, DIC Corporation.
  • a gas barrier laminate was obtained by non-solvent dry lamination using a urethane adhesive having gas barrier properties. The thickness of the adhesive layer was 5 ⁇ m. The weight of paper in the gas barrier laminate was 53% by mass.
  • Example 9 An anchor coat layer was formed on the surface of the paper in the same manner as in Example 1, and an AL deposition layer was formed on the anchor coat layer.
  • A-3210/A-3075 (trade name, manufactured by Mitsui Chemicals, Inc.) is extruded on the vapor deposition layer, and the vapor deposition layer and a low-density polyethylene resin (LDPE) film as a sealant layer (trade name: Novatic LC-600A, Japan Polyethylene Co., Ltd.) was laminated through A-3210/A-3075 to obtain a gas barrier laminate.
  • the thickness of the adhesive layer was 5 ⁇ m.
  • the weight of paper in the gas barrier laminate was 57% by mass.
  • Example 10 Gas barrier lamination was carried out in the same manner as in Example 1, except that the anchor coat layer was formed using a polyvinyl alcohol-based resin (degree of saponification: 98%, degree of polymerization: 500) instead of the coating liquid containing a salt of a carboxyl group. got a body The weight of paper in the gas barrier laminate was 53% by mass.
  • Example 11 Gas barrier lamination was carried out in the same manner as in Example 1, except that the anchor coat layer was formed using a polyvinyl alcohol-based resin (degree of saponification: 88%, degree of polymerization: 500) instead of the coating liquid containing a salt of a carboxyl group. got a body The weight of paper in the gas barrier laminate was 53% by mass.
  • Example 12 Gas barrier in the same manner as in Example 1, except that a modified polyvinyl alcohol-based resin (trade name: Exeval AQ4104, manufactured by Kuraray Co., Ltd.) was used instead of the coating liquid containing a carboxyl group salt to form the anchor coat layer. A laminate was obtained. The weight of paper in the gas barrier laminate was 53% by mass.
  • a modified polyvinyl alcohol-based resin trade name: Exeval AQ4104, manufactured by Kuraray Co., Ltd.
  • Example 13 A gas barrier laminate was obtained in the same manner as in Example 10, except that silica was used instead of AL for the deposited layer.
  • the weight of paper in the gas barrier laminate was 53% by mass.
  • Example 14 A gas barrier laminate was obtained in the same manner as in Example 10, except that EA-N370A/B (trade name, manufactured by Toyo Ink Co., Ltd.) was used instead of Takelac A525/Takenate A52 to form the adhesive layer.
  • the weight of paper in the gas barrier laminate was 53% by mass.
  • Example 15 An anchor coat layer was formed on the surface of the paper in the same manner as in Example 10, and an AL deposition layer was formed on the anchor coat layer.
  • A-3210/A-3075 (trade name, manufactured by Mitsui Chemicals, Inc.) is extruded on the vapor deposition layer, and the vapor deposition layer and a low-density polyethylene resin (LDPE) film as a sealant layer (trade name: Novatic LC-600A, Japan Polyethylene Co., Ltd.) was laminated through A-3210/A-3075 to obtain a gas barrier laminate.
  • the thickness of the adhesive layer was 0.2 ⁇ m.
  • the weight of paper in the gas barrier laminate was 57% by mass.
  • Paper (clay-coated paper, thickness of paper: 50 ⁇ m, thickness of clay-coating layer: 5 ⁇ m, basis weight: 55 g/m 2 ) and polyethylene terephthalate (PET) film having silica deposition layer provided on one surface and prepared.
  • An adhesive (trade name: Takelac A525/Takenate A52, urethane-based two-liquid type, manufactured by Mitsui Chemicals, Inc.) is applied to the surface of the paper, and the paper and the surface not provided with the vapor deposition layer of the PET film are bonded. pasted together.
  • LLDPE linear low-density polyethylene
  • TUX-MCS linear low-density polyethylene
  • an adhesive trade name: Takelac A525/Takenate
  • the thickness of the two adhesive layers was 5 ⁇ m.
  • the weight of paper in the gas barrier laminate was 36% by mass.
  • Paper (clay-coated paper, thickness of paper: 50 ⁇ m, thickness of clay-coating layer: 5 ⁇ m, basis weight: 55 g/m 2 ) and linear low-density polyethylene with a silica deposition layer provided on one surface
  • a resin (LLDPE) film (trade name: TUX-MCS, manufactured by Mitsui Chemicals Tohcello, Inc., thickness: 30 ⁇ m) was prepared.
  • An adhesive (trade name: Takelac A525 / Takenate A52, urethane-based two-liquid type, manufactured by Mitsui Chemicals, Inc.) is applied to the surface of the paper, and the paper and the surface on which the vapor deposition layer of the sealant layer is provided. pasted together.
  • the thickness of the adhesive layer was 5 ⁇ m.
  • the weight of paper in the gas barrier laminate was 58% by mass.

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
  • Wrappers (AREA)

Abstract

La présente divulgation concerne un corps stratifié barrière contre les gaz comprenant, dans l'ordre suivant, un matériau de base en papier, une couche de dépôt en phase vapeur, et une couche d'étanchéité. Si la distance de la surface principale de la couche de dépôt en phase vapeur sur le côté matériau de base en papier à la surface principale du matériau de base en papier sur le côté opposé à la couche de dépôt en phase vapeur est définie comme X, et la distance de la surface principale de la couche de dépôt en phase vapeur sur le côté couche d'étanchéité à la surface principale de la couche d'étanchéité sur le côté opposé à la couche de dépôt en phase vapeur est définie comme Y, alors la valeur X/Y, obtenue en divisant X par Y, est de 0,6 à 2,5.
PCT/JP2022/033931 2021-09-16 2022-09-09 Corps stratifié barrière contre les gaz et sac d'emballage WO2023042767A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2021151464A JP2023043702A (ja) 2021-09-16 2021-09-16 ガスバリア積層体及び包装袋
JP2021-151464 2021-09-16

Publications (1)

Publication Number Publication Date
WO2023042767A1 true WO2023042767A1 (fr) 2023-03-23

Family

ID=85602842

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2022/033931 WO2023042767A1 (fr) 2021-09-16 2022-09-09 Corps stratifié barrière contre les gaz et sac d'emballage

Country Status (2)

Country Link
JP (1) JP2023043702A (fr)
WO (1) WO2023042767A1 (fr)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004017449A (ja) * 2002-06-14 2004-01-22 Dainippon Printing Co Ltd 紙容器用積層体およびそれを用いた紙容器
JP2016020095A (ja) * 2015-09-14 2016-02-04 大日本印刷株式会社 包装材料及びそれよりなる紙容器
JP2016124565A (ja) * 2014-12-26 2016-07-11 大日本印刷株式会社 アルコール含有液用包装材料
JP2018171796A (ja) * 2017-03-31 2018-11-08 大日本印刷株式会社 易開封性ガスバリア積層体、及び該積層体からなる易開封性ガスバリア包装材料とピロー包装袋
JP2018533506A (ja) * 2015-10-29 2018-11-15 テトラ ラバル ホールディングス アンド ファイナンス エス エイ バリアフィルムを備えるラミネート包装材料及び該ラミネート包装材料から製造された包装容器
JP2020066233A (ja) * 2018-10-24 2020-04-30 大日本印刷株式会社 紙容器用包装材料及び液体紙容器
WO2021029170A1 (fr) * 2019-08-14 2021-02-18 三菱瓦斯化学株式会社 Composition de résine époxy, film barrière aux gaz et stratifié

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004017449A (ja) * 2002-06-14 2004-01-22 Dainippon Printing Co Ltd 紙容器用積層体およびそれを用いた紙容器
JP2016124565A (ja) * 2014-12-26 2016-07-11 大日本印刷株式会社 アルコール含有液用包装材料
JP2016020095A (ja) * 2015-09-14 2016-02-04 大日本印刷株式会社 包装材料及びそれよりなる紙容器
JP2018533506A (ja) * 2015-10-29 2018-11-15 テトラ ラバル ホールディングス アンド ファイナンス エス エイ バリアフィルムを備えるラミネート包装材料及び該ラミネート包装材料から製造された包装容器
JP2018171796A (ja) * 2017-03-31 2018-11-08 大日本印刷株式会社 易開封性ガスバリア積層体、及び該積層体からなる易開封性ガスバリア包装材料とピロー包装袋
JP2020066233A (ja) * 2018-10-24 2020-04-30 大日本印刷株式会社 紙容器用包装材料及び液体紙容器
WO2021029170A1 (fr) * 2019-08-14 2021-02-18 三菱瓦斯化学株式会社 Composition de résine époxy, film barrière aux gaz et stratifié

Also Published As

Publication number Publication date
JP2023043702A (ja) 2023-03-29

Similar Documents

Publication Publication Date Title
WO2020045629A1 (fr) Stratifié thermosoudable, substrat stratifié, stratifié pour couche intermédiaire barrière aux gaz, stratifié pour matériau d'emballage et matériau d'emballage
US8507059B2 (en) Multilayer film using solvent-free adhesive, method for producing same and packaging container
JP7248052B2 (ja) 無溶剤型接着剤を用いた易開封性ガスバリア積層体、及び該積層体からなる易開封性ガスバリア包装材料と易開封性ピロー包装袋
JP7248051B2 (ja) 無溶剤型接着剤を用いたガスバリア積層体、及び該積層体からなるガスバリア包装材料とピロー包装袋
US20240217223A1 (en) Gas barrier laminate and packaging bag
JP7275728B2 (ja) 無溶剤接着剤を用いた低溶剤臭ガスバリア積層体、及び該積層体からなる低溶剤臭ガスバリア包装材料と包装袋
JP5743149B2 (ja) 無溶剤型接着剤用樹脂組成物、及び接着剤
US20230242314A1 (en) Gas-barrier laminate and packaging bag
JP2018171796A (ja) 易開封性ガスバリア積層体、及び該積層体からなる易開封性ガスバリア包装材料とピロー包装袋
WO2018181900A1 (fr) Stratifié de barrière aux gaz, ainsi que matériau d'emballage de barrière aux gaz et sac d'emballage d'oreiller formés chacun dudit stratifié
JP7456469B2 (ja) 積層体及び包装材
US20230271760A1 (en) Layered gas-barrier product and packaging bag
JP2018001539A (ja) 積層体、及び積層体を用いた包装材
JP2021094751A (ja) ガスバリア積層体、並びにこれを含む包装材及び包装体
WO2023042767A1 (fr) Corps stratifié barrière contre les gaz et sac d'emballage
JP7225552B2 (ja) 易開封性ガスバリア積層体、及び該積層体からなる易開封性ガスバリア包装材料と包装袋
JP2019217764A (ja) 無溶剤接着剤を用いた低溶剤臭易開封性ガスバリア積層体、及び該積層体からなる低溶剤臭ガスバリア包装材料と包装袋
JP2020037187A (ja) 包装材料用積層体及び包装材料
US20230242313A1 (en) Gas-barrier layered body and packaging body
JP2019217763A (ja) 無溶剤接着剤を用いた低溶剤臭ガスバリア積層体、及び該積層体からなる低溶剤臭ガスバリア包装材料と包装袋
JP7563646B2 (ja) 易開封性包装材及び包装袋
JP2024151087A (ja) 紙、及びガスバリア積層体、並びに包装体
JP2023094681A (ja) 積層体および液体紙容器
JP2024002481A (ja) ガスバリア積層体、包装袋及び包装製品
WO2023176432A1 (fr) Matériau d'emballage pour contenu aqueux et sac d'emballage pour contenu aqueux

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22869914

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 22869914

Country of ref document: EP

Kind code of ref document: A1