WO2022138417A1 - Gas barrier laminate and packaging material - Google Patents

Gas barrier laminate and packaging material Download PDF

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Publication number
WO2022138417A1
WO2022138417A1 PCT/JP2021/046418 JP2021046418W WO2022138417A1 WO 2022138417 A1 WO2022138417 A1 WO 2022138417A1 JP 2021046418 W JP2021046418 W JP 2021046418W WO 2022138417 A1 WO2022138417 A1 WO 2022138417A1
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WO
WIPO (PCT)
Prior art keywords
gas barrier
layer
film
metal
metal compound
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PCT/JP2021/046418
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French (fr)
Japanese (ja)
Inventor
貴之 久保田
浩之 加賀谷
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Dic株式会社
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Publication date
Application filed by Dic株式会社 filed Critical Dic株式会社
Priority to JP2022520245A priority Critical patent/JP7272508B2/en
Publication of WO2022138417A1 publication Critical patent/WO2022138417A1/en

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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
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/40—Applications of laminates for particular packaging purposes

Definitions

  • the present invention is a gas barrier laminate, characterized in that a metal alkoxide (A) -containing layer and a metal compound (B) -containing layer are formed on at least one surface of a base material, and a gas barrier laminate. It relates to a package using it.
  • Laminates for packaging materials used for packaging foods and pharmaceuticals, or laminates used for packaging electronic device-related members, etc., are subject to alteration and oxidation of their contents and laminated members.
  • a gas barrier laminate is used to prevent.
  • Such a gas barrier laminate is required to block the permeation of oxygen and moisture to prevent deterioration of the contents.
  • a barrier film composed of a polymer having a high oxygen barrier property, a laminated film using the barrier film as a base material and laminating a coating layer, and the like have been used.
  • a vapor-deposited layer made of an inorganic compound is used as a first layer, and (1) a water-soluble polymer and (2) one or more kinds of metal alkoxides or metal alkoxide hydrolysates.
  • a gas barrier laminated film in which a coating agent containing an aqueous solution containing tin chloride or a water-alcohol mixed solution as a main component is applied, and a gas barrier coating layer formed by heating and drying is sequentially laminated as a second layer has been proposed. (See Patent Document 1).
  • this gas barrier laminated film exhibits high gas barrier properties, and has water resistance and moisture resistance.
  • the second layer of the film of the gas barrier film is a hydrogen bond between a metal alkoxide hydrolyzate and a water-soluble polymer having a hydroxyl group.
  • the film layer swells due to hydrothermal treatment, and there is a problem that the gas barrier property deteriorates.
  • An object of the present invention is to provide a gas barrier laminate having excellent gas barrier properties and excellent retort resistance (hereinafter referred to as retort resistance), and a package made of the gas barrier laminate. ..
  • the present invention is a gas barrier laminate, characterized in that a metal alkoxide (A) -containing layer and a metal compound (B) -containing layer are formed on at least one surface of a base material, and a gas barrier laminate.
  • A metal alkoxide
  • B metal compound
  • the present invention is a gas barrier laminate, characterized in that a metal alkoxide (A) -containing layer and a metal compound (B) -containing layer are formed on at least one surface of a base material. It relates to a laminate.
  • the present invention relates to the gas barrier laminate according to [1], wherein the metal compound (B) is a compound containing at least one selected from zinc, calcium, magnesium and titanium. Is.
  • the present invention relates to the gas barrier laminate according to [1] or [2], wherein the metal compound (B) is a metal oxide.
  • the present invention relates to the gas barrier laminate according to any one of [1] to [3], wherein the metal alkoxide (A) is one or more selected from alkoxysilanes. be.
  • the present invention relates to the gas barrier laminate according to any one of [1] to [4], wherein the metal compound (B) has an average particle size of 0.2 ⁇ m or less. be.
  • the present invention relates to the gas barrier laminate according to any one of [1] to [5], wherein the base material is a thin-film-deposited base material.
  • the present invention is a gas barrier laminate, characterized in that a metal alkoxide (A) -containing layer and a metal compound (B) -containing layer are sequentially formed on at least one surface of a base material.
  • the gas barrier laminate according to any one of [1] to [6].
  • the present invention relates to a package using the gas barrier laminate according to any one of [1] to [7].
  • gas barrier laminate and the package of the present invention excellent gas barrier properties and excellent retort resistance can be obtained, and therefore, as a laminate used for various packaging material applications and packaging applications such as electronic device-related members. It is useful.
  • the gas barrier laminate of the present invention is characterized in that a metal alkoxide (A) -containing layer and a metal compound (B) -containing layer are formed on at least one surface of the base material.
  • A metal alkoxide
  • B metal compound
  • the metal alkoxide (A) used in the present invention is a compound represented by the general formula R 1 n M (OR) m (M is an atom selected from a metal such as Si, Al, Ti, R is an alkyl group).
  • the present invention is not particularly limited as long as it forms a coating film layer by the sol-gel method, and may be a hydrolyzate of the metal alkoxide.
  • the metal alkoxide (A) is not particularly limited as long as the effect of the present invention can be obtained, but those having Si, Al, Ti, and Zr as M are preferably used, and among them, the most suitable barrier property is obtained. Therefore, those having Si and Al are particularly preferable.
  • Examples of the metal alkoxide (A) used in the present invention include tetramethoxysilane (Si (OCH 3 ) 4 ), tetraethoxysilane (hereinafter referred to as TEOS) (Si (OC 2 H 5 ) 4 ), and tetrapropoxysilane. (Si (OC 3 H 7 ) 4 ), tetrabutoxysilane (Si (OC 4 H 9 ) 4 ), normal propyl zirconeate, normal butyl zirconeate, tetraisopropyl titanate, tetranormal butyl titanate, butyl titanate dimer, tetraoctyl. Alkoxides such as titanate and triisopropoxyaluminum can be used.
  • the coating methods (A) and (B) of the present invention are not particularly limited, and are a spray method, a spin coat method, a dip method, a roll coat method, a blade coat method, a doctor roll method, a doctor blade method, and a curtain coat method.
  • Slit coating method, screen printing method, inkjet method, dispense method, die coating (die coating) method, direct gravure method, reverse gravure method, flexo method, knife coating method, dot coating method, etc. can. It was
  • the metal alkoxide (A) used in the present invention can form a gas barrier coating layer by hydrolysis and polycondensation reaction by the sol-gel method in the presence of various solvents such as water and organic solvents. ..
  • the thickness of the metal alkoxide (A) layer in the present invention is preferably in the range of 0.03 to 1.0 ⁇ m, and is particularly preferably in the range of 0.1 to 0.5 ⁇ m because of its excellent barrier properties and mechanical properties.
  • a silane coupling agent may be used together with the metal alkoxide (A) for the purpose of forming a stable metal alkoxide (A) -containing layer.
  • a silane coupling agent a known organic reactive group-containing organoalkoxysilane can be used, but an epoxy group-containing organoalkoxysilane is preferable because the formation of a coating film is good.
  • an epoxy group-containing organoalkoxysilane include ⁇ -glycidoxypropylmethyldiethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, and ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane. And so on.
  • silane coupling agent one kind or two or more kinds may be used as long as the effect of the present invention can be obtained, and the silane coupling agent is 1 with respect to 100 parts by mass of the total amount of the metal alkoxide (A). It is preferable to use it within the range of about 20 parts by mass.
  • the metal compound (B) used in the present invention is not particularly limited as long as it is a metal that can be ionized during hot water treatment, and zinc, titanium, zirconium, chromium, manganese, iron, cobalt, nickel, copper, and the like. Transition metals such as tin; alkaline earth metals such as beryllium, magnesium, calcium; simple metals selected from aluminum, silicon, etc., oxides, hydroxides, chlorides, carbonates, acetates, carboxylates and chelate A body or the like can be used.
  • a compound selected from zinc, calcium, magnesium, aluminum and titanium is preferable, and zinc, calcium and magnesium are selected because excellent gas barrier properties and excellent retort resistance are good. Compounds are particularly preferred.
  • metal compound (B) used in the present invention as described above, a simple metal, an oxide, a hydroxide, a chloride, a carbonate, an acetate, a carboxylate, a chelate, or the like can be used.
  • oxides, hydroxides, chlorides, carbonates and acetates are particularly preferable because a good coating film can be formed, and oxides and hydroxides are most preferable.
  • metal compound (B) used in the present invention zinc oxide, calcium carbonate, magnesium oxide, aluminum oxide and titanium alkoxide are more preferable, and zinc oxide, calcium carbonate and magnesium oxide are most preferable because excellent gas barrier properties can be obtained.
  • the shape of the metal compound (B) used in the present invention is not particularly limited, but it is preferably in the form of particles.
  • the average particle size thereof is not particularly limited as long as the effect of the present invention can be obtained, but it can be observed by a laser diffraction / scattering method, a scanning electron microscope, or the like. It is preferable that any of the measured average particle diameters is 0.2 ⁇ m or less, more preferably 0.1 ⁇ m or less because suitable gas barrier properties and suitable transparency can be obtained, and the ionization of the metal is rapid and the solgel. It is most preferably 0.07 ⁇ m or less because the formation is carried out rapidly.
  • the method for forming the layer using the metal compound (B) of the present invention is not particularly limited, but for example, a coating liquid containing the metal compound (B) is prepared, and the coating liquid is applied and dried. It can be formed by.
  • the coating liquid containing the metal compound (B) contains various solvents such as water and organic solvents, dispersants, surfactants, stabilizers, thickeners, resins, and defoamers to the extent that the effects of the present invention can be obtained. , Wetting agent, hardening agent, blocking inhibitor, lubricant, preservative, inorganic filler and the like may be contained.
  • the base material used for the gas barrier laminate of the present invention is not particularly limited as long as the effect of the present invention can be obtained, and a resin film, paper, metal leaf, wood, or the like can be used depending on the desired application. It can be selected as appropriate.
  • PET polyethylene terephthalate
  • polystyrene film polystyrene film
  • polyamide film polyacrylonitrile film
  • polyethylene film LLDPE: linear low density polyethylene film
  • HDPE high density polyethylene film
  • CPP unstretched
  • a polyolefin film such as a polypropylene film (OPP: biaxially stretched polypropylene film), a polyvinyl alcohol film, an ethylene-vinyl alcohol copolymer film, and a resin film such as a cycloolefin copolyma film can be used.
  • OPP polypropylene film
  • a polyvinyl alcohol film such as a polyvinyl alcohol film
  • ethylene-vinyl alcohol copolymer film such as a cycloolefin copolyma film
  • resin film such as a cycloolefin copolyma film
  • a resin film When a resin film is used as the base material, it may be stretched or an unstretched film may be used.
  • the stretched films have the advantages of being easy to coat and easy to use because they are excellent in dimensional stability and rigidity, and even when an unstretched film is used, the configuration of the present invention greatly enhances the barrier function. The effect is obtained.
  • the stretching treatment method it is common to melt-extrude the resin by an extrusion film forming method or the like to form a sheet, and then perform simultaneous biaxial stretching or sequential biaxial stretching. Further, in the case of sequential biaxial stretching, it is common to first perform longitudinal stretching treatment and then lateral stretching. Specifically, a method of combining longitudinal stretching using a speed difference between rolls and transverse stretching using a tenter is often used.
  • a metal vapor deposition treatment using aluminum or the like, or a vapor deposition treatment using an inorganic oxide such as silicon dioxide (SiOx) or aluminum oxide (AlOx) can be performed.
  • a thin-film deposition treatment using silicon dioxide or aluminum oxide is preferable from the viewpoint that suitable barrier performance can be obtained, boil / retort resistance is excellent, and the texture and texture of the base material are not impaired.
  • the method for forming the thin-film deposition layer on the surface of the substrate is not particularly limited as long as the effect of the present invention can be obtained, and the inorganic oxide is vapor-deposited by a vacuum such as PVD method, sputtering method, or chemical.
  • a method of forming a film on the surface of the substrate can be selected by the vapor phase growth method (CVD method), and it is preferable to use the substrate treated by the vapor deposition method because the barrier property is improved.
  • the film thickness of the coating film formed on the surface of the substrate can be appropriately set within a range that does not impair the effect of the present invention, but is in the range of 5 to 500 nm because both flexibility and fastness can be achieved. It is preferably in the range of 10 to 300 nm, and more preferably in the range of 10 to 300 nm.
  • the gas barrier laminate of the present invention is characterized in that a metal alkoxide (A) -containing layer and a metal compound (B) -containing layer are formed on at least one surface of the base material, and the effects of the present invention can be obtained.
  • the layer (A) and the layer (B) may be formed in no particular order on the substrate within a certain range, and a plurality of layers (A) and (B) may be formed respectively.
  • the order in which the (A) layer and the (B) layer are formed on the base material is not particularly limited, but the (A) layer and the (B) layer are sequentially formed on one surface of the base material. This is preferable because a particularly good barrier effect can be obtained and a robust laminate can be obtained.
  • the gas barrier laminate of the present invention may be provided with an additional coating layer other than the (A) layer and the (B) layer on the outermost surface of the laminate as long as the effect of the present invention is not impaired.
  • an additional coating layer a barrier film containing a gas barrier layer such as polyvinyl alcohol, an ethylene / vinyl alcohol copolymer, or vinylidene chloride for the purpose of imparting a higher barrier function, and various vapor-deposited films.
  • a layer made of a metal foil such as aluminum foil can be used.
  • the additional coating layer include a metal vapor-deposited film such as aluminum and a metal oxide-deposited film such as silica and alumina.
  • the type of film may be a stretched film or an unstretched film.
  • the laminate of the present invention may further contain another film or base material in addition to the above-mentioned structure.
  • the other base material in addition to the above-mentioned stretched film, unstretched film, and transparent vapor-deposited film, a porous base material such as paper, wood, and leather described later can also be used.
  • a known paper base material can be used without particular limitation. Specifically, it is manufactured by a known paper machine using natural fibers for papermaking such as wood pulp, but the papermaking conditions are not particularly specified.
  • natural fibers for papermaking include wood pulps such as coniferous tree pulp and broadleaf tree pulp, non-wood pulps such as Manila hemp pulp, sisal hemp pulp, and flax pulp, and pulp obtained by chemically modifying these pulps.
  • wood pulps such as coniferous tree pulp and broadleaf tree pulp
  • non-wood pulps such as Manila hemp pulp, sisal hemp pulp, and flax pulp
  • pulp obtained by chemically modifying these pulps As the type of pulp, chemical pulp, gland pulp, chemi-grand pulp, thermomechanical pulp and the like obtained by a sulfate cooking method, an acidic / neutral / alkaline sulfite cooking method, a soda salt cooking method and the like can be used.
  • a print layer may be provided on the outer surface or the inner surface side of the paper layer, if necessary.
  • PET film / alumina oxide vapor deposition layer / metal alkoxide (A) -containing layer / metal compound (B) -containing layer / CPP (non-stretched polypropylene) film PET.
  • a film / an alumina oxide vapor deposition layer / a metal compound (B) -containing layer / a metal alkoxide (A) -containing layer / a CPP film is raised, and if necessary, a vapor deposition layer, an anchor layer, an adhesive layer, and a printing layer are further placed between these layers. Etc. may be provided.
  • a transparent vapor-deposited Ny film may be used instead of the aluminum-deposited PET film, the transparent-deposited PET film, or the like.
  • the gas barrier laminate of the present invention is characterized in that a metal alkoxide (A) -containing layer and a metal compound (B) -containing layer are formed on at least one surface of the base material as described above. After the (A) -containing layer and the (B) -containing layer are laminated, reactions such as ion cross-linking proceed between the layers to exhibit stronger barrier performance.
  • the laminate of the present invention can be used as a multi-layer package for the purpose of protecting foods, pharmaceuticals, etc.
  • its layer structure may change depending on the contents, usage environment, and usage pattern.
  • the package of the present invention may be appropriately provided with an easy-opening process or a resealable means.
  • the package of the present invention is obtained by using the laminate having the above-mentioned structure, laminating the surfaces of the sealant films of the laminate facing each other, and then heat-sealing the peripheral ends thereof to form a bag.
  • the laminated body of the present invention is bent or overlapped so that the inner layer surface (the surface of the sealant film) faces each other, and the peripheral end thereof is, for example, a side seal type or a two-way seal type.
  • the packaging material of the present invention can take various forms depending on the contents, the environment in which it is used, and the form in which it is used. Self-supporting packaging materials (standing pouches), etc. are also possible.
  • a heat sealing method a known method such as a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high frequency seal, and an ultrasonic seal can be used. Since the effect of the present invention is preferably exhibited, the package of the present invention is preferably a package to be retort-treated.
  • the opening After filling the packaging material of the present invention with the contents from the opening, the opening is heat-sealed to manufacture a product using the packaging material of the present invention.
  • contents to be filled for example, as food, rice confectionery, bean confectionery, nuts, biscuits / cookies, wafer confectionery, marshmallow, pie, half-baked cake, candy, snack confectionery and other confectionery, bread, snack noodles, instant noodles.
  • Non-food items include tobacco, disposable body warmers, medicines such as infusion packs, liquid detergents for washing, liquid detergents for kitchens, liquid detergents for baths, liquid soaps for baths, liquid shampoos, liquid conditioners, cosmetics such as lotions and emulsions, and vacuum. It can also be used as a heat insulating material such as a heat insulating material and as various packaging materials such as a battery.
  • TEOS tetraethoxysilane
  • KBE-04 manufactured by Shin-Etsu Chemical Co., Ltd.
  • TEOS hydrolysis solution was prepared.
  • the PVA solution and the TEOS hydrolyzed solution were mixed so that the PVA / TEOS (SiO 2 equivalent) was 30/70 in terms of solid content mass ratio to prepare a coating liquid (a-1).
  • coating liquid a-2 containing metal alkoxide The coating liquid was prepared in the same manner except that aluminum triisopropoxide (Al (OC 3H 7 ) 3 , manufactured by Nacalai Tesque) was used instead of TEOS in the metal compound-containing coating agent a-1.
  • Al (OC 3H 7 ) 3 aluminum triisopropoxide (Al (OC 3H 7 ) 3 , manufactured by Nacalai Tesque) was used instead of TEOS in the metal compound-containing coating agent a-1.
  • TPT TEOS / tetraisopropyl titanate
  • Olga Tix TA-8 manufactured by Matsumoto Fine Chemical Co., Ltd.
  • the coating liquid was prepared in the same manner except that fine particle magnesium oxide (MgO) was used instead of the fine particle zinc oxide in the metal compound-containing coating agent b-1.
  • Fine particle magnesium oxide manufactured by Wako Pure Chemical Industries, Ltd., average particle size: 0.01 ⁇ m
  • the average particle size was 0.1 ⁇ m.
  • the coating liquid was prepared in the same manner except that calcium carbonate (CaCO3) was used instead of the fine particle zinc oxide of the metal compound-containing coating agent b-1.
  • Calcium carbonate was pulverized in a mortar made by Menou using a reagent manufactured by Wako Pure Chemical Industries, Ltd., dispersed in ethanol using an ultrasonic homogenizer, and a suspension having a CaCO 3 content of 30% was prepared and used. ..
  • the average particle size was 0.1 ⁇ m.
  • the coating liquid was prepared in the same manner except that zinc acetate (Zn (AcO) 2 ) was used instead of the fine particle zinc oxide of the metal compound-containing coating agent b-1.
  • Zinc acetate used was manufactured by Wako Pure Chemical Industries, Ltd.
  • the coating liquid was prepared in the same manner except that fine particle zinc oxide (FINEX50, manufactured by Sakai Chemical Industry Co., Ltd., average primary particle diameter 60 nm) having a different particle size was used instead of the fine particle zinc oxide of the metal compound-containing coating agent b-1. ..
  • the average particle size was 0.6 ⁇ m.
  • Example 1 A metal alkoxide-containing coating agent a-1 is coated on the vapor-deposited layer of an alumina oxide-deposited PET film (Barrierox 1011HG, manufactured by Toray Film Processing Co., Ltd.) with a bar coater, and 1 in a hot air dryer set at 120 ° C. It was dried for a minute to form a metal alkoxide-containing layer A-1 having a dry film thickness of about 0.3 ⁇ m. Then, the metal compound-containing coating liquid b-1 is coated on the layer A-1 with a bar coater, dried in a dryer set at 80 ° C. for 1 minute, and the metal compound-containing layer B having a dry film thickness of about 0.3 ⁇ m. -1 was formed.
  • an alumina oxide-deposited PET film Barrierox 1011HG, manufactured by Toray Film Processing Co., Ltd.
  • Example 2 The laminate [PET / alumina oxide vapor deposition layer / metal alkoxide-containing layer A] is the same as in Example 1 except that the metal compound-containing coating liquids b-2 to 6 are used instead of the metal compound-containing coating liquid b-1. -1 / Metal compound-containing layer B-2 to 6 / Adhesive / CPP] was produced.
  • Example 7 The laminate [PET / alumina oxide vapor deposition layer / metal alkoxide-containing layer A] is the same as in Example 1 except that the metal alkoxide-containing coating liquids a-2 to 3 are used instead of the metal alkoxide-containing coating liquid a-1. -2 to 3 / metal compound-containing layer B-1 / adhesive / CPP] was produced.
  • Example 9 A laminate [OPP / Alumina oxide-deposited layer / Metal alkoxide-containing layer A-1 / Metal compound-containing layer B in the same manner as in Example 1 except that an Alumina oxide-deposited OPP film was used instead of the Alumina oxide-deposited PET film. -1 / Adhesive / CPP] was manufactured.
  • Alumina oxide-deposited OPP film is a biaxially stretched polypropylene film (FOR, manufactured by Futamura Chemical Co., Ltd., thickness 20 ⁇ m), an acrylic coating agent (GAC-013S, manufactured by DIC) and a polyisocyanate-based curing agent (KR-90, DIC).
  • the anchor coating liquid which can be blended so that the mixing ratio is 5: 1, is applied and dried by the gravure coating method so that the dry film thickness is about 0.05 ⁇ m, and then a vacuum vapor deposition apparatus by an electron beam heating method.
  • metal aluminum was vapor-deposited and oxygen gas was introduced to form a thin-film vapor-deposited thin film layer made of aluminum oxide having a thickness of 20 nm on the anchor coat layer.
  • Example 10 A laminate [PET / aluminum-deposited layer / metal alkoxide-containing layer A] in the same manner as in Example 1 except that an aluminum-deposited PET film (VM-PET1310, manufactured by Toray Film Processing Co., Ltd.) was used instead of the alumina oxide-deposited PET film. -1 / Metal compound-containing layer B-1 / Adhesive / CPP] was produced.
  • Example 11 A laminate [PET / silica-film-deposited layer / metal alkoxide-containing layer A-] in the same manner as in Example 1 except that a silica-deposited PET film (Techbarrier L, manufactured by Mitsubishi Chemical Co., Ltd.) was used instead of the alumina oxide-deposited PET film. 1 / Metal compound-containing layer B-1 / Adhesive / CPP] was produced.
  • Example 12 A laminate [PET / metal alkoxide-containing layer A-1 / metal compound-containing layer B-1] in the same manner as in Example 1 except that a PET film (E5102, manufactured by Toyobo) was used instead of the alumina oxide-deposited PET film. / Adhesive / CPP] was manufactured.
  • a PET film E5102, manufactured by Toyobo
  • Adhesive / CPP Adhesive / CPP
  • Example 13 The laminate [PET / alumina oxide vapor deposition layer / metal compound-containing layer B-] is the same as in Example 1 except that the coating order of the metal compound-containing coating liquid b-1 and the metal alkoxide-containing coating liquid a-1 is reversed. 1 / Metal alkoxide-containing layer A-1 / Adhesive / CPP] was produced.
  • Example 14 In the coating of the metal alkoxide-containing coating liquid a-1, the laminate [PET / alumina oxide vapor-deposited layer / metal alkoxide-containing layer A-1 / metal is the same as in Example 1 except that the dry film thickness is 0.1 ⁇ m. Compound-containing layer B-1 / adhesive / CPP] was produced.
  • Example 15 In the coating of the metal alkoxide-containing coating liquid a-1, the laminate [PET / alumina oxide vapor-deposited layer / metal alkoxide-containing layer A-1 / metal is the same as in Example 1 except that the dry film thickness is 1.0 ⁇ m. Compound-containing layer B-1 / adhesive / CPP] was produced.
  • Example 16 In the coating of the metal compound-containing coating liquid b-1, the laminate [PET / alumina oxide vapor-deposited layer / metal alkoxide-containing layer A-1 / metal is the same as in Example 1 except that the dry film thickness is 0.1 ⁇ m. Compound-containing layer B-1 / adhesive / CPP] was produced.
  • Example 17 In the coating of the metal compound-containing coating liquid b-1, the laminate [PET / alumina oxide vapor-deposited layer / metal alkoxide-containing layer A-1 / metal is the same as in Example 1 except that the dry film thickness is 1.0 ⁇ m. Compound-containing layer B-1 / adhesive / CPP] was produced.
  • Example 2 A metal compound-free coating agent b-7 was used instead of the metal compound-containing coating agent b-1, and the laminate [PET / alumina oxide vapor deposition layer / metal alkoxide-containing layer A-1 / metal compound was used in the same manner as in Example 1. Free layer B-7 / adhesive / CPP] was obtained.
  • Example 4 The laminate [PET / alumina oxide vapor deposition layer / metal alkoxide-free layer A] is the same as in Example 1 except that the metal alkoxide-free coating liquid ieri-4 is used instead of the metal alkoxide-containing coating liquid a-1. -4 / Metal compound-containing layer B-1 / Adhesive / CPP] was produced.
  • Example 5 In the coating of the metal alkoxide-containing coating liquid a-1, the laminate [PET / alumina oxide vapor-deposited layer / metal alkoxide-containing layer A-1 / metal is the same as in Example 1 except that the dry film thickness is 0.05 ⁇ m. Compound-containing layer B-1 / adhesive / CPP] was produced.
  • Example 6 In the coating of the metal alkoxide-containing coating liquid a-1, the laminate [PET / alumina oxide vapor-deposited layer / metal alkoxide-containing layer A-1 / metal is the same as in Example 1 except that the dry film thickness is 2.0 ⁇ m. Compound-containing layer B-1 / adhesive / CPP] was produced.
  • Example 7 In the coating of the metal compound-containing coating liquid b-1, the laminate [PET / alumina oxide vapor-deposited layer / metal alkoxide-containing layer A-1 / metal is the same as in Example 1 except that the dry film thickness is 0.05 ⁇ m. Compound-containing layer B-1 / adhesive / CPP] was produced.
  • Example 8 In the coating of the metal compound-containing coating liquid b-1, the laminate [PET / alumina oxide vapor-deposited layer / metal alkoxide-containing layer A-1 / metal is the same as in Example 1 except that the dry film thickness is 2.0 ⁇ m. Compound-containing layer B-1 / adhesive / CPP] was produced.
  • Example 9 A laminate [PET / metal alkoxide-containing layer A-1 / adhesive] is used in the same manner as in Example 1 except that a PET film is used instead of the alumina oxide-deposited PET film and the metal compound-containing layer B-1 is omitted. / CPP] was manufactured.
  • Oxygen barrier property Adjust the aging-finished laminate to a size of 10 cm x 10 cm, use OX-TRAN2 / 21 (Made by Mocon: oxygen permeability measuring device), and follow JIS-K7126 (isopressure method) at 23 ° C. 0% RH. Oxygen permeability was measured under the atmosphere of (unit: cc / m2 ⁇ day ⁇ atm). Note that RH represents humidity.
  • ⁇ Evaluation> (Oxygen barrier property after retort treatment) Using the laminated body after aging, a pouch having a size of 210 mm in length ⁇ 150 mm in width having three sides as a sealing portion was prepared and filled with water as a content. Then, the retort sterilization treatment was performed at 121 ° C. for 30 minutes, and the oxygen permeability after the retort sterilization treatment was measured according to the above-mentioned oxygen barrier property measuring method.

Abstract

The present invention addresses the problem of providing: a gas barrier laminate which has excellent gas barrier properties and excellent retort treatment resistance (hereinafter referred to as retort resistance); and a packaging material which uses said gas barrier laminate. The inventors solved said problem by discovering that excellent gas barrier properties and excellent retort resistance can be obtained from a gas barrier laminate characterized in that a layer containing a metal alkoxide (A) and a layer containing a metal compound (B) are formed on one or more surfaces of a substrate, and from a packaging material which uses said laminate.

Description

ガスバリア性積層体及び包装材料Gas barrier laminates and packaging materials
　本発明は、ガスバリア性積層体であって、基材の少なくとも一面に金属アルコキシド（Ａ）含有層と、金属化合物（Ｂ）含有層が形成されていることを特徴とするガスバリア性積層体、およびそれを用いた包装体に関するものである。 The present invention is a gas barrier laminate, characterized in that a metal alkoxide (A) -containing layer and a metal compound (B) -containing layer are formed on at least one surface of a base material, and a gas barrier laminate. It relates to a package using it.
　食品や医薬品等を包装するのに用いられる包装材料用積層体、あるいは電子機器関連部材等を包装するために用いられる積層体などには、その内容物や積層された部材等の変質・酸化を防止するガスバリア性積層体が使用されている。 Laminates for packaging materials used for packaging foods and pharmaceuticals, or laminates used for packaging electronic device-related members, etc., are subject to alteration and oxidation of their contents and laminated members. A gas barrier laminate is used to prevent.
　このようなガスバリア性積層体としては、酸素や水分の透過を遮断し内容物の変質を防止することが求められている。これら要求に対し、従来は酸素バリア性が高い重合体で構成されるバリア性フィルムや、前記バリア性フィルムを基材としコーティング層を積層した積層フィルムなどが用いられてきた。 Such a gas barrier laminate is required to block the permeation of oxygen and moisture to prevent deterioration of the contents. In response to these demands, conventionally, a barrier film composed of a polymer having a high oxygen barrier property, a laminated film using the barrier film as a base material and laminating a coating layer, and the like have been used.
　前記従来のバリア性を有する積層フィルムとして、無機化合物からなる蒸着層を第１層とし、（１）水溶性高分子と、（２）Ｉ）１種類以上の金属アルコキシドまたは金属アルコキシド加水分解物、あるいはＩＩ）塩化錫を含む、水溶液、または水アルコール混合溶液とを主剤とするコーティング剤を塗布し、加熱、乾燥してなるガスバリア被覆層を第２層として順次積層したガスバリア性積層フィルムが提案されている（特許文献１参照）。
　しかしながらこのガスバリア性積層フィルムは、高いガスバリア性を示し、かつ耐水性、耐湿性を有するが、ガスバリア性フィルムの被膜第２層が金属アルコキシド加水分解物と水酸基を有する水溶性高分子との水素結合により形成されるため、水熱処理により被膜層が膨潤し、ボイル及びレトルト殺菌のような処理が必要な包材として使用すると、被膜層が膨潤し、ガスバリア性が劣化するという問題があった。 As the conventional laminated film having a barrier property, a vapor-deposited layer made of an inorganic compound is used as a first layer, and (1) a water-soluble polymer and (2) one or more kinds of metal alkoxides or metal alkoxide hydrolysates. Alternatively, II) a gas barrier laminated film in which a coating agent containing an aqueous solution containing tin chloride or a water-alcohol mixed solution as a main component is applied, and a gas barrier coating layer formed by heating and drying is sequentially laminated as a second layer has been proposed. (See Patent Document 1).
However, this gas barrier laminated film exhibits high gas barrier properties, and has water resistance and moisture resistance. However, the second layer of the film of the gas barrier film is a hydrogen bond between a metal alkoxide hydrolyzate and a water-soluble polymer having a hydroxyl group. When used as a packaging material that requires treatment such as boiling and retort sterilization, the film layer swells due to hydrothermal treatment, and there is a problem that the gas barrier property deteriorates.
特許第２７９００５４号公報Japanese Patent No. 2790054
　本発明は、優れたガスバリア性と優れた耐レトルト処理性（以下、耐レトルト性という）を有するガスバリア性積層体、および該ガスバリア性積層体を用いてなる包装体を提供することを課題とする。 An object of the present invention is to provide a gas barrier laminate having excellent gas barrier properties and excellent retort resistance (hereinafter referred to as retort resistance), and a package made of the gas barrier laminate. ..
　本発明は、ガスバリア性積層体であって、基材の少なくとも一面に金属アルコキシド（Ａ）含有層と、金属化合物（Ｂ）含有層が形成されていることを特徴とするガスバリア性積層体、および該積層体を用いた包装体により優れたガスバリア性と優れた耐レトルト性が得られ、前記課題を解決することができる。 The present invention is a gas barrier laminate, characterized in that a metal alkoxide (A) -containing layer and a metal compound (B) -containing layer are formed on at least one surface of a base material, and a gas barrier laminate. An excellent gas barrier property and an excellent retort resistance can be obtained by the package using the laminated body, and the above-mentioned problems can be solved.
［１］本発明は、ガスバリア性積層体であって、基材の少なくとも一面に、金属アルコキシド（Ａ）含有層と、金属化合物（Ｂ）含有層が形成されていることを特徴とするガスバリア性積層体に関するものである。 [1] The present invention is a gas barrier laminate, characterized in that a metal alkoxide (A) -containing layer and a metal compound (B) -containing layer are formed on at least one surface of a base material. It relates to a laminate.
［２］さらに本発明は、前記金属化合物（Ｂ）が亜鉛、カルシウム、マグネシウム、チタンから選択される一種以上を含む化合物であることを特徴とする［１］に記載のガスバリア性積層体に関するものである。 [2] Further, the present invention relates to the gas barrier laminate according to [1], wherein the metal compound (B) is a compound containing at least one selected from zinc, calcium, magnesium and titanium. Is.
［３］くわえて本発明は、前記金属化合物（Ｂ）が金属酸化物であることを特徴とする［１］または［２］に記載のガスバリア性積層体に関するものである。 [3] In addition, the present invention relates to the gas barrier laminate according to [1] or [2], wherein the metal compound (B) is a metal oxide.
［４］また本発明は、前記金属アルコキシド（Ａ）がアルコキシシランから選択される一種以上であることを特徴とする［１］～［３］のいずれかに記載のガスバリア性積層体に関するものである。 [4] The present invention relates to the gas barrier laminate according to any one of [1] to [3], wherein the metal alkoxide (A) is one or more selected from alkoxysilanes. be.
［５］さらに本発明は、前記金属化合物（Ｂ）の平均粒子径が０．２μｍ以下であることを特徴とする［１］～［４］のいずれかに記載のガスバリア性積層体に関するものである。 [5] Further, the present invention relates to the gas barrier laminate according to any one of [1] to [4], wherein the metal compound (B) has an average particle size of 0.2 μm or less. be.
［６］また本発明は、前記基材が、蒸着処理された基材であることを特徴とする［１］～［５］のいずれかに記載のガスバリア性積層体に関する。 [6] Further, the present invention relates to the gas barrier laminate according to any one of [1] to [5], wherein the base material is a thin-film-deposited base material.
［７］さらに本発明は、ガスバリア性積層体であって、基材の少なくとも一面に、金属アルコキシド（Ａ）含有層と、金属化合物（Ｂ）含有層が順次形成されていることを特徴とする［１］～［６］のいずれかに記載のガスバリア性積層体に関する。
［８］くわえて本発明は、［１］～［７］のいずれかに記載のガスバリア性積層体を用いてなる包装体に関するものである。 [7] Further, the present invention is a gas barrier laminate, characterized in that a metal alkoxide (A) -containing layer and a metal compound (B) -containing layer are sequentially formed on at least one surface of a base material. The gas barrier laminate according to any one of [1] to [6].
[8] In addition, the present invention relates to a package using the gas barrier laminate according to any one of [1] to [7].
本発明のガスバリア性積層体および包装体によれば、優れたガスバリア性と優れた耐レトルト性が得られることから、各種包装材料用途や、電子機器関連部材等の包装用途に用いられる積層体として有用である。 According to the gas barrier laminate and the package of the present invention, excellent gas barrier properties and excellent retort resistance can be obtained, and therefore, as a laminate used for various packaging material applications and packaging applications such as electronic device-related members. It is useful.
　本発明のガスバリア性積層体は基材の少なくとも一面に金属アルコキシド（Ａ）含有層と、金属化合物（Ｂ）含有層が形成されていることを特徴とするものである。また、本明細書において「～」は「～」という記載の前の値以上、「～」という記載の後の値以下を意味するものである。 The gas barrier laminate of the present invention is characterized in that a metal alkoxide (A) -containing layer and a metal compound (B) -containing layer are formed on at least one surface of the base material. Further, in the present specification, "-" means a value equal to or higher than the value before the description of "-" and a value after the description of "-".
　本発明において用いられる金属アルコキシド（Ａ）とは、一般式Ｒ１ ｎＭ（ＯＲ）ｍ（ＭはＳｉ、Ａｌ、Ｔｉなどの金属から選ばれる原子、Ｒはアルキル基）で表される化合物であり、ゾルゲル法により塗膜層を形成するものであれば特に限定されるものではなく、前記金属アルコキシドの加水分解物であってもよい。前記金属アルコキシド（Ａ）としては本発明の効果が得られる範囲において特に限定されるものではないが、ＭとしてＳｉ、Ａｌ、Ｔｉ、Ｚｒを有するものが好ましく用いられ、中でも好適なバリア性が得られることからＳｉ、Ａｌを有するものが特に好ましい。また金属アルコキシドに含まれるアルキル基としてはＣｎＨ２ｎ＋１で表されるアルキル基であれば良く、本発明の効果が得られる範囲において限定されるものではないが、特にｎ＝１～５のアルキル基を用いた場合にバリア性が向上することから好ましい。 The metal alkoxide (A) used in the present invention is a compound represented by the general formula R 1 n M (OR) m (M is an atom selected from a metal such as Si, Al, Ti, R is an alkyl group). The present invention is not particularly limited as long as it forms a coating film layer by the sol-gel method, and may be a hydrolyzate of the metal alkoxide. The metal alkoxide (A) is not particularly limited as long as the effect of the present invention can be obtained, but those having Si, Al, Ti, and Zr as M are preferably used, and among them, the most suitable barrier property is obtained. Therefore, those having Si and Al are particularly preferable. The alkyl group contained in the metal alkoxide may be an alkyl group represented by C n H2 n + 1 , and is not limited as long as the effect of the present invention can be obtained, but is particularly limited to an alkyl group having n = 1 to 5. It is preferable to use a group because the barrier property is improved.
　本発明において用いられる金属アルコキシド（Ａ）としては、例えばテトラメトキシシラン（Ｓｉ（ＯＣＨ３）４）、テトラエトキシシラン（以下、ＴＥＯＳとする）（Ｓｉ（ＯＣ２Ｈ５）４）、テトラプロポキシシラン（Ｓｉ（ＯＣ３Ｈ７）４）、テトラブトキシシラン（Ｓｉ（ＯＣ４Ｈ９）４）、ノルマルプロピルジルコネート、ノルマルブチルジルコネート、テトライソプロピルチタネート、テトラノルマルブチルチタネート、ブチルチタネートダイマー、テトラオクチルチタネート、トリイソプロポキシアルミニウムなどのアルコキドを用いることができる。 Examples of the metal alkoxide (A) used in the present invention include tetramethoxysilane (Si (OCH 3 ) 4 ), tetraethoxysilane (hereinafter referred to as TEOS) (Si (OC 2 H 5 ) 4 ), and tetrapropoxysilane. (Si (OC 3 H 7 ) 4 ), tetrabutoxysilane (Si (OC 4 H 9 ) 4 ), normal propyl zirconeate, normal butyl zirconeate, tetraisopropyl titanate, tetranormal butyl titanate, butyl titanate dimer, tetraoctyl. Alkoxides such as titanate and triisopropoxyaluminum can be used.
　金属アルコキシド（Ａ）を積層するためには各種公知の方法により基材上または後述する（Ｂ）層上に塗工すればよい。本発明の（Ａ）および（Ｂ）の塗工方法としては特に限定されず、スプレー法、スピンコート法、ディップ法、ロールコート法、ブレードコート法、ドクターロール法、ドクターブレード法、カーテンコート法、スリットコート法、スクリーン印刷法、インクジェット法、ディスペンス法、ダイコート（ダイコーティング）法、ダイレクトグラビア法、リバースグラビア法、フレキソ法、ナイフコート法、ドットコート法等公知の塗工方法を用いることができる。　 In order to laminate the metal alkoxide (A), it may be applied on the substrate or on the layer (B) described later by various known methods. The coating methods (A) and (B) of the present invention are not particularly limited, and are a spray method, a spin coat method, a dip method, a roll coat method, a blade coat method, a doctor roll method, a doctor blade method, and a curtain coat method. , Slit coating method, screen printing method, inkjet method, dispense method, die coating (die coating) method, direct gravure method, reverse gravure method, flexo method, knife coating method, dot coating method, etc. can. It was
　前記したように、本発明で用いる金属アルコキシド（Ａ）は、水や有機溶媒等の各種溶媒存在下でゾルゲル法により加水分解および重縮合反応させることでガスバリア性塗膜層を形成することができる。本発明における金属アルコキシド（Ａ）層の厚みとしては０．０３～１．０μｍの範囲が好ましく、バリア性と機械特性が優れることから０．１～０．５μｍの範囲が特に好ましい。 As described above, the metal alkoxide (A) used in the present invention can form a gas barrier coating layer by hydrolysis and polycondensation reaction by the sol-gel method in the presence of various solvents such as water and organic solvents. .. The thickness of the metal alkoxide (A) layer in the present invention is preferably in the range of 0.03 to 1.0 μm, and is particularly preferably in the range of 0.1 to 0.5 μm because of its excellent barrier properties and mechanical properties.
　本発明においては、安定な金属アルコキシド（Ａ）含有層を形成することを目的として、金属アルコキシド（Ａ）と共にシランカップリング剤を用いてもよい。このようなシランカップリング剤としては公知の有機反応性基含有オルガノアルコキシシランを用いることができるが、塗膜の形成が良好となることからエポキシ基含有オルガノアルコキシシランが好ましい。このようなエポキシ基含有オルガノアルコキシシランとしては、例えば、γ－グリシドキシプロピルメチルジエトキシシラン、γ－グリシドキシプロピルトリメトキシシラン、およびβ－（３，４－エポキシシクロヘキシル）エチルトリメトキシシランなどが挙げられる。    In the present invention, a silane coupling agent may be used together with the metal alkoxide (A) for the purpose of forming a stable metal alkoxide (A) -containing layer. As such a silane coupling agent, a known organic reactive group-containing organoalkoxysilane can be used, but an epoxy group-containing organoalkoxysilane is preferable because the formation of a coating film is good. Examples of such an epoxy group-containing organoalkoxysilane include γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. And so on.
前記シランカップリング剤は、本発明の効果が得られる範囲において１種又は２種以上を使用してもよく、シランカップリング剤は金属アルコキシド（Ａ）の合計量１００質量部に対して、１～２０質量部程度の範囲内で使用することが好ましい。   As the silane coupling agent, one kind or two or more kinds may be used as long as the effect of the present invention can be obtained, and the silane coupling agent is 1 with respect to 100 parts by mass of the total amount of the metal alkoxide (A). It is preferable to use it within the range of about 20 parts by mass. The
　本発明において用いられる金属化合物（Ｂ）としては、熱水処理時にイオン化可能な金属であれば特に制限されるものではなく、亜鉛、チタン、ジルコニウム、クロム、マンガン、鉄、コバルト、ニッケル、銅、スズなどの遷移金属；ベリリウム、マグネシウム、カルシウムなどのアルカリ土類金属；アルミニウム、ケイ素などから選ばれる金属の単体、酸化物、水酸化物、塩化物、炭酸塩、酢酸塩、カルボン酸塩やキレート体等を用いることができる。本発明において用いる金属化合物としては亜鉛、カルシウム、マグネシウム、アルミニウム、チタンから選択される化合物が好ましく、優れたガスバリア性と優れた耐レトルト性が良好となることから亜鉛、カルシウム、マグネシウムから選択される化合物が特に好ましい。 The metal compound (B) used in the present invention is not particularly limited as long as it is a metal that can be ionized during hot water treatment, and zinc, titanium, zirconium, chromium, manganese, iron, cobalt, nickel, copper, and the like. Transition metals such as tin; alkaline earth metals such as beryllium, magnesium, calcium; simple metals selected from aluminum, silicon, etc., oxides, hydroxides, chlorides, carbonates, acetates, carboxylates and chelate A body or the like can be used. As the metal compound used in the present invention, a compound selected from zinc, calcium, magnesium, aluminum and titanium is preferable, and zinc, calcium and magnesium are selected because excellent gas barrier properties and excellent retort resistance are good. Compounds are particularly preferred.
　本発明において用いる金属化合物（Ｂ）としては前記のように金属の単体、酸化物、水酸化物、塩化物、炭酸塩、酢酸塩、カルボン酸塩やキレート体等を用いることができる。この中でも特に酸化物、水酸化物、塩化物、炭酸塩、酢酸塩を用いると良好なコーティング膜が形成できることから好ましく、酸化物、水酸化物を用いることが最も好ましい。 As the metal compound (B) used in the present invention, as described above, a simple metal, an oxide, a hydroxide, a chloride, a carbonate, an acetate, a carboxylate, a chelate, or the like can be used. Of these, oxides, hydroxides, chlorides, carbonates and acetates are particularly preferable because a good coating film can be formed, and oxides and hydroxides are most preferable.
　本発明において用いる金属化合物（Ｂ）としては酸化亜鉛、炭酸カルシウム、酸化マグネシウム、酸化アルミニウム、チタンアルコキシドが更に好ましく、優れたガスバリア性が得られることから酸化亜鉛、炭酸カルシウム、酸化マグネシウムが最も好ましい。 As the metal compound (B) used in the present invention, zinc oxide, calcium carbonate, magnesium oxide, aluminum oxide and titanium alkoxide are more preferable, and zinc oxide, calcium carbonate and magnesium oxide are most preferable because excellent gas barrier properties can be obtained.
　本発明において用いられる金属化合物（Ｂ）としては、その形状は特に限定されるものではないが、粒子状であることが好ましい。金属化合物（Ｂ）として粒子状のものを使用する場合、その平均粒子径は本発明の効果が得られる範囲において特に限定されるものではないがレーザー回折散乱法や走査型電子顕微鏡による観察等により測定した平均粒子径のいずれかが０．２μｍ以下であることが好ましく、好適なガスバリア性と好適な透明性が得られることから０．１μｍ以下であることが更に好ましく、金属のイオン化が速くゾルゲル形成が迅速に行われることから０．０７μｍ以下であることが最も好ましい。 The shape of the metal compound (B) used in the present invention is not particularly limited, but it is preferably in the form of particles. When a particulate metal compound (B) is used, the average particle size thereof is not particularly limited as long as the effect of the present invention can be obtained, but it can be observed by a laser diffraction / scattering method, a scanning electron microscope, or the like. It is preferable that any of the measured average particle diameters is 0.2 μm or less, more preferably 0.1 μm or less because suitable gas barrier properties and suitable transparency can be obtained, and the ionization of the metal is rapid and the solgel. It is most preferably 0.07 μm or less because the formation is carried out rapidly.
　本発明の金属化合物（Ｂ）を用いて層を形成する方法としては特に限定されるものではないが、例えば金属化合物（Ｂ）を含有するコーティング液を調整し、コーティング液を塗工、乾燥することにより形成することができる。 The method for forming the layer using the metal compound (B) of the present invention is not particularly limited, but for example, a coating liquid containing the metal compound (B) is prepared, and the coating liquid is applied and dried. It can be formed by.
前記金属化合物（Ｂ）を含有するコーティング液は、本発明の効果が得られる範囲において水や有機溶媒などの各種溶媒、分散剤、界面活性剤、安定剤、増粘剤、樹脂、消泡剤、濡れ剤、硬化剤、ブロッキング防止剤、滑剤、防腐剤、無機充填剤などの添加剤を含有して良い。 The coating liquid containing the metal compound (B) contains various solvents such as water and organic solvents, dispersants, surfactants, stabilizers, thickeners, resins, and defoamers to the extent that the effects of the present invention can be obtained. , Wetting agent, hardening agent, blocking inhibitor, lubricant, preservative, inorganic filler and the like may be contained.
本発明のガスバリア性積層体に用いられる基材としては、本発明の効果が得られる範囲において特に限定されるものではなく、所望の用途に応じて樹脂製フィルムや紙や金属箔、木等を適宜選択することができる。例えば食品包装用としては、ポリエチレンテレフタレート（ＰＥＴ）フィルム、ポリスチレンフィルム、ポリアミドフィルム、ポリアクリロニトリルフィルム、ポリエチレンフィルム（ＬＬＤＰＥ：リニア低密度ポリエチレンフィルム、ＨＤＰＥ：高密度ポリエチレンフィルム）やポリプロピレンフィルム（ＣＰＰ：未延伸ポリプロピレンフィルム、ＯＰＰ：二軸延伸ポリプロピレンフィルム）等のポリオレフィンフィルム、ポリビニルアルコールフィルム、エチレン－ビニルアルコール共重合体フィルム、シクロオレフィンコポリマフィルム等の樹脂製フィルムを用いることができる。また、本発明に用いる基材としては、前記各種基材に下記の蒸着処理を行ったものを用いてもよい。 The base material used for the gas barrier laminate of the present invention is not particularly limited as long as the effect of the present invention can be obtained, and a resin film, paper, metal leaf, wood, or the like can be used depending on the desired application. It can be selected as appropriate. For example, for food packaging, polyethylene terephthalate (PET) film, polystyrene film, polyamide film, polyacrylonitrile film, polyethylene film (LLDPE: linear low density polyethylene film, HDPE: high density polyethylene film) and polypropylene film (CPP: unstretched). A polyolefin film such as a polypropylene film (OPP: biaxially stretched polypropylene film), a polyvinyl alcohol film, an ethylene-vinyl alcohol copolymer film, and a resin film such as a cycloolefin copolyma film can be used. Further, as the base material used in the present invention, those obtained by subjecting the various base materials to the following vapor deposition treatment may be used.
　前記基材として樹脂製フィルムを用いる場合は延伸処理を施されたものであってもよく、未延伸フィルムを用いても良い。前記延伸処理を施しているフィルム類は寸法安定性、剛性に優れることからコーティング操作が容易で使いやすい利点があり、未延伸フィルムを用いる場合にも本発明の構成により、バリア機能の強化に大きな効果が得られる。 When a resin film is used as the base material, it may be stretched or an unstretched film may be used. The stretched films have the advantages of being easy to coat and easy to use because they are excellent in dimensional stability and rigidity, and even when an unstretched film is used, the configuration of the present invention greatly enhances the barrier function. The effect is obtained.
前記延伸処理方法としては、押出製膜法等で樹脂を溶融押出してシート状にした後、同時二軸延伸あるいは逐次二軸延伸を行うことが一般的である。また逐次二軸延伸の場合は、はじめに縦延伸処理を行い、次に横延伸を行うことが一般的である。具体的には、ロール間の速度差を利用した縦延伸とテンターを用いた横延伸を組み合わせる方法が多く用いられる。 As the stretching treatment method, it is common to melt-extrude the resin by an extrusion film forming method or the like to form a sheet, and then perform simultaneous biaxial stretching or sequential biaxial stretching. Further, in the case of sequential biaxial stretching, it is common to first perform longitudinal stretching treatment and then lateral stretching. Specifically, a method of combining longitudinal stretching using a speed difference between rolls and transverse stretching using a tenter is often used.
　前記基材の表面に施される蒸着処理としては、アルミニウム等を用いた金属蒸着処理、二酸化ケイ素（ＳｉＯｘ）、酸化アルミニウム（ＡｌＯｘ）等の無機酸化物を用いた蒸着処理を行うことができる。中でも好適なバリア性能が得られ、ボイル・レトルト耐性に優れ、基材の風合い、質感を損なわない点から二酸化ケイ素、酸化アルミニウムを用いた蒸着処理が好ましい。 As the vapor deposition treatment applied to the surface of the base material, a metal vapor deposition treatment using aluminum or the like, or a vapor deposition treatment using an inorganic oxide such as silicon dioxide (SiOx) or aluminum oxide (AlOx) can be performed. Among them, a thin-film deposition treatment using silicon dioxide or aluminum oxide is preferable from the viewpoint that suitable barrier performance can be obtained, boil / retort resistance is excellent, and the texture and texture of the base material are not impaired.
　前記基材の表面に蒸着層を形成する方法としては、本発明の効果が得られる範囲において特に制限されるものではなく、前記無機酸化物をＰＶＤ法などの真空蒸着法、スパッタリング法、化学的気相成長法（ＣＶＤ法）、により基材表面に成膜する方法を選択することができ、蒸着法により処理された基材を用いるとバリア性が向上することから好ましい。 The method for forming the thin-film deposition layer on the surface of the substrate is not particularly limited as long as the effect of the present invention can be obtained, and the inorganic oxide is vapor-deposited by a vacuum such as PVD method, sputtering method, or chemical. A method of forming a film on the surface of the substrate can be selected by the vapor phase growth method (CVD method), and it is preferable to use the substrate treated by the vapor deposition method because the barrier property is improved.
　前記樹脂製フィルムにアルミニウム等の金属、シリカやアルミナ等の金属酸化物の蒸着層を積層したフィルム、ポリビニルアルコールやエチレン・ビニルアルコール共重合体、塩化ビニリデン等のガスバリア層を含有するバリア性フィルムを積層し併用してもよい。このようなフィルムを用いることで、水蒸気、酸素、アルコール、不活性ガス、揮発性有機物（香り）等に対するバリア性を備えた積層体とすることができる。 A film obtained by laminating a vapor-deposited layer of a metal such as aluminum or a metal oxide such as silica or alumina on the resin film, or a barrier film containing a gas barrier layer such as polyvinyl alcohol, an ethylene / vinyl alcohol copolymer, or vinylidene chloride. It may be laminated and used together. By using such a film, it is possible to obtain a laminated body having a barrier property against water vapor, oxygen, alcohol, an inert gas, a volatile organic substance (fragrance) and the like.
　前記基材の表面に形成される塗膜の膜厚としては本発明の効果を損なわない範囲において適宜設定することができるが、可撓性と堅牢性を両立できることから５～５００ｎｍの範囲であることが好ましく、１０～３００ｎｍの範囲であることが更に好ましい。 The film thickness of the coating film formed on the surface of the substrate can be appropriately set within a range that does not impair the effect of the present invention, but is in the range of 5 to 500 nm because both flexibility and fastness can be achieved. It is preferably in the range of 10 to 300 nm, and more preferably in the range of 10 to 300 nm.
本発明のガスバリア性積層体は基材の少なくとも一面に金属アルコキシド（Ａ）含有層と、金属化合物（Ｂ）含有層が形成されていることを特徴とするものであり、本発明の効果が得られる範囲において基材上に（Ａ）層と（Ｂ）層を順不同で形成してよく、（Ａ）層および（Ｂ）層をそれぞれ複数層形成してもよい。前記のように基材上に（Ａ）層と（Ｂ）層を形成する順序は特に限定されるものではないが、基材の一面に（Ａ）層、（Ｂ）層が順次形成されると特に良好なバリア効果が得られると共に堅牢な積層体が得られることから好ましい。 The gas barrier laminate of the present invention is characterized in that a metal alkoxide (A) -containing layer and a metal compound (B) -containing layer are formed on at least one surface of the base material, and the effects of the present invention can be obtained. The layer (A) and the layer (B) may be formed in no particular order on the substrate within a certain range, and a plurality of layers (A) and (B) may be formed respectively. As described above, the order in which the (A) layer and the (B) layer are formed on the base material is not particularly limited, but the (A) layer and the (B) layer are sequentially formed on one surface of the base material. This is preferable because a particularly good barrier effect can be obtained and a robust laminate can be obtained.
　本発明のガスバリア性積層体は、本発明の効果が損なわれない範囲において積層体の最外面に（Ａ）層、（Ｂ）層以外の付加的コーティング層を設けてもよい。このような付加的コーティング層としては、更に高いバリア機能を付与することを目的としてポリビニルアルコールや、エチレン・ビニルアルコール共重合体、塩化ビニリデン等のガスバリア層を含有するバリア性フィルムや、各種蒸着フィルムの他、アルミ箔などの金属箔による層を用いることができる。付加的コーティング層としては、アルミニウムなどの金属蒸着フィルム、シリカ、アルミナ等の金属酸化物蒸着フィルムなどが例示できる。またフィルムの種類としては延伸フィルムでも、未延伸フィルムでもよい。 The gas barrier laminate of the present invention may be provided with an additional coating layer other than the (A) layer and the (B) layer on the outermost surface of the laminate as long as the effect of the present invention is not impaired. As such an additional coating layer, a barrier film containing a gas barrier layer such as polyvinyl alcohol, an ethylene / vinyl alcohol copolymer, or vinylidene chloride for the purpose of imparting a higher barrier function, and various vapor-deposited films. In addition, a layer made of a metal foil such as aluminum foil can be used. Examples of the additional coating layer include a metal vapor-deposited film such as aluminum and a metal oxide-deposited film such as silica and alumina. The type of film may be a stretched film or an unstretched film.
　本発明の積層体は、上述した構成に加えて、更に他のフィルムや基材を含んでいてもよい。他の基材としては、上述した延伸フィルム、未延伸フィルム、透明蒸着フィルムに加え、後述の紙、木材、皮革等の多孔質の基材を使用することもできる。 The laminate of the present invention may further contain another film or base material in addition to the above-mentioned structure. As the other base material, in addition to the above-mentioned stretched film, unstretched film, and transparent vapor-deposited film, a porous base material such as paper, wood, and leather described later can also be used.
　紙としては、特に限定なく公知の紙基材を使用することができる。具体的には、木材パルプ等の製紙用天然繊維を用いて公知の抄紙機にて製造されるが、その抄紙条件は特に規定されるものではない。製紙用天然繊維としては、針葉樹パルプ、広葉樹パルプ等の木材パルプ、マニラ麻パルプ、サイザル麻パルプ、亜麻パルプ等の非木材パルプ、およびそれらのパルプに化学変性を施したパルプ等が挙げられる。パルプの種類としては、硫酸塩蒸解法、酸性・中性・アルカリ性亜硫酸塩蒸解法、ソーダ塩蒸解法等による化学パルプ、グランドパルプ、ケミグランドパルプ、サーモメカニカルパルプ等を使用することができる。 As the paper, a known paper base material can be used without particular limitation. Specifically, it is manufactured by a known paper machine using natural fibers for papermaking such as wood pulp, but the papermaking conditions are not particularly specified. Examples of natural fibers for papermaking include wood pulps such as coniferous tree pulp and broadleaf tree pulp, non-wood pulps such as Manila hemp pulp, sisal hemp pulp, and flax pulp, and pulp obtained by chemically modifying these pulps. As the type of pulp, chemical pulp, gland pulp, chemi-grand pulp, thermomechanical pulp and the like obtained by a sulfate cooking method, an acidic / neutral / alkaline sulfite cooking method, a soda salt cooking method and the like can be used.
また、市販の各種上質紙やコート紙、裏打ち紙、含浸紙、ボール紙や板紙などを用いることもできる。また紙層の外表面または内面側には、必要に応じて印刷層を設けてもよい。 Further, various commercially available high-quality papers, coated papers, backing papers, impregnated papers, cardboards, paperboards and the like can also be used. Further, a print layer may be provided on the outer surface or the inner surface side of the paper layer, if necessary.
　本発明のガスバリア性積層体のより具体的な構成例としては、ＰＥＴフィルム／酸化アルミナ蒸着層／金属アルコキシド（Ａ）含有層／金属化合物（Ｂ）含有層／ＣＰＰ（無延伸ポリプロピレン）フィルム、ＰＥＴフィルム／酸化アルミナ蒸着層／金属化合物（Ｂ）含有層／金属アルコキシド（Ａ）含有層／ＣＰＰフィルムが上げられ、必要に応じてこれらの層間にさらに蒸着層、アンカー層、接着剤層、印刷層等を設けてもよい。また、耐突き刺し性など、より強度が必要な場合にはアルミ蒸着ＰＥＴフィルム、透明蒸着ＰＥＴフィルム等に代えて透明蒸着Ｎｙフィルムを用いてもよい。 As a more specific configuration example of the gas barrier laminate of the present invention, PET film / alumina oxide vapor deposition layer / metal alkoxide (A) -containing layer / metal compound (B) -containing layer / CPP (non-stretched polypropylene) film, PET. A film / an alumina oxide vapor deposition layer / a metal compound (B) -containing layer / a metal alkoxide (A) -containing layer / a CPP film is raised, and if necessary, a vapor deposition layer, an anchor layer, an adhesive layer, and a printing layer are further placed between these layers. Etc. may be provided. Further, when higher strength such as piercing resistance is required, a transparent vapor-deposited Ny film may be used instead of the aluminum-deposited PET film, the transparent-deposited PET film, or the like.
　本発明のガスバリア性積層体は、前記のように基材の少なくとも一面に金属アルコキシド（Ａ）含有層と、金属化合物（Ｂ）含有層が形成されていることを特徴とするものである。これら（A）含有層と（B）含有層は積層後、層間でイオン架橋等の反応が進行し、より強固なバリア性能を発揮するものである。 The gas barrier laminate of the present invention is characterized in that a metal alkoxide (A) -containing layer and a metal compound (B) -containing layer are formed on at least one surface of the base material as described above. After the (A) -containing layer and the (B) -containing layer are laminated, reactions such as ion cross-linking proceed between the layers to exhibit stronger barrier performance.
　本発明の積層体は、食品や医薬品などの保護を目的とする多層包装体として使用することができる。多層包装体として使用する場合には、内容物や使用環境、使用形態に応じてその層構成は変化し得る。また、本発明の包装体に易開封処理や再封性手段を適宜設けてあってもよい。 The laminate of the present invention can be used as a multi-layer package for the purpose of protecting foods, pharmaceuticals, etc. When used as a multi-layer package, its layer structure may change depending on the contents, usage environment, and usage pattern. Further, the package of the present invention may be appropriately provided with an easy-opening process or a resealable means.
　本発明の包装体は、前記した構成の積層体を使用し、積層体のシーラントフィルムの面を対向して重ね合わせた後、その周辺端部をヒートシールして袋状にして得られる。製袋方法としては、本発明の積層体を折り曲げるか、あるいは重ねあわせてその内層の面（シーラントフィルムの面）を対向させ、その周辺端部を、例えば、側面シール型、二方シール型、三方シール型、四方シール型、封筒貼りシール型、合掌貼りシール型、ひだ付シール型、平底シール型、角底シール型、ガゼット型、その他のヒートシール型等の形態によりヒートシールする方法が挙げられる。本発明の包装材は内容物や使用環境、使用形態に応じて種々の形態をとり得る。自立性包装材（スタンディングパウチ）等も可能である。ヒートシールの方法としては、バーシール、回転ロールシール、ベルトシール、インパルスシール、高周波シール、超音波シール等の公知の方法で行うことができる。本発明の包装体としては本発明の効果が好適に発揮されることから、レトルト処理を行う包装体であることが好ましい。 The package of the present invention is obtained by using the laminate having the above-mentioned structure, laminating the surfaces of the sealant films of the laminate facing each other, and then heat-sealing the peripheral ends thereof to form a bag. As a bag making method, the laminated body of the present invention is bent or overlapped so that the inner layer surface (the surface of the sealant film) faces each other, and the peripheral end thereof is, for example, a side seal type or a two-way seal type. There are three-way sticker type, four-way sticker type, envelope sticker sticker type, gassho sticker sticker type, fold sticker sticker type, flat bottom sticker type, square bottom sticker type, gusset type, and other heat seal type. Be done. The packaging material of the present invention can take various forms depending on the contents, the environment in which it is used, and the form in which it is used. Self-supporting packaging materials (standing pouches), etc. are also possible. As a heat sealing method, a known method such as a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high frequency seal, and an ultrasonic seal can be used. Since the effect of the present invention is preferably exhibited, the package of the present invention is preferably a package to be retort-treated.
　本発明の包装材に、その開口部から内容物を充填した後、開口部をヒートシールして本発明の包装材を使用した製品が製造される。充填される内容物として、例えば食品としては、米菓、豆菓子、ナッツ類、ビスケット・クッキー、ウェハース菓子、マシュマロ、パイ、半生ケーキ、キャンディ、スナック菓子などの菓子類、パン、スナックめん、即席めん、乾めん、パスタ、無菌包装米飯、ぞうすい、おかゆ、包装もち、シリアルフーズなどのステープル類、漬物、煮豆、納豆、味噌、凍豆腐、豆腐、なめ茸、こんにゃく、山菜加工品、ジャム類、ピーナッツクリーム、サラダ類、冷凍野菜、ポテト加工品などの農産加工品、ハム類、ベーコン、ソーセージ類、チキン加工品、コンビーフ類などの畜産加工品、魚肉ハム・ソーセージ、水産練製品、かまぼこ、のり、佃煮、かつおぶし、塩辛、スモークサーモン、辛子明太子などの水産加工品、桃、みかん、パイナップル、りんご、洋ナシ、さくらんぼなどの果肉類、コーン、アスパラガス、マッシュルーム、玉ねぎ、人参、大根、じゃがいもなどの野菜類、ハンバーグ、ミートボール、水産フライ、ギョーザ、コロッケなどを代表とする冷凍惣菜、チルド惣菜などの調理済食品、バター、マーガリン、チーズ、クリーム、インスタントクリーミーパウダー、育児用調整粉乳などの乳製品、液体調味料、レトルトカレー、ペットフードなどの食品類が挙げられる。 After filling the packaging material of the present invention with the contents from the opening, the opening is heat-sealed to manufacture a product using the packaging material of the present invention. As the contents to be filled, for example, as food, rice confectionery, bean confectionery, nuts, biscuits / cookies, wafer confectionery, marshmallow, pie, half-baked cake, candy, snack confectionery and other confectionery, bread, snack noodles, instant noodles. , Dried noodles, pasta, sterile packaged rice, elephants, rice cakes, packaged rice cakes, staples such as cereal foods, pickles, boiled beans, natto, miso, frozen tofu, tofu, licked mushrooms, konjac, processed wild vegetables, jams, peanut cream, Processed agricultural products such as salads, frozen vegetables, processed potatoes, hams, bacon, sausages, processed chicken products, processed livestock products such as confectionery, fish hams and sausages, marine products, kamaboko, glue, boiled vegetables, Processed marine products such as bonito, salted, smoked salmon, and spicy cod roe, fruit meats such as peaches, oranges, pineapples, apples, pears, and cherries, vegetables such as corn, asparagus, mushrooms, onions, carrots, radishes, and potatoes. , Hamburgers, meat balls, fried fishery products, frozen side dishes such as gyoza and croquette, cooked foods such as chilled side dishes, butter, margarine, cheese, cream, instant creamy powder, dairy products such as baby-prepared powdered milk, liquids Foods such as seasonings, retort curry, and pet foods can be mentioned.
　また非食品としては、タバコ、使い捨てカイロ、輸液パック等の医薬品、洗濯用液体洗剤、台所用液体洗剤、浴用液体洗剤、浴用液体石鹸、液体シャンプー、液体コンディショナー、化粧水や乳液等の化粧品、真空断熱材等の断熱材、電池等、様々な包装材料としても使用され得る。 Non-food items include tobacco, disposable body warmers, medicines such as infusion packs, liquid detergents for washing, liquid detergents for kitchens, liquid detergents for baths, liquid soaps for baths, liquid shampoos, liquid conditioners, cosmetics such as lotions and emulsions, and vacuum. It can also be used as a heat insulating material such as a heat insulating material and as various packaging materials such as a battery.
以下、本発明を具体的な合成例、実施例を挙げてより詳細に説明するが、本発明はこれら実施例に限定されるものではない。なお、以下の例において、「部」及び「％」は、特に断りがない限り、「質量部」及び「質量％」をそれぞれ表す。 Hereinafter, the present invention will be described in more detail with reference to specific synthetic examples and examples, but the present invention is not limited to these examples. In the following examples, "parts" and "%" represent "parts by mass" and "% by mass", respectively, unless otherwise specified.
（金属アルコキシド含有コーティング液ａ－１の調製）
重合度２４００のＰＶＡ（ＰＶＡ６０－９８、クラレ製、完全ケン化ＰＶＡ）を固形分濃度が５％となるように水／ＩＰＡ（イソプロピルアルコール）＝９８／２（質量比）の混合溶媒にて溶解し、ＰＶＡ溶液を調製した。　次に、テトラエトキシシラン（Ｓｉ（ＯＣ２Ｈ５）４、以下「ＴＥＯＳ」と称す。ＫＢＥ－０４、信越化学製）に０．１Ｎ塩酸を加え、３０分間攪拌し加水分解させて固形分３％（ＳｉＯ２換算）のＴＥＯＳ加水分解溶液を調製した。ＰＶＡ溶液とＴＥＯＳ加水分解溶液とを、固形分質量比でＰＶＡ／ＴＥＯＳ（ＳｉＯ２換算）が３０／７０となるように混合し、コーティング液（ａ－１）を調製した。 (Preparation of coating liquid a-1 containing metal alkoxide)
PVA with a degree of polymerization of 2400 (PVA60-98, manufactured by Kuraray, fully saponified PVA) is dissolved in a mixed solvent of water / IPA (isopropyl alcohol) = 98/2 (mass ratio) so that the solid content concentration is 5%. Then, a PVA solution was prepared. Next, 0.1N hydrochloric acid was added to tetraethoxysilane (Si (OC 2 H 5 ) 4 , hereinafter referred to as "TEOS"; KBE-04, manufactured by Shin-Etsu Chemical Co., Ltd.), and the mixture was stirred for 30 minutes to be hydrolyzed to have a solid content of 3. % (SiO 2 equivalent) TEOS hydrolysis solution was prepared. The PVA solution and the TEOS hydrolyzed solution were mixed so that the PVA / TEOS (SiO 2 equivalent) was 30/70 in terms of solid content mass ratio to prepare a coating liquid (a-1).
（金属アルコキシド含有コーティング液ａ－２の調製）
金属化合物含有コーティング剤ａ－１におけるＴＥＯＳに代えて、アルミニウムトリイソプロポキシド（Ａｌ（ＯＣ３Ｈ７）３、ナカライテスク製）を用いた以外は、同様にコーティング液を調整した。 (Preparation of coating liquid a-2 containing metal alkoxide)
The coating liquid was prepared in the same manner except that aluminum triisopropoxide (Al (OC 3H 7 ) 3 , manufactured by Nacalai Tesque) was used instead of TEOS in the metal compound-containing coating agent a-1.
（金属アルコキシド含有コーティング液ａ－３の調製）
金属化合物含有コーティング剤ａ－１におけるＴＥＯＳに代えて、ＴＥＯＳ／テトライソプロピルチタネート（Ｔｉ(ＯＣ３Ｈ７)4、以下ＴＰＴと示す、オルガチックスＴＡ－８、マツモトファインケミカル製）＝９／１の混合液を用いた以外は、同様にコーティング液を調整した。 (Preparation of coating liquid a-3 containing metal alkoxide)
Instead of TEOS in the metal compound-containing coating agent a-1, TEOS / tetraisopropyl titanate (Ti (OC 3 H 7 ) 4 , hereinafter referred to as TPT, Olga Tix TA-8, manufactured by Matsumoto Fine Chemical Co., Ltd.) = 9/1. The coating liquid was adjusted in the same manner except that the liquid was used.
（金属アルコキシド非含有コーティング液ａ－４の調製）
重合度２４００のＰＶＡ（ＰＶＡ６０－９８）を固形分濃度が５％となるように水／ＩＰＡ＝９８／２（質量比）の混合溶媒にて溶解し、コーティング液（ａ－４）を調整した。 (Preparation of metal alkoxide-free coating liquid a-4)
PVA (PVA60-98) having a degree of polymerization of 2400 was dissolved in a mixed solvent of water / IPA = 98/2 (mass ratio) so that the solid content concentration was 5%, and the coating liquid (a-4) was adjusted. ..
（金属化合物含有コーティング剤ｂ－１の調製）
蒸留水６７．０ｇに、酸化亜鉛超微粒子（ＦＩＮＥＸ５０、堺化学工業製、平均一次粒子径２０ｎｍ）を３０．０ｇ、分散剤としてポリアクリル酸ナトリウム（アロンＴ－５０、東亜合成株式会社製。、固形分濃度４０％）を３．０ｇ加えて、高速撹拌機（Ｔ．Ｋ．フィルミックス、プライミクス株式会社製）を用いて十分に分散させて、１００．０ｇの酸化亜鉛超微粒子水分散液を得た。この酸化亜鉛超微粒子水分散液２５．０ｇに、蒸留水５５．１ｇとポリエステル樹脂水性分散体（エリーテルＫＴ－８８０３、ユニチカ株式会社製、固形分濃度３０重量％、ポリエステル樹脂の数平均分子量：１３，０００、Ｔｇ：６５℃、酸価：７ｍｇＫＯＨ／ｇ）４．１ｇと、水分散イソシアネート化合物（デュラネートＷＢ４０－１００、旭化成製。、固形分濃度１００％）０．４５ｇを加えて撹拌した後、ＩＰＡを１０．３ｇ加えて撹拌し、金属化合物含有コーティング液（ｂ－１）（固形分濃度１０重量％）を得た。平均粒径は0.1μmであった。 (Preparation of coating agent b-1 containing a metal compound)
30.0 g of zinc oxide ultrafine particles (FINEX50, manufactured by Sakai Chemical Industry Co., Ltd., average primary particle diameter 20 nm) in 67.0 g of distilled water, and sodium polyacrylate (Aron T-50, manufactured by Toa Synthetic Co., Ltd.) as a dispersant. Add 3.0 g (solid content concentration 40%) and sufficiently disperse using a high-speed stirrer (TK Philmix, manufactured by Primix Co., Ltd.) to obtain 100.0 g of an aqueous dispersion of zinc oxide ultrafine particles. Obtained. In 25.0 g of this zinc oxide ultrafine water dispersion, 55.1 g of distilled water and an aqueous dispersion of polyester resin (Elitel KT-8803, manufactured by Unitika Co., Ltd., solid content concentration 30% by weight, number average molecular weight of polyester resin: 13) 000, Tg: 65 ° C., acid value: 7 mgKOH / g) 4.1 g and water-dispersed isocyanate compound (Duranate WB40-100, manufactured by Asahi Kasei Co., Ltd., solid content concentration 100%) 0.45 g were added and stirred. 10.3 g of IPA was added and stirred to obtain a metal compound-containing coating liquid (b-1) (solid content concentration: 10% by weight). The average particle size was 0.1 μm.
（金属化合物含有コーティング剤ｂ－２の調製）
金属化合物含有コーティング剤ｂ－１においての微粒子酸化亜鉛に代えて、微粒子酸化マグネシウム（ＭｇＯ）を用いた以外は、同様にコーティング液を調整した。微粒子酸化マグネシウム（和光純薬工業株式会社製、平均粒径：０．０１μｍ）を用い、エタノール中に超音波ホモジナイザーを用いて分散させ、ＭｇＯ含有量３０％のサスペンジョンを調製して用いた。平均粒径は0.1μmであった。 (Preparation of coating agent b-2 containing metal compound)
The coating liquid was prepared in the same manner except that fine particle magnesium oxide (MgO) was used instead of the fine particle zinc oxide in the metal compound-containing coating agent b-1. Fine particle magnesium oxide (manufactured by Wako Pure Chemical Industries, Ltd., average particle size: 0.01 μm) was dispersed in ethanol using an ultrasonic homogenizer to prepare a suspension having an MgO content of 30%. The average particle size was 0.1 μm.
（金属化合物含有コーティング剤ｂ－３の調製）
金属化合物含有コーティング剤ｂ－１の微粒子酸化亜鉛に代えて、炭酸カルシウム（ＣａＣＯ３）を用いた以外は、同様にコーティング液を調整した。炭酸カルシウムは、和光純薬工業（株）製試薬を用い、メノウ製のすり鉢で微粉化し、エタノール中に超音波ホモジナイザーを用いて分散させ、ＣａＣＯ３含有量３０％のサスペンジョンを調製して用いた。平均粒径は0.1μmであった。 (Preparation of coating agent b-3 containing metal compound)
The coating liquid was prepared in the same manner except that calcium carbonate (CaCO3) was used instead of the fine particle zinc oxide of the metal compound-containing coating agent b-1. Calcium carbonate was pulverized in a mortar made by Menou using a reagent manufactured by Wako Pure Chemical Industries, Ltd., dispersed in ethanol using an ultrasonic homogenizer, and a suspension having a CaCO 3 content of 30% was prepared and used. .. The average particle size was 0.1 μm.
（金属化合物含有コーティング剤ｂ－４の調製）
ＭＥＫ（メチルエチルケトン）４５部及び酢酸エチル４５部に対し、ポリエステル樹脂（バイロンＧＫ－３６０、東洋紡製、数平均分子量：１６，０００、Ｔｇ：５６℃）を５部加え加温溶解させた後に、テトラブトキシドチタン（Ｔｉ（ＯＣ４Ｈ９）４、オルガチックス　ＴＡ－２１、マツモトファインケミカル製）を５部加え撹拌し、固形分濃度１０％の金属化合物含有コーティング液（ｂ－４）を得た。 (Preparation of coating agent b-4 containing metal compound)
To 45 parts of MEK (methyl ethyl ketone) and 45 parts of ethyl acetate, 5 parts of polyester resin (Byron GK-360, Toyobo, number average molecular weight: 16,000, Tg: 56 ° C.) was added and dissolved by heating, and then tetra. Five parts of butoxide titanium (Ti (OC 4 H 9 ) 4 , Olga Chix TA-21, manufactured by Matsumoto Fine Chemical Co., Ltd.) was added and stirred to obtain a metal compound-containing coating liquid (b-4) having a solid content concentration of 10%.
（金属化合物含有コーティング剤ｂ－５の調製）
金属化合物含有コーティング剤ｂ－１の微粒子酸化亜鉛に代えて、酢酸亜鉛（Ｚｎ（ＡｃＯ）2）を用いた以外は、同様にコーティング液を調整した。酢酸亜鉛は和光純薬工業（株）製を用いた。 (Preparation of coating agent b-5 containing metal compound)
The coating liquid was prepared in the same manner except that zinc acetate (Zn (AcO) 2 ) was used instead of the fine particle zinc oxide of the metal compound-containing coating agent b-1. Zinc acetate used was manufactured by Wako Pure Chemical Industries, Ltd.
（金属化合物含有コーティング剤ｂ－６の調製）
金属化合物含有コーティング剤ｂ－１の微粒子酸化亜鉛に代えて、粒径の異なる微粒子酸化亜鉛（ＦＩＮＥＸ５０、堺化学工業製、平均一次粒子径６０ｎｍ）を用いた以外は、同様にコーティング液を調整した。平均粒径は０．６μmであった。 (Preparation of coating agent b-6 containing a metal compound)
The coating liquid was prepared in the same manner except that fine particle zinc oxide (FINEX50, manufactured by Sakai Chemical Industry Co., Ltd., average primary particle diameter 60 nm) having a different particle size was used instead of the fine particle zinc oxide of the metal compound-containing coating agent b-1. .. The average particle size was 0.6 μm.
（金属化合物非含有コーティング剤ｂ－７の調製）
　ポリエステル樹脂水性分散体（エリーテルＫＴ－８８０３、ユニチカ株式会社製）３０ｇを蒸留水５０．０ｇとＩＰＡ１０．０ｇを加えて撹拌し、金属化合物非含有コーティング液（ｂ－５）（固形分濃度１０％）を得た。 (Preparation of coating agent b-7 containing no metal compound)
30 g of an aqueous dispersion of polyester resin (Elitel KT-8803, manufactured by Unitika Ltd.) was stirred by adding 50.0 g of distilled water and 10.0 g of IPA, and the coating liquid (b-5) containing no metal compound (solid content concentration 10%) was stirred. ) Was obtained.
（実施例１）
酸化アルミナ蒸着ＰＥＴフィルム（バリアロックス１０１１ＨＧ、東レフィルム加工株式会社製)の蒸着層の上にバーコーターで金属アルコキシド含有コーティング剤ａ－１を塗工し、１２０℃にセットした熱風乾燥機中で１分間乾燥させ乾燥膜厚約０．３μｍの金属アルコキシド含有層Ａ－１を形成した。その後、金属化合物含有コーティング液ｂ－１を層Ａ－１の上にバーコーターで塗工し、８０℃設定の乾燥機中で１分間乾燥させ乾燥膜厚約０．３μｍの金属化合物含有層Ｂ―１を形成した。続いてディックドライＬＸ－７０３ＶＬとＫＲ－９０（いずれもＤＩＣ製）を１５／１の配合比で配合し、不揮発分が２５％となるように酢酸エチルを配合して得た接着剤を、乾燥膜厚が２．５μｍになるように金属化合物含有層Ｂ―１の上に塗工し、温度５０℃に設定したドライヤーで希釈溶剤を揮発させた後、ＣＰＰフィルム（ＺＫ２０７、東レフィルム加工製）と貼り合わせた。４０℃で３日間エージングを行い評価用の積層体［ＰＥＴ／酸化アルミナ蒸着層／金属アルコキシド含有層Ａ―１／金属化合物含有層Ｂ－１／接着剤／ＣＰＰ］を得た。 (Example 1)
A metal alkoxide-containing coating agent a-1 is coated on the vapor-deposited layer of an alumina oxide-deposited PET film (Barrierox 1011HG, manufactured by Toray Film Processing Co., Ltd.) with a bar coater, and 1 in a hot air dryer set at 120 ° C. It was dried for a minute to form a metal alkoxide-containing layer A-1 having a dry film thickness of about 0.3 μm. Then, the metal compound-containing coating liquid b-1 is coated on the layer A-1 with a bar coater, dried in a dryer set at 80 ° C. for 1 minute, and the metal compound-containing layer B having a dry film thickness of about 0.3 μm. -1 was formed. Subsequently, Dick Dry LX-703VL and KR-90 (both manufactured by DIC) were blended at a blending ratio of 15/1, and ethyl acetate was blended so that the non-volatile content was 25%, and the obtained adhesive was dried. After coating on the metal compound-containing layer B-1 so that the film thickness becomes 2.5 μm and volatilizing the diluting solvent with a dryer set at a temperature of 50 ° C., a CPP film (ZK207, manufactured by Toray Film Co., Ltd.) I pasted it together. Aging was performed at 40 ° C. for 3 days to obtain a laminate [PET / alumina oxide vapor deposition layer / metal alkoxide-containing layer A-1 / metal compound-containing layer B-1 / adhesive / CPP].
（実施例２～６）
金属化合物含有コーティング液ｂ－１の代わりに、金属化合物含有コーティング液ｂ－２～６を用いた以外は、実施例１と同様にして積層体［ＰＥＴ／酸化アルミナ蒸着層／金属アルコキシド含有層Ａ―１／金属化合物含有層Ｂ－２～６／接着剤／ＣＰＰ］を製造した。 (Examples 2 to 6)
The laminate [PET / alumina oxide vapor deposition layer / metal alkoxide-containing layer A] is the same as in Example 1 except that the metal compound-containing coating liquids b-2 to 6 are used instead of the metal compound-containing coating liquid b-1. -1 / Metal compound-containing layer B-2 to 6 / Adhesive / CPP] was produced.
（実施例７～８）
金属アルコキシド含有コーティング液ａ－１の代わりに、金属アルコキシド含有コーティング液ａ－２～３を用いた以外は、実施例１と同様にして積層体［ＰＥＴ／酸化アルミナ蒸着層／金属アルコキシド含有層Ａ－２～３／金属化合物含有層Ｂ－１／接着剤／ＣＰＰ］を製造した。 (Examples 7 to 8)
The laminate [PET / alumina oxide vapor deposition layer / metal alkoxide-containing layer A] is the same as in Example 1 except that the metal alkoxide-containing coating liquids a-2 to 3 are used instead of the metal alkoxide-containing coating liquid a-1. -2 to 3 / metal compound-containing layer B-1 / adhesive / CPP] was produced.
　（実施例９）
酸化アルミナ蒸着ＰＥＴフィルムの代わりに、酸化アルミナ蒸着ＯＰＰフィルムを用いた以外は、実施例１と同様にして積層体［ＯＰＰ／酸化アルミナ蒸着層／金属アルコキシド含有層Ａ―１／金属化合物含有層Ｂ－１／接着剤／ＣＰＰ］を製造した。酸化アルミナ蒸着ＯＰＰフィルムは、二軸延伸ポリプロピレンフィルム（ＦＯＲ、フタムラ化学製、厚さ２０μｍ）の上にアクリル系コート剤（ＧＡＣ－０１３Ｓ、ＤＩＣ製）とポリイソシアネート系硬化剤（ＫＲ－９０、ＤＩＣ製）を混合比が５：１になるように配合し得たアンカーコーティング液を乾燥膜厚が約０．０５μｍになるようにグラビアコート法によって塗布乾燥した後に、電子線加熱方式による真空蒸着装置において、金属アルミニウムを蒸着させると共に酸素ガスを導入して、アンカーコート層の上に厚さ２０ｎｍの酸化アルミニウムからなる蒸着薄膜層を形成することで作成した。 (Example 9)
A laminate [OPP / Alumina oxide-deposited layer / Metal alkoxide-containing layer A-1 / Metal compound-containing layer B in the same manner as in Example 1 except that an Alumina oxide-deposited OPP film was used instead of the Alumina oxide-deposited PET film. -1 / Adhesive / CPP] was manufactured. Alumina oxide-deposited OPP film is a biaxially stretched polypropylene film (FOR, manufactured by Futamura Chemical Co., Ltd., thickness 20 μm), an acrylic coating agent (GAC-013S, manufactured by DIC) and a polyisocyanate-based curing agent (KR-90, DIC). The anchor coating liquid, which can be blended so that the mixing ratio is 5: 1, is applied and dried by the gravure coating method so that the dry film thickness is about 0.05 μm, and then a vacuum vapor deposition apparatus by an electron beam heating method. In, metal aluminum was vapor-deposited and oxygen gas was introduced to form a thin-film vapor-deposited thin film layer made of aluminum oxide having a thickness of 20 nm on the anchor coat layer.
（実施例１０）
　酸化アルミナ蒸着ＰＥＴフィルムの代わりに、アルミ蒸着ＰＥＴフィルム（ＶＭ－ＰＥＴ１３１０、東レフィルム加工製）を用いた以外は、実施例１と同様にして積層体［ＰＥＴ／アルミ蒸着層／金属アルコキシド含有層Ａ―１／金属化合物含有層Ｂ－１／接着剤／ＣＰＰ］を製造した。 (Example 10)
A laminate [PET / aluminum-deposited layer / metal alkoxide-containing layer A] in the same manner as in Example 1 except that an aluminum-deposited PET film (VM-PET1310, manufactured by Toray Film Processing Co., Ltd.) was used instead of the alumina oxide-deposited PET film. -1 / Metal compound-containing layer B-1 / Adhesive / CPP] was produced.
（実施例１１）
酸化アルミナ蒸着ＰＥＴフィルムの代わりに、シリカ蒸着ＰＥＴフィルム（テックバリアＬ、三菱ケミカル製）を用いた以外は、実施例１と同様にして積層体［ＰＥＴ／シリカ蒸着層／金属アルコキシド含有層Ａ―１／金属化合物含有層Ｂ－１／接着剤／ＣＰＰ］を製造した。 (Example 11)
A laminate [PET / silica-film-deposited layer / metal alkoxide-containing layer A-] in the same manner as in Example 1 except that a silica-deposited PET film (Techbarrier L, manufactured by Mitsubishi Chemical Co., Ltd.) was used instead of the alumina oxide-deposited PET film. 1 / Metal compound-containing layer B-1 / Adhesive / CPP] was produced.
（実施例１２）
酸化アルミナ蒸着ＰＥＴフィルムの代わりに、ＰＥＴフィルム（Ｅ５１０２、東洋紡製）を用いた以外は、実施例１と同様にして積層体［ＰＥＴ／金属アルコキシド含有層Ａ―１／金属化合物含有層Ｂ－１／接着剤／ＣＰＰ］を製造した。 (Example 12)
A laminate [PET / metal alkoxide-containing layer A-1 / metal compound-containing layer B-1] in the same manner as in Example 1 except that a PET film (E5102, manufactured by Toyobo) was used instead of the alumina oxide-deposited PET film. / Adhesive / CPP] was manufactured.
（実施例１３）
金属化合物含有コーティング液ｂ－１と金属アルコキシド含有コーティング液ａ－１の塗装順を逆にした以外は、実施例１と同様にして積層体［ＰＥＴ／酸化アルミナ蒸着層／金属化合物含有層Ｂ－１／金属アルコキシド含有層Ａ―１／接着剤／ＣＰＰ］を製造した。 (Example 13)
The laminate [PET / alumina oxide vapor deposition layer / metal compound-containing layer B-] is the same as in Example 1 except that the coating order of the metal compound-containing coating liquid b-1 and the metal alkoxide-containing coating liquid a-1 is reversed. 1 / Metal alkoxide-containing layer A-1 / Adhesive / CPP] was produced.
（実施例１４）
金属アルコキシド含有コーティング液ａ－１の塗装において、乾燥膜厚を０．１μｍとした以外は、実施例１と同様にして積層体［ＰＥＴ／酸化アルミナ蒸着層／金属アルコキシド含有層Ａ―１／金属化合物含有層Ｂ－１／接着剤／ＣＰＰ］を製造した。 (Example 14)
In the coating of the metal alkoxide-containing coating liquid a-1, the laminate [PET / alumina oxide vapor-deposited layer / metal alkoxide-containing layer A-1 / metal is the same as in Example 1 except that the dry film thickness is 0.1 μm. Compound-containing layer B-1 / adhesive / CPP] was produced.
（実施例１５）
金属アルコキシド含有コーティング液ａ－１の塗装において、乾燥膜厚を１．０μｍとした以外は、実施例１と同様にして積層体［ＰＥＴ／酸化アルミナ蒸着層／金属アルコキシド含有層Ａ―１／金属化合物含有層Ｂ－１／接着剤／ＣＰＰ］を製造した。 (Example 15)
In the coating of the metal alkoxide-containing coating liquid a-1, the laminate [PET / alumina oxide vapor-deposited layer / metal alkoxide-containing layer A-1 / metal is the same as in Example 1 except that the dry film thickness is 1.0 μm. Compound-containing layer B-1 / adhesive / CPP] was produced.
（実施例１６）
金属化合物含有コーティング液ｂ－１の塗装において、乾燥膜厚を０．１μｍとした以外は、実施例１と同様にして積層体［ＰＥＴ／酸化アルミナ蒸着層／金属アルコキシド含有層Ａ―１／金属化合物含有層Ｂ－１／接着剤／ＣＰＰ］を製造した。 (Example 16)
In the coating of the metal compound-containing coating liquid b-1, the laminate [PET / alumina oxide vapor-deposited layer / metal alkoxide-containing layer A-1 / metal is the same as in Example 1 except that the dry film thickness is 0.1 μm. Compound-containing layer B-1 / adhesive / CPP] was produced.
（実施例１７）
金属化合物含有コーティング液ｂ－１の塗装において、乾燥膜厚を１．０μｍとした以外は、実施例１と同様にして積層体［ＰＥＴ／酸化アルミナ蒸着層／金属アルコキシド含有層Ａ―１／金属化合物含有層Ｂ－１／接着剤／ＣＰＰ］を製造した。 (Example 17)
In the coating of the metal compound-containing coating liquid b-1, the laminate [PET / alumina oxide vapor-deposited layer / metal alkoxide-containing layer A-1 / metal is the same as in Example 1 except that the dry film thickness is 1.0 μm. Compound-containing layer B-1 / adhesive / CPP] was produced.
（比較例１）
　金属化合物含有層Ｂを省略した以外は実施例１と同様にして積層体［ＰＥＴ／酸化アルミナ蒸着層／金属アルコキシド含有層Ａ－１／接着剤／ＣＰＰ］を製造した。 (Comparative Example 1)
A laminate [PET / alumina oxide vapor deposition layer / metal alkoxide-containing layer A-1 / adhesive / CPP] was produced in the same manner as in Example 1 except that the metal compound-containing layer B was omitted.
（比較例２）
金属化合物含有コーティング剤ｂ－１の代わりに金属化合物非含有コーティング剤ｂ－７を用い、実施例１と同様にして積層体［ＰＥＴ／酸化アルミナ蒸着層／金属アルコキシド含有層Ａ―１／金属化合物非含有層Ｂ－７／接着剤／ＣＰＰ］を得た。 (Comparative Example 2)
A metal compound-free coating agent b-7 was used instead of the metal compound-containing coating agent b-1, and the laminate [PET / alumina oxide vapor deposition layer / metal alkoxide-containing layer A-1 / metal compound was used in the same manner as in Example 1. Free layer B-7 / adhesive / CPP] was obtained.
（比較例3）
金属アルコキシド含有層Aを省略した以外は実施例１と同様にして積層体［ＰＥＴ／酸化アルミナ蒸着層／金属化合物含有層B―１／接着剤／ＣＰＰ］を製造した。 (Comparative example 3)
A laminate [PET / alumina oxide vapor deposition layer / metal compound-containing layer B-1 / adhesive / CPP] was produced in the same manner as in Example 1 except that the metal alkoxide-containing layer A was omitted.
（比較例４）
金属アルコキシド含有コーティング液ａ－１の代わりに、金属アルコキシド非含有コーティング液а―４を用いた以外は、実施例１と同様にして積層体［ＰＥＴ／酸化アルミナ蒸着層／金属アルコキシド非含有層Ａ―４／金属化合物含有層Ｂ－１／接着剤／ＣＰＰ］を製造した。 (Comparative Example 4)
The laminate [PET / alumina oxide vapor deposition layer / metal alkoxide-free layer A] is the same as in Example 1 except that the metal alkoxide-free coating liquid а-4 is used instead of the metal alkoxide-containing coating liquid a-1. -4 / Metal compound-containing layer B-1 / Adhesive / CPP] was produced.
（比較例５）
金属アルコキシド含有コーティング液ａ－１の塗装において、乾燥膜厚を０．０５μｍとした以外は、実施例１と同様にして積層体［ＰＥＴ／酸化アルミナ蒸着層／金属アルコキシド含有層Ａ―１／金属化合物含有層Ｂ－１／接着剤／ＣＰＰ］を製造した。 (Comparative Example 5)
In the coating of the metal alkoxide-containing coating liquid a-1, the laminate [PET / alumina oxide vapor-deposited layer / metal alkoxide-containing layer A-1 / metal is the same as in Example 1 except that the dry film thickness is 0.05 μm. Compound-containing layer B-1 / adhesive / CPP] was produced.
（比較例６）
金属アルコキシド含有コーティング液ａ－１の塗装において、乾燥膜厚を２．０μｍとした以外は、実施例１と同様にして積層体［ＰＥＴ／酸化アルミナ蒸着層／金属アルコキシド含有層Ａ―１／金属化合物含有層Ｂ－１／接着剤／ＣＰＰ］を製造した。 (Comparative Example 6)
In the coating of the metal alkoxide-containing coating liquid a-1, the laminate [PET / alumina oxide vapor-deposited layer / metal alkoxide-containing layer A-1 / metal is the same as in Example 1 except that the dry film thickness is 2.0 μm. Compound-containing layer B-1 / adhesive / CPP] was produced.
（比較例７）
金属化合物含有コーティング液ｂ－１の塗装において、乾燥膜厚を０．０５μｍとした以外は、実施例１と同様にして積層体［ＰＥＴ／酸化アルミナ蒸着層／金属アルコキシド含有層Ａ―１／金属化合物含有層Ｂ－１／接着剤／ＣＰＰ］を製造した。 (Comparative Example 7)
In the coating of the metal compound-containing coating liquid b-1, the laminate [PET / alumina oxide vapor-deposited layer / metal alkoxide-containing layer A-1 / metal is the same as in Example 1 except that the dry film thickness is 0.05 μm. Compound-containing layer B-1 / adhesive / CPP] was produced.
（比較例８）
金属化合物含有コーティング液ｂ－１の塗装において、乾燥膜厚を２．０μｍとした以外は、実施例１と同様にして積層体［ＰＥＴ／酸化アルミナ蒸着層／金属アルコキシド含有層Ａ―１／金属化合物含有層Ｂ－１／接着剤／ＣＰＰ］を製造した。 (Comparative Example 8)
In the coating of the metal compound-containing coating liquid b-1, the laminate [PET / alumina oxide vapor-deposited layer / metal alkoxide-containing layer A-1 / metal is the same as in Example 1 except that the dry film thickness is 2.0 μm. Compound-containing layer B-1 / adhesive / CPP] was produced.
（比較例９）
酸化アルミナ蒸着ＰＥＴフィルムの代わりに、ＰＥＴフィルムを用い、また金属化合物含有層Ｂ－１を省略した以外は、実施例１と同様にして積層体［ＰＥＴ／金属アルコキシド含有層Ａ―１／接着剤／ＣＰＰ］を製造した。 (Comparative Example 9)
A laminate [PET / metal alkoxide-containing layer A-1 / adhesive] is used in the same manner as in Example 1 except that a PET film is used instead of the alumina oxide-deposited PET film and the metal compound-containing layer B-1 is omitted. / CPP] was manufactured.
＜評価＞
（酸素バリア性）
エージングが終了した積層体を１０ｃｍ×１０ｃｍのサイズに調整し、ＯＸ－ＴＲＡＮ２／２１（モコン社製：酸素透過率測定装置）を用い、ＪＩＳ－Ｋ７１２６（等圧法）に準じ、２３℃０％ＲＨの雰囲気下で酸素透過率を測定した（単位はｃｃ／ｍ２・ｄａｙ・ａｔｍ）。なおＲＨとは、湿度を表す。 <Evaluation>
(Oxygen barrier property)
Adjust the aging-finished laminate to a size of 10 cm x 10 cm, use OX-TRAN2 / 21 (Made by Mocon: oxygen permeability measuring device), and follow JIS-K7126 (isopressure method) at 23 ° C. 0% RH. Oxygen permeability was measured under the atmosphere of (unit: cc / m2 · day · atm). Note that RH represents humidity.
＜評価＞
（レトルト処理後酸素バリア性）
　エージングが終了した積層体を用いて、３辺をシール部とする縦２１０ｍｍ×横１５０ｍｍの大きさのパウチを作製し、内容物として水を充填した。その後、１２１℃、３０分間レトルト殺菌処理を行い、上記酸素バリア性の測定方法に従いレトルト殺菌処理後の酸素透過率を測定した。 <Evaluation>
(Oxygen barrier property after retort treatment)
Using the laminated body after aging, a pouch having a size of 210 mm in length × 150 mm in width having three sides as a sealing portion was prepared and filled with water as a content. Then, the retort sterilization treatment was performed at 121 ° C. for 30 minutes, and the oxygen permeability after the retort sterilization treatment was measured according to the above-mentioned oxygen barrier property measuring method.
＜評価＞
（フィルム透明性）
エージングが終了した積層体を１０ｃｍ×１０ｃｍのサイズに調整し、ヘーズメーターＮＤＨ５０００（日本電色製）を用い、ＪＩＳ－Ｋ７１３６に準じ、ヘイズを測定した（単位は％）。結果を以下の３段階で評価した。
〇：６未満
△：６以上１０未満
×：１０以上 <Evaluation>
(Film transparency)
The aging-finished laminate was adjusted to a size of 10 cm × 10 cm, and haze was measured using a haze meter NDH5000 (manufactured by Nippon Denshoku) according to JIS-K7136 (unit:%). The results were evaluated in the following three stages.
〇: Less than 6 △: 6 or more and less than 10 ×: 10 or more
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
表１～５より明らかなように、金属アルコキシド含有層と金属化合物含有層の組み合わせによってレトルト処理後のバリア性の劣化の少ないバリア積層体を得ることができた。 As is clear from Tables 1 to 5, a barrier laminate with less deterioration of the barrier property after the retort treatment could be obtained by the combination of the metal alkoxide-containing layer and the metal compound-containing layer.

Claims (8)

  1. 　ガスバリア性積層体であって、基材の少なくとも一面に、
    　金属アルコキシド（Ａ）含有層と、金属化合物（Ｂ）含有層から形成されていることを特徴とするガスバリア性積層体。     A gas barrier laminate, on at least one surface of the substrate,
    A gas barrier laminate characterized by being formed of a metal alkoxide (A) -containing layer and a metal compound (B) -containing layer.
  2. 　前記金属化合物（Ｂ）が亜鉛、カルシウム、マグネシウム、チタンから選択される一種以上を含む化合物であることを特徴とする請求項１に記載のガスバリア性積層体。 The gas barrier laminate according to claim 1, wherein the metal compound (B) is a compound containing at least one selected from zinc, calcium, magnesium, and titanium.
  3. 　前記金属化合物（Ｂ）が金属酸化物であることを特徴とする請求項１または２に記載のガスバリア性積層体。 The gas barrier laminate according to claim 1 or 2, wherein the metal compound (B) is a metal oxide.
  4. 　前記金属アルコキシド（Ａ）がアルコキシシランから選択される一種以上であることを特徴とする請求項１～３のいずれか一項に記載のガスバリア性積層体。 The gas barrier laminate according to any one of claims 1 to 3, wherein the metal alkoxide (A) is one or more selected from alkoxysilanes.
  5. 　前記金属化合物（Ｂ）の平均粒子径が0.2μｍ以下であることを特徴とする請求項１～４のいずれか一項に記載のガスバリア性積層体。 The gas barrier laminate according to any one of claims 1 to 4, wherein the metal compound (B) has an average particle size of 0.2 μm or less.
  6. 　前記基材が、蒸着処理された基材であることを特徴とする請求項１～５のいずれか一項に記載のガスバリア性積層体。 The gas barrier laminate according to any one of claims 1 to 5, wherein the substrate is a vapor-deposited substrate.
  7. 　ガスバリア性積層体であって、基材の少なくとも一面に、
    　金属アルコキシド（Ａ）含有層と、金属化合物（Ｂ）含有層が順次形成されていることを特徴とする請求項１～６のいずれか一項に記載のガスバリア性積層体。     A gas barrier laminate, on at least one surface of the substrate,
    The gas barrier laminate according to any one of claims 1 to 6, wherein the metal alkoxide (A) -containing layer and the metal compound (B) -containing layer are sequentially formed.
  8. 請求項１～７のいずれか一項に記載のガスバリア性積層体を用いてなる包装体。 A package using the gas barrier laminate according to any one of claims 1 to 7.
PCT/JP2021/046418 2020-12-22 2021-12-16 Gas barrier laminate and packaging material WO2022138417A1 (en)

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JP2019209645A (en) * 2018-06-07 2019-12-12 大日本印刷株式会社 Barrier film and packaging material
JP2020040254A (en) * 2018-09-07 2020-03-19 大日本印刷株式会社 Laminate for packaging material and packaging material
JP2020114631A (en) * 2019-01-17 2020-07-30 凸版印刷株式会社 Gas barrier laminate and package comprising the same

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JP2019209645A (en) * 2018-06-07 2019-12-12 大日本印刷株式会社 Barrier film and packaging material
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