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
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
• • 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
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
  • C09D129/02—Homopolymers or copolymers of unsaturated alcohols
  • C09D129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/60—Additives non-macromolecular
  • C09D7/63—Additives non-macromolecular organic

Definitions

• the present invention relates to a coating agent, a laminate obtained by using the coating agent, and a packaging material.
• Gas barrier materials are used in various fields for the purpose of preventing the intrusion of gases such as moisture and oxygen from the outside air.
• packaging materials used for packaging foods and beverages are externally used to protect the contents from various distributions, storage such as refrigeration, heat sterilization, etc., and to suppress oxidation for the purpose of long-term storage of foods. It is required to have an oxygen barrier property to prevent the invasion of oxygen from the body, a carbon dioxide barrier property, and a barrier property to various aroma components.
• solar cells, various displays such as liquid crystals, organic or inorganic electroluminescence (hereinafter referred to as "EL"), and electronic devices such as electronic paper protect their internal structures and absorb oxygen and water vapor from the outside.
• EL organic or inorganic electroluminescence
• a glass substrate is generally used as a sealing material for blocking, but the use of a transparent gas barrier film based on a plastic film is being considered for the purpose of making it thinner, lighter, or providing a flexible product. be. (See, for example, Patent Documents 1 and 2).
• Patent Document 3 As a means for imparting gas barrier properties to a plastic film, a method of applying and using a coating agent using polyvinyl alcohol, ethylene vinyl alcohol, or the like is known (Patent Document 3).
• the present invention has been made to solve at least a part of such a problem, and is a gas barrier coating agent having excellent adhesion to an olefin-based substrate, a laminate obtained by using the coating agent, and the like.
• the purpose is to provide packaging materials.
• the coating agent of the present invention contains a resin (A) and an aqueous solvent (B), and the resin contains a vinyl alcohol polymer (A1) and a polyalkyleneimine (A2) as essential components.
• A1 vinyl alcohol polymer
• A2 polyalkyleneimine
• Vinyl alcohol polymer (A1)) As the vinyl alcohol-based polymer (A1), a homopolymer of the vinyl ester (a1) or a hydrolyzate of the copolymer (A1-1), which is obtained by a known and commonly used method, can be used.
• the vinyl alcohol-based polymer (A1) is a reaction product (A1-2) of a hydrolyzate of a homopolymer or copolymer of vinyl ester (a1) and an aldehyde, and is obtained by a known and commonly used method. What is obtained can be used.
• Examples of the vinyl ester (a1) include vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl versatic acid, vinyl caproate, vinyl caprylate, vinyl laurate, vinyl palmitate, and stea.
• Examples thereof include vinyl acetate, vinyl oleate, vinyl benzoate and the like, and one type or a combination of two or more types can be used. It is preferable to use vinyl acetate.
• Examples of the polymerizable compound (a2) copolymerizable with the vinyl ester (a1) include ethylene, propene, 1-butene, isobutylene, 1,3-butadiene, isopropenyl acetate, 2-propenyl acetate, styrene, and ⁇ -methylstyrene.
• ethylene, isopropenyl acetate and 2-propenyl acetate are preferably used.
• the amounts used thereof can be adjusted as appropriate, but from the viewpoint of gas barrier properties, the blending amount of the polymerizable compound (a2) is the same as that of the vinyl ester (a1).
• the total amount of the polymerizable compound (a2) is preferably 60 mol% or less, more preferably 25 mol% or less.
• the degree of polymerization of the vinyl ester polymer which is the precursor of the vinyl alcohol polymer (A1-1) or (A-2) is not particularly limited, but is, for example, 500 to 10000, more preferably 800 to 6000, and more. It is preferably 1000 to 3000. This makes it possible to obtain a coating agent having an excellent balance between gas barrier properties and coating suitability.
• Aldehydes used for acetalization include aliphatic aldehydes such as formaldehyde, acetaldehyde, propyl aldehyde, butyl aldehyde, octyl aldehyde and dodecyl aldehyde; alicyclic aldehydes such as cyclohexanecarbaldehyde; benzaldehyde, naphthoaldehyde, anthraaldehyde and phenylacetaldehyde.
• Aromatic aldehydes such as tolualdehyde, dimethylbenzaldehyde, cuminaldehyde, benzylaldehyde; unsaturated aldehydes such as cyclohexene aldehyde, dimethylcyclohexene aldehyde, achlorine; aldehydes having a heterocycle such as furfural, 5-methylfurfural; glucose, glucosamine, etc.
• aldehydes having an amino group such as 4-aminobutylaldehyde, and aliphatic ketones such as 2-propanone, methylethylketone, 3-pentanone, and 2-hexanone; cyclopentanone, cyclohexanone, etc.
• Aromatic ketones such as an alicyclic ketone, acetophenone, and benzophenone can be used alone or in combination of two or more.
• organic acids and inorganic acids such as acetic acid, paratoluenesulfonic acid, nitric acid, sulfuric acid, and hydrochloric acid can be used as the acid catalyst used for acetalization.
• the vinyl alcohol-based polymer (A1) include polyvinyl alcohol, ethylene vinyl alcohol, polyvinyl butyral and the like. One type may be used alone, or two or more types may be used in combination. From the viewpoint of the balance between gas barrier property and adhesion, it is more preferable to use either or both of polyvinyl alcohol and ethylene vinyl alcohol in combination.
• the saponification degree is preferably 90% or more, and preferably 95% or more. It may be 100%.
• the degree of saponification can be measured by FTIR, for example, using a Nicolet 5700 FTIR spectrometer controlled by OMNIC software.
• the vinyl alcohol polymer (A1-2) is preferably an acetalized precursor having a saponification degree of 95% or more.
• Polyalkyleneimine (A2) Polyalkyleneimine (A2) is a resin having a polyalkyleneimine skeleton, and is obtained by polymerizing one or more of alkyleneimines (for example, ethyleneimine and propyleneimine) by a conventional method.
• alkyleneimines for example, ethyleneimine and propyleneimine
• the polyalkylene imine (A2) may be a linear polyalkylene imine composed of a linear polyalkylene imine chain or a branched polyalkylene imine having a branched polyalkylene imine chain.
• Examples of the polyalkyleneimine (A2) include polyethyleneimine and polypropyleneimine.
• the polyalkyleneimine (A2) may have a substituent (for example, a hydroxypropyl group or a hydroxyethyl group) introduced into at least a part of the nitrogen atom of the polyalkyleneimine chain.
• Those modified with an organic metal compound such as lenglycolate, titanium ethylacetacetate, titanium lactate, titanium triethanolaminate, and titanium stearate may be used, or two or more kinds of polyalkyleneimines may be used in combination. ..
• the polyalkyleneimine (A2) contributes to the improvement of the adhesion between the vinyl alcohol polymer (A1) and the olefin film by the amino group (NHR group, NH 2 group) and the ethylene group, and the adhesion is improved.
• the polyalkyleneimine (A2) preferably contains a branched polyalkyleneimine because it is effective for improvement.
• the degree of branching of the polyalkyleneimine (A2) can be expressed by the ratio of the primary, secondary and tertiary amino groups of the polyalkyleneimine (A2).
• the ratio of the primary amino group is 20 to 40%
• the ratio of the secondary amino group is 30 to 60%
• the ratio of the tertiary amino group is 30 to 60%.
• polyalkyleneimine (A2) having a ratio of 20 to 35%.
• the proportion of primary, secondary and tertiary amine groups contained in polyalkyleneimine (A2) can be measured by 13 C-NMR spectroscopy.
• the branched polyalkyleneimine is preferably branched polyethyleneimine.
• the number average molecular weight of polyalkyleneimine (A2) is preferably 5,000 or more, more preferably 9,000 or more, and even more preferably 50,000 or more because of its excellent adhesion.
• the upper limit is not particularly limited, but is 100,000 or less as an example.
• the number average molecular weight of polyalkyleneimine (A2) was measured by a GPC (gel permeation chromatography) method using pullulan as a standard substance.
• the blending amount of the polyalkylimine (A2) is preferably 1% by mass or more and 90% by mass or less of the total amount of the vinyl alcohol polymer (A1) and the polyalkylimine (A2). .. This makes it possible to more reliably improve the adhesion to the olefin-based substrate while maintaining the gas barrier property of the coating agent of the present invention. More preferably, it is 10% by mass or more and 50% by mass or less.
• the coating agent of the present invention does not contain polyalkyleneimine (A2), the adhesion to the olefin-based substrate is insufficient.
• the vinyl alcohol polymer (A1) is not contained (when the resin (A) is composed of only polyalkyleneimine (A2)), the coating film is sticky and is not suitable for post-processing.
• the coating agent of the present invention may contain a resin (A3) other than the vinyl alcohol polymer (A1) and the polyalkylimine (A2).
• a resin (A3) include cellulose resins, polyesters, polyurethanes, vinyl resins such as homopolymers or copolymers of olefins and styrenes, acrylic resins, epoxy resins, amide resins, natural rubbers, and composites thereof.
• a body for example, a core / shell type resin
• one type or a combination of two or more types can be used. If the amount of the resin (A3) is too large, the gas barrier property may be deteriorated.
• the amount of the resin (A3) is the resin (A) (vinyl alcohol polymer (A1), polyalkylimine (A2), It is preferable to keep it at 10% by mass or less of the total amount of the resin (A3). It is more preferably 5% by mass or less, and more preferably 1% by mass or less. It may be 0% by mass.
• the blending amount of the resin (A) in the coating agent of the present invention can be appropriately adjusted depending on the coating suitability and the like.
• aqueous solvent (B) As the aqueous solvent (B), water, a water-soluble organic solvent soluble in water, or the like can be used. As the water, pure water such as ion-exchanged water, ultra-filtered water, reverse osmosis water, distilled water, or ultrapure water can be used. Since the growth of mold or bacteria can be prevented, it is preferable to use water sterilized by irradiation with ultraviolet rays or addition of hydrogen peroxide from the viewpoint of long-term storage.
• water-soluble organic solvent examples include glycols such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, polyethylene glycol and polypropylene glycol; diols such as butanediol, pentandiol and hexanediol; propylene laurate.
• glycols such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, polyethylene glycol and polypropylene glycol
• diols such as butanediol, pentandiol and hexanediol
• propylene laurate examples of the water-soluble organic solvent
• Glycol esters such as glycols; diethylene glycol ethers such as diethylene glycol monoethyl, diethylene glycol monobutyl, diethylene glycol monohexyl, carbitol; glycol ethers such as cellosolve containing propylene glycol ethers, dipropylene glycol ethers, and triethylene glycol ethers; methanol , Ethanol, isopropyl alcohol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, butyl alcohol, pentyl alcohol and other alcohols; sulfolane, ester, ketone, ⁇ -butyrolactone and other lactones, N- (2) -Hydroxyethyl) Lactates such as pyrrolidone, various other solvents known as aqueous organic solvents such as glycerin and its polyalkylene oxide adducts and the like can be mentioned. These aqueous organic solvents can
• the coating agent of the present invention may further contain an additive (C) in addition to the resin (A) and the aqueous solvent (B).
• the additive (C) includes a layered inorganic compound, a cross-linking agent capable of reacting with a functional group of a vinyl alcohol polymer (A1) or a polyalkylimine (A2), an inorganic filler, an antifoaming agent, and a stabilizer (oxidation).
• a cross-linking agent capable of reacting with a functional group of a vinyl alcohol polymer (A1) or a polyalkylimine (A2)
• an inorganic filler an antifoaming agent
• an antifoaming agent an antifoaming agent
• stabilizer oxidation
• the layered inorganic compound examples include natural smectite, synthetic smectite, natural mica, synthetic mica, hydrotalcite and talc represented by montmorillonite and the like, and lipophilic treated smectite and lipophilic synthetic mica obtained by organically treating them.
• the blending amount of the layered inorganic compound is preferably 10 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the resin (A) because of the excellent balance between gas barrier property and adhesion.
• cross-linking agent examples include aldehydes such as formalin and glutal aldehyde; acetals such as diacetal compounds of glutal aldehyde; aliphatic polyisocyanates typified by hexamethylene diisocyanate and its derivatives (adduct, nurate, buretto, etc.).
• aldehydes such as formalin and glutal aldehyde
• acetals such as diacetal compounds of glutal aldehyde
• aliphatic polyisocyanates typified by hexamethylene diisocyanate and its derivatives (adduct, nurate, buretto, etc.).
• Aromatic aliphatic polyisocyanates represented by xylylene diisocyanates and their derivatives aromatic polyisocyanates represented by toluene diisocyanates and their derivatives
• isocyanates such as urethane prepolymers which are reaction products of these isocyanates and polyols
• Organic metal compounds such as titanium, silica, aluminum, zirconium, boron and alkoxide; Methylol ureas such as methylol urea and methylol melamine; carboxyl group-containing polymers such as polyacrylic acid-based polymers and maleic anhydride-based polymers.
• Carbodiimides such as p-phenylene-bis (2,6-xylylcarbodiimide), tetramethylene-bis (t-butylcarbodiimide), cyclohexane-1,4-bis (methylene-t-butylcarbodiimide; boric acid;
• Examples of the isocyanates include titanium lactate and the like. As the isocyanates, a blocked isocyanate using a known blocking agent may be used, or an emulsion type isocyanate may be used.
• the blending amount of the cross-linking agent is preferably 5 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the resin (A) because of the excellent balance between gas barrier property and adhesion.
• the laminate of the present invention is obtained by applying the coating agent of the present invention to a substrate and drying it.
• the dry coating film of the coating agent of the present invention is also simply referred to as a gas barrier coat layer.
• the base material to which the coating agent of the present invention can be applied is not particularly limited, and polyethylene terephthalate (PET) film, polystyrene film, polyamide film, polyacrylonitrile film, polyethylene film (OPE: biaxially stretched polyethylene film, LLDPE: low density).
• Polyethylene film HDPE: high-density polyethylene film
• polyolefin film such as polypropylene film (CPP: unstretched polypropylene film, OPP: biaxially stretched polypropylene film)
• polyvinyl alcohol film ethylene-vinyl alcohol copolymer film and the like can be mentioned. ..
• a film in which a metal such as aluminum or an inorganic vapor deposition layer such as a metal oxide such as silica or alumina is laminated on these films.
• a metal such as aluminum or an inorganic vapor deposition layer such as a metal oxide such as silica or alumina
• the coating agent of the present invention has excellent adhesion to these substrates including a polyolefin film, and can improve the gas barrier property of the substrate and the aroma retention property of various scent components.
• the method for applying the coating agent of the present invention is not particularly limited, and is 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, a curtain coat method, a slit coat method, and a screen.
• a printing method, an inkjet method, a dispense method, a die coating (die coating) method, a direct gravure method, a reverse gravure method, a flexographic method, a knife coating method, a dot coating method and the like can be used. It was
• the film thickness of the gas barrier coat layer can be appropriately adjusted depending on the type of the base material and the degree of the desired gas barrier property, but as an example, it is 0.2 ⁇ m or more and 2.0 ⁇ m or less. If the film thickness is too thin, the gas barrier property cannot be expected to be improved so much, and if the film thickness is too thick, the adhesion may be deteriorated.
• the laminate having the gas barrier coat layer may be laminated by an extrusion method on the laminate having the gas barrier coat layer.
• the other base material the same ones as those described above can be used.
• the adhesive for example, a two-component curable urethane-based solvent-based adhesive or a solvent-free adhesive, which is usually used for adhering a film, can be used. It is preferable to use an adhesive having an aromatic ring concentration of 0.5 mm Cincinnatil / g or more and 7.0 mm Cincinnatil / g or less in the cured coating film, and 3.5 mm Albanyl / g or more because it is a laminated body having excellent gas barrier properties. It is more preferable to use one having a concentration of 7.0 mmschreibl / g or less.
• the aromatic ring concentration of the adhesive is the total equivalent (Y) of the monomers having an aromatic ring to the total equivalent (X) of the monomers used in the synthesis of the polyol composition and the polyisocyanate composition to be blended in the adhesive. It is a value divided by the total solid content mass (Z) of.
• Z total solid content mass
• the monomer (y) is used when calculating the total equivalent of the monomers (Y). Equivalent to x times.
• the adhesive 1 used in the examples described later is a mixture of the polyol composition 1 and the polyisocyanate composition 1 so that the solid content mass ratio is 1: 1. Therefore, the aromatic ring concentration is 2.2 mm Albanyl / g according to the following formula.
• the laminate of the present invention may further have a print layer.
• the print layer is formed at an arbitrary position on the laminate by various printing inks such as gravure ink, flexo ink, offset ink, stencil ink, and inkjet ink by a general printing method conventionally used for printing on a polymer film.
• Ink may be a one-component type or a two-component type used in combination with a curing agent such as isocyanate.
• an OPP film or an OPE film can be used as the base material of the constituent examples (1) to (4), and a polyamide film such as PET film or nylon can be used. It can also be used.
• An LLDPE film or CPP film can be used as the sealant layer, and an aluminum-deposited LLDPE film or an aluminum-deposited CPP film can be used as the sealant layer having an inorganic-deposited layer.
• the configurations as shown in (5) and (6) are also preferable.
• the base material having an inorganic thin-film layer in the configuration (5) include an OPP film having an alumina-deposited layer.
• the base material having the inorganic thin-film layer in the configuration (6) include an aluminum-deposited OPP film.
• the packaging material of the present invention is obtained by using the laminate of the present invention, laminating the surfaces of the sealant films of the laminate facing each other, and then heat-sealing the peripheral ends thereof.
• the laminate 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.
• 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.
• the contents to be filled include rice confectionery, bean confectionery, nuts, biscuits and cookies, wafer confectionery, marshmallows, pies, half-baked cakes, candy, snack confectionery and other confectionery, bread, snack noodles, instant noodles, dried noodles, pasta.
• the packaging material of the present invention can also be used as a packaging material for pharmaceuticals such as cigarettes, disposable body warmers, infusion packs, cosmetics, and vacuum heat insulating materials.
• Example 1-20 A vinyl alcohol-based polymer (A1) and ion-exchanged water are charged in a reaction vessel equipped with a stirrer, a nitrogen gas introduction pipe, and a reflux cooling pipe, gradually heated to 90 ° C., and stirred for 4 hours to produce vinyl alcohol-based weight. After the coalescence (A) was dissolved, the mixture was cooled to room temperature to obtain an aqueous solution of the vinyl alcohol polymer (A1). An aqueous solution of polyalkyleneimine (A2), water, and isopropanol were added thereto so that the solid content of the resin (A) was 5% by mass and the water / IPA was 7/3, and the coating agent of Example 1-14 was added. Got The compounding ratios (solid content) of the vinyl alcohol polymer (A1) and the polyalkyleneimine (A2) in Examples 1-20 are as shown in Table 1-4.
• Comparative Example 1-3 The coating agents of Comparative Examples 1 and 2 were obtained in the same manner as in Examples except that polyalkyleneimine (A2) was not used.
• the coating agent of Comparative Example 3 was obtained in the same manner as in Example except that the vinyl alcohol polymer (A1) was not used.
• the vinyl alcohol-based polymer (A1) and polyalkyleneimine (A2) used in Examples and Comparative Examples are as follows.
• (Vinyl alcohol polymer (A1-1)) Polyvinyl alcohol, degree of polymerization: 2400, degree of saponification: 98% or more (vinyl alcohol-based polymer (A1-2))
• (Vinyl alcohol polymer (A1-4)) Excelval AQ-4104 (manufactured by Kuraray Co., Ltd.) was used.
• Adhesive 1 Preparation of Polyol Composition 1 25.0 parts of Coronate T-80 (Tosoh Corporation, 80% 2,4-isomer, 20% 2,6-isomer), Actol D-1000 (Mitsui Chemicals, average) A mixture of 35.3 parts of bifunctional polypropylene glycol having a molecular weight of 1000 and 36.1 parts of Actol D-400 (manufactured by the same company, bifunctional polypropylene glycol having an average molecular weight of 400) is heated to 100 ° C. and stirred for 4 hours to react. gone. At this time, the NCO content was 1.6%.
• the stirring was stopped, 42.9 parts of ethyl acetate was added thereto, and the stirring was started again to dissolve the mixture, and the temperature was lowered to 50 ° C. 3.6 parts of diethanolamine was added thereto, the temperature was raised to 75 ° C. using heat generation, and the temperature was maintained for 2 hours.
• the solid content hydroxyl value was 37.4 (mgKOH / g), and the non-volatile content was 70.7%.
• the polyol composition 1 and the polyisocyanate composition 1 prepared above were blended so that the solid content mass ratio was 1: 1 and diluted with ethyl acetate to prepare the adhesive 1.
• the aromatic ring concentration of the adhesive 1 is 2.2 mm réellel / g.
• Adhesive 2 Preparation of Polyol Composition 2
• a polyester reaction vessel equipped with a stirrer, a nitrogen gas introduction tube, a snyder tube, and a condenser
• 879.37 parts of ethylene glycol, 1580.52 parts of phthalic anhydride, and 0.10 parts of titanium tetraisopropoxide were charged and rectified.
• the internal temperature was maintained at 200 ° C. by gradually heating so that the temperature of the upper part of the tube did not exceed 100 ° C.
• the polyol composition 2 and the polyisocyanate composition 2 prepared above were blended so that the solid content mass ratio was 1: 1 and diluted with ethyl acetate to prepare the adhesive 2.
• the aromatic ring concentration of the adhesive 2 is 4.5 mm réellel / g.
• Example 1-17 Comparative Example 1-3
• the coating agent prepared in Examples and Comparative Examples was applied onto an OPP film (manufactured by Toyobo Co., Ltd., P2161) and dried in a hot air dryer set at 80 ° C. for 1 minute to form a gas barrier coat layer.
• the adhesive 1 or 2 was applied onto the barrier coat layer, the diluting solvent was volatilized by a dryer set at a temperature of 50 ° C., and then the adhesive 1 or 2 was bonded to a CPP film (manufactured by Toyobo Co., Ltd., P1128). Aging was performed at 40 ° C. for 3 days to obtain a laminate for evaluation (Structure Example 1: OPP film / gas barrier coat layer / adhesive layer / CPP film).
• the film thickness of the gas barrier coat layer is as shown in Table 1-4.
• the amount of the adhesive applied is 2.5 g / m 2 (solid content).
• 10 parts by mass of water-dispersed polyisocyanate Duranate WB40-100, manufactured by Asahi Kasei Corporation
• a gas barrier was prepared by blending 10 parts by mass of a filler (Kunipia-F, manufactured by Kunimine Kogyo Co., Ltd.) with 100 parts by mass of the solid content of the vinyl alcohol polymer (A1) and the polyalkyleneimine (A2).
• a coat layer was formed.
• Example 18 A coating agent prepared according to the formulation shown in Table 4 is applied onto an MDOPE film (Hybron PE25 manufactured by Tokyo Ink Co., Ltd.) having a film thickness of 25 ⁇ m, and dried in a hot air dryer set at 80 ° C. for 1 minute to form a gas barrier coat layer. Was formed. Subsequently, the adhesive 1 was applied onto the barrier coat layer, the diluting solvent was volatilized by a dryer set at a temperature of 50 ° C., and then an LLDPE film having a thickness of 60 ⁇ m (manufactured by Mitsui Chemicals Tocello Co., Ltd., TUX- It was pasted together with HC). Aging was performed at 40 ° C. for 3 days to obtain a laminate for evaluation (Structure Example 2: MDOPE film / gas barrier coat layer / adhesive layer / LLDPE film).
• Example 20 A coating agent prepared according to the formulation shown in Table 4 was applied onto a BOPE film having a film thickness of 25 ⁇ m, and dried in a hot air dryer set at 80 ° C. for 1 minute to form a gas barrier coat layer. Subsequently, the adhesive 1 was applied onto the barrier coat layer, the diluting solvent was volatilized by a dryer set at a temperature of 50 ° C., and then an LLDPE film having a thickness of 60 ⁇ m (manufactured by Mitsui Chemicals Tocello Co., Ltd., TUX- It was pasted together with HC). Aging was performed at 40 ° C. for 3 days to obtain a laminate for evaluation (Structure Example 3: BOPE film / gas barrier coat layer / adhesive layer / LLDPE film).
• 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 / m 2 , day, atm). Note that RH represents humidity. The results were evaluated in the following five stages and summarized in Table 1-4. Less than 5: 5 4: 5 or more and less than 10 3: 10 or more and 100 or less 2: 100 or more and less than 300 1: 300 or more
• the coating agent of the present invention has an excellent balance between gas barrier properties and adhesion to an olefin-based substrate.
• the adhesion to the olefin-based substrate was insufficient only with the vinyl alcohol-based polymer (A1) or the polyalkyleneimine (A2).

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