Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
  • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
  • C08J3/05—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from solid polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
  • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
• • 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
• • 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
  • C09D133/00—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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
  • C09D133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
• • 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
  • C09D133/00—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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
  • C09D133/04—Homopolymers or copolymers of esters
  • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
  • C09D133/08—Homopolymers or copolymers of acrylic acid esters
• • 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
  • C09D201/00—Coating compositions based on unspecified macromolecular compounds
  • C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
  • C09D201/06—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
• • 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
  • C09D201/00—Coating compositions based on unspecified macromolecular compounds
  • C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
  • C09D201/06—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
  • C09D201/08—Carboxyl groups
• • 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
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/02—Emulsion paints including aerosols
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D1/00—Processes for applying liquids or other fluent materials
  • B05D1/28—Processes for applying liquids or other fluent materials performed by transfer from the surfaces of elements carrying the liquid or other fluent material, e.g. brushes, pads, rollers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D2201/00—Polymeric substrate or laminate
  • B05D2201/02—Polymeric substrate
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D2252/00—Sheets
  • B05D2252/02—Sheets of indefinite length
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D2502/00—Acrylic polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D2520/00—Water-based dispersions
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
  • B05D3/14—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by electrical means
  • B05D3/141—Plasma treatment
  • B05D3/142—Pretreatment
  • B05D3/144—Pretreatment of polymeric substrates
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
  • B05D7/02—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber
  • B05D7/04—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber to surfaces of films or sheets
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2329/00—Characterised by the use of 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; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
  • C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
  • C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
  • C08J2433/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof

Definitions

• the present invention relates to a coating liquid for forming a gas barrier layer.
• the "gas barrier layer” means a layer used to suppress permeation of gas (for example, oxygen).
• Patent Documents 1 and 2 describe, as a gas barrier layer, a film containing polyvinyl alcohol and poly (meth) acrylic acid.
• the present invention was made in view of such circumstances, and an object thereof is to provide a coating liquid capable of forming a gas barrier layer exhibiting low oxygen permeability under high humidity.
• a coating liquid for forming a gas barrier layer which has a liquid medium containing water, and a resin having at least one functional group selected from the group consisting of a hydroxy group, a carboxy group, an amino group and a sulfo group And a coating liquid having an average particle diameter of 100 to 600 nm.
• the liquid organic medium is at least one selected from the group consisting of monohydric alcohols, glycols, dimethylformamide, dimethylsulfoxide and acetone.
• the monohydric alcohol is at least one selected from the group consisting of methanol, ethanol, propanol, isopropanol and butanol.
• the coating liquid according to the above [31], wherein the weight average molecular weight of the polyacrylic acid is 400,000 to 2,000,000.
• the coating liquid according to any one of the above [1] to [40], wherein the average particle diameter of the resin is 550 nm or less.
• the coating liquid according to any one of the above [1] to [40], wherein the average particle diameter of the resin is 500 nm or less.
• the coating liquid according to any one of the above [1] to [40], wherein the average particle diameter of the resin is 400 nm or less.
• a coating film used as a gas barrier layer which is formed from the coating liquid according to any one of the above [1] to [43].
• the coating film according to [44] above, wherein the thickness of the coating film after drying is 0.01 to 20 ⁇ m.
• a laminate comprising a substrate and the coating film according to any one of the above [44] to [46] formed on the substrate.
• the coating liquid of the present invention it is possible to form a gas barrier layer (coating film) exhibiting low oxygen permeability under high humidity.
• the liquid medium used in the present invention contains water.
• the liquid medium may consist of water, and may contain a liquid organic medium in addition to water.
• liquid medium means a medium which is liquid at 25 ° C and 1 atm
• liquid organic medium means an organic compound which is liquid at 25 ° C and 1 atm.
• the liquid organic medium may be used alone or in combination of two or more.
• liquid organic medium examples include monohydric alcohols, glycols, dimethylformamide, dimethyl sulfoxide, acetone and the like.
• monohydric alcohols include methanol, ethanol, propanol, isopropanol, butanol and the like.
• the liquid medium preferably comprises water and a monohydric alcohol, more preferably consists of water and a monohydric alcohol.
• the content of monohydric alcohol in the liquid medium is preferably 1 to 50% by weight, more preferably 100% by weight in total of water and monohydric alcohol. Is 5 to 50% by weight, more preferably 10 to 50% by weight.
• the monohydric alcohol is preferably at least one selected from the group consisting of ethanol and isopropanol, more preferably isopropanol.
• the content of the liquid medium is preferably 80 to 99.9% by weight, more preferably 85 to 99.5% by weight, and further preferably 100% by weight of the coating liquid. Is 90 to 99% by weight.
• the coating liquid of the present invention may be abbreviated as a resin having at least one functional group selected from the group consisting of a hydroxy group, a carboxy group, an amino group and a sulfo group (hereinafter abbreviated as "functional resin") )including.
• the amino group may be unsubstituted or substituted by an alkyl group or the like.
• the carboxy group, the amino group and the sulfo group may be in the form of a salt.
• the functional resin may be a homopolymer or a copolymer.
• the copolymer may be any of block copolymer, alternating copolymer, random copolymer, and a combination thereof.
• the resin having at least one functional group selected from the group consisting of a hydroxy group, a carboxy group and an amino group examples include polyvinyl alcohol (PVA), vinylamine-vinyl alcohol copolymer, (meth) acrylic acid-vinyl alcohol Examples thereof include copolymers, ethylene-vinyl alcohol copolymer (EVOH), polyacrylic acid, polymethacrylic acid, polysaccharides, and derivatives thereof.
• PVA polyvinyl alcohol
• EVOH ethylene-vinyl alcohol copolymer
• polyacrylic acid polymethacrylic acid
• polysaccharides polysaccharides
• derivatives thereof As resin which has a sulfo group, in resin which has hydroxy groups, such as polyvinyl alcohol, the derivative obtained by substituting the hydroxy group with a sulfo group etc. are mentioned, for example.
• the content of the functional resin is preferably 0.1 to 20% by weight, more preferably 0.5 to 15% by weight, and further preferably 100% by weight of the coating liquid. Is 1 to 10% by weight.
• the functional resin preferably comprises polyvinyl alcohol.
• the average degree of polymerization of polyvinyl alcohol is preferably 800 to 3,000, more preferably 900 to 2,500, and still more preferably 1,000 to 2,000.
• the saponification degree of polyvinyl alcohol is preferably 80 to 100%, more preferably 90 to 100%, and still more preferably 95 to 100%.
• the average degree of polymerization and the degree of saponification of polyvinyl alcohol can be measured according to JIS K 6726 : 1994 .
• the weight average molecular weight of polyvinyl alcohol is preferably 100,000 to 500,000, more preferably 150,000 to 400,000, still more preferably 170,000 to 300. , 000.
• the weight average molecular weight can be measured by gel permeation chromatography (GPC).
• polyvinyl alcohol When polyvinyl alcohol is used from the viewpoint of low oxygen permeability, film-forming ability and adhesion to a substrate, its content is preferably 0.05 to 10% by weight, per 100% by weight of the coating liquid, It is preferably 0.3 to 8% by weight, more preferably 0.7 to 6% by weight.
• the functional resin preferably comprises polyacrylic acid.
• the weight average molecular weight of polyacrylic acid is preferably 200,000 to 5,000,000, more preferably 300,000 to 3,000,000, and still more preferably 400. , 000 to 2,000,000.
• the weight average molecular weight can be measured by gel permeation chromatography (GPC).
• its content is preferably 0.05 to 10% by weight, more preferably 0. It is 2 to 7% by weight, more preferably 0.3 to 4% by weight.
• the functional resin more preferably comprises polyvinyl alcohol and polyacrylic acid, and still more preferably consists of polyvinyl alcohol and polyacrylic acid.
• the degree of saponification, average degree of polymerization, weight average molecular weight and content of polyvinyl alcohol, and weight average molecular weight and content of polyacrylic acid in this embodiment are as described above.
• the coating liquid of the present invention is characterized in that the average particle diameter of the functional resin is 100 to 600 nm.
• a gas barrier layer coating film having a low oxygen permeability even under high humidity as well as under low humidity It can be formed.
• the average particle size of the functional resin is a value measured as follows. First, the coating solution is diluted with water to prepare a diluted solution having a solid content concentration of 0.1 to 0.01% by weight, and this is used as a measurement sample.
• the solid content concentration means the concentration of components (functional resin and other components described later used as needed) other than the liquid medium (water or water and liquid organic medium) in the diluted solution. Do. Then, based on JIS Z 8828 : 2013 , the harmonic mean particle size is measured based on the scattered light intensity standard of the functional resin in the dilution liquid at 24 ° C. using a particle size measuring apparatus by a dynamic light scattering method. Used as the average particle size of the functional resin in the present invention.
• the average particle size of the functional resin is preferably 110 nm or more, more preferably 120 nm or more.
• the average particle diameter of the functional resin is preferably 550 nm or less, more preferably 500 nm or less, and particularly preferably 400 nm or less.
• the coating liquid of the present invention may contain other components different from the liquid medium and the resin as long as the effects of the present invention (low oxygen permeability under high humidity) are not significantly inhibited.
• examples of other components include inorganic layered compounds, chelate compounds, surfactants and the like. Any other component may be used alone or in combination of two or more.
• Examples of inorganic layered compounds include clay minerals.
• the clay mineral may be only one kind or two or more kinds.
• As the viscosity mineral for example, kaolinite, dickite, nacrite, halloysite, antigorite, chrysotile, pyrophyllite, montmorillonite, beidellite, nontronite, saponite, sauconite, Stephenite, hectorite, tetrasilylic mica, sodium
• the clay mineral may be improved in dispersibility or the like by treatment (for example, treatment with an organic substance, ion exchange, etc.).
• the inorganic layered compound is preferably a smectite clay mineral.
• One smectite clay mineral may be used alone, or two or more smectite clay minerals may be used.
• Examples of smectite clay minerals include montmorillonite, beidellite, nontronite, saponite, sauconite, Stephenite, and hectorite.
• the inorganic layered compound is more preferably montmorillonite.
• the smectite clay mineral (especially montmorillonite) may be improved in dispersibility and the like by treatment (for example, treatment with an organic substance, ion exchange, etc.).
• the average particle size of the inorganic stratiform compound in the coating liquid is preferably 0.02 to 3 ⁇ m, more preferably 0.1 to 2 ⁇ m, and still more preferably 0.2 to 1 ⁇ m.
• the average particle diameter of the inorganic stratiform compound in the coating liquid refers to a coating liquid measured using a laser diffraction / scattering type particle size distribution measuring apparatus (for example, "LA 910” manufactured by Horiba, Ltd.). It means the volume-based median diameter of the inorganic stratiform compound therein.
• the ratio (L / a) of the average particle diameter L of the inorganic layered compound in the above-mentioned coating liquid to the thickness a of the unit crystalline layer of the inorganic layered compound which can be measured by powder X-ray diffraction method is preferably It is 20 to 3,000, more preferably 100 to 2,000, and still more preferably 200 to 1,000.
• the inorganic layered compound means an inorganic compound having a layered crystal structure, and the thickness a of the unit crystal layer of the inorganic layered compound means the thickness of one layer of the crystal structure.
• an inorganic stratiform compound When an inorganic stratiform compound is used, its content is preferably 0.047 to 5% by weight, more preferably 0.05, per 100% by weight of the coating liquid, from the viewpoint of low oxygen permeability and membrane flexibility.
• the content is about 4.5 wt%, more preferably 0.1 to 4.4 wt%.
• the coating liquid of the present invention contains an inorganic stratiform compound
• the above-mentioned measurement method of the average particle size is performed using this coating liquid, and the average particle size of the inorganic stratiform compound and the average particle size of the functional resin can be distinguished.
• the latter measurement value is used as the average particle size of the functional resin in the present invention.
• the coating obtained by removing the inorganic layered compound by a process such as filtration of a coating liquid A liquid is prepared, the above-mentioned measurement method of average particle diameter is performed using this coating liquid, and the obtained measured value is used as an average particle diameter of the functional resin in the present invention.
• the coating liquid of the present invention in which the average particle diameter of the functional resin is 100 to 600 nm can be produced by performing high pressure dispersion treatment.
• high-pressure dispersion processing usually, a mixture containing a functional resin and a liquid medium is passed at high speed between capillaries or slits formed in a chamber of a high-pressure dispersion apparatus, and a functional function using shear grinding or cavitation. Refine the resin.
• a high pressure dispersing device including a single nozzle chamber for example, "Starburst” manufactured by Sugino Machine Co., Ltd.
• a high pressure dispersing device including a chamber having a breaker ring for example, "homogenizer” manufactured by Sanwa Engineering
• the average particle diameter of the functional resin can be made within the predetermined range of the present invention by using a high pressure dispersion device (for example, “homogenizer” manufactured by Nippon Tetra Pak Co., Ltd.).
• the pressure of the high pressure dispersion treatment is preferably 50 to 150 MPa.
• the number of high pressure dispersion treatments is preferably 2 or more, and usually 5 or less.
• the coating liquid of the present invention is applied onto a substrate and dried to form a coating (gas barrier layer), whereby a laminate (substrate / coating) can be produced. Therefore, the present invention provides not only the coating solution but also a laminate including the coating film used as a gas barrier layer, a substrate, and the coating film formed on the substrate.
• the laminate may have a coating formed from the coating liquid of the present invention on only one side thereof, and may have the above-mentioned coating on both sides thereof.
• Corona treatment, ozone treatment, electron beam treatment, anchor coating agent on the surface of the substrate to which the coating liquid is applied in order to enhance the adhesion between the coating film formed from the coating liquid of the present invention and the substrate Surface treatment, such as application of the above, may be performed.
• thermoplastic resin As a material of a base material, a thermoplastic resin, a thermosetting resin, a photocurable resin, paper, wood, a metal etc. are mentioned, for example. Of these, thermoplastic resins are preferred.
• thermoplastic resin for example, low density polyethylene, high density polyethylene, linear low density polyethylene, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-hexene copolymer, ethylene-octene copolymer Olefin resins such as polypropylene, poly-4-methylpentene-1, cyclic olefin resin, ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate copolymer, ionomer resin; polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate Ester-based resins such as: polyamide 6 (alias: nylon (registered trademark) 6), polyamide 66 (alias: nylon (registere
• the shape of the substrate is not particularly limited.
• a shape of a base material a woven fabric, a nonwoven fabric, a sheet, a film, a foam etc. are mentioned, for example.
• the substrate may also be a composite material.
• a base material of the composite material for example, one in which at least one selected from the group consisting of aluminum, alumina and silica is vapor-deposited on a resin.
• thermoplastic resin film When using a thermoplastic resin film as a base material, there is no limitation in particular in the manufacturing method of this film. Examples of the method for producing a film include extrusion, casting, calendering, uniaxial stretching, biaxial stretching and the like.
• the thickness of the substrate is preferably 1 to 1,000 ⁇ m, more preferably 5 to 800 ⁇ m.
• Coating methods include, for example, direct gravure method, reverse gravure method, microgravure method such as microgravure method; two-roll beat coating method, bottom feed three-row reverse coating method such as roll coating method; doctor knife method; Bar coating method; dipping method; spray coating method; curtain coating method; spin coating method; flexo coating method; screen coating method; coating method using brush etc. may be mentioned.
• drying includes, for example, drying by heating, drying by non-heating means such as reduced pressure, and drying by a combination thereof. Among these, drying by heating is preferable in terms of the simplicity of the apparatus.
• a drying furnace, a heat roll, an infrared heater, a microwave heater etc. are mentioned, for example.
• the drying temperature by heating is preferably 40 to 150 ° C., more preferably 50 to 140 ° C., and the drying time is preferably 0.01 to 1,440 minutes, more preferably 0.01 to 60 minutes. .
• the thickness (thickness after drying) of the coating film formed from the coating liquid of the present invention is preferably 0.01 to 20 ⁇ m, more preferably 0.05 to 10 ⁇ m.
• Another layer may be formed on the coating film formed from the coating liquid of this invention as a laminated body.
• another layer may be formed on the side on which the coating film formed from the coating liquid of the present invention is not formed.
• a heat seal layer etc. are mentioned, for example.
• Examples of the resin constituting the heat seal layer include low density polyethylene, high density polyethylene, linear low density polyethylene, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-hexene copolymer, ethylene- 4-Methyl-1-pentene copolymer, ethylene-octene copolymer, polypropylene, ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-acrylic acid copolymer Examples thereof include olefin resins such as copolymers and ionomer resins.
• the surface of the substrate on which the heat seal layer is formed is subjected to surface treatment such as corona treatment, ozone treatment, electron beam treatment, application of an anchor coating agent, etc. It may be
• the present invention provides a molded body obtained by further molding the laminate.
• the molding for example, JP-A-8-238667, JP-A-5-220913, JP-A-54-90265, JP-A-61-108542, JP-A-2006-137058, JP-A-2003. JP-A-5-23823, JP-A-2-69213, JP-A-3-176128, JP-A-5-104572, JP-A-61-249750, JP-A-61-244737, etc. Blow molding, vacuum forming, pressure forming, vacuum pressure forming, and the like.
• a molded object obtained a bottle, a bottle cap, a carton container, a cup, a plate, a tray, a press through pack, a tank, a tube, a syringe etc. are mentioned, for example.
• PVA polyvinyl alcohol
• PVA (1) polyvinyl alcohol, manufactured by Kuraray “RS 2117", weight average molecular weight: 190,000, degree of saponification: 99.6%, average degree of polymerization: 1,700
• PVA (2) polyvinyl alcohol, manufactured by Kuraray “Poval 105", weight average molecular weight: 65,000, degree of saponification: 98.5%, average degree of polymerization: 500
• PVA (3) polyvinyl alcohol, manufactured by Unitika Chemical Co., Ltd.
• PAA Polyacrylic acid
• PAA (1) polyacrylic acid, manufactured by Wako Pure Chemical Industries, Ltd., weight average molecular weight: 1,000,000
• PAA (2) polyacrylic acid, manufactured by Wako Pure Chemical Industries, Ltd., weight average molecular weight: 150,000
• PAA (3) polyacrylic acid, manufactured by Wako Pure Chemical Industries, Ltd., weight average molecular weight: 25,000
• High pressure dispersing device (1) (“Starburst” manufactured by Sugino Machine Co., Ltd., high pressure dispersing device including single nozzle chamber)
• High pressure dispersing device (2) (“Homogenizer H100” manufactured by Sanwa Engineering Co., Ltd., high pressure dispersing device including a chamber having a breaker ring)
• High pressure dispersing device (3) (“Microfluidizer M10-E / H” manufactured by Microfluidics Corporation, high pressure dispersing device including interaction chamber)
• Preparation of Coating Liquid Example 1 Preparation of Coating Liquid (1) (1) Preparation of Mixture Containing PVA (1) A dispersing pot ("Desspa MH-L" manufactured by Asada Iron Works Co., Ltd.) was used as an ion Exchanged water (112.86 g) and PVA (1) (5.94 g) were added, and the resulting mixture was heated to 95 ° C. while stirring at 1,500 rpm and a peripheral speed of 4.1 m / min. . The mixture is stirred for 30 minutes at 95 ° C., 1,500 rpm and a circumferential speed of 4.1 m / min, then cooled to 60 ° C.
• a dispersing pot (“Desspa MH-L" manufactured by Asada Iron Works Co., Ltd.) was used as an ion Exchanged water (112.86 g) and PVA (1) (5.94 g) were added, and the resulting mixture was heated to 95 ° C. while stirring at 1,500 rpm
• a mixture (about 454 g) containing PVA (1) and PAA (1) was treated at a treatment pressure of 150 MPa in a single nozzle chamber of a high pressure dispersion device (1). It was treated twice to obtain a dispersion.
• the obtained dispersion (about 454 g) and aqueous sodium hydroxide solution (0.83 g, concentration: 10% by weight) are mixed, and the obtained mixture is stirred at 23.degree. C., 1,500 rpm and a circumferential speed of 4.1 m / min.
• the mixture was stirred for 5 minutes to obtain a coating liquid (1) (PVA (1) content: 1.31% by weight, PAA (1) content: 0.33% by weight, water content: 51 .65 wt%, content of isopropanol: 46.7 wt%).
• Example 2 Preparation of Coating Liquid (2) (1) Preparation of Mixture Containing PVA (1) and PAA (1) In the same manner as Example 1, a mixture containing PVA (1) and PAA (1) About 454 g).
• Example 3 Preparation of Coating Liquid (3) (1) Preparation of Mixture Containing PVA (1) and PAA (1) In the same manner as Example 1, a mixture containing PVA (1) and PAA (1) About 454 g).
• Comparative Example 1 Preparation of Coating Liquid (4) (1) Preparation of Mixture Containing PVA (2) A dispersion pot ("Despa MH-L" manufactured by Asada Iron Works Co., Ltd.), ion exchange water (90 g), PVA ( 2) (10 g) was added and the resulting mixture was heated to 95 ° C. while stirring at 1,500 rpm and a circumferential speed of 4.1 m / min. The mixture was stirred for 30 minutes at 95 ° C., 1,500 rpm and a peripheral speed of 4.1 m / min, and then cooled to room temperature to obtain a mixture (100 g) containing PVA (2).
• a dispersion pot (“Despa MH-L” manufactured by Asada Iron Works Co., Ltd.), ion exchange water (90 g), PVA ( 2) (10 g) was added and the resulting mixture was heated to 95 ° C. while stirring at 1,500 rpm and a circumferential speed of 4.1 m /
• Comparative Example 2 Preparation of Coating Liquid (5) (1) Preparation of Mixture Containing PVA (3) A dispersion pot ("Despa MH-L" manufactured by Asada Iron Works Co., Ltd.), ion exchange water (100 g), PVA ( 3) (25 g) was added and the resulting mixture was warmed to 95 ° C. with stirring at 1,500 rpm and a circumferential speed of 4.1 m / min. The mixture was stirred for 30 minutes at 95 ° C., 1,500 rpm and a peripheral speed of 4.1 m / min, and then cooled to room temperature to obtain a mixture (125 g) containing PVA (3).
• a dispersion pot (“Despa MH-L” manufactured by Asada Iron Works Co., Ltd.), ion exchange water (100 g), PVA ( 3) (25 g) was added and the resulting mixture was warmed to 95 ° C. with stirring at 1,500 rpm and a circumferential speed of
• Comparative Example 3 Preparation of Coating Liquid (6) (1) Preparation of Mixture Containing PVA (1) and PAA (1) In the same manner as Example 1, a mixture containing PVA (1) and PAA (1) About 454 g).
• the number of lines of the gravure roll # 150 (that is, 150 grooves in 1 inch)
• the coating liquid (4) obtained in Comparative Example 1 was coated under the conditions of the number of lines of the gravure roll: # 250 (that is, 250 grooves in 1 inch).
• the obtained coating liquid (5) was applied under the conditions of the number of gravure roll lines: # 200 (that is, 200 grooves in 1 inch).
• the thickness of the coating on the substrate was 1 ⁇ m in each case.
• Table 1 also shows types and contents of resins used in Examples 1 to 3 and Comparative Examples 1 to 3, types of high-pressure dispersing devices used, and average particle sizes of the resins measured as described above. Do.
• the laminate (base material / coating film) formed from the coating liquid of Examples 1 to 3 in which the average particle diameter of the resin is 100 to 600 nm has the above-mentioned average particle diameter.
• the oxygen permeability under high humidity (85% RH) is lower than that of a laminate formed from the coating liquids of Comparative Examples 1 to 3 which do not satisfy the requirements.
• a gas barrier layer (coated film) exhibiting low oxygen permeability under high humidity can be formed.
• a laminate having the coating film formed on a substrate is useful as a packaging material for food, cosmetics and the like.

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