WO2014088109A1 - 混合液、混合液の製造方法、および多層構造体 - Google Patents
混合液、混合液の製造方法、および多層構造体 Download PDFInfo
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- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/048—Forming gas barrier coatings
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- 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
- C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
- C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D123/04—Homopolymers or copolymers of ethene
- C09D123/08—Copolymers of ethene
- C09D123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C09D123/0869—Acids or derivatives thereof
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- 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
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
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- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
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- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
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- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
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- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
- C08L101/14—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity the macromolecular compounds being water soluble or water swellable, e.g. aqueous gels
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
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- 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
- C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
- C09D123/26—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers modified by chemical after-treatment
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- 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
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- 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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/06—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- 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
- B32B2439/00—Containers; Receptacles
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- 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
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2400/00—Characterised by the use of unspecified polymers
- C08J2400/14—Water soluble or water swellable polymers, e.g. aqueous gels
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/26—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Definitions
- the present invention relates to a mixed solution, a method for producing the mixed solution, and a multilayer structure.
- JP-A-11-263802 discloses a method in which an adhesive layer made of an aqueous resin composition containing a chlorinated polyolefin is laminated on a substrate made of an olefin resin, and a coating film is laminated on the adhesive layer. Are listed.
- the coating film does not sufficiently adhere to the adhesive layer, and particularly under high humidity conditions, the coating film containing the inorganic layered compound and the substrate could not be firmly bonded via the adhesive layer made of the aqueous resin composition.
- the present invention provides a liquid mixture capable of forming a layer capable of firmly bonding a substrate and a coating film containing an inorganic stratiform compound even under high humidity conditions, and a method for producing the liquid mixture It is to provide. Further, the present invention provides a multilayer structure in which a base material and a coating film containing an inorganic layered compound are firmly bonded via an adhesive layer even under high humidity conditions.
- the present invention relates to a monomer unit based on an ⁇ -olefin having 2 to 20 carbon atoms, a monomer unit based on an ⁇ , ⁇ -unsaturated carboxylic acid ester, an ⁇ , ⁇ -unsaturated carboxylic acid and an ⁇ , ⁇ -unsaturated carboxylic acid anhydride and a monomer unit based on a compound selected from the group consisting of olefin polymers, and the content of the monomer unit based on the ⁇ -olefin is 50% by mass or more (However, a monomer unit based on an ⁇ -olefin having 2 to 20 carbon atoms, a monomer unit based on an ⁇ , ⁇ -unsaturated carboxylic acid ester, an ⁇ , ⁇ -unsaturated carboxylic acid, and an ⁇ , ⁇ -The total amount of monomer units based on a compound selected from the group consisting of unsaturated carboxylic acid an
- this invention concerns on the manufacturing method of the said liquid mixture which includes the following processes (1) and (2) in order in another surface.
- the present invention is directed to another aspect.
- a multilayer structure having a substrate and a first layer adjacent to the substrate, wherein the first layer is a monomer unit based on an ⁇ -olefin having 2 to 20 carbon atoms, ⁇ , a monomer unit based on a ⁇ -unsaturated carboxylic acid ester and a monomer unit based on a compound selected from the group consisting of an ⁇ , ⁇ -unsaturated carboxylic acid and an ⁇ , ⁇ -unsaturated carboxylic acid anhydride.
- an olefin polymer having a monomer unit content based on the ⁇ -olefin of 50% by mass or more (provided that the monomer unit based on the ⁇ -olefin having 2 to 20 carbon atoms and ⁇ , ⁇ - Monomers based on unsaturated carboxylic esters And a total amount of monomer units based on a compound selected from the group consisting of ⁇ , ⁇ -unsaturated carboxylic acid and ⁇ , ⁇ -unsaturated carboxylic acid anhydride), and water-soluble resin
- the multilayer structure is a layer containing
- the olefin polymer contained in the mixed liquid of the present invention includes a monomer unit based on an ⁇ -olefin having 2 to 20 carbon atoms, a monomer unit based on an ⁇ , ⁇ -unsaturated carboxylic acid ester, ⁇ , a monomer unit based on a compound selected from the group consisting of ⁇ -unsaturated carboxylic acid and ⁇ , ⁇ -unsaturated carboxylic acid anhydride, and the content of the monomer unit based on the ⁇ -olefin is 50 Olefin polymer having a mass% or more (however, a monomer unit based on an ⁇ -olefin having 2 to 20 carbon atoms, a monomer unit based on an ⁇ , ⁇ -unsaturated carboxylic acid ester, and ⁇ , ⁇ - The total amount of monomer units based on a compound selected from the group consisting of unsaturated carboxylic acids and ⁇ ,
- Examples of the ⁇ -olefin having 2 to 20 carbon atoms include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1- Examples include dodecene, 1-dodecadecene, 4-methyl-1-pentene and the like.
- the olefin polymer may include monomer units based on two or more ⁇ -olefins.
- the olefin polymer preferably has a monomer unit based on one or more ⁇ -olefins selected from the group consisting of ethylene and propylene 1-butene, and is based on a monomer unit based on propylene and 1-butene. It is more preferable to have a monomer unit.
- the olefin polymer is a polymer having a monomer unit based on propylene and a monomer unit based on 1-butene, a monomer unit based on propylene and a single amount based on 1-butene in the polymer
- the content of monomer units based on propylene is preferably 70 to 99 mol%.
- the content of the monomer unit based on the ⁇ -olefin having 2 to 20 carbon atoms in the olefin polymer is 50% by mass or more (however, the single amount based on the ⁇ -olefin having 2 to 20 carbon atoms)
- Examples of the ⁇ , ⁇ -unsaturated carboxylic acid ester include acrylic acid ester and methacrylic acid ester, and preferably (meth) acrylic acid and alcohol or glycidyl group having a linear or branched alkyl group.
- An ester with an alcohol having Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, (meth) acrylic acid i-butyl, 2-butyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, (meth) Examples include n-dodecyl acrylate, n-octadecyl (meth) acrylate, and glycidyl (meth) acrylate.
- the olefin polymer may include monomer units based on two or more kinds of ⁇ , ⁇ -unsaturated carboxylic acid esters.
- the content of the monomer unit based on the ⁇ , ⁇ -unsaturated carboxylic acid ester in the olefin polymer strongly bonds the substrate and the coating film containing the inorganic layered compound even under high humidity conditions. From the viewpoint of forming a layer that can be formed, it is preferably 0.1 to 40% by mass (provided that the monomer unit based on an ⁇ -olefin having 2 to 20 carbon atoms, The total amount of monomer units based on saturated carboxylic acid esters and monomer units based on compounds selected from the group consisting of ⁇ , ⁇ -unsaturated carboxylic acids and ⁇ , ⁇ -unsaturated carboxylic acid anhydrides is 100 masses. %).
- the compound selected from the group consisting of ⁇ , ⁇ -unsaturated carboxylic acid and ⁇ , ⁇ -unsaturated carboxylic acid anhydride includes acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid.
- examples include acids, crotonic acid, unsaturated dicarboxylic acid half esters, and unsaturated dicarboxylic acid half amides. Of these, acrylic acid, methacrylic acid, maleic acid, and maleic anhydride are preferable, and acrylic acid and maleic anhydride are more preferable.
- the olefin polymer may include a monomer unit based on two or more kinds of compounds selected from the group consisting of ⁇ , ⁇ -unsaturated carboxylic acid and ⁇ , ⁇ -unsaturated carboxylic acid anhydride.
- the content of the monomer unit based on a compound selected from the group consisting of ⁇ , ⁇ -unsaturated carboxylic acid and ⁇ , ⁇ -unsaturated carboxylic acid anhydride in the olefin polymer is high humidity conditions, From the viewpoint of forming a layer capable of firmly bonding the substrate and the coating film containing the inorganic stratiform compound, the content is preferably 0.1 to 10% by mass (however, the number of carbon atoms is 2 to 20).
- a monomer unit based on an ⁇ -olefin, a monomer unit based on an ⁇ , ⁇ -unsaturated carboxylic acid ester, and an ⁇ , ⁇ -unsaturated carboxylic acid and an ⁇ , ⁇ -unsaturated carboxylic acid anhydride is 100% by mass).
- Monomer unit based on a monomer unit based on the ⁇ , ⁇ -unsaturated carboxylic acid ester and a compound selected from the group consisting of ⁇ , ⁇ -unsaturated carboxylic acid and ⁇ , ⁇ -unsaturated carboxylic acid anhydride The amount ratio of ⁇ , ⁇ -unsaturated from the viewpoint of forming a layer capable of firmly bonding the base material and the coating film containing the inorganic layered compound even under high humidity conditions
- the monomer unit based on the carboxylic acid ester is 100 mol
- the monomer unit based on the compound selected from the group consisting of ⁇ , ⁇ -unsaturated carboxylic acid and ⁇ , ⁇ -unsaturated carboxylic acid anhydride is 0. It is preferably 7 to 200 mol.
- the olefin polymer includes a monomer unit based on the ⁇ -olefin having 2 to 20 carbon atoms, a monomer unit based on an ⁇ , ⁇ -unsaturated carboxylic acid ester, an ⁇ , ⁇ -unsaturated carboxylic acid, and an ⁇ .
- ⁇ -unsaturated carboxylic acid anhydride may have a monomer unit different from the monomer unit based on the compound selected from the group consisting of, for example, vinyl acetate based monomer unit May be.
- Examples of the method for preparing the olefin polymer used in the present invention include a prepolymer having a monomer unit based on an ⁇ -olefin having 2 to 20 carbon atoms, an ⁇ , ⁇ -unsaturated carboxylic acid ester, a method of adding a compound selected from the group consisting of ⁇ -unsaturated carboxylic acids and ⁇ , ⁇ -unsaturated carboxylic acid anhydrides, monomer units based on ⁇ -olefins having 2 to 20 carbon atoms and ⁇ , A compound selected from the group consisting of ⁇ , ⁇ -unsaturated carboxylic acid and ⁇ , ⁇ -unsaturated carboxylic acid anhydride is added to a prepolymer having a monomer unit based on ⁇ -unsaturated carboxylic acid ester.
- a monomer based on a compound selected from the group consisting of a monomer unit based on an ⁇ -olefin having 2 to 20 carbon atoms and an ⁇ , ⁇ -unsaturated carboxylic acid and an ⁇ , ⁇ -unsaturated carboxylic acid anhydride With units Method of adding ⁇ , ⁇ -unsaturated carboxylic acid ester to prepolymer, ⁇ -olefin having 2 to 20 carbon atoms, ⁇ , ⁇ -unsaturated carboxylic acid ester, ⁇ , ⁇ -unsaturated carboxylic acid And a method of copolymerizing with a compound selected from the group consisting of ⁇ , ⁇ -unsaturated carboxylic acid anhydrides.
- the olefin polymer has a weight average molecular weight of 30,000 to from the viewpoint of forming a layer capable of firmly bonding the base material and the coating film containing the inorganic stratiform compound even under high humidity conditions.
- a polymer in the range of 250,000 is preferred.
- the mixed solution of the present invention contains a water-soluble resin.
- Water-soluble here means that 1 g of resin is added to 1000 g of an aqueous medium to be described later, and a disperser (manufactured by Asada Tekko Co., Ltd., Despa MH-L, blade diameter 52 mm, rotation speed 3,100 rpm, container capacity 3 L, bottom surface-blade It is said that there is no undissolved residue visually after stirring at 95 ° C. for 90 minutes at a peripheral speed of 8.5 m / min.
- the mixed liquid of the present invention may contain two or more types of water-soluble resins.
- the water-soluble resin preferably contains a functional group such as a hydroxyl group, a carboxyl group, an amino group, a sulfonic acid group, a carboxylate group, or an ammonium group, and more preferably contains a hydroxyl group.
- Examples of the resin containing a hydroxyl group include polyvinyl alcohol, partially saponified polyvinyl alcohol, and polysaccharide.
- Examples of the resin containing a carboxyl group include polyacrylic acid, polymethacrylic acid, a polyacrylic acid partial neutralized product, and a polymethacrylic acid partial neutralized product.
- Polyvinylamine is mentioned as resin which has an amino group.
- the water-soluble resin is a resin containing two or more kinds of functional groups in one molecule, or a resin containing a first functional group and a resin containing a second functional group different from the first functional group It is preferable that it is a mixture. It is preferable that the functional groups contained in the water-soluble resin can form a covalent bond or an ionic bond.
- a copolymer having a monomer unit based on vinyl alcohol and a monomer unit based on one or more types selected from acrylic acid, methacrylic acid, and vinylamine is used.
- a polymer is mentioned.
- a mixture of a resin containing a first functional group and a resin containing a second functional group different from the first functional group a mixture of a resin containing a hydroxyl group and a resin containing a carboxyl group, the hydroxyl group And a mixture of a resin containing an amino group and a resin containing a hydroxyl group, a resin containing a carboxyl group, and a resin containing an amino group.
- the water-soluble resin can be easily dissolved in an aqueous medium and is easy to handle, and even under high humidity conditions, the substrate and the coating film containing the inorganic layered compound are firmly bonded. From the viewpoint of forming a layer that can be formed, a resin containing a hydroxyl group and a carboxyl group is more preferable.
- the content of the water-soluble resin in the mixed liquid of the present invention is preferably 2 to 40% by mass when the total amount of the olefin polymer and the water-soluble resin is 100% by mass, and preferably 5 to 30% by mass. %, More preferably 5 to 20% by mass.
- the content of the olefin polymer in the mixed liquid of the present invention is preferably 98 to 60% by mass, and 95 to 70% by mass, when the total amount of the olefin polymer and the water-soluble resin is 100% by mass. % Is more preferable, and 95 to 80% by mass is even more preferable.
- the aqueous medium contained in the mixed liquid of the present invention is a liquid medium containing water as a main component.
- the aqueous medium may be water alone or a mixture of water and the following liquid medium.
- Examples of the liquid medium different from water used as the aqueous medium include alcohol (methanol, ethanol, propanol, isopropanol, ethylene glycol, diethylene glycol and the like), dimethylformamide, dimethyl sulfoxide, acetone and the like, and alcohol is preferable.
- the total amount of the olefin polymer and the water-soluble resin is preferably 1 to 50% by mass, more preferably 3 to 40% by mass. It is more preferably ⁇ 30% by mass.
- the mixed liquid of the present invention is a known additive, for example, various stabilizers such as an antioxidant, an ultraviolet absorber, a light stabilizer, a colorant, an antifoaming agent, a viscosity adjusting agent, a wetting agent, depending on the purpose and application.
- various stabilizers such as an antioxidant, an ultraviolet absorber, a light stabilizer, a colorant, an antifoaming agent, a viscosity adjusting agent, a wetting agent, depending on the purpose and application.
- An additive such as an agent may be included.
- Two or more kinds of additives may be included.
- the olefin polymer and the water-soluble resin are dissolved or dispersed in the same aqueous medium. After the olefin polymer is dispersed in the aqueous medium, the water-soluble resin is added to the aqueous medium.
- a method of dispersing the olefin polymer in the aqueous medium includes a method of polymerizing the monomer after mixing the monomer and the aqueous medium (emulsion polymerization method), and a method of dispersing the polymer in the aqueous medium. And a method of dispersing in (a post-emulsification method).
- the obtained olefin polymer dispersion is preferably left at room temperature.
- the olefin polymer dispersion liquid in which the fine olefin polymer is uniformly dispersed can be obtained without agglomeration of the olefin polymer as the dispersoid in the dispersion liquid.
- (A) As a method of dispersing the olefin polymer in an aqueous medium (post-emulsification method), specifically, (A) The reactor is charged with an olefin polymer and an organic solvent, heated and stirred to dissolve the olefin polymer in the solvent, and then the resulting solution is selected from the group consisting of water and an organic solvent.
- An olefin polymer, optionally an organic solvent is charged into a kneader, heated and stirred to melt the olefin polymer, and then the molten olefin polymer is selected from the group consisting of water and an organic solvent.
- water is introduced at least once.
- the organic solvent an organic solvent capable of dissolving the olefin polymer is used, and specific examples include organic solvents such as toluene, xylene, and methylcyclohexane.
- a container provided with a heating device that can be heated and a stirrer that can give a shearing force or the like to the contents is used as the reactor.
- a sealed container, a pressure resistant container, or a sealed pressure resistant container is preferred.
- Examples of such a reactor include a pressure-resistant autoclave with a stirrer.
- Stirring may be performed at normal pressure or reduced pressure. Stirring can be performed, for example, at a rotational speed of about 50 to 1000 rpm. As the dispersion / stirring of the olefin polymer proceeds, it is preferable to increase the rotational speed.
- the temperature is usually 50 to 200 ° C, preferably 60 to 150 ° C, more preferably 70 to 100 ° C.
- Solvent removal is preferably performed under reduced pressure or under pressure.
- the pressure for removing the solvent under reduced pressure is usually -1 MPa to 0.1 MPa.
- the pressure for removing the solvent under pressure is usually 0.1 MPa to 1 MPa.
- examples of the kneader include a roll mill, a kneader, an extruder, a lab plast mill, a Banbury mixer, and the like.
- examples of the extruder include a single screw extruder having only one screw in the casing or a multi-screw extruder having two or more screws in the casing.
- Examples of the method for dispersing the olefin polymer in an aqueous medium using an extruder include the following methods.
- the olefin polymer is continuously supplied from the hopper of the extruder, heated and melt-kneaded, the emulsifier is supplied to the extruder from a supply port different from the hopper, and the molten olefin polymer and the emulsifier are kneaded with a screw. .
- water is supplied from at least one supply port provided in the compression zone, metering zone, degassing zone, etc. of the extruder, and these are kneaded with a screw, and then the kneaded product is continuously extruded from the die. .
- the olefin polymer dispersion it is preferable to add components other than those described above, for example, the above-mentioned additives such as an antifoaming agent and a viscosity modifier as appropriate at an arbitrary time.
- the emulsifier it is preferable to use the emulsifier within a desired range. However, when the emulsifier is used in excess, an excess emulsifier is removed from the obtained olefin polymer dispersion. It may be separated and removed.
- Examples of the method for separating and removing the emulsifier include a method using a centrifugal separator, a filtration filter having an average pore size smaller than the average particle size of the olefin polymer dispersion, or an ultrafiltration membrane.
- Surfactant is mentioned as an emulsifier used for an olefin polymer dispersion.
- examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants.
- the content of the emulsifier in the olefin polymer dispersion is usually 1 to 30 parts by mass, preferably 1 to 25 parts by mass, based on 100 parts by mass of the olefin polymer.
- the water-soluble resin aqueous solution used in the step of mixing the water-soluble resin aqueous solution with the olefin polymer dispersion can be obtained by mixing and stirring the water-soluble resin and the aqueous medium.
- the concentration of the water-soluble resin in the water-soluble resin aqueous solution is preferably 0.1 to 30% by mass (however, the total of the water-soluble resin and the aqueous medium is 100% by mass).
- the multilayer structure according to the present invention is a multilayer structure having a base material and a first layer adjacent to the base material, wherein the first layer is based on an ⁇ -olefin having 2 to 20 carbon atoms.
- a multilayer structure which is a layer containing a water-soluble resin and an olefin polymer having a monomer unit based on the ⁇ -olefin and a content of the monomer unit based on the ⁇ -olefin of 50% by mass or more. .
- Examples of the material constituting the substrate include metals, resins, wood, ceramics, and glass.
- Examples of the base material include paper, cloth, nonwoven fabric, and film.
- Examples of the metal include copper, iron, silver, aluminum and the like, and alloys thereof are also included.
- Examples of the ceramic include alumina, silica, zirconia, and titanium oxide.
- As the resin a thermoplastic resin, a thermosetting resin, a photocurable resin, or the like can be used.
- Thermoplastic resins include olefin resins, ethylene copolymers, ester resins, amide resins, polyarylate, acrylic resins, polystyrene, styrene resins, hydrophobic cellulose resins, chlorine resins, fluorine resins. , Hydrogen bonding resin, carbonate resin, sulfone resin, ether sulfone resin, ether ether ketone resin, phenylene oxide resin, methylene oxide resin, imide resin and the like.
- the olefin resin examples include polyethylene, ethylene- ⁇ -olefin copolymer, polypropylene, polybutene-1, poly-4-methylpentene-1, and cyclic olefin resin.
- the cyclic olefin resin is a homopolymer of a cyclic olefin or a copolymer of a cyclic olefin and another comonomer, and has an alicyclic structure in the main chain and / or side chain.
- cyclic olefin examples include monocyclic olefins such as cyclobutene, cyclopentene, cyclohexene and cyclooctene; substituted monocyclic olefins such as 3-methylcyclopentene, 4-methylcyclopentene and 3-methylcyclohexene; norbornene, 1,2- Examples include polycyclic olefins such as dihydrodicyclopentadiene and tetracyclododecene (dimethanooctahydronaphthalene); substituted polycyclic olefins such as 5-methylnorbornene.
- monocyclic olefins such as cyclobutene, cyclopentene, cyclohexene and cyclooctene
- substituted monocyclic olefins such as 3-methylcyclopentene, 4-methylcyclopentene and 3-methylcyclohexene
- norbornene 1,2- Examples
- Examples of the ethylene copolymer include an ethylene-vinyl acetate copolymer or a saponified product thereof, an ethylene- ⁇ , ⁇ unsaturated carboxylic acid ester copolymer, an ethylene- ⁇ , ⁇ unsaturated carboxylic acid copolymer, and the like.
- Examples of the ester resin include polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate.
- Examples of amide resins include nylon-6 (Ny-6), nylon-6,6, metaxylenediamine-adipic acid condensation polymer, polymethylmethacrylamide, polymetaxylylene adipamide (MXD6-Ny), and the like. It is done.
- Examples of the acrylic resin include polymethyl methacrylate.
- Examples of the styrenic resin include AS resin and ABS resin.
- Examples of the hydrophobic cellulose resin include cellulose triacetate and cellulose diacetate.
- Examples of the chlorine-based resin include polyvinyl chloride and polyvinylidene chloride.
- Examples of the fluorine-based resin include polyvinyl fluoride, polyvinylidene fluoride, polytetrafluoroethylene, an ethylene-tetrafluoroethylene copolymer, a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, and the like.
- hydrogen bonding resin examples include polyvinyl alcohol, ethylene-vinyl alcohol copolymer (EVOH), cellulose derivatives, and the like. Among these, the mass fraction of hydroxyl groups per unit mass of the resin satisfies a ratio of 20 to 60%. Polymers are preferred.
- thermosetting resin one or more types of thermoreactive compounds such as phenol resin, melamine resin, urea resin, ethyleneimine resin, epoxy compound, (meth) acryloyl compound, allyl compound, vinyl compound, etc. And a resin obtained by reacting in the presence of a thermal polymerization initiator.
- thermoreactive compounds such as phenol resin, melamine resin, urea resin, ethyleneimine resin, epoxy compound, (meth) acryloyl compound, allyl compound, vinyl compound, etc.
- a resin obtained by reacting in the presence of a thermal polymerization initiator As a photocurable resin, using a photoinitiator, an epoxy compound having two or more epoxy groups in one molecule, or an acrylic compound having two or more acryloyl groups or methacryloyl groups in one molecule Examples thereof include epoxy resins and acrylic resins obtained by polymerizing the compounds.
- the substrate may be a single layer or a multilayer.
- the substrate may be any of an unstretched film, a uniaxially stretched film, and a biaxially stretched film.
- the base material may be a multilayer film such as Ny-6 layer / MXD6-Ny layer / Ny-6 layer, polypropylene layer / ethylene-vinyl alcohol copolymer layer / polypropylene layer, aluminum, alumina, silica May be a film on which is deposited.
- an example of a preferable substrate is a substrate having a resin heat seal layer as one surface layer.
- the resin constituting the heat seal layer include an olefin resin, an ethylene copolymer, an ester resin, an acrylonitrile resin, and the like.
- the base material having the heat seal layer is, for example, a method of co-extruding a resin for forming a heat seal layer and a resin different from the resin for forming the heat seal layer, and dissolving the resin for forming the heat seal layer in a liquid medium.
- the base material precursor is a film formed of a layer different from the heat seal layer among the base materials having the heat seal layer.
- the surface of the base material precursor on which the heat seal layer is formed and the surface of the heat sealable resin film to be laminated with the base material precursor are preferably subjected to surface treatment described later.
- the olefin polymer contained in the first layer includes a monomer unit based on an ⁇ -olefin having 2 to 20 carbon atoms, a monomer unit based on an ⁇ , ⁇ -unsaturated carboxylic acid ester, a monomer unit based on a compound selected from the group consisting of an ⁇ , ⁇ -unsaturated carboxylic acid and an ⁇ , ⁇ -unsaturated carboxylic acid anhydride, and the content of the monomer unit based on the ⁇ -olefin Is an olefin polymer in which is 50% by mass or more (provided that a monomer unit based on an ⁇ -olefin having 2 to 20 carbon atoms, a monomer unit based on an ⁇ , ⁇ -unsaturated carboxylic acid ester, ⁇ , the total amount of monomer units based on a compound selected from the group consisting of ⁇ -unsaturated carboxylic acid and ⁇ , ⁇ -
- the water-soluble resin contained in the first layer As the water-soluble resin contained in the first layer, the water-soluble resin contained in the above-mentioned mixed liquid can be used.
- the substrate is a film
- the multilayer structure having the substrate and the first layer adjacent to the substrate has one substrate and one first layer, and one of the substrates
- a multi-layer structure in which a first layer is laminated adjacently on a surface, a base material, and two first layers, and in order of the first layer, the base material, and the first layer An example is a multilayer structure laminated adjacently.
- the multilayer structure according to the present invention may be a multilayer structure further having a second layer containing an inorganic layered compound and a resin adjacent to the first layer.
- the multilayer structure having the second layer is excellent in gas barrier properties and scratch resistance.
- the substrate is a film
- the multilayer structure having the substrate, the first layer adjacent to the substrate, and the second layer adjacent to the first layer includes one substrate and one substrate.
- the inorganic layered compound contained in the second layer refers to a product in which unit crystal layers are stacked to form a layered structure.
- the layered structure is a structure in which atoms that are strongly bonded by a covalent bond or the like and densely arranged are stacked almost in parallel by a weak bonding force such as van der Waals force.
- clay minerals having swelling property and cleaving property to a liquid medium are preferably used.
- Clay minerals generally include (i) a type having a two-layer structure having an octahedral layer with aluminum, magnesium, etc. as a central metal above the silica tetrahedral layer, and (ii) the silica tetrahedral layer is made of aluminum. And a type having a three-layer structure in which an octahedral layer having a central metal such as magnesium is sandwiched from both sides.
- Examples of the two-layer structure type clay mineral (i) include kaolinite-serpentine clay minerals.
- the clay mineral of the three-layer structure type (ii) includes clay minerals such as talc-pyrophyllite group, smectite group, vermiculite group, mica group, brittle mica group, chlorite group, etc., depending on the number of interlayer cations. .
- Specific examples of the kaolinite-serpentine family include kaolinite, dickite, nacrite, halloysite, antigolite, chrysotile, lizardite, amesite, burcherin, cronsteidite, nepoite, keriaite, fraponite, blindriaite, etc. Can be mentioned.
- talc-pyrophyllite group examples include talc, willemsite, kerolite, pimelite, pyrophyllite, ferripyrophyllite and the like.
- smectite group examples include montmorillonite, beidellite, nontronite, saponite, sauconite, stevensite, hectorite, bolcon score, and swinolite.
- vermiculite family include 3 octahedral vermiculite, 2 octahedral vermiculite, and the like.
- the mica group include tetrasilicic mica, sodium teniolite, muscovite, phlogopite, biotite, iron mica, East Knight, siderophyllite tetraferri iron mica, scale mica, polylysionite, celadonite , Iron ceradonite, iron alumina ceradon stone, alumino ceradon stone, mica mica, paragonite, and lipidolite.
- Specific examples of the brittle mica group include xanthophyllite, clintnite, bite mica, ananda stone, pearl mica, marguerite, and the like.
- chlorite group examples include clinochlore, chamosite, penanthite, nimite, bailicroa, donbasite, kukuite, and suedeite.
- these clay minerals treated with organic substances such as ion exchange and improved dispersibility are also used as inorganic layered compounds.
- organically modified clay minerals are also used as inorganic layered compounds.
- organic substance which processes a clay mineral well-known quaternary ammonium salts, such as a dimethyl distearyl ammonium salt and a trimethyl stearyl ammonium salt, a phosphonium salt, an imidazolium salt, etc. can be used.
- the smectite group, vermiculite group and mica group clay minerals which are the three-layer structure type clay mineral of (ii), are preferred, and the smectite group is particularly preferred.
- the smectite group montmorillonite, beidellite, nontronite, saponite, sauconite, stevensite, and hectorite are preferable, and montmorillonite is particularly preferably used from the viewpoint of swelling to a liquid medium and cleavage. Two or more kinds of inorganic layered compounds may be used.
- the aspect ratio of the inorganic layered compound is preferably 20 or more, more preferably 100 or more, and even more preferably 200 or more. Moreover, it is easy to swell and cleave, and from the viewpoint of film forming property, the aspect ratio of the inorganic layered compound is preferably 10,000 or less, more preferably 5000 or less, and still more preferably 3000 or less.
- the inorganic layered compound preferably has an average particle size of 5 ⁇ m or less. If the average particle size is too large, the transparency and film-forming property tend to be inferior. In products used for applications requiring transparency, the average particle size of the inorganic layered compound is preferably 1 ⁇ m or less.
- the aspect ratio and the average particle diameter of the inorganic layered compound are values in an inorganic layered compound dispersion containing the inorganic layered compound and a liquid medium that swells and cleaves the inorganic layered compound.
- L is the average particle diameter of the inorganic layered compound
- a is the unit thickness of the inorganic layered compound, that is, the thickness of the unit crystal layer of the inorganic layered compound, and is determined by the powder X-ray diffraction method (“instrumental analysis”). No. (a) "(1985, published by Kagaku Dojinsha, supervised by Jiro Shiokawa, p. 69).
- the average particle diameter of the inorganic layered compound is a particle diameter (volume-based median diameter) obtained by a diffraction / scattering method in a liquid medium. That is, it can be obtained by calculating a particle size distribution appropriate for the diffraction / scattering pattern from the diffraction / scattering pattern obtained when light is passed through the dispersion of the inorganic layered compound by the Mie scattering theory or the like. Specifically, for example, the measurement range of the particle size distribution is divided into appropriate sections, the representative particle diameter is determined for each section, and the particle size distribution, which is originally a continuous quantity, is converted into a discrete quantity and calculated. A method is mentioned.
- the inorganic layered compound used in the present invention preferably has a swelling value of 5 or more by the following swellability test, and more preferably has a swelling value of 20 or more. Further, those having a cleavage value of 5 or more by cleavage test described below are preferred, and those having a cleavage value of 20 or more are more preferred.
- the solvent for swelling and cleaving the inorganic layered compound in the present invention when the inorganic layered compound is a hydrophilic swellable inorganic layered compound, water, alcohols (methanol, ethanol, propanol, isopropanol, ethylene glycol, diethylene glycol, etc. ), Dimethylformamide, dimethyl sulfoxide, acetone and the like, among which water, alcohol, and a water-alcohol mixture are preferable.
- the inorganic layered compound is an organically modified inorganic layered compound
- aromatic hydrocarbons such as benzene, toluene and xylene, ethers such as ethyl ether and tetrahydrofuran, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone
- Aliphatic hydrocarbons such as n-pentane, n-hexane and n-octane
- halogenated hydrocarbons such as chlorobenzene, carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane and perchloroethylene
- ethyl acetate methacryl Methyl acid, dioctyl phthalate, dimethylformamide, dimethyl sulfoxide, methyl cellosolve, silicon oil and the like
- solvent such as benzene, toluene and xylene,
- the resin contained in the second layer examples include polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyvinylidene chloride, polyacrylonitrile, polysaccharides, polyacrylic acid and esters thereof, and urethane resins.
- the resin is water-soluble and contains two or more types of functional groups in one molecule, or is water-soluble and contains a first functional group, water-soluble, It is preferable that it is a mixture with resin containing the 2nd functional group different from the functional group.
- Water-soluble here means that 1 g of resin is added to 1000 g of the above-mentioned aqueous medium, and a disperser (manufactured by Asada Tekko Co., Ltd., Despa MH-L, blade diameter 52 mm, rotation speed 3,100 rpm, container capacity 3 L, bottom surface-blade It is said that there is no undissolved residue visually after stirring at 95 ° C. for 90 minutes at a peripheral speed of 8.5 m / min.
- a disperser manufactured by Asada Tekko Co., Ltd., Despa MH-L, blade diameter 52 mm, rotation speed 3,100 rpm, container capacity 3 L, bottom surface-blade
- the functional group contained in the resin is preferably a polar group such as a hydroxyl group, a carboxyl group, an amino group, a sulfonic acid group, a carboxylate group, or an ammonium group, and the functional groups are covalently bonded or ionically bonded. It is preferable that these bonds can be made.
- Examples of the resin containing two or more kinds of functional groups in one molecule include vinyl alcohol-acrylic acid copolymer, vinyl alcohol-methacrylic acid copolymer, vinyl alcohol-vinylamine copolymer, and acrylic acid-vinylamine copolymer. And methacrylic acid-vinylamine copolymer.
- the resin is a mixture of a resin containing a first functional group and a resin containing a second functional group different from the first functional group, polyvinyl alcohol, polyacrylic acid, polymethacrylic acid, polyvinyl
- polyvinyl alcohol a resin containing a first functional group
- polyacrylic acid a resin containing a second functional group different from the first functional group
- polyvinyl a resin containing a second functional group different from the first functional group
- polyvinyl alcohol polyacrylic acid
- polymethacrylic acid polyvinyl
- the resin can be easily dissolved in an aqueous liquid medium, is easy to handle, and has water resistance and gas barrier properties of a multilayer structure having a substrate, a first layer, and a second layer. From the viewpoint of scratch resistance, it is preferably a resin containing a hydroxyl group and a carboxyl group in one molecule, or a mixture of a resin containing a hydroxyl group and a resin containing a carboxyl group.
- the “hydroxyl group” does not include “—OH” in the carboxyl group.
- the resin containing a hydroxyl group and a carboxyl group in one molecule include a vinyl alcohol-acrylic acid copolymer and a vinyl alcohol-methacrylic acid copolymer.
- Examples of the resin containing a hydroxyl group include polyvinyl alcohol and polysaccharides.
- Examples of the resin containing a carboxyl group include polyacrylic acid, polymethacrylic acid, a partially neutralized polyacrylic acid, a partially neutralized polymethacrylic acid, and an acrylic acid-methacrylic acid copolymer.
- polyvinyl alcohol is preferable from the viewpoints of being easy to handle and capable of being dissolved in an aqueous medium, gas barrier properties and scratch resistance of the multilayer structure.
- Polyvinyl alcohol is a polymer having a monomer unit based on vinyl alcohol as a main component.
- polyvinyl alcohol examples include polymers obtained by hydrolyzing the acetate portion of vinyl acetate polymer (vinyl acetate polymer partial hydrolyzate or vinyl acetate polymer complete hydrolyzate), Examples include polymers obtained by hydrolyzing fluorovinyl acetate polymer, vinyl formate polymer, vinyl pivalate polymer, tert-butyl vinyl ether polymer, trimethylsilyl vinyl ether polymer, etc.
- the degree of “saponification” in polyvinyl alcohol is preferably 70 mol% or more, more preferably 85 mol% or more, and even more preferably 98% mol or more of a so-called completely saponified product.
- the degree of polymerization is more preferably from 100 to 5000, and more preferably from 200 to 3000.
- Polyvinyl alcohol derivatives having a functional group other than a hydroxyl group can also be used as the polyvinyl alcohol.
- the functional group other than a hydroxyl group include an amino group, a thiol group, a sulfone group, a phosphate group, a carboxylate group, a sulfonate ion group, Examples thereof include a phosphate ion group, an ammonium group, a phosphonium group, a silyl group, a siloxane group, an alkyl group, an allyl group, a fluoroalkyl group, an alkoxy group, a carbonyl group, and a halogen group.
- a part of hydroxyl groups in polyvinyl alcohol may be replaced with one or more of these functional groups.
- Polysaccharides are biopolymers synthesized in biological systems by condensation polymerization of various monosaccharides, and here include those chemically modified based on them. Examples thereof include cellulose and cellulose derivatives such as hydroxymethylcellulose and hydroxyethylcellulose, amylose, amylopectin, pullulan, curdlan, xanthan, chitin, and chitosan.
- the resin containing a carboxyl group is preferably at least one resin selected from polyacrylic acid, polymethacrylic acid, a polyacrylic acid partial neutralized product, and a polymethacrylic acid partial neutralized product.
- the weight average molecular weight of the resin containing a carboxyl group is preferably in the range of 2,000 to 10,000,000, more preferably 100,000 to 10,000,000.
- the polyacrylic acid partial neutralized product or the polymethacrylic acid partial neutralized product is neutralized by adding an alkali metal ion donating compound described later to an aqueous solution of polyacrylic acid or polymethacrylic acid. It can obtain by making it an alkali metal salt, and it can be set as a desired neutralization degree by adjusting the substance amount ratio of polyacrylic acid or polymethacrylic acid, and an alkali metal ion donor compound.
- the degree of neutralization is calculated by the following formula.
- the partially neutralized polyacrylic acid or the partially neutralized polymethacrylic acid is obtained by bringing an aqueous solution of a completely neutralized polyacrylic acid or a completely neutralized polymethacrylic acid into contact with a hydrogen ion-type ion exchange resin.
- a hydrogen ion-type ion exchange resin can also be obtained. Examples include a method of removing a residue of the hydrogen ion type ion exchange resin after mixing and stirring the polyacrylic acid complete neutralized product or the polymethacrylic acid complete neutralized solution with the hydrogen ion type ion exchange resin.
- polyacrylic acid having a desired degree of neutralization by adjusting the amount ratio of polyacrylic acid completely neutralized product or polymethacrylic acid completely neutralized product and hydrogen ion type ion exchange resin, aqueous solution temperature and stirring time A partially neutralized product or a partially neutralized polymethacrylic acid product can be obtained.
- a method in which an aqueous solution of a completely neutralized polyacrylic acid or a completely neutralized polymethacrylic acid is passed through a column filled with a hydrogen ion type ion exchange resin.
- a polyacrylic acid partial neutralized product or a polymethacrylic acid partial neutralized product having a desired degree of neutralization can be obtained by adjusting the speed and the aqueous solution temperature.
- the polyacrylic acid partial neutralized product and the polymethacrylic acid partial neutralized product have the above neutralization degree from the viewpoint of water resistance and transparency of the multilayer structure having the substrate, the first layer, and the second layer. Is preferably 0.1% to 20%.
- a mixture of a resin containing a hydroxyl group and a resin containing a carboxyl group and a resin containing a hydroxyl group and a carboxyl group in one molecule may be collectively referred to as “resin component containing a hydroxyl group and a carboxyl group”. is there.
- the amount of the hydroxyl group is preferably 30 to 95 mol%, and the carboxyl group Is 5 to 70 mol%.
- the amount of the hydroxyl group is 70 to 95 mol%, and the amount of the carboxyl group is 5 to 30 mol%.
- the total mass of hydroxyl groups and carboxyl groups is 30 to 60% by mass. It is preferable that it is 35 to 55% by mass.
- the total of the mass of the hydroxyl group and the mass of the carboxyl group is a value when the mass of the resin component containing the hydroxyl group and the carboxyl group is 100% by mass.
- the carboxyl group here includes the neutralized carboxyl group.
- the amount of hydroxyl group and carboxyl group contained in the resin component containing a hydroxyl group and a carboxyl group can be determined by a known NMR method, IR method or the like.
- a calibration curve can be obtained and calculated using a sample having a known molar ratio of hydroxyl group to carboxyl group.
- a mixture of a vinyl alcohol homopolymer (completely saponified product of an acetate portion of a vinyl acetate polymer) and an acrylic acid homopolymer and / or a methacrylic acid homopolymer is used, the hydroxyl group and The amount of carboxyl groups can be calculated.
- the total mass of the hydroxyl group and carboxyl group contained in the resin containing a hydroxyl group and a carboxyl group can also be determined by a known NMR method, IR method, or the like.
- a calibration curve can be obtained and calculated for a polyol polymer having a known number of polyol units and a polycarboxylic acid polymer having a known number of polycarboxylic acid units.
- the masses of hydroxyl groups and carboxyl groups are determined from the respective masses. The total mass of carboxyl groups.
- the second layer contains an alkali metal ion.
- alkali metal ions include sodium ions, lithium ions, and potassium ions.
- the mass of alkali metal ions contained in the second layer is 0.2 to 5 parts by mass, preferably 0.2 to 2 when the mass of the resin contained in the second layer is 100 parts by mass. Part by mass.
- the alkali metal ion is derived from an alkali metal ion donating compound. That is, when the resin contained in the second layer is a resin component containing a hydroxyl group and a carboxyl group, the second layer preferably contains an alkali metal ion donating compound. Examples of the alkali metal ion donating compound include sodium hydroxide, sodium hypophosphite, lithium hydroxide, potassium hydroxide and the like. Further, when the inorganic layered compound contained in the second layer is montmorillonite, sodium ions are contained between the montmorillonite layers, so that montmorillonite acts as an alkali metal ion donating compound. Therefore, the inorganic layered compound contained in the second layer is particularly preferably montmorillonite. Two or more kinds of alkali metal ion donor compounds may be used in combination.
- the second layer may further contain a plasticizer.
- the plasticizer is a compound in which at least one hydroxyl group is bonded to each of two or more consecutive carbon atoms in the molecule, and the molecular weight is 200 to 4000.
- the plasticizer is preferably dissolved in water from the viewpoint of good handling when the second layer is formed by coating.
- the plasticizer is preferably a multimer of polyhydric alcohols such as polysorbitol, polymannitol, polydulitol, polyxylitol, polyerythritol, polyglycerin, and most preferably polyglycerin. is there. Two or more plasticizers may be used.
- the plasticizer is preferably polyglycerin. Further, the molecular weight of the plasticizer is preferably 350 to 3000, and more preferably 500 to 2500. From the viewpoint of stretchability during thermoforming, the amount of the plasticizer contained in the second layer is preferably 20 to 150 parts by mass with respect to 100 parts by mass of the resin contained in the second layer, The amount is more preferably 120 parts by mass, further preferably 40 to 120 parts by mass, and most preferably 60 to 110 parts by mass.
- the second layer may contain a known additive, for example, an additive such as an antioxidant, an ultraviolet absorber, a light stabilizer, an antiblocking agent, and a colorant depending on the purpose and application. Two or more kinds of additives may be included.
- an additive such as an antioxidant, an ultraviolet absorber, a light stabilizer, an antiblocking agent, and a colorant depending on the purpose and application. Two or more kinds of additives may be included.
- the multilayer structure according to the present invention may further include a third layer containing a resin adjacent to the second layer.
- the resin contained in the third layer the resins described as the resin used in the second layer can be used.
- the resin used for the second layer and the resin used for the third layer may be the same or different.
- the third layer may further contain an inorganic layered compound.
- the third layer contains an inorganic layered compound, the third layer has a volume fraction of the inorganic layered compound contained in the third layer (however, the volume fraction of the third layer is 100% by volume).
- the third layer can be obtained from the volume fraction of the inorganic layered compound in the second layer (however, the volume fraction of the second layer is 100% by volume). It is preferable that the volume fraction of the inorganic layered compound in the layer (however, the volume fraction of the third layer is 100% by volume) is high. In the case of improving the transparency of the multilayer structure, the third layer is obtained from the volume fraction of the inorganic layered compound in the second layer (however, the volume fraction of the second layer is 100% by volume). It is preferable that the volume fraction of the inorganic layered compound in (in which the volume fraction of the third layer is 100% by volume) is low.
- the third layer may contain the plasticizer, alkali metal ions, and the like.
- the substrate When the substrate is a film, the substrate includes a substrate, a first layer adjacent to the substrate, a second layer adjacent to the first layer, and a third layer adjacent to the second layer.
- the multilayer structure includes one base material, one first layer, one second layer, and one third layer, and the base material, the first layer, and the second layer.
- the mixed liquid is applied to the surface of the substrate to form a first coating film, and then the aqueous medium is removed from the first coating film to obtain the first layer. Can be manufactured.
- a gravure method such as a direct gravure method or a reverse gravure method, a two-roll beat coating method, a bottom feed three reverses
- a roll coating method such as a coating method, a doctor knife method, a die coating method, a bar coating method, a dipping method, or a spray coating method can be applied. It is preferable to employ a dipping method, a spray coating method, or a gravure method because a layer can be easily provided.
- the first coating film may be formed on a part of the substrate surface or on the entire surface.
- the temperature condition for removing the aqueous medium from the first coating film is usually 20 to 150 ° C., preferably 30 to 140 ° C., more preferably 40 to 130 ° C., and further preferably 50 to 120 ° C. .
- the time for removing the aqueous medium is usually 1 second to 24 hours.
- the method for removing the aqueous medium includes a method in which a heat roll is brought into contact with the surface of a substrate on which the first coating film is not formed, a method in which a heat medium such as air is brought into contact with the first coating film, and an infrared ray And a method of heating by microwave and a method of heating by microwave.
- the surface of the substrate to which the mixed solution is applied such as corona treatment, ozone treatment, electron beam treatment, ion treatment, flame treatment using a gas such as silane, atmospheric pressure or reduced pressure plasma treatment, etc.
- Surface treatment may be performed in advance. Moreover, you may perform the said surface treatment also about a 1st layer and a 2nd layer.
- the second layer is a multilayer structure.
- the surface of the first layer is coated with a second coating liquid containing an inorganic layered compound, a resin and a liquid medium to form a second coating film, and then from the second coating film It can be formed by removing the liquid medium.
- a solvent that swells and cleaves the inorganic layered compound described above can be used as the liquid medium of the second coating liquid.
- the inorganic layered compound and the resin are dissolved or dispersed in the liquid medium, respectively, and then mixed to obtain a coating liquid. And a method of obtaining a coating liquid by dissolving or dispersing the inorganic layered compound and the resin in the same liquid medium.
- the plasticizer is included, the inorganic layered compound, resin, and plasticizer are each dissolved or dispersed in a liquid medium and then mixed to form a coating solution. And a method of obtaining a coating liquid by dissolving or dispersing in the same liquid medium.
- the inorganic layered compound is dispersed in the liquid solvent by high-pressure dispersion treatment.
- the high-pressure dispersion treatment is a method in which a mixed liquid obtained by mixing an inorganic layered compound in a liquid medium is passed through a plurality of thin tubes at a high speed and then merged, and the mixed liquids or the mixed liquid and the inner wall of the thin tube collide with each other. , A method of applying high shear and / or high pressure to the mixed solution.
- the mixed solution is passed through a thin tube having a tube diameter of about 1 ⁇ m to 1000 ⁇ m, and at this time, the maximum pressure of 100 kgf / cm 2 or more is applied. Maximum pressure is more preferably at 500 kgf / cm 2 or more, and particularly preferably 1000 kgf / cm 2 or more. Further, when the mixed liquid passes through the narrow tube, the maximum arrival speed of the dispersion is preferably 100 m / s or more, and the heat transfer speed due to pressure loss is preferably 100 kcal / hour or more.
- a high-pressure dispersion device such as an ultrahigh-pressure homogenizer (trade name: Microfluidizer) manufactured by Microfluidics Corporation, a nanomizer manufactured by Nanomizer, a Manton Gorin type high-pressure dispersion device, or a homogenizer manufactured by Izumi Food Machinery can be used.
- the mixed solution to be subjected to the high-pressure dispersion treatment may contain a resin.
- the second coating film can be formed by using a method similar to the method for forming the first coating film.
- the same conditions as the temperature condition, time, and heat source for removing the aqueous medium from the first coating film can be applied.
- a surfactant to the second coating liquid.
- a second coating liquid containing a surfactant to the surface of the first layer to form the second layer, the adhesion between the second layer and the first layer Can be improved.
- the content of the surfactant is usually 0.001 to 5% by mass in 100% by mass of the coating liquid.
- the surfactants used as the above-mentioned emulsifiers can be used.
- Fluorine type nonionic surfactants fluorine type nonionic surfactants
- ether type nonionic surfactants silicone type nonionic surfactants
- polymers and perfluoroalkylethylene oxide compounds Is preferable from the viewpoint of improving adhesion.
- the third layer is a second layer of the multilayer structure.
- a third coating solution containing a resin and a liquid medium is applied to the surface of the layer to form a third coating film, and then the liquid medium is removed from the third coating film. can do.
- a solvent that swells and cleaves the above-mentioned inorganic layered compound can be used as in the case of the second coating liquid.
- the third coating liquid can be prepared by the same method as the second coating liquid when the third coating liquid contains an inorganic layered compound or a plasticizer.
- the third coating liquid contains an inorganic layered compound
- it may be a coating liquid that has been subjected to a high-pressure dispersion treatment, as with the second coating liquid.
- a surfactant may be added to the third coating liquid.
- the method for forming the third coating film and the method for removing the liquid medium from the third coating film are the method for forming the second coating film and the method for removing the liquid medium from the second coating film, respectively. Can be used.
- the thickness of the first layer in the multilayer structure according to the present invention is usually in the range of 0.5 to 20 ⁇ m.
- the thickness is usually in the range of 0.05 to 10 ⁇ m, and the thickness of the second layer is the third layer. It is preferably thicker than the thickness of the layer.
- the multilayer structure according to the present invention when one or both of the second layer and the third layer contain a resin having two or more kinds of functional groups, the water resistance, gas barrier property and scratch resistance are improved. Therefore, it is preferable to dry-heat the multilayer structure according to the present invention.
- a structure obtained by subjecting a multilayer structure to a dry heat treatment may be referred to as a dry heat treatment body.
- the dry heat treatment is a treatment for holding the multilayer structure in an atmosphere of 100 ° C. or more and 300 ° C. or less and a water vapor concentration of less than 50 g / m 3 .
- the dry heat treatment temperature is preferably 120 ° C. or higher and 200 ° C. or lower.
- the time for the dry heat treatment is usually 1 second to 1 hour.
- the water vapor concentration during the dry heat treatment is preferably 0 to 40 g / m 3 .
- Examples of the dry heat treatment include a method in which the multilayer structure is brought into contact with a heat medium such as a hot roll or air, and a method in which the multilayer structure is heated with infrared rays or microwaves. Further, when the multilayer structure according to the present invention is thermoformed as described later, the heat treatment at the time of thermoforming can be the dry heat treatment.
- the dry heat-treated body is wet-heat treated.
- a structure obtained by wet-heat-treating a dry heat-treated body may be referred to as a wet-heat treated body.
- the wet heat treatment is a treatment for holding the dry heat-treated body in an atmosphere having a water vapor concentration exceeding 290 g / m 3 at a temperature of 100 ° C. or higher or in water of 80 ° C. or higher.
- the time for the wet heat treatment is usually 1 second to 1 hour. If the water vapor concentration at 100 ° C. or higher temperatures for processing the dry heat treatment thereof in an atmosphere of 290 g / m 3 greater, the temperature is preferably in the range of 120 ⁇ 200 ° C., the water vapor concentration in the range of 500 ⁇ 20000g / m 3 Is preferred. When the dry heat-treated body is treated in water at 80 ° C. or higher, the temperature is preferably within the range of 100 to 140 ° C. Before the wet heat treatment, the dry heat-treated body may be aged, for example, under conditions of 23 ° C. and humidity 50% RH.
- a drying treatment may be performed after the wet heat treatment.
- the drying treatment is usually a treatment method in which the wet heat treatment body is held at a humidity of 50% RH or less and a temperature of 20 to 100 ° C. for 1 second to 24 hours.
- the multilayer structure according to the present invention is used as a molded body such as a container or a bottle or a decorative sheet
- the multilayer structure is composed of the second layer and the third layer from the viewpoint of water resistance, gas barrier properties, and scratch resistance. It is preferable to have.
- the dry heat treatment body and the wet heat treatment body according to the present invention are used as a molded body such as a container or a bottle or a decorative sheet
- the second layer or the second layer is used from the viewpoint of water resistance, gas barrier properties, and scratch resistance.
- a dry heat-treated body and a wet heat-treated body of a multilayer structure having 3 layers are preferred.
- the first layer may be formed on at least one surface of a base material previously shaped into a predetermined shape, and then a second layer or a third layer may be formed as necessary.
- a first layer is formed on at least one surface of a preformed base material such as a parison, a second layer or a third layer is formed as necessary to form a multilayer structure, and then thermoforming. It may be shaped into a predetermined shape.
- the thermoforming is a forming method in which a base material or a multilayer structure is heat-treated and shaped into a predetermined shape, and examples thereof include blow molding, vacuum forming, pressure forming, and vacuum / pressure forming.
- the thermoforming is performed after holding the temperature of the base material to be thermoformed or the multilayer structure at 100 to 250 ° C. for 1 to 60 seconds, and then the base material or the multilayer structure.
- the temperature is within the range of not less than 30 ° C. lower than the glass transition temperature of the crystalline thermoplastic resin contained in the substrate and not more than 30 ° C. higher than the glass transition temperature of the crystalline thermoplastic resin. It is preferable to shape the material and the multilayer structure.
- the crystalline thermoplastic resin here is a thermoplastic resin having a glass transition temperature and a melting point. The glass transition temperature can be measured using a differential scanning calorimeter (DSC) or the like.
- the temperature of the multilayer structure is held at 100 to 250 ° C. for 1 to 60 seconds, and then the temperature of the substrate or the multilayer structure is included in the substrate.
- the base material or the multilayer structure is applied when the temperature is within a range of 30 ° C. lower than the glass transition temperature of the amorphous thermoplastic resin and 30 ° C. higher than the glass transition temperature of the amorphous thermoplastic resin.
- the amorphous thermoplastic resin here is a thermoplastic resin that has only a glass transition temperature and no melting point. The presence of the glass transition temperature and the melting point can be measured using the above-described DSC or the like.
- thermoforming the multilayer structure When the multilayer structure is thermoformed, the heat treatment at the time of thermoforming corresponds to the dry heat treatment. Therefore, the molded product obtained by thermoforming the multilayer structure is a dry heat treatment body.
- a wet heat-treated body can be obtained by wet-heat-treating a dry heat-treated body obtained by thermoforming the multilayer structure.
- the sheet-shaped multilayer structure is thermoformed to produce a dry heat treatment body, and then the dry heat treatment
- a plasticized thermoplastic resin By supplying a plasticized thermoplastic resin to the base material side of the body and shaping, a molded product can be obtained.
- the second layer and the third layer in the multilayer structure of the present invention contains a resin having two or more types of functional groups
- heat treatment is performed during the dry heat treatment or thermoforming.
- the reaction of the functional group further proceeds and the water resistance, gas barrier property, and scratch resistance become higher.
- the second layer or the third layer contains a plasticizer, the stretchability is excellent, so that the cracking of the second layer or the third layer can be suppressed during the thermoforming.
- the layer formed from the mixed liquid according to the present invention is made of a base material such as plastic, particularly a polyolefin base material, an amorphous resin base material such as polymethyl methacrylate, polyvinyl chloride, and polystyrene, even under high humidity conditions.
- a base material such as plastic, particularly a polyolefin base material, an amorphous resin base material such as polymethyl methacrylate, polyvinyl chloride, and polystyrene, even under high humidity conditions.
- the liquid mixture which concerns on this invention can be used as an adhesive agent or a primer agent.
- the multilayer structure comprising the substrate and the first layer according to the present invention is particularly firmly bonded to a layer containing an inorganic layered compound such as the second layer.
- the multilayer structure according to the present invention has the second layer or the third layer, it is excellent in water resistance and gas barrier properties, and is therefore suitable as a packaging material and container, and is further resistant to scratches, heat resistance, and optics. Since it is excellent in characteristics, it can be used as a molded product, a substrate, or a vacuum heat insulation panel used as a decorative sheet.
- examples of the shape of the multilayer structure include films, bags, pouches, bottles, bottle caps, carton containers, cups, dishes, trays, tanks, tubes, and syringes.
- the contents include foods and non-foods. Examples of foods include confectionery, processed foods, and beverages.
- Non-food items include toiletry products, fuels, pharmaceuticals, electronic components and electronic equipment.
- housing exterior parts include rain gutters, entrance decorative covers, and underfloor ventilation openings.
- house interior parts include interior door units, closet folding door units, skirting boards, tatami mats, edges, construction materials, sill slides, window frames, handrails, flooring, wall boards, ceiling boards, and the like.
- furniture members include decorative panels, drawers, front doors around sinks, bed bumpers, tables, chairs, various cases, lighting fixture parts, and picture frames.
- Automotive exterior parts include bumpers, door mirrors, and fender bodies.
- Automotive interior parts include instrument panels, dashboards, door trims, and body side trims.
- motorcycle exterior parts include hoods and cowlings.
- Home appliance parts include refrigerator doors and washing machine waterproof vans.
- the substrate include a display substrate and a solar cell substrate.
- the display substrate include a liquid crystal display substrate and a flexible display substrate such as an organic EL substrate.
- the solar cell substrate include a silicon solar cell substrate and a dye-sensitized solar cell substrate.
- the thickness of 0.5 ⁇ m or more was measured using a digital thickness gauge (contact thickness gauge, trade name: ultra-high precision deci-micro head MH-15M, manufactured by Nippon Optical Co., Ltd.). The thickness of less than 0.5 ⁇ m was determined by cross-sectional observation with a transmission electron microscope (TEM).
- TEM transmission electron microscope
- Amount of monomer unit based on compound selected from the group consisting of ⁇ , ⁇ -unsaturated carboxylic acid and ⁇ , ⁇ -unsaturated carboxylic acid anhydride in olefin polymer For the olefin polymer (1), monomer units based on a compound selected from the group consisting of ⁇ , ⁇ -unsaturated carboxylic acid and ⁇ , ⁇ -unsaturated carboxylic acid anhydride in the olefin polymer by the following method: The amount was measured. A solution prepared by dissolving 1.0 g of the olefin polymer in 20 ml of xylene was dropped into 300 ml of stirred methanol to precipitate the olefin polymer.
- the precipitated olefin polymer was collected and dried under vacuum (80 ° C., 8 hours).
- a film having a thickness of 100 ⁇ m was prepared by hot pressing using the dried olefin polymer, and an infrared absorption spectrum of the obtained film was measured. From absorption near 1780 cm ⁇ 1 , maleic anhydride in the olefin polymer was measured. The content (mass) of monomer units based on was quantified.
- the catalog value was adopted for the amount of the monomer unit based on the compound selected from the group consisting of ⁇ , ⁇ -unsaturated carboxylic acid and ⁇ , ⁇ -unsaturated carboxylic acid anhydride in the olefin polymer (2).
- the catalog value was a value obtained from an infrared absorption spectrum.
- Amount of monomer units based on ⁇ , ⁇ -unsaturated carboxylic acid ester in olefin polymer The amount of monomer units based on the ⁇ , ⁇ -unsaturated carboxylic acid ester contained in the olefin polymer (1) was measured by the following method. 50 mg of an olefin polymer was dissolved in 1.0 mL of deuterated o-dichlorobenzene, and 1 H-NMR was measured.
- Amount of hydroxyl group (mol) (mass of polyvinyl alcohol (g)) / (molecular weight per unit of monomer unit constituting polyvinyl alcohol)
- Amount of carboxyl group (mole) (mass of polyacrylic acid (g)) / (molecular weight per unit of monomer unit constituting polyacrylic acid)
- the mass of the resin is the sum of the mass of polyvinyl alcohol and the mass of polyacrylic acid in the second layer.
- the sodium ion concentration of the dried product of the coating liquid (5) was measured to determine the sodium ion concentration in the second layer.
- the sample preparation method is as follows. 1 g of a dried product of the coating solution was collected, 1 ml of 96% sulfuric acid was added thereto, and then ashed in an electric furnace, and the remaining residue was dissolved in 5% hydrochloric acid. The solution was subjected to an inductively coupled plasma optical emission spectrometer, and the sodium ion concentration was measured.
- the oxygen permeability of the dry heat-treated bodies (1) to (4) was measured under the condition of 23 ° C. and 90% RH using an ultrasensitive oxygen permeability measuring device (OX-TRANML, manufactured by MOCON) based on JIS K7126. Measured at It represents that gas barrier property is so high that oxygen permeability is small.
- the dry heat treatment bodies (1) to (4) were subjected to an adhesion test by the following method. Under the condition of 23 ° C. and 50% RH, 10 ⁇ 10 cuts of 2 mm square were made on the surface of the second layer. Cellophane tape was applied to the dry heat-treated body so as to cover all the cut portions of the second layer, and it was aged overnight at 23 ° C. and 0% RH. The cellophane tape was peeled off, and the number of eyes where the second layer remained on the dry heat-treated body was counted.
- Preparation of coating solution (1) Preparation of coating liquid (1) A 2 L separable flask reactor was equipped with a stirrer, thermometer, dropping funnel and reflux condenser, and the gas in the reactor was replaced with nitrogen. As a solvent, 616 parts by mass of xylene and a propylene-1-butene copolymer (obtained by the method described in Japanese Patent No. 40254401. 96 mol% of a monomer unit based on propylene, a monomer based on 1-butene (4 mol% unit) 100 parts by mass, maleic anhydride 50 parts by mass, and n-butyl methacrylate 25 parts by mass were added and heated to 140 ° C. and stirred to obtain a solution.
- Mw of the obtained polymer was 72,604, Mn was 40,750, molecular weight distribution (Mw / Mn) was 1.8, MFR was 4.2 g / 10 min, and olefin polymer (1) was 100% by mass.
- Mw / Mn molecular weight distribution
- MFR MFR was 4.2 g / 10 min
- olefin polymer (1) was 100% by mass.
- the monomer unit based on maleic anhydride was 1.7% by mass and the monomer unit based on n-butyl methacrylate was 1.3% by mass.
- 200 parts by mass of toluene and 100 parts by mass of the olefin polymer (1) were placed as a solvent, and stirred at 90 ° C. The union (1) was dissolved.
- a mixed solution of 10 parts by mass of Jeffermine M1000 (manufactured by Mitsui Chemicals Fine) and 10 parts by mass of isopropanol was added dropwise over 10 minutes. After further stirring for 5 minutes, 5 parts by mass of dimethylethanolamine was added and further stirred for 5 minutes to obtain an olefin polymer mixture (1). Subsequently, the stirring device was changed to TK Robotics (manufactured by PRIMIX Co., Ltd.), and a mixed solution of 100 parts by mass of isopropanol and 100 parts by mass of ion-exchanged water was stirred while stirring the olefin polymer mixed solution (1) with a disper blade.
- TK Robotics manufactured by PRIMIX Co., Ltd.
- olefin polymer preliminary dispersion (1) was put into a 2 L eggplant flask, a part of the solvent was distilled off under reduced pressure using an evaporator, and then filtered through a 200 mesh nylon net to obtain a coating solution (1 )
- the particle diameter of the dispersed olefin polymer (1) in the obtained coating liquid (1) is 4.6 ⁇ m, and the solid content concentration measured by the method according to JIS K-6828-1 is 38%. there were.
- the olefin polymer (2) (BONDINE HX8290 (manufactured by ARKEMA), a monomer unit based on ethylene, a monomer unit based on ethyl acrylate, and a monomer based on maleic anhydride Polymer having units) 100 parts by mass, as an emulsifier liquid, Latmul E-1000A (30% aqueous solution, manufactured by Kao Corporation) 17 parts by mass, Neugen EA-177 (Daiichi Kogyo Seiyaku Co., Ltd.) 5 parts by mass And the coating liquid (3) was obtained like the coating liquid (1) except using the mixed liquid of 5 mass parts of isopropanol.
- the particle diameter of the dispersed olefin polymer (2) in the obtained coating liquid (3) was 0.2 ⁇ m, and the solid content concentration measured by a method according to JIS K-6828-1 was 38%.
- the olefin polymer (2) is 100% by mass, the monomer unit based on ethylene is 80% by mass, the monomer unit based on maleic anhydride is 3% by mass, and the monomer unit based on ethyl acrylate is 17% by mass. It was mass%.
- Coating liquid (4) A coating liquid (4) was obtained in the same manner as the coating liquid (2) except that the coating liquid (3) was used instead of the coating liquid (1).
- the total amount of the olefin polymer (2) in the coating liquid (4) and the water-soluble resin composed of polyvinyl alcohol and polyacrylic acid is 100% by mass, the content of the water-soluble resin is 20% by mass. Met.
- coating liquid (5) In a dispersion kettle (trade name: Despa MH-L, manufactured by Asada Tekko Co., Ltd.), 1300 g of ion-exchanged water (specific electric conductivity 0.7 ⁇ s / cm or less) and polyvinyl 130 g of alcohol (AQ2117; manufactured by Kuraray Co., Ltd., degree of saponification; 99.6%, degree of polymerization 1,700) was mixed, and the temperature was raised to 95 ° C. under low speed stirring (1500 rpm, peripheral speed 4.1 m / min). Warm up. The mixed system was stirred at the same temperature for 30 minutes to dissolve the polyvinyl alcohol, and then cooled to 60 ° C.
- a dispersion kettle (trade name: Despa MH-L, manufactured by Asada Tekko Co., Ltd.), 1300 g of ion-exchanged water (specific electric conductivity 0.7 ⁇ s / cm or less) and polyvinyl 130 g of alcohol (AQ
- Kunipia G manufactured by Kunimine Industries Co., Ltd.
- clay mineral-containing liquid (1) 0.1% by mass of the nonionic surfactant (polydimethylsiloxane-polyoxyethylene copolymer, trade name: SH3746, manufactured by Toray Dow Corning Co., Ltd.) based on the clay mineral-containing liquid (1) (Based on the mass of the dispersion) under low speed stirring (1500 rpm, peripheral speed 4.1 m / min), and then adjusted with an ion exchange resin so that the pH of the system becomes 6, clay mineral dispersion ( 1) was prepared.
- the nonionic surfactant polydimethylsiloxane-polyoxyethylene copolymer, trade name: SH3746, manufactured by Toray Dow Corning Co., Ltd.
- a resin component (A3) solution was prepared by mixing 33 g of an average molecular weight of 1,000,000 (manufactured by Co., Ltd.) and stirring at low temperature (1500 rpm, peripheral speed 4.1 m / min) at room temperature.
- 2519 g of the clay mineral dispersion (1) and 1100 g of the resin component (A3) solution are gradually mixed under low speed stirring (1500 rpm, peripheral speed 4.1 m / min) to form a mixed liquid, and the mixed liquid is further mixed with a high pressure dispersing device.
- a coating liquid (5) was obtained.
- the cleaved montmorillonite average particle diameter L in the coating liquid (5) was 560 nm, the a value obtained from powder X-ray diffraction was 1.2156 nm, and the aspect ratio Z was 460.
- Example 1 A 150 ⁇ m sheet made of a cyclic olefin resin (trade name: Apel APL5014DP; manufactured by Mitsui Chemicals, Inc.) was used as a base material.
- the above-mentioned coating liquid (2) is applied to one surface of the base material using a bar coater (# 8) and dried at 80 ° C. for 20 minutes, so that the base material and the base material are adjacent to each other.
- a multilayer structure (1 ′) having a first layer was obtained. Furthermore, by applying the above-mentioned coating liquid (5) to the surface of the first layer of the multilayer structure (1 ′) using a bar coater (# 28), and drying at 80 ° C.
- a second layer was formed to obtain a multilayer structure (1) having a base material, a first layer, and a second layer.
- the thickness of the first layer was 5 ⁇ m
- the thickness of the second layer was 0.2 ⁇ m.
- the Na concentration in the second layer was 0.7%.
- the obtained multilayer structure (1) was subjected to a dry heat treatment to obtain a dry heat treated body (1), which was then aged in a 23 ° C., 50% RH atmosphere for 24 hours for evaluation. The results are shown in Table 1.
- Example 2 A multilayer structure (2) having a base material and a first layer adjacent to the base material in the same manner as in Example 1 except that the coating liquid (4) was used instead of the coating liquid (2). ') Got. Further, the second layer is formed on the surface of the first layer of the multilayer structure (2 ′) in the same manner as in Example 1, and the multilayer has the base material, the first layer, and the second layer. A structure (2) was obtained. The thickness of the first layer was 5 ⁇ m, and the thickness of the second layer was 0.2 ⁇ m. The Na concentration in the second layer was 0.7%. The obtained multilayer structure (2) was subjected to a dry heat treatment to obtain a dry heat treated body (2), which was then evaluated by aging for 24 hours in an atmosphere of 23 ° C. and 50% RH. The results are shown in Table 1.
- Example 1 A multilayer structure (3) having a base material and a first layer adjacent to the base material in the same manner as in Example 1 except that the coating liquid (1) was used instead of the coating liquid (2). ') Got. Further, the second layer is formed on the surface of the first layer of the multilayer structure (3 ′) in the same manner as in Example 1, and the multilayer includes the base material, the first layer, and the second layer. A structure (3) was obtained. The thickness of the first layer was 5 ⁇ m, and the thickness of the second layer was 0.2 ⁇ m. The Na concentration in the second layer was 0.7%. The obtained multilayer structure (3) was subjected to a dry heat treatment to obtain a dry heat treated body (3), which was then aged in a 23 ° C., 50% RH atmosphere for 24 hours for evaluation. The results are shown in Table 1.
- Example 2 A multilayer structure (4) having a base material and a first layer adjacent to the base material in the same manner as in Example 1 except that the coating liquid (3) was used instead of the coating liquid (2). ') Got. Further, the second layer is formed on the surface of the first layer of the multilayer structure (4 ′) in the same manner as in Example 1, and the base layer, the first layer, and the second layer are provided. A structure (4) was obtained. The thickness of the first layer was 5 ⁇ m, and the thickness of the second layer was 0.2 ⁇ m. The Na concentration in the second layer was 0.7%. The obtained multilayer structure (4) was subjected to a dry heat treatment to obtain a dry heat treated body (4), which was then aged in a 23 ° C., 50% RH atmosphere for 24 hours for evaluation. The results are shown in Table 1.
- a layer capable of firmly bonding a base material and a coating film containing an inorganic layered compound can be formed even under high humidity conditions.
- even under high humidity conditions it is possible to obtain a multilayer structure in which the base material and the coating film containing the inorganic layered compound are firmly bonded via the adhesive layer.
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Abstract
Description
また本発明は、他の面において、以下の工程(1)および(2)を順に含む前記混合液の製造方法に係るものである。
(1) 前記オレフィン重合体を水系媒体に分散し、オレフィン重合体分散液を得る工程
(2) 前記オレフィン重合体分散液に水溶性樹脂水溶液を混合する工程
またさらに本発明は、他の面において、基材と、基材に隣接する第1の層を有する多層構造体であって、前記第1の層が、炭素原子数2~20のα−オレフィンに基づく単量体単位と、α,β−不飽和カルボン酸エステルに基づく単量体単位と、α,β−不飽和カルボン酸およびα,β−不飽和カルボン酸無水物からなる群より選ばれる化合物に基づく単量体単位とを有し、前記α−オレフィンに基づく単量体単位の含有量が50質量%以上であるオレフィン重合体(ただし、炭素原子数2~20のα−オレフィンに基づく単量体単位と、α,β−不飽和カルボン酸エステルに基づく単量体単位と、α,β−不飽和カルボン酸およびα,β−不飽和カルボン酸無水物からなる群より選ばれる化合物に基づく単量体単位の合計量を100質量%とする)と、水溶性樹脂とを含有する層である多層構造体に係るものである。
本発明の混合液に含まれるオレフィン重合体は、炭素原子数2~20のα−オレフィンに基づく単量体単位と、α,β−不飽和カルボン酸エステルに基づく単量体単位と、α,β−不飽和カルボン酸およびα,β−不飽和カルボン酸無水物からなる群より選ばれる化合物に基づく単量体単位とを有し、前記α−オレフィンに基づく単量体単位の含有量が50質量%以上であるオレフィン重合体(ただし、炭素原子数2~20のα−オレフィンに基づく単量体単位と、α,β−不飽和カルボン酸エステルに基づく単量体単位と、α,β−不飽和カルボン酸およびα,β−不飽和カルボン酸無水物からなる群より選ばれる化合物に基づく単量体単位の合計量を100質量%とする)である。本発明の混合液は、2種類以上のオレフィン重合体を含んでもよい。
前記オレフィン重合体は、エチレン、プロピレン1−ブテンからなる群より選ばれる1種以上のα−オレフィンに基づく単量体単位を有することが好ましく、プロピレンに基づく単量体単位と1−ブテンに基づく単量体単位とを有することがより好ましい。オレフィン重合体がプロピレンに基づく単量体単位と1−ブテンに基づく単量体単位とを有する重合体である場合、該重合体中のプロピレンに基づく単量体単位と1−ブテンに基づく単量体単位の合計量を100モル%とするとき、プロピレンに基づく単量体単位の含有量が70~99モル%であることが好ましい。
本発明の混合液は水溶性樹脂を含む。ここでいう水溶性とは、樹脂1gを後述の水系媒体1000gに加え、分散機(浅田鉄工株式会社製、デスパMH−L、羽根径52mm、回転数3,100rpm、容器容量3L、底面−羽根間の距離28mm)にて、周速8.5m/分、95℃で90分間攪拌させた後、目視にて溶け残りが無いこという。本発明の混合液は、2種類以上の水溶性樹脂を含んでもよい。
カルボキシル基を含む樹脂としては、ポリアクリル酸、ポリメタアクリル酸、ポリアクリル酸部分中和物またはポリメタアクリル酸部分中和物が挙げられる。
アミノ基を有する樹脂としては、ポリビニルアミンが挙げられる。
本発明の混合液に含まれる水系媒体は、水を主成分とする液体媒体である。水系媒体は水のみであってもよく、水と下記液体媒体との混合物であってもよい。水系媒体として用いられる水とは異なる液体媒体としては、アルコール(メタノール、エタノール、プロパノール、イソプロパノール、エチレングリコール、ジエチレングリコールなど)、ジメチルホルムアミド、ジメチルスルホキシド、アセトン等が挙げられ、アルコールが好ましい。
本発明の混合液を100質量%としたとき、オレフィン重合体と水溶性樹脂との合計量は、1~50質量%であることが好ましく、3~40質量%であることがより好ましく、5~30質量%であることがより好ましい。
本発明の混合液の製造方法としては、オレフィン重合体と水溶性樹脂とを同じ水系媒体に溶解または分散する方法、オレフィン重合体を水系媒体に分散させた後、該水系媒体に水溶性樹脂を混合する方法、水系媒体に水溶性樹脂を溶解した後、該水系媒体にオレフィン樹脂を分散させる方法、オレフィン重合体、水溶性樹脂をそれぞれ水系媒体に溶解あるいは分散させた後、これらを混合する方法が挙げられるが、(1)前記オレフィン重合体を水系媒体に分散し、オレフィン重合体分散液を得る工程、および(2)前記オレフィン重合体分散液に水溶性樹脂水溶液を混合する工程を順に含むことが好ましい。
(a)反応器に、オレフィン重合体及び有機溶剤を投入し、これらを加熱および攪拌して、オレフィン重合体を溶剤に溶解し、次いで得られた溶液に水および有機溶剤からなる群より選ばれる液体媒体と、乳化剤とを投入し、これらを加熱及び攪拌し、この前後にさらに任意に水および有機溶剤からなる群より選ばれる液体媒体を投入して攪拌する方法(溶媒乳化法)、
(b)混練機に、オレフィン重合体、任意に有機溶剤を投入し、これらを加熱および攪拌して、オレフィン重合体を溶融し、次いで溶融したオレフィン重合体に水および有機溶剤からなる群より選ばれる液体媒体と、乳化剤とを投入し、これらを加熱及び攪拌し、この前後にさらに任意に水および有機溶剤からなる群より選ばれる液体媒体を投入して攪拌する方法(機械乳化法)等が挙げられる。ただし、(a)および(b)の方法のいずれにおいても、少なくとも1回水が投入される。
有機溶剤としては、オレフィン重合体を溶解させることのできる有機溶剤が用いられ、具体的には、トルエン、キシレン、メチルシクロヘキサン等の有機溶剤が挙げられる。
このような反応器としては、例えば、撹拌機付耐圧オートクレーブ等が挙げられる。
攪拌は、常圧または減圧のいずれで行なってもよい。また、撹拌は、例えば、50~1000rpm程度の回転数で行なうことができる。オレフィン重合体の分散/攪拌が進むにつれて、回転数を上げることが好ましい。
温度は、通常、50~200℃、好ましくは60~150℃、さらに好ましくは70~100℃である。
また、オレフィン重合体分散液の製造工程において、乳化剤は、所望の範囲内で使用することが好ましいが、乳化剤を過剰に用いた場合には、得られたオレフィン重合体分散液から過剰の乳化剤を分離除去してもよい。乳化剤の分離除去方法としては、例えば、遠心分離機、平均細孔径がオレフィン重合体分散液の平均粒子径よりも小さい細孔を有する濾過フィルターまたは限外濾過膜などを用いる方法が挙げられる。
本発明に係る多層構造体は、基材と、基材に隣接する第1の層を有する多層構造体であって、前記第1の層が、炭素原子数2~20のα−オレフィンに基づく単量体単位と、α,β−不飽和カルボン酸エステルに基づく単量体単位と、α,β−不飽和カルボン酸およびα,β−不飽和カルボン酸無水物からなる群より選ばれる化合物に基づく単量体単位とを有し、前記α−オレフィンに基づく単量体単位の含有量が50質量%以上であるオレフィン重合体と、水溶性樹脂とを含有する層である多層構造体である。
該基材を構成する材料としては、金属や、樹脂、木材、セラミック、ガラス等が挙げられる。
基材の形態は、紙や、布、不織布、フィルム等が挙げられる。
金属としては、銅、鉄、銀、アルミニウム等が挙げられ、またこれらの合金も含まれる。
セラミックとしては、アルミナ、シリカ、ジルコニア、酸化チタンが挙げられる。
樹脂としては熱可塑性樹脂や熱硬化性樹脂、光硬化性樹脂等を用いることができる。
熱可塑性樹脂としては、オレフィン系樹脂、エチレン系共重合体、エステル系樹脂、アミド系樹脂、ポリアリレート、アクリル系樹脂、ポリスチレン、スチレン系樹脂、疎水化セルロース系樹脂、塩素系樹脂、フッ素系樹脂、水素結合性樹脂、カーボネート樹脂、サルホン樹脂、エーテルサルホン樹脂、エーテルエーテルケトン樹脂、フェニレンオキシド樹脂、メチレンオキシド樹脂、イミド樹脂等が挙げられる。
環状オレフィン樹脂としては、環状オレフィンの単独重合体あるいは環状オレフィンと他のコモノマーとの共重合体であり、主鎖および/または側鎖に脂環式構造を有するものである。該環状オレフィンの具体例としては、シクロブテン、シクロペンテン、シクロヘキセン、シクロオクテン等の単環状オレフィン;3−メチルシクロペンテン、4−メチルシクロペンテン、3−メチルシクロヘキセン等の置換単環状オレフィン;ノルボルネン、1,2−ジヒドロジシクロペンタジエン、テトラシクロドデセン(ジメタノオクタヒドロナフタレン)等の多環状オレフィン;5−メチルノルボルネン等の置換多環状オレフィンが例示できる。
エステル系樹脂としては、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート等が挙げられる。
アミド系樹脂としては、ナイロン−6(Ny−6)、ナイロン−6,6、メタキシレンジアミン−アジピン酸縮重合体、ポリメチルメタクリルアミド、ポリメタキシリレンアジパミド(MXD6−Ny)等が挙げられる。
アクリル系樹脂としては、ポリメチルメタクリレート等が挙げられる。
スチレン系樹脂としては、AS樹脂、ABS樹脂等が挙げられる。
疎水化セルロース系樹脂としては、トリ酢酸セルロース、ジ酢酸セルロース等が挙げられる。
塩素系樹脂としては、ポリ塩化ビニル、ポリ塩化ビニリデン等が挙げられる。
フッ素系樹脂としては、ポリフッ化ビニル、ポリフッ化ビニリデン、ポリテトラフルオロエチレン、エチレン−テトラフルオロエチレン共重合体、テトラフルオロエチレン−パーフルオロアルキルビニルエーテル共重合体等が挙げられる。
水素結合性樹脂としては、ポリビニルアルコール、エチレン−ビニルアルコール共重合体(EVOH)、セルロース誘導体等が挙げられ、このうち、樹脂単位質量あたりの水酸基の質量分率が20~60%の割合を満たす重合体が好ましい。
光硬化性樹脂としては、光重合開始剤を用いて、1分子中に2つ以上のエポキシ基を有するエポキシ系化合物や、1分子中に2つ以上のアクリロイル基やメタアクリロイル基を有するアクリル系化合物を、それぞれ重合して得られるエポキシ系樹脂、アクリル系樹脂等が挙げられる。
本発明に係る多層構造体がフィルムである場合には、基材は無延伸フィルム、一軸延伸フィルム、二軸延伸フィルムのいずれかであってもよい。
また基材は、Ny−6層/MXD6−Ny層/Ny−6層やポリプロピレン層/エチレン−ビニルアルコール共重合体層/ポリプロピレン層のような多層フィルムであってもよく、アルミニウム、アルミナ、シリカが蒸着されたフィルムであってもよい。
前記第1の層に含有されるオレフィン系重合体は、炭素原子数2~20のα−オレフィンに基づく単量体単位と、α,β−不飽和カルボン酸エステルに基づく単量体単位と、α,β−不飽和カルボン酸およびα,β−不飽和カルボン酸無水物からなる群より選ばれる化合物に基づく単量体単位とを有し、前記α−オレフィンに基づく単量体単位の含有量が50質量%以上であるオレフィン重合体(ただし、炭素原子数2~20のα−オレフィンに基づく単量体単位と、α,β−不飽和カルボン酸エステルに基づく単量体単位と、α,β−不飽和カルボン酸およびα,β−不飽和カルボン酸無水物からなる群より選ばれる化合物に基づく単量体単位の合計量を100質量%とする)であり、上述の混合液に含まれるオレフィン重合体として例示したオレフィン重合体を用いることができる。
前記第1の層に含有される水溶性樹脂は、上述の混合液に含まれる水溶性樹脂を用いることができる。
基材がフィルムである場合、基材と、基材に隣接する第1の層を有する多層構造体としては、1つの基材と1つの第1の層とを有し、基材の一方の面に第1の層が隣接して積層されている多層構造体、1つの基材と2つの第1の層とを有し、第1の層、基材、第1の層の順にこれらが隣接して積層されている多層構造体が挙げられる。
本発明に係る多層構造体は、前記第1の層に隣接して、無機層状化合物および樹脂を含む第2の層をさらに有する多層構造体でもよい。該第2の層を有する多層構造体はガスバリア性、耐傷つき性に優れる。
基材がフィルムである場合、基材と、基材に隣接する第1の層と、第1の層に隣接する第2の層とを有する多層構造体としては、1つの基材と1つの第1の層と1つの第2の層とを有し、基材、第1の層、第2の層の順にこれらが隣接して積層されている多層構造体、1つの基材と2つの第1の層と1つの第2の層を有し、第1の層、基材、第1の層、第2の層の順にこれらが隣接して積層されている多層構造体、1つの基材と2つの第1の層と2つの第2の層を有し、第2の層、第1の層、基材、第1の層、第2の層の順にこれらが隣接して積層されている多層構造体が挙げられる。
カオリナイト−蛇紋石族の具体例としては、カオリナイト、ディッカイト、ナクライト、ハロイサイト、アンチゴライト、クリソタイル、リザーダイト、アメサイト、バーチェリン、クロンステダイト、ネポーアイト、ケリアイト、フレイポナイト、ブリンドリアイト等が挙げられる。
タルク−パイロフィライト族の具体例としては、タルク、ウィレムサイト、ケロライト、ピメライト、パイロフィライト、フェリパイロフィライト等が挙げられる。
スメクタイト族の具体例としては、モンモリロナイト、バイデライト、ノントロナイト、サポナイト、ソーコナイト、スチブンサイト、ヘクトライト、ボルコンスコアイト、スインホルダイト等が挙げられる。
バーミキュライト族の具体例としては、3八面体型バーミキュライト、2八面体型バーミキュライト等が挙げられる。
マイカ族の具体例としては、テトラシリリックマイカ、ナトリウムテニオライト、白雲母、金雲母、黒雲母、鉄雲母、イーストナイト、シデロフィライトテトラフェリ鉄雲母、鱗雲母、ポリリシオナイト、セラドン石、鉄セラドン石、鉄アルミノセラドン石、アルミノセラドン石、砥部雲母、パラゴナイト、レピドライト等が挙げられる。
脆雲母族の具体例としては、ザンソフィライト、クリントナイト、ビテ雲母、アナンダ石、真珠雲母、マーガイラト等が挙げられる。
緑泥石族の具体例としては、クリノクロア、シャモサイト、ペナンタイト、ニマイト、ベイリクロア、ドンバサイト、クッケアイト、スドーアイト等が挙げられる。
また、これら粘土鉱物を有機物でイオン交換等の処理し、分散性等を改良したもの(朝倉書店、「粘土の事典」参照;以下、有機修飾粘土鉱物と称する場合もある)も無機層状化合物として用いることができる。粘土鉱物を処理する上記有機物としては、公知のジメチルジステアリルアンモニウム塩やトリメチルステアリルアンモニウム塩等の第4級アンモニウム塩やフォスフォニウム塩、イミダゾリウム塩等を用いることができる。
2種類以上の無機層状化合物を用いてもよい。
100mlメスシリンダーに液体媒体100mlを入れ、これに無機層状化合物2gを徐々に加える。23℃にて24時間静置後、上記メスシリンダー内における無機層状化合物分散層と上澄みとの界面の目盛から無機層状化合物分散層の体積(ml)を読む。この数値(膨潤値)が大きい程、膨潤性が高いことを示す。
〔劈開性試験〕
無機層状化合物30gを液体媒体1,500ml中に徐々に加え、分散機(浅田鉄工株式会社製、デスパMH−L、羽根径52mm、回転数3,100rpm、容器容量3L、底面−羽根間の距離28mm)にて、周速8.5m/分、23℃で90分間分散させた後、この分散液100mlをメスシリンダーに採取する。60分静置後、上記メスシリンダー内における層状化合物分散層と上澄みとの界面の目盛から無機層状化合物分散層の体積(ml)を読む。この数値(劈開値)が大きい程、劈開性が高いことを示す。
中和度=(A/B)×100
A:ポリアクリル酸部分中和物またはポリメタアクリル酸部分中和物1g中の中和されて金属塩となったカルボキシル基のモル数
B:ポリアクリル酸部分中和物またはポリメタアクリル酸部分中和物1g中のカルボキシル基と中和されて金属塩となったカルボキシル基との合計モル数
中和度=(C/D)×100
C:ポリアクリル酸部分中和物またはポリメタアクリル酸部分中和物1g中の金属塩として存在するカルボキシル基のモル数
D:ポリアクリル酸部分中和物またはポリメタアクリル酸部分中和物1g中のイオン交換されて生成したカルボキシル基と金属塩として存在するカルボキシル基との合計モル数
水酸基とカルボキシル基とを含む樹脂成分に含まれる水酸基の量とカルボキシル基の量との合計を100モル%としたとき、好ましくは、該水酸基の量が30~95モル%であり、該カルボキシル基の量が5~70モル%である。より好ましくは、該水酸基の量が70~95モル%であり、該カルボキシル基の量が5~30モル%である。
また基材、第1の層、及び第2の層を有する多層構造体の耐水性、ガスバリア性、耐傷付性の観点から、水酸基の質量とカルボキシル基の質量の合計が30~60質量%であることが好ましく、より好ましくは35~55質量%である。前記水酸基の質量およびカルボキシル基の質量の合計は、該水酸基とカルボキシル基とを含む樹脂成分の質量を100質量%としたときの値である。ここで言うカルボキシル基とは、上記中和したカルボキシル基も含む。
水への溶解性の点から、該可塑剤としては、例えば、ポリソルビトール、ポリマンニトール、ポリズルシトール、ポリキシリトール、ポリエリトリトール、ポリグリセリン等の多価アルコールの多量体が好ましく、最も好ましくはポリグリセリンである。2以上の可塑剤を用いてもよい。
熱成形時の延伸性の点から、第2の層に含まれる可塑剤の量は、第2の層に含まれる樹脂100質量部に対して20~150質量部であることが好ましく、25~120質量部であることがより好ましく、40~120質量部であることがさらに好ましく、60~110質量部であることが最も好ましい。
本発明に係る多層構造体は、前記基材、第1の層、第2の層に加えて、さらに樹脂を含有する第3の層を第2の層に隣接して有していても良い。該第3の層に含まれる樹脂として、前記第2の層に用いられる樹脂として記載した樹脂を使用することができる。第2の層に使用する樹脂と第3の層に使用する樹脂とは同一であっても良く、異なる種類であっても良い。第3の層は、さらに無機層状化合物を含んでも良い。第3の層が無機層状化合物を含む場合、第3の層は、第3の層に含まれる無機層状化合物の体積分率(ただし、第3の層の体積分率を100体積%とする)が第2の層に含まれる無機層状化合物の体積分率(ただし、第2の層の体積分率を100体積%とする)とは異なる層である。
多層構造体の耐傷つき性を向上させる場合は、前記第2の層における無機層状化合物の体積分率(ただし、第2の層の体積分率を100体積%とする)より、前記第3の層における無機層状化合物の体積分率(ただし、第3の層の体積分率を100体積%とする)が高いことが好ましい。
多層構造体の透明性を向上させる場合は、前記第2の層における無機層状化合物の体積分率(ただし、第2の層の体積分率を100体積%とする)より、前記第3の層における無機層状化合物の体積分率(ただし、第3の層の体積分率を100体積%とする)が低いことが好ましい。
本発明の多層構造体は、上記混合液を基材表面に塗工し、第1の塗工膜を形成し、次いで前記第1の塗工膜から水系媒体を除去して、第1の層を形成することにより製造することができる。
第2の塗工液の液体媒体としては、前述の無機層状化合物を膨潤し劈開させる溶媒を用いることができる。
本発明に係る多層構造体において第2の層および第3の層のいずれか1層または両方が、2種類以上の官能基を有する樹脂を含む場合、耐水性、ガスバリア性、耐傷つき性を向上するために、本発明に係る多層構造体を、乾熱処理することが好ましい。多層構造体を乾熱処理して得られる構造体を、乾熱処理体と称することもある。乾熱処理とは、100℃以上300℃以下、水蒸気濃度が50g/m3未満の雰囲気下で多層構造体を保持する処理である。乾熱処理温度は、好ましくは120℃以上、200℃以下である。乾熱処理する時間は通常1秒間~1時間である。乾熱処理時の水蒸気濃度は、好ましくは0~40g/m3である。乾熱処理する方法としては、例えば多層構造体を熱ロールまたは空気等の熱媒と接触する方法、多層構造体を赤外線またはマイクロ波により加熱する方法等が挙げられる。また本発明に係る多層構造体を後述の熱成形する際は、熱成形時の加熱処理を該乾熱処理とすることができる。
本発明に係る多層構造体において第2の層および第3の層のいずれか1層または両方が、2種類以上の官能基を有する樹脂を含む場合、耐水性、ガスバリア性、耐傷つき性を向上するために、上記乾熱処理体を、湿熱処理することが好ましい。乾熱処理体を湿熱処理して得られる構造体を、湿熱処理体と称することもある。湿熱処理とは、100℃以上の温度で水蒸気濃度が290g/m3超の雰囲気下または80℃以上の水中で乾熱処理体を保持する処理である。湿熱処理する時間は、通常1秒間~1時間である。
100℃以上の温度で水蒸気濃度が290g/m3超の雰囲気下で乾熱処理体を処理する場合、温度は120~200℃の範囲内が好ましく、水蒸気濃度は500~20000g/m3の範囲内が好ましい。80℃以上の水中で乾熱処理体を処理する場合、温度は100~140℃の範囲内が好ましい。前記湿熱処理を施す前に、前記乾熱処理体を例えば23℃、湿度50%RH条件下でエージングしてもよい。
乾燥処理は、通常、湿度50%RH以下、温度20~100℃で1秒間~24時間、湿熱処理体を保持する処理方法である。
また予め所定の形状に賦形した基材の少なくとも一方の表面に上記第1の層を形成し、その後、必要に応じて第2の層や第3の層を形成しても良く、またシートあるいはパリソン等の予備成形した基材の少なくとも一方の表面に第1の層を形成し、必要に応じて第2の層や第3の層を形成して多層構造体とした後、熱成形により所定の形状に賦形しても良い。該熱成形とは、基材や、多層構造体を加熱処理して所定の形状に賦形する成形方法であり、ブロー成形、真空成形、圧空成形、真空圧空成形等が挙げられる。
多層構造体を熱成形する場合、熱成形時の加熱処理が上記乾熱処理に相当するため、多層構造体を熱成形して得られる成形品は、乾熱処理体である。多層構造体を熱成形して得られる乾熱処理体を湿熱処理して湿熱処理体を得ることができる。
包装材料や容器として使用する場合、多層構造体の形体としては、フィルム、袋、パウチ、ボトル、ボトルキャップ、カートン容器、カップ、皿、トレー、タンク、チューブ、シリンジが挙げられる。内容物としては食品類および非食品類が挙げられる。食品類としては、菓子類、加工食品、飲料品などが挙げられる。非食品類としては、トイレタリー製品、燃料、医薬品、電子部品および電子機器が挙げられる。
加飾シートとして用いた成形品としては、住宅外装部品、住宅内装部品、家具用部材、自動車外装部品、自動車内装部品、二輪車外装部品、家電部品、雑貨部品、看板などが挙げられる。住宅外装部品としては、雨樋、玄関化粧カバー、床下換気口などが挙げられる。住宅内装部品としては、インテリアドアユニット、クロゼット折戸ユニット、幅木、畳寄せ、回り縁、造作材、敷居すべり、窓額縁、手すり、床材、壁板、天井板などが挙げられる。家具用部材としては化粧板、引き出し、流し台回りの前面扉、ベットバンパー、テーブル、椅子、各種ケース、照明器具パーツ、額縁が挙げられる。自動車外装部品としては、バンパー、ドアミラー、フェンダーボディが挙げられる。自動車内装部品としては、インスツルメントパネル、ダッシュボード、ドアトリム、ボディーサイドトリムが挙げられる。二輪車外装部品としては、フード、カウリングなどが挙げられる。家電部品としては、冷蔵庫の扉、洗濯機防水バンなどが挙げられる。
また基板としては、ディスプレイ用基板、太陽電池用基板が挙げられる。ディスプレイ用基板としては、液晶ディスプレイ用基板、有機EL用などフレキシブルディスプレイ用基板などが挙げられる。また太陽電池用基板としては、シリコン型太陽電池用基板あるいは色素増感型太陽電池用基板などが挙げられる。
0.5μm以上の厚みは、デジタル厚み計(接触式厚み計、商品名:超高精度デシマイクロヘッド MH−15M、日本光学社製)を用いて測定した。0.5μm未満の厚みは、透過型電子顕微鏡(TEM)の断面観察より求めた。
ゲルパーミエイションクロマトグラフ(GPC)法によって、下記の条件で測定を行った。
装置:東ソー社製 HLC−8121GPC/HT
カラム:東ソー社製 TSKgel GMHHR−H(S)HT 4本
温度:145℃
溶媒:o−ジクロロベンゼン
溶出溶媒流速:1.0ml/分
試料濃度:1mg/ml
測定注入量:300μl
分子量標準物質:標準ポリスチレン
検出器:示差屈折
オレフィン重合体(1)について下記の方法で、オレフィン重合体中のα,β−不飽和カルボン酸およびα,β−不飽和カルボン酸無水物からなる群より選ばれる化合物に基づく単量体単位の量を測定した。オレフィン重合体1.0gをキシレン20mlに溶解した溶液を、攪拌されているメタノール300mlに滴下してオレフィン重合体を沈殿させた。沈殿したオレフィン重合体を回収し、真空乾燥した(80℃、8時間)。乾燥したオレフィン重合体を用いて熱プレスにより厚さ100μmのフィルムを作製し、得られたフィルムの赤外吸収スペクトルを測定して、1780cm−1付近の吸収より、オレフィン重合体中の無水マレイン酸に基づく単量体単位の含有量(質量)を定量した。
オレフィン重合体(2)中のα,β−不飽和カルボン酸およびα,β−不飽和カルボン酸無水物からなる群より選ばれる化合物に基づく単量体単位の量は、カタログ値を採用した。該カタログ値は、赤外吸収スペクトルにより求められた値であった。
オレフィン重合体(1)に含まれるα,β−不飽和カルボン酸エステルに基づく単量体単位の量を、下記の方法で測定した。オレフィン重合体50mgを重水素化o−ジクロロベンゼン1.0mLに溶解し、1H−NMRを測定した。ケミカルシフト0.7~1.9ppm領域の積分比と、ケミカルシフト3.9~4.2ppm領域の積分比から、炭素原子数2~20のα−オレフィンに基づく単量体単位の含有量に対するα,β−不飽和カルボン酸エステルに基づく単量体単位の含有量(質量)を算出した。またオレフィン重合体(2)に含まれるα,β−不飽和カルボン酸エステルに基づく単量体単位の量は、カタログ値を採用した。
レーザー回折・散乱式粒度分布測定装置(LA910、堀場製作所(株)製)を用いて測定した。後述する塗工液(5)中の粘土鉱物の平均粒径をペーストセルにて光路長50μmで測定し、さらに該塗工液(5)を200倍程度に希釈した液中の粘土鉱物の平均粒径をフローセル法にて光路長4mmで測定した。いずれの場合も平均粒径の値は変わらず、塗工液(5)中で粘土鉱物が充分に膨潤し劈開していることを確認した。この値を、第2の層中の粘土鉱物の平均粒径Lとみなした。
また塗工液(1)中の分散したオレフィン重合体(1)および塗工液(3)中の分散したオレフィン重合体(2)の平均粒径は、上述のフローセル法にて測定した。
X線回折装置(XD−5A、(株)島津製作所製)を用い、粘土鉱物の回折測定を粉末法により行い、粘土鉱物の単位厚さaを求めた。上述の方法で求めた平均粒径Lを用いて、該粘土鉱物のアスペクト比Zを、Z=L/aの式により算出した。なお塗工液(5)を乾燥したものについてもX線回折測定を行ない、粘土鉱物の面間隔が広がっていることを確認した。
多層構造体(1)~(4)において、第1の官能基を含む樹脂としてポリビニルアルコール(完全ケン化物)を用い、第2の官能基を含む樹脂としてポリアクリル酸を用いた。
以下の式により、ポリビニルアルコール中の水酸基の量(モル)およびポリアクリル酸中のカルボキシル基の量(モル)を算出し、それぞれの値を両者の和で除し、モル%単位でそれぞれの量を求めた(ただし、水酸基とカルボキシル基との合計量を100モル%とする)。
水酸基の量(モル)=(ポリビニルアルコールの質量(g))/(ポリビニルアルコールを構成するモノマー単位1単位あたりの分子量)
カルボキシル基の量(モル)=(ポリアクリル酸の質量(g))/(ポリアクリル酸を構成するモノマー単位1単位あたりの分子量)
多層構造体(1)~(4)において、第1の官能基を含む樹脂としてポリビニルアルコール(完全ケン化物)を用い、第2の官能基を含む樹脂としてポリアクリル酸を用いた。
以下の式より水酸基量およびカルボキシル基量を算出し、これらを合計した。
水酸基の質量(質量%)=(17/(ポリビニルアルコールを構成するモノマー単位1単位あたりの分子量))×(ポリビニルアルコールの質量(g)/樹脂の質量(g))×100
カルボキシル基の質量(質量%)=(45/ポリアクリル酸を構成するモノマー単位1単位あたりの分子量))×(ポリアクリル酸の質量(g)/樹脂の質量(g))×100
多層構造体(1)~(4)においては、樹脂の質量は、第2の層中のポリビニルアルコールの質量とポリアクリル酸の質量との和である。
誘導結合プラズマ発光分析装置(Optima3000、パーキンエルマー社製)を用いて、塗工液(5)の乾燥物について、ナトリウムイオン濃度を測定し、第2の層中のナトリウムイオン濃度を求めた。試料の調整方法は以下のとおりである。塗工液の乾燥物1gを採取し、これに96%硫酸1ml添加した後、電気炉で灰化し、残った残渣物を5%塩酸に溶解させた。該溶液を誘導結合プラズマ発光分析装置に供試し、ナトリウムイオン濃度を測定した。さらに第2の層中のポリビニルアルコールとポリアクリル酸と粘土鉱物との質量比と、上記ナトリウムイオン濃度とから、ポリビニルアルコールの質量とポリアクリル酸の質量の合計を100質量部としたときの、アルカリ金属イオンの質量を求めた。
210mm×300mmの多層構造体(1)~(4)を、130℃、水蒸気濃度5g/m3のオーブン中で10分間熱処理し、乾熱処理体(1)~(4)を得た。
上記乾熱処理体(1)~(4)の酸素透過度を、JIS K7126に基づき、超高感度酸素透過度測定装置(OX−TRANML、MOCON社製)にて、23℃90%RHの条件下にて測定した。酸素透過度が小さいほど、ガスバリア性が高いことを表す。
乾熱処理体(1)~(4)について、次の方法で接着性試験を行った。23℃50%RHの条件下で、第2の層表面に2mm角で10×10個の切れ目を入れた。第2の層の切れ目を入れた部分を全て覆うようにセロファンテープを乾熱処理体に貼り、それを23℃0%RHの条件下で一晩エージングした。セロファンテープを剥がし、乾熱処理体の上に第2の層が残っている目数を数えた。表1には、目数が100個の場合を○、目数が99~50個の場合を△、目数が49個以下の場合を×と表記した。残存する目数が多いほど、第1の層を介して基材と第2の層とがより強固に接着しているといえる。
23℃100%RHの条件下で一晩エージングした乾熱処理体にも、上記の方法で接着性試験を行った。
(1)塗工液(1)の作製
容量2Lのセパラブルフラスコ反応器に、攪拌器、温度計、滴下ロート、還流冷却管をつけて、反応器内の気体を窒素で置換した。ここに溶媒としてキシレン616質量部、プロピレン−1−ブテン共重合体(特許第4025401号公報に記載の方法で得た。プロピレンに基づく単量体単位96モル%、1−ブテンに基づく単量体単位4モル%)100質量部、無水マレイン酸50質量部、およびn−ブチルメタクリレート25質量部を入れ140℃に加熱、撹拌し、溶液を得た。その後、ジ−tertブチルパーオキサイド1質量部を添加し、5時間同温度で攪拌を続けてプロピレン—1−ブテン共重合体と無水マレイン酸との反応を行った。なお、加熱はオイルバスを用いた。
反応終了後、反応物の温度を室温まで下げ、アセトン1000質量部に投じ、沈殿した白色固体を濾取した。この白色固体をアセトンで洗浄し、減圧乾燥した結果、無水マレイン酸およびn−ブチルメタクリレートが付加されたオレフィン重合体(1)を得た。得られた重合体のMwは72,604、Mnは40,750、分子量分布(Mw/Mn)は1.8、MFRは4.2g/10min、オレフィン重合体(1)を100質量%としたとき無水マレイン酸に基づく単量体単位は1.7質量%、n−ブチルメタクリレートに基づく単量体単位は1.3質量%であった。
攪拌器、温度計、還流冷却管を備えた容量2Lのセパラブルフラスコ反応容器に、溶媒としてトルエン200質量部、オレフィン重合体(1)100質量部を入れ、90℃にて攪拌し、オレフィン重合体(1)を溶解した。次いで、乳化剤液として、ジェファーミンM1000(三井化学ファイン社製)10質量部およびイソプロパノール10質量部の混合液を10分間かけて滴下した。さらに5分間攪拌した後、ジメチルエタノールアミン5質量部を投入し、さらに5分間攪拌し、オレフィン重合体混合液(1)を得た。
続いて、攪拌装置をTKロボミクス(株式会社PRIMIX製)に代え、オレフィン重合体混合液(1)をディスパー翼にて攪拌しながら、イソプロパノール100質量部およびイオン交換水100質量部の混合液を30分間かけて滴下した。さらにイオン交換水300質量部を滴下し、乳白色のオレフィン重合体予備分散液(1)を得た。
得られたオレフィン重合体予備分散液(1)を、2Lナスフラスコに投入し、溶媒の一部をエバポレーターにて減圧留去し、その後、200メッシュナイロン網にてろ過し、塗工液(1)を得た。得られた塗工液(1)中の分散したオレフィン重合体(1)の粒径は4.6μm、であり、JIS K−6828−1に準じた方法で測定した固形分濃度は38%であった。
分散釜(商品名:デスパMH−L、浅田鉄工(株)製)に、イオン交換水(比電気伝導率0.7μs/cm以下)1235gと、ポリビニルアルコール(AQ2117;(株)クラレ製,ケン化度;99.6%、重合度1,700)65gとを混合し、低速撹拌下(1500rpm、周速度4.1m/分)で95℃に昇温した。該混合系を同温度で30分間攪拌してポリビニルアルコールを溶解させたのち、60℃に冷却し、ポリビニルアルコール水溶液を得た。ポリビニルアルコール水溶液を攪拌しながら、ポリアクリル酸(和光純薬工業(株)製、平均分子量1,000,000)16.3gを混合し、常温にて低速撹拌下(1500rpm、周速度4.1m/分)で水溶性樹脂水溶液を作製した。
前記塗工液(1)100gを攪拌しながら、水溶性樹脂水溶液116gを徐々に添加し、塗工液(2)を得た。塗工液(2)中のオレフィン重合体(1)と、ポリビニルアルコールとポリアクリル酸とからなる水溶性樹脂との合計量を100質量%としたとき、水溶性樹脂の含有量は20質量%であった。
オレフィン重合体(1)のかわりに、オレフィン重合体(2)(BONDINE HX8290(ARKEMA社製)、エチレンに基づく単量体単位とエチルアクリレートに基づく単量体単位と無水マレイン酸に基づく単量体単位とを有する重合体)100質量部を用い、乳化剤液としてラテムルE−1000A(30%水溶液、花王株式会社製)17質量部、ノイゲンEA−177(第一工業製薬株式会社製)5質量部およびイソプロパノール5質量部の混合液を用いる以外は、塗工液(1)と同様にして、塗工液(3)を得た。
得られた塗工液(3)中の分散したオレフィン重合体(2)の粒径は0.2μm、JIS K−6828−1に準じた方法で測定した固形分濃度は38%であった。オレフィン重合体(2)を100質量%としたとき、エチレンに基づく単量体単位は80質量%、無水マレイン酸に基づく単量体単位は3質量%、エチルアクリレートに基づく単量体単位は17質量%であった。
塗工液(1)のかわりに、塗工液(3)を用いたこと以外は塗工液(2)と同様にして、塗工液(4)を得た。塗工液(4)中のオレフィン重合体(2)と、ポリビニルアルコールとポリアクリル酸とからなる水溶性樹脂との合計量を100質量%としたとき、水溶性樹脂の含有量は20質量%であった。
分散釜(商品名:デスパMH−L、浅田鉄工(株)製)に、イオン交換水(比電気伝導率0.7μs/cm以下)1300gと、ポリビニルアルコール(AQ2117;(株)クラレ製,ケン化度;99.6%、重合度1,700)130gとを混合し、低速撹拌下(1500rpm、周速度4.1m/分)で95℃に昇温した。該混合系を同温度で30分間攪拌してポリビニルアルコールを溶解させたのち、60℃に冷却し、ポリビニルアルコール水溶液を得た。該ポリビニルアルコール水溶液(60℃)を前記同様の条件で攪拌しながら、1−ブタノール122g、イソプロピルアルコール122gおよびイオン交換水520gを混合してなるアルコール水溶液を5分間かけて滴下した。滴下終了後、高速攪拌(3,000rpm、周速度=8.2m/分)に切り替え、該攪拌系に高純度モンモリロナイト(商品名:クニピアG;クニミネ工業(株)製)82gを徐々に加え、添加終了後、60℃で60分間攪拌を続けた。その後、さらにイソプロパノール243gを15分間かけて加え、次いで該混合系を室温まで冷却し、粘土鉱物含有液(1)を得た。この粘土鉱物含有液(1)に対し、非イオン性界面活性剤(ポリジメチルシロキサン−ポリオキシエチレン共重合体、商品名:SH3746、東レ・ダウコーニング(株)製)0.1質量%(前記分散液の質量を基準とする)を低速撹拌下(1500rpm、周速度4.1m/分)において添加し、その後系のpHが6となるようにイオン交換樹脂で調整し、粘土鉱物分散液(1)を調製した。
またさらに別の分散釜(商品名:デスパMH−L、浅田鉄工(株)製)に、イオン交換水(比電気伝導率0.7μs/cm以下)1067gと、ポリアクリル酸(和光純薬工業(株)製、平均分子量1,000,000)33gとを混合し、常温にて低速撹拌下(1500rpm、周速度4.1m/分)で樹脂成分(A3)溶液を作製した。
粘土鉱物分散液(1)2519gと樹脂成分(A3)溶液1100gを、低速撹拌下(1500rpm、周速度4.1m/分)において徐々に混合して混合液とし、さらに該混合液を高圧分散装置(商品名:超高圧ホモジナイザーM110−E/H、Microfluidics Corporation製)を用いて、1100kgf/cm2の圧力条件で処理することにより、塗工液(5)を得た。
塗工液(5)中の劈開したモンモリロナイト平均粒径Lは560nm、粉末X線回折から得られるa値は1.2156nmであり、アスペクト比Zは460であった。
環状オレフィン樹脂(商品名:アペル APL5014DP;三井化学(株)製)製の150μmシートを基材として用いた。該基材の一方の表面に、前述の塗工液(2)をバーコータ(♯8)を用いて、塗工して、80℃で20分間乾燥することにより、基材と、基材に隣接する第1の層を有する多層構造体(1’)を得た。さらに多層構造体(1’)の第1の層の表面に、前述の塗工液(5)をバーコータ(♯28)を用いて、塗工して、80℃で20分間乾燥することにより、第2の層を形成し、基材、第1の層および第2の層を有する多層構造体(1)を得た。該第1の層の厚みは5μm、第2の層の厚みは0.2μmであった。また第2の層中のNa濃度は0.7%であった。得られた多層構造体(1)を乾熱処理し、乾熱処理体(1)を得た後、23℃50%RH雰囲気下で24時間エージングし、評価した。結果を表1に示した。
塗工液(2)のかわりに塗工液(4)を用いたこと以外は実施例1と同様にして、基材と、基材に隣接する第1の層とを有する多層構造体(2’)を得た。また、さらに多層構造体(2’)の第1の層の表面に、実施例1と同様にして、第2の層を形成し、基材、第1の層および第2の層を有する多層構造体(2)を得た。該第1の層の厚みは5μm、第2の層の厚みは0.2μmであった。また第2の層中のNa濃度は0.7%であった。得られた多層構造体(2)を乾熱処理し、乾熱処理体(2)を得た後、23℃50%RH雰囲気下で24時間エージングし、評価した。結果を表1に示した。
塗工液(2)のかわりに塗工液(1)を用いたこと以外は実施例1と同様にして、基材と、基材に隣接する第1の層とを有する多層構造体(3’)を得た。また、さらに多層構造体(3’)の第1の層の表面に、実施例1と同様にして、第2の層を形成し、基材、第1の層および第2の層を有する多層構造体(3)を得た。該第1の層の厚みは5μm、第2の層の厚みは0.2μmであった。また第2の層中のNa濃度は0.7%であった。得られた多層構造体(3)を乾熱処理し、乾熱処理体(3)を得た後、23℃50%RH雰囲気下で24時間エージングし、評価した。結果を表1に示した。
塗工液(2)のかわりに塗工液(3)を用いたこと以外は実施例1と同様にして、基材と、基材に隣接する第1の層とを有する多層構造体(4’)を得た。また、さらに多層構造体(4’)の第1の層の表面に、実施例1と同様にして、第2の層を形成し、基材、第1の層および第2の層を有する多層構造体(4)を得た。該第1の層の厚みは5μm、第2の層の厚みは0.2μmであった。また第2の層中のNa濃度は0.7%であった。得られた多層構造体(4)を乾熱処理し、乾熱処理体(4)を得た後、23℃50%RH雰囲気下で24時間エージングし、評価した。結果を表1に示した。
Claims (11)
- 炭素原子数2~20のα−オレフィンに基づく単量体単位と、
α,β−不飽和カルボン酸エステルに基づく単量体単位と、
α,β−不飽和カルボン酸およびα,β—不飽和カルボン酸無水物からなる群より選ばれる化合物に基づく単量体単位と
を有し、
前記α−オレフィンに基づく単量体単位の含有量が50質量%以上であるオレフィン重合体(ただし、炭素原子数2~20のα−オレフィンに基づく単量体単位と、α,β−不飽和カルボン酸エステルに基づく単量体単位と、α,β−不飽和カルボン酸およびα,β—不飽和カルボン酸無水物からなる群より選ばれる化合物に基づく単量体単位の合計量を100質量%とする)と、
水溶性樹脂と、
水系媒体と
を含む混合液。 - 前記オレフィン重合体が、プロピレンに基づく単量体単位と1−ブテンに基づく単量体単位とを有する第1項に記載の混合液。
- プロピレンに基づく単量体単位と1−ブテンに基づく単量体単位の合計量を100モル%とするとき、前記オレフィン重合体のプロピレンに基づく単量体単位の含有量が70~99モル%である第2項に記載の混合液。
- 水溶性樹脂が、水酸基を含む樹脂である第1項~第3項のいずれかに記載の混合液。
- オレフィン重合体と水溶性樹脂の合計量を100質量%とするとき、水溶性樹脂の含有量が2~40質量%である第1項~第4項のいずれかに記載の混合液。
- 以下の工程(1)および(2)を順に含む第1項~第5項のいずれかに記載の混合液の製造方法。
(1)前記オレフィン重合体を水系媒体に分散し、オレフィン重合体分散液を得る工程
(2)前記オレフィン重合体分散液に水溶性樹脂水溶液を混合する工程 - 基材と、基材に隣接する第1の層を有する多層構造体であって、
前記第1の層が、
炭素原子数2~20のα−オレフィンに基づく単量体単位と、
α,β−不飽和カルボン酸エステルに基づく単量体単位と、
α,β−不飽和カルボン酸およびα,β—不飽和カルボン酸無水物からなる群より選ばれる化合物に基づく単量体単位と
を有し、
前記α−オレフィンに基づく単量体単位の含有量が50質量%以上であるオレフィン重合体(ただし、炭素原子数2~20のα−オレフィンに基づく単量体単位と、α,β−不飽和カルボン酸エステルに基づく単量体単位と、α,β−不飽和カルボン酸およびα,β—不飽和カルボン酸無水物からなる群より選ばれる化合物に基づく単量体単位の合計量を100質量%とする)と、
水溶性樹脂とを含有する層である多層構造体。 - 前記第1の層に隣接して、無機層状化合物および樹脂を含む第2の層をさらに有する第7項に記載の多層構造体。
- 前記第2の層に含まれる樹脂が、2種類以上の官能基を含む樹脂である第8項に記載の多層構造体。
- 第9項に記載の多層構造体を乾熱処理して得られる乾熱処理体。
- 第10項に記載の乾熱処理体を湿熱処理して得られる湿熱処理体。
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CN201380062975.0A CN104837913B (zh) | 2012-12-04 | 2013-12-02 | 混合液、混合液的制造方法、及多层结构体 |
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