WO2020218118A1 - Coating agent and laminate - Google Patents

Coating agent and laminate Download PDF

Info

Publication number
WO2020218118A1
WO2020218118A1 PCT/JP2020/016596 JP2020016596W WO2020218118A1 WO 2020218118 A1 WO2020218118 A1 WO 2020218118A1 JP 2020016596 W JP2020016596 W JP 2020016596W WO 2020218118 A1 WO2020218118 A1 WO 2020218118A1
Authority
WO
WIPO (PCT)
Prior art keywords
meth
coating agent
vinyl
mass
hydroxyl group
Prior art date
Application number
PCT/JP2020/016596
Other languages
French (fr)
Japanese (ja)
Inventor
雄作 後藤
宇佐見　祐章
中嶋　道也
Original Assignee
Dic株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dic株式会社 filed Critical Dic株式会社
Publication of WO2020218118A1 publication Critical patent/WO2020218118A1/en

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/42—Applications of coated or impregnated materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D157/00—Coating compositions based on unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09D157/06—Homopolymers or copolymers containing elements other than carbon and hydrogen
    • C09D157/10—Homopolymers or copolymers containing elements other than carbon and hydrogen containing oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/20—Diluents or solvents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular

Definitions

  • the present invention relates to a coating agent and a laminate.
  • Packaging materials used for packaging foods, etc. are required to have functions such as protection of contents, retort resistance, heat resistance, transparency, and processability. Gas barrier properties are especially important for maintaining the quality of the contents.
  • Recently, not only packaging materials but also materials used for electronic materials such as solar cells and semiconductors are required to have high gas barrier properties.
  • Such a material is configured by, for example, laminating a base material and a coat layer having a gas barrier property. Therefore, a coating agent capable of forming a coat layer having a high gas barrier property is required.
  • Patent Document 1 describes that by combining a resin having a hydroxyl group and an isocyanate compound with a plate-like inorganic compound such as a clay mineral and a light blocking agent, properties such as gas barrier properties are improved.
  • Patent Document 2 describes a material containing modified clay as a main constituent component, and by using modified clay and using additives as necessary, the modified clay crystals are oriented and densely laminated. It is said that a film material having mechanical strength, gas barrier property, water resistance, thermal stability and flexibility that can be used as a self-supporting film can be obtained.
  • the coating agent can form a film (coat layer) having excellent film forming property (coating layer can be preferably formed) and blocking property in addition to gas barrier property.
  • An object of the present invention is to provide a coating agent capable of forming a film having excellent film-forming property and excellent blocking property, oxygen barrier property and water vapor barrier property on one aspect.
  • the present inventors include, as interlayer ions, a dihedral smectite containing at least one selected from the group consisting of ammonium ions, lithium ions, and hydrogen ions, a vinyl resin having a hydroxyl group, and an alcohol in a predetermined amount.
  • a coating agent capable of forming a film having excellent film-forming property and excellent blocking property, oxygen barrier property and water vapor barrier property can be obtained, and the present invention has been completed.
  • the present invention contains, on one side, a 28-hedron smectite, a vinyl resin having a hydroxyl group, and a solvent, and the 28-hedron smectite contains ammonium ions, lithium ions, and hydrogen as interlayer ions.
  • a coating agent containing at least one selected from the group consisting of ions, the solvent containing alcohol, and the content of alcohol being 20 to 80% by mass based on the total amount of the solvent. provide.
  • the octahedral smectite may be montmorillonite.
  • the sodium ion equivalent of the 2 octahedral smectite may be less than 10 meq / 100 g.
  • the sum of the ammonium ion equivalent, the lithium ion equivalent, and the hydrogen ion equivalent of the 2 octahedral smectite may be 50 to 120 meq / 100 g.
  • the coating agent may further contain polycarboxylic acid.
  • the hydroxide value of the vinyl resin having a hydroxyl group may be 800 to 1500.
  • the present invention provides a laminate having a base material and a coating layer obtained by coating the above-mentioned coating agent on the base material in another aspect.
  • the thickness of the coat layer may be 0.1 to 5 ⁇ m.
  • the laminate may be used as a packaging material.
  • a coating agent capable of forming a film having excellent film forming properties and excellent blocking properties, oxygen barrier properties and water vapor barrier properties.
  • the coating agent of one embodiment contains 28 octahedral smectites, a vinyl resin having a hydroxyl group, and a solvent.
  • the basic structure of clay minerals is composed of a tetrahedral sheet of Si—O and an octahedral sheet of Al—O, etc., and is called a dioctahedron when the cations entering the octahedral sheet are trivalent ions such as Al 3+. ..
  • the cation exchange capacity of the 2 octahedral smectite is usually 60 to 150 meq / 100 g. 2
  • montmorillonite and byderite are known.
  • the 2 octahedral smectite is a 2 octahedral smectite containing at least one selected from the group consisting of ammonium ion, lithium ion, and hydrogen ion as interlayer ions.
  • the sodium ion equivalent of the 2 octahedral smectite may be less than 10 meq / 100 g.
  • the sodium ion equivalent of the 2 octahedral smectite may be, for example, 5 meq / 100 g or less, or 2 meq / 100 g or less.
  • the sodium ion equivalent of 2 octahedral smectite can be measured by ion chromatography on the amount of cations eluted in a 1N ammonium acetate solution.
  • the total of the ammonium ion equivalent, the lithium ion equivalent, and the hydrogen ion equivalent of the 2 octahedral smectite may be 50 to 120 meq / 100 g.
  • the total of ammonium ion equivalent, lithium ion equivalent, and hydrogen ion equivalent of 2 octahedral smectite may be 50 meq / 100 g or more, 80 meq / 100 g or more, or 100 meq / 100 g or more, 120 meq / 100 g or less, or 110 meq /. It may be 100 g or less.
  • ammonium ion equivalent of octahedral smectite is the amount of cations eluted in a 1N potassium chloride solution
  • the lithium ion equivalent is the amount of cations eluted in a 1N ammonium acetate solution by ion chromatography. It can be obtained by doing.
  • the hydrogen ion equivalent can be obtained from the difference between the amount of cations before ion exchange and the amount of cations after ion exchange.
  • the amount of sodium ions eluted from montmorillonite into a 1N ammonium acetate solution before and after the ion exchange operation is measured by ion chromatography, and the hydrogen ion equivalent is measured from the difference. Can be obtained.
  • the method of exchanging the interlayer ion (cation) of the octahedral smectite with at least one selected from the group consisting of ammonium ion, lithium ion, and hydrogen ion may be an ordinary ion exchange method, for example, 2
  • the method may be a method in which the aqueous dispersion of octahedral smectite is treated with a cation exchange resin in which hydrogen ions, ammonium ions, or lithium ions are previously retained.
  • the method may be a method of passing the aqueous dispersion through a column filled with an ion exchange resin, or a method of mixing the ion exchange resin and the aqueous dispersion and stirring them in a batch.
  • amberlite IR120B-H is treated with lithium hydroxide in advance so that the ion exchange resin retains lithium ions.
  • An aqueous dispersion having a concentration of 2 octahedral smectite of 2% is passed through a column packed with an ion exchange resin holding lithium ions at a rate of 1 mL / min.
  • a dioctahedral smectite having lithium ions as interlayer ions can be obtained.
  • the content of octahedral smectite is 5 from the viewpoint of being more excellent in water vapor barrier property and oxygen barrier property (for example, oxygen barrier property under high humidity) with respect to the total amount of non-volatile content in the coating agent. It may be mass% or more, 20% by mass or more, 30% by mass or more, or 40% by mass or more. For example, the moldability of the coating agent is further improved, and the adhesion to the substrate is improved. From the viewpoint of the above, it may be 70% by mass or less, or 60% by mass or less.
  • the content of the octahedral smectite may be, for example, 5 to 70% by mass, 20 to 60% by mass, or 40 to 60% by mass with respect to the total amount of the non-volatile content in the coating agent.
  • the non-volatile component means a component other than the solvent in the coating agent.
  • the coating agent contains a vinyl resin having a hydroxyl group.
  • a vinyl resin having a hydroxyl group can be obtained, for example, by polymerizing an esterified product of an alcohol having a polymerizable double bond and then performing a saponification treatment.
  • the esterified product of the alcohol having a polymerizable double bond may be, for example, a vinyl ester.
  • the vinyl ester include vinyl acetate, vinyl chloroacetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate and the like.
  • the vinyl resin having a hydroxyl group can be obtained, for example, by polymerizing or copolymerizing a vinyl monomer having a hydroxyl group, or copolymerizing a vinyl monomer having a hydroxyl group and a vinyl monomer having no hydroxyl group.
  • the vinyl monomer having a hydroxyl group is a monomer having at least one group having a polymerizable double bond (for example, a vinyl group, a (meth) allyl group, or a (meth) acryloyl group) and a hydroxyl group.
  • a vinyl monomer having no hydroxyl group is a monomer having at least one group having a polymerizable double bond (for example, a vinyl group, a (meth) allyl group, or a (meth) acryloyl group) and having no hydroxyl group.
  • the (meth) allyl group means an allyl group or a metalyl group.
  • the (meth) acryloyl group means an acryloyl group or a methacryloyl group.
  • vinyl monomer having a hydroxyl group examples include (meth) allyl alcohol, vinyl alcohol, and alkenemonool or alkenediol having 4 to 12 carbon atoms such as 1-butene-3-ol; 2-.
  • Alkene ether having a polymerizable double bond at the end such as hydroxyethyl propenyl ether; hydroxystyrene; hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, ( 2-Hydroxybutyl (meth) acrylic acid, 3-hydroxybutyl (meth) acrylic acid, 4-hydroxybutyl (meth) acrylic acid; a compound obtained by ring-opening polymerization of ⁇ -caprolactone and a monoesterified product of (meth) acrylic acid, etc. Examples thereof include a hydroxyl group-containing vinyl monomer.
  • vinyl monomer having no hydroxyl group examples include olefins such as ethylene, propylene, isobutylene, butadiene and isoprene; halogenated olefins such as dichloroethylene and vinyl chloride; (meth) acrylic acid; (meth) acrylic.
  • (meth) acrylic acid esters examples include methyl (meth) acrylic acid, ethyl (meth) acrylic acid, n-propyl (meth) acrylic acid, isopropyl (meth) acrylic acid, n-butyl (meth) acrylic acid, Isobutyl (meth) acrylate, t-butyl (meth) acrylate, amyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, ( 2-Ethylhexyl acrylate, t-octyl acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, (meth) acrylic 2-Hydroxye
  • vinyl esters examples include the monomers exemplified above.
  • maleic acid diesters examples include dimethyl maleate, diethyl maleate, and dibutyl maleate.
  • fumaric acid diester examples include dimethyl fumarate, diethyl fumarate, dibutyl fumarate and the like.
  • the itaconic acid diester examples include dimethyl itaconic acid, diethyl itaconic acid, dibutyl itaconic acid and the like.
  • (meth) acrylamide examples include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, Nn- Butylacryl (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-nitrophenylacrylamide, N-ethyl-N-phenylacrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholin, diacetoneacrylamide, N -Methylol acrylamide, N-hydroxyethyl
  • styrene derivatives include methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, hydroxystyrene, methoxystyrene, butoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethylstyrene, Examples thereof include ⁇ -methylstyrene.
  • vinyl ethers include methyl vinyl ether, ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, octyl vinyl ether, methoxyethyl vinyl ether, phenyl vinyl ether and the like.
  • vinyl ketones examples include methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, phenyl vinyl ketone and the like.
  • maleimide examples include maleimide, butylmaleimide, cyclohexylmaleimide, phenylmaleimide and the like.
  • allyl compounds include allyl acetate, allyl alcohol, allylamine, N-allylaniline, allyl chloride, allyl bromide and the like.
  • the vinyl resin having a hydroxyl group may contain a hydroxyl group so that the hydroxyl value (unit: mgKOH / g) is in the range of, for example, 800 to 1500.
  • the hydroxyl value of the vinyl resin having a hydroxyl group may be, for example, 800 or more, 900 or more, 950 or more, or 1000 or more, and may be 1500 or less, 1400 or less, or 1300 or less.
  • the hydroxyl value of the vinyl resin having a hydroxyl group may be, for example, 800 to 1500, 900 to 1400, 950 to 1300, or 1000 to 1300.
  • the hydroxyl value can be measured by the hydroxyl value measuring method described in JIS-K0070. Further, when a vinyl resin is synthesized and used, the hydroxyl value can be calculated from the monomer composition used.
  • the weight average molecular weight of the vinyl resin having a hydroxyl group is the vinyl resin before the saponification treatment. It can be converted from the weight average molecular weight of.
  • the vinyl resin having a hydroxyl group is preferably a vinyl resin having a structural unit A (also referred to as a partial structure A) represented by the following formula (1) (hereinafter, also referred to as “vinyl resin A”).
  • a vinyl resin having a structural unit A also referred to as a partial structure A
  • the vinyl resin A has a hydroxyl group, not only the cohesive force of the vinyl resin is improved by the interaction between the hydroxyl groups, but also the affinity with the hemihedral smectite is increased, and therefore the gas barrier is even higher. It will exert its sexuality.
  • the vinyl resin A has the structural unit (A), not only the solubility in alcohol is improved, but also the coating agent can be imparted with water resistance, so that it has a water vapor barrier property and an oxygen barrier under high humidity. Further improvement in sex can be expected.
  • m represents 0 or 1
  • * represents a bond.
  • m is preferably 0.
  • the content of the structural unit A is preferably 85 mol% or more, more preferably 90 mol% or more, based on the total molar amount of the hydroxyl groups in the vinyl resin having a hydroxyl group. More preferably, it is 95 mol% or more, and preferably 99 mol% or less.
  • the content of the structural unit A is preferably 85 mol% or more and 99 mol% or less, and more preferably 90 mol% or more and 99 mol% or less, based on the molar amount of the total hydroxyl group in the vinyl resin having a hydroxyl group.
  • the content of the structural unit A in which m is 0 is preferably in the above range.
  • the vinyl resin having a hydroxyl group may contain a structural unit (other structural unit) other than the structural unit A.
  • the other structural unit may be, for example, a structural unit B (also referred to as a partial structure B) represented by the following formula (2).
  • the vinyl resin having a hydroxyl group preferably contains a structural unit A and further preferably a structural unit B.
  • the vinyl resin having a hydroxyl group may consist of only structural unit A and structural unit B.
  • R 1 represents a hydrogen atom and an alkyl group having 1 to 2 carbon atoms
  • n represents 0 or 1
  • * represents a bond.
  • R 1 is a hydrogen atom, a methyl group or an ethyl group
  • R 2 is a hydrogen atom or an acetyl group.
  • R 1 and R 2 do not become hydrogen atoms at the same time.
  • the content of the structural unit B is 1 mol% or more with respect to the total molar amount of the hydroxyl groups in the vinyl resin having a hydroxyl group from the viewpoint of excellent water resistance.
  • the content of the structural unit B is preferably 30 with respect to the total molar amount of the hydroxyl groups in the vinyl resin having a hydroxyl groups, from the viewpoint of excellent film forming property, film strength, adhesiveness of the composition, etc. when formed into a molded product. It is mol% or less, more preferably 15 mol% or less, still more preferably 10 mol% or less.
  • the content of the structural unit B is preferably 1 mol% or more and 30 mol% or less, more preferably 1 mol% or more and 15 mol% or less, and more preferably 1 mol% or more and 15 mol% or less, based on the total molar amount of the hydroxyl groups in the vinyl resin having a hydroxyl group. Is 1 mol% or more and 10 mol% or less. It is preferable that the content of the structural unit B in which R 1 is a hydrogen atom, R 2 is an acetyl group, and n is 0 is in the above range.
  • the molar% (A / (A + B) ⁇ 100) of the content of structural unit A with respect to the total content of structural unit A and structural unit B is gas barrier property. From the viewpoint of further improvement, it is preferably 85 mol% or more and 99 mol% or less.
  • the method for producing the vinyl resin having the structural unit A and / or the structural unit B is not particularly limited, and the vinyl resin can be produced by a known and commonly used method.
  • a vinyl resin having a hydroxyl group can be produced by polymerizing an esterified product of a hydroxyl group-containing vinyl monomer corresponding to the structural unit A or B and then performing a saponification treatment.
  • Examples of the hydroxyl group-containing vinyl monomer corresponding to the structural unit A include vinyl alcohol, allyl alcohol, and crotyl alcohol.
  • the ester in the esterified product of the hydroxyl group-containing vinyl monomer corresponding to the structural unit B may be an ester as exemplified above.
  • the esterified products of the hydroxyl group-containing vinyl monomer corresponding to the structural unit B vinyl acetate, allyl acetate, or crotyl acetate, which are acetic acid esters, are preferable.
  • One type of these may be used, or two or more types may be used in combination.
  • Examples of the hydroxyl group-containing vinyl monomer corresponding to the structural unit B include isopropenyl alcohol, metallic alcohol, isobutenyl alcohol and the like.
  • the esters in the esterified product of the hydroxyl group-containing vinyl monomer corresponding to the structural unit A are acetic acid ester, propanoic acid ester, butanoic acid ester, 2-methylpropanoic acid ester, pentanoic acid ester, 3-methylbutanoic acid ester, 2,2-. Examples thereof include dimethylpropanoic acid ester, hexanoic acid ester, cyclohexylcarboxylic acid ester and benzoic acid ester.
  • esterified products of the hydroxyl group-containing vinyl monomer corresponding to the structural unit A isopropenyl acetate, metharyl acetate, or isobutenyl acetate, which are acetic acid esters, are preferable. These may be used alone or in combination of two or more.
  • the vinyl resin having a hydroxyl group may be a homopolymer obtained by polymerizing a single monomer, or may be a copolymer obtained by copolymerizing a plurality of types of monomers.
  • a monomer having each of a vinyl group, a (meth) allyl group, and a (meth) acryloyl group may be used in combination.
  • a vinyl resin having a hydroxyl group can be obtained by polymerizing a vinyl monomer by radical polymerization, anionic polymerization, cationic polymerization or the like.
  • a polymerization initiator may be used at the time of polymerization. Examples of the polymerization initiator include thermal radical polymerization initiators, photoradical polymerization initiators, anionic polymerization initiators and cationic polymerization initiators.
  • thermal radical polymerization initiator examples include peroxides such as t-butyl peroxybenzoate, di-t-butyl peroxide, cumemper hydroxide, acetyl peroxide, benzoyl peroxide, and lauroyl peroxide; azobisisobutylnitrile, Examples thereof include azo compounds such as azobis-2,4-dimethylvaleronitrile and azobiscyclohexanecarbonitrile.
  • Examples of the photoradical polymerization initiator include 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, and 2,2-dimethoxy-1,2-diphenylethane-.
  • Examples thereof include 1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and the like.
  • anion polymerization initiator examples include organic alkali metals such as methyllithium, n-butyllithium, sec-butyllithium and t-butyllithium; organic alkaline earth metals such as methylmagnesium chloride and methylmagnesium bromide; lithium, sodium and potassium. Alkaline metals such as, etc. can be mentioned.
  • Cationic polymerization initiators include protonic acids such as hydrochloric acid, sulfuric acid, perchloric acid, trifluoroacetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, chlorosulfonic acid, fluorosulfonic acid; boron trifluoride, aluminum chloride, tetrachloride.
  • Examples thereof include Lewis acids such as titanium, ferric chloride and ferric chloride.
  • one kind of vinyl resin may be used alone, or a plurality of vinyl resins may be used in combination.
  • the vinyl resin may be a linear polymer or a branched polymer. When the vinyl resin is a branched polymer, it may be comb-shaped or star-shaped.
  • the content of the vinyl resin having a hydroxyl group is 30% by mass or more, or 40% by mass or more, from the viewpoint of further improving the water vapor barrier property and the oxygen barrier property with respect to the total amount of the non-volatile content in the coating agent. It may be 95% by mass or less, 80% by mass or less, 70% by mass or less, or 60% by mass or less from the viewpoint of further improving the moldability of the coating agent.
  • the coating agent further contains a solvent.
  • the solvent contains alcohol from the viewpoint of excellent drying property of the coating film.
  • the solvent may contain only alcohol. Examples of the alcohol include methanol, ethanol, 1-propanol, 2-propanol, and methoxypropanol (1-methoxy-2-propanol, etc.). Alcohol may contain one kind alone or a combination of two or more kinds.
  • solvent in addition to alcohol, for example, water, methyl ethyl ketone, acetone, ethyl acetate, butyl acetate, toluene, dimethylformamide, acetonitrile, methyl isobutyl ketone, cyclohexanone, methyl cellosolve, ethyl diglycol acetate, propylene glycol monomethyl ether acetate and the like can be used. It may be further contained.
  • the alcohol content is 20% by mass or more from the viewpoint of the effect of being able to form a film having excellent film-forming property and excellent blocking property with respect to the total amount of the solvent, and the viewpoint that the effect is more preferably exhibited. Therefore, it is preferably 25% by mass or more, 30% by mass or more, 35% by mass or more, 40% by mass or more, or 45% by mass or more.
  • the content of alcohol is 80% by mass or less from the viewpoint of the effect of being able to form a film having excellent oxygen barrier property and water vapor barrier property with respect to the total amount of the solvent, and from the viewpoint that the effect is more preferably exhibited.
  • the content of alcohol may be 20 to 80% by mass, 25 to 70% by mass, 30 to 60% by mass, or 40 to 50% by mass or less with respect to the total amount of the solvent.
  • Alcohol may contain ethanol from the viewpoint of being more excellent in drying property (blocking property).
  • the alcohol may contain only ethanol, and may contain ethanol and alcohols other than ethanol.
  • the alcohol other than ethanol may be, for example, at least one selected from the group consisting of methanol, 1-propanol, 2-propanol, and methoxypropanol.
  • the content of ethanol in the alcohol may be 50% by mass or more, 80% by mass or more, 95% by mass or more, or 100% by mass, based on the total amount of alcohol.
  • the content of the non-volatile component in the coating agent may be 1 to 10% by mass, preferably 2 to 8% by mass, and more preferably 4 to 7% by mass, based on the total amount of the coating agent.
  • the coating agent may further contain a polycarboxylic acid.
  • polycarboxylic acid means a compound having two or more carboxyl groups.
  • a resin having two or more carboxyl groups excluding vinyl resins having a hydroxyl group and a carboxyl group
  • examples of the polycarboxylic acid include polyacrylic acid, polymaleic acid, polyaspartic acid, and a copolymer of polyacrylic acid and polymaleic acid.
  • the content of the polycarboxylic acid may be 5% by mass or more, 10% by mass or more, or 15% by mass or more, and 30% by mass or less, based on the total content of the vinyl resin having a hydroxyl group and the polycarboxylic acid. It may be 25% by mass or less, or 20% by mass or less.
  • the coating agent contains a vinyl resin having a hydroxyl group and a resin other than the polycarboxylic acid (other resin)
  • the content of the polycarboxylic acid is the total content of the vinyl resin having a hydroxyl group, the polycarboxylic acid and the other resin. On the other hand, it may be within the above range.
  • the coating agent may further contain a modifier.
  • the modifier include a coupling agent, a silane compound, an acid anhydride and the like.
  • the coating agent contains these modifiers, the wettability of the 28-octahedral smectite is improved, and the dispersibility in the coating agent is further improved.
  • One type of modifier may be used alone, or a plurality of types may be used in combination.
  • the coupling agent examples include a silane coupling agent, a titanium coupling agent, a zirconium coupling agent, an aluminum coupling agent, and the like.
  • silane coupling agent examples include an epoxy group-containing silane coupling agent, an amino group-containing silane coupling agent, a (meth) acrylic group-containing silane coupling agent, and an isocyanate group-containing silane coupling agent.
  • epoxy group-containing silane coupling agent examples include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 2- (3,4 epoxycyclohexyl). ) Ethyltrimethoxysilane and the like.
  • amino group-containing silane coupling agent examples include 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, and 3-triethoxysilyl-N- (1,3-dimethyl). Butylidene) propylamine, N-phenyl- ⁇ -aminopropyltrimethoxysilane and the like can be mentioned.
  • examples of the (meth) acrylic group-containing silane coupling agent examples include 3-acryloyloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-methacryloxypropyltriethoxysilane.
  • isocyanate group-containing silane coupling agent examples include 3-isocyanatepropyltriethoxysilane and the like.
  • titanium coupling agent examples include isopropyltriisostearoyl titanate, isopropyltrioctanoyl titanate, isopropyldimethacrylisostearoyl titanate, isopropylisostearoyl diacrylic titanate, isopropyltris (dioctylpyrophosphate) titanate, and tetraoctylbis (ditridecyl).
  • Examples thereof include phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, and bis (dioctylpyrophosphate) ethylene titanate.
  • zirconium coupling agent examples include zirconium acetate, ammonium zirconium carbonate, zirconium fluoride and the like.
  • aluminum coupling agent examples include acetalkoxyaluminum diisopropyrate, aluminum diisopropoxymonoethylacetate, aluminumtrisethylacetate, aluminumtrisacetylacetonate and the like.
  • Examples of the silane compound include alkoxysilane, silazane, and siloxane.
  • alkoxysilanes include methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, and hexyltri.
  • Examples thereof include methoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, 1,6-bis (trimethoxysilyl) hexane, and trifluoropropyltrimethoxysilane.
  • Examples of the silazane include hexamethyldisilazane and the like.
  • Examples of the siloxane include hydrolyzable group-containing siloxane.
  • acid anhydrides examples include succinic anhydride, maleic anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, and methyl.
  • Hexahydrophthalic anhydride alkenyl succinic anhydride and the like can be mentioned.
  • the content of the modifier is preferably 0.1 to 30% by mass with respect to the total amount of the 28-octahedral smectite.
  • the content of the modifier is 0.1% by mass or more, the dispersibility of the 28-octahedral smectite in the coating agent becomes better.
  • the content of the modifier is 30% by mass or less, the influence of the modifier on the mechanical properties of the coating agent can be further suppressed.
  • the content of the modifier is preferably 0.3 to 20% by mass, more preferably 0.5 to 15% by mass.
  • the coating agent may contain various additives (excluding compounds corresponding to vinyl resins having hydroxyl groups, octahedral smectites, modifiers and solvents).
  • Additives include, for example, organic fillers, inorganic fillers, stabilizers (antioxidants, heat stabilizers, UV absorbers, etc.), plasticizers, antistatic agents, lubricants, antiblocking agents, colorants, crystal nucleating agents, etc. Examples thereof include an oxygen scavenger (a compound having an oxygen scavenging function) and an antistatic agent. These various additives are used alone or in combination of two or more.
  • examples of the inorganic filler include inorganic substances such as metals, metal oxides, resins, and minerals, and composites thereof.
  • specific examples of the inorganic filler include alumina, titanium, zirconia, copper, iron, silver, mica, talc, aluminum flakes, glass flakes, clay minerals and the like.
  • clay minerals may be used in combination for the purpose of improving the gas barrier property.
  • Examples of the compound having an oxygen trapping function include low molecular weight organic compounds that react with oxygen such as hindered phenol compounds, vitamin C, vitamin E, organic phosphorus compounds, gallic acid, and pyrogallol, and cobalt, manganese, nickel, and iron. , Transition metal compounds such as copper and the like.
  • tackifier examples include xylene resin, terpene resin, phenol resin, rosin resin and the like. By adding a tackifier, the adhesiveness to various film materials immediately after application can be improved.
  • the amount of the tackifier added is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the total amount of the coating agent.
  • the laminate of the embodiment has a base material and a coat layer formed by coating the above-mentioned coating agent on the base material.
  • the laminate is preferably used, for example, as a packaging material, an industrial material, or the like.
  • the laminate of the embodiment can be suitably used as a packaging material in various fields.
  • the method of coating the coating agent on the substrate is not particularly limited. As a specific method, various coating methods such as roll coating and gravure coating can be exemplified. Further, the coating device is not particularly limited. For example, by applying a coating agent on the base material and, if necessary, performing a drying treatment, a laminate having the base material and the coat layer formed on the base material can be obtained. For example, when the coating agent contains a solvent, the drying conditions may be appropriately set according to the type of solvent, the amount used, and the like. Drying may be carried out, for example, by holding at 50 ° C. to 100 ° C. for 0.5 minutes to 10 minutes.
  • the base material may be, for example, a plate, a sheet, or a film.
  • Examples of the material of the base material include polyethylene (PE), polypropylene (PP), polystyrene (PS), and polyethylene terephthalate (PET).
  • the base material may or may not be surface-treated on the surface to which the coating agent is applied.
  • Examples of the surface treatment include corona treatment.
  • the thickness of the base material may be, for example, 1 ⁇ m or more, 5 ⁇ m or more, or 10 ⁇ m or more, and may be 50 ⁇ m or less, 20 ⁇ m or less, or 15 ⁇ m or less.
  • the thickness of the coat layer may be, for example, 0.1 to 5 ⁇ m.
  • the thickness of the coat layer may be, for example, 0.5 ⁇ m or more, or 1 ⁇ m or more, and may be 10 ⁇ m or less, 5 ⁇ m or less, or 2 ⁇ m or less.
  • -Vinyl resin 1 polyvinyl alcohol, hydroxyl value: 1250, manufactured by Japan Vam & Poval Co., Ltd., JF-03
  • -Vinyl resin 2 polyvinyl alcohol, hydroxyl value: 1000, manufactured by Japan Vam & Poval Co., Ltd., JP-05
  • Clay dispersions 1 to 8 containing the compositions (unit: parts by mass) shown in Table 2 were prepared.
  • ammonium-type montmorillonite ammonium-type montmorillonite obtained by exchanging sodium ions of sodium-type montmorillonite (“Kunipia F” manufactured by Kunimine Industries, Ltd.) with ammonium ions was used.
  • lithium-type montmorillonite As the lithium-type montmorillonite, "Kunipia M” manufactured by Kunimine Industries, Ltd. was used. As the sodium-type montmorillonite, "Kunipia F” manufactured by Kunimine Industries, Ltd. was used.
  • the total of ammonium ion equivalent, lithium ion equivalent, and hydrogen ion equivalent of 2-octhedral smectite was 110 meq / 100 g for ammonium montmorillonite, 110 meq / 100 g for lithium montmorillonite, and 110 meq / 100 g for sodium montmorillonite.
  • the sodium ion equivalents of ammonium-type montmorillonite and lithium-type montmorillonite were less than 10 meq / 100 g.
  • the coating agents of Examples and Comparative Examples were prepared by combining the resin solutions (10 parts by mass) and the clay dispersion (20 parts by mass) shown in Table 3.
  • Table 3 shows the content of polycarboxylic acid with respect to the total content of vinyl resin having a hydroxyl group and polycarboxylic acid, the content of diocthedral smectite with respect to the total amount of non-volatile content (components other than solvent), and the content of alcohol with respect to the total amount of solvent.
  • the content, the content of ethanol with respect to the total amount of alcohol, and the content of non-volatile components (components other than solvent) in the coating agent are also shown.
  • the laminate X was heat-treated in a dryer at 60 ° C. for 5 seconds, then immediately folded in three and subjected to a load of 5 kgf for 24 hours to obtain a laminate Y. Open the tri-folded laminate Y, and at that time, if there is no resistance or sound between the coated surface and the base material surface, "A”, if there is no resistance but there is sound, "B”, the film When was stuck, the blocking property was evaluated as "C”.
  • the laminate X was immediately heat-treated in a dryer at 80 ° C. for 1 minute after coating. As a result, the laminated body Z was obtained.
  • the oxygen permeability and water vapor permeability of the obtained laminate Z were measured as follows.
  • the oxygen transmission rate was measured according to JIS-K7126 (isopressure method) using an oxygen transmission rate measuring device "OX-TRAN1 / 50" manufactured by Mocon Co., Ltd. at a temperature of 23 ° C. and an atmosphere of 75% RH. .. In addition, RH represents relative humidity.

Abstract

The present invention provides, as one aspect, a coating agent containing a dioctahedral smectite, a vinyl resin having a hydroxyl group, and a solvent, wherein the dioctahedral smectite includes, as an interlayer ion, at least one selected from the group consisting of ammonium ions, lithium ions, and hydrogen ions, the solvent contains an alcohol, and the contained amount of the alcohol with respect to the entire amount of the solvent is 20-80 mass%.

Description

コーティング剤及び積層体Coating agent and laminate
　本発明は、コーティング剤及び積層体に関する。 The present invention relates to a coating agent and a laminate.
　食品等の包装に用いられる包装材料には、内容物の保護、耐レトルト性、耐熱性、透明性、加工性等の機能が要求される。内容物の品質保持のためには、特にガスバリア性が重要となる。最近では、包装材料だけでなく、太陽電池、半導体等の電子材料に用いられる材料についても、高いガスバリア性が要求されるようになっている。このような材料は、例えば、基材とガスバリア性を有するコート層とが積層されて構成されている。したがって、高いガスバリア性を有するコート層を形成可能なコーティング剤が求められる。 Packaging materials used for packaging foods, etc. are required to have functions such as protection of contents, retort resistance, heat resistance, transparency, and processability. Gas barrier properties are especially important for maintaining the quality of the contents. Recently, not only packaging materials but also materials used for electronic materials such as solar cells and semiconductors are required to have high gas barrier properties. Such a material is configured by, for example, laminating a base material and a coat layer having a gas barrier property. Therefore, a coating agent capable of forming a coat layer having a high gas barrier property is required.
　特許文献１には、水酸基を有する樹脂及びイソシアネート化合物を、粘土鉱物等の板状無機化合物及び光遮断剤と組み合わせることで、ガスバリア性等の特性が向上することが記載されている。 Patent Document 1 describes that by combining a resin having a hydroxyl group and an isocyanate compound with a plate-like inorganic compound such as a clay mineral and a light blocking agent, properties such as gas barrier properties are improved.
　また、特許文献２には変性粘土を主要構成成分とする材料が記載されており、変性粘土を用い、必要に応じて添加剤を用い、変性粘土結晶を配向させ、緻密に積層させることにより、自立膜として利用可能な機械的強度、ガスバリア性、耐水性、熱安定性及びフレキシビリティーを備えた膜材が得られるとされる。 Further, Patent Document 2 describes a material containing modified clay as a main constituent component, and by using modified clay and using additives as necessary, the modified clay crystals are oriented and densely laminated. It is said that a film material having mechanical strength, gas barrier property, water resistance, thermal stability and flexibility that can be used as a self-supporting film can be obtained.
国際公開第２０１３／０２７６０９号International Publication No. 2013/027609 特開２００７－２７７０７８号公報Japanese Unexamined Patent Publication No. 2007-277078
　コーティング剤は、ガスバリア性に加えて、製膜性に優れ（コート層を好適に形成でき）、かつブロッキング性に優れる膜（コート層）を形成可能であることが望ましい。 It is desirable that the coating agent can form a film (coat layer) having excellent film forming property (coating layer can be preferably formed) and blocking property in addition to gas barrier property.
　本発明の目的は、一側面において、製膜性に優れ、かつブロッキング性、酸素バリア性及び水蒸気バリア性に優れる膜を形成可能なコーティング剤を提供することにある。 An object of the present invention is to provide a coating agent capable of forming a film having excellent film-forming property and excellent blocking property, oxygen barrier property and water vapor barrier property on one aspect.
　本発明者らは、層間イオンとして、アンモニウムイオン、リチウムイオン、及び水素イオンからなる群より選ばれる少なくとも１種を含有する２八面体型スメクタイトと、水酸基を有するビニル樹脂と、アルコールを所定量含む溶剤とを組み合わせることによって、製膜性に優れ、かつブロッキング性、酸素バリア性及び水蒸気バリア性に優れる膜を形成可能なコーティング剤が得られることを見出し、本発明を完成するに至った。 The present inventors include, as interlayer ions, a dihedral smectite containing at least one selected from the group consisting of ammonium ions, lithium ions, and hydrogen ions, a vinyl resin having a hydroxyl group, and an alcohol in a predetermined amount. We have found that by combining with a solvent, a coating agent capable of forming a film having excellent film-forming property and excellent blocking property, oxygen barrier property and water vapor barrier property can be obtained, and the present invention has been completed.
　すなわち、本発明は、一側面において、２八面体型スメクタイトと、水酸基を有するビニル樹脂と、溶剤と、を含有し、２八面体型スメクタイトが、層間イオンとして、アンモニウムイオン、リチウムイオン、及び水素イオンからなる群より選ばれる少なくとも１種を含有する２八面体型スメクタイトであり、溶剤はアルコールを含有し、アルコールの含有量は、溶剤全量に対して２０～８０質量％である、コーティング剤を提供する。 That is, the present invention contains, on one side, a 28-hedron smectite, a vinyl resin having a hydroxyl group, and a solvent, and the 28-hedron smectite contains ammonium ions, lithium ions, and hydrogen as interlayer ions. A coating agent containing at least one selected from the group consisting of ions, the solvent containing alcohol, and the content of alcohol being 20 to 80% by mass based on the total amount of the solvent. provide.
　２八面体型スメクタイトは、モンモリロナイトであってよい。２八面体型スメクタイトのナトリウムイオン当量は、１０ｍｅｑ／１００ｇ未満であってよい。２八面体型スメクタイトのアンモニウムイオン当量、リチウムイオン当量、及び水素イオン当量の合計は、５０～１２０ｍｅｑ／１００ｇであってよい。 The octahedral smectite may be montmorillonite. The sodium ion equivalent of the 2 octahedral smectite may be less than 10 meq / 100 g. The sum of the ammonium ion equivalent, the lithium ion equivalent, and the hydrogen ion equivalent of the 2 octahedral smectite may be 50 to 120 meq / 100 g.
　コーティング剤は、ポリカルボン酸を更に含有していてよい。水酸基を有するビニル樹脂の水酸価は、８００～１５００であってよい。 The coating agent may further contain polycarboxylic acid. The hydroxide value of the vinyl resin having a hydroxyl group may be 800 to 1500.
　本発明は、他の一側面において、基材と、上記のコーティング剤を基材上にコートしてなるコート層と、を有する、積層体を提供する。コート層の厚みは、０．１～５μｍであってよい。積層体は、包装材料として用いられてよい。 The present invention provides a laminate having a base material and a coating layer obtained by coating the above-mentioned coating agent on the base material in another aspect. The thickness of the coat layer may be 0.1 to 5 μm. The laminate may be used as a packaging material.
　本発明の一側面によれば、製膜性に優れ、かつブロッキング性、酸素バリア性及び水蒸気バリア性に優れる膜を形成可能なコーティング剤を提供することが可能となる。 According to one aspect of the present invention, it is possible to provide a coating agent capable of forming a film having excellent film forming properties and excellent blocking properties, oxygen barrier properties and water vapor barrier properties.
　以下、本発明の実施形態について詳細に説明する。ただし、本発明は以下の実施形態に限定されるものではない。本明細書において、個別に記載した上限値及び下限値は任意に組み合わせ可能である。 Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments. In the present specification, the upper limit value and the lower limit value described individually can be arbitrarily combined.
　一実施形態のコーティング剤は、２八面体型スメクタイトと、水酸基を有するビニル樹脂と、溶剤と、を含有する。 The coating agent of one embodiment contains 28 octahedral smectites, a vinyl resin having a hydroxyl group, and a solvent.
＜２八面体型スメクタイト＞
　粘土鉱物の基本構造は、Ｓｉ－Ｏの四面体シートとＡｌ－Ｏ等の八面体シートから構成され、八面体シートに入る陽イオンがＡｌ３＋など三価のイオンの場合に２八面体と呼ばれる。２八面体型スメクタイトの陽イオン交換容量は、通常６０～１５０ｍｅｑ／１００ｇである。２八面体型スメクタイトの具体的な構造としては、モンモリロナイト、バイデライトが知られている。 <2 Octahedral smectite>
The basic structure of clay minerals is composed of a tetrahedral sheet of Si—O and an octahedral sheet of Al—O, etc., and is called a dioctahedron when the cations entering the octahedral sheet are trivalent ions such as Al 3+. .. The cation exchange capacity of the 2 octahedral smectite is usually 60 to 150 meq / 100 g. 2 As a specific structure of octahedral smectite, montmorillonite and byderite are known.
　２八面体型スメクタイトは、層間イオンとして、アンモニウムイオン、リチウムイオン、及び水素イオンからなる群より選ばれる少なくとも１種を含有する２八面体型スメクタイトである。 The 2 octahedral smectite is a 2 octahedral smectite containing at least one selected from the group consisting of ammonium ion, lithium ion, and hydrogen ion as interlayer ions.
　２八面体型スメクタイトのナトリウムイオン当量は、１０ｍｅｑ／１００ｇ未満であってよい。２八面体型スメクタイトのナトリウムイオン当量は、例えば、５ｍｅｑ／１００ｇ以下、又は２ｍｅｑ／１００ｇ以下であってよい。２八面体型スメクタイトのナトリウムイオン当量は、１Ｎの酢酸アンモニウム溶液に溶出してくる陽イオン量をイオンクロマトグラフィーにより測定することができる。 The sodium ion equivalent of the 2 octahedral smectite may be less than 10 meq / 100 g. The sodium ion equivalent of the 2 octahedral smectite may be, for example, 5 meq / 100 g or less, or 2 meq / 100 g or less. The sodium ion equivalent of 2 octahedral smectite can be measured by ion chromatography on the amount of cations eluted in a 1N ammonium acetate solution.
　２八面体型スメクタイトのアンモニウムイオン当量、リチウムイオン当量、及び水素イオン当量の合計が、５０～１２０ｍｅｑ／１００ｇであってよい。２八面体型スメクタイトのアンモニウムイオン当量、リチウムイオン当量、及び水素イオン当量の合計は、５０ｍｅｑ／１００ｇ以上、８０ｍｅｑ／１００ｇ以上、又は１００ｍｅｑ／１００ｇ以上であってよく、１２０ｍｅｑ／１００ｇ以下、又は１１０ｍｅｑ／１００ｇ以下であってよい。２八面体型スメクタイトのアンモニウムイオン当量は、１Ｎの塩化カリウム溶液に溶出してくる陽イオン量、リチウムイオン当量は、１Ｎの酢酸アンモニウム溶液に溶出してくる陽イオン量をそれぞれイオンクロマトグラフィーにより測定することで求めることができる。また、水素イオン当量は、イオン交換前の陽イオン量とイオン交換後の陽イオン量の差から求めることができる。例えば、層間イオンがナトリウムであるモンモリトナイトを用いた場合は、イオン交換操作前後のモンモリロナイトから１Ｎの酢酸アンモニウム溶液に溶出してくるナトリウムイオン量をイオンクロマトグラフィー測定し、その差分から水素イオン当量を求めることができる。 The total of the ammonium ion equivalent, the lithium ion equivalent, and the hydrogen ion equivalent of the 2 octahedral smectite may be 50 to 120 meq / 100 g. The total of ammonium ion equivalent, lithium ion equivalent, and hydrogen ion equivalent of 2 octahedral smectite may be 50 meq / 100 g or more, 80 meq / 100 g or more, or 100 meq / 100 g or more, 120 meq / 100 g or less, or 110 meq /. It may be 100 g or less. 2 The ammonium ion equivalent of octahedral smectite is the amount of cations eluted in a 1N potassium chloride solution, and the lithium ion equivalent is the amount of cations eluted in a 1N ammonium acetate solution by ion chromatography. It can be obtained by doing. Further, the hydrogen ion equivalent can be obtained from the difference between the amount of cations before ion exchange and the amount of cations after ion exchange. For example, when montmorillonite having sodium interlayer ions is used, the amount of sodium ions eluted from montmorillonite into a 1N ammonium acetate solution before and after the ion exchange operation is measured by ion chromatography, and the hydrogen ion equivalent is measured from the difference. Can be obtained.
　２八面体型スメクタイトの層間イオン（陽イオン）をアンモニウムイオン、リチウムイオン、及び水素イオンからなる群より選ばれる少なくとも１種に交換する方法は、通常のイオン交換方法であってよく、例えば、２八面体型スメクタイトの水分散体を、水素イオン、アンモニウムイオン、又はリチウムイオンを予め保持させた陽イオン交換樹脂で処理する方法であってよい。当該方法は、イオン交換樹脂を充填したカラムへ上記水分散体を通液する方法であってよく、イオン交換樹脂と上記水分散体とを混合してバッチ攪拌する方法であってもよい。 The method of exchanging the interlayer ion (cation) of the octahedral smectite with at least one selected from the group consisting of ammonium ion, lithium ion, and hydrogen ion may be an ordinary ion exchange method, for example, 2 The method may be a method in which the aqueous dispersion of octahedral smectite is treated with a cation exchange resin in which hydrogen ions, ammonium ions, or lithium ions are previously retained. The method may be a method of passing the aqueous dispersion through a column filled with an ion exchange resin, or a method of mixing the ion exchange resin and the aqueous dispersion and stirring them in a batch.
　より具体的な例を挙げて説明すると、例えば、層間陽イオンをリチウムイオンに交換する場合、アンバーライトＩＲ１２０Ｂ－Ｈを予め水酸化リチウムで処理して、イオン交換樹脂にリチウムイオンを保持させる。このリチウムイオンを保持したイオン交換樹脂が充填されたカラムに、２八面体型スメクタイトの濃度が２％の水分散体を１ｍＬ／分の速度で通液する。通液後の水分散体を１１０℃のオーブンで終夜乾燥することで、層間イオンがリチウムイオンである２八面体型スメクタイトを得ることができる。 To explain with a more specific example, for example, when exchanging interlayer cations with lithium ions, amberlite IR120B-H is treated with lithium hydroxide in advance so that the ion exchange resin retains lithium ions. An aqueous dispersion having a concentration of 2 octahedral smectite of 2% is passed through a column packed with an ion exchange resin holding lithium ions at a rate of 1 mL / min. By drying the aqueous dispersion after passing the liquid in an oven at 110 ° C. overnight, a dioctahedral smectite having lithium ions as interlayer ions can be obtained.
　２八面体型スメクタイトの含有量は、コーティング剤中の不揮発分全量に対して、例えば、水蒸気バリア性及び酸素バリア性（例えば高湿度下での酸素バリア性）により一層優れる等の観点から、５質量％以上、２０質量％以上、３０質量％以上、又は４０質量％以上であってよく、例えば、コーティング剤の成形性がより一層優れたものとなり、かつ、基材への密着性が向上する等の観点から、７０質量％以下、又は６０質量％以下であってよい。２八面体型スメクタイトの含有量は、コーティング剤中の不揮発分全量に対して、例えば、５～７０質量％、２０～６０質量％、又は４０～６０質量％であってよい。不揮発分とは、コーティング剤中の溶剤以外の成分を意味する。 2 The content of octahedral smectite is 5 from the viewpoint of being more excellent in water vapor barrier property and oxygen barrier property (for example, oxygen barrier property under high humidity) with respect to the total amount of non-volatile content in the coating agent. It may be mass% or more, 20% by mass or more, 30% by mass or more, or 40% by mass or more. For example, the moldability of the coating agent is further improved, and the adhesion to the substrate is improved. From the viewpoint of the above, it may be 70% by mass or less, or 60% by mass or less. The content of the octahedral smectite may be, for example, 5 to 70% by mass, 20 to 60% by mass, or 40 to 60% by mass with respect to the total amount of the non-volatile content in the coating agent. The non-volatile component means a component other than the solvent in the coating agent.
＜水酸基を有するビニル樹脂＞
　コーティング剤は、水酸基を有するビニル樹脂を含有する。水酸基を有するビニル樹脂は、例えば、重合性二重結合を有するアルコールのエステル化物を重合した後、けん化処理をすることによって得ることができる。 <Vinyl resin with hydroxyl group>
The coating agent contains a vinyl resin having a hydroxyl group. A vinyl resin having a hydroxyl group can be obtained, for example, by polymerizing an esterified product of an alcohol having a polymerizable double bond and then performing a saponification treatment.
　重合性二重結合を有するアルコールのエステル化物は、例えば、ビニルエステルであってよい。ビニルエステルとしては、例えば、ビニルアセテート、ビニルクロロアセテート、ビニルプロピオネート、ビニルブチレート、ビニルメトキシアセテート、安息香酸ビニル等が挙げられる。 The esterified product of the alcohol having a polymerizable double bond may be, for example, a vinyl ester. Examples of the vinyl ester include vinyl acetate, vinyl chloroacetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate and the like.
　また、水酸基を有するビニル樹脂は、例えば、水酸基を有するビニルモノマーの重合若しくは共重合、又は水酸基を有するビニルモノマーと、水酸基を有しないビニルモノマーとの共重合によって得ることができる。水酸基を有するビニルモノマーは、重合性二重結合を有する基（例えば、ビニル基、（メタ）アリル基、又は（メタ）アクリロイル基）及び水酸基をそれぞれ少なくとも一つ有するモノマーである。水酸基を有しないビニルモノマーは、重合性二重結合を有する基（例えば、ビニル基、（メタ）アリル基、又は（メタ）アクリロイル基）を少なくとも一つ有し、かつ、水酸基を有しないモノマーである。（メタ）アリル基とは、アリル基又はメタリル基を意味する。（メタ）アクリロイル基とは、アクリロイル基又はメタクリロイル基を意味する。 Further, the vinyl resin having a hydroxyl group can be obtained, for example, by polymerizing or copolymerizing a vinyl monomer having a hydroxyl group, or copolymerizing a vinyl monomer having a hydroxyl group and a vinyl monomer having no hydroxyl group. The vinyl monomer having a hydroxyl group is a monomer having at least one group having a polymerizable double bond (for example, a vinyl group, a (meth) allyl group, or a (meth) acryloyl group) and a hydroxyl group. A vinyl monomer having no hydroxyl group is a monomer having at least one group having a polymerizable double bond (for example, a vinyl group, a (meth) allyl group, or a (meth) acryloyl group) and having no hydroxyl group. is there. The (meth) allyl group means an allyl group or a metalyl group. The (meth) acryloyl group means an acryloyl group or a methacryloyl group.
　水酸基を有するビニルモノマー（水酸基含有ビニルモノマー）としては、例えば、（メタ）アリルアルコール、ビニルアルコール、；１－ブテン－３－オール等の炭素数４～１２のアルケンモノオール又はアルケンジオール；２－ヒドロキシエチルプロペニルエーテル等の末端に重合性二重結合を有するアルケニルエーテル；ヒドロキシスチレン；（メタ）アクリル酸ヒドロキシエチル、(メタ)アクリル酸２－ヒドロキシプロピル、(メタ)アクリル酸３－ヒドロキシプロピル、(メタ)アクリル酸２－ヒドロキシブチル、(メタ)アクリル酸３－ヒドロキシブチル、(メタ)アクリル酸４－ヒドロキシブチル；ε－カプロラクトンを開環重合した化合物と（メタ）アクリル酸のモノエステル化物；等の水酸基含有ビニルモノマーが挙げられる。 Examples of the vinyl monomer having a hydroxyl group (hydroxyl-containing vinyl monomer) include (meth) allyl alcohol, vinyl alcohol, and alkenemonool or alkenediol having 4 to 12 carbon atoms such as 1-butene-3-ol; 2-. Alkene ether having a polymerizable double bond at the end such as hydroxyethyl propenyl ether; hydroxystyrene; hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, ( 2-Hydroxybutyl (meth) acrylic acid, 3-hydroxybutyl (meth) acrylic acid, 4-hydroxybutyl (meth) acrylic acid; a compound obtained by ring-opening polymerization of ε-caprolactone and a monoesterified product of (meth) acrylic acid, etc. Examples thereof include a hydroxyl group-containing vinyl monomer.
　水酸基を有しないビニルモノマー（水酸基非含有ビニルモノマー）としては、エチレン、プロピレン、イソブチレン、ブタジエン、イソプレン等のオレフィン；ジクロロエチレン、塩化ビニル、等のハロゲン化オレフィン；（メタ）アクリル酸；（メタ）アクリル酸エステル；ビニルエステル；マレイン酸ジエステル；フマル酸ジエステル；イタコン酸ジエステル；（メタ）アクリルアミド；スチレン及びその誘導体；ビニルエーテル；ビニルケトン；マレイミド；アリル化合物；（メタ）アクリロニトリル；ビニルピリジン、Ｎ－ビニルピロリドン、ビニルカルバゾール、Ｎ－ビニルイミダゾール、ビニルカプロラクトン等のビニル基が置換した複素環式基を有する化合物；Ｎ－ビニルホルムアミド、Ｎ－ビニルアセトアミド等のビニルアミドなどが挙げられる。 Examples of the vinyl monomer having no hydroxyl group (vinyl monomer containing no hydroxyl group) include olefins such as ethylene, propylene, isobutylene, butadiene and isoprene; halogenated olefins such as dichloroethylene and vinyl chloride; (meth) acrylic acid; (meth) acrylic. Acid ester; vinyl ester; maleic acid diester; fumaric acid diester; itaconic acid diester; (meth) acrylamide; styrene and its derivatives; vinyl ether; vinyl ketone; maleimide; allyl compound; (meth) acrylonitrile; vinylpyridine, N-vinylpyrrolidone, Compounds having a heterocyclic group substituted with a vinyl group such as vinylcarbazole, N-vinylimidazole and vinylcaprolactone; vinylamides such as N-vinylformamide and N-vinylacetamide can be mentioned.
　（メタ）アクリル酸エステルの例としては、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ｎ－プロピル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸ｎ－ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ｔ－ブチル、（メタ）アクリル酸アミル、（メタ）アクリル酸ｎ－ヘキシル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸ｔ－ブチルシクロヘキシル、（メタ）アクリル酸２－エチルヘキシル、（メタ）アクリル酸ｔ－オクチル、（メタ）アクリル酸ドデシル、（メタ）アクリル酸オクタデシル、（メタ）アクリル酸アセトキシエチル、（メタ）アクリル酸フェニル、（メタ）アクリル酸２－ヒドロキシエチル、（メタ）アクリル酸－２－ヒドロキシプロピル、（メタ）アクリル酸－３－ヒドロキシプロピル、（メタ）アクリル酸－４－ヒドロキシブチル、（メタ）アクリル酸２－メトキシエチル、（メタ）アクリル酸２－エトキシエチル、（メタ）アクリル酸２－（２－メトキシエトキシ）エチル、（メタ）アクリル酸３－フェノキシ－２－ヒドロキシプロピル、（メタ）アクリル酸－２－クロロエチル、（メタ）アクリル酸グリシジル、（メタ）アクリル酸－３，４－エポキシシクロヘキシルメチル、（メタ）アクリル酸ビニル、（メタ）アクリル酸－２－フェニルビニル、（メタ）アクリル酸－１－プロペニル、（メタ）アクリル酸アリル、（メタ）アクリル酸－２－アリロキシエチル、（メタ）アクリル酸プロパルギル、（メタ）アクリル酸ベンジル、（メタ）アクリル酸ジエチレングリコールモノメチルエーテル、（メタ）アクリル酸ジエチレングリコールモノエチルエーテル、（メタ）アクリル酸トリエチレングリコールモノメチルエーテル、（メタ）アクリル酸トリエチレングリコールモノエチルエーテル、（メタ）アクリル酸ポリエチレングリコールモノメチルエーテル、（メタ）アクリル酸ポリエチレングリコールモノエチルエーテル、（メタ）アクリル酸β－フェノキシエトキシエチル、（メタ）アクリル酸ノニルフェノキシポリエチレングリコール、（メタ）アクリル酸ジシクロペンテニル、（メタ）アクリル酸ジシクロペンテニルオキシエチル、（メタ）アクリル酸トリフロロエチル、（メタ）アクリル酸オクタフロロペンチル、（メタ）アクリル酸パーフロロオクチルエチル、（メタ）アクリル酸ジシクロペンタニル、（メタ）アクリル酸トリブロモフェニル、（メタ）アクリル酸トリブロモフェニルオキシエチル、（メタ）アクリル酸－γ－ブチロラクトン等が挙げられる。 Examples of (meth) acrylic acid esters include methyl (meth) acrylic acid, ethyl (meth) acrylic acid, n-propyl (meth) acrylic acid, isopropyl (meth) acrylic acid, n-butyl (meth) acrylic acid, Isobutyl (meth) acrylate, t-butyl (meth) acrylate, amyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, ( 2-Ethylhexyl acrylate, t-octyl acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, (meth) acrylic 2-Hydroxyethyl acid, -2-hydroxypropyl (meth) acrylate, -3-hydroxypropyl (meth) acrylate, -4-hydroxybutyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, ( 2-ethoxyethyl (meth) acrylate, 2- (2-methoxyethoxy) ethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, -2-chloroethyl (meth) acrylate, (meth) ) Glycidyl acrylate, (meth) acrylic acid-3,4-epoxycyclohexylmethyl, vinyl (meth) acrylic acid, (meth) -2-phenylvinyl acrylate, (meth) -1-propenyl acrylate, (meth) Allyl acrylate, -2-aryloxyethyl (meth) acrylate, propargyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, ( Triethylene glycol monomethyl ether (meth) acrylate, triethylene glycol monoethyl ether (meth) acrylate, polyethylene glycol monomethyl ether (meth) acrylate, polyethylene glycol monoethyl ether (meth) acrylate, β- (meth) acrylate Phenoxyethoxyethyl, nonylphenoxypolyethylene glycol (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, trifluoroethyl (meth) acrylate, octafluororo (meth) acrylate Pentyl, perfluorooctylethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, Examples thereof include (meth) tribromophenyl acrylate, (meth) tribromophenyloxyethyl acrylate, and (meth) acrylate-γ-butyrolactone.
　ビニルエステルの例としては、上記例示したモノマーが挙げられる。 Examples of vinyl esters include the monomers exemplified above.
　マレイン酸ジエステルの例としては、マレイン酸ジメチル、マレイン酸ジエチル、及びマレイン酸ジブチル等が挙げられる。 Examples of maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.
　フマル酸ジエステルの例としては、フマル酸ジメチル、フマル酸ジエチル、フマル酸ジブチル等が挙げられる。 Examples of the fumaric acid diester include dimethyl fumarate, diethyl fumarate, dibutyl fumarate and the like.
　イタコン酸ジエステルの例としては、イタコン酸ジメチル、イタコン酸ジエチル、イタコン酸ジブチル等が挙げられる。 Examples of the itaconic acid diester include dimethyl itaconic acid, diethyl itaconic acid, dibutyl itaconic acid and the like.
　（メタ）アクリルアミドの例としては、（メタ）アクリルアミド、Ｎ－メチル（メタ）アクリルアミド、Ｎ－エチル（メタ）アクリルアミド、Ｎ－プロピル（メタ）アクリルアミド、Ｎ－イソプロピル（メタ）アクリルアミド、Ｎ－ｎ－ブチルアクリル（メタ）アミド、Ｎ－ｔ－ブチル（メタ）アクリルアミド、Ｎ－シクロヘキシル（メタ）アクリルアミド、Ｎ－（２－メトキシエチル）（メタ）アクリルアミド、Ｎ，Ｎ－ジメチル（メタ）アクリルアミド、Ｎ，Ｎ－ジエチル（メタ）アクリルアミド、Ｎ－フェニル（メタ）アクリルアミド、Ｎ－ニトロフェニルアクリルアミド、Ｎ－エチル－Ｎ－フェニルアクリルアミド、Ｎ－ベンジル（メタ）アクリルアミド、（メタ）アクリロイルモルホリン、ジアセトンアクリルアミド、Ｎ－メチロールアクリルアミド、Ｎ－ヒドロキシエチルアクリルアミド、ビニル（メタ）アクリルアミド、Ｎ，Ｎ－ジアリル（メタ）アクリルアミド、Ｎ－アリル（メタ）アクリルアミド等が挙げられる。 Examples of (meth) acrylamide are (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, Nn- Butylacryl (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-nitrophenylacrylamide, N-ethyl-N-phenylacrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholin, diacetoneacrylamide, N -Methylol acrylamide, N-hydroxyethyl acrylamide, vinyl (meth) acrylamide, N, N-diallyl (meth) acrylamide, N-allyl (meth) acrylamide and the like can be mentioned.
　スチレン誘導体の例としては、メチルスチレン、ジメチルスチレン、トリメチルスチレン、エチルスチレン、イソプロピルスチレン、ブチルスチレン、ヒドロキシスチレン、メトキシスチレン、ブトキシスチレン、アセトキシスチレン、クロロスチレン、ジクロロスチレン、ブロモスチレン、クロロメチルスチレン、α－メチルスチレン等が挙げられる。 Examples of styrene derivatives include methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, hydroxystyrene, methoxystyrene, butoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethylstyrene, Examples thereof include α-methylstyrene.
　ビニルエーテルの例としては、メチルビニルエーテル、エチルビニルエーテル、２－クロロエチルビニルエーテル、ヒドロキシエチルビニルエーテル、プロピルビニルエーテル、ブチルビニルエーテル、ヘキシルビニルエーテル、オクチルビニルエーテル、メトキシエチルビニルエーテル、フェニルビニルエーテル等が挙げられる。 Examples of vinyl ethers include methyl vinyl ether, ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, octyl vinyl ether, methoxyethyl vinyl ether, phenyl vinyl ether and the like.
　ビニルケトンの例としては、メチルビニルケトン、エチルビニルケトン、プロピルビニルケトン、フェニルビニルケトン等が挙げられる。 Examples of vinyl ketones include methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, phenyl vinyl ketone and the like.
　マレイミドの例としては、マレイミド、ブチルマレイミド、シクロヘキシルマレイミド、フェニルマレイミドなどが挙げられる。 Examples of maleimide include maleimide, butylmaleimide, cyclohexylmaleimide, phenylmaleimide and the like.
　アリル化合物の例としては、酢酸アリル、アリルアルコール、アリルアミン、Ｎ－アリルアニリン、塩化アリル、臭化アリル等が挙げられる。 Examples of allyl compounds include allyl acetate, allyl alcohol, allylamine, N-allylaniline, allyl chloride, allyl bromide and the like.
　水酸基を有するビニル樹脂は、水酸基価（単位：ｍｇＫＯＨ／ｇ）が例えば８００～１５００の範囲になるように、水酸基を含んでいてよい。水酸基を有するビニル樹脂の水酸基価は、例えば、８００以上、９００以上、９５０以上、又は１０００以上であってよく、１５００以下、１４００以下、又は１３００以下であってもよい。水酸基を有するビニル樹脂の水酸基価は、例えば、８００～１５００、９００～１４００、９５０～１３００、又は１０００～１３００であってよい。水酸基価は、ＪＩＳ－Ｋ００７０に記載の水酸基価測定方法により測定することができる。また、ビニル樹脂を合成して用いる場合には、使用するモノマー組成から水酸基価を算出することも可能である。 The vinyl resin having a hydroxyl group may contain a hydroxyl group so that the hydroxyl value (unit: mgKOH / g) is in the range of, for example, 800 to 1500. The hydroxyl value of the vinyl resin having a hydroxyl group may be, for example, 800 or more, 900 or more, 950 or more, or 1000 or more, and may be 1500 or less, 1400 or less, or 1300 or less. The hydroxyl value of the vinyl resin having a hydroxyl group may be, for example, 800 to 1500, 900 to 1400, 950 to 1300, or 1000 to 1300. The hydroxyl value can be measured by the hydroxyl value measuring method described in JIS-K0070. Further, when a vinyl resin is synthesized and used, the hydroxyl value can be calculated from the monomer composition used.
　水酸基を有するビニル樹脂が、重合性二重結合を有するアルコールのエステル化物の重合体をけん化処理して得られる樹脂である場合、水酸基を有するビニル樹脂の重量平均分子量は、けん化処理前のビニル樹脂の重量平均分子量から換算することができる。けん化処理前のビニル樹脂（アセトキシ基（ＣＨ３Ｃ（＝Ｏ）Ｏ－）を有するビニル樹脂）のＧＰＣ（ゲルパーミエーションクロマトグラフィー）によるポリスチレン換算の重量平均分子量は、特に限定されないが、３００以上であってよく、４０００以下であってよい。 When the vinyl resin having a hydroxyl group is a resin obtained by saponifying a polymer of an esterified product of an alcohol having a polymerizable double bond, the weight average molecular weight of the vinyl resin having a hydroxyl group is the vinyl resin before the saponification treatment. It can be converted from the weight average molecular weight of. The polystyrene-equivalent weight average molecular weight of the vinyl resin (vinyl resin having an acetoxy group (CH 3 C (= O) O-)) before the saponification treatment by GPC (gel permeation chromatography) is not particularly limited, but is 300 or more. It may be 4000 or less.
　水酸基を有するビニル樹脂は、下記式（１）で表される構造単位Ａ（部分構造Ａともいう。）を有するビニル樹脂（以下、「ビニル樹脂Ａ」ともいう。）であることが好ましい。この場合、ビニル樹脂Ａが水酸基を有することから、水酸基間の相互作用によってビニル樹脂の凝集力が向上するだけでなく、２八面体型スメクタイトとの親和性が高くなり、それゆえより一層高いガスバリア性を発揮することとなる。また、ビニル樹脂Ａは構造単位（Ａ）を有することにより、アルコールへの溶解性が向上するだけでなく、コーティング剤に耐水性を付与できることから、水蒸気バリア性、及び高湿度下での酸素バリア性の更なる向上が期待できる。
Figure JPOXMLDOC01-appb-C000001
 The vinyl resin having a hydroxyl group is preferably a vinyl resin having a structural unit A (also referred to as a partial structure A) represented by the following formula (1) (hereinafter, also referred to as “vinyl resin A”). In this case, since the vinyl resin A has a hydroxyl group, not only the cohesive force of the vinyl resin is improved by the interaction between the hydroxyl groups, but also the affinity with the hemihedral smectite is increased, and therefore the gas barrier is even higher. It will exert its sexuality. Further, since the vinyl resin A has the structural unit (A), not only the solubility in alcohol is improved, but also the coating agent can be imparted with water resistance, so that it has a water vapor barrier property and an oxygen barrier under high humidity. Further improvement in sex can be expected.
Figure JPOXMLDOC01-appb-C000001
　式（１）中、ｍは、０又は１を表し、＊は、結合手を表す。ｍは、好ましくは０である。 In formula (1), m represents 0 or 1, and * represents a bond. m is preferably 0.
　水酸基を有するビニル樹脂が構造単位Ａを含む場合、構造単位Ａの含有量は、水酸基を有するビニル樹脂中の水酸基全体のモル量に対し、好ましくは８５モル％以上、より好ましくは９０モル％以上、更に好ましくは９５モル％以上であり、好ましくは９９モル％以下である。構造単位Ａの含有量は、水酸基を有するビニル樹脂中の水酸基全体のモル量に対し、好ましくは８５モル％以上９９モル％以下、より好ましくは９０モル％以上９９モル％以下である。ｍが０である構造単位Ａの含有量が上記の範囲であることが好ましい。 When the vinyl resin having a hydroxyl group contains the structural unit A, the content of the structural unit A is preferably 85 mol% or more, more preferably 90 mol% or more, based on the total molar amount of the hydroxyl groups in the vinyl resin having a hydroxyl group. More preferably, it is 95 mol% or more, and preferably 99 mol% or less. The content of the structural unit A is preferably 85 mol% or more and 99 mol% or less, and more preferably 90 mol% or more and 99 mol% or less, based on the molar amount of the total hydroxyl group in the vinyl resin having a hydroxyl group. The content of the structural unit A in which m is 0 is preferably in the above range.
　水酸基を有するビニル樹脂は、構造単位Ａ以外の構造単位（他の構造単位）を含んでいてもよい。他の構造単位は、例えば、下記式（２）で表される構造単位Ｂ（部分構造Ｂともいう。）であってよい。水酸基を有するビニル樹脂は、構造単位Ａを含み、更に、構造単位Ｂを含むことが好ましい。一実施形態において、水酸基を有するビニル樹脂は、構造単位Ａ及び構造単位Ｂのみからなっていてもよい。水酸基を有するビニル樹脂が構造単位Ｂを含有することで、成形体としたときの成膜性、膜強度、及びコーティング剤の接着性がより一層向上する。
Figure JPOXMLDOC01-appb-C000002
 The vinyl resin having a hydroxyl group may contain a structural unit (other structural unit) other than the structural unit A. The other structural unit may be, for example, a structural unit B (also referred to as a partial structure B) represented by the following formula (2). The vinyl resin having a hydroxyl group preferably contains a structural unit A and further preferably a structural unit B. In one embodiment, the vinyl resin having a hydroxyl group may consist of only structural unit A and structural unit B. When the vinyl resin having a hydroxyl group contains the structural unit B, the film-forming property, the film strength, and the adhesiveness of the coating agent when formed into a molded product are further improved.
Figure JPOXMLDOC01-appb-C000002
　式（２）中、Ｒ１は、水素原子、炭素数１～２のアルキル基を表し、ｎは、０又は１を表し、＊は、結合手を表す。Ｒ１は、具体的には、水素原子、メチル基又はエチル基であり、ｎは、好ましくは０である。Ｒ２は、水素原子、又はアセチル基である。ここで、Ｒ１とＲ２が同時に水素原子とならない。 In the formula (2), R 1 represents a hydrogen atom and an alkyl group having 1 to 2 carbon atoms, n represents 0 or 1, and * represents a bond. Specifically, R 1 is a hydrogen atom, a methyl group or an ethyl group, and n is preferably 0. R 2 is a hydrogen atom or an acetyl group. Here, R 1 and R 2 do not become hydrogen atoms at the same time.
　構造単位Ｂの含有量は、耐水性に優れる観点から、水酸基を有するビニル樹脂中の水酸基全体のモル量に対し、１モル％以上である。構造単位Ｂの含有量は、成形体としたときの成膜性、膜強度、組成物の接着性等に優れる観点から、水酸基を有するビニル樹脂中の水酸基全体のモル量に対し、好ましくは３０モル％以下、より好ましくは１５モル％以下、更に好ましくは１０モル％以下である。構造単位Ｂの含有量は、水酸基を有するビニル樹脂中の水酸基全体のモル量に対し、好ましくは１モル％以上３０モル％以下、より好ましくは１モル％以上１５モル％以下であり、更に好ましくは１モル％以上１０モル％以下である。Ｒ１が水素原子で、Ｒ２がアセチル基であり、ｎが０である構造単位Ｂの含有量が上記の範囲になることが好ましい。 The content of the structural unit B is 1 mol% or more with respect to the total molar amount of the hydroxyl groups in the vinyl resin having a hydroxyl group from the viewpoint of excellent water resistance. The content of the structural unit B is preferably 30 with respect to the total molar amount of the hydroxyl groups in the vinyl resin having a hydroxyl groups, from the viewpoint of excellent film forming property, film strength, adhesiveness of the composition, etc. when formed into a molded product. It is mol% or less, more preferably 15 mol% or less, still more preferably 10 mol% or less. The content of the structural unit B is preferably 1 mol% or more and 30 mol% or less, more preferably 1 mol% or more and 15 mol% or less, and more preferably 1 mol% or more and 15 mol% or less, based on the total molar amount of the hydroxyl groups in the vinyl resin having a hydroxyl group. Is 1 mol% or more and 10 mol% or less. It is preferable that the content of the structural unit B in which R 1 is a hydrogen atom, R 2 is an acetyl group, and n is 0 is in the above range.
　水酸基を有するビニル樹脂が構造単位Ａ及びＢを含む場合、構造単位Ａと構造単位Ｂの含有量の合計に対する構造単位Ａの含有量のモル％（Ａ／（Ａ＋Ｂ）×１００）は、ガスバリア性がより一層向上する観点から、８５モル％以上、９９モル％以下であることが好ましい。 When the vinyl resin having a hydroxyl group contains structural units A and B, the molar% (A / (A + B) × 100) of the content of structural unit A with respect to the total content of structural unit A and structural unit B is gas barrier property. From the viewpoint of further improvement, it is preferably 85 mol% or more and 99 mol% or less.
　構造単位Ａ及び／又は構造単位Ｂを有するビニル樹脂の製造方法としては特に限定されず、公知慣用の方法で製造することができる。例えば、構造単位Ａ又はＢに対応する水酸基含有ビニルモノマーのエステル化物を重合した後、けん化処理をすることにより、水酸基を有するビニル樹脂を製造することができる。 The method for producing the vinyl resin having the structural unit A and / or the structural unit B is not particularly limited, and the vinyl resin can be produced by a known and commonly used method. For example, a vinyl resin having a hydroxyl group can be produced by polymerizing an esterified product of a hydroxyl group-containing vinyl monomer corresponding to the structural unit A or B and then performing a saponification treatment.
　構造単位Ａに対応する水酸基含有ビニルモノマーとしては、ビニルアルコール、アリルアルコール、クロチルアルコール等が挙げられる。構造単位Ｂに対応する水酸基含有ビニルモノマーのエステル化物におけるエステルとは、上記例示したとおりのエステルであってよい。構造単位Ｂに対応する水酸基含有ビニルモノマーのエステル化物の中でも好ましくは、酢酸エステルである酢酸ビニル、酢酸アリル、又は酢酸クロチルである。これらは１種類を使用してもよいし、２種以上を併用してもかまわない。 Examples of the hydroxyl group-containing vinyl monomer corresponding to the structural unit A include vinyl alcohol, allyl alcohol, and crotyl alcohol. The ester in the esterified product of the hydroxyl group-containing vinyl monomer corresponding to the structural unit B may be an ester as exemplified above. Among the esterified products of the hydroxyl group-containing vinyl monomer corresponding to the structural unit B, vinyl acetate, allyl acetate, or crotyl acetate, which are acetic acid esters, are preferable. One type of these may be used, or two or more types may be used in combination.
　構造単位Ｂに対応する水酸基含有ビニルモノマーとしては、イソプロペニルアルコール、メタリルアルコール、イソブテニルアルコール等が挙げられる。構造単位Ａに対応する水酸基含有ビニルモノマーのエステル化物におけるエステルとは、酢酸エステル、プロパン酸エステル、ブタン酸エステル、２－メチルプロパン酸エステル、ペンタン酸エステル、３－メチルブタン酸エステル、２，２－ジメチルプロパン酸エステル、ヘキサン酸エステル、シクロヘキシルカルボン酸エステル、安息香酸エステル等が挙げられる。構造単位Ａに対応する水酸基含有ビニルモノマーのエステル化物の中でも好ましくは、酢酸エステルである酢酸イソプロペニル、酢酸メタリル、又は酢酸イソブテニルである。これらは１種類単独で使用してもよいし、２種以上を併用してもかまわない。 Examples of the hydroxyl group-containing vinyl monomer corresponding to the structural unit B include isopropenyl alcohol, metallic alcohol, isobutenyl alcohol and the like. The esters in the esterified product of the hydroxyl group-containing vinyl monomer corresponding to the structural unit A are acetic acid ester, propanoic acid ester, butanoic acid ester, 2-methylpropanoic acid ester, pentanoic acid ester, 3-methylbutanoic acid ester, 2,2-. Examples thereof include dimethylpropanoic acid ester, hexanoic acid ester, cyclohexylcarboxylic acid ester and benzoic acid ester. Among the esterified products of the hydroxyl group-containing vinyl monomer corresponding to the structural unit A, isopropenyl acetate, metharyl acetate, or isobutenyl acetate, which are acetic acid esters, are preferable. These may be used alone or in combination of two or more.
　水酸基を有するビニル樹脂は、単一のモノマーを重合させて得られるホモポリマーであってもよく、複数種のモノマーを共重合させて得られるコポリマーであっても構わない。このとき、ビニルモノマーとして、ビニル基、（メタ）アリル基、（メタ）アクリロイル基のそれぞれを有するモノマーを組み合わせて用いても構わない。 The vinyl resin having a hydroxyl group may be a homopolymer obtained by polymerizing a single monomer, or may be a copolymer obtained by copolymerizing a plurality of types of monomers. At this time, as the vinyl monomer, a monomer having each of a vinyl group, a (meth) allyl group, and a (meth) acryloyl group may be used in combination.
　水酸基を有するビニル樹脂は、ビニルモノマーをラジカル重合、アニオン重合、カチオン重合等により重合することによって得られる。重合の際には重合開始剤を用いてもよい。重合開始剤としては、熱ラジカル重合開始剤、光ラジカル重合開始剤、アニオン重合開始剤及びカチオン重合開始剤が挙げられる。 A vinyl resin having a hydroxyl group can be obtained by polymerizing a vinyl monomer by radical polymerization, anionic polymerization, cationic polymerization or the like. A polymerization initiator may be used at the time of polymerization. Examples of the polymerization initiator include thermal radical polymerization initiators, photoradical polymerization initiators, anionic polymerization initiators and cationic polymerization initiators.
　熱ラジカル重合開始剤としては、ｔ－ブチルパーオキシベンゾエート、ジ－ｔ－ブチルパーオキシド、クメンパーヒドロキシド、アセチルパーオキシド、ベンゾイルパーオキシド、ラウロイルパーオキシド等の過酸化物；アゾビスイソブチルニトリル、アゾビス－２，４－ジメチルバレロニトリル、アゾビスシクロヘキサンカルボニトリル等のアゾ化合物などが挙げられる。 Examples of the thermal radical polymerization initiator include peroxides such as t-butyl peroxybenzoate, di-t-butyl peroxide, cumemper hydroxide, acetyl peroxide, benzoyl peroxide, and lauroyl peroxide; azobisisobutylnitrile, Examples thereof include azo compounds such as azobis-2,4-dimethylvaleronitrile and azobiscyclohexanecarbonitrile.
　光ラジカル重合開始剤としては、例えば１－ヒドロキシ－シクロヘキシル－フェニル－ケトン、２－ヒドロキシ－２－メチル－１－フェニル－プロパン－１－オン、２，２－ジメトキシ－１，２－ジフェニルエタン－１－オン、２－メチル－１－（４－メチルチオフェニル）－２－モルフォリノプロパン－１－オン、２，４，６－トリメチルベンゾイル－ジフェニル－フォスフィンオキサイドなどが挙げられる。 Examples of the photoradical polymerization initiator include 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, and 2,2-dimethoxy-1,2-diphenylethane-. Examples thereof include 1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and the like.
　アニオン重合開始剤としては、メチルリチウム、ｎ－ブチルリチウム、ｓｅｃ－ブチルリチウム、ｔ－ブチルリチウム等の有機アルカリ金属；メチルマグネシウムクロリド、メチルマグネシウムブロミド等の有機アルカリ土類金属；リチウム、ナトリウム、カリウム等のアルカリ金属などが挙げられる。 Examples of the anion polymerization initiator include organic alkali metals such as methyllithium, n-butyllithium, sec-butyllithium and t-butyllithium; organic alkaline earth metals such as methylmagnesium chloride and methylmagnesium bromide; lithium, sodium and potassium. Alkaline metals such as, etc. can be mentioned.
　カチオン重合開始剤としては、塩酸、硫酸、過塩素酸、トリフルオロ酢酸、メタンスルホン酸、トリフルオロメタンスルホン酸、クロロスルホン酸、フルオロスルホン酸等のプロトン酸；三フッ化ホウ素、塩化アルミニウム、四塩化チタン、塩化第二スズ、塩化第二鉄等のルイス酸などが挙げられる。 Cationic polymerization initiators include protonic acids such as hydrochloric acid, sulfuric acid, perchloric acid, trifluoroacetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, chlorosulfonic acid, fluorosulfonic acid; boron trifluoride, aluminum chloride, tetrachloride. Examples thereof include Lewis acids such as titanium, ferric chloride and ferric chloride.
　実施形態では、１種のビニル樹脂を単独で用いてよく、複数のビニル樹脂を組み合わせて用いてもよい。ビニル樹脂は、直鎖型ポリマーであってよく、分岐型ポリマーであってもよい。ビニル樹脂が分岐型ポリマーである場合、くし型であってよく、星型であってもよい。 In the embodiment, one kind of vinyl resin may be used alone, or a plurality of vinyl resins may be used in combination. The vinyl resin may be a linear polymer or a branched polymer. When the vinyl resin is a branched polymer, it may be comb-shaped or star-shaped.
　水酸基を有するビニル樹脂の含有量は、コーティング剤中の不揮発分全量に対し、水蒸気バリア性及び酸素バリア性がより一層優れたものとなる観点から、３０質量％以上、又は４０質量％以上であってよく、コーティング剤の成形性がより一層優れたものとなる観点から、９５質量％以下、８０質量％以下、７０質量％以下、又は６０質量％以下であってよい。 The content of the vinyl resin having a hydroxyl group is 30% by mass or more, or 40% by mass or more, from the viewpoint of further improving the water vapor barrier property and the oxygen barrier property with respect to the total amount of the non-volatile content in the coating agent. It may be 95% by mass or less, 80% by mass or less, 70% by mass or less, or 60% by mass or less from the viewpoint of further improving the moldability of the coating agent.
＜溶剤＞
　コーティング剤は、溶剤を更に含有する。溶剤は、塗膜の乾燥性に優れる観点から、アルコールを含有する。溶剤は、アルコールのみを含有するものであってよい。アルコールとしては、例えば、メタノール、エタノール、１－プロパノール、２－プロパノール、メトキシプロパノール（１－メトキシー２－プロパノール等）が挙げられる。アルコールは、１種を単独で含んでいてもよく、２種以上を組み合わせて含んでいてもよい。 <Solvent>
The coating agent further contains a solvent. The solvent contains alcohol from the viewpoint of excellent drying property of the coating film. The solvent may contain only alcohol. Examples of the alcohol include methanol, ethanol, 1-propanol, 2-propanol, and methoxypropanol (1-methoxy-2-propanol, etc.). Alcohol may contain one kind alone or a combination of two or more kinds.
　溶剤は、アルコールに加えて、例えば、水、メチルエチルケトン、アセトン、酢酸エチル、酢酸ブチル、トルエン、ジメチルホルムアミド、アセトニトリル、メチルイソブチルケトン、シクロヘキサノン、メチルセロソルブ、エチルジグリコールアセテート、プロピレングリコールモノメチルエーテルアセテート等を更に含有してもよい。 As the solvent, in addition to alcohol, for example, water, methyl ethyl ketone, acetone, ethyl acetate, butyl acetate, toluene, dimethylformamide, acetonitrile, methyl isobutyl ketone, cyclohexanone, methyl cellosolve, ethyl diglycol acetate, propylene glycol monomethyl ether acetate and the like can be used. It may be further contained.
　アルコールの含有量は、溶剤全量に対して、製膜性に優れ、かつブロッキング性に優れる膜を形成可能という効果の観点から、２０質量％以上であり、当該効果が更に好適に奏される観点から、好ましくは、２５質量％以上、３０質量％以上、３５質量％以上、４０質量％以上、又は４５質量％以上である。アルコールの含有量は、溶剤全量に対して、酸素バリア性及び水蒸気バリア性に優れる膜を形成可能という効果の観点から、８０質量％以下であり、当該効果が更に好適に奏される観点から、好ましくは、７５質量％以下、７０質量％以下、６５質量％以下、６０質量％以下、５５質量％以下、又は５０質量％以下である。アルコールの含有量は、溶剤全量に対して、２０～８０質量％、２５～７０質量％、３０～６０質量％、又は４０～５０質量％以下であってもよい。 The alcohol content is 20% by mass or more from the viewpoint of the effect of being able to form a film having excellent film-forming property and excellent blocking property with respect to the total amount of the solvent, and the viewpoint that the effect is more preferably exhibited. Therefore, it is preferably 25% by mass or more, 30% by mass or more, 35% by mass or more, 40% by mass or more, or 45% by mass or more. The content of alcohol is 80% by mass or less from the viewpoint of the effect of being able to form a film having excellent oxygen barrier property and water vapor barrier property with respect to the total amount of the solvent, and from the viewpoint that the effect is more preferably exhibited. Preferably, it is 75% by mass or less, 70% by mass or less, 65% by mass or less, 60% by mass or less, 55% by mass or less, or 50% by mass or less. The content of alcohol may be 20 to 80% by mass, 25 to 70% by mass, 30 to 60% by mass, or 40 to 50% by mass or less with respect to the total amount of the solvent.
　アルコールは、乾燥性（ブロッキング性）により一層優れる観点から、エタノールを含有していてよい。アルコールは、エタノールのみを含有していてよく、エタノール及びエタノール以外のアルコールを含有していてよい。エタノール以外のアルコールは、例えば、メタノール、１－プロパノール、２－プロパノール、及びメトキシプロパノールからなる群より選択される少なくとも１種であってよい。アルコール中のエタノールの含有量は、アルコール全量に対して、５０質量％以上、８０質量％以上、又は９５質量％以上であってよく、１００質量％であってもよい。 Alcohol may contain ethanol from the viewpoint of being more excellent in drying property (blocking property). The alcohol may contain only ethanol, and may contain ethanol and alcohols other than ethanol. The alcohol other than ethanol may be, for example, at least one selected from the group consisting of methanol, 1-propanol, 2-propanol, and methoxypropanol. The content of ethanol in the alcohol may be 50% by mass or more, 80% by mass or more, 95% by mass or more, or 100% by mass, based on the total amount of alcohol.
　コーティング剤中の不揮発分の含有量は、コーティング剤全量を基準として、１～１０質量％であってよく、好ましくは２～８質量％であり、より好ましくは４～７質量％である。 The content of the non-volatile component in the coating agent may be 1 to 10% by mass, preferably 2 to 8% by mass, and more preferably 4 to 7% by mass, based on the total amount of the coating agent.
＜ポリカルボン酸＞
　コーティング剤は、ポリカルボン酸を更に含有してもよい。本明細書において、ポリカルボン酸とは、カルボキシル基を２個以上有する化合物を意味する。ポリカルボン酸としては、カルボキシル基を２個以上有する樹脂（但し、水酸基及びカルボキシル基を有するビニル樹脂を除く。）を用いることができる。ポリカルボン酸としては、例えば、ポリアクリル酸、ポリマレイン酸、ポリアスパラギン酸、又はポリアクリル酸とポリマレイン酸との共重合体が挙げられる。 <Polycarboxylic acid>
The coating agent may further contain a polycarboxylic acid. As used herein, the term polycarboxylic acid means a compound having two or more carboxyl groups. As the polycarboxylic acid, a resin having two or more carboxyl groups (excluding vinyl resins having a hydroxyl group and a carboxyl group) can be used. Examples of the polycarboxylic acid include polyacrylic acid, polymaleic acid, polyaspartic acid, and a copolymer of polyacrylic acid and polymaleic acid.
　ポリカルボン酸の含有量は、水酸基を有するビニル樹脂及びポリカルボン酸の合計含有量に対して、５質量％以上、１０質量％以上、又は１５質量％以上であってよく、３０質量％以下、２５質量％以下、又は２０質量％以下であってよい。コーティング剤が水酸基を有するビニル樹脂及びポリカルボン酸以外の樹脂（他の樹脂）を含有する場合、ポリカルボン酸の含有量は、水酸基を有するビニル樹脂、ポリカルボン酸及び他の樹脂の合計含有量に対して、上記範囲内であってよい。 The content of the polycarboxylic acid may be 5% by mass or more, 10% by mass or more, or 15% by mass or more, and 30% by mass or less, based on the total content of the vinyl resin having a hydroxyl group and the polycarboxylic acid. It may be 25% by mass or less, or 20% by mass or less. When the coating agent contains a vinyl resin having a hydroxyl group and a resin other than the polycarboxylic acid (other resin), the content of the polycarboxylic acid is the total content of the vinyl resin having a hydroxyl group, the polycarboxylic acid and the other resin. On the other hand, it may be within the above range.
＜他の成分＞
　コーティング剤は、修飾剤を更に含有してもよい。修飾剤としては、カップリング剤、シラン化合物、酸無水物等が挙げられる。コーティング剤がこれらの修飾剤を含有する場合、２八面体型スメクタイトの濡れ性が向上し、コーティング剤への分散性がより一層向上する。修飾剤は、１種を単独で用いてよく、複数種を組み合わせて用いてもよい。 <Other ingredients>
The coating agent may further contain a modifier. Examples of the modifier include a coupling agent, a silane compound, an acid anhydride and the like. When the coating agent contains these modifiers, the wettability of the 28-octahedral smectite is improved, and the dispersibility in the coating agent is further improved. One type of modifier may be used alone, or a plurality of types may be used in combination.
　カップリング剤としては、例えばシランカップリング剤、チタンカップリング剤、ジルコニウムカップリング剤、アルミカップリング剤等が挙げられる。 Examples of the coupling agent include a silane coupling agent, a titanium coupling agent, a zirconium coupling agent, an aluminum coupling agent, and the like.
　シランカップリング剤としては、例えばエポキシ基含有シランカップリング剤、アミノ基含有シランカップリング剤、（メタ）アクリル基含有シランカップリング剤、イソシアネート基含有シランカップリング剤等が挙げられる。エポキシ基含有シランカップリング剤としては、例えば３－グリシドキシプロピルトリメトキシシラン、３－グリシドキシプロピルトリエトキシシラン、３－グリシドキシプロピルメチルジエトキシシラン、２－（３，４エポキシシクロヘキシル）エチルトリメトキシシラン等が挙げられる。アミノ基含有シランカップリング剤としては、例えば３－アミノプロピルトリメトキシシラン、Ｎ－２－（アミノエチル）－３－アミノプロピルメチルジメトキシシラン、３－トリエトキシシリル－Ｎ－（１，３－ジメチルブチリデン）プロピルアミン、Ｎ－フェニル－γ－アミノプロピルトリメトキシシラン等が挙げられる。（メタ）アクリル基含有シランカップリング剤としては、例えば３－アクリロキシプロピルトリメトキシシラン、３－メタクリロキシプロピルトリメトキシシラン、３－メタクリロキシプロピルトリエトキシシラン等が挙げられる。イソシアネート基含有シランカップリング剤としては、例えば３－イソシアネートプロピルトリエトキシシラン等が挙げられる。 Examples of the silane coupling agent include an epoxy group-containing silane coupling agent, an amino group-containing silane coupling agent, a (meth) acrylic group-containing silane coupling agent, and an isocyanate group-containing silane coupling agent. Examples of the epoxy group-containing silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 2- (3,4 epoxycyclohexyl). ) Ethyltrimethoxysilane and the like. Examples of the amino group-containing silane coupling agent include 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, and 3-triethoxysilyl-N- (1,3-dimethyl). Butylidene) propylamine, N-phenyl-γ-aminopropyltrimethoxysilane and the like can be mentioned. Examples of the (meth) acrylic group-containing silane coupling agent include 3-acryloyloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-methacryloxypropyltriethoxysilane. Examples of the isocyanate group-containing silane coupling agent include 3-isocyanatepropyltriethoxysilane and the like.
　チタンカップリング剤としては、例えば、イソプロピルトリイソステアロイルチタネート、イソプロピルトリオクタノイルチタネート、イソプロピルジメタクリルイソステアロイルチタネート、イソプロピルイソステアロイルジアクリルチタネート、イソプロピルトリス（ジオクチルパイロホスフェート）チタネート、テトラオクチルビス（ジトリデシルホスファイト）チタネート、テトラ（２，２－ジアリルオキシメチル－１－ブチル）ビス（ジトリデシル）ホスファイトチタネート、ビス（ジオクチルパイロホスフェート）オキシアセテートチタネート、ビス（ジオクチルパイロホスフェート）エチレンチタネート等が挙げられる。 Examples of the titanium coupling agent include isopropyltriisostearoyl titanate, isopropyltrioctanoyl titanate, isopropyldimethacrylisostearoyl titanate, isopropylisostearoyl diacrylic titanate, isopropyltris (dioctylpyrophosphate) titanate, and tetraoctylbis (ditridecyl). Examples thereof include phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, and bis (dioctylpyrophosphate) ethylene titanate.
　ジルコニウムカップリング剤としては、例えば、酢酸ジルコニウム、炭酸ジルコニウムアンモニウム、フッ化ジルコニウム等が挙げられる。 Examples of the zirconium coupling agent include zirconium acetate, ammonium zirconium carbonate, zirconium fluoride and the like.
　アルミカップリング剤としては、アセトアルコキシアルミニウムジイソプロピレート、アルミニウムジイソプロポキシモノエチルアセトアセテート、アルミニウムトリスエチルアセトアセテート、アルミニウムトリスアセチルアセトネート等が挙げられる。 Examples of the aluminum coupling agent include acetalkoxyaluminum diisopropyrate, aluminum diisopropoxymonoethylacetate, aluminumtrisethylacetate, aluminumtrisacetylacetonate and the like.
　シラン化合物としては、アルコキシシラン、シラザン、シロキサン等が挙げられる。アルコキシシランとしては、メチルトリメトキシシラン、ジメチルジメトキシシラン、フェニルトリメトキシシラン、メチルトリエトキシシラン、ジメチルジエトキシシラン、フェニルトリエトキシシラン、ｎ－プロピルトリメトキシシラン、ｎ－プロピルトリエトキシシラン、ヘキシルトリメトキシシラン、ヘキシルトリエトキシシラン、オクチルトリエトキシシラン、デシルトリメトキシシラン、１，６－ビス（トリメトキシシリル）ヘキサン、トリフルオロプロピルトリメトキシシラン等が挙げられる。シラザンとしてはヘキサメチルジシラザン等が挙げられる。シロキサンとしては加水分解性基含有シロキサン等が挙げられる。 Examples of the silane compound include alkoxysilane, silazane, and siloxane. Examples of alkoxysilanes include methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, and hexyltri. Examples thereof include methoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, 1,6-bis (trimethoxysilyl) hexane, and trifluoropropyltrimethoxysilane. Examples of the silazane include hexamethyldisilazane and the like. Examples of the siloxane include hydrolyzable group-containing siloxane.
　酸無水物としては、無水コハク酸、無水マレイン酸、無水フタル酸、無水トリメリット酸、無水ピロメリット酸、テトラヒドロ無水フタル酸、メチルテトラヒドロ無水フタル酸、無水メチルナジック酸、ヘキサヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸アルケニル無水コハク酸等が挙げられる。 Examples of acid anhydrides include succinic anhydride, maleic anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, and methyl. Hexahydrophthalic anhydride alkenyl succinic anhydride and the like can be mentioned.
　修飾剤の含有量は、２八面体型スメクタイト全量に対し、０．１～３０質量％であることが好ましい。修飾剤の含有量が０．１質量％以上であれば、２八面体型スメクタイトのコーティング剤への分散性がより良好なものとなる。修飾剤の含有量が３０質量％以下であれば、コーティング剤に対する修飾剤の機械物性への影響をより抑えることができる。修飾剤の含有量は、好ましくは０．３～２０質量％であり、より好ましくは０．５～１５質量％である。 The content of the modifier is preferably 0.1 to 30% by mass with respect to the total amount of the 28-octahedral smectite. When the content of the modifier is 0.1% by mass or more, the dispersibility of the 28-octahedral smectite in the coating agent becomes better. When the content of the modifier is 30% by mass or less, the influence of the modifier on the mechanical properties of the coating agent can be further suppressed. The content of the modifier is preferably 0.3 to 20% by mass, more preferably 0.5 to 15% by mass.
　コーティング剤は、各種の添加剤（水酸基を有するビニル樹脂、２八面体型スメクタイト、修飾剤及び溶剤に該当する化合物は除く。）を含有してもよい。添加剤としては、例えば、有機フィラー、無機フィラー、安定剤（酸化防止剤、熱安定剤、紫外線吸収剤等）、可塑剤、帯電防止剤、滑剤、ブロッキング防止剤、着色剤、結晶核剤、酸素捕捉剤（酸素捕捉機能を有する化合物）、粘着付与剤等が例示できる。これらの各種添加剤は、単独で又は二種以上組み合わせて使用される。 The coating agent may contain various additives (excluding compounds corresponding to vinyl resins having hydroxyl groups, octahedral smectites, modifiers and solvents). Additives include, for example, organic fillers, inorganic fillers, stabilizers (antioxidants, heat stabilizers, UV absorbers, etc.), plasticizers, antistatic agents, lubricants, antiblocking agents, colorants, crystal nucleating agents, etc. Examples thereof include an oxygen scavenger (a compound having an oxygen scavenging function) and an antistatic agent. These various additives are used alone or in combination of two or more.
　添加剤のうち、無機フィラーとしては、金属、金属酸化物、樹脂、鉱物等の無機物及びこれらの複合物が挙げられる。無機フィラーの具体例としては、アルミナ、チタン、ジルコニア、銅、鉄、銀、マイカ、タルク、アルミニウムフレーク、ガラスフレーク、粘土鉱物等が挙げられる。これらの中でも、ガスバリア性を向上させる目的で、粘土鉱物を併用してもよい。 Among the additives, examples of the inorganic filler include inorganic substances such as metals, metal oxides, resins, and minerals, and composites thereof. Specific examples of the inorganic filler include alumina, titanium, zirconia, copper, iron, silver, mica, talc, aluminum flakes, glass flakes, clay minerals and the like. Among these, clay minerals may be used in combination for the purpose of improving the gas barrier property.
　酸素捕捉機能を有する化合物としては、例えば、ヒンダードフェノール系化合物、ビタミンＣ、ビタミンＥ、有機燐化合物、没食子酸、ピロガロール等の酸素と反応する低分子有機化合物や、コバルト、マンガン、ニッケル、鉄、銅等の遷移金属化合物等が挙げられる。 Examples of the compound having an oxygen trapping function include low molecular weight organic compounds that react with oxygen such as hindered phenol compounds, vitamin C, vitamin E, organic phosphorus compounds, gallic acid, and pyrogallol, and cobalt, manganese, nickel, and iron. , Transition metal compounds such as copper and the like.
　粘着付与剤としては、キシレン樹脂、テルペン樹脂、フェノール樹脂、ロジン樹脂等が挙げられる。粘着付与剤を添加することで塗布直後の各種フィルム材料に対する粘着性を向上させることができる。粘着性付与剤の添加量はコーティング剤全量１００質量部に対して０．０１～５質量部であることが好ましい。 Examples of the tackifier include xylene resin, terpene resin, phenol resin, rosin resin and the like. By adding a tackifier, the adhesiveness to various film materials immediately after application can be improved. The amount of the tackifier added is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the total amount of the coating agent.
＜積層体＞
　実施形態の積層体は、基材と、上述したコーティング剤を基材上にコートしてなるコート層と、を有する。積層体は、例えば、包装材料、工業材料等に好適に用いられる。実施形態の積層体は、様々な分野における包装材料として好適に利用することができる。 <Laminated body>
The laminate of the embodiment has a base material and a coat layer formed by coating the above-mentioned coating agent on the base material. The laminate is preferably used, for example, as a packaging material, an industrial material, or the like. The laminate of the embodiment can be suitably used as a packaging material in various fields.
　コーティング剤を基材上にコートする方法は特に限定されない。具体的な方法としては、ロールコート、グラビアコート等の各種コーティング方法を例示することができる。また、コーティング装置についても特に限定されない。例えば、基材上に、コーティング剤を塗工し、必要に応じて、乾燥処理を行うことによって、基材と、基材上に形成されたコート層とを備える積層体を得ることができる。乾燥条件は、例えば、コーティング剤が溶剤を含む場合には、溶剤の種類、使用量等に応じて適宜設定してよい。乾燥は、例えば、５０℃～１００℃の条件で、０．５分間～１０分間保持することによって実施してよい。 The method of coating the coating agent on the substrate is not particularly limited. As a specific method, various coating methods such as roll coating and gravure coating can be exemplified. Further, the coating device is not particularly limited. For example, by applying a coating agent on the base material and, if necessary, performing a drying treatment, a laminate having the base material and the coat layer formed on the base material can be obtained. For example, when the coating agent contains a solvent, the drying conditions may be appropriately set according to the type of solvent, the amount used, and the like. Drying may be carried out, for example, by holding at 50 ° C. to 100 ° C. for 0.5 minutes to 10 minutes.
　基材は、例えば、板状、シート状、又はフィルム状であってよい。基材の材質としては、例えば、ポリエチレン（ＰＥ）、ポリプロピレン（ＰＰ）、ポリスチレン（ＰＳ）、ポリエチレンテレフタラート（ＰＥＴ）を挙げることができる。 The base material may be, for example, a plate, a sheet, or a film. Examples of the material of the base material include polyethylene (PE), polypropylene (PP), polystyrene (PS), and polyethylene terephthalate (PET).
　基材は、コーティング剤を塗工する面上を表面処理されていてもよく、表面処理されていなくてもよい。表面処理としては、例えば、コロナ処理が挙げられる。基材の厚みは、例えば、１μｍ以上、５μｍ以上、又は１０μｍ以上であってよく、５０μｍ以下、２０μｍ以下、又は１５μｍ以下であってよい。 The base material may or may not be surface-treated on the surface to which the coating agent is applied. Examples of the surface treatment include corona treatment. The thickness of the base material may be, for example, 1 μm or more, 5 μm or more, or 10 μm or more, and may be 50 μm or less, 20 μm or less, or 15 μm or less.
　コート層の厚みは、例えば、０．１～５μｍであってよい。コート層の厚みは、例えば、０．５μｍ以上、又は１μｍ以上であってよく、１０μｍ以下、５μｍ以下、又は２μｍ以下であってよい。 The thickness of the coat layer may be, for example, 0.1 to 5 μm. The thickness of the coat layer may be, for example, 0.5 μm or more, or 1 μm or more, and may be 10 μm or less, 5 μm or less, or 2 μm or less.
　以下、実施例により、本発明を更に具体的に説明するが、本発明はこれに限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.
＜コーティング剤の調製＞
　ビニル樹脂として、以下のビニル樹脂１～２を準備した。
・ビニル樹脂１（ポリビニルアルコール、水酸基価：１２５０、日本酢ビ・ポバール株式会社製、ＪＦ－０３）
・ビニル樹脂２（ポリビニルアルコール、水酸基価：１０００、日本酢ビ・ポバール株式会社製、ＪＰ－０５） <Preparation of coating agent>
The following vinyl resins 1 and 2 were prepared as the vinyl resins.
-Vinyl resin 1 (polyvinyl alcohol, hydroxyl value: 1250, manufactured by Japan Vam & Poval Co., Ltd., JF-03)
-Vinyl resin 2 (polyvinyl alcohol, hydroxyl value: 1000, manufactured by Japan Vam & Poval Co., Ltd., JP-05)
　イオン交換水と、エタノール又は１－プロパノールと、水酸基価１２５０の上記ポリビニルアルコール（ビニル樹脂１）、又は水酸基価１０００の上記ポリビニルアルコール（ビニル樹脂２）と、ポリアクリル酸（東亞合成株式会社製、ジュリマーＡＣ－１０Ｌ）とを表１に示す組成（単位：質量部）で含む樹脂溶液１～５を準備した。 Ion-exchanged water, ethanol or 1-propanol, the above-mentioned polyvinyl alcohol (vinyl resin 1) having a hydroxyl value of 1250, or the above-mentioned polyvinyl alcohol (vinyl resin 2) having a hydroxyl value of 1000, and polyacrylic acid (manufactured by Toa Synthetic Co., Ltd.) Resin solutions 1 to 5 containing Julimer AC-10L) in the composition (unit: parts by mass) shown in Table 1 were prepared.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　イオン交換水と、エタノールと、１－プロパノールと、２八面体型スメクタイトとして、アンモニウム型モンモリロナイト（ＮＨ４－ＭＭＴ）、リチウム型モンモリロナイト（Ｌｉ－ＭＭＴ）、又はナトリウム型モンモリロナイト（Ｎａ－ＭＭＴ）とを表２に示す組成（単位：質量部）で含む、粘土分散液１～８を準備した。アンモニウム型モンモリロナイトとしては、ナトリウム型モンモリロナイト（クニミネ工業株式会社製「クニピアＦ」）のナトリウムイオンをアンモニウムイオンに交換することにより得られたアンモニウム型モンモリロナイトを用いた。リチウム型モンモリロナイトとしては、クニミネ工業株式会社製「クニピアＭ」を用いた。ナトリウム型モンモリロナイトとしては、クニミネ工業株式会社製「クニピアＦ」を用いた。 Ion-exchanged water, ethanol, 1-propanol, and ammonium montmorillonite (NH 4 -MMT), lithium montmorillonite (Li-MMT), or sodium montmorillonite (Na-MMT) as diocthedral smectites. Clay dispersions 1 to 8 containing the compositions (unit: parts by mass) shown in Table 2 were prepared. As the ammonium-type montmorillonite, ammonium-type montmorillonite obtained by exchanging sodium ions of sodium-type montmorillonite (“Kunipia F” manufactured by Kunimine Industries, Ltd.) with ammonium ions was used. As the lithium-type montmorillonite, "Kunipia M" manufactured by Kunimine Industries, Ltd. was used. As the sodium-type montmorillonite, "Kunipia F" manufactured by Kunimine Industries, Ltd. was used.
　２八面体型スメクタイトのアンモニウムイオン当量、リチウムイオン当量、及び水素イオン当量の合計は、アンモニウム型モンモリロナイトでは１１０ｍｅｑ／１００ｇ、リチウム型モンモリロナイトでは１１０ｍｅｑ／１００ｇ、ナトリウム型モンモリロナイトでは１１０ｍｅｑ／１００ｇであった。アンモニウム型モンモリロナイト及びリチウム型モンモリロナイトのナトリウムイオン当量は、１０ｍｅｑ／１００ｇ未満であった。 The total of ammonium ion equivalent, lithium ion equivalent, and hydrogen ion equivalent of 2-octhedral smectite was 110 meq / 100 g for ammonium montmorillonite, 110 meq / 100 g for lithium montmorillonite, and 110 meq / 100 g for sodium montmorillonite. The sodium ion equivalents of ammonium-type montmorillonite and lithium-type montmorillonite were less than 10 meq / 100 g.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　表３に示す種類の樹脂溶液（１０質量部）及び粘土分散液（２０質量部）を組み合わせて、実施例及び比較例のコーティング剤を準備した。表３には、水酸基を有するビニル樹脂及びポリカルボン酸の合計含有量に対するポリカルボン酸の含有量、不揮発分（溶剤以外の成分）全量に対する２八面体型スメクタイトの含有量、溶剤全量に対するアルコールの含有量、アルコール全量に対するエタノールの含有量、及びコーティング剤中の不揮発分（溶剤以外の成分）の含有量も示す。 The coating agents of Examples and Comparative Examples were prepared by combining the resin solutions (10 parts by mass) and the clay dispersion (20 parts by mass) shown in Table 3. Table 3 shows the content of polycarboxylic acid with respect to the total content of vinyl resin having a hydroxyl group and polycarboxylic acid, the content of diocthedral smectite with respect to the total amount of non-volatile content (components other than solvent), and the content of alcohol with respect to the total amount of solvent. The content, the content of ethanol with respect to the total amount of alcohol, and the content of non-volatile components (components other than solvent) in the coating agent are also shown.
＜製膜性、ブロッキング性、酸素透過性及び水蒸気透過性の評価＞
　上述した方法により得られたコーティング剤を用いて、コロナ処理された１２μｍの基材（ＰＥＴ（ポリエチレンテレフタレート）フィルム、商品名：Ｅ－５１００、東洋紡株式会社製）のコロナ処理面に、バーコーターを用いて、各コーティング剤を乾燥後の塗工量が０．５ｇ／ｍ２になるように塗工して、積層体Ｘを得た。このときの塗工面を光学顕微鏡で観察し、塗工面が平滑である場合を「Ａ」、平滑でない場合を「Ｂ」として、製膜性を評価した。また、比較例２については、製膜できなかった。このような場合を「Ｃ」として評価した。 <Evaluation of film-forming property, blocking property, oxygen permeability and water vapor permeability>
Using the coating agent obtained by the above method, a bar coater was applied to the corona-treated surface of a 12 μm base material (PET (polyethylene terephthalate) film, trade name: E-5100, manufactured by Toyobo Co., Ltd.) that had been corona-treated. Each coating agent was applied so that the coating amount after drying was 0.5 g / m 2 , and a laminate X was obtained. The coated surface at this time was observed with an optical microscope, and the film-forming property was evaluated with the case where the coated surface was smooth as "A" and the case where the coated surface was not smooth as "B". Further, in Comparative Example 2, the film could not be formed. Such a case was evaluated as "C".
　次に、積層体Ｘを塗工後直ぐに６０℃の乾燥機中で５秒間加熱処理した後すぐに三つ折りにして、２４時間５ｋｇｆの加重をかけ、積層体Ｙを得た。三つ折りにされた積層体Ｙを開き、そのときに、塗工面と基材面との間で抵抗や音がない場合は「Ａ」、抵抗はないが音がする場合は「Ｂ」、フィルムが張り付いてしまっている場合は「Ｃ」として、ブロッキング性を評価した。 Next, immediately after coating the laminate X, it was heat-treated in a dryer at 60 ° C. for 5 seconds, then immediately folded in three and subjected to a load of 5 kgf for 24 hours to obtain a laminate Y. Open the tri-folded laminate Y, and at that time, if there is no resistance or sound between the coated surface and the base material surface, "A", if there is no resistance but there is sound, "B", the film When was stuck, the blocking property was evaluated as "C".
　続いて、積層体Ｘを塗工後直ぐに８０℃の乾燥機中で１分加熱処理した。これにより、積層体Ｚを得た。得られた積層体Ｚについて、以下のとおり酸素透過率及び水蒸気透過率を測定した。 Subsequently, the laminate X was immediately heat-treated in a dryer at 80 ° C. for 1 minute after coating. As a result, the laminated body Z was obtained. The oxygen permeability and water vapor permeability of the obtained laminate Z were measured as follows.
（酸素透過率の測定）
　酸素透過率の測定は、ＪＩＳ－Ｋ７１２６（等圧法）に準じ、モコン社製の酸素透過率測定装置「ＯＸ－ＴＲＡＮ１／５０」を用いて、温度２３℃、７５％ＲＨの雰囲気下で実施した。なお、ＲＨとは相対湿度を表す。 (Measurement of oxygen permeability)
The oxygen transmission rate was measured according to JIS-K7126 (isopressure method) using an oxygen transmission rate measuring device "OX-TRAN1 / 50" manufactured by Mocon Co., Ltd. at a temperature of 23 ° C. and an atmosphere of 75% RH. .. In addition, RH represents relative humidity.
（水蒸気透過率の測定）
　水蒸気透過率の測定は、「防湿包装材料の透過湿度試験方法」ＪＩＳ　Ｚ０２０８に準じ、透湿カップを用いて、温度４０℃、９０％ＲＨの雰囲気下で実施した。 (Measurement of water vapor permeability)
The measurement of the water vapor transmittance was carried out in an atmosphere of a temperature of 40 ° C. and 90% RH using a moisture permeable cup according to JIS Z0208 of "Permeation Humidity Test Method for Moisture-Proof Packaging Material".
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005

Claims (9)

  1. 　２八面体型スメクタイトと、水酸基を有するビニル樹脂と、溶剤と、を含有し、
    　前記２八面体型スメクタイトが、層間イオンとして、アンモニウムイオン、リチウムイオン、及び水素イオンからなる群より選ばれる少なくとも１種を含有する２八面体型スメクタイトであり、
    　前記溶剤がアルコールを含有し、
    　前記アルコールの含有量が、前記溶剤全量に対して２０～８０質量％である、コーティング剤。     2 Contains octahedral smectite, vinyl resin having a hydroxyl group, and a solvent.
    The diocthedral smectite is a diocteohedral smectite containing at least one selected from the group consisting of ammonium ion, lithium ion, and hydrogen ion as interlayer ions.
    The solvent contains alcohol
    A coating agent having an alcohol content of 20 to 80% by mass based on the total amount of the solvent.
  2. 　前記２八面体型スメクタイトがモンモリロナイトである、請求項１に記載のコーティング剤。 The coating agent according to claim 1, wherein the 2-octahedral smectite is montmorillonite.
  3. 　前記２八面体型スメクタイトのナトリウムイオン当量が、１０ｍｅｑ／１００ｇ未満である、請求項１又は２に記載のコーティング剤。 The coating agent according to claim 1 or 2, wherein the sodium ion equivalent of the 2-octahedral smectite is less than 10 meq / 100 g.
  4. 　前記２八面体型スメクタイトのアンモニウムイオン当量、リチウムイオン当量、及び水素イオン当量の合計が、５０～１２０ｍｅｑ／１００ｇである、請求項１～３のいずれか一項に記載のコーティング剤。 The coating agent according to any one of claims 1 to 3, wherein the sum of the ammonium ion equivalent, the lithium ion equivalent, and the hydrogen ion equivalent of the two octahedral smectite is 50 to 120 meq / 100 g.
  5. 　ポリカルボン酸を更に含有する、請求項１～４のいずれか一項に記載のコーティング剤。 The coating agent according to any one of claims 1 to 4, further containing a polycarboxylic acid.
  6. 　前記ビニル樹脂の水酸基価が、８００～１５００である、請求項１～５のいずれか一項に記載のコーティング剤。 The coating agent according to any one of claims 1 to 5, wherein the vinyl resin has a hydroxyl value of 800 to 1500.
  7. 　基材と、請求項１～６のいずれか一項に記載のコーティング剤を前記基材上にコートしてなるコート層と、を有する、積層体。 A laminate having a base material and a coating layer obtained by coating the base material with the coating agent according to any one of claims 1 to 6.
  8. 　前記コート層の厚みが０．１～５μｍである、請求項７に記載の積層体。 The laminate according to claim 7, wherein the coat layer has a thickness of 0.1 to 5 μm.
  9. 　包装材料として用いられる、請求項７又は８に記載の積層体。 The laminate according to claim 7 or 8, which is used as a packaging material.
PCT/JP2020/016596 2019-04-25 2020-04-15 Coating agent and laminate WO2020218118A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2019-083906 2019-04-25
JP2019083906A JP2022092074A (en) 2019-04-25 2019-04-25 Coating agent and laminate

Publications (1)

Publication Number Publication Date
WO2020218118A1 true WO2020218118A1 (en) 2020-10-29

Family

ID=72942071

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2020/016596 WO2020218118A1 (en) 2019-04-25 2020-04-15 Coating agent and laminate

Country Status (2)

Country Link
JP (1) JP2022092074A (en)
WO (1) WO2020218118A1 (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002014458A1 (en) * 2000-08-11 2002-02-21 Nihon Parkerizing Co., Ltd. Water-based composition for protective film formation
JP2007277078A (en) * 2006-03-11 2007-10-25 National Institute Of Advanced Industrial & Technology Film using denatured clay
JP2011512436A (en) * 2008-02-15 2011-04-21 ビーエーエスエフ コーティングス ゲゼルシャフト ミット ベシュレンクテル ハフツング Aqueous coating composition, process for its production and use thereof
JP2013059930A (en) * 2011-09-14 2013-04-04 Kohjin Holdings Co Ltd Gas barrier film and manufacturing method
WO2018168947A1 (en) * 2017-03-14 2018-09-20 Dic株式会社 Resin composition, molded article, laminate, gas barrier material, coating material, and adhesive

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002014458A1 (en) * 2000-08-11 2002-02-21 Nihon Parkerizing Co., Ltd. Water-based composition for protective film formation
JP2007277078A (en) * 2006-03-11 2007-10-25 National Institute Of Advanced Industrial & Technology Film using denatured clay
JP2011512436A (en) * 2008-02-15 2011-04-21 ビーエーエスエフ コーティングス ゲゼルシャフト ミット ベシュレンクテル ハフツング Aqueous coating composition, process for its production and use thereof
JP2013059930A (en) * 2011-09-14 2013-04-04 Kohjin Holdings Co Ltd Gas barrier film and manufacturing method
WO2018168947A1 (en) * 2017-03-14 2018-09-20 Dic株式会社 Resin composition, molded article, laminate, gas barrier material, coating material, and adhesive

Also Published As

Publication number Publication date
JP2022092074A (en) 2022-06-22

Similar Documents

Publication Publication Date Title
US11286384B2 (en) Resin composition, molded article, laminate, gas barrier material, coating material, and adhesive
JP5322280B2 (en) Optical pressure-sensitive adhesive composition
JP5057807B2 (en) Retardation film containing acrylic resin and styrene resin
TWI401303B (en) Adhesive film and image displaying device
TWI553085B (en) Pressure sensitive adhesive sheet, optical film with pressure sensitive adhesive and optical laminate
TWI428412B (en) Adhesive composition, adhesive optical film and image display device
Amirshaqaqi et al. Investigation of corrosion behavior of aluminum flakes coated by polymeric nanolayer: Effect of polymer type
KR102153297B1 (en) Aqueous dispersion-type adhesive composition for transparent conductive layer, adhesive layer for transparent conductive layer, optical film with adhesive layer, and liquid crystal display device
TW201329180A (en) Adhesive optical film
KR20160048719A (en) Polyolefin-type adhesive agent composition
WO2020218124A1 (en) Coating agent and laminate
Zhang et al. Towards transparent PMMA/S i O 2 nanocomposites with promising scratch‐resistance by manipulation of SiO 2 aggregation followed by in situ polymerization
JP6482642B2 (en) Polymerization composition and method for producing the same, coating composition containing the same, method for producing coating composition using these, and method for producing coating
JP2021169574A (en) Resin composition, gas barrier material, coating agent, and laminate
WO2020218118A1 (en) Coating agent and laminate
WO2020218125A1 (en) Resin composition
WO2020218119A1 (en) Resin composition
JP6814454B2 (en) Composition, gas barrier material, coating material, adhesive, molded product, laminate, and method for producing the molded product.
WO2012077674A1 (en) Resin composition and uses thereof
TW202231801A (en) Composition, curable composition, and cured product
JP2015105279A (en) Curable resin composition
JP2022034316A (en) Carbon nanotube dispersion, and coating including the same
WO2020203766A1 (en) Gas barrier composition, coating agent, and laminate
JP7211726B2 (en) the film
CN112534021A (en) Resin composition for vibration damping material

Legal Events

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

Ref document number: 20794038

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20794038

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: JP