[go: up one dir, main page]

WO2003025058A1 - Dispersion aqueuse de copolymere ethylene/alcool vinylique - Google Patents

Dispersion aqueuse de copolymere ethylene/alcool vinylique Download PDF

Info

Publication number
WO2003025058A1
WO2003025058A1 PCT/JP2002/009159 JP0209159W WO03025058A1 WO 2003025058 A1 WO2003025058 A1 WO 2003025058A1 JP 0209159 W JP0209159 W JP 0209159W WO 03025058 A1 WO03025058 A1 WO 03025058A1
Authority
WO
WIPO (PCT)
Prior art keywords
ethylene
copolymer
aqueous dispersion
carboxylic acid
unsaturated carboxylic
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/JP2002/009159
Other languages
English (en)
Japanese (ja)
Inventor
Eiichi Araki
Yuhei Funabiki
Keizo Michihata
Satoshi Hirofuji
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sumitomo Seika Chemicals Co Ltd
Kuraray Co Ltd
Original Assignee
Sumitomo Seika Chemicals Co Ltd
Kuraray Co Ltd
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 Sumitomo Seika Chemicals Co Ltd, Kuraray Co Ltd filed Critical Sumitomo Seika Chemicals Co Ltd
Priority to JP2003529844A priority Critical patent/JPWO2003025058A1/ja
Publication of WO2003025058A1 publication Critical patent/WO2003025058A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
    • C09D129/02—Homopolymers or copolymers of unsaturated alcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen
    • C08L23/0853—Ethene vinyl acetate copolymers
    • C08L23/0861—Saponified copolymers, e.g. ethene vinyl alcohol copolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen
    • C08L23/0869—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen with unsaturated acids, e.g. [meth]acrylic acid; with unsaturated esters, e.g. [meth]acrylic acid esters

Definitions

  • the present invention relates to aqueous dispersions. More specifically, the present invention relates to an aqueous dispersion of an ethylene nobule alcohol copolymer.
  • Ethylene / butyl alcohol-based copolymer obtained by saponification of ethylene / butyl acetate copolymer, etc. is extremely excellent in gas barrier properties such as oxygen, fragrance retention, oil resistance, and chemical resistance. Because of its superiority, it is suitably used for molded articles such as various films, sheets, and containers. It is also attracting attention as a material for protective coating on metal surfaces, paper, wood, etc. In particular, the gas barrier property is extremely superior to other resin films, and it is used for food packaging films, sheets, laminates, hollow containers, etc., which need to prevent oxidation of the contents or retain the scent. Very useful as a material.
  • a method of forming EVOH into a film, a sheet, or the like a method of melt extrusion or injection molding of EVOH, a method of laminating an EVOH film, and the like are widely practiced.
  • a method of applying and drying an EVOH solution or an aqueous dispersion has been proposed because a relatively thin film can be formed and a film having a complicated shape such as a hollow container can be easily formed. I have.
  • the EVOH solution increases viscosity at high concentrations and is difficult to use.
  • the solution is an organic solvent such as dimethyl sulfoxide, or a mixed solvent of alcohol and water.
  • the working environment is deteriorated due to volatilization, and equipment for collecting the organic solvent is required, which is economically disadvantageous.
  • the method of applying an aqueous dispersion of EVOH is considered to be advantageous from the above-mentioned working environment and economic point of view because the dispersion medium is water, and is expected.
  • Examples of the EVOH aqueous dispersion include, for example, EVOH as a surfactant or polyethylene oxide, canolepoxy methinoresenorelose, hydroxyxetinole cellulose, polyester
  • EVOH aqueous dispersion emulsified and dispersed in the presence of a water-soluble polymer protective colloid such as rivul alcohol has been proposed (Japanese Patent Application Laid-Open Nos. 54-184184, 56-108). No. 6143).
  • the dispersion stability and standing stability are insufficient, and the film-forming properties are poor, so that the obtained coating film has insufficient gas barrier properties.
  • the resin component is concentrated by a centrifugal separation method, and a high-concentration EVOH aqueous dispersion having a low viscosity and excellent storage stability (Japanese Patent Application Laid-Open No. 5-179001) ), Specific EVOH aqueous dispersions modified with peroxides and the like (Japanese Patent Application Laid-Open No. 7-118471) have been proposed.
  • the aqueous dispersion obtained by the former method also has insufficient film-forming properties, and it is hard to say that the long-term storage stability is sufficient. In the latter method, a special treatment is required for the resin, the process is complicated, and the long-term storage stability is not sufficient.
  • An object of the present invention is to provide an aqueous dispersion of an ethylene-z-vinyl alcohol-based copolymer having high concentration, excellent long-term stability, and excellent gas barrier properties of a coating film obtained.
  • the present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a specific ethylene / vinyl alcohol-based copolymer is used as a dispersoid, and a specific ethylene / bi,] 3-unsaturated carboxylic acid-based copolymer is used. It has been found that an aqueous dispersion of ethylene-Z-Biel-alcohol based on ethylene glycol as a dispersion stabilizer has excellent long-term stability at high concentration and excellent gas barrier properties of the obtained coating film. completed.
  • the present invention is an ethylene content of 1 5-6 5 mol%, a saponification degree 8 0 mole 0/0 or more ethylene / Bulle alcohol copolymer as the dispersoid, as a dispersion stabilizer, is neutralized with a base Containing ethylene / ⁇ , ⁇ -unsaturated carboxylic acid copolymers This is an aqueous dispersion of Z-vinyl alcohol copolymer.
  • the ratio of the above ethylene / a,] 3-unsaturated carboxylic acid copolymer is ethylene z vinyl alcohol copolymer 1
  • the amount is 0.01 to 20 parts by weight based on 0.0 part by weight.
  • the degree of neutralization of the above ethylene Za, J3-unsaturated carboxylic acid copolymer with a base is preferably 30 to 100 mol%.
  • the content of the structural unit derived from a,] 3-unsaturated carboxylic acid in the ethylene / hi, J3-unsaturated carboxylic acid copolymer is preferably 5 to 30% by weight.
  • the ethylene / ⁇ , 3-unsaturated carboxylic acid copolymer is an ethylene ⁇ ,
  • the base is preferably an alkali metal hydroxide.
  • the aqueous ethylene-butyl alcohol-based copolymer dispersion of the present invention preferably contains an inorganic filler. It is preferable that the inorganic filler is a salt of water-swellable furoic acid.
  • a laminate having a coating film formed from the aqueous dispersion of the ethylene / butyl alcohol-based copolymer of the present invention on at least one surface of a substrate is also one of the present invention.
  • the first feature of the present invention is that the use of an ethyleneno ⁇ , ⁇ monounsaturated carboxylic acid-based copolymer neutralized with a base as a dispersion stabilizer makes it possible to use a high concentration and agglomeration of particles during storage. This makes it possible to obtain an ethylene // butyl alcohol-based copolymer aqueous dispersion excellent in long-term stability without increasing the particle size or increasing the viscosity of the copolymer.
  • the second feature of the present invention is that, since the particle size of the ethylene butyl alcohol-based copolymer particles dispersed in the aqueous dispersion medium is small and the low-temperature film-forming property is good, the transparency is high and the gas barrier property is high.
  • the advantage is that a coating film excellent in the above can be obtained.
  • the ethylene-vinyl alcohol copolymer (hereinafter, abbreviated as EVOH) used in the present invention is composed of ethylene, biel acetate, butyl formate, butyl propionate, vinyl benzoate, vinyl trifluoroacetate, and vinyl valinate. It can be obtained by copolymerization with a vinyl ester such as this and saponifying.
  • saponified ethylene / vinyl acetate copolymer examples thereof include saponified vinyl onate copolymer, saponified ethylene / vinyl benzoate copolymer, saponified ethylene / vinyl trifluoroacetate copolymer, and saponified ethylene / vinyl vivalate copolymer.
  • a copolymerizable monomer other than ethylene and vinyl ester may be copolymerized in an amount of 5 mol% or less.
  • the ethylene content in the EVOH is 15-65 mol 0 /. , Preferably 20-5
  • the saponification degree is at least 80 mol%, preferably at least 95 mol%, more preferably at least 97 mol%. If the degree of saponification is less than 80 mol%, the gas barrier properties of the obtained coating film will be insufficient.
  • the degree of polymerization of EVOH can be determined from the intrinsic viscosity measured at 30 ° C. in a water-phenol mixed solvent (weight ratio: 15 to 85).
  • the ethylene / ⁇ , 3-unsaturated carboxylic acid-based copolymer used as the dispersion stabilizer in the present invention includes a copolymer of ethylene and ⁇ ,] 3-unsaturated carboxylic acid or ethylene and a, J3- Copolymers of unsaturated carboxylic acids and ⁇ , -unsaturated carboxylic esters can be mentioned.
  • 3-unsaturated carboxylic acid include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid.
  • Examples of the ⁇ ,] 3-unsaturated carboxylic acid ester include methyl acrylate, Ethyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate, monomethyl maleate, dimethyl methyl maleate, chloro Methyl tonate, methyl fumarate, methyl itaconate and the like can be mentioned.
  • ethylene Za, j3-unsaturated carboxylic acid copolymer examples include: ethylene / acrylic acid copolymer, ethylene / methacrylic acid copolymer, ethylene z-crotonic acid copolymer, ethylene / maleic Acid copolymer, ethylene Z fumaric acid copolymer, ethylene / itaconic acid copolymer and the like.
  • ethylene Z acrylic acid copolymer and ethylene Z methacrylic acid copolymer can be preferably used from the viewpoint of the dispersion stabilizing effect.
  • ethylene- ⁇ , j3-unsaturated carboxylic acid / h, J3-unsaturated carboxylic acid ester copolymer examples include ethylene / methyl methyl acrylate / coacrylate, ethylene / acrylic acid / acrylic acid Ethyl copolymer, ethylene / meth'acrylic acid / methyl methacrylate copolymer, ethylene nocrotonic acid Z methyl crotonate copolymer, ethylene / methyl maleate maleate copolymer, ethylene / fumaric acid / fumaric acid Methyl copolymer, ethylene / itaconic acid methyl itaconate copolymer and the like can be mentioned.
  • an ethylene / acrylic acid / ethyl acrylate copolymer can be preferably used from the viewpoint of a dispersion stabilizing effect.
  • These ethylene ⁇ ,] 3-unsaturated carboxylic acid copolymers may be used alone or in combination of two or more.
  • the content of the structural unit derived from ⁇ , / 3-unsaturated carboxylic acid in the ethylene / tri-, unsaturated carboxylic acid-based copolymer is not particularly limited, but is usually 5 to 30% by weight. , Preferably 15 to 25 weight. / 0 .
  • the content of the constituent unit derived from ⁇ ,] 3-unsaturated carboxylic acid is less than 5% by weight, the dispersion stabilizing effect may be reduced. If the content of the constituent unit derived from ⁇ , 3-unsaturated carboxylic acid exceeds 30% by weight, the water resistance and gas barrier property of the obtained coating film may be impaired.
  • the amount of the ethyleneno ⁇ , / 3-unsaturated carboxylic acid copolymer used is not particularly limited. However, it is usually 0.01 to 20 parts by weight, preferably 0.05 to 5 parts by weight, based on 100 parts by weight of EVOH. If the amount of the ethylene- ⁇ , / 3-unsaturated carboxylic acid copolymer is less than 0.01 parts by weight, the dispersing effect may not be expected. When the amount of the ethylene- ⁇ ,] 3-unsaturated carboxylic acid-based copolymer exceeds 20 parts by weight, the copolymer is easily dispersed, but may impair the gas barrier properties and water resistance of the obtained coating film. There is.
  • the degree of neutralization of the ethylene Za, ⁇ -unsaturated carboxylic acid-based copolymer with a base is not particularly limited. 1 0 0 mol% have been neutralized, preferably 4 0-1 00 mol%, more preferably 5 0-1 0 0 mole 0/0. If the degree of neutralization of the 3 0 mole 0/0 less than, for reduced properties as a dispersion stabilizer, which may be obtained with excellent stability EVOH aqueous dispersions difficult.
  • Examples of the base include, but are not particularly limited to, usually, alkali metal hydroxides such as sodium hydroxide, hydroxylic lime, ammonia, and organic amines. Among them, alkali metal hydroxides are suitably used from the viewpoint of the stability of the obtained EVOH aqueous dispersion.
  • the method for producing the EVOH aqueous dispersion of the present invention is not particularly limited, and a known method can be used. For example, a method of dissolving EVOH and a dispersion stabilizer in a solvent, then cooling and precipitating and dispersing, and then removing the solvent; heating the EVOH and the dispersion stabilizer to a solvent that dissolves at high temperatures but becomes insoluble at low temperatures After dissolving and then cooling the solution to precipitate and disperse, replacing the solvent with water; contacting the solution of EVOH and the dispersion stabilizer with a poor solvent or cooling to remove precipitated particles.
  • a method of dispersing the obtained particles in water there is a method of dispersing the obtained particles in water.
  • a method in which EVOH is dissolved in a solvent, then cooled, precipitated and dispersed, and then the solvent is removed is suitably used. More specifically, an ethylene / ⁇ , ⁇ -unsaturated carboxylic acid copolymer neutralized with EVOH and a dispersion stabilizer base is dissolved in a mixed solvent at 50 to 75 ° C. with stirring. Then, the mixture is cooled to ⁇ 10 to 30 ° C., and the EVOH particles are precipitated and dispersed to have a weight average particle size of 1 m or less, preferably 0.5 ⁇ or less, more preferably 0.3 ⁇ or less. , Add water as needed, The solvent is removed under normal pressure or reduced pressure, and an EVOH aqueous dispersion having a desired concentration can be obtained.
  • Examples of the solvent for dissolving the EVOH include water, monohydric alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, and n-butyl alcohol; dihydric alcohols such as ethylene glycol and propylene glycol; glycerin and the like. Phenols such as phenol and cresonole; amines such as ethylenediamine and trimethylenediamine; and mixed solvents such as dimethyl sulfoxide, dimethylacetamide and N-methylpyrrolidone. Among them, a mixed solvent of water Z alcohol, particularly water / methyl alcohol, water / ethyl alcohol, water / n-propyl alcohol, water / isopropyl alcohol, and the like are preferably used.
  • the concentration of EVOH in the EVOH aqueous dispersion is 15% by weight or more, preferably 20% by weight. / 0 or more, more preferably 25% by weight or more.
  • the upper limit of the concentration is not particularly limited. However, if the concentration is too high, the storage stability of the aqueous dispersion may become poor and the viscosity may increase. Therefore, the concentration is usually 50% by weight or less, preferably 4% by weight. 0% by weight or less.
  • aqueous dispersion of the present invention can be added to the EVOH aqueous dispersion of the present invention as long as the object of the present invention is not hindered. Further, an aqueous dispersion of another resin, a stabilizer against light or heat, a pigment, a lubricant, a fungicide, a film-forming aid, or the like can be added.
  • the inorganic filler examples include a salt of water-swellable firocheic acid, talc, myriki, cres, calcium carbonate, and gypsum.
  • a salt of water-swellable phyllokeic acid is preferably used, and specific examples thereof include smectites such as montmorillonite, beidelite, nontronite, savonite, hectolite, sauconite, and stibnite. And the like. Among them Smectites, especially montmoring mouths, are preferably used.
  • the amount of the inorganic filler added is usually 0.0 with respect to 100 parts by weight of E VOH.
  • the effect of improving gas barrier properties may not be expected. 'If the amount of the inorganic filler exceeds 20 parts by weight, the effect of improving the gas barrier property can be expected, but the viscosity of the aqueous dispersion becomes too high, which may impair the stability of the aqueous dispersion.
  • the method of adding the inorganic filler is not particularly limited.
  • Examples include a method of adding an inorganic filler to an EVOH solution.
  • a coating film can be formed on a substrate by applying the EVOH aqueous dispersion on a substrate and performing a dry heat treatment.
  • the thickness of the EVOH coating film is usually 0.5 to 15; um, preferably 1 to: L0; uin, and more preferably 2 to 6 ⁇ . If the thickness of the coating film is less than 0.5 ⁇ , there is a concern that the gas barrier property may be deteriorated due to pinholes and the like, and even if the coating film exceeds 15 m, it is not economical.
  • the substrate examples include rolled or biaxially stretched films of high-density polyethylene, polypropylene, nylon, polyester, polycarbonate, polychloride bilidene, and polystyrene.
  • Substrates other than the above-mentioned films include various molded products such as sheets, cups and bottles, paper, nonwoven fabric, woven fabric, fiber aggregates such as fiberglass casings, inorganic materials such as cement, metals, and wallpaper made of polyvinyl chloride resin. And photographic printing paper.
  • the method for applying the EVOH aqueous dispersion of the present invention to a substrate is not particularly limited, and includes a casting head method, a roll coating method, an air knife coating method, a gravure opening single coating method, a doctor low coating method, and a doctor knife coating method.
  • Known coating methods such as curtain flow coating, spraying, dipping, and brushing can be employed.
  • Examples of the method for drying and heat-treating the substrate coated with the EVOH aqueous dispersion by the above method include a dry heat treatment method such as an infrared irradiation method and a hot air drying method.
  • the temperature for the drying and heat treatment is 30 to 230 ° C, preferably 50 to 230 ° C, and more preferably 80 to 230 ° C.
  • the drying and heat treatment time varies depending on the temperature, but is usually 5 seconds to 10 minutes, preferably 1 to 5 minutes.
  • the surface of the base material may be previously anchor-coated with an adhesive.
  • the adhesive is not particularly limited, and examples thereof include polyurethane-based and polyester-based adhesives.
  • surface treatment such as corona discharge treatment, sputtering treatment, high frequency treatment, flame treatment, chromic acid treatment, and solvent etching treatment can be applied to the substrate surface.
  • another resin layer may be laminated by a conventionally known method on the laminate comprising the substrate and the coating film obtained from the aqueous EVOH dispersion of the present invention obtained by the above method, to form a multilayer.
  • the lamination method include an extrusion lamination method and a dry lamination method. .
  • the adhesive resin is not particularly limited as long as it does not cause delamination in a practical stage, and examples thereof include, but are not limited to, a modified olefin polymer containing a hydroxyl group; and a modified olefin polymer containing a glycidyl group.
  • carboxyl groups such as maleic anhydride-grafted polyethylene, maleic anhydride-grafted polypropylene, maleic anhydride-grafted ethylene z-ethyl acrylate copolymer, and maleic anhydride-grafted ethylene Z-vinyl acetate copolymer, etc.
  • Modified olefin polymer containing glycidyl group such as glycidyl-modified polyethylene, glycidyl-modified polypropylene, glycidyl-modified ethylene / ethyl acrylate copolymer, and glycidyl-modified ethylene / vinyl acetate copolymer Polymer; alkoxysilane-modified polyethylene, Al Modified olefin polymers containing an alkoxysilane group, such as coxysilane-modified polypropylene and alkoxysilane-modified ethylene / vinyl acetate copolymers, can be mentioned.
  • the laminate obtained in this way is extremely suitable for containers such as bags, cups, tubes, trays, bottles, etc. composed of laminates of films, sheets, etc., for general food packaging, pharmaceutical packaging, and retort food packaging. It is. BEST MODE FOR CARRYING OUT THE INVENTION
  • Ethylene acetate Bulle copolymer saponified as dispersoid (ethylene content 3 2 molar 0/0, a saponification degree 9 9.5 mole 0/0, the degree of polymerization 1 0 0 0) 5 parts by weight of methyl alcohol 5 7 wt Parts, 36 parts by weight of water and as dispersion stabilizer obtained above:
  • the resulting solution was cooled to 5 ° C under stirring to precipitate and disperse particles.
  • an alcohol-based copolymer dispersion was obtained. Subsequently, methyl alcohol in the obtained ethylene / vinyl alcohol-based copolymer dispersion was distilled off, and an aqueous dispersion of ethylene Z-butyl alcohol-based copolymer having an average particle diameter of 0.15 ⁇ m and a concentration of 30% by weight was removed. The obtained aqueous dispersion of ethylene butyl alcohol-based copolymer was allowed to stand at 40 ° C. for 180 days, but no aggregation was observed and the stability was good.
  • Example 1 the ethylene Z content 27 mol%, degree of saponification 99.5 mol. /.
  • An aqueous dispersion of an ethylene / vinyl alcohol copolymer having an average particle size of 0.16 ⁇ m and a concentration of 25% by weight was prepared in the same manner as in Example 1 except that the polymerization degree was changed to 100. I got
  • the obtained aqueous dispersion of ethylene Z-Butyl alcohol-based copolymer was left at 40 ° C. for 180 days, but no aggregation was observed and the stability was good.
  • Example 1 was repeated, except that the ethylene / acrylic acid copolymer was changed to an ethylene / acrylic acid Z-ethyl acrylate copolymer (acrylic acid content: 21% by weight). An aqueous ethylene / vinyl alcohol copolymer dispersion having a diameter of 0.14 / z ni and a concentration of 27% by weight was obtained.
  • Example 1 was repeated, except that the ethylene Z acrylic acid copolymer was changed to an ethylene Z methacrylic acid co-copolymer (methacrylic acid content: 21% by weight). The average particle diameter was 0.1. An aqueous ethylene-vinyl alcohol-based copolymer dispersion having a concentration of 7 ⁇ and a concentration of 29% by weight was obtained.
  • the obtained aqueous dispersion of ethylenenovinyl alcohol copolymer was left at 40 ° C. for 180 days, but no aggregation was observed and the stability was good.
  • Example 1 100 parts by weight of the aqueous ethylene-vinyl alcohol-based copolymer dispersion obtained in Example 1 and 10 parts by weight of a 1% by weight colloid solution of montmorillonite (trade name "Kunipia F" of Kunimine Industry Co., Ltd.) After mixing, the mixture was diluted with water to obtain an aqueous dispersion of ethylene Z vinyl alcohol-based copolymer having a concentration of 25% by weight.
  • montmorillonite trade name "Kunipia F” of Kunimine Industry Co., Ltd.
  • Example 1 was repeated except that 57 parts by weight of methyl alcohol and 36 parts by weight of water were changed to 38 parts by weight of isopropyl alcohol and 55 parts by weight of water.
  • An aqueous ethylene / vinyl alcohol copolymer dispersion having a concentration of 0.17 ⁇ and a concentration of 30% by weight was obtained.
  • the obtained aqueous dispersion of ethylene / vinyl alcohol copolymer was allowed to stand at 40 ° C. for 180 days, but no aggregation was observed and the stability was good.
  • Ethylene / acetate Bulle copolymer saponified as dispersoid (ethylene content 3 2 molar 0/0, a saponification degree 9 9.5 mole 0/0, the degree of polymerization 1 0 0 0) 5 parts by weight of isopropyl alcohol 3 8 parts by weight and 56.6 parts by weight of water 0.4 part by weight of the aqueous solution of the ethylene / acrylic acid copolymer obtained above as a dispersion stabilizer was dissolved by heating at 67 ° C. The resulting solution was cooled to 5 ° C. with stirring to precipitate and disperse the particles to obtain an ethylene / vinyl alcohol-based copolymer dispersion.
  • the obtained aqueous dispersion of ethylene Z vinyl alcohol copolymer was left at 40 ° C. for 180 days, but no aggregation was observed and the stability was good.
  • Aqueous dispersion of ethylene / butyl alcohol-based copolymer obtained in Example 7 100 4 parts by weight of Montmorillonite (trade name "Kunipia F” of Kunimine Industry Co., Ltd.). / 0 after mixing the colloidal solution 23 parts by weight, it was diluted with water to give a concentration of 2 '6 by weight percent Echiren / vinyl alcohol copolymer aqueous dispersion.
  • the obtained aqueous dispersion of ethylene Z vinyl alcohol copolymer was left at 40 ° C. for 180 days, but no aggregation was observed and the stability was good.
  • Example 1 Apply a urethane anchor coating agent (trade name “AD 335 A / CAT 10” of Toyo Morton Co., Ltd.) to the corona-treated surface of a biaxially stretched polypropylene film (Toseguchi Co., Ltd., film thickness 20 ⁇ ).
  • a urethane anchor coating agent trade name “AD 335 A / CAT 10” of Toyo Morton Co., Ltd.
  • the ethylene / vinyl alcohol copolymer aqueous dispersion obtained in Example 1 was applied by an air knife coating method, dried at 110 ° C. for 5 minutes, and heat-treated, to obtain a laminate (EVOH layer thickness) of the present invention. 2 ⁇ ) was obtained.Oxygen barrier property of the obtained laminate was measured using OX-TRAN10 / 5OA of Modern Control at 20 ° C, relative humidity of 0% and 85%.
  • the oxygen permeation amounts were 2.3 cc / m 2 ⁇ day ⁇ a tm and 12 cc / m 2 ⁇ day ⁇ a tm, respectively.
  • the oxygen permeation amount is 20 cc / m 2 ⁇ day ⁇ a tm or less, it can be judged that the oxygen barrier property is excellent.
  • a laminate was obtained in the same manner as in Example 9, except that the aqueous ethylene / vinyl alcohol copolymer dispersion obtained in Example 2 was used.
  • the obtained laminate was evaluated for oxygen barrier property in the same manner as in Example 9, and the oxygen permeation amount was 1.8 cc / m 2 ⁇ day. ⁇ atm s 10 c cZm 2 'day' a tm.
  • a laminate was obtained in the same manner as in Example 9, except that the aqueous dispersion of the ethylene Z vinyl alcohol copolymer obtained in Example 3 was used. Same as Example 9 for the obtained laminate.
  • the oxygen permeation amounts were 1. S cc / m 2 ⁇ day ⁇ atm N ⁇ 1 cc / m 2 ⁇ day ⁇ atm, respectively.
  • a laminate was obtained in the same manner as in Example 9 except that the aqueous dispersion of ethylenenobutyl alcohol-based copolymer obtained in Example 4 was used.
  • the obtained laminate was evaluated for oxygen barrier properties in the same manner as in Example 9, and the oxygen permeation amount was 1.9 cc / m 2 ⁇ day ⁇ at 9 ccm ”at 'day' atm 7
  • a laminate was obtained in the same manner as in Example 9, except that the aqueous dispersion of ethylene Z butyl alcohol-based copolymer obtained in Example 5 was used.
  • the obtained laminate was evaluated for oxygen barrier property in the same manner as in Example 9, and the oxygen permeation amount was 1.3 cc / m 2 ⁇ day ⁇ at 8. Ice / m 2 ⁇ day ⁇ It was atm. From the observation of the surface and the cross section of the coating film by an optical microscope (magnification: 100 times), no aggregates or local aggregates of montmorillonite were observed.
  • Example 9 Using the aqueous ethylene / vinyl alcohol copolymer dispersion obtained in Example 6, the same procedure as in Example 9 was carried out to obtain a laminate.
  • the oxygen permeation amount was 2.4 cc / m 2 -day ⁇ atm and 12 cc / m 2 , respectively. day ⁇ a tm.
  • Example 16 A laminate was obtained in the same manner as in Example 9, except that the aqueous ethylene-vinyl alcohol-based copolymer dispersion obtained in Example 7 was used.
  • the oxygen permeation amount was 1.9 cc / m 2 'day' atm ⁇ 9 cc / m "-day- a tm 7 (Example 16)
  • a laminate was obtained in the same manner as in Example 9 using the aqueous dispersion of ethylene Z butyl alcohol-based copolymer obtained in Example 8.
  • the oxygen permeation amount was 1.2 CC Zm 2 ⁇ day ⁇ atm N 7.8 cc / m 2 ⁇ day ⁇ It was atm. From the observation of the surface and the cross section of the coating film with an optical microscope (magnification: 100 times), no aggregates or local aggregates of montmorillonite were found. (Example 17)
  • a biaxially stretched polyethylene terephthalate film (Diafoil Hext Co., Ltd., 12 m thick) is coated with a urethane anchor coating agent (trade name "AD 335 A / CAT 10" of Toyo Morton Co., Ltd.) on the surface. Then, the aqueous dispersion of the ethylene / vinyl alcohol copolymer obtained in Example 8 was applied by an air knife coating method, dried at 210 ° C. for 5 minutes, and heat-treated to obtain a laminate of the present invention (EVOH A layer thickness of 2 ⁇ m) was obtained.
  • a urethane anchor coating agent trade name "AD 335 A / CAT 10" of Toyo Morton Co., Ltd.
  • the obtained laminate was evaluated for oxygen barrier properties in the same manner as in Example 9, and the oxygen permeation amount was 0.4 cc / m 2 .day.a tm and 2.5 cc / m 2 ⁇ day, respectively. ⁇ A In addition, from an optical microscope observation (magnification: 100 times) of the surface and cross section of the coating film, no aggregates or localized aggregates of montmorillonite were found.
  • Example 2 When the same operation as in Example 1 was performed except that the ethylene / acrylic acid copolymer partially neutralized aqueous liquid was not added in Example 1, the precipitated particles aggregated when cooled to 5 ° C. However, an aqueous dispersion of an ethylene novinyl alcohol copolymer could not be obtained.
  • Example 2 The same operation as in Example 2 was performed except that the aqueous solution of the ethylene / acrylic acid copolymer partially neutralized was not used in Example 2, but when cooled to 5 ° C, precipitated particles aggregated. However, an aqueous dispersion of an ethylene novinyl alcohol copolymer could not be obtained.
  • the aqueous ethylene / butyl alcohol copolymer dispersion of the present invention contains an ethylene / bier alcohol copolymer having an ethylene content of 15 to 65 mol% and a saponification degree of 80 mol% or more, and a dispersion stabilizer. Excellent stability during storage because it contains ethylene / tri-unsaturated carboxylic acid copolymer neutralized with a base. Further, the coating film obtained from the aqueous dispersion of the ethylene Z-butyl alcohol-based copolymer of the present invention has excellent oxygen barrier properties and is of high industrial value.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Paints Or Removers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne une dispersion aqueuse de copolymère éthylène/alcool vinylique présentant une teneur élevée et une excellente stabilité à long terme et conférant d'excellentes propriétés de perméabilité au gaz à un film de revêtement. Cette dispersion comprend un copolymère éthylène/alcool vinylique possédant une teneur en éthylène comprise entre 15 et 65 % mol et un degré de saponification d'au moins 80 % mol comme ingrédient dispersé et comprend également, comme stabilisateur de dispersion, un copolymère éthylène/acide carboxylique α,β-insaturé neutralisé par une base.
PCT/JP2002/009159 2001-09-12 2002-09-09 Dispersion aqueuse de copolymere ethylene/alcool vinylique Ceased WO2003025058A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2003529844A JPWO2003025058A1 (ja) 2001-09-12 2002-09-09 エチレン／ビニルアルコール系共重合体水性分散液

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2001276697 2001-09-12
JP2001-276697 2001-09-12

Publications (1)

Publication Number Publication Date
WO2003025058A1 true WO2003025058A1 (fr) 2003-03-27

Family

ID=19101359

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2002/009159 Ceased WO2003025058A1 (fr) 2001-09-12 2002-09-09 Dispersion aqueuse de copolymere ethylene/alcool vinylique

Country Status (2)

Country Link
JP (1) JPWO2003025058A1 (fr)
WO (1) WO2003025058A1 (fr)

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005021638A3 (fr) * 2003-08-25 2005-05-26 Dow Global Technologies Inc Dispersion aqueuse, son procede de production et son utilisation
WO2005085331A1 (fr) 2004-02-27 2005-09-15 Dow Global Technologies Inc. Dispersions polymeres aqueuses et produits issus de ces dispersions
WO2006057351A1 (fr) * 2004-11-25 2006-06-01 Sumitomo Seika Chemicals Co., Ltd. Dispersion aqueuse de copolymere ethylene/alcool vinylique
JP2007083409A (ja) * 2005-09-20 2007-04-05 Mitsubishi Plastics Ind Ltd ガスバリア性積層フィルム
JP2009006508A (ja) * 2007-06-26 2009-01-15 Sumitomo Seika Chem Co Ltd 積層フィルム
US7947776B2 (en) 2003-08-25 2011-05-24 Dow Global Technologies Llc Aqueous dispersion, its production method, and its use
AU2008201547B2 (en) * 2003-08-25 2012-01-19 Dow Global Technologies Llc Aqueous dispersion, its production method, and its use
JP4864699B2 (ja) * 2004-05-14 2012-02-01 住友精化株式会社 エチレン／ビニルアルコール系共重合体水性分散液の製造方法
JP2012511620A (ja) * 2008-12-12 2012-05-24 ダウ グローバル テクノロジーズ エルエルシー コーティング組成物、コーティング組成物を製造する工程、コートされた物品、およびそのような物品を形成する方法
AU2012202309B2 (en) * 2003-08-25 2013-12-05 Dow Global Technologies Llc Aqueous dispersion, its production method, and its use
US8618210B2 (en) 2003-08-25 2013-12-31 Dow Global Technologies, Llc Aqueous polymer dispersions and products from those dispersions
US8946329B2 (en) 2003-08-25 2015-02-03 Dow Global Technologies Llc Coating compositions
US9169406B2 (en) 2003-08-25 2015-10-27 Dow Global Technologies Llc Coating compositions
US9422444B2 (en) 2012-12-28 2016-08-23 Dow Global Technologies Llc Coating compositions
JP2016222920A (ja) * 2015-06-03 2016-12-28 日本ペイント・サーフケミカルズ株式会社 水性樹脂分散体、水性樹脂分散体の製造方法、親水化処理剤、親水化処理方法、金属材料及び熱交換器
WO2017194330A1 (fr) * 2016-05-12 2017-11-16 Basf Se Compositions aqueuses de revêtement contenant une dispersion de polymère à faible conductivité électrique et des phyllosilicates pour revêtements de barrière contre l'oxygène
US9938413B2 (en) 2012-12-28 2018-04-10 Dow Global Technologies Llc Coating composition and articles made therefrom
JP2022523042A (ja) * 2019-01-25 2022-04-21 マイケルマン，インコーポレーテッド エチレンビニルアルコールコポリマー／エチレンアクリル酸コポリマーブレンドバリア被覆
JP2023096409A (ja) * 2021-12-27 2023-07-07 株式会社アプトデイト 電子部品用ケース材料、電子部品用ケース材料の製造方法、電子部品用ケース及び電子部品用ケースの製造方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5915438A (ja) * 1982-07-16 1984-01-26 Toyo Ink Mfg Co Ltd 水性樹脂組成物
JPS6211543A (ja) * 1985-07-09 1987-01-20 Mitsui Petrochem Ind Ltd 水性分散物の製法
JPH04233963A (ja) * 1990-07-31 1992-08-21 E I Du Pont De Nemours & Co 粘り強くしたエチレン（ビニルアルコール）共重合体樹脂
JPH0539392A (ja) * 1990-09-21 1993-02-19 Kuraray Co Ltd 樹脂組成物、その製法および積層体
JPH11193340A (ja) * 1997-10-28 1999-07-21 Mitsui Chem Inc 水性分散体及びその製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5915438A (ja) * 1982-07-16 1984-01-26 Toyo Ink Mfg Co Ltd 水性樹脂組成物
JPS6211543A (ja) * 1985-07-09 1987-01-20 Mitsui Petrochem Ind Ltd 水性分散物の製法
JPH04233963A (ja) * 1990-07-31 1992-08-21 E I Du Pont De Nemours & Co 粘り強くしたエチレン（ビニルアルコール）共重合体樹脂
JPH0539392A (ja) * 1990-09-21 1993-02-19 Kuraray Co Ltd 樹脂組成物、その製法および積層体
JPH11193340A (ja) * 1997-10-28 1999-07-21 Mitsui Chem Inc 水性分散体及びその製造方法

Cited By (37)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7947776B2 (en) 2003-08-25 2011-05-24 Dow Global Technologies Llc Aqueous dispersion, its production method, and its use
AU2008201547B2 (en) * 2003-08-25 2012-01-19 Dow Global Technologies Llc Aqueous dispersion, its production method, and its use
US9416291B2 (en) 2003-08-25 2016-08-16 Dow Global Technologies Llc Coating compositions
US9169406B2 (en) 2003-08-25 2015-10-27 Dow Global Technologies Llc Coating compositions
CN102585376B (zh) * 2003-08-25 2015-08-12 陶氏环球技术有限责任公司 水分散体、其生产方法及其用途
EP2264098A1 (fr) * 2003-08-25 2010-12-22 Dow Global Technologies Inc. Procédé de production d'une dispersion aqueuse
AU2012202309B2 (en) * 2003-08-25 2013-12-05 Dow Global Technologies Llc Aqueous dispersion, its production method, and its use
US8946329B2 (en) 2003-08-25 2015-02-03 Dow Global Technologies Llc Coating compositions
US8618210B2 (en) 2003-08-25 2013-12-31 Dow Global Technologies, Llc Aqueous polymer dispersions and products from those dispersions
EP2272910A1 (fr) * 2003-08-25 2011-01-12 Dow Global Technologies Inc. Dispersion aqueuse
CN102585376A (zh) * 2003-08-25 2012-07-18 陶氏环球技术有限责任公司 水分散体、其生产方法及其用途
WO2005021638A3 (fr) * 2003-08-25 2005-05-26 Dow Global Technologies Inc Dispersion aqueuse, son procede de production et son utilisation
CN102391536A (zh) * 2004-02-27 2012-03-28 陶氏环球技术有限责任公司 含水聚合物分散体和从那些分散体得到的产物
WO2005085331A1 (fr) 2004-02-27 2005-09-15 Dow Global Technologies Inc. Dispersions polymeres aqueuses et produits issus de ces dispersions
JP4864699B2 (ja) * 2004-05-14 2012-02-01 住友精化株式会社 エチレン／ビニルアルコール系共重合体水性分散液の製造方法
US8664313B2 (en) 2004-05-14 2014-03-04 Sumitomo Seika Chemicals Co., Ltd. Method for producing aqueous ethylene/vinyl alcohol based copolymer dispersion
US8912264B2 (en) 2004-11-25 2014-12-16 Sumitomo Seika Chemicals Co., Ltd. Aqueous ethylene/vinyl alcohol copolymer dispersion
CN101065439B (zh) * 2004-11-25 2010-12-29 住友精化株式会社 乙烯/乙烯醇类共聚物水性分散液
WO2006057351A1 (fr) * 2004-11-25 2006-06-01 Sumitomo Seika Chemicals Co., Ltd. Dispersion aqueuse de copolymere ethylene/alcool vinylique
JP5112701B2 (ja) * 2004-11-25 2013-01-09 住友精化株式会社 エチレン／ビニルアルコール系共重合体水性分散液
JP2007083409A (ja) * 2005-09-20 2007-04-05 Mitsubishi Plastics Ind Ltd ガスバリア性積層フィルム
JP2009006508A (ja) * 2007-06-26 2009-01-15 Sumitomo Seika Chem Co Ltd 積層フィルム
JP2012511620A (ja) * 2008-12-12 2012-05-24 ダウ グローバル テクノロジーズ エルエルシー コーティング組成物、コーティング組成物を製造する工程、コートされた物品、およびそのような物品を形成する方法
US9938413B2 (en) 2012-12-28 2018-04-10 Dow Global Technologies Llc Coating composition and articles made therefrom
US9422444B2 (en) 2012-12-28 2016-08-23 Dow Global Technologies Llc Coating compositions
EP3305847A4 (fr) * 2015-06-03 2018-07-18 Nippon Paint Surf Chemicals Co., Ltd. Dispersion de résine aqueuse, procédé de production d'une dispersion de résine aqueuse, agent d'hydrophilisation, procédé d'hydrophilisation, matériau métallique, et échangeur de chaleur
JP2016222920A (ja) * 2015-06-03 2016-12-28 日本ペイント・サーフケミカルズ株式会社 水性樹脂分散体、水性樹脂分散体の製造方法、親水化処理剤、親水化処理方法、金属材料及び熱交換器
US10676632B2 (en) 2015-06-03 2020-06-09 Nippon Paint Surf Chemicals Co., Ltd. Aqueous resin dispersion, production method for aqueous resin dispersion, hydrophilization agent, hydrophilization method, metal material, and heat exchanger
US11505714B2 (en) 2015-06-03 2022-11-22 Nippon Paint Surf Chemicals Co., Ltd. Aqueous resin dispersion, production method for aqueous resin dispersion, hydrophilization agent, hydrophilization method, metal material, and heat exchanger
WO2017194330A1 (fr) * 2016-05-12 2017-11-16 Basf Se Compositions aqueuses de revêtement contenant une dispersion de polymère à faible conductivité électrique et des phyllosilicates pour revêtements de barrière contre l'oxygène
CN109153875A (zh) * 2016-05-12 2019-01-04 巴斯夫欧洲公司 用于氧气阻隔涂层的含低电导率的聚合物分散体和层状硅酸盐的水性涂料组合物
JP2019522069A (ja) * 2016-05-12 2019-08-08 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ 低電気伝導率を有するポリマー分散液とフィロケイ酸塩とを含有する酸素バリアコーティング用の水性コーティング組成物
JP7086004B2 (ja) 2016-05-12 2022-06-17 ビーエーエスエフ ソシエタス・ヨーロピア 低電気伝導率を有するポリマー分散液とフィロケイ酸塩とを含有する酸素バリアコーティング用の水性コーティング組成物
JP7086004B6 (ja) 2016-05-12 2022-07-04 ビーエーエスエフ ソシエタス・ヨーロピア 低電気伝導率を有するポリマー分散液とフィロケイ酸塩とを含有する酸素バリアコーティング用の水性コーティング組成物
JP2022523042A (ja) * 2019-01-25 2022-04-21 マイケルマン，インコーポレーテッド エチレンビニルアルコールコポリマー／エチレンアクリル酸コポリマーブレンドバリア被覆
JP7521817B2 (ja) 2019-01-25 2024-07-24 マイケルマン，インコーポレーテッド エチレンビニルアルコールコポリマー／エチレンアクリル酸コポリマーブレンドバリア被覆
JP2023096409A (ja) * 2021-12-27 2023-07-07 株式会社アプトデイト 電子部品用ケース材料、電子部品用ケース材料の製造方法、電子部品用ケース及び電子部品用ケースの製造方法

Also Published As

Publication number Publication date
JPWO2003025058A1 (ja) 2004-12-24

Similar Documents

Publication Publication Date Title
WO2003025058A1 (fr) Dispersion aqueuse de copolymere ethylene/alcool vinylique
JP5112701B2 (ja) エチレン／ビニルアルコール系共重合体水性分散液
TWI406763B (zh) Air barrier film, gas barrier layered body and manufacturing method thereof
JP4864818B2 (ja) 積層フィルム
JPH07330994A (ja) エチレン−酢酸ビニル系共重合体ケン化物溶液、水性分散液及び積層体
JP3333784B2 (ja) 水性組成物および積層体
TWI330135B (en) Gas barrier laminated film
JP2011042725A (ja) 金属蒸着層保護コート剤及び積層体
JP3400128B2 (ja) 水性組成物および積層体
WO2003000780A1 (fr) Procede de traitement de surface de film de resine thermoplastique
JP3194614B2 (ja) 水性分散液
JP2001172443A (ja) バリア性に優れたエチレン−ビニルアルコール共重合体水性組成物
JP4290228B2 (ja) 積層体の製法
JPH04183738A (ja) 樹脂水性分散液の製造方法
JP3210717B2 (ja) 水性分散液および分散安定剤
JP3131505B2 (ja) 多層構造体
JP2001226553A (ja) 樹脂組成物および積層体
WO1994024171A1 (fr) Procede de production d'une solution polymere oxydee et procede de production d'un stratifie au moyen de ladite solution
JP3257695B2 (ja) 水性分散液
JP3228482B2 (ja) 分散安定剤および水性分散液
JP3212044B2 (ja) 多層構造体の製法
JP4476410B2 (ja) 水性樹脂組成物および積層体の製法
JP3378316B2 (ja) 酸化処理ポリマー溶液の製造法および該溶液を用いた積層体の製造法
JP3426635B2 (ja) 変性エチレン−ビニルアルコール系共重合体、分散安定剤および水性分散液
JPH08244176A (ja) 積層体の製法

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): CA CN JP KR

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FR GB GR IE IT LU MC NL PT SE SK TR

121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 2003529844

Country of ref document: JP

122 Ep: pct application non-entry in european phase