WO2006059773A1 - 水系重合性単量体組成物、ガスバリア性フィルム及び該フィルムの製造方法 - Google Patents
水系重合性単量体組成物、ガスバリア性フィルム及び該フィルムの製造方法 Download PDFInfo
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- WO2006059773A1 WO2006059773A1 PCT/JP2005/022399 JP2005022399W WO2006059773A1 WO 2006059773 A1 WO2006059773 A1 WO 2006059773A1 JP 2005022399 W JP2005022399 W JP 2005022399W WO 2006059773 A1 WO2006059773 A1 WO 2006059773A1
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
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- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/10—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of paper or cardboard
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- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
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- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- C08J7/18—Chemical modification with polymerisable compounds using wave energy or particle radiation
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- 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
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
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- B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
- B05D3/061—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using U.V.
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- B05D3/068—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using ionising radiations (gamma, X, electrons)
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- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/02—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber
- B05D7/04—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber to surfaces of films or sheets
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- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
Definitions
- the present invention relates to a single-layer or multi-layer gas barrier film excellent in gas barrier properties such as oxygen gas barrier properties and suitable for packaging materials such as food packaging materials, and an aqueous polymerizable monomer composition used for the production thereof.
- Poly (meth) acrylic acid means polyacrylic acid or polymethacrylic acid or a mixture thereof.
- a film is prepared by heat-treating a coating film made of a mixture of poly (meth) acrylic acid and polybulal alcohol or saccharide, and then the film is immersed in a medium containing an alkali metal or an alkaline earth metal.
- a method for producing a gas barrier film having improved hot water resistance and water vapor resistance by introducing an ionic bond between poly (meth) acrylic acid and a metal US Patent No. 1). 6, 0 2 2, 9 1 3 specification; reference 1).
- a metal compound layer is formed on the surface of a coating film formed from a mixture of poly (meth) acrylic acid or a partially neutralized product thereof and polyvinyl alcohol or saccharide, and the ionic bond is formed by the migration of the metal compound into the coating film.
- a method for producing a film having excellent gas barrier properties, hot water resistance, and water vapor resistance by forming is proposed (US Pat. No. 6,605,344, specification 2).
- the polyvalent metal ions are transferred from the polyvalent metal compound-containing layer to the polycarboxylic acid polymer layer to produce a polycarboxylic acid polyvalent metal salt by reaction of the carboxyl group of the polycarboxylic acid polymer with the polyvalent metal compound.
- Has been proposed U.S. Patent Application Publication No. 2 0 0 5/0 1 3 1 1 6 2; Reference 3). According to this method, a film having excellent gas barrier properties can be obtained.
- Document 3 also discloses a method for producing a gas barrier film by applying an aqueous coating solution containing a mixture of a polycarboxylic acid polymer and a polyvalent metal compound, followed by drying.
- an aqueous coating solution containing a mixture of a polycarboxylic acid polymer and a polyvalent metal compound since the polycarboxylic acid polymer and the polyvalent metal compound are likely to react in an aqueous solution and cause non-uniform precipitation, it is difficult to prepare an aqueous coating solution in which each component is uniformly dissolved. is there.
- the reaction between the polycarboxylic acid polymer and the polyvalent metal compound can be suppressed by adding a volatile amine such as ammonia water.
- a volatile amine such as ammonia water
- Another object of the present invention is to use the aqueous polymerizable monomer composition.
- An object of the present invention is to provide a production method capable of producing a single-layer or multilayer gas barrier film comprising a carboxylic acid polymer film by a simple method.
- ⁇ , 3-unsaturated carboxylic acid monomer and the carboxyl groups of ⁇ , monounsaturated carboxylic acid monomer are 10 to 90. % Of the amount of polyvalent metal ions that neutralize the amount of the water-based polymerizable monomer composition that is dissolved or dispersed in 20 to 85% by weight of water based on the total amount of the composition. did.
- aqueous polymerizable monomer composition When the aqueous polymerizable monomer composition is applied as a coating liquid onto a substrate, a uniform coating film can be formed.
- a wet coating is polymerized by ionizing radiation and / or heat treatment, a cured coating can be obtained without causing problems such as gel precipitation and film whitening. I found out.
- This cured coating film is an ionic crosslinked polycarboxylic acid polymer film excellent in oxygen gas barrier properties.
- the production method of the present invention differs from the conventional method of ion-crosslinking (ion bonding) a polycarboxylic acid polymer film, and polymerizes an ⁇ , -unsaturated carboxylic acid monomer in the presence of a polyvalent metal ion.
- This is a method of simultaneously producing a polycarboxylic acid polymer and ionic crosslinking with a polyvalent metal ion, which greatly simplifies the film production process and is suitable for continuous production.
- the cured coating film obtained by the production method of the present invention is a ionic crosslinked polycarboxylic acid having a structure in which a polycarboxylic acid polymer produced by polymerization of an ⁇ , 3-unsaturated carboxylic acid is ion-crosslinked with a polyvalent metal ion. It is a polymer film.
- the ion-crosslinked polycarboxylic acid polymer film of the present invention is excellent in gas barrier properties such as oxygen gas barrier properties. Since the ion-crosslinked polycarboxylic acid polymer film of the present invention is ion-crosslinked with polyvalent metal ions, it can be used as a single-layer or multi-layer gas barrier film for packaging materials under normal use conditions. The appearance, shape, and gas barrier properties are not impaired.
- the aqueous polymerizable monomer composition is applied onto the substrate 1 to form a wet coating film, and another substrate 2 is coated on the surface of the coating film.
- the film is kept wet with ionizing radiation and is subjected to soot or heat treatment.
- a gas barrier multilayer film having good interlayer adhesion can be obtained.
- Multi-layer films with various functions can be obtained by selecting the types of base material 1 and base material 2 and arranging additional layers.
- the present invention has been completed based on these findings.
- the ⁇ , / 3-unsaturated carboxylic acid monomer and the polyvalent metal in an amount that neutralizes 10 to 90% of the carboxyl groups of the ⁇ ,] 3-unsaturated carboxylic acid monomer.
- An aqueous polymerizable monomer composition that is dissolved or dispersed in 20 to 85% by weight of water based on the total amount of the composition is provided.
- 5 0 X 10- 4 cm 3 ( STP) / (m 2 ⁇ s ⁇ MP a) gas barrier film comprising the following ionic crosslinking Porikaru Bonn acid polymer film is provided.
- the gas barrier film of the present invention may be a single layer of an ion-crosslinked polycarboxylic acid polymer film, but may be “substrate Z ion-crosslinked polycarboxylic acid polymer film” or “substrate 1 / ion-crosslinked polycarboxylic acid”. It may be a multilayer gas barrier film having the layer structure of “acid polymer film Z substrate 2”. In order to give various functions to the single layer or multilayer gas barrier film of the present invention, various additional layers may be provided by a lamination method or a coating method.
- Step 1 of applying a water-based polymerizable monomer composition according to any one of claims 1 to 8 on a substrate to form a wet coating film;
- the a, monounsaturated carboxylic acid monomer used in the present invention means that a carboxyl group is bonded to at least one carbon atom of two carbon atoms forming a carbon-carbon double bond of the unsaturated carboxylic acid. It is an unsaturated carboxylic acid compound of the structure. Since the carbon-carbon double bond is an ethylenic double bond, this unsaturated carboxylic acid has a function as a polymerizable monomer.
- the a, / 3-unsaturated carboxylic acid monomer used in the present invention can generally be divided into an unsaturated monocarboxylic carboxylic acid having one carboxyl group and an unsaturated dicarboxylic acid having two carboxylic groups.
- the unsaturated dicarboxylic acid has a structure in which a carboxyl group is bonded to each of two carbon atoms that form an ethylenic carbon-carbon double bond, and two carbon atoms that form an ethylenic carbon-carbon double bond. Some of them have a structure in which a force loxyl group is bonded to one carbon atom and a carboxyl group is bonded to the other carbon atom.
- the a, i3-unsaturated carboxylic acid monomer may have another carbon-carbon double bond in addition to the ethylenic carbon-carbon double bond.
- Examples of the ct, / 3-unsaturated carboxylic acid monomer used in the present invention include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, senesic acid, tiglic acid, sorbic acid, maleic acid, fumaric acid, and itacone. And at least one unsaturated carboxylic acid compound selected from the group consisting of acids, citraconic acid, mesaconic acid, and acid anhydrides thereof.
- acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, senesic acid (ie ⁇ ,] 3-dimethylacrylic acid), and tiglic acid (ie 2 monomethylcrotonic acid) are ⁇ ,] 3 _Monoethylenically unsaturated monocarboxylic acid compound.
- Sorbic acid is an ⁇ , / 3-unsaturated monocarboxylic acid compound, but has two carbon-carbon double bonds.
- Cinnamic acid may be cis or trans.
- Maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid are ⁇ , j3_monoethylenically unsaturated dicarboxylic acid compounds.
- As the acid anhydride maleic anhydride, itaconic anhydride, and citraconic anhydride are preferable. However, this These acid anhydrides are often in the form of free acids in the aqueous polymerizable monomer composition.
- the a, i3-unsaturated carboxylic acid monomer used as a raw material may be in the form of ⁇ , ⁇ -unsaturated carboxylic acid monomer as described above, but ⁇ ,) 3-unsaturated carboxylic acid monomer It may be in the form of a polyvalent metal salt.
- the polyvalent metal salt of ⁇ ,] 3-unsaturated carboxylic acid monomer is generally obtained by completely neutralizing the carboxyl group of ⁇ ,] 3-unsaturated carboxylic acid monomer with the polyvalent metal salt. Therefore, when it is used alone, the amount of polyvalent metal ions becomes excessive.
- a polyvalent metal salt of ct,] 3-unsaturated carboxylic acid use it in combination with ⁇ ,) 3-unsaturated carboxylic acid monomer in the water-based polymerizable monomer composition.
- the amount of polyvalent metal ions present is adjusted so as to neutralize 10 to 90% of the carboxyl groups of the ⁇ ,) 3-unsaturated carboxylic acid monomer.
- monounsaturated carboxylic acid monomer acrylic acid, methacrylic acid, cinnamic acid, sensioic acid, tiglic acid, sorbic acid, itaconic acid, maleic acid, and citraconic acid are preferable, and acrylic acid and methacrylic acid Acrylic acid is particularly preferable from the viewpoints of characteristics such as gas barrier properties and cost.
- Monomers other than (meth) acrylic acid such as itaconic acid, citraconic acid and maleic acid are preferably used in combination with acrylic acid or methacrylic acid as a minor component of less than 50% by weight.
- the a, j3-unsaturated carboxylic acid monomers can be used alone or in combination of two or more.
- the polyvalent metal ion is a polyvalent metal ion derived from a polyvalent metal compound.
- the polyvalent metal compound generally used is a compound that generates a polyvalent metal ion by ion dissociation in water.
- the polyvalent metal compound is a single polyvalent metal atom having a valence of 2 or more and a polyvalent metal compound. Therefore, the polyvalent metal compound used in the present invention includes a polyvalent metal atom alone.
- polyvalent metals include Periodic Group 2 metals such as beryllium, magnesium, and calcium; transition metals such as titanium, zirconium, chromium, manganese, iron, cobalt, nickel, copper, and zinc; and aluminum Can It is not limited to these. Of these, zinc, calcium, copper, magnesium, ano-remium, and iron are preferable.
- H, / 3-Unsaturated carboxylic acid metal salt has different solubility in water depending on the type of metal, but from the viewpoint of solubility, zinc and calcium are particularly preferred as the metal species.
- polyvalent metal compound examples include, but are not limited to, polyvalent metal oxides, hydroxides, carbonates, organic acid salts, and inorganic acid salts.
- polyvalent metal oxide oxide submarine, magnesium oxide, and iron (III) oxide are preferable.
- organic acid salts include acetate, oxalate, citrate, lactate, phosphate, phosphite, hypophosphite, stearate, a,) 3-monoethylenic acid
- examples include, but are not limited to, saturated carboxylates.
- 3-Monoethylenically unsaturated carboxylates include, for example, zinc diacrylate, calcium diacrylate, magnesium diacrylate, copper diacrylate, and aluminum acrylate.
- inorganic acid salts include, but are not limited to, chlorides, sulfates, and nitrates.
- Alkyl alkoxides of polyvalent metals can also be used as polyvalent metal compounds. These polyvalent metal compounds can be used alone or in combination of two or more.
- polyvalent metal compounds from the viewpoint of dispersion stability of the aqueous polymerizable monomer composition (coating liquid) and gas barrier properties of a film formed from the aqueous polymerizable monomer composition, beryllium, magnesium, Compounds of calcium, copper, cobalt, nickel, zinc, aluminum, iron and zirconium are preferred, and compounds of divalent metals such as beryllium, magnesium, calcium, copper, zinc, konololeto and nickel: iron, aluminum Trivalent metal compounds such as are more preferred.
- Preferred divalent metal compounds include, for example, oxides such as zinc oxide, magnesium oxide, copper oxide, nickel oxide, and cobalt oxide; carbonates such as calcium carbonate; calcium lactate, zinc lactate, zinc diacrylate, calcium diacrylate Organic acid salts such as magnesium diacrylate and copper diacrylate; alkoxides such as magnesium methoxide; but are not limited thereto.
- Trivalent metal compounds include oxides such as iron oxide ( ⁇ ); aluminum acrylate And organic acid salts such as The polyvalent metal compound is used as an aqueous solution or water dispersion.
- the polyvalent metal compounds can be used alone or in combination of two or more.
- the water-based polymerizable monomer composition of the present invention is used as a coating liquid (coating liquid) applied on a substrate when an ion-crosslinked polycarboxylic acid polymer film is produced by a coating method. .
- the water-based polymerizable monomer composition of the present invention neutralizes 10 to 90% of the ⁇ , monounsaturated carboxylic acid monomer and the carboxyl group of the a,) 3-unsaturated carboxylic acid monomer.
- the amount of polyvalent metal ions to be dissolved is dispersed or contained in 20 to 85% by weight of water based on the total amount of the composition.
- As the a, 3-unsaturated carboxylic acid monomer at least one ⁇ ,] 3-unsaturated carboxylic acid is used.
- the polyvalent metal ion source a polyvalent metal compound which dissociates into polyvalent metal ions in water is used.
- the polyvalent metal ion is 10 to 90% of the carboxy group, preferably 15 to 8 7%, more preferably 20 to 8% of the ⁇ , / 3-unsaturated carboxylic acid monomer. Used in an amount to neutralize 5%. This percentage is called the degree of neutralization. The lower limit of the degree of neutralization can be increased to 25%, further 30% or 40%. ⁇ ,; The amount ratio of polyvalent metal ion to 3-unsaturated carboxylic acid monomer is expressed in terms of a chemical equivalent to the carboxyl group of ⁇ , i3-unsaturated carboxylic acid monomer. 90, preferably 0.15 to 0.87, and more preferably 0.20 to 0.85. The lower limit of this chemical equivalent can be increased to 0.25, even 0.30 or 0.40.
- a, i3 If the chemical equivalent of polyvalent metal ions to the carboxyl group of the unsaturated carboxylic acid monomer is too small and the degree of neutralization is too low, the oxygen gas barrier properties of the resulting film under high humidity conditions Decreases.
- a,] 3 If the chemical equivalent of the polyvalent metal ion to the carboxyl group of the unsaturated carboxylic acid monomer is too large and the degree of neutralization is too high, the solubility of the metal ions will be reduced and uniform. Water-based polymerizable monomer composition May not be obtained, the polymerization reactivity of the coating film in a wet state may be reduced, or the resulting film may be whitened.
- the amount of polyvalent metal ions and the degree of neutralization are preferably adjusted in consideration of the type of ⁇ , ⁇ -unsaturated carboxylic acid monomer used, the type and valence of the polyvalent metal compound, and the like.
- the aqueous polymerizable monomer composition of the present invention can contain monovalent metal ions such as sodium and potassium as long as the uniformity as a solution is not impaired.
- the aqueous polymerizable monomer composition of the present invention contains 20 to 85% by weight of water based on the total amount of the composition. If the water content is too small, it will be difficult to uniformly dissolve or disperse the ⁇ ,) 3-unsaturated carboxylic acid monomer and the polyvalent metal compound. In the aqueous polymerizable monomer composition, it is preferable that the ⁇ , 3-unsaturated carboxylic acid monomer and the polyvalent metal compound are uniformly dissolved. In particular, when a large amount of undissolved polyvalent metal compound is present, it becomes difficult to obtain a homogeneous film. On the other hand, if the content of water is too large, gel is deposited in the process of polymerizing the wet coating film to deteriorate the appearance of the film, or it becomes difficult to remove water after polymerization.
- the water content depends on the solubility of the polyvalent metal compound used in water, it is preferably 25 to 83% by weight, more preferably 28 to 82% by weight, based on the total amount of the composition. . In order to balance the polymerization reactivity in the wet coating film and the water removal efficiency after polymerization, it is more preferable that the water content is 30 to 70% by weight.
- the solid content concentration of the aqueous polymerizable monomer composition of the present invention is 15 to 80% by weight, preferably 17 to 75% by weight, more preferably 18 to 72% by weight. In the present invention, the “solid content concentration” means the weight% of components (total amount) other than water.
- the solid content concentration is adjusted to the range of 70 to 30% by weight.
- water may be generated by the reaction of ⁇ ,) 3-unsaturated rubonic acid monomer with a polyvalent metal compound.
- the water content in the water-based polymerizable monomer composition of the present invention takes into account the water resulting from the reaction between the ⁇ , ⁇ monounsaturated carboxylic acid monomer and the polyvalent metal compound. To calculate.
- the water-based polymerizable monomer composition of the present invention uses water as a solvent.
- a small amount of an organic solvent for example, alcohols
- the water-based polymerizable monomer composition of the present invention can contain a polymerization initiator as required.
- a polymerization initiator a photopolymerization initiator and a thermal polymerization initiator are representative.
- a photopolymerization initiator and a thermal polymerization initiator may be used in combination.
- Thermal polymerization initiators include azo compounds and peroxides that are activated by irradiation with ionizing radiation.
- Photoinitiators are sometimes referred to simply as photoinitiators or sensitizers.
- Photopolymerization initiators include, for example, acetophenones, benzophenones, Michler ketones, benzyls, benzoins, benzoyne ethers, benzyldimethyl ketals, thixanthones, and mixtures of two or more thereof.
- Preferred examples of the photopolymerization initiator include acetophenones such as acetophenone, 2,2-jetoxycetophenone, m-chloroacetophenone, p-tert-butynoletrichloroacetophenone, 4-diaquatophenone, and benzophenones such as benzophenone.
- Michler ketones such as Michler ketone; Benzyls such as benzyl and benzylmethyl ether; Benzoins such as benzoin and 2-methylenobenzoin; Benzoinmethy / leetenole, Benzoinethyl ether, Benzynsopropyl ether, Benzyne / Rheichi Benzoine ethers such as tellurium; benzyldimethyl ketanoles such as benzyldimethyl ketal; thixanthones such as thixanthone; propiophenone, anthraquinone, Setoin, butyroin, Toruoin, benzo I le benzoate, alpha - ⁇ acyloxime esters can be exemplified Karubonizore compound such.
- Examples of the photopolymerization initiator include sulfur compounds such as tetramethinoretiuram disulfide, tetraethylthiuram disulfide, tetramethylthiuram monosulfide, thixanthone, 2_black mouth thixanthone;
- Examples thereof include azo compounds such as zobisisobutyronitrile and azobis-1,4-dimethyl / levaleronitrile; peroxides such as benzoyl peroxide and tert-butyl peroxide.
- photopolymerization initiators When these photopolymerization initiators are added to the water-based polymerizable monomer composition, they are usually from 0.001 to 10% by weight, preferably 0. 0 Add 1 to 5% by weight.
- the photopolymerization initiator is not necessarily added. However, in the case of performing polymerization by irradiation with ultraviolet rays, it is preferable to add a photopolymerization initiator in order to increase the polymerization efficiency.
- a hydrogen abstraction-type photopolymerization initiator such as benzophenone
- a part of the ⁇ , —unsaturated carboxylic acid monomer is grafted to the plastic film used as the substrate, and the substrate and the ion-crosslinked Carboxylic acid polymer Interlayer adhesion between the film layer can be enhanced.
- General-purpose additives such as other sensitizers and light stabilizers may be added together with the photopolymerization initiator.
- thermal polymerization initiators include persulfates such as potassium persulfate and ammonium persulfate; 2,2'-azobis [2-methyl- ⁇ - (2-hydroxyxetyl) propionamide], 2,2'-azobis [2-Methyl- ⁇ - [1,1 bis (hydroxymethyl) ethyl] propionamide], 2, 2 '—Azobis (4-methoxy-2,4-dimethylvaleronitrile), 4, A' — Azobis (4-cyananovaleric acid), 2, 2 '— Azobis (methyl isobutyrate), 1, 2' — Azobis ( ⁇ , N '— Dimethylenisobutylamidine) Dihydrochloride, 2, 2' — Azobis [2 —Methyl- ⁇ — (2-Hyd
- the water-based polymerizable monomer composition of the present invention includes an ⁇ ,) 3-unsaturated carboxylic acid monomer as long as it does not inhibit the ion crosslinking reaction with the polyvalent metal ion, if necessary.
- Other polymers for example, polybutyl alcohol, polyethylene glycol, polypropylene glycol, chitosan, etc.
- glycerin for example, polybutyl alcohol, polyethylene glycol, polypropylene glycol, chitosan, etc.
- glycerin for example, polybutyl alcohol, polyethylene glycol, polypropylene glycol, chitosan, etc.
- glycerin for example, polybutyl alcohol, polyethylene glycol, polypropylene glycol, chitosan, etc.
- glycerin for example, polybutyl alcohol, polyethylene glycol, polypropylene glycol, chitosan, etc.
- glycerin for example, polybutyl alcohol,
- polyfunctional monomer examples include diethylene glycol ditalylate, neopentyl glycol diacrylate, polyethylene glycol 40 0 diacrylate, 1,3-butanediol diacrylate, 1,4 monobutanediol diarylate.
- 1,6-Hexanediol diacrylate diethylene glycol diacrylate, neopentyl glycol diacrylate, hydroxypivalic acid ester neopentyl diacrylate, tripropylene diol glycol diacrylate, dicyclopentyl Acrylates, dicyclopentenyl oxychetyl acrylate, 1,4-butanediol diglycidyl ether diacrylate, diethylene glycol diglycidyl ether diacrylate, dipropylene glycol didady Diacrylates such as diether ether acrylate; Dimethacrylates such as ethylene gallic dimethacrylate and dipropylene glycol dimethacrylate; Triatalylates such as trimethylolpropane tritalate and pentaerythritol tritalate; Trimethylolethane Examples thereof include trimethacrylates such as trimethacrylate and trimethylolpropane trimethacrylate; polyfunctional (meth)
- the water-based polymerizable monomer composition of the present invention is water resistant without adding a polyfunctional monomer.
- Ion-crosslinked polycarboxylic acid polymer film having good heat resistance, hot water resistance, and water vapor resistance can be obtained, but if it is necessary to increase the degree of crosslinking, a polyfunctional monomer may be added in a small range. it can.
- the polyfunctional monomer is preferably 30 parts by weight or less, more preferably 20 parts by weight or less, particularly preferably 10 parts by weight or less, based on 100 parts by weight of the ⁇ , / 3-unsaturated carboxylic acid monomer. Used in proportions. When a polyfunctional monomer is used, the lower limit of the amount used is preferably 0.001 part by weight with respect to 100 parts by weight of the c,] 3-unsaturated carboxylic acid monomer.
- monofunctional attalylic acid esters such as 2-ethylhexyl acrylate and 2-hydroxyhexyl acrylate are methacrylic acid. Esters can be added in small proportions. Moreover, in order to adjust the viscosity of the aqueous polymerizable monomer composition, a photopolymerizable prepolymer may be added in a small proportion.
- Step 1 of applying a water-based polymerizable monomer composition according to any one of claims 1 to 8 on a substrate to form a wet coating film;
- the water-based polymerizable monomer composition is composed of an a, —unsaturated carboxylic acid monomer and an amount of polyvalent metal that neutralizes 10 to 90% of the carboxyl groups of the a, i3—unsaturated carboxylic acid monomer.
- An ion is a water-based polymerizable monomer composition that is dissolved or dispersed in 20 to 85% by weight of water in the total amount S of the composition.
- the ion-crosslinked polycarboxylic acid polymer film obtained by the production method of the present invention has an oxygen permeability of 50 X measured under a high humidity condition of a temperature of 30 ° C. and a relative humidity of 80%. 10 0 " 4 cm 3 (STP) / (m 2 ⁇ s ⁇ MP a) or less, and excellent in oxygen gas barrier properties.
- a multi-layer gas barrier film having a layer structure of “substrate / ion-crosslinked polycarboxylic acid polymer film” is obtained. If a separation step of the base material and the ion-bridged polycarboxylic acid polymer film is arranged after step 2, a single-layer gas barrier film made of an ion-crosslinked polyforce sulfonic acid polymer film can be obtained.
- a step of forming a wet coating film on the substrate 1 in the step 1 and then coating the surface of the coating film with another substrate 2 can be mentioned.
- the wet state of the coating film can be effectively maintained between the substrate 1 and the substrate 2.
- a multilayer film having a layer structure of “base material 1 Z ion-crosslinked polycarboxylic acid polymer film base material 2” can be obtained by this additional step.
- an additional step of peeling at least one of substrate 1 and substrate 2 from the multilayer film containing the layer structure of “substrate 1 Zion crosslinked polycarboxylic acid polymer film Z substrate 2” May be arranged.
- the layer configuration of an ion-crosslinked polystrength rubonic acid polymer film, or “base 1 noion cross-linked polycarboxylic acid polymer film” or “ion cross-linked polycarboxylic acid polymer film base 2” can be formed.
- a multilayered gas barrier film can be obtained.
- a multilayer gas barrier film containing a layer configuration of “base material ion-crosslinked polycarboxylic acid polymer film” or “base material 1 noion cross-linked polycarboxylic acid polymer film base material 2” A step of forming another layer on at least one surface by a lamination method or a coating method can be exemplified. By this additional step, a multilayer film having 3 layers or 4 layers or more can be obtained.
- a molded article excellent in gas barrier properties can be obtained.
- the base material is generally used in the form of a film or a sheet, but may be a molded body having a three-dimensional shape such as a plastic container if desired. Examples of other base materials include glass plates, metal plates, and aluminum foil.
- the base material used for applying the aqueous polymerizable monomer composition functions as a support for the coating film.
- the type of plastic composing the base plastic film is not particularly limited.
- high density polyethylene high density polyethylene, medium density polyethylene, low density polyethylene, linear low density polyethylene, polypropylene, poly 4-methylpentene, Olefin polymers such as cyclic polyolefin and acid-modified products thereof; poly (vinyl acetate), ethylene / vinyl acetate copolymer, saponified ethylene / vinyl acetate copolymer, vinyl acetate polymers such as poly (bull alcohol) and the like
- Modified products Polyesterenes such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate; Aliphatic polyesters such as poly ⁇ -force prolactone, polyhydroxybutyrate, polyhydroxyvalerate; Nylon 6, Nylon 6 6 Polyamides such as nylon 12, nylon 6, nylon 6 6 copolymer, nylon 6 12 copolymer, metaxylene adipamide / nylon 6 copolymer; polyethylene glycol, polyether
- the substrate is preferably an unstretched film or a stretched film made of these plastics.
- the plastic film can be subjected to pretreatment such as etching, corona discharge, plasma treatment, electron beam irradiation, or an adhesive can be applied in advance.
- pretreatment such as etching, corona discharge, plasma treatment, electron beam irradiation, or an adhesive can be applied in advance.
- Use inorganic materials such as silicon oxide, aluminum oxide, aluminum, and silicon nitride on the surface of plastic films; thin films such as metal compounds by vapor deposition, sputtering, and ion plating. Can do.
- the surface of the plastic film used as the substrate may be printed.
- the plastic film may be a multilayer film made of a multilayer film made of a plurality of plastic films or other materials such as paper.
- the plastic film may be an oxygen-absorbing resin composition film having oxygen-absorbing ability, or an oxygen-absorbing multilayer film of the film and another plastic film.
- any coating method such as spraying, dating, coating using a coater, printing using a printing machine, or the like is applied to one or both sides of the substrate.
- a coating method such as spraying, dating, coating using a coater, printing using a printing machine, or the like is applied to one or both sides of the substrate.
- gravure coaters such as direct gravure method, reverse gravure method, kiss reverse gravure method, offset gravure method;
- Various methods such as dip coater, bar coater, comma coater and die coater can be adopted.
- ⁇ , / 3-unsaturated carboxylic acid monomer is polymerized by irradiation with ionizing radiation, heating, or both.
- these polymerizable monomers are also polymerized along with the ⁇ , i3-unsaturated carboxylic acid monomer.
- the ionization of the wet coating film formed from the aqueous polymerizable monomer composition Upon irradiation with radiation and Z or heat treatment, ⁇ ,] 3-unsaturated carboxylic acid monomer is polymerized to form a polycarboxylic acid polymer.
- the resulting polycarboxylic acid polymer is ionically crosslinked by polyvalent metal ions.
- the ionically crosslinked polycarboxylic acid polymer forms a cured coating film. Since the cured coating film is a polycarboxylic acid polymer film ionically cross-linked with polyvalent metal ions, it retains the film shape even when it contains moisture, and exhibits good oxygen gas barrier properties.
- the oxygen gas barrier property can be further improved by removing water in the cured coating film.
- the moisture can be removed by heat-treating the cured coating film to volatilize the moisture, or allowing the moisture-permeable substrate to permeate through the moisture-permeable substrate. it can.
- the thickness of the wet coating film is usually 0.001 ⁇ i! ⁇ 1 mm, preferably 0 ⁇ 01 ⁇ : ⁇ ⁇ , more preferably 0.1 to 10 / zm.
- the coating amount of the water-based polymerizable monomer composition depends on the water content or the solid content concentration, but is preferably 0.01 to 1000 gZm 2, preferably 0.1 to L 00 gZm 2 or more. preferably from 1 ⁇ 80 g / m 2.
- ultraviolet rays, electron beams (beta rays), gamma rays, and alpha rays are preferable, and ultraviolet rays and electron beams are more preferable.
- To irradiate with ionizing radiation use a device that generates each radiation source.
- an accelerated electron beam usually extracted from an electron beam accelerator of 20 to 2000 kV is used.
- the irradiation dose of the accelerated electron beam is usually 1 to 300 kGy, preferably 5 to 200 kGy.
- the penetration depth of the electron beam into the irradiated object changes depending on the acceleration voltage. The higher the acceleration voltage, the deeper the electron beam penetrates.
- the adhesion between the substrate and the cured coating can be improved by the graft reaction of the ⁇ , ⁇ -unsaturated carboxylic acid monomer to the substrate such as a plastic film.
- UV irradiation equipment such as germicidal lamps, fluorescent lamps for ultraviolet rays, carbon arc, xenon lamps, low pressure mercury lamps, medium pressure mercury lamps, high pressure mercury lamps, ultra high pressure mercury lamps, metal halide lamps, and electrodeless lamps. Irradiate light with a wavelength range of 200 to 400 nm.
- the lamp input of the UV irradiation device is input per emission length l cm. Displayed in number of feet (WZ cm). As the number of knots per unit length increases, the generated ultraviolet intensity increases.
- the lamp input is usually selected from the range of 30 to 30 O WZ cm.
- the light emission length is usually selected from the range of 40 to 25 O mm.
- the wet coating film is usually 50 to 25 ° C, preferably 60 to 220 ° C, more preferably 70 °. Heat to ⁇ 200 ° C.
- the heating means include a method of heating the coating film using a heater, and a method of passing the coating film through a heating furnace whose temperature is controlled.
- the heating time is usually:! To 120 minutes, preferably 3 to 60 minutes, more preferably 5 to 30 minutes. From the viewpoint of gas barrier properties of the cured coating, it is preferable that the heating time is lengthened as the heating temperature is low and the heating time is shortened as the heating temperature is high.
- irradiation with ionizing radiation and Z or heat treatment is performed in an inert gas atmosphere such as nitrogen gas, carbon dioxide gas, or rare gas. It is preferable to carry out below.
- an inert gas atmosphere such as nitrogen gas, carbon dioxide gas, or rare gas. It is preferable to carry out below.
- the surface of the wet coating film formed on the base material (support) is covered with another base material (coating material). It is preferable to do.
- other base materials used as the coating material include, but are not limited to, a light transmissive plastic film, a glass plate, paper, and aluminum foil.
- the base material used as a support (hereinafter referred to as “base material 1”) and the base material used as a coating material (hereinafter referred to as “base material 2”) are not necessarily ionizing radiation. It is not necessary to use a permeable substrate.
- the base material 1 used as a support is an ionizing radiation transmissive base material and is irradiated with ionizing radiation such as ultraviolet rays from the back surface of the coating film (the back surface of the base material 1), it is used as a coating material.
- the base material 2 to be used it is not always necessary to use an ionizing radiation transparent base material.
- the wet state of the paint film is maintained by coating the wet paint film surface formed on the base material 1 (support) with another base material 2 (coating material).
- a light transmissive substrate such as a light transmissive plastic film or a glass plate
- the wet state of the paint film is maintained by coating the wet paint film surface formed on the base material 1 (support) with another base material 2 (coating material).
- the materials of Base 1 and Base 2 are the same or Different types may be used.
- the substrate 1 and the substrate 2 are an ionizing radiation transmitting substrate (for example, a light transmitting plastic film). It is more preferable to use an ionizing radiation transparent substrate as the substrate 2 for covering the surface.
- the light transmissive plastic film can be appropriately selected from the aforementioned plastic films that can be used as a support, such as a polyolefin film, a polyester film, and a polyamide film.
- the light transmissivity means a property capable of transmitting ionizing radiation such as ultraviolet rays, and the light transmittance is not limited.
- a plastic film that is transparent or translucent can be used as a light-transmitting plastic film.
- an ionizing radiation transmissive substrate that transmits an accelerating electron beam may be used, and the type of substrate may be a transparent or translucent substrate such as a light transmissive plastic film. It is not limited.
- a coating film of an aqueous polymerizable monomer composition is formed on a substrate (support) such as a plastic film or paper, and the surface of the coating film is immediately applied to another substrate (coating material). It is preferable to carry out continuous treatment by transporting to an ionizing radiation irradiation device and Z or a heating device while keeping the wet state of the coating film.
- the carrying speed can be appropriately set in consideration of the treatment efficiency at which the ion-bridged polycarboxylic acid polymer film produced can exhibit sufficient oxygen gas barrier properties by irradiation with ionizing radiation and / or heat treatment.
- a cured coating film can be formed by irradiation with ionizing radiation such as ultraviolet rays, and then heat treatment (additional heat treatment) can be performed. Additional heat treatment may also be performed when forming a cured coating by heating.
- the cured coating film is a polycarboxylic acid polymer film that is ion-crosslinked with polyvalent metal ions, so it retains the shape of the film even when it contains moisture, and exhibits good oxygen gas barrier properties. In such a case, the oxygen gas barrier property can be further improved by removing moisture in the cured coating film.
- the moisture in the cured coating film is volatilized through the base material 1 (support) and / or the base material 2 (coating material), but heat treatment can increase the water removal efficiency and removal speed. it can. Heat treatment is based on base material 1 and Or after the substrate 2 is peeled off.
- the cured coating should be treated at a temperature of typically 50-250 ° C, preferably 60-220 ° C, more preferably 70-200 ° C. To do.
- the treatment time depends on the heating temperature and other treatment conditions, but for continuous treatment, it is usually from 1 second to 60 minutes, preferably from 5 seconds to 30 minutes, more preferably from 10 seconds to 20 minutes. is there. This heat treatment
- the multilayer structure having the layer structure of “base material (support), wet film Z base material (coating material)” can be carried out in a dry heat atmosphere by conveying it into a heating furnace. It can also be carried out by bringing the structure into contact with a heating roll. When either one of the base materials is a glass plate or an aluminum foil, heat treatment can be performed after the base material is peeled off.
- a multilayer structure having a layer structure of “base material (support) Z wet coating Z base material (coating material)” is rolled. It can be carried out by leaving it in a heating furnace kept at a relatively low temperature (for example, a temperature of 30 to 180 ° C.) without being wound or wound.
- the standing time is not particularly limited and can be appropriately selected depending on the heat treatment temperature. However, from the viewpoint of production efficiency, a range of usually 30 minutes to 24 hours is preferable.
- Water can also be removed by leaving the multilayer structure for a long time at room temperature and humidity without performing the heat treatment. Also, moisture can be removed by leaving a container (bag, tray, tube, etc.) formed using a single-layer or multilayer gas barrier film in the atmosphere.
- the ionic crosslinked polycarboxylic acid polymer film of the present invention is excellent in oxygen gas barrier property. That is, ionically crosslinked Porikaruboshi acid polymer film of the present invention, temperature 30 ° C, the oxygen permeability measured at high humidity conditions of 80% relative humidity, usually 50 X 10- 4 cm 3 (STP ) / ( m 2 ⁇ s ⁇ MP a) or less, preferably 3 OX 10 1 4 cm 3 (STP) / (m 2 -s ⁇ MP a) or less, more preferably 20 X 10 _4 cm 3 (STP) / (m 2 ⁇ s ⁇ MP a), particularly preferably not more than 10 X 10- 4 cm 3 (STP ) / (m 2 - s ⁇ MP a) or less. In many cases, this oxygen permeability
- the lower limit of the oxygen permeability of the ion-crosslinked polycarboxylic acid polymer film of the present invention is usually
- the ion-crosslinked polycarboxylic acid polymer film (cured coating film) of the present invention peels the substrate or substrate 1 (support) and substrate 2 (coating material) to form a single-layer gas barrier film.
- Can be used as The ion-crosslinked polycarboxylic acid polymer film of the present invention can be used as a base material or a multilayer gas barrier film integrated with the base material 1 and / or the base material 2.
- a single layer of the ion-crosslinked polycarboxylic acid polymer film of the present invention or a multilayer gas barrier film having the ion-crosslinked polycarboxylic acid polymer film layer may be used integrally with other layers or molded articles. it can.
- Various methods including a lamination method and a coating method can be employed for integration with other layers or molded bodies. 6. Manufacturing method of multilayer gas barrier film:
- the multilayer gas barrier film having the layer structure of “base Z ion-crosslinked polycarboxylic acid polymer film” of the present invention can be obtained by the production method including the steps 1 and 2 described above.
- the method for producing the multilayer gas barrier film of the present invention includes the following steps I to III:
- Step II of coating the wet coating surface with another substrate 2 The wet coating film is treated with ionizing radiation and / or heating to polymerize the c, 3-unsaturated carboxylic acid monomer, and the resulting polymer is converted to a polyvalent metal.
- ionically cross-linked with ions temperature 3 0 ° C, a relative humidity of 80% for high Shimejo matter an oxygen permeability measured at the 5 0 X 1 0 - 4 cm 3 (STP) / (m 2 - s ⁇ MP a)
- a production method comprising the step III of forming the following ionically crosslinked polycarboxylic acid polymer film. Additional steps may be arranged between each step I to III or after step III.
- a multi-layer gas barrier film having a layer structure of “base material 1 Z ion-crosslinked polystrengthen polymer film base material 2” can be produced.
- paper or plastic film can be used as the substrate 1 (support) and the substrate 2 (coating material).
- the paper or plastic film may be a single layer or a multilayer, and may be a composite of paper and a plastic film. If necessary, the plastic film can be pretreated by etching, corona discharge, plasma treatment, electron beam irradiation, or pre-applied with an adhesive.
- the substrates 1 and 2 may be plastic films on which inorganic or metal thin films are formed. If necessary, the multilayer film of the present invention can be laminated with another plastic film, paper, metal foil or the like on the surface of the substrate 1 and / or the substrate 2 by a lamination method or a coating method. Further, an inorganic vapor deposition film such as a silicon oxide can be formed on the multilayer film of the present invention by a vapor deposition method.
- the ion-crosslinked polycarboxylic acid polymer film has various functions such as heat resistance, flex resistance, wear resistance, light shielding, heat sealability, oil resistance, etc. It can be used as a gas barrier packaging material. Even when the multi-layer gas barrier film is applied to uses other than packaging materials, a multi-layer structure suitable for each use can be obtained. For example, a multilayer film having heat sealability can be obtained by using a substrate 1 or 2 as a polyolefin film. By making the base material 1 or the base material 2 a polyester film or a polyamide film, a multilayer film excellent in heat resistance, wear resistance and the like can be obtained.
- base material 1 or base material 2 By using base material 1 or base material 2 as an aluminum vapor-deposited film or aluminum foil laminated film, light shielding properties and gas barrier properties are reduced. Can be further improved.
- the surface of the base material 1 or the base material 2 may be printed.
- the oxygen gas barrier property can be further improved by using the substrate 1 and / or the substrate 2 as an oxygen-absorbing film.
- a wet coating film formed using an aqueous polymerizable monomer composition containing an ⁇ , monounsaturated carboxylic acid monomer is irradiated with ionizing radiation or heated. In other words, the ⁇ , 3-unsaturated carboxylic acid monomer is polymerized to form a cured coating film.
- the adhesion between the resulting ion-crosslinked polycarboxylic acid polymer film and substrate 1 and substrate 2 is improved.
- the use of a hydrogen abstraction type photopolymerization initiator can further improve the adhesion to the substrate.
- c, j3 unsaturated force Cured coating (ion-crosslinked polycarboxylic acid polymer film) due to graft reaction of rubonic acid monomer to substrate 1 and / or substrate 2 The adhesion between the two can be improved.
- the multilayer gas barrier film of the present invention is a multilayer film having a layer structure of at least “base 1 ion-crosslinked polycarboxylic acid polymer film base 2”. It is preferable that one or both of the substrate 1 and the substrate 2 is a plastic film.
- the thickness of each layer can be appropriately determined according to the purpose of use. From the viewpoint of gas barrier properties, the thickness (dry thickness) of the ion-bridged polycarboxylic acid polymer film is usually from 0.001 m to l mm, preferably from 0.01 to: 100 ⁇ m. It is preferable to adjust so as to be in the range of 0.1 to 10.
- the base material 1 and the base material 2 is a plastic film
- the wet coating film is irradiated with ionizing radiation through the base material 1 and Z or the base material 2.
- a method for performing the treatment As the plastic film, a normal light-transmitting transparent or translucent plastic film can be used.
- the wet coated film surface formed on the substrate 1 is coated with the light-transmitting plastic film substrate 2, and in step III, the plastic film substrate 2 is passed through.
- the wet coating film is irradiated with ultraviolet rays or electron beams.
- Base material 1 and base material 2 may be the same type of base material or different types of base materials. Yes.
- Step IV for heat-treating the cured coating film can be further arranged as desired.
- the heat treatment conditions are the same as described above.
- the monolayer and multilayer gas barrier films of the present invention can be used as gas barrier packaging materials and packaging materials for heat sterilization.
- the gas barrier film of the present invention is particularly suitable as a packaging material for foods, beverages, medicines, pharmaceuticals, electronic parts, precision metal parts and the like that are susceptible to alteration by oxygen.
- the gas barrier film of the present invention can also be used as a vacuum heat insulating material.
- the shape of the package formed using the gas barrier film of the present invention include a flat bouch, a standing bouch, a buzz with a nozure, a pillow bag, a gusset bag, a shell-type packaging bag, and the like.
- the layer structure (type of base material) of the multilayer gas barrier film By selecting the layer structure (type of base material) of the multilayer gas barrier film, the package can be easily opened, easily torn, shrinkable, suitable for microwave ovens, UV shielding, oxygen absorption, design, etc. Can be granted.
- the shape of the packaging container formed using the gas barrier film of the present invention include bottles, trays, cups, and tubes.
- the gas barrier film of the present invention can also be used for applications such as packaging container lids and mouth seals.
- packaging container lids and mouth seals For these packaging containers and lids, by selecting the layer structure of the multilayer gas barrier film, easy opening, tearing, shrinkage, microwave oven suitability, UV shielding ability, oxygen absorption, designability Etc. can be given.
- As a method for forming a packaging bag or packaging container various methods employed in the technical field such as a heat-sealing method can be employed. Beauty example
- the oxygen permeability in the present invention is measured by the following measurement method.
- the oxygen permeability of the film is controlled by Modern Control 1) Using an oxygen permeability tester Oxtran (registered trademark) 220 made by the company, measurement was performed under the conditions of a temperature of 30 ° C. and a relative humidity of 80%. The measurement method was performed according to AS TM D 3 985-81 (corresponding to the JISK 7126 method). The unit of the measured value is cm 3 (STP) / (m 2 ⁇ s ⁇ MP a). “STP” means standard conditions (0 ° C, 1 atm) to define the volume of oxygen.
- the oxygen permeability of the multilayer film was measured in the state of the multilayer film. However, since the oxygen permeability of the film and paper used as the substrate is sufficiently large, the measured value is an ion-crosslinked polycarboxylic acid polymer. It can be evaluated that it substantially matches the oxygen permeability of the film.
- the plastic film used as the substrate is as follows.
- PET # 12 Polyethylene terephthalate film, Lumira (registered trademark) P 60 manufactured by Toray Industries, Inc., thickness 12 ⁇ ;
- OPP # 20 Biaxially stretched polypropylene film, Torayan (registered trademark) BO manufactured by Toray Industries, Inc., 20 m thick, single-sided corona-treated product;
- PE # 30 unstretched polyethylene film (LLDPE film), T. U. X (registered trademark) manufactured by Toseguchi Co., Ltd. — HC, thickness 30 / xm;
- Acrylic acid manufactured by Wako Pure Chemical Industries, Ltd.
- acid galvanized acid manufactured by Wako Pure Chemical Industries, Ltd.
- 16 g are dissolved in distilled water, and Benzofenone (manufactured by Wako Pure Chemical Industries, Ltd.) is added to 0.04 g.
- Benzofenone manufactured by Wako Pure Chemical Industries, Ltd.
- an aqueous polymerizable monomer composition No. 1 was obtained.
- the polyvalent metal ion of composition No. 1 was a divalent dumbbell ion, the content thereof was 0.93 g, and the chemical equivalent of zinc ion to the carboxyl group of acrylic acid was 0.69. .
- composition No. 1 had a solids concentration of 56% by weight and a water content of 44% by weight.
- the composition No. 1 is shown in Table 1.
- Examples 2 to 9 (Composition No. 2 to 9) Instead of 3.0 g of acrylic acid, ⁇ , —unsaturated carboxylic acid monomers shown in Table 1 were used, and the content of each component was Aqueous polymerizable monomer compositions No. 2 to 9 were obtained in the same manner as in Example 1 except that the changes were made as shown in Table 1.
- the types and sources of ⁇ , 13-unsaturated carboxylic acids used are acrylic acid (manufactured by Wako Pure Chemical Industries), methacrylic acid (manufactured by Wako Pure Chemical Industries), cinnamic acid (manufactured by Wako Pure Chemical Industries), senesic acid (manufactured by Aldrich) Tiglic acid (manufactured by Wako Pure Chemical Industries), sorbic acid (manufactured by Wako Pure Chemical Industries), itaconic acid (manufactured by Wako Pure Chemical Industries), maleic acid (manufactured by Wako Pure Chemical Industries), and citraconic acid (manufactured by Wako Pure Chemical Industries).
- the composition is shown in Table 1.
- Examples 10 and 1 1 (Composition No. 10-: L 1) Acrylic acid (manufactured by Wako Pure Chemical Industries) and zinc diacrylate (manufactured by Aldrich) are dissolved in distilled water, and benzophenone (Wako Pure Chemical Industries, Ltd.) is dissolved there. Were added to obtain water-based polymerizable monomer compositions No. 10 and 11. The composition is shown in Table 1.
- Examples 12-: 18 (Composition No. 12-: L 8) Acrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.) and the metal compound shown in Table 2 were dissolved in distilled water, and benzophenone (manufactured by Wako Pure Chemical Industries, Ltd.) was added thereto. By addition, water-based polymerizable monomer compositions No. 12 to 18 were obtained.
- each metal compound is calcium diacrylate (manufactured by Nippon Distillation Industry), copper diacrylate (manufactured by Nippon Distillation Industry), magnesium diacrylate (manufactured by Nippon Distillation Industry), aluminum acrylate (manufactured by Nippon Distillation Industry, A 1—AAP-3; a solution containing 17% by weight of an acrylic acid component and 8% by weight of an aluminum oxide component), iron oxide (III) (manufactured by Wako Pure Chemical Industries), and zinc diacrylate (manufactured by Aldrich).
- the composition is shown in Table 2.
- Example 1 9 (Composition No. 1 9)
- Acrylic acid (manufactured by Wako Pure Chemical Industries) and zinc oxide (manufactured by Wako Pure Chemical Industries, Ltd.) are dissolved in distilled water, benzophenone (manufactured by Wako Pure Chemical Industries, Ltd.) is added thereto, and an aqueous system polymerizable monomer composition No. 56 is added. Obtained. Composition No. 56 has a high solid content of 85% by weight (water content is 15% by weight). The composition is shown in Table 3.
- Randomness Code Type 4 (g) 4 (g) Type Amount (g) * (g) (g) (g) Type Amount (g) Chemical Equivalent (wt.%) No.
- the coating solution having the same composition as the water-based polymerizable monomer composition No. 1 prepared above is used on a polyethylene terephthalate film (PET # 12).
- the coating was carried out with a bar having a wet coating amount (wetg / m 2 ) of 12 gZm 2 .
- a biaxially stretched 6 nylon film (ONy # 1 5) is applied to the surface of the coating film, and a multilayer structure with a “substrate (PET) wet coating / substrate (ONy)” layer structure is provided. A structure was obtained.
- UV irradiation device manufactured by Nihon Batteries
- the multilayer structure After irradiation, the multilayer structure is heat-treated in a gear oven at 120 ° C for 5 minutes to obtain a multilayer film having a polycarboxylic acid polymer film (gas barrier film) ion-crosslinked with zinc ions in the intermediate layer. It was. The oxygen permeability of the multilayer film was measured.
- Table 4 shows the layer structure, UV irradiation conditions, heat treatment conditions, and oxygen permeability. In the following Examples and Comparative Examples, unless otherwise specified, coating was performed using the same table coater as described above, and when irradiating ultraviolet rays, the same UV irradiation apparatus as described above was used. Examples 23-27
- a coating solution having the same composition as the aqueous polymerizable monomer composition No. 7 prepared above was applied onto a polyethylene terephthalate film (PET # 12) using a desktop coater at a wet coating amount of 24 g. Apply with m 2 bar and quickly extend 2 axes An expanded polypropylene film (OPP # 20) was placed on the surface of the coating film to obtain a multilayer structure having a layer structure of “substrate (PET) / wet coating film / substrate (OPP)”.
- UV on the base material (OPP) of the above multi-layered structure with UV irradiation device (COMPACT UV CONVEYOR CS0T-40 manufactured by Nihon Battery Co., Ltd.) with lamp output of 160 W / cm, transfer speed of 10 m / min, and lamp height of 24 cm Irradiated with light.
- heat treatment was performed with a gear oven at 80 ° C. for 10 minutes to obtain a multilayer film having a gas barrier film in the middle.
- the oxygen permeability of the multilayer film was measured.
- Table 4 shows the layer structure, UV irradiation conditions, heat treatment conditions, and oxygen permeability. Examples 29 and 30
- each coating solution having the same composition as each of the aqueous polymerizable monomer compositions No. 8 and 9 was used. Except for the above, a multilayer film having a gas barrier film as an intermediate layer was produced in the same manner as in Example 28 and evaluated in the same manner. Table 4 shows the layer structure, UV irradiation conditions, heat treatment conditions, and oxygen permeability.
- Example 22 PET # 12 No. 1 12 ONy # 15 120 5 120 5 IX 10-4 Example 23 PET # 12 No. 2 12 ONy # 15 120 5 120 5 10 X 10-4 Example 24 PET # 12 No 3 12 ONy # 15 120 5 120 5 14X 10-4 Example 25 PET # 12 No. 4 12 ONy # 15 120 5 120 5 15 X 10-4 Example 26 PET # 12 No. 5 12 ONy # 15 120 5 120 5 15 X 10-4 Example 27 PET # 12 No. 6 12 ONy # 15 120 5 120 5 15 X 10-4 Example 28 PET # 12 No. 7 24 OPP # 20 160 10 80 10 4 X 10 -4 Example 29 PET # 12 No. 8 24 OPP # 20 160 10 80 10 5 X 10-4 Example 30 PET # 12 No. 9 24 OPP # 20 160 10 80 10 5 X 10-4
- UV light was irradiated from above the substrate (PE) of the multilayer structure with a UV irradiation device under the conditions of a lamp output of 80 W / cm and a conveying speed of SmZm i ru lamp height of 24 cm.
- heat treatment was performed in a gear oven at 70 ° C. for 15 minutes to obtain a multilayer film having a gas barrier film as an intermediate layer.
- Table 5 shows the layer structure, UV irradiation conditions, heat treatment conditions, and oxygen permeability. Examples 32-37
- each coating solution having the same composition as each of the aqueous polymerizable monomer compositions No. 1 to 16 was used.
- a multilayer film having a gas barrier film as an intermediate layer was prepared in the same manner as in Example 31, and evaluated in the same manner. Table 5 shows the layer structure, UV irradiation conditions, heat treatment conditions, and oxygen permeability.
- a coating solution having the same composition as the water-based polymerizable monomer composition No. 17 is coated on a polyethylene terephthalate film (PET # 12) using a desktop coater with a wet coating amount of 6 gZm 2 .
- UV light is irradiated from above the base material (CPP) of the multilayer structure with a UV irradiation device under the conditions of a lamp output of 120 WZcm, a conveyance speed of 10 mmin, and a lamp height of 24 cm, and then in a gear oven at 1 10 ° C. Heat treatment was performed for 3 minutes to obtain a multilayer film having a gas barrier film as an intermediate layer.
- Layer composition, UV irradiation conditions, heat treatment conditions, and oxygen permeability Table 5 shows. Examples 39 and 40
- each coating liquid having the same composition as each of the aqueous polymerizable monomer compositions No. 18 and 19 is used.
- a multilayer film having a gas barrier film as an intermediate layer was prepared in the same manner as in Example 38 except that the same was evaluated.
- Table 5 shows the layer structure, UV irradiation conditions, heat treatment conditions, and oxygen permeability.
- a coating solution having the same composition as the water-based polymerizable monomer composition No. 20 is applied onto a polyethylene terephthalate film (PET # 12) using a desktop coater at a wet coating amount of 12 g / m. Apply with the bar 2 and immediately coat the biaxially stretched 6 nylon film ( ⁇ Ny # 15) on the surface of the coating, and the layer of “substrate (PET) / wet coating / substrate (ONy)” A multilayer structure with composition was obtained.
- the multilayer structure base material (ONy) is irradiated with UV light using a UV irradiation device under the conditions of a lamp output of 120 W / cm, a conveyance speed of 10 m Zmin, and a lamp height of 24 cm, and then in a gear oven.
- a multilayer film having a gas barrier film as an intermediate layer was obtained by heat treatment at ° C for 3 minutes.
- Table 5 shows the layer structure, UV irradiation conditions, heat treatment conditions, and oxygen permeability.
- Example 41 a multilayer film having a gas barrier film as an intermediate layer was prepared and evaluated in the same manner.
- Table 5 shows the layer structure, UV irradiation conditions, heat treatment conditions, and oxygen permeability.
- Base material 1 Base material 2 Lamp output Conveying speed Temperature 30r / 80% RH
- Example 46 instead of the unstretched polyethylene film (PE # 30) as the base material (coating material) to be coated on the coating surface, use a biaxially stretched polypropylene film (OPP # 20) or a biaxially stretched 6 nylon film (ONy # 15).
- a multilayer film having a gas barrier film as an intermediate layer was obtained in the same manner as in Example 43, except that it was used.
- Table 6 shows the layer structure, UV irradiation conditions, heat treatment conditions, and oxygen permeability.
- Example 22 a multilayer film having a gas barrier film as an intermediate layer was obtained in the same manner as in Example 22 except that the conveyance speed was changed from ⁇ in to ZmZmin and heat treatment after UV irradiation was not performed. Produced. Table 6 shows the layer structure, UV irradiation conditions, heat treatment conditions, and oxygen permeability. Examples 47 and 48
- Example 46 and Example 46 except that the base material (coating material) was changed from biaxially stretched 6 nylon film (ONy # 15) to unstretched polypropylene film (CPP # 60) or unstretched polyethylene film (PE # 30).
- base material coating material
- CPP # 60 unstretched polypropylene film
- PE # 30 unstretched polyethylene film
- Table 6 shows the layer structure, UV irradiation conditions, heat treatment conditions, and oxygen permeability. Comparative Example 7
- Example 6 In place of the coating solution having the same composition as the aqueous polymerizable monomer composition No. 1, a coating solution having the same composition as the aqueous polymerizable monomer composition No. 5 1 is used, and the UV irradiation conditions A multilayer film was produced in the same manner as in Example 22 except that the heat treatment conditions were changed as shown in Table 6.
- Table 6 shows the layer structure, UV irradiation conditions, heat treatment conditions, and oxygen permeability. From the results shown in Table 6, it can be seen that the polyacrylic acid film not ionically crosslinked has insufficient oxygen gas barrier properties. That is, the polyacrylic acid film does not exhibit sufficient oxygen gas barrier properties under high humidity conditions. Comparative Example 8
- Example 6 a coating solution having the same composition as the water-based polymerizable monomer composition No. 52 is used, and the UV irradiation conditions and heat treatment conditions are shown in Table 6.
- Table 6 shows the layer structure, UV irradiation conditions, heat treatment conditions, and oxygen permeability. From the results shown in Table 6, it can be seen that the film without unsaturated carboxylic acid has insufficient oxygen gas barrier properties. Comparative Example 9
- a multilayer film was produced in the same manner as in Example 22 except that UV irradiation was not performed.
- the coating film remained in solution, and the resulting multilayer film had poor oxygen gas barrier properties. Comparative Example 1 0
- the coating liquid having the same composition as that of the aqueous polymerizable monomer composition No. 53 was used in place of the coating liquid having the same composition as that of the aqueous polymerizable monomer composition No. 1.
- a multilayer film was produced in the same manner as in Example 22.
- Layer structure, UV irradiation condition Table 6 shows the conditions, heat treatment conditions, and oxygen permeability.
- the coating liquid having the same composition as the aqueous polymerizable monomer composition No. 5 4 was used in place of the coating liquid having the same composition as that of the aqueous polymerizable monomer composition No. 1.
- a multilayer film was produced in the same manner as in Example 22.
- Table 6 shows the layer structure, UV irradiation conditions, heat treatment conditions, and oxygen permeability. From the results shown in Table 6, it can be seen that the ion-crosslinked polycarboxylic acid film with insufficient ion crosslinking has insufficient oxygen gas barrier properties. Comparative Example 1 2
- the coating liquid having the same composition as the aqueous polymerizable monomer composition No. 5 5 was used in place of the coating liquid having the same composition as that of the aqueous polymerizable monomer composition No. 1.
- a multilayer film was produced in the same manner as in Example 22.
- Table 6 shows the layer structure, UV irradiation conditions, heat treatment conditions, and oxygen permeability.
- the ion-crosslinked polycarboxylic acid film formed using a water-based polymerizable monomer composition (coating solution) with a low solid content concentration had gel deposited in the coating film, and a homogeneous film could not be obtained. . Further, this multilayer film had poor oxygen gas barrier properties. Comparative Example 1 3
- the coating liquid having the same composition as the aqueous polymerizable monomer composition No. 5 6 was used in place of the coating liquid having the same composition as that of the aqueous polymerizable monomer composition No. 1.
- a multilayer film was produced in the same manner as in Example 22. Table 6 shows the layer structure, UV irradiation conditions, heat treatment conditions, and oxygen permeability.
- a water-based polymerizable monomer composition (coating solution) with a high solid content concentration is a slurry-like solution that is difficult to coat. It was difficult.
- the film formed using this coating solution became whitish during UV irradiation, and a powdery gel was deposited.
- This multilayer film had poor oxygen gas barrier properties.
- Base material 1 Base material 2 Lamp output Conveyance speed Temperature Time 30t: / 80% RH
- Example 43 Paper No. 1 12 PE # 30 120 10 90 1 2 X 10-4 Example 44 Paper No. 1 12 OPP # 20 120 10 90 1 2 X 10-4 Example 45 Paper No. 1 12 ONy # 15 120 10 90 1 2 X 10-4 Example 46 PET # 12 No. 1 12 ONy # 15 120 2--2 X 10-4 Example 47 PET # 12 No. 1 12 CPP # 60 120 2--2 X 10-4 Example 48 PET # 12 No. 1 12 PE # 30 120 2--2 X 10-4 Comparative Example 7 PET # 12 No. 51 12 ONy # 15 120 10 120 5 1 X 10-2 Comparative Example 8 PET # 12 No. 52 12 ONy # 15 120 10 120 5 IX 10-2 Comparative Example 9 PET # 12 No.
- Example 54 Acrylic acid 0.95 Zinc diacrylate 2.92-3.23 7.10 Zn "0.92 0.68 54 No.27
- Example 56 Atalic acid 0.36 Diacrylic Magnesium acid 1.44-5.01 6.80 Mg + 2 0.21 0.78 26 No.29
- Example 57 Atalic acid 2.05 A1-AA P-3 5.00-2.94 10.00 Al + 3 0.20 0.55 31 No.30 Ducyl diacrylate 2.85 Zn + 2 0.90
- a 1-AAP-3 A solution containing aluminum acrylate, 7% by weight of acrylic acid component and 8% by weight of aluminum oxide component, manufactured by Nippon Distilled Industries.
- Example 59 A solution containing aluminum acrylate, 7% by weight of acrylic acid component and 8% by weight of aluminum oxide component, manufactured by Nippon Distilled Industries.
- the multilayer structure After irradiation, the multilayer structure is heat-treated at 180 ° C for 15 minutes in a gear oven to obtain a multilayer film having a polycarboxylic acid polymer film (gas barrier film) ion-crosslinked with zinc ions in the intermediate layer. It was. The oxygen permeability of the multilayer film was measured. Table 8 shows the layer structure, EB irradiation conditions, heat treatment conditions, and oxygen permeability. In the following examples and comparative examples, when performing electron beam irradiation, the same EB irradiation apparatus as described above was used. Examples 60-69
- each coating liquid having the same composition as each of the aqueous polymerizable monomer compositions No. 23 to 31 is used. Except that the types of Substrate 1 and Z or Substrate 2, coating amount, EB irradiation acceleration voltage and irradiation dose, and heat treatment conditions were changed as shown in Table 8, they were the same as Example 59.
- a multilayer film having an ion-crosslinked polycarboxylic acid polymer film as an intermediate layer was prepared and evaluated in the same manner. In Example 69, heat treatment after EB irradiation was not performed. Table 8 shows the layer structure, EB irradiation conditions, heat treatment conditions, and oxygen permeability.
- Base material 1 Base material 2 Acceleration voltage Transport speed Irradiation dose Temperature Time 30/80% RH
- Example 64 OPP # 20 No. 27 12 CPP # 60 150 10 100 80 3 5 10-4
- Example 65 OPP # 20 No.28 12 CPP # 60 150 10 100 80 3 12x10-4
- Example 66 OPP # 20 No.29 12 CPP # 60 150 10 100 80 3 34x10-4
- the multilayer finalome of the present invention containing a ion-crosslinked polycarboxylic acid polymer film layer obtained by EB irradiation is excellent in oxygen gas barrier properties.
- An ion-crosslinked polycarboxylic acid film having insufficient ion crosslinking (Comparative Example 17) has insufficient oxygen gas barrier properties.
- the ion-crosslinked polystrengthen rubonic acid film (Comparative Example 18) formed using a water-based polymerizable monomer composition having a low solid content concentration has a gel deposited in the coating film, and a homogeneous film cannot be obtained. It was. This multilayer film had poor oxygen gas barrier properties.
- the aqueous polymerizable monomer composition No. 56 having a high solid content concentration was a slurry-like solution and was difficult to coat.
- the film formed using this coating solution (Comparative Example 19) whitened during EB irradiation, and a powdered gel was deposited.
- This multilayer film had poor oxygen gas barrier properties.
- Examples 70 to 78 (Composition Nos. 32 to 40) As shown in Table 9, various unsaturated carboxylic acids and metal compounds were dissolved in distilled water, and water-based polymerizable monomer compositions No. 32 to Got 40. The source of each component is the same as above. The composition is shown in Table 9. Comparative Examples 20 to 25 (Composition No.
- Example 70 Acrylic acid 0.80 Magnesium diacrylate 3.10 Benzoph; rNon 0.04 4.50 8.44 M +2 0.45 0.77 47 No.32
- Example 71 Acrylic acid 0.55 Calcium diacrylate 0.95 Benzophenone 0.01 5.48 6.99 Ca + 2 0.21 0.58 22 No.33
- Example 72 Acrylic acid 3.10 Copper diacrylate 1.50 Benzophenone 0.01 9.20 13.81 Cu "0.46 0.25 33 No.34
- Example 73 Acrylic acid 1.40 Zinc diacrylate 2.80 Benzophenone 0.02 5.00 9.22 Zn + 2 0.93 0.61 46 No.35
- Example 74 Atallic acid 2.50 ZnO 1.00 Benzophenone 0.02 2.00 5.52 Zn + 2 0.80 0.71 64 No.36
- Example 75 Methacrylic acid 5.43 Iron (III) oxide 0.96 Benzophenone 0.02 8.65 15.06 Fe
- a 1-AAP-3 A solution containing aluminum acrylate, 7% by weight of acrylic acid component and 8% by weight of aluminum oxide component, manufactured by Nippon Distilled Industries.
- the multilayer structure was heat-treated in a gear oven at 120 ° C for 5 minutes to obtain a multilayer film containing a polystrength sulfonic acid polymer film (gas barrier film) ion-crosslinked with magnesium ions. It was. The oxygen permeability of the multilayer film was measured.
- Table 10 shows the layer structure, UV irradiation conditions, heat treatment conditions, and oxygen permeability. In the following Examples and Comparative Examples, the same UV irradiation apparatus as described above was used unless otherwise specified.
- Example 82 a coating solution having the same composition as the aqueous polymerizable monomer composition No. 32, a coating solution having the same composition as each of the aqueous polymerizable monomer compositions No. 33 and 34 was used. Except for this, a multilayer film was produced under the same conditions as in Example 79 and evaluated in the same manner. Table 10 shows the layer structure, UV irradiation conditions, heat treatment conditions, and oxygen permeability.
- Example 82 shows the layer structure, UV irradiation conditions, heat treatment conditions, and oxygen permeability.
- Example 83 Using a coating liquid having the same composition as the aqueous polymerizable monomer composition No. 35 On a biaxially stretched 6 nylon film (ONy # 15) with a wet coating weight of 24 gZm 2 and a lamp output of 16 Ow / cm, transport speed of 5 m / min, lamp height The coating film was irradiated with ultraviolet rays at a thickness of 24 cm. No heat treatment was performed after irradiation. Table 10 shows the layer structure, UV irradiation conditions, and oxygen permeability. Example 83
- Example 84 Using a coating solution having the same composition as the aqueous polymerizable monomer composition No. 36, apply a wet coating weight of 24 gZm 2 on a glass plate, and immediately after coating. A biaxially stretched 6 nylon film (ONy # 15) was applied to the surface of the coating film to obtain a multilayer structure having a layer configuration of “glass plate Z wet coating film Z substrate (ONy)”. Next, ultraviolet rays were irradiated from above the substrate (ONy) at a lamp output of 160 w / cm, a conveyance speed of 5 m / min, and a lamp height of 24 cm. After irradiation, the glass plate was peeled off. No heat treatment was performed. The oxygen permeability of the multilayer film was measured. Table 10 shows the layer structure, UV irradiation conditions, and oxygen permeability. Example 84
- Example 85 a coating solution having the same composition as that of the aqueous polymerizable monomer composition No. 36 is used. Instead, a coating solution having the same composition as that of the aqueous polymerizable monomer composition No. 37 is used. Instead, a multilayer film was obtained under the same conditions as in Example 83 except that aluminum foil was used, and the oxygen permeability was evaluated. Table 10 shows the layer structure, UV irradiation conditions, and oxygen permeability. Example 85
- a wet coating amount of 12 g / m 2 on an unstretched polyethylene film (PE # 30). was applied to obtain a multilayer structure having the layer structure of “substrate (PE) wet film”.
- UV light was irradiated from above the wet film under the conditions of a lamp output of 12 OW / cm and a conveying speed of ZmZm in lamp height of 24 cm.
- the multilayer structure was heat treated in a gear oven at 80 ° C for 1 minute to obtain a multilayer film.
- the oxygen permeability of the multilayer film was measured. Table 10 shows the layer structure, UV irradiation conditions, heat treatment conditions, and oxygen permeability. Examples 86-87
- a coating liquid having the same composition as each of the aqueous polymerizable monomer compositions No. 39 and 40 is used.
- a laminated film was prepared and evaluated in the same manner. Table 10 shows the layer structure, UV irradiation conditions, heat treatment conditions, and oxygen permeability. Comparative Examples 26-31
- a coating solution having the same composition as each of the aqueous polymerizable monomer compositions No. 57 to 62 was used in place of the coating liquid having the same composition as that of the aqueous polymerizable monomer composition No. 32.
- a film was produced in the same manner as in Example 79 except for the above.
- Table 10 shows the layer structure, UV irradiation conditions, heat treatment conditions, and oxygen permeability.
- Base material 1 Base material 2 Lamp output Conveyance speed Temperature 30 ° C / 80% RH
- Example 80 PET # 12 No.33 6-120 5 120 5 4x10-4
- Example 81 PET # 12 No.34 6-120 5 120 5 22x10-4
- Example 82 ONy # 15 No.35 24-160 5--8x10-4
- Example 83 Glass plate No.36 24 ONy # 15 160 5-.-5x10-4
- Example 84 Aluminum foil No.37 24 ONy # 15 160 5--20x10-4
- Example 86 CPP # 60 No.39 12-120 2 80 1 11x10-4
- Example 87 OPP # 20 No.40 12-120 2 80 1 1 x10-4 Comparative Example 26 PET # 12 No.57 6-120 5 120 5 IX 10-2 Comparative Example 27 PET # 12 No.58 6-120 5 120 5 1 10-2 Comparative Example 28 PET # 12 No.59 6-120 5 120 5 lx 10-2 Comparative Example 29 PET # 12 No.60 6-120 5 120 5 1x10-2
- Example 83 after the UV irradiation, the glass plate was peeled off, and the oxygen transmission rate was measured.
- Example 84 after the UV irradiation, the aluminum foil was peeled off and then the oxygen permeability was measured. As is clear from the results shown in Table 10, the multilayer film of the present invention containing an ion-bridged polycarboxylic acid polymer film layer obtained by UV irradiation is excellent in oxygen gas barrier properties.
- the aqueous polymerizable monomer composition No. 62 with a high solid content concentration was a slurry-like solution and was difficult to coat. It can be seen that the film formed using this coating solution (Comparative Example 31) has insufficient oxygen gas barrier properties.
- Examples 8 8 to 9 4 Composition No. 4 1 to 4 7) As shown in Table 11, various unsaturated carboxylic acids and metal compounds were dissolved in distilled water, and water-based polymerizable monomers were used. Compositions No. 4 1-4 were obtained. The source of each component is the same as above. The composition is shown in Table 11. Table 1 1
- the multilayer structure After irradiation, the multilayer structure is heat-treated in a gear oven at 180 ° C for 15 minutes to produce a multilayer film with a polycarboxylic acid polymer film ion-crosslinked with zinc ions, and its oxygen permeability is measured. did.
- Table 12 shows the layer structure, EB irradiation conditions, heat treatment conditions, and oxygen permeability. Examples 96-97
- Example 98 a coating liquid having the same composition as that of the water-based polymerizable monomer composition No. 41, a coating liquid having the same composition as that of the water-based polymerizable monomer composition No. 42 or No. 43 is used.
- a multilayer film was produced in the same manner as in Example 95 except that the coating amount and the heat treatment conditions were changed as shown in Table 12, and the oxygen permeability was measured.
- Table 12 shows the layer structure, EB irradiation conditions, heat treatment conditions, and oxygen permeability.
- a coating liquid having the same composition as that of the water-based polymerizable monomer composition No. 44 apply a wet coating weight of 12 g / m 2 on a glass plate. After that, a biaxially stretched 6 nylon film (ONy # 15) was immediately covered on the surface of the coating to obtain a multilayer structure having a layer configuration of “glass plate / wet coating / substrate (ONy)”. . Next, an electron beam was irradiated from above the glass plate under the conditions of an acceleration voltage of 250 kV, a transfer speed of 1 Om / min, and an irradiation dose of 100 kGy.
- Example 99 After irradiation, the multilayer structure was heat-treated in a gear oven at 70 ° C for 15 minutes. Then, after peeling a glass plate, the oxygen permeability of the multilayer film was measured. Table 12 shows the layer structure, EB irradiation conditions, heat treatment conditions, and oxygen permeability. Example 99
- Example 100 a coating solution having the same composition as that of the aqueous polymerizable monomer composition No. 44, a coating solution having the same composition as that of the aqueous polymerizable monomer composition No. 45 is used, and a glass plate is used. Instead of this, a multilayer film was obtained under the same conditions as in Example 98 except that an aluminum foil was used, and the oxygen permeability was evaluated. Table 12 shows the layer structure, EB irradiation conditions, heat treatment conditions, and oxygen permeability.
- Example 100 shows the layer structure, EB irradiation conditions, heat treatment conditions, and oxygen permeability.
- the coating solution having the same composition as the water-based polymerizable monomer composition No. 46 prepared above was placed on a biaxially stretched polypropylene film (OPP # 20) in a wet state using a desktop coater. Coating was carried out with a bar having a coating amount of 6 g / m 2 to obtain a multilayer structure having a layer structure of “substrate (OP P) / wet coating film”.
- an EB irradiation device is used to irradiate an electron beam under the conditions of an acceleration voltage of 150 kV, a transfer speed of 1 Om / min, and an irradiation dose of 100 kGy, and then ion-crosslinked polycarboxylic acid polymer layer.
- a multilayer film with was obtained. No heat treatment was performed after irradiation. The oxygen permeability of the multilayer film was measured. Table 12 shows the layer structure, EB irradiation conditions, and oxygen permeability.
- Example 101 shows the layer structure,
- the coating liquid having the same composition as the aqueous polymerizable monomer composition No. 47 was used in place of the coating liquid having the same composition as that of the aqueous polymerizable monomer composition No. 46.
- a multilayer film was produced in the same manner as in Example 100 and evaluated in the same manner.
- Table 12 shows the layer structure, EB irradiation conditions, and oxygen permeability. Comparative Examples 32-37
- each coating solution having the same composition as each of the aqueous polymerizable monomer compositions No. 57 to 62 is used.
- a multilayer film was prepared in the same manner as in Example 96 except that Evaluation was performed in the same manner.
- Table 12 shows the layer structure, EB irradiation conditions, heat treatment conditions, and oxygen permeability.
- Example 98 after the heat treatment, the glass plate was peeled off, and the oxygen permeability was measured.
- Example 99 the oxygen permeability was measured after the aluminum foil was peeled off after the heat treatment.
- the multilayer film of the present invention (Examples 95 to 101) is excellent in oxygen gas barrier properties.
- the water-based polymerizable monomer composition No. 62 having a high solid content concentration was a slurry-like solution and was difficult to coat. It can be seen that the film formed using this coating solution (Comparative Example 37) has insufficient oxygen gas barrier properties.
- Example 102 Composition No. 48
- the polyvalent metal ion is divalent zinc ion
- the content is 1.OO g
- the chemical equivalent of zinc ion to the power lpoxyl group of attalic acid is 0.74. It was.
- the total amount of this composition is 7.64 g, the amount of water is 3.40 g (48% by weight)
- the solid content concentration was 52% by weight.
- the aqueous polymerizable monomer composition prepared in Example 102 contains a thermal polymerization initiator.
- Example 103
- a coating liquid having the same composition as the polymerizable monomer composition No. 48 prepared above was applied onto a polyethylene terephthalate film (PET # 12) using a desktop coater with a wet coating amount of 1 Coating was done with a 2 g / m 2 bar. After coating, quickly coat the biaxially stretched 6 nylon film (ONy # 1 5) on the surface of the coating, and the layer structure of “base (PET) / wet coating / substrate (ONy)” A multilayer structure with Next, the multilayer structure was heated with the gear open at 180 ° C. for 15 minutes to obtain a multilayer film. The oxygen permeability of the multilayer film was 16 ⁇ 10 4 cm 3 (STP) / (m 2 ⁇ s ⁇ MP a).
- Example 103 is an experimental example in which a multilayer film having an ion-crosslinked polycarboxylic acid polymer layer was prepared by performing a polymerization process by heating.
- a single-layer or multi-layer gas barrier film having excellent gas barrier properties and good use resistance as a packaging material can be obtained by a simple process.
- the aqueous polymerizable monomer composition of the present invention is excellent in uniform solubility or dispersibility of each component, and can form a coating film having a uniform composition and thickness.
- Polymerization reaction of ⁇ , 3_unsaturated carboxylic acid is performed by irradiating or heating a wet coating film formed using the aqueous polymerizable monomer composition of the present invention with ionizing radiation.
- the ion-crosslinked polycarboxylic acid polymer film having excellent gas barrier properties can be continuously produced without causing problems such as gel precipitation and whitening. According to the production method of the present invention, it is possible to obtain a multi-layered gas parallax film excellent in adhesion between the produced ion-crosslinked polycarboxylic acid polymer film and a base material layer such as another plastic film.
- the gas barrier film of the present invention is a food, beverage, It can be used as packaging material for chemicals, pharmaceuticals, electronic parts, precision metal parts, etc.
- Examples of the gas barrier film of the present invention include flat bags, standing pouches, pouches with nozzles, pillow bags, gusset bags, and shell-type packaging bags; packaging containers such as bottles, cups, trays, and tubes; It can be used after being processed into a shape.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Toxicology (AREA)
- Wood Science & Technology (AREA)
- General Chemical & Material Sciences (AREA)
- Laminated Bodies (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Chemically Coating (AREA)
- Paints Or Removers (AREA)
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE602005019467T DE602005019467D1 (de) | 2004-12-01 | 2005-11-30 | Polymerisierbares monomer enthaltende wässrige zusammensetzung, gasbarrierefolie und herstellungsverfahren dafür |
JP2006546714A JP4788602B2 (ja) | 2004-12-01 | 2005-11-30 | 水系重合性単量体組成物から形成されたガスバリア性フィルム及び該フィルムの製造方法 |
EP05814368A EP1829902B1 (en) | 2004-12-01 | 2005-11-30 | Aqueous polymerizable monomer composition, gas-barrier film, and method for producing such film |
US11/792,051 US8158213B2 (en) | 2004-12-01 | 2005-11-30 | Aqueous polymerizable monomer composition, gas barrier film and production process of the film |
AT05814368T ATE458012T1 (de) | 2004-12-01 | 2005-11-30 | Polymerisierbares monomer enthaltende wässrige zusammensetzung, gasbarrierefolie und herstellungsverfahren dafür |
Applications Claiming Priority (2)
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JP2004349002 | 2004-12-01 | ||
JP2004-349002 | 2004-12-01 |
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WO2006059773A1 true WO2006059773A1 (ja) | 2006-06-08 |
Family
ID=36565197
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PCT/JP2005/022399 WO2006059773A1 (ja) | 2004-12-01 | 2005-11-30 | 水系重合性単量体組成物、ガスバリア性フィルム及び該フィルムの製造方法 |
Country Status (6)
Country | Link |
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US (1) | US8158213B2 (ja) |
EP (1) | EP1829902B1 (ja) |
JP (2) | JP4788602B2 (ja) |
AT (1) | ATE458012T1 (ja) |
DE (1) | DE602005019467D1 (ja) |
WO (1) | WO2006059773A1 (ja) |
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Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS51141808A (en) | 1975-05-29 | 1976-12-07 | Asada Kagaku Kogyo Kk | Process for preparation of reactive carboxylic acid divalent metal com plexes |
JPH0853389A (ja) | 1994-03-04 | 1996-02-27 | Sartomer Co Inc | 水系硬化性および硬化組成物並びに塗料または接着剤の基材への付着方法 |
JP2002003256A (ja) * | 2000-03-22 | 2002-01-09 | Sika Ag | 高流動性で、高強度でかつ自己緊結性コンクリートのためのセメント分散性ポリマー |
WO2002020068A1 (de) * | 2000-09-04 | 2002-03-14 | Stockhausen Gmbh & Co. Kg | Pulverförmige, vernetzte, wässrige flüssigkeiten sowie blut absorbierende polymere |
JP2002080502A (ja) * | 2000-07-07 | 2002-03-19 | Nippon Shokubai Co Ltd | 低分子量(メタ)アクリル酸(塩)系重合体、その製造方法および用途 |
JP2003057185A (ja) * | 2001-08-10 | 2003-02-26 | Idemitsu Petrochem Co Ltd | 酸素ガス検知材料とその製造法 |
JP2003128804A (ja) * | 2001-10-26 | 2003-05-08 | Toyo Ink Mfg Co Ltd | ガスバリア性フィルム及び該フィルムの製造方法 |
JP2003286349A (ja) | 2001-01-29 | 2003-10-10 | Nippon Kayaku Co Ltd | 成形体 |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3067180A (en) * | 1958-11-28 | 1962-12-04 | Int Latex Corp | Carboxylic elastomers |
US4072528A (en) * | 1972-09-27 | 1978-02-07 | E. I. Du Pont De Nemours And Company | Oxygen barrier layers for photopolymerizable elements |
DE3114266A1 (de) * | 1981-04-09 | 1982-11-04 | Röhm GmbH, 6100 Darmstadt | Verfahren zur herstellung vernetzter acrylelastomerer |
JPH06397B2 (ja) * | 1988-08-10 | 1994-01-05 | ダイニック株式会社 | 高吸水性シートおよびその製法 |
JPH0689050B2 (ja) * | 1989-06-19 | 1994-11-09 | 株式会社トクヤマ | 硬化性組成物 |
JP3021603U (ja) * | 1995-08-11 | 1996-02-27 | 有限会社ジャパン・アート・オリジン | 看 板 |
US6361925B1 (en) * | 1996-03-04 | 2002-03-26 | Ciba Specialty Chemicals Corporation | Photoinitiator mixtures and compositions with alkylphenylbisacylphosphine oxides |
US6218465B1 (en) * | 1997-03-05 | 2001-04-17 | Nippon Shokubai Co., Ltd. | Crosslinked elastomer and producing process thereof |
TWI236483B (en) * | 2000-07-07 | 2005-07-21 | Nippon Catalytic Chem Ind | Low molecular weight (methyl) acrylic acid (acrylate) polymer and preparation process and use thereof |
AU2003235098C1 (en) * | 2002-04-23 | 2008-06-05 | Toppan Printing Co., Ltd. | Film and process for producing the same |
TWI411618B (zh) * | 2004-05-10 | 2013-10-11 | Tohcello Co Ltd | Air barrier film, gas barrier layered body and manufacturing method thereof |
EP1829902B1 (en) * | 2004-12-01 | 2010-02-17 | Kureha Corporation | Aqueous polymerizable monomer composition, gas-barrier film, and method for producing such film |
-
2005
- 2005-11-30 EP EP05814368A patent/EP1829902B1/en active Active
- 2005-11-30 US US11/792,051 patent/US8158213B2/en active Active
- 2005-11-30 WO PCT/JP2005/022399 patent/WO2006059773A1/ja active Application Filing
- 2005-11-30 JP JP2006546714A patent/JP4788602B2/ja not_active Expired - Fee Related
- 2005-11-30 DE DE602005019467T patent/DE602005019467D1/de active Active
- 2005-11-30 AT AT05814368T patent/ATE458012T1/de not_active IP Right Cessation
-
2010
- 2010-10-22 JP JP2010237350A patent/JP4788836B2/ja not_active Expired - Fee Related
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS51141808A (en) | 1975-05-29 | 1976-12-07 | Asada Kagaku Kogyo Kk | Process for preparation of reactive carboxylic acid divalent metal com plexes |
JPH0853389A (ja) | 1994-03-04 | 1996-02-27 | Sartomer Co Inc | 水系硬化性および硬化組成物並びに塗料または接着剤の基材への付着方法 |
JP2002003256A (ja) * | 2000-03-22 | 2002-01-09 | Sika Ag | 高流動性で、高強度でかつ自己緊結性コンクリートのためのセメント分散性ポリマー |
JP2002080502A (ja) * | 2000-07-07 | 2002-03-19 | Nippon Shokubai Co Ltd | 低分子量(メタ)アクリル酸(塩)系重合体、その製造方法および用途 |
WO2002020068A1 (de) * | 2000-09-04 | 2002-03-14 | Stockhausen Gmbh & Co. Kg | Pulverförmige, vernetzte, wässrige flüssigkeiten sowie blut absorbierende polymere |
JP2003286349A (ja) | 2001-01-29 | 2003-10-10 | Nippon Kayaku Co Ltd | 成形体 |
JP2003057185A (ja) * | 2001-08-10 | 2003-02-26 | Idemitsu Petrochem Co Ltd | 酸素ガス検知材料とその製造法 |
JP2003128804A (ja) * | 2001-10-26 | 2003-05-08 | Toyo Ink Mfg Co Ltd | ガスバリア性フィルム及び該フィルムの製造方法 |
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Also Published As
Publication number | Publication date |
---|---|
JP4788602B2 (ja) | 2011-10-05 |
JP2011063806A (ja) | 2011-03-31 |
EP1829902A1 (en) | 2007-09-05 |
DE602005019467D1 (de) | 2010-04-01 |
EP1829902B1 (en) | 2010-02-17 |
JPWO2006059773A1 (ja) | 2008-06-05 |
EP1829902A4 (en) | 2008-05-14 |
JP4788836B2 (ja) | 2011-10-05 |
US8158213B2 (en) | 2012-04-17 |
US20080090018A1 (en) | 2008-04-17 |
ATE458012T1 (de) | 2010-03-15 |
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