WO2000061369A1 - Film formant barriere aux gaz et procede de production associe - Google Patents

Film formant barriere aux gaz et procede de production associe Download PDF

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Publication number
WO2000061369A1
WO2000061369A1 PCT/JP2000/002312 JP0002312W WO0061369A1 WO 2000061369 A1 WO2000061369 A1 WO 2000061369A1 JP 0002312 W JP0002312 W JP 0002312W WO 0061369 A1 WO0061369 A1 WO 0061369A1
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WIPO (PCT)
Prior art keywords
film
gas barrier
mass
polymer
vinyl polymer
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PCT/JP2000/002312
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English (en)
Japanese (ja)
Inventor
Tsunetoshi Matsuda
Tetsuya Miyagawa
Atsuhiro Ishikawa
Yoshihiro Umemura
Sadami Nanjo
Kiyotaka Nakanishi
Kenjin Shiba
Kazunari Nanjo
Toyoki Uyama
Shigemi Majima
Shoji Okamoto
Arihiro Anada
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Unitika Ltd.
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Publication date
Priority claimed from JP10128699A external-priority patent/JP4311806B2/ja
Priority claimed from JP14955099A external-priority patent/JP4689780B2/ja
Priority claimed from JP11210537A external-priority patent/JP2001030349A/ja
Priority claimed from JP22981999A external-priority patent/JP4463902B2/ja
Priority claimed from JP28579999A external-priority patent/JP4302260B2/ja
Application filed by Unitika Ltd. filed Critical Unitika Ltd.
Publication of WO2000061369A1 publication Critical patent/WO2000061369A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/048—Forming gas barrier coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2435/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Derivatives of such polymers

Definitions

  • the present invention relates to a gas barrier film having a coating layer formed thereon and a method for producing the same.
  • Thermoplastic resin films such as polyamides and polyesters are used in a wide range of applications as packaging materials because of their excellent strength, transparency and moldability. However, when used for applications requiring long-term storage, such as retorted foods, higher gas barrier properties are required.
  • PVDC polyvinylidene chloride
  • polyvinyl alcohol does not generate toxic gases and has high gas barrier properties in low-humidity atmospheres.
  • PVA often cannot be used for packaging water-containing foods and the like because the gas barrier property rapidly decreases as the humidity increases.
  • JP-A-8-66991 states that a layer consisting of a 25 to 50% partially neutralized isobutylene-maleic acid copolymer and PVA has excellent water resistance. It is shown.
  • JP-A-49-16949 describes a method for making a PVA film water-resistant by mixing an alkyl vinyl ether-maleic acid copolymer with PVA.
  • water resistance ie, water insolubility
  • gas barrier properties are different properties.
  • water-soluble polymers are made water-resistant by crosslinking molecules.
  • gas barrier properties prevent the penetration and diffusion of relatively small molecules such as oxygen, and simply cross-linking a polymer does not always provide gas barrier properties.
  • three-dimensional crosslinkable polymers such as epoxy resin and phenol resin do not have gas barrier properties.
  • a liquid composition consisting of a water-soluble polymer is coated on a film.
  • an aqueous solution consisting of PVA or polysaccharide and a partially neutralized product of polyacrylic acid or polyacrylic acid is coated on a film and heat-treated.
  • a method has been proposed in which both polymers are crosslinked by an ester bond (jP—A—10—23718).
  • gas barrier properties are developed by highly advanced cross-linking by an esterification reaction.
  • this requires long-time heating at a high temperature, which causes a problem in productivity.
  • the present invention provides a gas barrier film in which a coating agent capable of exhibiting high gas barrier properties even under high humidity is applied to at least one surface of a thermoplastic resin film, and
  • the aim is to provide a method that can be industrially manufactured at low cost.
  • the present inventors have assiduously studied and, as a result, have found that the above-mentioned problems can be solved by laminating a coating agent composed of a specific resin composition on the film surface and heat-treating the same, and have reached the present invention.
  • the gist of the present invention is as follows.
  • a gas barrier film comprising a vinyl polymer (A) containing at least 40 mol% of vinyl alcohol units and a vinyl polymer (B) containing at least 10 mol% of maleic acid units co one Bok layer containing preparative provided on one side at least of a thermoplastic resin film Lum, (a) and (B) the mass ratio of 9 7 / / 3-2 0 da 8 0 Deari, Coat
  • the oxygen permeability coefficient of the layer is not more than 500 m 1 ⁇ / m 2 / day / MPa.
  • the vinyl polymer (A) is polyvinyl alcohol.
  • the crosslinking agent is contained in the range of 0.1 to 20 parts by mass relative to the total of 100 parts by mass of the vinyl polymer (A) and the vinyl polymer (B).
  • the cross-linking agent is a melamine compound or an isocyanate compound.
  • the water-swellable inorganic stratiform compound is contained in the range of 0.1 to 50 parts by mass with respect to a total of 100 parts by mass of the vinyl polymer (A) and the vinyl polymer (B). .
  • the water-swellable inorganic layered compound is fluorine mica.
  • the oxygen permeability coefficient of the coating layer is not more than 250 ml-11 m / mz / day ZMPa.
  • thermoplastic resin is nylon 6.
  • Oxygen permeability is below 180 ml Zm 2 Z day ZM Pa (15 m equivalent of nylon film).
  • thermoplastic resin is polyethylene terephthalate.
  • the film is stretched in at least one of the longitudinal and transverse directions of the film, and then heat-treated.
  • the pH force of the coating agent is in the range of 2.8 to 3.7.
  • a coating agent comprising a mixture of a polymer containing vinyl alcohol units in a predetermined ratio or more and a polymer containing maleic anhydride units in a predetermined ratio or more is coated on a film and heat-treated.
  • a thermoplastic resin film having high gas barrier properties even under humidity can be industrially manufactured at low cost.
  • thermoplastic resin film is suitable.
  • the film include polyamide resin such as Nylon 6, Nylon 66, and Nylon 46, and polyethylene ethylene.
  • Futari Polyester resin such as polyester, polyethylene naphtholate, polybutylene terephthalate, polybutylene terephthalate, polyolefin resin such as polypropylene, polyethylene, etc., or a film thereof, or a film thereof.
  • Laminate This film may be an unstretched film or a stretched film.
  • This film can be produced by heating or melting a thermoplastic resin with an extruder, extruding it through a T-die, and cooling and solidifying it with a cooling roll to obtain an unstretched film.
  • the film is stretched by a simultaneous biaxial stretching method or a sequential biaxial stretching method after winding the unstretched film once or continuously with the process of producing the unstretched film. From the viewpoint of performance such as mechanical properties and thickness uniformity of the film, a method in which a flat type film forming method using a T-die and a tensile stretching method are preferred.
  • the coating layer constituting the gas barrier film of the present invention contains a vinyl polymer (A) containing a vinyl alcohol unit and a vinyl polymer (B) containing a maleic acid unit.
  • a vinyl-based polymer (A) containing a vinyl alcohol unit (hereinafter sometimes simply referred to as “polymer (A)”) is a polymer of a vinyl ester or a vinyl ester and another vinyl-based monomer. Can be obtained by completely or partially saponifying the copolymer of
  • Vinyl esters include vinyl formate, vinyl acetate, and propion Examples thereof include vinyl acid, vinyl pivalate, and vinyl versatate. Among them, vinyl acetate is industrially preferable.
  • vinyl monomers to be copolymerized with vinyl esters include unsaturated monocarboxylic acids such as crotonic acid, acrylic acid, and methyl acrylate, and esters, salts, anhydrides, amides, and nitriles thereof. And unsaturated dicarboxylic acids such as maleic acid, itaconic acid and fumaric acid and salts thereof, ⁇ -olefins having 2 to 30 carbon atoms, alkyl vinyl ethers, vinyl pyrrolidone and the like.
  • unsaturated monocarboxylic acids such as crotonic acid, acrylic acid, and methyl acrylate
  • esters salts, anhydrides, amides, and nitriles thereof.
  • unsaturated dicarboxylic acids such as maleic acid, itaconic acid and fumaric acid and salts thereof, ⁇ -olefins having 2 to 30 carbon atoms, alkyl vinyl ethers, vinyl pyrrolidone and the like.
  • the above polymer is saponified and all or a part of the vinyl ester group becomes a vinyl alcohol unit.
  • Known methods for the alcoholic acid saponification and the acid-genation can be used as the method for the salification.
  • the method of alcoholysis using methanol in methanol is preferable, and the degree of saponification is 10. It is preferable from the viewpoint of gas barrier properties that the value is close to 0%, but when the saponification degree is close to 100%, there is a concern that the aqueous solution may gel when the temperature of the aqueous solution becomes low. Management is required. If the degree of saponification is slightly reduced to, for example, about 97%, the stability of the solution is remarkably increased, and the barrier performance is hardly reduced. However, if the degree of saponification is too low, the barrier performance decreases.
  • the preferred degree of saponification is about 80% or more.
  • the content of vinyl alcohol units in the vinyl polymer (III) must be at least 40 mol% based on all vinyl group units.
  • the content of the vinyl alcohol unit is less than 40 mol%, a film having a sufficient gas barrier property cannot be obtained.
  • the hydroxyl group of the vinyl alcohol unit acts as a reactive group that forms a crosslinked structure by reacting with the vinyl polymer ( ⁇ ⁇ ) containing the maleic acid unit.
  • the strong cohesive force of unreacted hydroxyl groups in the vinyl alcohol unit works effectively to enhance gas barrier properties.
  • the most preferred example of the vinyl-based polymer (A) is polyvinyl alcohol (hereinafter referred to as “PVA”), but copolymers of water-free maleic acid groups or other vinyl-based polymers may also be used. Good, or a partially modified vinyl alcohol unit may be used.
  • PVA polyvinyl alcohol
  • a vinyl polymer (B) containing maleic acid units (hereinafter sometimes simply referred to as “polymer (B)”) is prepared by a known method such as solution radical polymerization of maleic anhydride and another vinyl monomer. It is obtained by polymerizing with.
  • vinyl monomers include alkyl vinyl ethers having 3 to 30 carbon atoms, such as methyl vinyl ether and ethyl vinyl ether, methyl (meth) acrylate, ethyl (meth) acrylate, and (meth) acrylyl.
  • (Meth) acrylic acid esters such as butyl acid, vinyl esters such as vinyl vinyl formate, styrene, p-styrenesulfonic acid, and C2-C30 olefins such as ethylene, propylene and isobutylene, etc. Is mentioned. These mixtures can also be used.
  • alkyl vinyl ethers and lower olefins are the most preferable in terms of improving gas barrier properties.
  • the maleic anhydride copolymer is excellent.
  • Maleic phosphate units in the polymer (B) is a this Toga ⁇ 1 is 1 0 mol% or more. If the content of maleic acid units is less than 10 mol%, poly The formation of the crosslinked structure by the reaction with the vinyl alcohol unit in the monomer (A) is insufficient, and the gas barrier property is reduced.
  • the maleic acid may be partially esterified or amidated, and a part of the carboxyl group of the maleic acid may be neutralized by an alkali compound.
  • an appropriate amount of an alcohol compound is added to the carboxyl group in the polymer (B) to stabilize the liquid. Properties and the performance of the coated film can be improved.
  • the amount of the alkali compound to be added should be appropriately selected depending on the type and blending amount of the polymer to be used. In particular, when a methyl vinyl ether-maleic anhydride copolymer is used as the polymer (B), the alkali compound is added. It is preferable to add the compound in an amount of 0.1 to 20% equivalent to the lipoxyl gas of the polymer (B) and adjust the pH of the solution to 2.8 to 3.7. By doing so, the gas barrier properties of the obtained film are remarkably improved.
  • the present invention it is necessary to coat the thus prepared coating agent on a film, dry it, and further perform a heat treatment to advance a crosslinking reaction.
  • a heat treatment to advance a crosslinking reaction.
  • Any alkali compound may be used as long as it can neutralize the carboxyl group in the polymer (B), such as hydroxides of alkali metals and alkaline earth metals, ammonium hydroxide, and organic amines. Is mentioned.
  • the maleic acid units in the polymer (B) are adjacent carbohydrates in the dry state. The xyl group is liable to become a maleic anhydride structure dehydrated and cyclized, and when wet or in an aqueous solution the ring is opened to form a maleic acid structure.
  • the composition ratio of the polymer (A) containing a vinyl alcohol unit and the polymer (B) containing a maleic acid unit is expressed by mass. It is necessary that the ratio be in the range of 97/3 to 20/80. Outside of this range, the gas barrier properties of the film will be insufficient, especially in a high humidity atmosphere.
  • the amount of the cross-linking agent is less than 0.1 part by mass, a sufficient cross-linking effect cannot be obtained. If the amount is more than 20 parts by mass, the cross-linking agent acts as an inhibitor of gas barrier properties, resulting in gas barrier properties. Will decrease.
  • Such a cross-linking agent examples include a compound containing a plurality of functional groups that react with a hydroxyl group or a carboxyl group in a molecule or a metal complex having a polyvalent coordination site.
  • a cross-linking agent include a compound containing a plurality of functional groups that react with a hydroxyl group or a carboxyl group in a molecule or a metal complex having a polyvalent coordination site.
  • an isocyanate compound a melamin compound, an epoxy compound, a carbodiimide compound, a silyl group-containing compound, a zirconium salt compound and the like.
  • inorganic layered compound refers to an inorganic compound in which unit crystal layers overlap to form a layered structure.
  • Preferred examples of the inorganic layered compound include montmorillonite, pidelite, savonite, hectolite, sauconite, vermiculite, fluoromica, muscovite, paragonite, phlogopite, biotite, levy dry , Margarite clintonite, anandite, chlorite, donpasite, suidoite, cookeite, clinocroix, shamosite, nimaito, tetrasiririkmai power, evening Rek, non-filo-light, nacryate, force-origin, eightloite, chrysotile, sodium teniolite, zansofilite, anti-golite, date kite, hide mouth talcite, etc. Swellable fluoromica or montmorillonite is particularly preferred.
  • inorganic stratiform compounds may be naturally occurring, artificially synthesized or modified, or may be those treated with an organic substance such as an onium salt. .
  • swellable fluoromica-based minerals are most preferred in terms of transparency.
  • This swellable fluoromica-based mineral is represented by the following formula and can be easily synthesized by a known production method.
  • MF ⁇ ⁇ (a M g F 2 - b M g O).
  • the compounding amount of these inorganic layered compounds is preferably from 0.1 to 50 parts by mass. If the amount is less than 0.1 part by mass, the effect of improving gas barrier properties is insufficient. Conversely, if the amount is more than 50 parts by weight, gas barrier properties are further enhanced. When the layered silicate becomes difficult to disperse evenly in the coating liquid, the performance of the coating layer becomes uneven, and the flexibility of the obtained gas barrier film is reduced. Problems are more likely to occur in various processing steps for packaging materials such as.
  • an acrylic copolymer containing 70% by mass or more of an acrylonitrile unit is added to 200 parts by mass of the total of the polymer (A) and the polymer (B).
  • the liquid properties of the coating agent can be improved.
  • the coating agent composed of the polymer (A) and the polymer (B) has a high viscosity of the liquid and may be restricted in use depending on the production equipment. However, if the concentration of the solution is too low as a countermeasure, it takes a long time to dry the coating film after coating the coating agent on the film, which is undesirable because the productivity is lowered. Generally, a coating agent having a high concentration and a low viscosity is generally preferred.
  • a possible method is to add a water-dispersible component to the coating agent. Addition of an aqueous dispersion such as general acrylic latex or vinyl acetate-based latex will result in a gas barrier. This is not preferred because the properties are reduced.
  • Acryl-based copolymers containing 70% by mass or more of acrylonitrile units have excellent gas barrier properties and can be added to a coating agent consisting of polymer (A) and polymer (B). Thus, the viscosity of the coating agent can be reduced without lowering the gas barrier properties.
  • the acrylonitrile copolymer contains acrylonitrile in an amount of 70% by mass or less, desirably 80% by mass or more, and the rest is acrylonitrile.
  • One or more vinyl monomers copolymerizable with nitrile are 30% by mass or less, preferably 20% by mass or less. If the acrylonitrile content of the acrylonitrile copolymer is less than 70%, sufficient gas barrier properties cannot be obtained.
  • the vinyl monomer copolymerizable with acrylonitrile is not particularly limited, but is a compound having a carbon-carbon unsaturated double bond, and includes (meth) acrylates, (Meth) acrylamides, (meth) acrylates having a functional group bonded thereto, vinylidenes, urethanes having an unsaturated bond, silicons having an unsaturated bond, fluorine-based unsaturated monomers Can use body.
  • unsaturated carboxylic esters specifically, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and the like are preferable.
  • the acryl-based copolymer is preferably prepared by emulsion polymerization of an acrylonitrile monomer and another vinyl-based monomer in the presence of a power emulsifier which can be produced by a known method.
  • emulsifiers include fatty acid minerals, organic sulfonates, polyvinyl alcohol, methyl vinyl ether-maleic anhydride copolymers, and copolymers of olefin-maleic anhydride such as isobutylene-maleic anhydride, polyvinylpyrrole. And one or a mixture of two or more of these. .
  • the type of polymerization initiator, surfactant, etc. is not particularly limited.However, since these substances remain in the coating film formed from the latex and cause deterioration of the gas barrier property, the amount of the substances used is limited. It is preferable that the amount is as small as possible.
  • the nitrile copolymer of [polymer] 3 ⁇ 4 has poor melt fluidity, It is desirable to add a molecular weight regulator to reduce the molecular weight.
  • the high nitrile copolymer thus obtained is used as a mixture with the polymer (A) and the polymer (B).
  • the mixing ratio is within a range of 200 parts by mass or less with respect to the total 100 parts by mass of the polymer (A) and the polymer (B). If the amount of the high nitrile copolymer exceeds 200 parts by mass, the gas barrier properties decrease, and the film-forming properties deteriorate, so that a good coating film cannot be obtained.
  • the amount of the coating agent is determined in consideration of these amounts.
  • This coating agent includes heat stabilizers, antioxidants, reinforcing agents, pigments, deterioration inhibitors, weathering agents, flame retardants, plasticizers, release agents, lubricants, etc., as long as the properties are not significantly impaired. It may be added.
  • heat stabilizer examples include hindered phenols, phosphorus compounds, hindered amines, zeo compounds, copper compounds, alkali metal halides, and mixtures thereof. .
  • the coating agent can be adjusted by a known method using a dissolving pot equipped with a stirrer or the like.
  • a dissolving pot equipped with a stirrer or the like for example, polymer (A) and polymer (B)
  • the thickness of the coat layer containing the polymer (A) and the polymer (B) is desirably at least greater than 0.1 m in order to sufficiently enhance the gas barrier properties of the film.
  • the polymer concentration when the coating agent is coated on the film can be appropriately changed depending on the viscosity and reactivity of the liquid, the specifications of the equipment used, and the like. If the concentration is too low, it becomes difficult to coat a layer having a sufficient thickness necessary to exhibit gas barrier properties, and it is likely to cause a problem that a long time is required in a subsequent drying step. On the other hand, if the concentration of the solution is too high, problems may occur in the mixing operation and the storage stability. From such a viewpoint, the polymer concentration is preferably in the range of 1 to 50% by mass of the whole solution.
  • the coating method of the coating agent on the film is not particularly limited, and ordinary methods such as gravure mouth coating, reverse roll coating, meyer bar coating, and die coating are used. be able to.
  • the coating may be performed before stretching the film, or may be performed on the stretched film.
  • the surface of the film is subjected to a corona discharge treatment prior to coating, or a polyester-based resin, an acrylic-based resin,
  • a commonly known treatment such as coating a primer resin with a resin, a polyvinyl alcohol resin, a silyl group-containing resin, a melamine resin, or a mixture thereof may be applied.
  • the unstretched film is coated and dried, and then supplied to a ten-stretch type stretching machine to stretch the film simultaneously in the Ji row direction and the width direction (simultaneously).
  • a ten-stretch type stretching machine to stretch the film simultaneously in the Ji row direction and the width direction (simultaneously).
  • 2 ⁇ Nobunaka) Heat treatment After stretching in the running direction of the film using a multi-stage heat roll or the like, coating is performed, and after drying, the film may be stretched in the width direction by a ten-in-one stretching machine (sequentially) Biaxial stretching). It is also possible to combine the stretching in the running direction with the simultaneous stretching in two directions. Coating prior to stretching, followed by stretching and heat treatment, is preferred because the high temperature during stretching and heat treatment can be used for the crosslinking reaction.
  • the moisture content of the coat layer before stretching is preferably 0.1 to 50% by mass, more preferably 1 to 50% by mass, and particularly preferably 2 to 50% by mass. If the water content is less than 0.1% by mass, the coating layer is liable to peel or crack. On the other hand, if the water content exceeds 50% by mass, the drying efficiency of the coat layer is reduced and causes troubles such as film cutting during stretching.
  • the moisture content of the coat layer before stretching varies depending on the solid content of the coating agent, the thickness of the coat layer, etc., but should be controlled to the desired range by changing the temperature and drying time of the dryer. Can be.
  • the coat layer is a force formed on one or both sides of the film.
  • the temperature is 150 ° C. or higher, preferably 18 ° C. It is preferable to carry out heat treatment in an atmosphere of 0 or more.
  • the heat treatment temperature be 230 ° C or less.
  • the coated film thus obtained exhibits excellent gas barrier properties by itself, and the gas barrier properties are improved particularly as the heat treatment time is increased. However, too long a heat treatment will reduce productivity.
  • the gas barrier property can be further enhanced by irradiating the coated, dried, and heat-treated film with an electron beam.
  • the amount of the irradiated electron beam is 1 Mrad or more. 20 M rad or less is preferable, and l M rad or more and 15 M rad or less is more preferable. If the irradiation amount of the electron beam is less than 1 Mrad, sufficient cross-linking by irradiation with the electron beam cannot be introduced, and the improvement of the gas nori- bility based on the irradiation of the electron beam becomes insufficient. Conversely, if the irradiation dose is more than 20 Mrad, the gas barrier properties will decrease.
  • Oxygen permeability The oxygen permeability in an atmosphere at 20 ° C and a relative humidity of 85% was measured using a Mocon oxygen barrier measuring instrument.
  • the gas barrier properties of the film vary depending on the type and thickness of the base film and the thickness of the coating layer. Therefore, the oxygen permeability coefficient of the coating layer itself was evaluated.
  • This oxygen permeability coefficient was determined by the following equation.
  • the oxygen permeability of the coated film can be estimated from the above equation if P c and L are known.
  • the oxygen permeability of the film used in the following examples at 20 ° C. and 85% RH was as follows.
  • This film was a biaxially stretched PET film (900 ml / m 2 Z day / MP a, if the film strength biaxially stretched nylon film (thickness 1 is 4 0 0 ml Zm 2 / day ZM P a. Therefore, this value is the calculation of the oxygen permeability coefficient of the coat layer Was used.
  • the moisture content of the coat is determined after coating the film with the coating agent. Is dried, and the coat film of Nobenaka is collected. The total mass of the coat layer is a gram, and the mass of water in the coat layer is b gram. (B / a) XI 00 (mass% ). The mass of water in the coat layer was determined by subtracting the mass after completely drying the coat layer from the total mass of the coat layer.
  • the appearance of the coated film was visually evaluated. When no peeling or cracking of the coat layer was observed, the evaluation was “good”. Conversely, if peeling or cracking of the coat layer was observed, it was evaluated as “poor”.
  • polymer (A) a polyvinyl alcohol UF040G (99% saponification degree, average polymerization degree 500) manufactured by Unitika Chemical Co., Ltd. was dissolved in pure water to obtain a 10% by mass aqueous solution.
  • polymer (A) a polyvinyl alcohol UF040G (99% saponification degree, average polymerization degree 500) manufactured by Unitika Chemical Co., Ltd. was dissolved in pure water to obtain a 10% by mass aqueous solution.
  • polymer (A) a polyvinyl alcohol UF040G (99% saponification degree, average polymerization degree 500) manufactured by Unitika Chemical Co., Ltd. was dissolved in pure water to obtain a 10% by mass aqueous solution.
  • polymer (A) a polyvinyl alcohol UF040G (99% saponification degree, average polymerization degree 500) manufactured by Unitika Chemical Co., Ltd. was dissolved in pure water to obtain a 10% by mass aqueous solution.
  • This coating agent was coated on a biaxially stretched PET film (thickness: 12 m) with a Meyer bar coat so that the coating thickness after drying was about 2 m, and dried at 100 ° C for 2 minutes. Thereafter, heat treatment was performed at 200 ° C. for 5 minutes.
  • the resulting film has an excellent oxygen permeability of 40 m 1/2 / day / MP, and the estimated oxygen permeability coefficient of the coating layer is 84 ml-m / m 2 Z day ZM Pa.
  • Example 2 The same operation as in Example 1 was performed using only the PVA aqueous solution as the coating agent.
  • the resulting film has an oxygen permeability of 410 m 1 / m 2 / day / MPa, which is insufficient for gas packaging for food packaging films.
  • the oxygen permeation coefficient was 1657 ml ⁇ m / 2 Z day ZMPa.
  • Example 1 The same operation as in Example 1 was performed by changing the types and ratios of the polymer (A) and the polymer (B), and the oxygen permeability of the obtained film and the oxygen permeability coefficient of the coat layer were determined.
  • the results are shown in Table 1.
  • Isoban is an isobutylene-maleic anhydride copolymer manufactured by Kuraray Co., Ltd.
  • SMA1000 and SMA2000 are styrene-monomaleic anhydride copolymers manufactured by Atochem
  • E MA is an ethylene-maleic anhydride copolymer manufactured by ALDRICH.
  • the film of the present invention is useful because it has excellent gas barrier properties, and its coating agent has much better performance than PVA, which is generally used as a gas barrier coating agent. It turns out that it is. table 1
  • Example 2 The same operation as in Example 1 was performed by changing the type and amount of the alkali, and the coating agent was adjusted.
  • the obtained coating agent was coated on a PET film in the same manner as in Example 1, dried at 100 ° C. for 2 minutes, and then heat-treated for different times.
  • Table 2 shows the oxygen permeability of the obtained film and the oxygen permeability coefficient of the coating layer.
  • the above-mentioned UF040G was dissolved in pure water to obtain a 20% by mass aqueous solution.
  • the above-mentioned GANTREZAN 119 was dissolved in an aqueous solution containing 5 mol% of sodium hydroxide with respect to the carboxylic acid unit to obtain a 20% by mass solution.
  • both aqueous solutions were mixed so that the mass ratio of the polymer (A) and the polymer (B) became (A) / (B) 70Z30, to prepare a coating agent.
  • the temperature of the thin cylinder was 260 ° C, and the temperature of the T die was 2 ° C.
  • the PET resin was extruded in a sheet form, closely adhered to a cooling roll adjusted to a surface temperature of 10 ° C, and rapidly cooled to obtain an unstretched film having a thickness of 120m.
  • the unstretched film is guided through a gravure roll type coater, coated with a coating agent so that the coat thickness after drying becomes 20 m, and heated in a hot air dryer at 80 ° C. Dried for 30 seconds.
  • this film is fed to a ten-set simultaneous biaxial stretching machine, preheated at 100 ° C for 2 seconds, and then tripled in the vertical direction and 3.5 times in the horizontal direction at 95 ° C.
  • the film was stretched at twice the magnification.
  • Table 2 shows the oxygen permeability of the obtained film and the oxygen permeability coefficient of the coating layer.
  • Nylon 6 resin was extruded in a sheet shape at a temperature of 260 ° C. for the thin cylinder and 270 ° C. for the T-die, The film was quenched by closely contacting it on a cooling roll adjusted to a surface temperature of 10 ° C. to obtain an unstretched film having a thickness of 150 Aim. Subsequently, the unstretched film was led to a gravure roll type coater overnight, and the same liquid as used in Example 13 was coated and dried under the same conditions. Next, a film was produced under the same conditions as in Example 13 except that the temperature condition during stretching was set to 170 ° C.
  • Table 2 shows the oxygen permeability of the obtained film and the oxygen permeability coefficient of the coating layer.
  • Base film Film thickness (A) 1 (B) Alkali compound Alkali compound pH heat treatment temperature heat treatment Coat Oxygen permeability Acid in coat layer
  • Example 10 0 PET 12 90/10 NaOH 2 3.5 200 60 1.8 73 143
  • Example 1 PET 12 70/30 Ca (OH) 2 5 3.0 200 15 2.0 95 212
  • Example 1 2 PET 12 70/30 NH 3 15 3.7 200 15 2.1 170 440
  • Example 1 PET 12 70/30 NaOH 5 2.9 200 15 2.0 75 164
  • Example 14 Nylon 15 70/30 NaOH 5 2.9 200 15 2.0 65 155 00 Comparative Example 4 PET 12 80/20 NaOH 1 2.8 150 60 2.0 530 2578 ⁇
  • the above-mentioned UF040G was dissolved in pure water to obtain a 10% by mass aqueous solution.
  • the above-mentioned GANTREZAN 119 was dissolved in an aqueous solution containing 2 mol% of sodium hydroxide with respect to the carboxyl group to obtain a 10% by mass solution.
  • an isocyanate compound dispersion (Elastron BN11) manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd. was mixed with a polymer having a mass ratio of the isocyanate compound of 100 (solid) of polymer (A) and polymer (B). It was added so as to be 5 parts by mass with respect to parts by mass, and stirred to prepare a coating agent.
  • This coating agent was coated on a biaxially stretched PET film (thickness: 12 xm) using a Meyer bar so that the coating thickness after drying was about 2 m, and dried at 100 ° C for 2 minutes. Thereafter, heat treatment was performed at 200 ° C. for 10 seconds.
  • the oxygen permeability of the obtained film at 20 ° C. and 85% RH showed an excellent value of 70 m 1 / z / day / MPa as shown in Table 3.
  • Example 15 The same operation as in Example 15 was performed by changing the types and ratios of the polymer (A) and the polymer (B), and the type and amount of the crosslinking agent, respectively, to thereby obtain an oxygen permeability and a coat of the obtained film.
  • the oxygen permeability coefficient of the layer was determined. The results are shown in Table 3.
  • Example 14 The same stretched nylon film as that of Example 14 was led to a gravure roll type co-polymer overnight, and the composition was as shown in Table 3 and the crosslinking agent was as shown in Table 3. A film was produced under the same conditions as in Example 14 using a coating agent to which was added.
  • Table 3 shows the oxygen permeability of the obtained film and the oxygen permeability coefficient of the coating layer.
  • Isocyanate (I): Daiichi Kogyo Seiyaku Co., Ltd .: I Laston BN11 Isocyane h (II): Daiichi Kogyo Seiyaku Co., Ltd .: I Last Q E-37 Melamine: Mitsui Cytec: Cyme 1325
  • I-honki Made by Tokyo Kasei Co., Ltd .: Fushi-tanshi-shi-Rusi-Gerishishi-ru I-Terkar-ki-shi: Imide: Nisshinbo Co., Ltd .: Calho-shi 'Ra-E-shi' ruconium salt First rare element '; / Luco' / -Lu AC-7
  • the above UFO40G was dissolved in pure water to obtain a 20% by mass aqueous solution.
  • the above-described GANTEZAN 119 was dissolved in an aqueous solution containing 2 mol% of sodium hydroxide with respect to the carboxyl group to obtain a 20% by mass solution.
  • This coating agent was coated on a biaxially stretched PET filem (thickness: 12 zm) using a Meyer bar so that the coating thickness after drying was about 2 m, and dried at 100 ° C for 2 minutes. Thereafter, heat treatment was performed at 200 ° C. for 15 seconds.
  • the oxygen permeability of the obtained film at 20 and 85% RH showed an excellent value of 26 m 1 / m 2 / day / MPa as shown in Table 4.
  • Example 26 The same operation as in Example 26 was performed after changing the kind and amount of the inorganic layered compound, the composition of the coating agent, and the base film. The results are shown in Table 4.
  • Table 4 Somasif is a swellable synthetic fluoromica manufactured by Corp Chemical.
  • Example 14 The same unstretched nylon film as that of Example 14 was led to the gravure roll type co-polymer overnight, and the same coating agent as that used in Example 26 was used. Was coated so that the coat thickness after drying was 11 m, and a film was produced under the same conditions as in Example 14.
  • Table 4 shows the oxygen permeability of the obtained film and the oxygen permeability coefficient of the coat layer.
  • the above-mentioned UF • 40G was dissolved in pure water to obtain a 10% by mass aqueous solution.
  • Table 4 shows the oxygen permeability of the obtained film and the oxygen permeability coefficient of the coat layer.
  • the above UFO40G was dissolved in pure water to obtain a 10% by mass aqueous solution.
  • the above-mentioned GANTREZAN 119 was dissolved in an aqueous solution containing 2 mol% of sodium hydroxide with respect to the carboxyl group to obtain a 10% by mass solution.
  • the lonitrile copolymer emulsion (97% by mass of acrylonitrile) was added in an amount of 43 parts by mass based on 100 parts by mass of the solid content of the polymer (A) and the polymer (B). Parts, and stirred to prepare a coating agent.
  • This coating agent was coated on a biaxially stretched PET film (thickness: 12 m) using a Meyer bar so that the coating thickness after drying was about 2 m, and dried at 100 ° C for 2 minutes. Thereafter, heat treatment was performed at 200 for 10 seconds. Table 5 shows the performance of the obtained gas barrier film.
  • This coating agent was coated on a biaxially stretched PET film (Emblend PET 12 manufactured by Unitika Ltd., thickness 12 m) with a Meyer bar so that the coating thickness after drying was about 2 m. After drying at 00 ° C for 2 minutes, heat treatment was performed at 200 ° C for 10 seconds. Table 5 shows the results.
  • Comparative Example 6 In Comparative Example 6, in which the content of the acrylonitrile copolymer was larger than the range of the present invention, no good coating film was obtained. In Comparative Example 7 using a copolymer having a low acrylonitrile ratio, the gas barrier property was poor.
  • Neutralization Gantrez 2% (NaOH). Iso /, ': 603 ⁇ 4 (Paint, SMA: 53 ⁇ 4 (NaOH) Heat treatment 200 ° (:, 10 seconds
  • the above-mentioned UF040G as the polymer (A) was dissolved in pure water to obtain a 10% by mass aqueous solution.
  • the above-mentioned GANTREZAN 119 was dissolved in an aqueous solution containing 5 mol% of sodium hydroxide with respect to the carboxyl group to obtain a 10% by mass solution.
  • This coating agent was coated on a biaxially stretched PET film (thickness: 12 m) using a Meyer bar so that the coating thickness after drying was about 2 m, and dried at 100 for 2 minutes. Heat treatment was performed at 200 ° C. for 10 seconds. Thereafter, the film was introduced into an electron beam irradiation apparatus (Curetron, manufactured by Nissin High Voltage), and the film was irradiated with an electron beam at an accelerating voltage of 175 kV and at a dose shown in Table 6.
  • an electron beam irradiation apparatus Carbon, manufactured by Nissin High Voltage
  • Table 6 shows that the gas barrier property can be further improved by irradiating the coated film with an electron beam according to the present invention.
  • Comparative Example 8 that is, when only PVA was coated, no improvement in gas barrier properties was observed even when electron beams were irradiated.
  • Example 37 The same coating agent as that of Example 37 was prepared, and the same non-rolled nylon film as that of Example 14 was obtained.
  • the unstretched film was guided to a gravure roll type coater overnight, and the coating agent prepared above was coated so that the coat thickness after drying became 20 m, and the temperature was adjusted to 80 ° C. Drying was performed in a hot air drier so that the moisture content of the coat layer became the value shown in Table 7.
  • Table 7 shows the oxygen permeability of the obtained film and the oxygen permeability coefficient of the coat layer.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Paints Or Removers (AREA)

Abstract

Ce film possédant des propriétés de barrière aux gaz comprend un film de résine thermoplastique sur un côté duquel au moins on a formé une couche de revêtement comprenant un polymère vinylique (A) se composant d'au moins 40 moles % d'unités d'alcool vinylique, et un polymère vinylique (B) se composant d'au moins 10 moles % d'unités d'acide maléique, le rapport pondéral entre (A) et (B) étant compris entre 97/3 et 20/80. La couche de revêtement possède un coefficient de perméabilité à l'oxygène de l'ordre de 500 ml. νm/m2/jour/MPa ou moins. Ce film possède de très bonnes propriétés de barrière aux gaz, même dans des conditions de forte humidité.
PCT/JP2000/002312 1999-04-08 2000-04-07 Film formant barriere aux gaz et procede de production associe WO2000061369A1 (fr)

Applications Claiming Priority (10)

Application Number Priority Date Filing Date Title
JP10128699A JP4311806B2 (ja) 1999-04-08 1999-04-08 ガスバリア性フィルムおよびその製造方法
JP11/101286 1999-04-08
JP14955099A JP4689780B2 (ja) 1999-05-28 1999-05-28 ガスバリア性フィルムおよびその製造方法
JP11/149550 1999-05-28
JP11/210537 1999-07-26
JP11210537A JP2001030349A (ja) 1999-07-26 1999-07-26 ガスバリア性フィルムの製造方法
JP22981999A JP4463902B2 (ja) 1999-08-16 1999-08-16 ガスバリア性フィルムの製造方法
JP11/229819 1999-08-16
JP11/285799 1999-10-06
JP28579999A JP4302260B2 (ja) 1999-10-06 1999-10-06 ガスバリア性フィルム

Publications (1)

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WO2000061369A1 true WO2000061369A1 (fr) 2000-10-19

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002048265A1 (fr) * 2000-12-12 2002-06-20 Unitika Ltd. Composition de resine etanche au gaz, materiau de revetement etanche au gaz et moulage etanche au gaz

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05193070A (ja) * 1991-06-14 1993-08-03 Imperial Chem Ind Plc <Ici> 高分子フィルム
JPH05310976A (ja) * 1992-05-11 1993-11-22 Unitika Ltd 易接着性ポリエステルフィルム及びその製造法
JPH0841218A (ja) * 1994-07-27 1996-02-13 Kureha Chem Ind Co Ltd ガスバリヤー性フィルム及びその製造方法
JPH09151264A (ja) * 1995-11-30 1997-06-10 Toray Ind Inc ガスバリアフィルム
JPH09151263A (ja) * 1995-11-30 1997-06-10 Toray Ind Inc ガスバリアフィルム及びその製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05193070A (ja) * 1991-06-14 1993-08-03 Imperial Chem Ind Plc <Ici> 高分子フィルム
JPH05310976A (ja) * 1992-05-11 1993-11-22 Unitika Ltd 易接着性ポリエステルフィルム及びその製造法
JPH0841218A (ja) * 1994-07-27 1996-02-13 Kureha Chem Ind Co Ltd ガスバリヤー性フィルム及びその製造方法
JPH09151264A (ja) * 1995-11-30 1997-06-10 Toray Ind Inc ガスバリアフィルム
JPH09151263A (ja) * 1995-11-30 1997-06-10 Toray Ind Inc ガスバリアフィルム及びその製造方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002048265A1 (fr) * 2000-12-12 2002-06-20 Unitika Ltd. Composition de resine etanche au gaz, materiau de revetement etanche au gaz et moulage etanche au gaz
US6783857B2 (en) 2000-12-12 2004-08-31 Unitika Ltd. Gas barrier resin composition, gas barrier coating material, and gas-barrier molding

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