JP4334512B2 - Method for producing film laminate - Google Patents

Description

The present invention relates to a method for producing a film laminate that is excellent in transparency and also excellent in gas barrier properties, water vapor barrier properties, and bending resistance (gelboflex resistance).

  The functions required for packaging of foods and the like are diverse, but the gas barrier property is an important function from the viewpoint of protecting the quality of the contents. In recent years, gas barrier properties have become more and more necessary due to diversification of distribution forms, packaging techniques, additive regulations, and changes in preferences. Nevertheless, gas barrier properties were also a weak point of general plastic materials. Examples of factors that alter the quality of food include oxygen, light, heat, and moisture. In particular, oxygen is important as a causative substance. The barrier material is an essential material for the means to effectively block oxygen and at the same time to control the quality change of food such as gas filling and vacuum packaging. Not only oxygen gas but also various gases, water vapor, organic solvent vapor, aroma It can be used for rust prevention, deodorization, sublimation prevention, etc., and used in many fields such as confectionery bags, bonito packs, retort pouches, carbon dioxide beverage containers, etc. ing.

  Among films made of thermoplastic resins, particularly oriented films such as polypropylene, polyester, and polyamide have excellent mechanical properties, heat resistance, transparency, and the like, and are widely used as packaging materials. However, when these films are used for food packaging, the oxygen and other gas barrier properties are insufficient, which can easily lead to oxidative deterioration and alteration of the contents due to aerobic microorganisms, or permeation of perfume components. It tends to cause various problems, such as loss of flavor, moistened contents by moisture from the outside world and poor mouthfeel, and conversely, loss of moisture of food and loss of flexibility of food. . Therefore, usually, a method such as laminating other film layers having good gas barrier properties is often used. Conventionally, various transparent plastic materials with high gas barrier properties are also known. For example, although there are films made of polyvinyl alcohol or polyethylene vinyl alcohol copolymer, these plastic materials still transmit oxygen that cannot be ignored. It is.

  Moreover, although the composition which consists of an inorganic layered compound and resin is also known, although this was excellent in gas barrier property, it had the tendency for the Haze value to be high, ie, to be inferior to transparency. In addition, when the clay fraction was increased in order to improve the barrier property, there was a problem that the haze and the bending resistance were deteriorated.

The present invention provides a method for producing a film laminate having excellent transparency and excellent gas barrier properties, water vapor barrier properties, and flex resistance.

As a result of intensive studies to solve the above problems, the present invention has been achieved.
That is, the present invention includes a step of laminating an inorganic layer (A) composed of an inorganic layered compound on at least one surface of the base material layer (C), and a resin containing a high hydrogen bonding resin on the surface of the inorganic layer (A). And a step of laminating the layer (B) . A method for producing a film laminate is provided.

According to the present invention, it is possible to obtain a film having excellent transparency and excellent gas barrier properties, water vapor barrier properties, and flex resistance. The film laminate obtained using the production method of the present invention has a gas barrier property that greatly exceeds the resin and approaches the gas barrier property of metals and ceramics, so metal and inorganic materials such as aluminum foil and glass are essential. It can be used for certain applications and has excellent transparency, so the contents can be confirmed, and can be said to be a material that breaks the common sense of conventional barrier resin compositions.

The present invention will be described in detail below.
The “inorganic layered compound” used in the present invention refers to an inorganic compound in which unit crystal layers are stacked to form a layered structure. In other words, the “layered compound” is a compound or substance having a layered structure, and the “layered structure” is a van der Waals surface in which atoms are strongly bonded by covalent bonds or the like and closely arranged. A structure that is stacked in parallel by weak binding force such as force.

  The “inorganic layered compound” that can be used in the present invention is one having an “aspect ratio” measured by the method described later of usually from 50 to 5000 and a particle size of 5 μm or less. From the viewpoint of gas barrier properties, this aspect ratio is preferably 100 or more (particularly 200 or more). When the aspect ratio is less than 50, the gas barrier property is not sufficiently developed. On the other hand, it is technically difficult to obtain an inorganic layered compound having an aspect ratio exceeding 5000, and the cost and cost are expensive. From the viewpoint of ease of production, this aspect ratio is preferably 3000 or less (more preferably 1500 or less). In view of the balance between gas barrier properties and manufacturability, the aspect ratio is more preferably in the range of 200 to 3000.

Further, from the viewpoint of film formability or moldability when formed into a film, the “particle diameter” measured by the method described later is preferably 5 μm or less . The particle size is more preferably 3 μm or less. When the film of the present invention is used for applications in which transparency is important (for example, food packaging applications), the particle size is particularly preferably 1 μm or less.

Specific examples of the inorganic layered compound used in the present invention include graphite, phosphate derivative compounds (such as zirconium phosphate compounds), chalcogenides, and clay minerals. Here, the “chalcogen compound” is a dichalcogenide of group IV (Ti, Zr, Hf), group V (V, Nb, Ta) and group VI (Mo, W), which has the formula MX ₂ (M is the above element) , X represents chalcogen (S, Se, Te).

  The particle size of the inorganic layered compound used in the present invention refers to the particle size obtained by a dynamic light scattering method in a solvent.

(Method for obtaining average particle size)
The average particle diameter of the particles in the liquid can be determined by a diffraction / scattering method, a dynamic light scattering method, a method of changing electrical resistance, a method of image processing after microscopic photography in liquid, and the like. When the resin and particles coexist in the dynamic light scattering method, it is difficult to evaluate because the apparent liquid viscosity changes from that of a pure solvent. The method of image processing after microscopic photography has a problem of resolution and is difficult to use. The method based on the diffraction / scattering method has substantially no scattering in the aqueous resin liquid (that is, it is transparent), and when the particle-derived scattering is dominant, only the particle size distribution information can be obtained regardless of the presence or absence of the resin. Since it is obtained, it is used relatively preferably.

(Average particle size measurement by diffraction / scattering method)
Particle size distribution and average particle size measurement by the diffraction / scattering method is performed by calculating the particle size distribution with the most consistent pattern using the Mie scattering theory, etc., for the diffraction / scattering pattern obtained when light is passed through the dispersion. Made. Commercially available devices include laser diffraction / light scattering particle size measuring devices LS230, LS200, LS100, manufactured by Coulter, Inc., laser diffraction particle size distribution measuring devices SALD2000, SALD2000A, SALD3000, manufactured by Shimadzu Corporation, and laser diffraction / scattering particle size distribution manufactured by Horiba, Ltd. Measuring devices LA910, LA700, LA500, Nikkiso Microtrac SPA, Microtrac FRA, and the like can be mentioned.

(Aspect ratio measurement method)
An aspect ratio (Z) is a ratio calculated | required from the relationship of Z = L / a. Here, L is the particle size (volume-based median diameter) of the inorganic layered compound obtained by the particle size measurement method by the diffraction / scattering method described above in the dispersion, and a is the unit thickness of the inorganic layered compound. is there. This “unit thickness a” is a value determined based on the measurement of the inorganic layered compound alone by a powder X-ray diffraction method to be described later. More specifically, as shown schematically in the graph of FIG. 1 with 2θ on the horizontal axis and the intensity of the X-ray diffraction peak on the vertical axis, it corresponds to the lowest angled peak among the observed diffraction peaks. The interval determined based on the Bragg equation (nλ = 2Dsinθ, n = 1, 2, 3...) Is defined as “unit thickness a” (for details of the powder X-ray diffraction method). (See, for example, Jiro Shiokawa's “Guide to Instrumental Analysis (a)” p. 69 (1985) published by Kagaku Dojinsha). In the present specification, “aspect ratio” or “particle diameter” means “aspect ratio Z” defined above or “particle diameter L determined by diffraction / scattering method”.

  From the viewpoint of easily giving a large aspect ratio, an inorganic layered compound having a property of swelling and cleaving in a solvent is preferably used. The degree of the “swelling / cleavage” property of the inorganic layered compound used in the present invention to the solvent can be evaluated by the following “swelling / cleavage” test. The swelling property of the inorganic layered compound is preferably about 5 or more (more preferably about 20 or more) in the following swelling test. On the other hand, the cleavage property of the inorganic layered compound is preferably about 5 or more (more preferably about 20 or more) in the following cleavage test. In these cases, a solvent having a density smaller than that of the inorganic layered compound is used as the solvent. When the inorganic layered compound is a natural swellable clay mineral, it is preferable to use water as the solvent.

<Swellability test>
Add 100 mL of solvent to a 100 mL graduated cylinder, and slowly add 2 g of the inorganic layered compound. After standing, the volume of the inorganic layered compound dispersion layer is read from the scale of the interface between the inorganic layered compound dispersion layer and the supernatant after 23 ° C. and 24 hours. The larger this value, the higher the swelling property.

<Cleavage test>
Slowly add 30 g of inorganic layered compound to 1500 mL of solvent, and use a disperser (manufactured by Asada Tekko Co., Ltd., Desper MH-L, blade diameter 52 mm, rotation speed 3100 rpm, container capacity 3 L, bottom-blade distance 28 mm) After dispersion at 8.5 m / sec for 90 minutes (23 ° C.), 100 mL of the dispersion is taken, placed in a graduated cylinder and allowed to stand for 60 minutes, and then the volume of the inorganic layered compound dispersion layer is read from the interface with the supernatant.

  As the inorganic layered compound that swells and cleaves in the solvent, a clay mineral that swells and cleaves in the solvent is particularly preferably used. Such clay-based minerals are generally of a type having a two-layer structure having an octahedral layer with a central metal of aluminum, magnesium, etc. on the upper part of the silica tetrahedral layer, and a silica tetrahedral layer, such as aluminum, magnesium, etc. Is a type having a three-layer structure in which an octahedral layer having a central metal is narrowed from both sides. Examples of the former two-layer structure type include kaolinite group and antigolite group. Examples of the latter three-layer structure type include smectite group, vermiculite group, mica group, etc. depending on the number of interlayer cations. Can do.

  More specifically, these clay minerals include kaolinite, dickite, nacrite, halloysite, antigolite, chrysotile, pyrophyllite, montmorillonite, hectorite, tetrasilic mica, sodium teniolite, muscovite, Examples include margarite, talc, vermiculite, phlogopite, xanthophyllite, chlorite. For clay minerals, reference can be made to articles such as Haruo Shiramizu, “Clay Mineralogy”, 1988, Asakura Shoten Co., Ltd.

  The solvent for swelling the inorganic layered compound is not particularly limited. For example, in the case of a natural swellable clay mineral, alcohols such as water and methanol, dimethylformamide, dimethyl sulfoxide, acetone and the like can be mentioned. Are more preferred.

In the method for producing a film laminate of the present invention, the resin layer (B) is provided on the inorganic layer (A). The resin used for the resin layer (B) used in the present invention is not particularly limited. For example, polyvinyl alcohol (PVA), ethylene-vinyl alcohol copolymer (EVOH), polyvinylidene chloride (PVDC), polyacrylonitrile ( PAN), polysaccharides, polyacrylic acid and esters thereof.

  Preferable examples of the resin include high hydrogen bond resins that satisfy a ratio of 20% to 60% by weight of hydrogen bond groups or ionic groups per unit weight of the resin. More preferable examples include those in which the weight percentage of hydrogen bonding groups or ionic groups per unit weight of the high hydrogen bonding resin satisfies a ratio of 30% to 50%. “Hydrogen bonding group” refers to a group having at least one hydrogen bonded directly to an atom (heteroatom) other than carbon. The “ionic group” refers to a group having at least one “positive or negative” charge that is localized to the extent that water molecules can be hydrated in water. Examples of the hydrogen bonding group of the high hydrogen bonding resin include a hydroxyl group, an amino group, a thiol group, a carboxyl group, a sulfonic acid group, and a phosphoric acid group. The ionic group includes a carboxylate group, a sulfonic acid ion group, and a phosphoric acid group. An ionic group, an ammonium group, a phosphonium group, etc. are mentioned. Among the hydrogen bonding group or ionic group of the high hydrogen bonding resin, more preferable examples include a hydroxyl group, an amino group, a carboxyl group, a sulfonic acid group, a carboxylate group, a sulfonic acid ion group, and an ammonium group. It is done.

  Specific examples of the high hydrogen bonding resin include, for example, polyvinyl alcohol and its analogs, vinyl alcohol resins such as ethylene-vinyl alcohol copolymer having a vinyl alcohol fraction of 41 mol% or more; hydroxymethyl cellulose, hydroxyethyl cellulose, Polysaccharides such as carboxymethyl cellulose, amylose, amylopectin, pullulan, curdlan, xanthan, chitin, chitosan, cellulose; polyacrylic acid, sodium polyacrylate, poly-2-hydroxyethyl acrylate, poly-2-hydroxyethyl methacrylate, poly Acrylic resins such as acrylamide, ethylene-acrylic acid copolymer and salts thereof; polyaminoamide-based resins such as diethylenetriamine-adipic acid polycondensate, polystyrene sulfonic acid, polyester Hydrogen-bonding groups such as sodium styrenesulfonate, polyvinylpyridine and salts thereof, polyethyleneimine and salts thereof, polyallylamine and salts thereof, polyvinylpyrrolidone, polyvinylsulfonic acid and salts thereof, polyvinylthiol, polyethylene glycol, polypropylene glycol and polyglycerin And resins having an ionic group in the molecule.

  More preferable examples of the high hydrogen bonding resin include polyvinyl alcohol, polysaccharides, and ethylene-vinyl alcohol copolymers having a vinyl alcohol fraction of 40 mol% to 80 mol%. Here, polyvinyl alcohol is a polymer having a monomer unit of vinyl alcohol as a main component. As such “polyvinyl alcohol”, for example, a polymer obtained by hydrolysis or transesterification (saponification) of an acetate portion of a vinyl acetate polymer (to be exact, a copolymer of vinyl alcohol and vinyl acetate was obtained. And a polymer obtained by saponifying a vinyl trifluoroacetate polymer, a vinyl formate polymer, a vinyl pivalate polymer, a t-butyl vinyl ether polymer, a trimethylsilyl vinyl ether polymer, etc. For details, see, for example, edited by Poval Society, “World of PVA”, 1992, Kobunshi Publishing Co., Ltd .; Nagano et al., “Poval”, 1981, Kobunshi Publishing Co., Ltd. ). The degree of “saponification” in polyvinyl alcohol is preferably 70% or more, more preferably 85% or more, and more preferably 98% or more of a so-called fully saponified product in terms of mole percentage. The degree of polymerization is more preferably from 100 to 5000, and more preferably from 200 to 3000.

  The polysaccharide referred to here is a biopolymer synthesized in a biological system by condensation polymerization of various monosaccharides, and here includes those chemically modified based on them. For example, cellulose and cellulose derivatives such as hydroxymethylcellulose, hydroxyethylcellulose, carboxymethylcellulose, amylose, amylopectin, pullulan, curdlan, xanthan, chitin, chitosan, and the like can be given. The ethylene-vinyl alcohol copolymer (hereinafter referred to as EVOH) is an EVOH having a vinyl alcohol fraction of 40 mol% to 80 mol%, more preferably 45 mol% to 75 mol%. means. The EVOH melt index (measured under conditions of a temperature of 190 ° C. and a load of 2160 g; hereinafter referred to as MI) is not particularly limited, but is 0.1 to 50 g / 10 min. Furthermore, EVOH referred to in the present invention may be modified with a small amount of a copolymerization monomer as long as the object of the present invention is not impaired.

  When the resin used in the present invention is a high hydrogen bond resin, a crosslinker for hydrogen bond groups can be used for the purpose of improving the water resistance (meaning barrier properties after a water resistance environment test). Preferable examples of the crosslinking agent include titanium coupling agents, silane coupling agents, melamine coupling agents, epoxy coupling agents, isocyanate coupling agents, copper compounds, zirconium compounds and the like. From the viewpoint of improving water resistance, a zirconium compound is particularly preferably used. Specific examples of the zirconium compound include, for example, zirconium halides such as zirconium oxychloride, hydroxyzirconium chloride, zirconium tetrachloride and zirconium bromide; zirconium salts of mineral acids such as zirconium sulfate, basic zirconium sulfate and zirconium nitrate; formic acid Zirconium salts of organic acids such as zirconium, zirconium acetate, zirconium propionate, zirconium caprylate, zirconium stearate; ammonium zirconium carbonate, sodium zirconium sulfate, ammonium zirconium acetate, sodium zirconium oxalate, sodium zirconium citrate, zirconium ammonium citrate, etc. And the like. The addition amount of the cross-linking agent is not particularly limited, but the ratio (K = CN / HN) of the number of moles of cross-linking groups (CN) of the cross-linking agent to the number of moles of hydrogen bonding groups (HN) of the resin is 0. It is preferable to use so that it may become the range of 001-10. The mole ratio K is more preferably in the range of 0.01 to 1.

The film laminate obtained by the production method of the present invention is molded into various forms and used, and the form of the molded product is not particularly limited. For example, it is preferable to use it for a film, a sheet, a container (tray, bottle, etc.) because the gas barrier property is sufficiently exhibited.

  The base material of the base material layer (C) used for this invention is not specifically limited, There is no restriction | limiting in particular in forms, such as a film form, a sheet form, a bottle form, a tray form. As the material, known or general materials such as resin, paper, aluminum foil, wood, cloth, and nonwoven fabric can be used according to the purpose and application. In particular, when it is in the form of a film, it may be stretched uniaxially or biaxially in addition to non-stretching. Of course, known undercoating or corona treatment may be applied, and these surface treatments may be applied not only to the film form but also to other forms of the substrate as long as the effects of the invention are not impaired.

  As the resin constituting the base layer (C), polyethylene (low density, high density), ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-hexene copolymer, ethylene-octene copolymer, Polyolefin resins such as polypropylene, ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate copolymer, ionomer resin; polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate; nylon-6, nylon -6,6, amide resins such as metaxylenediamine-adipic acid condensation polymer, polymethylmethacrylamide; acrylic resins such as polymethylmethacrylate; polystyrene, styrene-acrylonitrile copolymer, styrene-acrylonitrile-buta Styrene or acrylonitrile resins such as ene copolymers and polyacrylonitrile; halogen-containing resins such as polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, and polytetrafluoroethylene (Teflon); polyvinyl alcohol and ethylene-vinyl alcohol copolymers , Hydrogen bonding resins such as cellulose derivatives; biodegradable resins such as pullulan, curdlan, chitin, chitosan, etc .; hydrophobized cellulose resins such as cellulose triacetate and cellulose diacetate; polycarbonate resins, polysulfone resins, polyether mons Examples thereof include engineering resins such as phon resin, polyether ether ketone resin, polyphenylene oxide resin, polymethylene oxide resin, and liquid crystal resin.

  Among these, biaxially stretched polypropylene, polyethylene terephthalate, nylon, polyvinylidene chloride coated bi-axially stretched polypropylene called polyethylene, polyethylene terephthalate, nylon and non-stretched polypropylene deposited with nylon, aluminum, silica, alumina, etc. (CPP), biaxially oriented polypropylene (OPP), polyethylene terephthalate (PET), nylon (ONy) and the like are preferably used as the resin constituting the base material layer (C).

A sealant resin layer may be further laminated on the film laminate obtained by the production method of the present invention. The sealant resin layer means an unstretched thermoplastic resin layer, and refers to a film obtained by extruding a thermoplastic resin by an inflation molding method, a T-die molding method or the like, and a film having a substantially small resin orientation. Refers to that. The film thickness is not particularly limited, but is preferably 1 μm or more in order to obtain sufficient heat seal strength.

  The thermoplastic resin used in the unstretched thermoplastic resin layer is polypropylene, polyethylene (low density, high density), ethylene-propylene copolymer, from the problems of desorption such as heat seal strength, food fragrance, and resin odor. Ethylene-butene copolymer, ethylene-hexene copolymer, ethylene-4-methyl-1-pentene copolymer, ethylene-octene copolymer, polypropylene, ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate copolymer Polyolefin resins such as polymers, ethylene-methyl acrylate copolymers, ethylene-acrylic acid copolymers, and ionomer resins, and polyester resins such as polyethylene terephthalate and polybutylene terephthalate are preferably used.

  Moreover, as a method of laminating the inorganic layer (A) and the resin layer (B) on the base material layer (C), extrusion lamination, dry lamination, coating, and the like can be mentioned. preferable. As the coating method, the surface of the base material layer (C) is coated with the coating liquid for the inorganic layer (A), dried, preferably heat-treated, and the resin layer (B) is coated on the layer. A method of coating the liquid is preferred. Further, the interface between the two may be subjected to a treatment such as a corona treatment or an anchor coating agent. Coating methods include direct gravure method, reverse gravure method, micro gravure method, roll coating method such as two roll beat coating method, bottom feed three reverse coating method, doctor knife method, die coating method, dip coating method, bar Examples of the method include a coating method and a coating method combining these. Regarding the order of lamination, it is preferable from the viewpoint of transparency that the inorganic layer (A) is laminated on the base material layer (C) and the resin layer (B) is laminated thereon.

  The total thickness of the inorganic layer (A) and the resin layer (B) is preferably 10 μm or less, more preferably 2 μm or less, and even more preferably 1 μm or less in terms of dry thickness. If it is 1 μm or less, it has the advantage that the transparency of the laminate is remarkably excellent, so it is more preferable for applications requiring transparency. The lower limit is not particularly limited, but is preferably 1 nm or more, more preferably 10 nm or more, and particularly preferably 100 nm or more in order to obtain effective gas barrier properties. Moreover, the ratio of the thickness of the inorganic layer (A) and the resin layer (B) is preferably 5/1 to 1/5 in terms of transparency and barrier properties.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these.

The measurement method of physical properties is described below.
(Thickness measurement)
The thickness of 0.5 μm or more was measured with a commercially available digital thickness gauge (contact thickness gauge, trade name: ultra-high precision deci-micro head MH-15M, manufactured by Nippon Optical Co., Ltd.). On the other hand, the thickness of less than 0.5 μm is determined by gravimetric analysis (the weight measurement value of a film of a certain area is divided by the area and further divided by the specific gravity of the composition) or the lamination of the composition of the present invention and the substrate. In the case of the body, the ratio of the resin composition layer of the present invention to the base material is determined from the elemental analysis method (the specific inorganic element analysis value of the laminate (derived from the composition layer) and the ratio of the specific element fraction of the inorganic layered compound alone. Method).
[Aspect ratio calculation]
Using an X-ray diffraction apparatus (XD-5A, manufactured by Shimadzu Corporation), diffraction measurement was performed by a powder method using an inorganic layered compound alone. Thereby, the interplanar spacing (unit thickness) a of the inorganic layered compound was determined. Using the particle diameter L obtained by the above-mentioned dynamic light scattering method, the aspect ratio Z was determined by the equation Z = L / a.
[Oxygen permeability measurement]
Measurement was carried out under conditions of 23 ° C. and 50% RH with an ultrasensitive oxygen permeability measuring device (OX-TRAN ML, manufactured by MOCON).
[Water vapor permeability measurement]
The measurement was performed under the conditions of 40 ° C. and 90% RH by a JIS-compliant cup method.
[transparency]
The total light transmittance at a wavelength of 500 nm was measured with a spectrophotometer (Hitachi, Ltd., self-recording spectrophotometer 330 type). About haze (Haze), it measured using the haze meter (made by Suga Test Instruments).
[Flexibility test]
The film laminate was aged for 24 hours in an environment of 23 ° C. and 50% RH, and then 100 times using a gel bath flex tester with a thermostatic bath (Tester Sangyo Co., Ltd.).

[Coating fluid]
Coating liquid C: Natural montmorillonite (Kunipia F; manufactured by Kunimine Kogyo Co., Ltd.) is dispersed as powder (E) in ion-exchanged water (0.7 μS / cm or less) to 3.3 wt%. Coating liquid C And
Coating solution D: Polyvinyl alcohol (PVA117H; manufactured by Kuraray Co., Ltd., saponification degree: 99.6%, polymerization degree 1700) is dissolved in ion-exchanged water (0.7 μS / cm or less) to 6.7 wt%. Is the coating liquid D.
Coating solution E: Polyvinyl alcohol (PVA117H; manufactured by Kuraray Co., Ltd., saponification degree: 99.6%, polymerization degree 1700) was dissolved in ion-exchanged water (0.7 μS / cm or less) to 1.5 wt%. Further, natural montmorillonite (Kunipia F; manufactured by Kunimine Kogyo Co., Ltd.) is added and dispersed so that the final solid content concentration is 4.8 wt% (so that the weight ratio of inorganic layered compound / resin = 33/15). Mix) Coating liquid E.
Coating solution F: Polyvinyl alcohol (PVA117H; manufactured by Kuraray Co., Ltd., saponification degree: 99.6%, polymerization degree 1700 was dissolved in ion-exchanged water (0.7 μS / cm or less) to 5.2 wt%. Let it be coating liquid F.
Coating solution G: Polyvinyl alcohol (PVA117H; manufactured by Kuraray Co., Ltd., saponification degree: 99.6%, polymerization degree 1700 was dissolved in ion-exchanged water (0.7 μS / cm or less) to 0.1 wt%, and Natural montmorillonite (Kunipia F; manufactured by Kunimine Kogyo Co., Ltd.) is added and dispersed so that the final solid content concentration is 3.4 wt% (mixed so that the inorganic layered compound / resin = 33/1 by weight ratio). ) Coating liquid G. Coating liquid H: Polyvinyl alcohol (PVA117H; manufactured by Kuraray Co., Ltd., saponification degree: 99.6%, polymerization degree 1700 in ion exchange water (0.7 μS / cm or less) 6.6 wt% This is dissolved to make coating solution H.
Coating liquid K: Polyvinyl alcohol (PVA117H; manufactured by Kuraray Co., Ltd., saponification degree: 99.6%, polymerization degree 1700 is dissolved in ion-exchanged water (0.7 μS / cm or less), and further natural montmorillonite (Kunipia F; Kunimine Industries) Co., Ltd.) is added and dispersed so that the final solid content concentration is 6.2 wt% (mixed so that the weight ratio is inorganic layered compound / resin = 33/15).

Example 1
A microgravure coating of the coating liquid C was performed using a base film of a 20 μm-thick biaxially stretched polypropylene (OPP) film (Pyrene P2102; manufactured by Toyobo Co., Ltd.) as a base (test). Coater: Yasui Seiki Co., Ltd .: Micro gravure coating method, coating speed 6 m / min, gravure roll mesh diagonal line # 150, drying temperature 100 ° C.), film thickness after drying 0.1 μm. On the upper side of the coating surface of the coating liquid C, the coating liquid D was overcoated by a microgravure method (coating speed 6 m / min, gravure roll mesh oblique line # 150, drying temperature 100 ° C.), film after drying Thickness 0.4 μm. Then, the haze of the coated film was measured. In addition, an adhesive Eunoflex J3 (manufactured by Sanyo Chemical Industries Co., Ltd., coating film thickness 4 μd ry) is applied to the coated surface of the above coated film, and a linear polyethylene (LL; Sekifill Corporation) with a thickness of 40 μm K101) and dry lamination. The dry lamination film was subjected to 100 bending resistance tests. Then, oxygen permeability was measured. Table 1 shows the results.

(Comparative Example 1)
A microgravure coating of coating liquid E was performed using a base film of a 20 μm-thick biaxially oriented polypropylene (OPP) film (pyrene P2102; manufactured by Toyobo Co., Ltd.) as a base material (test) Coater; manufactured by Yasui Seiki Co., Ltd .: micro gravure coating method, coating speed 6 m / min, gravure roll mesh diagonal line # 150, drying temperature 100 ° C.), film thickness after drying 0.2 μm. On the upper side of the coating surface of the coating liquid E, the coating liquid F was overcoated by a microgravure method (coating speed 6 m / min, gravure roll mesh oblique line # 150, drying temperature 100 ° C.), film after drying Thickness 0.3 μm. Then, the haze of the coated film was measured. Moreover, the adhesive Eunoflex J3 (manufactured by Sanyo Chemical Industries Co., Ltd., coating film thickness 4 μd ry) was applied to the coated surface of the coated film, and dry lamination was performed with linear polyethylene (LL) having a thickness of 40 μm. . The dry lamination film was subjected to 100 bending resistance tests. Then, oxygen permeability was measured. The results are shown in Table 1.

(Comparative Example 2)
A microgravure coating of the coating liquid G was carried out using a film subjected to a single-sided corona treatment of a 20 μm-thick biaxially oriented polypropylene (OPP) film (Pyrene P2102; manufactured by Toyobo Co., Ltd.) (test) Coater; Yasui Seiki Co., Ltd .: Micro gravure coating method, coating speed 6 m / min, gravure roll mesh diagonal line # 150, drying temperature 100 ° C.), film thickness after drying 0.1 μm. On the upper side of the coating surface of the coating solution G, the coating solution H was overcoated by a microgravure method (coating speed 6 m / min, gravure roll mesh diagonal # 150, drying temperature 100 ° C.), film after drying Thickness 0.4 μm. Then, the haze of the coated film was measured. Further, the adhesive Eunoflex J3 (manufactured by Sanyo Chemical Industries Co., Ltd., coating thickness 4 μd ry) was applied to the coated surface of the coated film, and dry lamination was performed with linear polyethylene (LL) having a thickness of 40 μm. . The dry lamination film was subjected to 100 bending resistance tests. Then, oxygen permeability was measured. The results are shown in Table 1.

(Comparative Example 3)
A microgravure coating of the coating liquid K was performed using a base film of a 20 μm-thick biaxially stretched polypropylene (OPP) film (Pyrene P2102; manufactured by Toyobo Co., Ltd.) as a base (test). Coater: Yasui Seiki Co., Ltd .: Microgravure coating method, coating speed 6 m / min, gravure roll mesh diagonal line # 90, drying temperature 100 ° C.), film thickness after drying 0.5 μm. Then, the haze of the coated film was measured. Further, the adhesive Eunoflex J3 (manufactured by Sanyo Chemical Industries Co., Ltd., coating thickness 4 μd ry) was applied to the coated surface of the coated film, and dry lamination was performed with linear polyethylene (LL) having a thickness of 40 μm. . The dry lamination film was subjected to 100 bending resistance tests. Then, oxygen permeability was measured. The results are shown in Table 1.

(Comparative Example 4)
A microgravure coating of coating liquid E was performed using a base film of a biaxially stretched polypropylene (OPP) film (pyrene P2102; manufactured by Toyobo Co., Ltd.) having a thickness of 20 μm and subjected to corona treatment (test). Coater; manufactured by Yasui Seiki Co., Ltd .: micro gravure coating method, coating speed 6 m / min, gravure roll mesh diagonal line # 150, drying temperature 100 ° C.), film thickness after drying 0.2 μm. Then, the haze of the coated film was measured. Further, the adhesive Eunoflex J3 (manufactured by Sanyo Chemical Industries Co., Ltd., coating thickness 4 μd ry) was applied to the coated surface of the coated film, and dry lamination was performed with linear polyethylene (LL) having a thickness of 40 μm. . The dry lamination film was subjected to 100 bending resistance tests. Then, oxygen permeability was measured. The results are shown in Table 1.

注）ゲルボ：耐屈曲性テスト

Note) Gelbo: Bending resistance test

FIG. 1 is a graph schematically showing the relationship between the X-ray diffraction peak of an inorganic layered compound and the “unit thickness a” of the compound.

Claims (1)

A step of laminating an inorganic layer (A) composed of an inorganic layered compound on at least one side of the base material layer (C);
Laminating a resin layer (B) containing a high hydrogen bonding resin on the surface of the inorganic layer (A);
The manufacturing method of the film laminated body characterized by including.

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