JP2007055189A - Method for manufacturing coated film and coated film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing a coated film (a gas barrier film) to which excellent gas barrier properties can be imparted, even in the case wherein the film is manufactured by a laminating process using a take-up device etc. <P>SOLUTION: This method comprises (1) a coating process to apply a coating liquid containing a hydrolytically condensable organic metal compound (alkoxysilane etc.) onto at least one surface of a base film, (2) a drying process to dry the film after the coating process (1), and (3) a lamination process to laminate the film under a moist condition after the drying process (2). In this method, the film is dried in a moist atomosphere in the drying process (2). In the drying process (2), the film may be moistened and dried under such a condition that the temperature be 40 to 170°C and the humidity [mass(kg) of water vapor/mass(kg) of dried air (dry air)] be 0.012 to 0.2. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for producing a coated film (gas barrier film) having excellent gas barrier properties against oxygen and the like, and a coated film obtained by this method.

  Packaging films used for foods, pharmaceuticals, precision electronic parts, etc. are required to have high transparency for the visibility and aesthetics of the contents, as well as to prevent deterioration of the contents due to moisture absorption and oxidation. Therefore, a high gas barrier property is required. In recent years, with the spread of microwave ovens, cooked or semi-cooked foods (hereinafter collectively referred to as cooked foods) may be heated in a microwave oven while being packaged. In addition, the cooked food is often retorted after packaging. Therefore, such a packaging film may be required to have resistance to retort processing and heating in a microwave oven.

  Such a packaging film can usually be constituted at least by a base film and a gas barrier layer formed on the base film, and various laminated films have been proposed. For example, in JP-A-1-202435 (Patent Document 1) and JP-A-1-202436 (Patent Document 2), a silicon oxide vapor-deposited layer and a heat seal layer or protection are provided on the surface of a base film. A packaging material for a microwave oven and a packaging material for a retort food, in which a layer is formed, are disclosed.

A gas barrier film in which a gas barrier layer is formed of a condensate of a hydrolyzable condensable compound such as a metal alkoxide is also known. For example, in JP-A-8-309913 (Patent Document 3), at least one surface of a base film layer contains a silane coupling agent via an inorganic thin film layer made of silicon oxide or the like. A barrier composite film coated with a barrier resin layer is disclosed. Japanese Patent No. 3119113 (Patent Document 4) discloses a polymer organic compound (A) having a primary and / or secondary amino group in a molecule such as polyethyleneimine and a functional group capable of reacting with the amino group. Disclosed is a surface-treated resin molded article in which the surface of a resin molded article is coated with a surface coating composition containing a group-containing compound (B), an organosilane compound (C) and / or a hydrolysis condensate thereof, and an alcohol. Has been. Furthermore, JP-A-2003-128121 (Patent Document 5) discloses an organic compound having in its molecule a nitrogen atom having active hydrogen bonded to at least a part of the surface of a molded body (A) made of polyester, polyolefin or polyamide. A gas barrier layer (B) and a metal layer or metal oxide layer (C) using a composition obtained by reacting (I) with an organic compound (II) having a functional group capable of reacting with active hydrogen, A packaging material is disclosed which has a water vapor transmission rate of 5 g / m ² · 24 hours at 40 ° C. and 90% RH.

  However, in the gas barrier film described in these documents, hydrolysis condensation such as a silane coupling agent cannot be performed efficiently, and sufficient gas barrier properties cannot be imparted. In particular, when producing such a gas barrier film by winding it in a roll shape, there is insufficient moisture for hydrolysis or diffusion (or diffusion) of by-products (such as alcohol) that accompanies hydrolysis. Since it becomes difficult to generate, it is difficult to efficiently obtain a film having a high gas barrier property.

  On the other hand, in order to improve gas barrier properties, it is known to perform an aging treatment after forming a barrier layer containing a hydrolyzable compound on a substrate. For example, in JP-A-2002-292810 (Patent Document 6), polyvinyl alcohol, a specific alkoxysilane having an amino group and / or an imino group, a specific alkoxysilane having an epoxy group, and water or a lower alcohol are added. A first step of applying a composition containing water in a specific ratio on a polyester substrate and drying to form a gas barrier layer; and a second step of aging the substrate on which the gas barrier layer is formed; A method for producing a gas barrier film having a third step of laminating on the gas barrier layer is disclosed. In this document, with respect to aging, the aging time is preferably 20 hours or more, more preferably 24 hours or more, the aging temperature is preferably 20 ° C. to 40 ° C., and the humidity during aging is 50% RH to 80%. It is stated that RH is preferred.

  Japanese Patent Laying-Open No. 2003-191404 (Patent Document 7) discloses a laminate including a base material layer made of a thermoplastic resin film and a gas barrier layer made of a hydrolyzate of silicon alkoxide, a layered silicate, and a polyvinyl alcohol resin. In the body manufacturing method, a gas barrier coating agent comprising an aqueous solution obtained by hydrolyzing silicon alkoxide in the presence of a layered silicate dispersed in an aqueous solution of a polyvinyl alcohol-based resin is applied onto the base layer. In addition, a method is disclosed in which an aging treatment is further performed after a gas barrier layer is formed by drying at a predetermined temperature. According to this document, the aging treatment is preferably performed in an atmosphere of a temperature of 30 ° C. to 80 ° C. and a relative humidity of 30% RH to 100% RH, and the aging treatment is performed in an atmosphere of a relative humidity of 30% RH or more. As a result, hydrolysis of the alkoxy group of the silicon alkoxide remaining in the gas barrier layer and subsequent polycondensation reaction or hydrogen bonding with the polyvinyl alcohol resin proceeds, and the free volume in the coating layer is reduced, aging It is described that the number of days required for processing may be set to be in the range of 1 day to 10 days.

  In this document, as a method for performing an aging treatment, a film in which a gas barrier coating agent is applied and dried on the base material layer is subjected to an aging treatment in a constant temperature and humidity chamber in which humidity and relative humidity are set. When winding in a roll shape, lowering the winding tension and providing a gap between gas barrier films and then aging treatment in a constant temperature and humidity chamber, or spraying water vapor to the gas barrier layer when winding in a roll shape It describes that an aging method or the like may be used.

  Further, JP-A-7-323261 (Patent Document 8) discloses a compound having a specific silane compound (A) and a functional group having reactivity with an amino group in the silane compound (A) in the molecule. A method for producing a coating film is disclosed in which a coating composition containing (B) is applied to a substrate and then dried in a heated and humidified atmosphere to form a film. In this document, it is described that the heating conditions for dry coating are preferably 50 ° C. or higher, 5% RH or higher in relative humidity, and preferably 1 second or longer. The prepared coating composition was applied to a 25 μm PET film with a bar coater and dried at 80 ° C. and 60% RH for 30 seconds.

However, even when an aging treatment as described in these documents is performed, when a gas barrier film is laminated and manufactured by winding or the like, it is still difficult to efficiently obtain a film having a high gas barrier property.
JP-A-1-202435 (Claims) JP-A-1-202436 (Claims) JP-A-8-309913 (Claims) Japanese Patent No. 3119113 (Claims) JP 2003-128121 A (Claims) JP 2002-292810 A (Claims) JP 2003-191404 A (claims, paragraph numbers [0087] to [0094]) JP-A-7-323261 (Claims, paragraph numbers [0039] [0045])

  Therefore, the objective of this invention is providing the manufacturing method of the coat film (gas barrier film) which can provide the outstanding gas barrier property efficiently, even if manufactured by lamination | stacking, such as winding.

  Another object of the present invention is to provide a method for efficiently producing a coated film having a high gas barrier property by lamination (for example, winding of the film).

  As a result of intensive investigations to achieve the above-mentioned problems, the inventors of the present invention have applied a coating process in which a base film is coated with a coating solution containing a hydrolytic condensable organometallic compound, a drying process for drying the film, and a film winding. In a manufacturing method of a series of coat films (gas barrier films) including a lamination step of laminating by removing, etc., by drying the film under humidification in the drying step, and laminating the film under humidification in the lamination step The present inventors completed the present invention by finding that a coat film having high gas barrier properties can be efficiently produced even when the films are laminated while the hydrolysis and condensation of the hydrolysis-condensable organometallic compound can be remarkably accelerated. .

  That is, the method for producing a coated film of the present invention includes a coating step (1) for coating a coating liquid containing a hydrolytic condensable organometallic compound (A) on at least one surface of a base film, and this coating step (1 ) And then a drying step (2) for drying the film, and after this drying step (2), a laminating step (3) for laminating the film under humidification, wherein the drying is performed. Step (2) includes a humidifying step of humidifying the film.

  In the drying step (2), the humidification treatment may be performed under heating. For example, the drying step (2) is performed at a temperature of 55 to 150 ° C. and humidity (mixing ratio, water content) [mass of water vapor ( kg) / mass of dry air (dry air) (kg)] may be a step including a humidifying step of humidifying the film under a humidifying condition of 0.03 to 0.18. In the lamination step (3), humidity (or moisture content) [mass of water vapor (kg) / mass of dry air (dry air) (kg)] is in a humidified condition of about 0.015 to 0.06. You may laminate.

  In the laminating step (3), for example, the film that has undergone the drying step (2) may be laminated while being wound. The manufacturing method may include an aging treatment step (4) for further aging the laminated film after the lamination step (3).

  In particular, the aging treatment step (4) may be an aging step (4) for aging treatment under humidification. For example, in the aging step (4), a temperature of 30 to 130 ° C. and humidity [mass of steam (kg ) / Mass of dry air (dry air) (kg)] Aging treatment may be performed under a humidified condition of 0.016 to 0.05.

  In the typical production method, (i) the drying step (2) includes a temperature of 60 to 150 ° C. and humidity [mass of water vapor (kg) / mass of dry air (dry air) (kg)] 0.035 to 0. (Ii) In the laminating step (3), a temperature of 30 to 100 ° C. and a humidity [mass of water vapor (kg) / dry air (dry air) ) Mass (kg)] under a humidified condition of 0.016 to 0.05 without winding water droplets, (iii) in the aging step (4), temperature 30 to 130 ° C. and humidity [water vapor Mass (kg) / mass of dry air (dry air) (kg)] Under humidified conditions of 0.017 to 0.045, the film wound without adhering water droplets was subjected to aging treatment for 12 to 20 hours. May be.

  The base film may be composed of, for example, a base film formed of a polypropylene resin, a polyester resin, or a polyamide resin. The base film is formed of a base film and a metal oxide (for example, at least one metal oxide selected from aluminum oxide and silicon oxide) formed on at least one surface of the base film. It may be comprised with the made inorganic layer.

  The coating solution may be an aqueous solution composed of a hydrolytic condensable organometallic compound [in particular, an organosilicon compound such as alkoxysilanes] and an aqueous solvent (water, alcohols, etc.). Further, the coating solution may be a coating solution (aqueous solution) further containing an amino group-containing compound, such as (A1) a functional group capable of reacting with an amino group and An aqueous coating liquid composed of an organosilicon compound having a hydrolytic condensable group, (B) a compound having an amino group, and (C) an alcohol may be used.

The coated film obtained by the said manufacturing method is also contained in this invention. Such a coated film has high gas barrier properties despite being manufactured by lamination such as winding. For example, the oxygen permeability of the laminated film at a temperature of 20 ° C. and a humidity of 90% RH may be 60 ml / m ² · day · MPa or less.

  In the method of the present invention, after coating a coating solution containing a hydrolytic condensable organometallic compound, it is dried under humidification, and is laminated under humidification in the laminating step, so that moisture can be effectively supplied into the film and wound. Even if it manufactures by lamination | stacking, such as taking off, the gas barrier property excellent in the laminated | multilayer film (gas barrier film) can be provided efficiently. Further, in the method of the present invention, a coated film having a high gas barrier property can be efficiently incorporated by laminating (for example, winding up the film), which can be incorporated into a series of manufacturing processes that undergo a coating process, a drying process, and a laminating process. Can be manufactured. In particular, in the present invention, since it can be produced by lamination such as winding, a coated film can be obtained industrially advantageously and is highly practical.

  The manufacturing method of the coated film (laminated film, laminated coated film) of the present invention includes a coating step (1) of coating (coating) a coating liquid containing a hydrolytic condensable organometallic compound on at least one surface of a base film. In addition, after this coating step (1), a drying step (2) for drying the film and a lamination step (3) for laminating the film after the drying step (2) are included, and at least the drying step ( The film is humidified in 2) and the laminating step (3). In the present invention, by combining drying under humidification and lamination under humidification, a film having excellent gas barrier properties can be obtained even when lamination is performed by winding.

  That is, a coating layer formed of a coating solution containing a hydrolytic condensable organometallic compound develops a gas barrier performance as a result of a hydrolysis-condensation reaction proceeding with water, but a film on which such a gas barrier layer is formed, In order to continuously produce industrially, it is advantageous to manufacture in the form of a laminated film laminated by, for example, winding in a roll shape, instead of a single film not laminated. However, since such a laminated film is laminated in multiple layers (for example, thousands or tens of thousands), the hydrolysis and condensation reaction is extremely progressed because it takes a long time for water to penetrate into the film. It is slow and difficult to produce industrially. In order to advance such a hydrolysis-condensation reaction, it is also known to age the film under humidification, but even with such aging, in an industrially acceptable period (for example, about one month) Sufficient gas barrier performance cannot be expressed.

[Base film]
The base film can be composed at least of a base film (base film, base film layer).

(Base film)
The base film may be paper, metal (metal film), or the like, but is usually a film made of resin (resin film, plastic film) in many cases. Examples of the resin constituting the base film (base film layer, core layer) include various resins that can be formed, such as olefin resins [for example, polyethylene resins (polyethylene, ethylene-propylene copolymer, ethylene-acrylic). Propylene-containing 80 weight by weight such as ethyl acid copolymer, ionomer), polypropylene resin (eg, polypropylene, propylene-ethylene copolymer, propylene-butene-1 copolymer, propylene-ethylene-butene-1 copolymer) % Of propylene-based resin and the like), polyolefin such as poly-4-methylpentene-1], polyester-based resin [for example, polyalkylene terephthalate (polyethylene terephthalate, polybutylene terephthalate, etc.), polyalkylene naphthalate (polyethylene- , 6-naphthalate, etc.), polyamide resins (polyamide 6, polyamide 11, polyamide 12, polyamide 66, polyamide 610, polyamide 6/66, polyamide 66/610, polyamide) MXD, etc.), vinyl chloride resins (polyvinyl chloride, etc.), vinylidene chloride resins (vinylidene chloride-vinyl chloride copolymer, vinylidene chloride-acrylonitrile copolymer, vinylidene chloride- (meth) acrylic acid ester copolymer, etc.) ), Styrene resin (polystyrene, styrene-acrylonitrile copolymer, styrene-acrylonitrile-butadiene copolymer, etc.), polyvinyl alcohol resin (polyvinyl alcohol, ethylene-vinyl alcohol copolymer, etc.) , Polyimide resins (polyimide, polyamideimide, polyetherimide, etc.), polycarbonate resins, polysulfone resins (polysulfone, polyethersulfone, etc.), polyphenylene ether resins, polyphenylene sulfide resins (polyphenylene sulfide, etc.), cellulose resins Examples include cellulose ether resins, cellophane, etc., polyether ether ketone, polyparaxylene, polyacrylonitrile, copolymers containing these various resin (polymer) components, and the like. These polymers may be used alone or in combination of two or more.

The base film may be a single film or a composite film composed of a plurality of layers (for example, a laminate of different or similar plastic films). Among these base films, non-chlorine resins such as olefin resins (polypropylene resins such as polypropylene), polyester resins (eg, aromatic polyester resins such as poly C _2-4 alkylene arylate or copolyester) ), A polyamide-based resin is preferable, and a base film composed of a polypropylene-based resin, a polyester-based resin, or a polyamide-based resin (particularly a polyester-based resin) is particularly preferable. The base film is usually composed of a thermoplastic resin in many cases.

  For the base film (or base film), if necessary, stabilizers (antioxidants, ultraviolet absorbers, light stabilizers, heat stabilizers, etc.), crystal nucleating agents, flame retardants, flame retardant aids , Fillers, plasticizers, impact modifiers, reinforcing agents, colorants, dispersants, antistatic agents, foaming agents, antibacterial agents, lubricants (for example, inorganic lubricants such as silica-based fine powder and alumina-based fine powder, polyethylene Organic lubricants such as organic fine powder and acrylic fine powder), hydrocarbon polymer (styrene resin, terpene resin, petroleum resin, dicyclopentadiene resin, coumarone resin such as coumarone indene resin, phenol resin, rosin And derivatives thereof and hydrogenated resins thereof), waxes (higher fatty acid amides, higher fatty acids and salts thereof, higher fatty acid esters, mineral-based, plant-based natural waxes, synthetic waxes such as polyethylene) Box, etc.) may be added. These additives can be used alone or in combination of two or more.

  The base film (or base film) may be an unstretched film or a stretched (uniaxial or biaxial) film. As the stretched film, a biaxially stretched film is usually used in many cases. As the stretching method, for example, a conventional stretching method such as roll stretching, roll stretching, belt stretching, tenter stretching, tube stretching, or a combination of these can be applied. The draw ratio can be appropriately set according to the desired film properties, and is, for example, about 1.5 to 20 times, preferably about 2 to 15 times in at least one direction.

  The thickness of the base film (or base film) can be appropriately selected in consideration of packaging suitability, mechanical strength, flexibility and the like, and is usually 5 to 200 μm, preferably 7 to 100 μm, more preferably 8 to 50 μm, In particular, it may be about 10 to 30 μm (for example, 10 to 25 μm).

  The surface of the base film may be subjected to surface treatment such as discharge treatment such as corona discharge or glow discharge, acid treatment such as chromic acid treatment, and soot treatment.

  An undercoat layer may be formed on the surface of the base film (base film layer) instead of or together with the surface treatment. The undercoat layer is made of various resins such as thermoplastic resins, thermosetting resins, photo-curable (or actinic ray curable) resins (electron beam curable resins, ultraviolet curable resins, etc.), coupling agents, etc. Can be configured. Examples of the component of the undercoat layer include thermoplastic resins such as acrylic resins, vinyl chloride-vinyl acetate copolymers, polyvinyl butyral, cellulose polymers, and rosin-modified maleic resins; urethane resins, epoxy resins, and the like. Thermosetting resin; Photocurable resin such as urethane (meth) acrylate. These components can be used alone or in combination of two or more. The undercoat layer may contain a colorant such as a general-purpose dye or pigment. The content of the colorant is appropriately selected within a range that does not impair the transparency of the film, and may usually be about 1 to 30% by weight with respect to the resin constituting the undercoat layer. The thickness of the undercoat layer is not particularly limited, and may usually be about 0.1 to 5 μm. The method for forming the primer layer is not particularly limited, and an organic or aqueous coating agent containing the components of the primer layer is applied by a conventional coating method such as a roll coating method, a gravure coating method, a reverse coating method, or a spray coating method. And drying or curing. In addition, when using a photocurable resin, you may irradiate actinic light.

  In addition, the light transmittance of the base film (or base film) may be transparent or opaque depending on the use of the laminated film, but in the laminated film for applications requiring visibility and aesthetics, it is white. The total light transmittance with light is usually 40% or more (for example, about 45 to 99%), preferably 60% or more (for example, about 70 to 98%), more preferably 80% or more (for example, 85 to 85%). About 95%).

(Inorganic layer)
The base film may be composed of the base film alone, or may be composed of the base film and an inorganic layer formed on at least one surface of the base film.

  Although it does not specifically limit as an inorganic substance which forms an inorganic layer, Usually, it is preferable that it is a metal component which can form a transparent thin film, For example, beryllium, magnesium, calcium, strontium, barium etc. Periodic Table 2A group elements (metal elements); transition metal elements such as titanium, zirconium, ruthenium, hafnium, tantalum; periodic table 2B elements such as zinc; periodic table 3B elements such as aluminum, gallium, indium, thallium; Periodic table 4B group elements such as silicon, germanium and tin; simple substance (metal simple substance) such as periodic table 6B group elements such as selenium and tellurium, compounds containing these elements (usually inorganic compounds), for example, oxides, halogens And nitride, carbide, nitride and the like. These inorganic substances can be used alone or in combination of two or more.

  Among these inorganic substances (metal components), the inorganic layer is preferably composed of at least one metal component selected from an aluminum component and a silicon component.

  As an aluminum component, for example, in addition to aluminum alone (metal simple substance), a compound containing aluminum element (usually an inorganic compound), for example, oxide (aluminum oxide or aluminum oxide), halide, carbide, nitride, etc. Can be mentioned. Aluminum components may be used alone or in combination of two or more. Of these aluminum components, aluminum oxide is preferred.

  Examples of the silicon component include silicon (silicon simple substance), a compound containing silicon element (usually an inorganic compound), for example, oxide (silicon oxide or silicon oxide), halide, carbide, nitride, and the like. It is done. A silicon component may be individual or may combine 2 or more types. Of these silicon components, silicon oxide is preferred. The silicon oxide (silicon oxide) includes not only silicon monoxide and silicon dioxide but also a composition formula SiOx (where 0 <x ≦ 2, preferably 0.8 ≦ x ≦ 1.5). Silicon oxide.

  Among the metal components, in addition to being excellent in transparency and barrier properties, silicon oxide and aluminum oxide can form a dense thin film, and adhere to the components of the base film and the barrier layer described later. Sex (or affinity) is high. Therefore, even if a mechanical external force is applied, cracks and defects are not generated in the inorganic layer, and high gas barrier properties can be maintained for a long period of time.

  Therefore, the inorganic layer is particularly preferably composed of at least one metal oxide selected from aluminum oxide and silicon oxide.

  Note that in a packaging material (for example, a packaging material for electromagnetic wave heating), a non-conductive inorganic material such as a metal component having low conductivity, such as an oxide, halide, carbide, or nitride, can be suitably used. Preferred non-conductive metal components include aluminum oxide, silicon oxide (or silica) and the like.

  By combining such an inorganic layer composed of a metal component and a barrier layer (particularly, a barrier layer composed of a specific component described later), the inorganic layer and the base film and / or the barrier layer are adhered to each other. Efficiency can be improved efficiently. Such an inorganic layer should just be formed in at least one surface of a base film, and may be formed in both surfaces of a base film. The inorganic layer may be usually formed on one surface of the base film. In particular, the inorganic layer is often formed between the base film (and the undercoat layer) and the barrier layer. In addition, although an inorganic layer may be transparent or opaque, in the laminated | multilayer film of the use for which visibility etc. are requested | required, it usually has transparency in many cases.

  The thickness of the inorganic layer can be selected from the range of 50 to 5000 mm (0.005 to 5 μm), for example, 100 to 5000 mm (0.01 to 0.5 μm), preferably 200 to 3000 mm (0.02 to 0.3 μm). ), More preferably about 300 to 1500 mm (0.03 to 0.15 μm), particularly about 400 to 1000 mm (0.04 to 0.1 μm).

  The inorganic layer may be formed by a conventional method, for example, a physical method (vacuum vapor deposition method, reactive vapor deposition method, sputtering method, reactive sputtering method, ion plating method, reactive ion plating method, etc.), chemical method, etc. It can be formed by coating the surface of a base film (base film) with the inorganic material (CVD method, plasma CVD method, laser CVD method, etc.). In many cases, the inorganic layer is formed by a physical method such as vapor deposition, and the inorganic layer can be formed on one surface or both surfaces of a base film (base film).

  In addition, as described later, the base film further includes various coating layers and laminate layers, such as a heat seal layer, a slipping layer, an antistatic layer, a decorative printing film layer, and a reinforcing layer made of nylon film or the like. An ultraviolet blocking layer (for example, a UV blocking coating layer described in JP-A No. 2003-128121) may be formed.

[Coating solution]
The coating solution for forming the barrier layer is composed of at least a hydrolytic condensable organometallic compound (A). By applying a coating solution containing such a hydrolytic condensable organometallic compound (hereinafter sometimes simply referred to as a hydrolytic condensable compound, hydrolyzable compound, etc.) to the base film, the hydrolytic condensable compound Is condensed or polycondensed, and gas barrier properties are expressed or imparted to the barrier layer.

(Hydrolytic condensable organometallic compound)
The hydrolytic condensable organometallic compound (A) may be an organometallic compound having a hydrolytic condensable group. Examples of the hydrolytic condensable group include metal atoms (aluminum, silicon, titanium, zirconium, etc. Silicon) hydrolyzable groups [eg, alkoxy groups (eg, C _1-4 alkoxy groups such as methoxy group, ethoxy group, propoxy group, butoxy group, preferably lower alkoxy groups such as C _1-2 alkoxy group), etc.] A hydrocarbon group, a halogen atom (a chlorine atom, a bromine atom, particularly a chlorine atom)] directly bonded (for example, an alkoxysilyl group, a halosilyl group), and the like. The hydrolytic condensable organometallic compound may have a hydrolytic condensable group alone or in combination of two or more.

  The hydrolytic condensable organometallic compound (A) may have at least a hydrolytic condensable group. In addition to the hydrolytic condensable group, a functional group [for example, a hydroxyl group, an amino group, a substituted amino group, Mercapto group, epoxy group, carboxyl group or derivative group thereof (acid anhydride group, acid halide group, etc.), isocyanate group, thioisocyanate group, oxazolinyl group, aldehyde group, ketone group, haloalkyl group, polymerizable group (vinyl group) , An allyl group, a (meth) acryloyl group, a vinylene group, and the like)] (a silane coupling agent and the like). The hydrolytic condensable organometallic compound (A) may have these functional groups singly or in combination of two or more.

Specific hydrolysis-condensable organometallic compounds (A) include organometallic compounds that can be condensed or polycondensed by hydrolysis, such as organosilicon compounds, organoaluminum compounds [for example, trialkoxyaluminate (trimethoxyaluminate). , Tri-C _1-4 alkoxyaluminates such as triethoxyaluminate and tripropoxyaluminate)], organotitanium compounds [eg dialkoxytitanates such as dialkyldiC _1-4 alkoxytitanates (such as diethyldiethoxytitanate) s; (such as trimethoxy titanate) tri C _1-4 alkoxy titanates, (such as ethyl trimethoxy titanate) alkyl tri C _1-4 alkoxy titanates, thoria such Arirutori C _1-4 alkoxy titanates (such as phenyltrimethoxysilane titanate) Kokishichitaneto like; tetramethoxy titanate, tetraethoxy titanate, tetraalkoxy titanates such as tetra-C _1-4 alkoxy titanates such as tetra propoxy titanate, etc.) and the like. Of these hydrolytic condensable organometallic compounds, organosilicon compounds are particularly preferred. Hydrolytic condensable organometallic compounds may be used alone or in combination of two or more.

  Examples of organosilicon compounds include halosilanes and alkoxysilanes, with alkoxysilanes being preferred. Examples of the alkoxysilanes include alkoxysilanes that can be hydrolyzed and condensed by a sol-gel method, for example, alkoxysilanes represented by the following formula (1) or condensates thereof.

R ¹ _m Si (OR ² ) _n (1)
(In the formula, R ¹ represents a hydrogen atom, a hydroxyl group, a halogen atom or a hydrocarbon group optionally having a functional group, R ² represents a hydrocarbon group, m is 0 or an integer of 1 or more, n Is an integer of 1 or more, and m + n = 4.)
In the formula (1), examples of the hydrocarbon group represented by the group R ¹ include linear groups such as an alkyl group (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group) A branched C _1-8 alkyl group, preferably a C _1-6 alkyl group, more preferably a C _1-4 alkyl group, an alkenyl group (for example, a C _2-6 alkenyl group such as a vinyl group, an allyl group, preferably Is a C _2-4 alkenyl group, more preferably a C _2-3 alkenyl group), a cycloalkyl group (eg, a C _3-8 cycloalkyl group such as a cyclohexyl group), an aryl group (eg, a C _6- such as a phenyl group). ₁₅ aryl group, preferably C _6-10 aryl group, more preferably C _6-8 aryl group). Of these, preferred hydrocarbon groups include alkyl groups (C _1-4 alkyl groups and the like) and the like.

In the hydrocarbon group represented by the group R ¹ , the functional group includes, for example, the above-described functional group {for example, an amino group or a substituted amino group [for example, an aminoalkylamino group (such as an amino C ₂ such as a 2-aminoethylamino group). _-4 alkylamino group, etc.), alkenylamino group ( _C2-4 alkenylamino group such as allylamino group, etc.)], mercapto group, (meth) acryloyl group, epoxy group, isocyanate group, etc.}. These functional groups may be substituted alone or in combination of two or more with a hydrocarbon group. In addition, when the substitution number m is plural, the plural groups R ¹ may be the same or different.

Examples of the group R ² include an alkyl group and a cycloalkyl group. Usually, the group R ² may be an alkyl group. Examples of the alkyl group include a linear or branched C _1-4 alkyl group such as a methyl group and an ethyl group, preferably a C _1-2 alkyl group. The preferable number n of substitution is 2 to 4, more preferably 3 or 4. In addition, when the substitution number n is plural, the groups R ² may be the same or different.

  The alkoxysilane represented by the formula (1) may be monoalkoxysilanes (for example, alkoxysilane having n = 1 in the formula (1) such as vinyldimethylethoxysilane). Silanes (alkoxysilanes with n = 2 in the formula (1)), trialkoxysilanes (alkoxysilanes with n = 3 in the formula (1)), tetraalkoxysilanes (n in the formula (1)) = 4 alkoxysilanes).

Representative dialkoxysilane having, for example, dialkyl dialkoxy silanes (e.g., di-C _1-4 alkyl di C _1-4 alkoxysilane such as dimethyldimethoxysilane), diaryl dialkoxy silane, an amino group dialkoxy silane (for example, an amino C _1-4 alkyl C _1-4 alkyl di C _1-4 alkoxysilane such as 3-aminopropyl methyl dimethoxy silane; 3- such [N-(2-aminoethyl) amino] propyl methyl dimethoxysilane etc. (amino C _1-4 alkylamino) C _1-4 alkyl -C _1-4 alkyl di C _1-4 alkoxysilane), mercapto C such dialkoxysilanes (e.g., 3-mercaptopropyl methyl dimethoxy silane having a mercapto group _1-4 alkyl C _1-4 alkyl di C _1-4 alkoxysilane), alkenyl Dialkoxysilane having (e.g., mono- or di-C _2-4 Arukeniruji C _1-4 alkoxysilane such as vinyldimethoxymethylsilane), dialkoxysilane having a (meth) acryloyl group (e.g., 3- (meth) acrylate b alkoxy such as (meth) acryloyloxy C _1-4 alkyl C _1-4 alkyl di C _1-4 alkoxysilane such as methyl dimethoxysilane), dialkoxy silanes having an epoxy group [e.g., 3-glycidyloxypropyl methyl dimethoxy silane , (Glycidyloxy C _1-4 alkyl) C _1-4 alkyl diC _1-4 alkoxysilane etc.] such as 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropylethyldiethoxysilane, and the like.

Representative trialkoxysilanes include, for example, trialkoxysilane (eg, tri-C _1-4 alkoxysilane such as trimethoxysilane), alkyltrialkoxysilane (eg, methyltrimethoxysilane, ethyltrimethoxysilane, C _1-4 alkyltri C _1-4 alkoxysilane such as ethyltriethoxysilane), aryltrialkoxysilane (eg C _6-10 aryltri C _1-4 alkoxysilane such as phenyltrimethoxysilane), amino group amino C _1-4 alkyl tri C _1-4 alkoxysilane such as trialkoxysilanes (e.g., 2-aminoethyl trimethoxysilane having; 2- [N-(2-aminoethyl) amino] such as ethyltrimethoxysilane N- (amino C _2-4 alkyl) amino C _1-4 alkyl tri-C _1-4 alkoxysilane), trialkoxysilane having a mercapto group (for example, mercapto C _2-4 alkyltri-C _1-4 alkoxysilane such as 3-mercaptopropyltrimethoxysilane), trialkoxysilane having an alkenyl group ( For example, C _2-4 alkenyl tri-C _1-4 alkoxysilane such as vinyltrimethoxysilane), trialkoxysilane having a (meth) acryloyl group [for example, 2- (meth) acryloxyethyltrimethoxysilane, 2- (Meth) acryloyloxy C _1-4 alkyl tri C _1-4 alkoxy silane etc. such as (meth) acryloxyethyl triethoxy silane], trialkoxy silanes having an epoxy group {for example, (glycidyloxyalkyl) trialkoxy silane (For example, glycidyloxymethyl Glycidyloxy C _1-4 alkyltri-C such as trimethoxysilane, 2-glycidyloxyethyltrimethoxysilane, 2-glycidyloxyethyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane _1-4 alkoxysilane, etc.), epoxycycloalkyltrialkoxysilane [for example, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- ( 3,4-epoxycyclohexyl) propyltrimethoxysilane, 3- (3,4-epoxycyclohexyl) propyltriethoxysilane, and other epoxy C _5-8 cycloalkyl C _1-4 alkyltri C _1-4 alkoxysilanes, etc.] } Trialkoxysilanes having an isocyanate group (e.g., .gamma. isocyanoacetate trimethoxysilane, etc. isocyano C _1-4 alkyl tri C _1-4 alkoxysilane such as .gamma. isocyanoacetate triethoxysilane) and the like.

Typical tetraalkoxysilanes include tetraalkoxysilanes corresponding to the above-exemplified di- or trialkoxysilanes, such as tetraalkoxysilanes [tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, _1-4 alkoxysilane, etc.].

  Examples of the alkoxysilane condensate (or hydrolysis condensate) include, for example, the alkoxysilane condensate (or polymerized product) represented by the formula (1). Such a condensate (or partial condensate) may be a condensate of a single (or the same type) alkoxysilane, or a condensate of a plurality (or different types) of alkoxysilanes (for example, different types of tetrasilanes). A condensate of alkoxysilane).

  The alkoxysilane condensate (alkoxysilane condensate) may be, for example, an oligomer of about 2 to 10 mer, preferably about 2 to 8 mer, more preferably about 3 to 6 mer.

  The alkoxysilane condensate may be a network condensate (or partial condensate), or may be a linear or linear condensate (or partial condensate). Typical alkoxysilane condensates include condensates (partial condensates) of tetraalkoxysilanes (tetraalkoxysilanes exemplified above), for example, linear alkoxysilane condensation represented by the following formula (2) Things are included.

(In the formula, R ² is the same as above. D represents an integer of 2 or more)
In the above formula (2), preferred groups R ² include C _1-4 alkyl groups (particularly C _1-2 alkyl groups) such as a methyl group and an ethyl group. As described above, the plurality of groups R ² may be the same group or different groups. Further, the preferable degree of condensation d may be, for example, about 2 to 8, preferably about 2 to 6, and more preferably about 3 to 5.

  Further, the organosilicon compounds include complex compounds of the alkoxysilanes, triacyloxysilanes (such as methyltriacetoxysilane), trialkylsilanols (such as trimethylsilanol), and polymer organosilicon compounds containing these compounds. Is also included.

  The organosilicon compounds (alkoxysilanes) may be used alone or in combination of two or more.

The coating liquid may contain a resin component [particularly a resin having gas barrier properties (gas barrier resin)] as necessary. Examples of the resin component include vinylidene chloride copolymers, vinyl alcohol polymers {polyvinyl alcohol, fatty acid vinyl esters and copolymerizable monomers [olefins such as C _2-4 olefins (ethylene, propylene, butene, etc.)]. Saponified products of (meth) acrylic monomers such as (meth) acrylic acid and (meth) acrylic acid esters; alkyl vinyl ethers; vinyl pyrrolidone and the like] (for example, ethylene-vinyl alcohol copolymer) Etc.) etc.}. The resin components may be used alone or in combination of two or more.

  When the resin component is used, the ratio of the resin component is, for example, 1 to 1000 parts by weight, preferably 3 to 500 parts by weight, more preferably 5 to 200 parts by weight with respect to 100 parts by weight of the hydrolytic condensable organometallic compound. It may be about a part.

The coating solution may be solvent-free, but usually contains a solvent in many cases. The solvent is not particularly limited as long as it can dissolve or disperse the hydrolytic condensable organometallic compound (A). For example, alcohols [alkanols such as methanol, ethanol, 2-propanol, butanol, pentanol; ethylene; Alkylene glycols such as glycol; (poly) oxyalkylene glycols such as diethylene glycol and triethylene glycol; alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether; (poly) oxy such as diethylene glycol monomethyl ether and triethylene glycol monomethyl ether Alkylene glycol monoalkyl ethers], ketones (such as acetone), hydrocarbons (for example, aromatic hydrocarbons such as toluene; fats such as hexane) Family hydrocarbons), esters (methyl acetate, acetates such as ethyl acetate, etc.), ethers (ethyl phenol ether, propyl ether, and cyclic ethers such as tetrahydrofuran), water and the like. Among these, from the viewpoint of stability and the like, aqueous solvents such as water and alcohols (for example, C _1-4 alkanols such as methanol and ethanol) are preferable. A solvent can be used individually or in combination of 2 or more types.

  The ratio of the solvent is, for example, 0.1 to 30 parts by weight, preferably 0.3 to 20 parts by weight, more preferably 0.5 to 10 parts by weight (1 part by weight based on 1 part by weight of the hydrolytic condensable organometallic compound ( For example, it may be about 0.8 to 5 parts by weight), particularly about 1 to 3 parts by weight.

  In many cases, the coating solution is an aqueous coating solution composed of at least an aqueous solvent (for example, water and / or a solution of the alcohol).

  The coating solution may contain a component capable of promoting hydrolysis condensation such as an acid component (for example, a volatile acid component such as hydrochloric acid) as necessary. In addition, for the coating liquid, if necessary, stabilizers (antioxidants, ultraviolet absorbers, light stabilizers, heat stabilizers, etc.), plasticizers, colorants, fillers, dispersants, antistatic agents. An antibacterial agent or preservative, a viscosity modifier, an antifoaming agent, and the like may be added. These additives can be used alone or in combination of two or more.

  Furthermore, in order to improve the gas barrier property of the barrier layer, the coating liquid is a compound having an amino group, an inorganic layered compound [for example, smectite group clay mineral (montmorillonite, etc.) depending on the type of the hydrolytic condensable organometallic compound. ), Vermiculite group clay minerals (such as vermiculite), kaolin type minerals (such as halloysite), phyllosilicates (such as talc, muscovite, phlogopite), jamonite group minerals (such as antigolite), chlorite group minerals (black) And various compounds such as Wright, Cookite, Nantite, etc.). These compounds may be used alone or in combination of two or more.

  For example, when the hydrolysis-condensable organometallic compound is composed of at least a compound having a functional group capable of reacting with an amino group and a hydrolysis-condensable group (A1), the coating solution further has an amino group. The compound (B) may be included. It is also known to improve gas barrier properties by combining the hydrolysis-condensable organometallic compound (A), a water-soluble polymer (such as a vinyl alcohol polymer) and an inorganic layered compound (for example, JP-A-2001-80003, JP-A-2003-191404, etc.).

  Below, the coating liquid containing the compound (B) which has an amino group is explained in full detail as one aspect | mode of the coating liquid for improving the gas barrier property of a barrier layer.

(Coating liquid containing compound (B) having amino group)
The coating solution (coating solution containing a compound (B) having an amino group) is composed of a compound (A1) having a functional group capable of reacting with an amino group and a hydrolytic condensable group and a compound (B) having an amino group. And at least. The barrier layer formed with such a coating solution is usually a condensate (or reaction product) containing the compound (A1) and the compound (B) having an amino group as a condensation component (co-condensation component). Often configured. Specifically, the barrier layer formed of such a coating solution has the compound (B) having an amino group and the compound (A1) bonded through the amino group and the reactive compound (A1). And a condensate condensed with a hydrolytic condensable group of a condensing component described later. Such a condensate (or cross-linked product) may be a precondensate having an unreacted (or remaining) hydrolytic condensable group (for example, an alkoxy group).

(Compound (A1))
As the compound (A1) having a functional group capable of reacting with an amino group, among the hydrolysis-condensable organometallic compound (A), a functional group capable of reacting with an amino group [for example, epoxy group, carboxyl Hydrolyzable condensable organometallic compounds having a group or an inductive group thereof (an acid anhydride group, an acid halide group, etc.), an isocyanate group, a thioisocyanate group, an oxazolinyl group, an aldehyde group, a ketone group, an alkyl halide group, etc. Can be mentioned. Among these functional groups, an epoxy group and an isocyanate group are preferable from the viewpoints of reactivity, water resistance (or hot water resistance), and an epoxy group is particularly preferable. The compound (A1) may be a compound having a functional group capable of reacting with at least one amino group.

  Examples of the compound (A1) having a functional group capable of reacting with a typical amino group include alkoxysilanes having an epoxy group (for example, dialkoxysilanes having the epoxy group exemplified above, and epoxy groups exemplified above). For example, trialkoxysilanes having an isocyanate group (for example, trialkoxysilanes having an isocyanate group as exemplified above). A compound (A1) may be individual or may combine 2 or more types.

(Compound (B) having an amino group)
In the compound (B) having an amino group, examples of the amino group include an amino group (—NH ₂ ), a substituted amino group (eg, an N-alkylamino group such as a methylamino group), and an imino group (—NH—). Etc. are also included. A preferred amino group is a group containing a nitrogen atom to which a hydrogen atom (active hydrogen atom) capable of reacting with the compound (A1) is bonded, for example, an amino group (—NH ₂ ) or an imino group (—NH—). The compound (B) having an amino group may have these amino groups alone or in combination of two or more thereof (for example, an amino group and an imino group).

The compound (B) having an amino group is a low molecular weight compound [for example, alkanolamine (C _2-6 alkanolamine such as ethanolamine, preferably C _2-4 alkanolamine, etc.) depending on the type of compound (A1). In general, the polymer is often a polymer (or oligomer) having the amino group.

The polymer having a typical amino group (or polymeric compounds), for example, polyalkylene imine (poly C _1-6 alkylene imines etc.), poly C _2-6 alkenyl amine such polyalkenylamine (polyallylamine, preferably And poly _C2-4 alkenylamine), polyoxyalkylene alkylamine (polyoxyethylene alkylamine, etc.) and the like.

The polyalkylene imines, polymethylene imine, polyethyleneimine, polypropyleneimine, poly isopropylene imine, polybutylene imine, homo C _1-6 alkylene imine such as polyisobutylene imine (preferably poly C _1-4 alkylene imine), these And copolyalkyleneimines (copoly C _1-4 alkyleneimines etc.) corresponding to these homopolyalkyleneimines. The structure of the polyalkyleneimine may be linear or branched and is usually branched.

  The polyalkyleneimine may be synthesized by a conventional method [such as ring-opening polymerization of alkyleneimine (for example, ethyleneimine)], or a commercially available product may be used. For example, polyalkyleneimine (polyethyleneimine) is available from, for example, Nippon Shokubai Co., Ltd. Epomin series ("Epomin SP-003", "Epomin SP-006", "Epomin SP-012", "Epomin SP-018"). ”,“ Epomin SP-103 ”,“ Epomin SP-110 ”,“ Epomin SP-200 ”,“ Epomin SP-300 ”,“ Epomin SP-1000 ”,“ Epomin SP-1020 ”, etc.).

  Further, polyalkenylamine (polyallylamine) may be synthesized by a conventional method (such as radical polymerization of alkenylamine), and is commercially available (for example, “PAA-L”, “PAA-” manufactured by Nitto Boseki Co., Ltd.). H "etc.) may be used.

  A preferred compound (B) having an amino group is a polyalkyleneimine (particularly polyethyleneimine). Polyalkyleneimine is excellent in film formability, transparency, flexibility and the like, and can be suitably used.

  In addition, the compound (B) having an amino group may be usually soluble in an aqueous solvent.

  The number average molecular weight of the polymer (or oligomer) having an amino group is, for example, 250 or more (for example, about 250 to 200,000), preferably 300 or more (for example, about 300 to 100,000), more preferably 400 or more (for example, 400 To about 50,000), and usually 500 or more (for example, about 500 to 10,000).

  In the coating solution, the amount (content) of the amino group-containing compound (B) can be selected from a range of about 5 to 1000 parts by weight with respect to 100 parts by weight of the compound (A1). It may be about 500 parts by weight, preferably about 20 to 400 parts by weight, and more preferably about 30 to 300 parts by weight (for example, 50 to 250 parts by weight).

  The condensate may include at least the compound (A1) and the compound (B) having an amino group as a condensing component, and may further include (A2) another condensing component (or a cocondensation component). When such other condensation components are used, the gas barrier property can be further improved.

(Other condensation component (A2))
Although it does not specifically limit as another condensation component (A2), Among the said hydrolytic condensable organometallic compounds (A), it is a non-reactive hydrolytic condensable organometallic compound (or said compound ( A1) hydrolysis-condensable organometallic compounds that do not belong to the category, that is, hydrolysis-condensable organometallic compounds having no functional group capable of reacting with the amino group), for example dialkoxysilanes, trialkoxysilanes (For example, alkyltrialkoxysilane), tetraalkoxysilane, condensate of alkoxysilane (for example, condensate of tetraalkoxysilane) and the like.

In the coating liquid containing a compound having an amino group, as a preferable condensation component (A2), an organosilicon compound (an organosilicon compound not belonging to the category of the compound (A1)), for example, tetraalkoxysilane (for example, tetramethoxysilane) is used. , Tetra _C1-4 alkoxysilanes such as tetraethoxysilane, especially tetra C1 ₂ alkoxysilanes), tetraalkoxysilane condensates (for example, 2 to 10 mer), and the like.

  The condensation component (A2) may be used alone or in combination of two or more.

  In the coating solution containing the compound (B) having an amino group, the use amount (content) of the condensation component (A2) (for example, the organosilicon compound such as a tetraalkoxysilane or a tetraalkoxysilane condensate) is as described above. The total amount of the compound (A1) and the compound (B) having an amino group can be selected from a range of about 0 to 200 parts by weight (for example, 3 to 180 parts by weight), for example, 5 to 150 parts by weight. Part, preferably 8 to 130 parts by weight, more preferably about 10 to 100 parts by weight (for example, 20 to 100 parts by weight).

Moreover, the coating liquid containing the compound (B) which has an amino group contains the solvent normally like the above. As the solvent, the same solvents as those exemplified above can be used, and in particular, aqueous solvents such as alcohols (C) (for example, C _1-4 alkanols such as methanol and ethanol) can be suitably used. The solvents may be used alone or in combination of two or more.

  The amount of solvent used may be in the same range as described above. Particularly, the amount of the solvent used is, for example, 10 to 3000 weights with respect to 100 parts by weight of the total amount of the constituent components of the barrier layer (compound (A1), amino group-containing compound (B), condensation component (A2), etc.). For example, about 30 to 2000 parts by weight, preferably about 50 to 1500 parts by weight (for example, 80 to 1000 parts by weight), more preferably about 90 to 900 parts by weight (for example, 100 to 800 parts by weight). It may be.

  In addition, the coating liquid containing the compound (B) having an amino group may further contain a polyfunctional compound [polyfunctional compound having an epoxy group (polyglycidyl ethers, polyglycidyl esters), isocyanate group, if necessary. A polyfunctional compound having a carboxyl group (such as an aliphatic dicarboxylic acid such as adipic acid or tartaric acid, a polymer having a carboxyl group such as polyacrylic acid, etc.) May be. These polyfunctional compounds may be used alone or in combination of two or more.

  Moreover, the coating liquid containing the compound (B) which has an amino group may contain a conventional additive (for example, surfactant etc.) like the above.

  The coating solution containing the amino group-containing compound (B) may contain a resin component (or a gas barrier resin, the resin component exemplified above, etc.), but usually such a resin component (for example, vinyl In many cases, it does not contain a gas barrier resin such as an alcohol polymer. When a coating solution containing an amino group-containing compound (B) is used, the gas barrier property can be improved efficiently and at a high level even if it does not contain a resin component (particularly a gas barrier resin).

  The coating solution can be usually prepared by mixing the hydrolytic condensable organometallic compound (A), a solvent, and other components (a compound having an amino group (B), an additive, etc.) as necessary.

  In the coating solution, the hydrolytic condensable organometallic compound may partially react (partial condensation reaction, precondensation reaction, bond formation reaction). That is, the hydrolyzable condensable organometallic compound in the coating solution is a reaction between hydrolyzable condensable organometallic compounds, a compound having an amino group and a hydrolyzable condensable organometallic compound before being applied to the base film. Reactions such as the reaction may be partially proceeding. In particular, the coating solution may be a sol solution (aqueous solution) obtained by partially condensing the hydrolysis-condensable compound (such as the organosilane compound) in order to improve the coating property. The reaction in the coating solution may be performed, for example, at normal temperature or under heating (for example, a temperature of 30 to 100 ° C., preferably about 40 to 80 ° C.), or may be performed in air or under an inert atmosphere. The reaction time may be, for example, about 5 minutes to 10 hours, preferably about 10 minutes to 6 hours, and more preferably about 30 minutes to 4 hours.

  In addition, the reaction may be performed in the same solvent system or may be performed by newly adding a solvent. The addition of the solvent may be performed in one step or may be performed in multiple steps. Specifically, the hydrolysis-condensable organometallic compound (A) or (A1) [and the compound (B) having an amino group as necessary, and further the condensation component (A2) if necessary] in a solvent ( After precondensation, a solvent may be further added to condense. When the condensation component (A2) is used, for example, (1) after the amine compound (B) and the compound (B) are reacted in a solvent, the condensation component (A2) and the solvent are further reacted. (2) The compound (B) having an amino group and the compound (A1) are reacted in a solvent, and after further condensation by adding a solvent, the condensation component (A2) (And a solvent if necessary) may be added for condensation.

  In the condensation reaction, the solvent to be newly added is not particularly limited as long as it is a solvent capable of hydrolyzing the compound (A1) or the condensation component (A2). For example, water, alcohols (the exemplified alcohols such as methanol) Etc.). These solvents may be used alone or in combination of two or more.

  The viscosity of the coating solution (solution viscosity) can be selected according to the coating property and coating method of the coating solution, and the viscosity of the coating solution at a temperature of 20 ° C. is usually 2 to 10,000 mPa · s (2 to 10,000 cps), Preferably, it may be about 5 to 7000 mPa · s (5 to 7000 cps), more preferably about 10 to 5000 mPa · s (10 to 5000 cps). The viscosity of the coating solution may be adjusted by, for example, adding an additive (for example, the compound having an amino group) or by partially hydrolyzing the hydrolysis-condensable organometallic compound. May be.

[Production method of laminated film]
(Coating process (1))
In the coating step (1), the coating liquid is coated (coated) on at least one surface of the base film.

  The coating method of the coating solution is not particularly limited as long as cracks and defects are not generated in the inorganic layer, and conventional methods such as a roll coating method, a dip coating method, a bar coating method, a nozzle coating method, a die coating method, and a spray coating are used. Various printing methods such as a method, a spin coating method, a curtain coating method, a flow coating method, screen printing, gravure printing, and curved surface printing, or a combination of these can be employed.

  The coating amount (or thickness) of the coating solution can be selected from the range of about 0.01 to 20 μm (for example, 0.1 to 10 μm) after drying, for example, 0.2 to 5 μm, preferably 0.3 to It may be about 3 μm, more preferably about 0.5 to 2 μm.

  In addition, application | coating of the said coating liquid can be performed using the coating apparatus corresponding to the said coating methods, such as a roll coater (gravure roll coater etc.) and a die coater, for example.

(Drying process (2))
In the drying step (2), the film obtained through the coating step (1) is dried. In the present invention, the film is humidified in this drying step. That is, the drying step (2) includes at least a humidification step (humidification drying step) for humidifying the film (humidification drying treatment). The dried film (humidified and dried), combined with the humidification effect in the laminating process described later, can sufficiently accelerate the condensation reaction of the hydrolytic condensable organometallic compound, or the dried film will be described later. Even if it uses for a lamination process, the film which has high gas-barrier property can be obtained efficiently.

  In drying under humidification (humidification drying), the humidification condition depends on the temperature, but the humidity [mass of water vapor (kg) / mass of dry air (dry air) (kg)] is, for example, 0.015 or more (E.g., 0.016-0.3), preferably 0.02-0.25 (e.g., 0.025-0.2), more preferably 0.03-0.18 (e.g., 0.032- About 0.17), and usually about 0.035 to 0.16 (for example, 0.04 to 0.15).

  Further, the humidification drying may be usually performed under heating. In humidification drying, temperature (heating temperature) is 35-180 degreeC (for example, 40-170 degreeC), for example, Preferably it is 45-160 degreeC (for example, 50-155 degreeC), More preferably, it is about 55-150 degreeC, Usually, it may be 60 to 150 ° C. (for example, about 70 to 145 ° C.). In addition, when using a humidifier (or humidifier), the temperature in humidification drying may be the temperature in a humidifier or the surface temperature of a film, and may be the temperature which shows the surface temperature of a film normally. .

  The humidifying and drying time can be appropriately selected according to the humidity (humidity), the coating amount of the coating solution, and the like. For example, it is 5 seconds or longer (for example, 10 seconds to 1 hour), preferably 15 seconds to 30 minutes, and more preferably 20 It may be about 2 to 20 minutes (for example, 20 seconds to 10 minutes), usually about 20 seconds to 8 minutes (for example, 25 seconds to 5 minutes). The “humidification time” means a drying time under humidification, and when the film is continuously humidified and dried, it means a time when the processing portion on the film passes through the humidification area. Similarly, the terms using “time” (the time until the drying step (2) is used, the time until the drying step (3) described later, etc.) are the same in the continuous step.

  Humidification drying (humidification treatment) may be performed using a humidifier equipped with at least a humidifier. The humidifier may be a steam humidifier or water spray humidifier. In the present invention, a steam humidifier humidifier can be suitably used. As the humidifier of the steam humidification method, for example, a steam generator (for example, an electrothermal steam generator, an electrode-type steam generator, a pan-type steam generator, etc.), humidification is performed using steam produced by a steam boiler or the like. Steam humidifier etc. are mentioned. The humidifier (humidifier) may include a heating means for humidifying under heating.

  Further, it is usually preferable to perform humidification without causing water droplets to adhere to the film (or the film surface) (or without causing condensation on the film). That is, the humidification can be usually performed by bringing water vapor into contact with the film, but is preferably performed to such an extent that the water vapor is not condensed on the film. When the humidification process is performed to such an extent that no water droplets are attached, a high-quality film excellent in gas barrier properties can be easily and efficiently produced without causing blocking. That is, when dew condensation is generated on the film by a method such as water spraying or steam spraying, there is a risk that dew condensation will be sandwiched in the laminated film and blocking will occur.

  In addition, the drying process (2) should just include the humidification process which humidifies a film at least, and may include the other drying process. For example, the drying step may be constituted by the humidification step and conventional drying (drying under non-humidification).

  Typically, the film after coating the coating liquid (the film that has undergone the coating process (1)) may be preliminarily dried (preliminary drying) to remove the solvent before being subjected to the humidification process. Good. In the preliminary drying, for example, the coated surface of the film may be dried to such an extent that a part or all of the liquid component (such as a solvent) can be removed from the coated surface of the coating solution. The preliminary drying temperature may be, for example, about 40 to 200 ° C, preferably 60 to 180 ° C, and more preferably about 80 to 150 ° C.

  In addition, after apply | coating a coating liquid (and after pre-drying), time until it uses for the humidification process of the apply | coated film is not specifically limited, However, Industrially, for example, 1 second-5 minutes, Preferably it is 3 Second to 1 minute, more preferably about 5 to 40 seconds.

  In addition, the time until the humidified and dried film is subjected to the laminating step (3) is not particularly limited, but the film is laminated while keeping the humidified state of the coated surface as much as possible. -3 minutes, preferably 5 seconds to 1 minute, more preferably about 10 to 40 seconds.

(Lamination process (3))
In a lamination process (3), the film which passed through the drying process (2) is laminated | stacked under humidification (humidification lamination | stacking). In the present invention, it is humidified and dried in the dry layer step, and by laminating under humidification, the film is laminated in a state where moisture exists between the films. Therefore, even if the film after application and drying is subjected to lamination, the film is efficiently laminated. A film having excellent gas barrier properties can be prepared.

  As a lamination method, various methods, for example, (i) a method of winding up a film, (ii) a method of laminating a plurality of films (sheet-like film), and (iii) folding or folding a single continuous film The method of laminating and laminating while being mentioned. Among these methods, industrially, the method (i) of laminating films by winding is advantageous.

  In the lamination step (3), the humidification (humidification lamination) condition depends on the temperature, but is humidity [mass of water vapor (kg) / mass of dry air (dry air) (kg)], for example, 0.011 or more. (E.g. 0.012-0.2), preferably 0.013-0.15, more preferably 0.014-0.1 (e.g. 0.015-0.06), especially 0.016-0. .05 (for example, about 0.02 to 0.04). Further, the humidification lamination may be performed under conditions of a temperature of 10 to 150 ° C., preferably 20 to 120 ° C., more preferably 30 to 100 ° C., particularly about 35 to 70 ° C.

  In addition, humidification lamination | stacking can be performed using a conventional humidifier (For example, the humidifier illustrated by the term of the said drying process (2) etc.). Similarly to the above, when humidifying in the laminating step, it is usually preferable to humidify the film (or film surface) without attaching water droplets (or without causing condensation on the film).

  In the laminating step (3), the number of laminated films (the number of film overlaps and the number of windings) can be selected from the range of 10 or more (for example, about 100 to 1000000), for example, 100 or more (for example, about 200 to 500000). ), Preferably 500 or more (for example, about 1,000 to 300,000), more preferably 5000 or more (for example, about 10,000 to 200,000). In particular, when a film is laminated by winding in a roll shape, the film winding tension is, for example, 50 N / m or more (for example, 60 to 300 N / m), preferably 70 to 200 N / m, and more preferably 90. About 150 N / m may be sufficient. Moreover, when laminating | stacking by winding, winding speed | velocity may be about 10-500 m / min, for example, Preferably it is 20-400 m / min, More preferably, about 30-300 m / min may be sufficient. In this invention, even if it laminates | stacks with such a lamination | stacking number, winding tension | tensile_strength, and winding speed, high gas barrier property can be provided.

  In addition, lamination | stacking may be performed using the lamination apparatus which can laminate | stack a film, for example, when laminating | stacking by winding, it can be performed using a conventional winding apparatus.

(Aging process (4))
The film after the lamination step (3), (laminated film) may be subjected to an aging treatment (4) as necessary. That is, the manufacturing method of the laminated | multilayer film of this invention may include the aging process (4) which carries out an aging process further after a lamination process (3). By combining such an aging treatment after lamination of the film and the humidification drying (and humidification lamination), the gas barrier property of the laminated film can be further improved.

  In the aging treatment, the aging treatment conditions can be appropriately selected. For example, the aging treatment temperature is 20 to 200 ° C. (for example, 25 to 160 ° C.), preferably 30 to 150 ° C., more preferably 30 to 130 ° C., usually 35 to 35 ° C. It may be about 125 ° C.

  The aging treatment may be performed under non-humidification or humidification, and is preferably performed under humidification. When the aging treatment is performed under humidification, even if the moisture sandwiched between the films in the drying and laminating steps evaporates or volatilizes over time, the film can be aged while being replenished with moisture. The condensation reaction can be promoted. In the aging treatment, the humidification condition is humidity [mass of water vapor (kg) / mass of dry air (dry air) (kg)], for example, 0.011 or more (for example, 0.012 to 0.3), preferably Is 0.014 to 0.2, more preferably 0.015 to 0.1 (for example, 0.016 to 0.05), particularly 0.017 to 0.045 (for example, 0.02 to 0.04). It may be a degree. Note that the humidification in the aging treatment may be performed at the same or higher humidity (particularly higher humidity) than the humidity in the lamination step from the viewpoint of replenishing the film with moisture.

  Furthermore, in the aging treatment, the aging time is, for example, 6 hours or more (for example, about 7 hours to 30 days), preferably 8 hours or more (for example, about 9 hours to 25 days), more preferably 10 hours or more (for example, , About 12 hours to 20 days), more preferably 1 day or more (for example, about 1.5 to 16 days).

  The aging treatment under humidification can be performed using a conventional humidifier (for example, the humidifier exemplified in the section of the drying step (2)). Similarly to the above, when humidifying in the aging step, it is usually preferable to humidify the film (or film surface) without attaching water droplets (or without causing condensation on the film).

  In the production method of the present invention, the series of steps including the coating step (1), the drying step (2), the laminating step (3), and, if necessary, the aging step (4) are intermittent (stages). Or individually) or continuously. Industrially, it is a continuous process in which the above steps are continuously performed, but is preferable.

  Such a production method of the present invention includes a coating apparatus for applying the coating liquid to the base film, a humidifying apparatus (humidification drying apparatus) for drying the base film coated with the coating liquid under humidification, It can be performed using a manufacturing apparatus (manufacturing unit) provided with at least a laminating apparatus for laminating a film after humidification under humidification.

  That is, the manufacturing apparatus (manufacturing unit) includes: (i) a coating apparatus for coating the coating liquid on at least one surface of the base film in the coating process (1); and (ii) a coating process (1). ) At least a humidifying device for drying the film obtained through humidification, and (iii) a laminating device for laminating the film subjected to the drying step (2) under humidification. In such a manufacturing unit, the apparatus exemplified above can be used for each of the coating device, the humidifying device, and the laminating device (winding device and the like). The manufacturing unit may further include other devices (such as a humidifier used for the aging process).

[Laminated film]
The coated film obtained by the production method of the present invention (a film composed of a base film and a barrier layer formed on at least one surface of the base film) was formed of a hydrolytic condensable organometallic compound. In spite of laminating a film composed of a barrier layer by winding or the like, it has excellent gas barrier properties (or fragrance retention). For example, the oxygen permeability (unit ml / m ² · day · MPa) of the coated film of the present invention depends on the type of components of the base film and the barrier layer, but the temperature is 20 ° C. and the humidity is 90% RH atmosphere. Under, for example, 100 or less (for example, 0.1 to 80), preferably 60 or less (for example, 0.5 to 55), more preferably 40 or less (for example, 1 to 35), particularly 2 to 30 (for example, 3 to 25).

  Moreover, the said coat film is excellent also in transparency, for example, a haze is 10% or less (for example, 1 to 10%), Preferably it is 9% or less (for example, 1 to 9%), More preferably, it is 8% or less ( For example, it may be about 1 to 8%).

  In addition, according to the kind and use of a film, the coating film of this invention (the coating film obtained through the said manufacturing method) is further various coating layers and laminate layers, for example, a heat seal layer, a slipping layer. Further, an antistatic layer, a decorative printing film layer, a reinforcing layer made of nylon film or the like, an ultraviolet blocking layer (for example, a UV blocking coating layer described in JP-A No. 2003-128121), or the like may be formed. These coating layers and laminate layers may be formed on the barrier layer of the coated film obtained through the above-described production method, with or without an adhesive layer (or anchor layer), inside the barrier layer. It may be formed on the surface (for example, the surface of the base film where the barrier layer is not formed or between the base film and the barrier layer). When forming inside a barrier layer, you may form in the suitable step (for example, barrier layer formation etc.) of the said manufacturing method, and you may form in the coat film which passed through the said manufacturing method.

  In particular, when the laminated film of the present invention is used for packaging, a heat seal layer may be further formed. Such a heat seal layer may be formed on the barrier layer, may be formed on the other surface (the surface where the inorganic layer is not formed) of the base film, or a combination thereof. When forming a heat seal layer, usually, a heat seal layer is often formed at least on the barrier layer.

  Examples of the polymer (or sealant) constituting the heat seal layer include heat bondable polymers (heat seal polymers) such as olefin polymers, vinyl acetate-vinyl chloride copolymers, polyesters, polyamides, rubber polymers, and the like. It is done. These heat bondable polymers can be used alone or in combination of two or more.

  Examples of the heat-sealable olefin polymer include polyethylene such as low density polyethylene and linear low density polyethylene, ethylene-butene-1 copolymer, ethylene- (4-methylpentene-1) copolymer, ethylene- Hexene-1 copolymer, ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylate copolymer, ionomer, polypropylene, propylene-butene-1 copolymer, ethylene -Propylene copolymer, ethylene-propylene-butene-1 copolymer, ethylene-propylene-diene copolymer, modified polyolefin such as maleic anhydride-modified polyethylene and maleic anhydride-modified polypropylene. Preferred olefin-based polymers include polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, amorphous polyolefin (for example, amorphous polypropylene), ethylene-propylene copolymer, and the like. When the heat seal layer is formed by laminating, preferred heat-bonding polymers (films) include unstretched polypropylene films, unstretched ethylene-propylene copolymer films, and the like.

  The heat-sealable polyester includes an amorphous polyester, for example, an aliphatic diol, at least one dicarboxylic acid selected from an aliphatic dicarboxylic acid and an asymmetric aromatic dicarboxylic acid (such as isophthalic acid), and a symmetric structure as necessary. Aliphatic polyesters containing aromatic dicarboxylic acids (such as terephthalic acid) as constituent components are included. Examples of the heat-sealable polyamide include nylon 11, nylon 12, nylon 6/12, and the like. Examples of the rubber-based polymer include butyl rubber, isobutylene rubber, chloroprene rubber, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-acrylonitrile-butadiene copolymer, and the like.

  The thickness of the heat seal layer can be appropriately selected, for example, in the range of about 3 to 100 μm, depending on the use of the coat film, and when the heat seal layer is formed by laminating the film, for example, 20 to 100 μm, Preferably, it may be about 30 to 80 μm.

  In addition, the thickness of the whole laminated film may be, for example, about 5 to 300 μm, preferably 10 to 200 μm, and more preferably about 15 to 100 μm (for example, 20 to 80 μm).

  The method of the present invention is capable of sufficiently promoting the condensation reaction of the hydrolytic condensable organometallic compound even if a barrier layer composed of the hydrolytic condensable organometallic compound is laminated, and easily and efficiently an excellent gas barrier. Can be obtained. In particular, since it can be laminated by winding it up in a roll shape, etc., a film having high gas barrier properties can be mass-produced without requiring complicated processing, which is extremely advantageous industrially.

  The coated film obtained by the method of the present invention can be used in various applications that require gas barrier properties, such as food for microwave oven, retort food, frozen food, microwave sterilization, flavor barrier, pharmaceuticals, precision electronic parts, etc. It can be suitably used as various packaging films and balloon films such as balloons. In addition, when food is packaged, the contents can be stored for a long period of time while suppressing deterioration and alteration. The form of the package using the film obtained by the method of the present invention is not particularly limited. For example, it is a solid packaging bag such as hamburger, shumai, gyoza, or a liquid product such as curry, soup, coffee, or tea. It can be used as a packaging bag. A packaging bag containing these foods can be retorted or heated in a microwave oven as it is. Further, by using it as an inner bag of a paper container such as a sake pack, the contents can be heated by microwave heating or the like.

  In addition, packaging forms using packaging materials include bags, cups, tubes, standing bags, trays and other containers, lid materials, and paper pack inner materials that contain sake, soy sauce, mirin, oil, milk, juice, etc. Is mentioned.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

  In the examples, the oxygen permeability was measured as follows.

[Oxygen permeability (O2-TR)]
In accordance with ASTM D-3985, oxygen permeability (oxygen permeability) was measured using an oxygen permeability measuring device (“OX-TRAN 2/20 SH MODULE” manufactured by MOCON). The measurement conditions are 20 ° C. and relative humidity 90% RH.

(Synthesis Example 1)
Polyethyleneimine (Nippon Shokubai Co., Ltd., “Epomin SP-018”) 7.22 parts by weight, γ-glycidoxypropyltrimethoxysilane (3-glycidyloxypropyltrimethoxysilane) 3.56 parts by weight, methanol 51 .1 part by weight was mixed, reacted under stirring at 65 ° C. under a nitrogen atmosphere for 3 hours, and cooled to room temperature. Subsequently, a mixed solution of 52.0 parts by weight of tetramethoxysilane oligomer (manufactured by Tama Chemical Co., Ltd., “M silicate 51”) and 15.4 parts by weight of methanol was added to this reaction solution, and the mixture was stirred at room temperature for 1 hour The coating liquid (1) was prepared by reacting.

(Synthesis Example 2)
Polyethyleneimine (made by Nippon Shokubai Co., Ltd., “Epomin SP-018”) 2.6 parts by weight, γ-glycidoxypropyltrimethoxysilane (3-glycidyloxypropyltrimethoxysilane) 2.3 parts by weight, methanol 54 The parts by weight were mixed, stirred for 3 hours in a nitrogen atmosphere at 60 ° C., and cooled to room temperature. Next, a mixed solution of 1.0 part by weight of water and 5.4 parts by weight of methanol was added to the reaction solution and reacted for 30 minutes. Further, an oligomer of tetramethoxysilane (manufactured by Tama Chemical Industry Co., Ltd., “M silicate 51 ]) A liquid mixture of 11.3 parts by weight and 24 parts by weight of methanol was added and reacted at room temperature for 24 hours to prepare a coating liquid (2).

Example 1
The coating liquid (1) obtained in Synthesis Example 1 is applied to a biaxially stretched polypropylene film (20 μm) at a coating amount of 1.0 g / m ² (dry weight) using a die coater, and a dryer is used. And pre-dried at a temperature of 90 ° C.

  Next, the pre-dried film was humidified and dried for 1 minute using a humidifier at a temperature of 100 ° C. and humidity [unit: mass of steam (kg) / mass of dry air (kg), the same applies hereinafter] 0.070. After that, it was wound up by a winder while being humidified by a humidifier under the conditions of a temperature of 40 ° C. and a humidity of 0.017. The time from humidification drying to winding was 25 seconds, and the winding conditions were a winding tension of 95 N / m and a winding speed of 125 m / min.

Subsequently, after winding up the film, the film in a roll state was subjected to an aging treatment for 2 days under a heating and humidifying condition of a temperature of 45 ° C. and a humidity of 0.018 to obtain a coated film. The resulting coated film had an oxygen permeability of 30 ml / m ² · day · MPa.

(Example 2)
The coating liquid (1) obtained in Synthesis Example 1 is applied to a biaxially stretched polypropylene film (20 μm) at a coating amount of 1.0 g / m ² (dry weight) using a die coater, and a dryer is used. And pre-dried at a temperature of 90 ° C.

  Next, the pre-dried film was humidified and dried for 1 minute using a humidifier at a temperature of 100 ° C. and humidity [unit: mass of steam (kg) / mass of dry air (kg), the same applies hereinafter] 0.100. After that, it was wound up with a winder while being humidified with a humidifier under conditions of a temperature of 50 ° C. and a humidity of 0.025. The time from humidification drying to winding was 25 seconds, and the winding conditions were a winding tension of 95 N / m and a winding speed of 125 m / min.

Subsequently, after winding up the film, the roll film was subjected to aging treatment for 7 days under heating and humidification conditions of a temperature of 50 ° C. and a humidity of 0.020 to obtain a coated film. The obtained coated film had an oxygen permeability of 22 ml / m ² · day · MPa.

(Example 3)
The coating liquid (1) obtained in Synthesis Example 1 was applied to a polyethylene terephthalate film (12 μm) at a coating amount of 1.0 g / m ² (dry weight) using a die coater, and the temperature was measured using a dryer. Pre-dried at 90 ° C.

  Next, the pre-dried film is humidified and dried for 30 seconds at a temperature of 135 ° C. and a humidity of 0.140 using a humidifier, and further humidified by a humidifier at a temperature of 60 ° C. and a humidity of 0.035. It was wound up using a winding device. The time from humidification drying to winding was 25 seconds, and the winding conditions were a winding tension of 95 N / m and a winding speed of 125 m / min.

Subsequently, after winding up the film, the roll film was subjected to an aging treatment for 14 days under heating and humidification conditions of a temperature of 60 ° C. and a humidity of 0.032 to obtain a coated film. The obtained coated film had an oxygen permeability of 15 ml / m ² · day · MPa.

Example 4
The coating liquid (1) obtained in Synthesis Example 1 was applied to a polyamide film (15 μm) at a coating amount of 1.0 g / m ² (dry weight) using a die coater, and the temperature was 90 ° C. using a dryer. Pre-dried at ℃.

  Next, the pre-dried film is humidified and dried for 4 minutes using a humidifier at a temperature of 80 ° C. and a humidity of 0.080, and further humidified by a humidifier at a temperature of 50 ° C. and a humidity of 0.025. It was wound up using a winding device. The time from humidification drying to winding was 25 seconds, and the winding conditions were a winding tension of 95 N / m and a winding speed of 125 m / min.

Next, after winding up the film, the roll film was subjected to aging treatment for 10 days under heating and humidification conditions of a temperature of 50 ° C. and a humidity of 0.023 to obtain a coated film. The obtained coated film had an oxygen permeability of 20 ml / m ² · day · MPa.

(Example 5)
The coating liquid (1) obtained in Synthesis Example 2 was applied to a biaxially stretched polypropylene film (20 μm) at a coating amount of 1.0 g / m ² (dry weight) using a die coater, and a dryer was used. And pre-dried at a temperature of 90 ° C.

  Next, the pre-dried film is humidified and dried for 2 minutes at a temperature of 100 ° C. and a humidity of 0.040 using a humidifier, and further humidified by a humidifier at a temperature of 50 ° C. and a humidity of 0.025. It was wound up using a winding device. The time from humidification drying to winding was 25 seconds, and the winding conditions were a winding tension of 95 N / m and a winding speed of 125 m / min.

Subsequently, after winding up the film, the roll film was subjected to an aging treatment for 7 days under heating and humidification conditions of a temperature of 50 ° C. and a humidity of 0.023 to obtain a coated film. The resulting coated film had an oxygen permeability of 50 ml / m ² · day · MPa.

(Example 6)
The coating liquid (1) obtained in Synthesis Example 2 was applied to a biaxially stretched polypropylene film (20 μm) at a coating amount of 1.0 g / m ² (dry weight) using a die coater, and a dryer was used. And pre-dried at a temperature of 90 ° C.

  Next, the pre-dried film is humidified and dried for 1 minute at a temperature of 60 ° C. and a humidity of 0.050 using a humidifier, and further humidified by a humidifier at a temperature of 40 ° C. and a humidity of 0.025. It was wound up using a winding device. The time from humidification drying to winding was 25 seconds, and the winding conditions were a winding tension of 95 N / m and a winding speed of 125 m / min.

Subsequently, after winding up the film, the roll film was subjected to aging treatment for 4 days under heating and humidification conditions of a temperature of 40 ° C. and a humidity of 0.025 to obtain a coated film. The resulting coated film had an oxygen permeability of 40 ml / m ² · day · MPa.

(Example 7)
The coating liquid (1) obtained in Synthesis Example 2 was applied to a polyamide film (15 μm) at a coating amount of 1.0 g / m ² (dry weight) using a die coater, and the temperature was 90 ° C. using a dryer. Pre-dried at ℃.

  Next, the pre-dried film is humidified and dried for 30 seconds at a temperature of 120 ° C. and a humidity of 0.120 using a humidifier, and further humidified by a humidifier at a temperature of 60 ° C. and a humidity of 0.040. It was wound up using a winding device. The time from humidification drying to winding was 25 seconds, and the winding conditions were a winding tension of 95 N / m and a winding speed of 125 m / min.

Subsequently, after winding up the film, the roll film was subjected to aging treatment for 10 days under heating and humidification conditions of a temperature of 50 ° C. and a humidity of 0.030 to obtain a coated film. The resulting coated film had an oxygen permeability of 27 ml / m ² · day · MPa.

(Example 8)
The coating liquid (1) obtained in Synthesis Example 2 was applied to a polyethylene terephthalate film (12 μm) at a coating amount of 1.0 g / m ² (dry weight) using a die coater, and the temperature was measured using a dryer. Pre-dried at 90 ° C.

  Next, the pre-dried film is humidified and dried for 48 seconds at a temperature of 125 ° C. and a humidity of 0.040 using a humidifier, and further humidified by a humidifier at a temperature of 50 ° C. and a humidity of 0.025. It was wound up using a winding device. The time from humidification drying to winding was 25 seconds, and the winding conditions were a winding tension of 95 N / m and a winding speed of 125 m / min.

Subsequently, after winding up the film, the roll film was subjected to aging treatment for 10 days under heating and humidification conditions of a temperature of 120 ° C. and a humidity of 0.022 to obtain a coated film. The resulting coated film had an oxygen permeability of 12 ml / m ² · day · MPa.

(Comparative Example 1)
The coating liquid (1) obtained in Synthesis Example 1 is applied to a biaxially stretched polypropylene film (20 μm) at a coating amount of 1.0 g / m ² (dry weight) using a die coater, and a dryer is used. And pre-dried at a temperature of 90 ° C.

  The pre-dried film was then dried at a temperature of 100 ° C. for 1 minute. The humidity during drying was 0.010. Further, the dried film was wound using a winder while being humidified by a humidifier under conditions of a temperature of 40 ° C. and a humidity of 0.017. The time from humidification drying to winding was 25 seconds, and the winding conditions were a winding tension of 95 N / m and a winding speed of 125 m / min.

Subsequently, after winding up the film, the film in a roll state was subjected to an aging treatment for 2 days under a heating and humidifying condition of a temperature of 45 ° C. and a humidity of 0.018 to obtain a coated film. The resulting coated film had an oxygen permeability of 210 ml / m ² · day · MPa.

(Comparative Example 2)
The coating liquid (1) obtained in Synthesis Example 1 is applied to a biaxially stretched polypropylene film (20 μm) at a coating amount of 1.0 g / m ² (dry weight) using a die coater, and a dryer is used. And pre-dried at a temperature of 90 ° C.

  Next, the pre-dried film was humidified and dried for 1 minute under the conditions of a temperature of 100 ° C. and a humidity of 0.070 using a humidifier, and further wound up using a winder at a temperature of 40 ° C. In addition, the humidity at the time of winding was 0.010. The time from humidification drying to winding was 25 seconds, and the winding conditions were a winding tension of 95 N / m and a winding speed of 125 m / min.

Next, after the film was wound, the roll film was subjected to aging treatment for 7 days under heating and humidification conditions of a temperature of 45 ° C. and a humidity of 0.025 to obtain a coated film. The resulting coated film had an oxygen permeability of 300 ml / m ² · day · MPa.

(Comparative Example 3)
The coating liquid (1) obtained in Synthesis Example 2 was applied to a polyethylene terephthalate film (12 μm) at a coating amount of 1.0 g / m ² (dry weight) using a die coater, and the temperature was measured using a dryer. Pre-dried at 90 ° C.

  The pre-dried film was then dried at a temperature of 100 ° C. for 4 minutes. The humidity during drying was 0.007. Furthermore, the dried film was wound up using a winder while being humidified by a humidifier under conditions of a temperature of 50 ° C. and a humidity of 0.040. The time from humidification drying to winding was 25 seconds, and the winding conditions were a winding tension of 95 N / m and a winding speed of 125 m / min.

Subsequently, after winding up the film, the roll film was subjected to an aging treatment for 7 days under heating and humidification conditions of a temperature of 50 ° C. and a humidity of 0.040 to obtain a coated film. The resulting coated film had an oxygen permeability of 160 ml / m ² · day · MPa.

  Table 1 shows the results obtained in Examples and Comparative Examples.

Claims (11)

  A coating process (1) for coating a coating solution containing the hydrolytic condensable organometallic compound (A) on at least one surface of the base film, and a drying process (2) for drying the film after this coating process (1) ) And a laminating step (3) for laminating the film under humidification after the drying step (2), wherein the drying step (2) humidifies the film. The manufacturing method of the coat film containing this.   In the drying step (2), the film is humidified under a humidification condition of a temperature of 55 to 150 ° C. and a humidity [mass of water vapor (kg) / mass of dry air (dry air) (kg)] of 0.03 to 0.18. The manufacturing method of Claim 1 including the humidification process to perform.   The production method according to claim 1, wherein in the laminating step (3), lamination is performed under a humidified condition of humidity [mass of water vapor (kg) / mass of dry air (dry air) (kg)] 0.015 to 0.06.   The manufacturing method according to claim 1, wherein in the laminating step (3), the film having undergone the drying step (2) is laminated while being wound.   The manufacturing method according to claim 1, further comprising an aging step (4) for performing an aging treatment under humidification after the laminating step (3).   In the aging step (4), an aging treatment is performed at a temperature of 30 to 130 ° C. and a humidity [mass of water vapor (kg) / mass of dry air (dry air) (kg)] of 0.016 to 0.05. Item 6. The production method according to Item 5.   (I) The drying step (2) is performed under humidification conditions of a temperature of 60 to 150 ° C. and humidity [mass of water vapor (kg) / mass of dry air (dry air) (kg)] of 0.035 to 0.16. Including a step of humidifying without attaching water droplets to the film, (ii) in the laminating step (3), temperature 30 to 100 ° C. and humidity [mass of water vapor (kg) / mass of dry air (dry air) (kg )] The film is wound up under the conditions of 0.016 to 0.05 without adhering water droplets. (Iii) In the aging step (4), the temperature is 30 to 130 ° C. and the humidity [mass of steam (kg) / 6. The process according to claim 5, wherein the film wound without adhering water droplets is subjected to an aging treatment for 12 hours to 20 days under the condition of mass (kg) of dry air (dry air) 0.017 to 0.045. .   The manufacturing method of Claim 1 with which the base film is comprised with the base film formed with the polypropylene resin, the polyester-type resin, or the polyamide-type resin.   The base film is composed of a base film and an inorganic layer formed on at least one surface of the base film and composed of at least one metal oxide selected from aluminum oxide and silicon oxide. The manufacturing method of Claim 8.   The coating solution was composed of (A1) an organosilicon compound having a functional group capable of reacting with an amino group and a hydrolytic condensable group, (B) a compound having an amino group, and (C) an alcohol. The production method according to claim 1, which is an aqueous coating solution. The manufacturing method of Claim 1 which obtains the coated film whose oxygen permeability in temperature 20 degreeC and humidity 90% RH atmosphere is 60 ml / m < ² > * day * MPa or less.