JP2005161759A - Coated film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a gas-barrier coated film having high thrust strength. <P>SOLUTION: The coated film comprises an aromatic polyamide film and a silicon-containing gas-barrier coating layer. To put it concretely, the coated film includes the aromatic polyamide film (A) and the coating layer (B) formed by using a composition containing a compound (b-i) having a polar group, an organic silicon compound (b-ii) expressed by formula 1 (wherein R<SP>1</SP>is an alkyl group which can have a hydrogen atom or a functional group; R<SP>2</SP>can be the same or different and is a hydrogen atom or an alkyl group; x is 0 or 1; y is 3 or 4; and x+y=4), and/or its hydrolytic condensate (b-iii). <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a gas barrier coating film. More specifically, the present invention relates to a gas barrier coating film having excellent puncture strength.

  In recent years, in the fields of packaging, medicine, and the like, there is an increasing demand for gas barrier coating films having extremely small gas permeability such as oxygen, nitrogen, carbon dioxide, and water vapor. In response, various gas barrier coating films have been developed in recent years.

  Gas barrier coating films are required to have various properties such as thermal stability, moisture resistance, environmental properties, transparency, and flexibility. In order to meet this demand, the present inventors have already proposed a coating film made of a polysiloxane polymer (for example, see Patent Document 1). Such a coated film is excellent in high gas barrier properties and other characteristics, and is very useful for various applications.

However, higher performance improvements are also desired. For example, with respect to a food protective coating film, it is desired to improve the piercing strength. When packaging foods having protrusions such as boned meat and fish, the protrusions of the food often break through the coating film during transportation or display. If a thick coating film is produced, the piercing strength can be improved, but this causes an increase in packaging costs and an increase in dust.
JP-A-8-295848

  Accordingly, an object of the present invention is to provide a gas barrier coating film having high piercing strength.

  The present invention relates to an aromatic nylon film (A), a compound (bi) containing a polar group, and a chemical formula 1:

(In the formula, R ¹ is a hydrogen atom or an alkyl group which may have a functional group, R ² may be the same or different, and is a hydrogen atom or an alkyl group, and x is 0 or 1. Yes, y is 3 or 4, and x + y = 4)
And a coating layer (B) formed using a composition containing the organosilicon compound (b-ii) and / or its hydrolysis condensate (b-iii).

  The coated film of the present invention has high gas barrier properties and high piercing strength.

  In the present invention, an aromatic nylon film is used as a substrate, and a silicon-based film having excellent gas barrier properties is disposed on the substrate. By employing such a combination, a coated film having high gas barrier properties and high piercing strength can be obtained. The aromatic nylon film and the silicon-based film have high piercing strength and gas barrier properties, respectively, but a more suitable coated film can be obtained by combining them.

  First, each layer which comprises the coating film of this invention is demonstrated in order.

  The aromatic nylon film (A) is a film composed of nylon having an aromatic structure in the main chain. The aromatic structure means a structure that causes aromaticity. For example, a benzene ring, a pyridine ring, a naphthalene ring, and the like are present in the main chain. Some of these may be substituted. For example, the hydrogen atom of the benzene ring may be substituted with a methyl group and may exist in the main chain as a toluene type structure. Nylon is a general term for linear synthetic polyamides having an amide bond. That is, in the aromatic nylon film (A), monomer units are bonded by amide bonds, and an aromatic structure exists in a portion constituting the main chain of at least one monomer unit.

  Since the aromatic nylon film (A) of the present invention has a high piercing strength, the piercing strength of the resulting coated film is also very high. In addition, the puncture strength and gas barrier properties can be further improved by combining with the silicon-based coating layer (B) defined in the present invention.

  Specific examples of the aromatic nylon include metaxylylene adipamide (MXA) and metaxylenediamine-6 nylon (MXD6). However, the technical scope of the present invention is not limited to these.

  The aromatic nylon film (A) may be synthesized by polymerization, or a commercially available film may be used. The synthesis method is not particularly limited, and a general nylon synthesis method can be used. Examples thereof include polycondensation of a diamine having an aromatic structure with a dibasic acid, polycondensation of a diamine with a dibasic acid having an aromatic structure, and polycondensation of an ω-amino acid having an aromatic structure.

  The shape of the aromatic nylon film (A) is not particularly limited, and may be determined in consideration of the intended use and workability. The thickness is not particularly limited, but if it is too thin, the film strength may be insufficient, and if it is too thick, the raw material cost increases. For this reason, the thickness of the aromatic nylon film (A) is generally 5 to 500 μm, preferably 7 to 50 μm, and more preferably 10 to 30 μm.

  The coating layer (B) contains at least a polar group-containing compound (bi), and an organosilicon compound (b-ii) represented by Chemical Formula 1 and / or a hydrolysis condensate thereof (b-iii). Formed using the composition. Usually, a film containing these components is applied to obtain a film. For the method for preparing the coating layer composition, the methods described in JP-A-8-295848 can be appropriately referred to.

  Since the coating layer (B) of this invention has high gas barrier property, the gas barrier property of the obtained coating film is also very high. In addition, the puncture strength and gas barrier properties can be further improved by combining with an aromatic nylon film.

  The compound (bi) containing a polar group (hereinafter also referred to as “polar group-containing compound”) is not particularly limited as long as it contains a polar group. Examples of the polar group include an amino group, a hydroxyl group, a carboxyl group, a formyl group, a mercapto group, a sulfino group, a sulfo group, and an imino group. Among these, in view of gas barrier properties, moisture resistance, environmental properties, transparency, flexibility, and the like of the resulting coating layer (B), an amino group, a hydroxyl group, or a carboxyl group is preferable. This is particularly effective in improving the flexibility of the resulting coated film.

  The molecular weight of the polar group-containing compound (bi) is not particularly limited, but a polymer compound is preferable in consideration of the film forming property and flexibility of the coating layer (B) to be formed. The polymer compound as the polar group-containing compound (bi) may be inferior in flexibility of the formed coating layer (B) if the number average molecular weight is too small, or may be an aromatic nylon film (A) or other There exists a possibility that the film forming property at the time of coating and laminating | stacking on a coating layer (B) may be inferior. For this reason, 250 or more are preferable and, as for the number average molecular weight of the high molecular compound as a polar group containing compound (bi), 300 or more are more preferable. On the other hand, if the number average molecular weight is too large, the formed coating layer (B) may have poor transparency, and the coating layer (B) may have poor flexibility. For this reason, the number average molecular weight of the polymer compound as the polar group-containing compound (bi) is preferably 200,000 or less, more preferably 100,000 or less, and particularly preferably 10,000 or less. However, a polymer compound having a complicated structure that cannot be measured by the number average molecular weight can also be used as the polar group-containing compound (bi).

  Specific examples of the polar group-containing compound (bi) include low molecular compounds such as ethanolamine, and high molecular compounds such as polyalkyleneimine and polyallylamine.

Examples of the polyalkyleneimine include polymethyleneimine, polyethyleneimine, polypropyleneimine, polyisopropyleneimine, polybutyleneimine, polyisobutyleneimine and the like. Polyalkylenimines can be prepared using various known synthetic methods. Commercially available polyalkyleneimines may be used. For example, Epomin ^TM series manufactured by Nippon Shokubai Co., Ltd .; Epomin SP-003, Epomin SP-006, Epomin SP-012, Epomin SP-018, Epomin SP-103, Epomin SP-110, Epomin SP-200, Epomin SP- Polyethyleneimine such as 300, Epomin SP-1000, Epomin SP-1020 (all are trade names) can be used. As polyallylamine, polyallylamine synthesized by various known methods, or commercially available polyallylamine such as PAA-L and PAA-H (both trade names) manufactured by Nitto Boseki Co., Ltd. can be used. These may be used alone or in combination of two or more. Among the above-mentioned polar group-containing compounds (bi), polyalkyleneimine is preferable and polyethyleneimine is particularly preferable in consideration of thermal stability, transparency, flexibility, and adhesion of the coating layer (B). .

  The organosilicon compound (b-ii) is a compound represented by Chemical Formula 1.

In Chemical Formula 1, R ¹ is a hydrogen atom or an alkyl group which may have a functional group. The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, specifically, a linear alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group, a branched alkyl group such as an isopropyl group or an isobutyl group, a cyclopropyl group, A cyclic alkyl group such as a cyclobutyl group is exemplified. From the viewpoint of forming a dense coating layer, a methyl group or an ethyl group is preferable. The functional group that can be included in the alkyl group is not particularly limited, and examples thereof include an amino group, an epoxy group, a (meth) acryl group, a thiol group, a hydroxyl group, and a vinyl group. In particular, when it has a vinyl group, it has an effect of improving heat resistance.

In Chemical Formula 1, R ² is a hydrogen atom or an alkyl group. The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, specifically, a linear alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group, a branched alkyl group such as an isopropyl group or an isobutyl group, a cyclopropyl group, Examples thereof include a cyclic (alicyclic) alkyl group such as a cyclobutyl group. From the viewpoint of forming a dense coating layer, a methyl group or an ethyl group is preferable. R ² may be the same or different.

  In Chemical Formula 1, x is 0 or 1, y is 3 or 4, and x + y = 4. When y = 4, the pressure resistance, heat resistance, water resistance and the like of the coating layer (B) to be formed can be improved.

  Specific examples of the organosilicon compound (b-ii) include tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, and methyltributoxy. Silane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltributoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltributoxysilane, γ-mercaptopropyltrimethoxy Silane, γ-mercaptopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-aminopropyltrimethyl Alkoxysilanes such as toxisilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-hydroxypropyltrimethoxysilane, γ-hydroxypropyltriethoxysilane And complex compounds thereof, methyltriacetoxysilane, trimethylsilanol, and high molecular weight organosilicon compounds containing these compounds. Considering the moisture resistance and water resistance of the coating layer (B), tetramethoxysilane and tetraethoxysilane are preferable. In addition, these may be used individually by 1 type, or may be used in combination of 2 or more types.

  The hydrolysis-condensation product (b-iii) of the organosilicon compound is a compound obtained by hydrolysis condensation of the organosilicon compound (b-ii) represented by Chemical Formula 1. Instead of or in addition to the organosilicon compound, a hydrolysis condensate (b-iii) of the organosilicon compound may be included. That is, the composition for coating layers of this invention may contain the organosilicon compound (b-ii) and may contain the hydrolysis-condensation product (b-iii) of the organosilicon compound. Of course, both may be included. By including the hydrolysis-condensation product (b-iii) of the organosilicon compound, unintentional drying of the coating layer composition when forming the coating layer (B) can be prevented. These hydrolysis-condensation reactions proceed even with moisture present in the air, but the reaction efficiency may be improved using a known catalyst such as an acid or a base. In consideration of workability, the hydrolysis reaction is preferably performed in a solvent.

  The composition for a coating layer includes components other than the polar group-containing compound (bi), the organosilicon compound (b-ii) represented by Chemical Formula 1, and its hydrolysis condensate (b-iii). It may be.

  For example, the coating layer composition further includes an organic compound (b-iv) having a functional group in the molecule that can react with the polar group contained in the compound (bi) to form a chemical bond. It is.

  The organic compound (b-iv) is not particularly limited as long as it has a functional group in the molecule that can react with the polar group contained in the polar group-containing compound (bi) to form a chemical bond. Such a functional group is determined according to the polar group contained in the polar group-containing compound (bi), and is not particularly limited. For example, when the polar group is a polar group having an N—H bond, an epoxy group, carboxyl group, isocyanate group, thioisocyanate group, oxazolinyl group, (meth) acryl group, aldehyde group, ketone group, alkyl halide group Etc. can be used. Among these, an epoxy compound having an epoxy group is preferable in view of easy reaction with active hydrogen bonded to a nitrogen atom and hot water resistance. In addition, when the component which consists of organic compounds (b-iv) is included in the composition for coating layers, it is especially effective in improving the film forming property of the composition for coating layers.

  The organic compound (b-iv) is not particularly limited, but 2-ethylhexyl glycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, nonaethylene glycol diglycidyl. Ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, glycerol diglycidyl ether, trimethylolpropane diglycidyl ether Aliphatic mono- and diglycidyl ethers; glycerol triglycidyl Polyglycidyl ethers such as ether, diglycerol triglycidyl ether, triglycidyl tris (2-hydroxyethyl) isocyanurate, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether; adipic acid diglycidyl ester, o-phthalic acid di Aliphatic and aromatic mono-, diglycidyl esters such as glycidyl ester and phenyl glycidyl ether; bisphenol A diglycidyl ether, resorcinol diglycidyl ether, hydroquinone diglycidyl ether, bisphenol S diglycidyl ether, bisphenol F diglycidyl ether, etc. Glycidyls having an aromatic ring or a hydrogenated ring thereof (including nucleus-substituted derivatives); having a glycidyl group as a functional group Ligomers; Isocyanates such as hexamethylene diisocyanate, tolylene diisocyanate, 1,4-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, triphenylmethane triisocyanate, tolidine diisocyanate, xylylene diisocyanate, dicyclohexylmethane diisocyanate; tartaric acid, adipic acid And dicarboxylic acids such as polyacrylic acid and the like; and oxazolinyl group-containing polymers. These may be used alone or in combination of two or more. Among the organic compounds (b-iv) exemplified above, organic compounds having an aromatic ring or an aliphatic ring are preferable. By using an organic compound having an aromatic ring or an aliphatic ring, the water resistance of the coating layer (B) can be improved.

  The organic compound (b-iv) has the chemical formula 2:

May be included in the molecule (hereinafter also referred to as “SiOR ³ group”). In the formula, R ³ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. The alkyl group having 1 to 4 carbon atoms may be any of a linear alkyl group, a branched alkyl group, and a cyclic (alicyclic) alkyl group. Among the alkyl groups, a methyl group or an ethyl group is preferable from the viewpoint of densifying the coating layer (B).

When in the organic compound (b-iv) has a SiOR ³ groups are hydrolyzed condensate proceeds in ³ groups SiOR in before or after the reaction with the polar group-containing compound (b-i). Further, cohydrolytic condensation proceeds with the hydrolyzable condensing group contained in the organosilicon compound (b-ii). By the action of these condensation polymerizations, it is possible to quickly form a dense coating layer (B) having excellent hard coat properties. Moreover, it also has the effect of improving the adhesion of the coating layer (B).

Specific examples of the organic compound (b-iv) having a SiOR ³ group include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltriisopropoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane , Β- (3,4-epoxycyclohexyl) ethyltriisopropoxysilane, β- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethylmethyldiethoxysilane, and other epoxies And Silanes having SiOR ³ groups Pulling agent (hereinafter also simply referred to as epoxy group-containing silane coupling agent); γ-isocyanopropyltrimethoxysilane, γ-isocyanopropyltriethoxysilane, γ-isocyanopropylmethyldimethoxysilane, γ-isocyano Examples thereof include an isocyanate group such as propylmethyldiethoxysilane and a SiOR ³ group-containing silane coupling agent (hereinafter also simply referred to as an isocyanate group-containing silane coupling agent). These may be used alone or in combination of two or more.

  A composition for a coating layer is prepared by combining the above-mentioned components (b-i) to (b-iii) and, if necessary, other components such as (b-iv). What is necessary is just to select the combination of a component in consideration of the characteristic of the coating layer obtained. For example, polyethylenimine (bi), tetramethoxysilane (b-ii) or a hydrolyzed condensate of tetraethoxysilane (b-iii), and an epoxy group-containing silane coupling agent (b-iv) are blended. As another example, an amino group-containing silane coupling agent (bi), tetramethoxysilane (b-ii), tetraethoxysilane (b-iii), and an epoxy compound having an aromatic ring or an aliphatic ring ( b-iv).

  As the solvent used for the preparation of the coating layer composition, a solvent (b-v) described later can be used. In this case, the blending amount of each raw material component should be determined according to the presence or absence of the use of other additives, etc., and cannot be uniquely defined, but normal amounts are defined below.

  The compounding amount of the polar group-containing compound (bi) is usually 5 to 70% by mass, preferably with respect to the total compounding amount of the constituent components of the coating layer composition (excluding the solvent (bb)). Is in the range of 10-60 mass%, more preferably 15-40 mass%.

  The compounding amount of the organosilicon compound (b-ii) and / or its hydrolysis condensate (b-iii) is the total compounding component of the composition for the coating layer (excluding the solvent (bb)) Is usually in the range of 10 to 80 mass%, preferably 20 to 70 mass%, more preferably 30 to 60 mass%. In addition, "the compounding quantity of an organosilicon compound (bi) and / or its hydrolysis-condensation product (b-iv)" means the total compounding quantity of both, and only any one is a composition for coating layers. When it is contained in a product, it means one blending amount.

  The compounding amount of the organic compound (b-iv) is usually 5 to 50% by mass, preferably 7 with respect to the total compounding amount of the constituent components of the coating layer composition (excluding the solvent (bv)). It is -35 mass%, More preferably, it is the range of 10-20 mass%.

  The solvent (bv) in which (bi) to (b-iii) are blended includes the polar group-containing compound (bi), the organic compound (b-iv), the organosilicon compound (b-ii), and It is not particularly limited as long as it is a hydrolyzed condensate (b-iii) of an organosilicon compound and a compound that can dissolve these reactants. Specifically, alcohols such as methanol, ethanol, 2-propanol, butanol, and ethylene glycol; ketones such as acetone and methyl ethyl ketone; aromatic hydrocarbons such as toluene, benzene, and xylene; hexane, heptane, octane, and the like Hydrocarbons; acetates such as methyl acetate and ethyl acetate; other examples include ethyl phenol ether, propyl ether, tetrahydrofuran, and water. Among these, alcohols such as methanol and ethanol are preferable because they are excellent in stability during hydrolysis and storage stability. The solvent may be selected in consideration of compatibility with the components (bi) to (b-iii) to be used.

  Although the compounding quantity of a solvent (bv) is not specifically limited, When the total mass of the composition for coating layers (here solvent (bv) is included) is 100 mass%, it is 20-97 normally. It is in the range of mass%, preferably 50 to 95 mass%, more preferably 70 to 95 mass%, particularly preferably 75 to 90 mass%. When the blending amount of the solvent (b-v) is less than 20% by mass, the reaction stability of the coating layer composition may be inferior, and the viscosity of the coating layer composition increases during coating. There is a risk that uniform coating will not be possible. On the other hand, if it exceeds 97% by mass, the productivity in forming the coating layer (B) may be inferior, and the active ingredient is too low in concentration, so that the necessary coating layer (B) thickness is required. May not be secured.

  In the coating layer composition, various additives such as a curing catalyst, a wettability improver, a plasticizer, an antifoaming agent, and a thickener are further blended in an appropriate amount within a range that does not impair the properties of the coating layer composition. Also good.

  The manufacturing method of the composition for coating layers is not specifically limited, For example, the following method is used. However, there is no limitation to these.

(1) Polar group-containing compound (bi), organosilicon compound (b-ii) and / or hydrolysis condensate (b-iii) thereof, organic compound (b-iv), solvent (b- (2) A method of reacting a compounding component (which may contain other optional components) comprising (2) a polar group-containing compound (bi) and an organic compound (b) in advance in a solvent (bb) -Iv) and then adding organosilicon compound (b-ii) and / or its hydrolysis condensate (b-iii) (3) Solvent containing polar group-containing compound (bi) (Bv) Method of hydrolytic condensation of organosilicon compound (b-ii) and organic compound (b-iv) Solvent (bv) is a suitable solvent depending on the preparation stage and method May be replenished or added in a timely manner.

  What is necessary is just to determine reaction conditions according to the composition to be used, for example, it is made to react at about 30-80 degreeC for about 0.5 to 5 hours.

  The coating layer (B) is formed using the coating layer composition thus prepared. Various coating methods and printing methods can be used to apply the coating layer composition. For example, various printing such as roll coating, dip coating, bar coating, nozzle coating, die coating, spray coating, spin coating, curtain coating, flow coating, screen printing, gravure printing, curved surface printing, etc. Law. These may be combined. Usually, the composition for a coating layer is supplied so that the thickness after drying of the coating layer (B) to be formed is 0.1 to 3.0 μm, preferably 0.3 to 1.5 μm. If the thickness of the coating layer (B) after drying is less than 0.1 μm, sufficient gas barrier properties may not be exhibited. On the other hand, when the thickness of the coating layer (B) after drying exceeds 3.0 μm, the gas barrier property may be deteriorated due to generation of cracks or insufficient adhesion strength.

  After coating, the coating layer composition is cured and dried. When heating is performed, the heating is preferably performed at a temperature lower than the heat resistance temperature of the aromatic nylon film (A). Here, the heat resistant temperature means an upper limit temperature at which the characteristics of the nylon film can be substantially maintained, and means a glass transition point, a crystallization temperature, or a decomposition point. The conditions for curing and drying are not particularly limited, but in order to form the coating layer (B) quickly, it may be treated at 60 to 120 ° C. for 1 to 300 seconds. You may dry in water vapor | steam or mist presence.

  In order to develop a high gas barrier property in the coating layer (B) even in a high-temperature and high-humidity environment, an aging treatment is preferably performed after curing and drying. Examples of the aging treatment include heat treatment and corona treatment. Specifically, heat treatment is performed at 40 to 60 ° C. for 1 to 7 days.

  In forming the coating layer (B) by coating the coating layer composition, the coating layer composition having the same composition may be coated several times, or the coating layer compositions having different compositions may be coated. The coating layer (B) may be formed into a multilayer structure by coating an object several times.

Since the covering film of the present invention has the above-mentioned aromatic nylon film (A) and covering layer (B), it has high piercing strength and high oxygen permeability. Specifically, the covering film of the present invention preferably has a puncture strength at 20 ° C. and 65% Rh of 1.0 kgf / mm or more. The oxygen permeability at 20 ° C. and 90% Rh is preferably ² cm ³ / m ² · 24 hrs · atm or less.

  The piercing strength is a measure showing the durability with which a hole is not opened in a film when a force is applied by a sharp object. The coated film of the present invention preferably has a puncture strength measured at a temperature of 20 ° C. and a humidity of 65% Rh of 1.0 kgf / mm or more. The piercing strength measurement is not particularly limited as long as it is a reproducible measurement method. When the puncture strength varies depending on the measurement device or the measurement means, the puncture strength measured by the measurement method used in the “Example” is defined as “the puncture strength” in the present invention. In measuring the piercing strength, it is preferable to measure the piercing strength several times, for example, five times, and take the average in order to eliminate statistical errors. The puncture strength is compared as a converted value per 1 mm of film thickness. Therefore, when the piercing strength was measured for a film having a thickness of 0.5 mm, if the film was broken at a value of 0.6 kgf, the piercing strength of this film was 1.2 kgf / mm or more.

  Oxygen permeability is a measure of the ease with which oxygen molecules can permeate the coating film. The coated film of the present invention has an oxygen permeability measured under the conditions of a temperature of 20 ° C. and a humidity of 90% Rh, preferably 1.0 kgf / mm or more. The measurement of oxygen permeability is not particularly limited as long as it is a reproducible measurement method. In the case where the oxygen permeability varies depending on the measuring device or measuring means, the oxygen permeability measured by the measurement method used in the “Example” is referred to as “oxygen permeability” in the present invention. In measuring the oxygen permeability, it is preferable to measure the oxygen permeability several times, for example, five times, and take the average in order to eliminate statistical errors.

  A heat seal layer (C) may be laminated on the covering film according to the present invention. The heat seal layer (C) is a layer having a function of fusing and sealing a space during film packaging. The material of the heat seal layer (C) is not particularly limited. For example, films having various heat sealing properties such as polyolefin films and ethylene vinyl alcohol copolymer films can be used. The thickness of the sealant layer is preferably 10 to 200 μm, more preferably 20 to 100 μm, and particularly preferably 30 to 70 μm.

  The heat seal layer (C) is fixed by forming an adhesive layer on the surface of the layer on which the heat seal layer (C) is disposed, and disposing the heat seal (C) on the adhesive layer and bonding them. . The adhesive layer can be formed by applying a liquid containing an adhesive resin such as a urethane resin to a desired portion and drying. Of course, other methods may be used. The thickness of the adhesive layer is sufficient as long as it can secure adhesiveness.

  The site where the heat seal layer (C) is disposed is not particularly limited. If it is desired to simplify the laminated structure, a heat seal layer (C) may be further laminated on the coating layer (B) via an adhesive layer. In this case, the lamination order is aromatic nylon film (A) / covering layer (B) / adhesive layer / heat seal layer (C). However, other laminated configurations may be employed. For example, the heat seal layer (C) may be disposed on the side of the aromatic nylon film (A) where the coating layer (B) is not disposed. In this case, the stacking order is coating layer (B) / aromatic nylon film (A) / adhesion layer / heat seal layer (C). Depending on the case, other films, such as a polyethylene terephthalate, may be used as a base material at the time of forming a coating layer (B). A specific example of the stacking order is polyethylene terephthalate layer / adhesive layer / coating layer (B) / aromatic nylon film (A) / adhesive layer / heat seal layer (C).

The coated film of the present invention can be applied to various uses that require gas barrier properties such as packaging materials and medical materials. Considering the usefulness as a food, it is preferable that the coating film on which the heat seal layer (C) of the present invention is formed is excellent in retort resistance. The retort resistance means a property that the film does not deteriorate in a high-temperature and high-pressure steam-containing atmosphere. Specifically, the coated film of the present invention has an oxygen permeability of preferably 5 cm ³ / m ² · 24 hrs · atm or less after being held at 120 ° C. and 2.3 atm for 30 minutes in the presence of water. Here, “in the presence of water” means a state in which at least one surface of the film is in contact with a composition containing water. For example, the laminated film is placed in an autoclave containing water so that one surface of the laminated film is in contact with water. Then, after pressurizing the inside of the autoclave, the temperature in the autoclave is raised to 120 ° C. and held for 30 minutes.

  The measurement of oxygen permeability is not particularly limited as long as it is a reproducible measurement method. In the case where the oxygen permeability varies depending on the measuring device or measuring means, the oxygen permeability measured by the measurement method used in the “Example” is referred to as “oxygen permeability” in the present invention. As described above, when measuring the oxygen permeability, in order to eliminate a statistical error, the oxygen permeability may be measured several times, for example, five times, and an average thereof may be taken.

  The usefulness of the present invention will be specifically described using examples and comparative examples. In addition, the apparatus and conditions used for the measurement of each physical property are as follows.

[Puncture test]
The coated film to be measured was stretched horizontally in a natural state so that no wrinkles were present. From above, a stick having a punch diameter of 1.6 mmφ was pressed vertically onto the coated film at a constant speed of 100 mm / min. The rod material was stainless steel. The force when the film is perforated is measured, and the value obtained by converting the maximum value at this time into the strength per 1 mm of the film thickness is defined as the piercing strength.

[Oxygen permeability measurement]
An oxygen permeability measuring device MH manufactured by Modern Controls was used. The measurement was performed at 20 ° C. and 90% Rh.

[Measurement of oxygen permeability after retort treatment]
The laminated film as a sample was placed in an autoclave where water was present. Thereafter, the temperature inside the autoclave was raised to 120 ° C., and the pressure was raised to 2.3 atm. In this state, the laminated film was held for 30 minutes. Thereafter, the laminated film was taken out from the autoclave and the oxygen permeability was measured. The measurement was performed at 20 ° C. and 90% Rh. For measurement, an oxygen permeability measuring device MH manufactured by Modern Controls was used.

<Synthesis Example 1>
Polyethyleneimine (50 g: EPOMIN ^TM SP-018 manufactured by Nippon Shokubai Co., Ltd.) as the polar group-containing compound (bi), and γ-glycidoxypropyltrimethoxysilane (organic compound (b-iv) having a SiOR ³ group ( 30 g) and a mixture containing ethanol (500 g) as a solvent (b-v) were reacted at 65 ° C. for 3 hours and cooled to room temperature. Next, water (5 g) and ethanol (300 g) were added to the reaction solution and reacted for 30 minutes, and a tetramethoxysilane oligomer (100 g: Tama Chemical Industry Co., Ltd.) was obtained as a hydrolytic condensate (b-iii) of an organosilicon compound. A mixture of M silicate 51) and ethanol (200 g) was added. This was made to react at room temperature for 1 hour, and it was set as the composition 1 for coating layers.

<Synthesis Example 2>
Polyethyleneimine (35 g: EPOMIN ^TM SP-018 manufactured by Nippon Shokubai Co., Ltd.) as the polar group-containing compound (bi), and γ-glycidoxypropyltrimethoxysilane (organic compound (b-iv) having a SiOR ³ group ( 50 g), and a mixed solution containing ethanol (530 g) as a solvent (b-v) was reacted at 65 ° C. for 3 hours and cooled to room temperature. Next, water (1.5 g) and methanol (640 g) were added to this reaction solution and reacted for 30 minutes, and tetramethoxysilane oligomer (250 g: Tama Chemical) was used as the hydrolytic condensate (b-iii) of the organosilicon compound. A mixed solution of M silicate 51) and ethanol (265 g) manufactured by Kogyo Co., Ltd. was added. This was made to react at room temperature for 1 hour, and it was set as the composition 2 for coating layers.

<Example 1>
The coating layer composition 1 is applied to a metaxylylene adipamide (MXA) film (thickness 15 μm) as an aromatic nylon film (A) with a bar coater so that the thickness of the coating layer after drying becomes 1 μm. And dried at 100 ° C. for 10 seconds. Then, it aged at 50 degreeC for 5 days, and obtained the covering film 1 with which the aromatic nylon film (A) and the coating layer (B) were laminated | stacked.

When the puncture strength of the covering film 1 was measured according to the above method, the puncture strength was 1.1 kgf / mm. The oxygen permeability at 20 ° C. and 90% Rh was 0.5 cm ³ / m ² · 24 hrs · atm. The results are shown in Table 1.

<Example 2>
On the coating layer of the coating film 1 obtained in Example 1, a urethane adhesive was applied so that the thickness after drying was 1.5 μm and dried at 80 ° C. for 30 seconds to form an adhesive layer. . Thereafter, an unstretched polypropylene (CCP) film having a thickness of 60 μm was bonded to the surface of the adhesive layer. After disposing the CCP film, this was aged at 40 ° C. for 2 days to form a heat seal layer (C), and a laminated film 2 was obtained.

When the puncture strength of the covering film 2 was measured according to the above method, the puncture strength was 1.3 kgf / mm. The oxygen permeability at 20 ° C. and 90% Rh was 0.3 cm ³ / m ² · 24 hrs · atm. The oxygen permeability of the laminated film 2 after the retort treatment was 3.2 cm ³ / m ² · 24 hrs · atm. The results are shown in Table 1.

<Example 3>
A coating film 3 was obtained by the same procedure as in Example 1 except that the coating layer composition 2 obtained in Synthesis Example 2 was used as the coating layer composition.

When the puncture strength of the covering film 3 was measured according to the above method, the puncture strength was 1.0 kgf / mm. The oxygen permeability at 20 ° C. and 90% Rh was 0.4 cm ³ / m ² · 24 hrs · atm. The results are shown in Table 1.

<Example 4>
An adhesive layer and a heat seal layer (C) were formed on the coated film 3 obtained in Example 3 by the same procedure as in Example 2, and a coated film 4 was obtained.

When the puncture strength of the coating film 4 was measured according to the above method, the puncture strength was 1.2 kgf / mm. The oxygen permeability at 20 ° C. and 90% Rh was 0.1 cm ³ / m ² · 24 hrs · atm. The oxygen permeability of the laminated film 4 after the retort treatment was 3.0 cm ³ / m ² · 24 hrs · atm. The results are shown in Table 1.

<Comparative Example 1>
Comparison was made in the same manner as in Example 1 except that a polyethylene terephthalate (PET) film (thickness 15 μm) was used instead of the metaxylylene adipamide (MXA) film as the aromatic nylon film (A). A coated film 1 was obtained.

When the puncture strength of the comparative coated film 1 was measured according to the above method, the puncture strength was 0.7 kgf / mm. The oxygen permeability at 20 ° C. and 90% Rh was 0.5 cm ³ / m ² · 24 hrs · atm. The results are shown in Table 1.

<Result>
As shown in Table 1, the coating film of the present invention is excellent in piercing strength and gas barrier properties.

Claims (4)

An aromatic nylon film (A),
Compound (bi) containing a polar group, as well as chemical formula 1:

(In the formula, R ¹ is a hydrogen atom or an alkyl group which may have a functional group, R ² may be the same or different, and is a hydrogen atom or an alkyl group, and x is 0 or 1. Yes, y is 3 or 4, and x + y = 4)
And a coating layer (B) formed using a composition containing the organosilicon compound (b-ii) and / or its hydrolyzed condensate (b-iii). 2. The puncture strength at 20 ° C. and 65% Rh is 1.0 kgf / mm or more, and the oxygen permeability at 20 ° C. and 90% Rh is 2 cm ³ / m ² · 24 hrs · atm or less. Coating film.   Furthermore, the coating film of Claim 1 or 2 which has a heat seal layer (C). The coated film according to claim 3, wherein the oxygen permeability after holding at 120 ° C. and 2.3 atm for 30 minutes in the presence of water is 5 cm ³ / m ² · 24 hrs · atm or less.