JP2007217642A - Two pack-type curable gas-barrier polyurethane-based resin and layered film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a two pack-type curable polyurethane-based resin exhibiting excellent gas-barrier properties to oxygen, water vapor, a perfume component or the like even in high humidity. <P>SOLUTION: The two pack-type curable gas-barrier polyurethane-based resin comprising a polyisocyanate component (A) and a polyol component and/or a polyamine component (B) is prepared so as to contain a crosslinked cyclic hydrocarbon group and an araliphatic hydrocarbon group in the resin. The proportion of the crosslinked cyclic hydrocarbon group may be ≥10 wt.%. The ratio (weight ratio) of the crosslinked cyclic hydrocarbon group to the araliphatic hydrocarbon group may be nearly (99/1)-(20/80). The proportion of tri- or poly-functional components in the polyisocyanate component (A) and the active hydrogen-containing component (B) may be ≥5 wt.% based on the total amount of the components (A) and (B). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a two-component curable polyurethane resin having a high gas barrier property and a long pot life (pot life), and a coating film (or laminated film) obtained by coating or laminating this polyurethane resin on a substrate.

  Gas barrier films and packaging materials using the same are already known. Aluminum foil is known as the most excellent oxygen gas barrier packaging material, but aluminum foil alone is weak in pinhole resistance, so it cannot be used except for special applications. Used as. Although the gas barrier property of the laminate film including the aluminum foil is very excellent, it is difficult to judge whether the heat sealing is surely performed as well as the contents cannot be visually recognized because of the opaqueness.

  As an oxygen gas barrier film, a polyvinylidene chloride or vinylidene chloride copolymer (hereinafter simply referred to as PVDC) film and a coating film are known. In particular, the PVDC coating film is known as a laminated film having a high barrier property against oxygen gas and water vapor. Since PVDC has almost no hygroscopicity and has a high gas barrier property even under high humidity, various base films for coating can be used regardless of humidity. For example, films such as biaxially stretched polypropylene (hereinafter simply referred to as OPP), biaxially stretched nylon (hereinafter simply referred to as ON), biaxially stretched polyester (hereinafter simply referred to as biaxially stretched polyethylene terephthalate simply as OPET), cellophane, etc. are used. Has been. The laminated film makes use of gas barrier properties and is used for various food packaging regardless of whether it is a dried product or a water (wet container). After these packaging materials are used, they are usually disposed of as general waste from households. However, PVDC generates harmful gases by combustion, and further generates highly chlorinated organochlorine compounds by incineration at low temperatures. It is also a cause of the occurrence. For this reason, the transition from PVDC to other materials is strongly desired. However, from the viewpoint of performance and cost, a material that can replace PVDC has not yet appeared.

  For example, a polyvinyl alcohol (hereinafter, simply referred to as PVA) film is also known as an oxygen gas barrier film. The PVA film has a very excellent oxygen gas barrier property in a state of low moisture absorption. However, if the hygroscopicity is large and the relative humidity exceeds 70%, the oxygen gas barrier property is drastically lowered, and the contents are limited to dry matter. In order to improve the hygroscopicity of PVA, there are a method of copolymerizing with ethylene to form an ethylene-vinyl alcohol copolymer (hereinafter simply referred to as EVOH), a method of modifying a part of the alcohol of PVA and making it water resistant, etc. It is being considered. In JP-A-4-345842 (Patent Document 1), an alkoxysilane, a silane coupling agent, and PVA are polycondensed by a sol-gel method, and the resulting composite polymer is laminated on a base film of a thermoplastic resin. Laminated films have been proposed. However, the resin obtained by any method has not yet achieved satisfactory performance.

  JP-A-1-2522631 (Patent Document 2) discloses a gas barrier packaging material composed of polyamide obtained by reacting an aliphatic dicarboxylic acid with 4,4′-methylenebis (phenylisocyanate). It is disclosed that this film exhibits excellent gas barrier properties on the high humidity side. JP-A-10-140072 (Patent Document 3) discloses an aqueous dispersion for gas barrier coating composed of polyallyl alcohol, and a multilayer structure in which a film layer of the aqueous dispersion is formed on a substrate. It is disclosed that it exhibits excellent gas barrier properties and transparency. However, even these films have not yet achieved satisfactory performance in terms of gas barrier properties and water resistance under high humidity.

  Recently, films having a high oxygen gas barrier property have also been produced by vapor deposition of inorganic oxide films. For example, in Japanese Patent Publication No. 53-12953 (Patent Document 4), a transparent thin film layer is formed by vapor-depositing silicon oxide to a thickness of 100 to 3000 mm on at least one surface of a flexible plastic film, and is resistant to moisture and moisture. A wet transparent film is disclosed. Japanese Patent Application Laid-Open No. 62-179935 (Patent Document 5) discloses a packaging film in which an amorphous aluminum oxide thin layer is formed on a transparent plastic substrate. However, since inorganic oxide films use methods such as physical vapor deposition and chemical vapor deposition, the substrate film itself is required to have durability, and is applied only to limited substrates. In addition, since it is an inorganic oxide, its flexibility is low, and cracks and the like are likely to occur during the secondary processing of the film, resulting in a decrease in gas barrier properties.

JP-A-6-220221 (Patent Document 6) is a film formed from a mixture containing polyvinyl alcohol and poly (meth) acrylic acid in a weight ratio of 95: 5 to 20:80, A gas barrier film having an oxygen permeability coefficient measured under a condition of 80% relative humidity of 1.25 × 10 ⁻³ ml (STP) · cm / m ² · h · atm (Pa) or less is disclosed. This document also describes that a gas barrier film is obtained by forming a film from the mixture and then heat-treating the film under specific conditions (for example, 100 to 250 ° C.). However, since it is necessary to perform heat treatment at a high temperature, the base material to which the mixture is applied is greatly restricted, and cannot be applied to, for example, a general-purpose polypropylene film.

  Japanese Patent No. 3275432 (Patent Document 7) has (A) an amino group-containing silane compound and (B) two or more functional groups capable of reacting with the amino group or alkoxy group of the silane compound in the molecule. An aqueous surface treatment composition for a gas barrier containing a reactive compound composed of a reaction product with an organic compound, an anionic surfactant and water is disclosed. This document may use a reaction product of (A) an amino group-containing silane compound, (B) the organic compound, and (C) an organometallic compound, and a hydrolysis reaction product of these reaction products. It is also described that may be used. However, since this composition contains an anionic surfactant, it is difficult to greatly improve the gas barrier property.

Japanese Patent Application Laid-Open No. 2001-98047 (Patent Document 8) discloses a gas barrier polyurethane resin obtained by a reaction of a diisocyanate component and a C _2-8 alkylene glycol, and the total concentration of urethane groups and urea groups is 15% by weight or more. Is disclosed. In this document, a dihydroxycarboxylic acid such as dimethylolpropionic acid is reacted with an alkylene glycol, the resulting prepolymer is neutralized with an amine, chain extended with a chain extender such as diamine or hydrazine, and an aqueous dispersion is prepared. Obtaining is also described. When the urethane resin described in this document is used, there is no risk of environmental contamination and the gas barrier property can be improved. However, the water-based urethane resin is required not only to have good gas barrier properties but also to be suitable for film coating such as dispersion stability as a coating agent, transparency after film formation, and adhesion to a substrate.

JP 2004-10656 A (Patent Document 9) discloses a thermosetting gas barrier polyurethane resin containing a resin cured product obtained by reacting an active hydrogen-containing compound (A) and an organic polyisocyanate compound (B). In the cured resin, 20% by weight or more of the xylylene skeleton structure is contained, and the proportion of the trifunctional or higher compound in the (A) and (B) is based on the total amount of (A) and (B). A thermosetting gas barrier polyurethane resin having a content of 7% by weight or more is disclosed. This polyurethane resin has high adhesion to the base film and is excellent in gas barrier properties. However, this polyurethane resin has a low gas barrier property under high humidity and a short pot life.
JP-A-4-345841 (Claims) Japanese Patent Application Laid-Open No. 1-252631 (claims, column of effect of invention) Japanese Patent Laid-Open No. 10-140072 (claims, column of effect of invention) Japanese Examined Patent Publication No. 53-12953 (Claims) Japanese Patent Laid-Open No. 62-179935 (Claims) JP-A-6-220221 (Claims) Japanese Patent No. 3275432 (Claims) JP 2001-98047 A (claims, paragraph numbers [0035] to [0039], [0076] to [0079]) JP 2004-10656 A (Claim 1)

  Accordingly, an object of the present invention is to provide a two-component curable polyurethane resin excellent in gas barrier properties against oxygen, water vapor, aroma components, etc. even under high humidity, and a laminated film (or laminated body) using this resin. Is to provide.

  Another object of the present invention is to provide a two-component curable polyurethane resin having a long pot life (pot life) and a laminate film (or laminate) using this resin.

  As a result of intensive studies to solve the above problems, the present inventor has found that in a two-component curable polyurethane resin containing a polyisocyanate component (A) and a polyol component and / or a polyamine component (B), the resin is a crosslinked ring. It has been found that the inclusion of the formula hydrocarbon group and the araliphatic hydrocarbon group can significantly improve the gas barrier property under high humidity, and the present invention has been completed.

  That is, the two-component curable gas barrier polyurethane resin of the present invention is a two-component curable polyurethane containing a polyisocyanate component (A) and at least one active hydrogen-containing component (B) selected from a polyol component and a polyamine component. This resin has a crosslinked cyclic hydrocarbon group and an araliphatic hydrocarbon group in the resin. The proportion of the crosslinked cyclic hydrocarbon group may be 10% by weight or more. The ratio (weight ratio) between the bridged cyclic hydrocarbon group and the araliphatic hydrocarbon group may be about bridged cyclic hydrocarbon group / aromatic aliphatic hydrocarbon group = 99/1 to 10/90. Furthermore, the bridged cyclic hydrocarbon group may be a group represented by the following formula (1), and the araliphatic hydrocarbon group may be a xylylene group.

(Wherein A ¹ and A ² are a direct bond, or a linear or branched alkylene group, j is an integer of 1 or more, and n is the same or different and represents 0 or an integer of 1 or more)
Moreover, the ratio of the trifunctional or higher component among the polyisocyanate component (A) and the active hydrogen-containing component (B) is 5% by weight or more based on the total amount of the component (A) and the component (B). Also good. The trifunctional or higher functional component may be a polyisocyanate component composed of an adduct of diisocyanate and a trifunctional or higher functional C _3-12 aliphatic polyol. In the polyurethane resin of the present invention, the total concentration of urethane groups and urea groups may be 15% by weight or more.

  The present invention also includes a laminated film in which a coating layer composed of the polyurethane resin is laminated on at least one surface of the base film. Furthermore, the present invention includes a gas barrier laminating adhesive containing the polyurethane resin.

  In the present invention, since the two-component curable polyurethane resin has a crosslinked cyclic hydrocarbon group and an araliphatic hydrocarbon group, it has a high gas barrier property (oxygen, water vapor, aroma even under high humidity). Gas barrier property against components) can be realized. In addition, since the solubility and stability are high, the pot life is long and the precipitation of low molecular components can be suppressed. Therefore, when the composition of the present invention is used as a coating agent, the coating workability is excellent.

  The two-component curable gas barrier polyurethane resin of the present invention contains a polyisocyanate component (A) and at least one active hydrogen-containing component (B) selected from a polyol component and a polyamine component.

[Polyisocyanate component (A)]
The polyisocyanate component (A) includes aromatic polyisocyanates, araliphatic polyisocyanates, alicyclic polyisocyanates, aliphatic polyisocyanates, and polyisocyanate derivatives thereof.

  Examples of the aromatic diisocyanate include tolylene diisocyanate (2,4- or 2,6-tolylene diisocyanate or a mixture thereof) (TDI), phenylene diisocyanate (m-, p-phenylene diisocyanate or a mixture thereof), 4,4. '-Diphenyl diisocyanate, 1,5-naphthalene diisocyanate (NDI), diphenylmethane diisocyanate (4,4'-, 2,4'-, or 2,2'-diphenylmethane diisocyanate or mixtures thereof) (MDI), Examples include 4,4′-toluidine diisocyanate (TODI) and 4,4′-diphenyl ether diisocyanate.

  Examples of the araliphatic diisocyanate include xylylene diisocyanate (1,3- or 1,4-xylylene diisocyanate or a mixture thereof) (XDI), tetramethylxylylene diisocyanate (1,3- or 1,4-tetramethyl). Examples thereof include xylylene diisocyanate or a mixture thereof (TMXDI) and ω, ω′-diisocyanate-1,4-diethylbenzene.

  The alicyclic diisocyanate includes a monocyclic alicyclic diisocyanate and a bridged cyclic alicyclic diisocyanate. Monocyclic alicyclic diisocyanates include 1,3-cyclopentane diisocyanate, 1,3-cyclopentene diisocyanate, cyclohexane diisocyanate (1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate), 3-isocyanate methyl-3, 5,5-trimethylcyclohexyl isocyanate (isophorodiisocyanate, IPDI), methylene bis (cyclohexyl isocyanate) (4,4'-, 2,4'- or 2,2'-methylene bis (cyclohexyl isocyanate) or mixtures thereof) (water MDI), methylcyclohexane diisocyanate (methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate), bis (isocyanate) Tomechiru) cyclohexane (1,3- or 1,4-bis (isocyanatomethyl) cyclohexane or mixtures thereof) (hydrogenated XDI) and the like.

In the bridged cyclic alicyclic diisocyanate, the bridged cyclic hydrocarbon corresponding to the bridged cyclic hydrocarbon group may be a saturated hydrocarbon or an unsaturated hydrocarbon. Examples of such a bridged cyclic hydrocarbon include bicycloalkanes {for example, C _6-20 bicycloalkane such as norbornane, norpinane, bicyclo [2.2.2] octane, preferably C _6-15 bicycloalkane, More preferably C _7-10 bicycloalkane}, bicycloalkenes (C _6-20 bicycloalkene such as norbornene, preferably C _6-15 bicycloalkene etc.), tricycloalkanes (C _8-20 tricyclo such as adamantane). Alkane) and the like, such as a bridged 2 to 4 cyclic hydrocarbon. In addition, the bridged cyclic hydrocarbon is usually bonded to a carbon atom located at a non-adjacent position or a hydrocarbon group (for example, alkylene such as methylene group, ethylene group, propane-2,2-diyl group, or the like). A condensed cyclic hydrocarbon having at least a bridged cyclic hydrocarbon ring bonded via an alkylidene group to form a ring (hydrocarbon ring) and having only a condensed ring in which adjacent carbon atoms form a ring (for example, , Decalin, etc.).

The bridged cyclic hydrocarbon may have a substituent. Examples of the substituent include an alkyl group (for example, a C _1-6 alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group, preferably a C _1-4 alkyl group, more preferably a C _{1- 2} alkyl groups), cycloalkyl groups (eg C _5-10 cycloalkyl groups such as cyclohexyl groups), aryl groups (eg C _6-10 aryl groups such as phenyl groups, tolyl groups, xylyl groups), A hydrocarbon group such as an aralkyl group (eg, a C _6-10 aryl-C _1-4 alkyl group such as a benzyl group); an alkoxy group (eg, a C _1-4 alkoxy group such as a methoxy group); an acyl group (eg, C _1-6 acyl group such as acetyl group); alkoxycarbonyl group (for example, C _1-4 alkoxycarbonyl group such as methoxycarbonyl group) Halogen atom (for example, fluorine atom, chlorine atom, etc.); nitro group; cyano group and the like. Preferred substituents include an alkyl group (C _1-6 alkyl group) and the like. The substituents may be substituted with a bridged cyclic hydrocarbon alone or in combination of two or more. The number of substituents may be 0 or an integer of 1 or more (for example, 1 to 10, preferably 1 to 6, more preferably about 1 to 4).

  The bridged cyclic hydrocarbon only needs to have at least a bridged cyclic hydrocarbon group (bridged cyclic hydrocarbon ring unit), and a ring in which adjacent carbon atoms are condensed (ortho-condensed (ortho-condensed), etc.). You may have 1 or multiple (for example, about 2-4) (condensed ring).

  As typical bridged cyclic hydrocarbons, bicycloalkanes which may have a substituent (for example, bicycloalkanes which may have an alkyl group such as norbornane, 2,2-dimethylnorbornane and bornane). And bicycloalkanes having a condensed ring (or bicycloalkanes forming a condensed ring) (for example, 4,7-methanoperhydroindene).

In the crosslinked cyclic alicyclic polyisocyanate, the isocyanate group (—NCO) may be directly bonded to the crosslinked cyclic hydrocarbon or may be bonded via a linking group. Examples of the linking group include a divalent hydrocarbon group such as an alkylene group or an alkylidene group (for example, a C _1-10 alkylene or alkylidene group such as a methylene group or an ethylene group, preferably a C _1-6 alkylene or alkylidene group, Preferably, C _1-4 alkylene or alkylidene group is used.

  Further, the number of isocyanate groups (or linking groups to which isocyanate groups are bonded, such as isocyanate methyl groups) may be plural (for example, 2 to 4), and is usually 2 to 3 (particularly 2) (that is, 2). Diisocyanate). In addition, the substitution position of the isocyanate group (or the linking group thereof) is not particularly limited, but may usually be the bridge head position of the crosslinked cyclic hydrocarbon. For example, the norbornane ring is often substituted with at least two carbon atoms at the 2, 3, 5, 6, and 7 positions (for example, the 2 and 5 positions, the 2 and 6 positions, and the like).

  The polyisocyanate having a typical crosslinked cyclic hydrocarbon group includes a compound represented by the following formula (2).

(Wherein A ¹ and A ² are a direct bond, or a linear or branched alkylene group, j is an integer of 1 or more, and n is the same or different and represents 0 or an integer of 1 or more)
In the above formula (2), examples of the linear or branched alkylene group in A ¹ and A ² include a linear or branched alkylene group having 1 to 6 carbon atoms. A ¹ and A ² are preferably a direct bond, a linear or branched C _1-4 alkylene group, and more preferably a linear or branched C _1-2 alkylene group (particularly a methylene group). J may be an integer of 1 or more, and is, for example, 1 to 4, preferably 1 to 3, more preferably 1 or 2, and particularly 1. The number n of the condensed rings may be 0 or an integer of 1 or more, and is, for example, 0 to 4, preferably 0 to 3, more preferably 0 to 2, particularly 0.

Specific polyisocyanates represented by the above formula (2) include compounds in which A ¹ and A ² are methylene groups, j is 1 to 2, and n is 0 or 1, such as 2,5-diisocyanate. Natomethylbicyclo [2.2.1] heptane (2,5-diisocyanatomethylnorbornane), 2,6-diisocyanatomethylbicyclo [2.2.1] heptane (2,6-diisocyanatomethylnorbornane) ), 2,5-diisocyanatomethylbicyclo [2.2.2] octane, 2,6-diisocyanatomethylbicyclo [2.2.2] octane, 3 (4), 8 (9) -di ( Shianatomechiru) tricyclo [5.2.1.0 ^2,6] decane, 3 (4), 8 (9) - di (Shianatomechiru) tricyclo [5.2.2.0 ^{2, 6]} undecane.

  Examples of the aliphatic diisocyanate include trimethylene diisocyanate, 1,2-propylene diisocyanate, butylene diisocyanate (tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate), hexamethylene. Examples thereof include diisocyanate, pentamethylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, and 2,6-diisocyanate methyl capate.

  Examples of these polyisocyanate derivatives include multimers (dimers, trimers, pentamers, and heptamers) of the polyisocyanate monomers, and urethane-modified products (for example, the polyisocyanate monomers). Or a modified urethane product obtained by modifying or reacting a part of the isocyanate group with a monool or polyol), a biuret modified product (for example, a biuret modified product produced by the reaction of the polyisocyanate monomer and water). , Allophanate-modified products (for example, allophanate-modified products produced from the reaction of the polyisocyanate monomer and monool or polyol component), urea-modified products (for example, by the reaction of the polyisocyanate monomer and diamine) Produced urea modified products), oxadiazine trione (for example, the poly Isocyanate oxadiazinetrione like produced by reaction of the monomer and carbon dioxide gas), and others.

Among these derivatives, a derivative capable of forming a trifunctional or higher functional isocyanate group, for example, an adduct of the component having three or more active hydrogen atoms and the diisocyanate is preferable. Examples of the component having three or more active hydrogen atoms include tri- or higher functional polyols, for example, C _3-12 aliphatic polyols such as glycerin, trimethylolethane, trimethylolpropane, and sorbitol. Such an adduct is preferably an adduct having a low content of unreacted monomer. An adduct having a low unreacted monomer content can be produced by using a conventional separation and purification method such as thin-film distillation or extraction. The isocyanate group concentration of the adduct body is, for example, about 1 to 30% by weight, preferably about 3 to 25% by weight, and more preferably about 5 to 20% by weight.

  These polyisocyanates can be used alone or in combination of two or more. Of these, from the viewpoint of gas barrier properties, polyisocyanate compounds including compounds having a hydrocarbon ring (aromatic polyisocyanates such as TDI, MDI and NDI, araliphatic polyisocyanates such as XDI and TMXDI, IPDI and hydrogenated XDI) , Alicyclic polyisocyanates such as hydrogenated MDI), in particular, from the viewpoint of improving gas barrier properties and film-forming properties under high humidity, cross-linked cyclic alicyclic polyisocyanates, araliphatic polyisocyanates (for example, XDI etc.) are preferred. Among these, from the viewpoint of improving the stability and solubility of the resin, a bridged cyclic alicyclic polyisocyanate such as 2,5-diisocyanatomethylbicyclo [2.2.1] heptane, and 2,6- Preference is given to at least one compound selected from diisocyanatomethylbicyclo [2.2.1] heptane (norbornane diisocyanate).

Furthermore, from the point which can improve gas-barrier property, these polyisocyanates (especially bridged cyclic alicyclic polyisocyanate, araliphatic polyisocyanate) and trifunctional or more than polyol ( _C3-12 aliphatic polyol). Adduct bodies are particularly preferred. Specific examples include adducts of norbornane diisocyanate and trimethylolpropane, adducts of xylylene diisocyanate and trimethylolpropane, and the like.

[Active hydrogen-containing component (B)]
The active hydrogen-containing component (B) is a component having a plurality of active hydrogen atoms, specifically, at least one selected from a polyol component and a polyamine component.

  As the polyol component, a low molecular weight polyol component to an oligomer or a prepolymer (polyester polyol, polyurethane polyol, polycarbonate polyol, etc.) can be used. From the viewpoint of gas barrier properties, a low molecular weight polyol is preferable.

  Examples of the low molecular weight polyol include aliphatic polyol, aromatic polyol, alicyclic polyol, polyether polyol, urethane group-containing polyol, polyamine alkylene oxide adduct, amide group-containing polyol, and the like. These polyol components can be used alone or in combination of two or more.

Aliphatic polyols include ethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, pentanediol, 3-methyl-1,5-pentanediol, hexanediol, neopentyl glycol And C _3-12 aliphatic polyols such as linear or branched C _2-10 alkanediols such as heptanediol and octanediol, glycerin, trimethylolethane, trimethylolpropane and sorbitol.

  Examples of the aromatic polyol include bisphenol A, bishydroxyethyl terephthalate, catechol, resorcin, hydroquinone, 1,3- or 1,4-xylylenediol or a mixture thereof.

  Examples of the alicyclic diol include hydrogenated bisphenol A, hydrogenated xylylene diol, cyclohexane diol, and cyclohexane dimethanol.

Examples of the polyether polyol include poly C _2-4 alkylene glycol such as diethylene glycol, triethylene glycol, tetraethylene glycol, and dipropylene glycol.

Examples of urethane group-containing polyols include compounds having a plurality of active hydrogen atoms (such as alkanediols such as ethylene glycol) and polyisocyanates (such as aromatic diisocyanates such as xylylene diisocyanate and alicyclic diisocyanates such as norbornane diisocyanate). Reaction product of alkylene carbonate ( _C2-4 alkylene carbonate such as ethylene carbonate (ethylene carbonate) and propylene carbonate) and polyamine compound or amine compound having hydroxy group (alkanolamine such as ethanolamine) Etc.

The alkylene oxide adduct of polyamine is 1 to 10 moles relative to a polyamine compound described later (for example, an aliphatic diamine such as ethylenediamine, an aromatic diamine such as xylylenediamine, and an alicyclic diamine such as isophoronediamine). The compound etc. which added the alkylene oxide ( _C2-4 alkylene oxides, such as ethylene oxide and a propylene oxide) of about (preferably 2-6 mol, more preferably 3-4 mol) are mentioned. In particular, as the polyamine compound, a bridged cyclic alicyclic diamine (polyamine having a bridged cyclic hydrocarbon group), for example, 2,5-diaminomethylbicyclo [2.2.1] heptane, and 2,6-diaminomethyl A diamine having the above-mentioned bridged cyclic hydrocarbon group such as at least one compound selected from bicyclo [2.2.1] heptane (norbornanediamine) is preferred.

Examples of the amide group-containing polyol include hydroxycarboxylic acid (such as hydroxy C _2-10 alkane-carboxylic acid such as lactic acid, malic acid, methylolpropionic acid, methylolbutanoic acid, and methylolhexanoic acid), and an amine compound (ethanol). Reaction products with polyamine compounds and amine compounds having hydroxyl groups (alkanolamines such as ethanolamine) and cyclic esters (ε-caprolactone, γ-butyrolactone, etc.) Etc.

  Polyamine components include diamines, hydrazines, hydrazine derivatives, and the like. These polyamine components can be used alone or in combination of two or more.

Examples of the diamine include alkylene diamines (for example, ethylene diamine, trimethylene diamine, tetramethylene diamine, butane diamine, pentamethylene diamine, hexamethylene diamine, 2,5-dimethylhexamethylene diamine, 2,2,4-trimethylhexamethylene diamine, C _2-10 alkylene diamines such as 2,4,4-trimethylhexamethylene diamine and octamethylene diamine, polyalkylene polyamines such as di to tetraalkylene polyamines such as diethylenetriamine and triethylenetetramine), N-alkyl substituted alkylene diamines (N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethyl-1,3-propylenediamine, N, N, N ′, N′-tetramethyl-1, 6 -Hexanediamine, N, N-dimethyl-1,2-ethylenediamine, N, N-dimethyl-1,3-propanediamine, etc.), aromatic amines (for example, m- or p-phenylenediamine, 1,3- or 1,4-xylylenediamine or a mixture thereof, diaminodiphenylmethane, diaminodiphenylsulfone, etc.), monocyclic alicyclic amines [for example, hydrogenated xylylenediamine, bis (4-aminocyclohexyl) methane, isophoronediamine, bis ( 4-amino-3-methylcyclohexyl) methane, mensendiamine, N-aminoethylpiperazine, etc.], spirocyclic alicyclic amines [for example, 3,9-bis (3-aminopropyl) -2,4,8 , 10-tetraoxaspiro [5.5] undecane and the like], a bridged cyclic alicyclic diamine [for example, Diamines having the above-mentioned bridged cyclic hydrocarbon groups such as rubornanediamine], hydroxyl group-containing diamines (2-[(2-aminoethyl) amino] ethanol, 2-aminoethylaminopropanol, 3-aminopropylaminoethanol) Amino group such as amino C _2-6 alkylamino C _2-3 alkyl alcohol), acid group-containing diamine (for example, diamino aromatic carboxylic acid such as 3,4-diaminobenzoic acid, 1,3-phenylenediamine-4,6) -Disulfonic acid, diaminosulfonic acid such as 2,4-diaminotoluene-5-sulfonic acid, etc.).

Examples of the hydrazine and hydrazine derivatives include hydrazine, hydroxyl group-containing hydrazine (hydrazide C _2-3 alkyl alcohol such as 2-hydrazide ethanol), dicarboxylic acid hydrazide [aliphatic dicarboxylic acid hydrazide (succinic acid dihydrazide, adipic acid dihydrazide, glutaric acid). C _4-20 alkane-dicarboxylic acid dihydrazide such as dihydrazide and dodecanedioic acid dihydrazide), aromatic dicarboxylic acid hydrazide (isophthalic acid dihydrazide, phthalic acid dihydrazide, naphthalenedicarboxylic acid dihydrazide and the like C _6-10 arene dicarboxylic acid hydrazide, etc. ) Etc.].

  Among these active hydrogen-containing components, from the viewpoint of gas barrier properties, tri- or higher functional polyol components [polyamines (such as aromatic diamines such as xylylenediamine and cross-linked cyclic alicyclic diamines such as norbornane diamine) are included in 3-6. A compound obtained by adding a mole of alkylene oxide (such as ethylene oxide)] or a polyol having a urethane group [a compound having a plurality of active hydrogen atoms (such as ethylene glycol) and a polyisocyanate (such as xylylene diisocyanate or norbornane diisocyanate). , A reaction product of an alkylene carbonate (such as ethylene carbonate) and an amine compound having a hydroxy group (such as ethanolamine)], a polyalkylene polyamine (such as diethylenetriamine or triethylenetetramine) Alkylene polyamines, etc.) and the like are preferable.

  In the case of a hydroxyl group, the concentration of the functional group (hydroxyl group or amino group) of the active hydrogen-containing component is, for example, a hydroxyl value of 10 to 900 mgKOH / g, preferably 50 to 850 mgKOH / g, more preferably 100 to 800 mgKOH / g. It is about g.

  The ratio (molar ratio) between the polyisocyanate component (A) and the active hydrogen-containing component (B) is, for example, isocyanate group / active hydrogen atom = 2/1 to 1/2, preferably 1.5 / 1 to 1 /. It is about 1.5, more preferably about 1.3 / 1 to 1 / 1.3 (particularly 1.15 / 1 to 1 / 1.15).

[Other ingredients]
The two-part curable polyurethane resin of the present invention further includes solvents such as esters (ethyl acetate, ethyl formate, etc.), ethers (tetrahydrofuran, dioxane, etc.), ketones (acetone, methyl ethyl ketone, etc.), aromatics. Add hydrocarbons (toluene, xylene, etc.), nitriles (acetonitrile, etc.), carbonates (dimethyl carbonate, diethyl carbonate, etc.), amides (dimethylformamide, dimethylacetamide, etc.), sulfoxides (dimethyl sulfoxide, etc.) May be. These solvents can be used alone or in combination of two or more. Of these solvents, ketones such as methyl ethyl ketone, esters such as ethyl acetate, and the like are widely used. The ratio of the solvent is, for example, about 10 to 2000 parts by weight, preferably 50 to 1000 parts by weight, and more preferably about 100 to 800 parts by weight (particularly 150 to 400 parts by weight) with respect to 100 parts by weight of the polyurethane resin. .

  These solvents may be added to the polyisocyanate component (A) and the component (B) having an active hydrogen atom before mixing the two liquids. For example, the solvent can be added so that the solid content is about 5 to 95% by weight, preferably about 10 to 90% by weight, and more preferably about 15 to 85% by weight (particularly 20 to 80% by weight).

  In the two-part curable polyurethane resin of the present invention, a conventional additive such as a chain extender (for example, the polyamine, water, hydrazine, hydrazine derivative, etc.) is used as long as the gas barrier property is not impaired as required. ), Coupling agents (such as silane coupling agents and titanium coupling agents), curing accelerators (such as lead or zuz compounds), fillers (silica, alumina, mica, talc, aluminum flakes, glass flakes, etc.) Particles), thixotropic agent, viscosity modifier, dispersant, wetting agent, plasticizer, defoaming agent, crosslinking agent, colorant, leveling agent, lubricant, anti-blocking agent, flame retardant, stabilizer (antioxidant) UV absorbers, heat stabilizers), antistatic agents, crystal nucleating agents and the like may be added. These additives can be used alone or in combination of two or more.

  Although the addition amount of these additives can be suitably selected according to the kind, for example, 30 parts by weight or less (for example, 0.1 to 30 parts by weight) with respect to 100 parts by weight of the polyurethane resin (solid content) The amount is preferably 0.5 to 20 parts by weight, more preferably about 1 to 10 parts by weight.

[Two-component curable polyurethane resin]
The two-component curable polyurethane resin containing the polyisocyanate component (A) and the active hydrogen-containing component (B) has a crosslinked cyclic hydrocarbon group and an araliphatic hydrocarbon group in the resin.

  The crosslinked cyclic hydrocarbon group and the araliphatic hydrocarbon group may be derived from any component of the component (A) and the component (B), respectively.

  The cross-linked cyclic hydrocarbon group is a cross-linked cyclic hydrocarbon group exemplified in the section of the cross-linked cyclic alicyclic diisocyanate, and is preferably a group represented by the following formula (1).

(Wherein A ¹ and A ² are a direct bond, or a linear or branched alkylene group, j is an integer of 1 or more, and n is the same or different and represents 0 or an integer of 1 or more)
The proportion of the crosslinked cyclic hydrocarbon group may be 10% by weight or more (for example, 10 to 90% by weight) in the polyurethane resin, preferably 20 to 80% by weight, more preferably 25 to 75% by weight (particularly 30 to 70% by weight).

  Examples of the araliphatic hydrocarbon group include a xylylene group (1,3- or 1,4-xylylene group), a tetramethylxylylene group (1,3- or 1,4-tetramethylxylylene group), 1 , 4-diethylbenzene group and the like. Of these, a xylylene group is preferred.

  The ratio (weight ratio) between the bridged cyclic hydrocarbon group and the araliphatic hydrocarbon group is, for example, about bridged cyclic hydrocarbon group / aromatic aliphatic hydrocarbon group = 99/1 to 10/90, preferably Is 97 / 3-20 / 80, more preferably about 95 / 5-30 / 70 (particularly 90 / 10-40 / 60). When the ratio of both is in this range, the polyurethane resin has high gas barrier properties under high humidity, and stability and solubility are improved, and workability as a coating agent is improved. In particular, when importance is attached to gas barrier properties under high humidity, for example, the ratio (weight ratio) of both is about a crosslinked cyclic hydrocarbon group / aromatic aliphatic hydrocarbon group = 99/1 to 50/50. , Preferably 97/3 to 70/30, more preferably about 95/5 to 80/20.

  Further, in the two-component curable polyurethane resin of the present invention, it is preferable that a trifunctional or higher functional component is included among the polyisocyanate component (A) and the active hydrogen-containing component (B). A trifunctional or higher functional component may also be derived from any of the components (A) and (B).

The trifunctional or higher functional component may be, for example, a trifunctional or higher polyisocyanate component [such as an adduct of a diisocyanate and a trifunctional or higher C _3-12 aliphatic polyol], a trifunctional or higher polyol component [polyamine (xylylenediamine, etc. And the like obtained by adding about 3 to 6 moles of alkylene oxide (such as ethylene oxide) to a crosslinked cyclic alicyclic diamine such as aromatic diamine or norbornane diamine). These trifunctional or higher functional components can be used alone or in combination of two or more. Of these tri- or higher functional components, tri- or higher functional polyisocyanate components (such as adducts of norbornene diisocyanate and trimethylolpropane) are preferred.

  The proportion of the trifunctional or higher functional component is 5% by weight or more (5 to 100% by weight), preferably 10 to 99% by weight, more preferably 20%, based on the total amount of the component (A) and the component (B). It is about -95 weight% (especially 30-90 weight%). When the proportion of the trifunctional or higher component is large, the gas barrier property under high humidity is improved.

  In general, the two-component curable polyurethane resin of the present invention preferably has a high total concentration of urethane groups and urea groups from the viewpoint of gas barrier properties. Specifically, the total concentration of urethane groups and urea groups in the polyurethane resin is, for example, 15% by weight or more (for example, 20 to 60% by weight), preferably 20% by weight or more (25 to 55% by weight), and more preferably. Is about 30% by weight or more (for example, 35 to 50% by weight). The urethane group concentration and the urea group (urea group) concentration are the molecular weight of the urethane group (59 g / equivalent) or the molecular weight of the urea group (primary amino group (amino group): 58 g / equivalent, secondary amino group (imino group). ): 57 g / equivalent), based on the charged amount of all reaction components. In the case of using a mixture, the concentration of the urethane group and urea group can be calculated based on the charge base of the reaction components, that is, the use ratio of each component.

[Method for preparing two-component curable polyurethane resin]
The two-component curable polyurethane resin of the present invention can be prepared by mixing the polyisocyanate component (A), the active hydrogen-containing component (B), and an organic solvent or additive as necessary. Examples of the mixing method include conventional methods such as a method using a mixer or a stirrer.

  The two-component curable polyurethane resin thus prepared is coated on a substrate and then cured by heating. The heating temperature is, for example, about 40 to 180 ° C, preferably 60 to 160 ° C, and more preferably about 80 to 150 ° C.

The cured product of the two-component curable polyurethane resin of the present invention has a remarkably high gas barrier property (particularly gas barrier property under high humidity). For example, the oxygen permeability of the polyurethane resin (unit: ml / m ² · atm · day) is, for example, 100 or less (for example, 1 to 80), preferably 60 or less, and more preferably about 40 or less at a thickness of 5 μm under the conditions of a temperature of 20 ° C. and a humidity of 65% RH.

In particular, the polyurethane resin has a high gas barrier property even at extremely high humidity. For example, the oxygen permeability (unit: ml / m ² · atm · day) of the polyurethane resin is 20 ° C. and humidity. Under the condition of 90% RH, at a thickness of 5 μm, it is 120 or less (for example, 1 to 100), preferably 80 or less, more preferably about 60 or less.

  The two-component curable polyurethane resin of the present invention has a long pot life (for example, pot life at room temperature) and adheres to a base material (wood, paper, fabric, metal, ceramics such as glass, plastic, etc.). In addition, since it has a high gas barrier property, it is useful as a resin for various coating agents, and can be used as, for example, paints, printing inks, coating agents, and adhesives. In particular, since it exhibits high gas barrier properties, it is useful for forming a barrier resin molded product. For example, a polyurethane-based resin may be used alone as a film molded product. In a preferred embodiment, the two-component curable polyurethane resin is useful as a gas barrier coating agent for imparting high gas barrier properties to a substrate such as a film or a container. In particular, the two-component curable polyurethane resin of the present invention is suitable for forming a laminated film (or laminate) in which a coating layer composed of a polyurethane resin is laminated on at least one surface of a base film. .

As the base film of the laminated film (laminate), a film composed of a thermoplastic resin is usually used. Examples of the thermoplastic resin include polyolefin resins (for example, poly C _2-10 olefin resins such as polyethylene, polypropylene, propylene-ethylene copolymer), polyester resins (for example, polyethylene terephthalate, polybutylene terephthalate, etc.). ), Polyamide resins (eg, polyamide 6, aliphatic polyamide of polyamide 66, aromatic polyamides such as polymetaxylylene adipamide), vinyl resins (eg, polystyrene, polyvinyl acetate, ethylene-vinyl acetate) Polymers, polyvinyl alcohol, ethylene-vinyl alcohol copolymers, etc.), acrylic resins (for example, homo- or copolymers of (meth) acrylic monomers such as polymethyl methacrylate and polyacrylonitrile), cellophane, etc. Can be exemplified. These resins can be used alone or in combination of two or more.

  As the base film, a single layer film composed of a single resin or a single layer or a laminated film using a plurality of resins can be used. Moreover, as a base material, you may use the laminated base material which laminated | stacked these resin on other base materials (metal, wood, paper, ceramics, etc.).

  Preferred examples of the base film include polyolefin resin films (particularly polypropylene), polyester resin films (particularly polyethylene terephthalate resin), and polyamide resin films (particularly nylon (registered trademark) film).

  Such a base film may be an unstretched film, may be a uniaxial or biaxially oriented film, and is a film that has been surface-treated (corona discharge treatment, etc.), anchor coat or undercoat treatment. Also good. Furthermore, the base film may be a laminated film in which a plurality of resins or metals are laminated. In particular, the polyurethane-based resin is used as an anchor coat agent or undercoat agent for a base film, and a composite film in which an inorganic layer is laminated by vapor deposition or sputtering of a metal oxide such as aluminum or a metal oxide such as alumina or silica, In the composite film in which the inorganic layer of the metal or metal oxide formed on the material film is topcoated or overcoated with the polyurethane resin, the gas barrier property can be further improved. The thickness of the inorganic vapor deposition layer may be, for example, about 100 to 3000 angstrom, preferably about 200 to 2000 angstrom, and more preferably about 300 to 1500 angstrom.

  The thickness of the base film is 1 to 200 μm, preferably 5 to 120 μm, and more preferably about 10 to 100 μm.

  The thickness of the coating layer (coating layer after drying) containing the two-component curable polyurethane resin is, for example, 0.1 to 50 μm, preferably 0.2 to 40 μm, more preferably 0.5 to 30 μm (for example, 1 ˜20 μm), usually about 2-10 μm.

  There are no particular restrictions on the method of laminating the base film, and conventional methods such as gravure coating, reverse coating, roll coating, bar coating, spray coating, air knife coating, and dipping can be used. These can be laminated in an appropriate combination. After applying or laminating a polyurethane resin on a substrate, a laminated film (or laminate) can be formed by removing the solvent in the drying step to form a film.

  In addition, after laminating | stacking a polyurethane resin to a base material plastic film, by extending | stretching at least to one direction, the crystallinity degree by an extending | stretching effect can be improved and gas barrier property can also be improved.

  The two-component curable polyurethane-based resin can be used in various modes. For example, in a composite film, an overcoat agent for constituting a surface layer of the composite film, a base film layer and a resin layer, You may coat as an anchor coating agent interposed between several resin layers. Further, when the polyurethane resin itself has an adhesive force, it may be coated as an adhesive.

  In the present invention, a two-component curable polyurethane resin having a high gas barrier property (especially a gas barrier property under high humidity) and a long pot life and a gas barrier laminate obtained by laminating the same can be obtained. In addition, the polyurethane-based resin has excellent adhesion to a base film on which plastics and metal oxides are laminated, and is excellent in processing suitability such as printing and adhesion. It can be used in various fields.

  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 following examples, “%” represents wt% unless otherwise specified.

(Synthesis example of polyisocyanate component 1)
446.3 g of norbornane diisocyanate (mixture of 2,5-diisocyanatomethylbicyclo [2.2.1] heptane and 2,6-diisocyanatomethylbicyclo [2.2.1] heptane, NBDI) and trimethylolpropane 33.7 g was mixed and reacted at 70 ° C. for 10 hours under a nitrogen atmosphere. From this reaction solution, unreacted norbornane diisocyanate was distilled off using a thin-film distillation apparatus to obtain a norbornane diisocyanate adduct (NBDI-TMP adduct) of trimethylolpropane. This NBDI-TMP adduct was dissolved in ethyl acetate to a solid content of 75% to obtain polyisocyanate component 1. The NCO% of this polyisocyanate component 1 was 10.9%.

(Synthesis example of polyisocyanate component 2)
463.3 g of 1,3-bis (isocyanatomethyl) benzene (xylylene diisocyanate, XDI) and 36.7 g of trimethylolpropane were mixed and reacted at 70 ° C. for 6 hours in a nitrogen atmosphere. From this reaction solution, unreacted xylylene diisocyanate was distilled off using a thin film distillation apparatus to obtain a xylylene diisocyanate adduct (XDI-TMP adduct) of trimethylolpropane. This XDI-TMP adduct was dissolved with ethyl acetate to a solid content of 75% to obtain polyisocyanate component 2. The NCO% of this polyisocyanate component 2 was 11.8%.

(Synthesis example of polyisocyanate component 3)
Isophorone diisocyanate (IPDI) 468.6 g and trimethylolpropane 31.4 g were mixed and reacted at 70 ° C. for 10 hours in a nitrogen atmosphere. From this reaction solution, unreacted isophorone diisocyanate was distilled off using a thin-film distillation apparatus to obtain an isophorone diisocyanate adduct (IPDI-TMP adduct) of trimethylolpropane. This IPDI-TMP adduct was dissolved with ethyl acetate to a solid content of 75% to obtain polyisocyanate component 3. NCO% of this polyisocyanate compound 3 was 10.3%.

(Synthesis example of polyisocyanate component 4)
464.4 g of 1,3-bis (isocyanatomethyl) cyclohexane (hydrogenated xylylene diisocyanate, H6XDI) and 35.6 g of trimethylolpropane were mixed and reacted at 70 ° C. for 10 hours in a nitrogen atmosphere. From this reaction solution, unreacted hydrogenated xylylene diisocyanate was distilled off using a thin film distillation apparatus to obtain a hydrogenated xylylene diisocyanate adduct (H6XDI-TMP adduct) of trimethylolpropane. This H6XDI-TMP adduct was dissolved with ethyl acetate to a solid content of 75% to obtain polyisocyanate component 4. The NCO% of this polyisocyanate component 4 was 11.5%.

(Polyol component 1)
As the polyol component 1, Brownon MXDA-EO-4 (Aoki Yushi Kogyo Co., Ltd., hydroxyl value 701.4 mgKOH / g) was used.

(Synthesis example of polyol component 2)
202.4 g of monoethanolamine and 297.6 g of ethylene carbonate were mixed and subjected to a ring-opening reaction at 70 ° C. for 8 hours to obtain a urethane group-containing polyol component 2 (MEAEC). The hydroxyl value of this urethane group-containing polyol component 2 was 748.1 mgKOH / g.

(Synthesis example of polyol component 3)
258.8 g of norbornane diisocyanate (NBDI), 116.2 g of ethylene glycol, and 125 g of MEK were mixed and reacted at 75 ° C. for 8 hours to obtain a polyol component 3 (EG-NBDI) having a solid content of 75%. The hydroxyl value of this polyol component 3 was 138.5 mgKOH / g.

Example 1
6.41 parts by weight of polyisocyanate component 1, 1.44 parts by weight of polyol component 1, and 17.15 parts by weight of methyl ethyl ketone were sufficiently mixed to prepare a coating solution. This coating solution was applied on a corona discharge-treated surface of a biaxially stretched polyethylene terephthalate film (thickness 12 μm, PET, hereinafter referred to as “# 12PET”) with a Meyer bar so as to have a dry thickness of 5 μm, and then at 130 ° C. for 30 seconds. After drying, the laminated film 1 was obtained by aging at 40 degreeC for 2 days. The pot life of this coating solution was 8 hours (the pot life was defined as the time until the solution was solidified when the coating solution was turbid or no turbidity occurred). The urethane group concentration of the urethane resin layer of the laminated film 1 was 35.9% by weight, and the NBDI content was 62.6% by weight. The ratio of norbornane group to xylylene group was norbornane / xylylene = about 83/17. Next, the oxygen gas barrier property of the laminated film 1 was measured using an oxygen permeability measuring device (MOCON OXTRAN 10 / 50A, manufactured by Modern Control Co., Ltd.) at a temperature of 20 ° C., a relative humidity of 65% and a 90% atmosphere. As a result, they were 23.1 ml / m ² · day and 18.9 ml / m ² · day, respectively. The results are shown in Table 1.

Example 2
3.54 parts by weight of polyisocyanate component 1, 3.3 parts by weight of polyisocyanate component 2, 1.49 parts by weight of polyol component 2 and 18.16 parts by weight of methyl ethyl ketone are mixed well to prepare a coating solution. did. This coating solution was applied onto a corona discharge-treated surface of a biaxially stretched polyethylene terephthalate film (# 12PET) with a Meyer bar so as to have a dry thickness of 5 μm, dried at 130 ° C. for 30 seconds, and then heated at 40 ° C. for 2 seconds. A laminated film 2 was obtained by aging for a day. The pot life of this coating solution was 6 hours. The urethane group concentration of the urethane resin layer of the laminated film 2 was 37.4% by weight, and the NBDI content was 32.7% by weight. The ratio of norbornane group to xylylene group was norbornane / xylylene = about 54/46. Next, the oxygen gas barrier property of this laminated film 2 was measured using an oxygen permeability measuring device (MOCON OXTRAN 10 / 50A, manufactured by Modern Control Co., Ltd.) at a temperature of 20 ° C., a relative humidity of 65% and a 90% atmosphere. As a result, they were 16.7 ml / m ² · day and 27.7 ml / m ² · day, respectively. The results are shown in Table 1.

Example 3
3.75 parts by weight of polyisocyanate component 2, 4.59 parts by weight of polyol component 3 and 16.66 parts by weight of methyl ethyl ketone were sufficiently mixed to prepare a coating solution. This coating solution was applied on a corona discharge-treated surface of a biaxially stretched polyethylene terephthalate film (# 12PET) with a Meyer bar so as to have a dry thickness of 5 μm, dried at 130 ° C. for 30 seconds, and then at 40 ° C. for 2 days. A laminated film 3 was obtained by aging. The pot life of this coating solution was 6 hours. The urethane group concentration of the urethane resin layer of the laminated film 3 was 44.2% by weight, and the NBDI content was 38% by weight. The ratio of norbornane group to xylylene group was norbornane / xylylene = about 53/47. Next, the oxygen gas barrier property of the laminated film 3 was measured using an oxygen permeability measuring device (MOCON OXTRAN 10 / 50A, manufactured by Modern Control Co., Ltd.) at a temperature of 20 ° C., a relative humidity of 65% and a 90% atmosphere. As a result, they were 23.1 ml / m ² · day and 27.7 ml / m ² · day, respectively. The results are shown in Table 1.

Comparative Example 1
6.5 parts by weight of polyisocyanate component 3, 1.37 parts by weight of polyol component 1 (MXDA-EO-4), and 17.13 parts by weight of methyl ethyl ketone were sufficiently mixed to prepare a coating solution. This coating solution was applied on a corona discharge-treated surface of a biaxially stretched polyethylene terephthalate film (# 12PET) with a Meyer bar so as to have a dry thickness of 5 μm, dried at 130 ° C. for 30 seconds, and then at 40 ° C. for 2 days. A laminated film 4 was obtained by aging. The pot life of this coating solution was 12 hours. The urethane group concentration of the urethane resin layer of the laminated film 4 was 34.2% by weight, and the NBDI content was 0% by weight. Next, the oxygen gas barrier property of this laminated film 4 was measured using an oxygen permeability measuring device (MOCON OXTRAN 10 / 50A manufactured by Modern Control Co., Ltd.) at a temperature of 20 ° C., a relative humidity of 65% and a 90% atmosphere. The results were 83.3 ml / m ² · day and 79.7 ml / m ² · day, respectively. The results are shown in Table 1.

Comparative Example 2
6.34 parts by weight of polyisocyanate component 4, 1.49 parts by weight of polyol component 1 (MXDA-EO-4), and 17.17 parts by weight of methyl ethyl ketone were sufficiently mixed to prepare a coating solution. This coating solution was applied on a corona discharge-treated surface of a biaxially stretched polyethylene terephthalate film (# 12PET) with a Meyer bar so as to have a dry thickness of 5 μm, dried at 130 ° C. for 30 seconds, and then at 40 ° C. for 2 days. A laminated film 5 was obtained by aging. The pot life of this coating solution was 4 hours. The urethane group concentration of the urethane resin layer of the laminated film 5 was 37.2% by weight, and the NBDI content was 0% by weight. Subsequently, the oxygen gas barrier property of the obtained laminated film 5 was measured using an oxygen permeability measuring device (MOCON OXTRAN 10 / 50A manufactured by Modern Control Co., Ltd.) at a temperature of 20 ° C., a relative humidity of 65% and an atmosphere of 90%. Were 44.4 ml / m ² · day and 47.4 ml / m ² · day, respectively. The results are shown in Table 1.

Comparative Example 3
6.3 parts by weight of polyisocyanate component 2, 1.52 parts by weight of polyol component 1 (MXDA-EO-4), and 17.18 parts by weight of methyl ethyl ketone were sufficiently mixed to prepare a coating solution. This coating solution was applied on a corona discharge-treated surface of a biaxially stretched polyethylene terephthalate film (# 12PET) with a Meyer bar so as to have a dry thickness of 5 μm, dried at 130 ° C. for 30 seconds, and then at 40 ° C. for 2 days. A laminated film 6 was obtained by aging. The pot life of this coating solution was 2 hours. The urethane group concentration of the urethane resin layer of the laminated film 6 was 37.9% by weight, and the NBDI content was 0% by weight. Subsequently, the oxygen gas barrier property of the obtained laminated film 6 was measured using an oxygen permeability measuring device (manufactured by Modern Control, MOCON OXTRAN 10 / 50A) at a temperature of 20 ° C., a relative humidity of 65% and an atmosphere of 90%. Were 13.0 ml / m ² · day and 42.4 ml / m ² · day, respectively.

Comparative Example 4
The oxygen permeability of the biaxially stretched polyethylene terephthalate film (# 12PET) at 20 ° C., 65% relative humidity, and 90% atmosphere was 100 ml / m ² · day and 90 ml / m ² · day, respectively.

  As is apparent from Table 1, the gas barrier properties of the examples are higher than those of the comparative examples even in a high humidity environment.

Claims (9)

  A two-component curable polyurethane-based resin comprising a polyisocyanate component (A) and at least one active hydrogen-containing component (B) selected from a polyol component and a polyamine component, wherein a crosslinked cyclic hydrocarbon group is contained in the resin -Component curable gas-barrier polyurethane-based resin having an araliphatic hydrocarbon group.   The polyurethane-based resin according to claim 1, wherein the ratio of the crosslinked cyclic hydrocarbon group is 10% by weight or more in the resin.   The ratio (weight ratio) between the bridged cyclic hydrocarbon group and the araliphatic hydrocarbon group is bridged cyclic hydrocarbon group / aromatic aliphatic hydrocarbon group = 99/1 to 10/90. Polyurethane resin. The polyurethane-based resin according to claim 1, wherein the crosslinked cyclic hydrocarbon group is a group represented by the following formula (1), and the araliphatic hydrocarbon group is a xylylene group.

(Wherein A ¹ and A ² are a direct bond, or a linear or branched alkylene group, j is an integer of 1 or more, and n is the same or different and represents 0 or an integer of 1 or more)   2. The proportion of the trifunctional or higher functional component in the polyisocyanate component (A) and the active hydrogen-containing component (B) is 5% by weight or more based on the total amount of the (A) component and the (B) component. The polyurethane resin described. The polyurethane-based resin according to claim 5, wherein the trifunctional or higher functional component is a polyisocyanate component composed of an adduct of diisocyanate and a trifunctional or higher functional C _3-12 aliphatic polyol.   The polyurethane resin according to claim 1, wherein the total concentration of urethane groups and urea groups is 15% by weight or more.   A laminated film in which a coating layer composed of the polyurethane-based resin according to claim 1 is laminated on at least one surface of a base film.   A gas barrier laminating adhesive comprising the polyurethane resin according to claim 1.