JP6199706B2 - Polyurethane laminate - Google Patents

Description

  The present invention relates to a polyurethane laminate, and more particularly to a polyurethane laminate having excellent gas barrier properties.

  Conventionally, a film made of polyvinylidene chloride or a vinylidene chloride copolymer (hereinafter abbreviated as PVDC) is known as a film excellent in oxygen gas barrier properties.

  However, PVDC produces harmful gases upon combustion.

  Therefore, films made of polyvinyl alcohol or an ethylene / vinyl alcohol copolymer are known. However, these films have a disadvantage that they are inferior in gas barrier properties under high humidity.

  Further, vapor deposition films in which an inorganic oxide is deposited on the film are also known, but they have a problem that they are low in flexibility and have a gas barrier property deterioration due to cracks and the like during secondary processing.

  Then, the gas barrier film which made the resin composition containing a polyurethane resin and a layered inorganic compound into a film as a film with favorable gas barrier property also under high humidity is proposed (refer patent document 1).

JP 2001-98047 A

  However, the film described in Patent Document 1 requires a relatively large amount of the layered inorganic compound. Therefore, transparency and adhesion may be insufficient.

  An object of the present invention is to provide a polyurethane laminate capable of improving not only gas barrier properties but also adhesion to a substrate and transparency.

  In order to achieve the above object, the polyurethane laminate of the present invention is laminated on a base material, a first layer made of the first polyurethane resin, laminated on the base material, and laminated on the first layer. A second layer made of a second polyurethane resin in which an inorganic compound is dispersed, each of the first polyurethane resin and the second polyurethane resin comprising xylylene diisocyanate and / or hydrogenated xylylene diisocyanate, and carbon It is characterized by being obtained by a reaction between an isocyanate group-terminated prepolymer obtained by reacting at least a diol of 2 to 6 with a chain extender containing a polyamine.

  In the polyurethane laminate of the present invention, each of the first polyurethane resin and the second polyurethane resin includes xylylene diisocyanate and / or hydrogenated xylylene diisocyanate, a diol having 2 to 6 carbon atoms, and a hydrophilic group. An aqueous polyurethane resin obtained by the reaction of an isocyanate group-terminated prepolymer obtained by reacting at least an active hydrogen group-containing compound containing a polyamine and a chain extender is prepared as a polyurethane dispersion in which water is dispersed. The first layer is formed by applying and drying the polyurethane dispersion, and the second layer is applying and drying a mixture of the polyurethane dispersion and the layered inorganic compound. By shape It is preferable that the.

  In the polyurethane laminate of the present invention, the mass of the second layer is 40 parts by mass or more and 90 parts by mass or less with respect to 100 parts by mass of the total mass of the first layer and the mass of the second layer. It is preferable that

  In the polyurethane laminate of the present invention, the mass of the layered inorganic compound is 1 part by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the total mass of the first layer and the mass of the second layer. It is preferable that

  In the polyurethane laminate of the present invention, it is preferable that the active hydrogen group-containing compound containing a hydrophilic group is polyhydroxyalkanoic acid.

  In the polyurethane laminate of the present invention, it is preferable that the layered inorganic compound is swellable.

  The polyurethane laminate of the present invention can improve not only gas barrier properties but also adhesion to a substrate and transparency.

FIG. 1 is a schematic configuration diagram showing an embodiment of the polyurethane laminate of the present invention.

  In FIG. 1, the polyurethane laminate 1 includes a base material 2, a first layer 3 laminated on the base material 2, and a second layer 4 laminated on the first layer 3.

  The substrate 2 is not particularly limited, and is formed from, for example, plastic (for example, thermoplastic resin, thermosetting resin, etc.), paper, cloth, wood, metal, ceramics, etc., preferably plastic, more preferably It is formed from a thermoplastic resin.

  Examples of the thermoplastic resin include polyolefin resins (eg, polyethylene, polypropylene, propylene-ethylene copolymer), polyester resins (eg, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc.), polyamide resins ( For example, nylon 6 (registered trademark), nylon 66 (registered trademark), polymetaxylylene adipamide, etc.), vinyl resin (for example, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polystyrene, polyvinyl acetate, etc.), Acrylic resins (for example, polymethyl methacrylate, polyacrylonitrile, etc.), polycarbonate resins (for example, bisphenol A type polycarbonate, etc.), cellulose resins (for example, cellophane, acetic acid, etc.) Cellulose and the like) and the like. Preferably, polyolefin resin, polyester resin, and polyamide resin are used. More preferably, polypropylene, polyethylene terephthalate, and nylon 6 (registered trademark) are used.

  The base material 2 consists of a single layer or the same kind or two or more kinds of laminates.

  The shape of the substrate 2 is not particularly limited, and examples thereof include a film shape, a sheet shape, a bottle shape, and a cup shape. Preferably, a film form is mentioned.

  The substrate 2 may be an unstretched substrate, a uniaxial or biaxially stretched substrate, and the substrate 2 may be subjected to a surface treatment (corona discharge treatment, etc.), an anchor coat or an undercoat treatment. Moreover, a metal oxide such as a metal such as aluminum, silica, alumina, or a mixture of silica and alumina may be further vapor-deposited.

  The thickness of the base material 2 is, for example, 3 μm or more, preferably 5 μm or more, and for example, 500 μm or less, preferably 200 μm or less.

  The first layer 3 is made of xylylene diisocyanate and / or hydrogenated xylylene diisocyanate and a first polyurethane resin obtained by reacting an isocyanate group-terminated prepolymer obtained by reacting at least a polyol with a chain extender, Is formed. Such a first layer 3 is preferably formed by applying and drying a polyurethane dispersion containing the first polyurethane resin on the substrate 2 from the viewpoint of manufacturing efficiency.

  In order to prepare the first polyurethane resin as a polyurethane dispersion, the first polyurethane resin is synthesized as an aqueous polyurethane resin, and the obtained aqueous polyurethane resin is dispersed in water.

  More specifically, in this method, for example, first, xylylene diisocyanate and / or hydrogenated xylylene diisocyanate, a polyol (excluding an active hydrogen group-containing compound containing a hydrophilic group), and a hydrophilic group are contained. To react with an active hydrogen group-containing compound to synthesize an isocyanate group-terminated prepolymer.

  As xylylene diisocyanate (XDI), 1,2-xylylene diisocyanate (o-XDI), 1,3-xylylene diisocyanate (m-XDI), 1,4-xylylene diisocyanate (p-XDI) are structural isomers. Named as body.

  These xylylene diisocyanates can be used alone or in combination of two or more. As xylylene diisocyanate, 1,3-xylylene diisocyanate and 1,4-xylylene diisocyanate are preferable, and 1,3-xylylene diisocyanate is more preferable.

Further, as hydrogenated xylylene diisocyanate (also known as bis (isocyanatomethyl) cyclohexane) (H ₆ XDI), 1,2-hydrogenated xylylene diisocyanate (o-H ₆ XDI), 1,3-hydrogenated xylylene diene Isocyanate (m-H ₆ XDI), 1,4-hydrogenated xylylene diisocyanate (p-H ₆ XDI) are listed as structural isomers.

  These hydrogenated xylylene diisocyanates can be used alone or in combination of two or more. The hydrogenated xylylene diisocyanate is preferably 1,3-hydrogenated xylylene diisocyanate, 1,4-hydrogenated xylylene diisocyanate, and more preferably 1,3-hydrogenated xylylene diisocyanate.

  Moreover, derivatives thereof are included as xylylene diisocyanate and / or hydrogenated xylylene diisocyanate.

  Examples of the derivatives of xylylene diisocyanate and / or hydrogenated xylylene diisocyanate include, for example, multimers of xylylene diisocyanate and / or hydrogenated xylylene diisocyanate (for example, dimers, trimers (for example, isocyanurate modified products, Iminooxadiazinedione-modified products), pentamers, heptamers, etc.), allophanate-modified products (for example, xylylene diisocyanate and / or hydrogenated xylylene diisocyanate and a low molecular weight polyol described later) Modified products, etc.), polyol modified products (for example, polyol modified products (alcohol adducts, etc.) produced by the reaction of xylylene diisocyanate and / or hydrogenated xylylene diisocyanate with the low molecular weight polyol described later), biuret, etc. Properties (for example, biuret modified products produced by reaction of xylylene diisocyanate and / or hydrogenated xylylene diisocyanate with water or amines), urea modified products (for example, xylylene diisocyanate and / or hydrogenated xylylene diene) Modified ureas produced by reaction of isocyanate and diamine), modified oxadiazine trione (eg, oxadiazine trione produced by reaction of xylylene diisocyanate and / or hydrogenated xylylene diisocyanate and carbon dioxide) Carbodiimide modified products (carbodiimide modified products produced by decarboxylation condensation reaction of xylylene diisocyanate and / or hydrogenated xylylene diisocyanate), uretdione modified products, uretonimine modified products, etc. .

  These derivatives can be used alone or in combination of two or more.

  The xylylene diisocyanate and / or hydrogenated xylylene diisocyanate is preferably a combination of xylylene diisocyanate and hydrogenated xylylene diisocyanate.

  By using xylylene diisocyanate and hydrogenated xylylene diisocyanate in combination, adhesion to the substrate and transparency can be improved.

  When the xylylene diisocyanate and the hydrogenated xylylene diisocyanate are used in combination, the combined ratio thereof is, for example, 60 parts by mass or more of the xylylene diisocyanate with respect to 100 parts by mass of the total amount of the xylylene diisocyanate and the hydrogenated xylylene diisocyanate. Preferably, it is 70 parts by mass or more, more preferably 80 parts by mass or more, for example, 95 parts by mass or less, preferably 93 parts by mass or less, more preferably 90 parts by mass or less. The hydrogenated xylylene diisocyanate is, for example, 5 parts by mass or more, preferably 7 parts by mass or more, more preferably 10 parts by mass or more, for example, 40 parts by mass or less, preferably 30 parts by mass or less. More preferably, it is 20 parts by mass or less.

  Moreover, other polyisocyanate can also be used together as needed.

  Other polyisocyanates include, for example, polyisocyanates such as aromatic polyisocyanates, araliphatic polyisocyanates (excluding xylylene diisocyanate), aliphatic polyisocyanates, and alicyclic polyisocyanates (excluding hydrogenated xylylene diisocyanate). Etc.

  Examples of the aromatic polyisocyanate 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 aromatic diisocyanates such as 4,4′-toluidine diisocyanate (TODI) and 4,4′-diphenyl ether diisocyanate.

  Examples of the araliphatic polyisocyanate (excluding xylylene diisocyanate) include, for example, tetramethylxylylene diisocyanate (1,3- or 1,4-tetramethylxylylene diisocyanate or a mixture thereof) (TMXDI), ω, ω′- And aromatic aliphatic diisocyanates such as diisocyanate-1,4-diethylbenzene.

  Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, 1,2-propylene diisocyanate, butylene diisocyanate (tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate), 1 , 5-pentamethylene diisocyanate (PDI), 1,6-hexamethylene diisocyanate (also known as hexamethylene diisocyanate) (HDI), 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6- Aliphatic diisocyanates such as diisocyanate methyl capate are listed.

Examples of the alicyclic polyisocyanate (excluding hydrogenated xylylene diisocyanate) include 1,3-cyclopentane diisocyanate, 1,3-cyclopentene diisocyanate, cyclohexane diisocyanate (1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate). ), 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (also known as isophorone diisocyanate) (IPDI), methylenebis (cyclohexyl isocyanate) (also known as bis (isocyanatocyclohexyl) methane) (4,4'-, 2,4′- or 2,2′-methylenebis (cyclohexyl isocyanate) These Trans, Trans-form, Trans, Cis-form, Cis, Cis-form, or its _Compound) (H 12 MDI), methylcyclohexane diisocyanate (methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate), norbornane diisocyanate (various isomers or mixtures thereof) (NBDI), alicyclic such as Group diisocyanate and the like. Preferably, 4,4′-bis (isocyanatocyclohexyl) methane is used.

  Other polyisocyanates include derivatives of the same kind as described above.

  These other polyisocyanates can be used alone or in combination of two or more. Preferred are araliphatic polyisocyanates and alicyclic polyisocyanates, more preferred are alicyclic polyisocyanates, and still more preferred are bis (isocyanatocyclohexyl) methane.

  When other polyisocyanates (excluding xylylene diisocyanate and hydrogenated xylylene diisocyanate) are blended, the blending ratio is xylylene diisocyanate and / or hydrogenated xylylene diisocyanate (if used in combination, those For example, 30 parts by mass or less, preferably 20 parts by mass or less with respect to 100 parts by mass.

  Preferably, xylylene diisocyanate and bis (isocyanatocyclohexyl) methane are used in combination.

  By using xylylene diisocyanate and bis (isocyanatocyclohexyl) methane in combination, it is possible to improve the adhesion to the substrate and the transparency.

  When xylylene diisocyanate and bis (isocyanatocyclohexyl) methane are used in combination, xylylene diisocyanate is, for example, 60 parts by mass or more, preferably 100 parts by mass relative to the total amount of xylylene diisocyanate and bis (isocyanatocyclohexyl) methane. 70 parts by mass or more, more preferably 80 parts by mass or more, for example, 95 parts by mass or less, preferably 93 parts by mass or less, more preferably 90 parts by mass or less. Bis (isocyanatocyclohexyl) methane is, for example, 5 parts by mass or more, preferably 7 parts by mass or more, more preferably 10 parts by mass or more, for example, 40 parts by mass or less, preferably 30 parts by mass. Hereinafter, it is more preferably 20 parts by mass or less.

  The polyol contains a diol having 2 to 6 carbon atoms as an essential component.

  The diol having 2 to 6 carbon atoms is an organic compound having 2 to 6 carbon atoms having two hydroxyl groups. Specifically, for example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4- Butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 1,3- Or an alkanediol having 2 to 6 carbon atoms such as 1,4-cyclohexanediol, for example, an ether diol having 2 to 6 carbon atoms such as diethylene glycol, triethylene glycol, and dipropylene glycol, such as 1,4-dihydroxy-2- C2-C6 alkenediol, such as butene, is mentioned.

  These diols having 2 to 6 carbon atoms can be used alone or in combination of two or more.

  The diol having 2 to 6 carbon atoms is preferably an alkane diol having 2 to 6 carbon atoms, more preferably ethylene glycol.

  In addition, the polyol can further contain other polyol compounds (excluding the above-described diol having 2 to 6 carbon atoms) as an optional component. Examples of such a polyol compound include low molecular weight polyols excluding the above-described diol having 2 to 6 carbon atoms.

  The low molecular weight polyol (excluding the above-mentioned diol having 2 to 6 carbon atoms) is a polyol compound having a number average molecular weight of 400 or less. When the number average molecular weight exceeds 400, the gas barrier property of the polyurethane laminate 1 (described later) may be deteriorated.

  Examples of the low molecular weight polyol (excluding the above-described diol having 2 to 6 carbon atoms) include, for example, alkane-1,2-diol, 2,6-dimethyl-1-octene-3,8-diol having 7 to 20 carbon atoms, 1,3- or 1,4-cyclohexanedimethanol and mixtures thereof, dihydric alcohols (diols) having 7 or more carbon atoms such as hydrogenated bisphenol A and bisphenol A, for example, trihydric alcohols such as glycerin and trimethylolpropane (Triol), for example, tetramethylolmethane (pentaerythritol), tetravalent alcohols such as diglycerin, for example, pentavalent alcohols such as xylitol, for example, sorbitol, mannitol, allitol, iditol, dulcitol, altitol, inositol, dipentol Erythritol, etc. Hexahydric alcohols such as 7-valent alcohols such as perseitol, for example, 8 monohydric alcohol and sucrose.

  Examples of the low molecular weight polyol (excluding the above-mentioned diol having 2 to 6 carbon atoms) include polyalkylene oxide having a number average molecular weight of 400 or less. Such a polyalkylene oxide can be obtained by, for example, adding a low molecular weight polyol as described above or an alkylene oxide such as ethylene oxide and / or propylene oxide by using a known polyamine as an initiator, thereby adding polyethylene glycol, polypropylene glycol, It can be obtained as polyethylene polypropylene glycol (random or block copolymer). Examples thereof also include polytetramethylene ether glycol having a number average molecular weight of 400 or less obtained by ring-opening polymerization of tetrahydrofuran.

  These low molecular weight polyols (excluding the diol having 2 to 6 carbon atoms described above) can be used alone or in combination of two or more.

  As the low molecular weight polyol (excluding the above-mentioned diol having 2 to 6 carbon atoms), a trihydric alcohol is preferably used, and glycerin and trimethylolpropane are more preferable.

  Moreover, Preferably, C2-C6 diol and trihydric alcohol are used together. By using a diol having 2 to 6 carbon atoms and a trihydric alcohol in combination, the first polyurethane resin can have a high molecular weight, and an improvement in coating strength can be expected.

  When the diol having 2 to 6 carbon atoms and the trihydric alcohol are used in combination, the combination ratio is such that the trivalent alcohol is, for example, 100 parts by mass of the total amount of the diol having 2 to 6 carbon atoms and the trihydric alcohol. 0.1 parts by mass or more, preferably 1 part by mass or more, for example, 20 parts by mass or less, preferably 10 parts by mass or less.

  When a low molecular weight polyol (excluding the above-mentioned diol having 2 to 6 carbon atoms) is blended, the blending ratio is, for example, 90 parts by mass or less, preferably 70 parts per 100 parts by mass of the total polyol. It is below mass parts.

  An active hydrogen group-containing compound containing a hydrophilic group is a compound containing a hydrophilic group such as a nonionic group or an ionic group and containing an active hydrogen group such as an amino group or a hydroxyl group, specifically Examples thereof include an active hydrogen group-containing compound containing a nonionic group and an active hydrogen group-containing compound containing an ionic group.

  Examples of the active hydrogen group-containing compound containing a nonionic group include polyoxyethylene glycol, one-end blocked polyoxyethylene glycol, and a polyol containing a polyoxyethylene side chain.

  The polyol containing a polyoxyethylene side chain is a compound having a polyoxyethylene group in the side chain and having two or more hydroxyl groups, and can be synthesized as follows.

  That is, first, the above-mentioned diisocyanate and one-end-capped polyoxyethylene glycol (for example, alkoxy polyoxyethylene monool capped at one end with an alkyl group having 1 to 4 carbon atoms having a number average molecular weight of 200 to 6000, preferably 300 to 3000) is subjected to a urethanation reaction in an excess ratio of the isocyanate group of the diisocyanate with respect to the hydroxyl group of the one-end blocked polyoxyethylene glycol, and if necessary, the unreacted diisocyanate is removed to remove polyoxy An ethylene chain-containing monoisocyanate is obtained.

  Next, polyoxyethylene chain-containing monoisocyanate and dialkanolamine (for example, diethanolamine) are approximately equal in amount of the isocyanate group of polyoxyethylene group-containing monoisocyanate with respect to the secondary amino group of dialkanolamine. The urea reaction is carried out at a rate of

  In the active hydrogen group-containing compound containing a nonionic group, the number average molecular weight of the nonionic group, specifically, the polyoxyethylene group is, for example, 600 to 6000.

The diisocyanate for obtaining a polyol containing a polyoxyethylene side chain is preferably an aliphatic diisocyanate such as hexamethylene diisocyanate (HDI), 1,4- or 1,3-bis (isocyanatomethyl) cyclohexane (H ₆ ). XDI), 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (also known as isophorone diisocyanate) (IPDI), 4,4′-methylenebis (cyclohexyl isocyanate) (H ₁₂ MDI), 2,6-bis ( And alicyclic diisocyanates such as isocyanatomethyl) norbonane (NBDI).

  An active hydrogen group-containing compound containing an ionic group includes, for example, an anionic group such as a carboxylic acid, a cationic group such as a quaternary amine, and an active hydrogen group such as two or more hydroxyl groups or amino groups. A compound having both an anionic group and two or more hydroxyl groups, more preferably a compound having both a carboxylic acid and two hydroxyl groups (an active hydrogen group-containing compound containing a carboxy group) (For example, a carboxy group-containing polyol)).

  Examples of the carboxyl group-containing polyol include 2,2-dimethylolacetic acid, 2,2-dimethylollactic acid, 2,2-dimethylolpropionic acid (also known as dimethylolpropionic acid), 2,2-dimethylolbutanoic acid, 2 , 2-dimethylolbutyric acid, polyhydroxyalkanoic acid such as 2,2-dimethylolvaleric acid, and the like, preferably 2,2-dimethylolpropionic acid.

  These active hydrogen group-containing compounds containing a hydrophilic group can be used alone or in combination, preferably an active hydrogen group-containing compound containing an ionic group, more preferably a carboxy group-containing polyol, More preferably, polyhydroxyalkanoic acid is mentioned.

  By using polyhydroxyalkanoic acid, it is possible to further improve gas barrier properties, adhesion to a substrate, and transparency.

  In order to synthesize an isocyanate group-terminated prepolymer, the above components are mixed in an equivalent ratio (isocyanate group / active hydrogen group) of isocyanate group to active hydrogen group (hydroxyl group and amino group), preferably a ratio exceeding 1. , 1.1-10. And said each component is made to react by well-known polymerization methods, such as bulk polymerization and solution polymerization, Preferably, solution polymerization in which the adjustment of reactivity and a viscosity is easier.

  In bulk polymerization, for example, the above components are blended in a nitrogen atmosphere and reacted at a reaction temperature of 75 to 85 ° C. for about 1 to 20 hours.

  In solution polymerization, for example, the above components are blended in an organic solvent under a nitrogen atmosphere and reacted at a reaction temperature of 20 to 80 ° C. for about 1 to 20 hours.

  Examples of the organic solvent include acetone, methyl ethyl ketone, ethyl acetate, tetrahydrofuran, acetonitrile, and the like, which are inert to isocyanate groups and rich in hydrophilicity.

  This polymerization reaction is allowed to react until the isocyanate group content in the reaction solution is 15% by mass or less, preferably 10% by mass or less.

  Further, in the above polymerization, for example, a reaction catalyst such as amine, tin, or lead may be added as necessary, and an unreacted polyisocyanate (xylylene diene) is obtained from the resulting isocyanate group-terminated prepolymer. (Including isocyanate and / or hydrogenated xylylene diisocyanate) can be removed by a known method such as distillation or extraction.

  For example, when an anionic group is contained, it is preferably neutralized by adding a neutralizing agent to form a salt of the anionic group.

  Examples of the neutralizing agent include conventional bases such as organic bases (eg, tertiary amines (trialkylamines having 1 to 4 carbon atoms such as trimethylamine and triethylamine, dimethylethanolamine, methyldiethanolamine, triethanolamine, Alkanolamines such as isopropanolamine, heterocyclic amines such as morpholine), inorganic bases (ammonia, alkali metal hydroxides (lithium hydroxide, sodium hydroxide, potassium hydroxide, etc.), alkaline earth metal hydroxides) (Magnesium hydroxide, calcium hydroxide, etc.) and alkali metal carbonates (sodium carbonate, potassium carbonate, etc.)). These bases can be used alone or in combination of two or more.

  The neutralizing agent is added at a rate of 0.4 equivalents or more, preferably 0.6 equivalents or more per equivalent of anionic group, and for example, 1.2 equivalents or less, preferably 1 equivalent or less. Add in.

  The isocyanate group-terminated prepolymer thus obtained is a polyurethane prepolymer having two or more free isocyanate groups at its molecular ends, and the isocyanate group content (in terms of solid content excluding the solvent) Isocyanate group content) is, for example, 0.3% by mass or more, preferably 0.5% by mass or more, more preferably 1.0% by mass or more, and for example, 15% by mass or less, preferably It is 12 mass% or less, More preferably, it is 10 mass% or less.

  The average number of functional groups of the isocyanate group is, for example, 1.5 or more, preferably 1.9 or more, more preferably 2.0 or more, and for example, 3.0 or less, preferably 2.5. It is as follows.

  If the average number of functional groups of the isocyanate group is within the above range, the above stable polyurethane dispersion can be obtained, and substrate adhesion, gas barrier properties and the like can be ensured.

  The number average molecular weight (number average molecular weight by GPC measurement using standard polystyrene as a calibration curve) is, for example, 500 or more, preferably 800 or more, and for example, 10,000 or less, preferably 5000 or less. .

  The hydrophilic group concentration of the isocyanate group-terminated prepolymer is, for example, 0.1 mmol / g or more, preferably 0.2 mmol / g or more, for example, 1.2 mmol / g or less, preferably 1 0.0 mmol / g or less, more preferably 0.8 mmol / g or less.

  When the hydrophilic group concentration of the isocyanate group-terminated prepolymer is within the above range, the above-described stable polyurethane dispersion can be obtained.

  Next, in this method, the isocyanate group-terminated prepolymer obtained above and the chain extender are reacted in, for example, water to obtain a polyurethane dispersion of the first polyurethane resin.

  The chain extender contains polyamine as an essential component.

  Examples of polyamines include aromatic polyamines, araliphatic polyamines, alicyclic polyamines, aliphatic polyamines, amino alcohols, primary amino groups, or alkoxysilyls having primary and secondary amino groups. Examples thereof include compounds and polyoxyethylene group-containing polyamines.

  Examples of the aromatic polyamine include 4,4'-diphenylmethanediamine and tolylenediamine.

  Examples of the araliphatic polyamine include 1,3- or 1,4-xylylenediamine or a mixture thereof.

  Examples of the alicyclic polyamine include 3-aminomethyl-3,5,5-trimethylcyclohexylamine (also known as isophoronediamine), 4,4′-dicyclohexylmethanediamine, 2,5 (2,6) -bis ( Aminomethyl) bicyclo [2.2.1] heptane, 1,4-cyclohexanediamine, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, bis- (4-aminocyclohexyl) methane, diaminocyclohexane 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] undecane, 1,3- and 1,4-bis (aminomethyl) cyclohexane and mixtures thereof Etc.

  Examples of the aliphatic polyamine include ethylenediamine, propylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexamethylenediamine, and hydrazine (including hydrate). , Diethylenetriamine, triethylenetetramine, tetraethylenepentamine, 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopentane and the like.

  Examples of amino alcohols include 2-((2-aminoethyl) amino) ethanol (also known as N- (2-aminoethyl) ethanolamine) and 2-((2-aminoethyl) amino) -1-methylpropanol. (Alternative name: N- (2-aminoethyl) isopropanolamine).

  Examples of the alkoxysilyl compound having a primary amino group or a primary amino group and a secondary amino group include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and N-phenyl-γ. An alkoxysilyl group-containing monoamine such as aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane (also known as N-2- (aminoethyl) -3-aminopropyltrimethoxysilane), N -Β (aminoethyl) γ-aminopropyltriethoxysilane (also known as N-2- (aminoethyl) -3-aminopropyltriethoxysilane), N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane (also known as: : N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane , N-beta (aminoethyl) .gamma.-aminopropyl methyl diethoxy silane (also known as: N-2-(aminoethyl) -3-aminopropyl methyl diethoxy silane) and the like.

  Examples of the polyoxyethylene group-containing polyamine include polyoxyalkylene ether diamines such as polyoxyethylene ether diamine. More specifically, for example, PEG # 1000 diamine manufactured by Nippon Oil & Fats, Jeffamine ED-2003, EDR-148, XTJ-512 manufactured by Huntsman, and the like can be mentioned.

  These polyamines can be used alone or in combination of two or more.

  The polyamine is preferably a combination of an alkoxysilyl compound having a primary amino group and a secondary amino group and an amino alcohol, or a single use of an amino alcohol, and more preferably a single use of an amino alcohol. Can be mentioned.

  In order to react the isocyanate group-terminated prepolymer with the chain extender in water, for example, first, the isocyanate group-terminated prepolymer is dispersed in water by adding the isocyanate group-terminated prepolymer to water, and then the chain is elongated. An agent is added, and the isocyanate group-terminated prepolymer is chain extended with a chain extender.

  In order to disperse the isocyanate group-terminated prepolymer in water, the isocyanate group-terminated prepolymer is added with stirring water at a ratio of 100 to 1000 parts by mass of water with respect to 100 parts by mass of the isocyanate group-terminated prepolymer.

  Thereafter, the chain extender is stirred in water in which the isocyanate group-terminated prepolymer is dispersed in water, and the equivalent ratio of the active hydrogen groups (amino group and hydroxyl group) of the chain extender to the isocyanate group of the isocyanate group-terminated prepolymer (active) (Hydrogen group / isocyanate group) is dropped so as to have a ratio of 0.6 to 1.2, for example.

  The chain extender is reacted by dropping, and after completion of the dropping, for example, the reaction is completed at room temperature with further stirring. The reaction time until the completion of the reaction is, for example, 0.1 hour or more, and for example, 10 hours or less.

  Contrary to the above, water is added to the isocyanate group-terminated prepolymer to disperse the isocyanate group-terminated prepolymer in water, and then a chain extender is added thereto to chain-extend the isocyanate group-terminated prepolymer. The chain can be extended by an agent.

  Moreover, in this method, an organic solvent and water can be removed as needed, and also solid content concentration can be adjusted by adding water.

  The solid content concentration of the polyurethane dispersion of the obtained first polyurethane resin is, for example, 10% by mass or more, preferably 15% by mass or more, more preferably 20% by mass or more, and for example, 60% by mass or less. , Preferably, it is 50 mass% or less, More preferably, it is 45 mass% or less.

  The pH of the polyurethane dispersion is, for example, 5 or more, preferably 6 or more, and for example, 11 or less, preferably 10 or less.

  The viscosity of the polyurethane dispersion at 25 ° C. is, for example, 3 mPa · s or more, preferably 5 mPa · s or more, and for example, 2000 mPa · s or less, preferably 1000 mPa · s or less.

  The average particle diameter of the polyurethane dispersion is, for example, 10 nm or more, preferably 20 nm or more, and for example, 500 nm or less, preferably 300 nm or less.

  The total value of the urethane group concentration and the urea group concentration of the polyurethane dispersion is a charge calculation value, for example, 20% by mass or more, preferably 25% by mass or more, and for example, 50% by mass or less, preferably 45 mass% or less.

  Moreover, various additives can be mix | blended as needed. Examples of additives include silane coupling agents, alkoxysilane compounds, stabilizers (antioxidants, heat stabilizers, UV absorbers, etc.), plasticizers, antistatic agents, lubricants, antiblocking agents, surfactants, Examples thereof include dispersion stabilizers, colorants (pigments, dyes, etc.), fillers, colloidal silica, inorganic particles, inorganic oxide particles, and crystal nucleating agents.

  The additive may be blended in advance with each of the above raw material components, or may be blended with the synthesized isocyanate group-terminated prepolymer or polyurethane resin, and further blended simultaneously with the blending of these components. May be.

  Moreover, the mixing ratio of the additive is not particularly limited, and is appropriately set according to the purpose and application.

  Moreover, you may mix | blend the thermoplastic resin which has gas barrier property in the range which does not impair gas barrier property as needed.

  Examples of the thermoplastic resin having gas barrier properties include polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyvinylidene chloride or vinylidene chloride copolymer, starch, polysaccharides such as cellulose, and the like.

  And in order to form the 1st layer 3, an anchor coat agent (AC agent) is prepared by adjusting the density | concentration of the dispersion of the 1st polyurethane resin obtained by the said method, for example. And the obtained anchor coat agent is apply | coated on the base material 2, and it is made to dry.

  The solid content concentration of the anchor coating agent is, for example, 0.5% by mass or more, preferably 1% by mass or more, and for example, 30% by mass or less, preferably 25% by mass or less.

  Moreover, a hardening | curing agent can be mix | blended with an anchor coating agent as needed.

  Examples of the curing agent include an epoxy curing agent, a melamine curing agent, a carbodiimide curing agent, an aziridine curing agent, an oxazoline curing agent, and an isocyanate curing agent. Among these, as for the isocyanate curing agent, more specifically, a water-dispersible isocyanate curing agent (for example, a block isocyanate (for example, a tolylene diisocyanate block isocyanate, a hexamethylene diisocyanate block isocyanate, a xylylene diisocyanate). Type blocked isocyanate, hydrogenated xylylene diisocyanate type blocked isocyanate, etc.) and non-blocked polyisocyanate containing a hydrophilic group).

  When the curing agent is blended, the blending ratio is, for example, 0.1 mass part or more, preferably 1 in terms of solid content with respect to the solid content of 100 mass parts of the first polyurethane resin. For example, it is 50 parts by mass or less, preferably 30 parts by mass or less.

  Further, the application method of the anchor coating agent is not particularly limited, and known coating methods such as gravure coating method, reverse coating method, roll coating method, bar coating method, spray coating method, air knife coating method, dipping method, etc. Is mentioned.

  Moreover, when creating the base material 2, you may apply in-line.

  Specifically, when the base material 2 is in the form of a film, the anchor coating agent is applied and dried by a gravure coating method or the like after the uniaxial stretching treatment in the longitudinal direction at the time of film formation, and then the biaxial stretching treatment is performed. Layer 3 can be provided on the substrate 2.

  Moreover, when the base material 2 is bottle-shaped, after apply | coating and drying an anchor coating agent by the dipping method etc. to the preform before blow molding, it can blow-mold and can provide the 1st layer 3 on the base material 2. .

  Moreover, as for drying conditions, drying temperature is 40 degreeC or more, for example, Preferably, it is 50 degreeC or more, for example, 200 degrees C or less, Preferably, it is 180 degrees C or less. The drying time is, for example, 0.1 minutes or more, preferably 0.2 minutes or more, for example, 10 minutes or less, preferably 5 minutes or less.

  Thereby, the first layer 3 made of the first polyurethane resin can be formed on the substrate 2.

The thickness of the first layer 3, as the amount of lamination of the first polyurethane resin (after drying), for example, 0.05 g / ^{m 2} or more, preferably, 0.1 g / ^{m 2} or more, more preferably, 0.2 g / m ² or more, for example, 5 g / m ² or less, preferably 3 g / m ² or less, more preferably 1.0 g / m ² or less, and further preferably 0.4 g / m ² or less. .

  The second layer 4 is layered on a second polyurethane resin obtained by reaction of xylylene diisocyanate and / or hydrogenated xylylene diisocyanate and an isocyanate group-terminated prepolymer obtained by reacting a polyol with a chain extender. It is formed by dispersing an inorganic compound. From the viewpoint of production efficiency, such a second layer 4 is preferably obtained by applying and drying a mixture of the polyurethane dispersion containing the second polyurethane resin and the layered inorganic compound on the first layer 3 and drying. Is formed.

  The method for preparing the second polyurethane resin as a polyurethane dispersion is the same as the method for preparing the first polyurethane resin as a polyurethane dispersion.

  That is, the second polyurethane resin prepared as a polyurethane dispersion includes the above-described xylylene diisocyanate and / or hydrogenated xylylene diisocyanate (and the other polyisocyanate used as necessary) and the above-described polyol (and An isocyanate group-terminated prepolymer obtained by the reaction of the above-mentioned other polyol compound used as necessary) and an active hydrogen group-containing compound containing a hydrophilic group is used as a chain extender (and as required) It can be obtained by reacting with the above-mentioned diol having 2 to 6 carbon atoms and other low molecular weight polyols.

  The raw material composition of the first polyurethane resin and the raw material composition of the second polyurethane resin may be different from each other, but are preferably the same as each other.

  If the raw material composition of the first polyurethane resin and the raw material composition of the second polyurethane resin are the same as each other, it is possible to further improve the adhesion to the substrate and the transparency.

  Examples of the layered inorganic compound include a swellable layered inorganic compound and a non-swellable layered inorganic compound. From the viewpoint of gas barrier properties, a swellable layered inorganic compound is preferable.

  A swellable layered inorganic compound is a clay mineral composed of extremely thin unit crystals and having a property that a solvent coordinates or absorbs and swells between unit crystal layers.

  Specific examples of the swellable layered inorganic compound include, for example, hydrous silicates (phyllosilicate minerals, etc.), such as kaolinite group clay minerals (halloysite, kaolinite, enderite, dickite, nacrite, etc.), anti Golite clay mineral (antigolite, chrysotile, etc.), smectite clay mineral (montmorillonite, beidellite, nontronite, saponite, hectorite, soconite, stevensite, etc.), vermiculite clay mineral (vermiculite, etc.), mica or mica Group clay minerals (mica such as muscovite and phlogopite, margarite, tetrasilic mica, teniolite, etc.), synthetic mica and the like.

  These swellable layered inorganic compounds may be natural clay minerals or synthetic clay minerals. In addition, they can be used alone or in combination of two or more, and preferably include smectite group clay minerals (such as montmorillonite), mica group clay minerals (such as water-swelling mica), and synthetic mica, more preferably synthetic mica. Is mentioned.

  The average particle size of the layered inorganic compound is, for example, 50 nm or more, preferably 100 nm or more, and usually 100 μm or less, for example, 75 μm or less, preferably 50 μm or less. Further, the aspect ratio of the layered inorganic compound is, for example, 10 or more, preferably 20 or more, more preferably 100 or more, and for example, 5000 or less, preferably 4000 or less, more preferably 3000 or less. .

  In order to form the second layer 4, for example, first, a polyurethane dispersion containing the second polyurethane resin and a layered inorganic compound are mixed, and a hybrid coating agent is prepared as a mixture. Then, the obtained hybrid coating agent is applied on the first layer 3 and dried.

  In order to prepare a mixture (hybrid coating agent), first, a layered inorganic compound is dispersed in water, and then a polyurethane dispersion containing a second polyurethane resin is added to the dispersion.

  The blending ratio of the second polyurethane resin and the layered inorganic compound is such that the layered inorganic compound is 0.1 parts by mass or more, preferably 1 part per 100 parts by mass of the total mass of the second polyurethane resin and the layered inorganic compound. For example, 50 parts by mass or less, preferably 30 parts by mass or less.

  When the blending ratio of the second polyurethane resin and the layered inorganic compound is in the above range, the gas barrier property can be maintained, and the adhesion to the substrate, transparency, and low cost can be improved.

  The total concentration of the second polyurethane resin and the layered inorganic compound in the resulting mixture (hybrid coating agent) is, for example, 0.1% by mass or more, preferably 0.5% by mass or more, and for example, 15% by mass. % Or less, preferably 12% by mass or less.

  In the mixture (hybrid coating agent), since the layered inorganic compound may be agglomerated secondarily, it is preferable that the layered inorganic compound is dispersed or mixed in a solvent and then subjected to mechanical forced dispersion treatment in which shearing force acts. For example, the dispersion is performed by using a dispersion treatment by a homomixer, a colloid mill, a jet mill, a kneader, a bead mill, a sand mill, a ball mill, a three-roll mill, an ultrasonic dispersing apparatus, or the like.

  Moreover, the said hardening | curing agent can also be mix | blended with a hybrid coating agent as needed.

  When the curing agent is blended, the blending ratio is, for example, 0.1 parts by mass or more in terms of solid content with respect to the solid content of 100 parts by mass of the second polyurethane resin. The amount is preferably 1 part by mass or more, and for example, 50 parts by mass or less, preferably 30 parts by mass or less.

  Moreover, the application method of the hybrid coating agent is not particularly limited, and examples thereof include the above-described known coating methods.

  As for the drying conditions, the drying temperature is, for example, 40 ° C. or higher, preferably 50 ° C. or higher, for example 200 ° C. or lower, preferably 180 ° C. or lower. The drying time is, for example, 0.1 minutes or more, preferably 0.2 minutes or more, for example, 10 minutes or less, preferably 5 minutes or less.

  Thereby, the second layer 4 made of the second polyurethane resin and the layered inorganic compound can be formed on the first layer 3.

The thickness of the second layer 4 is, for example, 0.1 g / m ² or more, preferably 0.2 g / m ² or more, more preferably, as the lamination amount of the second polyurethane resin and the layered inorganic compound (after drying). and a 0.6 g / ^{m 2} or more, and is, for example, 10 g / ^{m 2} or less, preferably, 7 g / ^{m 2} or less, more preferably 3 g / ^{m 2} or less.

  And as mentioned above, the polyurethane layered product 1 can be obtained by forming the first layer 3 on the substrate 2 and forming the second layer 4 on the first layer 3.

  The thickness of the polyurethane laminate 1 is, for example, 5 μm or more, preferably 10 μm or more, and for example, 1 mm or less, preferably 0.5 mm or less.

In the polyurethane laminate 1, the total thickness of the first layer 3 and the second layer 4 is, for example, 0.1 g / m ² or more, preferably 0.2 g / m ² or more as the amount of lamination after drying. More preferably, it is 0.8 g / m ² or more, for example, 20 g / m ² or less, preferably 15 g / m ² or less, more preferably 10 g / m ² or less, and further preferably 5 g / m ² or less. m ² or less.

  In addition, the thickness ratio between the first layer 3 and the second layer 4 is based on the height (μm) with respect to the total thickness of the first layer 3 and the second layer 4. 1% or more, preferably 2% or more, for example, 50% or less, preferably 20% or less. The second layer 4 is, for example, 50% or more, preferably 80% or more, for example, 99% or less, preferably 98% or less.

  The mass ratio of the first layer 3 and the second layer 4 is such that the mass of the first layer 3 is, for example, 0.01 parts by mass or more, preferably 0.1 mass with respect to 100 mass parts of the total mass. Part by mass or more, more preferably 0.2 part by mass or more, further preferably 10 parts by mass or more, for example, 60 parts by mass or less, preferably 50 parts by mass or less, more preferably 30 parts by mass or less, More preferably, it is 20 parts by mass or less. Moreover, the mass of the 2nd layer 4 is 40 mass parts or more, for example, Preferably, it is 50 mass parts or more, More preferably, it is 70 mass parts or more, More preferably, it is 80 mass parts or more, for example, 99.99. It is 99.9 mass parts or less, More preferably, it is 99.8 mass parts or less, More preferably, it is 90 mass parts or less.

  When the mass ratio between the first layer 3 and the second layer 4 is in the above range, the adhesion to the substrate and the transparency can be improved.

  Moreover, in the polyurethane laminated body 1, the mass ratio of the layered inorganic compound is such that the mass of the layered inorganic compound is, for example, 0 with respect to 100 parts by mass of the total mass of the first layer 3 and the mass of the second layer 4. 0.1 parts by mass or more, preferably 0.2 parts by mass or more, more preferably 1 parts by mass or more, for example, 90 parts by mass or less, preferably 70 parts by mass or less, more preferably 50 parts by mass or less. It is.

  If the mass ratio of the layered inorganic compound is in the above range, the adhesion to the substrate and the transparency can be improved, and the compounding ratio of the layered inorganic compound can be reduced, so that the cost can be improved. .

  Moreover, you may age the obtained polyurethane laminated body 1 at 30-50 degreeC for about 2 to 5 days as needed.

  And the polyurethane laminated body 1 obtained in this way is excellent not only in gas barrier property but the adhesiveness with respect to a base material, transparency of a base material, and low cost property. Therefore, it is suitably used in the field of gas barrier films, specifically, food packaging films, optical films, industrial films and the like.

  In addition, the hybrid coating agent, which is a mixture of the second polyurethane resin and the layered inorganic compound, is mixed with a colorant such as a pigment to prepare a printing ink, which is then applied to a plastic film, paper, various containers, and the like. Therefore, it can be suitably used as a printing film or printed body.

  In the above-described embodiment, the first layer 3 and the second layer 4 are laminated on the entire surface of the one surface in the thickness direction of the substrate 2, but the present invention is not limited to this. The first layer 3 and the second layer 4 can be partially laminated.

  Further, the first layer 3 and / or the second layer 4 can be further laminated on the first layer 3 and the second layer 4.

  The first layer 3 may be formed by in-line coating at the time of forming each thermoplastic film.

Next, although this invention is demonstrated based on an Example and a comparative example, this invention is not limited by the following Example. In the following description, “part” and “%” are based on mass unless otherwise specified. In addition, the numerical value of the Example shown below can be substituted to the corresponding numerical value (namely, upper limit value or lower limit value) described in embodiment.
<Preparation of polyurethane dispersion (PUD)>
(Preparation Example 1 (Preparation of PUD1))
1,3-xylylene diisocyanate (m-XDI) (trade name: Takenate 500, manufactured by Mitsui Chemicals), 169.9 parts by mass, 1,3-bis (isocyanatomethyl) cyclohexane (m-H ₆ XDI) (product) Name: Takenate 600, manufactured by Mitsui Chemicals) 29.2 parts by mass, 35.9 parts by mass of ethylene glycol, 3.4 parts by mass of trimethylolpropane, 18.2 parts by mass of dimethylolpropionic acid and 115.8 parts by mass of methyl ethyl ketone as a solvent The components were mixed and reacted at 65 to 70 ° C. in a nitrogen atmosphere until the isocyanate group content of the reaction solution reached 6.79% by mass or less. In this way, a carboxy group- and isocyanate group-containing prepolymer (isocyanate group-terminated prepolymer) was synthesized. In this reaction, the equivalent ratio of isocyanate group to active hydrogen group (isocyanate group / active hydrogen group) was 1.4. Moreover, the average number of functional groups of the isocyanate group of the synthesized carboxy group and isocyanate group-containing prepolymer was 2.05, and the hydrophilic group concentration was 0.53 mmol / g.

  Next, the carboxy group- and isocyanate group-containing prepolymer solution was cooled to 40 ° C. and then neutralized with 13.6 parts by mass of triethylamine. A solution of a carboxy group- and isocyanate group-containing prepolymer was dispersed in 751.5 parts by mass of ion-exchanged water with homodisper, and 2-((2-aminoethyl) amino) ethanol 29.8 in 59.6 parts by mass of ion-exchanged water. An aqueous amine solution in which parts by mass were dissolved was added to cause a chain extension reaction. In this reaction, the equivalent ratio of active hydrogen groups to isocyanate groups (active hydrogen groups / isocyanate groups) was 0.95.

  After the chain extension reaction, the reaction is aged for 1 hour, and then methyl ethyl ketone and ion-exchanged water are distilled off with an evaporator, and the polyurethane resin is prepared with ion-exchanged water so that the solid content of the polyurethane resin is 30% by mass. Got.

The pH of PUD1 (measurement method conforms to JIS Z 8802, the same applies hereinafter) is 8.5, and the viscosity at 25 ° C. (measurement method conforms to JIS K 7117, the same applies hereinafter) is 15 mPa ·. The average particle size was 80 nm (measuring instrument: Coulter counter N5, manufactured by Beckman, the same applies hereinafter). The total value of the urethane group concentration and the urea group concentration (calculated charge value, the same applies hereinafter) was 40.7% by mass.
(Preparation Example 2 (Preparation of PUD2))
1,3-xylylene diisocyanate (m-XDI) (trade name: Takenate 500, manufactured by Mitsui Chemicals) 143.3 parts by mass, 4,4′-bis (isocyanatocyclohexyl) methane (H ₁₂ MDI) (trade name) : Vestanat H ₁₂ MDI, manufactured by Evonik) 25.0 parts by mass, 28.1 parts by mass of ethylene glycol, 5.5 parts by mass of trimethylolpropane, 13.1 parts by mass of dimethylolpropionic acid, and 121.1 parts by mass of methyl ethyl ketone as a solvent The mixture was reacted at 65 to 70 ° C. in a nitrogen atmosphere until the isocyanate group content of the reaction solution reached 6.12% by mass or less. In this way, a carboxy group- and isocyanate group-containing prepolymer was synthesized. In this reaction, the equivalent ratio of isocyanate group to active hydrogen group (isocyanate group / active hydrogen group) was 1.4. Moreover, the average number of functional groups of the isocyanate group of the synthesized carboxy group and isocyanate group-containing prepolymer was 2.1, and the hydrophilic group concentration was 0.46 mmol / g.

  Next, the carboxy group- and isocyanate group-containing prepolymer solution was cooled to 40 ° C. and then neutralized with 9.8 parts by mass of triethylamine. A solution of a carboxy group-containing and isocyanate group-containing prepolymer was dispersed in 839.8 parts by mass of ion-exchanged water with homodisper, and 2-((2-aminoethyl) amino) ethanol 23.3 was added to 46.6 parts by mass of ion-exchanged water. An amine aqueous solution in which parts by mass were dissolved was added, and then 2.0 parts by mass of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane (trade name: KBM-603, manufactured by Shin-Etsu Chemical Co., Ltd.) was added. To cause chain extension reaction. In this reaction, the equivalent ratio of active hydrogen groups to isocyanate groups (active hydrogen groups / isocyanate groups) was 0.95.

  After chain elongation reaction, aging reaction is performed for 1 hour, and then methyl ethyl ketone and ion-exchanged water are distilled off with an evaporator, and prepared with ion-exchanged water so that the polyurethane resin solid content is 25% by mass, polyurethane dispersion (PUD2) Got.

In addition, pH of PUD2 was 8.6, the viscosity in 25 degreeC was 15 mPa * s, and the average particle diameter was 90 nm. The total value of the urethane group concentration and the urea group concentration was 39.7% by mass.
(Preparation Example 3 (Preparation of PUD3))
1,3-xylylene diisocyanate (m-XDI) (trade name: Takenate 500, manufactured by Mitsui Chemicals) 130.4 parts by mass, 4,4′-bis (isocyanatocyclohexyl) methane (H ₁₂ MDI) (Vestanat H ₁₂ MDI (manufactured by Evonik) 26.0 parts by mass, 14.6 parts by mass of ethylene glycol, 2.5 parts by mass of trimethylolpropane, polypropylene glycol (number average molecular weight: 400, trade name: Actol P-400, Mitsui Chemicals, Inc.) 75.3 parts by mass, 15.2 parts by mass of dimethylolpropionic acid and 118.0 parts by mass of methyl ethyl ketone as a solvent were mixed, and the isocyanate group content of the reaction solution was 4.75 to 65 ° C. under a nitrogen atmosphere. It was made to react until it became 98 mass% or less. In this way, a carboxy group- and isocyanate group-containing prepolymer was synthesized. In this reaction, the equivalent ratio of isocyanate group to active hydrogen group (isocyanate group / active hydrogen group) was 1.4. Moreover, the average functional group number of the isocyanate group of the synthesized carboxy group and isocyanate group-containing prepolymer was 2.05, and the hydrophilic group concentration was 0.43 mmol / g.

  Next, the carboxy group- and isocyanate group-containing prepolymer solution was cooled to 40 ° C. and then neutralized with 11.3 parts by mass of triethylamine. A solution of a carboxy group-containing and isocyanate group-containing prepolymer was dispersed in 813.5 parts by mass of ion-exchanged water using a homodisper, and 2-((2-aminoethyl) amino) ethanol 20.2 was added to 40.3 parts by mass of ion-exchanged water. An amine aqueous solution in which parts by mass were dissolved was added, and then 4.4 parts by mass of N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane (trade name: KBM-602, manufactured by Shin-Etsu Chemical Co., Ltd.) was added. A chain extension reaction was performed. In this reaction, the equivalent ratio of active hydrogen groups to isocyanate groups (active hydrogen groups / isocyanate groups) was 0.95.

  After chain extension reaction, aging reaction is performed for 1 hour, and then methyl ethyl ketone and ion-exchanged water are distilled off by an evaporator, and the polyurethane resin is prepared with ion-exchanged water so that the solid content of the polyurethane resin is 30% by mass, and polyurethane dispersion (PUD3) Got.

In addition, pH of PUD3 was 8.2, the viscosity in 25 degreeC was 25 mPa * s, and the average particle diameter was 85 nm. The total value of the urethane group concentration and the urea group concentration was 30.6% by mass.
(Preparation Example 4 (Preparation of PUD4))
1,3-bis (isocyanatomethyl) cyclohexane (m-H ₆ XDI) (trade name: Takenate 600, manufactured by Mitsui Chemicals) 166.5 parts by mass, ethylene glycol 26.6 parts by mass, dimethylolpropionic acid 14. 4 parts by mass and 84.8 parts by mass of acetonitrile as a solvent were mixed and reacted at 70 to 72 ° C. in a nitrogen atmosphere until the isocyanate group content of the reaction solution reached 9.24% by mass or less. In this way, a carboxy group- and isocyanate group-containing prepolymer was synthesized. The equivalent ratio of isocyanate groups to active hydrogen groups in this reaction (isocyanate groups / active hydrogen groups) was 1.6. Moreover, the average number of functional groups of the isocyanate group of the synthesized carboxy group and isocyanate group-containing prepolymer was 2.0, and the hydrophilic group concentration was 0.52 mmol / g.

  Subsequently, the carboxy group- and isocyanate group-containing prepolymer solution was cooled to 40 ° C. and then neutralized with 10.7 parts by mass of triethylamine. A solution of a carboxy group-containing and isocyanate group-containing prepolymer was dispersed in 822.7 parts by mass of ion-exchanged water with homodisper, and 2-((2-aminoethyl) amino) ethanol 31.8 was added to 63.6 parts by mass of ion-exchanged water. An aqueous amine solution in which parts by mass were dissolved was added to cause a chain extension reaction. In this reaction, the equivalent ratio of active hydrogen groups to isocyanate groups (active hydrogen groups / isocyanate groups) was 0.95.

  After the chain extension reaction, the reaction is aged for 1 hour, and then methyl ethyl ketone and ion-exchanged water are distilled off with an evaporator, and prepared with ion-exchanged water so that the solid content of polyurethane resin is 25% by mass, polyurethane dispersion (PUD4) Got.

In addition, pH of PUD4 was 8.7, the viscosity in 25 degreeC was 10 mPa * s, and the average particle diameter was 75 nm. The total value of the urethane group concentration and the urea group concentration was 39.5% by mass.
(Preparation Example 5 (Preparation of PUD5))
1,3-Xylylene diisocyanate (m-XDI) (trade name: Takenate 500, manufactured by Mitsui Chemicals) 167.2 parts by mass, 28.5 parts by mass of ethylene glycol, 5.5 parts by mass of trimethylolpropane, dimethylolpropion 12.3 parts by mass of acid and 95.5 parts by mass of acetone as a solvent were mixed and reacted in a nitrogen atmosphere at 50 to 55 ° C. until the isocyanate group content of the reaction solution reached 7.50% by mass or less. In this way, a carboxy group- and isocyanate group-containing prepolymer was synthesized. In this reaction, the equivalent ratio of isocyanate group to active hydrogen group (isocyanate group / active hydrogen group) was 1.45. Moreover, the average functional group number of the isocyanate group of the synthesized carboxy group and isocyanate group-containing prepolymer was 2.1, and the hydrophilic group concentration was 0.43 mmol / g.

  Next, the carboxy group- and isocyanate group-containing prepolymer solution was cooled to 40 ° C. and then neutralized with 9.2 parts by mass of triethylamine. A solution of a carboxy group- and isocyanate group-containing prepolymer was dispersed in 831.8 parts by mass of ion-exchanged water with homodisper, and 2-((2-aminoethyl) amino) ethanol 27.3 was added to 54.6 parts by mass of ion-exchanged water. An aqueous amine solution in which parts by mass were dissolved was added to cause a chain extension reaction. In this reaction, the equivalent ratio of active hydrogen groups to isocyanate groups (active hydrogen groups / isocyanate groups) was 0.95.

  After the chain extension reaction, the reaction is aged for 1 hour, and then methyl ethyl ketone and ion-exchanged water are distilled off with an evaporator, and the polyurethane resin is prepared with ion-exchanged water so that the solid content of the polyurethane resin is 25% by mass. Got.

The pH of PUD5 was 8.6, the viscosity at 25 ° C. was 15 mPa · s, and the average particle size was 120 nm. The total value of the urethane group concentration and the urea group concentration was 41.1% by mass.
(Preparation Example 6 (Preparation of PUD-H1))
77.6 parts by mass of isophorone diisocyanate (IPDI) (Vestanat IPDI, manufactured by Evonik), polyester polyol (polyester polyol composed of adipic acid, 1,6-hexanediol, neopentyl glycol, trade name: Takelac U-5620, number average molecular weight 2000) 177.4 parts by mass, 13.3 parts by mass of triethylene glycol, 1.0 part by mass of trimethylolpropane, 11.9 parts by mass of dimethylolpropionic acid and 96.7 parts by mass of methyl ethyl ketone as a solvent, It was made to react at 65-70 degreeC under atmosphere until the isocyanate group content rate of the reaction solution became 2.59 mass% or less. In this way, a carboxy group- and isocyanate group-containing prepolymer was synthesized. In this reaction, the equivalent ratio of isocyanate groups to active hydrogen groups (isocyanate groups / active hydrogen groups) was 1.5. Moreover, the average functional group number of the isocyanate group of the synthesized carboxy group and isocyanate group-containing prepolymer was 2.05, and the hydrophilic group concentration was 0.30 mmol / g.

  Next, the carboxy group- and isocyanate group-containing prepolymer solution was cooled to 40 ° C. and then neutralized with 8.9 parts by mass of triethylamine. A solution of a carboxy group- and isocyanate group-containing prepolymer was dispersed in 838.5 parts by mass of ion-exchanged water with homodisper, and 2-((2-aminoethyl) amino) ethanol 7.7 was added to 15.4 parts by mass of ion-exchanged water. An amine aqueous solution in which 2.2 parts by mass of ethylenediamine and 2.2 parts by mass of ethylenediamine were dissolved was added to cause chain elongation reaction. In this reaction, the equivalent ratio of active hydrogen groups to isocyanate groups (active hydrogen groups / isocyanate groups) was 0.95.

  After the chain extension reaction, the reaction is aged for 1 hour, and then methyl ethyl ketone and ion-exchanged water are distilled off with an evaporator, and prepared with ion-exchanged water so that the solid content of the polyurethane resin is 30% by mass. H1) was obtained.

The pH of PUD-H1 was 7.8, the viscosity at 25 ° C. was 30 mPa · s, and the average particle size was 50 nm. The total value of the urethane group concentration and the urea group concentration was 13.4% by mass.
(Preparation Example 7 (Preparation of PUD-H2))
Isophorone diisocyanate (IPDI) (Vestanat IPDI, manufactured by Evonik) 146.9 parts by mass, hexamethylene diisocyanate (HDI) (trade name: Takenate 700, manufactured by Mitsui Chemicals) 55.6 parts by mass, ethylene glycol 30.7 parts by mass, Mixing 3.0 parts by weight of trimethylolpropane, 17.7 parts by weight of dimethylolpropionic acid and 125.8 parts by weight of methyl ethyl ketone as a solvent, the isocyanate group content of the reaction solution is 7 at 70 to 75 ° C. in a nitrogen atmosphere. It was made to react until it became 32 mass% or less. In this way, a carboxy group- and isocyanate group-containing prepolymer was synthesized. In this reaction, the equivalent ratio of isocyanate groups to active hydrogen groups (isocyanate groups / active hydrogen groups) was 1.5. Moreover, the average number of functional groups of the isocyanate group of the synthesized carboxy group and isocyanate group-containing prepolymer was 2.05, and the hydrophilic group concentration was 0.53 mmol / g.

  Next, the carboxy group- and isocyanate group-containing prepolymer solution was cooled to 40 ° C. and then neutralized with 13.4 parts by mass of triethylamine. A solution of a carboxy group- and isocyanate group-containing prepolymer was dispersed in 788.4 parts by mass of ion-exchanged water with a homodisper, and 2-((2-aminoethyl) amino) ethanol 32.7 was added to 65.4 parts by mass of ion-exchanged water. An aqueous amine solution in which parts by mass were dissolved was added to cause a chain extension reaction. In this reaction, the equivalent ratio of active hydrogen groups to isocyanate groups (active hydrogen groups / isocyanate groups) was 0.95.

  After the chain extension reaction, the reaction is aged for 1 hour, and then methyl ethyl ketone and ion-exchanged water are distilled off with an evaporator, and prepared with ion-exchanged water so that the solid content of the polyurethane resin is 30% by mass. H2) was obtained.

The pH of PUD-H2 was 8.0, the viscosity at 25 ° C. was 45 mPa · s, and the average particle size was 75 nm. The total value of the urethane group concentration and the urea group concentration was 38.1% by mass.
<Preparation of anchor coat (AC) agent>
(Preparation Example 8 (Preparation of AC1)
16.33 parts by mass of ion-exchanged water was added to 3.33 parts by mass of PUD 1 and mixed with a stirrer to obtain AC1 having a solid content concentration of 5% by mass.
(Preparation Example 9 (Preparation of AC2)
Add 17.0 parts by mass of ion-exchanged water to 2.86 parts by mass of PUD1, mix with a stirrer, then water-dispersible polyisocyanate (isocyanate group content: 15.8% by mass, curing agent, trade name) : Takenate WD-725, manufactured by Mitsui Chemicals Co., Ltd.) 0.14 parts by mass was added, dispersed, and mixed at room temperature for 20 minutes to obtain AC2 having a solid content concentration of 5% by mass.
(Preparation Example 10 (Preparation of AC3)
16.33 parts by mass of ion-exchanged water was added to 3.33 parts by mass of PUD-H1 and mixed with a stirrer to obtain AC3 having a solid content concentration of 5% by mass.
(Preparation Example 11 (Preparation of AC4)
16.33 parts by mass of ion-exchanged water was added to 3.33 parts by mass of PUD-H2, and mixed with a stirrer to obtain AC4 having a solid content concentration of 5% by mass.
<Preparation of hybrid coat (HBC) agent>
(Preparation Example 12 (Preparation of HBC1))
To 12.53 parts by mass of ion-exchanged water, 2.67 parts by mass of synthetic mica (trade name: NTS-5, average particle size 11 μm, manufactured by Topy Industries Co., Ltd.) was mixed with a stirrer at room temperature for 20 minutes and dispersed. . Next, 4.8 parts by mass of PUD1 was added and mixed at room temperature for 30 minutes to obtain HBC1 having a solid content concentration of 8% by mass. In addition, the mass ratio of the layered inorganic compound in HBC1 is 10 parts by mass with respect to 100 parts by mass of the total amount of the polyurethane resin and the layered inorganic compound.
(Preparation Example 13 (Preparation of HBC2))
In 10.4 parts by mass of ion-exchanged water, 5.33 parts by mass of synthetic mica (trade name: NTS-5, average particle diameter of 11 μm, manufactured by Topy Industries, Ltd.) was mixed with a stirrer at room temperature for 20 minutes and dispersed. . Next, 4.27 parts by mass of PUD1 was added and mixed at room temperature for 30 minutes to obtain HBC2 having a solid content concentration of 8% by mass. In addition, the mass of the layered inorganic compound in HBC2 is 20 parts by mass with respect to 100 parts by mass of the total amount of the polyurethane resin and the layered inorganic compound.
(Preparation Example 14 (Preparation of HBC3))
In 11.73 parts by mass of ion-exchanged water, 4.0 parts by mass of synthetic mica (trade name: MEB-3, average particle size of 3 μm, manufactured by Coop Chemical Co., Ltd.) was mixed with a stirrer at room temperature for 20 minutes and dispersed. . Next, 4.27 parts by mass of PUD1 was added and mixed at room temperature for 30 minutes to obtain HBC3 having a solid content concentration of 8 parts by mass. In addition, the mass of the layered inorganic compound in HBC3 is 20 parts by mass with respect to 100 parts by mass of the total amount of the polyurethane resin and the layered inorganic compound.
(Preparation Example 15 (Preparation of HBC4))
In 10.4 parts by mass of ion-exchanged water, 5.33 parts by mass of synthetic mica (trade name: NTS-5, average particle diameter of 11 μm, manufactured by Topy Industries, Ltd.) was mixed with a stirrer at room temperature for 20 minutes and dispersed. . Next, 4.27 parts by mass of PUD3 was added and mixed at room temperature for 30 minutes to obtain HBC4 having a solid content concentration of 8% by mass. In addition, the mass of the layered inorganic compound in HBC4 is 20 parts by mass with respect to 100 parts by mass of the total amount of the polyurethane resin and the layered inorganic compound.
(Preparation Example 16 (Preparation of HBC5))
To 12.16 parts by mass of ion-exchanged water, 4.00 parts by mass of synthetic mica (trade name: MEB-3, average particle size of 3 μm, manufactured by Coop Chemical Co., Ltd.) was mixed with a stirrer at room temperature for 20 minutes and dispersed. . Next, 3.66 parts by weight of PUD 1 was added and mixed at room temperature for 30 minutes. Thereafter, 0.18 parts by mass of water-dispersible polyisocyanate (isocyanate group content: 15.8% by mass, curing agent, trade name: Takenate WD-725, manufactured by Mitsui Chemicals) was added and dispersed at room temperature. By mixing for 20 minutes, HBC5 having a solid content concentration of 8% by mass was obtained. In addition, the mass of the layered inorganic compound in HBC5 is 20 parts by mass with respect to 100 parts by mass of the total amount of the polyurethane resin and the layered inorganic compound.
(Preparation Example 17 (Preparation of HBC6))
To 11.43 parts by mass of ion-exchanged water, 4.00 parts by mass of synthetic mica (trade name: MEB-3, average particle size of 3 μm, manufactured by Coop Chemical Co., Ltd.) was mixed with a stirrer at room temperature for 20 minutes and dispersed. . Next, 4.39 parts by weight of PUD 2 was added and mixed at room temperature for 30 minutes. Thereafter, 0.18 parts by mass of water-dispersible polyisocyanate (isocyanate group content: 14.0% by mass, curing agent, trade name: Takenate XWD-HS30, manufactured by Mitsui Chemicals) was added and dispersed at room temperature. By mixing for 20 minutes, HBC6 having a solid content concentration of 8% by mass was obtained. In addition, the mass of the layered inorganic compound in HBC6 is 20 parts by mass with respect to 100 parts by mass of the total amount of the polyurethane resin and the layered inorganic compound.
(Preparation Example 18 (Preparation of HBC7))
In 11.57 parts by mass of ion-exchanged water, 2.67 parts by mass of synthetic mica (trade name: NTS-5, average particle size 11 μm, manufactured by Topy Industries, Ltd.) was mixed with a stirrer at room temperature for 20 minutes and dispersed. . Next, 5.76 parts by mass of PUD4 was added and mixed at room temperature for 30 minutes to obtain HBC7 having a solid content concentration of 8% by mass. In addition, the mass of the layered inorganic compound in HBC7 is 10 parts by mass with respect to 100 parts by mass of the total amount of the polyurethane resin and the layered inorganic compound.
(Preparation Example 19 (Preparation of HBC8))
In 11.57 parts by mass of ion-exchanged water, 2.67 parts by mass of synthetic mica (trade name: NTS-5, average particle size 11 μm, manufactured by Topy Industries, Ltd.) was mixed with a stirrer at room temperature for 20 minutes and dispersed. . Next, 5.76 parts by mass of PUD5 was added and mixed at room temperature for 30 minutes to obtain HBC8 having a solid content concentration of 8% by mass. In addition, the mass of the layered inorganic compound in HBC8 is 10 parts by mass with respect to 100 parts by mass of the total amount of the polyurethane resin and the layered inorganic compound.
(Preparation Example 20 (Preparation of HBC9))
To 12.53 parts by mass of ion-exchanged water, 2.67 parts by mass of synthetic mica (trade name: NTS-5, average particle size 11 μm, manufactured by Topy Industries Co., Ltd.) was mixed with a stirrer at room temperature for 20 minutes and dispersed. . Next, 5.76 parts by mass of PUD-H2 was added and mixed at room temperature for 30 minutes to obtain HBC9 having a solid content concentration of 8% by mass. In addition, the mass of the layered inorganic compound in HBC9 is 10 parts by mass with respect to 100 parts by mass of the total amount of the polyurethane resin and the layered inorganic compound.
<Preparation of polyurethane laminate>
(Example 1 (Preparation of polyurethane laminate 1))
A polyethylene terephthalate film (biaxially stretched polyester film, trade name: Toyobo Ester Film E5102, manufactured by Toyobo Co., Ltd., thickness 12 μm) as a base material has a dry thickness of 0.2 g / m ² as the first layer. The AC1 was applied using a bar coater.

Next, the film coated with AC1 was placed in a drying oven set at 110 ° C. for 1 minute and dried. Next, on the obtained first layer, HBC1 was applied as a second layer so as to have a dry thickness of 0.8 g / m ² using the same coating method and drying conditions as above, and polyurethane lamination Body 1 was obtained.
(Example 2 (Preparation of polyurethane laminate 2))
A polyethylene terephthalate film (biaxially stretched polyester film, trade name: Toyobo Ester Film E5102, manufactured by Toyobo Co., Ltd., thickness 12 μm) as a base material has a dry thickness of 0.2 g / m ² as the first layer. The AC1 was applied using a bar coater.

Next, the film coated with AC1 was placed in a drying oven set at 110 ° C. for 1 minute and dried. Next, on the obtained first layer, HBC2 was applied as a second layer so as to have a dry thickness of 0.8 g / m ² using the same coating method and drying conditions as described above, and polyurethane lamination Body 2 was obtained.
(Example 3 (Preparation of polyurethane laminate 3))
To a polyethylene terephthalate film (biaxially stretched polyester film, trade name: Toyobo Ester Film E5102, manufactured by Toyobo Co., Ltd., thickness 12 μm) as a base material, the thickness when dried is 0.5 g / m ² as the first layer. The AC1 was applied using a bar coater.

Next, the film coated with AC1 was placed in a drying oven set at 110 ° C. for 1 minute and dried. Next, on the obtained first layer, HBC1 was applied as a second layer so as to have a dry thickness of 0.5 g / m ² using the same coating method and drying conditions as described above, and the polyurethane layer was laminated. Body 3 was obtained.
(Example 4 (Preparation of polyurethane laminate 4))
A polyethylene terephthalate film (biaxially stretched polyester film, trade name: Toyobo Ester Film E5102, manufactured by Toyobo Co., Ltd., thickness 12 μm) as a base material has a dry thickness of 0.2 g / m ² as the first layer. The AC1 was applied using a bar coater.

Next, the film coated with AC1 was placed in a drying oven set at 110 ° C. for 1 minute and dried. Next, on the obtained first layer, HBC3 was applied as a second layer so as to have a dry thickness of 0.8 g / m ² using the same coating method and drying conditions as described above, and polyurethane lamination Body 4 was obtained.
(Example 5 (Preparation of polyurethane laminate 5))
A polyethylene terephthalate film (biaxially stretched polyester film, trade name: Toyobo Ester Film E5102, manufactured by Toyobo Co., Ltd., thickness 12 μm) as a base material has a dry thickness of 0.2 g / m ² as the first layer. The AC1 was applied using a bar coater.

Next, the film coated with AC1 was placed in a drying oven set at 110 ° C. for 1 minute and dried. Next, on the obtained first layer, HBC4 was applied as a second layer so that the thickness when dried was 0.8 g / m ^{2 by} the same coating method and drying conditions as described above, and the polyurethane layer was laminated. Body 5 was obtained.
(Example 6 (Preparation of polyurethane laminate 6))
To a polypropylene film (biaxially stretched polypropylene film, trade name: Pyrene film-OT P2161, manufactured by Toyobo Co., Ltd., thickness 20 μm) as a base material, the thickness when dried is 0.2 g / m ² as the first layer. AC2 was applied using a bar coater.

Next, the film coated with AC2 was placed in a drying oven set at 80 ° C. for 1 minute and dried. Next, HBC5 was applied as a second layer on the obtained first layer using the same coating method and drying conditions as described above so that the thickness when dried was 0.8 g / m ² and dried. Then, it was made to age at 40 degreeC for 3 days, and the polyurethane laminated body 6 was obtained.
(Example 7 (Preparation of polyurethane laminate 7))
To a polypropylene film (biaxially stretched polypropylene film, trade name: Pyrene film-OT P2161, manufactured by Toyobo Co., Ltd., thickness 20 μm) as a base material, the thickness when dried is 0.2 g / m ² as the first layer. AC2 was applied using a bar coater.

Next, the film coated with AC2 was placed in a drying oven set at 80 ° C. for 1 minute and dried. Next, HBC6 was applied as a second layer on the obtained first layer using the same coating method and drying conditions as described above so that the dry thickness was 0.8 g / m ² and dried. Then, it was made to age at 40 degreeC for 3 days, and the polyurethane laminated body 7 was obtained.
(Example 8 (Preparation of polyurethane laminate 8))
A polyethylene terephthalate film (biaxially stretched polyester film, trade name: Toyobo Ester Film E5102, manufactured by Toyobo Co., Ltd., thickness 12 μm) as a base material has a dry thickness of 0.2 g / m ² as the first layer. The AC1 was applied using a bar coater.

Next, the film coated with AC1 was placed in a drying oven set at 110 ° C. for 1 minute and dried. Next, on the obtained first layer, by applying the same coating method and drying conditions as described above, HBC7 was applied as the second layer so that the dry thickness was 0.8 g / m ^2, and the polyurethane layer was laminated. Body 8 was obtained.
(Example 9 (Preparation of polyurethane laminate 9))
A polyethylene terephthalate film (biaxially stretched polyester film, trade name: Toyobo Ester Film E5102, manufactured by Toyobo Co., Ltd., thickness 12 μm) as a base material has a dry thickness of 0.2 g / m ² as the first layer. The AC1 was applied using a bar coater.

Next, the film coated with AC1 was placed in a drying oven set at 110 ° C. for 1 minute and dried. Next, on the obtained first layer, the same coating method and drying conditions as described above were applied, and HBC8 was applied as the second layer so that the thickness when dried was 0.8 g / m ^2. Body 9 was obtained.
(Comparative Example 1 (Preparation of polyurethane laminate 10))
A bar coater with a polyethylene terephthalate film (biaxially stretched polyester film, trade name: Toyobo Ester Film E5102, manufactured by Toyobo Co., Ltd., thickness 12 μm) as a substrate so that the thickness of HBC1 when dried is 1.0 g / m ^2. The film was applied to a drying oven set at 110 ° C. for 1 minute and dried to obtain a polyurethane laminate 10.
(Comparative Example 2 (Preparation of polyurethane laminate 11))
Bar coater so that the thickness of HBC2 when dried is 1.0 g / m ^{2 on} a polyethylene terephthalate film (biaxially stretched polyester film, trade name: Toyobo Ester Film E5102, manufactured by Toyobo Co., Ltd., thickness 12 μm) as a base material The film was applied to a drying oven set at 110 ° C. for 1 minute and dried to obtain a polyurethane laminate 11.
(Comparative Example 3 (Preparation of polyurethane laminate 12))
Bar coater so that HBC3 has a dry thickness of 1.0 g / m ^{2 on} a polyethylene terephthalate film (biaxially stretched polyester film, trade name: Toyobo Ester Film E5102, manufactured by Toyobo Co., Ltd., thickness 12 μm) as a base material The film was applied to a drying oven set at 110 ° C. for 1 minute and dried to obtain a polyurethane laminate 12.
(Comparative Example 4 (Preparation of polyurethane laminate 13))
A polyethylene terephthalate film (biaxially stretched polyester film, trade name: Toyobo Ester Film E5102, manufactured by Toyobo Co., Ltd., thickness 12 μm) as a base material has a dry thickness of 0.2 g / m ² as the first layer. AC3 was applied using a bar coater.

Next, the film coated with AC3 was placed in a drying oven set at 110 ° C. for 1 minute and dried. Next, on the obtained first layer, HBC1 was applied as a second layer so as to have a dry thickness of 0.8 g / m ² using the same coating method and drying conditions as above, and polyurethane lamination Body 13 was obtained.
(Comparative Example 5 (Preparation of polyurethane laminate 14))
A polyethylene terephthalate film (biaxially stretched polyester film, trade name: Toyobo Ester Film E5102, manufactured by Toyobo Co., Ltd., thickness 12 μm) as a base material has a dry thickness of 0.2 g / m ² as the first layer. AC4 was applied using a bar coater.

Next, the film coated with AC4 was placed in a drying oven set at 110 ° C. for 1 minute and dried. Next, on the obtained first layer, HBC9 was applied as a second layer so as to have a dry thickness of 0.8 g / m ² using the same coating method and drying conditions as above, and polyurethane lamination was performed. Body 14 was obtained.
(Comparative Example 6 (Preparation of polyurethane laminate 15))
Bar coater so that HBC5 has a dry thickness of 1.0 g / m ^{2 on} a polypropylene film (biaxially stretched polypropylene film, trade name: pyrene film-OT P2161, manufactured by Toyobo Co., Ltd., thickness 20 μm) as a base material. The film was applied to a drying oven set at 80 ° C. for 1 minute, dried and then cured at 40 ° C. for 3 days to obtain a polyurethane laminate 15.
(Evaluation)
About each obtained polyurethane laminated body, the oxygen permeability, haze value, and adhesive strength were measured with the following method. The results are shown in Tables 1 and 2.
<Oxygen permeability measurement>
Using an oxygen permeation measuring device (OX-TRAN 2/20, manufactured by MOCON), each polyurethane laminate at 20 ° C. with a relative humidity of 50% (50% RH) and a relative humidity of 80% (80% RH). The amount of oxygen permeation per 1 m ² , 1 day and 1 atmosphere was measured.
<Haze measurement>
The haze value of each polyurethane laminate was measured using a turbidimeter (NDR2000, manufactured by Nippon Denshoku Industries Co., Ltd.).
<Adhesive strength (laminate strength)>
For each polyurethane laminate, dry laminate adhesive (Takenate A-626 (isocyanate-based adhesive, manufactured by Mitsui Chemicals)) and Takenate A-65 (isocyanate-based adhesive, manufactured by Mitsui Chemicals) were used. Takenate A-65 blended at a ratio of 10/1) was applied so that the thickness upon drying was 3.0 g / m ² , and a polypropylene film (unstretched polypropylene film for retort, trade name: RXC) −22, manufactured by Mitsui Chemicals, Inc., thickness 60 μm) and cured at 40 ° C. for 3 days, the adhesive strength of each polyurethane laminate was measured by a T-shaped peel test in accordance with JIS K 6854.

The details of the abbreviations in the table are as follows.
PET (# 12): Polyethylene terephthalate film (biaxially stretched polyester film, trade name: Toyobo Ester Film E5102, manufactured by Toyobo Co., Ltd., thickness 12 μm)
OPP (# 20): polypropylene film (biaxially stretched polypropylene film, trade name: pyrene film-OT P2161, manufactured by Toyobo Co., Ltd., thickness 20 μm)

DESCRIPTION OF SYMBOLS 1 Polyurethane laminated body 2 Base material 3 1st layer 4 2nd layer

Claims (6)

A substrate;
A first layer laminated on the substrate and made of a first polyurethane resin;
A second layer made of a second polyurethane resin laminated on the first layer and having a layered inorganic compound dispersed therein,
Each of the first polyurethane resin and the second polyurethane resin is:
It is obtained by reaction of an isocyanate group-terminated prepolymer obtained by reacting at least xylylene diisocyanate and / or hydrogenated xylylene diisocyanate and a diol having 2 to 6 carbon atoms with a chain extender containing a polyamine. A polyurethane laminate that is characterized. Each of the first polyurethane resin and the second polyurethane resin is:
An isocyanate group-terminated prepolymer obtained by reacting at least a xylylene diisocyanate and / or a hydrogenated xylylene diisocyanate, a diol having 2 to 6 carbon atoms, and an active hydrogen group-containing compound containing a hydrophilic group, and a polyamine An aqueous polyurethane resin obtained by a reaction with a chain extender is prepared as a polyurethane dispersion obtained by water dispersion,
The first layer is
It is formed by applying and drying the polyurethane dispersion,
The second layer is
The polyurethane laminate according to claim 1, wherein the polyurethane laminate is formed by applying and drying a mixture of the polyurethane dispersion and the layered inorganic compound.   The mass of the second layer is 40 parts by mass or more and 90 parts by mass or less with respect to 100 parts by mass of the total mass of the mass of the first layer and the mass of the second layer. 3. The polyurethane laminate according to 1 or 2.   The mass of the layered inorganic compound is 1 part by mass or more and 50 parts by mass or less with respect to a total amount of 100 parts by mass of the mass of the first layer and the mass of the second layer. The polyurethane laminated body as described in any one of 1-3.   The polyurethane laminate according to claim 2, wherein the active hydrogen group-containing compound containing a hydrophilic group is a polyhydroxyalkanoic acid.   The polyurethane layered product according to any one of claims 1 to 5, wherein the layered inorganic compound is swellable.