Gas barrier polyurethane resin composition and gas barrier laminate

Abstract

To provide a gas barrier polyurethane resin composition which is excellent in adhesion, blocking resistance, gas barrier property and peel strength, and a gas barrier laminate containing the same.SOLUTION: A gas barrier polyurethane resin composition contains a gas barrier polyurethane resin which is a reactant of a polyol compound, a polyhydroxy acid and a polyisocyanate compound, where the polyol compound contains a diol compound having 2 to 6 carbon atoms and a diol compound having 7 to 10 carbon atoms, in the diol compound having 2 to 6 carbon atoms, at least 20 mass% or more of 2-methyl-1,3-propanediol is contained, the polyhydroxy acid is a compound represented by general formula (1), and the polyisocyanate compound contains xylylene diisocyanate and / or hydrogenated xylylene diisocyanate.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a gas barrier polyurethane resin composition and a gas barrier laminate. [Background technology]

[0002] A gas barrier laminate (gas barrier film) is known in which a polyurethane layer with gas barrier properties is formed by applying a polyurethane resin solution, obtained by dissolving polyurethane resin in an organic solvent, or an aqueous polyurethane resin dispersion, obtained by dispersing polyurethane resin in water, to a substrate and drying it. This technology is useful in addressing environmental problems such as microplastics because paper can be used as the substrate.

[0003] As an example of such a gas barrier polyurethane resin, Patent Document 1 proposes a polyurethane resin in which a diisocyanate component such as an aromatic diisocyanate is reacted with a diol component such as an alkylene glycol having 2 to 8 carbon atoms, and the total concentration of urethane groups and urea groups is 15% by weight or more. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2001-98047 [Overview of the project] [Problems that the invention aims to solve]

[0005] The aforementioned patent document specifically describes a gas barrier polyurethane resin obtained by reacting an aromatic diisocyanate with a diol selected from alkylene glycols having 2 to 8 carbon atoms. However, with conventional technology, it has been difficult to achieve a balance between adhesiveness, blocking resistance, gas barrier properties, and peel strength.

[0006] The present invention aims to provide a gas barrier polyurethane resin composition and a gas barrier laminate containing the same, which exhibit excellent adhesion, blocking resistance, gas barrier properties, and peel strength. [Means for solving the problem]

[0007] [Item 1] That is, the present invention contains a gas barrier polyurethane resin which is a reaction product of a polyol compound, a polyhydroxy acid, and a polyisocyanate compound, wherein the polyol compound contains a diol compound having 2 to 6 carbon atoms and a diol compound having 7 to 10 carbon atoms, wherein at least 20% by mass or more of 2-methyl-1,3-propanediol is contained in the diol compound having 2 to 6 carbon atoms, and the polyhydroxy acid is of general formula (1): [ka] (In general formula (1), R 1 The compound is represented by (), and the polyisocyanate compound relates to a gas barrier polyurethane resin composition containing xylylene diisocyanate and / or hydrogenated xylylene diisocyanate.

[0008] [Item 2] The present invention also relates to the gas barrier polyurethane resin composition described in Item 1, wherein the diol compound having 7 to 10 carbon atoms contains a diol compound having a cyclic structure.

[0009] [Item 3] The present invention also relates to the gas barrier polyurethane resin composition described in Item 2, wherein the diol compound having a cyclic structure is one or more selected from the group consisting of cyclohexanedimethanol, xylylene glycol, and adamantanediol.

[0010] [Item 4] The present invention also relates to a gas barrier polyurethane resin composition according to any one of the preceding items 1 to 3, which contains an organic solvent or an aqueous medium.

[0011] [Item 5] The present invention also relates to a gas barrier laminate in which a gas barrier polyurethane resin composition described in any of the preceding items 1 to 4 is applied to a substrate. [Effects of the Invention]

[0012] The mechanism of action for the water vapor barrier improvement effect in the gas barrier polyurethane resin composition of the present invention is presumed to be as follows. However, the present invention is not limited to this mechanism of action.

[0013] The gas barrier polyurethane resin composition of the present invention contains a gas barrier polyurethane resin which is a reaction product of a polyol compound, a polyhydroxy acid, and a polyisocyanate compound. The polyol compound contains a diol compound having 2 to 6 carbon atoms and a diol compound having 7 to 10 carbon atoms, and of the diol compound having 2 to 6 carbon atoms, at least 20% by mass or more of 2-methyl-1,3-propanediol is contained in the diol compound having 2 to 6 carbon atoms. The polyhydroxy acid is a compound represented by the above general formula (1), and the polyisocyanate compound contains xylylene diisocyanate and / or hydrogenated xylylene diisocyanate. It is believed that the hydrophobic skeletal structure derived from the diol compound having 7 to 10 carbon atoms reduces the solubility of water vapor in the resulting urethane resin film, thereby improving water vapor barrier properties. Furthermore, it is believed that the polyurethane resin into which carboxyl groups have been introduced improves adhesion and peel strength. [Modes for carrying out the invention]

[0014] The gas barrier polyurethane resin composition of the present invention contains a gas barrier polyurethane resin which is a reaction product of a polyol compound, a polyhydroxy acid, and a polyisocyanate compound (having structural units derived from the polyol compound, structural units derived from the polyhydroxy acid, and structural units derived from the polyisocyanate compound).

[0015] <Polyol compounds> The polyol compound contains a diol compound having 2 to 6 carbon atoms and a diol compound having 7 to 10 carbon atoms, and the diol compound having 2 to 6 carbon atoms contains at least 20% by mass of 2-methyl-1,3-propanediol.

[0016] From the viewpoint of gas barrier properties, the C2-C6 diol compound preferably contains 40% by mass or more of 2-methyl-1,3-propanediol, more preferably 60% by mass or more, and even more preferably 70% by mass or more.

[0017] The C2-C6 diol compound may be any C2-C6 diol compound other than 2-methyl-1,3-propanediol (other C2-C6 diol compounds) as long as the performance does not deteriorate. Examples of the other C2-C6 diol compounds include alkylene glycols such as ethylene glycol, 1,3- or 1,2-propylene glycol, 1,4-, 1,3- or 1,2-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, polyetherdiols such as diethylene glycol, triethylene glycol, and dipropylene glycol, catechol, resorcinol, hydroquinone, and cyclohexanediol.

[0018] Examples of the diol compound having 7 to 10 carbon atoms include alkylene glycols such as 2,4 - diethyl - 1,5 - pentanediol, 2,2,4 - trimethylpentane - 1,3 - diol, 1,5 - or 1,7 - heptanediol, 1,8 - octanediol, 1,9 - nonanediol, 1,10 - decanediol; polyether diols such as tetraethylene glycol, pentaethylene glycol, tripropylene glycol, dibutylene glycol; aromatic diols such as xylylene glycol, alicyclic diols such as hydrogenated xylylene diol, cyclohexanedimethanol, and the like. Among these, from the viewpoint of gas barrier properties, it is preferable to contain a diol compound having a cyclic structure.

[0019] The mass ratio of the diol compound having 2 to 6 carbon atoms to the diol compound having 7 to ¹0 carbon atoms (diol compound having 2 to 6 carbon atoms / diol compound having 7 to 10 carbon atoms) is preferably in the range of 0.1 to 9, more preferably in the range of 1 to 8, and even more preferably in the range of 1.5 to 7 from the viewpoint of water vapor permeability.

[0020] <Polyhydroxy acid> The polyhydroxy acid is a compound represented by the general formula (1):

Chemical formula

[0021] Examples of the polyhydroxy acid include dimethylolpropionic acid, dimethylolbutanoic acid, and the like.

[0022] The polyhydroxy acid can be used within a range that adjusts the acid value of the gas barrier polyurethane resin to make it water-soluble or water-dispersible. For example, the gas barrier polyurethane resin typically has an acid value of 5 to 100 mg KOH / g, preferably 10 to 70 mg KOH / g, and more preferably 15 to 60 mg KOH / g.

[0023] <Polyisocyanate compounds> The polyisocyanate compound contains xylylene diisocyanate and / or hydrogenated xylylene diisocyanate.

[0024] The polyisocyanate compound may be any polyisocyanate compound other than xylylene diisocyanate and / or hydrogenated xylylene diisocyanate (other polyisocyanate compounds), as long as the performance does not deteriorate. Examples of the other polyisocyanate compounds include: m- or p-phenylenediisocyanate or mixtures thereof, 4,4′-diphenyldiisocyanate, 1,5-naphthalenediisocyanate (NDI), 4,4′-, 2,4′- or 2,2′-diphenylmethanediisocyanate or mixtures thereof (MDI), 2,4- or 2,6-tolylenediisocyanate or mixtures thereof (TDI), 4,4′-toluidinediisocyanate (TODI), 4,4′-diphenyletherdiisocyanate and other aromatic diisocyanates, 1,3- or 1,4-tetramethylxylylenediisocyanate or mixtures thereof (TMXDI), ω,ω′-diisocyanate-1,4-diethylbenzene and other aromatic aliphatic diisocyanates, 1,3-cyclopentenediisocyanate, 1,4-cyclohexanediisocyanate, 1,3- Alicyclic diisocyanates such as chlorohexane diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate; IPDI), 4,4′-, 2,4′- or 2,2′-dicyclohexylmethane diisocyanate or mixtures thereof (hydrogenated MDI), methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, Examples of aliphatic diisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-, 2,3- or 1,3-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, and 2,6-diisocyanate methyl capeate.

[0025] The molar equivalent (NCO / OH) of the NCO group of the isocyanate compound and the total OH groups of the polyol compound and polyhydroxy acid is preferably about 0.6 to 2.0, and more preferably about 0.7 to 1.5.

[0026] <Chain extenders and reaction inhibitors> The gas barrier polyurethane resin may be chain-extended using a chain-extending agent, or the reaction may be stopped using a reaction-stopping agent. Examples of the chain-extending agent include aliphatic diamines such as ethylenediamine, propylenediamine, tetramethylenediamine, and hexamethylenediamine; alicyclic diamines such as isophoronediamine and 4,4'-dicyclohexylmethanediamine; aromatic diamines such as toluylenediamine; aromatic aliphatic diamines such as xylenediamine; hydroxyl-containing diamines such as N-(2-hydroxyethyl)ethylenediamine, N-(2-hydroxyethyl)propylenediamine, and N,N'-di(2-hydroxyethyl)ethylenediamine; and diol compounds such as ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, diethylene glycol, and triethylene glycol. Furthermore, polyamines such as diethylenetriamine and triethylenetetramine may be used in combination, to the extent that the polyurethane polyurea resin does not gel. Furthermore, examples of reaction stoppers include alkylamine compounds (e.g., n-butylamine, di-n-butylamine, etc.), alkanolamine compounds (e.g., monoethanolamine, diethanolamine, etc.), and monoalcohol compounds (methanol, ethanol, etc.). In addition, the compounds listed as chain extenders can also be used as reaction stoppers.

[0027] <medium> In the gas barrier polyurethane resin composition of the present invention, it is preferable to use a medium to dissolve or disperse the gas barrier polyurethane resin composition. Examples of such mediums include organic solvents and aqueous media.

[0028] The organic solvent is preferably one that facilitates the reaction between the polyol compound and the polyisocyanate compound. Examples include ketone-based organic solvents (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), ester-based organic solvents (e.g., methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, isobutyl acetate, etc.), and hydrocarbon-based solvents (e.g., toluene, methylcyclohexane, etc.).

[0029] The aqueous medium contains at least water and, if necessary, a water-miscible organic solvent. Examples of the water-miscible organic solvent include alcohols such as ethanol and isopropanol; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; cellosolves; carbitols; and nitriles such as acetonitrile.

[0030] <Method for manufacturing gas barrier polyurethane resin> When the gas barrier polyurethane resin is used as a composition containing the organic solvent, for example, it can be produced by reacting the polyol compound, the polyhydroxy acid, the polyisocyanate compound, and, if necessary, the chain extender and the reaction stopper, in the organic solvent. Alternatively, when the gas barrier polyurethane resin is used as a composition containing the aqueous medium, for example, it can be obtained by reacting the polyol compound, the polyhydroxy acid, and the polyisocyanate compound in the water-miscible organic solvent, adding a basic compound and / or a surfactant, then adding water to emulsify, and further adding the chain extender and the reaction stopper, if necessary, after the reaction has been carried out, removing the ketone-based solvent and further adding the aqueous medium. From the viewpoint of solvent resistance, the gas barrier polyurethane resin composition is preferably an aqueous gas barrier polyurethane resin composition in which the gas barrier polyurethane resin is dispersed in the aqueous medium.

[0031] The basic compound is preferably a volatile basic compound. Examples of volatile basic compounds include organic amines such as triethylamine and N,N-dimethylethanolamine. In addition, inorganic alkali compounds such as sodium hydroxide and potassium hydroxide, and non-volatile amine compounds such as triethylenediamine and triethanolamine can also be used in combination, as long as the drying performance does not deteriorate.

[0032] Examples of the aforementioned surfactants include anionic surfactants such as higher alcohol sulfate salts, alkylbenzene sulfonates, and polyoxyethylene alkyl sulfate salts; and nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, and sorbitan derivatives.

[0033] The gas barrier polyurethane resin composition may be blended with a thermoplastic resin, to the extent that the gas barrier properties are not impaired. Examples of the thermoplastic resin include polyolefin resins (e.g., polyethylene, polypropylene, polybutene, polymethylpentene, etc.), polyester resins (e.g., polyethylene terephthalate, polybutylene terephthalate, etc.), polyamide resins (e.g., nylon 6, nylon 12, nylon 66, polymetaxylylene adipamide, etc.), vinyl resins (e.g., polystyrene, polyvinyl chloride, polymethyl methacrylate, etc.), and polycarbonate resins (e.g., bisphenol A type polycarbonate, etc.). Furthermore, if necessary, gas barrier resins such as PVDC, polyvinyl alcohol, and ethylene-vinyl alcohol copolymers may be used.

[0034] Various additives may be added to the gas barrier polyurethane resin composition, provided that they do not impair the gas barrier properties. Examples of such additives include silane coupling agents, layered inorganic compounds, stabilizers (antioxidants, heat stabilizers, UV absorbers, etc.), plasticizers, antistatic agents, lubricants, antiblocking agents, colorants, fillers, and nucleating agents.

[0035] <Gas barrier laminate> The gas barrier laminate of the present invention is formed by applying the gas barrier polyurethane resin composition to a substrate and drying it.

[0036] The above-mentioned coating methods can include, for example, conventional methods such as roll coating using a labia cylinder, doctor knife method, air knife / nozzle coating method, bar coating method, spray coating method, dip coating method, and coating methods that combine these methods.

[0037] The amount of the aforementioned gas barrier polyurethane resin composition to be applied is 0.1 g / m² after drying. 2 More than 2g / m 2 The following is preferable:

[0038] The substrate is not particularly limited and may be a plastic film, paper, cloth, metal, ceramics, etc. Examples of the plastic film include stretched and unstretched polyolefins such as polyethylene and polypropylene, polyester, nylon, cellophane, and vinylon. Furthermore, for these resin films, films obtained by pre-processing such as coating or kneading with an anti-fogging agent, or surface coating or kneading with a matting agent can also be used. The paper preferably contains, for example, pulp, fillers, and various auxiliary agents.

[0039] Examples of the pulp used include chemical pulps such as bleached hardwood kraft pulp (LBKP), bleached softwood kraft pulp (NBKP), unbleached hardwood kraft pulp (LUKP), unbleached softwood pulp (NUKP), and sulfite pulp; mechanical pulps such as stone-ground pulp and thermomechanical pulp; wood fibers such as deinked pulp and recycled paper pulp; and non-wood fibers obtained from kenaf, bamboo, hemp, etc., which can be blended as appropriate.

[0040] As the aforementioned filler, known fillers such as white carbon, talc, kaolin, clay, heavy calcium carbonate, light calcium carbonate, titanium dioxide, zeolite, and synthetic resin fillers can be used.

[0041] Examples of the aforementioned additives include yield enhancers, water-repellent enhancers, paper strength enhancers, internal sizing agents, dyes, fluorescent whitening agents, pH adjusters, defoamers, pitch control agents, slime control agents, and the like.

[0042] The manufacturing method (papermaking) for the base layer of the above-mentioned paper is not particularly limited and can be used to manufacture the paper using known methods such as acidic papermaking, neutral papermaking, and alkaline papermaking, including a long-screen former, on-top hybrid former, and gap former machine. Furthermore, the base layer of the above-mentioned paper may be a single layer or composed of two or more layers. In addition, the surface of the base layer of the paper may be treated with various chemicals. The thickness of the base layer of the above-mentioned paper is not particularly limited and can be appropriately selected according to the application. [Examples]

[0043] The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

[0044] <Manufacturing of gas barrier polyurethane resin> <Example 1> In a four-necked flask equipped with a reflux condenser, nitrogen gas inlet tube, stirring rod, and thermometer, 15 parts by mass of 2-methyl-1,3-propanediol, 8 parts by mass of cyclohexanedimethanol, 8.22 parts by mass of dimethylolbutanoic acid, and 86.32 parts by mass of methyl ethyl ketone were charged and stirred at 40°C until dissolved. Then, 43.11 parts by mass of 1,3-hydrogenated xylylene diisocyanate and 0.02 parts by mass of tetra-n-butoxytitanium (TBT) were charged and reacted under reflux at 80°C for 5 hours. After cooling to 25°C, 86.32 parts by mass of isopropyl alcohol were charged to obtain a gas barrier polyurethane resin (solid content 30%).

[0045] <Example 2> In a four-necked flask equipped with a reflux condenser, nitrogen gas inlet tube, stirring rod, and thermometer, 15 parts by mass of 2-methyl-1,3-propanediol, 7.67 parts by mass of p-xylylene glycol, 8.22 parts by mass of dimethylolbutanoic acid, and 86.32 parts by mass of methyl ethyl ketone were charged and stirred at 40°C until dissolved. Then, 43.11 parts by mass of 1,3-hydrogenated xylylene diisocyanate and 0.02 parts by mass of TBT were charged and reacted under reflux at 80°C for 5 hours. After cooling to 25°C, 86.32 parts by mass of isopropyl alcohol were charged to obtain a gas barrier polyurethane resin (solid content 30%).

[0046] <Example 3> In a four-necked flask equipped with a reflux condenser, nitrogen gas inlet tube, stirring rod, and thermometer, 15 parts by mass of 2-methyl-1,3-propanediol, 7.67 parts by mass of p-xylylene glycol, 8.22 parts by mass of dimethylolbutanoic acid, and 94.87 parts by mass of methyl ethyl ketone were charged and stirred at 40°C until dissolved. Then, 43.11 parts by mass of 1,3-hydrogenated xylylene diisocyanate, 20.88 parts by mass of 1,3-xylylene diisocyanate, and TBT were added. 0.02 parts by mass of [the substance] was charged and reacted at 80°C for 5 hours under reflux. After cooling, a solution of 5.33 parts by mass of triethylamine dissolved in 245.95 parts by mass of water was charged and stirred at 20-30°C for 10 minutes. Then, 5.2 parts by mass of aminoethylethanolamine was charged and reacted at 20-30°C for 30 minutes. After that, it was heated to 40°C under reduced pressure for 3 hours, and the mixture was degassed and stirred to remove methyl ethyl ketone by distillation to obtain a water-based gas barrier polyurethane resin (solid content 30%).

[0047] <Example 4> In a four-necked flask equipped with a reflux condenser, nitrogen gas inlet tube, stirring rod, and thermometer, 15 parts by mass of 2-methyl-1,3-propanediol, 8 parts by mass of cyclohexanedimethanol, 8.22 parts by mass of dimethylolbutanoic acid, and 94.87 parts by mass of methyl ethyl ketone were charged and stirred at 40°C until dissolved. Then, 43.11 parts by mass of 1,3-hydrogenated xylylene diisocyanate, 20.88 parts by mass of 1,3-xylylene diisocyanate, and TB were added. 0.02 parts by mass of T was charged and reacted at 80°C for 5 hours under reflux. After cooling, a solution of 5.33 parts by mass of triethylamine dissolved in 240.82 parts by mass of water was charged and stirred at 20-30°C for 10 minutes. Then, 3.00 parts by mass of ethylenediamine was charged and reacted at 20-30°C for 30 minutes. After that, it was heated to 40°C under reduced pressure and stirred for 3 hours to degas and remove methyl ethyl ketone by distillation to obtain an aqueous gas barrier polyurethane resin (solid content 30%).

[0048] <Example 5> In a four-necked flask equipped with a reflux condenser, nitrogen gas inlet tube, stirring rod, and thermometer, 15 parts by mass of 2-methyl-1,3-propanediol, 7.67 parts by mass of p-xylylene glycol, 8.22 parts by mass of dimethylolbutanoic acid, and 94.87 parts by mass of methyl ethyl ketone were charged and stirred at 40°C until dissolved. Then, 43.11 parts by mass of 1,3-hydrogenated xylylene diisocyanate and 20.88 parts by mass of 1,3-xylylene diisocyanate were added. 0.02 parts by mass of TBT was charged and reacted at 80°C for 5 hours under reflux. After cooling, a solution of 5.33 parts by mass of triethylamine dissolved in 240.8 parts by mass of water was charged and stirred at 20-30°C for 10 minutes. Then, 3.00 parts by mass of ethylenediamine was charged and reacted at 20-30°C for 30 minutes. After that, it was heated to 40°C under reduced pressure and stirred for 3 hours to degas and remove methyl ethyl ketone by distillation to obtain an aqueous gas barrier polyurethane resin (solid content 30%).

[0049] <Example 6> In a four-necked flask equipped with a reflux condenser, nitrogen gas inlet tube, stirring rod, and thermometer, 15 parts by mass of 2-methyl-1,3-propanediol, 2.42 parts by mass of p-xylylene glycol, 5.19 parts by mass of dimethylolbutanoic acid, and 73.17 parts by mass of methyl ethyl ketone were charged and stirred at 40°C until dissolved. Then, 34.03 parts by mass of 1,3-hydrogenated xylylene diisocyanate, 16.49 parts by mass of 1,3-xylylene diisocyanate, and 0.02 parts by mass of TBT were added. The mixture was charged, reacted at 80°C for 5 hours under reflux, cooled, and a solution of 3.77 parts by mass of triethylamine dissolved in 181.29 parts by mass of water was charged. The mixture was stirred at 20-30°C for 10 minutes. Then, 2.06 parts by mass of aminoethylethanolamine and 1.18 parts by mass of ethylenediamine were charged, and the mixture was reacted at 20-30°C for 30 minutes. After that, the mixture was heated to 40°C under reduced pressure for 3 hours, and the mixture was degassed and stirred to remove methyl ethyl ketone by distillation to obtain a water-based gas barrier polyurethane resin (solid content 30%).

[0050] <Comparative Example 1> In a four-necked flask equipped with a reflux condenser, nitrogen gas inlet tube, stirring rod, and thermometer, 15 parts by mass of neopentyl glycol and 43.61 parts by mass of methyl ethyl ketone were charged and stirred at 40°C until dissolved. Then, 22.38 parts by mass of 1,3-hydrogenated xylylene diisocyanate and 0.02 parts by mass of TBT were charged and reacted under reflux at 80°C for 5 hours. After cooling to 25°C, 43.61 parts by mass of isopropyl alcohol were charged to obtain a gas barrier polyurethane resin (solid content 30%).

[0051] <Comparative Example 2> In a four-necked flask equipped with a reflux condenser, nitrogen gas inlet tube, stirring rod, and thermometer, 15 parts by mass of neopentyl glycol, 16 parts by mass of cyclohexanedimethanol, and 86.46 parts by mass of methyl ethyl ketone were charged and stirred at 40°C until dissolved. Then, 43.11 parts by mass of 1,3-hydrogenated xylylene diisocyanate and 0.02 parts by mass of TBT were charged and reacted under reflux at 80°C for 5 hours. After cooling to 25°C, 86.46 parts by mass of isopropyl alcohol were charged to obtain a gas barrier polyurethane resin (solid content 30%).

[0052] <Comparative Example 3> In a four-necked flask equipped with a reflux condenser, nitrogen gas inlet tube, stirring rod, and thermometer, 15 parts by mass of 1,3-propanediol and 53.24 parts by mass of methyl ethyl ketone were charged and stirred at 40°C until dissolved. Then, 30.63 parts by mass of 1,3-hydrogenated xylylene diisocyanate and 0.02 parts by mass of TBT were charged and reacted under reflux at 80°C for 5 hours. After cooling to 25°C, 53.24 parts by mass of isopropyl alcohol were charged to obtain a gas barrier polyurethane resin (solid content 30%).

[0053] <Comparative Example 4> In a four-necked flask equipped with a reflux condenser, nitrogen gas inlet tube, stirring rod, and thermometer, 15 parts by mass of 2-methyl-1,3-propanediol and 47.68 parts by mass of methyl ethyl ketone were charged and stirred at 40°C until dissolved. Then, 25.86 parts by mass of 1,3-hydrogenated xylylene diisocyanate and 0.02 parts by mass of TBT were charged and reacted under reflux at 80°C for 5 hours. After cooling to 25°C, 47.68 parts by mass of isopropyl alcohol were charged to obtain a gas barrier polyurethane resin (solid content 30%).

[0054] <Comparative Example 5> In a four-necked flask equipped with a reflux condenser, nitrogen gas inlet tube, stirring rod, and thermometer, 15 parts by mass of 2-methyl-1,3-propanediol, 5.75 parts by mass of p-xylylene glycol, and 61.92 parts by mass of methyl ethyl ketone were charged and stirred at 40°C until dissolved. Then, 32.33 parts by mass of 1,3-hydrogenated xylylene diisocyanate and 0.02 parts by mass of TBT were charged and reacted under reflux at 80°C for 5 hours. After cooling to 25°C, 61.92 parts by mass of isopropyl alcohol were charged to obtain a gas barrier polyurethane resin (solid content 30%).

[0055] The following evaluations were performed using the gas barrier polyurethane resins obtained from each example and comparative example. The results are shown in Table 1.

[0056] <Substrate: Preparation of silica-deposited PET> A 0.1 μm thick adhesive layer was formed by coating one side surface of a PET film (E5100, 12 μm thick, manufactured by Toyobo Co., Ltd.) with a mixture of isocyanate compound ("Coronate L" manufactured by Nippon Polyurethane Industries Co., Ltd.) and saturated polyester ("Byron 300" manufactured by Toyobo Co., Ltd.) in a 1:1 mass ratio and drying. Then, using a vacuum deposition apparatus, 1 × 10⁻¹⁶ layers were deposited. -5 Silica was evaporated using a heating method under Torr vacuum to form a 20 nm thick silica deposition layer on the adhesive layer, thereby obtaining silica-deposited PET.

[0057] <Substrate: Fabrication of alumina-deposited PET> A 0.1 μm thick adhesive layer was formed by coating one side surface of a PET film (E5100, 12 μm thick, manufactured by Toyobo Co., Ltd.) with a mixture of isocyanate compound ("Coronate L" manufactured by Nippon Polyurethane Industries Co., Ltd.) and saturated polyester ("Byron 300" manufactured by Toyobo Co., Ltd.) in a 1:1 mass ratio and drying. Next, aluminum was evaporated using a vacuum deposition apparatus, and oxygen gas was supplied using a gas flow control device, resulting in a 1 × 10⁻¹⁶ layer. -4 A 20 nm thick alumina deposition layer was formed on the adhesive layer using Torr vapor deposition to obtain alumina-deposited PET.

[0058] <Fabrication of gas barrier laminates (1)> On the vapor-deposited surfaces of the silica-deposited PET and alumina-deposited PET described above, the gas barrier polyurethane resin compositions of each example and comparative example described above were diluted to a solid content of 10%, dried, and then applied at a rate of 0.3 g / m². 2 The material was spread using a Φ0.05 diatom bar and dried. For each of the resulting laminates, the following properties were evaluated: adhesion, solvent resistance, blocking resistance, and gas barrier properties (water vapor permeability).

[0059] <Evaluation of Adhesion> The adhesion of each resulting laminate was evaluated based on the ratio of the area where the ink film peeled off the substrate when cellophane tape was applied to the coated surface and the tape was removed, according to the following evaluation criteria. An A or B is acceptable, with A being preferred. A: It doesn't peel off at all. B: The area that peels off is less than 20%. C: The peeling area is 20% or more.

[0060] <Evaluation of Blocking Resistance> The coated surface of each laminate and each base material were overlapped, and a load of 3 kg / cm 2 was applied, and they were left at a temperature of 40 °C for 1 day. Then, the ink surface and the film surface were peeled, and the transfer of the ink film to the film surface was evaluated according to the following evaluation criteria. It may be A or B, and A is preferred. A: It peels off without resistance and there is no transfer of the ink film at all. B: There is resistance, but there is no transfer of the ink film at all. C: Transfer of less than 50% of the ink film is observed. D: Transfer of 50 - 100% of the ink film is observed.

[0061] <Evaluation of Solvent Resistance> A cotton swab impregnated with ethyl acetate was applied to the coated surface of each laminate, and the coated surface was evaluated visually according to the following evaluation criteria. A: It does not dissolve. B: It dissolves when rubbed strongly. C: It partially dissolves by friction due to the weight of the cotton swab. D: It dissolves.

[0062] <Evaluation of Gas Barrier Property (Water Vapor Transmission Rate)> After each laminate was left in an atmosphere of 40 °C and 90% RH for 72 hours, according to JIS K7129B method, using a water vapor transmission rate measuring device (manufactured by Mocon, product name: PERMATRAN - 3 / 34G), the water vapor transmission rate (WVTR value) (g / m 2 ·day·atm) was measured. The measurement of the water vapor transmission rate (WVTR value) was carried out in an atmosphere of 40 °C and 90% RH.

[0063] <Production of Gas Barrier Laminate (2)> On the vapor-deposited surfaces of the silica-deposited PET and alumina-deposited PET described above, Shin-Etsu Chemical's silane coupling agent "KBM-403" was added to the gas barrier polyurethane resin composition of each example and comparative example, so that the solid content ratio was gas barrier polyurethane resin composition / silane coupling agent = 95 / 5. The mixture was then diluted to a solid content of 10%, dried, and applied at a rate of 0.3 g / m². 2 The surface was spread using a Φ0.05 diaphragm bar and dried. Next, an adhesive (Takelac A-515 / Takenate A-50 (manufactured by Mitsui Chemicals, Inc.), 30% solids) was applied to the coated surface using a Φ0.15 diaphragm bar, and an unstretched polypropylene film (RXC-22, 60 μm thick, manufactured by Mitsui Chemicals Tohcello Co., Ltd.) was bonded to it. The laminates were left at 40°C for 3 days to obtain each laminate. The peel strength of each laminate was measured.

[0064] <Evaluation of Peel Strength> Each laminate was cut into 15mm widths after 1 day at 40°C, and the T-type peel strength (N / 15mm) was measured as the dry laminate strength using a peel tester (manufactured by Yasuda Seiki Seisakusho Co., Ltd.). A value of 3.0 (N / 15mm) or higher was considered acceptable.

[0065] [Table 1]

Claims

1. It contains a polyol composition, a polyhydroxy acid, and a gas barrier polyurethane resin which is a reaction product of a polyisocyanate compound. The polyol composition contains a diol compound having 2 to 6 carbon atoms and a diol compound having 7 to 10 carbon atoms. The aforementioned diol compounds having 7 to 10 carbon atoms are diol compounds having a cyclic structure. The diol compound having 2 to 6 carbon atoms contains at least 20% by mass of 2-methyl-1,3-propanediol. The aforementioned polyhydroxy acid has the general formula (1): 【Chemistry 1】 (In general formula (1), R １ (represented by ) is a compound that has a linear or branched alkyl group having a hydrogen atom or 1 to 8 carbon atoms. The gas barrier polyurethane resin composition is characterized in that the polyisocyanate compound contains xylylene diisocyanate and / or hydrogenated xylylene diisocyanate.

2. The gas barrier polyurethane resin composition according to claim 1, characterized in that the diol compound having a cyclic structure is one or more selected from the group consisting of cyclohexanedimethanol, xylylene glycol, and adamantanediol.

3. A gas barrier polyurethane resin composition according to claim 1 or 2, characterized by containing an organic solvent or an aqueous medium.

4. A gas barrier laminate characterized in that the gas barrier polyurethane resin composition described in claim 1 or 2 is applied to a substrate.

5. A gas barrier laminate characterized in that the gas barrier polyurethane resin composition described in Claim 3 is applied to a substrate.

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