JP4434907B2 - Aqueous polyurethane resin composition and laminated film - Google Patents

Description

  The present invention relates to an aqueous polyurethane resin composition (or a coating composition or an aqueous resin composition for a coating agent) excellent in gas barrier properties and adhesion to a substrate such as plastic, and this composition is coated or laminated on a substrate. The present invention relates to a coating film (or laminated film).

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

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

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

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

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

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

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

Japanese Patent Application Laid-Open No. 2001-98047 (Patent Document 8) discloses a gas barrier polyurethane resin obtained by reaction of a diisocyanate component and a C _2-8 alkylene glycol, wherein the total concentration of urethane groups and urea groups is 15% by weight or more. Is disclosed. In this document, a dihydroxycarboxylic acid such as dimethylolpropionic acid is reacted with an alkylene glycol, the resulting prepolymer is neutralized with an amine, chain extended with a chain extender such as diamine or hydrazine, and an aqueous dispersion is prepared. Obtaining is also described. When the urethane resin described in this document is used, the gas barrier property can be improved. However, the urethane resin is required to have higher gas barrier properties and adhesion to the substrate. In particular, from the viewpoint of safety and hygiene, there is a demand for higher gas barrier properties as well as solvent resistance and water resistance in view of safety and hygiene, etc.
JP-A-4-345841 (Claims) Japanese Patent Application Laid-Open No. 1-252631 (claims, column of effect of invention) Japanese Patent Laid-Open No. 10-140072 (claims, column of effect of invention) Japanese Examined Patent Publication No. 53-12953 (Claims) Japanese Patent Laid-Open No. 62-179935 (Claims) JP-A-6-220221 (Claims) Japanese Patent No. 3275432 (Claims) JP 2001-98047 A (claims, paragraph numbers [0035] to [0039], [0076] to [0079])

  Accordingly, an object of the present invention is to provide an aqueous polyurethane resin composition having excellent gas barrier properties against oxygen, water vapor, aroma components, and the like, and a laminated film (or laminate) containing the resin composition.

  Another object of the present invention is to provide an aqueous polyurethane resin composition having a high gas barrier property even under high humidity as well as solvent resistance and water resistance, and a laminated film using the composition.

  Still another object of the present invention is that there is no fear of environmental pollution, and it is suitable for processing as a packaging material such as solvent resistance, water resistance, coating workability, adhesion to a substrate film, and adhesion to a printing ink. It is in providing the outstanding resin composition and the laminated | multilayer film (or laminated body) using this resin composition.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors constituted a polyurethane resin having a specific urethane group and urea group concentration and an acid value, and a polyamine compound to constitute an aqueous polyurethane resin composition. The inventors have found that a film material having a high gas barrier property can be obtained without fear of environmental pollution, and has completed the present invention.

That is, the aqueous polyurethane resin composition of the present invention comprises (i) a polyurethane resin having a total concentration of urethane groups and urea groups of 15% by weight or more (for example, 25 to 60% by weight) and having acid groups; ii) a polyamine compound. As the polyurethane resin (i), (A) a polyisocyanate compound, (B) polyhydroxy acids, and a polyol component comprising _{(C) C 2-6} alkylene glycol 90 wt% or more, (D) a chain extender An aqueous polyurethane resin obtained by reaction with the components and neutralized with a neutralizing agent is used. Polyamine compounds (ii) include alkylene diamines, hydroxyl group-containing diamines, polyalkylene polyamines, N-alkyl substituted alkylene diamines, N-alkyl substituted polyalkylene polyamines, alicyclic polyamines, aromatic polyamines. In addition, at least one selected from adducts obtained by adding alkylene oxide to these polyamine compounds, and urethane-modified polyamine compounds are used. The polyisocyanate compound (A) may contain at least one selected from the group of aromatic, araliphatic and alicyclic polyisocyanates (for example, aromatic, araliphatic and alicyclic polyisocyanates). 30% by weight or more of at least one selected from the group may be included). (B) As a polyhydroxy acid, at least 1 type of organic acid selected from the group of polyhydroxycarboxylic acid and polyhydroxysulfonic acid can be used, for example . Before SL (A) the polyisocyanate compound, xylylene diisocyanate and hydrogenated xylylene least one kind consists polyisocyanate selected from isocyanates (for example, at least one member selected from xylylene diisocyanate and hydrogenated xylylene diisocyanate Polyisocyanate contained in a proportion of 20% by weight or more). The chain extender may be at least one selected from, for example, diamine, water, hydrazine, and hydrazine derivatives. Such polyurethane resin (i) may be an aqueous dispersion dispersed in water or an aqueous solution dissolved in water.

  The amine value of the polyamine compound (ii) may be about 100 to 1900 mg KOH / g, and the ratio of the polyurethane resin (i) to the polyamine compound (ii) is determined based on acid groups and basic nitrogen atoms (or amino groups). Can be selected from the range of about 10/1 to 1/10.

  The polyamine compound (ii) can be bonded to the acid group of the polyurethane resin (i). That is, a laminate that is highly cross-linked by ion-bonding an acid group of a polyurethane resin containing a high concentration of urethane groups and urea groups and an amino group of a polyamine compound, and has excellent gas barrier properties against oxygen, water vapor, or aroma components. Useful to form the body.

  Further, the neutralizing agent and the polyamine compound can be used in various combinations, but the neutralizing agent is composed of a volatile base selected from ammonia and amines and has a stronger basicity than the neutralizing agent. When the compound (ii) is used, liberation or volatilization of the neutralizing agent can be promoted, and crosslinking of the polyurethane resin by the polyamine compound (ii) can be promoted.

  The present invention provides a laminated film (or laminated) in which a coating layer composed of the polyurethane resin composition is laminated on at least one surface of a base film in addition to the aqueous resin for a coating agent composed of the polyurethane resin composition. Body).

In the present specification, for the polyamine compound (ii), the nitrogen atom of the amino group (—NH ₂ ), the nitrogen atom of the imino group (> NH) and the tertiary nitrogen atom (≡N) are simply converted to a basic nitrogen atom. May be collectively referred to. Moreover, it may be simply referred to as “bond” including ionic bond (or bond by salt formation reaction) and covalent bond (covalent bond by amide bond formation reaction, imide bond formation reaction, etc.).

  In the present invention, since the concentration of urethane groups and urea groups is high and a polyurethane resin having an acid group is combined with a polyamine compound, even an aqueous polyurethane resin composition has high gas barrier properties (oxygen, water vapor, fragrance). Gas barrier property against components) can be realized. Further, by utilizing the crosslinking of the polyurethane resin with a polyamine compound, it is possible to obtain a high gas barrier property even under high humidity as well as solvent resistance and water resistance. Furthermore, since it is an aqueous composition, there is no risk of environmental contamination, and it is suitable for processing as a packaging material, such as solvent resistance, water resistance, coating workability, adhesion to a substrate film, and adhesion to a printing ink. Are better.

  The aqueous polyurethane resin composition of the present invention constitutes an anionic self-emulsifying polyurethane resin, and (i) a polyurethane resin having a high total concentration of urethane groups and urea groups and having an acid group (or an aqueous polyurethane resin) And (ii) a polyamine compound.

[Polyurethane resin]
The total concentration of urethane groups and urea groups (urea groups) in the polyurethane resin is 15% by weight or more (for example, 20 to 60% by weight), preferably 25 to 60% by weight (for example, 30 to 55) from the viewpoint of gas barrier properties. % By weight), more preferably about 35 to 55% by weight (particularly 35 to 50% by weight). The urethane group concentration and the urea group concentration are the molecular weight of the urethane group (59 g / equivalent) or the molecular weight of the urea group (primary amino group (amino group): 58 g / equivalent, secondary amino group (imino group): 57 g / Equivalent) is a value obtained by dividing the molecular weight of the repeating structural unit structure. In the case of using a mixture, the concentration of the urethane group and urea group can be calculated based on the charge base of the reaction components, that is, the use ratio of each component.

  Examples of the acid group of the polyurethane resin (anionic self-emulsifying polyurethane resin) include a carboxyl group and a sulfonic acid group. The acid group may be located at the terminal or side chain (particularly at least the side chain) of the polyurethane resin. This acid group is usually neutralizable with a neutralizing agent (base) and may form a salt with the base. The acid group can be bonded to the amino group (imino group or tertiary nitrogen atom) of the polyamine compound (ii).

  The acid value of the polyurethane resin can be selected within a range where water solubility or water dispersibility can be imparted, and is usually 5 to 100 mgKOH / g, preferably 10 to 70 mgKOH / g (for example, 10 to 60 mgKOH / g), and more preferably 15 It is about -60 mgKOH / g (for example, 16-50 mgKOH / g).

  Polyurethane resins usually have at least rigid units (units composed of hydrocarbon rings) and short chain units (for example, units composed of hydrocarbon chains). That is, the repeating structural unit of the polyurethane resin is usually derived from a polyisocyanate component, a polyhydroxy acid component, a polyol component or a chain extender component (especially at least a polyisocyanate component), and a hydrocarbon ring (aromatic and / or Non-aromatic hydrocarbon ring). The proportion of the hydrocarbon ring unit in the repeating unit of the polyurethane resin is about 10 to 70% by weight, preferably about 15 to 65% by weight, and more preferably about 20 to 60% by weight.

  The number average molecular weight of the polyurethane resin can be selected from the range of about 800 to 1,000,000, preferably 800 to 200,000, more preferably about 800 to 100,000.

  The polyurethane resin may be crystalline in order to enhance gas barrier properties. The glass transition point of the polyurethane resin is 100 ° C. or higher (for example, about 100 to 200 ° C.), preferably 110 ° C. or higher (for example, about 110 to 180 ° C.), more preferably 120 ° C. or higher (for example, 120 to 150). Degrees Celsius).

The polyurethane resin has a high gas barrier property, and the oxygen permeability (unit: ml / m ² · atm · day, temperature 20 ° C. and humidity 80% RH) of the polyurethane resin is, for example, 200 or less (for example, 10 to 200) at a thickness of 5 μm. ), Preferably 120 or less (for example, 20 to 100), and may be about 10 to 80.

  In the present invention, the humidity dependency is small even though it is an aqueous polyurethane resin, and the ratio of oxygen permeability at 50% RH and oxygen permeability at 80% RH is the former / the latter = 1/1 to 1/3, Preferably it is 1/1 to 1 / 2.5, more preferably about 1/1 to 1/2. Therefore, it is not significantly affected by humidity and exhibits excellent gas barrier properties even under high humidity.

  Such a polyurethane resin (i) can be obtained by a reaction of at least (A) a polyisocyanate compound (particularly a diisocyanate compound) and (B) a polyhydroxy acid (for example, polyhydroxyalkanoic acid, particularly dihydroxy acid). In addition to the components (A) and (B), the polyurethane resin (i) comprises (C) a polyol component (particularly a diol component such as alkylene glycol) and (D) a chain extender (particularly a bifunctional chain extender). It can also be obtained by reaction with at least one component selected from

(A) Polyisocyanate compound The polyisocyanate compound includes aromatic polyisocyanate, araliphatic polyisocyanate, alicyclic polyisocyanate, aliphatic polyisocyanate and the like. As the polyisocyanate compound, a diisocyanate compound is usually used.

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

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

  Examples of the alicyclic diisocyanate include 1,3-cyclopentene diisocyanate, cyclohexane diisocyanate (1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate), 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (iso Holodiisocyanate, IPDI), methylene bis (cyclohexyl isocyanate) (4,4'-, 2,4'- or 2,2'-methylene bis (cyclohexyl isocyanate)) (hydrogenated MDI), methylcyclohexane diisocyanate (methyl-2,4) Cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate), bis (isocyanatomethyl) cyclohexane (1,3- or 1,4-bis (iso Anetomechiru) cyclohexane or mixtures thereof) (hydrogenated XDI) and the like.

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

  As the polyisocyanate compound (particularly diisocyanate compound) (A), it is preferable to use a polyisocyanate compound containing a compound having a hydrocarbon ring. Examples of such compounds include aromatic, araliphatic and alicyclic polyisocyanates (particularly diisocyanates). More specifically, among the diisocyanate components, the aromatic diisocyanate is preferably TDI, MDI, NDI, the araliphatic diisocyanate is preferably XDI, TMXDI, and the alicyclic diisocyanate is IPDI, hydrogenated. XDI, hydrogenated MDI and the like are preferable. From the viewpoint of gas barrier properties, aromatic diisocyanates (TDI, MDI, NDI, etc.), araliphatic diisocyanates (XDI, TMXDI, etc.) and alicyclic diisocyanates (IPDI, hydrogenated XDI, hydrogenated MDI, etc.) are preferred. MDI, XDI, hydrogenated XDI and the like are preferable. These polyisocyanate compounds can be used alone or in combination of two or more.

  The content of at least one polyisocyanate compound selected from aromatic, araliphatic and alicyclic polyisocyanates is 30% by weight or more (30 to 100% by weight, preferably based on the whole polyisocyanate compound (A). Is 50 to 100% by weight, more preferably 70 to 100% by weight.

  In particular, the polyisocyanate compound preferably contains at least one selected from xylylene diisocyanate and hydrogenated xylylene diisocyanate. The proportion of xylylene diisocyanate and / or hydrogenated xylylene diisocyanate can usually be selected from the range of 10 wt% or more (10 to 100 wt%) with respect to the whole polyisocyanate compound (A), and usually 20 wt% or more. (20 to 100% by weight, preferably 25 to 100% by weight, more preferably 30 to 100% by weight).

  These diisocyanate components can be used singly or in combination of two or more, and a tri- or higher functional polyisocyanate can be used in combination as required.

(B) Polyhydroxy acid As the polyhydroxy acid, carboxylic acid or sulfonic acid, in particular, at least one organic acid selected from polyhydroxycarboxylic acid and polyhydroxysulfonic acid can be used.

Examples of the polyhydroxycarboxylic acid (particularly dihydroxycarboxylic acid) include dihydroxy C _2-10 alkane-carboxylic acid such as dimethylolpropionic acid, dimethylolbutanoic acid, 2,2-dimethylolhexanoic acid, and dihydroxymaleic acid. Examples thereof include C _4-10 alkane-polycarboxylic acid or dihydroxy C _4-10 alkene-polycarboxylic acid, and dihydroxy C _6-10 arene-carboxylic acid such as 2,6-dihydroxybenzoic acid. These polyhydroxy acids can be used alone or in combination of two or more. Preferred polyhydroxy acids are polyhydroxyalkane carboxylic acids, especially dihydroxy alkanoic acids such as dihydroxy C _2-8 alkane-carboxylic acids.

Examples of polyhydroxysulfonic acid (particularly dihydroxysulfonic acid) include dihydroxy C _2-10 alkanesulfonic acid such as dihydroxybutane-2-sulfonic acid, and dihydroxy aromatic sulfonic acid such as 3,5-dihydroxybenzenesulfonic acid. . These polyhydroxysulfonic acids can also be used alone or in combination of two or more.

  The polyhydroxy acid may be used in the form of a salt. Examples of polyhydroxy acid salts include ammonium salts, amine salts (such as trialkylamine salts), metal salts (such as sodium salts), and the like.

  The polyurethane resin (i) can be obtained by reaction with at least the component (A) and the component (B). In addition, the acid value of polyurethane resin (i) can be adjusted with the usage-amount of the said polyhydroxy acid (B). Therefore, in the reaction with the polyisocyanate compound, the polyhydroxy acid may be used in a proportion of 100 mol% based on the total of the polyol component and the chain extender component, but is combined with the polyol component and / or the chain extender component. Often used. The amount of polyhydroxy acid used is usually about 1 to 70 mol%, preferably about 2 to 50 mol% (for example, 5 to 50 mol%), based on the total amount of polyhydroxy acid, polyol component and chain extender component. You can choose from a range of

(C) Polyol component As the polyol component (particularly the diol component), a low molecular weight glycol to an oligomer can be used, but from the viewpoint of gas barrier properties, usually an alkylene glycol (for example, ethylene glycol, propylene glycol, trimethylene glycol). , 1,3-butanediol, 1,4-butanediol, pentanediol, hexanediol, neopentylglycol, heptanediol, octanediol, and other linear or branched C _2-10 alkylene glycol), (poly) Low molecular weight glycols such as oxy C _2-4 alkylene glycol (diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, etc.) are used. The preferred glycol component is a C _2-8 polyol component [eg, C _2-6 alkylene glycol (particularly ethylene glycol, 1,2- or 1,3-propylene glycol, 1,4-butanediol, 1,6-hexane). Diol, 3-methyl-1,5-pentanediol, etc.], di- or trioxy C _2-3 alkylene glycol (diethylene glycol, triethylene glycol, dipropylene glycol, etc.), and particularly preferred diol components are C _2-8 alkylene. Glycol (especially C _2-6 alkylene glycol).

  These diol components can be used alone or in combination of two or more. Further, if necessary, aromatic diol (for example, bisphenol A, bishydroxyethyl terephthalate, catechol, resorcin, hydroquinone, 1,3- or 1,4-xylylene diol or a mixture thereof), alicyclic diol (for example, Low molecular weight diol components such as hydrogenated bisphenol A, hydrogenated xylylene diol, cyclohexanediol, cyclohexanedimethanol, etc.). Furthermore, if necessary, a tri- or higher functional polyol component, for example, a polyol component such as glycerin, trimethylolethane, or trimethylolpropane can be used in combination.

The polyol component preferably contains at least a C _2-8 polyol component [particularly C _2-6 alkylene glycol]. The ratio of the C _2-8 polyol component [particularly, C _2-6 alkylene glycol] to the entire polyol component can be selected from the range of about 50 to 100% by weight, and usually 70% by weight or more (70 to 100% by weight), Preferably it is 80 weight% or more (80-100 weight%), More preferably, it is 90 weight% or more (90-100 weight%).

(D) Chain extender As the chain extender, at least one selected from the group of polyamine, water, hydrazine and hydrazine derivatives can be used, and usually nitrogen-containing compounds having an active hydrogen atom, particularly diamines, hydrazines and hydrazines. At least one selected from derivatives is used.

Examples of the diamine component as a chain extender include aliphatic amines (for example, ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4 , 4-trimethylhexamethylenediamine, _C2-10 alkylenediamine such as octamethylenediamine, etc.), aromatic amines (for example, m- or p-phenylenediamine, 1,3- or 1,4-xylylenediamine or its) Mixtures), alicyclic amines (such as hydrogenated xylylenediamine, bis (4-aminocyclohexyl) methane, isophoronediamine, bis (4-amino-3-methylcyclohexyl) methane), hydroxyl group-containing diamines (2 -[(2-aminoethyl ) Amino] ethanol, 2-aminoethylamino propanol, 3-aminopropyl and an amino C _2-6 alkylamino C _2-3 alkyl alcohols, such as aminoethanol), acid group-containing diamine (e.g., 3,4-diaminobenzoic acid Diamino aromatic carboxylic acid such as 1,3-phenylenediamine-4,6-disulfonic acid, diaminosulfonic acid such as 2,4-diaminotoluene-5-sulfonic acid, etc.).

Examples of hydrazine and hydrazine derivatives include hydrazine, hydroxyl group-containing hydrazine (such as hydrazino C _2-3 alkyl alcohol such as _2- hydrazinoethanol), dicarboxylic acid hydrazide [aliphatic dicarboxylic acid hydrazide (succinic acid dihydrazide, adipic acid dihydrazide, glutar C _4-20 alkane-dicarboxylic acid dihydrazide such as acid dihydrazide, dodecanedioic acid dihydrazide), aromatic dicarboxylic acid hydrazide (isophthalic acid dihydrazide, phthalic acid dihydrazide, naphthalenedicarboxylic acid dihydrazide, etc.) C _6-10 arene dicarboxylic acid hydrazide, etc. ) Etc.]. These chain extender components can be used alone or in combination of two or more.

Among these chain extenders, from the viewpoint of gas barrier properties, usually a low molecular weight chain extender having 8 or less carbon atoms (C _2-8 , especially C _2-6 ), for example, diamine (for example, ethylenediamine, tetramethylenediamine). , pentamethylenediamine, C _2-6 alkylenediamine, such as hexamethylenediamine, 2-amino-ethylamino ethanol, xylylenediamine), hydrazine, hydrazine derivatives (e.g., 2-hydrazino ethanol, adipic acid dihydrazide) is used Is done. In addition, the chain extender can use triamine or more polyamine components (polyamine, polyhydrazide, etc.) together as needed.

If necessary, in the preparation of a polyurethane resin, a compound having a reactive group with respect to an isocyanate group, such as an acid anhydride (for example, maleic anhydride, phthalic anhydride, succinic anhydride, trimellitic anhydride, Obtained by the reaction of a compound having a reactive group with respect to an isocyanate group (dihydroxy compound such as diol, diamine, etc.) or a compound having a carboxyl group, or a compound having these carboxyl groups. Oligoester polyols; oxysulfonic acid (for example, 2-oxyethanesulfonic acid, phenolsulfonic acid, etc.), sulfocarboxylic acid (for example, sulfobenzoic acid, sulfosuccinic acid, 5-sulfoisophthalic acid, etc.), amino group-containing sulfonic acid (For example, sulfanilic acid Etc.) compound having a sulfonic acid group, such as, or a compound oligoester polyols obtained by copolymerizing with these sulfonic acid groups; polyoxy C _2-4 alkylene compound containing a reactive group to isocyanate group (e.g., ethylene oxide A compound containing 30% by weight or more of a unit and having a number average molecular weight of about 300 to 10,000) or an oligoester ether polyol obtained by copolymerizing these polyoxyalkylene compounds may be used.

In order to prepare an aqueous solution in which the polyurethane resin (i) is dissolved in water or an aqueous dispersion in which the polyurethane resin (i) is dispersed in water, the acid groups of the polyurethane resin (i) are neutralized with a neutralizing agent or a base. ing. Neutralizing agents include conventional bases such as organic bases [eg tertiary amines (tri-C _1-4 alkylamines such as trimethylamine and triethylamine, dimethylethanolamine, methyldiethanolamine, triethanolamine, triisopropanolamine]. Alkanolamines, heterocyclic amines such as morpholine)], inorganic bases [ammonia, alkali metal hydroxides (lithium hydroxide, sodium hydroxide, potassium hydroxide, etc.), alkaline earth metal hydroxides (water) Magnesium oxide, 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.

In particular, from the viewpoint of gas barrier properties, volatile bases such as tri-C _1-3 alkylamines such as triethylamine, alkanolamines such as dimethylethanolamine, and ammonia are preferable. When a volatile base (such as a base selected from ammonia and amines) is used as a neutralizing agent, crosslinking of the polyurethane resin (i) can be promoted by the polyamine compound (ii), which is useful for improving gas barrier properties. .

  The degree of neutralization with the neutralizing agent may be, for example, 30 to 100%, preferably 50 to 100%, particularly about 75 to 100%.

  The aqueous polyurethane resin composition is usually composed of the polyurethane resin, a neutralizing agent, and an aqueous medium. Examples of the aqueous medium include water, water-soluble or hydrophilic solvents (for example, alcohols such as ethanol and isopropanol; Examples thereof include ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; cellosolves; carbitols; nitriles such as acetonitrile), or a mixed solvent thereof. The aqueous medium is usually water or an aqueous solvent containing water as a main component.

  The polyurethane resin may be in any form of an aqueous solution dissolved in an aqueous medium or an aqueous dispersion dispersed in an aqueous medium. In the aqueous dispersion, the particle diameter of the dispersed particles (polyurethane resin particles) is not particularly limited, and may be, for example, an average particle diameter of 20 to 500 nm, preferably 25 to 300 nm, more preferably about 30 to 200 nm.

  The production method of the polyurethane resin or the composition thereof is not particularly limited, and the polyurethane resin can be prepared by using a usual polyurethane water-based technology such as an acetone method or a prepolymer method. In the urethanization reaction, a urethanization catalyst such as an amine catalyst, a tin catalyst, or a lead catalyst may be used as necessary. For example, in an inert solvent (a ketone such as acetone, an ether such as tetrahydrofuran, a nitrile such as acetonitrile, etc.), a polyisocyanate compound (A) and a polyhydroxy acid (B) and, if necessary, a polyol component (C) and / or Alternatively, the polyurethane resin can be prepared by reacting with the chain extender component (D). More specifically, a polyisocyanate compound (A), a polyhydroxy acid (B), and a polyol component (C) are reacted in an inert organic solvent (particularly, a hydrophilic or water-soluble organic solvent) to form a terminal isocyanate group. The aqueous polyurethane resin is produced by adding a chain extender component (D) and reacting it by removing the organic solvent after neutralizing with a neutralizer and dissolving or dispersing in an aqueous medium. Can be prepared.

  The ratio between the polyisocyanate compound (A) and the total amount of each component having an active hydrogen atom [polyhydroxy acid (B), polyol component (C) and chain extender component (D)] is gas barrier and aqueous. The total amount of active hydrogen atoms (or organic groups having active hydrogen atoms) of each component (B), (C) and (D) with respect to 1 mole of isocyanate group of the polyisocyanate compound It is about 0.5 to 1.5 mol, preferably 0.7 to 1.3 mol, more preferably about 0.8 to 1.2 mol. Moreover, the ratio (molar ratio) of the hydroxyl group of the polyhydroxy acid (B) and the hydroxyl group of the polyol component (C) among the compounds (B), (C) and (D) having an active hydrogen atom is the former. / The latter = 100/0 to 5/95, preferably 80/20 to 5/95, more preferably about 60/40 to 10/90. The ratio (molar ratio) between the total hydroxyl groups of the polyhydroxy acid (B) and the polyol component (C) and the active hydrogen atoms (particularly amino groups) of the chain extender component (D) is the former / the latter = 100/0 to 10 / 90, preferably 100/0 to 25/75, more preferably about 95/5 to 40/60.

[Crosslinking agent]
In the present invention, a high gas barrier property is exhibited by bonding with an acid group of a polyurethane resin by a polyamine compound as a crosslinking agent. The bond between the polyamine compound and the acid group of the polyurethane resin may be an ionic bond (for example, an ionic bond between a tertiary amino group and a carboxyl group) or a covalent bond (for example, an amide bond). May be. Therefore, as the polyamine compound, various polyamines having a plurality of basic nitrogen atoms selected from a primary amino group, a secondary amino group, and a tertiary amino group can be used.

  As the polyamine compound, various compounds can be used as long as they can bind to an acid group and improve the gas barrier property, and usually have an amine value of 100 to 1900 mgKOH / g, preferably 150 to 1900 mgKOH / g (for example, 200 to 1700 mgKOH / g). More preferably, a polyamine of about 200 to 1900 mgKOH / g (for example, 300 to 1500 mgKOH / g) can be used, and the amine value may be about 300 to 1900 mgKOH / g.

Polyamine compounds include alkylenediamines (ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, 1,4-butanediamine, 1,6-hexamethylenediamine, 2,5-dimethylhexamethylenediamine, trimethyl C _2-10 alkylene diamine such as hexamethylene diamine), hydroxyl group-containing diamine (amino C _2-6 alkyl amino C _2-3 alkyl alcohol etc. exemplified in the above-mentioned chain extender section), polyalkylene polyamines (diethylene triamine) , Di-tetraalkylene polyamines such as triethylenetetramine), N-alkyl substituted alkylenediamines (N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethyl-1) , 3-propylenediamine, N, N, ', N'-tetramethyl-1,6-hexanediamine, N, N-dimethyl-1,2-ethylenediamine, N, N-dimethyl-1,3-propanediamine, etc.), N-alkyl-substituted polyalkylene polyamines Aliphatic polyamines such as isophorone diamine, mensen diamine, hydrogenated metaxylylene diamine, N-aminoethylpiperazine, diaminodicyclohexylmethane, bis (aminomethyl) cyclohexane, 3,9-bis (3-aminopropyl) ) Alicyclic polyamines such as -2,4,8,10-tetraoxaspiro [5.5] undecane; aromatic polyamines such as diaminobenzene, xylylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone; these polyamine compounds Alkylene oxide (ethylene Adducts oxide EO and propylene oxide PO C _2-4 alkylene oxide) are added adduct such as (alkylene oxide of about 1 to 6 moles added, for example, ethylenediamine EO4 mol adduct, xylylenediamine EO4 mole adduct Etc.).

In addition, as the polyamine compound (iii), a silicon compound (such as a silane coupling agent) having a plurality of basic nitrogen atoms (including nitrogen atoms such as amino groups), such as 2- [N- (2-aminoethyl), is used. ) Amino] ethyltrimethoxysilane, 3- [N- (2-aminoethyl) amino] propyltriethoxysilane and the like [(2-aminoC _2-4 alkyl) amino C _1-4 alkyl] tri C _1-2 Alkoxysilanes, [(amino C _2-4 alkyl) amino C _2-4 alkyl] C _1-4 alkyldiC _1-2 alkoxysilanes corresponding to these trialkoxysilanes, and the like can also be used.

Furthermore, as a polyamine compound, it can be used also as a modified polyamine compound, for example, a urethane-modified polyamine compound. The urethane-modified polyamine compound includes a polyisocyanate compound (for example, a diisocyanate such as hexamethylene diisocyanate or a modified product thereof) and an alcoholic polyamine (a hydroxyl group-containing tertiary amine such as dimethylethanolamine or dimethylpropanolamine (particularly a dialkyl C _{2). -4} alkanolamine)) and the like. In the preparation of the urethane-modified polyamine compound, not only the polyisocyanate compound (A) exemplified above but also a modified product of the polyisocyanate compound (A) (dimer, trimer, allophanate, biuret, etc.) Can be used.

  Furthermore, oligomers or polymer compounds such as polyethyleneimine, polyallylamine, and polyvinylamine can also be used.

These polyamine compounds can be used alone or in combination of two or more. Among these polyamine compounds, short-chain aliphatic polyamines (polyamines such as C _2-8 alkylene diamine, amino C _2-4 alkylamino C _2-3 alkyl alcohol, di- or tri-C _2-3 alkylene polyamine, these Of polyamines in which a methyl group is substituted on the nitrogen atom, or di- or tri-C _2-3 alkylene polyamines), monocyclic polyamines (diamines such as diaminobenzene and xylylenediamine), and C in these polyamine compounds. Adducts added with 1 to 4 moles of _2-3 alkylene oxide, silicon compounds having a plurality of basic nitrogen atoms (such as silane coupling agents), and urethane-modified polyamine compounds are preferred.

  Furthermore, among these polyamine compounds, preferred compounds are soluble or dispersible in an aqueous solvent, and are particularly water-soluble or water-dispersible. Furthermore, a polyamine having a higher basicity than the neutralizing agent is preferable. In particular, when the neutralizing agent is the volatile base (ammonia or amines), if a strongly basic polyamine is used, the neutralizing agent that neutralizes the acid group of the polyurethane resin (i) is liberated, and the polyurethane resin The bond between the acid group (i) and the polyamine can be easily realized.

  The ratio of the polyurethane resin (i) and the polyamine compound (ii) is not particularly limited as long as the gas barrier property can be improved. As an equivalent ratio of an acid group and a basic nitrogen atom (nitrogen atom such as an amino group), for example, 10/1 to 0.1 / 1, preferably 5/1 to 0.2 / 1, more preferably about 3/1 to 0.3 / 1 (for example, 2/1 to 0.5 / 1). May be.

  The water-based polyurethane resin composition may contain various additives as long as the gas barrier properties are not impaired. Additives include silane coupling agents, reactive curing agents (water-dispersible (water-soluble) polyisocyanates, water-dispersible (water-soluble) carbodiimides, water-soluble epoxy compounds, water-dispersible (water-soluble) oxazolidone compounds, water-soluble And aziridine-based compounds), stabilizers (antioxidants, heat stabilizers, ultraviolet absorbers, etc.), plasticizers, antistatic agents, lubricants, antiblocking agents, colorants, fillers, crystal nucleating agents and the like.

Examples of silane coupling agents include hydrolyzable alkoxysilane compounds such as halogen-containing alkoxysilanes (chlorotri-C _1-2 alkoxysilanes such as chlorotriethoxysilane, 2-chloroethyltriethoxysilane, and 3-chloropropyltrimethoxysilane. such as chloro C _2-4 alkyl tri C _1-2 alkoxysilane), such as an epoxy group-containing alkoxysilane [2- glycidyloxy triethoxysilane, 3-glycidyloxypropyl glycidyloxy C _2-4 alkyl, such as trimethoxysilane Tri-C _1-2 alkoxysilanes, glycidyloxydi C _2-4 alkyldi-C _1-2 alkoxysilanes corresponding to these trialkoxysilanes, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3 , 4-Epoxycyclohexane Xyl) ethyltriethoxysilane, 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane and other (epoxycycloalkyl) C _2-4 alkyltri C _1-2 alkoxysilanes, etc.], amino group-containing alkoxysilanes [2 - aminoethyl trimethoxysilane, amino C _2-4 alkyl tri C _1-2 alkoxysilane such as 3-aminopropyltriethoxysilane, amino C _2-4 alkyl C _2-4 alkyl di C corresponding to these trialkoxysilanes _1-2 alkoxysilanes, mercapto group-containing alkoxysilanes (mercapto C _2-4 alkyltri-C _1-2 alkoxysilanes such as 2-mercaptoethyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, etc., corresponding to these trialkoxysilanes Merukaputoji C _2-4 alkyl C _1-4 alkyl to Di etc. C _1-2 alkoxysilane), alkoxysilane having a vinyl group or ethylenically unsaturated bond group (vinyltrimethoxysilane, vinyl tri C _1-2 alkoxysilane such as vinyltriethoxysilane, 2- (meth) acryloxy (Meth) acryloxy C _2-4 alkyltri C _1-2 alkoxysilanes such as ethyltrimethoxysilane, 2- (meth) acryloxyethyltriethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, these tri Examples include (meth) acryloxy C _2-4 alkyl C _1-2 alkyldiC _1-2 alkoxysilane and the like corresponding to alkoxysilane. Examples of the silane coupling agent include silicon compounds having a plurality of basic nitrogen atoms described in the above-mentioned polyamine compound. These silane coupling agents can be used alone or in combination of two or more.

  The proportion of the silane coupling agent is 30 parts by weight or less (for example, 0.1 to 30 parts by weight), preferably 0.5 to 20 parts by weight, and more preferably 1 to 10 parts by weight with respect to 100 parts by weight of the polyurethane resin. About a part.

  Furthermore, the aqueous polyurethane resin composition may contain a reactive curing agent as necessary within a range not impairing the gas barrier property. The reactive curing agent is water-dispersible or water-soluble, and for example, a polyisocyanate compound, a polycarbodiimide compound, a polyepoxy compound, a polyoxazoline compound, and / or an aziridine compound is used. Since these reactive curing agents chemically react with reactive active sites such as carboxyl groups, hydroxyl groups, and amino groups in the aqueous polyurethane resin composition, adhesion to the base film, water resistance, Boil and retort properties can be improved. From this point, it is advantageous to use a reactive curing agent.

  The ratio of the reactive curing agent is 30 parts by weight or less (for example, 0.1 to 30 parts by weight), preferably 0.5 to 20 parts by weight, and more preferably 1 to 10 parts by weight with respect to 100 parts by weight of the polyurethane resin. About a part.

  Further, the swellable inorganic layered compound is effective for further improving the gas barrier property. In a composition dissolved or dispersed in an aqueous solvent, by using an inorganic layered compound swollen with the solvent, a polyurethane resin or a polyamine compound penetrates or penetrates between layers of the swollen inorganic compound, thereby improving gas barrier properties. Therefore, the aqueous polyurethane resin composition is advantageously combined with a swellable inorganic layered compound (water-swellable inorganic layered compound).

  Examples of inorganic layered compounds include hydrous silicates (phyllosilicate minerals, etc.), such as kaolinite group clay minerals (halloysite, kaolinite, enderite, dickite, nacrite, etc.), antigolite group clay minerals (antigolite). , Chrysotile, etc.), smectite group clay minerals (montmorillonite, beidellite, nontronite, saponite, hectorite, soconite, stevensite, etc.), vermiculite group clay minerals (such as vermiculite), mica or mica group clay minerals (muscovite, phlogopite) And mica, margarite, tetrasilic mica, teniolite, etc.). These clay minerals may be natural clay minerals or synthetic clay minerals. Swellable inorganic layered compounds can be used alone or in combination of two or more. Among these inorganic layered compounds, smectite group clay minerals (such as montmorillonite) and mica group clay minerals (such as water-swellable mica) are particularly preferable.

  The average particle diameter of the swellable inorganic layered compound is usually 10 μm or less (for example, 50 nm to 5 μm), preferably about 100 nm to 3 μm. The aspect ratio of the swellable inorganic layered compound may be, for example, about 50 to 5,000, preferably about 100 to 3,000, and more preferably about 200 to 2,000.

  The ratio of the swellable inorganic layered compound is 1 to 200 parts by weight, preferably 3 to 100 parts by weight, and more preferably about 5 to 50 parts by weight with respect to 100 parts by weight of the polyurethane resin (i) in terms of solid content. is there.

  The aqueous polyurethane resin composition of the present invention has high adhesion to a substrate (wood, paper, fabric, metal, ceramics such as glass, plastic, etc.) and gas barrier properties, and therefore various aqueous resins for coating agents or compositions thereof. For example, it can be used as a paint, printing ink, coating agent and the like. In particular, even an aqueous composition exhibits high gas barrier properties, and thus is useful for forming a barrier resin molded product. For example, the aqueous polyurethane resin composition may be used alone as a film molded product. In a preferred form, the aqueous polyurethane resin composition is useful as a gas barrier coating agent for imparting high gas barrier properties to substrates such as films and containers. In particular, the aqueous polyurethane resin composition (aqueous solution or aqueous dispersion) of the present invention forms a laminated film (or laminate) in which a coating layer composed of the polyurethane resin composition is laminated on at least one surface of a base film. Suitable for doing.

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

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

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

  Such a base film may be an unstretched film, may be a uniaxial or biaxially oriented film, and is a film that has been surface-treated (corona discharge treatment, etc.), anchor coat or undercoat treatment. Also good. Furthermore, the base film may be a laminated film in which a plurality of resins or metals are laminated. In particular, the resin composition is used as an anchor coat agent or an undercoat agent for a base film, a metal such as aluminum, a composite film in which an inorganic layer of metal oxide such as alumina or silica is laminated by vapor deposition or sputtering, In the composite film in which the inorganic layer of the metal or metal oxide formed on the base film is top-coated or overcoated with the resin composition, the gas barrier property can be further improved. The thickness of the inorganic vapor deposition layer may be, for example, about 100 to 3000 angstrom (10 to 300 nm), preferably about 200 to 2000 angstrom (20 to 200 nm), and more preferably about 300 to 1500 angstrom (30 to 150 nm).

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

  The thickness of the coating layer (coating layer after drying) containing the aqueous polyurethane resin composition is, for example, 0.1 to 50 μm, preferably 0.2 to 30 μm, more preferably 0.5 to 10 μm (for example, 1 to 8 μm). And usually about 1 to 5 μm.

  There are no particular restrictions on the method of laminating the base film, and conventional methods such as gravure coating, reverse coating, roll coating, bar coating, spray coating, air knife coating, and dipping can be used. These can be laminated in an appropriate combination. After apply | coating or laminating | stacking a water-based polyurethane resin composition to a base material, a laminated film (or laminated body) can be formed by removing a solvent by a drying process and forming into a film.

  In addition, after laminating the aqueous polyurethane resin composition on the base plastic film, stretching in at least one direction can improve the crystallinity due to the stretching effect and improve the gas barrier property.

  In addition, the aqueous polyurethane resin composition can be used in various modes. For example, in a composite film, an overcoat agent for constituting a surface layer of the composite film, a base film layer and a resin layer, or a plurality of You may coat as an anchor coating agent interposed between resin layers. Further, when the polyurethane resin itself has an adhesive force, it may be coated as an adhesive.

  In the present invention, an aqueous polyurethane resin composition having a high gas barrier property and a gas barrier laminate obtained by laminating the same can be obtained without using a chlorine-based compound or a volatile organic compound that pollutes the environment. In addition, the water-based polyurethane resin composition has excellent adhesion to a base film on which plastics and metal oxides are laminated, and has excellent processability such as printing and adhesion. It can be used in various fields.

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

Production Example 1 (Polyurethane resin A)
mXDI (metaxylylene diisocyanate) 45.5 g, hydrogenated XDI (1,3-bis (isocyanatomethyl) cyclohexane) 93.9 g, ethylene glycol 24.8 g, dimethylolpropionic acid 13.4 g and methyl ethyl ketone 80.2 g as solvent. Were mixed and reacted at 70 ° C. for 5 hours under a nitrogen atmosphere. Next, this carboxyl group-containing urethane prepolymer solution was neutralized with 9.6 g of triethylamine at 40 ° C. This polyurethane prepolymer solution was dispersed in 624.8 g of water with a homodisper, subjected to chain extension reaction with 21.1 g of 2-[(2-aminoethyl) amino] ethanol, and methyl ethyl ketone was distilled off to obtain a solid content. An aqueous dispersion type polyurethane resin A having 25% by weight and an average particle size of 90 nm was obtained. The acid value of this resin is 26.9 mgKOH / g, and the total of the urethane group concentration and the urea group concentration is 39.6% by weight.

Production Example 2 (Polyurethane resin B)
145.7 g of hydrogenated XDI (1,3-bis (isocyanatomethyl) cyclohexane), 24.2 g of ethylene glycol, 14.8 g of dimethylolpropionic acid and 83.6 g of acetone as a solvent were mixed, and 6 at 55 ° C. in a nitrogen atmosphere. Reacted for hours. Next, this carboxyl group-containing urethane prepolymer solution was neutralized with 10.6 g of triethylamine at 40 ° C. By dispersing 278.9 g of this polyurethane prepolymer solution in 655.8 g of water with homodisper, performing chain extension reaction with 23.4 g of 2-[(2-aminoethyl) amino] ethanol, and distilling off acetone, A water-dispersed polyurethane resin B having a solid content of 25% by weight and an average particle size of 110 nm was obtained. The acid value of this resin is 28.2 mgKOH / g, and the total of the urethane group concentration and the urea group concentration is 38.9% by weight.

Production Example 3 (Polyurethane resin C)
47.1 g of mXDI (metaxylylene diisocyanate), 111.1 g of isophorone diisocyanate, 21.7 g of ethylene glycol, 20.1 g of dimethylolpropionic acid and 91.9 g of methyl ethyl ketone as a solvent were mixed and reacted at 70 ° C. for 5 hours under nitrogen atmosphere I let you. Subsequently, this carboxyl group-containing urethane prepolymer solution was neutralized with 14.4 g of triethylamine at 40 ° C. By dispersing 306.3 g of this polyurethane prepolymer solution in 713.5 g of water with homodisper, performing chain extension reaction with 23.4 g of 2-[(2-aminoethyl) amino] ethanol, and distilling off methyl ethyl ketone, A water-dispersed polyurethane resin C having a solid content of 25% by weight and an average particle diameter of 85 nm was obtained. The acid value of this resin is 35.4 mgKOH / g, and the total of the urethane group concentration and the urea group concentration is 35.8% by weight.

Production Example 4 (Polyurethane resin D)
Hydrogenated XDI (1,3-bis (isocyanatomethyl) cyclohexane) 135.9 g, ethylene glycol 24.2 g, dimethylolbutanoic acid 16.3 g and acetonitrile 80.1 g as a solvent were mixed and mixed at 70 ° C. under a nitrogen atmosphere. Reacted for hours. Next, this carboxyl group-containing urethane prepolymer solution was neutralized with 10.6 g of triethylamine at 40 ° C. 267.1 g of this polyurethane prepolymer solution was dispersed in 655.1 g of water with homodisper, subjected to chain extension reaction with 31.4 g of adipic acid dihydrazide, and acetonitrile was distilled off to obtain a solid content of 25% by weight. A water-dispersed polyurethane resin D having a particle size of 100 nm was obtained. The acid value of this resin is 28.3 mgKOH / g, and the total of the urethane group concentration and the urea group concentration is 36.6% by weight.

Production Example 5 (Polyurethane resin E (low acid value type))
XDI (xylylene diisocyanate) 55.9 g, hydrogenated XDI (1,3-bis (isocyanatomethyl) cyclohexane) 115.3 g, ethylene glycol 34.8 g, dimethylolpropionic acid 10.1 g and methyl ethyl ketone 95.8 g as a solvent. The mixture was mixed and reacted at 70 ° C. for 5 hours under a nitrogen atmosphere. Next, this carboxyl group-containing urethane prepolymer solution was neutralized with 7.4 g of triethylamine at 40 ° C. This polyurethane prepolymer solution was dispersed in 750.0 g of water with homodisper, subjected to chain extension reaction with 26.5 g of 2-[(2-aminoethyl) amino] ethanol, and distilled off methyl ethyl ketone to obtain a solid content. An aqueous dispersion type polyurethane resin E having 25% by weight and an average particle diameter of 68 nm was obtained. The acid value of this resin is 16.8 mgKOH / g, and the total of the urethane group concentration and the urea group concentration is 41.8% by weight.

Production Example 6 (urethane-modified polyamine compound A)
Hydrogenated XDI (1,3-bis (isocyanatomethyl) cyclohexane) 97.1 g and dimethylethanolamine 93.6 g were added dropwise and mixed, and reacted at 60 ° C. for 2 hours in a nitrogen atmosphere to obtain urethane-modified polyamine compound A. Obtained. The amine value of this amine compound was 309 mgKOH / g.

Production Example 7 (urethane-modified polyamine compound B)
To 186 g of Takenate D-170HN (hexamethylene diisocyanate allophanate / trimer) manufactured by Mitsui Takeda Chemical Co., Ltd., 93.6 g of dimethylethanolamine was added dropwise and mixed, and reacted at 60 ° C. for 2 hours in a nitrogen atmosphere. Modified polyamine compound B was obtained. The amine value of this amine compound was 211 mgKOH / g.

(Polyamine compound)
The following compounds were used as the polyamine compound (ii).

Ethylenediamine (EDA, amine value 1867mgKOH / g)
2-[(2-Aminoethyl) amino] ethanol (AEEA, amine number 1077 mg KOH / g)
Adduct obtained by adding 4 mol of ethylene oxide to ethylenediamine (EDA-EO4, amine value 468 mgKOH / g)
Metaxylylenediamine (mXDA, amine value 824 mgKOH / g)
Adduct obtained by adding 4 mol of ethylene oxide to metaxylylenediamine (mXDA-EO4, amine value 349 mgKOH / g)
γ- (2-aminoethyl) aminopropylmethyldimethoxysilane (AEAPS, amine value 544 mg KOH / g).

Examples 1 to 16 and Reference Example The polyurethane resins A to E and polyamine compounds (including the urethane-modified polyamine compounds A and B) were mixed at a weight ratio shown in Table 1, and then applied to a substrate film. The film was dried at ° C for 30 seconds to obtain laminated films. The oxygen gas barrier property of the obtained laminated film was measured under the conditions of 20 ° C. and 50% RH, and 20 ° C. and 80% RH using an oxygen permeability measuring device (MOCON OXTRAN 10 / 50A, manufactured by Modern Control). Each was measured. As the base film, biaxially stretched polyethylene terephthalate (thickness 15 μm, PET) and biaxially stretched nylon (thickness 25 μm, NY) were used. The results are shown in Tables 1 and 2 together with the coating amount.

Comparative Examples 1-4
A laminated film was obtained in the same manner as in Example except that the polyurethane resins A to D were applied to the base film without adding any polyamine compound. The results are shown in Table 2 together with the coating amount.

Comparative Examples 5-6
The oxygen permeability of the base film was measured in the same manner as described above. The results are shown in Table 2.

  As is clear from Tables 1 and 2, the Examples show higher gas barrier properties than the comparative examples, and the gas barrier properties are higher even in a high humidity environment.

Claims (11)

(I) An aqueous polyurethane resin composition comprising a polyurethane resin having a total concentration of urethane groups and urea groups of 15% by weight or more and having an acid group, and (ii) a polyamine compound , wherein the polyurethane resin (i) Is obtained by reaction of (A) a polyisocyanate compound, (B) a polyhydroxy acid, (C) a polyol component containing 90% by weight or more of C _2-6 alkylene glycol, and (D) a chain extender component. And an aqueous polyurethane resin neutralized with a neutralizing agent, wherein the polyamine compound (ii) is an alkylene diamine, a hydroxyl group-containing diamine, a polyalkylene polyamine, an N-alkyl-substituted alkylene diamine, an N-alkyl-substituted poly Alkylene polyamines, alicyclic polyamines, aromatic polyamines, these polyamine compounds An aqueous polyurethane resin composition which is at least one selected from adducts added with lenoxide and urethane-modified polyamine compounds . Before SL polyisocyanate compound (A), aromatic, araliphatic and alicyclic claim 1 aqueous polyurethane resin composition according comprises at least one member selected from the group of polyisocyanates. Polyurethane resin (i) comprises a following (A), (B) and component, component (C), obtained by reaction of minutes adult (D), the total of the urethane group and urea group concentration of 25 to 60 The water-based polyurethane resin composition according to claim 1, wherein the aqueous polyurethane resin composition is in wt% and neutralized with a neutralizing agent.
(A) Polyisocyanate compound containing at least 30% by weight selected from the group of aromatic, araliphatic and alicyclic polyisocyanates (B) selected from the group of polyhydroxycarboxylic acids and polyhydroxysulfonic acids at least one organic acid (C) polyols polyol compound containing 90 wt% or more carbon atoms. 2 to 6 (D) a polyamine, water, at least one chain extender selected from the group of hydrazine and hydrazine derivatives.   The aqueous polyurethane resin composition according to claim 3, wherein the chain extender is at least one selected from diamines, hydrazines, and hydrazine derivatives.   The aqueous polyurethane resin composition according to claim 2 or 3, wherein the (A) polyisocyanate compound of the polyurethane resin (i) is a polyisocyanate containing 20% by weight or more of at least one selected from xylylene diisocyanate and hydrogenated xylylene diisocyanate. object.   The aqueous polyurethane resin composition according to claim 1 or 2, wherein the polyurethane resin (i) is an aqueous dispersion dispersed in water.   The aqueous polyurethane resin composition according to claim 1 or 2, wherein the polyurethane resin (i) is an aqueous solution dissolved in water.   The aqueous polyurethane resin composition according to claim 1, wherein the polyamine compound (ii) is capable of binding to an acid group of the polyurethane resin (i).   The amine value of the polyamine compound (ii) is 100 to 1900 mgKOH / g, and the ratio of the polyurethane resin (i) and the polyamine compound (ii) is 10/1 to 1 as an equivalent ratio of acid groups to basic nitrogen atoms. The aqueous polyurethane resin composition according to claim 1, which is 1/10.   The aqueous resin composition for coating agents comprised with the polyurethane resin composition in any one of Claims 1 thru | or 9.   The laminated film by which the coating layer comprised with the polyurethane resin composition in any one of Claims 1 thru | or 9 is laminated | stacked on the at least single side | surface of the base film.