Barrier aqueous composition and laminate

Abstract

The present invention aims to provide an aqueous barrier composition and a laminate having excellent barrier properties. The aqueous barrier composition comprises a urethane resin (A) containing a polyol (a1), a polyisocyanate (a2), and a chain extender (a3) ​​as essential reaction components, and one or more waxes (B) selected from the group consisting of paraffin wax, carnauba, and alkyl ketene dimer, wherein the ratio of component (A) to component (B) based on the weight of the non-volatile content is (A) / (B) = 25 / 75 to 95 / 5.

Description

Technical Field

[0001] The present invention relates to a barrier water-based composition and a laminate. Background Art

[0002] In applications such as packaging materials for food and pharmaceuticals, or electronic devices such as organic electroluminescence (EL) devices, barrier properties are required for product quality. For example, in packaging applications, barrier properties are imparted to a substrate by coating and drying a barrier composition to form a film, in order to prevent gases such as water vapor and oxygen, or liquids such as water and oil, from entering the substrate from the outside or from flowing out from the inside. Furthermore, known barrier compositions include polyvinyl alcohol and polyvinylidene chloride (PVDC) (Patent Document 1, etc.).

[0003] However, polyvinyl alcohol is susceptible to humidity and has difficulty in achieving water vapor barrier properties, particularly under high temperature and high humidity conditions. Furthermore, the use of polyvinylidene chloride generates harmful gases during incineration, which is not environmentally preferable.

[0004] Another known technology is a multilayer resin sheet in which a water vapor barrier resin layer composed of an olefin resin is laminated on both sides of an oxygen barrier resin layer with adhesive layers interposed therebetween (Patent Document 2). However, this technology also has the problem of increasing the amount of petroleum-derived plastic used.

[0005] One method for reducing the use of petroleum-derived plastics is to apply a small amount of a diluted barrier composition to a substrate. Furthermore, aqueous barrier compositions are now preferred for reducing volatile organic compound (VOC) emissions.

[0006] [Prior art literature]

[0007] [Patent Document]

[0008] [Patent Document 1] Japanese Patent Application Laid-Open No. 8-134242

[0009] [Patent Document 2] International Publication No. 2017 / 221374 Summary of the Invention

[0010] [Problems to be solved by the invention]

[0011] An object of the present invention is to provide an aqueous barrier composition and a laminated sheet having excellent barrier properties.

[0012] [Technical means to solve the problem]

[0013] The present inventors have diligently studied and found that a water-based barrier composition comprising a specific urethane resin and wax solves the aforementioned problems, thereby completing the present invention. Specifically, the present invention relates to the following water-based barrier composition and laminated sheet.

[0014] 1. A barrier aqueous composition comprising a urethane resin (A) containing a polyol (a1), a polyisocyanate (a2), and a chain extender (a3) ​​as essential reaction components, and at least one wax selected from the group consisting of paraffin wax, carnauba wax, and an alkyl ketene dimer (B), wherein the ratio of component (A) to component (B) based on the weight of the non-volatile content is (A) / (B) = 25 / 75 to 95 / 5.

[0015] 2. The aqueous barrier composition according to item 1, wherein the component (a1) contains a polyether polyol.

[0016] 3. The aqueous barrier composition according to item 1 or 2, wherein the component (a3) ​​contains a dialkanol alkanoic acid.

[0017] 4. The aqueous barrier composition according to any one of items 1 to 3, wherein the reaction component further comprises (meth)acrylic acid hydroxyalkyl ester (a4).

[0018] 5. The aqueous barrier composition according to any one of items 1 to 4, wherein the reaction component further comprises a monoalkyl (meth)acrylate (a5) having no hydroxyl group.

[0019] 6. The aqueous barrier composition according to any one of items 1 to 5, further comprising a rosin resin and / or a hardener.

[0020] 7. A laminated board, wherein at least one side of a substrate has a coating layer of the aqueous barrier composition as described in any one of items 1 to 6.

[0021] [Effects of the Invention]

[0022] The aqueous barrier composition according to the present invention exhibits excellent barrier properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] none DETAILED DESCRIPTION

[0024] The aqueous barrier composition of the present invention comprises a resin selected from a specific urethane resin (A) (hereinafter referred to as component (A)) and a wax (B) (hereinafter referred to as component (B)).

[0025] The term "barrier" in the present invention refers to a barrier against water vapor, oxygen, water, oil, etc. Applications requiring such a barrier include packaging materials or containers for food, pharmaceuticals, and sundries, building materials, precision equipment, electronic devices, and industrial materials.

[0026] Component (A) is a reaction component that requires a urethane resin, a polyol (a1) (hereinafter referred to as component (a1)), a polyisocyanate (a2) (hereinafter referred to as component (a2)), and a chain extender (a3) ​​(hereinafter referred to as component (a3)).

[0027] Component (a1) is a compound having two or more hydroxyl groups in the molecule. Examples thereof include low molecular weight glycols such as ethylene glycol, diethylene glycol, 1,2-propylene glycol, and 1,4-butylene glycol, polyether polyols, poly(meth)acrylic acid polyols, polyester polyols, and polycarbonate polyols. These may be used alone or in combination of two or more. Among these, polyether polyols are preferred.

[0028] Examples of the polyether polyol include polyethylene glycol, polypropylene glycol, polybutylene glycol, polytetramethylene glycol, polyhexamethylene glycol, polyheptamethylene glycol, polydecamethylene glycol, polyoxyethylene-polyoxypropylene glycol, polyoxytetramethylene-polyoxyethylene glycol, and polyoxytetramethylene-polyoxypropylene glycol. The polyether polyol may be used in any of random and block structures.

[0029] Examples of commercially available polyether polyols include Adeka Polyether P-400, Adeka Polyether G-400, Adeka Polyether T-400, Adeka Polyether AM-302, Adeka Polyether P1000, and Adeka Polyether P2000 (all manufactured by Adeka Co., Ltd.); Polyethylene glycol #1,540 (manufactured by Nacalatech); Tesque (manufactured by Co., Ltd.); Dipropylene glycol, Polypropylene glycol 400 (all manufactured by Junsei Chemical Co., Ltd.); PEG #200, PEG #300, PEG #400, PEG #600, PEG #1000, PEG #1500, PEG #2000, PEG #4000, UNIOL D-200, UNIOL D-700, UNIOL D-1000, UNIOL D-1200, UNIOL D-2000, UNIOL D-4000, Uniol PB-500, Uniol PB-700, Uniol PB-1000, Uniol PB-2000, Polycerin DC-1100, Polycerin DC-1800E, Polycerin DC-3000E, Polycerin DCB-1000, Polycerin DCB-2000, Polycerin DCB-4000 (all manufactured by NOF Corporation), etc.

[0030] Examples of the component (a2) include aliphatic diisocyanates such as methylene diisocyanate, isopropylene diisocyanate, butane-1,4-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and dimer diisocyanates obtained by substituting carboxyl groups of dimer acids with isocyanate groups.

[0031] Alicyclic diisocyanates such as cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis(isocyanatemethyl)cyclohexane, and methylcyclohexane diisocyanate;

[0032] Aromatic diisocyanates such as 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-diphenyltetramethylmethane diisocyanate, 1,4-phenylene diisocyanate, toluene diisocyanate, xylene diisocyanate, m-tetramethylxylylenediisocyanate, 1,5-naphthalene diisocyanate, 4,4'-dibenzyl diisocyanate, and 1,3-phenylene diisocyanate;

[0033] Amino acid diisocyanates such as lysine diisocyanate, etc. These may be used alone or in combination of two or more. In addition, as component (a2), their isocyanuric acid forms, adduct forms, or biuret forms may also be used.

[0034] The usage ratio of the component (a1) and the component (a2) is preferably set to the number of moles of the isocyanate group (NCO) of the component (a2). (a2) ) and the molar number of hydroxyl groups of component (a1) (OH (a1) ) ratio (NCO (a2) / OH (a1) ) is calculated to be around 1.1 / 1 to 8 / 1.

[0035] The component (a3) ​​is a chain extender.

[0036] Examples of the component (a3) ​​include diamines such as ethylenediamine, propylenediamine, hexamethylenediamine, isophoronediamine, dimer diamine, dicyclohexylmethane-4,4′-diamine, 2-hydroxyethylethylenediamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine, and di-2-hydroxypropylethylenediamine.

[0037] Triamines such as diethylenetriamine, dipropylenetriamine, and dibutyltriamine;

[0038] Tetramines such as triethylenetetramine and tripropylenetetramine;

[0039] N-alkyldialkanolamines such as N-methyldiethanolamine, N-ethyldiethanolamine, N-propyldiethanolamine, N-isopropyldiethanolamine, N-butyldiethanolamine, N-isobutyldiethanolamine, N-oleyldiethanolamine, N-stearyldiethanolamine, N-methyldiisopropanolamine, N-ethyldiisopropanolamine, N-propyldiisopropanolamine, and N-butyldiisopropanolamine;

[0040] Hydrazine or its hydrazine derivatives (such as adipic acid hydrazide);

[0041] Dialkyl alkanoic acids such as glyceric acid, dioxymaleic acid, dioxyfumaric acid, dihydroxymethylacetic acid, dihydroxymethylpropionic acid, dihydroxymethylbutyric acid, dihydroxymethylvaleric acid, and dihydroxymethylhexanoic acid;

[0042] Aromatic hydroxycarboxylic acids such as 4,4-di(hydroxyphenyl)butyric acid, 4,4-di(hydroxyphenyl)valeric acid, and 2,6-dioxybenzoic acid may be used alone or in combination of two or more. Among these, dialkanol alkanoic acids are preferred in terms of making the resulting component (A) easily soluble or dispersible in water.

[0043] Alternatively, the dialkanolamine may be used as a quaternary salt thereof. The quaternary salt is obtained by reacting the dialkanolamine with a quaternary agent. Examples of the quaternary agent include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; organic acids such as dimethylsulfuric acid, acetic acid, and propionic acid; and organic halogen compounds such as methyl chloride, benzyl chloride, and epichlorohydrin.

[0044] In addition, the carboxyl groups of the dialkanol alkanoic acid and the aromatic hydroxycarboxylic acid may be neutralized with a neutralizing agent.

[0045] Examples of the neutralizing agent include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; ammonia; and organic amines such as trimethylamine, triethylamine, triethanolamine, triisopropanolamine, N,N-dimethylethanolamine, and N,N-diethylethanolamine. These may be used alone or in combination of two or more.

[0046] The amount of component (a3) ​​used is usually 1 to 30% by weight, preferably 3 to 20% by weight, based on 100% by weight of the reaction components constituting component (A).

[0047] The component (A) of the present invention may contain a hydroxyalkyl (meth)acrylate (a4) (hereinafter referred to as the component (a4)) as a reaction component.

[0048] Examples of the component (a4) include 2-hydroxyethyl (meth)acrylate, 2-hydroxy-n-propyl (meth)acrylate, 3-hydroxy-n-propyl (meth)acrylate, 3-hydroxy-n-butyl (meth)acrylate, 4-hydroxy-n-butyl (meth)acrylate, and 6-hydroxy-n-hexyl (meth)acrylate. These may be used alone or in combination of two or more. Among these, components having a hydroxyalkyl group having 2 to 3 carbon atoms are preferred from the perspective of excellent reactivity, and 2-hydroxyethyl (meth)acrylate and 2-hydroxy-n-propyl (meth)acrylate are more preferred.

[0049] The amount of the component (a4) used is usually 10% by weight or less, preferably 0.1 to 5% by weight, relative to 100% by weight of the reaction components constituting the component (A).

[0050] The component (A) of the present invention may contain a monoalkyl (meth)acrylate (a5) having no hydroxyl group (hereinafter referred to as the component (a5)) as a reaction component.

[0051] Examples of the component (a2-5) include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, n-pentyl (meth)acrylate, cyclopentyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, myristyl (meth)acrylate, isomyristyl (meth)acrylate, palmitate (meth)acrylate, stearyl (meth)acrylate, and isostearyl (meth)acrylate. These may be used alone or in combination of two or more. Among these, components having an alkyl group with 12 to 18 carbon atoms are preferred from the perspective of improving barrier performance, and more preferred are lauryl (meth)acrylate, myristyl (meth)acrylate, palmityl (meth)acrylate, and stearyl (meth)acrylate.

[0052] The amount of the component (a5) used is usually 50% by weight or less, preferably 10 to 40% by weight, relative to 100% by weight of the reaction components constituting the component (A).

[0053] The reaction components may further include a chain extension inhibitor (a6) (hereinafter referred to as component (a6)). Examples of component (a6) include monohydric alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, and isobutanol; monoamines such as ethylamine, n-propylamine, diethylamine, di-n-propylamine, and di-n-butylamine; and alkanol monoamines such as monoethanolamine and diethanolamine. These may be used alone or in combination of two or more.

[0054] The amount of the component (a6) used is usually 5% by weight or less, preferably 3% by weight or less, based on 100% by weight of the reaction components constituting the component (A).

[0055] Component (A) can be obtained, for example, by reacting component (a1) and component (a2) to produce a urethane prepolymer, and then reacting the urethane prepolymer with component (a3) ​​and, if necessary, components (a4) to (a6).

[0056] The reaction conditions for the step of obtaining the urethane prepolymer are generally a temperature of about 40° C. to 150° C., preferably about 60° C. to 100° C. The reaction time is generally about 1 hour to 20 hours, preferably about 1 hour to 10 hours.

[0057] Next, the reaction conditions for reacting component (a3) ​​and, if necessary, components (a4) to (a6) with the urethane prepolymer are generally at a temperature of about 20°C to 100°C, preferably about 30°C to 80°C. The reaction time is generally about 1 to 10 hours, preferably about 1 to 5 hours. The mixing method and order of the components are not particularly limited.

[0058] The production of these components (A) may be carried out in the absence of a solvent or in the presence of a solvent.

[0059] Examples of the solvent include: aromatic hydrocarbons such as benzene, toluene, ethylbenzene, n-propylbenzene, tert-butylbenzene, o-xylene, m-xylene, p-xylene, tetralin, decalin, and aromatic naphtha; aliphatic hydrocarbons such as n-hexane, n-heptane, n-octane, isooctane, and n-decane; alicyclic hydrocarbons such as cyclohexane; esters such as ethyl acetate, n-butyl acetate, n-amyl acetate, 2-hydroxyethyl acetate, 2-butoxyethyl acetate, 3-methoxybutyl acetate, and methyl benzoate; acetone, methyl ethyl ketone, and methyl isobutyl ketone. , isophorone, cyclohexanone, methylcyclohexanone and other ketones; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether and other glycol ethers; methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol and other alcohols; N, N-dimethylformamide, N, N-dimethylacetamide and other amides; N-methylpyrrolidone and other amines; ion exchange water, purified water, tap water, soft water, hard water, industrial water and other water; dimethyl sulfoxide and the like. These may be a single kind or two or more may be combined. In addition, after the reaction is completed, the solvent may also be removed by distillation under reduced pressure.

[0060] The amount of the solvent used is preferably adjusted so that the reaction concentration becomes 10% by weight or more.

[0061] Furthermore, in the above reaction, the component (B) described later may be added.

[0062] Component (A) may further contain a pigment, a water-retaining agent, a defoaming agent, a preservative, a leveling agent, a colorant, an anti-blocking agent, an antioxidant, an ultraviolet absorber, a thickener, a dispersant, a filler, and the like.

[0063] The weight average molecular weight of the obtained component (A) is 5000 to 2000000. In addition, the weight average molecular weight is a value measured by gel permeation chromatography (GPC) using polystyrene as a standard substance.

[0064] The viscosity of a solution of component (A) having a nonvolatile content of 35% by weight at 25° C. is usually 5 to 20,000 mPa·s, preferably 10 to 10,000 mPa·s. The “viscosity” herein refers to a value measured using a Brookfield viscometer.

[0065] Component (B) comprises one or more waxes selected from the group consisting of paraffin wax, carnauba wax, and alkyl ketene dimer, and is a component that imparts barrier properties. Alkyl ketene dimer is abbreviated as "AKD." Below, the wax component (B) may also be referred to as paraffin wax, carnauba wax, or AKD wax.

[0066] Paraffin wax is obtained by separating and refining highly crystalline hydrocarbons from the distillate obtained by vacuum distillation of crude oil. It mainly contains straight-chain hydrocarbons (normal paraffins).

[0067] As physical properties of paraffin wax, for example, the melting point is preferably 45°C to 80°C, more preferably 55°C to 80°C.

[0068] In the present invention, paraffin wax is preferably used as an aqueous emulsion using a dispersant. Examples of the dispersant include nonionic surfactants, cationic surfactants, and anionic surfactants described in Japanese Patent Application Laid-Open No. 2013-237941.

[0069] Examples of commercially available solid and / or liquid paraffin waxes include "paraffin 115," "paraffin 120," "paraffin 125," "paraffin 130," "paraffin 135," "paraffin 140," "paraffin 145," "paraffin 150," "paraffin 155," and "HNP-51" (all manufactured by Nippon Seiro Co., Ltd.). Examples of commercially available aqueous emulsions include "Sizepine W-116H" (manufactured by Arakawa Chemical Industries, Ltd.). These may be used alone or in combination of two or more.

[0070] Carnauba is an ingredient collected from palm trees in the coconut family, and its wax is called carnauba wax.

[0071] Carnauba wax is a naturally derived wax with wax esters as its main component, and also contains free fatty acids, free alcohols and hydrocarbons.

[0072] The physical properties of carnauba wax include, for example, a melting point of preferably 60° C. to 110° C., and more preferably 80° C. to 90° C. The acid value is preferably 10 mg·KOH / g or less.

[0073] Examples of commercially available carnauba wax include "Selosol 524" (manufactured by Chukyo Oil & Fats Co., Ltd.), "EMUSTAR-0413" (manufactured by Nippon Seiwa Co., Ltd.), "Carnauba Wax No. 1 Flakes," "Carnauba Wax No. 1 Powder," "Carnauba Wax No. 2 Flakes," "Carnauba Wax No. 2 Powder," "Carnauba Wax No. 3 Flakes," and "Carnauba Wax No. 3 Powder" (all manufactured by Toyo Chemical Co., Ltd.).

[0074] Examples of AKD include components represented by the following general formula (1): 1 and R 2 represent alkyl or alkenyl groups, respectively, and may be the same or different).

[0075]

[0076] Examples of the alkyl group include butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, docosyl, tetracosyl, hexacosyl, octacosyl, triacontyl, and dotriacontyl. These may be branched.

[0077] Examples of the alkenyl group include butenyl, pentenyl, hexenyl, heptenyl, octenyl,

[0078] Nonenyl, decenyl, undecenyl, dodecenyl, tetradecenyl, hexadecenyl, octadecenyl, eicosenyl, docosenyl, tetracosenyl, hexacosenyl, octacosenyl, triacontenyl, dotriacontenyl, etc. These may be branched.

[0079] These AKDs may be used alone or in combination of two or more. 1 and R 2 Each of them is represented by an alkyl group or an alkenyl group having 14 to 24 carbon atoms, and more preferably R 1 and R 2 Each of the alkyl groups is represented by an alkyl group having 14 to 24 carbon atoms, i.e., tetradecyl (carbon number: 14), hexadecyl (carbon number: 16), octadecyl (carbon number: 18), eicosyl (carbon number: 20), docosyl (carbon number: 22), and tetracosyl (carbon number: 24).

[0080] In the present invention, AKD is preferably used in the form of an aqueous emulsion prepared using a known emulsifier. Examples of emulsifiers used to prepare the aqueous emulsion and methods for preparing the emulsion include those described in Japanese Patent Application Laid-Open No. 2-19592, Japanese Patent Application Laid-Open No. 2-293493, and Japanese Patent Application Laid-Open No. 2012-211422.

[0081] In addition, examples of commercially available products include “Sizepine K-287”, “Sizepine K-903-20”, “Sizepine K-931”, and “Sizepine K-924” (all manufactured by Arakawa Chemical Industries, Ltd.), “AD1602”, “AD1606”, “AD1608”, “AD1612”, “AD1614”, “AD1638”, “AD1640”, “SE2360”, and “SE2380” (all manufactured by Seikyo PMC Co., Ltd.), “KDG” series, and “SAK” series (all manufactured by Toho Chemical Co., Ltd.).

[0082] Component (B) may further contain a pigment, a water-retaining agent, a defoaming agent, a preservative, a leveling agent, a colorant, an anti-blocking agent, an antioxidant, an ultraviolet absorber, a thickener, a dispersant, a filler, and the like.

[0083] The content ratio of component (A) to component (B) based on the weight of the non-volatile content is (A) / (B) = 25 / 75 to 95 / 5. When the content ratio is within this range, the film of the barrier aqueous composition exhibits excellent barrier properties. From the same perspective, the content ratio is preferably (A) / (B) = 30 / 70 to 90 / 10, and more preferably (A) / (B) = 50 / 50 to 90 / 10.

[0084] The barrier aqueous composition of the present invention is obtained by mixing component (A) and component (B), and optionally water. Mixing conditions include, for example, a temperature of 10°C to 90°C (preferably 20°C to 80°C). The order, method, and duration of mixing the components are not particularly limited.

[0085] The aqueous barrier composition of the present invention may further include rosin resins such as gum rosin, wood rosin, tall oil rosin, saponified rosin, hydrogenated rosin, fumaric rosin, maleic rosin, and rosin esters; non-rosin resins such as acrylic resins, styrene-butadiene resins, polyester resins, modified polyolefin resins, petroleum resins, and polyvinyl alcohol; hardeners such as carbodiimide-based hardeners, polyisocyanate-based hardeners, aziridine-based hardeners, and melamine-based hardeners; and additives such as pigments, water-retaining agents, defoaming agents, antioxidants, preservatives, leveling agents, colorants, oil-proofing agents, water-proofing agents, anti-blocking agents, anti-slip agents, and heat-sealing agents. These additives may be present alone or in combination. Furthermore, the amount of these additives, so as not to impair barrier performance, is preferably 20 parts by weight or less, and more preferably 10 parts by weight or less, relative to a total of 100 parts by weight of component (A) and component (B).

[0086] As the physical properties of the obtained barrier aqueous composition, the non-volatile content concentration is usually 5% by weight to 50% by weight, and preferably 10% by weight to 40% by weight.

[0087] The viscosity of a solution of an aqueous oil repellent having a nonvolatile content concentration of 30% by weight at a temperature of 25° C. is usually 10 to 1000 mPa·s, preferably 20 to 500 mPa·s.

[0088] The laminate of the present invention is a substrate having a coating layer of the barrier aqueous composition on at least one side thereof.

[0089] The laminate can be obtained, for example, by applying the aqueous barrier composition on at least one side of a substrate and drying the composition.

[0090] Examples of the substrate include base paper, support films, and metal plates.

[0091] Examples of base paper include chemical pulps such as broadleaf pulp (bleached broadleaf kraft pulp (LBKP)) and conifer pulp (bleached needle kraft pulp (NBKP)); mechanical pulps such as groundwood pulp (ground pulp (GP)), refiner groundpulp (RGP), and thermo-mechanical pulp (TMP); and pulps obtained by making paper using various papermaking machines using deinked waste paper pulp (DIP), mercerized pulp, and waste paper pulp. More specifically, examples include bleached kraft paper, unbleached kraft paper, premium paper, medium-weight paper, lightly coated paper, coated paper, converted base paper, cardboard, whiteboard, liner, translucent paper, transparent paper, and parchment paper. In addition, pulp containing a pH adjuster such as aluminum sulfate, sulfuric acid or sodium hydroxide; papermaking chemicals such as a sizing agent, a paper strengthening agent (for example, starch or polyacrylamide), and a wetting agent; and a filler such as talc, clay, kaolin, titanium dioxide, and calcium carbonate can also be used.

[0092] Examples of the support film include polyimide resins such as polyimide and polyimide-silica hybrids; polyolefin resins such as polyethylene, polypropylene, and cycloolefin polymers; polyester resins such as polyethylene terephthalate, polyethylene naphthalate, polybutylene succinate, polybutylene succinate-adipate, polybutylene adipate-terephthalate, polyhydroxyalkanoate, and polylactic acid; acrylic resins such as polymethyl methacrylate; polytetrafluoroethylene (PTFE), perfluoroalkoxyalkane (PFA), and polyvinylidene fluoride. Fluorine-based resins such as polyvinyl fluoride (PVDF); aromatic polyester resins obtained from ethylene terephthalate, phenol, phthalic acid, hydroxynaphthoic acid, etc. and p-hydroxybenzoic acid (so-called liquid crystal polymers; manufactured by Kuraray Co., Ltd., "Vecstar", etc.); cellulose resins such as acetyl cellulose and cellophane; polystyrene resins, polycarbonate resins, acrylonitrile-butadiene-styrene resins, etc. These may be used alone or in combination of two or more.

[0093] Examples of the metal plate include aluminum plates, aluminum-plated steel plates, and Al-Si alloy-plated steel plates; zinc-based metal plates such as galvanized steel plates, Zn-Fe alloy-plated steel plates, Zn-Co alloy-plated steel plates, Zn-Co-Cr alloy-plated steel plates, Zn-Cr-Ni alloy-plated steel plates, Zn-Cr-Fe alloy-plated steel plates, Zn-Al alloy-plated steel plates, Zn-Mg alloy-plated steel plates, Zn-Al-Mg alloy-plated steel plates, and Zn-Ni alloy-plated steel plates; copper plates, steel plates, titanium plates, stainless steel plates, tinplate plates, nickel-plated steel plates, chrome-plated steel plates, and phosphoric acid-treated steel plates. These may be used alone or in combination of two or more.

[0094] Furthermore, as the base paper, support film or metal plate, materials further provided with an anchor layer, a filler layer, a water-resistant layer, an oil-resistant layer, an antistatic layer or the like on one or both surfaces may be used.

[0095] Examples of methods for applying the barrier aqueous composition include a rod coater, a knife coater, a size press coater, a roll coater, a reverse roll coater, a curtain coater, a gravure coater, an air knife coater, a calender, a gate roll coater, a knife coater, a two-roll size press, or a doctor bar meter. The amount of coating liquid applied (in terms of non-volatile content) is not particularly limited, but is generally 0.1 g / m². 2 ~10g / m 2 About 1g / m 2 ~6g / m 2 about.

[0096] The coated substrate is dried by heat. Examples of heat sources include hot air dryers, infrared heaters, and rotary dryers. Drying conditions include, for example, a temperature of 80°C to 220°C (preferably 100°C to 200°C) and a drying time of 0.1 to 180 minutes (preferably 0.5 to 60 minutes).

[0097] In the laminated plate obtained by the above-mentioned production method, a heat seal layer, a water-resistant layer, an oil-resistant layer, etc. may be provided on the film of the aqueous barrier composition.

[0098] [Example]

[0099] Hereinafter, the present invention will be described with reference to Examples, but the present invention is not limited thereto. In addition, unless otherwise specified, "parts" and "%" in Examples and Comparative Examples are based on weight.

[0100] Production Example 1

[0101] Into a reaction vessel equipped with a stirrer, a thermometer, a cooling tube, and a nitrogen inlet tube were placed 38.1 parts of dimethylolbutyric acid, 314.5 parts of Polycerin DCB-2000 (polyoxytetramethylene-polyoxypropylene glycol, number average molecular weight 2000, manufactured by NOF Corporation), 128.9 parts of isophorone diisocyanate, 12.7 parts of 2-hydroxyethyl acrylate, and 256.1 parts of stearyl methacrylate. The mixture was reacted at 85°C for 5 hours under a nitrogen stream to obtain 750.3 parts of a urethane prepolymer. Subsequently, the urethane prepolymer was added and dispersed in an aqueous solution containing 1208.0 parts of water, 225.0 parts of isopropyl alcohol, 26.6 parts of triethylamine, and 27.8 parts of adipic acid dihydrazide, while stirring, and the mixture was reacted at 50°C for 3 hours. Next, 5.0 parts of an azo polymerization initiator (trade name: "V-601", manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added, and the mixture was reacted at 80°C for 3 hours. Furthermore, a predetermined amount of water was added to obtain a urethane resin (A-1) having a nonvolatile content of 35%, a viscosity of 300 mPa·s, and a pH of 8.0.

[0102] Production Example 2

[0103] In a reaction vessel equipped with a stirrer, thermometer, cooling tube, and nitrogen inlet, 59.4 parts of dimethylolbutyric acid, 489.9 parts of PTMG1000 (polytetramethylene glycol, number average molecular weight 1000, manufactured by Mitsubishi Chemical Corporation), 275.5 parts of isophorone diisocyanate, and 12.7 parts of 2-hydroxyethyl acrylate were added and reacted at 85°C for 5 hours under a nitrogen flow to produce 826.8 parts of a urethane prepolymer. Subsequently, the urethane prepolymer was added and dispersed in an aqueous solution containing 1340.0 parts of water, 225.0 parts of isopropyl alcohol, 40.5 parts of triethylamine, and 43.3 parts of adipic acid dihydrazide while stirring, and the mixture was reacted at 50°C for 3 hours. Next, 0.1 part of an azo polymerization initiator (trade name: "V-50", manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added, and the mixture was reacted at 80°C for 1 hour. Furthermore, a predetermined amount of water was added to obtain a urethane resin (A-2) having a non-volatile matter concentration of 35%, a viscosity of 600 mPa·s, and a pH of 8.0.

[0104] Production Example 3

[0105] In a reaction vessel equipped with a stirrer, a thermometer, a cooling tube, and a nitrogen inlet, 59.4 parts of dimethylolbutyric acid, 489.9 parts of Polycerin DCB-2000, and 200.8 parts of isophorone diisocyanate were added and reacted at 85°C for 5 hours under a nitrogen stream to obtain 750.1 parts of a urethane prepolymer. Subsequently, the urethane prepolymer was added and dispersed in an aqueous solution containing 1208.0 parts of water, 225.0 parts of isopropyl alcohol, 26.6 parts of triethylamine, 40.5 parts of adipic acid dihydrazide, and 43.3 parts of adipic acid dihydrazide while stirring. The mixture was reacted at 50°C for 3 hours, and a predetermined amount of water was then added to obtain a urethane resin (A-3) having a non-volatile content of 35%, a viscosity of 800 mPa·s, and a pH of 8.0.

[0106] Example 1

[0107] 142.9 parts (50 parts of nonvolatile components) of the urethane resin (A-1), 166.7 parts (50 parts of nonvolatile components) of paraffin wax (trade name: "Sizepine W-116H", manufactured by Arakawa Chemical Industries, Ltd.), and 23.7 parts of ion-exchanged water were mixed to obtain an aqueous barrier composition.

[0108] Examples 2 to 19, Comparative Examples 1 to 6

[0109] Except having changed into the composition and content shown in Table 1, it carried out similarly to Example 1, and obtained the water-based barrier composition.

[0110] (Production of laminated board (1))

[0111] In the commercially available white kraft paper (basic weight 70g / m 2 , air permeability resistance: 80 seconds, moisture permeability: 10000g / m 2 · 24h or more) by using an arbitrary wire bar to apply the barrier water composition of each embodiment and comparative example, and then dry it in a hot air dryer set at 120°C for 3 minutes to obtain a laminate (1).

[0112] (Moisture Permeability)

[0113] The moisture permeability test method (cup method) of Japanese Industrial Standards (JIS) Z 0208 was used for measurement. The moisture permeability of the laminate (1) (cut into a circle with a diameter of 7 cm) was measured per 1 m in an environment of temperature 40°C and humidity 90%. 2 The number of grams of water vapor that passes through an area in 24 hours.

[0114] [Table 1]

[0115]

[0116] ※1: The weight parts of components (A) and (B) are expressed based on the weight of the non-volatile components.

[0117] ※2: The weight parts of the additives are expressed as the weight of the non-volatile components relative to 100 parts by weight (non-volatile components) of the total of the components (A) and (B).

[0118] ※2: The weight parts of the additives are expressed as the weight of the non-volatile components relative to 100 parts by weight (non-volatile components) of the total of the components (A) and (B).

[0119] ※3: The coating amount is expressed as a value based on solid content.

[0120] In Table 1, the symbols represent the following compounds.

[0121] (resin)

[0122] A-1: Urethane resin of Production Example 1

[0123] A-2: Urethane resin of Production Example 2

[0124] A-3: Urethane resin of Production Example 3

[0125] C-1: Olefin resin (trade name: "Polymaron 482S", manufactured by Arakawa Chemical Industries, Ltd., aqueous solution)

[0126] (wax)

[0127] B-1: Paraffin wax (trade name: Sizepine W-116H, manufactured by Arakawa Chemical Industries, Ltd., emulsion)

[0128] B-2: Carnauba wax (trade name: "EMUSTAR-0413", manufactured by Nippon Seira Co., Ltd., emulsion)

[0129] B-3: AKD-based emulsion (trade name: "Sizepine K-924", manufactured by Arakawa Chemical Industries, Ltd., emulsion)

[0130] D-1: Polyethylene wax (trade name: "CHEMIPEARL W401", manufactured by Mitsui Chemicals Co., Ltd., emulsion)

[0131] D-2: Fatty acid wax (trade name: "Sizepine CA-956", manufactured by Arakawa Chemical Industries, Ltd., emulsion)

[0132] (additive)

[0133] E-1: Saponified rosin (trade name: Sizepine E, manufactured by Arakawa Chemical Industries, Ltd., aqueous solution)

[0134] E-2: Rosin-based resin (trade name: Sizepine N-817, manufactured by Arakawa Chemical Industries, Ltd., emulsion)

[0135] E-3: Carbodiimide-based hardener (trade name: "Carbodilite SV-02", manufactured by Nisshinbo Chemical Co., Ltd., aqueous solution)

[0136] (Production of laminated board (2))

[0137] On the commercially available processed base paper (basic weight 50g / m 2 , Air permeability resistance: 90 seconds, Moisture permeability: 10000g / m 2 · 24h or more) after applying the barrier water composition of Example 1 using an arbitrary wire rod, and then drying it in a hot air dryer set at 120°C for 3 minutes to obtain a coating amount of 5g / m 2 The moisture permeability was measured in the same manner as in the previous paragraph and the result was 30 g / m 2 ·24h, showing good barrier properties.

[0138] (Production of laminated board (3))

[0139] A commercially available polyethylene terephthalate film (trade name: "Cosmoshine A4100", thickness 50 μm, moisture permeability: 13 g / m 2 · 24h, manufactured by Toyobo Co., Ltd.) After applying the barrier water composition of Example 1 using an arbitrary wire rod, it was dried in a hot air dryer set at 120°C for 3 minutes to obtain a coating amount of 5g / m 2 The moisture permeability was measured in the same manner as in the previous paragraph and the result was 4 g / m 2 ·24h, showing good barrier properties.

[0140] (Production of laminated board (4))

[0141] A commercially available triacetyl cellulose film (trade name: "FT TD80ULM", thickness 80 μm, moisture permeability: 330 g / m 2 · 24h, Fujifilm Corporation (manufactured) was coated with the barrier water composition of Example 12 using an arbitrary wire rod, and then dried in a hot air dryer set at 170°C for 3 minutes to obtain a coating amount of 5g / m 2The moisture permeability was measured in the same manner as in the previous paragraph and the result was 4 g / m 2 ·24h, showing good barrier properties.

Claims

1. A barrier water composition comprising: A urethane resin (A) containing a polyol (a1), a polyisocyanate (a2), and a chain extender (a3) ​​as essential reaction components; and Wax (B) is one or more selected from the group consisting of paraffin wax, carnauba wax and alkyl ketene dimer, in, The content ratio of the component (A) and the component (B) in terms of non-volatile matter weight is (A) / (B) = 25 / 75 to 95 / 5 The component (a3) ​​comprises a dialkanol alkanoic acid, The barrier aqueous composition is a barrier aqueous composition against water vapor.

2. The barrier aqueous composition according to claim 1, wherein The component (a1) contains a polyether polyol.

3. The barrier aqueous composition according to claim 1 or 2, wherein The reaction components further comprise a hydroxyalkyl (meth)acrylate (a4).

4. The barrier aqueous composition according to claim 1 or 2, wherein The reaction components further include a monoalkyl (meth)acrylate (a5) having no hydroxyl group.

5. The barrier aqueous composition according to claim 3, wherein The reaction components further include a monoalkyl (meth)acrylate (a5) having no hydroxyl group.

6. The barrier aqueous composition according to claim 1 or 2, wherein The barrier aqueous composition further contains a rosin resin and / or a hardener.

7. The barrier aqueous composition according to claim 3, wherein The barrier aqueous composition further contains a rosin resin and / or a hardener.

8. The barrier aqueous composition according to claim 4, wherein The barrier aqueous composition further contains a rosin resin and / or a hardener.

9. The barrier aqueous composition according to claim 5, wherein The barrier aqueous composition further contains a rosin resin and / or a hardener.

10. A laminated board, comprising a substrate having a coating layer of the aqueous barrier composition according to any one of claims 1 to 9 on at least one side thereof.

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