Aquatic urethane resin components, multilayer body and parts.

Abstract

Invention details;

Description

Aqueous urethane resin composition, laminate and article

[0001] The present invention relates to an aqueous urethane resin composition having excellent barrier resistance, adhesiveness, and blocking resistance, and to a laminate and an article using the aqueous urethane resin composition.

[0002] Forming a metal vapor-deposited film on the surface of a resin film can impart high gas barrier properties, and resin molded products with such vapor-deposited surfaces are widely used in everyday products such as packaging materials for foods and beverages.

[0003] The resin molded body is required to have good adhesion between the substrate and the vapor-deposited film. However, depending on the type of resin constituting the substrate, the adhesion to the vapor-deposited film may be poor. To improve the adhesion, for example, a formulation has been proposed in which a primer layer is provided on the surface of the substrate.

[0004] For example, it is known to use a resin layer containing a polyolefin resin as a primer, such as a vapor-deposited film laminate in which a resin layer containing a polyolefin resin and a vapor-deposited film are laminated in this order on a substrate, wherein the polyolefin resin is a polyolefin resin containing, as a main component, an olefin component (A) consisting of an alkene having 2 to 4 carbon atoms and containing 2 to 40 mass % of a (meth)acrylic acid ester component (B) (see, for example, Patent Document 1). However, these laminates have insufficient barrier resistance, adhesion, and blocking resistance, and do not satisfy the increasingly high performance requirements of recent years.

[0005] Therefore, there has been a demand for materials that have excellent barrier resistance, adhesiveness, and blocking resistance.

[0006] JP 2011-31526 A

[0007] The problem to be solved by the present invention is to provide an aqueous urethane resin composition having excellent barrier resistance, adhesion, and blocking resistance, and a laminate and an article using the aqueous urethane resin composition.

[0008] As a result of intensive research to solve the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by using a urethane resin having a specific aromatic ring concentration, which is made from a specific polyol compound as an essential raw material, and have thereby completed the present invention.

[0009] Specifically, the present invention relates to an aqueous urethane resin composition containing a urethane resin (A) having a polyol compound (a1) and a polyisocyanate compound (a2) as essential raw materials, and an aqueous medium (B), wherein the polyol compound (a1) contains a polyester polyol derived from diethylene glycol and / or ethylene glycol, and the urethane resin (A) has an aromatic ring concentration of 1.4 mol / kg or more, and a laminate and an article using the same.

[0010] The aqueous urethane resin composition of the present invention has excellent barrier resistance, adhesion, and blocking resistance, and can therefore be suitably used as a film primer or a coating agent for leather, textiles, metal products, etc. Furthermore, the aqueous urethane resin composition of the present invention uses raw materials with low greenhouse gas emissions, and therefore makes a significant contribution to carbon neutrality.

[0011] The aqueous urethane resin composition of the present invention contains a polyol compound (a1) and a polyisocyanate compound (a2) as essential raw materials.

[0012] As the polyol compound (a1), a polyester polyol is used as an essential component.

[0013] The polyester polyol is obtained by subjecting a polycarboxylic acid and a polyhydric alcohol to an esterification reaction, and at least one of diethylene glycol and ethylene glycol is used as the polyhydric alcohol.

[0014] Examples of the polycarboxylic acid include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid, their acid anhydrides, and esters thereof, and aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, maleic acid, pimelic acid, suberic acid, azelaic acid, itaconic acid, sebacic acid, chlorendic acid, 1,2,4-butanetricarboxylic acid, decanedicarboxylic acid, cyclohexanedicarboxylic acid, dimer acid, and fumaric acid, their acid anhydrides, and esters thereof. These polycarboxylic acids, their acid anhydrides, and their esters can be used alone or in combination of two or more.

[0015] In addition to diethylene glycol and ethylene glycol, other polyhydric alcohols may be used as needed, for example, aromatic diols such as benzenedimethanol, toluenedimethanol, and xylene dimethanol, and aliphatic polyols such as propylene glycol, 1,3-propylene diol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, triethylene glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, and neopentyl glycol ethylene glycol. These polyhydric alcohols may be used alone or in combination of two or more.

[0016] Among these, polyester polyols containing diethylene glycol and / or ethylene glycol and phthalic acid as essential raw materials are preferred, as they can give aqueous urethane resin compositions with excellent barrier resistance, adhesiveness, and blocking resistance.

[0017] In the esterification reaction for producing the polyester polyol, it is preferable to use an esterification catalyst for the purpose of promoting the esterification reaction. Examples of the esterification catalyst include metals such as titanium, tin, zinc, aluminum, zirconium, magnesium, hafnium, and germanium; and metal compounds such as titanium tetraisopropoxide, titanium tetrabutoxide, titanium oxyacetylacetonate, dibutyltin oxide, dibutyltin diacetate, dibutyltin dilaurate, tin octoate, 2-ethylhexanetin, zinc acetylacetonate, zirconium tetrachloride, zirconium tetrachloride tetrahydrofuran complex, hafnium tetrachloride, hafnium tetrachloride tetrahydrofuran complex, germanium oxide, and tetraethoxygermanium.

[0018] Furthermore, as the polyol compound (A), polyol compounds other than the polyester polyols can also be used as necessary.

[0019] Examples of the other polyol compounds include polyether polyols, polycarbonate polyols, etc. These polyol compounds can be used alone or in combination of two or more.

[0020] The content of the polyol compound (a1) in the raw materials for the urethane resin (A) is preferably in the range of 30 to 85% by mass, more preferably 50 to 85% by mass, because an aqueous urethane resin composition having excellent barrier resistance, adhesiveness, and blocking resistance can be obtained.

[0021] Examples of the polyisocyanate compound (a2) include aromatic polyisocyanates such as phenylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate, and carbodiimidized diphenylmethane polyisocyanate; aliphatic polyisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, dimer acid diisocyanate, and norbornene diisocyanate; and alicyclic diisocyanates such as norbornane diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated diphenylmethane diisocyanate. These polyisocyanate compounds can be used alone or in combination of two or more. Among these, toluene diisocyanate is preferred because it can provide an aqueous urethane resin composition having excellent barrier resistance, adhesiveness, and blocking resistance.

[0022] The content of the polyisocyanate compound (a2) in the raw materials for the urethane resin (A) is preferably in the range of 15 to 70 mass %, more preferably 15 to 50 mass %, because an aqueous urethane resin composition having excellent barrier resistance, adhesiveness, and blocking resistance can be obtained.

[0023] The aromatic ring concentration of the urethane resin (A) is 1.4 mol / kg or more, and since an aqueous urethane resin composition having excellent barrier resistance, adhesiveness, and blocking resistance can be obtained, the aromatic ring concentration is preferably in the range of 2 to 4 mol / kg, and more preferably in the range of 2.5 to 3.5 mol / kg.

[0024] The method for producing the urethane resin (A) is not particularly limited, and any method may be used. For example, the urethane resin (A) may be produced by reacting all of the reaction raw materials including the polyol compound (a1) and the polyisocyanate compound (a2) at once, or by reacting the reaction raw materials sequentially.

[0025] Examples of the aqueous medium (B) include ion-exchanged water, distilled water, etc. These aqueous media can be used alone or in combination of two or more.

[0026] The aqueous urethane resin composition of the present invention may also contain a crosslinking agent (C) if necessary.

[0027] Examples of the crosslinking agent (C) include a melamine crosslinking agent, a carbodiimide crosslinking agent, a water-dispersible polyisocyanate crosslinking agent, an epoxy crosslinking agent, an oxazoline crosslinking agent, and an aziridine crosslinking agent. These crosslinking agents can be used alone or in combination of two or more. Among these, carbodiimide crosslinking agents and water-dispersible polyisocyanate crosslinking agents are preferred because they provide an aqueous urethane resin composition having excellent barrier resistance, adhesiveness, and blocking resistance.

[0028] The amount of the crosslinking agent (C) used is preferably in the range of 6 to 20 mass %, and more preferably in the range of 9 to 20 mass %, of the solid content of the aqueous urethane resin composition, since an aqueous urethane resin composition having excellent barrier resistance, adhesiveness, and blocking resistance can be obtained.

[0029] The method for producing the aqueous urethane resin composition is not particularly limited, and any method may be used, for example, a method of mixing the urethane resin (A) and the aqueous medium (B).

[0030] Examples of methods for mixing the urethane resin (A) and the aqueous medium (B) include methods using a reaction vessel equipped with a stirring blade; a kneader such as a kneader, a continuous kneader, a taper roll, a single-screw extruder, a twin-screw extruder, a triple-screw extruder, a universal mixer, a Plastomill, or a Bodeta-type kneader; a rotary dispersion mixer such as a homomixer, a static mixer, FILMICS, an Ebara Milder, a Clearmix, an Ultra-Turrax, a Cavitron, or a Biomixer; an ultrasonic dispersion device; or a device such as an in-line mixer that has no moving parts and can mix by the flow of the fluid itself.

[0031] The mass ratio [(A) / (B)] of the urethane resin (A) to the aqueous medium (B) is preferably in the range of 50 / 50 to 80 / 20, and more preferably in the range of 50 / 50 to 70 / 30, since an aqueous urethane resin composition having excellent barrier resistance, adhesiveness, and blocking resistance can be obtained.

[0032] The aqueous urethane resin composition of the present invention may contain other additives as needed.

[0033] Examples of the other additives include surfactants, emulsifiers, thickeners, urethane catalysts, fillers, flame retardants, leveling agents, antiblocking agents, etc. These additives can be used alone or in combination of two or more.

[0034] Examples of the surfactant include nonionic surfactants such as polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene styrylphenyl ether, polyoxyethylene sorbitol tetraoleate, and polyethylene-polypropylene copolymer; anionic surfactants such as fatty acid salts such as sodium oleate, alkyl sulfate ester salts, alkylbenzene sulfonates, alkyl sulfosuccinates, naphthalene sulfonates, polyoxyethylene alkyl sulfates, sodium alkanesulfonates, and sodium alkyldiphenyl ether sulfonates; and cationic surfactants such as alkylamine salts, alkyltrimethylammonium salts, and alkyldimethylbenzylammonium salts.

[0035] Examples of the emulsifier include nonionic emulsifiers such as polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene styrylphenyl ether, polyoxyethylene sorbitol tetraoleate, and polyethylene-polypropylene copolymer; anionic emulsifiers such as fatty acid salts such as sodium oleate, alkyl sulfate ester salts, alkylbenzene sulfonates, alkyl sulfosuccinates, naphthalene sulfonates, polyoxyethylene alkyl sulfates, sodium alkanesulfonates, and sodium alkyldiphenyl ether sulfonates; and cationic emulsifiers such as alkylamine salts, alkyltrimethylammonium salts, and alkyldimethylbenzylammonium salts. These emulsifiers can be used alone or in combination of two or more.

[0036] Examples of the thickener include associative and acid thickeners.

[0037] Examples of the urethane catalyst include organotin catalysts and bismuth catalysts.

[0038] Examples of the filler include calcium carbonate and silica.

[0039] Examples of the flame retardant include phosphorus-based flame retardants.

[0040] Examples of the leveling agent include silicon-based leveling agents.

[0041] Examples of the anti-blocking agent include acrylic agents and cellulose ester agents.

[0042] The laminate of the present invention has a primer layer made of the aqueous urethane resin composition on the surface of a substrate, and a vapor-deposited layer on the surface of the primer layer.

[0043] The substrate is not particularly limited, and a thermoplastic resin film can be appropriately selected depending on the desired application. For example, for food packaging, polyolefin films such as polyethylene terephthalate (PET) film, polystyrene film, polyamide film, polyacrylonitrile film, polyethylene film (LLDPE: linear low-density polyethylene film, HDPE: high-density polyethylene film), polypropylene film (CPP: unstretched polypropylene film, OPP: biaxially oriented polypropylene film), polyvinyl alcohol film, ethylene-vinyl alcohol copolymer film, cycloolefin copolymer film, etc. can be used. These films can be preferably used with or without stretching treatment.

[0044] The article of the present invention includes the laminate, and examples thereof include packaging materials.

[0045] The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to the examples given below.

[0046] The number average molecular weights of the polyester polyols used in the examples and comparative examples are values ​​measured by gel permeation chromatography (GPC) under the following conditions.

[0047] Measurement apparatus: High-speed GPC apparatus ("HLC-8220GPC" manufactured by Tosoh Corporation) Column: The following columns manufactured by Tosoh Corporation were used, connected in series: "TSKgel G5000" (7.8 mm I.D. x 30 cm) x 1, "TSKgel G4000" (7.8 mm I.D. x 30 cm) x 1, "TSKgel G3000" (7.8 mm I.D. x 30 cm) x 1, "TSKgel G2000" (7.8 mm I.D. x 30 cm) x 1 Detector: RI (differential refractometer) Column temperature: 40°C Eluent: Tetrahydrofuran (THF) Flow rate: 1.0 mL / min Injection volume: 100 μL (tetrahydrofuran solution with a sample concentration of 0.4% by mass) Standard sample: A calibration curve was prepared using the following standard polystyrene.

[0048] (Standard polystyrene) "TSKgel Standard Polystyrene A-500" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene A-1000" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene A-2500" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene A-5000" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-1" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-2" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-4" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-10" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-20" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-40" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-80" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-128" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-288" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-550" manufactured by Tosoh Corporation

[0049] Synthesis Example 1 Synthesis of Polyester Polyol (1) 520 parts by mass of phthalic anhydride, 480 parts by mass of diethylene glycol, and 0.05 parts by mass of titanium tetraisopropoxide were charged into a polyester reaction vessel equipped with a stirrer, a nitrogen gas inlet tube, a distillation tube, a water separator, etc., and the mixture was gradually heated so that the temperature at the top of the distillation tube did not exceed 100° C., and the internal temperature was maintained at 220° C. When the acid value reached 10 mgKOH / g or less, heating was continued under reduced pressure of 100 torr, and the esterification reaction was terminated when the acid value reached 1 mgKOH / g or less, thereby obtaining a polyester polyol (1) having a number average molecular weight of 985.

[0050] Synthesis Example 2 Synthesis of Polyester Polyol (2) A polyester reaction vessel equipped with a stirrer, a nitrogen gas inlet tube, a distillation tube, a water separator, etc. was charged with 462 parts by mass of phthalic anhydride, 539 parts by mass of diethylene glycol, and 0.05 parts by mass of titanium tetraisopropoxide, and the mixture was gradually heated so that the temperature at the top of the distillation tube did not exceed 100° C., and the internal temperature was maintained at 220° C. When the acid value reached 10 mgKOH / g or less, heating was continued under reduced pressure of 100 torr, and the esterification reaction was terminated when the acid value reached 1 mgKOH / g or less, thereby obtaining a polyester polyol (2) having a number average molecular weight of 509.

[0051] Synthesis Example 3 Synthesis of Polyester Polyol (3) A polyester reaction vessel equipped with a stirrer, a nitrogen gas inlet tube, a distillation tube, a water separator, etc. was charged with 661 parts by mass of phthalic anhydride, 339 parts by mass of ethylene glycol, and 0.05 parts by mass of titanium tetraisopropoxide, and the mixture was gradually heated so that the temperature at the top of the distillation tube did not exceed 100° C., and the internal temperature was maintained at 220° C. When the acid value reached 10 mgKOH / g or less, heating was continued under reduced pressure of 100 torr, and the esterification reaction was terminated when the acid value reached 1 mgKOH / g or less, thereby obtaining a polyester polyol (3) having a number average molecular weight of 1,001.

[0052] Synthesis Example 4 Synthesis of Polyester Polyol (4) 621 parts by mass of phthalic anhydride, 380 parts by mass of ethylene glycol, and 0.05 parts by mass of titanium tetraisopropoxide were charged into a polyester reaction vessel equipped with a stirrer, a nitrogen gas inlet tube, a distillation tube, a water separator, etc., and the mixture was gradually heated so that the temperature at the top of the distillation tube did not exceed 100° C., and the internal temperature was maintained at 220° C. When the acid value reached 10 mgKOH / g or less, heating was continued under reduced pressure of 100 torr, and the esterification reaction was terminated when the acid value reached 1 mgKOH / g or less, thereby obtaining a polyester polyol (4) having a number average molecular weight of 518.

[0053] Synthesis Example 5 Synthesis of Polyester Polyol (5) A polyester reaction vessel equipped with a stirrer, a nitrogen gas inlet tube, a distillation tube, a water separator, and the like was charged with 595 parts by mass of adipic acid, 405 parts by mass of 1,4-butylene glycol, and 0.05 parts by mass of titanium tetraisopropoxide, and the mixture was gradually heated so that the temperature at the top of the distillation tube did not exceed 100° C., and the internal temperature was maintained at 220° C. When the acid value reached 10 mgKOH / g or less, heating was continued under reduced pressure of 100 torr, and the esterification reaction was terminated when the acid value reached 1 mgKOH / g or less, thereby obtaining a polyester polyol (5) having a number average molecular weight of 2,000.

[0054] The compositions of the polyester polyols (1) to (5) obtained in Synthesis Examples 1 to 5 are shown in Table 1.

[0055]

[0056] Example 1: Synthesis of aqueous urethane resin composition (1) To a four-neck flask equipped with a thermometer, a stirrer, a reflux condenser, and a nitrogen inlet tube, 124 parts by mass of the polyester polyol (1) obtained in Synthesis Example 1, 11 parts by mass of 2,2-dimethylolpropionic acid (DMPA), and 139 parts by mass of methyl ethyl ketone were added, and then 36 parts by mass of tolylene diisocyanate was added, and the mixture was reacted at 75°C for 8 hours. The mixture was then cooled to 50°C, and 8.5 parts by mass of triethylamine was added to neutralize the mixture, yielding a urethane resin. 682 parts by mass of ion-exchanged water was then added to solubilize the mixture. The resulting transparent reaction product was heated under reduced pressure at 40 to 60°C to remove methyl ethyl ketone, and then ion-exchanged water was added to adjust the concentration, yielding a stable aqueous urethane resin composition (1) with a non-volatile content of 23% by mass.

[0057] (Examples 2 to 4: Synthesis of aqueous urethane resin compositions (2) to (4)) Aqueous urethane resin compositions (2) to (4) were obtained in the same manner as in Example 1, except that the polyester polyol used in Example 1 was changed to one shown in Table 2.

[0058] Comparative Example 1: Synthesis of aqueous urethane resin composition (R1) An aqueous urethane resin composition (R1) was obtained in the same manner as in Example 1, except that the polyester polyol used in Example 1 was changed to one shown in Table 2.

[0059] (Comparative Example 2: Synthesis of aqueous urethane resin composition (R2)) An aqueous urethane resin composition (R2) was obtained in the same manner as in Example 1, except that the polyester polyol used in Example 1 was changed to the polytetramethylene glycol shown in Table 2.

[0060] The compositions of the aqueous urethane resin compositions (1) to (4) obtained in Examples 1 to 4 and the aqueous urethane resin compositions (R1) and (R2) obtained in Comparative Examples 1 and 2 are shown in Table 2.

[0061]

[0062] (Examples 5 to 10: Preparation of primer coating agents (1) to (6)) A crosslinking agent was added to 10 parts by mass of the aqueous urethane resin composition obtained in the examples according to Table 3, and the mixture was diluted with water as an aqueous medium, thereby obtaining primer coating agents (1) to (6) with a non-volatile content of 10% by mass.

[0063] Comparative Examples 3 to 6: Preparation of primer coating agents (R1) to (R4) Primer coating agents (R1) to (R4) with a non-volatile content of 10% by mass were obtained in the same manner as in Examples 5 to 10 using the formulations shown in Table 3.

[0064] The following evaluations were carried out using the primer coating agents (1) to (6) and (R1) to (R4) obtained in the above Examples and Comparative Examples.

[0065] [Method for evaluating blocking resistance] A substrate that had been subjected to corona treatment was attached to an OPP substrate ("FOR" manufactured by Futamura Chemical Co., Ltd., 20 μm thick) coated with the primer coating agent obtained in the examples and comparative examples, and subjected to a pressure of 2 kgf / cm ２ The substrate was left to stand in a dryer at 40°C for 16 hours under a load of 1.0 g, and then the substrate was peeled off and the adhesiveness was evaluated according to the following criteria.

[0066] ◯: No stickiness at all, easily peeled off. Δ: Some stickiness, but no change to the coated surface. ×: Strong stickiness, surface defects observed on the coated surface.

[0067] [Method for Evaluating Adhesion] In the present invention, adhesion was evaluated by measuring the laminate adhesive strength.

[0068] An adhesive was prepared by blending DIC Dry LX-703VL (a solvent-based polyester polyol manufactured by DIC Graphics Corporation) and KR-90 (a polyisocyanate crosslinking agent manufactured by DIC Graphics Corporation) at a mass ratio of 15 / 1 on the surface of an OPP substrate (FOR manufactured by Futamura Chemical Co., Ltd., 20 μm thick) that had been coated with the primer coating agent obtained in the Examples and Comparative Examples, and then blending ethyl acetate so that the non-volatile content was 30%.

[0069] The adhesive obtained was applied using a bar coater at a coating amount of 3.0 g / m ２ The adhesive layer was formed by applying a coating solution containing 1500 ppm of ethylenediaminetetraacetic acid (E2), and the solvent was evaporated using hot air at 80°C using a dryer. A CPP film (RXC-22, count 50, manufactured by Mitsui Tocello Co., Ltd.) was then laminated onto the adhesive layer. The film was then placed in a dryer at 40°C for aging, yielding a laminate film for evaluation. The laminate film was cut into 15 mm widths in the coating direction, and the laminate film was peeled at a 180° angle using a desktop precision universal testing machine (Autograph AGS-X, manufactured by Shimadzu Corporation) at an ambient temperature of 23°C and a peel rate of 300 mm / min. The tensile strength measured was the laminate strength. The laminate strength was measured in units of N / 15 mm.

[0070] [Method for Evaluating Barrier Resistance] In the present invention, the barrier resistance was evaluated by measuring oxygen permeability.

[0071] Vapor deposition was carried out on an OPP substrate (Futamura Chemical Co., Ltd. "FOR", 20 μm thick) coated with the primer coating agent obtained in the Examples and Comparative Examples, and the oxygen permeability (cc / (m)) was measured in accordance with JIS-K7126 (constant pressure method) under an atmosphere of 23°C x 0% RH (relative humidity) using MOCON "OX-TRAN2 / 22". ２ ·day·atm) was measured.

[0072] Table 3 shows the compositions and evaluation results of the primer coating agents (1) to (6) and (R1) to (R4) obtained in the above Examples and Comparative Examples.

[0073]

[0074] "AE-301" in Table 3 indicates "AE-301" (aqueous modified polypropylene resin) manufactured by Nippon Paper Industries Co., Ltd.

[0075] "Carbodilite SV-02" in Table 3 refers to "Carbodilite SV-02" (carbodiimide crosslinking agent) manufactured by Nisshinbo Chemical Inc.

[0076] "Bayhydur Ultra 3100" in Table 3 indicates "Bayhydur Ultra 3100" (polyisocyanate crosslinking agent) manufactured by Sumika Covestro Urethane Co., Ltd.

[0077] Examples 5 to 10 shown in Table 3 are examples of primer coating agents containing the aqueous urethane resin composition of the present invention. These primer coating agents were confirmed to have excellent barrier resistance, adhesion, and blocking resistance.

[0078] On the other hand, Comparative Example 3 shown in Table 3 is an example of a primer coating agent containing an aqueous urethane resin composition in which a polyester polyol containing no diethylene glycol or ethylene glycol was used as a raw material for the urethane resin. It was confirmed that this primer coating agent had significantly insufficient barrier resistance.

[0079] Comparative Example 4 shown in Table 3 is an example of a primer coating agent containing an aqueous urethane resin composition that does not use polyester polyol as a raw material for the urethane resin. It was confirmed that this primer coating agent had significantly insufficient blocking resistance.

[0080] Comparative Examples 5 and 6 shown in Table 3 are examples of primer coating agents that do not use an aqueous urethane resin composition. It was confirmed that these primer coating agents were significantly insufficient in barrier resistance.

Claims

DEPCT681. Aquatic urethane resin composition which includes: (A) urethane resin made from (a1) polyol compounds and (a2) polyisocyanate compounds as necessary raw materials; and (B) aquatic intermediates, in which polyol compounds (a1) include polyester polyols made from diethylene glycol and / or ethylene glycol as raw materials, and urethane resin (A) has an aromatic ring concentration of 1.4 mol / kg or more.

2. Aquatic urethane resin composition according to claim 1, in which polyester polyols are made from diethylene glycol and / or ethylene glycol and phthalic acid compounds.

3. An aqueous urethane resin composition under claim 1, in which the polyisocyanate compound (a2) is toluene diisocyanate; 4. An aqueous urethane resin composition under claim 1, in which the aqueous urethane resin is further incorporated to (C) crosslinking aids; 5. A laminated sheet incorporating: a primer layer formed from any one of the aqueous urethane resin compositions under claims 1 to 4 on the substrate surface; and an adhesion layer on the surface of that primer layer; 6. A material incorporating a laminated sheet incorporating the composition under claim 5;