JP2015013914A - Aqueous urethane resin composition and article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aqueous urethane resin composition providing an article which can be heat-sensitively coagulated and has excellent texture or surface appearance.SOLUTION: There is provided an aqueous urethane resin composition which contains an aqueous urethane resin (A) and water (B) and further contains 5 to 100 pts.mass of an organic solvent (C) based on 100 pts.mass of the urethane resin (A). The aqueous urethane resin composition of the present invention can provide an article which can be heat-sensitively coagulated and has excellent texture or surface appearance. Therefore, the aqueous urethane resin composition of the present invention can be used for various applications such as shoes, bags, clothing materials, furniture components such as tables or sofas, interior materials for automobile such as vehicle sheets or handles, moisture-permeable waterproof materials, leather-like sheets such as synthetic leathers or artificial leathers, gloves, nonwoven belts, heat insulation materials, abrasive materials and core materials for felt pens.

Description

  The present invention relates to an aqueous urethane resin composition that can be used, for example, in the production of leather-like sheets, gloves and the like.

  Aqueous urethane resin composition in which urethane resin is dispersed in water can reduce the burden on the environment compared to conventional organic solvent-based urethane resin compositions. For example, coating agents, adhesives, and leather-like In recent years, it has been suitably used as a material for producing sheets and gloves.

As the aqueous urethane resin composition, for example, an aqueous urethane resin composition obtained by reacting polycarbonate polyol, organic diisocyanate and dimethylolpropionic acid, and an aqueous urethane resin composition containing water are disclosed (for example, (See Patent Document 1).

  However, the water-based urethane resin composition does not thermally coagulate, and thus has problems such as poor flexibility (texture) and poor surface appearance such as cracks on the surface of the article.

JP 2005-146089 A

  The problem to be solved by the present invention is to provide a water-based urethane resin composition that can be thermally coagulated and gives an article having excellent texture and surface appearance.

In the aqueous urethane resin composition containing the aqueous urethane resin (A) and water (B), the present invention relates to an organic solvent in the range of 5 to 100 parts by mass with respect to 100 parts by mass of the aqueous urethane resin (A). It further relates to an aqueous urethane resin composition characterized by further containing C).

  The aqueous urethane resin composition of the present invention can be heat-sensitively coagulated and can give an article excellent in texture and surface appearance. Accordingly, the water-based urethane resin composition of the present invention includes shoes, bags, clothing, furniture members such as chairs and sofas, automobile interior materials such as vehicle seats and handles, moisture-permeable waterproof materials, synthetic leather, artificial leather, and the like. It can be used in various applications such as leather-like sheets, gloves, non-woven belts, heat insulating materials, abrasives, and felt pen core materials.

  The aqueous urethane resin composition of the present invention contains an aqueous urethane resin (A), water (B) and an organic solvent (C).

  The aqueous urethane resin (A) can be dispersed in water (B), for example, those having hydrophilic groups such as nonionic groups, anionic groups, and cationic groups, and dispersions of emulsifiers and the like. An agent that is forcibly dispersed in water (B) can be used. Among these, it is preferable to use a water-based urethane resin having a nonionic group or a water-based urethane resin dispersed in water (B) using a nonionic emulsifier described later, from the viewpoint of further improving the heat-sensitive coagulation property.

  As the aqueous urethane resin having a nonionic group, one having a polyoxyethylene structure can be used, for example, a polyol (a-1) containing a polyether polyol (a-1-1) having a polyoxyethylene structure. ), A polyisocyanate (a-2) and, if necessary, a product obtained by reacting a chain extender (a-3) can be used.

  As polyether polyol (a-1-1) which has the said polyoxyethylene structure, polyoxyethylene polyoxypropylene glycol, polyoxyethylene polyoxytetramethylene glycol etc. can be used, for example.

  Examples of the polyether polyol (a-1-1) include those obtained by addition polymerization of alkylene oxide containing ethylene oxide using one or more compounds having two or more active hydrogen atoms as an initiator. Can be used.

  Examples of the initiator include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, glycerin, and trimethylolethane. Trimethylolpropane and the like can be used.

  As said alkylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, etc. can be used in combination with ethylene oxide, for example.

  The weight average molecular weight of the polyether polyol (a-1-1) is in the range of 500 to 8,000 for imparting good water dispersibility and heat-sensitive coagulation to the aqueous urethane resin (A). It is preferable that the range is 600 to 4,000. In addition, the weight average molecular weight of the said polyether polyol (a-1-1) shows the value measured on condition of the following by gel permeation chromatography (GPC) method.

Measuring device: High-speed GPC device (“HLC-8220GPC” manufactured by Tosoh Corporation)
Column: The following columns manufactured by Tosoh Corporation were connected in series.
"TSKgel G5000" (7.8 mm ID x 30 cm) x 1 "TSKgel G4000" (7.8 mm ID x 30 cm) x 1 "TSKgel G3000" (7.8 mm ID x 30 cm) x 1 “TSKgel G2000” (7.8 mm ID × 30 cm) × 1 detector: RI (differential refractometer)
Column temperature: 40 ° C
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 mL / min Injection amount: 100 μL (tetrahydrofuran solution with a sample concentration of 0.4 mass%)
Standard sample: A calibration curve was prepared using the following standard polystyrene.

(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

  Examples of the polyol that can be used other than the polyether polyol (a-1-1) as the polyol (a-1) include polyether polyols and polyesters other than the polyether polyol (a-1-1). Polyol, polycarbonate polyol, polybutadiene polyol, polyacryl polyol and the like can be used. The weight average molecular weight of the polyol (a-1) is preferably in the range of 500 to 8,000. In addition, the weight average molecular weight of the said polyol (a-1) shows the value obtained by measuring similarly to the weight average molecular weight of the said polyether polyol (a-1-1).

  Examples of the polyisocyanate (a-2) include aromatic polyisocyanates such as phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate, carbodiimidized diphenylmethane polyisocyanate; hexamethylene diisocyanate, lysine Aliphatic or alicyclic polyisocyanates such as diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, dimer acid diisocyanate and norbornene diisocyanate can be used. These polyisocyanates may be used alone or in combination of two or more.

  Examples of the chain extender (a-3) include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, and 4,4′-dicyclohexylmethane. Diamine, 3,3′-dimethyl-4,4′-dicyclohexylmethanediamine, 1,4-cyclohexanediamine, -hydroxymethylaminoethylamine, N-hydroxyethylaminoethylamine, N-hydroxypropylaminopropylamine, N-ethylamino Ethylamine, N-methylaminopropylamine, ethylenetriamine, dipropylenetriamine, triethylenetetramine, hydrazine, N, N'-dimethylhydrazine, 1,6-hexamethylenebishydrazine, succinic acid dihydrazide Adipic acid dihydrazide, glutaric acid dihydrazide, sebacic acid dihydrazide, isophthalic acid dihydrazide, β-semicarbazide propionic acid hydrazide, 3-semicarbazide-propyl-carbazate, semicarbazide-3-semicarbazide methyl-3,5,5- Chain extender having an amino group such as trimethylcyclohexane; ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, saccharose , Methylene glycol, glycerin, sorbitol, bisphenol A, 4,4′-dihydroxydiphenyl, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy A chain extender having a hydroxyl group such as sidiphenylsulfone, hydrogenated bisphenol A, hydroquinone, or trimethylolpropane can be used. These chain extenders may be used alone or in combination of two or more.

  As a manufacturing method of the water-based urethane resin which has the said nonionic group, for example, the said polyol (a-1) and the said polyisocyanate (a-2) are mixed in absence of a solvent or presence of an organic solvent, 50 degreeC. By reacting at about 100 ° C. for about 3 hours to 10 hours to obtain a urethane prepolymer having an isocyanate group, supplying water (B) described below and an emulsifier as necessary, mixing, stirring, Examples include a method in which the water-based urethane resin (A) is dispersed in the water (B), and then the urethane prepolymer and the chain extender (a-3) are mixed and reacted. In addition, when mixing the said urethane prepolymer and the said water (B), you may use machines, such as a homogenizer, as needed. When the organic solvent solution is contained in the mixed solution of the urethane prepolymer, the water (B), and the chain extender (a-3), it is preferable to remove the solvent thereafter.

  Examples of the organic solvent include ketone solvents such as acetone and methyl ethyl ketone; ether solvents such as tetrahydrofuran and dioxane; acetate solvents such as ethyl acetate and butyl acetate; nitrile solvents such as acetonitrile; dimethylformamide, N-methylpyrrolidone and the like. An amide solvent or the like can be used. These organic solvents may be used alone or in combination of two or more.

  The reaction of the polyol (a-1), the polyisocyanate (a-2), and the chain extender (a-3) is performed by reacting the hydroxyl group of the polyol (a-1) with the chain extender (a-3). ) And the equivalent ratio of the isocyanate group of the polyisocyanate (a-2) [isocyanate group / (hydroxyl group + amino group)] is 0.5 to 1.5. The range is preferable, and the range of 0.9 to 1.1 is more preferable.

  As an aqueous | water-based urethane resin disperse | distributed in water (B) using the said nonionic emulsifier, the thing similar to the aqueous | water-based urethane resin which has the said nonionic group can be used. However, as the polyol (a-1), the polyether polyol (a-1-1) is not necessarily an essential component.

  Examples of the nonionic emulsifier include polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene sorbitol tetraoleate, polyoxyethylene / polyoxypropylene copolymer, and the like. be able to.

  The number average molecular weight of the aqueous urethane resin (A) is preferably in the range of 30,000 to 500,000 from the viewpoint that the texture and surface appearance of the article can be further improved. In addition, the number average molecular weight of the said water-based urethane resin shows the value obtained by measuring similarly to the weight average molecular weight of the said polyether polyol (a-1-1).

  As content of the said water-based urethane resin (A), it is preferable that it is the range of 10-40 mass% in water-based urethane resin composition from points, such as a viscosity and a heat-sensitive coagulation property, It is the range of 15-30 mass%. Preferably there is.

  As said water (B), ion-exchange water, distilled water, etc. can be used, for example. As content of the said water (B), it is preferable that it is the range of 10-80 mass% in water-based urethane resin composition from points, such as a viscosity and a heat-sensitive coagulation property, and it is the range of 20-70 mass%. Is more preferable.

  Examples of the organic solvent (C) include ketone solvents such as acetone and methyl ethyl ketone; alcohol solvents such as methanol, ethanol, n-propanol, and isopropanol; polyalkylene glycol solvents such as ethylene glycol, diethylene glycol, and propylene glycol; Alkyl ether solvents: lactam solvents such as N-methyl-2-pyrrolidone can be used. These organic solvents may be used alone or in combination of two or more. As the organic solvent (C), one or more organic solvents selected from the group consisting of a ketone solvent and an alcohol solvent are used from the viewpoint that the miscibility with the water (B), the heat-sensitive coagulation property, and the like can be further improved. It is preferable.

  As content of the said organic solvent (C), it is essential when solving the subject of this invention that it is the range of 5-100 mass parts with respect to 100 mass parts of said water-based urethane resins (A). When the content of the organic solvent (C) is less than 5 parts by mass, the heat-sensitive coagulation temperature becomes high, the workability and formability are poor, and the texture and surface appearance of the article are poor. If it exceeds 100 parts by mass, it may solidify at room temperature, or the dispersibility of the water-based urethane resin may be poor and may not be solidified. As content of the said organic solvent (C), it is 10-90 mass parts with respect to 100 mass parts of said water-based urethane resins (A) from the point which can improve further the heat-sensitive coagulation property, the texture of articles | goods, and surface appearance. It is preferable that it is the range of 20-80 mass parts.

  The water-based urethane resin composition of the present invention contains the water-based urethane resin (A), the water (B) and the organic solvent (C) as essential components, and various additives as necessary. It may be included. Examples of the additive include associative thickeners, alkali-soluble thickeners, crosslinking agents, urethanization catalysts, silane coupling agents, fillers, thixotropic agents, tackifiers, waxes, heat stabilizers. , Light-resistant stabilizer, fluorescent brightening agent, foaming agent, thermoplastic resin, thermosetting resin, pigment, dye, conductivity imparting agent, antistatic agent, moisture permeability improver, water repellent, oil repellent, hollow foam , Water-containing compound, flame retardant, water-absorbing agent, moisture-absorbing agent, deodorant, foam stabilizer, anti-foaming agent, antifungal agent, antiseptic, algal inhibitor, pigment dispersant, anti-blocking agent, hydrolysis inhibitor Etc. can be used.

  As a manufacturing method of the aqueous | water-based urethane resin composition of this invention, the method of mix | blending the said organic solvent (C) with the solution containing the water-based urethane resin (A) and water (B) obtained by the said method, for example. Can be mentioned.

  Since the aqueous urethane resin composition of the present invention is excellent in texture and surface appearance, it can be used for various substrates.

  Examples of the base material include fiber base materials such as woven fabrics and non-woven fabrics; leather-like sheets; plated steel plates such as galvanized steel plates and aluminum-zinc alloy steel plates; aluminum plates, aluminum alloy plates, electromagnetic steel plates, copper plates, and stainless steel plates. Metal base materials such as polycarbonate base materials, polyester base materials, acrylonitrile-butadiene-styrene base materials, polyacryl base materials, polystyrene base materials, polyurethane base materials, epoxy resin base materials, polyvinyl chloride base materials, polyamide base materials Plastic base materials such as materials; glass base materials and the like can be used.

  The aqueous urethane resin composition of the present invention can form a film by, for example, applying it directly to the substrate surface, and then drying and curing. It is also possible to form a film by applying the aqueous urethane resin composition of the present invention to the release paper surface, drying and curing, and then laminating the substrate on the coated surface. Moreover, when using a fiber base material as said base material, the said fiber base material can be impregnated in the said water-based urethane resin composition, and this coating material can also be dried and hardened | cured and a film | membrane can also be formed.

  Examples of the method for applying and impregnating the aqueous urethane resin composition onto the substrate include a spray method, a curtain coater method, a flow coater method, a roll coater method, a brush coating method, and a dipping method.

  The method for proceeding with the drying and curing may be a method of curing for about 1 to 10 days at room temperature, but from the viewpoint of rapidly proceeding curing, at a temperature of 50 ° C. to 250 ° C. for 1 second. A method of heating for about ~ 600 seconds is preferred. Moreover, when using the plastic base material which is easy to deform | transform and discolor at comparatively high temperature, it is preferable to cure at comparatively low temperature of about 30 degreeC-100 degreeC.

  Although the film thickness of the film formed using the aqueous urethane resin composition of the present invention can be appropriately adjusted according to the use of the substrate, it is usually preferably about 0.5 μm to 100 μm.

[Example 1] Preparation of aqueous urethane resin composition (X-1) In a four-necked flask equipped with a stirrer, a thermometer, and a reflux tube, 500 mass of polytetramethylene glycol (weight average molecular weight: 1,300) was added. Parts, 1,3-butanediol 15.3 parts by mass, trimethylolpropane 11.1 parts by mass, polyethylene glycol (number average molecular weight: 600) 39.4 parts by mass, isophorone diisocyanate 223.4 parts by mass, 425 parts by mass of methyl ethyl ketone and 0.2 part by mass of dibutyltin dilaurate were added and reacted at 70 ° C. until the isocyanate (NCO)% reached 1.8% to obtain a urethane prepolymer having an isocyanate group. This urethane prepolymer was mixed with 1,239 parts by mass of an emulsifier aqueous solution in which 55.2 parts by mass of polyoxyethylene distyrenated phenyl ether (HLB (Hydrophile-Lipophile Balance): 14) was dissolved. After emulsifying and dispersing, 220 parts by mass of a chain extender aqueous solution in which 22 parts by mass of anhydrous piperazine was dissolved was added to cause chain elongation. Subsequently, methyl ethyl ketone was distilled off under reduced pressure to obtain an aqueous urethane resin (A-1) having a solid content of 40% by mass. By adding and mixing 90 parts by mass of water and 10 parts by mass of acetone with respect to 100 parts by mass of this aqueous urethane resin (A-1), an aqueous urethane resin composition (X-1) was obtained.

[Example 2] Preparation of aqueous urethane resin composition (X-2) By adding and mixing 70 parts by mass of water and 30 parts by mass of acetone with respect to 100 parts by mass of the aqueous urethane resin (A-1), an aqueous solution was obtained. A urethane resin composition (X-2) was obtained.

[Example 3] Preparation of water-based urethane resin composition (X-3) To 100 parts by weight of the water-based urethane resin (A-1), 90 parts by weight of water and 10 parts by weight of methyl ethyl ketone were added and mixed to form an aqueous solution. A urethane resin composition (X-3) was obtained.

[Example 4] Preparation of aqueous urethane resin composition (X-4) To 100 parts by mass of the aqueous urethane resin (A-1), 90 parts by mass of water and 10 parts by mass of isopropyl alcohol were added and mixed. An aqueous urethane resin composition (X-4) was obtained.

[Example 5] Preparation of water-based urethane resin composition (X-5) To 100 parts by weight of the water-based urethane resin (A-1), 90 parts by weight of water and 10 parts by weight of methanol were added and mixed to form an aqueous solution. A urethane resin composition (X-5) was obtained.

[Comparative Example 1] Preparation of aqueous urethane resin composition (X-6) 100 parts by mass of water was added to and mixed with 100 parts by mass of the aqueous urethane resin (A-1). X-6) was obtained.

[Comparative Example 2] Preparation of aqueous urethane resin composition (X-7) To 100 parts by mass of the aqueous urethane resin (A-1), 98.4 parts by mass of water and 1.6 parts by mass of acetone were added and mixed. As a result, an aqueous urethane resin composition (X-7) was obtained.

[Comparative Example 3] Preparation of aqueous urethane resin composition (X-8) By adding and mixing 50 parts by mass of acetone with respect to 100 parts by mass of the aqueous urethane resin (A-1), an aqueous urethane resin composition ( X-8) was obtained.

[Thermal solidification (Method for measuring thermal solidification temperature)]
What was adjusted so that the non volatile matter of the aqueous | water-based urethane resin composition obtained by the said method might be 20 mass% was 1 degreeC / min using the viscosity and viscoelasticity measuring apparatus "Reo Stress" (made by HAAKE). The viscosity was measured while heating under conditions. The temperature at which the viscosity exceeded 100 mPa · s was defined as the solidification temperature. In addition, what has solidified immediately at room temperature,
Evaluated as “not measurable”. In addition, since the article was not obtained when the thermal coagulation evaluation was “not measurable”, the following measurement was not performed and “−” was written.

[Production method of work cloth]
100 parts by mass of the aqueous urethane resin obtained by the above method and 100 parts by mass of water were stirred with a mechanical mixer at 2,000 rpm for 2 minutes to obtain an aqueous urethane resin compounded liquid. The aqueous urethane resin compounded liquid was impregnated into a non-woven fabric having a basis weight of 300 g / m ² made of polyester fiber, and squeezed so that the wet pickup would be 100%. Subsequently, it dried for 10 minutes at 100 degreeC using the gear type hot air dryer, and the work cloth was obtained by evaporating the water | moisture content and organic solvent which are contained in the said work cloth.

[Fabric texture test]
The texture of the work cloth obtained by the above method was evaluated by tactile sensation as follows.
“A”: rich in flexibility, “B”: somewhat flexible, “C”: poor flexibility, “D”: hard

[Glove making method]
Nylon gloves were attached in advance, and a hand mold heated to 90 ° C. was immersed for 10 seconds in the aqueous urethane resin compounded liquid obtained in the above [Process Fabric Preparation Method] from the glove palm. After dipping, the handprint was heated in a hot air dryer at 120 ° C. and dried to obtain a glove.

[Glove texture, surface appearance, cross-section test]
The texture, surface appearance, and cross section of the glove obtained by the above method were evaluated as follows by touch and visual observation.
(Gloves texture)
“A”: rich in flexibility, “B”: somewhat flexible, “C”: poor flexibility, “D”: hard (gloves surface appearance)
“T”: no crack on the surface of the glove, “F”: crack on the surface of the glove (cross section of the glove)
“T”: Water-based urethane resin does not penetrate into the inside of the glove.
“F”: Water-based urethane resin penetrates and penetrates to the inside of the glove.

  It was found that the aqueous urethane resin composition of the present invention can be heat-sensitively coagulated, and an article having excellent texture and surface appearance can be obtained.

  On the other hand, Comparative Example 1 is an embodiment that does not contain an organic solvent (C), and Comparative Example 2 is an embodiment in which the content of the organic solvent (C) is less than the range defined in the present invention. Further, the texture was poor and the surface appearance was poor.

  Further, Comparative Example 3 is an embodiment in which the content of the organic solvent (C) exceeds the range specified in the present invention, but processing evaluation was impossible because it immediately solidified after blending.

Claims (3)

In the aqueous urethane resin composition containing the aqueous urethane resin (A) and water (B), the organic solvent (C) in the range of 5 to 100 parts by mass is further added to 100 parts by mass of the aqueous urethane resin (A). An aqueous urethane resin composition characterized by containing. The aqueous urethane resin composition according to claim 1, wherein the organic solvent (C) is at least one selected from the group consisting of a ketone solvent and an alcohol solvent. An article obtained by using the aqueous urethane resin composition according to claim 1 or 2.