JP7289314B2 - Aqueous resin composition, film, and moisture-permeable waterproof fabric - Google Patents

Description

TECHNICAL FIELD The present invention relates to an aqueous resin composition, a film, and a moisture-permeable waterproof fabric.

Polyurethane resins are widely used in the production of moisture-permeable clothing because of their mechanical strength and good texture. In this application, solvent-based urethane resins containing N,N-dimethylformamide (DMF) have hitherto been the mainstream. However, against the backdrop of DMF regulations in Europe, stricter VOC emission regulations in China and Taiwan, and DMF regulations by major apparel makers, there is a demand to eliminate DMF from urethane resins that make up moisture-permeable clothing.

In order to respond to such changes of the times, urethane resin compositions in which urethane resin is dispersed in water have been widely studied (see, for example, Patent Document 1). However, among the moisture-permeable clothing, functional shoes and moisture-permeable waterproof clothing must have excellent moisture permeability, but a water-based urethane material with excellent moisture permeability has not yet been found.

JP 2007-119749 A

The problem to be solved by the present invention is to provide a water-containing resin composition having excellent moisture permeability and water elution resistance.

The present invention provides an anionic urethane resin (X), an acrylic resin (Y ), a cross-linking agent (Z), and water (V).

The present invention also provides a dry film of the aqueous resin composition and a moisture-permeable waterproof fabric having the same.

INDUSTRIAL APPLICABILITY The aqueous resin composition of the present invention is an environmentally friendly material containing water, and can form a film having high moisture permeability and excellent elution resistance to water. Therefore, the water-based resin composition of the present invention can be used particularly suitably as a material used for moisture-permeable waterproof fabrics.

The aqueous resin composition of the present invention contains an anionic urethane resin (X), a specific acrylic resin (Y), a cross-linking agent (Z), and water (V).

The aqueous resin composition is obtained by cross-linking the anionic groups of the anionic urethane resin (X), specific amounts of carboxyl groups and hydroxyl groups of the acrylic resin (Y), and a cross-linking agent (Z). , can exhibit excellent water elution resistance. Further, since the acrylic resin (Y) has an oxyethylene group, high moisture permeability can be exhibited.

The term "aqueous" in the water-based resin composition of the present invention means that the anionic urethane resin (X) or the acrylic resin (Y) is dispersed in water (V), and the resin composition contains water ( V) shows what is stably present in

The anionic urethane resin (X) is a urethane resin having an anionic group. can be done.

Examples of the compound (x1) having an anionic group include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolbutyric acid, 2,2-dimethylolpropionic acid, 2 ,2-valeric acid and other carboxyl group-containing compounds; 3,4-diaminobutanesulfonic acid, 3,6-diamino-2-toluenesulfonic acid, 2,6-diaminobenzenesulfonic acid, N-(2-aminoethyl )-2-aminosulfonic acid, N-(2-aminoethyl)-2-aminoethylsulfonic acid, N-2-aminoethane-2-aminosulfonic acid, N-(2-aminoethyl)-β-alanine, these A compound having a sulfonyl group such as a salt of can be used. These compounds may be used alone or in combination of two or more.

The usage rate of the compound (x1) having an anionic group is preferably in the range of 0.1 to 20% by mass, more preferably 0.5 to 10% by mass, in the raw materials constituting the anionic urethane resin (X). % range is more preferred.

The polyol (x2) has two or more hydroxyl groups other than the compound (x1). For example, polyether polyol, polycarbonate polyol, polyester polyol, and the like can be used. These polyols may be used alone or in combination of two or more.

The number average molecular weight of the polyol (x2) is, for example, in the range of 500 to 100,000. The number average molecular weight of the polyol (x2) is a value measured by a gel permeation column chromatography (GPC) method.

If necessary, the polyol (x2) may be used in combination with a chain extender having a number average molecular weight of less than 500 (preferably in the range of 50 to 450). Incidentally, the number average molecular weight of the chain extender indicates the chemical formula weight calculated from the chemical formula.

Examples of the chain extender include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 1,2-cyclohexanediamine, and 1,3-cyclohexane. Chain extension having an amino group such as diamine, 1,4-cyclohexanediamine, 4,4'-dicyclohexylmethanediamine, 3,3'-dimethyl-4,4'-dicyclohexylmethanediamine, 1,4-cyclohexanediamine, hydrazine, etc. Agent; ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, sucrose, methylene glycol, glycerin , sorbitol, bisphenol A, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl ether, trimethylolpropane, and other chain extenders having a hydroxyl group. These chain extenders may be used alone or in combination of two or more.

Examples of the polyisocyanate (x3) include aliphatic polyisocyanates such as hexamethylene diisocyanate and lysine diisocyanate; Aromatic polyisocyanates such as phenylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate, and carbodiimidated diphenylmethane polyisocyanate can be used. These polyisocyanates may be used alone or in combination of two or more.

As a method for producing the anionic urethane resin (X), for example, a compound having an anionic group (x1), a polyol (x2), a polyisocyanate (x3), and, if necessary, a chain extender are collectively charged. Reaction method: A compound (x1) having an anionic group, a polyol (x2), and a polyisocyanate (x3) are reacted to obtain a urethane prepolymer having an isocyanate group, and then the urethane prepolymer and the chain extension A method of reacting agents and the like can be mentioned.

As a molar ratio [NCO / (OH + NH)] of the hydroxyl group and amino group possessed by the polyol (x2), the compound (x1) having an anionic group, the chain extender, and the isocyanate group possessed by the polyisocyanate (x3) is preferably in the range of 1.1 to 3, more preferably in the range of 1.2 to 2.

All of the above reactions are carried out, for example, at 50 to 100° C. for 30 minutes to 10 hours.

When producing the anionic urethane resin (X), the isocyanate groups remaining in the anionic urethane resin (X) may be deactivated. When deactivating the isocyanate group, it is preferable to use an alcohol having one hydroxyl group, such as methanol. The amount of the alcohol used is in the range of 0.001 to 10 parts by mass with respect to 100 parts by mass of the anionic urethane resin (X).

Moreover, an organic solvent may be used when producing the anionic urethane resin (X). Examples of the organic solvent include ketone compounds such as acetone and methyl ethyl ketone; ether compounds such as tetrahydrofuran and dioxane; acetic ester compounds such as ethyl acetate and butyl acetate; nitrile compounds such as acetonitrile; Amide compounds and the like can be used. These organic solvents may be used alone or in combination of two or more. It is preferable that the organic solvent is finally removed by a distillation method or the like.

The acid value of the anionic urethane resin (X) is in the range of 5 to 35 mgKOH/g from the viewpoint of improving the crosslinkability with the crosslinker (Z) and obtaining even better resistance to water elution. is preferred, and the range of 10 to 20 mgKOH/g is more preferred. The method for measuring the acid value of the anionic urethane resin (X) will be described later in Examples.

The content of the anionic urethane resin (X) (=solid content) in the aqueous resin composition is preferably in the range of 25 to 40% by mass.

The acrylic resin (Y) has an oxyethylene group, an acid value in the range of 10 to 50 mgKOH/g, and a hydroxyl group in the range of 20 to 80 mgKOH/g.

Specifically, the acrylic resin (Y) includes a (meth)acrylic monomer (y1) having an oxyethylene group, a (meth)acrylic monomer (y2) having a hydroxyl group, and a (meth)acrylic monomer having a carboxyl group. It is preferable to use a polymer of a (meth)acrylic monomer composition starting from the monomer (y3). In the present invention, the (meth)acrylic monomer refers to an acrylic monomer and/or a methacrylic monomer.

As the (meth)acrylic monomer (y1) having the oxyethylene group, for example, polyethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, and the like can be used. These monomers may be used alone or in combination of two or more.

Examples of the (meth)acrylic monomer (y2) having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, ) acrylate, glycerol mono(meth)acrylate and the like can be used. These monomers may be used alone or in combination of two or more.

As the (meth)acrylic monomer (y3) having a carboxyl group, for example, (meth)acrylic acid, propyl(meth)acrylic acid, isopropyl(meth)acrylic acid, crotonic acid, fumaric acid and the like can be used. These monomers may be used alone or in combination of two or more.

The use ratio (mass ratio) of the (meth)acrylic monomers (y1) to (y3) is such that the acid value and hydroxyl group of the acrylic resin (Y) are easily adjusted within the ranges specified in the present application, and (y1) / (y2) / (y3) = (20 to 60) / (5 to 18.5) / (1.5 to 6) in terms of obtaining even better water elution resistance is preferred, and the range of (25-40)/(6-10)/(1.8-4) is more preferred.

As the (meth)acrylic monomer composition, other than the (meth)acrylic monomers (y1) to (y2) can be used in combination. (Meth)acrylic monomers having an acid group, (meth)acrylic monomers having a quaternary ammonium group, (meth)acrylic monomers having an amino group, (meth)acrylic monomers having a cyano group, (meth)acrylic monomers having an imide group Monomers, (meth)acrylic monomers having a methoxy group, (meth)acrylic monomers having an aromatic ring; (meth)acrylic acid alkyl esters (y5) other than these; styrene, α-methylstyrene, chlorostyrene, chloromethylstyrene , methyl vinyl ether, ethyl vinyl ether, and isobutyl vinyl ether. These monomers may be used alone or in combination of two or more. Among these, from the viewpoint of obtaining even better film strength, water dispersion stability, and water elution resistance, a (meth)acrylic monomer (y4) having an amide group and / or an alkyl (meth)acrylate Esters (y5) are preferably used.

Examples of the (meth)acrylic monomer (y4) having an amide group include (meth)acrylamide, (meth)acryloylmorpholine, N-methylol (meth)acrylamide, N-methoxyethyl (meth)acrylamide, N,N- Dimethylacrylamide, N,N-diethylacrylamide, N-isopropylacrylamide and the like can be used. These monomers may be used alone or in combination of two or more.

When the (meth)acrylic monomer (y4) having an amide group is used, the usage rate is preferably in the range of 20 to 60% by mass, more preferably 25 to 40% by mass in the (meth)acrylic monomer composition. is more preferred.

Examples of the (meth)acrylic acid alkyl ester (y5) include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, sec-butyl ( meth) acrylate, isobutyl (meth) acrylate, 2-ethylbutyl (meth) acrylate, n-pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, n-octyl ( meth)acrylate, nonyl (meth)acrylate, dodecyl (meth)acrylate, 3-methylbutyl (meth)acrylate, isooctyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, stearyl (meth)acrylate, isostearyl Aliphatic (meth)acrylates such as (meth)acrylate, neopentyl (meth)acrylate, hexadecyl (meth)acrylate, isoamyl (meth)acrylate; isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate alicyclic (meth)acrylates such as These monomers may be used alone or in combination of two or more.

When the (meth)acrylic acid alkyl ester (y5) is used, the usage rate is preferably in the range of 5 to 18.5% by mass in the (meth)acrylic monomer composition, and more preferably 6 to 10% by mass. preferable.

As a method for producing the acrylic resin (Y), known radical polymerization can be used. A method of mixing and stirring at a temperature in the range of 40 to 90° C. or allowing the mixture to stand still for, for example, 1 to 20 hours to allow radical polymerization to proceed can be mentioned. When an organic solvent is used during the production, it is preferably distilled off in the end.

Examples of the polymerization initiator include peroxides such as hydrogen peroxide, potassium persulfate, sodium persulfate and ammonium persulfate; benzoyl peroxide, t-butylperoxy-2-ethylhexanoate, and cumene hydroperoxide. organic peroxides such as; Azo compounds such as butyronitrile, 2,2′-azobis(2-methylbutyronitrile) and 2,2′-azobis(2,4-dimethylvalerate nitrile) can be used. These polymerization initiators may be used alone or in combination of two or more. The amount of the polymerization initiator used is, for example, in the range of 0.001 to 5 parts by mass with respect to 100 parts by mass of the (meth)acrylic monomer.

The content of the oxyethylene group in the acrylic resin (Y) is from 0.3 to 0.3 in order to maintain a high level of moisture permeability and obtain even better water dispersion stability and water elution resistance. It is preferably in the range of 1.5 mol/kg, more preferably in the range of 1.0 to 1.2 mol/kg.

The acid value of the acrylic resin (Y) is preferably in the range of 10 to 30 mgKOH/g from the viewpoint of obtaining even better water elution resistance. A method for measuring the acid value of the acrylic resin (Y) will be described in Examples.

The hydroxyl value of the acrylic resin (Y) is preferably in the range of 10 to 40 mgKOH/g from the viewpoint of obtaining even better water elution resistance. The method for measuring the hydroxyl value of the acrylic resin (Y) will be described in Examples.

The content of the acrylic resin (Y) (=solid content) in the aqueous resin composition is preferably in the range of 30 to 60% by mass.

As the cross-linking agent (Z), for example, a polyisocyanate cross-linking agent (z1), a carbodiimide cross-linking agent (z2), an epoxy cross-linking agent, a melamine cross-linking agent, or the like can be used. These cross-linking agents may be used alone or in combination of two or more. Among these, the polyisocyanate cross-linking agent (z1) and/or the carbodiimide cross-linking agent (z2) are used from the viewpoint of improving the crosslinkability with the anionic urethane resin (X) and the acrylic resin (Y). It is more preferable to use the polyisocyanate cross-linking agent (z1) and the carbodiimide cross-linking agent (z2) in combination from the point that even more excellent water elution resistance can be obtained.

When the polyisocyanate cross-linking agent (z1) and the carbodiimide cross-linking agent (z2) are used in combination, their molar ratio [(z1)/(z2)] is in the range of 40/60 to 80/20. is preferred, and a range of 50/50 to 70/30 is more preferred.

Examples of the polyisocyanate crosslinking agent (z1) include polyisocyanates such as tolylene diisocyanate, chlorophenylene diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, and hydrogenated diphenylmethane diisocyanate; Trimethylolpropane adducts; isocyanurate forms thereof; buret forms thereof; polyisocyanate cross-linking agents having water dispersibility, etc. can be used. Among these, it is preferable to use a polyisocyanate cross-linking agent having water dispersibility from the viewpoint of obtaining even more excellent water dispersion stability and water elution resistance.

As the water-dispersible polyisocyanate cross-linking agent, for example, a mixture obtained by mixing and emulsifying the polyisocyanate and a surfactant can be used. Examples of the surfactant include surfactants having anionic groups such as carboxyl groups and sulfonic acid groups; surfactants having cationic groups such as tertiary amino groups; nonionic surfactants such as polyoxyalkylene groups; A surfactant having a group can be used. Among these, it is preferable to use a surfactant having an anionic group from the viewpoint of obtaining even more excellent water dispersion stability and water elution resistance.

Examples of the water-dispersible polyisocyanate cross-linking agent include "Aquanate 100", "Aquanate 110", "Aquanate 200", and "Aquanate 210" (manufactured by Tosoh Corporation), "Bayhydur TPLS" -2032", "SBU-Isocyanate L801", "Baihydur VPLS-2319", "Baihydur 3100", "VPLS-2336", "VPLS-2150/1", "Baihydur 305", "Baihydur XP-2655" (above , Sumika Bayer Urethane Co., Ltd.), “Takenate WD-720”, “Takenate WD-725”, “Takenate WD-220” (manufactured by Mitsui Chemicals, Inc.), “Rezamin D-56” (Dainichiseika (manufactured by Kogyo Co., Ltd.) and the like can be obtained as commercial products.

Examples of the carbodiimide cross-linking agent (z2) include N,N'-dicyclohexylcarbodiimide, N,N'-diisopropylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, N-[3-(dimethyl Amino)propyl]-N'-ethylcarbodiimide, N-[3-(dimethylamino)propyl]-N'-ethylcarbodiimide methiodide, N-tert-butyl-N'-ethylcarbodiimide, N-cyclohexyl-N' - Carbodiimide compounds such as (2-morpholinoethyl) carbodiimide meso-p-toluenesulfonate, N,N'-di-tert-butylcarbodiimide, N,N'-di-p-tolylcarbodiimide; in the presence of a carbodiimidation catalyst A carbodiimide compound obtained by a known condensation reaction of polyisocyanate; a carbodiimide compound obtained from a polyisocyanate and a polyalkylene oxide, etc. can be used. These carbodiimide compounds may be used alone or in combination of two or more.

Examples of the preferred carbodiimide cross-linking agent (z2) include "Carbodilite V-02", "Carbodilite V-02-L2", "Carbodilite SV-02", "Carbodilite V-10" and "Carbodilite" manufactured by Nisshinbo Chemical Co., Ltd. SW-12G", "Carbodilite E-02", "Carbodilite E-03A", "Carbodilite E-05" and the like can be obtained as commercial products.

The amount of the cross-linking agent (z) used is preferably in the range of 0.01 to 50 parts by mass with respect to a total of 100 parts by mass of the anionic urethane resin (X) and the acrylic resin (Y). A range of 1 to 10 parts by mass is more preferable.

As the water (v), ion-exchanged water, distilled water, or the like can be used. The content of water (v) is preferably in the range of 50 to 80% by mass in the aqueous resin composition.

The aqueous resin composition of the present invention contains the anionic urethane resin (X), the acrylic resin (Y), the cross-linking agent (Z), and the water (V) as essential components. may contain other additives.

Examples of other additives include neutralizing agents, cross-linking agents, thickeners, urethanization catalysts, fillers, foaming agents, pigments, dyes, oil repellents, hollow foams, flame retardants, antifoaming agents, and leveling agents. agents, antiblocking agents and the like can be used. These additives may be used alone or in combination of two or more.

Examples of the method of forming a film with the water-based resin composition include a method of applying the water-based resin composition onto a substrate and drying at a temperature in the range of 40 to 150° C. for 1 to 30 minutes, for example. be done.

Examples of the substrate include plastic substrates; fiber substrates such as non-woven fabrics, woven fabrics, and knitted fabrics. Among these, it is preferable to use a fiber base material from the viewpoint of obtaining good flexibility. Examples of materials constituting the fiber base material include polyester fiber, nylon fiber, acrylic fiber, acetate fiber, rayon fiber, polylactic acid fiber, cotton, hemp, silk, wool, and blended fibers thereof. can. If necessary, the surface of the base material may be subjected to antistatic treatment, release treatment, water repellent treatment, water absorption treatment, antibacterial deodorant treatment, antibacterial treatment, ultraviolet shielding treatment, and the like.

The thickness of the film is, for example, in the range of 5 to 100 μm.

As described above, the aqueous resin composition of the present invention is an environmentally friendly material containing water, has high moisture permeability, and can form a film having excellent elution resistance to water. can be particularly preferably used as a material used for a moisture-permeable waterproof fabric.

Examples of the method for producing the moisture-permeable waterproof fabric include a method of adhering the film to a fiber base material using a known adhesive; a method of directly applying the water-based resin composition on the fiber base material and drying it. etc.

The present invention will be described in more detail below using examples.

[Synthesis Example 1] Synthesis of acrylic resin (Y-1) composition N,N-dimethylacrylamide (hereinafter abbreviated as "DMAA"), Methoxy polyethylene glycol acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd. "AM-90G", average number of added moles of oxyethylene group is 9 mol, hereinafter abbreviated as "AM-90G"), 2-hydroxyethyl methacrylate (hereinafter, abbreviated as "HEMA") and acrylic acid (hereinafter abbreviated as "AA") were charged in this order so that the molar ratio was 30/60/7/3, and the total amount of acrylic monomers was To this, 50% by mass of 1-propoxy-2-propanol and 2% by mass of an azo polymerization initiator "V-601" manufactured by Wako Pure Chemical Industries, Ltd. were added and reacted for 6 hours. Then, 3.8% by mass of triethylamine is added to the total amount of acrylic monomers to neutralize the carboxyl groups of the acrylic resin, ion-exchanged water is added, and then 1-propoxy-2-propanol is distilled under reduced pressure. By removing it, an acrylic resin (Y-1) composition (solid content: 50% by mass, acid value: 23.36 mgKOH/g, hydroxyl value: 30.18 mgKOH/g) was obtained.

[Synthesis Examples 2 to 7, Comparative Synthesis Examples 1 to 3]
Acrylic resins (Y-2) to (Y-7), (YR-1) to ( YR-3) A composition (same solid content) was obtained.

[Example 1] Preparation of film for evaluation Anionic urethane dispersion ("Hydran WLS-250" manufactured by DIC Corporation, solid content: 35% by mass, acid value of urethane resin: 10 mgKOH/g, abbreviated as "PUD" hereinafter) ) 100 parts by mass, thickener ("Hydran Assistant T10" manufactured by DIC Corporation) 1 part by mass, acrylic resin (Y-1) obtained in Synthesis Example 1 10 parts by mass, polyisocyanate cross-linking agent (Sumika Bayer Urethane Co., Ltd. "Bayhidur XP-2655", a self-emulsifying polyisocyanate cross-linking agent using a surfactant having a sulfonic acid group, hereinafter abbreviated as "NCO".) 8 parts by mass, carbodiimide cross-linking agent (Nisshinbo Chemical "Carbodilite V-02-L2" manufactured by Co., Ltd., hereinafter abbreviated as "NCN".) 0.6 parts by mass of the mixed solution is dried on a flat release paper ("EK-100D" manufactured by Lintec Corporation). A film for evaluation was obtained by coating so that the film thickness afterward would be 20 μm, drying at 70° C. for 2 minutes, and further drying at 120° C. for 2 minutes.

[Examples 2 to 7, Comparative Examples 1 to 5]
A film for evaluation was obtained in the same manner as in Example 1, except that the type of acrylic resin (Y) used was changed as shown in Tables 1 and 2.

[Method for measuring number average molecular weight]
The number average molecular weights of polyols and the like used in Examples and the like are values obtained by measuring under the following conditions by a gel permeation column 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 and used.
"TSKgel G5000" (7.8mm I.D. x 30cm) x 1 "TSKgel G4000" (7.8mm I.D. x 30cm) x 1 "TSKgel G3000" (7.8mm I.D. x 30cm) x 1 Book "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 created 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

[Method for measuring acid value of anionic urethane resin (X)]
The anionic urethane dispersion used in Examples and Comparative Examples was dried, and 0.05 g to 0.5 g of the dried and solidified resin particles were weighed into a 300 mL Erlenmeyer flask, and then the mass ratio of tetrahydrofuran and ion-exchanged water was determined. About 80 mL of a mixed solvent of [tetrahydrofuran/ion-exchanged water] of 80/20 was added to obtain a mixture thereof.
Next, after mixing a phenolphthalein indicator into the mixed solution, it is titrated with a 0.1 mol/L aqueous solution of potassium hydroxide that has been standardized in advance. According to, the acid value (mgKOH/g) of the anionic urethane resin (X) was determined.
Formula A = (B x f x 5.611)/S (1)
In the formula, A is the solid acid value of the resin (mgKOH/g), B is the amount (mL) of the 0.1 mol/L potassium hydroxide aqueous solution used for titration, and f is the 0.1 mol/L potassium hydroxide aqueous solution. The factor S is the mass (g) of the resin particles, and 5.611 is the formula weight of potassium hydroxide (56.11/10).

[Method for measuring acid value of acrylic resin (Y)]
Acid value of acrylic resin (Y) in the same manner as in [Method for measuring acid value of anionic urethane resin (X)], except that the anionic urethane dispersion is changed to an acrylic resin (Y) composition. was measured.

[Method for measuring hydroxyl value of acrylic resin (Y)]
The hydroxyl value of the acrylic resin (Y) is the number of mg of potassium hydroxide required to acetylate the hydroxyl groups contained in 1 g of the sample. The hydroxyl value of the acrylic resin (Y) was measured and calculated according to JISK1557-1:2007 A method (acetylation method).

[Method for evaluating moisture permeability]
The moisture permeability (g/m ² /24h) of the resulting evaluation film was measured according to JISL1099:2012 A-1 method (calcium chloride method) and evaluated as follows.
"A": Moisture permeability is 3,000 (g/ ^m2 /24h) or more.
"B": Moisture permeability is 2,000 (g/m ² /24h) or more and less than 3,000 (g/m ² /24h).
"C": The moisture permeability is less than 1,000 (g/m ² /24h).

[Method for evaluating water elution resistance]
An evaluation sample having a thickness of 30 μm was cut into a size of 5 cm×5 cm, immersed in ion-exchanged water at 25° C. for 24 hours, and then taken out.
Water elution rate (%) = (weight of film before immersion (g) - weight of film after immersion (g)) / (weight of film before immersion (g)) x 100 (2)
"A": Water elution rate is 2 or less "B": Water elution rate is 2 or more and less than 8 "C": Water elution rate is 8 or more

The abbreviations in the table are as follows.
"HEA": 2-hydroxyethyl acrylate "MMA"; methyl methacrylate "EA"; ethyl acrylate "BA"; butyl acrylate In addition, the unit of acid value and hydroxyl group in the table is mgKOH/g.

It has been found that the aqueous resin composition of the present invention can provide a film having excellent moisture permeability and resistance to water elution.

On the other hand, Comparative Example 1, in which the acrylic resin (Y) was not used, was poor in moisture permeability.

Comparative Example 2 is an embodiment using an acrylic resin having no oxyethylene group, but the moisture permeability was poor.

Comparative Example 3 is an embodiment using an acrylic resin having a hydroxyl value of 0, but the resistance to water elution was insufficient.

Comparative Example 4 is an embodiment using an acrylic resin having an acid value of 0, but the water elution resistance was insufficient.

Comparative Example 5 is an embodiment in which the cross-linking agent (Z) is not used, but the resistance to water elution was poor.

Claims (1)

Anionic urethane resin (X) (excluding those having terminal unsaturated groups) 25 to 40% by mass, having a polyoxyethylene group, having an acid value in the range of 10 to 50 mgKOH/g, and having a polyoxyethylene group content is in the range of 0.3 to 1.5 mol/kg, and the hydroxyl value is in the range of 10 to 80 mgKOH/g acrylic resin (Y), the cross-linking agent (Z), and water (V) An aqueous resin composition containing 50 to 80% by mass,
The cross-linking agent (Z) is a combination of a polyisocyanate cross-linking agent (z1) and a carbodiimide cross-linking agent (z2),
Furthermore, the amount of the crosslinking agent (Z) used is 0.01 to 50 parts by mass with respect to the total 100 parts by mass of the anionic urethane resin (X) and the acrylic resin (Y). A moisture-permeable waterproof fabric characterized by having a film as a raw material.