TW202413559A - Water-based dispersion of moisture-permeable waterproof material and manufacturing method thereof - Google Patents

Abstract

The water-based dispersion of the moisture-permeable waterproof material of the present invention contains composite resin particles (C) containing a polyurethane resin (U) and a vinyl resin (V). The polyurethane resin (U) is a reaction product of an active hydrogen component (a), a polyisocyanate component (b) and a chain extender (d). The active hydrogen component (a) contains a polyol (a3) having two or more hydroxyl groups and an alkoxy polyoxyethylene chain.

Description

Water-based dispersion of moisture-permeable and waterproof material and its production method

The present invention relates to an aqueous dispersion of a moisture-permeable and waterproof material and a method for producing the same.

The manufacturing method of moisture-permeable waterproof fabric is generally as follows: the surface layer is coated with urethane resin on release paper, dried, and then an adhesive is coated on it, dried, and then bonded to the fiber fabric to be heat-pressed. In the previous method of manufacturing moisture-permeable waterproof fabric, a polyurethane resin with a hydrophilic chain segment dissolved in an organic solvent such as dimethylformamide, toluene, and methyl ethyl ketone is used as the surface layer. The moisture-permeable waterproof fabric is manufactured using a dry method, so a large amount of solvent is sometimes released during the drainage and exhaust process during manufacturing. Based on such a situation, in order to prevent water pollution and air pollution in the working environment, a skin layer using a water-based polyurethane resin without organic solvents is being studied. As such a water-based polyurethane resin, a water-based dispersion of a polyurethane resin for a moisture-permeable waterproof material using polyethylene glycol and a diol having a carboxyl group as raw materials is known (for example, refer to Patent Document 1). However, if the amount of polyethylene glycol used is increased in order to further improve the moisture permeability, there is a problem that the stability of the water-based dispersion decreases, and the resin settles due to poor emulsification or changes over time. As a method for improving such problems, a water-based polyurethane resin using a diol having ethylene oxide as a side chain as a raw material is known (for example, refer to Patent Document 2). However, when the water-based polyurethane resin is processed into a film-like epidermis, the moisture permeability and water resistance are not sufficient. Prior Art Documents Patent Documents

Patent document 1: Japanese Patent No. 4283577 Patent document 2: Japanese Patent No. 5479296

[The problem that the invention wants to solve]

The present invention is made in view of the above-mentioned problems. The purpose of the present invention is to provide an aqueous dispersion of a moisture-permeable and waterproof material that has excellent stability over time and excellent moisture permeability and water resistance when processed into a film. [Technical means to solve the problem]

The inventors of the present invention have made intensive research to solve the above-mentioned problems and have achieved the present invention. That is, the present invention is as follows. [1] An aqueous dispersion of a moisture-permeable waterproof material, which contains composite resin particles (C) containing a polyurethane resin (U) and a vinyl resin (V), wherein the polyurethane resin (U) is a reaction product of an active hydrogen component (a), a polyisocyanate component (b) and a chain extender (d), and the active hydrogen component (a) contains a polyol (a3) having two or more hydroxyl groups and an alkoxypolyoxyethylene chain. [2] An aqueous dispersion of a moisture-permeable waterproof material as described in [1], wherein the weight ratio of the oxyethylene groups contained in the composite resin particles (C) is 10 to 30% by weight based on the weight of the composite resin particles (C). [3] An aqueous dispersion of a moisture-permeable waterproof material as described in [1] or [2], wherein the ratio (W1:W2) of the weight W1 of the polyurethane resin (U) to the weight W2 of the vinyl resin (V) is 90:10 to 50:50. [4] An aqueous dispersion of a moisture-permeable waterproof material as described in any one of [1] to [3], wherein the active hydrogen component (a) further comprises a condensation polyester polyol of a polycarboxylic acid having 2 to 10 carbon atoms and a polyol having 2 to 20 carbon atoms. [5] A method for producing an aqueous dispersion of a moisture-permeable waterproof material, which comprises composite resin particles (C) containing a polyurethane resin (U) and a vinyl resin (V), wherein the polyurethane resin (U) is a resin having a side chain containing polyoxyethylene groups. The method for producing an aqueous dispersion of a moisture-permeable waterproof material comprises the following steps 1 to 5. Step 1: reacting an active hydrogen component (a) of a polyol having two or more hydroxyl groups and an alkoxypolyoxyethylene chain with a polyisocyanate component (b) to obtain an amine prepolymer; Step 2: adding a vinyl monomer (M) to the amine prepolymer; Step 3: dispersing the product obtained in step 2 in an aqueous medium to obtain a dispersion of the amine prepolymer; Step 4: extending the amine prepolymer in the dispersion by a chain extender (d); Step 5: after step 4, polymerizing the vinyl monomer (M). [6] A method for producing an aqueous dispersion of a moisture-permeable waterproof material as described in [5], wherein the active hydrogen component (a) further comprises a condensation-type polyester polyol of a polycarboxylic acid having 2 to 10 carbon atoms and a polyol having 2 to 20 carbon atoms. [Effect of the invention]

According to the present invention, a water-based dispersion of a moisture-permeable and waterproof material having excellent stability over time and excellent moisture permeability and water resistance when processed into a film can be provided.

[1. Aqueous dispersion of moisture-permeable waterproof material] The aqueous dispersion of moisture-permeable waterproof material of the present invention contains composite resin particles (C) containing polyurethane resin (U) and vinyl resin (V). In this specification, "aqueous dispersion of moisture-permeable waterproof material" is simply described as "aqueous dispersion".

The polyurethane resin (U) is a reaction product of an active hydrogen component (a), a polyisocyanate component (b) and a chain extender (d), wherein the active hydrogen component (a) contains a polyol (a3) having two or more hydroxyl groups and an alkoxypolyoxyethylene chain. The polyurethane resin (U) is a resin having a side chain containing a polyoxyethylene group. In the present invention, a side chain refers to a portion branched from a main chain (a chain-like portion containing an amine ester bond).

The active hydrogen component (a) as a material of the polyurethane resin (U) is a component capable of reacting with an isocyanate compound, and contains a polyol (a3) having two or more hydroxyl groups and an alkoxypolyoxyethylene chain as an essential component. In addition to the above-mentioned polyol (a3), the active hydrogen component (a) may also contain a high molecular weight polyol (a1) having a number average molecular weight (hereinafter, abbreviated as Mn) of 300 or more, which is different from the polyol (a3), and/or a low molecular weight polyol (a2) having an Mn or a chemical formula weight of less than 300.

Examples of the polymer polyol (a1) having an Mn of 300 or more include polyester polyol, polyether polyol, polyether ester polyol, and castor oil-based polyol. The polymer polyol (a1) may be used alone or in combination of two or more.

Examples of the polyester polyol having an Mn of 300 or more include condensed polyester polyol having an Mn of 300 or more, polylactone polyol having an Mn of 300 or more, and polycarbonate polyol having an Mn of 300 or more.

Examples of the condensation polyester polyol having an Mn of 300 or more include compounds obtained by condensing a low molecular weight polyol having an Mn or a chemical formula weight of less than 300 with a polycarboxylic acid having 2 to 20 carbon atoms or an ester-forming derivative thereof [anhydride, lower (1 to 4 carbon atoms) alkyl ester, acyl halide, etc.].

Examples of the low molecular weight polyol having an Mn or chemical formula weight of less than 300 constituting the above-mentioned condensed polyester polyol include: polyols having 2 to 20 carbon atoms; alkylene oxide (hereinafter abbreviated as AO) adducts having 2 to 12 carbon atoms of polyols having 2 to 20 carbon atoms and having an Mn or chemical formula weight of less than 300; AO adducts having 2 to 12 carbon atoms of bisphenols (bisphenol A, bisphenol S, bisphenol F, etc.) and having an Mn or chemical formula weight of less than 300; bis(2-hydroxyethyl) phthalate and its AO adducts having 2 to 12 carbon atoms and having an Mn or chemical formula weight of less than 300, etc.

As the polyol having 2 to 20 carbon atoms, there can be mentioned: linear or branched aliphatic diols having 2 to 12 carbon atoms [straight-chain alcohols such as ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-dodecanediol, diethylene glycol, triethylene glycol, and tetraethylene glycol; 1,2-butanediol, 1,3-butanediol or 2,3-butanediol, 2-methyl-1,4-butanediol, neopentyl glycol, 2,2-diethyl-1,3-propanediol, 2-methyl- 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,6-hexanediol, 3-methyl-1,6-hexanediol, 2-methyl-1,7-heptanediol, 3-methyl-1,7-heptanediol, 4-methyl-1,7-heptanediol, 2-methyl-1,8-octanediol, 3-methyl-1,8-octanediol and 4-methyloctanediol and other branched alcohols]; alicyclic diols with 6 to 20 carbon atoms [1,4-cyclohexanediol, 1,3-cyclohexanedimethanol or 1,4-cyclohexanedimethanol, 1,4-cycloheptanediol, 2,5-bis(hydroxymethyl)-1,4-diol alkane, 2,7-norbornanediol, tetrahydrofuran dimethanol, 1,4-bis(hydroxyethoxy)cyclohexane, 1,4-bis(hydroxymethyl)cyclohexane and 2,2-bis(4-hydroxycyclohexyl)propane, etc.]; aromatic aliphatic diols with 8 to 20 carbon atoms [m-xylene glycol or p-xylene glycol, di(hydroxyethyl)benzene and di(hydroxyethoxy)benzene, etc.]; triols with 3 to 20 carbon atoms [aliphatic triols (glycerol and trihydroxymethylpropane, etc.)]; tetra- to octa-alcohols with 5 to 20 carbon atoms [aliphatic polyols (neopentatriol, sorbitol, mannitol, sorbitan, diglycerol and dipentatriol, etc.); sugars (sucrose, glucose, mannose, fructose, methyl glucoside and its derivatives)], etc.

Examples of the AO having 2 to 12 carbon atoms include ethylene oxide, 1,2-propylene oxide or 1,3-propylene oxide, 1,2-butylene oxide, 1,3-butylene oxide or 2,3-butylene oxide, tetrahydrofuran, 3-methyltetrahydrofuran, styrene oxide, α-olefin oxide, and epichlorohydrin.

Examples of polycarboxylic acids having 2 to 20 carbon atoms or their ester-forming derivatives include aliphatic dicarboxylic acids (succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, octadecanedicarboxylic acid, decylsuccinic acid, fumaric acid, and cis-1,1,2-dicarboxylic acid), alicyclic dicarboxylic acids (dimer acid), aromatic dicarboxylic acids (terephthalic acid, isophthalic acid, phthalic acid, tert-butylisophthalic acid, 2,6-naphthalenedicarboxylic acid, and 4,4'-biphenyldicarboxylic acid), trivalent or higher polycarboxylic acids (trimellitic acid and pyromellitic acid), their anhydrides (succinic anhydride, cis-1,2-dicarboxylic anhydride, phthalic anhydride, and trimellitic anhydride), their acetyl halides (adipic acid dichloride), their low molecular weight alkyl esters (dimethyl succinate and dimethyl phthalate), and combinations thereof. Among them, preferred are aliphatic dicarboxylic acids having 2 to 10 carbon atoms and their ester-forming derivatives, and more preferred is adipic acid. The polycarboxylic acids may be used alone or in combination of two or more.

As the condensation polyester polyol having Mn of 300 or more, from the viewpoint of excellent moisture permeability during film processing, the condensation product of an aliphatic polycarboxylic acid and Mn or a low molecular weight polyol having a chemical formula weight of less than 300 is preferred, and the condensation polyester polyol of an aliphatic polycarboxylic acid having a carbon number of 2 to 10 and Mn or a polyol having a chemical formula weight of less than 300 and a carbon number of 2 to 20 is more preferred, and the ester of an aliphatic dicarboxylic acid having a carbon number of 2 to 10 and Mn or an aliphatic diol having a chemical formula weight of less than 300 and a carbon number of 2 to 20 is further preferred, and the condensation polyester polyol of adipic acid and 3-methyl-1,5-pentanediol is particularly preferred.

Examples of polylactone polyols having an Mn of 300 or more include those obtained by ring-opening polymerization of lactone monomers having 3 to 12 carbon atoms (β-propiolactone, γ-butyrolactone, γ-valerolactone, ε-caprolactone, η-octanolactone, 11-undecanoic acid lactone, and 12-dodecanoic acid lactone (Dodecanoid), etc.) using the above-mentioned polyols having 2 to 20 carbon atoms as initiators. The lactone monomers may be used alone or in combination of two or more.

Examples of the polycarbonate polyol having an Mn of 300 or more include polycarbonate polyols prepared by subjecting one or more of the above-mentioned polyols having 2 to 20 carbon atoms (preferably aliphatic diols having 3 to 9 carbon atoms, and more preferably aliphatic diols having 4 to 6 carbon atoms) to a dehydration reaction and condensation reaction with a low molecular weight carbonate compound (e.g., dialkyl carbonates having an alkyl group having 1 to 6 carbon atoms, alkylene carbonates having an alkylene group having 2 to 6 carbon atoms, and diaryl carbonates having an aryl group having 6 to 9 carbon atoms). As the polycarbonate polyol, for example, commercially available polycarbonate polyols such as ETERNACOLL UH series [polyhexamethylene carbonate diol, manufactured by Ube Industries, Ltd.], DURANOL G4672 [polycarbonate diol using 1,4-butanediol/1,6-hexanediol = 70/30 (molar ratio) and Mn = 2000, manufactured by Asahi Kasei Chemicals Co., Ltd.], etc. can also be used.

Examples of polyether polyols having an Mn of 300 or more include compounds obtained by adding AO having a carbon number of 2 to 12 to the above-mentioned low molecular weight polyols having an Mn or a chemical formula weight of less than 300. AO may be used alone or in combination of two or more. In the latter case, block addition (chain end type, balanced type, active secondary type, etc.), random addition, or a combination thereof may be used. Examples of AO having a carbon number of 2 to 12 include those mentioned above.

The AO addition to low molecular weight polyols having a Mn or a chemical formula weight of less than 300 is carried out, for example, in the absence of a catalyst or in the presence of a catalyst (alkaline catalyst, amine catalyst, acidic catalyst, etc.) (especially in the second half of the AO addition), at normal pressure or under pressure in one stage or multiple stages.

Specific examples of polyether polyols having an Mn of 300 or more include poly(oxyethylene) polyols, poly(oxypropylene) polyols, poly(oxytetramethylene) polyols, poly(oxy-3-methyltetramethylene) polyols, tetrahydrofuran/ethylene oxide copolymers, and tetrahydrofuran/3-methyltetrahydrofuran copolymers.

Examples of the polyether ester polyol having an Mn of 300 or more include those obtained by condensing one or more of the above polyether polyols with one or more of the polycarboxylic acids having 2 to 20 carbon atoms or their ester-forming derivatives exemplified as the raw materials of the above condensation-type polyester polyol having an Mn of 300 or more.

Examples of castor oil-based polyols include castor oil, partially dehydrated castor oil, polyester polyols formed from castor oil fatty acids and the above-mentioned polyols or polyoxyalkylene polyols having 2 to 20 carbon atoms (monoglyceride or diglyceride of castor oil fatty acids, monoesters, diesters or triesters formed from castor oil fatty acids and trihydroxymethyl propane, and monoesters or diesters formed from castor oil fatty acids and polyoxypropylene glycol, etc.), those obtained by adding AO having 2 to 12 carbon atoms to castor oil, and mixtures of two or more thereof. Examples of AO having 2 to 12 carbon atoms include those mentioned above.

As the high molecular weight polyol (a1), from the viewpoint of excellent moisture permeability during film processing, polyester polyol is preferred, condensation polyester polyol and polycarbonate polyol are more preferred, condensation polyester polyol of polycarboxylic acid having 2 to 10 carbon atoms and polyol having 2 to 20 carbon atoms is more preferred, and condensation polyester polyol of adipic acid and 3-methyl-1,5-pentanediol is particularly preferred.

From the viewpoint of excellent moisture permeability during film processing, the Mn of the high molecular weight polyol (a1) is preferably 350 or more, more preferably 1,000 to 5,000, and particularly preferably 1,500 to 3,000.

The Mn of the polyol in the present invention can be measured by gel permeation chromatography under the following conditions, for example. Apparatus: "Waters Alliance 2695" [manufactured by Waters Corporation] Column: "Guardcolumn Super H-L" (1 column), and "one column each of TSKgel SuperH2000, TSKgel SuperH3000, and TSKgel SuperH4000 (all manufactured by Tosoh Co., Ltd.)" Sample solution: 0.25 wt% tetrahydrofuran solution Solution injection volume: 10 μL Flow rate: 0.6 ml/min Measurement temperature: 40°C Detection device: Refractive index detector Reference substance: Standard polyethylene glycol

As the low molecular weight polyol (a2) having an Mn or a chemical formula weight of less than 300, there can be mentioned: the same as the components of the condensed polyester polyol having an Mn of 300 or more, i.e., the "low molecular weight polyol having an Mn or a chemical formula weight of less than 300", or dialkanolamines such as diethanolamine and diisopropanolamine. As the low molecular weight polyol (a2), preferably, a linear or branched aliphatic diol having 2 to 12 carbon atoms, a triol having 3 to 20 carbon atoms, and a tetrahydric to octahydric alcohol having 5 to 20 carbon atoms, more preferably, 1,4-butanediol, 1,3-propylene glycol, and trihydroxymethylpropane.

As the polyol (a3) having two or more hydroxyl groups and having an alkoxypolyoxyethylene chain, there can be mentioned a polyol obtained by bonding an aliphatic polyol having 3 to 20 carbon atoms (e.g., trihydroxymethylpropane and glycerol) and an alkoxypolyoxyethylene chain. As the polyol (a3) having two or more hydroxyl groups and having an alkoxypolyoxyethylene chain, trihydroxymethylpropane having a methoxypolyoxyethylene group is preferred.

Examples of commercially available polyols (a3) having two or more hydroxyl groups and an alkoxypolyoxyethylene chain include TEGOMER D3403 [a polyoxyethylene glycol diol with a number average molecular weight (Mn) of 1,200, manufactured by Evonik Industries AG] and Ymer N90, Ymer N120, and Ymer N180 [polyethylene glycol-modified trihydroxymethylpropane with Mn of 1,200, 1,000, and 600, manufactured by Perstorp].

The active hydrogen component (a) may contain, in addition to the above-mentioned polyols (a1) to (a3), a compound (a4) containing an ionic group and an active hydrogen atom different from the above. Examples of the compound (a4) include a compound (a41) containing an anionic group and an active hydrogen atom, and a compound (a42) containing a cationic group and an active hydrogen atom. The compound (a4) may be used alone or in combination of two or more.

Examples of the compound (a41) containing an anionic group and an active hydrogen atom include: a compound containing a carboxyl group as an anionic group and having at least an amino group as a group containing an active hydrogen atom [for example, amino acids (glycine, alanine, valine, lysine, aspartic acid, glutamine, cysteine, serine, and threonine, etc.)]; a compound containing a carboxyl group as an anionic group and having a hydroxyl group as a group containing an active hydrogen atom and having 2 to 10 carbon atoms [dihydroxyalkylalkanoic acids (for example, 2,2-dihydroxymethylpropionic acid, 2,2-dihydroxymethylbutyric acid, 2,2- [2,2-dihydroxymethylheptanoic acid and 2,2-dihydroxymethyloctanoic acid), tartaric acid, etc.]; compounds containing a sulfonic acid group (sulfonic acid group) as an anionic group, having a hydroxyl group as a group containing an active hydrogen atom, and having a carbon number of 2 to 16 [3-(2,3-dihydroxypropoxy)-1-propanesulfonic acid and sulfoisophthalic acid di(ethylene glycol) ester, etc.]; compounds containing an amine sulfonic acid group as an anionic group, having a hydroxyl group as a group containing an active hydrogen atom, and having a carbon number of 2 to 10 [N,N-bis(2-hydroxyethyl)amine sulfonic acid, etc.]; and salts obtained by neutralizing these compounds with a neutralizer.

Examples of the neutralizing agent for neutralizing the compound (a41) containing an anionic group and an active hydrogen atom include ammonia, an amine compound having 1 to 20 carbon atoms, or an alkali metal hydroxide (sodium hydroxide, potassium hydroxide, lithium hydroxide, etc.). Examples of the amine compound having 1 to 20 carbon atoms include primary amines such as monomethylamine, monoethylamine, monobutylamine, and monoethanolamine; secondary amines such as dimethylamine, diethylamine, dibutylamine, diethanolamine, diisopropanolamine, and methylpropanolamine; and tertiary amines such as trimethylamine, triethylamine, dimethylethylamine, dimethylmonoethanolamine, and triethanolamine.

As a neutralizing agent for neutralizing the compound (a41) containing anionic groups and active hydrogen atoms, a compound having a high vapor pressure at 25°C is more suitable from the viewpoint of the stability of the aqueous dispersion over time and the excellent moisture permeability when processed into a film. Based on the above viewpoint, as a neutralizing agent for neutralizing the compound (a41) containing anionic groups and active hydrogen atoms, an alkali metal hydroxide and an amine compound having 1 to 20 carbon atoms are more preferably sodium hydroxide, monomethylamine, monoethylamine, dimethylamine, diethylamine, trimethylamine, triethylamine and dimethylethylamine, and sodium hydroxide is more preferably used.

Among the compounds (a41) containing anionic groups and active hydrogen atoms, compounds containing a carboxyl group as anionic groups, a hydroxyl group as a group containing active hydrogen atoms, and having 2 to 10 carbon atoms are preferred, from the viewpoint of excellent temporal stability of aqueous dispersions and excellent moisture permeability when processed into films. More preferred are 2,2-dihydroxymethylpropionic acid, 2,2-dihydroxymethylbutyric acid and salts thereof, and further preferred is 2,2-dihydroxymethylpropionic acid and salts thereof.

Examples of the compound (a42) containing a cationic group and an active hydrogen atom include a compound having a tertiary amine group as a cationic group and a hydroxyl group as a group containing an active hydrogen atom, for example, a salt obtained by neutralizing a compound such as a diol having a carbon number of 1 to 20 and containing a tertiary amine group [N-alkyldialkanolamine (e.g., N-methyldiethanolamine, N-propyldiethanolamine, N-butyldiethanolamine and N-methyldipropanolamine)], an N,N-dialkylmonoalkanolamine (e.g., N,N-dimethylethanolamine) and a trialkanolamine (e.g., triethanolamine) with a neutralizer.

Examples of the neutralizing agent for neutralizing the compound (a42) containing a cationic group and an active hydrogen atom include monocarboxylic acids having 1 to 10 carbon atoms (e.g., formic acid, acetic acid, propionic acid, etc.), carbonic acid, dimethyl carbonate, dimethyl sulfate, methyl chloride, and chlorotoluene.

The active hydrogen component (a) may contain, in addition to the above-mentioned polyols (a1) to (a3) and compound (a4), a reaction terminator (a5) different from them. Examples of the reaction terminator (a5) include monoalcohols having 1 to 20 carbon atoms (methanol, ethanol, butanol, octanol, decanol, dodecanol, myristyl alcohol, cetyl alcohol, and stearyl alcohol), monoamines having 1 to 20 carbon atoms (monoalkylamines or dialkylamines such as monomethylamine, monoethylamine, monobutylamine, dibutylamine, and monooctylamine, and monoalkanolamines such as monoethanolamine and 2-amino-2-methylpropanol).

As the active hydrogen component (a), preferably, in addition to the polyol (a3), a condensation-type polyester polyol further comprises a polyhydric fatty acid having 2 to 10 carbon atoms and a polyhydric alcohol having 2 to 20 carbon atoms. Particularly preferably, a condensation-type polyester polyol comprising the polyol (a3), a polyhydric fatty acid having 2 to 10 carbon atoms and a polyhydric alcohol having 2 to 20 carbon atoms, and also comprising the low molecular weight polyol (a2).

The polyisocyanate component (b) as a material of the polyurethane resin (U) may be an organic polyisocyanate having two or more isocyanate groups, for example, an aromatic polyisocyanate having 8 to 26 carbon atoms (b1), an aliphatic polyisocyanate having 4 to 22 carbon atoms (b2), an alicyclic polyisocyanate having 8 to 18 carbon atoms (b3), an aromatic aliphatic polyisocyanate having 10 to 18 carbon atoms (b4), and modified products of these organic polyisocyanates (b5).

Examples of the aromatic polyisocyanate (b1) having 8 to 26 carbon atoms include 1,3-phenylenediisocyanate or 1,4-phenylenediisocyanate, 2,4-toluene diisocyanate or 2,6-toluene diisocyanate (hereinafter, toluene diisocyanate is abbreviated as TDI), crude TDI, 4,4'-diphenylmethane diisocyanate or 2,4'-diphenylmethane diisocyanate (hereinafter, diphenylmethane diisocyanate is abbreviated as MDI (hereinafter referred to as MDI), crude MDI, polyaryl polyisocyanate, 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, 4,4',4''-triphenylmethane triisocyanate, and m-isocyanatophenylsulfonyl isocyanate or p-isocyanatophenylsulfonyl isocyanate.

Examples of the aliphatic polyisocyanate (b2) having 4 to 22 carbon atoms include ethylene diisocyanate, tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, hexamethylene diisocyanate (hereinafter abbreviated as HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, methyl 2,6-diisocyanatohexanoate, bis(2-isocyanatoethyl) fumarate, bis(2-isocyanatoethyl) carbonate, and 2-isocyanatoethyl-2,6-diisocyanatohexanoate.

Examples of the alicyclic polyisocyanate (b3) having 8 to 18 carbon atoms include isophorone diisocyanate (hereinafter abbreviated as IPDI), 4,4'-dicyclohexylmethane diisocyanate (hereinafter abbreviated as hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, bis(2-isocyanatoethyl)-4-cyclohexene-1,2-dicarboxylate, and 2,5-norbornane diisocyanate or 2,6-norbornane diisocyanate.

Examples of the aromatic aliphatic polyisocyanate (b4) having 10 to 18 carbon atoms include m-xylylenediisocyanate, p-xylylenediisocyanate, and α,α,α',α'-tetramethylxylylenediisocyanate.

As the modified product (b5), there can be mentioned the above-mentioned organic polyisocyanate containing an urethane group, a carbodiimide group, an allophanate group, a urea group, a biuret group, a uretdione group, a urethimine group, an isocyanuric acid group or Modified products of oxazolidinone group [e.g., modified MDI (amine-modified MDI, carbodiimide-modified MDI and trialkyl phosphate-modified MDI, etc.), amine-modified TDI, biuret form of HDI, isocyanurate form of HDI and isocyanurate form of IPDI].

Among them, from the viewpoint of water resistance during film processing, preferred are alicyclic polyisocyanates (b3) having 8 to 18 carbon atoms and their modified products, and more preferred are IPDI, hydrogenated MDI and isocyanurate of IPDI. The polyisocyanate component (b) may be used alone or in combination of two or more.

The chain extender (d) is a compound that can react with an isocyanate compound. In addition, the chain extender (d) is a compound that can react with a reactant (amine prepolymer) of an active hydrogen component (a) and a polyisocyanate component (b). Examples of the chain extender (d) include water, a (poly)amine compound (d1) having an anionic ion group, and a Mn compound (d2) having no anionic ion group or a (poly)amine compound having a chemical formula weight of less than 500. In addition, the above-mentioned polyol (a1), polyol (a2), compound (a4) and reaction terminator (a5) can also be used as the chain extender (d).

As the (poly)amine compound (d1), for example, a polyamine having a carboxyl group [such as "Disponil (registered trademark) PUD" manufactured by BASF] and a neutralized salt thereof can be used.

Examples of the (poly)amine compound (d2) include aliphatic polyamines having 2 to 36 carbon atoms [alkylene diamines such as ethylenediamine and hexamethylenediamine; polyalkylene polyamines having alkylene carbon atoms of 2 to 6 and nitrogen atoms of 3 to 7 such as diethylenetriamine, dipropylenetriamine, dihexyltriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine and hexaethyleneheptamine {poly (di- to hexa)alkylene (carbon atoms of 2 to 6) poly (tri- to hepta)amines}, etc.], alicyclic polyamines having 6 to 20 carbon atoms (1,3-diaminocyclohexane or 1,4-diaminocyclohexane, 4,4'- dicyclohexylmethanediamine or 2,4'-dicyclohexylmethanediamine and isophoronediamine, etc.), aromatic polyamines with 6 to 20 carbon atoms (1,3-phenylenediamine or 1,4-phenylenediamine, 2,4-toluenediamine or 2,6-toluenediamine, 4,4'-methylenebisaniline or 2,4'-methylenebisaniline, etc.), aromatic aliphatic polyamines with 8 to 20 carbon atoms [1,3-phenylenediamine or 1,4-phenylenediamine, bis(aminoethyl)benzene, bis(aminopropyl)benzene and bis(aminobutyl)benzene, etc.], heterocyclic polyamines with 3 to 20 carbon atoms [2,4-diamino-1,3,5-triaminobenzene, etc.] , Piper and N-(2-aminoethyl)piperidin etc.], hydrazine or its derivatives (for example, dibasic acid dihydrazide such as adipic acid dihydrazide), etc.

As the chain extender (d), aliphatic polyamines, alicyclic polyamines and polyamine compounds having anionic ion groups are preferred, and two or more selected from ethylenediamine, isophoronediamine and polyamines having a carboxyl group are more preferred.

In the aqueous dispersion of the present invention, the polyurethane resin (U) is a resin having a side chain containing polyoxyethylene groups. The side chain containing polyoxyethylene groups can be introduced by reacting an active hydrogen component (a) containing a polyol (a3) having two or more hydroxyl groups and an alkoxypolyoxyethylene chain with a polyisocyanate component (b).

In the present invention, the monomer (M) having a vinyl group constituting the vinyl resin (V) includes a monofunctional vinyl monomer (M1) and a difunctional or higher-functional vinyl monomer (M2). The monomer (M) having a vinyl group may be used alone or in combination of two or more.

Examples of the monofunctional vinyl monomer (M1) include esters of unsaturated alcohols or hydroxystyrenes with monocarboxylic acids having 1 to 12 carbon atoms (e.g., vinyl acetate, vinyl butyrate, vinyl propionate, butyric acid vinyl esters). Ester), isopropylene acetate, methyl 4-vinylbenzoate, methoxyvinyl acetate, vinyl benzoate and acetyloxystyrene, etc.], aliphatic (meth)acrylates [for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, hexadecyl (meth)acrylate, heptadecyl (meth)acrylate and eicosyl (meth)acrylate, etc.], (meth)acrylates having an alicyclic structure [cyclohexyl (meth)acrylate, isoborneol (meth)acrylate and methylnorbornene (meth)acrylate, etc.], (meth)acrylates having an aromatic ring structure [ Esters [benzyl (meth)acrylate and phenyl (meth)acrylate, etc.], (meth)acrylates having a hydroxyl group [2-hydroxyethyl (meth)acrylate, etc.], esters of (meth)acrylic acid, unsaturated carboxylic acids other than (meth)acrylic acid and alcohols [di(cyclo)alkyl fumarate (two alkyl groups are linear or branched carbon numbers of 2 to 8) and di(cyclo)alkyl menthate (two alkyl groups are linear or branched carbon numbers of 2 to 8)], and unsaturated carboxylic acid esters of polyoxyalkylene (carbon numbers of 2 to 4) monoalcohols having a polymerization degree of 5 to 50 [for example, ester group-containing vinyl monomers such as methanol ethylene oxide 10 mol adduct (meth)acrylate and lauryl alcohol ethylene oxide 30 mol adduct (meth)acrylate, etc.], etc. In this specification, (meth)acrylate means acrylate and/or methacrylate. As the monofunctional vinyl monomer (M1), from the viewpoint of moisture permeability during film processing, aliphatic (meth)acrylate is preferred, and methyl (meth)acrylate is more preferred.

The monofunctional vinyl monomer (M1) may be used alone or in combination of two or more. In addition, as monofunctional vinyl monomers other than those described above, for example, monofunctional vinyl monomers described in WO2020/105569 may be used.

Examples of the difunctional or higher vinyl monomer (M2) include divinylbenzene, tricyclodecanedimethanol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, glycerol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, Acid ester, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, propoxylated bisphenol A di(meth)acrylate, propoxylated ethoxylated bisphenol A di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, 9,9-bis[4-(2-(methyl ) acryloxyethoxy) phenyl] fluorene, ethoxylated isocyanuric acid tri(meth)acrylate, ε-caprolactone modified tri-(2-(meth)acryloyloxyethyl) isocyanurate, pentaerythritol tri(meth)acrylate, trihydroxymethylpropane tri(meth)acrylate, di-trihydroxymethylpropane tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate Acrylate, dipentatriol hexa(meth)acrylate, dipentatriol poly(meth)acrylate, tripentatriol poly(meth)acrylate, polypentatriol poly(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, allyl (meth)acrylate, triallyl isocyanurate, diallyl isophthalate, diallyl isocyanurate, and diallyl maleate. Among them, polyethylene glycol di(meth)acrylate is preferred. The difunctional or higher vinyl monomer (M2) may be used alone or in combination of two or more.

From the viewpoint of water resistance during film processing, the monomer (M) having a vinyl group preferably includes an aliphatic (meth)acrylate, and more preferably includes methyl (meth)acrylate.

From the viewpoint of the stability of the aqueous dispersion over time and the water resistance during film processing, the ratio (W1:W2) of the weight W1 of the polyurethane resin (U) to the weight W2 of the vinyl resin (V) in the aqueous dispersion is preferably 90:10 to 50:50, more preferably 80:20 to 60:40.

From the viewpoint of the stability of the aqueous dispersion over time and the moisture permeability and water resistance during film processing, the weight ratio of the oxyethylene group contained in the composite resin particles (C) in the aqueous dispersion is preferably 10 to 30% by weight, more preferably 12 to 20% by weight, based on the weight of the composite resin particles (C).

From the viewpoint of the handling property and stability over time of the aqueous dispersion, the volume average particle size (Dv) of the composite resin particles in the aqueous dispersion is preferably 0.01 to 1 μm, more preferably 0.02 to 0.7 μm, and particularly preferably 0.03 to 0.4 μm. The volume average particle size (Dv) can be measured, for example, using a light scattering particle size distribution measuring device [ELS-8000 {manufactured by Otsuka Electronics Co., Ltd.}].

The aqueous dispersion may contain an aqueous medium as a component other than the composite resin particles. Examples of the aqueous medium include water and a mixture of water and an organic solvent. Examples of the organic solvent include ketone solvents (e.g., acetone and methyl ethyl ketone), ester solvents (e.g., ethyl acetate), ether solvents (e.g., tetrahydrofuran), amide solvents (e.g., N,N-dimethylformamide and N-methylpyrrolidone), alcohol solvents (e.g., isopropyl alcohol), and aromatic hydrocarbon solvents (e.g., toluene). The organic solvent may be used alone or in combination of two or more. The aqueous medium is preferably water.

From the viewpoint of dispersion stability, the aqueous dispersion may contain a surfactant (E). As the surfactant (E), there may be mentioned: a reactive surfactant (E1) having a free radical reactive group and a non-reactive surfactant (E2). One type may be used alone, or two or more types may be used in combination, including a reactive surfactant (E1) and a non-reactive surfactant (E2). Among them, from the viewpoint of water resistance during film processing, the reactive surfactant (E1) is preferred.

As the reactive surfactant (E1), there is no particular limitation as long as it has free radical reactivity. Specifically, there can be mentioned: ADEKA REASOAP [registered trademark, manufactured by ADEKA Co., Ltd.] SE-10N, SR-10, SR-20, SR-30, ER-20, ER-30; AQUALON [registered trademark, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.] HS-10, KH-05, KH-10, KH-1025; Eleminol [registered trademark, manufactured by Sanyo Chemical Industries, Ltd.] JS-20; Latemul [registered trademark, manufactured by Kao Co., Ltd.] PD-104, PD-420, PD-430; Ionet [registered trademark, manufactured by Sanyo Chemical Industries, Ltd.] MO-200, etc.

Examples of non-reactive surfactants (E2) include nonionic surfactants (E21), anionic surfactants (E22), cationic surfactants (E23), amphoteric surfactants (E24) and other emulsifying and dispersing agents (E25).

Examples of the nonionic surfactant (E21) include AO addition type nonionic surfactants and polyol type nonionic surfactants. Examples of the AO addition type include ethylene oxide (hereinafter abbreviated as EO) adducts of aliphatic alcohols having 10 to 20 carbon atoms, EO adducts of phenols, EO adducts of nonylphenols, EO adducts of alkylamines having 8 to 22 carbon atoms, and EO adducts of poly(oxypropylene) glycols. Examples of the polyol type include fatty acid (8 to 24 carbon atoms) esters of poly(tri- to octa- or more-valent) alcohols (2 to 30 carbon atoms) (e.g., glycerol monostearate, glycerol monooleate, sorbitan monolaurate, sorbitan monooleate, etc.) and alkyl (4 to 24 carbon atoms) poly (degree of polymerization 1 to 10) glycosides.

Examples of the anionic surfactant (E22) include: ether carboxylic acids or salts thereof having a carbon number of 8 to 24 (sodium lauryl ether acetate and (poly)oxyethylene (addition mole number 1 to 100) sodium lauryl ether acetate, etc.); sulfates or ether sulfates having a carbon number of 8 to 24 and salts thereof (sodium lauryl sulfate, (poly)oxyethylene (addition mole number 1 to 100) sodium lauryl sulfate, (poly)oxyethylene (addition mole number 1 to 100) triethanolamine lauryl sulfate and (poly)oxyethylene (addition mole number 1 to 100) sodium coconut fatty acid monoethanolamide sulfate, etc.); sulfonates having a carbon number of 8 to 24 (sodium dodecylbenzenesulfonate, etc.); Sulfosuccinates with 1 or 2 alkyl groups with 8 to 24 carbon atoms; phosphates or ether phosphates with alkyl groups with 8 to 24 carbon atoms and their salts [sodium lauryl phosphate and sodium (poly)oxyethylene (addition molar number 1 to 100) lauryl ether phosphate, etc.]; fatty acid salts with alkyl groups with 8 to 24 carbon atoms [sodium laurate and triethanolamine laurate, etc.]; acylated amino acid salts with alkyl groups with 8 to 24 carbon atoms [sodium coconut oil fatty acid methyl taurine, sodium coconut oil fatty acid sarcosine, triethanolamine coconut oil fatty acid sarcosine, triethanolamine N-coconut oil fatty acid acyl-L-glutamine, sodium N-coconut oil fatty acid acyl-L-glutamine and sodium lauryl methyl-β-alanine, etc.].

Examples of the cationic surfactant (E23) include quaternary ammonium salt type [stearyl trimethyl ammonium chloride, behenyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, and ethyl sulfated lanolin fatty acid aminopropyl ethyl dimethyl ammonium, etc.] and amine salt type [stearic acid diethylaminoethyl amide lactate, dilaurylamine hydrochloride, and oleylamine lactate, etc.].

Examples of the amphoteric surfactant (E24) include betaine-type amphoteric surfactants [coconut oil fatty acid amidopropyl dimethylaminoacetic acid betaine, lauryl dimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, lauryl hydroxysulfonic acid betaine and laurylamidoethyl hydroxyethyl carboxymethyl betaine sodium hydroxypropyl phosphate, etc.] and amino acid-type amphoteric surfactants [sodium β-laurylaminopropionate, etc.].

Examples of other emulsifying and dispersing agents (E25) include polyvinyl alcohol, starch and its derivatives, cellulose derivatives such as carboxymethyl cellulose, methyl cellulose and hydroxyethyl cellulose, and carboxyl group-containing (co)polymers such as sodium polyacrylate, and emulsifying and dispersing agents having an amine ester group or an ester group as described in the specification of U.S. Patent No. 5,906,704 [for example, those obtained by linking polycaprolactone polyol and polyether diol by polyisocyanate], etc.

When a surfactant (E) is used, its usage amount is preferably 0.5 to 10 wt %, more preferably 1 to 3 wt %, relative to the weight of the vinyl monomer (M), from the viewpoint of water resistance during film processing and stability of the aqueous dispersion over time.

The aqueous dispersion may also contain any components such as a crosslinking agent, a viscosity modifier, a defoaming agent, a preservative, a weathering stabilizer, and an antifreeze agent. As the optional component, for example, the crosslinking agent, viscosity modifier, defoaming agent, preservative, weathering stabilizer, and antifreeze agent described in International Publication No. 2020/105569 may be used.

From the viewpoint of the ease of handling of the aqueous dispersion, the solid content concentration (content of components other than volatile components) of the aqueous dispersion is preferably 20 to 65% by weight, and more preferably 25 to 55% by weight. The solid content concentration can be obtained in the following manner: about 1 g of the aqueous dispersion is thinly spread on a Petri dish, accurately weighed, and then heated at 130°C for 45 minutes using a circulating constant temperature dryer, and the weight after heating is accurately weighed, and the ratio (percentage) of the residual weight after heating to the weight before heating is calculated.

The viscosity of the aqueous dispersion at 25°C is preferably 10 to 100,000 mPa·s, more preferably 10 to 5,000 mPa·s. The viscosity can be measured using a BL type viscometer. The pH of the aqueous dispersion at 25°C is preferably 2 to 12, more preferably 4 to 10. The pH can be measured using a pH Meter M-12 [manufactured by Horiba, Ltd.].

In the aqueous dispersion of the present invention, the content of urethane bonds of the polyurethane resin (U) is preferably 0.8 mmol/g to 1.8 mmol/g, and more preferably 0.9 mmol/g to 1.4 mmol/g, based on the weight of the composite resin particles (C) from the viewpoint of mechanical strength, etc. The content of urethane bonds can be calculated based on the content of N atoms quantitatively determined by a nitrogen analyzer, the ratio of urethane groups to urea groups quantitatively determined by ¹ H-NMR, and the contents of allophanate groups and biurea groups.

In the aqueous dispersion of the present invention, the content of urea bonds in the polyurethane resin (U) is preferably 0.2 to 0.7 mmol/g, and more preferably 0.3 to 0.69 mmol/g, based on the weight of the composite resin particles (C). The content of urea bonds can be calculated based on the content of N atoms quantitatively determined by a nitrogen analyzer, the ratio of urethane groups to urea groups quantitatively determined by ¹ H-NMR, and the contents of allophanate groups and biurea groups.

As for the nitrogen analyzer, for example, a nitrogen analyzer [ANTEK7000 (manufactured by Antec Corporation)] can be used. As for the ¹ H-NMR measurement, the method described in "Structural Study of Polyurethane Resin by NMR: Takeda Research Institute Report 34 (2), 224-323 (1975)" is used. That is, ¹ H-NMR is measured, and when an aliphatic group is used, the weight ratio of the urea group to the urethane group is calculated from the ratio of the integral amount of hydrogen derived from the urea group at a chemical shift of around 6 ppm to the integral amount of hydrogen derived from the urethane group at a chemical shift of around 7 ppm, and the contents of the urethane group and the urea group are calculated from the weight ratio, the content of the N atom, and the content of the allophanate group and the biurea group. When an aromatic isocyanate is used, the weight ratio of the urea group to the amine group is calculated from the ratio of the integral amount of hydrogen derived from the urea group at a chemical shift of around 8 ppm to the integral amount of hydrogen derived from the amine group at a chemical shift of around 9 ppm, and the content of the urea group is calculated from the weight ratio and the above-mentioned content of N atoms.

The aqueous dispersion of the present invention can exhibit excellent water resistance when processed into a film. The details of the mechanism by which the present invention achieves this effect are not clear, but it is speculated as follows. In an aqueous dispersion containing a polyurethane resin and a vinyl resin prepared separately, the compatibility of the two resins is not good. In contrast, the composite resin particles contained in the aqueous dispersion of the present invention contain a polyurethane resin and a vinyl resin. That is, in the composite resin particles contained in the aqueous dispersion of the present invention, since the two resins exist in one particle, the two resins are uniformly dispersed in the aqueous dispersion, and the functions of the two resins are balanced. As a result, according to the present invention, the water resistance during film processing is more excellent than that of an aqueous dispersion containing a polyurethane resin and a vinyl resin prepared separately. In addition, according to the aqueous dispersion of the present invention, the stability over time is excellent and the moisture permeability during film processing is excellent. Although the details of the mechanism by which the present invention achieves this effect are unclear, it is speculated as follows. When the aqueous dispersion contains composite resin particles of a polyurethane resin and a vinyl resin, and the polyurethane resin has a polyoxyethylene group in the main chain (chain portion containing amine ester bonds) of the polymer but does not have a polyoxyethylene group in the side chain, the particles may sometimes aggregate with each other due to changes over time to produce sediment. On the other hand, the composite resin particles in the aqueous dispersion of the present invention include a polyurethane resin having polyoxyethylene groups in the side chains. Due to the action of the polyoxyethylene groups in the side chains, the aggregation of the composite resin particles is suppressed, thereby providing an aqueous dispersion with excellent stability over time.

[2. Method for producing a water-based dispersion of a moisture-permeable waterproof material] The method for producing a water-based dispersion of a moisture-permeable waterproof material of the present invention is a method for producing a water-based dispersion of a moisture-permeable waterproof material containing composite resin particles (C) containing a polyurethane resin (U) and a vinyl resin (V), and the polyurethane resin (U) is a resin having a side chain containing polyoxyethylene. The method for producing a water-based dispersion of a moisture-permeable waterproof material includes the following steps 1 to 5. Step 1: reacting an active hydrogen component (a) of a polyol having two or more hydroxyl groups and an alkoxypolyoxyethylene chain with a polyisocyanate component (b) to obtain an amine prepolymer; Step 2: adding a monomer (M) having a vinyl group to the above amine prepolymer; Step 3: dispersing the product obtained in step 2 in an aqueous medium to obtain a dispersion of the amine prepolymer; Step 4: extending the amine prepolymer in the above dispersion by a chain extender (d); Step 5: after step 4, polymerizing the above monomer (M) having a vinyl group. The manufacturing method of the present invention can be used to manufacture the water-based dispersion of the moisture-permeable and waterproof material of the present invention.

Step 1 is a step of reacting an active hydrogen component (a) containing a polyol having two or more hydroxyl groups and an alkoxy polyoxyethylene chain with a polyisocyanate component (b) to obtain an amine prepolymer. The amine prepolymer is a polymer containing polyoxyethylene groups in the side chain.

The active hydrogen component (a) used in step 1 includes a polyol (a3) having two or more hydroxyl groups and an alkoxy polyoxyethylene chain as an essential component. The active hydrogen component (a) and the polyol (a3) are the same as the active hydrogen component (a) and the polyol (a3) in the description of "1. Aqueous dispersion for moisture-permeable waterproof material" above, and the preferred embodiments are also the same.

The active hydrogen component (a) may include, in addition to the above-mentioned polyol (a3), a compound selected from a high molecular weight polyol (a1) having an Mn of 300 or more, a low molecular weight polyol (a2) having an Mn or a chemical formula weight of less than 300, a compound (a4) having an ionic group and an active hydrogen atom, and a reaction terminator (a5). The above-mentioned polyol (a1), the above-mentioned polyol (a2), the above-mentioned compound (a4), and the above-mentioned reaction terminator (a5) are the same as the polyol (a1), the polyol (a2), the compound (a4), and the reaction terminator (a5) in the description of "1. Aqueous dispersion for moisture-permeable waterproof material".

From the viewpoint of providing a film having excellent substrate adhesion, the active hydrogen component (a) in step 1 preferably comprises the above-mentioned polyol (a3) and a condensation-type polyester polyol of a polycarboxylic acid having 2 to 10 carbon atoms and a polyol having 2 to 20 carbon atoms. It is particularly preferred that the above-mentioned polyol (a3) and a condensation-type polyester polyol of a polycarboxylic acid having 2 to 10 carbon atoms and a polyol having 2 to 20 carbon atoms also comprise a low molecular weight polyol (a2).

The polyisocyanate component (b) used in step 1 is the same as the polyisocyanate component (b) in the description of "1. Aqueous dispersion for moisture-permeable waterproof material", and the preferred embodiment is also the same.

In step 1, it is preferred to react the active hydrogen component (a) and the polyisocyanate component (b) in such a manner that the equivalent ratio of isocyanate groups to the groups containing active hydrogen atoms (referring to hydroxyl groups and amino groups, excluding carboxyl groups, sulfonic acid groups and sulfamic acid groups) contained in the active hydrogen component (a) (isocyanate groups/groups containing active hydrogen atoms) becomes 1.01 to 3, and it is more preferred to react in such a manner that the equivalent ratio becomes 1.1 to 2.

The reaction temperature in step 1 is preferably 20-150° C., more preferably 60-110° C., and the reaction time is preferably 2-30 hours.

In step 1, a catalyst may be used to promote the reaction. Examples of the catalyst include the catalyst described in International Publication No. 2020/105569. In addition, in step 1, a radical scavenger may be used to suppress the abnormal increase in the viscosity of the reaction system. Examples of the radical scavenger include the radical scavenger described in International Publication No. 2020/105569.

Step 2 is a step of adding a monomer (M) having a vinyl group to the amine prepolymer obtained in step 1.

As the monomer (M) having a vinyl group used in step 2, the same monomer (M) as described in "1. Aqueous dispersion of moisture-permeable waterproof material" can be cited. As the monomer (M) having a vinyl group, based on the viewpoint of water resistance during film processing, it is preferred to include aliphatic (meth)acrylate, and more preferably to include methyl (meth)acrylate. Furthermore, when the above preferred monomer is used in step 2, the monomer obtained in step 2 functions as an emulsifying solvent to promote the dispersion of the amine prepolymer in step 3.

The ratio of the weight Wup of the amine prepolymer to the weight Wm of the monomer (M) having a vinyl group (Wup:Wm) in the starting step 2 is preferably 90:10 to 50:50, more preferably 80:20 to 60:40.

In step 2, the temperature of the amine prepolymer when the vinyl group-containing monomer (M) is added is preferably 30 to 60° C. After step 1 and before step 2, a step of cooling the amine prepolymer obtained in step 1 may be performed. The cooling method is not particularly limited, and for example, air cooling to a desired temperature may be used.

Step 3 is a step of dispersing the product obtained in step 2 in an aqueous medium to obtain a dispersion of an amine prepolymer. "The product obtained in step 2" refers to a mixture containing an amine prepolymer and a monomer (M) having a vinyl group.

The aqueous medium used in step 3 is the same as the aqueous medium described in "1. Aqueous dispersion for moisture-permeable waterproof material", and the preferred embodiment is also the same.

When the product obtained in step 2 is dispersed in an aqueous medium, a surfactant may be used from the viewpoint of dispersion stability. As the surfactant, reactive surfactants and non-reactive surfactants having free radical reactive groups may be cited. One type may be used alone or two or more types may be used in combination. As the surfactant, for example, reactive surfactants and non-reactive surfactants having free radical reactive groups described in International Publication No. 2020/105569 may be cited.

When the product obtained in step 2 is dispersed in an aqueous medium, the above-mentioned compound (a4) having an ionic group and an active hydrogen atom may also be used from the viewpoint of dispersion stability. When using a compound (a4) having an ionic group and an active hydrogen atom, the neutralizer for neutralizing the compound (a41) containing an anionic group and an active hydrogen atom and the compound (a42) containing a cationic group and an active hydrogen atom can be added at any of the following times: before the amine prepolymerization reaction (before starting step 1), during the amine prepolymerization reaction (during step 1), after the amine prepolymerization reaction, before water diffusion (after step 1, before step 3), during water diffusion (during step 3), or after water diffusion (after step 3). From the perspective of the stability of the aqueous dispersion, it is preferably added before water diffusion (before step 3) or during water diffusion (during step 3). The preferred implementation temperature of step 3 is 0-100°C, and the preferred time is 1-180 minutes.

Step 4 is a step of extending the urethane prepolymer in the dispersion of the urethane prepolymer obtained in step 3 by using a chain extender (d). By performing step 4, a dispersion of a polyurethane resin containing a monomer (M) having a vinyl group is obtained.

The chain extender (d) used in step 4 is the same as the chain extender in the description of "1. Aqueous dispersion for moisture-permeable waterproof material", and the preferred example is also the same. Chain extender (d) can be used alone or in combination of two or more. Furthermore, chain extender (d) can also be used as active hydrogen component (a) in step 1. The implementation temperature of step 4 is preferably 0 to 100°C, and the time is preferably 1 to 240 minutes.

Step 5 is performed after step 4 to polymerize the monomer (M) having a vinyl group. By performing step 5, the monomer (M) having a vinyl group in the polyurethane resin obtained in step 4 is polymerized to obtain an aqueous dispersion containing composite resin particles containing a polyurethane resin and a vinyl resin.

As the polymerization initiator used in the polymerization in step 5, the following common free radical polymerization initiators can be used: persulfate-based initiators such as sodium persulfate, potassium persulfate and ammonium persulfate; azo-based initiators such as azobisisobutyronitrile; organic peroxides such as benzoyl peroxide, isopropylbenzene hydroperoxide, tert-butyl perbenzoate and tert-butyl hydroperoxide; hydrogen peroxide. They can be used alone or in combination of two or more. As the polymerization initiator, hydrogen peroxide is preferred. The amount of the polymerization initiator used is based on the weight of the vinyl monomer (M) used for polymerization, and is preferably 0.05 to 5% by weight. The polymerization initiator can be used in the required amount at the beginning of the polymerization, or can be added separately at arbitrary intervals.

In the polymerization process in step 5, a reducing agent may be used as needed together with the above-mentioned polymerization initiator. Examples of such reducing agents include reducing organic compounds such as ascorbic acid, metal salts of ascorbic acid, tartaric acid, citric acid, glucose, and metal salts of formaldehyde sulfoxylate, and reducing inorganic compounds such as sodium thiosulfate, sodium sulfite, sodium bisulfite, and sodium metabisulfite. As the reducing agent, a metal salt of ascorbic acid is preferred, and a sodium salt of ascorbic acid is more preferred.

In addition, during the polymerization process, a chain transfer agent may be used as needed. Examples of such chain transfer agents include n-dodecyl mercaptan, tert-dodecyl mercaptan, n-butyl mercaptan, 2-ethylhexyl ethanethiolate, 2-butyl ethanol, β-butyl propionic acid, and α-methylstyrene dimer. Furthermore, sodium acetate, sodium citrate, sodium bicarbonate, etc. may be used as buffers as needed. Polyvinyl alcohol, water-soluble cellulose derivatives, and alkali metal salts of polymethacrylic acid may also be used as protective colloids.

The polymerization reaction in step 5 is preferably carried out at a temperature in the range of 20°C to 150°C, more preferably 40°C to 100°C. The reaction time is preferably 1 minute to 50 hours. The polymerization reaction is preferably carried out in the presence of an inert gas. As the inert gas, nitrogen gas or the like can be mentioned.

The method for producing the aqueous dispersion of the present invention may use an organic solvent in any of the production steps. The organic solvent is not particularly limited, and may include: ketone solvents having 3 to 10 carbon atoms (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), ester solvents having 2 to 10 carbon atoms (ethyl acetate, butyl acetate, γ-butyrolactone, etc.), ether solvents having 4 to 10 carbon atoms (diisopropyl ether, diisopropyl ether, etc.), and the like. alkane, tetrahydrofuran, ethyl solvent and diethylene glycol dimethyl ether, etc.), amide solvents with 3 to 10 carbon atoms (N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone and N-methylcaprolactam, etc.), sulfoxide solvents with 2 to 10 carbon atoms (dimethyl sulfoxide, etc.), alcohol solvents with 1 to 8 carbon atoms (methanol, ethanol, isopropanol and octanol, etc.) and hydrocarbon solvents with 4 to 10 carbon atoms (cyclohexane, toluene and xylene, etc.). When an organic solvent is used, the solvent may be removed in the subsequent step.

In the production method of the present invention, the aqueous dispersion after step 5 may also contain a crosslinking agent, a viscosity adjuster, a defoaming agent, a preservative, a weathering stabilizer, an antifreeze agent, etc. The specific examples thereof are the same as those described in "1. Aqueous dispersion for moisture-permeable waterproof material".

According to the production method of the present invention, by carrying out step 1, polyoxyethylene groups are introduced into the side chains of the prepolymer of polyurethane resin, and then by carrying out steps 2 to 5, an aqueous dispersion containing composite resin particles can be obtained, and the composite resin particles include polyurethane resin having polyoxyethylene groups in the side chains and vinyl resin. As a result, according to the production method of the present invention, a film with excellent substrate adhesion, transparency and glossiness can be provided, and an aqueous dispersion with excellent doping stability can be obtained.

[3. Use of the aqueous dispersion of the present invention] The aqueous dispersion of the present invention and the aqueous dispersion obtained by the production method of the present invention can be coated on a release substrate (e.g., release paper, release cloth, etc.) and then dried to produce a moisture-permeable and waterproof film.

An example of a method for producing the above-mentioned moisture-permeable and waterproof film is described. A coating liquid composed of the aqueous dispersion of the present invention is prepared and applied on release paper using a doctor blade coater, a tube coater, a rod coater, or the like. Thereafter, the coating liquid is dried at a temperature of about 100 to 160°C for about 30 seconds to about 5 minutes using a dryer such as an air oven, thereby forming a film composed of composite resin particles. Regarding the thickness of the film, when used as a moisture-permeable and waterproof cloth, it is preferably about 10 to 50 μm. The thickness of the film can be appropriately set according to its use. The thickness of the film can be adjusted by adjusting the slit gap of the coating machine when applying the coating liquid, or by repeatedly applying and drying.

Since the film made using the aqueous dispersion of the present invention has excellent moisture permeability and water resistance, it is suitable for use in: outdoor clothing for fishing or mountaineering, ski-related clothing, windbreakers, sportswear, golf clothing, raincoats, casual jackets, outdoor work clothes, gloves, shoes and tents and other mountaineering equipment, diapers, sanitary products and other hygienic materials that require moisture permeability. [Example]

The present invention is described in more detail below by way of examples, but the present invention is not limited to the examples. In the following description, parts represent parts by weight. [Example 1] 99.6 parts of KURARAY POLYOL P-2010 [manufactured by Kuraray Co., Ltd.], 9.1 parts of 1,4-butanediol, and 59.7 parts of Ymer N120 [manufactured by Perstorp] were added to a reaction apparatus equipped with a stirrer and a heating device as an active hydrogen component (a), and 70.2 parts of isophorone diisocyanate was added as a polyisocyanate component (b), and stirred at 80°C for 5 hours to carry out an amine esterification reaction. The reaction liquid obtained by the amine esterification reaction was cooled to 60°C, 102.3 parts of methyl methacrylate was added as a monomer (M) having a vinyl group, and the mixture was cooled to 50°C to obtain an amine prepolymer solution containing a monomer (M) having a vinyl group. The obtained amine prepolymer solution was temperature-adjusted to 50°C, and 532.0 parts of ion-exchanged water were added over 30 minutes while stirring at 200 rpm to obtain an aqueous dispersion of the amine prepolymer. 76.0 parts of a 10.0 wt % aqueous solution of isophorone diamine and 47.1 parts of a 5.0 wt % aqueous solution of Disponil (registered trademark) PUD were added to the obtained aqueous dispersion as a chain extender (d), and the mixture was stirred at 50°C for 3 hours to perform a chain extension reaction. Next, the dispersion after the chain extension reaction was cooled to 40°C, and 2.1 parts of a 5.0 wt% aqueous solution of hydrogen peroxide was added as a polymerization initiator under a nitrogen flow, and 6.1 parts of a 5.0 wt% aqueous solution of sodium ascorbate was added as a reducing agent. The mixture was stirred at 40°C for 3 hours to carry out polymerization, and an aqueous dispersion of composite resin particles with a solid content concentration of 35.0 wt% was obtained (Q-1).

[Example 2] In a reaction apparatus equipped with a stirrer and a heating device, 99.0 parts of KURARAY POLYOL P-2010 [manufactured by Kuraray Co., Ltd.], 7.9 parts of 1,4-butanediol, 1.8 parts of dihydroxymethyl propionic acid, and 59.7 parts of Ymer N120 [manufactured by Perstorp] were added as active hydrogen component (a), and 70.2 parts of isophorone diisocyanate was added as polyisocyanate component (b), and stirred at 80°C for 5 hours to carry out amine esterification reaction. The reaction liquid obtained by the amine esterification reaction was cooled to 60°C, 102.3 parts of methyl methacrylate was added as a monomer (M) having a vinyl group, and the mixture was cooled to 50°C to obtain an amine ester prepolymer solution containing a monomer (M) having a vinyl group. The obtained amine prepolymer solution was adjusted to 50°C, stirred at 200 rpm, and 547.8 parts of ion exchange water were added over 30 minutes to obtain an aqueous dispersion of the amine prepolymer. 17.9 parts of a 5.0 wt% aqueous solution of ethylenediamine and 76.0 parts of a 10.0 wt% aqueous solution of isophoronediamine were added to the obtained aqueous dispersion as a chain extender (d), and 9.6 parts of a 5.0 wt% aqueous solution of sodium hydroxide was added as a neutralizer, and stirred at 50°C for 3 hours to carry out a chain extension reaction. Next, the dispersion after the chain extension reaction was cooled to 40°C, and 2.1 parts of a 5.0 wt% aqueous solution of hydrogen peroxide was added as a polymerization initiator under a nitrogen flow, and 6.1 parts of a 5.0 wt% aqueous solution of sodium ascorbate was added as a reducing agent. The mixture was stirred at 40°C for 3 hours to carry out polymerization, and an aqueous dispersion of composite resin particles with a solid content concentration of 35.0 wt% was obtained (Q-2).

[Example 3] Except that the neutralizer (aqueous solution of sodium hydroxide) in Example 2 is not used and the amount of ion exchange water used is 554.5 parts, the same operation as in Example 2 is performed to obtain an aqueous dispersion of composite resin particles (Q-3).

[Examples 4 to 17] Using the raw materials listed in Tables 1-1 and 1-2, the same method as in Example 1 was used to obtain aqueous dispersions (Q-4) to (Q-17) of composite resin particles of Examples 4 to 17.

[Comparative Example 1] 37.0 parts of KURARAY POLYOL P-2010 [manufactured by Kuraray Co., Ltd.], 116.6 parts of PEG-2000 [manufactured by Sanyo Chemical Industries, Ltd.], 6.3 parts of 1,4-butanediol, and 8.6 parts of dihydroxymethyl propionic acid were added to a reaction apparatus equipped with a stirrer and a heating device as an active hydrogen component (a), 70.2 parts of isophorone diisocyanate was added as a polyisocyanate component (b), and 102.3 parts of methyl methacrylate was added as a monomer having a vinyl group (M), and stirred at 80°C for 5 hours to carry out an amine esterification reaction. Next, the obtained reaction solution was cooled to 50°C, and 6.4 parts of triethylamine was added to obtain an amine ester prepolymer solution. The obtained amine prepolymer liquid was adjusted to 50°C, stirred at 200 rpm, and 539.1 parts of ion exchange water were added over 30 minutes to obtain an aqueous dispersion of the amine prepolymer. 76.0 parts of a 10.0 wt% aqueous solution of isophorone diamine as a chain extender (d) and 47.1 parts of a 5.0 wt% aqueous solution of Disponil (registered trademark) PUD were added to the obtained aqueous dispersion, and stirred at 50°C for 3 hours to carry out a chain extension reaction. After the chain extension reaction, precipitation of a large amount of resin was confirmed in the aqueous dispersion, and the polyurethane resin was not uniformly dispersed in the water, so the subsequent polymerization of the vinyl monomer was not carried out. Therefore, it was not possible to obtain an aqueous dispersion in this case and no evaluation test was performed.

[Comparative Example 2] In a reaction apparatus equipped with a stirrer and a heating device, 107.0 parts of KURARAY POLYOL P-2010 [manufactured by Kuraray Co., Ltd.], 46.6 parts of PEG-2000 [manufactured by Sanyo Chemical Industries, Ltd.], 6.3 parts of 1,4-butanediol, and 8.6 parts of dihydroxymethyl propionic acid were added as active hydrogen component (a), 70.2 parts of isophorone diisocyanate was added as polyisocyanate component (b), and 102.3 parts of methyl methacrylate was added as monomer (M) having a vinyl group, and stirred at 80°C for 5 hours to carry out an amine esterification reaction. Next, the obtained reaction solution was cooled to 50°C, and 6.4 parts of triethylamine was added to obtain an amine ester prepolymer solution. The obtained amine prepolymer solution was adjusted to 50°C, stirred at 200 rpm, and 539.1 parts of ion exchange water were added over 30 minutes to obtain an aqueous dispersion of the amine prepolymer. 76.0 parts of a 10.0 wt% aqueous solution of isophorone diamine as a chain extender (d) and 47.1 parts of a 5.0 wt% aqueous solution of Disponil (registered trademark) PUD were added to the obtained aqueous dispersion, stirred at 50°C for 3 hours, and a chain extension reaction was performed. Next, the aqueous dispersion after the chain extension reaction was cooled to 40°C, and 2.1 parts of a 5.0 wt% aqueous solution of hydrogen peroxide was added as a polymerization initiator under a nitrogen flow, and 6.1 parts of a 5.0 wt% aqueous solution of sodium ascorbate was added as a reducing agent, and the mixture was stirred at 40°C for 3 hours to polymerize, thereby obtaining an aqueous dispersion (Q'-2) of composite resin particles with a solid content concentration of 35.0 wt%. The polyurethane resin contained in the composite resin particles is a resin without a side chain containing polyoxyethylene.

[Table 1-1] Embodiment 1 2 3 4 5 6 7 8 9 10 Aqueous dispersion (Q) Q-1 Q-2 Q-3 Q-4 Q-5 Q-6 Q-7 Q-8 Q-9 Q-10 Blending amount (parts by weight) Polyol (a1) Polyester diol KURARAY POLYOL P-2010 99.6 99.0 99.0 - 98.7 99.6 99.6 99.6 119.5 45.5 ETERNACOLL UH-200 - - - 99.6 - - - - - - Polyether polyol PTMG-1000 - - - - - - - - - - PEG-2000 - - - - - - - - - - Low molecular weight polyol (a2) 1,4-Butanediol 9.1 7.9 7.9 9.1 10.1 9.1 9.1 9.1 10.1 6.4 Polyol (a3) Ymer N120 59.7 59.7 59.7 59.7 - 59.7 59.7 59.7 38.9 116.6 Ymer N90 - - - - 59.7 - - - - - Compounds containing ionic groups and active hydrogen atoms (a4) 2-Hydroxymethylpropionic acid - 1.8 1.8 - - - - - - - Polyisocyanate component (b) Isophorone diisocyanate 70.2 70.2 70.2 70.2 70.2 70.2 70.2 70.2 70.2 70.2 Chain extender (d) 5.0 wt% ethylenediamine aqueous solution - 17.9 17.9 - - - - - - - 10.0 wt% isophorone diamine aqueous solution 76.0 76.0 76.0 76.0 76.0 76.0 76.0 76.0 76.0 76.0 5 wt% diethylenetriamine aqueous solution - - - - - - - - - - 5.0 wt% Disponil PUD aqueous solution 47.1 - - 47.1 47.1 47.1 47.1 47.1 47.1 47.1 Neutralizer 5.0 wt% sodium hydroxide aqueous solution - 9.6 - - - - - - - - Triethylamine - - - - - - - - - - Monomers with vinyl groups (M) Monofunctional vinyl monomer (M1) Methyl Methacrylate 102.3 102.3 102.3 102.3 102.3 85.4 238.7 26.5 102.3 102.3 Vinyl monomers with two or more functional groups (M2) PEG#400 dimethacrylate - - - - - 16.9 - - - - Ion exchange water 532.0 547.8 554.5 531.8 531.8 531.8 773.9 396.2 531.8 531.8 5.0 wt% hydrogen peroxide aqueous solution 2.1 2.1 2.1 2.1 2.1 2.1 4.8 0.5 2.1 2.1 5.0 wt% sodium ascorbate aqueous solution 6.1 6.1 6.1 6.1 6.1 6.1 16.7 1.9 6.1 6.1 Ratio of the weight W1 of the polyurethane resin (U) to the weight W2 of the vinyl resin (V) (W1:W2) 70:30 70:30 70:30 70:30 70:30 70:30 50:50 90:10 70:30 70:30 Ratio of the weight of oxyethylene groups to the weight of the composite resin (C) (wt%) 15 15 15 15 15 19 11 20 10 30 Time stability of aqueous dispersions ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Moisture permeability test A-1 moisture permeability (g/ ^m2・24 hrs) 2800 2900 2700 2300 2800 3200 2000 3200 2000 3400 B-1 Moisture permeability (g/ ^m2・24 hrs) 54000 55000 45000 40000 55000 67000 30000 75000 40000 90000 Water pressure test (mmH ₂ O) 18000 18000 20000 20000 20000 12000 20000 12000 20000 10000

[Table 1-2] Embodiment Comparison Example 11 12 13 14 15 16 17 1 2 Aqueous dispersion (Q) Q-11 Q-12 Q-13 Q-14 Q-15 Q-16 Q-17 - Q'-2 Blending amount (parts by weight) Polyol (a1) Polyester diol KURARAY POLYOL P-2010 64.0 88.2 99.6 - - - 98.3 37.0 107.0 ETERNACOLL UH-200 - - - 88.2 - 98.3 - - - Polyether polyol PTMG-1000 - - - - 89.9 - - PEG-2000 - - - - - - - 116.6 46.6 Low molecular weight polyol (a2) 1,4-Butanediol 7.3 7.8 8.4 7.8 4.8 9.3 9.3 6.3 6.3 Polyol (a3) Ymer N120 97.2 71.8 59.8 71.8 71.8 - - - - Ymer N90 - - - - - 59.7 59.7 - - Compounds containing ionic groups and active hydrogen atoms (a4) 2-Hydroxymethylpropionic acid - 1.0 1.0 1.0 1.0 1.0 1.0 8.6 8.6 Polyisocyanate component (b) Isophorone diisocyanate 70.2 70.2 70.2 70.2 72.4 70.2 70.2 70.2 70.2 Chain extender (d) 5.0 wt% ethylenediamine aqueous solution - 17.9 - 17.9 17.7 17.9 17.9 - - 10.0 wt% isophorone diamine aqueous solution 76.0 76.1 42.3 76.1 74.9 76.1 76.1 76.0 76.0 5 wt% diethylenetriamine aqueous solution - - 47.9 - - - - 5.0 wt% Disponil PUD aqueous solution 47.1 - - - - - - 47.1 47.1 Neutralizer 5.0 wt% sodium hydroxide aqueous solution - - - 6.3 - - - - - Triethylamine - - - - - - - 6.4 6.4 Monomers with vinyl groups (M) Monofunctional vinyl monomer (M1) Methyl Methacrylate 102.3 102.3 102.4 102.3 102.4 102.4 102.4 102.3 102.3 Vinyl monomers with two or more functional groups (M2) PEG#400 dimethacrylate - - - - - - - - - Ion exchange water 531.8 557.9 554.9 557.9 557.9 557.2 557.2 539.1 539.1 5.0 wt% hydrogen peroxide aqueous solution 2.1 2.1 2.1 2.1 2.1 2.1 2.1 - 2.1 5.0 wt% sodium ascorbate aqueous solution 6.1 6.1 6.1 6.1 6.1 6.1 6.1 - 6.1 Ratio of the weight W1 of the polyurethane resin (U) to the weight W2 of the vinyl resin (V) (W1:W2) 70:30 70:30 70:30 70:30 70:30 70:30 70:30 70:30 70:30 Ratio of the weight of oxyethylene groups to the weight of the composite resin (C) (wt%) 25 18 16 18 18 15 15 30 12 Time stability of aqueous dispersions ○ ○ ○ ○ ○ ○ ○ No rating × Moisture permeability test A-1 moisture permeability (g/ ^m2・24 hrs) 3200 3000 2800 3000 2600 2600 2800 2400 B-1 Moisture permeability (g/ ^m2・24 hrs) 80000 56000 52000 54000 50000 48000 55000 40000 Water pressure test (mmH ₂ O) 18000 20000 20000 20000 18000 20000 20000 16000

Among the raw materials used in Examples 1 to 17 and Comparative Examples 1 to 3, the compositions of the raw materials represented by trade names are as follows. ・KURARAY POLYOL P-2010: Polyester polyol condensed from 3-methyl-1,5-pentanediol and adipic acid, Mn=2000 [manufactured by Kuraray Co., Ltd.] ・ETERNACOLL UH-200: Polyhexamethylene carbonate diol with Mn=2000, [manufactured by Ube Industries, Ltd.] ・PTMG-1000: Poly(oxytetramethylene) glycol with Mn=1000 [manufactured by Mitsubishi Chemical Co., Ltd.] ・PEG-2000: Polyoxyethylene glycol with Mn=2000 [manufactured by Sanyo Chemical Industries, Ltd.] ・Ymer N120: Polyethylene glycol modified with aliphatic polyol with Mn=1,000 [manufactured by Perstorp] ・Ymer N90: Polyethylene glycol modified with aliphatic polyol with Mn=1,200 [manufactured by Perstorp] ・Disponil (registered trademark) PUD: modified amine with carboxyl group (amine value: 410 mg/KOH: 40 wt% aqueous solution) [manufactured by BASF] ・NeoCryl (registered trademark) A-1105: acrylic water-based resin with 50 wt% solid content [manufactured by Covestro] (used only in Comparative Example 3) "PEG#400 dimethacrylate" in Table 1-1 and Table 1-2 is dimethacrylate of polyethylene glycol with Mn=400.

[Comparative Example 3] In a reaction apparatus equipped with a stirrer and a heating device, 99.6 parts of KURARAY POLYOL P-2010 [manufactured by Kuraray Co., Ltd.], 9.1 parts of 1,4-butanediol, and 59.7 parts of Ymer N120 [manufactured by Perstorp] were added as active hydrogen component (a), and 70.2 parts of isophorone diisocyanate was added as polyisocyanate component (b), and stirred at 80°C for 5 hours to carry out amine esterification reaction. After the obtained reaction liquid was cooled to 60°C, 436.2 parts of ion exchange water adjusted to 60°C were added over 30 minutes while stirring at 200 rpm to obtain an aqueous dispersion of amine ester prepolymer. 76.0 parts of a 10.0 wt% aqueous solution of isophorone diamine as a chain extender (d) and 47.1 parts of a 5.0 wt% aqueous solution of Disponil (registered trademark) PUD were added to the obtained aqueous dispersion, and the mixture was stirred at 60°C for 3 hours to carry out a chain extension reaction. Next, the dispersion after the chain extension reaction was cooled to 25°C and mixed with 204.6 parts of an acrylic water-based resin NeoCryl (registered trademark) A-1105 [manufactured by Covestro] to obtain an aqueous dispersion (Q'-3) containing a polyurethane resin and an acrylic resin with a solid content concentration of 35.0 wt%. The polyurethane resin contained in the aqueous dispersion (Q'-3) is not compounded with an acrylic aqueous resin (an example of a vinyl resin). The polyurethane resin contained in the aqueous dispersion is a resin having a side chain containing polyoxyethylene groups. The "total weight of resins" in Table 2 means the total weight of the polyurethane resin and the acrylic aqueous resin contained in the aqueous dispersion.

[Table 2] Comparison Example 3 Aqueous dispersion Q'-3 Blending amount (parts by weight) Polyol (a1) Polyester diol KURARAY POLYOL P-2010 99.6 Low molecular weight polyol (a2) 1,4-Butanediol 9.1 Polyol (a3) Ymer N120 59.7 Polyisocyanate component (b) Isophorone diisocyanate 70.2 Chain extender (d) 10.0 wt% isophorone diamine aqueous solution 76.0 5.0 wt% Disponil PUD aqueous solution 47.1 Ion exchange water 436.2 Acrylic water-based resin NeoCryl A-1105 204.6 Ratio of the weight W1 of the polyurethane resin to the weight W2 of the vinyl resin (V) (W1:W2) 30:70 Ratio of the weight of oxyethylene groups to the total weight of the resin (wt%) 15 Time stability of aqueous dispersions ○ Moisture permeability test A-1 moisture permeability (g/ ^m2・24 hrs) 2200 B-1 Moisture permeability (g/ ^m2・24 hrs) 35000 Water pressure test (mmH ₂ O) 8000

Using the aqueous dispersions (Q-1) to (Q-17) of Examples 1 to 17 and the aqueous dispersions (Q'-2) to (Q'-3) of Comparative Examples 2 and 3, the stability of the aqueous dispersions over time and the moisture permeability and water pressure resistance of the membranes prepared using the aqueous dispersions were evaluated according to the following steps. The evaluation results are shown in Tables 1-1, 1-2 and 2.

[Time-dependent stability of aqueous dispersions] The aqueous dispersions of Examples 1 to 17 and Comparative Examples 2 to 3 were left at 40°C for 7 days, and the generation of sediment was evaluated by visual inspection. The case where no sediment was generated was marked as ○, and the case where sediment was generated was marked as ×.

[Moisture permeability] The aqueous dispersion of each example was applied on release paper in such a way that the thickness of the film after drying became 20 μm, and dried at 80°C for 10 minutes, and further dried at 120°C for 1 minute to obtain a film (sheet material) made of the aqueous dispersion. The moisture permeability (A-1 moisture permeability and B-1 moisture permeability) of the obtained film was measured. (A-1 moisture permeability) The moisture permeability of the film (A-1 moisture permeability) was measured according to the A-1 method (calcium chloride method) of JIS L-1099-2012. If the A-1 moisture permeability is 2000 g/m ²・24 hours or more, it is good. (B-1 moisture permeability) The moisture permeability of the membrane (B-1 moisture permeability) is measured according to the B-1 method (potassium acetate method) of JIS L-1099-2012. If the B-1 moisture permeability is 30,000 g/ ^m2 , 24 hours or more, it is considered good.

[Water pressure resistance (water resistance)] The aqueous dispersion of each example was applied on release paper in such a way that the thickness of the film after drying became 20 μm, and dried at 80°C for 10 minutes, and further dried at 120°C for 1 minute to obtain a film for water resistance measurement. The water pressure resistance of the obtained film for water resistance measurement was measured in accordance with JIS L1092-1998 (high water pressure resistance method). When the test piece was stretched by applying water pressure, nylon taffeta (density equivalent to warp + weft = 210 yarns/2.54 cm) was stacked on the test piece, and it was installed in a testing machine for measurement. If the water pressure resistance is 10000 mmH ₂ O or more, it is good. The upper limit is 20000 _mmH2O .

According to the results shown in Table 1-1, Table 1-2 and Table 2, it can be seen that the aqueous dispersion of the embodiment has excellent temporal stability, and the film formed using the aqueous dispersion of the embodiment has excellent moisture permeability and water resistance. On the other hand, the temporal stability of the aqueous dispersion of Comparative Example 2, which contains a polyurethane resin having a main chain and no polyurethane resin on the side chain, is poor, and regarding the aqueous dispersion of Comparative Example 3, which does not contain composite resin particles of polyurethane resin and ethylene resin, it can be seen that the water resistance of the film formed using the aqueous dispersion is poor. [Industrial Applicability]

The aqueous dispersion of the present invention and the aqueous dispersion obtained by the production method of the present invention have excellent stability over time, and excellent moisture permeability and water resistance when processed into a film. Therefore, the aqueous dispersion can be used as a moisture-permeable and waterproof material used in outdoor clothing, ski-related clothing, windproof clothing, sportswear, golf clothing, raincoats, casual jackets, outdoor work clothes, gloves, shoes, tents and other mountaineering equipment for fishing or mountaineering.

without

without

Claims (6)

A water-based dispersion of a moisture-permeable waterproof material, which contains composite resin particles (C) containing a polyurethane resin (U) and a vinyl resin (V). The polyurethane resin (U) is a reaction product of an active hydrogen component (a), a polyisocyanate component (b) and a chain extender (d). The active hydrogen component (a) contains a polyol (a3) having two or more hydroxyl groups and an alkoxy polyoxyethylene chain. As for the aqueous dispersion of moisture-permeable waterproof material of claim 1, the weight ratio of the oxyethylene groups contained in the composite resin particles (C) is 10 to 30 weight % based on the weight of the composite resin particles (C). The aqueous dispersion of moisture-permeable waterproof material of claim 1 or 2, wherein the ratio (W1:W2) of the weight W1 of the polyurethane resin (U) to the weight W2 of the vinyl resin (V) is 90:10 to 50:50. The aqueous dispersion of a moisture-permeable waterproof material as claimed in claim 1 or 2, wherein the active hydrogen component (a) further comprises a condensation-type polyester polyol of a polycarboxylic acid having 2 to 10 carbon atoms and a polyol having 2 to 20 carbon atoms. A method for producing a water-based dispersion of a moisture-permeable waterproof material, which is a method for producing a water-based dispersion of a moisture-permeable waterproof material containing composite resin particles (C) containing a polyurethane resin (U) and a vinyl resin (V), wherein the polyurethane resin (U) is a resin having a side chain containing polyoxyethylene groups, and the method for producing a water-based dispersion of a moisture-permeable waterproof material comprises the following steps 1 to 5; Step 1: reacting an active hydrogen component (a) containing a polyol having two or more hydroxyl groups and an alkoxypolyoxyethylene chain with a polyisocyanate component (b) to obtain an amine prepolymer; Step 2: adding a monomer (M) having a vinyl group to the amine prepolymer; Step 3: dispersing the product obtained in step 2 in an aqueous medium to obtain a dispersion of an amine prepolymer; Step 4: extending the amine prepolymer in the dispersion by a chain extender (d); and Step 5: after step 4, polymerizing the monomer (M) having a vinyl group. The method for producing an aqueous dispersion of a moisture-permeable waterproof material as claimed in claim 5, wherein the active hydrogen component (a) further comprises a condensation-type polyester polyol of a polycarboxylic acid having 2 to 10 carbon atoms and a polyol having 2 to 20 carbon atoms.