WO2024024812A1

WO2024024812A1 - Aqueous dispersion for moisture-permeable waterproof material, and method for producing same

Info

Publication number: WO2024024812A1
Application number: PCT/JP2023/027300
Authority: WO
Inventors: 耕平社領; 裕文井上
Original assignee: 三洋化成工業株式会社
Priority date: 2022-07-27
Filing date: 2023-07-26
Publication date: 2024-02-01

Abstract

This aqueous dispersion for a moisture-permeable waterproof material contains composite resin particles (C) including 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), said active hydrogen component (a) including a polyol (a3) that has at least two hydroxyl groups and has an alkoxy polyoxyethylene chain.

Description

Aqueous dispersion for moisture permeable waterproof material and method for producing the same

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

The general method for producing moisture-permeable waterproof fabrics is to apply a urethane resin for the skin layer on a release paper, dry it, then apply an adhesive on top of this, dry it, and then bond it with a fiber fabric by thermocompression. It is true.
In the conventional manufacturing method of moisture-permeable waterproof fabric, a polyurethane resin having a hydrophilic segment dissolved in an organic solvent such as dimethylformamide, toluene, or methyl ethyl ketone is used as the skin layer, and moisture-permeable waterproof fabric is manufactured using a dry method. During manufacturing, large amounts of solvent may be released into waste water and exhaust gas.
Under these circumstances, a skin layer using a water-based polyurethane resin that does not contain organic solvents is being considered in order to prevent work environment, water pollution, and air pollution.
As such an aqueous polyurethane resin, an aqueous dispersion of a polyurethane resin for moisture permeable and waterproof materials is known, which uses polyethylene glycol and a diol having a carboxy group as raw materials (for example, see Patent Document 1).
However, when the amount of polyethylene glycol used is increased in order to further improve moisture permeability, the stability of the aqueous dispersion decreases, resulting in problems such as poor emulsification and sedimentation of the resin due to changes over time.
As a method to improve such problems, water-based polyurethane resins made from diols having ethylene oxide in their side chains are known (for example, see Patent Document 2). The moisture permeability and water resistance when processed into layers were insufficient.

Patent No. 4283577 Patent No. 5479296

The present invention has been made in view of the above problems, and an object of the present invention is to provide an aqueous dispersion for a moisture-permeable waterproof material that has excellent stability over time and excellent moisture permeability and water resistance when processed into a film. It's about doing.

As a result of intensive studies to solve the above problems, the inventors have arrived at the present invention. That is, the present invention is as follows.
[1] An aqueous dispersion for 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) has two or more hydroxyl groups. An aqueous dispersion for a moisture-permeable waterproof material, which is a reaction product of an active hydrogen component (a) containing a polyol (a3) having an alkoxypolyoxyethylene chain, a polyisocyanate component (b), and a chain extender (d).
[2] The moisture-permeable waterproof material according to [1], wherein the weight percentage of 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). Aqueous dispersion.
[3] According to [1] or [2], the ratio (W1:W2) of the weight W1 of the polyurethane resin (U) and the weight W2 of the vinyl resin (V) is 90:10 to 50:50. Aqueous dispersion for breathable and waterproof materials.
[4] The active hydrogen component (a) further contains a condensed polyester polyol of a polyhydric carboxylic acid having 2 to 10 carbon atoms and a polyhydric alcohol having 2 to 20 carbon atoms [1] to [3] The aqueous dispersion for a moisture-permeable waterproof material according to any one of the items.
[5] A method for producing an aqueous dispersion for 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 polyoxyethylene A method for producing an aqueous dispersion for a moisture-permeable and waterproof material, which is a resin having a side chain containing a group, and includes the following steps 1 to 5.
Step 1: A step of reacting an active hydrogen component (a) containing a polyol having two or more hydroxyl groups and an alkoxypolyoxyethylene chain and a polyisocyanate component (b) to obtain a urethane prepolymer;
Step 2: Adding a monomer (M) having a vinyl group to the urethane prepolymer;
Step 3: Dispersing the material obtained in Step 2 in an aqueous medium to obtain a urethane prepolymer dispersion;
Step 4: extending the urethane prepolymer in the dispersion with a chain extender (d);
Step 5: A step carried out after Step 4, in which the vinyl group-containing monomer (M) is polymerized.
[6] The moisture permeable device according to [5], wherein the active hydrogen component (a) further contains a condensed polyester polyol of a polycarboxylic acid having 2 to 10 carbon atoms and a polyhydric alcohol having 2 to 20 carbon atoms. A method for producing an aqueous dispersion for waterproof materials.

According to the present invention, it is possible to provide an aqueous dispersion for a moisture permeable waterproof material that has excellent stability over time and excellent moisture permeability and water resistance when processed into a film.

[1. Aqueous dispersion for breathable and waterproof materials]
The aqueous dispersion for a moisture-permeable waterproof material of the present invention contains composite resin particles (C) containing a polyurethane resin (U) and a vinyl resin (V). In this specification, the "aqueous dispersion for moisture-permeable and waterproof materials" may be simply referred to as "aqueous dispersion."

The polyurethane resin (U) is produced by the reaction of an active hydrogen component (a) containing a polyol (a3) having two or more hydroxyl groups and an alkoxypolyoxyethylene chain, a polyisocyanate component (b), and a chain extender (d). It is a thing. The polyurethane resin (U) is a resin having a side chain containing a polyoxyethylene group. In the present invention, the side chain refers to a part branched from the main chain (a chain part containing a urethane bond).

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

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

Examples of polyester polyols with Mn of 300 or more include condensed polyester polyols with Mn of 300 or more, polylactone polyols with Mn of 300 or more, and polycarbonate polyols with Mn of 300 or more.

The condensed polyester polyol having an Mn of 300 or more may include Mn or a low-molecular polyol having a chemical formula weight of less than 300, a polycarboxylic acid having 2 to 20 carbon atoms, or an ester-forming derivative thereof [acid anhydride, lower (1 carbon number) -4) Those obtained by condensation with alkyl esters, acid halides, etc.].

The low-molecular-weight polyols having Mn or chemical formula weight of less than 300 that constitute the condensed polyester polyol include polyhydric alcohols having 2 to 20 carbon atoms; alkylenes having 2 to 12 carbon atoms in polyhydric alcohols having 2 to 20 carbon atoms; Oxide (hereinafter abbreviated as AO) adducts with Mn or chemical formula weight of less than 300; AO adducts with 2 to 12 carbon atoms of bisphenol (bisphenol A, bisphenol S, bisphenol F, etc.) with Mn or Examples include those having a chemical formula weight of less than 300; bis(2-hydroxyethyl) terephthalate and its AO adducts having 2 to 12 carbon atoms and having Mn or a chemical formula weight of less than 300.

Polyhydric alcohols having 2 to 20 carbon atoms include linear or branched aliphatic dihydric alcohols having 2 to 12 carbon atoms [ethylene glycol, 1,3-propanediol, 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 Straight chain alcohols such as 1,2-, 1,3- 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 Branched alcohols such as 4-methyloctanediol]; Alicyclic dihydric alcohols having 6 to 20 carbon atoms [1,4-cyclohexanediol, 1,3- or 1,4-cyclohexanedimethanol, 1,4-cyclo Heptanediol, 2,5-bis(hydroxymethyl)-1,4-dioxane, 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 dihydric alcohols having 8 to 20 carbon atoms [m- or p-xylylene diol, bis(hydroxyethyl)benzene and bis(hydroxyethyl) ) benzene, etc.]; trihydric alcohols with 3 to 20 carbon atoms [aliphatic triols (glycerin and trimethylolpropane, etc.), etc.]; tetrahydric to octahydric alcohols with 5 to 20 carbon atoms [aliphatic polyols (pentaerythritol, sorbitol, etc.) (mannitol, sorbitan, diglycerin, dipentaerythritol, etc.); sugars (sucrose, glucose, mannose, fructose, methyl glucoside and derivatives thereof); and the like.

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

Examples of polycarboxylic acids having 2 to 20 carbon atoms or ester-forming derivatives thereof include aliphatic dicarboxylic acids (succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, octadecanedicarboxylic acid, decylsuccinic acid, fumaric acid, maleic acid, etc.), alicyclic dicarboxylic acids (dimer acid, etc.), aromatic dicarboxylic acids (terephthalic acid, isophthalic acid, phthalic acid, t-butyl isophthalic acid, 2,6-naphthalene dicarboxylic acid, and 4,4'-biphenyl dicarboxylic acids, etc.), trivalent or higher polycarboxylic acids (trimellitic acid and pyromellitic acid, etc.), their anhydrides (succinic anhydride, maleic anhydride, phthalic anhydride, trimellitic anhydride, etc.), Examples include acid halides of (adipate dichloride, etc.), low molecular weight alkyl esters thereof (dimethyl succinate, dimethyl phthalate, etc.), and combinations thereof. Among these, preferred are aliphatic dicarboxylic acids having 2 to 10 carbon atoms and ester-forming derivatives thereof, and more preferred is adipic acid. The polyhydric carboxylic acids may be used alone or in combination of two or more.

As condensed polyester polyols having Mn of 300 or more, polycondensates of aliphatic polycarboxylic acids and Mn or low-molecular polyols having a chemical formula weight of less than 300 are used from the viewpoint of having excellent moisture permeability when processed into a film. Preferably, a condensation type polyester polyol of an aliphatic polycarboxylic acid having 2 to 10 carbon atoms and Mn or a polyhydric alcohol having 2 to 20 carbon atoms and having a chemical formula weight of less than 300 is more preferable, and an aliphatic polycarboxylic acid having 2 to 10 carbon atoms Esters of dicarboxylic acids and Mn or aliphatic dihydric alcohols having a chemical formula weight of less than 300 and having 2 to 20 carbon atoms are more preferred, and condensed polyester polyols of adipic acid and 3-methyl-1,5-pentanediol are particularly preferred. preferable.

As polylactone polyols having Mn of 300 or more, lactone monomers having 3 to 12 carbon atoms (β-propiolactone, γ-butyrolactone, γ-valerolactone, ε -caprolactone, η-caprylolactone, 11-undecanolactone, 12-dodecanoid, etc.) ring-opening polymerized. The lactone monomers may be used alone or in combination of two or more.

The polycarbonate polyol having Mn of 300 or more includes one or more of the above polyhydric alcohols having 2 to 20 carbon atoms (preferably aliphatic dihydric alcohols having 3 to 9 carbon atoms, more preferably 4 to 6 carbon atoms); Dealcoholization from a low-molecular carbonate compound (for example, dialkyl carbonate having an alkyl group with 1 to 6 carbon atoms, alkylene carbonate having an alkylene group having 2 to 6 carbon atoms, diaryl carbonate having an aryl group having 6 to 9 carbon atoms, etc.) Examples include polycarbonate polyols produced by condensation while reacting. As the polycarbonate polyol, for example, ETERNACOLL UH series [polyhexamethylene carbonate diol, manufactured by Ube Industries, Ltd.], Duranol G4672 [1,4-butanediol/1,6-hexanediol = 70/30 (molar ratio)] A commercially available polycarbonate polyol such as the polycarbonate diol with Mn=2000 used, manufactured by Asahi Kasei Chemicals Co., Ltd. may also be used.

Examples of the polyether polyol having Mn of 300 or more include compounds obtained by adding AO having 2 to 12 carbon atoms to the above-mentioned Mn or a low molecular weight polyol having a chemical formula weight of less than 300. One type of AO may be used alone or two or more types may be used in combination, and in the latter case, block addition (chip type, balanced type, active secondary type, etc.), random addition, or a combination of these may be used. Examples of the AO having 2 to 12 carbon atoms include those mentioned above.

The addition of AO to low-molecular-weight polyols with Mn or formula weight less than 300 can be carried out, for example, without a catalyst or in the presence of a catalyst (alkali catalyst, amine catalyst, acidic catalyst, etc.) (especially in the later stages of AO addition). It is carried out in one stage or in multiple stages under normal pressure or increased pressure.

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

As the polyether ester polyol having Mn of 300 or more, one or more of the above polyether polyols and a polyhydric carboxylic acid having 2 to 20 carbon atoms or an ester thereof exemplified as a raw material for the condensed polyester polyol having Mn of 300 or more may be used. Examples include those obtained by condensation polymerization with one or more types of sexual derivatives.

Castor oil-based polyols include castor oil, partially dehydrated castor oil, polyester polyols made from castor oil fatty acids and the above-mentioned polyhydric alcohols or polyoxyalkylene polyols having 2 to 20 carbon atoms (mono- or diglycerides of castor oil fatty acids, castor oil-based polyols). (mono-, di- or triester from oil fatty acid and trimethylolpropane, mono- or diester from castor oil fatty acid and polyoxypropylene glycol, etc.), AO having 2 to 12 carbon atoms added to castor oil and mixtures of two or more thereof. Examples of the AO having 2 to 12 carbon atoms include those mentioned above.

From the viewpoint of excellent moisture permeability when processed into a film, the polymer polyol (a1) is preferably a polyester polyol, more preferably a condensed polyester polyol or a polycarbonate polyol, and more preferably a polyol having 2 or more carbon atoms. It is a condensation type polyester polyol of 10 polycarboxylic acids and a polyhydric alcohol having 2 to 20 carbon atoms, and particularly preferably a polycondensation type polyester polyol of adipic acid and 3-methyl-1,5-pentanediol. .

The Mn of the polymer polyol (a1) is preferably 350 or more, more preferably 1,000 to 5,000, particularly preferably 1,500 to 3,000, from the viewpoint of excellent moisture permeability when processed into a film. It is.

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

The low-molecular polyol (a2) with Mn or chemical formula weight of less than 300 is exemplified in the explanation of "low-molecular polyol with Mn or chemical formula weight of less than 300" which is a component constituting the condensed polyester polyol with Mn of 300 or more. Dialkanolamines such as diethanolamine, diisopropanolamine, etc. are mentioned. The low molecular weight polyol (a2) is preferably a linear or branched aliphatic dihydric alcohol having 2 to 12 carbon atoms, a trihydric alcohol having 3 to 20 carbon atoms, or a tetrahydric to octahydric alcohol having 5 to 20 carbon atoms. 1,4-butanediol, 1,3-propanediol and trimethylolpropane are more preferred.

The polyol (a3) having two or more hydroxyl groups and an alkoxypolyoxyethylene chain is a polyol (a3) in which an aliphatic polyol having 3 to 20 carbon atoms (such as trimethylolpropane and glycerin) is bonded to an alkoxypolyoxyethylene chain. There are many things that can be mentioned. The polyol (a3) having two or more hydroxyl groups and an alkoxypolyoxyethylene chain is preferably trimethylolpropane having a methoxypolyoxyethylene group.

As a commercially available polyol (a3) having two or more hydroxyl groups and an alkoxypolyoxyethylene chain, for example, TEGOMER D3403 [a glycol having a polyoxyethylene group with a number average molecular weight (Mn) of 1,200, Evonik Industries AG] and Ymer N90, Ymer N120, Ymer N180 [trimethylolpropane modified with polyethylene glycol with Mn=1,200, 1,000, 600, manufactured by Perstorp].

In addition to the above polyols (a1) to (a3), the active hydrogen component (a) may also contain a compound (a4) containing an ionic group and an active hydrogen atom different from these. 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. Compound (a4) may be used alone or in combination of two or more.

The compound (a41) containing an anionic group and an active hydrogen atom includes, for example, a compound containing a carboxyl group as an anionic group and at least an amino group as an active hydrogen atom-containing group [for example, an amino acid (glycine, alanine, valine, , lysine, aspartic acid, glutamic acid, cysteine, serine, threonine, etc.), compounds containing a carboxyl group as an anionic group, a hydroxyl group as an active hydrogen atom-containing group, and having 2 to 10 carbon atoms [dialkylol Alkanoic acids (e.g. 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolheptanoic acid and 2,2-dimethyloloctanoic acid), tartaric acid, etc.], sulfone as anionic group Compounds containing an acid group (sulfo group), a hydroxyl group as an active hydrogen atom-containing group, and having 2 to 16 carbon atoms [3-(2,3-dihydroxypropoxy)-1-propanesulfonic acid and sulfoisophthalic acid] di(ethylene glycol) ester, etc.], a compound containing a sulfamic acid group as an anionic group, a hydroxyl group as an active hydrogen atom-containing group, and having 2 to 10 carbon atoms [N,N-bis(2-hydroxylethyl ) sulfamic acid, etc.) and salts obtained by neutralizing these compounds with a neutralizing agent.

Examples of the neutralizing agent used 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, hydroxide potassium and lithium hydroxide). Examples of amine compounds 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; Examples include amines and tertiary amines such as trimethylamine, triethylamine, dimethylethylamine, dimethylmonoethanolamine, and triethanolamine.

As a neutralizing agent used for neutralizing the compound (a41) containing an anionic group and an active hydrogen atom, from the viewpoint of the stability of the aqueous dispersion over time and the excellent moisture permeability when processed into a film, Compounds that have a high vapor pressure at are suitable.
From the above viewpoint, as the neutralizing agent used for neutralizing the compound (a41) containing an anionic group and an active hydrogen atom, an alkali metal hydroxide and an amine compound having 1 to 20 carbon atoms are preferable, Sodium hydroxide, monomethylamine, monoethylamine, dimethylamine, diethylamine, trimethylamine, triethylamine and dimethylethylamine are more preferred, and sodium hydroxide is even more preferred.

Among the compounds (a41) containing an anionic group and an active hydrogen atom, those containing a carboxy group as an anionic group are preferred from the viewpoint of excellent stability over time of an aqueous dispersion and excellent moisture permeability when processed into a film. A compound having a hydroxyl group as an active hydrogen atom-containing group and having 2 to 10 carbon atoms, more preferably 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, and salts thereof. Among them, 2,2-dimethylolpropionic acid and its salts are more preferred.

The compound (a42) containing a cationic group and an active hydrogen atom is a compound having a tertiary amino group as a cationic group and a hydroxyl group as an active hydrogen atom-containing group, such as a tertiary amino group having 1 to 20 carbon atoms. group-containing diols [N-alkyl dialkanolamines (e.g. N-methyldiethanolamine, N-propyldiethanolamine, N-butyldiethanolamine and N-methyldipropanolamine)], N,N-dialkylmonoalkanolamines (e.g. N,N -dimethylethanolamine) and trialkanolamine (eg, triethanolamine), which are neutralized with a neutralizing agent.

Neutralizing agents used for neutralizing the compound (a42) containing a cationic group and an active hydrogen atom include monocarboxylic acids having 1 to 10 carbon atoms (for example, formic acid, acetic acid, propanoic acid, etc.), carbonic acid, dimethyl carbonate, etc. , dimethyl sulfate, methyl chloride and benzyl chloride.

In addition to the above-mentioned polyols (a1) to (a3) and compound (a4), the active hydrogen component (a) may contain a reaction terminator (a5) different from these. As the reaction terminator (a5), monoalcohols having 1 to 20 carbon atoms (methanol, ethanol, butanol, octanol, decanol, dodecyl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, etc.), monoamines having 1 to 20 carbon atoms; (mono- or dialkylamines such as monomethylamine, monoethylamine, monobutylamine, dibutylamine and monooctylamine, and monoalkanolamines such as monoethanolamine and 2-amino-2-methylpropanol).

The active hydrogen component (a) preferably contains, in addition to the polyol (a3), a condensed polyester polyol of a polyhydric fatty acid having 2 to 10 carbon atoms and a polyhydric alcohol having 2 to 20 carbon atoms; Particularly preferred are those containing a low molecular weight polyol (a2) together with (a3) and a condensed polyester polyol of a polyhydric fatty acid having 2 to 10 carbon atoms and a polyhydric alcohol having 2 to 20 carbon atoms.

Examples of the polyisocyanate component (b) which is a material for the polyurethane resin (U) include organic polyisocyanates having two or more isocyanate groups, such as aromatic polyisocyanates (b1) having 8 to 26 carbon atoms, carbon Aliphatic polyisocyanate (b2) having 4 to 22 carbon atoms, alicyclic polyisocyanate (b3) having 8 to 18 carbon atoms, araliphatic polyisocyanate (b4) having 10 to 18 carbon atoms, and modification of these organic polyisocyanates (b5) etc.

Examples of the aromatic polyisocyanate (b1) having 8 to 26 carbon atoms include 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (hereinafter, tolylene diisocyanate is referred to as TDI). (abbreviation), crude TDI, 4,4'- or 2,4'-diphenylmethane diisocyanate (hereinafter, diphenylmethane diisocyanate is abbreviated 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''-triphenyl Mention may be made of methane triisocyanate and m- 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, 2,6-diisocyanatomethyl caproate, 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, Mention may be made of methylcyclohexylene diisocyanate, bis(2-isocyanatoethyl)-4-cyclohexene-1,2-dicarboxylate and 2,5- or 2,6-norbornane diisocyanate.

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

The modified product (b5) includes a modified product containing a urethane group, a carbodiimide group, an allophanate group, a urea group, a biuret group, a uretdione group, a uretoimine group, an isocyanurate group, or an oxazolidone group of the organic polyisocyanate [for example, modified MDI (urethane modified (MDI, carbodiimide-modified MDI, trihydrocarbyl phosphate-modified MDI, etc.), urethane-modified TDI, biuret form of HDI, isocyanurate form of HDI, and isocyanurate form of IPDI].

Among these, preferred from the viewpoint of water resistance when processed into a film are alicyclic polyisocyanates (b3) having 8 to 18 carbon atoms and modified products thereof, and more preferred are IPDI and hydrogenated MDI. and isocyanurate form 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. Moreover, it is a compound that can react with the reactant (urethane prepolymer) of the active hydrogen component (a) and the polyisocyanate component (b). As the chain extender (d), water, a (poly)amine compound having an anionic ionic group (d1), Mn not having an anionic ionic group, or a (poly)amine compound having a chemical formula weight of less than 500 (d2) etc. Moreover, as the chain extender (d), the above-mentioned polyol (a1), polyol (a2), compound (a4) and reaction terminator (a5) may be used.

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

The above (poly)amine compound (d2) includes aliphatic polyamines having 2 to 36 carbon atoms [alkylene diamines such as ethylenediamine and hexamethylene diamine; diethylenetriamine, dipropylenetriamine, dihexylenetriamine, triethylenetetramine, tetraethylenepentamine; , polyalkylene polyamines in which the alkylene group has 2 to 6 carbon atoms and 3 to 7 nitrogen atoms such as pentaethylenehexamine and hexaethyleneheptamine {poly(di-hexa)alkylene (carbon number 2 to 6) poly (tri-hepta)amine}, etc.), alicyclic polyamines having 6 to 20 carbon atoms (1,3- or 1,4-diaminocyclohexane, 4,4'- or 2,4'-dicyclohexylmethane diamine, and isophorone diamine) etc.), aromatic polyamines having 6 to 20 carbon atoms (1,3- or 1,4-phenylene diamine, 2,4- or 2,6-tolylene diamine, 4,4'- or 2,4'-methylene bisaniline, etc.), aromatic aliphatic polyamines having 8 to 20 carbon atoms [1,3- or 1,4-xylylenediamine, bis(aminoethyl)benzene, bis(aminopropyl)benzene, bis(aminobutyl)benzene, etc. ], heterocyclic polyamines having 3 to 20 carbon atoms [2,4-diamino-1,3,5-triazine, piperazine and N-(2-aminoethyl)piperazine, etc.], hydrazine or its derivatives (such as adipic acid dihydrazide) dibasic acid dihydrazide), etc.

As the chain extender (d), aliphatic polyamines, alicyclic polyamines, and polyamine compounds having anionic ionic groups are preferable, and it is more preferable to use two or more selected from ethylenediamine, isophoronediamine, and polyamines having a carboxyl group. preferable.

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

In the present invention, the monomer (M) having a vinyl group constituting the vinyl resin (V) includes a monofunctional vinyl monomer (M1), a difunctional or more functional vinyl monomer (M2), etc. can be mentioned. One type of monomer (M) having a vinyl group may be used, or two or more types may be used in combination.

As the monofunctional vinyl monomer (M1), esters of unsaturated alcohols or hydroxystyrene and monocarboxylic acids having 1 to 12 carbon atoms [for example, vinyl acetate, vinyl butyrate, vinyl propionate, vinyl butyrate, isopropenyl acetate, methyl-4-vinylbenzoate, vinyl methoxy acetate, vinyl benzoate and acetoxystyrene], aliphatic (meth)acrylates [such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, ) acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, hexadecyl (meth)acrylate, heptadecyl (meth)acrylate, eicosyl (meth)acrylate, etc.], (meth)acrylate having an alicyclic structure [cyclohexyl (meth)acrylate, etc.] ) acrylate, isobornyl (meth)acrylate, methylnorbornene (meth)acrylate, etc.], (meth)acrylate having an aromatic ring [benzyl (meth)acrylate, phenyl (meth)acrylate, etc.], (meth)acrylate having a hydroxyl group [2 -hydroxyethyl (meth)acrylate, etc.], (meth)acrylic acid, ester of alcohol with unsaturated carboxylic acid other than (meth)acrylic acid [di(cyclo)alkyl fumarate (two alkyl groups are carbon numbers and di(cyclo)alkyl maleate (the two alkyl groups are linear or branched groups having 2 to 8 carbon atoms), and Polyoxyalkylene (carbon number 2 to 4) monool unsaturated carboxylic acid ester with a degree of polymerization of 5 to 50 [for example, methyl alcohol ethylene oxide 10 mole adduct (meth)acrylate and lauryl alcohol ethylene oxide 30 mole adduct (meth)acrylate, etc. ester group-containing vinyl monomer, etc.]. (Meth)acrylate as used herein means acrylate and/or methacrylate.
From the viewpoint of moisture permeability when processed into a film, the monofunctional vinyl monomer (M1) is preferably aliphatic (meth)acrylate, more preferably methyl (meth)acrylate.

As the monofunctional vinyl monomer (M1), one type may be used, or two or more types may be used in combination. Further, as a monofunctional vinyl monomer other than the above, for example, a monofunctional vinyl monomer described in WO2020/105569 may be used.

Examples of the vinyl monomer (M2) having two or more functionalities include divinylbenzene, tricyclodecane dimethanol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, and 1,10-decanediol di(meth)acrylate. (meth)acrylate, ethylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, glycerin di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ) acrylate, 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 (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-(meth)acrylate, ) Acryloyloxyethoxy)phenyl]fluorene, ethoxylated isocyanuric tri(meth)acrylate, ε-caprolactone modified tris-(2-(meth)acryloxyethyl)isocyanurate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate (meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, Dipentaerythritol poly(meth)acrylate, tripentaerythritol poly(meth)acrylate, polypentaerythritol poly(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, allyl ( Examples include meth)acrylate, triallyl isocyanurate, diallyl iso(tere)phthalate, diallyl isocyanurate, and diallyl maleate. Among these, polyethylene glycol di(meth)acrylate is preferred. As the bifunctional or more functional vinyl monomer (M2), one type may be used, or two or more types may be used in combination.

From the viewpoint of water resistance when processed into a film, the vinyl group-containing monomer (M) preferably contains aliphatic (meth)acrylate, and more preferably contains methyl (meth)acrylate.

The ratio (W1:W2) between the weight W1 of the polyurethane resin (U) and the weight W2 of the vinyl resin (V) in the aqueous dispersion is determined from the viewpoint of stability over time of the aqueous dispersion and water resistance when processed into a film. Therefore, the ratio is preferably 90:10 to 50:50, more preferably 80:20 to 60:40.

The weight ratio of oxyethylene groups contained in the composite resin particles (C) in the aqueous dispersion is determined from the viewpoint of the stability of the aqueous dispersion over time and the moisture permeability and water resistance when processed into a film. ) is preferably 10 to 30% by weight, more preferably 12 to 20% by weight.

The volume average particle diameter (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 from the viewpoint of handling properties and stability over time of the aqueous dispersion. , particularly preferably 0.03 to 0.4 μm. The volume average particle diameter (Dv) can be measured using, for example, a light scattering particle size distribution analyzer [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. Aqueous media include water and mixtures of water and organic solvents.
Examples of organic solvents 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), Examples include alcohol solvents (eg, isopropyl alcohol) and aromatic hydrocarbon solvents (eg, toluene). The organic solvents may be used alone or in combination of two or more. Water is preferred as the aqueous medium.

The aqueous dispersion may contain a surfactant (E) from the viewpoint of dispersion stability. Examples of the surfactant (E) include a reactive surfactant (E1) having a radically reactive group and a non-reactive surfactant (E2), and one type may be used alone, or a reactive surfactant (E2) may be used. Two or more types may be used in combination, including a combination of a reactive surfactant (E1) and a non-reactive surfactant (E2). Among these, the reactive surfactant (E1) is preferred from the viewpoint of water resistance when processed into a film.

The reactive surfactant (E1) is not particularly limited as long as it has radical reactivity, but specific examples include Adekariasoap [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, Eleminor [registered trademark, manufactured by Sanyo Chemical Industries, Ltd.] JS-20, Latemul [registered trademark, manufactured by Kao Corporation] PD-104, PD-420, PD-430, Ionet [registered trademark, manufactured by Sanyo Chemical Industries, Ltd.] ) manufactured by MO-200.

Non-reactive surfactants (E2) include nonionic surfactants (E21), anionic surfactants (E22), cationic surfactants (E23), amphoteric surfactants (E24) and other emulsifiers. A dispersant (E25) is mentioned.

Examples of the nonionic surfactant (E21) include AO addition type nonionic surfactants and polyhydric alcohol type nonionic surfactants. Examples of AO addition types include ethylene oxide (hereinafter abbreviated as EO) adducts of aliphatic alcohols having 10 to 20 carbon atoms, EO adducts of phenol, EO adducts of nonylphenol, and EO of alkyl amines having 8 to 22 carbon atoms. Examples include adducts and EO adducts of poly(oxypropylene) glycol. Polyhydric alcohol types include fatty acids (8 carbons) of polyhydric (3-8 or higher) alcohols (2-30 carbon atoms). -24) esters (eg, glycerin monostearate, glycerin monooleate, sorbitan monolaurate, sorbitan monooleate, etc.) and alkyl (carbon atoms 4 to 24) poly(polymerization degree 1 to 10) glycosides.

Examples of the anionic surfactant (E22) include ether carboxylic acids having a hydrocarbon group having 8 to 24 carbon atoms or salts thereof [lauryl ether sodium acetate and (poly)oxyethylene (additional mole number 1 to 100) lauryl ether Sodium acetate, etc.]; Sulfuric esters or ether sulfuric esters having a hydrocarbon group having 8 to 24 carbon atoms, and their salts [sodium lauryl sulfate, (poly)oxyethylene (additional mole number 1 to 100) sodium lauryl sulfate, (poly) ) Oxyethylene (additional mole number 1-100) lauryl sulfate triethanolamine and (poly)oxyethylene (additional mole number 1-100) coconut oil fatty acid monoethanolamide sodium sulfate, etc.]; Hydrocarbon group having 8 to 24 carbon atoms Sulfonates having one or two hydrocarbon groups having 8 to 24 carbon atoms [such as sodium dodecylbenzenesulfonate]; Sulfosuccinates having one or two hydrocarbon groups having 8 to 24 carbon atoms; Phosphate esters or ethers having hydrocarbon groups having 8 to 24 carbon atoms Phosphoric acid esters and their salts [sodium lauryl phosphate and (poly)oxyethylene (additional mole number 1 to 100) sodium lauryl ether phosphate, etc.]; Fatty acid salts having a hydrocarbon group having 8 to 24 carbon atoms [lauric acid Sodium and triethanolamine laurate, etc.]; Acylated amino acid salts having a hydrocarbon group having 8 to 24 carbon atoms [sodium coconut oil fatty acid methyltaurine, sodium coconut oil fatty acid sarcosine, coconut oil fatty acid sarcosine triethanolamine, N-coconut oil fatty acyl-L-glutamic acid triethanolamine, N-coconut oil fatty acyl-L-sodium glutamate, sodium lauroylmethyl-β-alanine, etc.].

Examples of the cationic surfactant (E23) include quaternary ammonium salt types [stearyltrimethylammonium chloride, behenyltrimethylammonium chloride, distearyldimethylammonium chloride, and ethyl sulfate lanolin fatty acid aminopropylethyldimethylammonium] and amine salts. types [stearic acid diethylaminoethylamide lactate, dilaurylamine hydrochloride, oleylamine lactate, etc.].

Examples of the amphoteric surfactant (E24) include betaine type amphoteric surfactants [coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazoli [sodium hydroxypropyl phosphate, etc.] and amino acid type amphoteric surfactants [sodium β-lauryl aminopropionate, etc.].

Examples of other emulsifying dispersants (E25) include polyvinyl alcohol, starch and its derivatives, cellulose derivatives such as carboxymethyl cellulose, methyl cellulose and hydroxyethyl cellulose, carboxy group-containing (co)polymers such as sodium polyacrylate, and U.S. Pat. Emulsifying and dispersing agents having urethane groups or ester groups (for example, those in which polycaprolactone polyol and polyether diol are linked with polyisocyanate) described in No. 5906704 can be mentioned.

When using the surfactant (E), the amount used is determined based on the weight part of the vinyl group-containing monomer (M) from the viewpoint of water resistance when processed into a film and stability over time of the aqueous dispersion. The amount is preferably 0.5 to 10% by weight, more preferably 1 to 3% by weight.

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

The solid content concentration (content of components other than volatile components) of the aqueous dispersion is preferably 20 to 65% by weight, more preferably 25 to 55% by weight from the viewpoint of ease of handling the aqueous dispersion. The solid content concentration was determined by thinly spreading approximately 1 g of the aqueous dispersion on a Petri dish, weighing it accurately, heating it for 45 minutes at 130°C using a circulating constant temperature dryer, then weighing it accurately, and calculating the weight before heating. It can be obtained by calculating the ratio (percentage) of the weight remaining after heating to the weight.

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. pH can be measured using pH Meter M-12 [manufactured by Horiba, Ltd.].

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

In the aqueous dispersion of the present invention, the urea group bond content of the polyurethane resin (U) is preferably 0.2 to 0.7 mmol/g based on the weight of the composite resin particles (C) from the viewpoint of mechanical strength; More preferably, it is 0.3 to 0.69 mmol/g.
The urea group bond content can be calculated from the N atom content determined by a nitrogen analyzer, the ratio of urethane groups to urea groups, and the content of allophanate groups to biuret groups determined by ¹ H-NMR.

As for the nitrogen analyzer, for example, a nitrogen analyzer [ANTEK7000 (manufactured by Antec Corporation)] can be used.
¹ H-NMR measurement is carried out by the method described in "Structural research of polyurethane resins by NMR: Takeda Research Institute Bulletin 34 (2), 224-323 (1975)". That is, when ¹ H-NMR is measured, when an aliphatic compound is used, it can be determined that the urea group is a The weight ratio of the urethane groups is calculated, and the urethane group and urea group contents are calculated from the weight ratio, the above N atom content, and the allophanate group and biuret group contents. When aromatic isocyanate is used, the weight ratio of the urea group and the urethane group is calculated from the ratio of the integrated amount of hydrogen derived from the urea group with a chemical shift of around 8 ppm and the integrated amount of hydrogen derived from the urethane group with a chemical shift of around 9 ppm. The urea group content is calculated from the weight ratio and the above N atom content.

According to the aqueous dispersion of the present invention, the effect is that it has excellent water resistance when processed into a film. Although the details of the mechanism by which this effect is obtained by the present invention are unknown, it is presumed as follows.
In an aqueous dispersion containing separately prepared polyurethane resin and vinyl resin, the two resins do not have good compatibility. On the other hand, the composite resin particles contained in the aqueous dispersion of the present invention contain a polyurethane resin and a vinyl resin. In other words, in the composite resin particles contained in the aqueous dispersion of the present invention, two types of resin are present in one particle, so the two types of resin are uniformly dispersed in the aqueous dispersion, and the two types of resin are dispersed uniformly in the aqueous dispersion. Functions are performed evenly. As a result, according to the present invention, the water resistance when processed into a film is superior to that of an aqueous dispersion prepared separately and containing a polyurethane resin and a vinyl resin.
Furthermore, the aqueous dispersion of the present invention has excellent stability over time and excellent moisture permeability when processed into a film. Although the details of the mechanism by which this effect is obtained by the present invention are unknown, it is presumed as follows.
In an aqueous dispersion containing composite resin particles of a polyurethane resin and a vinyl resin that have a polyoxyethylene group in the main chain of the polymer (chain part containing urethane bonds) but do not have a polyoxyethylene group in the side chain. , particles may aggregate with each other due to changes over time, producing sediment.
On the other hand, the composite resin particles in the aqueous dispersion of the present invention contain a polyurethane resin containing a polyoxyethylene group in the side chain. Due to the action of the polyoxyethylene groups contained in the side chains, aggregation of the composite resin particles is suppressed, thereby making it possible to provide an aqueous dispersion with excellent stability over time.

[2. Manufacturing method of aqueous dispersion for moisture-permeable waterproof material]
The method for producing an aqueous dispersion for a moisture-permeable waterproof material of the present invention is a method for producing an aqueous dispersion for a moisture-permeable waterproof material containing composite resin particles (C) containing a polyurethane resin (U) and a vinyl resin (V). The polyurethane resin (U) is a resin having a side chain containing a polyoxyethylene group, and includes the following steps 1 to 5.
Step 1: A step of reacting an active hydrogen component (a) containing a polyol having two or more hydroxyl groups and an alkoxypolyoxyethylene chain and a polyisocyanate component (b) to obtain a urethane prepolymer;
Step 2: Adding a monomer (M) having a vinyl group to the urethane prepolymer;
Step 3: Dispersing the material obtained in Step 2 in an aqueous medium to obtain a urethane prepolymer dispersion;
Step 4: extending the urethane prepolymer in the dispersion with a chain extender (d);
Step 5: A step carried out after Step 4, in which the vinyl group-containing monomer (M) is polymerized.
By the production method of the present invention, the aqueous dispersion for a moisture-permeable waterproof material of the present invention can be produced.

Step 1 is a step in which an active hydrogen component (a) containing a polyol having two or more hydroxyl groups and an alkoxypolyoxyethylene chain and a polyisocyanate component (b) are reacted to obtain a urethane prepolymer. The urethane prepolymer is a polymer containing polyoxyethylene groups in side chains.

The active hydrogen component (a) used in Step 1 contains a polyol (a3) having two or more hydroxyl groups and an alkoxypolyoxyethylene 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 explanation of "1. Aqueous dispersion for moisture permeable and waterproof materials" above, and the preferable ones are also the same. It is.

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

From the viewpoint of being able to provide a film with excellent adhesion to the substrate, the active hydrogen component (a) in step 1 includes a polycarboxylic acid having 2 to 10 carbon atoms and a polyhydric carboxylic acid having 2 to 20 carbon atoms, as well as the polyol (a3). Those containing a condensed polyester polyol with a polyhydric alcohol are preferred, and together with the polyol (a3) and a condensed polyester polyol of a polyhydric carboxylic acid having 2 to 10 carbon atoms and a polyhydric alcohol having 2 to 20 carbon atoms, Particularly preferred are those containing molecular polyol (a2).

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

In step 1, the active hydrogen component (a) and the polyisocyanate component (b) are combined with active hydrogen atom-containing groups (referring to hydroxyl groups and amino groups, carboxy groups, sulfo groups, and sulfamine groups) contained in the active hydrogen component (a). The reaction is preferably carried out so that the equivalent ratio of isocyanate groups to (excluding acid groups) (isocyanate groups/active hydrogen atom-containing groups) is 1.01 to 3, and preferably 1.1 to 2. More preferred.

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

In step 1, a catalyst can be used to promote the reaction. Examples of the catalyst include the catalyst described in International Publication No. 2020/105569.
Furthermore, in step 1, a radical scavenger can be used to suppress 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 urethane prepolymer obtained in Step 1.

Examples of the monomer (M) having a vinyl group used in step 2 include those similar to the monomer (M) having a vinyl group in the explanation of "1. Aqueous dispersion for moisture permeable and waterproof materials". .
As the monomer (M) having a vinyl group, from the viewpoint of water resistance when processed into a film, those containing aliphatic (meth)acrylate are preferable, and those containing methyl (meth)acrylate are more preferable. In addition, when the above-mentioned preferred monomer is used in Step 2, in the product obtained by performing Step 2, the monomer acts as an emulsifying solvent and promotes the dispersion of the urethane prepolymer in Step 3. .

When starting Step 2, the ratio of the weight Wup of the urethane prepolymer to the weight Wm of the monomer (M) having a vinyl group (Wup:Wm) is preferably 90:10 to 50:50, More preferably, the ratio is 80:20 to 60:40.

In step 2, the temperature of the urethane prepolymer when adding the vinyl group-containing monomer (M) is preferably 30 to 60°C. After Step 1 and before Step 2, a step of cooling the urethane prepolymer obtained in Step 1 may be performed. Although the cooling method is not particularly limited, examples include a method of air cooling to a desired temperature.

Step 3 is a step in which the material obtained in Step 2 is dispersed in an aqueous medium to obtain a urethane prepolymer dispersion. "What was obtained in step 2" is a mixture containing a urethane prepolymer and a monomer (M) having a vinyl group.

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

When dispersing the product obtained in step 2 in an aqueous medium, a surfactant may be used from the viewpoint of dispersion stability. Examples of the surfactant include reactive surfactants having radically reactive groups and non-reactive surfactants, and one type may be used alone or two or more types may be used in combination. Examples of the surfactant include reactive surfactants and non-reactive surfactants having a radically reactive group described in International Publication No. 2020/105569.

When dispersing the product obtained in step 2 in an aqueous medium, the compound (a4) having an ionic group and an active hydrogen atom may be used from the viewpoint of dispersion stability.
When using a compound (a4) having an ionic group and an active hydrogen atom, for neutralization of 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 neutralizing agent used can be used before the urethane prepolymerization reaction (before starting Step 1), after the urethane prepolymerization reaction (during Step 1), after the urethane prepolymerization reaction, and before the water dispersion step (after Step 1). , before step 3), during the water dispersion step (during step 3), or after the water dispersion step (after step 3), but from the viewpoint of the stability of the aqueous dispersion. It is preferably added before the water dispersion step (before step 3) or during the water dispersion step (during step 3).
The temperature at which step 3 is carried out is preferably 0 to 100°C, and the time is preferably 1 to 180 minutes.

Step 4 is a step in which the urethane prepolymer in the urethane prepolymer dispersion obtained in Step 3 is extended 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 explanation of "1. Aqueous dispersion for moisture permeable and waterproof material", and preferable ones are also the same. The chain extender (d) may be used alone or in combination of two or more. Note that the chain extender (d) can also be used as the active hydrogen component (a) in Step 1.
The temperature at which step 4 is carried out is preferably 0 to 100°C, and the time is preferably 1 to 240 minutes.

Step 5 is a step performed after step 4, and is a step of polymerizing the monomer (M) having a vinyl group. By performing step 5, the monomer (M) having a vinyl group in the polyurethane resin obtained by performing step 4 becomes a polymer, and an aqueous dispersion containing composite resin particles containing a polyurethane resin and a vinyl resin is obtained. You get a body.

The polymerization initiators used in the polymerization in step 5 include persulfate initiators such as sodium persulfate, potassium persulfate, and ammonium persulfate; azo initiators such as azobisisobutyronitrile; benzoyl peroxide; Common radical polymerization initiators such as organic peroxides such as cumene hydroperoxide, tert-butyl peroxybenzoate and tert-butyl hydroperoxide; hydrogen peroxide; and the like can be used. These may be used alone or in combination of two or more. Hydrogen peroxide is preferred as the polymerization initiator.
The amount of the polymerization initiator used is preferably 0.05 to 5% by weight, based on the weight of the vinyl group-containing monomer (M) used in the polymerization.
The polymerization initiator may be used in the required amount all at once at the time of polymerization initiation, or may be divided and added at arbitrary intervals.

In the polymerization in Step 5, a reducing agent may be used together with the polymerization initiator as necessary. Such reducing agents include reducing organic compounds such as ascorbic acid, metal salts of ascorbic acid, tartaric acid, citric acid, metal salts of glucose and formaldehyde sulfoxylates, and sodium thiosulfate, sodium sulfite, sodium bisulfite, and metabisulfate. Examples include reducing inorganic compounds such as sodium sulfite. The reducing agent is preferably a metal salt of ascorbic acid, more preferably a sodium salt of ascorbic acid.

Furthermore, in the polymerization, a chain transfer agent may be used as necessary. Examples of such chain transfer agents include n-dodecylmercaptan, tert-dodecylmercaptan, n-butylmercaptan, 2-ethylhexylthioglycolate, 2-mercaptoethanol, β-mercaptopropionic acid, and α-methylstyrene dimer. It will be done.
Furthermore, if necessary, sodium acetate, sodium citrate, sodium bicarbonate, etc. may be used as a buffer, and polyvinyl alcohol, water-soluble cellulose derivatives, alkali metal salts of polymethacrylic acid, etc. may be used as protective colloids. .

The polymerization reaction in step 5 is preferably carried out at a temperature 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. Examples of the inert gas include nitrogen gas.

In the method for producing an aqueous dispersion of the present invention, an organic solvent can be used in any production step.
Organic solvents are not particularly limited, and include ketone solvents with 3 to 10 carbon atoms (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), ester solvents with 2 to 10 carbon atoms (ethyl acetate, butyl acetate, γ-butyrolactone, etc.) , ether solvents with 4 to 10 carbon atoms (dioxane, tetrahydrofuran, ethyl cellosolve, 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.), alcoholic solvents with 1 to 8 carbon atoms (methanol, ethanol, isopropyl alcohol, octanol, etc.), and carbon atoms 4 to 10 hydrocarbon solvents (cyclohexane, toluene, xylene, etc.). When an organic solvent is used, the solvent may be removed in a subsequent step.

In the production method of the present invention, the aqueous dispersion after step 5 may contain a crosslinking agent, a viscosity modifier, an antifoaming agent, a preservative, a weathering stabilizer, an antifreeze agent, and the like. These specific examples are the same as those explained in "1. Aqueous dispersion for moisture-permeable and waterproof materials."

According to the production method of the present invention, by performing Step 1, polyoxyethylene groups are introduced into the side chains of the prepolymer of polyurethane resin, and by further performing Steps 2 to 5, polyoxyethylene groups are introduced into the side chains. An aqueous dispersion containing composite resin particles containing a polyurethane resin and a vinyl resin can be obtained. As a result, according to the production method of the present invention, it is possible to provide a film with excellent substrate adhesion, transparency, and gloss, and to obtain an aqueous dispersion with excellent formulation stability.

[3. Uses 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 have moisture-permeable and waterproof properties by being applied to a release base (e.g., release paper, release cloth, etc.) and then dried. It can be a film.

An example of a method for manufacturing the above moisture-permeable and waterproof film will be explained. A coating solution consisting of the aqueous dispersion of the present invention is prepared and coated onto release paper using a knife coater, pipe coater, bar coater, or the like. Thereafter, it is dried at about 100 to 160° C. for about 30 seconds to 5 minutes in a dryer such as an air oven to form a film made of composite resin particles. The thickness of the film is preferably about 10 to 50 μm when used as a moisture permeable waterproof fabric. The thickness of the film can be appropriately set depending on its use. The thickness of the film can be adjusted by adjusting the clearance of the slit of the coater when applying the coating liquid, and by repeating coating and drying.

Films made using the aqueous dispersion of the present invention have excellent moisture permeability and water resistance, so they can be used for outdoor wear such as fishing and mountain climbing, ski-related wear, windbreakers, athletic wear, golf wear, rain wear, casual wear, etc. It can be suitably used for backsheets for sanitary materials such as coats, outdoor work clothes, gloves, shoes, climbing equipment such as tents, disposable diapers, and sanitary products that require moisture permeability, such as sanitary products.

EXAMPLES The present invention will be specifically explained below with reference to Examples, but the present invention is not limited to these Examples. In addition, below, parts represent parts by weight.
[Example 1]
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.] as the active hydrogen component (a), 9.1 parts of 1,4-butanediol, and Ymer were added. 59.7 parts of N120 [manufactured by Perstorp] and 70.2 parts of isophorone diisocyanate as the polyisocyanate component (b) were charged, and the mixture was stirred at 80° C. for 5 hours to perform a urethanization reaction.
The reaction solution obtained by the urethanization 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. A urethane prepolymer liquid containing M) was obtained.
The temperature of the obtained urethane prepolymer liquid was adjusted to 50°C, and while stirring at 200 rpm, 532.0 parts of ion-exchanged water was added over 30 minutes to obtain an aqueous dispersion of urethane prepolymer.
To the obtained aqueous dispersion were added 76.0 parts of a 10.0% by weight aqueous solution of isophoronediamine and 47.1 parts of a 5.0% by weight aqueous solution of Disponil (registered trademark) PUD as the chain extender (d). The chain extension reaction was performed by stirring at ℃ for 3 hours.
Subsequently, the dispersion after the chain extension reaction was cooled to 40°C, and 2.1 parts of a 5.0% by weight aqueous solution of hydrogen peroxide was added as a polymerization initiator and 5.0 parts of sodium ascorbate was added as a reducing agent under a nitrogen stream. 6.1 parts of a wt % aqueous solution was added and polymerized by stirring at 40° C. for 3 hours to obtain an aqueous dispersion (Q-1) of composite resin particles with a solid content concentration of 35.0 wt %.

[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, and di- 1.8 parts of methylolpropionic acid, 59.7 parts of Ymer N120 [manufactured by Perstorp], and 70.2 parts of isophorone diisocyanate as the polyisocyanate component (b) were charged, and the mixture was stirred at 80°C for 5 hours to perform a urethanization reaction. Ta.
The reaction solution obtained by the urethanization 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. A urethane prepolymer liquid containing M) was obtained.
The temperature of the obtained urethane prepolymer liquid was adjusted to 50°C, and while stirring at 200 rpm, 547.8 parts of ion-exchanged water was added over 30 minutes to obtain an aqueous dispersion of urethane prepolymer.
To the obtained aqueous dispersion were added 17.9 parts of a 5.0% by weight aqueous solution of ethylenediamine as a chain extender (d) and 76.0 parts of a 10.0% by weight aqueous solution of isophoronediamine, and sodium hydroxide as a neutralizing agent. 9.6 parts of a 5.0% by weight aqueous solution was added and stirred at 50°C for 3 hours to perform a chain extension reaction.
Subsequently, the dispersion after the chain extension reaction was cooled to 40°C, and 2.1 parts of a 5.0% by weight aqueous solution of hydrogen peroxide was added as a polymerization initiator and 5.0 parts of sodium ascorbate was added as a reducing agent under a nitrogen stream. 6.1 parts of a wt % aqueous solution was added and polymerized by stirring at 40° C. for 3 hours to obtain an aqueous dispersion (Q-2) of composite resin particles with a solid content concentration of 35.0 wt %.

[Example 3]
In Example 2, the same operation as in Example 2 was performed except that no neutralizing agent (aqueous solution of sodium hydroxide) was used and the amount of ion-exchanged water used was 554.5 parts, and composite resin particles An aqueous dispersion (Q-3) was obtained.

[Examples 4 to 17]
Aqueous dispersions of composite resin particles of Examples 4 to 17 (Q-4) to (Q-17 ) was obtained.

[Comparative example 1]
In a reaction apparatus equipped with a stirrer and a heating device, 37.0 parts of Kuraray Polyol P-2010 [manufactured by Kuraray Co., Ltd.] and PEG-2000 [manufactured by Sanyo Chemical Industries, Ltd.] were added as the active hydrogen component (a). 116.6 parts, 6.3 parts of 1,4-butanediol, 8.6 parts of dimethylolpropionic acid, 70.2 parts of isophorone diisocyanate as the polyisocyanate component (b), a monomer having a vinyl group (M ) was charged with 102.3 parts of methyl methacrylate, and the mixture was stirred at 80°C for 5 hours to carry out a urethanization reaction. Next, the obtained reaction solution was cooled to 50° C., and 6.4 parts of triethylamine was added to obtain a urethane prepolymer solution.
The temperature of the obtained urethane prepolymer liquid was adjusted to 50° C., and while stirring at 200 rpm, 539.1 parts of ion-exchanged water was added over 30 minutes to obtain an aqueous dispersion of urethane prepolymer.
76.0 parts of a 10.0% by weight aqueous solution of isophorone diamine and 47.1 parts of a 5.0% by weight aqueous solution of Disponil (registered trademark) PUD as the chain extender (d) were added to the obtained aqueous dispersion, and the mixture was heated at 50°C. The mixture was stirred for 3 hours to perform a chain elongation reaction. After carrying out the chain extension reaction, a lot of resin was observed to settle in the aqueous dispersion, and the polyurethane resin was not uniformly dispersed in water, so the subsequent polymerization of the vinyl monomer was not carried out. Therefore, an aqueous dispersion was not obtained in this example, and no evaluation test was conducted.

[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.] and PEG-2000 [manufactured by Sanyo Chemical Industries, Ltd.] were added as the active hydrogen component (a). 46.6 parts, 6.3 parts of 1,4-butanediol, 8.6 parts of dimethylolpropionic acid, 70.2 parts of isophorone diisocyanate as the polyisocyanate component (b), a monomer having a vinyl group (M ) was charged with 102.3 parts of methyl methacrylate and stirred at 80°C for 5 hours to carry out a urethanization reaction. Next, the obtained reaction solution was cooled to 50° C., and 6.4 parts of triethylamine was added to obtain a urethane prepolymer solution.
The temperature of the obtained urethane prepolymer liquid was adjusted to 50° C., and while stirring at 200 rpm, 539.1 parts of ion-exchanged water was added over 30 minutes to obtain an aqueous dispersion of urethane prepolymer.
To the obtained aqueous dispersion were added 76.0 parts of a 10.0% by weight aqueous solution of isophoronediamine and 47.1 parts of a 5.0% by weight aqueous solution of Disponil (registered trademark) PUD as the chain extender (d). The chain extension reaction was carried out by stirring at ℃ for 3 hours.
Subsequently, the aqueous dispersion after the chain extension reaction was cooled to 40°C, and 2.1 parts of a 5.0% by weight aqueous solution of hydrogen peroxide as a polymerization initiator and 5.0 parts of sodium ascorbate as a reducing agent were added under a nitrogen stream. 6.1 parts of a 0% by weight aqueous solution was added and polymerized by stirring at 40°C for 3 hours to obtain an aqueous dispersion (Q'-2) of composite resin particles with a solid content concentration of 35.0% by weight. The polyurethane resin contained in the composite resin particles is a resin that does not have a side chain containing a polyoxyethylene group.

The composition of the raw materials expressed by trade names among the raw materials used in Examples 1 to 17 and Comparative Examples 1 to 3 is as follows.
・Kuraray Polyol P-2010: Condensation type polyester polyol of 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 Corporation]
・PEG-2000: Polyoxyethylene glycol with Mn=2000 [manufactured by Sanyo Chemical Industries, Ltd.]
・Ymer N120: Aliphatic polyol-modified polyethylene glycol with Mn=1,000 [manufactured by Perstorp]
・Ymer N90: Aliphatic polyol-modified polyethylene glycol with Mn=1,200 [manufactured by Perstorp]
・Disponil (registered trademark) PUD: modified amine having a carboxyl group (amine value: 410 mg/KOH: 40% by weight aqueous solution) [manufactured by BASF]
・NeoCryl (registered trademark) A-1105: Acrylic water-based resin with a solid content of 50% by weight [manufactured by Covestro] (used only in Comparative Example 3)
"PEG #400 dimethacrylate" in Tables 1-1 and 1-2 is polyethylene glycol dimethacrylate 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.] as the active hydrogen component (a), 9.1 parts of 1,4-butanediol, and Ymer were added. 59.7 parts of N120 [manufactured by Perstorp] and 70.2 parts of isophorone diisocyanate as the polyisocyanate component (b) were charged, and the mixture was stirred at 80° C. for 5 hours to perform a urethanization reaction.
After the obtained reaction solution was cooled to 60° C., 436.2 parts of ion-exchanged water adjusted to 60° C. was added over 30 minutes while stirring at 200 rpm to obtain an aqueous dispersion of urethane prepolymer.
To the obtained aqueous dispersion were added 76.0 parts of a 10.0% by weight aqueous solution of isophoronediamine and 47.1 parts of a 5.0% by weight aqueous solution of Disponil (registered trademark) PUD as the chain extender (d), and the mixture was heated at 60°C. The mixture was stirred for 3 hours to perform a chain elongation reaction.
Subsequently, the dispersion after the chain extension reaction was cooled to 25°C, and 204.6 parts of acrylic water-based resin NeoCryl (registered trademark) A-1105 [manufactured by Covestro] was mixed to form a solid containing polyurethane resin and acrylic resin. An aqueous dispersion (Q'-3) having a concentration of 35.0% by weight was obtained. The polyurethane resin contained in the aqueous dispersion (Q'-3) is not combined 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 a polyoxyethylene group.
The "total weight of resin" in Table 2 means the total weight of the polyurethane resin and acrylic aqueous resin contained in the aqueous dispersion.

[Evaluation test]
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 following procedure was carried out. Evaluation tests were conducted on the stability of the aqueous dispersion over time, and on the moisture permeability and water pressure resistance of the film produced using the aqueous dispersion. The evaluation results are shown in Tables 1-1, 1-2, and 2.

[Stability of aqueous dispersion over time]
The aqueous dispersions of Examples 1 to 17 and Comparative Examples 2 to 3 were allowed to stand at 40° C. for 7 days, and the occurrence of sediment was visually evaluated. The case where no sediment was generated was evaluated as ○, and the case where sediment was generated was evaluated as ×.

[Moisture permeability]
The aqueous dispersion of each example was applied onto release paper so that the film thickness after drying would be 20 μm, and the aqueous dispersion was dried at 80°C for 10 minutes and then at 120°C for 1 minute. A film (sheet material) was obtained. 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 (A-1 moisture permeability) of the film was measured based on the A-1 method (calcium chloride method) of JIS L-1099-2012. A-1 moisture permeability is good if it is 2000 g/m ² ·24 hours or more.
(B-1 moisture permeability)
The moisture permeability (B-1 moisture permeability) of the film was measured based on the B-1 method (potassium acetate method) of JIS L-1099-2012. B-1 moisture permeability is good if it is 30,000 g/m ² ·24 hours or more.

[Water pressure resistance (water resistance)]
The aqueous dispersion of each example was applied onto release paper so that the film thickness after drying would be 20 μm, and dried at 80°C for 10 minutes and then at 120°C for 1 minute to form a sample for water resistance measurement. Got the film. The water pressure resistance of the obtained film for measuring water resistance was measured according to JIS L1092-1998 (high water pressure resistance method). When the test piece was elongated by applying water pressure, nylon taffeta (density: warp + weft = 210 threads/2.54 cm) was layered on top of the test piece, and then the test piece was attached to a testing machine and measured. The water pressure resistance is preferably 10,000 mmH ₂ O or more. The upper limit is 20000 _mmH2O .

From the results shown in Table 1-1, Table 1-2, and Table 2, the aqueous dispersion of the example has excellent stability over time, and the film formed using the aqueous dispersion of the example has good moisture permeability and water resistance. It turns out that he has excellent sex. On the other hand, the aqueous dispersion of Comparative Example 2 containing a polyurethane resin containing a polyoxyethylene group in its main chain but not having a polyoxyethylene group in its side chain had poor stability over time, and the composite resin of a polyurethane resin and a vinyl resin Regarding the aqueous dispersion of Comparative Example 3 that did not contain particles, it was found that the water resistance of the film formed using the aqueous dispersion was inferior.

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, so they can be used outdoors during fishing, mountain climbing, etc. In the use of aqueous dispersions for breathable and waterproof materials used in clothing, ski-related wear, windbreakers, athletic wear, golf wear, rain wear, casual coats, outdoor workwear, gloves, shoes, and mountaineering equipment such as tents. Particularly useful.

Claims

An aqueous dispersion for a moisture permeable waterproof material containing composite resin particles (C) containing a polyurethane resin (U) and a vinyl resin (V),
The polyurethane resin (U) contains an active hydrogen component (a) containing a polyol (a3) having two or more hydroxyl groups and an alkoxypolyoxyethylene chain, a polyisocyanate component (b), and a chain extender (d). An aqueous dispersion for breathable and waterproof materials that is a reactant.
The aqueous dispersion for a moisture-permeable waterproof material according to claim 1, wherein the weight proportion of 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). .
The moisture-permeable waterproof material according to claim 1 or 2, wherein the ratio (W1:W2) of the weight W1 of the polyurethane resin (U) and the weight W2 of the vinyl resin (V) is 90:10 to 50:50. Aqueous dispersion.
The moisture-permeable waterproofing according to claim 1 or 2, wherein the active hydrogen component (a) further contains a condensed polyester polyol of a polycarboxylic acid having 2 to 10 carbon atoms and a polyhydric alcohol having 2 to 20 carbon atoms. Aqueous dispersion for materials.
A method for producing an aqueous dispersion for a moisture-permeable waterproof material containing composite resin particles (C) containing a polyurethane resin (U) and a vinyl resin (V), the polyurethane resin (U) containing a polyoxyethylene group. A method for producing an aqueous dispersion for a moisture-permeable and waterproof material, which is a resin having a side chain and includes the following steps 1 to 5.
Step 1: A step of reacting an active hydrogen component (a) containing a polyol having two or more hydroxyl groups and an alkoxypolyoxyethylene chain and a polyisocyanate component (b) to obtain a urethane prepolymer;
Step 2: Adding a monomer (M) having a vinyl group to the urethane prepolymer;
Step 3: Dispersing the material obtained in Step 2 in an aqueous medium to obtain a urethane prepolymer dispersion;
Step 4: extending the urethane prepolymer in the dispersion with a chain extender (d);
Step 5: A step carried out after Step 4, in which the vinyl group-containing monomer (M) is polymerized.
The moisture-permeable waterproof material according to claim 5, wherein the active hydrogen component (a) further contains a condensed polyester polyol of a polyhydric carboxylic acid having 2 to 10 carbon atoms and a polyhydric alcohol having 2 to 20 carbon atoms. Method for producing an aqueous dispersion.