JP2014141643A - Polyurethane resin for moisture-permeable waterproof material and polyurethane resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyurethane resin composition for a moisture-permeable waterproof material, which is excellent in all of moisture permeability, waterproofness, and washing resistance.SOLUTION: The polyurethane resin for moisture-permeable waterproof material is obtained by reacting a compound (S1) represented by the general formula (1) and having at least one active hydrogen atom and an active hydrogen component (A1) containing a diol (a1) having an ionic group with an organic polyisocyanate component (B). [In the formula, Xand Xrepresent residues of specific active hydrogen-containing compounds from which a specific number of active hydrogen atoms are removed; a, b, and c represent specific integers; and Y represents a residue a specific aromatic polycarboxylic acid from which all carboxyl groups are removed.]

Description

  The present invention relates to a polyurethane resin. More specifically, the present invention relates to a polyurethane resin suitable for a moisture permeable waterproof material.

Conventionally, as a moisture permeable material used for a moisture permeable waterproof material, a material using a microporous sheet such as a polytetrafluoroethylene resin stretched porous film or a polyurethane resin wet film-forming film (for example, Patent Document 1) is known. However, the conventional porous sheet has a problem that it becomes clogged with sweat, dirt, and the like, resulting in a decrease in moisture permeability and a problem that sufficient waterproofness cannot be obtained.
As a solution to such a problem, a nonporous sheet coated with a moisture-permeable polyurethane resin having hydrophilicity has been proposed (see, for example, Patent Documents 2 to 4). In these moisture-permeable polyurethane resins, a polyol component such as polyoxyethylene glycol, which is a hydrophilic segment, or a block copolymer of polyoxyethylene and polyoxypropylene is introduced.
These non-porous sheets are remarkably improved in moisture permeability by reducing the thickness of the polyurethane resin film. However, since the resin strength is low, the sheet strength is lowered and sufficient waterproofness cannot be obtained. In addition, since the permanent set of the resin is large, there is a problem that sufficient washing resistance cannot be obtained, such as plastic deformation of the resin after washing and generation of wrinkles.

JP 59-15825 A Japanese Patent Publication No.54-961 Japanese Unexamined Patent Publication No. 64-62320 Japanese Patent Application Laid-Open No. 4-180813

  This invention is made | formed in view of the said problem, and the subject of this invention is providing the polyurethane resin for moisture-permeable waterproof materials excellent in all of moisture permeability, waterproofness, and wash resistance.

  The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems. That is, the present invention relates to an active hydrogen component (A1) containing a compound (S1) represented by the general formula (1) and having at least one active hydrogen and a diol (a1) having an ionic group, and an organic polyisocyanate component ( A polyurethane resin composition containing a polyurethane resin for moisture permeable and waterproof materials (U) and a polyurethane resin and a compound (S) represented by the general formula (1), which is obtained by reacting with B) A polyurethane resin composition for moisture permeable and waterproof material obtained by reacting the active hydrogen component (A2) containing the diol (a1) having an ionic group with the organic polyisocyanate component (B). (W).

In the general formula (1), X ¹ represents a residue obtained by removing c active hydrogens from an m-valent active hydrogen-containing compound; c represents an integer satisfying 1 ≦ c ≦ m; X ² represents a residue obtained by removing one active hydrogen from an active hydrogen-containing compound, a plurality of X ² may be the same or different, and X ² and X ¹ may be the same or different. Y represents a residue obtained by removing all carboxyl groups from a trivalent or higher valent aromatic polycarboxylic acid, the aromatic ring of Y is composed of carbon atoms, and the carbon atoms have substituents other than carboxyl groups. And / or a halogen atom may be bonded, but at least one carbon atom is not bonded to a substituent; a represents an integer of 1 or more, b represents an integer of 0 or more, and 2 ≦ a + b ≦ d−2 is satisfied; d is a carbocycle of the aromatic polycarboxylic acid. This represents the number of hydrogen atoms bonded to the carbon atoms constituting the aromatic ring when all the substituents including the sil group are substituted with hydrogen atoms, that is, the number of sites that can be substituted on the aromatic ring.

  Since the polyurethane resin of the present invention is excellent in hydrophilicity and resin strength and has a small permanent strain, the use of the polyurethane resin of the present invention provides a moisture-permeable and waterproof material excellent in moisture permeability, waterproofness and washing resistance. .

  The polyurethane resin (U) for moisture permeable and waterproof material of the present invention is an active hydrogen containing a compound (S1) represented by the general formula (1) and having at least one active hydrogen and a diol (a1) having an ionic group It is obtained by reacting the component (A1) with the organic polyisocyanate component (B). By using the compound (S1) as at least a part of the active hydrogen component (A1) and incorporating the compound (S1) into the skeleton of the polyurethane resin (U), the polyurethane resin exhibits the predetermined effect.

  Moreover, the polyurethane resin composition (W) for moisture-permeable and waterproof material of the present invention reacts the active hydrogen component (A2) containing the diol (a1) having an ionic group with the organic polyisocyanate component (B). The resulting polyurethane resin and the compound (S) represented by the general formula (1) are contained. Even when the compound (S) represented by the general formula (1) is added to the polyurethane resin in which the compound (S1) represented by the general formula (1) and having at least one active hydrogen is not incorporated, the compound ( The same effect as the polyurethane resin (U) incorporating S1) is obtained. The polyurethane resin used in the polyurethane resin composition (W) may be a polyurethane resin (U) in which the compound (S1) is incorporated or a polyurethane resin in which the compound (S1) is not incorporated. It may be a mixture.

Examples of the compound (S) represented by the general formula (1) include a compound (S1) having at least one active hydrogen and a compound (S2) having no active hydrogen. For the polyurethane resin (U) for moisture permeable and waterproof material of the present invention, the compound (S1) having at least one of these active hydrogens is used, and the polyurethane resin composition (W) for moisture permeable and waterproof material of the present invention is used. For the compound, either compound (S1) or compound (S2) can be used.
Compound (S1) and (S2) may be used individually by 1 type, and may use 2 or more types together.

  Hereinafter, the compound (S) represented by the general formula (1) will be described. The composition, numerical values, and the like described as a preferable range as the compound (S) are at least one activity incorporated in the polyurethane resin (U). The case of the compound (S1) having hydrogen and the case of the compound (S) added to the polyurethane resin composition (W) are the same unless otherwise specified.

X ¹ in the general formula (1) represents a residue obtained by removing c active hydrogens from an m-valent active hydrogen-containing compound.

  Examples of the active hydrogen-containing compound include a hydroxyl group-containing compound, ammonia, an amino group-containing compound, and a thiol group-containing compound. An active hydrogen containing compound may be used individually by 1 type, or may use 2 or more types together.

  Examples of the hydroxyl group-containing compound include monovalent alcohols having 1 to 20 carbon atoms, polyhydric alcohols having 2 to 20 carbon atoms, phenols, and alkylene oxides thereof (hereinafter abbreviated as AO).

  Examples of monohydric alcohols having 1 to 20 carbon atoms include alkanols having 1 to 20 carbon atoms (methanol, ethanol, butanol, octanol, decanol, dodecyl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, etc.), and those having 2 to 20 carbon atoms. Alkenol (oleyl alcohol, linoleyl alcohol, etc.), aromatic aliphatic alcohol having 7 to 20 carbon atoms (benzyl alcohol, naphthyl ethanol, etc.) and the like can be mentioned.

  The polyhydric alcohol having 2 to 20 carbon atoms includes a dihydric alcohol having 2 to 20 carbon atoms [aliphatic diol (ethylene glycol, propylene glycol, 1,3- or 1,4-butanediol, 1,6-hexanediol). , Neopentylene glycol and 1,10-decanediol, etc.), alicyclic diols (cyclohexanediol, cyclohexanedimethanol, etc.) and araliphatic diols [1,4-bis (hydroxyethyl) benzene, etc.]], carbon 3 to 20 trihydric alcohols [aliphatic triols (such as glycerin and trimethylolpropane)] and 4 to 8 carbon atoms having 5 to 20 carbons [aliphatic polyols (pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin) And dipentaerythritol, etc.) and sugars (sho , Glucose, mannose, fructose, methyl glucoside and derivatives thereof) and the like.

  Examples of the phenols include monovalent phenols (phenol, 1-hydroxynaphthalene, anthrol, 1-hydroxypyrene, etc.) and polyhydric phenols (phloroglucin, pyrogallol, catechol, hydroquinone, bisphenol A, bisphenol F, bisphenol S, 1 , 3,6,8-tetrahydroxynaphthalene, 1,4,5,8-tetrahydroxyanthracene, a condensate of phenol and formaldehyde (novolak) and polyphenols described in US Pat. No. 3,265,641].

  Examples of amino group-containing compounds include monohydrocarbylamines having 1 to 20 carbon atoms [alkylamines (such as butylamine), benzylamine and aniline], aliphatic polyamines having 2 to 20 carbon atoms (ethylenediamine, 1,6-hexanediamine). And diethylenetriamine, etc.), C6-C20 alicyclic polyamines (diaminocyclohexane, dicyclohexylmethanediamine, isophoronediamine, etc.), C2-C20 aromatic polyamines (phenylenediamine, tolylenediamine, diphenylmethanediamine, etc.), C2-C20 heterocyclic polyamine (such as piperazine and N-aminoethylpiperazine), alkanolamine (such as monoethanolamine, diethanolamine and triethanolamine), dicarboxylic acid and excess polyamine Polyamide polyamine, polyether polyamine, hydrazine (such as hydrazine and monoalkylhydrazine), dihydrazide (such as succinic acid dihydrazide and terephthalic acid dihydrazide), guanidine (such as butylguanidine and 1-cyanoguanidine), dicyandiamide, and the like It is done.

  Examples of the thiol group-containing compound include monovalent thiol compounds having 1 to 20 carbon atoms (alkanethiol such as ethanethiol, benzenethiol and phenylmethanethiol) and polyvalent thiol compounds (1,2-ethanedithiol and 1, 6-hexanedithiol etc.).

  In addition, as an active hydrogen containing compound, the compound which has 2 or more types of active hydrogen containing functional groups (a hydroxyl group, an amino group, a thiol group, etc.) in a molecule | numerator can also be used.

  Moreover, as an active hydrogen containing compound, the AO adduct of the said active hydrogen containing compound can also be used.

  As AO to be added to the active hydrogen-containing compound, AO having 2 to 4 carbon atoms, ethylene oxide (hereinafter abbreviated as EO), 1,2-propylene oxide (hereinafter abbreviated as PO), 1,3-propyloxide 1,2-, 1,3- or 2,3-butylene oxide and tetrahydrofuran (hereinafter abbreviated as THF). Of these, EO, PO and THF are preferred from the viewpoints of waterproofness and washing resistance. AO may be used alone or in combination of two or more. As an addition method when two or more of AO are used in combination, block addition or random addition may be used. It may be used in combination.

The number of added moles of AO is preferably 8 to 100, more preferably 10 to 80, from the viewpoint of waterproofness. The hydroxyl value of the AO adduct is preferably 18 to 360 mgKOH / g.
In the present invention, the hydroxyl value is measured according to JIS K1557-1.

As the active hydrogen-containing compound for introducing X ¹ into the compound (S), preferred are a hydroxyl group-containing compound, an amino group-containing compound and an AO adduct thereof, more preferably from the viewpoint of waterproofness and washing resistance. Is a polyhydric alcohol having 2 to 20 carbon atoms, a polyether polyol obtained by adding AO to a polyhydric alcohol having 2 to 20 carbon atoms, an aliphatic polyamine having 2 to 20 carbon atoms and a polyvalent thiol compound, particularly preferred Is a polyether polyol in which AO is added to a polyhydric alcohol having 2 to 20 carbon atoms and a polyhydric alcohol having 2 to 20 carbon atoms, most preferably a polyether polyol in which AO is added to a polyhydric alcohol having 2 to 20 carbon atoms. It is.

  The valence m of the active hydrogen-containing compound is usually 1 to 20, preferably 1 to 8, more preferably 1 to 4, and particularly preferably 2 from the viewpoint of waterproofness and washing resistance.

  C in the general formula (1) represents an integer satisfying 1 ≦ c ≦ m, and is preferably 1 to 8, more preferably 1 to 4, particularly preferably 2 from the viewpoint of waterproofness and washing resistance.

X ² in the general formula (1) represents a residue obtained by removing one active hydrogen from a 1-20 valent active hydrogen-containing compound, and the plurality of X ² may be the same or different.
Examples of the active hydrogen-containing compound used to constitute X ² include the same compounds as the active hydrogen-containing compound represented by X ¹ described above, and X ² and X ¹ may be the same or different. From the viewpoint of waterproofness and washing resistance, X ¹ and at least one X ² are preferably different groups.
The valence of X ² is usually 1 to 20, preferably 1 to 8, more preferably 1 to 4, particularly preferably 1 to 2, and most preferably 2 from the viewpoints of waterproofness and washing resistance. is there.

Although it is possible to introduce the X ¹ and X ² in the compound (S) by reacting the active hydrogen-containing compound to the trivalent or higher polycarboxylic acids used to construct the Y described below, X ¹ and In the case where X ² is a diol having 2 to 4 carbon atoms or a polyether polyol having 2 to 4 carbon atoms in the repeating unit, it is equivalent by adding the AO having 2 to 4 carbon atoms to the carboxyl group of the polycarboxylic acid. Can be obtained.

  Y in General formula (1) represents the residue remove | excluding all the carboxyl groups from trivalent or more aromatic polycarboxylic acid. The aromatic ring of Y is composed of carbon atoms, and a substituent other than a carboxyl group and / or a halogen atom may be bonded to the carbon atom, but at least one carbon atom is not bonded to a substituent. Must be bonded to a hydrogen atom.

  Examples of the substituent other than the carboxyl group include an alkyl group, vinyl group, allyl group, cycloalkyl group, amino group, hydroxyl group, hydroxyamino group, nitro group, thiol group, aryl group, and cyano group.

Examples of the trivalent or higher valent aromatic polycarboxylic acid used for constituting Y include aromatic polycarboxylic acids having 9 to 30 carbon atoms such as trimellitic acid, 1,2,3-benzenetricarboxylic acid, trimesic acid, Hemicitic acid, 1,2,4-, 1,3,6- or 2,3,6-naphthalenetricarboxylic acid and tricarboxylic acids such as 2,3,6-anthracentricarboxylic acid; pyromellitic acid, 3,3 ′, 4,4′-benzophenone tetracarboxylic acid, 2,2 ′, 3,3′-benzophenone tetracarboxylic acid, 2,3,3 ′, 4′-benzophenone tetracarboxylic acid, 3,3 ′, 4,4′- Biphenyltetracarboxylic acid, 2,2 ′, 3,3′-biphenyltetracarboxylic acid, 2,3,3 ′, 4′-biphenyltetracarboxylic acid, 4,4′-oxybisphthalic acid, diphenylmethane Tracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid and 4,4 ′-(hexa) And tetracarboxylic acids such as fluoroisopropylidene) bisphthalic acid. Aromatic polycarboxylic acid may be used individually by 1 type, and may use 2 or more types together.
In producing the compound (S), these ester-forming derivatives [acid anhydrides, lower alkyl (carbon number 1 to 4) esters (methyl esters, ethyl esters, isopropyl esters, etc.) and acid halides (acid chlorides) Etc.)] can also be used.

  Of these aromatic polycarboxylic acids, from the viewpoint of waterproofness and washing resistance, each of the two carbon atoms that form the aromatic ring and are adjacent to the carbon atom that constitutes the aromatic ring and to which no substituent is bonded. And having a structure in which one carboxyl group is further bonded to at least one of the carbon atoms adjacent to the carbon atom to which the carboxyl group is bonded is more preferable. .

  For example, when the aromatic ring of the aromatic polycarboxylic acid is a benzene ring, the aromatic polycarboxylic acid preferably has a structure in which a carboxyl group is bonded to the 1-position and the 3-position, and more preferably, the 4-position of the benzene ring to which the carboxyl group is bonded and It has a structure in which a carboxyl group is further bonded to the 6-position.

  From the viewpoint of waterproofness and washing resistance, a monocyclic compound is particularly preferable as the aromatic polycarboxylic acid used for constituting Y, and trimellitic acid and pyromellitic acid are most preferable.

  In the general formula (1), a represents an integer of 1 or more, b represents an integer of 0 or more, and 2 ≦ a + b ≦ d−2 is satisfied, and d includes all carboxyl groups of the aromatic polycarboxylic acid. Represents the number of hydrogen atoms bonded to the carbon atom constituting the aromatic ring, that is, the number of sites that can be substituted on the aromatic ring. For example, when the aromatic ring is a benzene ring composed of 6 carbon atoms, d is 6, a + b can take a value of 2 to 4, and when the aromatic ring is a naphthalene ring composed of 10 carbon atoms, d is 8, and a + b can take a value of 2-6. When the aromatic ring is a monocyclic aromatic ring, a + b is preferably 2 or 3 from the viewpoint of waterproofness and washing resistance. From the viewpoint of waterproofness and washing resistance, b is preferably ½ or less of a, and 0 is particularly preferable.

The hydroxyl value of the compound (S) in the present invention is preferably 0 or 70 to 500 mgKOH / g from the viewpoint of waterproofness and texture.
The hydroxyl value in the case of compound (S1) is preferably 70 to 500 mgKOH / g, more preferably 75 to 350 mgKOH / g. When the hydroxyl value of the compound (S1) is less than 70 mgKOH / g, the waterproof property of the polyurethane resin tends to be lowered, and when it exceeds 500 mgKOH / g, the texture of the polyurethane resin tends to be lowered.
In the case of the compound (S2), the hydroxyl value is 0.

  The concentration of Y in the compound (S) means the number of millimoles of the residue Y in 1 g of the compound (S), and from the viewpoint of waterproofness and washing resistance of the polyurethane resin, preferably 1.0 to 6.0 mmol / g, more preferably 1.1 to 3.5 mmol / g. If the concentration of Y is less than 1.0 mmol / g, the waterproofness of the polyurethane resin tends to decrease, and if it exceeds 6.0 mmol / g, the texture of the polyurethane resin may be deteriorated.

  The carbonyl group concentration of the compound (S) means the number of millimoles of the carbonyl group in 1 g of the compound (S), preferably from 3.0 to 20 mmol / g, from the viewpoint of waterproofness and washing resistance of the polyurethane resin. Preferably it is 3.3-11 mmol / g. When the carbonyl group concentration is less than 3.0 mmol / g, the waterproof property of the polyurethane resin tends to be lowered, and when the carbonyl group concentration exceeds 20 mmol / g, the texture may be deteriorated.

The number of mole average functional groups of the compound (S) is preferably 0 to 8, more preferably 2 to 6, particularly preferably 2 to 4, from the viewpoint of waterproofness of the polyurethane resin.
The number of mole average functional groups in the present invention is a value obtained by dividing the sum of values obtained by multiplying the number of functional groups having active hydrogen of each component in the composition by the number of moles of each component by the sum of the number of moles of each component. The number of moles of each component is a value obtained by dividing the weight of each component by the molecular weight of each component. As the molecular weight used in the calculation, the chemical formula weight is used when the molecular weight is not distributed as in the case of a low molecular weight compound, and the number average molecular weight (hereinafter abbreviated as Mn) is used when the molecular weight is distributed. Mn of the compound (S) and polyol in the present invention is measured by gel permeation chromatography using THF as a solvent and polyoxypropylene glycol as a standard substance. The sample concentration may be 0.25% by weight, the column stationary phase may be TSKgel SuperH2000, TSKgel SuperH3000, TSKgel SuperH4000 (both manufactured by Tosoh Corporation), and the column temperature may be 40 ° C.

The compound (S1) having at least one active hydrogen incorporated in the skeleton of the polyurethane resin (U) is a compound in which at least one of X ¹ , X ² and Y in the general formula (1) has an active hydrogen. . More specifically, at least the valences x and c of X ¹ satisfy m> c, or Y is substituted with a substituent having an active hydrogen such as an amino group, a hydroxyl group, a hydroxyamino group and a thiol group, When the active hydrogen-containing compound constituting X ² is divalent or higher, or b is 1 or higher, the compound (S1) has at least one active hydrogen.

  The content of the compound (S1) incorporated in the skeleton of the polyurethane resin (U) is 0 on the basis of the total weight of the active hydrogen component (A1) and the organic polyisocyanate component (B) from the viewpoint of waterproofness and washing resistance. It is preferably 0.01 to 10% by weight, and more preferably 0.02 to 5% by weight.

  Examples of the diol (a1) having an ionic group in the present invention include a diol (a11) having an anionic group and a diol (a12) having a cationic group.

  Examples of the diol (a11) having an anionic group include 3- (2,3-dihydroxypropoxy) -1-propanesulfonic acid, N, N-bis (2-hydroxyalkyl) sulfamic acid (alkyl group having 1 to 1 carbon atoms). 6), bis (2-hydroxyethyl) phosphate, dialkyl alkanoic acid (having 5 to 24 carbon atoms, such as 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-diethyl Methylol heptanoic acid and 2,2-dimethyloloctanoic acid, etc.) and salts thereof [for example, salts of amines having 1 to 20 carbon atoms (triethylamine, alkanolamine, morpholine, etc.) and / or alkali metal salts (sodium salt, etc.) And diols represented by the general formula (2).

  The diol represented by the general formula (2) is a dicarboxylic acid (c) represented by the general formula (3) or an ester-forming derivative thereof [di-lower alkyl (carbon number 1 to 4) ester of (c) (for example, Methyl, ethyl, n- or i-propyl and n-, i-, sec- or t-butyl esters), acid anhydrides and acid halides (eg acid chloride) etc.] represented by general formula (4) Diester obtained by reacting 2 mol of diol (d).

  E and f in the general formula (2) and p in the general formula (4) are each independently an integer of 1 to 100.

A ³ is the A ¹ and A ² as well as the general formula in formula (2) (4) are each independently a divalent hydrocarbon group having 2 to 20 carbon atoms, in each of A ¹ when there are a plurality of identical it may be different, or different and a ² are identical when a plurality of, a ³ may have respectively be the same or different when there are a plurality.
By using two or more diols having different A ³ and / or p in the general formula (4), diols having different A ¹ and A ² and / or e and f in the general formula (2) can be obtained.

  The diol (d) represented by the general formula (4) includes an aliphatic diol having 2 to 12 carbon atoms, an alicyclic diol having 4 to 20 carbon atoms, an araliphatic diol having 8 to 20 carbon atoms, and these. Or an AO adduct having 2 to 8 or more carbon atoms (preferably 2 to 4 carbon atoms) to a diol or a dihydric phenol having 6 to 20 carbon atoms.

  AO may be used individually by 1 type, or may use 2 or more types together. The AO addition format may be random, block, or a combination thereof.

  Examples of the aliphatic diol having 2 to 12 carbon atoms (preferably 2 to 10 carbon atoms) include ethylene glycol, 1,2- or 1,3-propylene glycol, trimethylene glycol, 1,2-, 1,3- 2,3- or 1,4-butanediol, 1,6-hexanediol, neopentylene glycol and dodecanediol.

  Examples of the alicyclic diol having 4 to 20 carbon atoms (preferably 6 to 10 carbon atoms) include bis (hydroxymethyl) cyclohexane, cyclohexane-1,2-, 1,3- or 1,4-diol, and cyclopentane. -1,2- or 1,3-diol, and a hydride of a C6-C20 dihydric phenol described below (for example, hydrogenated bisphenol A).

  Examples of the araliphatic diol having 8 to 20 carbon atoms include bis (hydroxymethyl) benzene (xylylene glycol) and bis (hydroxyethyl) benzene.

  Examples of the dihydric phenol having 6 to 20 carbon atoms include monocyclic dihydric phenols (hydroquinone, catechol, resorcin, and the like) and bisphenols (bisphenol A, bisphenol B, bisphenol C, bisphenol F, and bisphenol S).

  Among the diols (d), those having a Mn of 600 to 3,000 are preferred from the viewpoint of waterproofness and washing resistance of the polyurethane resin (U), and more preferably those having a Mn of 800 to 2,500. It is. Among the diols having Mn in such a range, alkylene glycol and polyoxyalkylene glycol are preferable from the viewpoint of hygroscopicity, waterproofness and washing resistance of the polyurethane resin (U).

Table In Q- in formula (2) and (3), an anionic group protonic acid having a pKa of -10～4 general formula ^{R 0 -Q-H + (R} 0 is H or CH ₃₎ It is a residue obtained by removing R ⁰ and proton (H +) from a protonic acid having a pKa of −10 to 4 (preferably 0 to 3).

  The pKa of the protonic acid is described in, for example, “Chemical Handbook (Revised 4th Edition) Fundamentals II” (Edited by Chemical Society of Japan), page 317 (issued in May 1993). Such protonic acids include sulfur atom-containing acids such as methanesulfonic acid (pKa = 1.8), sulfuric acid (pKa = 1.99) and sulfamic acid (pKa = 0.99); and phosphorus atom-containing acids, Examples thereof include phosphonic acid (pKa = 1.5), phosphoric acid (pKa = 2.15), and phosphinic acid (pKa = 1.23).

As the anionic group Q-, an anion of a sulfur atom-containing acid, such as —SO ₃ —, —OSO ₃ — and —NHSO ₃ —; an anion of a phosphorus atom-containing acid, such as —O—P (═O) (— OR ) -O-, -OP (= O) (-O-) ₂ , -P (= O) (-OR) -O- and -P (= O) (-O-) ₂ . R in these formulas represents an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group having 2 to 4 carbon atoms.

In the general formulas (2) and (3), h is 1 or 2, and M ^h + is an h-valent cation.
Examples of the cation (M ^h +) include a proton (H +) and a monovalent or divalent cation selected from a metal cation, an aminium ion, an ammonium ion, and a quaternary ammonium ion.
Metals forming M ^h + include alkali metals (eg, sodium and potassium), alkaline earth metals (eg, calcium and magnesium), and other (eg, Group 8, Group 12 and Group 13) metals (eg, zinc, aluminum and Iron).

  Examples of amines that form aminium ions include hydrocarbyl groups having 1 to 10 carbon atoms (for example, alkyl, alkenyl, cycloalkyl, aryl, and aralkyl groups) and / or hydroxyalkyl groups having 2 to 4 carbon atoms (for example, hydroxyethyl). A group) (two or more of these groups may combine to form a heterocyclic ring with the nitrogen atom), 1, 2 or tertiary, aliphatic, alicyclic, aromatic or Heterocyclic amines are mentioned.

  Specifically, primary amines such as C1-C20 aliphatic, cycloaliphatic, araliphatic or aromatic monoamines [monoalkylamines (eg methyl, ethyl, n-butyl and octylamine), cyclohexylamines] Benzylamine, arylamine (eg aniline, toluidine and naphthylamine)] and alkanolamine [mono-, di- or tri-alkanolamine (2 to 4 carbon atoms of the hydroxyalkyl group), eg mono-, di- or tri -Ethanolamine]; secondary amines (2 to 12 carbon atoms) such as di (hydrocarbyl and / or hydroxyalkyl) amines (eg dimethylamine, dibutylamine, dicyclohexylamine, diethanolamine and ethylethanolamine) and heterocyclic rings Secondary amines (eg morpholine) Piperidine and piperazine); tertiary amines (3 to 15 carbon atoms), such as tri (hydrocarbyl and / or hydroxyalkyl) amines (eg trimethylamine, tributylamine, triethanolamine and diethylethanolamine); and heterocyclic tertiary And amines such as N-methylmorpholine and pyridine.

  Examples of the quaternary ammonium ion include those obtained by quaternizing the tertiary amine (for example, tetraalkylammonium, trialkylbenzylammonium and trialkylhydroxyalkylammonium).

J in general formula (2) and (3) is an integer of 1-4.
Z in the general formulas (2) and (3) represents j proton acids (salts) from dicarboxylic acid (c) having j proton acid (salt) groups {-Q- (M ^h +) ₁ / _h }. Represents a group and a residue excluding two carboxyl groups. As the residue Z, an alkoxy group, a hydroxyl group, a cyano group, an aldehyde group, a nitro group, or a divalent hydrocarbon group (aliphatic, alicyclic ring) which may be substituted with one or more of halogen atoms (2 + j) -valent hydrocarbon group obtained by removing j hydrogen atoms from the formula and aromatic hydrocarbon group. From the viewpoint of the waterproofness and washing resistance of the polyurethane resin (U), an aromatic hydrocarbon group, particularly a benzenetriyl group, is preferable.

  As the divalent hydrocarbon group, a divalent aliphatic hydrocarbon group (having 1 to 16 carbon atoms, preferably 3 to 12 carbon atoms) (alkylene group and alkenylene group such as methylene group, ethylene group, propylene group, butylene group) , Pentylene group, hexylene group, octylene group, decylene group, tridecylene group, hexadecylene group, ethenylene group, propenylene group, and alkyl or alkenyl-substituted ethylene group); a divalent alicyclic hydrocarbon group (3 to 16 carbon atoms are preferred) 5-12) [(bi) cycloalkylene group and (bi) cycloalkenylene group such as cyclopropylene group, cyclobutylene group, cyclopentylene group, (bi) cyclohexylene group, cycloheptylene group, cyclooctylene group , Methylenebis (cyclohexylene) group and cyclohexyl-substituted ethylene group]; A divalent aromatic hydrocarbon group (having 6 to 16 carbon atoms, preferably 6 to 15 carbon atoms) [(bi) arylene group such as phenylene group, tolylene group, xylylene group, methylene (bisphenylene) group, naphthylene group, and Phenyl substituted ethylene group] and the like.

  Z includes 14 or less carbon atoms, particularly 10 or less carbon atoms from the viewpoint of compatibility with the polymer diol (a2) other than (a1) and a solvent described later, and 3 or more carbon atoms from the viewpoint of hydrolysis resistance. Those having 4 or more carbon atoms are preferred.

  Examples of the dicarboxylic acid (c) represented by the general formula (3) include sulfonic acid group-containing dicarboxylic acid (c1), sulfuric acid group-containing dicarboxylic acid (c2), sulfamic acid group-containing dicarboxylic acid (c3), and phosphoric acid group-containing Dicarboxylic acid (c4), phosphonic acid group-containing dicarboxylic acid (c5) and salts thereof [Proton of protonic acid group having pKa of −10 to 4 represents the alkali (earth) metal cation, aminium ion, ammonium ion and Converted into a cation selected from the group consisting of quaternary ammonium ions].

  Examples of the sulfonic acid group-containing dicarboxylic acid (c1) include dicarboxylic acids having 2 to 20 carbon atoms (aliphatic dicarboxylic acids (for example, succinic acid, adipic acid and sebacic acid), aromatic dicarboxylic acids (for example, terephthalic acid and isophthalic acid), and Sulfonated products such as sulfobenzene dicarboxylic acid (such as 5-sulfo-ortho-, iso- or terephthalic acid) and sulfoaromatic dicarboxylic acid (c11) such as sulfonaphthalenedicarboxylic acid; sulfo Sulfoaliphatic dicarboxylic acids (c12) such as alkanes or sulfoalkene dicarboxylic acids (eg sulfosuccinic acid, sulfoglutaric acid, sulfoadipic acid, sulfopimelic acid, sulfosuberic acid, sulfoazelineic acid, sulfosebacic acid and sulfomaleic acid); Represented by general formula (5) Substituted sulfosuccinate (c13), and the like.

R ¹ in the general formula (5) is a hydrocarbyl group having 1 to 13 carbon atoms (for example, alkyl, alkenyl, cycloalkyl, aralkyl and aryl), an alkoxy group (for example, methoxy group and ethoxy group), a hydroxyl group, a cyano group, It represents an aldehyde group, a nitro group or a halogen atom (for example, chlorine and bromine).

  As the sulfate group-containing dicarboxylic acid (c2), a sulfate of hydroxydicarboxylic acid [for example, mono- or di-hydroxyalkanedioic acid (for example, tartronic acid, malic acid and tartaric acid)] [hydroxyl group for sulfating agent (for example, fuming sulfuric acid) And the like.

  Examples of the sulfamic acid group-containing dicarboxylic acid (c3) include sulfamic acid products of aminodicarboxylic acids (for example, asparagine and glutamic acid) (those obtained by converting amino groups to sulfamic acid groups with fuming sulfuric acid or chlorosulfuric acid).

  As the phosphoric acid group-containing dicarboxylic acid (c4), a phosphoric acid ester of the hydroxydicarboxylic acid [a hydroxyl group obtained by phosphoric acid esterification with a phosphorylating agent (for example, phosphorus pentoxide and phosphorus oxychloride) and its acid group A partially alkyl ester or partially hydroxyalkyl ester obtained by reacting a part with alcohol or AO] and the like.

  Examples of the phosphonic acid group-containing dicarboxylic acid (c5) include phosphonates of the above hydroxydicarboxylic acid (hydroxyl groups converted to phosphonic acid groups by phosphorous esterification with phosphorus trichloride and isomerized, and a part of the acid groups) In the same manner as described above, and the like.

  The diol represented by the general formula (2) is obtained by reacting (esterifying or transesterifying) a dicarboxylic acid (c) or an ester-forming derivative thereof and the diol (d) in an inert organic solvent (T). Can be manufactured.

  The inert organic solvent (T) is not particularly limited as long as it does not participate in the reaction (esterification or transesterification) and dissolves (c), (d) and the diol having an anionic group to be generated. Examples of the inert organic solvent (T) include amide solvents [for example, dimethylformamide, dimethylacetamide and N-alkyl (1 to 3 carbon atoms) -2-pyrrolidone (for example, N-methyl-2-pyrrolidone)], ether solvents (Eg dioxane and THF), ketone solvents (eg cyclohexanone, methyl ethyl ketone and methyl isobutyl ketone), aromatic hydrocarbon solvents (eg toluene and xylene) and sulfoxide solvents (eg dimethyl sulfoxide) and mixtures of two or more thereof Is mentioned.

  As the inert organic solvent (T), amide solvents are preferable from the viewpoint of reactivity and the solubility of the polyurethane resin (U), dimethylformamide and dimethylacetamide are more preferable, and dimethylformamide is particularly preferable.

  The weight ratio [(T) / (c)] of the inert organic solvent (T) to (c) is usually 3/1 to 10/1, preferably 4/1 to 7/1 from the viewpoint of the viscosity of the solution. is there. The weight ratio [(T) / {(c) + (d)}] of the inert organic solvent (T) and the total amount of (c) and (d) is usually 2/1 to 9/1, preferably Is 3/1 to 7/1.

The reaction between (c) and (d) is performed in the presence or absence of a catalyst. As the catalyst, a usual esterification or transesterification catalyst can be used. For example, alkali metals (for example, sodium and potassium), alkaline earth metals (for example, magnesium and calcium), metals of group 4, (for example, titanium), groups 7 to 10 Organic acids (2 to 8 carbon atoms) of metals selected from the group consisting of group metals (eg manganese, iron, cobalt and nickel), group 12 metals (eg zinc and cadmium) and group 14 metals (eg tin and lead) 8 carboxylic acids such as acetic acid, propionic acid, octanoic acid and maleic acid) salts and organometallic complexes of these metals (eg triethanolamine chelate). Of these, organometallic complexes are preferable from the viewpoint of reaction rate and coloring, and more preferable are triethanolamine chelates of metals of Group 4 or 14, particularly diisopropoxytitanium bis (triethanolaminate). .
From the viewpoint of reaction rate and coloring, the catalyst is preferably used in an amount of 0.01 to 5% by weight, particularly 0.03 to 3% by weight, based on the weight of (d).

  The reaction between the component (c) and the component (d) is conducted by esterification or transesterification under ordinary esterification or transesterification conditions, for example, at a temperature of 110 to 190 ° C. under normal pressure or reduced pressure (0.098 to 0.001 MPa). It can be carried out by removing water or alcohol produced by transesterification.

  (C) A diol having an anionic group with a low content of (d) is produced by reacting (d) with component (d) in an inert organic solvent (T) (esterification or transesterification). can do. The content of unreacted (d) is preferably 4% by weight or less, particularly preferably 3% by weight or less, based on the weight of the diol having an anionic group.

Of the diol (a11) having an anionic group, a salt or metal salt of an amine having 1 to 20 carbon atoms and a metal salt of the diol represented by the general formula (2) is preferable from the viewpoint of moisture permeability. It is a salt of amines having 1 to 20 carbon atoms of 24 dialkyrol alkanoic acids. When the diol (a11) is a diol represented by the general formula (2), a metal salt of a diester of 5-sulfoisophthalic acid with ethylene glycol or polyoxyalkylene glycol is more preferable, and 5-sulfoisophthalic acid is particularly preferable. Alkali (earth) metal salts of diesters of acids with ethylene glycol or polyoxyalkylene glycols, most preferred are the alkali metal salts. In the case where the diol (a11) is a salt of an amine having 1 to 20 carbon atoms of a dialkyrol alkanoic acid having 5 to 24 carbon atoms, it is more preferable that the diol (a11) has 1 to 1 carbon atoms of a dialkyrol alkanoic acid having 5 to 10 carbon atoms. A salt of 20 amines, particularly preferred is a salt of an amine having 1 to 3 carbon atoms of a dialkylolalkanoic acid having 5 to 10 carbon atoms, particularly preferred is 2,2-dimethylolpropionic acid or 2,2 -A salt of an amine having 1 to 3 carbon atoms of dimethylolbutanoic acid, most preferably a triethylamine salt of 2,2-dimethylolpropionic acid.
The diol (a11) having an ionic group may be used alone or in combination of two or more.

  Examples of the diol (a12) having a cationic group include diols having a tertiary aminium group or a quaternary ammonium base.

  Examples of the diol having a tertiary aminium group include acids (alkyl acids having 1 to 8 carbon atoms) dialkanol (2 to 4 carbon atoms) amine (N-methyldiethanolamine, etc.) [organic acids such as carboxylic acids having 1 to 8 carbon atoms ( Acetic acid etc.) and sulfonic acids (toluenesulfonic acid etc .; inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid etc.)].

  As the diol having a quaternary ammonium base, a quaternizing agent [an alkyl group having 1 to 8 carbon atoms or an alkyl group having 1 to 8 carbon atoms] dialkanol (2 to 4 carbon atoms) amine (such as N-methyldiethanolamine). And quaternized compounds having a benzyl group such as sulfate ester, carbonate ester and halide (eg, dimethyl sulfate, dimethyl carbonate, methyl chloride and benzyl chloride)].

Of the diol (a12) having a cationic group, from the viewpoint of permanent strain, a neutralized product of an alkyl (carbon number 1 to 8) dialkanol (carbon number 2 to 4) amine with an acid and an alkyl (carbon number 1) -8) Quaternization of dialkanol (2-4 carbon atoms) with dimethyl sulfate, more preferably quaternization of N-methyldiethanolamine acetate or hydrochloride and N-butyldipropanolamine with dimethyl sulfate. Sulfate.
The diol (a12) having a cationic group may be used alone or in combination of two or more.

  The hydroxyl value of the diol (a1) having an ionic group is preferably 2 to 300 mgKOH / g from the viewpoint of waterproofness and texture.

  The content of the ionic group in the polyurethane resin (U) introduced by (a1) is preferably 0.05 to 0 based on the weight of the polyurethane resin (U) from the viewpoint of moisture permeability and washing resistance. .50 mmol / g, more preferably 0.08 to 0.13 mmol / g. If it is less than 0.05 mmol / g, the moisture permeability tends to decrease, and if it exceeds 0.50 mmol / g, the washing resistance tends to decrease.

  The active hydrogen component (A1) can further contain a polymer diol (a2) other than (a1) as long as the moisture permeability of the polyurethane resin (U) is not inhibited.

  Examples of the polymer diol (a2) other than (a1) include polymer polyether diol (a21) and polymer polyester diol (a22).

  Examples of the polymer polyether diol (a21) include polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol, and polyoxypropylene / polyoxytetramethylene block copolymer diol.

  Examples of the polymer polyester diol (a22) include condensed polyester diol, polylactone diol, and polycarbonate diol.

The condensed polyester diol is obtained, for example, by reacting the divalent alcohol having 2 to 20 carbon atoms with the dicarboxylic acid having 2 to 20 carbon atoms.
Examples of the dicarboxylic acid having 2 to 20 carbon atoms include aliphatic dicarboxylic acids (for example, succinic acid, adipic acid and sebacic acid), aromatic dicarboxylic acids (for example, terephthalic acid and isophthalic acid), and mixtures of two or more thereof. It is done.

  Specific examples of the condensed polyester diol include polyethylene adipate diol, polybutylene adipate diol, polyhexamethylene adipate diol, polyhexamethylene isophthalate diol, polyneopentylene adipate diol, polyethylene propylene adipate diol, polyethylene butylene adipate diol, poly Butylene hexamethylene adipate diol, polydiethylene adipate diol, poly (polytetramethylene ether) adipate diol, poly (3-methylpentylene adipate) diol, polyethylene azelate diol, polyethylene sebacate diol, polybutylene azelate diol, polybutylene Sebacate diol and polyneopentylene terephthalate diol It is.

The polylactone diol is a polyaddition product of a lactone to the dihydric alcohol having 2 to 20 carbon atoms. As the lactone, lactones having 4 to 12 carbon atoms (for example, γ-butyrolactone, γ-valerolactone, and ε-caprolactone). ) And the like.
Specific examples of the polylactone polyol include polycaprolactone diol, polyvalerolactone diol, and polycaprolactone triol.

Examples of the polycarbonate diol include the dihydric alcohol having 2 to 20 carbon atoms and a low-molecular carbonate compound (for example, an alkylene carbonate having an alkyl group having 1 to 6 carbon atoms, an alkylene group having 2 to 6 carbon atoms, and carbon). And polycarbonate polyols produced by condensing a diaryl carbonate having an aryl group of several 6 to 9 with a dealcoholization reaction. Two or more divalent alcohols having 2 to 20 carbon atoms and low molecular carbonate compounds may be used in combination.
Specific examples of the polycarbonate polyol include polyhexamethylene carbonate diol, polypentamethylene carbonate diol, polytetramethylene carbonate diol, and poly (tetramethylene / hexamethylene) carbonate diol (for example, 1,4-butanediol and 1,6-hexane). And a diol obtained by condensing a diol with a dialkyl carbonate while causing a dealcoholization reaction).

  The hydroxyl value of the polymer diol (a2) other than (a1) is preferably 2 to 150 mgKOH / g, more preferably 5 to 70 mgKOH / g, from the viewpoint of waterproofness and texture.

  The active hydrogen component (A1) can further contain a chain extender (a3) and a reaction terminator (a4).

  Examples of the chain extender (a3) include water, the aforementioned polyhydric alcohol having 2 to 20 carbon atoms, and diamines having 2 to 10 carbon atoms (for example, ethylenediamine, propylenediamine, 1,6-hexanediamine, isophoronediamine, toluenediamine, and the like). Piperazine), polyalkylene polyamines (for example, diethylenetriamine and triethylenetetramine), hydrazine and its derivatives (for example, dibasic acid dihydrazides such as adipic acid dihydrazide) and C2-C10 amino alcohols (for example, ethanolamine, diethanolamine, 2 -Amino-2-methylpropanol and triethanolamine) and the like. A chain extender may be used individually by 1 type, or may use 2 or more types together.

  As the reaction terminator (a4), monoalcohols having 1 to 8 carbon atoms (such as methanol, ethanol, isopropanol, n-butanol, cellosolves and carbitols) and monoamines having 1 to 10 carbon atoms (monomethylamine, Mono- or dialkylamines such as monoethylamine, monobutylamine, dibutylamine and monooctylamine; mono- or dialkanolamines such as monoethanolamine, diethanolamine and diisopropanolamine). A reaction terminator may be used individually by 1 type, or may use 2 or more types together.

  As an organic polyisocyanate component (B), what is conventionally used for manufacture of a polyurethane can be used, C2-C22 aliphatic polyisocyanate (b1) which has 2-3 or more isocyanate groups, C8-C18 alicyclic polyisocyanate (b2), C8-C26 aromatic polyisocyanate (b3), C10-C18 araliphatic polyisocyanate (b4), and modification of these polyisocyanates A thing (b5) etc. are mentioned. An organic polyisocyanate component (B) may be used individually by 1 type, and may use 2 or more types together.

  Examples of the aliphatic polyisocyanate (b1) having 4 to 22 carbon atoms include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, and 2,2,4-trimethylhexa Methylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylcaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate and 2-isocyanatoethyl-2,6-diisocyanate Hexanoate is mentioned.

  Examples of the alicyclic polyisocyanate (b2) having 8 to 18 carbon atoms include isophorone diisocyanate (hereinafter abbreviated as IPDI), 4,4-dicyclohexylmethane diisocyanate (hereinafter abbreviated as hydrogenated MDI), cyclohexylene diisocyanate, and methyl. Examples include cyclohexylene diisocyanate, bis (2-isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate and 2,5- or 2,6-norbornane diisocyanate.

  Examples of the aromatic polyisocyanate (b3) having 8 to 26 carbon atoms include 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (hereinafter abbreviated as TDI), and crude product. TDI, 4,4′- or 2,4′-diphenylmethane diisocyanate (hereinafter 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 "-triphenylmethane triisocyanate and m-or p-isocyanatophenylsulfonyl isocyanate is mentioned.

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

  As the modified polyisocyanate (b5) of (b1) to (b4), the modified polyisocyanate (urethane group, carbodiimide group, allophanate group, urea group, biuret group, uretdione group, uretoimine group, isocyanurate group) Or modified product containing oxazolidone group, etc .; free isocyanate group content is usually 8 to 33% by weight, preferably 10 to 30% by weight, especially 12 to 29% by weight), such as modified MDI (urethane modified MDI, carbodiimide modified MDI) And modified products of polyisocyanates such as urethane-modified TDI, biuret-modified HDI, isocyanurate-modified HDI, and isocyanurate-modified IPDI.

  Of these, aromatic polyisocyanates (b3) having 8 to 26 carbon atoms are preferred from the viewpoint of tensile strength, more preferred are aromatic diisocyanates having 8 to 26 carbon atoms, and particularly preferred are MDI and TDI. It is. The isocyanate group content (NCO%) of the organic polyisocyanate component (B) as a whole is preferably 25 to 45% by weight.

  The weight average molecular weight (hereinafter abbreviated as Mw) of the polyurethane resin (U) for moisture permeable and waterproof material of the present invention is preferably 50,000 to 1,000,000, more preferably 100, from the viewpoint of improving tensile strength. 000-500,000.

  The Mw of the polyurethane resin (U) in the present invention is measured by gel permeation chromatography using dimethylformamide as a solvent and polystyrene as a standard substance. The sample concentration may be 0.25 wt%, the column stationary phase may be TSKgel SuperH2000, TSKgel SuperH3000, TSKgel SuperH4000 (both manufactured by Tosoh Corporation), and the column temperature may be 40 ° C.

  The manufacturing method of the polyurethane resin (U) for moisture-permeable waterproof materials of this invention is not specifically limited, It can manufacture by a well-known method etc. For example, the active hydrogen component (A1), the polyisocyanate component (B), and if necessary, an organic solvent and an additive may be charged together and reacted, or the active hydrogen component (A1) and the polyisocyanate component (B) Can be reacted to obtain an isocyanate group-terminated prepolymer, and then an elongation reaction can be carried out with a chain extender. Furthermore, by using a kneader or the like as the reaction apparatus, the reaction can be performed in the absence of a solvent.

  The polyurethane resin used in the polyurethane resin composition (W) is not particularly limited as long as it has the diol (a1) having an ionic group as a constituent unit of the resin molecule, and the compound (S1) is used as a constituent component of the molecule. For example, the diol (a1) having the ionic group and the polymer diol (a2) other than the (a1) if necessary, the chain extender (a3), Examples thereof include polyurethane resins obtained by reacting the active hydrogen component (A2) containing the reaction terminator (a4) and the compound (S1) with the organic polyisocyanate component (B).

  The content of the compound (S) in the polyurethane resin composition (W) is preferably 0.01 to 10% by weight, more preferably 0.02 to 5% by weight, based on the weight of the polyurethane resin. However, when the polyurethane resin (U) in which the compound (S1) is incorporated is used, the content is a value based on the total amount of the compound (S1) incorporated in the polyurethane resin and the compound (S) to be added.

  The addition time of the polyurethane resin and the compound (S) in producing the polyurethane resin composition (W) is not particularly limited, and (S) may be added after the polyurethane resin is produced, and the compound (S) is active. In the case of the compound having no hydrogen (S2), the polyurethane resin may be produced in the presence of (S2).

  The polyurethane resin (U) for moisture-permeable and waterproof material of the present invention can be used as an organic solvent solution by mixing with the inert organic solvent (T) if necessary. Moreover, the polyurethane resin composition (W) of this invention can contain the said inert organic solvent (T) as needed.

  The polyurethane resin (U) of the present invention can be used by adding pigments, stabilizers and other additives, if necessary, and the polyurethane resin composition (W) of the present invention can be used by adding pigments, stabilizers and other, if necessary. The additive may be contained.

  It does not specifically limit as a pigment, A well-known organic pigment and / or an inorganic pigment can be used, and it is 0-5 weight% normally with respect to a polyurethane resin, Preferably it mix | blends 0.1-3 weight%. Examples of organic pigments include insoluble azo pigments, soluble azo pigments, copper phthalocyanine pigments, and quinacridone pigments. Examples of inorganic pigments include chromates, ferrocyan compounds, metal oxides, selenium sulfide compounds, metal salts. (Sulfates, silicates, carbonates, phosphates, etc.), metal powders, carbon black and the like.

The stabilizer is not particularly limited, and a known antioxidant and / or ultraviolet absorber can be used, and is usually 0 to 5% by weight, preferably 0.1 to 3% by weight based on the polyurethane resin. The
Antioxidants include phenolic [2,6-di-t-butyl-p-cresol and butylated hydroxyanisole, etc.]; bisphenol [2,2′-methylenebis (4-methyl-6-t-butylphenol) Etc.]; phosphorus-based [triphenyl phosphite and diphenylisodecyl phosphite etc.] and the like.

Examples of the ultraviolet absorber include benzophenone [2,4-dihydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone and the like]; benzotriazole [2- (2′-hydroxy-5′-methylphenyl) benzotriazole and the like]; Salicylic acid type [phenyl salicylate and the like]; hindered amine type [bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and the like] and the like.
Other additives include anti-fusing agents and flame retardants.

  The pigment, stabilizer and other additives can be added at any stage during the production of the polyurethane resin, and may be added after the production. Moreover, when a polyurethane resin composition (W) contains a pigment, a stabilizer, another additive, etc., it can be added in the arbitrary steps at the time of manufacture of a polyurethane resin, and may be added after the manufacture.

  The polyurethane resin (U) and the polyurethane resin composition (W) of the present invention are used for a polyurethane resin layer of a moisture permeable waterproof material, which is a composite material in which a polyurethane resin layer is provided on at least one surface of a fibrous base material.

  The base material of the fibrous base material may be any of cellulose fibers such as cotton, hemp and rayon, and synthetic fibers such as polyester, polyamide and polyolefin. Moreover, as a form of the fibrous base material, those having any structure such as a woven fabric, a knitted fabric, and a non-woven fabric can be used, but a woven fabric and a knitted fabric are preferable.

  The moisture-permeable and waterproof material using the polyurethane resin (U) or the polyurethane resin composition (W) of the present invention includes outdoor wear, ski-related wear, windbreaker, athletic wear, golf wear, and rainwear for fishing and mountain climbing. It can be suitably used for mountain climbing equipment such as casual coats, outdoor work clothes, gloves, shoes and tents.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to these. In the following, parts represent parts by weight.

Production Example 1 [Production of Compound (S1-1)]
To a stainless steel autoclave with a stirrer and a temperature controller, propylene glycol PO / EO block adduct (“Sanix PL-910” manufactured by Sanyo Chemical Industries, Ltd .; Mn900, hydroxyl value 124.7 mgKOH / g) 900 parts, Charge 384 parts of trimellitic anhydride and 1.0 part of alkali catalyst (N-ethylmorpholine) and react for 5 hours at 0.20 MPa and 130 ± 10 ° C. under nitrogen atmosphere to half-esterify the acid anhydride group. Thus, an ester compound obtained by reacting 2 mol of trimellitic anhydride with 1 mol of the PO / EO block adduct of propylene glycol was obtained. Subsequently, 198 parts of EO was added dropwise over 5 hours while controlling the pressure at 100 ± 10 ° C. so that the pressure was 0.50 MPa or less, and then aged for 1 hour at 100 ± 10 ° C. to form a carboxyl group of the ester compound. A compound (S1-1) to which EO was added was obtained.

Production Example 2 [Production of Compound (S1-2)]
The same procedure as in Production Example 1 was conducted except that 900 parts of the PO / EO block adduct of propylene glycol was changed to 1000 parts of polyoxytetramethylene glycol ("PTMG1000" manufactured by Mitsubishi Chemical Corporation; Mn1000, hydroxyl value 112.2 mgKOH / g). Compound (S1-2) was obtained.

Production Example 3 [Production of Compound (S1-3)]
900 parts of PO / EO block adduct of propylene glycol was added to 1500 parts of polyoxypropylene triol (“Sanix GP-1500” manufactured by Sanyo Chemical Industries, Ltd .; Mn 1500, hydroxyl value 112.2 mgKOH / g), and trimellitic anhydride was added. A compound (S1-3) was obtained in the same manner as in Production Example 1, except that the charge amount was changed to 576 parts and the charge amount of EO was changed to 299 parts.

Production Example 4 [Production of Compound (S1-4)]
Add 900 parts of PO / EO block adduct of propylene glycol to 1000 parts of polyoxypropylene glycol (“SANNICS PP-1000” manufactured by Sanyo Chemical Industries, Ltd .; Mn1000, hydroxyl value 112.2 mgKOH / g), and charge EO Compound (S1-4) was obtained in the same manner as in Production Example 1 except that the amount was changed to 101 parts.

Production Example 5 [Production of Compound (S1-5)]
Production Example 1 except that 900 parts of the propylene glycol PO / EO block adduct is changed to 1000 parts of polyoxyethylene glycol (“PEG-1000” manufactured by Sanyo Chemical Industries, Ltd .; Mn1000, hydroxyl value 112.2 mgKOH / g). In the same manner, compound (S1-5) was obtained.

Production Example 6 [Production of Compound (S1-6)]
Production Example 1 except that 900 parts of PO / EO block adduct of propylene glycol is changed to 200 parts of polyoxyethylene glycol (“PEG-200” manufactured by Sanyo Chemical Industries, Ltd .; Mn200, hydroxyl value 561.0 mgKOH / g) In the same manner, compound (S1-6) was obtained.

Production Example 7 [Production of Compound (S1-7)]
Compound (S1-7) was obtained in the same manner as in Production Example 1 except that 900 parts of the propylene glycol PO / EO block adduct was changed to 62 parts of ethylene glycol.

Production Example 8 [Production of Compound (S1-8)]
In a stainless steel autoclave equipped with a stirrer and a temperature controller, 116 parts of 1,6-hexanediamine, 384 parts of trimellitic anhydride, 1.0 part of an alkali catalyst (N-ethylmorpholine) and 246 parts of THF as a solvent were charged. Under a nitrogen atmosphere, reaction was carried out at 80 ± 10 ° C. for 2 hours to half-amidize the acid anhydride group portion, and an amide compound in which 2 mol of trimellitic anhydride was reacted with 1 mol of 1,6-hexanediamine was obtained. Subsequently, 198 parts of EO was added dropwise over 5 hours while controlling the pressure at 80 ± 10 ° C. so that the pressure was 0.50 MPa or less, then aged at 80 ± 10 ° C. for 1 hour, and the solvent was used at 80 ± 10 ° C. and 10 kPa. Was distilled off to obtain a compound (S1-8) in which EO was added to the carboxyl group of the amide compound.

Production Example 9 [Production of Compound (S1-9)]
A stainless steel autoclave equipped with a stirrer and a temperature controller was charged with 150 parts of 1,6-hexanedithiol, 384 parts of trimellitic anhydride, 0.1 part of a ruthenium (III) chloride catalyst and 246 parts of THF as a solvent, and a nitrogen atmosphere Then, the reaction was carried out at 50 ± 10 ° C. for 2 hours to half-esterify the acid anhydride group part to obtain a thioester compound in which 2 mol of trimellitic anhydride was reacted with 1 mol of 1,6-hexanedithiol. Subsequently, 198 parts of EO was added dropwise over 5 hours while controlling the pressure at 80 ± 10 ° C. so that the pressure was 0.50 MPa or less, then aged at 80 ± 10 ° C. for 1 hour, and the solvent was used at 80 ± 10 ° C. and 10 kPa. Was distilled off to obtain a compound (S1-9) in which EO was added to the carboxyl group of the thioester compound.

Production Example 10 [Production of Compound (S1-10)]
900 parts of propylene glycol PO / EO block adduct is added to 400 parts of polyoxyethylene glycol (“PEG-200” manufactured by Sanyo Chemical Industries, Ltd .; Mn200, hydroxyl value 561.0 mgKOH / g), and 384 parts of trimellitic anhydride are added. A compound (S1-10) was obtained in the same manner as in Production Example 1, except that 218 parts of pyromellitic anhydride was changed to 99 parts of the EO charge.

Production Example 11 [Production of Compound (S1-11)]
Compound (S1-11) was obtained in the same manner as in Production Example 1, except that 384 parts of trimellitic anhydride was changed to 484 parts of 1,2,4-naphthalenetricarboxylic acid 1,2-anhydride.

Production Example 12 [Production of Compound (S1-12)]
A stainless steel autoclave equipped with a stirrer and a temperature controller was charged with 62 parts of ethylene glycol, 192 parts of trimellitic anhydride and 1.0 part of an alkali catalyst (N-ethylmorpholine), 0.20 MPa, 130 ± in a nitrogen atmosphere. The reaction was carried out at 10 ° C. for 5 hours to half-esterify the acid anhydride group part to obtain an ester compound in which 1 mol of trimellitic anhydride was reacted with 1 mol of ethylene glycol. Subsequently, 99 parts of EO were added dropwise over 5 hours while controlling the pressure at 100 ± 10 ° C. so that the pressure was 0.50 MPa or less, and then aged for 1 hour at 100 ± 10 ° C. to form a carboxyl group of the ester compound. The compound (S1-12) to which EO was added was obtained.

Production Example 13 [Production of Compound (S2-1)]
A stainless steel autoclave equipped with a stirrer and temperature controller, propylene glycol PO / EO block adduct ("Sanix PL-910" manufactured by Sanyo Chemical Industries, Ltd .; Mn900, hydroxyl value 124.7), 900 parts, anhydrous tri 384 parts of merit acid and 404 parts of triethylamine were charged and reacted in a nitrogen atmosphere at 0.20 MPa and 80 ± 5 ° C. for 2 hours to half-esterify the acid anhydride group part, and PO / EO block adduct 1 of propylene glycol An esterified product obtained by reacting 2 moles of trimellitic anhydride with 2 moles was obtained. Subsequently, 508 parts of benzyl chloride was added and reacted at 70 ± 5 ° C. for 2 hours. Thereafter, liquid separation was performed to obtain a compound (S2-1) in which the carboxyl group of the esterified product was a benzyloxycarbonyl group.

Comparative Production Example 1 [Production of Compound (S1′-1)]
900 parts of a PO / EO block adduct of propylene glycol is added to 3200 parts of polyoxypropylene triol (“Sanix GP-3000” manufactured by Sanyo Chemical Industries, Ltd .; Mn 3200, hydroxyl value 52.6 mg KOH / g), and trimellitic anhydride 384 is added. A polyol (S1′-1) was obtained in the same manner as in Production Example 1 except that the part was changed to 444 parts of phthalic anhydride and the charge amount of EO was changed to 149 parts.

Comparative Production Example 2 [Production of Compound (S1′-2)]
A polyol (S1′-2) was obtained in the same manner as in Example 1 except that 384.0 parts of trimellitic anhydride was changed to 296 parts of phthalic anhydride and the charge amount of EO was changed to 99.0 parts.

  Table 1 shows the analysis results of the compounds obtained in Production Examples 1 to 13 and Comparative Production Examples 1 and 2.

Production Example 14 [Production of Diol (a11-1) Having Anionic Group]
In a reaction vessel equipped with a stirrer, thermometer and reflux condenser, 423.2 parts of dimethyl sodium 5-sulfoisophthalate, 176.1 parts of ethylene glycol, 400.4 parts of dimethylacetamide and diisopropoxytitanium bis (triethanolamine) Nate) 0.30 part was charged, and transesterification was carried out at 140 to 160 ° C. to remove the produced methanol to obtain a 56% dimethylacetamide solution of the diol (a11-1) having an anionic group.

Production Example 15 [Production of Diol (a11-2) Having Anionic Group]
A reaction vessel equipped with a stirrer, a thermometer and a reflux condenser was charged with 100 parts of 2,2-dimethylolpropionic acid and 500 parts of dimethylformamide, and the temperature was adjusted to 30 ° C. or less, and 75.4 parts of triethylamine was added dropwise. . The mixture was homogenized for 30 minutes to obtain a 26% dimethylformamide solution of the diol (a11-2) having an anionic group.

<Examples 1-31 and Comparative Examples 1-6>
According to the formulation shown in Table 2 and Table 3, the compound (S1) in the active hydrogen component (A1), the diol (a1) having an ionic group, the polymer diol (a2) other than (a1), the chain extender ( a3), the organic polyisocyanate component (B) and the inert organic solvent (T) are charged into a reaction vessel, and are allowed to react at 70 ° C. for 12 hours in a dry nitrogen atmosphere. Thereafter, a reaction stopper (a4) is charged, The terminal termination reaction was performed for 1 hour, and the solutions of the polyurethane resins (U-1) to (U-31) of the present invention and the polyurethane resins (U′-1) to (U′-6) for comparison were obtained. . The parts of diols (a11-1) and (a11-2) having an anionic group in Tables 2 and 3 were obtained by removing the inert organic solvent from the solutions of diols (a11-1) and (a11-2). This represents the number of parts of the active ingredient, and the number of parts of the inert organic solvent contained in the solutions (a11-1) and (a11-2) is the sum of the inert organic solvent charged during the urethanization reaction. It described in the column of the inert organic solvent (T). Further, the diols (a12-1), (a12-2) and (a13-3) having a cationic group in Tables 2 and 3 are N-methyldiethanolamine hydrochloride and N-butyldipropanolamine, respectively. Sulfate quaternized with sulfuric acid and acetate of N-methyldiethanolamine.

<Examples 32 to 40 and Comparative Examples 7 to 8>
In accordance with the formulation shown in Table 4, the diol (a1) having an ionic group in the active hydrogen component (A2), the polymer diol (a2) other than (a1), the chain extender (a3), the organic polyisocyanate component ( B) and an inert organic solvent (T) were charged into a reaction vessel and reacted at 70 ° C. for 12 hours in a dry nitrogen atmosphere. Thereafter, a reaction terminator (a4) was charged and a terminal termination reaction was performed for 1 hour. Thereafter, the compound (S) as an additive shown in Table 4 was added and stirred at 60 ° C. for 15 minutes, and the polyurethane resin compositions (W-1) to (W-9) of the present invention and a polyurethane for comparison were used. Resin compositions (W′-1) to (W′-2) were obtained. In Table 4, the number of parts of the diols (a11-1) and (a11-2) having an anionic group is the same as that of the active ingredient obtained by removing the inert organic solvent from the solution of the diols (a11-1) and (a11-2). The number of parts of the inert organic solvent contained in the solutions (a11-1) and (a11-2) is combined with the inert organic solvent charged during the urethanization reaction. ) Column.

Tensile strength, permanent strain, moisture permeability, water pressure resistance and washing resistance results and compounds (or compounds) measured or evaluated using the polyurethane resin solutions and polyurethane resin compositions obtained in Examples 1 to 40 and Comparative Examples 1 to 8 Table 5 and Table 6 show the content and addition amount of S).
In Tables 5 and 6, “content (%) of compound (S1) in polyurethane resin” is an active hydrogen component based on the total weight of active hydrogen component (A1) and organic polyisocyanate component (B). This represents the content (% by weight) of the compound (S1) in [A1] [excluding the comparative compound (S1 ′)], and “content (%) of the compound (S) in the polyurethane resin composition” is The content (% by weight) based on the weight of the polyurethane resin in the polyurethane resin composition of the compound (S) [excluding the comparative compound (S ′)] when used by adding the compound (S) ). Moreover, each measurement and evaluation were performed with the following method.

[1] Method for measuring tensile strength A polyurethane resin solution or polyurethane resin composition is applied to a release-treated glass plate to a thickness of 0.7 mm, dried in a circulating dryer at 70 ° C. for 3 hours, and then glass. By peeling from the plate, a tensile strength test film having a thickness of about 0.2 mm was produced.
The obtained film for tensile test was left in a room adjusted to a temperature of 25 ° C. and a humidity of 65% RH for 1 day, and then the tensile strength was measured according to JIS K 6251.

[2] Permanent strain measurement method A test piece prepared in the same manner as the film for tensile strength test was allowed to stand in a room adjusted to a temperature of 25 ° C. and a humidity of 65% RH for one day, and then installed in an atmosphere at 25 ° C. Using a Ron-type tensile tester (Autograph manufactured by Shimadzu Corporation), after stretching for 300% at a tension speed of 50 cm / min and holding for 30 minutes, return to the state before stretching at the same speed as the tension speed. The distance (L ₅ ) between the marked lines after 30 minutes was measured, and the permanent strain was measured from the following equation using the distance (L ₀ ) between the marked lines before the test.
Permanent strain (%) = {1− (L ₅ −L ₀ ) / L ₀ } × 100
The smaller the permanent set, the better the washing resistance.

[3] Method of measuring moisture permeability A polyurethane resin solution or polyurethane resin composition is applied to a release-treated glass plate to a thickness of 25 μm, dried in a circulating dryer at 70 ° C. for 3 hours, and then from the glass plate. By peeling off, a film for measuring moisture permeability having a thickness of 7 μm was produced.
The moisture permeability of the obtained film for measuring moisture permeability was measured based on the JIS L 1099-1998 calcium chloride method (A-1).

[4] Method for measuring water pressure resistance With respect to a test piece prepared in the same manner as the film for measuring moisture permeability, the water pressure resistance was measured according to the JIS L 1092-1998 high water pressure resistance method. When the test piece was stretched by applying water pressure, a nylon taffeta (density: warp yarn + weft yarn = 210 yarns / 2.54 cm equivalent) was overlaid on the test piece, and then attached to a tester for measurement.

[5] Evaluation method for washing resistance A polyurethane resin solution or a polyurethane resin composition is applied onto a release paper so as to have a film thickness of 10 μm using a bar coater, placed in an air oven and dried at 120 ° C. for 2 minutes. The skin layer was obtained.
Next, 100 parts of Samprene LQ-120 [manufactured by Sanyo Chemical Industry Co., Ltd.], 9 parts of Coronate HL [manufactured by Nippon Polyurethane Industry Co., Ltd.] and 0.02 part of “U-CAT SA102” manufactured by Sun Apro Co., Ltd. as a catalyst The applied adhesive layer resin solution was applied onto the skin layer so as to have a film thickness of 20 μm using a bar coater, then placed in an air oven and dried at 120 ° C. for 2 minutes to form an adhesive layer on the skin layer. .
Next, polyester taffeta (83 dtex) is overlaid on the adhesive layer, and is pressure-bonded at 120 ° C. and 1 MPa for 20 seconds using a hot press machine (Tester Sangyo Co., Ltd., tabletop test press SA-302). A waterproof cloth was obtained.
The obtained moisture-permeable waterproof fabric was subjected to a washing treatment in accordance with JIS L 0217-103 method, and the appearance change was evaluated. The case where the appearance did not change was rated as ◯, and the case where there was wrinkle or float was marked as ×.

  Since the polyurethane resin (U) and the polyurethane resin composition (W) for moisture permeable and waterproof material of the present invention are excellent in all of moisture permeability, waterproof property and washing resistance, outdoor wear for fishing and mountain climbing, It is particularly useful for the production of moisture-permeable and waterproof materials used for ski-related wear, windbreakers, athletic wear, golf wear, rainwear, casual coats, outdoor work clothes, gloves, shoes, and climbing equipment such as tents.

Claims (21)

Reaction of active hydrogen component (A1) containing compound (S1) represented by general formula (1) and having at least one active hydrogen and diol (a1) having an ionic group with organic polyisocyanate component (B) A polyurethane resin (U) for moisture-permeable and waterproof material, characterized in that it is obtained.

[In the general formula (1), X ¹ represents a residue obtained by removing c active hydrogens from an m-valent active hydrogen-containing compound; c represents an integer satisfying 1 ≦ c ≦ m; X ² represents a residue obtained by removing one active hydrogen from an active hydrogen-containing compound, a plurality of X ² may be the same or different, and X ² and X ¹ may be the same or different Y represents a residue obtained by removing all carboxyl groups from a trivalent or higher valent aromatic polycarboxylic acid, and the aromatic ring of Y is composed of carbon atoms, and the carbon atoms are substituted with other than carboxyl groups. A group and / or a halogen atom may be bonded, but at least one carbon atom is not bonded to a substituent; a represents an integer of 1 or more, b represents an integer of 0 or more, and 2 ≦ a + b ≦ d−2 is satisfied; d is the carbo of the aromatic polycarboxylic acid. This represents the number of hydrogen atoms bonded to the carbon atom constituting the aromatic ring when all the substituents including the xyl group are substituted with hydrogen atoms, that is, the number of sites that can be substituted on the aromatic ring. ]   The polyurethane resin for moisture permeable and waterproof material according to claim 1, wherein the compound (S1) has a hydroxyl value of 70 to 500 mgKOH / g.   The polyurethane resin for moisture-permeable and waterproof material according to claim 1 or 2, wherein the concentration of Y in the compound (S1) is 1.0 to 6.0 mmol / g.   The polyurethane resin for moisture-permeable and waterproof material according to any one of claims 1 to 3, wherein the compound (S1) has a carbonyl group concentration of 3.0 to 20 mmol / g.   The trivalent or higher valent aromatic polycarboxylic acid has a structure in which a carboxyl group is bonded to two carbon atoms adjacent to a carbon atom constituting the aromatic ring and not having a substituent bonded thereto. The polyurethane resin for moisture-permeable and waterproof materials described in any one of the above.   The polyurethane resin for moisture-permeable and waterproof material according to claim 5, wherein the trivalent or higher aromatic polycarboxylic acid has a structure in which a carboxyl group is further bonded to at least one of carbon atoms adjacent to the carbon atom to which the carboxyl group is bonded. .   The polyurethane resin for moisture-permeable and waterproof material according to any one of claims 1 to 6, wherein the trivalent or higher aromatic polycarboxylic acid is trimellitic acid and / or pyromellitic acid. X ¹ in the general formula (1) is a residue obtained by removing two active hydrogens from a polyether polyol obtained by adding an alkylene oxide to a polyhydric alcohol having 2 to 20 carbon atoms, and c is 2. 8. The polyurethane resin for moisture-permeable and waterproof material according to any one of 7.   The diol (a1) having an ionic group is a diol (a11) having an anionic group or a diol (a12) having a cationic group, and the content of the ionic group in the polyurethane resin is polyurethane resin (U) It is 0.05-0.50 mmol / g based on the weight of, The polyurethane resin for moisture-permeable waterproof materials in any one of Claims 1-8.   The polyurethane resin for moisture-permeable and waterproof materials according to any one of claims 1 to 9, wherein the active hydrogen component (A1) further contains a chain extender (a3) and a reaction terminator (a4).   11. The polyurethane resin for moisture-permeable and waterproof material according to claim 1, wherein the content of the compound (S1) is 0.01 to 10% by weight based on the weight of the polyurethane resin. A polyurethane resin composition containing a polyurethane resin and a compound (S) represented by the general formula (1), wherein the polyurethane resin contains a diol (a1) having an ionic group (A2) ) And an organic polyisocyanate component (B), and a polyurethane resin composition (W) for moisture-permeable and waterproof material.

[In the general formula (1), X ¹ represents a residue obtained by removing c active hydrogens from an m-valent active hydrogen-containing compound; c represents an integer satisfying 1 ≦ c ≦ m; X ² represents a residue obtained by removing one active hydrogen from an active hydrogen-containing compound, a plurality of X ² may be the same or different, and X ² and X ¹ may be the same or different Y represents a residue obtained by removing all carboxyl groups from a trivalent or higher valent aromatic polycarboxylic acid, and the aromatic ring of Y is composed of carbon atoms, and the carbon atoms are substituted with other than carboxyl groups. A group and / or a halogen atom may be bonded, but at least one carbon atom is not bonded to a substituent; a represents an integer of 1 or more, b represents an integer of 0 or more, and 2 ≦ a + b ≦ d−2 is satisfied; d is the carbo of the aromatic polycarboxylic acid. This represents the number of hydrogen atoms bonded to the carbon atom constituting the aromatic ring when all the substituents including the xyl group are substituted with hydrogen atoms, that is, the number of sites that can be substituted on the aromatic ring. ]   The polyurethane resin composition for moisture-permeable and waterproof materials according to claim 12, wherein the compound (S) has a hydroxyl value of 0 or 70 to 500 mgKOH / g.   The polyurethane resin composition for moisture permeable and waterproof materials according to claim 12 or 13, wherein the concentration of Y in the compound (S) is 1.0 to 6.0 mmol / g.   The polyurethane resin composition for moisture-permeable and waterproof materials according to any one of claims 12 to 14, wherein the compound (S) has a carbonyl group concentration of 3.0 to 20 mmol / g.   The trivalent or higher valent aromatic polycarboxylic acid has a structure in which a carboxyl group is bonded to two carbon atoms adjacent to a carbon atom constituting the aromatic ring and not bonded to a substituent. Any one of the polyurethane resin compositions for moisture-permeable waterproof materials.   The polyurethane resin for moisture-permeable and waterproof material according to claim 16, wherein the trivalent or higher aromatic polycarboxylic acid has a structure in which a carboxyl group is further bonded to at least one of carbon atoms adjacent to the carbon atom to which the carboxyl group is bonded. Composition.   The polyurethane resin composition for moisture-permeable and waterproof materials according to any one of claims 12 to 17, wherein the trivalent or higher aromatic polycarboxylic acid is trimellitic acid and / or pyromellitic acid. X ¹ in the general formula (1) is a residue obtained by removing two active hydrogens from a polyether polyol obtained by adding an alkylene oxide to a polyhydric alcohol having 2 to 20 carbon atoms, and c is 2. 8. The polyurethane resin for moisture-permeable and waterproof material according to any one of 7.   The diol (a1) having an ionic group is a diol (a11) having an anionic group or a diol (a12) having a cationic group, and the content of the ionic group in the polyurethane resin composition is that of the polyurethane resin set. The polyurethane resin composition for moisture-permeable and waterproof material according to any one of claims 12 to 19, which is 0.05 to 0.50 mmol / g based on weight.   The content of the compound (S) is 0.01 to 10% by weight based on the weight of the polyurethane resin, The polyurethane resin composition for moisture permeable and waterproof material according to any one of claims 12 to 20.