JP2016138183A - Anionic diol excellent in dyeability and urethane resin using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide anionic diol useful for manufacturing a polyurethane resin excellent in dyeability and durability.SOLUTION: There is provided anionic diol for dyeable urethane resin represented by the formula (1) and having number average molecular weight (Mn) of 1,200 to 15,000 (B). (1), where n is an integer of 1 to 4, m is 1 or 2, Mis a monovalent cation, Q is a bivalent group having formula weight of 60 to 200, a plurality of Mand Q may be same or different, Z is a (n+2) valent organic group having formula weight of 50 to 200, A is a residue which two hydrogen atoms are removed from polymer diol having number average molecular weight of 500 to 5000 and two A may be same or different.SELECTED DRAWING: None

Description

The present invention relates to an anionic diol having excellent dyeability, and more particularly to an anionic diol imparting good dyeability to a polyurethane resin, a urethane resin having this as a constituent, and a fiber product containing the same.

  Conventionally, a polyurethane resin is dyeable and hygroscopic using a high molecular weight polyol comprising a sulfonate group-containing polyester polyol obtained by copolymerizing a dibasic acid having a sulfonate group and terephthalic acid and / or isophthalic acid as an acid component. Etc. are known (see, for example, Patent Document 1). Patent Document 2 proposes an acidic (salt) group-containing dicarboxylic acid diester composition having a high degree of freedom in resin modification by reducing the free diol content and excellent dyeability.

JP 59-6210 A Japanese Patent No. 3851290

However, in the case of Patent Document 1, the polyurethane resin produced using a sulfonate group-containing polyester polyol has good dyeability, but hydrolysis resistance is improved by copolymerizing terephthalic acid and / or isophthalic acid. However, the level of hydrolysis resistance is not fully satisfactory in practice. In Patent Document 2, the acid (salt) group-containing dicarboxylic acid diester composition has a high degree of freedom in resin modification and improved dyeability, but has not yet provided a urethane resin that satisfies the mechanical properties.
That is, the problem to be solved by the present invention is to provide an anionic diol useful for producing a polyurethane resin excellent in dyeability and durability.

［式中、ｎは１〜４の整数であり、ｍは１又は２である。Ｍ⁺は１価のカチオンである。Ｑは式量が６０〜２００である２価の基であり、上記の一般式（２）で示される化合物のｐＫａが−１０〜４である。複数個あるＭ⁺及びＱは同じでも異なっていてもよい。Ｚは式量が５０〜２００である（ｎ＋２）価の有機基である。Ａは数平均分子量が５００〜５０００である高分子ジオールから２個の水素原子を除いた残基であり、２個あるＡは同じでも異なっていてもよい。］ 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 is represented by the following general formula (1) and has a number average molecular weight (Mn) of 1,200 to 15,000 for an anionic diol (B) for a dyeable urethane resin; A dyeable urethane resin (U) comprising B) as a polyol component; a synthetic leather formed from the urethane resin (U).

[Wherein, n is an integer of 1 to 4, and m is 1 or 2. M ⁺ is a monovalent cation. Q is a divalent group having a formula weight of 60 to 200, and the pKa of the compound represented by the general formula (2) is -10 to 4. A plurality of M ⁺ and Q may be the same or different. Z is an (n + 2) -valent organic group having a formula weight of 50 to 200. A is a residue obtained by removing two hydrogen atoms from a polymer diol having a number average molecular weight of 500 to 5000, and the two A may be the same or different. ]

The anionic diol having excellent dyeability according to the present invention is excellent in dyeability, and a urethane resin using the anionic diol is also excellent in dyeability and mechanical properties.

[Anionic diol for dyeable urethane resin (B)]
The anionic diol (B) for dyeable urethane resin of the present invention is represented by the above general formula (1). In the general formula (1), n is an integer of 1 to 4, preferably 1 or 2, and M ⁺ is a monovalent cation. m is 1 or 2, and preferably 1. Q is a divalent group having a formula weight of 60 to 200, and the pKa of the compound represented by the general formula (2) is -10 to 4. [The pKa of protonic acid is described in, for example, “Chemical Handbook (Revised 4th Edition) Fundamentals II” (edited by the Chemical Society of Japan), page II317 (issued in May 1993) ] Protonic acid having a pKa smaller than -10 deteriorates the water resistance of the polyurethane resin, and cannot withstand the mechanical impact in the dyeing process. In addition, when the pKa is larger than 4, the dyeability of the polyurethane resin is deteriorated. Such protic acids include S-containing acids such as methanesulfonic acid (1.8), sulfuric acid (1.99) and sulfamic acid (0.99); and P-containing acids such as phosphonic acid (1.5). , Phosphoric acid (2.15), phosphinic acid (1.23) and the like are included [inside () is pKa].

The anionic group (—QO ⁻ ) includes an anion of an S-containing acid, such as —SO ₃ ⁻ , —OSO ₃ ^—, and —NHSO ₃ ⁻ ; an anion of a P-containing acid, such as —O—P (═O). (-OR ¹⁾ -O ^-, and -P (= O) (- oR 1) -O - there. In addition, —O—P (═O) (— O ⁻ ) ₂ and —P (═O) (— O ⁻ ) ₂ in which m is 2 in the general formula (1) are included. In the formula, R ¹ represents a C (carbon number, the same shall apply hereinafter) 1 to 6 alkyl group or a C 2 to 4 hydroxyalkyl group.
A preferred anionic group is a sulfonic acid (salt) group-containing group —SO ₃ ^— from the viewpoint of the physical properties of the resulting urethane resin. Plural Qs may be the same or different.

Z is an (n + 2) -valent organic group having a formula weight of 50 to 200. Z represents a residue obtained by removing n protonic acid (salt) groups and two carboxyl groups from the protonic acid group-containing dicarboxylic acid (a1) shown below. Residue Z is a hydrocarbon group (aliphatic, alicyclic) in which a hydrogen atom may be substituted with one or more of an alkoxy group, a hydroxyl group, a cyano group, an aldehyde group, a nitro group, or a halogen atom. Formula and aromatic hydrocarbon groups). Z is a (2 + n) -valent hydrocarbon obtained by removing n hydrogen atoms from the following divalent hydrocarbon group (which may be substituted with an alkoxy, hydroxyl, cyano, aldehyde or nitro group or a halogen atom): A group is included. From the viewpoint of the physical properties of the polyurethane resin, an aromatic hydrocarbon group, particularly a phenylene group is preferred.

Divalent hydrocarbon group aliphatic hydrocarbon group (C1-16, preferably C3-12): alkylene and alkenylene groups such as methylene, ethylene, propylene, butylene, pentylene, hexylene, octylene, decylene, tridecylene, hexadecylene, ethenylene and propenylene Groups, and alkyl or alkenyl substituted ethylene groups; alicyclic hydrocarbon groups (C3-16, preferably C5-12): (bi) cycloalkylene and (bi) cycloalkenylene groups such as cyclopropylene, cyclobutylene, cyclopentylene , (Bi) cyclohexylene, cycloheptylene and cyclooctylene, methylenebis (cyclohexylene) and cyclohexyl substituted ethylene groups; aromatic hydrocarbon groups (C6-16, preferably C6-15): (bi) arylene , Such as phenylene, tolylene, xylylene, methylene (bisphenylene) Nafuteniren and phenyl-substituted ethylene group; and alkoxy, hydroxyl, cyano, hydrocarbon group substituted with an aldehyde or nitro group or a halogen atom. Z is preferably C14 or less, particularly C10 or less from the viewpoint of compatibility with other active hydrogen atom-containing compound (A1) or solvent, and C3 or more, particularly C4 or more, from the viewpoint of hydrolysis resistance.

In the general formula (1), the cation (M ⁺ ) includes a proton H ⁺ and a monovalent cation selected from a metal ion and ammonium. In the present invention, ammonium includes NH ₄ ⁺ , a proton adduct of the following amine, and quaternary ammonium.
Metals that form M ⁺ include alkali metals (eg, sodium and potassium). A plurality of M ⁺ may be the same or different.

The amine has a C1-10 hydrocarbon group (eg alkyl, alkenyl, cycloalkyl, aryl and aralkyl groups) and / or a C2-4 hydroxyalkyl group (eg hydroxyethyl group) (two of these groups). Or may be combined to form a heterocyclic ring with N), 1, 2, and tertiary aliphatic, alicyclic, aromatic and heterocyclic amines. Specifically, primary amines, such as the following [listed as initiators for (A111)] primary monoamines, alkanolamines and polyamines; secondary amines (C2-12) such as di (hydrocarbyl and / or hydroxy). Alkyl) amines (eg dimethylamine, dibutylamine, dicyclohexylamine, diethanolamine and ethylethanolamine), and heterocyclic secondary amines (eg morpholine, piperidine and piperazine); and tertiary amines (C3-15) such as tri (hydro Carbyl and / or hydroxyalkyl) amines (eg trimethylamine, tributylamine, triethanolamine and diethylethanolamine), and heterocyclic tertiary amines (eg N-methylmorpholine and pyridine) And later tertiary amine catalyst. Ammonium includes NH ₄ ⁺ and quaternary ammonium such as those obtained by quaternizing the above tertiary amine (for example, tetraalkylammonium, trialkylbenzylammonium and trialkylhydroxyalkylammonium). Of these, metals, particularly alkali metals, are preferable from the viewpoint of dyeability of the polyurethane resin.

［式中、ｎ、Ｑ、Ｚは一般式（１）と同じである。］
（ａ１）の具体例には、下記（ａ１１）〜（ａ１５）のプロトン酸基含有ジカルボン酸、およびそれらの塩［プロトン酸基のプロトンを上記アルカリ金属、アンモニウムおよびアミンからなる群から選ばれるカチオンに変換してなるもの］が含まれる。［下記ジカルボン酸へのプロトン酸基の導入は、プロトン酸の形で行ってもその塩の形で行ってもよく、また遊離のカルボン酸の形で行ってもそのエステル形成性誘導体（後述）の形で行ってもよい。］ The proton acid group-containing dicarboxylic acid (a1) is a compound represented by the following general formula (6).

[Wherein, n, Q and Z are the same as those in the general formula (1). ]
Specific examples of (a1) include the following (a11) to (a15) protonic acid group-containing dicarboxylic acids and salts thereof [the proton of the protonic acid group is a cation selected from the group consisting of the above alkali metals, ammonium and amines] To be converted into]. [Introduction of a protonic acid group into the following dicarboxylic acid may be carried out in the form of a protonic acid or in the form of a salt thereof, or in the form of a free carboxylic acid, and its ester-forming derivative (described later). It may be done in the form of ]

(A11) Sulfonic acid group-containing dicarboxylic acid A sulfonated product of a dicarboxylic acid (listed as a raw material for a polyester polyol), such as (a111) sulfoaromatic dicarboxylic acid: sulfobenzenedicarboxylic acid (for example, 5-sulfo-ortho-, iso -And terephthalic acid), and sulfonaphthalenedicarboxylic acid; (a112) sulfoaliphatic dicarboxylic acid: sulfoalkane or alkene dicarboxylic acid (eg sulfosuccinic, sulfoglutaric, sulfoadipine, sulfopimerin, sulfosuberin, sulfoazeline, sulfosebacine and sulfomaleic acid) And (a113) substituted sulfosuccinic acid

(A12) sulfate-containing dicarboxylic acid hydroxydicarboxylic acid [eg mono- and di-hydroxyalkanedioic acid (eg tartron, apple and tartaric acid)] sulfate ester [hydroxyl group sulfated with sulfating agent (eg fuming sulfuric acid) thing]
(A13) Sulphamic acid group-containing dicarboxylic acid Sulfaminated product of aminodicarboxylic acid (for example, asparagine and glutamic acid) (formed by converting amino group to sulfamic acid group with fuming sulfuric acid or chlorosulfuric acid)

(A14) Phosphoric acid ester-containing dicarboxylic acid hydroxydicarboxylic acid (above) phosphate ester [hydroxyl group phosphorylated with a phosphorylating agent (for example, phosphorus pentoxide and phosphorus oxychloride) and its acid group (OH ) Is reacted with an alcohol or alkylene oxide (hereinafter abbreviated as AO) [C2-8 or more, preferably C2-4, such as those described in (b12) below] to produce a partial alkyl ester or partial hydroxyalkyl. Esterified product]
(A15) Phosphonated product of phosphonic acid group-containing dicarboxylic acid hydroxydicarboxylic acid (above) [hydroxyl group converted to phosphonic acid group by phosphorous esterification with phosphorus trichloride and isomerization, and its acid group (OH) Partial alkyl ester or partial hydroxyalkyl ester converted in the same manner as above]

The diol (b1) represented by HAH constituting the group A in the general formula (1) includes the following. Two A may be the same or different.
(B11) an aliphatic diol having a hydrocarbon diol number average molecular weight of 500 to 5000 (C34 or higher, preferably C34 to 140: alkylene or alkenylene glycol); an alicyclic diol (C34 or higher, preferably C34 to 140). ); An araliphatic diol (C34 or higher); and a polybutadiene-based diol described in (A113) described later.

(B12) (Poly) oxyalkylenediol compound having two active hydrogen atoms having a number average molecular weight of 500 to 5,000 [for example, polyalkylene glycol [for example, polyethylene glycol, polypropylene glycol and polytetramethylene ether glycol (hereinafter, PEG, PPG respectively) And abbreviation PTMG)] and polyoxyalkylene ethers of dihydric phenols [AO adducts of bisphenol A, etc.].

(B13) Polycarbonate diol One or more kinds of polyhydric alcohols having 2 to 20 carbon atoms (preferably aliphatic dihydric alcohols having 3 to 15 carbon atoms, more preferably 4 to 12 carbon atoms) (preferably 2 to 2 carbon atoms). 4 types) and a low-molecular carbonate compound (for example, an alkyl group having 1 to 6 carbon atoms, an alkylene carbonate having 2 to 6 carbon atoms, and a diaryl carbonate having 6 to 9 carbon atoms) From the above, polycarbonate diol having a number average molecular weight of 500 to 5,000 produced by condensation while causing a dealcoholization reaction is mentioned.

  The polyhydric alcohol having 2 to 20 carbon atoms used for the production of (b13) is a linear or branched aliphatic dihydric alcohol having 2 to 12 carbon atoms [ethylene glycol, 1,3-propylene glycol, 1,4-butane. Diol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-dodecanediol, diethylene glycol, triethylene glycol, Linear alcohols such as tetraethylene glycol; 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- Branched alcohols such as heptanediol, 2-methyl-1,8-octanediol, 3-methyl-1,8-octanediol and 4-methyloctanediol]; alicyclic dihydric alcohols having 6 to 20 carbon atoms [ 1,4-cyclohexanediol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanediol, 1,3-cyclopentanediol, 1,4-cycloheptanediol, 2,5-bis (hydroxymethyl) -1, 4-dioxane, 2,7-norbornanediol, tetrahydrofuran dimethanol, 1,4-bis (hydroxyethoxy) silane Hexane, 1,4-bis (hydroxymethyl) cyclohexane, 2,2-bis (4-hydroxycyclohexyl) propane, and the like]; an aromatic ring-containing dihydric alcohol having 8 to 20 carbon atoms [m- or p-xylylene glycol, Bis (hydroxyethyl) benzene and bis (hydroxyethoxy) benzene, etc.]; trivalent alcohols having 3 to 20 carbon atoms [aliphatic triols (such as glycerin and trimethylolpropane)]; 4 to 8 valences having 5 to 20 carbon atoms Alcohol [aliphatic polyol (pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin, dipentaerythritol, etc.); saccharide (sucrose, glucose, mannose, fructose, methylglucoside and derivatives thereof)], and the like.

  The polycarbonate diol (b13) includes an amorphous polycarbonate diol (b131) having a melting point of 20 ° C. or lower and a crystalline polycarbonate diol (b132) having a melting point higher than 20 ° C.

  The amorphous polycarbonate diol (b131) having a melting point of 20 ° C. or lower uses, for example, a dihydric alcohol or alicyclic dihydric alcohol having a branched structure as the polyhydric alcohol having 2 to 20 carbon atoms, or two or more kinds thereof. It is manufactured by using together the dihydric alcohol.

Among (b1), from the viewpoint of the dyeability and mechanical properties of the polyurethane resin, a number average molecular weight of 600 or more and 4,000 or less [hereinafter abbreviated as Mn, by gel permeation chromatography (GPC) method; And more preferably those having Mn of 500 or more and 2,000 or less. Among such Mn diols, polyalkylene glycol and polycarbonate diol are preferable from the viewpoint of dyeability and mechanical properties of the polyurethane resin, and more preferable are polycarbonate diols represented by the general formula (5) [wherein R Are the same or plural kinds of aliphatic hydrocarbon groups or alicyclic hydrocarbon groups having 4 to 12 carbon atoms, and n is an integer of 2 to 50. ].

The anionic diol (B) for the dyeable urethane resin is obtained by reacting the dicarboxylic acid (a1) component [dicarboxylic acid or its ester-forming derivative, the same applies hereinafter] with the diol (b1) in an inert solvent. It can be produced by (esterification or transesterification). Ester-forming derivatives include di-lower alkyl (C1-4) esters of (a1) (eg methyl, ethyl, n- and i-isopropyl and n-, i-, sec- and t-butyl esters), acid anhydrides Products and acid halides (eg acid chloride). From the viewpoint of reactivity, dialkyl (C1-2) esters, particularly dimethyl esters are preferred. Of these, from the viewpoint of dyeability of the polyurethane resin, dimethyl sulfobenzenedicarboxylate (particularly dimethyl 5-sulfoisophthalate) and its sulfonic acid salt are preferred, and metal salts, particularly alkali metal salts are preferred.

The molar ratio of component (b1) / (a1) is preferably at least 1.8 / 1, more preferably at least 1.9 / 1, especially at least 2.0 / 1 from the viewpoint of reaction rate; From this point, it is preferably at most 3/1, more preferably at most 2.9 / 1, particularly at most 2.8 / 1.

The inert solvent dissolves the protonic acid group-containing dicarboxylic acid (a1) component, the diol (b1) and the anionic diol (B) for the dyeable urethane resin without participating in the reaction (esterification or transesterification). If it is, it will not specifically limit, The 1 type, or 2 or more types of mixture of the organic solvent (C21) mentioned later is mentioned. When used as a polyol component for forming a polyurethane, amide solvents [dimethylformamide and dimethylacetamide (hereinafter abbreviated as DMF and DMAc, respectively), and N-alkyl ( C1-3: methyl, ethyl, n- and i-propyl) -2-pyrrolidone], more preferably DMF and DMAc. The ratio of the solvent / (a1) component is usually 3/1 to 10/1, and preferably 4/1 to 7/1 from the viewpoint of the viscosity of the solution. The ratio of solvent / [(a1) component + (b1)] is usually 2/1 to 9/1, preferably 3/1 to 7/1. Above and below, ratios, parts and percentages represent weight ratios, parts by weight and percentages by weight, respectively, unless otherwise specified.

The reaction between component (a1) and (b1) is carried out in the presence or absence of a catalyst. As the catalyst, an ordinary esterification or transesterification catalyst can be used. For example the group consisting of alkali metals (eg sodium and potassium), alkaline earth metals (eg magnesium and calcium), group IIB (eg zinc and cadmium), group VIIB (eg manganese) and group VIII (eg iron, cobalt and nickel) And organic acid (C2-8 carboxylic acids such as acetic acid, propionic acid, octanoic acid and maleic acid) salts selected from Of these, acetates are preferred from the viewpoint of reaction rate and coloring, and more preferred are group VIIB metal acetates, especially manganese acetate.
From the viewpoint of reaction rate and coloring, the catalyst is preferably used in an amount of 0.01 to 5%, particularly 0.03 to 3%, based on the weight of (b1).

The reaction between the protonic acid group-containing dicarboxylic acid (a1) component and the diol (b1) is carried out under normal esterification or transesterification conditions, for example, at a temperature of 110 to 190 ° C. under normal pressure or reduced pressure (0.098 to 0). 0.001 MPa) can be carried out by removing water or alcohol produced by esterification or transesterification.

By reacting (a1) component and (b1) in an inert solvent (esterification or transesterification), (B) having a low content of unreacted (b1) can be produced. The content of unreacted (b1) is preferably 4% or less, particularly 3% or less, based on the weight of (B).

The dyeable urethane resin (U) of the present invention includes an anionic diol (B) for a dyeable urethane resin and a compound containing a polyol composition (P) containing an active hydrogen compound (C1) other than (B). It is obtained by reacting an isocyanate compound (J).

Examples of the active hydrogen compound (C1) other than (B) include a high molecular polyol (C11), a low molecular polyol (C12), and other active H compounds (C13).
The polymer polyol (C11) has an OH equivalent (molecular weight per hydroxyl group based on hydroxyl value) of at least 250, preferably 250 to 3,000, more preferably 350 to 2,500, particularly 400 to 2,000. (C11) usually has a Mn of 500 to 5,000 or more, preferably 700 to 4,500, especially 900 to 4,000; preferably 6,000 or less, especially 700 to 4,000. It has a molecular weight (hereinafter abbreviated as Mw, according to GPC method; the same applies hereinafter). (C11) has 2 to 8 or more, preferably 2 to 3, particularly 2 hydroxyl groups. (C11) includes at least one of the following (C111) to (C115). Of these, (C111) and (C112) are preferred.

(C111) Polyether polyol (C111) includes at least two (2 to 8 or more) active hydrogen atoms as an initiator and one or more of AO (for example, EO, PO and THF). A compound having a structure to which (random and / or block) is added, and a mixture of two or more of these are included. The initiator includes a polyfunctional active H compound [a compound having two or more active hydrogen atom-containing groups (for example, a hydroxyl group, an amino group, a carboxyl group and / or a mercapto group)], and a primary monoamine; Examples include polyhydric alcohols, polyhydric phenols, amines, polycarboxylic acids, and hydroxycarboxylic acids.

Examples of the polyhydric alcohol include dihydric alcohols such as the hydrocarbon diol of (b11) and (b12) (poly) oxyalkylene diol and (b13) polycarbonate diol; and trivalent or higher (trivalent to octavalent or More) polyols such as (cyclo) alkane polyols and their intramolecular or intermolecular dehydrates [eg glycerin, trimethylolpropane, 1,2,6-hexanetriol, cyclohexanetriol, pentaerythritol, sorbitol, mannitol, sorbitan , Diglycerin and other polyglycerins and dipentaerythritol], sugars and their derivatives (glycosides) (eg sucrose, glucose, fructose, mannose, lactose and methylglucoside) It is.

Polyhydric phenols include dihydric phenols such as monocyclic dihydric phenols (eg hydroquinone, catechol and resorcin), and bisphenols (eg bisphenol A, bisphenol F, bisphenol C and bisphenol S), and trihydric or higher polyhydric phenols. For example, monocyclic phenols (eg pyrogallol and phloroglucin) and formaldehyde low condensates of monohydric phenols (eg phenol) (eg novolac resins and resole intermediates). Examples of the polycarboxylic acid and hydroxycarboxylic acid include those listed as the raw material of (C112) described later.

Amines include primary monoamines, alkanolamines and polyamines.
Primary monoamines include monohydrocarbyl amines such as C1-20 aliphatic, cycloaliphatic, araliphatic and aromatic monoamines [monoalkylamines (eg methyl, ethyl, n-butyl and octylamine), cyclohexylamines. , Benzylamine, arylamine (eg aniline, toluidine and naphthylamine)]; alkanolamines [mono-, di- and tri-alkanolamines (C2-4 of hydroxyalkyl groups), eg mono-, di- and tri- Ethanolamine].

Polyamines include diamines and polyamines having from 3 to 5 or more primary and / or secondary amino groups, such as aliphatic, cycloaliphatic, araliphatic and aromatic polyamines [see below, for example. Polyamines corresponding to (B1) (isocyanate groups replaced by amino groups) (eg ethylenediamine, hexamethylenediamine, isophoronediamine, dicyclohexylmethanediamine, xylylenediamine, tolylenediamine and diethyltolylenediamine), and poly Alkylene (C2-4) polyamines (for example, diethylenetriamine and triethylenetetraamine)], heterocyclic polyamines, for example, those described in JP-B No. 55-21044 [for example, piperazine, aminoalkyl (C2-6) piperazine (for example, aminoethyl) Piperazine) and 1,4-diaminoalkyl (C2-6) piperazine (eg 1,4-diaminoethylpiperazine)]; partial alkyl substituents of these polyamines [eg N-alkyl (C1-4) of diamines (eg ethylenediamine) ) Substituents and N, N- or N, N′-dialkyl (C1-4) Substituents].

Specific examples of (C111) include polyether diols such as polyalkylene glycol [eg PEG, PPG, PTMG, poly-3-methyltetramethylene ether glycol, copolymer polyalkylene ether diol [THF / EO copolymer diol and THF / MTHF copolymer diol] (copolymerization ratio, for example, 1/9 to 9/1)], aromatic ring-containing polyoxyalkylene diol [polyoxyalkylene bisphenol A (such as EO and / or PO adduct of bisphenol A)] And tri- or more functional polyether polyols such as polyoxypropylene triol [eg PO addition of glycerin]; and one or more of these coupled with alkylene dihalide (C1-4) (eg 2 Ether polio Which was coupled with methylene dichloride Le) and the like. Of these, polyether diols, particularly PTMG, are preferred.

(C112) The polyester polyol (C112) includes at least one of the following (C1121) to (C1124).
(C1121) Condensed polyester polyol (C1121) has a structure in which a polyol (a diol and, if necessary, a trivalent or higher polyol) and a polycarboxylic acid (a dicarboxylic acid and, if necessary, a trivalent or higher polycarboxylic acid) are (heavy) condensed. And a mixture of two or more thereof. (C1121) is obtained by condensation of a polyol with a polycarboxylic acid (dicarboxylic acid and, if necessary, a trivalent or higher polycarboxylic acid) or an ester-forming derivative thereof, or by reacting a polyol with a polycarboxylic acid anhydride and AO. Can be manufactured.

As the polyol, a low molecular polyol and / or a polyether polyol can be used. Examples of the low-molecular polyol include a low-molecular diol and a combination of this with a low proportion (for example, 10 equivalent% or less) of a tri- or higher-valent low molecular polyol. Examples of the low molecular weight diol include the above-mentioned hydrocarbon diols (a21) (eg, EG, 1,4-butanediol and 1,6-hexanediol), (a221) monooxyalkylene diols (eg, diethylene glycol) and ( a222) dihydroxyalkyl monohydrocarbylamine (for example, N-methyldiethanolamine); as a tri- or higher valent low molecular polyol, for example, the polyhydric alcohol (for example, glycerin, trimethylolpropane) mentioned as the initiator of (C111), And amine-based polyols [N-hydroxyalkyl substituted polyamines listed as initiators of (C111), such as tetrakis (hydroxypropyl) ethylenediamine, and trialkanolamines such as triethanolamine As the polyether polyol, a ring-opening polymer of AO having an OH equivalent of 500 or less and an AO adduct of the polyfunctional active H compound or primary monoamine mentioned in (C111), such as polyoxyethylene polyol (for example, PEG), polyoxypropylene polyol (eg PPG), polyoxytetramethylene polyol (eg PTMG), PO and / or EO adducts of bisphenol A.

As the polycarboxylic acid, dicarboxylic acid, and a dicarboxylic acid and a small proportion (for example, 10 equivalent% or less) of 3 to 4 or more polycarboxylic acid can be used. Examples thereof include C2-12 saturated and unsaturated aliphatic polycarboxylic acids, such as saturated dicarboxylic acids (eg succinic, adipine, azelain, sebatin and dodecanedicarboxylic acid), unsaturated dicarboxylic acids (eg malee, fumar and Itaconic acid), tricarboxylic acids (e.g. hexane tricarboxylic acid); C8-15 aromatic polycarboxylic acids such as dicarboxylic acids (e.g. terephthalic, isophthalic and phthalic acids), tri- and tetra-carboxylic acids (e.g. trimellitic and pyromellitic) Acid); and C6-40 alicyclic polycarboxylic acids (eg, dimer acid). The ester-forming derivatives include acid anhydrides, lower alkyl (C1-4) esters, and acid halides (eg, acid chloride).

(C1122) The polylactone polyol (C1122) includes a compound having a structure in which a lactone (C4-15) is subjected to ring-opening polymerization using a polyol as an initiator, and a mixture of two or more thereof. (C1122) can be produced by ring-opening polymerization of a lactone to a polyol or by condensation of a polyol and a hydroxycarboxylic acid. Lactones include those of C4-15, such as ε-caprolactone, γ-butyrolactone and γ-valerolactone. Examples of the hydroxycarboxylic acid include those having 3 to 15 carbon atoms, such as those corresponding to the above-mentioned lactone (opened) (for example, hydroxycaproic acid), lactic acid, m-, p- and o-hydroxybenzoic acid. As the polyol, a low molecular polyol and / or a polyether polyol can be used; they have a low molecular diol and / or a low molecular polyol having a valence of 3 or more mentioned in the above (C1121), and an OH equivalent of 500 or less. Polyether polyols (diols and / or trivalent or higher polyols) are included.

(C1123) Polycarbonate polyol (C1123) is polyol and alkylene (C2-4) carbonate (eg ethylene carbonate) or lower dialkyl (C1-4) carbonate carbonate (eg dimethyl carbonate, diethyl carbonate and di-i-propyl carbonate) It can be obtained by reaction with (condensation) or diphenyl carbonate (transesterification). As the polyol used in these productions, the same low molecular polyol and / or polyether polyol as in the above (C1122) can be used.

(C1124) Castor oil-based polyol (C1124) includes castor oil (ricinoleic acid triglyceride) and transesterification products thereof. The latter is obtained by transesterification between castor oil and a polyol, and as the polyol, the same low molecular polyol and / or polyether polyol as in (C1122) can be used.

(C113) Polybutadiene-based polyol (C113) includes polybutadiene polyol and hydrogenated products thereof. Polybutadiene polyols include, for example, homopolymers and copolymers of butadiene having a hydroxyl group at the end [for example, butadiene / styrene copolymer and butadiene / acrylonitrile copolymer] (copolymerization ratio, 100/0 to 70/30), polybutadiene structure having 1,2- Those having a vinyl structure, those having a 1,4-trans structure, those having a 1,4-cis structure, and those having two or more of these structures [preferably 1,2-vinyl / 1,4-trans / 1 , 4-cis ratio (10-30) / (50-70) / (10-30)]. The hydrogenated product includes those having a hydrogenation rate of 20 to 100%.

(C114) Acrylic polyol Acrylic polyol (C114) is obtained by introducing a hydroxyl group into an acrylic copolymer [alkyl (C1-20) (meth) acrylate or a copolymer of these and another monomer (for example, styrene)]. Hydroxyethyl (meth) acrylate is mainly used for introducing a hydroxyl group.

(C115) Polymer polyol (C115) includes those obtained by polymerizing vinyl monomers in situ in polyol and those obtained by grafting a polymer of polyol and vinyl monomer (preferably the former The polymer content is, for example, 5 to 70%. As the polyol, for example, the above (C111) and / or (C112), and a mixture (mixing ratio, for example, 100/0 to 20/80) of one or more of these with the low molecular polyol can be used.
Vinyl monomers include acrylic monomers [eg (meth) acrylonitrile and alkyl (C1-20) (meth) acrylate (eg methyl methacrylate)], aromatic vinyl monomers (eg styrene etc.), aliphatic hydrocarbon monomers [eg C2 -8 or more alkenes and alkadienes (eg α-olefins and butadienes)], and combinations of two or more of these [eg acrylonitrile / styrene combinations (copolymerization ratio 100 / 0-20 / 80)]. .

(C12) includes a low molecular diol having a OH equivalent of less than 250 and a low molecular polyol having a valence of 3 or more (from 3 to 8 or more). (C12) includes the low molecular diol and / or trivalent or higher molecular weight polyol (for example, dihydric alcohol and trihydric or higher polyhydric alcohol, dihydroxyalkyl monohydrocarbylamine and amine-based polyol mentioned in the above (C1121). ), And polyether polyols having a OH equivalent weight of less than 250 (diols and / or trivalent or higher polyols) [these polyols or initiators described in (C111) (for example, polyhydric alcohols, polyhydric phenols and amines) A polyether polyol having a structure in which one or more of AO are added can be used.

Other active H compounds (C13) include polyamine (C131), amino alcohol (C132), and monofunctional active H compound (C133). (C131) includes aliphatic, cycloaliphatic, araliphatic and aromatic polyamines, and heterocyclic polyamines listed as initiators for (C111); and polyether polyamines such as polyols [the above low molecular polyols ( C12) and / or polyether polyol (C111)] (poly (aminopropyl ether)) (obtained by cyanoethylating and hydrogenating the hydroxyl group of the polyol); these include equivalents of 250 to 3,000 or more ( High molecular polyamines (C1311) having a molecular weight per primary and secondary amino groups (based on primary and secondary amine values) and low molecular polyamines (C1312) having an equivalent weight of less than 250 are included. These polyamines are used in a form in which the amino group is blocked (for example, a ketimine-blocked or aldimine-blocked form as described in JP-A No. 54-118466: for example, a methylethylketiminated form). May be. (C132) includes mono- and dialkanolamines (C2-4 of hydroxyalkyl groups), such as monoethanolamine and diethanolamine; and hydrocarbyl (C1-10) alkanolamines (C2-4 of hydroxyalkyl groups), For example, ethylethanolamine and butylethanolamine are included.

(C133) includes the compounds having one active hydrogen atom-containing group described above, for example, a monofunctional amino compound (C1331) and a monofunctional hydroxyl compound (C1332). (C1331) includes monofunctional primary amino compounds, for example, monohydrocarbyl (C1-20, preferably C1-4; hereinafter the same) amine (for example, butylamine) as an initiator of the above (C111), and tertiary amino group Containing primary amino compound [in which a part of the amino group of (C131) (with one amino group remaining) is tertiaryized (dihydrocarbylated), for example, aliphatic, alicyclic, aromatic N, N-dihydrocarbyl substituents of aliphatic and aromatic diamines (eg, N, N-dimethylaminoethylamine)]; and monofunctional secondary amino compounds, eg, primary amino groups of the above compounds are secondary ( Hydrocarbylated) [eg N, N, N′-tos of dihydrocarbylamine (eg dibutylamine), aliphatic, cycloaliphatic, araliphatic and aromatic diamines Hydrocarbyl substituted derivatives (N, N-dimethylaminoethyl methylamine) include. (C1332) includes hydrocarbyl alcohols [C1-20 aliphatic, alicyclic and aromatic monohydric alcohols such as alkanols (eg methyl, ethyl, n- and i-propyl and butyl alcohol), cycloalkanols (For example, cyclohexyl alcohol), and benzyl alcohol; and tertiary amino group-containing monohydric alcohols, such as dihydrocarbylalkanolamines [hydroxyalkyl (C2-4) substitutions of the above dihydrocarbylamines (for example, diethylethanolamine and Dibutylethanolamine)], and AO adducts thereof (addition moles 1-5 or more).

In the present invention, the active hydrogen compound (C1) other than (B) is 0 to 95 mol% with respect to the anionic diol (B) for the dyeable urethane resin, from the viewpoint of the dyeability and mechanical properties of the polyurethane resin. Especially preferably, it contains in the ratio of 30-90 mol%. The content ratio of (B) can be appropriately selected according to the use of the polyurethane resin and the required performance.

The anionic diol (B) for dyeable urethane resins of the present invention can be used as a dyeability imparting agent for resins such as polyurethane resins and polyester resins.

[Polyol composition (P)]
The polyol composition (P) of the present invention comprising an anionic diol (B) for dyeable urethane resin and an active hydrogen compound (C1) other than (B) is used for forming a polyurethane, that is, a polyol composition (P ) And the polyisocyanate component (J) are used to produce a polyurethane resin.
The polyol composition (P) according to another embodiment of the present invention comprises the above (B) and the active hydrogen compound (C1) other than the above (B) and / or (B). As the blending component (C2), an organic solvent (C21) and / or an additive (C22) are used.

The organic solvent (C21) is not particularly limited as long as it does not react with an isocyanate group under the conditions of polyurethane formation and dissolves (B) and (C1). (C21) includes dimethylformamide (hereinafter abbreviated as DMF) and a solvent having no active hydrogen atom. The latter includes other amide solvents [for example, dimethylacetamide (hereinafter abbreviated as DMAc), and N-alkyl (C1-3) -2-pyrrolidone (for example, N-methyl-2-pyrrolidone)], ester solvents (for example, Ethyl acetate and butyl acetate), 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), as well as mixtures of two or more thereof. From the viewpoint of reactivity during polyurethane production and solubility of the polyurethane resin, amide solvents are preferred, and DMAc and DMF are more preferred. The amount of the solvent is usually 3 to 10 times based on the weight of (B) [or the total weight of (B) and (C1)], and preferably 4 to 7 times from the viewpoint of the viscosity of the solution.

As the additive (C22), those usually used for polyurethane production can be used. (C22) includes stabilizer (C221) [e.g. antioxidant (C2211), UV absorber (C2212), hydrolysis inhibitor (C2213) and antibacterial / antifungal agent (C2214)]; filling / coloring agent (C222) [eg filler (C2221) and colorant (C2222)], flame retardant / plastic / release agent (C223) [eg flame retardant (C2231), plasticizer (C2232) and release agent (C2233)] , Surfactant (C224) [e.g. antistatic agent (C2241), emulsification (C2242) and foam stabilizer (C2243)], dispersant (C225), catalyst (C226) and blowing agent (C227), and 2 of these A combination of more than one species is included.

Examples of the antioxidant (C2211) include hindered phenols [for example, 2,6-di-t-butyl-p-cresol (BHT) and 2,2′-methylenebis (4-methyl-6-t-butylphenol). ], Sulfur-based [eg dilauryl 3,3′-thiodipropionate (DLTDP) and distearyl 3,3′-thiodipropionate (DSTDP)], phosphorus-based [eg triphenyl phosphite (TPP) and triiso Decyl phosphite (TDP)] and amines [for example octyl diphenylamine, Nn-butyl-p-aminophenol and N, N-diisopropyl-p-phenylenediamine].

Examples of the ultraviolet absorber (C2212) include benzophenone (for example, 2-hydroxybenzophenone and 2,4-dihydroxybenzophenone), salicylate (for example, phenyl salicylate and 2,4-di-t-butylphenyl-3,5). -Di-t-butyl-4-hydroxybenzoate), benzotriazoles [eg (2'-hydroxyphenyl) benzotriazole and (2'-hydroxy-5'-methylphenyl) benzotriazole], acrylics [eg ethyl- 2-cyano-3,3′-diphenyl acrylate and methyl-2-carbomethoxy-3- (paramethoxybenzyl) acrylate]. Examples of the hydrolysis inhibitor (C2213) include carbodiimides (stavaxol 1, PCD, etc.), 4-t-butylcatechol, azodicarbonamid, azodicarboxylate and fatty acid amide.

Examples of the antibacterial / antifungal agent (C2214) include benzoic acid, paraoxybenzoic acid ester, sorbic acid, halogenated phenol (for example, 2,4,6-tribromophenol sodium salt, 2,4,6-trichlorophenol sodium salt) , Parachlorometaxylenol, pentachlorophenol and pentachlorophenol laurate), organic iodine (eg 4-chlorophenyl-3-iodopropargyl formal, 5-chloro-2-methyl-4-isothiazolin-3-one and 2- Methyl-4-isothiazolin-3-one), nitriles (eg 2,4,5,6-tetrachloroisophthalonitrile), thiocyano (eg methylene bisthianocyanate), N-haloalkylthioimides (eg N-tetrachloroethyl- Thio-tetrahydr Phthalimide and N-trichloromethyl-thio-phthalimide), copper agent (eg 8-oxyquinoline copper), benzimidazole (eg 2-4-thiazolylbenzimidazole), benzothiazole (eg 2-thiocyanomethylthiobenzothiazole) , Trihaloallyl (for example, 3-bromo-2,3-diiodo-2-propenylethyl carbonate), triazole (for example, azaconazole), and organic nitrogen sulfur compound (for example, Suraoff 39).

Examples of the filler (C2221) include metal powders (for example, aluminum powder and copper powder), metal oxides (for example, alumina, wollastonite, silica, talc, mica, leechite, kaolin clay, calcined kaolin and clay), metal Hydroxide (eg, aluminum hydroxide), metal sulfide (eg, molybdenum disulfide), metal salt (eg, calcium carbonate, calcium silicate, barium sulfate and barite), fiber [eg, inorganic fiber [eg, carbon fiber, fiber, α-fibrin, glass fibers, metal (eg aluminum) fibers, ceramic whiskers, titanium whiskers and asbestos] and organic fibers (eg cotton, jute, nylon, acrylic and rayon fibers), microballoons (eg glass, shirasu and phenol) Resin balloon), carbon ( In example carbon black, graphite and carbon nanotubes), an organic powder (e.g. wood powder), mineral powders (e.g. coal powder) and the like.

As the colorant (C2222), pigments such as inorganic pigments [eg white pigments (eg titanium oxide, lithopone, lead white and zinc white), cobalt compounds (eg aureolin, cobalt green, cerulean blue, cobalt blue and cobalt violet), Iron compounds (eg Bengala and bitumen), chromium compounds (eg chromium oxide, chrome lead and barium chromate) and sulfides (eg cadmium sulfide, cadmium yellow and ultramarine)] and organic pigments [eg azo pigments (eg azo lakes, monoazo, Disazo and chelate azo pigments) and polycyclic pigments (eg, benzimidazoline, phthalocyanine, quinacridone, dioxazine, isoindolinone, thioindigo, perylene, quinophthalone and anthraquinone pigments); Fee, such as azo, anthraquinone, indigoid, sulfide, triphenylmethane, pyrazolone, stilbene, diphenylmethane, xanthene, alizarin, acridine, quinoneimine, thiazole, methine, nitro, and nitroso and aniline dyes.

Examples of the flame retardant (C2231) include organic [phosphorus-containing [for example, phosphate esters (for example, tricresyl phosphate and tris (2,3 dibromopropyl) phosphate)], bromine-containing (for example, tetrabromobisphenol A and decabromo). Biphenyl ether) and chlorine-containing [eg chlorinated paraffin and (anhydrous) hetic acid] and inorganic [eg antimony trioxide, borates (eg zinc borate and barium metaborate), aluminum hydroxide, red phosphorus, Magnesium hydroxide and ammonium polyphosphate].

Examples of the plasticizer (C2232) include monocarboxylic acid esters [C10-30, such as fatty acid esters [for example, butyl stearate (BS), methoxyethyl oleate (MEO), methyl acetylricinoleate (MAR), ethyl acetylricinoleate). (EAR), methoxyethyl acetylricinoleate (MEAR) and glycerin triheptanoic acid ester] and aromatic carboxylic acid esters [C18-30, such as diEG dibenzoate and triEG dibenzoate]]; dicarboxylic acid esters {eg aromatic Dicarboxylic acid esters [C10-40, such as phthalic acid esters [eg, dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP), heptylnonyl phthalate (HNP), di-2 phthalate] Ethylhexyl (DOP), di-n-octyl phthalate (DNOP), di-i-octyl phthalate (DIOP), di-s-octyl phthalate (DCapP), di (79 alkyl) phthalate (D79P), phthalate Acid-i-decyl (DIDP), ditridecyl phthalate (DTDP), dicyclohexyl phthalate (DCHP), butyl benzyl phthalate (BBP), ethyl phthalyl ethyl glycolate (EPEG) and butyl phthalyl butyl glycolate (BPBG) ] And aliphatic dicarboxylic acid esters [C10-40, eg adipic acid esters [eg di-2-ethylhexyl adipate (DOA), diisodecyl adipate (DIDA) and di (methylcyclohexyl) adipate]], azelaic acid esters [ For example, azelaic acid -N-hexyl (DNHZ) and di-2-ethylhexyl azelate (DOZ)] and sebacic acid esters [eg dibutyl sebacate (DBS) and di-2-ethylhexyl sebacate (DOS)]]}; tricarboxylic acid esters { For example, aliphatic tricarboxylic acid ester [C9-60, such as citrate ester [for example, triethyl citrate (TEC), tributyl citrate (TBC), triethyl citrate (ATEC), acetyl tributyl citrate (ATBC), acetyl citrate] Epoxide [C10-40, such as epoxidized soybean oil (ESO) and 4,5-epoxycyclohexane-1,2-dicarboxylate di-2-] Ethylhe Xyl (E-PS)]; phosphate esters [C10-30, such as tributyl phosphate (TBP), triphenyl phosphate (TPP), tricresyl phosphate (TCP), diphenyl monocresyl phosphate, phosphate-2 -Ethylhexyldiphenyl, tripropylene glycol phosphate, tributoxyethyl phosphate, trichloroethyl phosphate, triethyl phosphate and trixyl phosphate]; chlorinated hydrocarbons [C10-30, eg aromatic hydrocarbons (eg chlorinated naphthalene) And chlorinated diphenyl) and chlorinated paraffins] and petroleum resins.

Examples of the release agent (C2233) (lubricant) include liquid paraffin, hardened oil, wax (for example, carnauba wax, whale wax, ibota wax, montan wax and beeswax), alcohol (C12-20, for example, cetyl alcohol and stearyl alcohol). ), Fatty acids (eg stearic acid), fatty acid esters (C16-36, eg butyl stearate, cetyl stearate, EG monostearate and methylhydroxystearate), fatty acid amides (C12-24, eg palmitic acid amide, ricinoleic acid) Amides, stearic acid amides, oleic acid amides and erucic acid amides), fatty acid metal salts such as calcium stearate, lead stearate and barium stearate.

Antistatic agents (C2241) include surfactant type antistatic agents, for example, cationic surfactants described in US Pat. No. 4,331,447 [for example, alkyl (C8-20, the same applies hereinafter) trimethylammonium salt, dialkyl Dimethylammonium salts and alkyldimethylbenzylammonium salts], amphoteric surfactant surfactants [eg betaine type such as alkyldimethylbetaine, and alanine type such as N-alkyl-β-aminopropionate], anionic surfactants [eg Sulfuric acid ester salts such as alkyl sulfuric acid ester salts and polyoxyalkylene (C2-4, the same shall apply hereinafter) alkyl ether sulfuric acid ester salts; Sulfonate salts, such as dialkylsulfosuccinates and alkylbenzene sulfonates; and carboxylate salts, such as alkyl (polyoxyalkylene) ether carboxylates and soaps; and nonionic surfactants [eg poly Fatty acid (C8-20) esters of oxyethylene types, such as polyoxyethylene alkyl ethers, and polyhydric alcohol types such as polyhydric alcohols [described in (C111) initiators: sorbitan, etc.), and alkylolamide types, Fatty acids (C8-20) mono- and di-ethanolamides]; and polymeric antistatic agents (Mn 5,000-50,000) [eg polyether ester amides (eg US Pat. No. 5,652,326) Included in the document)].

Surfactants as emulsifiers (C2242) include nonionic, cationic, anionic and amphoteric surfactants as described below and in US Pat. Nos. 3,929,678 and 4,331,447 Agent is included.
1) Nonionic surfactant:
AO-added nonionics such as active hydrogen atom-containing compounds having hydrophobic groups (C8-24 or higher) [saturated and unsaturated, higher alcohols (C8-18), higher aliphatic amines (C8-24) and Higher fatty acids (C8-24) etc .: for example alkyl or alkenyl (eg dodecyl, stearyl, oleyl) alcohol and amine, and alkane or alkenoic acid (eg laurin, stearin and oleic acid)] (poly) oxyalkylene derivatives [AO ( C2-4, such as EO, PO, butylene oxide and combinations of two or more thereof, particularly EO (1 to 500 moles or more) adducts (molecular weight 174 to Mn30,000), and polyalkylene glycols (such as PEG ; Molecular weight 150-Mn6,000) Higher fatty acid mono- and di-esters]; higher fatty acid (above) esters of polyhydric alcohols (divalent to octavalent or higher, such as ethylene glycol, glycerin, trimethylolpropane, pentaerythritol, sorbitan and sucrose) Poly) oxyalkylene derivatives (same as above; molecular weight 320 to Mn 30,000; for example, Tween-type nonionics); (poly) oxyalkylene derivatives of (alkanol) amides of higher fatty acids (above) (same as above; molecular weight 330 to Mn 30,000); (Poly) oxyalkylene derivatives of polyhydric alcohol (above) alkyl (C3-60) ether (same as above; molecular weight 180-Mn30,000); and polyoxypropylene polyol [polyhydric alcohol (above) and polyamine [above (C111) The start of the The polyoxypropylene derivative (for example, PPG and ethylenediamine PO adduct; Mn 500 to 5,000)] of the polyoxypropylene derivative (for example, PPG and ethylenediamine PO adducts) [Pluronic and Tetronic nonionics] Polyhydric alcohol (C3-60) type nonionics, for example, fatty acid (C8-20) ester of polyhydric alcohol (above), polyhydric alcohol (above) alkyl (C3-60) ether, and fatty acid (above) alkanol Amides; and amine oxide type nonionics such as (hydroxy) alkyl (C10-18: dodecyl, stearyl, oleyl, 2-hydroxydodecyl, etc.) di (hydroxy) alkyl (C1-3: methyl, ethyl, 2-hydroxyethyl) Etc.) Amineoxy .

2) Cationic surfactant:
Quaternary ammonium salt type cationics, for example, tetraalkylammonium salts (C11-100), such as alkyl (C8-18: lauryl, stearyl, etc.) trimethylammonium salts and dialkyl (C8-18: decyl, octyl, etc.) dimethylammonium Salt; trialkylbenzylammonium salt (C 17-80), such as lauryldimethylbenzylammonium salt; alkyl (C8-60) pyridinium salt, such as cetylpyridinium salt; (poly) oxyalkylene (C2-4, degree of polymerization 1-100) Or more) trialkylammonium salts (C12-100), such as polyoxyethylene lauryldimethylammonium salts; and acyl (C8-18) aminoalkyl (C2-4) or acyl (C8-18) oxy Alkyl (C2-4) tri [(hydroxy) alkyl (C1-4)] ammonium salts, such as stearamide ethyl diethylmethylammonium salts (sapamine-type quaternary ammonium salts) [these salts include, for example, halides (eg, chloride and Bromide), alkyl sulfates (eg, methosulfate) and salts of organic acids (described below); and amine salt-type cationics: primary to tertiary amines [eg higher aliphatic amines (C1 2-60: lauryl, stearyl). And cetylamine, hardened beef tallow amine, rosinamine, etc.), polyoxyalkylene derivatives of aliphatic amines (C8-20) (above; EO adducts, etc.), and acylaminoalkyl or acyl (C8-18) oxyalkyldi (hydroxy) ) Alkyl (above) amine For example, stearoyloxyethyldihydroxyethylamine, stearamide ethyldiethylamine), inorganic acids (hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, etc.) and organic acids (C2-22: acetic acid, propion, laurin, olein, succinate, adipine and Azelaic acid, benzoic acid, etc.) salts.

3) Anionic surfactant:
Carboxylic acids (salts), such as higher fatty acids (above), ether carboxylic acids [higher alcohols (above) or AO adducts thereof, such as carboxymethylates of EO (1-10 mol) adducts], and salts thereof; Sulfate ester salts such as sulfates of the above higher alcohols or their AO adducts (alkyl and alkyl ether sulfates, sulfated oils (natural unsaturated oils or unsaturated salts neutralized by sulfation) ), Sulfated fatty acid esters (salts neutralized by sulphating lower fatty acid esters of unsaturated fatty acids) and sulfated olefins (salts neutralized by sulphating C12-18 olefins); sulfonates, eg alkylbenzenes Sulfonate, alkylnaphthalene sulfonate, sulfosuccinic acid dialkyl ester type, -Olefin (C12-18) sulfonate and N-acyl-N-methyltaurine (eg Igepon T-type); and phosphate ester salts such as the higher alcohols or their AO adducts [eg EO (1-10 mol) ) Adducts] or phosphate ester salts of alkyl (C4-60) phenol AO adducts (same as above) (alkyl, alkyl ethers and alkylphenyl ether phosphates).

4) Amphoteric surfactant:
Carboxylic acid (salt) type amphoterics, eg amino acid type amphoterics, eg alkyl (C8-18) aminopropionic acid (salt), and betaine type amphoterics, eg alkyl (same as above) di (hydroxy) Alkyl (above) betaine (alkyldimethylbetaine, alkyldihydroxyethylbetaine, etc.); sulfate ester (salt) type amphoterics, for example, alkyl (same as above) amine sulfate ester (salt), and hydroxyalkyl (C2-4: hydroxy) Ethyl etc.) Imidazoline sulfate ester (salt); Sulfonic acid (salt) type amphoterics, such as alkyl (same as above: pentadecyl etc.) sulfotaurine, and imidazoline sulfonic acid (salt); Foterix, for example glycerin Phosphate ester (salt) of higher fatty acid (above) ester.

Salts in the above anionic and amphoteric surfactants include metal salts such as alkali metals (eg lithium, sodium and potassium), alkaline earth metals (eg calcium and magnesium) and group IIB metals (eg zinc). Ammonium salts; and amine salts and quaternary ammonium salts. The amine constituting the salt includes C1-20 amines such as hydroxylamine [C2-10, eg (di) alkanolamines (eg 2-aminoethanol and diethanolamine), cycloalkanolamines (eg 3-aminomethyl-3 , 5,5-trimethylcyclohexanol) and alkyl alkanolamines (eg methylethanolamine and ethylethanolamine)], tertiary amino group-containing diols and primary monoamines, secondary monoamines (eg dialkylamines and morpholines), and their Alkylation (C1-4) and / or hydroxyalkylation (C2-4) products (AO adducts): eg mono-, di- and tri- (hydroxy) alkyl (amines) (mono-, di- and tri-) Ethanolamine And ethylamine, diethylethanolamine, morpholine, N- methylmorpholine, N- hydroxyethyl morpholine and the like). Quaternary ammonium salts include quaternized products of these amines [quaternizing agents or dialkyl carbonates described in US Pat. No. 4,271,217 (carbonates having a C1-4 alkyl group, such as dimethyl, Quaternized product with diethyl and di-i-propyl carbonate).

The foam stabilizer (C2243) includes silicone surfactants such as polyoxyethylene-modified polydimethylsiloxane.

The dispersant (C225) includes the following.
Water-soluble polymer (Mn: 1,000 to 100,000 or more, preferably 3,000 to 10,000; solubility in water: at least 1 g / 100 g, preferably at least 10 g / 100 g): nonionic water Polymers such as polyvinyl alcohol, polyacrylamide and polyethylene oxide; and anionic water-soluble polymers such as naphthalene sulfonic acid formalin condensates (Mn 1,000 to 10,000); sulfo group-containing monomers [unsaturated sulfonic acids such as alkene sulfones. Alkenyl and alkyl (C1-18) alkenyl esters of acids (eg, vinyl sulfonic acid), unsaturated aromatic sulfonic acids (eg, styrene sulfonic acid), sulfocarboxylic acids (eg, sulfosuccinic acid) (eg, methyl vinyl sulfosuccinic acid) Nate), sulfo (hydroxy) alkyl (meth) acrylate and the corresponding (meth) acrylamide [eg sulfoethyl (meth) acrylate, 2- (meth) acrylamide-2-methylpropanesulfonic acid]] and / or carboxyl group-containing monomer [ Unsaturated mono- and di-carboxylic acids and their anhydrides, such as (meth) acrylic, (iso) croton, cinnamon, (anhydrous) malein, fumar and (anhydrous) itaconic acid; dicarboxylic acid monoesters: dicarboxylic acids as described above Monoalkyl (C1-8 or more) esters of acids, such as maleic, fumaric, itacone and monoalkyl esters of citraconic acid; and salts thereof, such as alkali metal salts, alkaline earth metal salts, ammonium salts, amines (C2 -24) salt and Quaternary ammonium (C4-24) salts] or (co) polymers of these with other monomers such as polystyrene sulfonate (Mn 1,000-100,000), poly (meth) acrylate (Mn 2,000) ˜50,000), (meth) acrylic acid (salt) / alkyl (meth) acrylate copolymers and maleic acid (salt) / vinyl acetate copolymers; and cellulose derivatives such as carboxymethylcellulose. The salts in the anionic polymer include those similar to those in the anionic and amphoteric surfactants [for example, alkali metal (for example, sodium and potassium) salts].

Catalysts (C226) include metal catalysts such as tin-based catalysts (for example trimethyltin laurate, trimethyltin hydroxide, dimethyltin dilaurate, dibutyltin dilaurate and stannous octoate), lead-based catalysts (for example lead oleate, 2 -Lead ethylhexanoate, lead naphthenate and lead octenoate); amine catalysts, eg aliphatic tertiary amines [eg trihydrocarbylamine (triethylamine and dimethylcyclohexylamine), tetrahydrocarbylalkylenediamine (eg tetramethylethylenediamine) And pentahydrocarbyl diethylenetriamine (eg, pentamethyldiethylenetriamine)], and heterocyclic amines [eg, N-methylmorpholine, triethylenediamine, and US Pat. No. 452 104, such as 1,8-diaza-bicyclo (5,4,0) undecene-7 [DBU (registered trademark) manufactured by San Apro Co., Ltd.]]; and two or more of these Combination is included.

Examples of the blowing agent (C227) include water, a physical blowing agent [volatile (low boiling point) liquid], for example, alternative CFC [hydrochlorofluorocarbon (HCFC), for example, R123, R22, R124; hydrofluorocarbon (HFC), for example, R134a. , R125, R32, R152a], and combinations of both.

The addition amount of (C22) can be appropriately selected according to the purpose of addition and the required performance. In general, however, based on the weight of (B) [or the sum of (B) and (C1)] Such an amount is preferred.
Stabilizer (C221) total 10% or less, especially 0.05-5%
Antioxidant (C2211) 5% or less, especially 0.05 to 1%
Ultraviolet absorber (C2212) 5% or less, especially 0.05 to 1%
Hydrolysis inhibitor (C2213) 5% or less, especially 0.05 to 1%
Antibacterial / antifungal agent (C2214) 10% or less, especially 0.01-5%
Filling / coloring agent (C222) total 80% or less, especially 5-70%
Filler (C2221) 80% or less, especially 5-70%
Colorant (C2222) 5% or less, especially 0.1 to 3%
Flame retardant / plastic / release agent (C223) total 30% or less, especially 5-25%
Flame retardant (C2231) 30% or less, especially 5-25%
Plasticizer (C2232) 30% or less, especially 5-20%
Release agent (C2233) 5% or less, especially 0.1 to 2%
Surfactant (C224) total 5% or less, especially 0.1-3%
Antistatic agent (C2241) 5% or less, especially 0.1 to 3%
Emulsifier (C2242) 5% or less, especially 0.1 to 3%
Foam stabilizer (C2243) 5% or less, especially 0.1 to 3%
Dispersant (C225) 5% or less, especially 0.1 to 3%
Catalyst (C226) 5% or less Especially 0.1 to 3%
The foaming agent (C227) is used in an amount that gives a foamed polyurethane resin having a predetermined density (described later).

The content of the compounding component (C2) with respect to (B) constituting the polyol composition (P) is preferably 0 to 1000%, particularly 100 to 500%.
The polyol composition (P) of the present invention preferably has a viscosity (25 ° C.) of 50 to 50,000 mPa · s, particularly 100 to 30,000 mPa · s.

The anionic diol (B) of the present invention is used to produce a dyeable urethane resin (U) by reacting with an isocyanate compound (J). The isocyanate compound (J) comprises an organic polyisocyanate (J1) and / or an isocyanate group-terminated urethane prepolymer (J2). As (J1) and (J2), those conventionally used for polyurethane production can be used. (J1) and (J2) usually have 2 to 5 or more (preferably 2 to 3, particularly 2) isocyanate groups (NCO groups). (J1) includes C (excluding carbon in the NCO group, the same shall apply hereinafter) 2-18 aliphatic polyisocyanate, C4-15 alicyclic polyisocyanate, C8-15 araliphatic polyisocyanate, C6- 20 aromatic polyisocyanates and modified products of these polyisocyanates (for example, modified products having a carbodiimide group, a urethane group, a urea group, an isocyanurate group, a uretoimine group, an allophanate group, a biuret group, an oxazolidone group and / or a uretdione group) ), And mixtures of two or more thereof. Specific examples thereof include the following.

Aliphatic polyisocyanates: diisocyanates such as ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 2,2,4- and / or 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2 , 6-diisocyanatoethyl caproate, bis (2-isocyanatoethyl) fumarate and bis (2-isocyanatoethyl) carbonate; and trifunctional or higher polyisocyanates (eg triisocyanates), eg 1,6,11- Undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate, lysine ester triisocyanate (Phosgenates of the reaction product of lysine and alkanolamine), 2-isocyanatoethyl-2,6-diisocyanatohexanoate, and 2- and / or 3-isocyanatopropyl-2,6- Diisocyanato hexanoate;

Alicyclic polyisocyanates: diisocyanates such as isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, bis (2-isocyanatoethyl) -4- Cyclohexylene-1,2-dicarboxylate and 2,5- and / or 2,6-norbornane diisocyanate; and trifunctional or higher polyisocyanates (eg triisocyanates), such as bicycloheptane triisocyanates; araliphatic polyisocyanates: m- and / or p-xylylene diisocyanate (XDI), diethylbenzene diisocyanate and α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI);

Aromatic polyisocyanates: diisocyanates, such as 1,3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI), 4,4'- and / or 2, 4'-diphenylmethane diisocyanate (MDI), 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanate Natodiphenylmethane and 1,5-naphthylene diisocyanate; and tri- or higher functional polyisocyanates (eg triisocyanates) such as crude TDI, crude MDI (polymethylene polyphenylene polyisocyanate); and modified polyisocyanates: eg modified hydrogenated MDI (carbodiimide modification) Attachment MDI, and trihydrocarbylphosphate preparative modified hydrogenated MDI), biuret-modified HDI, isocyanurate modified HDI and isocyanurate modified IPDI.

In the isocyanate compound (J1), from the viewpoint of mechanical properties of the dyeable urethane resin (U) to be obtained, the carbon number of the residue excluding all isocyanate groups is preferably 6 to 15, particularly preferably 8 to 13. .

The isocyanate group-terminated urethane prepolymer (J2) is derived from the polyol composition (P) and an excess of the above (J1). As (P) used for the production of (J2), an anionic diol (B), a high molecular polyol (C11) and, if necessary, a low molecular polyol (C12) are used. Here, (B), (C11) and (C12) are the same as the above-mentioned anionic diol (B), high molecular polyol (C11) and low molecular polyol (C12), respectively.

(J2) is a combination of an active hydrogen compound (C1) [(C11) and / or (C12)] other than (J1) and (B) with a one-step method or a part of a multi-step method [(C1), for example ( After reacting C11), the remainder of (C1), for example, (C12) is reacted] can be produced by performing a urethanization reaction. The equivalent ratio (NCO / OH ratio) between (J1) and (C1) in the production of (J2) is usually 1.1 to 10, preferably 1.4 to 4, and more preferably 1.4 to 2. is there. Furthermore, (J1) per 0.1 equivalents, 0.1-0.5 equivalents, especially 0.2-0.4 equivalents of (C11) and 0 or 0.01-0.2 equivalents, especially 0.05- It is preferred to use 0.15 equivalents of (C12).

(J2) is generally from 150 to 5,000, preferably from 200 to 4,000, more preferably from 300 to 3,000, particularly preferably from 350 to 2, from the viewpoint of good physical properties (for example, tensile elongation) of polyurethane resin. Having an isocyanate group equivalent of 1,000 (hereinafter abbreviated as NCO equivalent). Preferred among (C1) is (C11) and the combined use of (C11) and (C12) [in such a ratio that the NCO equivalent (average) as a whole falls within the above range].

The method for producing the dyeable urethane resin (U) by reacting the anionic diol (B) and the isocyanate compound (J) of the present invention includes a one-step method (one-shot method) and a two-step method (prepolymer method). The latter includes the semi-prepolymer method and the complete prepolymer method. In the one-step method, an anionic diol (B) or an anionic diol (B) and a component comprising a high molecular polyol (C11) and / or a low molecular polyol (C12) are reacted at the same time as (J) to make the dyeable. There is a method for producing a urethane resin (U).

The two-stage method (prepolymer method) includes 1) a method via an isocyanate-terminated prepolymer and 2) a method via a hydroxy-terminated prepolymer. In the method 1), the polyol composition (P) as described above, that is, an active hydrogen compound other than (B) and (B) (C1) [(C11) and / or (C12) (weight ratio 99/1). ~ 50/50)] and an excess equivalent (NCO / OH ratio) of (J1) is reacted with an isocyanate-terminated prepolymer (semi-prepolymer or complete prepolymer) with a curing agent component comprising an active hydrogen compound. In the production of the polyurethane resin, a method of using (B) as at least a part of the polyol composition (P) and / or as a part of the curing agent component is included.

As the curing agent component, an active hydrogen compound is used, and a low molecular polyfunctional active H compound (chain extender and / or cross-linking agent) and a combination of this with a combination of a reaction terminator are preferred. Low molecular polyfunctional active hydrogen compounds include trivalent or higher molecular weight polyols in (C12) and (C1312), and combinations thereof. (C132) and / or (C133) can be used as the reaction terminator.

The reaction terminator may be contained in the curing agent component [trivalent or higher molecular weight polyol and / or (C1312) in (C12)], and the prepolymer reacts with the curing agent component (chain extension). ) (After reaching a predetermined molecular weight or viscosity), the reaction may be stopped by adding a reaction terminator. Also, in the above method, a composition comprising (C1312) in a blocked form (ketimine-block or aldimine-blocked form) and a prepolymer [formed from (B)] is formed. In addition, after applying to a base material, a polyurethane resin may be produced by heating to regenerate a free amino group and reacting with a prepolymer.

In the method 2), (J1) is reacted with an excess equivalent (OH / NCO ratio 1.1 to 10, preferably 1.4 to 4, particularly 1.4 to 2) of the polyol composition (P). In producing a polyurethane resin by reacting the hydroxy-terminated prepolymer with the component (J) [(J1) and / or (J2)], at least a part of the polyol composition (P) used for the prepolymer production A method using (B) is included.

In the above method, as the component (J), a blocked form (block body) is used, a composition comprising this and the polyol composition (P) is formed, applied to the substrate, and then heated. Then, the free isocyanate group may be regenerated and reacted with (P) to produce a polyurethane resin. Examples of the blocking agent used for forming the block body include phenol, active methylene compound (C—H acid compound), lactam, oxime, sulfite, tertiary alcohol, and secondary aromatic described in US Pat. No. 4,524,104. At least one selected from the group consisting of amine, imide and mercaptan can be used.

In the production of the polyurethane resin (U), in the urethanization reaction between the polyol composition (P) and the isocyanate component (J), the equivalent ratio of NCO / active hydrogen atom-containing group is usually 0.6 / 1 to 1.5 /. 1, preferably 0.8 / 1 to 1.2 / 1. Further, a polyisocyanurate resin can be formed by using isocyanate in a large excess (for example, the equivalent ratio is usually 1.5 / 1 to 50/1 or more).

The urethanization reaction may be performed in the absence of a solvent or in the presence of a solvent inert to the isocyanate group. As the solvent, those similar to the above (C21) can be used.

The reaction temperature for urethanization is usually 30 to 180 ° C, preferably 60 to 120 ° C. In the reaction, a catalyst used in a normal urethane reaction may be used. As the catalyst, one or more of the above (C326) can be used.

The Mn of the polyurethane resin (U) varies depending on the use and type (thermoplastic or thermosetting) of the resin, but in general, Mn of at least 10,000, particularly at least 30,000 is preferred from the viewpoint of resin physical properties and durability. It is preferable to have. The thermoplastic (linear, solvent-soluble) polyurethane resin preferably has a Mn of 80,000 or less, particularly 70,000 or less. Thermosetting (three-dimensional structure, solvent insoluble) polyurethane resins have Mn higher than the above range. (U) preferably has a protonic acid (salt) group content of 0.01 to 7 mmol / g, in particular 0.1 to 5 mmol / g. The soft segment content of (U) [total content of (B) and polymer polyol (C11) having an OH equivalent weight of at least 250 based on the total weight of (B) and (C11)] is preferably 30 ~ 90%, in particular 50-80%.

Moreover, the polyurethane resin (U) can obtain a dyeable film having excellent dyeability and excellent film characteristics by being contained alone or in another film-forming polymer. The proportion of (U) when contained in another film-forming polymer is preferably 10% by weight, more preferably 30% by weight with respect to the weight of the whole polymer from the viewpoint of dyeability and film strength. From the viewpoint of the texture, the upper limit is preferably 80% by weight, more preferably 70% by weight.

Examples of the other film-forming polymer include polyolefin (polyethylene, polypropylene, etc.), polyamide (6-nylon, 6,6-nylon, etc.), polyester (polyethylene terephthalate, polybutylene terephthalate, etc.) and the like.

Synthetic leather etc. are mentioned as a textile product which consists of a film of this invention. Synthetic leather is a form in which a urethane resin is processed into a woven or non-woven fabric, and synthetic leather obtained using the non-woven fabric may be called artificial leather, but the synthetic leather shown here also includes artificial leather. As a method for producing synthetic leather, a conventionally known method may be used, and examples thereof include a dry treatment method and a wet treatment method. As a dry processing method, for example, a polyurethane resin solution in which a foaming agent is added to a base material is coated, and this is heated in a furnace at a high temperature to decompose and foam the foaming agent to form a sponge layer. There is a method of applying a resin solution to form a dense skin layer on the surface. As the wet processing method, for example, a method described in JP-A-54-38996, for example, a method of immersing a substrate coated with a polyurethane resin solution in a coagulation bath, a method of partially coagulating with water vapor and then immersing in a coagulation bath Etc. Examples of the coagulation bath for coagulating the polyurethane resin include non-solvents or poor solvents for polyurethane resins such as water and methanol. Examples of uses of the textile product made of the film include bags, belts, clothing, furniture, and automobile seats.

EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to this.

Example 1
In a reaction vessel equipped with a stirrer, a thermometer and a reflux condenser, 137 parts of 5-sulfoisophthalic acid dimethyl sodium salt, DURANOL T5650E [Mn500, manufactured by Asahi Kasei Chemicals Corporation] and 468 parts of DMF and 600 parts of DMF were further added. .9 parts is added, transesterification is carried out at 140 to 160 ° C., the produced methanol is removed, and a DMF solution of a sulfonic acid group-containing anionic diol (B-1) in a pale yellow liquid at a concentration of 50.2% Got.

Example 2
In a reaction vessel equipped with a stirrer, a thermometer and a reflux condenser, 137 parts of 5-sulfoisophthalic acid dimethyl sodium salt, DURANOL T5652 [Mn2000, manufactured by Asahi Kasei Chemicals Corporation] and 1872 parts of DMF 2000 parts were further added. .9 parts was added, transesterification was performed at 140 to 160 ° C., the produced methanol was removed, and a DMF solution of a sulfonic acid group-containing anionic diol (B-2) having a concentration of 50.1% as a pale yellow liquid Got.

Example 3
To a reaction vessel equipped with a stirrer, a thermometer, and a reflux condenser, 114 parts of 5-sulfoisophthalic acid, DURANOL T5650E [Mn500, manufactured by Asahi Kasei Chemicals Corporation], 468 parts, and further 0.9 parts of manganese acetate were added. The esterification reaction is performed at ˜160 ° C., and the produced water is removed. Further, 630 parts of DMF was added, and neutralization reaction was performed with 47 parts of triethylamine to obtain a DMF solution of a sulfonic acid group-containing anionic diol (B-3) as a pale yellow liquid at a concentration of 50.0%.

Example 4
Into a reaction vessel equipped with a stirrer, a thermometer and a reflux condenser, 137 parts of 5-sulfoisophthalic acid dimethyl sodium salt, PTG 650SN [Mn650, manufactured by Hodogaya Chemical Co., Ltd.] 608 parts and DMF 740 parts are added, and manganese acetate is further added. 0.9 part was added, transesterification was performed at 140 to 160 ° C., the produced methanol was removed, and DMF of a sulfonic acid group-containing anionic diol (B-4) having a concentration of 50.2% as a pale yellow liquid A solution was obtained.

Example 5
Into a reaction vessel equipped with a stirrer, a thermometer and a reflux condenser, 160 parts of 3-sulfo-1,8-naphthalenedicarboxylic acid, DURANOL T5650E [Mn500, manufactured by Asahi Kasei Chemicals Corporation] and 620 parts of DMF are further added. 0.9 part of manganese acetate was added, transesterification was performed at 140 to 160 ° C., and the produced methanol was removed, and a sulfonic acid group-containing anionic diol (B-5) having a concentration of 50.1% as a pale yellow liquid Of DMF was obtained.

Example 6
Into a reaction vessel equipped with a stirrer, a thermometer and a reflux condenser, 137 parts of 5-sulfoisophthalic acid dimethyl sodium salt, Kuraray polyol C-5090 [Mn5000, manufactured by Kuraray Co., Ltd.] 4625 parts and DMF 4700 parts are further added. 0.9 part of manganese was added, transesterification was performed at 140 to 160 ° C., and the produced methanol was removed, and the sulfonic acid group-containing anionic diol (B-6) was a pale yellow liquid at a concentration of 50.3%. A DMF solution was obtained.

Comparative Example 1
Into a reaction vessel equipped with a stirrer, a thermometer and a reflux condenser, 137 parts of dimethylsodium 5-sulfoisophthalate, 58 parts of EG, and 200 parts of DMF were added, and 0.9 part of manganese acetate was further added. Transesterification was performed to remove the produced methanol, and a DMF solution of a comparative sulfonic acid group-containing anionic diol (B′-1) having a concentration of 49.5% and a pale yellow liquid was obtained.

Comparative Example 2
In a reaction vessel equipped with a stirrer and a thermometer, 137 parts of 5-sulfoisophthalic acid dimethyl sodium salt, 185 parts of PEG-200 [Mn200, manufactured by Sanyo Chemical Industries, Ltd.] and 320 parts of DMF were added. The resultant methanol was removed, and the DMF of a comparative sulfonic acid group-containing anionic diol (B′-2) having a concentration of 50.2% and a light yellow liquid was removed. A solution was obtained.

Comparative Example 3
In a reaction vessel equipped with a stirrer and a thermometer, 137 parts of 5-sulfoisophthalic acid dimethyl sodium salt, 370 parts of PEG-400 [Mn400, manufactured by Sanyo Chemical Industries, Ltd.] and 500 parts of DMF were added. The resultant methanol was removed, and the DMF of a comparative sulfonic acid group-containing anionic diol (B′-3) of a pale yellow liquid at a concentration of 50.4% was added. A solution was obtained.

Comparative Example 4
In a reaction vessel equipped with a stirrer, a thermometer and a reflux condenser, 137 parts of 5-sulfoisophthalic acid dimethyl sodium salt, PEG-6000S [Mn 8,300, manufactured by Sanyo Chemical Industries, Ltd.] 7,670 parts and DMF 7,700 Part, 0.9 part of manganese acetate was further added, transesterification was carried out at 140-160 ° C., the produced methanol was removed, and the sulfonate group-containing anion was compared with a pale yellow liquid at a concentration of 50.3%. A DMF solution of the sex diol (B′-4) was obtained.

Tables 1 and 2 below summarize the anionic diol (B) produced and the comparative anionic diol (B ′).

実施例７
撹拌機、温度計および還流冷却管の付いた反応容器にスルホン酸基含有アニオン性ジオール（Ｂ−１）のＤＭＦ溶液を１，２１０部とＥＧ３１部およびサンエスター ２４６２５−Ｙ（Ｍｎ２，０００、三洋化成工業（株）製）１，２５０部を入れ、均一混合して組成物（Ｂ）を得た。ここにジフェニルメタンジイソシアネート３７５部およびＤＭＦ４，７００部を加え、６５℃で反応させ、ポリウレタン樹脂（Ｕ−１）の溶液を得た。得られたポリウレタン樹脂のＭｎは４５，０００であった。（Ｕ−１）の溶液をガラス板上に流延して７０℃で３時間乾燥した後、減圧（０．００５ＭＰａ）下、７０℃で３時間乾燥して膜厚２００μのフィルムを得た。

Example 7
In a reaction vessel equipped with a stirrer, a thermometer and a reflux condenser, 1,210 parts of a DMF solution of a sulfonic acid group-containing anionic diol (B-1), 31 parts of EG, and Sanester 24625-Y (Mn2,000, Sanyo) 1,250 parts (made by Kasei Kogyo Co., Ltd.) were added and mixed uniformly to obtain a composition (B). To this, 375 parts of diphenylmethane diisocyanate and 4,700 parts of DMF were added and reacted at 65 ° C. to obtain a solution of polyurethane resin (U-1). Mn of the obtained polyurethane resin was 45,000. The solution of (U-1) was cast on a glass plate, dried at 70 ° C. for 3 hours, and then dried at 70 ° C. for 3 hours under reduced pressure (0.005 MPa) to obtain a film having a thickness of 200 μm.

Examples 8-12, Comparative Examples 5-9
The solutions of the dyeable urethane resins (U-2 to U-6, U′-1 to U′-5) produced in Examples 8 to 12 and Comparative Examples 5 to 9 are the same as in Example 1. Manufacture according to the preparation table in Table 3.
Each film obtained in Examples 7-12 and Comparative Examples 5-9 was evaluated by the following method, and the evaluation results are shown in Table 3.

<Evaluation method>
1. Dry film properties [1] Method for measuring tensile strength An organic solvent solution of urethane resin (U) or (U ') is applied on a release-treated glass plate to a thickness of 0.7 mm, and air circulation drying at 70 ° C. After drying with a machine for 3 hours, a film for tensile strength test having a thickness of about 0.2 mm was produced by peeling from the glass plate.
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
[3] Evaluation of dyeability The degree of dyeing of the film treated under the following dyeing conditions was evaluated according to the following level.
○ It is dyed dark red.
× Dye has fallen off and the film is transparent.
[4] Light fastness The film treated under the following dyeing conditions was measured according to JIS L0842 (fade meter test).
The light fastness was evaluated by the following series.
Grade 5 No change in color before and after light resistance test.
Grade 4 A slight color change is observed before and after the weather resistance test.
Grade 3 Change in color before and after light resistance test.
Grade 2 A large color change is observed before and after the light resistance test.
First grade The color change is large before and after the light resistance test, and the red color due to the dye has almost disappeared.
[5] Fastness to wet friction The film treated under the following dyeing conditions was measured according to JIS L0849 (gray scale test).
The wet friction fastness was evaluated by a series based on a gray scale test for contamination according to JIS L0805: 2005. Grade 5 shows the best wet friction fastness, and grade 1 shows the worst wet friction fastness.

The stained samples subjected to the evaluations [3] to [5] described above were subjected to the following staining method.
・ Dyeing method (staining conditions)
Bath ratio 1:50
(Dye bath)
Dye Kayacryl Red GL-ED [Nippon Kayaku Co., Ltd.] 2.0%
Acetic acid 1.5%
Sodium acetate 0.5%
Soup glass 1g / L
The film is put into a dye bath at 60 ° C., heated to 80 ° C. over 10 minutes, and further heated to 120 ° C. over 40 minutes. Dye for 30 minutes at this temperature. Then, it was washed with hot water at 60 ° C. for 10 minutes and dried.

Since the urethane resin using the anionic diol for dyeable urethane resin of the present invention is excellent in dyeability and mechanical properties, it is a nonwoven fabric binder, a binder and an outer skin for synthetic leather, a binder for pigment printing, a wool shrinking agent. It can be used as an anti-pilling agent, a binder for hook-and-loop fasteners, other fiber reinforcing agents, a texture adjusting agent, etc., and is suitably used as a fiber processing agent. Textile products using this can be used for clothing, shoes, bags, furniture, etc. It can be applied to a wide range of applications such as automobile interiors and industrial materials.

Claims (10)

An anionic diol (B) for a dyeable urethane resin represented by the following general formula (1) and having a number average molecular weight (Mn) of 1,200 to 15,000.

[Wherein, n is an integer of 1 to 4, and m is 1 or 2. M ⁺ is a monovalent cation. Q is a divalent group having a formula weight of 60 to 200, and the pKa of the compound represented by the general formula (2) is -10 to 4. A plurality of M ⁺ and Q may be the same or different. Z is an (n + 2) -valent organic group having a formula weight of 50 to 200. A is a residue obtained by removing two hydrogen atoms from a polymer diol having a number average molecular weight of 500 to 5000, and the two A may be the same or different. ] In general formula (1), Q is _{-SO 2} -, - OSO 2 - or -NH-SO ₂ - anionic diol according to claim 1 which is (B). The anionic diol (B) according to claim 1 or 2, wherein M ⁺ is a monovalent cation selected from the group consisting of protons, metal ions, and ammonium. The anionic diol (B) according to any one of claims 1 to 3, represented by the following general formula (3) or (4).

[Wherein, A and Q are the same as those in the general formula (1), and Z ¹ is a residue obtained by removing (n + 2) hydrogen atoms from an aromatic compound having 6 to 12 carbon atoms. ] In general formula (1), A is a residue remove | excluding two hydrogen atoms from the polycarbonate diol shown by the following general formula (5), The anionic diol of any one of Claims 1-4 (B).

[Wherein, R represents a divalent aliphatic hydrocarbon group having 4 to 12 carbon atoms or a divalent alicyclic hydrocarbon group, and a plurality of R may be the same or different. n is an integer of 2-50. ] A dyeability imparting agent containing the anionic diol (B) according to any one of claims 1 to 5. A dyeable urethane resin obtained by reacting a polyol composition (P) containing the anionic diol (B) for a dyeable urethane resin according to any one of claims 1 to 5 and an isocyanate compound (J). (U). The urethane resin (U) according to claim 7, wherein the number average molecular weight (Mn) is 10,000 to 80,000. The urethane resin (U) according to claim 7 or 8, wherein the residue obtained by removing all isocyanate groups from the isocyanate compound (J) has 6 to 15 carbon atoms.   The synthetic leather which has a membrane | film | coat which has a porous film formed by wet-coagulating the organic solvent solution of the urethane resin (U) of any one of Claims 7-9.