JPH0672176B2 - Polyurethane manufacturing method - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a sulfonic acid group (salt) -containing polyurethane.

[Conventional technology]

Conventionally, as a method for producing a sulfonic acid (salt) group-containing polyurethane, a method in which an addition product of allyl alcohol and sodium bisulfite is used to react with polyisocyanate is known. (For example, Japanese Patent Publication No. 42-24192).

[Problems to be solved by the invention]

However, this compound has a problem that only a small amount of sulfonic acid (salt) groups can be introduced into polyurethane.

[Means for solving problems]

The present inventors have arrived at the present invention as a result of extensive studies on a method for producing a polyurethane capable of containing a larger amount of sulfonic acid (salt) groups.

That is, the present invention is a process for preparing polyurethane by reacting an isocyanate compound (A) and the active hydrogen atom-containing compound (B), the general formula Z-X-O-A- SO 3 M as at least a part of (B) (1) (where Z is And R is H, CH ₃ or C ₂ H ₅ . X is a direct bond, Or -CH ₂ - Z is in When Or -CH ₂ -. A is -CH ₂ CH ₂ CH ₂ - or Is. M is a cation. ) The compound (B ₁ ) represented by the formula ( ₁ ) is used to prepare a sulfonic acid (salt) group-containing polyurethane.

As the cation of M in the general formula (1), cations of H, alkali metal (lithium, sodium, potassium, etc.), ammonium and amine [(mono-, di-, tri- or tetra) alkyl (wherein the carbon number of the alkyl group is usually 1 to
18) Ammonium (methylammonium, diethylammonium, tributylammonium, tetramethylammonium, tetraethylammonium, tetra-n-butylammonium, trimethyllaurylammonium, etc.), alkanolammonium (2-propanolammonium, methyldiethanolammonium, triethanolammonium, etc.) ] Is given.

Of M, sodium, potassium, ammonium and tetraalkylammoniums are preferable.

Specific examples of the compound (B ₁ ) represented by the general formula (1) include the following compounds.

[1] General formula Compounds represented by: Compounds having a group represented by the general formula (2) as shown in Table-1 are mentioned.

[2] General formula Compounds represented by: Compounds having a group represented by the general formula (3) as shown in Table 2 are mentioned.

The compound of the general formula (1) can be synthesized by the general formula (1)
When M is an alkali metal, the general formula Z-X-OH (4)
[Wherein Z and X have the same meanings as in the case of the general formula (1)], and a mono (meth) allyl compound of a triol compound {general formula (5) [In the formula, R ′ is H or CH ₃ · Z, and X has the same meaning as in the general formula (1). ] Is shown. } And alkali metal bisulfite in a molar ratio of 1: 1.
It can be synthesized by reacting at 05 to 1.20 in water or an aqueous alcohol solution at about 80 ° C. As another method, it can be synthesized by reacting the acetal compound of the general formula (5) with an alkali metal bisulfite and then hydrolyzing the acetal group.

When M in the general formula (1) is an ammonium salt or an amine salt, the above-mentioned alkali metal salt and an ammonium salt or amine salt of a mineral acid (hydrochloric acid, sulfuric acid, etc.) are reacted in an alcohol (ethanol, isopropyl alcohol, etc.). It can be synthesized by separating and removing the alkali metal salt of the mineral acid that precipitates.

In the present invention, the compound (B ₁ ) represented by the general formula ( ₁ )
Besides, other active hydrogen atom-containing compounds can be used. Other active hydrogen atom-containing compounds include high molecular weight polyols (B ₂ ) and low molecular weight active hydrogen atom-containing compounds (B ₃ ).

Polymer polyols include polyether polyols and polyester polyols, both of which are commonly used as raw materials for polyurethanes, and can be used alone or as a mixture.

Examples of the polyether polyol include those obtained by adding an alkylene oxide to an active hydrogen-containing compound such as polyhydric alcohol, polyhydric phenol, amines and phosphoric acid.

Polyhydric alcohols include glycols (ethylene glycol, propylene glycol, 1,3 butylene glycol, 1,4 butanediol, hexylene glycol, 1,6 hexanediol, etc.), 3 to 8 alcohols (glycerin, trimethylol) Propane, hexanetriol, pentaerythritol, diglycerin, α-methylglucoside, dipentaerythritol, sorbitol,
Xylitol, mannitol, glucose, fructose,
Satsukarose etc.) and the like.

Examples of polyvalent phenols include pyrogallol, hydroquinone, bisphenol A, bisphenol sulfone, and condensation products of phenol and formaldehyde.

Amines include ammonia, alkanolamines (monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, etc. and other alkanolamines, etc.), aliphatic mono- or polyamines (ethylenediamine, diethylenetriamine, hexamethylenediamine and other Aliphatic amines), aromatic mono- or polyamines (aniline, phenylenediamine, diaminotoluene, xylylenediamine, methylenedianiline, diphenyl ether diamine and other aromatic amines), alicyclic amines (Isophorodiamine and other alicyclic amines), heterocyclic amines (aminoethylpiperazine and other Japanese Patent Publications (aminoethylpiperazine and other Japanese Patent Publication 55-21) Heterocyclic amines described in 044) and the like.

As the alkylene oxide, ethylene oxide, propylene oxide butylene oxide, epichlorohydrin,
Examples thereof include styrene oxide. Preferred alkylene oxides are propylene oxide and a combination system of propylene oxide and ethylene oxide (random, block and mixed system of both). The addition reaction of the alkylene oxide can be carried out by a usual method, and is carried out in one step or multiple steps under normal pressure or under pressure in the absence of a catalyst or a catalyst (alkali catalyst, amine catalyst, acidic catalyst).

As the polyester polyol, 2-3 hydric alcohols (ethylene glycol, propylene glycol, 1,3
Butylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, glycerin, trimethylolpropane, etc.) and / or the above polyether polyols and aliphatic dicarboxylic acids, acid anhydrides and ester-forming properties Carboxylic acid derivatives of (glutaric acid, adipic acid, sebacic acid, maleic anhydride,
Examples thereof include those produced by condensation reaction with phthalic anhydride, dimethyl terephthalate, etc .; and those produced by ring-opening polymerization of lactones (caprolactone, etc.).

Preferred among the high molecular weight polyols are divalent polyether diols and polyester diols.

The equivalent weight of these polymeric polyols is usually 200-4,000,
It is preferably 400 to 3,000.

Further, a low molecular weight active hydrogen atom-containing compound (B ₃ ) can also be used.

The low molecular weight active hydrogen-containing compound is usually called a cross-linking agent or a chain extender, and at least two, preferably two.
Compounds having an equivalent weight (molecular weight per active hydrogen-containing group) of less than 5 to less than 5 active hydrogens can be used. Specific examples thereof include dihydric and trihydric alcohols (ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-
Butanediol, 1,6-hexanediol, glycerin, trimethylolpropane, etc.), amines (diethanolamine, triethanolamine, triisopropanolamine, ethylenediamine, diethylenetriamine, isophoronediamine, diaminotoluene, diethyltoluenediamine, methylenedianiline, methylene) Bis orthochloroaniline and the like) and the above-mentioned dihydric and trihydric alcohols, tetrahydric and octahydric alcohols (pentaerythritol, methyl glucoside, sorbitol, sucrose etc.), polyhydric phenols (bisphenol A, hydroquinone etc.), the above Amine, other amines (aminoethylpiperazine, aniline, etc.) with a small amount of ethylene oxide and / or propylene oxide such as propylene oxide Polyhydroxy compound equivalent weight less than 200 pressure, such as water and dimethylolpropionic pyrone acid can be mentioned.

Of these, preferred are glycols, diamines,
Examples include water and dimethylolpropionic acid.

Also, as a low molecular weight active hydrogen-containing compound (B ₃ ), it is usually called an end-capping agent, and monoalcohols, monoalcohols (hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, tripropyl alcohol, Examples thereof include methylolpropane diallyl ether); amines (butylamine, diallylamine, etc.).

Of these, preferred are hydroxyethyl acrylate and hydroxypropyl acrylate.

Among the active hydrogen atom-containing compounds, the amount of (B ₁ ) in (B) is usually 0.01 to 50 equivalent%, preferably 0.5 to 20 equivalent%. If the amount of (B ₁ ) is less than 0.01 equivalent%, the performance (dyeability, dispersibility, antistatic property, etc.) due to sulfonic acid groups will not be exhibited, and if it exceeds 50 equivalent%, the reaction system of (B ₁ ) will be used. Is insufficiently dissolved, and the urethanization reaction does not proceed sufficiently.

The amount of (B ₂ ) in (B) is 10 equivalent% or more, preferably 80 to
It is 40 equivalent%. When the amount of (B ₂ ) is less than 10 equivalent%, the polyurethane resin physical properties (tensile strength, elongation, impact resistance, etc.) are not exhibited. The amount of (B ₃ ) in (B) is usually 50 equivalent% or less, preferably 10 to 40 equivalent%. The amount of (B ₃ )
If it exceeds 50 equivalent%, the polyurethane resin physical properties (tensile strength, elongation, impact resistance, etc.) will not be exhibited.

As the isocyanate compound used in the present invention, those conventionally used in the production of polyurethane can be used.
Thus, the number of carbon atoms (NCO
6 to 20 aromatic isocyanates (excluding carbon in the group) [eg phenyl isocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI), crude TDI,
2,4'- and / or 4,4'-diphenylmethane diisocyanate (MDI), crude MDI [crude diaminophenylmethane {condensation product of formaldehyde with aromatic amine (aniline) or mixture thereof: diaminodiphenyl A mixture of phenylmethane and a small amount (for example, 5 to 20% by weight) of a trifunctional or more polyamine} phosgene compound: polyallyl polyisocyanate (PAPI)]]: Aliphatic isocyanate having 2 to 18 carbon atoms [eg stearyl isocyanate , Hexamethylene diisocyanate, lysine diisocyanate, etc.]: alicyclic isocyanate having 4 to 15 carbon atoms [eg cyclohexyl isocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate]: araliphatic isocyanate having 8 to 15 carbon atoms [eg xylylene diisoso Anates and the like]: and modified products of these isocyanates (urethane group, carbodiimide group, allophanate group, urea group, buretet group, uretdione group, uretonimine group, isocyanurate group, oxazolidone group-containing modified product, etc.): and Japanese Patent Application No. 59 Isocyanates other than the above described in JP-A-199160: and mixtures of two or more thereof.

Of these, aromatic, aliphatic, alicyclic, and aromatic-aliphatic diisocyanates are preferable.

In the present invention, the isocyanate index [NCO / active hydrogen atom-containing group equivalent ratio × 100] is usually 80 to 140, preferably 95.
~ 110.

The polyurethane can be produced by a usual method for producing polyurethane. For example, there are a method of dividing (A) and (B) and carrying out a multi-stage reaction (prepolymer method) and a method of reacting (A) and (B) together (one shot method). Method is preferred. Examples of the prepolymer method include a method in which a diisocyanate compound, a high molecular weight diol and a compound of the general formula (1) (a sulfonate-containing diol) are reacted in advance and then reacted with a low molecular weight diamine to complete the reaction. The sulfonate-containing diol of the general formula (1) is reacted in advance, then reacted with a high molecular weight diol and then with a low molecular weight diamine,
A method of completing the reaction can be mentioned.

In the present invention, the reaction can be carried out using a solvent which is inert to the isocyanate group. As the solvent, an amide solvent (N-methylpyrrolidone, dimethylformamide, dimethylacetamide, etc.), a ketone solvent (acetone, methyl ethyl ketone, Methyl isobutyl ketone, cyclohexanone, etc.), aromatic hydrocarbon solvents (toluene, xylene, etc.), ester solvents (ethyl acetate, cellosolve acetate, etc.), ether solvents (dioxane, tetrahydrofuran, etc.), sulfoxide solvents (dimethyl sulfoxide, etc.) ) And mixed solvents of two or more thereof. The amount of solvent is usually 0-400 relative to the amount of polyurethane
%. The reaction temperature is usually mild, for example 20
To 150 ° C., preferably 20 to 100 ° C., and the reaction time is usually 3 to 20 hours. The reaction pressure is usually normal pressure, but may be higher pressure.

In addition, catalysts usually used for accelerating the reaction, such as amine-based catalysts (triethylenediamine, N-methylmorpholine, triethylamine, etc.), tin-based catalysts (dibutyltin dilaurate, etc.), lead-based catalysts (lead octylate, etc.), etc. You may use.

The molecular weight of the polyurethane obtained in the present invention is usually 10,000 to 10
It is 0,000, preferably 50,000 to 800,000.

The content of the sulfonic acid (salt) group (SO ₃ M) is (SO ₃ ^- as)
Generally 0.1 to 20% by weight, preferably 0.5
~ 10% by weight. When the content of sulfonic acid (salt) groups is low, superiority in various performances (dyeability, dispersibility, antistatic property, etc.) with polyurethanes that do not contain sulfonate groups is not seen, and the content is also high. If the content is high, the molecular weight of the polyurethane will decrease, and the characteristics of resin properties (tensile strength, elongation, impact resistance, etc.) as polyurethane cannot be obtained.

In using the polyurethane obtained in the present invention, additives such as a plasticizer, a cross-linking agent, a pigment, a coloring agent, a repelling agent, a heat stabilizer, and an ultraviolet absorber are added as necessary to improve the performance of the polyurethane. May be included. Additives such as heat stabilizers and ultraviolet absorbers are preferably added during the production of polyurethane.

The polyurethane obtained in the present invention can be made into an aqueous polyurethane dispersion by a usual method (for example, the method described in Japanese Patent Publication No. 42192/42). For example, water is added to the acetone solvent (concentration of about 60%) of polyurethane obtained in the present invention with stirring, and then acetone is distilled off under heating to obtain a polyurethane resin water dispersion (concentration of about 45%). You can

〔Example〕

The present invention will be further described below with reference to examples, but the present invention is not limited thereto.

Parts in the examples indicate parts by weight.

Synthesis Example 1 Synthesis method of 3- (2,3-dihydroxypropoxy) -1-propanesulfonic acid sodium salt (compound a in Table 1) 3- (2-propenyloxy) -1,2-propanediol (glycerin Monoallyl ether) 132 g (1.0 mol)
And 63 g (0.5 mol) of sodium sulfite are dissolved in 200 g of water,
Sodium bisulfite 109g (1.05
(Mol) was dissolved in 150 g of water and added dropwise over 1 hour. After reacting at the same temperature for 2 hours, water was distilled off under reduced pressure, 300 g of isopropyl alcohol was added, insoluble matter was passed through, and isopropyl alcohol was distilled off. 213 g of powdered target product (yield 90
%) Was obtained.

Synthesis Example 2 3- (2,2-bis (hydroxymethyl) butoxy) -2
-Methyl-1-propanesulfonic acid sodium salt (Table 2
Compound) of trimethylolpropane monomethallyl ether acetal compound 214 g (1.0 mol) and sodium sulfite 63 g (0.
(5 mol) was dissolved in 150 g of water, and 109 g (1.05 mol) of sodium bisulfite dissolved in 150 g of water was added dropwise over 1 hour while passing air at 60 ° C. 50% after reacting at the same temperature for 2 hours
Sulfuric acid was added to adjust to PH _3, and the mixture was further stirred at 60 ° C. for 1 hour, then evaporated under reduced pressure, and 300 g of isopropyl alcohol was added
The insoluble matter was passed and the isopyr alcohol was distilled off. 254 g (yield 87%) of the target product in powder form was obtained.

Synthesis Example 3 3- (2,2-bis (hydroxymethyl) butoxy) -2
-Methyl-1-propanesulfonic acid tetraethylammonium salt (compound of Table 2) Synthesis method 146 g (0.5 mol) of (compound) obtained in Synthesis Example 2 and 83 g (0.5 mol) of tetraethylammonium chloride were dissolved in 200 g of isopropyl alcohol. , Stir at 60 ℃ for 1 hour,
The mixture was cooled to 20 ° C., insoluble matter was passed, and isopropyl alcohol was distilled off. 190 g (95%) of the desired product in powder form was obtained.

Example 1 47 parts of compound a of Synthesis Example 1, 2000 parts of polytetramethylene glycol having a molecular weight of 2,000 and 157 parts of 1,4-butanediol were mixed with 6900 parts of dimethylformamide and uniformly dissolved. To this solution, 737 parts of diphenylmethane-4,4-diisocyanate was added and reacted at 70 ° C.

This polyurethane solution had a solid content of 30%, a viscosity of 1000 ps, and a sulfonate group content of 0.7% in the solid content.

Example 2 24 parts of compound a of Synthesis Example 1, 2000 parts of polyester diol from 1,4-butanediol adipic acid having a molecular weight of 2000,
157 parts of 1,4-butanediol and 6800 parts of dimethylformamide were mixed and uniformly dissolved. To this solution was added 713 parts of diphenylmethane-4,4'-diisocyanate, and the mixture was heated to 70 ° C.
It reacted with. This polyurethane solution has a solid content of 30%, a viscosity of 700 ps and a sulfonate group content of 0.35% of the solid content.
It was.

Comparative Example 1 The same operation as in Example 1 was carried out except that 12 parts of ethylene glycol was used instead of the compound a in Example 1. This polyurethane solution had a solid content of 30% and a viscosity of 800 ps.

Comparative Example 2 1,6-hexanediol 10 was used in place of the compound a of Example 2.
The same operation as in Example 2 was carried out except for using parts. This polyurethane solution had a solid content of 30% and a viscosity of 800 ps.

Test Example 1 Examples 1 and 2 and Comparative Examples 1 and 2 A wet porous film was formed by the following method using the polyurethane solution, and a dyeing test of this film was performed. The results are shown in Table 3.

Dyeing test (preparation of wet porous film) After adding dimethylformamide to the stock solution to adjust the solid content to 20%, spread it on a glass plate to a thickness of 1 mm, submerge it in water at 40 ° C, coagulate for 15 minutes, coagulate film Was peeled from the glass plate, washed with water for 10 minutes and dried at 80 ° C. A white porous film having a thickness of 0.8 mm was obtained.

(Dyeing method) The film was put into the dyebath at a bath ratio of 1:20 and dyed at 95 ° C for 40 minutes. Four
After cooling to 0 ° C. or lower, it was washed with water and dried.

Example 3 27 parts of the compound of Synthesis Example 2, polyesterdiol 514 from 1,4-butanediol adipic acid having a molecular weight of 2,000
Parts, 85 parts of tolylene diisocyanate and 200 parts of acetone were reacted at 80 ° C. for 8 hours under pressure. Then cool to 50 ° C,
Acetone 440 parts and isophorone diamine 17 parts were added, and the reaction was carried out at the same temperature for 2 hours. Then, 1000 parts of water was added, and acetone was distilled off under heating to obtain a polyurethane aqueous dispersion.
The dispersion had a solid content of 40% and a viscosity of 60 cps, and the sulfonate group content was 1.3% of the solid content. The results are shown in Table 4.

Comparative Example 3 The procedure of Example 3 was repeated, except that 25 parts of dimethylolpropionic acid triethylamine salt was used in place of the compound of Example 3. The solid content of this dispersion was 40% and the viscosity was 450 cps.

Test Example 2 An adhesive (heat resistant creep) test was conducted on the dispersions of Example 3 and Comparative Example 3.

(1) Adhesive composition (2) Measuring method This adhesive composition is applied (120 / m ² ) on plywood and 0.2 mm
The semi-rigid PVC sheet of 3 is pressure-bonded and dried at room temperature for 5 days.
Plywood / semi-hard PVC plate is cut into a width of 25 mm and a length of 100 mm, a PVC sheet is loaded with 500 g, and placed in a constant temperature bath at 60 ° C.
Measure the peeled length (mm). The measurement results are shown in Table 4.

Example 4 76 parts of the compound of Synthesis Example 3, 200 parts of polypropylene glycol having a molecular weight of 2,000, 32 parts of dihydroxyethyl bisphenol A and 95 parts of isophorone diisocyanate were added to 80 parts.
The reaction was carried out at ℃ for 8 hours. Then, 400 parts of acetone and 5 parts of isophoronediamine were added, and the mixture was reacted under pressure at 80 ° C. for 3 hours. Then, 420 parts of water was added, and acetone was distilled off at 80 ° C. to obtain an almost translucent polyurethane solution. The polyurethane solution had a solid content of 40% and a viscosity of 2500 cps, and the sulfonate content was 5% of the solid content. I made a film. Further, a film was similarly prepared for the urethane emulsion obtained in Comparative Example 3.

The volume resistance of those films was measured. The measurement results are shown in Table 5.

Preparation of film for volume resistance test 100 parts of polyurethane solution and 2 parts of water-soluble glycidyl ether (Our Glyciel STE-250) were uniformly mixed, spread on a glass plate, and dried at room temperature to give a transparent film with a thickness of 0.5 mm. obtain.

Volume resistance measurement Takeda Riken Ultra Insulator is used for measurement at 20 ℃ and 65% RH.

Table 5 Measurement Results Volume Resistance S / cm Example 4 7 × 10 ⁻⁶ Comparative Example 3 2 × 10 ⁻⁹ Example 5 38 parts of the compound of Synthesis Example 3, 200 parts of polycaprolactone having a molecular weight of 1,000, and dicyclohexylmethane-4,4 79 parts of ′ -diisocyanate and 320 parts of methyl isobutyl ketone
The reaction was carried out at 00 ° C for 15 hours. This polyurethane solution has a solid content
The viscosity was 50,000 CPS at 50%.

A magnetic paint was prepared from the urethane resin and used as a magnetic tape binder to evaluate the dispersibility of magnetic powder. Further, a magnetic coating material was similarly prepared by using a 50% methyl isobutyl ketone solution of a commercially available urethane resin (Nitporan 5033).

Dispersion test of magnetic powder Preparation of magnetic coating γ-Fe ₂ O ₃ magnetic 100 parts Urethane solution of Example 5 50 parts Toluene 50 parts Methyl ethyl ketone 100 parts Nitrocellulose (cell line made by Daicel) 1 part 40 hours in the above ball mill A magnetic paint was prepared by mixing and dispersing.

Preparation of Magnetic Film The paint thus prepared was applied onto a polyester film of 15 μm using a bar coater so that the coating thickness of the solid content was 5 to 6 μ, and immediately this was subjected to magnetic field orientation through a parallel magnetic field of 6,000 Elsted. Then, the solvent was removed by leaving it in a circulating air dryer at 70 to 80 ° C. for about 30 minutes. In this state, it was calendered to smooth the surface (calendar times 1 to 6
Times). Further, this was allowed to stand in a constant temperature bath at 40 to 50 ° C. for 40 hours to cure the magnetic layer to obtain a magnetic film.

Evaluation of dispersibility The glossiness of the magnetic coating surface of the magnetic film was examined. It can be said that the higher the gloss, the better the dispersibility. As a measuring instrument, a digital variable angle gloss meter VC-ID type manufactured by Nippon Denshoku Industries Co., Ltd. was used. The regular reflectance at a measuring angle of 75 ° is the reflectance of a standard glass plate.
The relative reflectance (%) of each sample is shown when the value is 100.

The evaluation results are shown in Table 6.

[Effects of the Invention] The present invention has the following effects.

(1) The solubility of the sulfonic acid (salt) group-containing compound in the reaction system during the production of the urethane resin is sufficient. The conventional one (Japanese Patent Publication No. 42-24192) was not enough.

(2) Therefore, sulfonic acid group-containing polyurethane having various compositions can be produced.

(3) In addition, polyurethane having a high content of sulfonate group can be produced.

(4) Alternatively, the shape of polyurethane can be resin, solution, water dispersion, or aqueous solution.

(5) Sulfonate group-containing polyurethane has performance such as dyeability, water absorption, antistatic property, heat resistance, adhesiveness, dispersibility, and biocompatibility as compared with polyurethane of similar composition containing no sulfonate group. Are better.

Because of the above effects, the polyurethane according to the present invention is used alone or in combination with other synthetic or natural resins for coating agents such as fibers, leather, papers, wood, metals, plastics, and adhesives, paints and inks. It is suitable for resin base materials, magnetic powder binders, paste materials for textile printing and paper industry, base materials for artificial leather and artificial storage, and base materials for immobilizing enzymes and fungi.

Continuation of the front page (56) Reference JP-A-55-11522 (JP, A) JP-A-61-200113 (JP, A) JP-A-61-236762 (JP, A) JP-B-47-22707 (JP , B1) JP-B-42-24192 (JP, B1)

Claims (2)

[Claims] 1. A method for producing a polyurethane by reacting an isocyanate compound (A) with an active hydrogen atom-containing compound (B), wherein as at least a part of (B), a compound of the general formula Z--X--O--A--SO _{3 is used.} M (1) (where Z is And R is H, CH ₃ or C ₂ H ₅ . X is a direct bond, Or -CH ₂ - Z is in When Or -CH ₂ -. A is -CH ₂ CH ₂ CH ₂ - or Is. M is a cation. ) A method for producing a sulfonic acid (salt) group-containing polyurethane, which comprises using the compound (B ₁ ) represented by: 2. The method according to claim 1, wherein the content of the sulfonic acid (salt) group in the polyurethane is 0.01 to 20% with respect to the weight of the polyurethane resin.