JP4421490B2 - Aqueous polyurethane resin composition and method for producing the same - Google Patents

Description

  The present invention relates to an aqueous polyurethane resin composition. Specifically, the present invention relates to a water-soluble or water-dispersible aqueous polyurethane resin composition containing a novel sulfonic acid quaternary ammonium salt in a molecular chain by a urethane bond, and a method for producing the same.

  Conventionally, as a method for producing an aqueous solution and an aqueous dispersion (aqueous dispersion) of a polyurethane resin, a method of dispersing a polyurethane resin in water by using a surfactant, a hydrophilic polyol such as polyethylene glycol as a polyol component There are known a method for making a urethane resin self-dispersing using styrene, a method for introducing a hydrophilic group such as an anionic group or a cationic group into a polyurethane resin, and a method for using these in combination.

  Among these, the polyurethane resin dispersion produced by adding a surfactant has problems such as the stability of the dispersion and deterioration of the performance of the polyurethane resin due to the influence of the added surfactant. Further, in the method of making a polyurethane resin self-emulsifying using a hydrophilic polyol, it is necessary to introduce the hydrophilic polyol into the molecule at a certain rate in order to make the urethane resin water-soluble, Since this hydrophilic polyol functions as a soft segment in the polyurethane resin, the ratio of the hydrophilic polyol to the soft segment portion is fixed. For this reason, the range of performance as a polyurethane resin is narrowed.

  On the other hand, as a method for introducing a hydrophilic group such as an anion group or a cation group into a polyurethane resin, a polymer is introduced by introducing a polar group such as a sulfonic acid group, a carboxylic acid group, or a quaternary ammonium group as one component of the polymer. There are many known methods for making the aqueous solution.

  As a method for introducing these polar groups into a polyurethane resin, (1) a method of using a raw material monomer or oligomer having these polar groups when synthesizing a polymer, (2) an unsaturated portion or an alcohol group of the polymer Or a sulfonic acid group is introduced, or the amino group of the polymer is alkylated to introduce a quaternary ammonium group. In general, when a polar group is introduced into a polyurethane resin by the production method (1), a method using a diol component having a polar group as a raw material is used, and many quaternary ammonium diols are known in introducing a cationic group. ing. On the other hand, when an anionic group is introduced into the polyurethane resin by the production method (1), a diol component containing sulfonic acid, phosphoric acid, or carboxylic acid (and salts thereof) is also used.

  However, among these, sulfonate components and phosphate-containing diol components are generally poorly soluble in solvents used in the production of polyurethane, and particularly diol components having a high content of sulfonic acid groups are difficult to use with these organic solvents. It is difficult to use because it is soluble or insoluble.

  In addition, as a method for introducing a sulfonic acid group, a method using a polyester polyol oligomer containing a sulfonic acid group as a raw material is known, but in this method, the content ratio of the sulfonic acid group must be low. Moreover, since the composition and molecular weight of the oligomer are limited, the molecular design of the polyurethane resin cannot be freely performed. On the other hand, the use of 3,3-dimethylolpropionic acid or the like is known as the carboxylic acid group-containing diol. However, since the carboxylic acid group is weakly anionic, the effect of polymer modification (modification) is not sufficient.

As a method for introducing a sulfonic acid group, a sulfonic acid group-containing diol that is soluble in an organic solvent used in the production of polyurethane is known (for example, see Patent Document 1). As a specific example, N, N-bis (2-hydroxyethyl) tetraethylammonium salt obtained by reacting N, N-bis (2-hydroxyethyl) aminoethylsulfonic acid and tetraethylammonium hydroxide is described. . However, this compound is not practical because it is in the form of a solid at room temperature and not only has difficulty in handling but also uses a relatively expensive ammonium salt.
JP 2001-354742 A

  The present invention is soluble in an organic solvent used for the production of polyurethane, is in the form of a liquid at ordinary temperature, and is useful as a sulfonic acid group-containing polyol component that is easy to handle, and is at least 3 (up to 6) per molecule. The present invention provides a sulfonic acid quaternary ammonium salt having a specific structure having a hydroxyl group. The present invention provides a technique that can easily make a polyurethane aqueous by introducing a sulfonic acid group into the molecule by utilizing this.

  As a result of various studies, the present inventor has introduced two hydroxyl groups on the amino group side, and also introduces at least one 2-hydroxyalkyl group on the ammonium salt side into one molecule. A novel N, N-bis (2-hydroxyethyl) aminoethylsulfonic acid quaternary ammonium salt having at least three hydroxyl groups in the form of a liquid at ordinary temperature and easy to handle is applied to the synthesis of polyurethane. The present invention has been reached.

  That is, the gist of the present invention is an aqueous polyurethane resin composition comprising an aqueous solution or aqueous dispersion in which an aqueous polyurethane resin containing a sulfonic acid group is dissolved or dispersed in water, and the polyurethane resin is represented by the following general formula: A water-based polyurethane resin composition comprising the quaternary ammonium salt of N, N-bis (2-hydroxyalkyl) aminoethylsulfonic acid represented by (1) in a molecular chain by a urethane bond.

(Wherein R1 and R2 represent the same or different alkylene group having 2 to 4 carbon atoms, at least one of R3 to R6 represents the same or different 2-hydroxyalkyl group having 2 to 4 carbon atoms, and The remainder represents the same or different linear, branched or cyclic alkyl group having 1 to 18 carbon atoms.)

  The present invention also provides a compound in which the polyurethane resin contains another active hydrogen group together with the quaternary ammonium salt of N, N-bis (2-hydroxyalkyl) aminoethylsulfonic acid represented by the general formula (1). Is contained in the molecular chain, and also resides in the aqueous polyurethane resin composition according to claim 1.

  In the general formula (1), R1 and R2 are both ethylene groups, at least one of R3 to R6 is a 2-hydroxyethyl group or a 2-hydroxypropyl group, and the remainder is a methyl group. Or an ethyl group, a propyl group, a butyl group, or a benzyl group.

  Further, the present invention contains N, N-bis (2-hydroxyethyl) aminoethylsulfonic acid trimethylmono-2-hydroxyethyl quaternary ammonium salt represented by the formula (2) in the molecular chain by a urethane bond. It exists also in the water-based polyurethane resin composition characterized by these.

  Moreover, this invention contains N, N-bis (2-hydroxyethyl) aminoethylsulfonic acid dimethyldi-2-hydroxyethyl quaternary ammonium salt shown by Formula (3) in a molecular chain by a urethane bond. It exists also in the water-based polyurethane resin composition characterized.

  Moreover, this invention contains the N, N-bis (2-hydroxyethyl) aminoethylsulfonic acid monomethyltri-2-hydroxyethyl quaternary ammonium salt shown by Formula (4) in a molecular chain by a urethane bond. It exists also in the water-based polyurethane resin composition characterized by these.

  Moreover, this invention contains the N, N-bis (2-hydroxypropyl) aminoethylsulfonic acid monomethyltri-2-hydroxyethyl quaternary ammonium salt shown by Formula (6) in a molecular chain by a urethane bond. It exists also in the water-based polyurethane resin composition characterized by these.

  In the present invention, the N, N-bis (2-hydroxyethyl) aminoethylsulfonic acid trimethyl mono-2-hydroxypropyl quaternary ammonium salt represented by the formula (11) is contained in the molecular chain by a urethane bond. It exists also in the water-based polyurethane resin composition characterized by these.

  In the present invention, the N, N-bis (2-hydroxyethyl) aminoethylsulfonic acid monomethyltri-2-hydroxypropyl quaternary ammonium salt represented by the formula (15) is contained in the molecular chain by a urethane bond. It exists also in the water-based polyurethane resin composition characterized by these.

  Moreover, this invention contains N, N-bis (2-hydroxyethyl) aminoethylsulfonic acid dimethyl di-2-hydroxypropyl quaternary ammonium salt shown by Formula (13) in a molecular chain by a urethane bond. It exists also in the water-based polyurethane resin composition characterized.

  In addition, the present invention provides N, N-bis (2-hydroxyalkyl) aminoethylsulfonic acid quaternary ammonium salt represented by the following general formula (1) together with a compound containing another active hydrogen group as necessary. , A step of reacting with an organic polyisocyanate compound in a solvent-free or inert solvent with respect to an isocyanate group, and after making the obtained reaction solution aqueous with water, or with water or as required The present invention also includes a method for producing an aqueous polyurethane resin composition, which comprises a step of chain extension and aqueous formation with water to which a chain extender such as an amine is added, and then distilling off the solvent as necessary. .

(Wherein R1 and R2 represent the same or different alkylene group having 2 to 4 carbon atoms, at least one of R3 to R6 represents the same or different 2-hydroxyalkyl group having 2 to 4 carbon atoms, and The remainder represents the same or different linear, branched or cyclic alkyl group having 1 to 18 carbon atoms.)

  A novel quaternary ammonium salt of sulfonic acid having at least 3 (up to 6) hydroxyl groups in one molecule with 2 amino groups and at least 1 2-hydroxyalkyl group introduced on the ammonium salt side is urethane-bonded. Can be introduced into the polymer molecule. Of the maximum 6 hydroxyl groups, at least 1, preferably 2 or more hydroxyl groups are involved in the urethane bond. The sulfonic acid quaternary ammonium salt is in the form of a liquid at room temperature and is easy to handle, and is expected to improve the hardness of the urethane film and reduce the odor of the formed coating film.

  An aqueous polyurethane composition excellent in water solubility and water dispersibility can be formed, and is useful in a wide range of fields such as aqueous paints, aqueous inks, adhesives, and various coating agents.

  In the general formula (1) of the present invention, R1 and R2 represent the same or different alkylene groups having 2 to 4 carbon atoms. Specific examples include an ethylene group, a propylene group, and a butylene group. At least one of R3 to R6 represents the same or different 2-hydroxyalkyl group having 2 to 4 carbon atoms. Specific examples of the 2-hydroxyalkyl group include a 2-hydroxyethyl group, a 2-methyl-2-hydroxyethyl group, and a 2-ethyl-2-hydroxyethyl group.

  In the sulfonic acid quaternary ammonium salt of the present invention, at least one of R3 to R6 in the general formula (1) needs to be a 2-hydroxyalkyl group. Tetrahydroxyammonium salts in which all four of R3 to R6 are 2-hydroxyalkyl groups may be used, three are 2-hydroxyalkyl groups and the remaining one is a linear, branched or cyclic group having 1 to 18 carbon atoms. The two alkyl groups may be 2-hydroxyalkyl groups, and the remaining two may be the same or different C 1-18 linear, branched or cyclic alkyl groups. Examples of the alkyl group include methyl group, ethyl group, propyl, butyl group, octyl group, dodecyl group, stearyl group, cyclohexyl group, cyclohexylmethyl group, and benzyl group.

  Preferable specific examples of the ammonium sulfonate as described above include various compounds represented by the formulas (2), (3), (4), (6), (11), (13), and (15). (5) (7) (8) (9) (10) (12) (14) (16) (17) (18) and the compound of (19) are also mentioned.

  In the sulfonic acid quaternary ammonium salt represented by the general formula (1), the corresponding aminoethylsulfonic acid quaternary ammonium salt is reacted with an alkylene oxide such as ethylene oxide, propylene oxide or butylene oxide to convert the amino group to bis (2 Produced by conversion to a -hydroxyalkyl) amino group. As reaction conditions, alkylene oxide is 2.0 to 3.0 mol, preferably 2.0 to 2.8 mol, and reaction temperature is 20 to 90 ° C., preferably 30 to 80 ° C., with respect to 1 mol of amino group. The degree is used.

  As the alkylene oxide, ethylene oxide and propylene oxide are preferably used because of their high reactivity and high activity of hydroxyl groups in the product. A mixture of two or more alkylene oxides can be used. When the reaction temperature is too high, side reactions increase, and when alkylene oxide is used in an amount exceeding 3 moles, side reactions such as Hofmann decomposition reactions increase, so the reaction temperature is usually selected from the above range.

  Although the above reaction proceeds even without a catalyst, a ring-opening addition reaction catalyst such as a tertiary amine or an alkali hydroxide can be used as necessary. As the reaction solvent, water is usually used, but if necessary, methanol, ethanol, isopropanol, toluene and the like can be mixed to control the solubility.

  The aminoethylsulfonic acid quaternary ammonium salt is usually used in an amount of 20 to 250 parts by weight, preferably 40 to 200 parts by weight, per 100 parts by weight of the solvent (water). If the amount is less than the above, the reaction efficiency is not only poor, but a reaction by-product from water and alkylene oxide is generated in a large amount, which is not preferable. On the other hand, if the amount is too large, the reaction becomes non-uniform and the viscosity becomes high, which may hinder smooth reaction.

  To describe the embodiment of the reaction, first, aminoethylsulfonic acid quaternary ammonium salt (taurine salt) is added to a predetermined amount of reaction medium (water), and alkylene oxide is added continuously or intermittently at a predetermined reaction temperature. . When the taurine salt is obtained as an aqueous solution, water as a reaction medium is not necessarily required, and can be added as appropriate in consideration of the concentration of the reactant. The reaction pressure during this period is not particularly limited, but usually 0.5 MPa or less is sufficient. Moreover, although reaction time changes with the kind of raw material to be used, and reaction temperature, 1 to 10 hours are normally sufficient including reaction time after the reaction pressure generated by addition of alkylene oxide returns to atmospheric pressure. If unreacted alkylene oxide remains after completion of the reaction, it can be removed by reducing the pressure of the reaction system to obtain the desired product. If the form of the target product is an aqueous solution, it can be commercialized as it is, can be concentrated if necessary, and can be diluted or adjusted with an organic solvent or the like.

In addition, aminoethylsulfonic acid quaternary ammonium salt includes aminoethylsulfonic acid (taurine: H ₂ NCH ₂ CH ₂ SO ₃ H), monoalkyltri-2-hydroxyethylammonium hydroxide, dialkyldi-2-hydroxyethylammonium. It can be synthesized by a neutralization reaction with hydroxide, trialkylmono-2-hydroxyethylammonium hydroxide or the like. In addition, monoalkyltri-2-hydroxyethylammonium hydroxide can be produced, for example, by reacting 3 times mole of ethylene oxide with a monomethylamine aqueous solution.

  Further, a taurine salt such as taurine sodium salt, potassium salt, ammonium salt or the like is used as a raw material, and 2-fold moles of ethylene oxide are added thereto to form N, N-bis (2-hydroxyethyl) aminoethyl sulfonate. The sulfonate can be converted to a monoalkyltri-2-hydroxyethyl quaternary ammonium salt or a dialkyldi-2-hydroxyethyl quaternary ammonium salt by an ion exchange method. However, this ion exchange method is not very advantageous economically because a special apparatus such as an ion exchange membrane is required as compared with the neutralization method described above.

  N, N-bis (2-hydroxyethyl) aminoethylsulfonic acid quaternary ammonium salt can be produced by adding diethanolamine to vinylsulfonic acid salt. It can also be produced by dehydrochlorination of taurine chloride and diethanolamine.

  The polyurethane resin contained in the aqueous polyurethane resin composition (aqueous solution and / or aqueous dispersion) in the present invention is produced using the sulfonic acid quaternary ammonium salt and various organic polyisocyanates.

  In the present invention, as the organic isocyanate compound, those conventionally used for polyurethane production can be used. Such an organic isocyanate compound is not particularly limited, but representative examples thereof include hexamethylene diisocyanate (HDI) as aliphatic polyisocyanate, isophorone diisocyanate (IPDI), norbornene diisocyanate (as alicyclic polyisocyanate). NDI), araliphatic polyisocyanate as xylylene diisocyanate (XDI), aromatic polyisocyanate as 2,4- or 2,6-toluene diisocyanate (TDI), diphenylmethane-2,4′- or 4, 4'-diisocyanate (MDI), etc. are mentioned, respectively. These isocyanates may be used alone or in a mixture of two or more. Of these, preferred are MDI, HDI and IPDI, and particularly preferred is HDI.

  In this invention, the compound which has an active hydrogen group other than the sulfonic acid quaternary ammonium salt shown by General formula (1) can be contained in a molecular chain. Although it does not specifically limit as a compound which has an active hydrogen group, For example, a high molecular polyol, a low molecular weight active hydrogen compound, etc. are mentioned. Representative examples of the polymer polyol include polyether polyol, polyester polyol, and silicone polyol. Examples of the polyether polyol include compounds having a structure in which an alkylene oxide is added to a polyfunctional compound containing an active hydrogen group. For example, an alkylene oxide adduct of polyhydric phenols such as bisphenol A and an alkylene of amines such as hexamethylenediamine. And oxide adducts. Moreover, these can also be used in mixture of 2 or more types.

  Low molecular weight active hydrogen compounds include bifunctional polyols such as ethylene glycol, propylene glycol, 1,3- or 1,4-butanediol, neopentyl glycol, and diethylene glycol, and trifunctional groups such as glycerin, trimethylolpropane, and sorbitol. The above polyols, polyhydric phenols such as bisphenol A, and amines such as monoethanolamine, diethanolamine, triethanolamine, ethylenediamine, hexamethylenediamine, diethylenetriamine, isophoronediamine, tolylenediamine, and mixtures of two or more of these Can be mentioned.

  Moreover, the monofunctional active hydrogen containing compound normally called a terminal sealing material can be used as a compound which has an active hydrogen group. Although not particularly limited, for example, monoalcohols such as methanol, ethanol, propanol, butanol and higher alcohols, or alkylene oxide adducts of these monoalcohols, oximes such as methyl ethyl ketoxime, lactams such as ε-caprolactam, And amines such as dibutylamine, and these can be used alone or as a mixture of two or more.

  The polyurethane resin contained in the aqueous polyurethane resin aqueous solution and aqueous dispersion of the present invention can be produced by a known method. Examples of the production method include organic polyisocyanate and sulfonic acid quaternary ammonium salt and active hydrogen group-containing compound component, and an isocyanate group: active hydrogen group equivalent ratio in the range of 0.4 to 3.0: 1.0. The organic solvent is usually reacted at 20 to 150 ° C., preferably at 40 to 80 ° C. for 2 to 20 hours, and then usually made aqueous at 10 to 60 ° C., preferably 20 to 40 ° C. A method for obtaining the desired aqueous polyurethane resin by distilling off under reduced pressure. In addition, you may add the amine of the chain extender etc. which are a well-known method to the water to add.

  In the production of a polyurethane resin, an isocyanate compound and an active hydrogen-containing compound (including the sulfonic acid quaternary ammonium salt of the present invention and, if necessary, another active hydrogen compound) are reacted in one step to directly produce polyurethane. The production method may be a two-stage method (prepolymer method) in which an isocyanate compound is excessively used to form a urethane prepolymer once, and then the prepolymer is reacted with a polyol compound, an amine or the like.

  The content of the sulfonic acid group in the polyurethane resin necessary for the aqueous formation can be arbitrarily determined according to the purpose. The upper limit of the content is determined by the molecular weight of the isocyanate compound to be used and the quaternary ammonium salt of sulfonic acid as long as the required properties of the polyurethane resin are satisfied. In general, when the polyurethane resin is used for the purpose of self-dispersing, it is preferably 1.0 to 5.0% by weight based on the solid content of the polyurethane resin. If it exceeds 5.0% by weight, it is not a self-dispersed body but an aqueous solution, but the film performance of the polyurethane resin deteriorates.

  However, when a hydrophilic polyol such as polyethylene glycol is used in combination with the polyol component, an aqueous dispersion of the polyurethane resin can be obtained even if the polyol component is less than 1.0%. On the other hand, when making it water-soluble, it is preferable to use 5.0% by weight or more, and it is particularly effective to use it in combination with other hydrophilic groups. In addition, when the sulfonic acid quaternary ammonium salt is contained to give characteristics other than making the polyurethane resin aqueous, there is no particular upper limit on the content. The content of the sulfonic acid group in the resin solid content is adjusted by changing the use ratio of the sulfonic acid quaternary ammonium salt represented by the general formula (1).

  In the production process of the aqueous polyurethane composition, it is necessary to react the sulfonic acid quaternary ammonium salt represented by the general formula (1), the organic polyisocyanate compound, and a compound containing an active hydrogen group as necessary. Depending on the solvent, an inert solvent for the isocyanate group may be used.

  The solvent inert to the isocyanate group is not particularly limited, but amide solvents such as N-methylpyrrolidone, dimethylformamide, dimethylacetamide, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, toluene, Examples thereof include aromatic hydrocarbon solvents such as xylene and ether solvents such as dioxane and tetrahydrofuran. These may be used in combination of two or more. The amount of the solvent is usually 0 to 200% by weight with respect to the solid content of the polyurethane resin. The reaction temperature is usually 20 to 150 ° C, preferably 30 to 80 ° C. The reaction time is usually 3 to 20 hours. The reaction pressure is usually performed under normal pressure, but may be performed under pressure.

  In order to promote the reaction, for example, an amine catalyst (triethylenediamine, N-methylmorpholine, triethylamine, etc.), a tin catalyst (dibutyltin dilaurate, etc.), a lead catalyst (lead octylate, etc.), etc. are used. Also good.

  The solid content of the aqueous polyurethane resin aqueous solution and aqueous dispersion finally obtained in the present invention is usually 10 to 70% by weight, and this can be adjusted according to the purpose.

  Moreover, these water-based polyurethane resins can form a favorable coating film by volatilizing water, for example, by heating at 10 to 180 ° C., preferably 30 to 180 ° C., after application to a substrate. . The aqueous polyurethane resin aqueous solution and aqueous dispersion of the present invention include an emulsion stabilizer, an antioxidant, an ultraviolet absorber, a pigment, a colorant, an antifoaming agent, a flow regulator, a water repellent, a slippery agent as necessary. Various additives such as property-imparting agents and fillers can also be added.

  EXAMPLES Next, although an Example is given and this invention is demonstrated further more concretely, this invention is not restrict | limited by these Examples. The chemical analysis, instrumental analysis, and evaluation of the aqueous polyurethane composition were performed according to the following methods.

(1) Hydroxyl value A predetermined amount of sample is reacted with an excess of acetic anhydride in a pyridine solvent under slight boiling, and the resulting acetic acid and the remaining acetic acid are automatically titrated (AT-420, manufactured by Kyoto Electronics Industry Co., Ltd.). And titrate with an aqueous N / 2 potassium hydroxide solution. The hydroxyl value was calculated from the difference from the blank and displayed in units of mgKOH / g.

(2) Acid value A predetermined amount of the sample is titrated with an N / 10 HCl aqueous solution using an automatic titrator (AT-420, manufactured by Kyoto Electronics Industry Co., Ltd.). Thereafter, the sulfonic acid groups are similarly back titrated with an N / 10 KOH aqueous solution. The acid value was calculated from the titration value and displayed in units of mgKOH / g.

(3) Alkali value A predetermined amount of sample is titrated with an N / 10 HCl aqueous solution using an automatic titrator (AT-420, manufactured by Kyoto Electronics Industry Co., Ltd.). The alkali value was calculated from the titration value and displayed in units of mgKOH / g.

(4) Infrared absorption spectrum analysis It measured using JASCO Corporation FT-IR-610.

(5) Nuclear magnetic resonance analysis It measured using Hitachi Ltd. RS-NMR and R-1200.

(6) Solvent solubility of sulfonic acid quaternary ammonium salt Using N-methylpyrrolidone and dimethylformamide as solvents, the solubility of sulfonic acid quaternary ammonium salt 10% at a temperature of 20 ° C was visually evaluated.
Evaluation criteria: ○: Completely dissolved
×: Unmelted

(7) Dispersibility of aqueous composition (dispersion)
The urethane dispersion was collected in a test tube and allowed to stand at room temperature for one month, and the presence or absence of separation and particle settling was visually confirmed.
Evaluation criteria: ○: No sedimentation or separation of particles
Δ: Precipitation of a small amount of particles
×: Sedimentation and separation of a large amount of particles

(8) Applicability (coating film formation state)
A urethane dispersion was applied on the glass plate and dried at 100 ° C. for 3 hours, and the formation state of the coating film was visually evaluated.
Evaluation criteria: ○: A uniform and transparent coating film is formed, and there is no crack
Δ: A transparent film was formed although there were some cracks
X: There was a large amount of cracks, and a partially opaque coating film was formed

(9) Heat resistance (coating film formation state)
A urethane dispersion was applied on a glass plate, dried at 70 ° C. for 3 hours, and further heated to a predetermined temperature (170 ° C. or 190 ° C.), and the state of the coating film after 1 hour was visually evaluated.
Evaluation criteria: ○: No burning or yellowing
Δ: Slightly burnt and yellowing
×: Significant burning and yellowing

[Production Example 1]
(N, N-bis (2-hydroxyethyl) aminoethylsulfonic acid monomethyltri-2-hydroxyethyl quaternary ammonium salt)
(1) Production of Taurine Quaternary Ammonium Salt In a 1.5 L metal autoclave, 200 g of monomethylamine aqueous solution (40%) and 324 g of water were placed and sealed, and then 364 g of ethylene oxide was added while maintaining the temperature at 45-50 ° C. The reaction was carried out by continuously feeding over 4.5 hours. During this time, the pressure was kept at 0.15 MPa or less. After completion of the ethylene oxide feed, an aging reaction was further carried out at the same temperature for 30 minutes to obtain 879 g of a quaternary ammonium salt aqueous solution.

Next, 579 g of the obtained quaternary ammonium aqueous solution and 200 g of taurine were neutralized in a 1 L four-neck flask, 142 g of water was added, and 912 g of a taurine quaternary ammonium salt aqueous solution having a solid content of 50% was obtained.
(2) Reaction with alkylene oxide After putting 600 g of the taurine quaternary ammonium salt aqueous solution prepared above in a metal autoclave having a capacity of 1.5 L and sealing, 96 g of ethylene oxide was added over 3 hours while maintaining the temperature at 45 to 50 ° C. The reaction was carried out by feeding continuously. During this time, the pressure was kept at 0.15 MPa or less. After completion of the ethylene oxide feed, an aging reaction was further performed at the same temperature for 30 minutes. The reaction between the taurine salt and the alkylene oxide was performed using 600 g of a taurine quaternary ammonium salt aqueous solution having a solid content of 50% (solid content: 300 g, water: 300 g). Therefore, in Table 1, the reaction medium is 300 g of water. Is displayed.

  Thereafter, water in the reaction product was dehydrated and removed at 110 ° C. under reduced pressure (1.3 kPa · abs) to obtain 384 g of a product liquid at room temperature.

  When the product was chemically analyzed, the water content was 0.2%, the hydroxyl value was 723, the acid value was 144, and the alkali value was 144. The purity calculated from the results of the chemical analysis was 97%.

  Further, from the infrared absorption spectrum and 1H-NMR, the structure of N, N-bis (2-hydroxyethyl) aminoethylsulfonic acid monomethyltri-2-hydroxyethyl quaternary ammonium salt represented by the following formula (4) was identified. It was done.

IR (KBr) 2948 cm ⁻¹ , 1174 cm ⁻¹ , 1038 cm ⁻¹ , 951 cm ⁻¹ , 741 cm ⁻¹
1H-NMR (D ₂ O) δ = 3.2 to 3.5 (m, 4H, —SO ₂ —CH ₂ —CH ₂ —) δ = 3.3 (s, 3H, N ⁺ —CH ₃ )
The results are shown in Table 1.

[Production Example 2]
(N, N-bis (2-hydroxyethyl) aminoethylsulfonic acid dimethyldi-2-hydroxyethyl quaternary ammonium salt)
(1) Production of Taurine Quaternary Ammonium Salt In a 1.5 L metal autoclave, 200 g of dimethylamine aqueous solution (50%) and 200 g of water were placed and sealed, and then 200 g of ethylene oxide was added while maintaining the temperature at 45-50 ° C. The reaction was carried out by continuously feeding over 3 hours. During this time, the pressure was kept at 0.15 MPa or less. After completion of the ethylene oxide feed, a further aging reaction was carried out at the same temperature for 30 minutes to obtain 594 g of a quaternary ammonium salt aqueous solution.

Next, 483 g of the obtained aqueous quaternary ammonium solution and 200 g of taurine were neutralized in a 1 L four-necked flask, 142 g of water was added, and 817 g of an aqueous taurine quaternary ammonium salt solution having a solid content of 50% was obtained.
(2) Reaction with alkylene oxide After putting 600 g of the taurine quaternary ammonium salt aqueous solution prepared above in a metal autoclave having a capacity of 1.5 L and sealing, 107 g of ethylene oxide was added over 3 hours while maintaining the temperature at 45 to 50 ° C. The reaction was carried out by feeding continuously. During this time, the pressure was kept at 0.15 MPa or less. After completion of the ethylene oxide feed, an aging reaction was further performed at the same temperature for 30 minutes.

  Thereafter, water in the reaction product was dehydrated and removed at 110 ° C. under reduced pressure (1.3 kPa · abs) to obtain 395 g of a liquid product at room temperature.

  When the product was chemically analyzed, it had a water content of 0.2%, a hydroxyl value of 633, an acid value of 159, and an alkali value of 159, and the purity calculated from the results of the chemical analysis was 99%.

  The structure of N, N-bis (2-hydroxyethyl) aminoethylsulfonic acid dimethyldi-2-hydroxyethyl quaternary ammonium salt represented by the following formula (3) was identified from the infrared absorption spectrum and 1H-NMR. It was.

^{IR (KBr) 3039cm -1, 2944cm} -1, 1172cm -1, 1037cm -1, 959cm -1, 739cm -1
1H-NMR (D ₂ O) δ = 3.2 to 3.5 (m, 4H, —SO ₂ —CH ₂ —CH ₂ —) δ = 3.3 (s, 6H, N ⁺ —CH ₃ )
The results are shown in Table 1.

[Production Example 3]
(N, N-bis (2-hydroxyethyl) aminoethylsulfonic acid trimethyl mono-2-hydroxyethyl quaternary ammonium salt)
(1) Production of Taurine Quaternary Ammonium Salt 400 g of trimethylamine aqueous solution (30%) was put in a 1.5 L metal autoclave and sealed, and then 89 g of ethylene oxide was added over 1.5 hours while maintaining the temperature at 45-50 ° C. The reaction was carried out by feeding continuously. During this time, the pressure was kept at 1.5 atm or less. After completion of the ethylene oxide feed, a ripening reaction was further carried out at the same temperature for 30 minutes to obtain 485 g of a quaternary ammonium salt aqueous solution.

Next, 453 g of the obtained quaternary ammonium aqueous solution and 200 g of taurine were neutralized in a 1 L four-necked flask, 77 g of water was added, and 722 g of a taurine quaternary ammonium salt aqueous solution having a solid content of 50% was obtained.
(2) Reaction with alkylene oxide After putting 600 g of the taurine quaternary ammonium salt aqueous solution prepared above in a metal autoclave having a capacity of 1.5 L and sealing it, 122 g of ethylene oxide was taken for 3 hours while maintaining the temperature at 45 to 50 ° C. The reaction was carried out by feeding continuously. During this time, the pressure was kept at 0.15 MPa or less. After completion of the ethylene oxide feed, an aging reaction was further performed at the same temperature for 30 minutes.

  Thereafter, water in the reaction product was dehydrated and removed at 110 ° C. under reduced pressure (1.3 kPa · abs) to obtain 409 g of a liquid product at room temperature.

  When the product was chemically analyzed, it had a water content of 0.1%, a hydroxyl value of 540, an acid value of 173, and an alkali value of 173, and the purity calculated from the results of the chemical analysis was 98%.

  In addition, the structure of N, N-bis (2-hydroxyethyl) aminoethylsulfonic acid trimethylmono-2-hydroxyethyl quaternary ammonium salt represented by the following formula (2) was identified from the infrared absorption spectrum and 1H-NMR. It was done.

IR (KBr) 3034 cm ⁻¹ , 2948 cm ⁻¹ , 1176 cm ⁻¹ , 1038 cm ⁻¹ , 957 cm ⁻¹ , 742 cm ⁻¹
1H-NMR (D ₂ O) δ = 3.2 to 3.5 (m, 4H, —SO ₂ —CH ₂ —CH ₂ —) δ = 3.3 (s, 9H, N ⁺ —CH ₃ )
The results are shown in Table 1.

[Production Example 4]
(N, N-bis (2-methyl-2-hydroxyethyl) aminoethylsulfonic acid monomethyltri-2-hydroxyethyl quaternary ammonium salt)
(1) Production of Taurine Quaternary Ammonium Salt In a 1.5 L metal autoclave, 200 g of monomethylamine aqueous solution (40%) and 324 g of water were placed and sealed, and then 364 g of ethylene oxide was added while maintaining the temperature at 45-50 ° C. The reaction was carried out by continuously feeding over 4.5 hours. During this time, the pressure was kept at 0.15 MPa or less. After completion of the ethylene oxide feed, an aging reaction was further carried out at the same temperature for 30 minutes to obtain 879 g of a quaternary ammonium salt aqueous solution.

Next, 579 g of the obtained quaternary ammonium aqueous solution and 200 g of taurine were neutralized in a 1 L four-neck flask, 142 g of water was added, and 912 g of a taurine quaternary ammonium salt aqueous solution having a solid content of 50% was obtained.
(2) Reaction with alkylene oxide After putting 600 g of the aqueous taurine quaternary ammonium salt solution prepared above in a metal autoclave having a capacity of 1.5 L and sealing it, 127 g of propylene oxide was maintained for 4 hours while maintaining the temperature at 50 to 55 ° C. The reaction was continued by feeding continuously. During this time, the pressure was kept at 0.15 MPa or less. After completion of the propylene oxide feed, an aging reaction was further performed at the same temperature for 2 hours.

  Thereafter, water in the reaction product was dehydrated and removed at 110 ° C. under reduced pressure (1.3 kPa · abs) to obtain 414 g of a product liquid at room temperature.

  When the product was chemically analyzed, the water content was 0.2%, the hydroxyl value was 720, the acid value was 145, and the alkali value was 146. The purity calculated from the results of the chemical analysis was 96%.

  Further, from the infrared absorption spectrum and 1H-NMR, N, N-bis (2-methyl-2-hydroxyethyl) aminoethylsulfonic acid monomethyltri-2-hydroxyethyl quaternary ammonium salt represented by the following formula (6) The structure of was identified.

^{IR (KBr) 2960cm -1, 1180cm} -1, 1041cm -1, 948cm -1, 740cm -1
1H-NMR (D ₂ O) δ = 3.2 to 3.5 (m, 4H, —SO ₂ —CH ₂ —CH ₂ —) δ = 3.3 (s, 3H, N ⁺ —CH ₃ ) δ = 2.8 (d, 6H, -N -C (CH 3) -)
The results are shown in Table 1.

[Production Example 5]
(N, N-bis (2-hydroxyethyl) aminoethylsulfonic acid trimethyl mono-2-hydroxypropyl quaternary ammonium salt)
(1) Production of Taurine Quaternary Ammonium Salt 400 g of trimethylamine aqueous solution (30%) was placed in a 1.5 L metal autoclave and sealed, and then 118 g of propylene oxide was added over 2 hours while maintaining the temperature at 45-50 ° C. The reaction was carried out by continuously feeding. During this time, the pressure was kept at 0.15 MPa or less. After completion of the propylene oxide feed, an aging reaction was further performed at the same temperature for 2 hours to obtain 513 g of a quaternary ammonium salt aqueous solution.

  Next, 470 g of the obtained quaternary ammonium aqueous solution and 200 g of taurine were neutralized in a 1 L capacity four-necked flask, and 104 g of water was added to obtain 767 g of an aqueous taurine quaternary ammonium salt solution having a solid content of 50%.

(2) Reaction with alkylene oxide After placing 600 g of the aqueous taurine quaternary ammonium salt solution prepared above in a metal autoclave having a capacity of 1.5 L and sealing, 115 g of ethylene oxide was added over 3 hours while maintaining the temperature at 45 to 50 ° C. The reaction was carried out by feeding continuously. During this time, the pressure was kept at 0.15 MPa or less. After completion of the ethylene oxide feed, an aging reaction was further performed at the same temperature for 30 minutes.

  Thereafter, water in the reaction product was dehydrated and removed at 110 ° C. under reduced pressure (1.3 kPa · abs) to obtain 402 g of a liquid product at room temperature.

  When the product was chemically analyzed, it had a water content of 0.2%, a hydroxyl value of 525, an acid value of 164, and an alkali value of 164, and the purity calculated from the results of the chemical analysis was 97%.

  Further, from the infrared absorption spectrum and 1H-NMR, the structure of the trimethylmono-2-hydroxypropyl quaternary ammonium salt of N, N-bis (2-hydroxyethyl) aminoethylsulfonic acid represented by the following formula (11) was identified. It was done.

IR (KBr) 3033 cm ⁻¹ , 2937 cm ⁻¹ , 1173 cm ⁻¹ , 1036 cm ⁻¹ , 977 cm ⁻¹ , 737 cm ⁻¹
1H-NMR (D ₂ O) δ = 3.2 to 3.5 (m, 4H, —SO ₂ —CH ₂ —CH ₂ —) δ = 3.3 (s, 9H, N ⁺ —CH ₃ ) δ = 1.3 (d, 3H, -N -C (CH 3) -)
The results are shown in Table 1.

[Production Example 6]
(N, N-bis (2-hydroxyethyl) aminoethylsulfonic acid dimethyldi-2-hydroxypropyl quaternary ammonium salt)
(1) Production of Taurine Quaternary Ammonium Salt After putting 200 g of dimethylamine aqueous solution (50%) and 263 g of water in a metal autoclave with a capacity of 1.5 L and sealing, 264 g of propylene oxide while keeping the temperature at 45 to 50 ° C. Was continuously fed over 4 hours to carry out the reaction. During this time, the pressure was kept at 0.15 MPa or less. After completion of the propylene oxide feed, an aging reaction was further carried out at the same temperature for 2 hours to obtain 719 g of a quaternary ammonium salt aqueous solution.

  Next, 573 g of the obtained aqueous quaternary ammonium solution and 200 g of taurine were neutralized in a 1 L four-necked flask, 142 g of water was added, and 905 g of an aqueous taurine quaternary ammonium salt solution having a solid content of 50% was obtained.

(2) Reaction with alkylene oxide After putting 600 g of the taurine quaternary ammonium salt aqueous solution prepared above in a metal autoclave having a capacity of 1.5 L and sealing it, 128 g of ethylene oxide was taken for 3 hours while maintaining the temperature at 45 to 50 ° C. The reaction was carried out by feeding continuously. During this time, the pressure was kept at 0.15 MPa or less. After completion of the ethylene oxide feed, an aging reaction was further performed at the same temperature for 30 minutes.

  Thereafter, water in the reaction product was dehydrated and removed at 110 ° C. under reduced pressure (1.3 kPa · abs) to obtain 415 g of a liquid product at room temperature.

  When the product was chemically analyzed, it had a water content of 0.2%, a hydroxyl value of 611, an acid value of 147, and an alkali value of 147, and the purity calculated from the results of the chemical analysis was 98%. The chemical formula is shown in the following formula (13).

[Production Example 7]
(N, N-bis (2-hydroxyethyl) aminoethylsulfonic acid monomethyltri-2-hydroxypropyl quaternary ammonium salt)
(1) Production of Taurine Quaternary Ammonium Salt In a metal autoclave with a capacity of 1.5 L, 200 g of monomethylamine aqueous solution (40%) and 440 g of water were put and sealed, and then 480 g of propylene oxide while keeping the temperature at 45 to 50 ° C. Was continuously fed over 6 hours to carry out the reaction. During this time, the pressure was kept at 0.15 MPa or less. After completion of the propylene oxide feed, an aging reaction was further performed at the same temperature for 2 hours to obtain 1109 g of an aqueous quaternary ammonium salt solution.

  Next, 714 g of the obtained quaternary ammonium aqueous solution and 200 g of taurine were neutralized in a 1 L four-necked flask, 142 g of water was added, and 1045 g of a taurine quaternary ammonium salt aqueous solution having a solid content of 50% was obtained.

(2) Reaction with alkylene oxide After placing 600 g of the aqueous solution of taurine quaternary ammonium salt prepared in a metal autoclave having a capacity of 1.5 L and sealing it, 111 g of ethylene oxide was taken for 3 hours while maintaining the temperature at 45 to 50 ° C. The reaction was carried out by feeding continuously. During this time, the pressure was kept at 0.15 MPa or less. After completion of the ethylene oxide feed, an aging reaction was further performed at the same temperature for 30 minutes.

  Thereafter, water in the reaction product was dehydrated and removed at 110 ° C. under reduced pressure (1.3 kPa · abs) to obtain 398 g of a product liquid at room temperature.

  When the product was chemically analyzed, it was found to have a water content of 0.3%, a hydroxyl value of 690, an acid value of 129, and an alkali value of 130, and the purity calculated from the results of the chemical analysis was 97%. The chemical formula is shown in the following formula (15).

[Comparative Production Example 1]
(N, N-bis (2-hydroxyethyl) aminoethylsulfonic acid tetramethyl quaternary ammonium salt)
(1) Production of Taurine Quaternary Ammonium Salt 583 g of quaternary ammonium aqueous solution (25%) and 200 g of taurine are neutralized in a 1 L four-necked flask to obtain 775 g of an aqueous taurine quaternary ammonium salt solution having a solid content of 41%. It was.

(2) Reaction with alkylene oxide After placing 741 g of the aqueous taurine quaternary ammonium salt solution prepared above in a metal autoclave having a capacity of 1.5 L and sealing it, 140 g of ethylene oxide was taken over 3 hours while maintaining the temperature at 45 to 50 ° C. The reaction was carried out by feeding continuously. During this time, the pressure was kept at 0.15 MPa or less. After completion of the ethylene oxide feed, an aging reaction was further performed at the same temperature for 30 minutes.

  Thereafter, water in the reaction product was dehydrated and removed at 110 ° C. under reduced pressure (1.3 kPa · abs) to obtain 427 g of a product that was liquid at room temperature.

When the product was chemically analyzed, the water content was 0.2%, the hydroxyl value was 385, the acid value was 192, and the alkali value was 190, and the purity calculated from the results of the chemical analysis was 99%.
The reaction product had a melting point of about 75 ° C. and was in the form of a solid at room temperature.

[Example 1]
In a 1 L reaction vessel equipped with a stirrer, thermometer, and condenser, 90 g of polypropylene glycol (average molecular weight 2000), 15.1 g of hexamethylene diisocyanate (HDI), 224 g of solvent (N-methylpyrrolidone), and a tin-based catalyst The reaction was carried out at 60 ° C. for 12 hours with stirring. Next, 7.0 g of liquid N, N-bis (2-hydroxyethyl) aminoethylsulfonic acid monomethyltri-2-hydroxyethyl quaternary ammonium salt produced in Production Example 1 was added and stirred at 60 ° C. for 12 hours. Reacted. Next, after the reaction solution was cooled to 35 ° C., 500 g of distilled water was added, and the mixture was further stirred for 30 minutes. As a result, an aqueous polyurethane composition (dispersion) having a solid dispersion concentration of 13.4% and good dispersion stability was obtained. In addition, it was confirmed that the obtained polyurethane dispersion was applied to a substrate and dried to form a coating film. The blending amounts are summarized in Table 2, and the evaluation results are summarized in Table 3.

[Example 2]
Instead of the liquid N, N-bis (2-hydroxyethyl) aminoethylsulfonic acid monomethyltri-2-hydroxyethyl quaternary ammonium salt used in Example 1, the N, N-bis prepared in Production Example 2 was used. (2-hydroxyethyl) aminoethylsulfonic acid dimethyldi-2-hydroxyethyl quaternary ammonium salt, except that 8.0 g is used, polyurethane having a solid content concentration of 13.5% and good dispersion stability in the same manner as in Example 1. A dispersion was obtained. In addition, it was confirmed that the obtained polyurethane dispersion was applied to a substrate and dried to form a coating film.

[Example 3]
Instead of the liquid N, N-bis (2-hydroxyethyl) aminoethylsulfonic acid monomethyltri-2-hydroxyethyl quaternary ammonium salt used in Example 1, the N, N-bis prepared in Production Example 3 was used. Good dispersion stability at a solids concentration of 13.6% in the same manner as in Example 1 except that 9.4 g of trimethylmono-2-hydroxyethyl quaternary ammonium salt of (2-hydroxyethyl) aminoethylsulfonic acid was used. A polyurethane dispersion was obtained. In addition, it was confirmed that the obtained polyurethane dispersion was applied to a substrate and dried to form a coating film.

[Example 4]
Instead of the liquid N, N-bis (2-hydroxyethyl) aminoethylsulfonic acid monomethyltri-2-hydroxyethyl quaternary ammonium salt used in Example 1, the N, N-bis produced in Production Example 4 was used. (2-Methyl-2-hydroxyethyl) aminoethylsulfonic acid monomethyltri-2-hydroxyethyl quaternary ammonium salt was used in the same manner as in Example 1 except that 7.0 g was used. A polyurethane dispersion having good properties was obtained. In addition, it was confirmed that the obtained polyurethane dispersion was applied to a substrate and dried to form a coating film.

[Example 5]
Instead of the liquid N, N-bis (2-hydroxyethyl) aminoethylsulfonic acid monomethyltri-2-hydroxyethyl quaternary ammonium salt used in Example 1, the N, N-bis prepared in Preparation Example 5 was used. Good dispersion stability at a solids concentration of 13.6% in the same manner as in Example 1 except that 9.6 g of (2-hydroxyethyl) aminoethylsulfonic acid trimethylmono-2-hydroxypropyl quaternary ammonium salt was used. A polyurethane dispersion was obtained. In addition, it was confirmed that the obtained polyurethane dispersion was applied to a substrate and dried to form a coating film.

[Example 6]
Instead of the liquid N, N-bis (2-hydroxyethyl) aminoethylsulfonic acid monomethyltri-2-hydroxyethyl quaternary ammonium salt used in Example 1, the N, N-bis produced in Production Example 6 was used. (2-hydroxyethyl) aminoethylsulfonic acid dimethyldi-2-hydroxypropyl quaternary ammonium salt 8.3 g of polyurethane having a solid content concentration of 13.5% and good dispersion stability in the same manner as in Example 1. A dispersion was obtained. In addition, it was confirmed that the obtained polyurethane dispersion was applied to a substrate and dried to form a coating film.

[Example 7]
Instead of the liquid N, N-bis (2-hydroxyethyl) aminoethylsulfonic acid monomethyltri-2-hydroxyethyl quaternary ammonium salt used in Example 1, the N, N-bis produced in Production Example 7 was used. Dispersion stability with a solid content concentration of 13.4% is good as in Example 1 except that 7.3 g of (2-hydroxyethyl) aminoethylsulfonic acid monomethyltri-2-hydroxypropyl quaternary ammonium salt is used. A polyurethane dispersion was obtained. In addition, it was confirmed that the obtained polyurethane dispersion was applied to a substrate and dried to form a coating film.

[Comparative Example 1]
Instead of the liquid N, N-bis (2-hydroxyethyl) aminoethylsulfonic acid monomethyltri-2-hydroxyethyl quaternary ammonium salt used in Example 1, N at room temperature solid produced in Comparative Production Example 1 , N-bis (2-hydroxyethyl) aminoethylsulfonic acid tetramethyl quaternary ammonium salt (13.1 g) and the amount of distilled water was changed from 500 g to 480 g. An 8% polyurethane dispersion was obtained. At the time of polyurethane production reaction, there is a difficulty in handling a solid ammonium salt as a raw material, and the solubility in a solvent (N-methylpyrrolidone) is insufficient, so that a relatively large amount of solvent is required. Moreover, the coating film formation state was also bad compared with others.

[Example 8]
A 1 L reaction vessel equipped with a stirrer, thermometer, and condenser is charged with 90 g of polypropylene glycol (average molecular weight 2000), 15.1 g of hexamethylene diisocyanate (HDI), and a tin-based catalyst and stirred at 60 ° C. for 2 hours. Reacted. Next, 168 g of solvent (acetone) and 7.0 g of liquid N, N-bis (2-hydroxyethyl) aminoethylsulfonic acid monomethyltri-2-hydroxyethyl quaternary ammonium salt prepared in Production Example 1 were added, and the boiling point was increased. The reaction was carried out for 6 hours under stirring in the state (about 57 ° C.). Next, after the reaction solution was cooled to 35 ° C., 280 g of distilled water was added, and the mixture was further stirred for 30 minutes. Finally, the solvent acetone was distilled off by topping under reduced pressure to obtain an aqueous polyurethane composition (dispersion) having a solid content concentration of 28.6% and good dispersion stability. In addition, it was confirmed that the obtained polyurethane dispersion was applied to a substrate and dried to form a coating film.

[Example 9]
Instead of the liquid N, N-bis (2-hydroxyethyl) aminoethylsulfonic acid monomethyltri-2-hydroxyethyl quaternary ammonium salt used in Example 8, the N, N-bis prepared in Preparation Example 2 was used. (2-hydroxyethyl) aminoethylsulfonic acid dimethyldi-2-hydroxyethyl quaternary ammonium salt, except that 8.0 g was used, and a polyurethane having a good dispersion stability having a solid content concentration of 28.8% in the same manner as in Example 8. A dispersion was obtained. In addition, it was confirmed that the obtained polyurethane dispersion was applied to a substrate and dried to form a coating film.

[Example 10]
Instead of the liquid N, N-bis (2-hydroxyethyl) aminoethylsulfonic acid monomethyltri-2-hydroxyethyl quaternary ammonium salt used in Example 8, the N, N-bis prepared in Preparation Example 3 was used. Good dispersion stability at a solid content concentration of 29.0% in the same manner as in Example 8 except that 9.4 g of trimethylmono-2-hydroxyethyl quaternary ammonium salt of (2-hydroxyethyl) aminoethylsulfonic acid was used. A polyurethane dispersion was obtained. In addition, it was confirmed that the obtained polyurethane dispersion was applied to a substrate and dried to form a coating film.

[Example 11]
Instead of the liquid N, N-bis (2-hydroxyethyl) aminoethylsulfonic acid monomethyltri-2-hydroxyethyl quaternary ammonium salt used in Example 8, the N, N-bis prepared in Preparation Example 5 was used. Good dispersion stability at a solid content concentration of 29.1% in the same manner as in Example 8 except that 9.6 g of (2-hydroxyethyl) aminoethylsulfonic acid trimethylmono-2-hydroxypropyl quaternary ammonium salt was used. A polyurethane dispersion was obtained. In addition, it was confirmed that the obtained polyurethane dispersion was applied to a substrate and dried to form a coating film.

[Comparative Example 2]
Instead of the liquid N, N-bis (2-hydroxyethyl) aminoethylsulfonic acid monomethyltri-2-hydroxyethyl quaternary ammonium salt used in Example 8, N of solid at room temperature prepared in Comparative Production Example 1 was used. , N-bis (2-hydroxyethyl) aminoethylsulfonic acid tetramethyl quaternary ammonium salt was used in the same manner as in Example 8 to obtain a polyurethane dispersion having a solid content concentration of 29.7%. . At the time of polyurethane production reaction, there is a difficulty in handling a solid ammonium salt as a raw material, and the solubility in a solvent (acetone) is insufficient, so that a relatively large amount of solvent is required. Moreover, the coating film formation state was also bad compared with others.

[Comparative Example 3]
Instead of the liquid N, N-bis (2-hydroxyethyl) aminoethylsulfonic acid monomethyltri-2-hydroxyethyl quaternary ammonium salt used in Example 8, N of solid at room temperature prepared in Comparative Production Example 1 was used. , N-bis (2-hydroxyethyl) aminoethylsulfonic acid tetramethyl quaternary ammonium salt 9.2 g was used in the same manner as in Example 8 to obtain a polyurethane dispersion having a solid content concentration of 28.6%. . At the time of polyurethane production reaction, there is a difficulty in handling a solid ammonium salt as a raw material, and the solubility in a solvent (acetone) is insufficient, so that a relatively large amount of solvent is required. Moreover, the coating film formation state was also bad compared with others.

The aqueous polyurethane resin composition of the present invention has good water solubility or water dispersibility, and can be used for aqueous paints, aqueous inks, adhesives, various coating agents and the like.

Claims (11)

The aqueous polyurethane resin containing a sulfonic acid group-containing aqueous polyurethane resin comprising an aqueous solution or an aqueous dispersion dissolved or dispersed in water, wherein the polyurethane resin is represented by the following general formula (1) N, An aqueous polyurethane resin composition comprising N-bis (2-hydroxyalkyl) aminoethylsulfonic acid quaternary ammonium salt in a molecular chain by a urethane bond.

(Wherein R1 and R2 represent the same or different alkylene group having 2 to 4 carbon atoms, at least one of R3 to R6 represents the same or different 2-hydroxyalkyl group having 2 to 4 carbon atoms, and The remainder represents the same or different linear, branched or cyclic alkyl group having 1 to 18 carbon atoms.)   The polyurethane resin contains a compound containing another active hydrogen group in the molecular chain together with the quaternary ammonium salt of N, N-bis (2-hydroxyalkyl) aminoethylsulfonic acid represented by the general formula (1). The aqueous polyurethane resin composition according to claim 1.   In general formula (1), R1 and R2 are both ethylene groups, at least one of R3 to R6 is a 2-hydroxyethyl group or 2-hydroxypropyl group, and the remainder is a methyl group, an ethyl group, a propyl group, The aqueous polyurethane resin composition according to claim 1 or 2, which is a butyl group or a benzyl group. Aqueous polyurethane comprising N, N-bis (2-hydroxyethyl) aminoethylsulfonic acid trimethylmono-2-hydroxyethyl quaternary ammonium salt represented by formula (2) in a molecular chain by a urethane bond Resin composition.

An aqueous polyurethane resin comprising N, N-bis (2-hydroxyethyl) aminoethylsulfonic acid dimethyldi-2-hydroxyethyl quaternary ammonium salt represented by the formula (3) in a molecular chain by a urethane bond Composition.

An aqueous polyurethane characterized by containing N, N-bis (2-hydroxyethyl) aminoethylsulfonic acid monomethyltri-2-hydroxyethyl quaternary ammonium salt represented by the formula (4) in the molecular chain by a urethane bond Resin composition.

A water-based polyurethane comprising N, N-bis (2-hydroxypropyl) aminoethylsulfonic acid monomethyltri-2-hydroxyethyl quaternary ammonium salt represented by the formula (6) in a molecular chain by a urethane bond Resin composition.

Aqueous polyurethane comprising N, N-bis (2-hydroxyethyl) aminoethylsulfonic acid trimethylmono-2-hydroxypropyl quaternary ammonium salt represented by formula (11) in a molecular chain by a urethane bond Resin composition.

An aqueous polyurethane comprising N, N-bis (2-hydroxyethyl) aminoethylsulfonic acid monomethyltri-2-hydroxypropyl quaternary ammonium salt represented by the formula (15) in a molecular chain by a urethane bond Resin composition.

An aqueous polyurethane resin comprising N, N-bis (2-hydroxyethyl) aminoethylsulfonic acid dimethyldi-2-hydroxypropyl quaternary ammonium salt represented by the formula (13) in a molecular chain by a urethane bond Composition.

With a N, N-bis (2-hydroxyalkyl) aminoethylsulfonic acid quaternary ammonium salt represented by the following general formula (1) and, if necessary, a compound containing another active hydrogen group, without solvent, Alternatively, a step of reacting with an organic polyisocyanate compound in a solvent inert to an isocyanate group, and after making the obtained reaction solution aqueous with water, or water or a chain such as an amine if necessary A method for producing an aqueous polyurethane resin composition comprising the step of distilling off the solvent as necessary after chain extension and aqueous formation with water to which an extender is added.

(Wherein R1 and R2 represent the same or different alkylene group having 2 to 4 carbon atoms, at least one of R3 to R6 represents the same or different 2-hydroxyalkyl group having 2 to 4 carbon atoms, and The remainder represents the same or different linear, branched or cyclic alkyl group having 1 to 18 carbon atoms.)