JP2004203972A - Polyurethane-hydrophilizing agent and water-dispersible polyurethane resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyurethane-hydrophilizing agent which gives excellent hydrophilicity to polyurethanes, and to provide a water-dispersible polyurethane resin which has excellent storage stability, mechanical stability, and the like, and is stable against pH change. <P>SOLUTION: This polyurethane-hydrophilizing agent contains a compound represented by general formula (1): MOSO<SB>2</SB>-(CH<SB>2</SB>)<SB>m</SB>-HN-(CH<SB>2</SB>)<SB>n</SB>-NH-(CH<SB>2</SB>)<SB>m</SB>-SO<SB>3</SB>M [M is an alkali metal, an alkaline earth metal, an organic base, a group derived from the organic base, ammonium group, or H; (m) is an integer of 2 to 6; (n) is an integer of 2 to 10]. The water-dispersible polyurethane resin obtained by reacting a diol component with an organic diisocyanate to obtain the terminal isocyanate group-having prepolymer and then reacting the prepolymer with the above-described polyurethane-hydrophilizing agent. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a polyurethane hydrophilic agent used for hydrophilizing a polyurethane resin, a water-dispersible polyurethane resin obtained by using the hydrophilic agent, and a method for producing the water-dispersible polyurethane resin.
[0002]
[Prior art]
The water-dispersible dispersion of polyurethane is useful for various uses such as paints, fiber treatment, and adhesion. As such a water-dispersible polyurethane, a urethane resin containing a carboxyl group as a hydrophilic group is known. However, storage stability is poor due to easy hydrolysis, and stability due to pH change and heat resistance of the film are poor. Is also inadequate. A method for producing a sulfonic acid group-containing urethane dispersion by introducing a sulfonic acid (salt) group into a urethane resin using taurine is also known (for example, see Patent Document 1), but using taurine. When a sulfonic acid (salt) group is introduced by the above method, only a small amount of a sulfonic acid (salt) group can be introduced into the polyurethane. Therefore, the molecular weight of the urethane resin is restricted in order to obtain an aqueous dispersion. A method of obtaining an aqueous polyurethane dispersion using, for example, N- (2-aminoethyl) -2-aminoethanesulfonic acid salt as a diaminosulfonic acid salt is also known (for example, see Patent Document 2). In order to obtain the diaminosulfonic acid salt, there is a problem that the hydroxyalkanesulfonic acid and the diamine must be reacted under high temperature and high pressure.
[0003]
[Patent Document 1]
Japanese Patent Application Laid-Open No. Sho 42-24192
[Patent Document 2]
Canadian Patent No. 988323 Specification
[Problems to be solved by the invention]
An object of the present invention is to provide a polyurethane hydrophilizing agent which gives polyurethane excellent hydrophilicity, and a water-dispersible polyurethane resin which is excellent in storage stability, mechanical stability and the like and is stable against pH change. is there.
[0006]
[Means for Solving the Problems]
The present inventor has conducted intensive studies, and as a result, a polyurethane dispersion in which a polyurethane hydrophilized using a specific sulfonate is dispersed in water has excellent storage stability and mechanical stability. Was also found to be stable, and the present invention was completed.
[0007]
That is, the present invention provides a polyurethane hydrophilizing agent, a water-dispersible polyurethane resin, and a method for producing the water-dispersible polyurethane resin as described below.
Item 1. General formula (1);
_{MOSO 2 - (CH 2) m} -HN- (CH 2) n -NH- (CH 2) m -SO 3 M (1)
(In the formula, M represents an alkali metal, an alkaline earth metal, an organic base, a group derived from an organic base, an ammonium group, or a hydrogen atom. M represents an integer of 2 to 6, and n represents an integer of 2 to 10. A polyurethane hydrophilizing agent containing a compound represented by the formula:
Item 2. General formula (1);
_{MOSO 2 - (CH 2) m} -HN- (CH 2) n -NH- (CH 2) m -SO 3 M (1)
(In the formula, M represents an alkali metal, an alkaline earth metal, an organic base, a group derived from an organic base, an ammonium group, or a hydrogen atom. M represents an integer of 2 to 6, and n represents an integer of 2 to 10. And a compound represented by the general formula (2):
_{H 2 N- (CH 2) n} -NH- (CH 2) m -SO 3 M (2)
(In the formula, M represents an alkali metal, an alkaline earth metal, an organic base, a group derived from an organic base, an ammonium group, or a hydrogen atom. M represents an integer of 2 to 6, and n represents an integer of 2 to 10. A polyurethane hydrophilizing agent containing a compound represented by the formula:
Item 3. A water-dispersible polyurethane resin obtained by reacting a diol component with an organic diisocyanate to obtain a prepolymer having a terminal isocyanate group, and then reacting the prepolymer with the polyurethane hydrophilizing agent according to item 1.
Item 4. A water-dispersible polyurethane resin obtained by reacting a diol component with an organic diisocyanate to obtain a prepolymer having a terminal isocyanate group, and then reacting the prepolymer with the polyurethane hydrophilizing agent according to item 2.
Item 5. After obtaining a prepolymer having a terminal isocyanate group by reacting a diol component and an organic diisocyanate, a water-dispersible polyurethane resin characterized by reacting the prepolymer with the polyurethane hydrophilizing agent according to item 1 Production method.
Item 6. After obtaining a prepolymer having a terminal isocyanate group by reacting a diol component and an organic diisocyanate, a water-dispersible polyurethane resin characterized by reacting the prepolymer with a polyurethane hydrophilizing agent according to item 2 Production method.
[0008]
BEST MODE FOR CARRYING OUT THE INVENTION
The polyurethane hydrophilizing agent of the present invention has a general formula (1);
_{MOSO 2 - (CH 2) m} -HN- (CH 2) n -NH- (CH 2) m -SO 3 M (1)
(In the formula, M represents an alkali metal, an alkaline earth metal, an organic base, a group derived from an organic base, an ammonium group, or a hydrogen atom. M represents an integer of 2 to 6, and n represents an integer of 2 to 10. Is shown.). M is preferably an alkali metal, and more preferably sodium. m is preferably 2. n is preferably 2.
[0009]
Further, another polyurethane hydrophilizing agent of the present invention has a general formula (1):
_{MOSO 2 - (CH 2) m} -HN- (CH 2) n -NH- (CH 2) m -SO 3 M (1)
(In the formula, M represents an alkali metal, an alkaline earth metal, an organic base, a group derived from an organic base, an ammonium group, or a hydrogen atom. M represents an integer of 2 to 6, and n represents an integer of 2 to 10. And a compound represented by the general formula (2):
_{H 2 N- (CH 2) n} -NH- (CH 2) m -SO 3 M (2)
(In the formula, M represents an alkali metal, an alkaline earth metal, an organic base, a group derived from an organic base, an ammonium group, or a hydrogen atom. M represents an integer of 2 to 6, and n represents an integer of 2 to 10. Is shown.). M is preferably an alkali metal, and more preferably sodium. m is preferably 2. n is preferably 2.
[0010]
The polyurethane hydrophilizing agent of the present invention can be used to hydrophilize a polyurethane resin.
[0011]
The polyurethane hydrophilizing agent of the present invention can be obtained, for example, by an addition reaction of a sulfonate containing an ethylenic double bond with a diamine.
[0012]
Examples of the ethylenic double bond-containing sulfonate include vinyl sulfonate, allyl sulfonate, 1-butene-4-sulfonate, 1-pentene-5-sulfonate, 1-hexene-6-sulfonate And the like. Among them, vinyl sulfonate is preferred.
[0013]
Examples of the diamine include ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexamethylenediamine, 1,7-heptanediamine, 1,8-octanediamine, And aliphatic diamines such as 9,9-nonanediamine and 1,10-decanediamine. Among them, ethylenediamine is preferred.
[0014]
In order to carry out the addition reaction between the ethylenic double bond-containing sulfonic acid salt and the diamine, for example, an aqueous solution of the ethylenic double bond-containing sulfonic acid salt is added to the diamine, and about 0 to 120 ° C (preferably about 50 to 110 ° C) ) And react for 0.5 to 20 hours (preferably 2 to 10 hours). The amount of the diamine used is preferably about 0.5 to 2 in a molar ratio to the amount of the ethylenic double bond-containing sulfonate. Depending on the amount of the diamine used, an addition reaction product in which one or two of the amino groups of the diamine are added to the ethylenic double bond-containing sulfonate, or a mixture thereof is obtained. The addition reaction product in which two amino groups of the diamine are added to the ethylenic double bond-containing sulfonate corresponds to the compound represented by the general formula (1), and one of the amino groups of the diamine is ethylene. The addition reaction product added to the sulfonic acid salt having an acidic double bond corresponds to the compound represented by the general formula (2). The concentration of the aqueous solution at the time of the reaction is not particularly limited, but is preferably about 15 to 60% by mass, so that the reaction easily proceeds uniformly.
[0015]
The polyurethane dispersion obtained by using the polyurethane hydrophilizing agent containing the compound represented by the general formula (1) has excellent storage stability and mechanical stability. The addition reaction product represented by the general formula (1) is obtained by mixing a diamine and an ethylenic double bond-containing sulfonic acid salt with a diamine / ethylenic double bond-containing sulfonic acid salt at a ratio of about 1/2 (molar ratio). And can be easily obtained according to the above reaction conditions.
[0016]
The polyurethane hydrophilizing agent of the present invention may contain a mixture of the compound represented by the general formula (1) and the compound represented by the general formula (2). The mixture may be one obtained by simultaneously synthesizing both by a reaction, or one obtained by synthesizing both separately and then mixing. The mass ratio of the compound of the general formula (1) to the compound of the general formula (2) in the mixture is preferably in the range of the compound of the general formula (1) / the compound of the general formula (2) = 9/1 to 1/9.
[0017]
In the present invention, the diol component used in obtaining the prepolymer refers to a compound having two hydroxyl groups, and may be appropriately selected from those used in the production of ordinary urethane resins. Specific examples thereof include ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, and 3-methyl-1,5-pentanediol. , 1,6-hexanediol, neopentyl glycol, diethylene glycol, trimethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, and the like, as well as diols with these diols. Polyester di obtained by esterification reaction with dicarboxylic acid components such as acid, adipic acid, azelaic acid, sebacic acid, terephthalic acid, isophthalic acid, phthalic acid, 2,5-naphthalenedicarboxylic acid and 2,6-naphthalenedicarboxylic acid Lumpur, polycaprolactone diol, polytetramethylene glycol, polycarbonate diol, polyether diol.
[0018]
In the present invention, the organic diisocyanate used for obtaining the prepolymer refers to a compound having two isocyanate groups, and can be appropriately selected from those used in the production of ordinary urethane resins. Specific examples thereof include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4 '-Diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 1,5-naphthalenediisocyanate, 1,5-tetrahydronaphthalenediisocyanate, and the like. Examples of the aliphatic diisocyanate include tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate. Examples of the alicyclic diisocyanate include 1,3-cyclohexylene diisocyanate, 1,4-cyclohexylene diisocyanate, and isophorone diisocyanate. DOO, 4,4'-dicyclohexylmethane diisocyanate.
[0019]
In the method for producing a water-dispersible polyurethane resin according to the present invention, first, a diol component is reacted with an organic diisocyanate to obtain a prepolymer having a terminal isocyanate group. In the production reaction of the prepolymer, the amount of the organic diisocyanate to be used may be about 1.1 to 2.5, preferably about 1.2 to 2.0 in equivalent ratio to the diol component. This reaction can be carried out in the absence of a solvent, but in order to carry out the reaction uniformly, dioxane, acetone, methyl ethyl ketone, acetonitrile, ethyl acetate, even using an organic solvent inert to isocyanate groups such as tetrahydrofuran. Good. The reaction may be performed at about 30 to 150 ° C (preferably about 50 to 120 ° C) for about 0.1 to 20 hours (preferably about 0.5 to 10 hours). The number average molecular weight of the obtained prepolymer is about 500 to 50,000.
[0020]
Thus, after obtaining the prepolymer having a terminal isocyanate group, it is diluted with an organic solvent inert to the isocyanate group as described above, and the solid content of the prepolymer solution is about 10 to 60% by mass, Preferably, the content is suitably about 20 to 50% by mass.
[0021]
Next, the above-mentioned polyurethane hydrophilizing agent is added, and the reaction is carried out at about 30 to 100 ° C. for about 0.1 to 20 hours, whereby a water-dispersible polyurethane resin can be obtained. The hydrophilizing agent can be added as a solid content, but by adding it as an aqueous solution having a concentration of about 20 to 50% by mass, the dispersibility in the prepolymer solution is improved, and a more uniform reaction is achieved. It can be performed. The use amount of the polyurethane hydrophilizing agent is preferably about 0.05 to 1.2 equivalents to the terminal isocyanate group of the prepolymer. The resulting polyurethane resin has a number average molecular weight of about 1,000 to 200,000. Next, water is added thereto to form an aqueous dispersion, and the organic solvent is removed by a heating operation, a decompression operation, or the like, whereby a water-dispersible polyurethane resin is obtained. It is appropriate to adjust the solid content of the obtained resin to be about 10 to 70% by mass, preferably about 25 to 50% by mass.
[0022]
The water-dispersible polyurethane resin obtained by the method of the present invention may be, for example, various kinds of paints and coatings, adhesives, fiber treatments, leather, glass fiber sizing agents, etc. It can be used effectively for applications.
[0023]
【The invention's effect】
The polyurethane hydrophilizing agent of the present invention imparts excellent hydrophilicity to polyurethane.
[0024]
In addition, the water-dispersible polyurethane resin obtained by the method of the present invention has excellent storage stability, mechanical stability, etc., and is stable against pH changes, and the resulting film has heat resistance and solvent resistance. And so on.
[0025]
【Example】
Next, the present invention will be described in more detail with reference to examples.
[0026]
Example 1
To a four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser, 150 parts by mass of an ethylene glycol-adipic acid-based polyester (OH value: 56) is added, and after dissolving at 60 ° C., 32 parts by mass of isophorone diisocyanate is added. , 80 ° C, and reacted at this temperature for 4 hours. After the reaction was completed, the reaction mixture was diluted with 350 parts by mass of acetone to obtain a prepolymer solution having a number average molecular weight of about 3,000.
[0027]
Next, 1040 parts by mass of an aqueous solution of sodium vinyl sulfonate (concentration: 25% by mass) was added to 60 parts by mass of ethylenediamine, and the mixture was reacted at 100 ° C. for 8 hours to give a pale yellow color containing the two-component addition reaction product. An aqueous solution was obtained (adjusted to a solid content of 40% by mass). IR analysis confirmed the disappearance of the double bond. Further, NMR analysis of the product, NMR spectrum (D ₂ O, δppm) is, 2.4~2.6 (4H, m, N -C H 2 -C H 2 -N), 2. 7~2.8 (8H, m, N- C H 2 -C H 2 -SO 3 Na × 2) it was. Thereby, it was confirmed that the obtained addition reaction product was obtained by adding 2 mol of sodium vinylsulfonate to 1 mol of ethylenediamine (corresponding to the compound of the general formula (1)).
[0028]
To the prepolymer solution, 20 parts by mass of a 40% by mass aqueous solution of the hydrophilizing agent as the addition reaction product was added, and the mixture was stirred at 50 ° C. for 30 minutes. Next, 450 parts by mass of water was added to prepare an aqueous dispersion. The milky white dispersion thus obtained was gradually heated to about 100 ° C., and acetone was removed to obtain a milky white polyurethane dispersion.
[0029]
The product had a nonvolatile content of 30% by mass, a viscosity of 20 mPa · s / 25 ° C., a particle size of 120 nm, and a number average molecular weight of about 40,000, and was excellent in storage stability and pH stability. The resulting film was transparent, elastic, and excellent in adhesiveness.
[0030]
Example 2
To a four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser, 150 parts by mass of polytetramethylene glycol (OH value: 56) was added, and after dissolving at 60 ° C, 32 parts by mass of isophorone diisocyanate was added. And reacted at this temperature for 4 hours. After the completion of the reaction, the reaction mixture was diluted with 350 parts by mass of acetone to obtain a prepolymer solution having a number average molecular weight of about 3,000.
[0031]
Then, 520 parts by mass of an aqueous solution of sodium vinyl sulfonate (concentration: 25% by mass) was added to 60 parts by mass of ethylenediamine, and the reaction was carried out at 100 ° C. for 8 hours. A pale yellow aqueous solution containing the substance was obtained (adjusted to a solid content of 40% by mass). IR analysis confirmed the disappearance of the double bond. When two kinds of compounds (compound 1 and compound 2) were isolated from the obtained addition reaction product and subjected to NMR analysis, the NMR spectrum (D ₂ O, δ ppm) of compound 1 was 2.4 to 2. 6 (4H, m, N- C H 2 -C H 2 -N), was 2.7~2.8 (8H, m, N- C H 2 -C H 2 -SO 3 Na × 2) . Further, NMR spectrum of Compound ₂ (D 2 O, δppm) is, 2.4~2.6 (4H, m, N -C H 2 -C H 2 -N), 2.7~2.8 (4H , m, was _{N-C H 2 -C H 2} -SO 3 Na). As a result, the obtained addition reaction product was obtained by adding 2 mol of sodium vinyl sulfonate to 1 mol of ethylenediamine (compound 1, corresponding to the compound of the above general formula (1)) and 1 mol of ethylenediamine to 1 mol of sodium vinyl sulfonate It was confirmed that the mixture was a mixture with 1 mol of the compound (compound 2, corresponding to the compound of the above general formula (2)).
[0032]
To the prepolymer solution, 20 parts by mass of a 40% by mass aqueous solution of the hydrophilizing agent as the addition reaction product was added, and the mixture was stirred at 50 ° C. for 30 minutes. Next, 450 parts by mass of water was added to prepare an aqueous dispersion. The milky white dispersion thus obtained was gradually heated to about 100 ° C., and acetone was removed to obtain a milky white polyurethane dispersion.
[0033]
This product had a nonvolatile content of 30% by mass, a viscosity of 30 mPa · s / 25 ° C., a particle size of 150 nm, and a number average molecular weight of about 40,000, and was excellent in storage stability and pH stability. The resulting film was transparent, elastic, and excellent in adhesiveness.

Claims (6)

General formula (1);
_{MOSO 2 - (CH 2) m} -HN- (CH 2) n -NH- (CH 2) m -SO 3 M (1)
(In the formula, M represents an alkali metal, an alkaline earth metal, an organic base, a group derived from an organic base, an ammonium group, or a hydrogen atom. M represents an integer of 2 to 6, and n represents an integer of 2 to 10. A polyurethane hydrophilizing agent containing a compound represented by the formula: General formula (1);
_{MOSO 2 - (CH 2) m} -HN- (CH 2) n -NH- (CH 2) m -SO 3 M (1)
(In the formula, M represents an alkali metal, an alkaline earth metal, an organic base, a group derived from an organic base, an ammonium group, or a hydrogen atom. M represents an integer of 2 to 6, and n represents an integer of 2 to 10. And a compound represented by the general formula (2):
_{H 2 N- (CH 2) n} -NH- (CH 2) m -SO 3 M (2)
(In the formula, M represents an alkali metal, an alkaline earth metal, an organic base, a group derived from an organic base, an ammonium group, or a hydrogen atom. M represents an integer of 2 to 6, and n represents an integer of 2 to 10. A polyurethane hydrophilizing agent containing a compound represented by the formula: A water-dispersible polyurethane resin obtained by reacting a diol component with an organic diisocyanate to obtain a prepolymer having a terminal isocyanate group, and then reacting the prepolymer with the polyurethane hydrophilizing agent according to claim 1. A water-dispersible polyurethane resin obtained by reacting a diol component with an organic diisocyanate to obtain a prepolymer having a terminal isocyanate group, and then reacting the prepolymer with the polyurethane hydrophilizing agent according to claim 2. A water-dispersible polyurethane resin comprising reacting a diol component with an organic diisocyanate to obtain a prepolymer having a terminal isocyanate group, and then reacting the prepolymer with the polyurethane hydrophilizing agent according to claim 1. Manufacturing method. A water-dispersible polyurethane resin comprising reacting a diol component with an organic diisocyanate to obtain a prepolymer having a terminal isocyanate group, and then reacting the prepolymer with the polyurethane hydrophilizing agent according to claim 2. Manufacturing method.