TWI394766B - Phosphorous-containing waterborne polyurethane - Google Patents

Description

Phosphorus-containing waterborne polyurethane resin

This invention relates to a flame retardant aqueous polyurethane tree, and more particularly to a phosphorus containing aqueous polyurethane resin.

At present, the common types of flame retardants are intumescent flame retardants, inorganic fireproof materials, intumescent inks, and phosphorus-nitrogen flame retardants. When the above flame retardant is applied to the textile processing industry, problems such as difficulty in processing or poor washing fastness often occur. Even processed textiles may face problems such as insufficient flame retardancy and poor transparency, which can seriously detract from the physical properties and usability of processed textiles.

Therefore, the related industries need a flame retardant material suitable for the textile processing industry, and the textile processed by the flame retardant material does not substantially detract from the original physical properties of the textile, in addition to good washing fastness and high flame retardancy. With usability.

Therefore, the present invention provides a phosphorus-containing aqueous polyurethane resin which, when applied to textile processing, can obtain a textile having good washing fastness and high flame retardancy.

According to a specific embodiment of the present invention, the phosphorus-containing aqueous polyurethane resin contains at least 9,10-dihydro-9-oxo-10-phosphaphenone 10-oxide (9,10-dihydro-9-oxa-) 10-phosphaphenanthrene 10-oxide, DOPO) diol derivative and sodium sulfonate, wherein diol derivative of DOPO The system is grafted onto the main chain of the aqueous polyurethane resin by condensation polymerization of a hydroxyl group of a substituent on phosphorus with a monomer of the polyurethane resin.

Another aspect of the invention provides a composite flame retardant fabric and a method of preparing the same.

According to a specific embodiment of the present invention, the method comprises forming a phosphorus-containing aqueous polyurethane resin layer on the first textile; and placing the second textile on the phosphorus-containing aqueous polyurethane resin layer and bonding the second textile and the phosphorus-containing aqueous polyurethane resin layer . Wherein, the main chain of the phosphorus-containing aqueous polyurethane resin contains at least a diol derivative of DOPO and a sodium sulfonate, wherein the diol derivative of DOPO is obtained by condensation polymerization of a hydroxyl group of a substituent on phosphorus with a monomer of a polyurethane resin. The reaction is grafted onto the main chain of the aqueous polyurethane resin.

According to another embodiment of the present invention, the composite flame-retardant fabric comprises a first textile, a second textile, and a phosphorus-containing aqueous polyurethane resin layer. Wherein the phosphorus-containing aqueous polyurethane resin layer is interposed between the first textile and the second textile, wherein the main chain of the phosphorus-containing aqueous polyurethane resin comprises at least a diol derivative of DOPO and sodium sulfonate, wherein the diol of DOPO is derived The system is grafted onto the main chain of the aqueous polyurethane resin by condensation polymerization of a hydroxyl group of a substituent on phosphorus with a monomer of the polyurethane resin.

One aspect of the present invention provides a phosphorus-containing aqueous polyurethane resin, which is a reactive aqueous polyurethane resin and is prepared using an environmentally friendly halogen-free formulation. By applying the above phosphorus-containing aqueous polyurethane resin to textile processing, a textile having good washing fastness and high flame retardancy can be obtained. In addition, the above phosphorus-containing aqueous polyurethane resin can also be used for water Or oily coatings to impart flame retardant properties to the coating.

Another aspect of the present invention provides a composite flame-retardant fabric and a preparation method thereof, which are obtained by using the phosphorus-containing aqueous polyurethane resin proposed in the above aspect of the present invention to obtain the composite flame-retardant fabric. The obtained composite flame-retardant fabric has high flame retardancy and good washing fastness.

Hereinafter, the above-mentioned phosphorus-containing aqueous polyurethane resin, a preparation method thereof, and the above composite flame-retardant fabric and a preparation method thereof will be respectively described in detail in the specific examples of the present invention, and the washing fastness and flame retardancy test of the composite flame-retardant fabric are carried out.

(I) phosphorus-containing aqueous polyurethane resin and preparation method thereof

According to a specific embodiment of the present invention, in the prepolymerization stage of the aqueous polyurethane resin, a diol derivative of DOPO is added to participate in the prepolymerization of the aqueous polyurethane resin. Thereafter, a diamine-based compound having a sulfonate group is added to obtain a polyurethane resin, and then water is added to prepare an aqueous polyurethane resin.

Specifically, the method for preparing the above aqueous polyurethane resin comprises the steps of: (1) adding a bifunctional isocyanate to a diol derivative of DOPO and a diol polymer oligomer or a polyol polymer oligomer; a condensation polymerization reaction in which a diol derivative of DOPO is grafted onto a main chain of a polyurethane prepolymer by condensation polymerization of a hydroxyl group of a substituent on phosphorus with a monomer of a polyurethane resin; (2) in the above polyurethane prepolymer a diamine-based monomer compound, a sulfonate diamine-based monomer compound, and acetone are added to the polymer to obtain a polyurethane solution; (3) water is added to the polyurethane solution, and the mixture is stirred at a low rotation speed. The reaction is carried out to obtain a phosphorus-containing aqueous polyurethane resin.

According to an embodiment of the present invention, the glycol macromolecular oligomer or polyol high molecular oligomer used in the above step may be a polyester diol or a polyester polyol, a polyether diol or a polyether polyol. , polycarbonate diol or polycarbonate polyol, polylactone diol or polylactone polyol. Further, the molecular weight of the diol polymer oligomer or the polyol polymer oligomer used is about 600 to 5,000.

According to an embodiment of the present invention, the difunctional isocyanate used in the above step may be an aliphatic isocyanate, an aromatic isocyanate, an alicyclic isocyanate or a mixture of the above compounds. According to a particular embodiment of the invention, the difunctional isocyanate used is hexamethylene diisocyanate (HDI).

According to an embodiment of the present invention, the amino group monomer compound used in the above step has a molecular weight of about 30 to 400. The above diamine-based monomer compound can be used as a chain extender.

According to an embodiment of the present invention, the structural formula of the sulfonate diamine monomer compound used in the above step is as follows: Wherein m = 2-12, n = 1-3, and A is potassium or sodium. In addition to being a chain extender, the sulfonate diamine-based monomer compound can also increase the hydrophilicity and flame retardancy of the polyurethane resin. According to an embodiment of the present invention, the proportion of the sulfonate monomer in the phosphorus-containing aqueous polyurethane resin is about 1-3%.

According to an embodiment of the present invention, the amount of the diol derivative of DOPO used in the above step can be controlled so that the obtained phosphorus-containing aqueous polyurethane tree is obtained. In the fat, the phosphorus content is more than 880 ppm, and at this time, the phosphorus-containing waterborne polyurethane resin has a better flame retarding effect.

Further, according to an embodiment of the present invention, the diol derivative of DOPO used in the above step may be DOPO-hydroquinone (DOPO-HQ). However, in accordance with the principles and spirit of the present invention, other DOPO diol derivatives may also be employed, as long as the hydroxyl groups of the substituents on the phosphorus of the DOPO diol derivative and the monomers of the urethane resin are capable of undergoing the prepolymerization stage of the urethane resin. The condensation polymerization reaction may be carried out by grafting onto the main chain of the polyurethane prepolymer.

By way of illustration and not limitation, according to an experimental example of the present invention, a phosphorus-containing aqueous polyurethane resin is prepared as follows: (1) 4.877 g of DOPO-HQ is added to 193.3 g of poly(butylene glycol adipate) (poly(butylene) In the adipate) diol (abbreviated as PBA), after the DOPO-HQ is dissolved, the water in the solution is removed by heating; (2) 187.4 g of the step (1) solution and 187.4 g of PBA are stirred; (3) 53.97 g of HDI is added to the reaction system of step (2) for stirring, and the temperature of the reaction system is controlled to be below 100 ° C. After the stirring is completed, the reaction system is cooled to room temperature; (4) 237 g of acetone is slowly added to the step (3). In the reaction system; (5) mixing 2.7 g of hydrazine, 2.28 g of diethanolamine, and 23.16 g of sulfonate diamine monomer EES200L (purchased from Poly and International), and dropping into the reaction system of step (4) Medium, and stirred at 55 ° C; (6) adding 556.3 ml of slow water, and stirring at low speed for one night; (7) pumping acetone in the reaction system of step (6) to obtain Phosphorus waterborne polyurethane resin.

According to the above experimental example, the obtained phosphorus-containing aqueous polyurethane resin had a solid content of about 50.5% and a total amount of about 1 L.

Table 1 below shows the amounts of the reactants used in the above experimental examples (Experimental Example 1) and another Experimental Example (Experimental Example 2) of the present invention.

Therefore, according to the above specific embodiment, the phosphorus-containing aqueous polyurethane resin of the present invention comprises a 9,10-dihydro-9-oxo-10-phosphaphenanthrene 10-oxide (DOPO) in the main chain thereof. An alcohol derivative and a sodium sulfonate, wherein the diol derivative of DOPO is grafted onto the main chain of the aqueous polyurethane resin by condensation polymerization of a hydroxyl group of a substituent on the phosphorus with a monomer of the polyurethane resin.

(II) Analysis of composition and flame retardancy of phosphorus-containing waterborne polyurethane resin

The relationship between the phosphorus content in the above and other phosphorus-containing aqueous polyurethane resins and the ratio of sulfonate monomer and flame retardancy was analyzed in the relevant tests. Table 2 lists the results of some analyses. The flame retardancy test is based on the flow rate of oxygen and nitrogen according to ASTM D2863-00 to determine the minimum oxygen capacity available for combustion. The value obtained is the Limited Oxygen Index (LOI). In general, oxygen accounts for about 20% of air, so basically the LOI has a flame retardant effect as long as it is greater than 20.

According to relevant tests, in the phosphorus-containing waterborne polyurethane resin, the phosphorus content must be at least 880 ppm to exhibit a good flame retardant effect. Therefore, according to an embodiment of the present invention, the phosphorus-containing aqueous polyurethane resin has a phosphorus content of at least 880 ppm. Meanwhile, it can be found from Table 2 that since the phosphorus content in Experimental Example 3 is high, the LOI value thereof is relatively increased.

According to an embodiment of the present invention, in the phosphorus-containing aqueous polyurethane resin, the proportion of the sulfonate monomer is about 1-3%.

(III) composite flame retardant fabric and preparation method thereof

According to a specific embodiment of the present invention, a method for preparing a composite flame-retardant fabric comprises the steps of: (1) forming a phosphorus-containing aqueous polyurethane resin layer on the first textile, wherein the main chain of the phosphorus-containing aqueous polyurethane resin contains at least DOPO An alcohol derivative and sodium sulfonate, and the diol derivative of the above DOPO is grafted onto the main chain of the aqueous polyurethane resin by condensation polymerization of a hydroxyl group of a substituent on the phosphorus with a monomer of the polyurethane resin; and (2 And placing the second textile on the phosphorus-containing aqueous polyurethane resin layer and bonding the second textile and the phosphorus-containing aqueous polyurethane resin layer.

According to an embodiment of the invention, the first textile and the second textile may each be a polyester, a polyamine, a polyamide, a polyacrylonitrile, a hydrazine or a blended textile as described above. Further, according to an embodiment of the present invention, the first textile and the second textile may be the same or different textile types.

According to an embodiment of the present invention, a phosphorus-containing aqueous urethane resin layer may be formed on the first textile by a coating process or other suitable technique in the step (1). In accordance with an embodiment of the present invention, a second textile and a phosphorus-containing aqueous polyurethane resin layer may be joined using a heating process or other suitable technique in step (2).

(IV) Anti-flame test and washing fastness analysis of composite flame retardant fabric

The composite flame retardant fabric was prepared by using Nylon textiles and the phosphorus-containing waterborne polyurethane resin prepared in the above Experimental Example 1 and Experimental Example 2, and flameproofing was carried out. Wash fastness analysis.

The anti-flame test uses the textile anti-flame test CNS 10285 A-1 primary flame test.

The phosphorus-containing water-based polyurethane resin layers with thickness of 0 mm (control group), 0.2 mm, 0.3 mm, 0.4 mm, and 0.5 mm were formed on the Nylon textiles, and the flame-proof effects of water washing before washing and ten times of washing were respectively tested. To compare the washing fastness of the composite flame retardant fabric. Some test results are listed in Table 3.

It can be found from Table 3 that the composite flame retardant fiber prepared according to the embodiment of the present invention, whether before washing or after washing for ten times, the remaining flame time (the CNS10285 A-1 primary flameproof standard is within 50 seconds), the afterburning time (CNS10285 A-1 primary flameproof standard is less than 20 seconds) or carbonized area (CNS10285 A-1 primary flameproof standard is less than 40 cm ² ), all comply with CNS10285 A-1 first-class flameproof standard. On the other hand, the control group which does not contain the aqueous polyurethane resin proposed in the specific examples of the present invention is out of grade (i.e., does not conform to the primary and secondary flameproof standards of CNS10285 A-1).

While the present invention has been described above by way of a preferred embodiment, it is not intended to limit the invention, and the present invention may be modified and modified without departing from the spirit and scope of the invention. The scope of protection is subject to the definition of the scope of the patent application.

Claims (12)

A phosphorus-containing aqueous polyurethane resin comprising at least 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide (9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide, a diol derivative of DOPO) and a sodium sulfonate, wherein the diol derivative of the DOPO is grafted to the main chain of the aqueous polyurethane resin by condensation polymerization of a hydroxyl group of a substituent on the phosphorus with a monomer of the polyurethane resin The ratio of the sulfonate in the phosphorus aqueous polyurethane resin is about 1-3%, and the phosphorus content is at least 880 ppm. A composite flame-retardant fabric comprising: at least: a first textile; a second textile; and a phosphorus-containing aqueous polyurethane resin layer interposed between the first textile and the second textile, wherein the phosphorus-containing aqueous polyurethane resin is a diol derivative containing at least 9,10-dihydro-9-0xa-10-phosphaphenanthrene 10-oxide (DOPO) in the chain and a sulfonate a sodium salt, wherein the diol derivative of the DOPO is grafted onto the main chain of the aqueous polyurethane resin by condensation polymerization of a hydroxyl group of a substituent on the phosphorus with a monomer of the polyurethane resin, and the phosphorus aqueous polyurethane resin is The proportion of sulfonate is about 1-3% and the phosphorus content is at least 880 ppm. The composite flame retardant fabric of claim 2, wherein The first textile and the second textile are respectively of a polyester, a polyamine, a polyamide, a polyacrylonitrile, a hydrazine or a blended textile as described above. The composite flame-retardant fabric of claim 2, wherein the first textile and the second textile are the same or different textile types. The composite flame-retardant fabric of claim 2, wherein the phosphorus-containing aqueous polyurethane resin layer joins the first textile and the second textile. The composite flame-retardant fabric of claim 2, wherein the composite flame-retardant fabric meets the first-class flameproof standard of CNS 10285 A-1. The composite flame retardant fabric of claim 2, wherein the composite flame retardant fabric has an oxygen limit index (LOI) greater than 20. A method for preparing a composite flame-retardant fabric, comprising: forming a phosphorus-containing aqueous polyurethane resin layer on a first textile, wherein the phosphorus-containing aqueous polyurethane resin comprises at least 9,10-dihydro-9-oxygen in a main chain thereof a diol derivative of 10-, 10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide (DOPO) and sodium sulfonate, wherein the diol derivative of DOPO is utilized on phosphorus The hydroxyl group of the substituent and the monomer of the polyurethane resin are grafted onto the main chain of the aqueous polyurethane resin by condensation polymerization; A second textile is disposed on the phosphorus-containing aqueous polyurethane resin layer and joins the second textile and the phosphorus-containing aqueous polyurethane resin layer. The method for preparing a composite flame-retardant fabric according to claim 8, wherein the first textile and the second textile are respectively polyester, polyamine, polyamine, polyacrylonitrile, hydrazine or the above Blended textiles. The method for preparing a composite flame-retardant fabric according to claim 8, wherein the first textile and the second textile are the same or different textile types. The method for preparing a composite flame-retardant fabric according to claim 8, wherein the weight ratio of the sulfonate monomer in the phosphorus-containing aqueous polyurethane resin is about 1-3%. The method for preparing a composite flame-retardant fabric according to claim 8, wherein the phosphorus-containing aqueous polyurethane resin has a phosphorus content of at least 880 ppm.