AQUEOUS POLYURETHANE DISPERSIONS, PREPOLYMERS, AND SHAPED ARTICLES MADE THEREFROM

Abstract

Aqueous polyurethane dispersions, prepolymers for formation of these dispersions, methods for their use in shaping articles, as well as shaping articles produced thereby are provided.

Claims

1. A prepolymer for use in an aqueous polyurethane dispersion comprising a glycol, an isocyanate and a diol compound.

2. The prepolymer of claim 1 further comprising 1-hexanol.

3. A prepolymer for use in an aqueous polyurethane dispersion consisting of a glycol, an isocyanate and a diol.

4. A prepolymer for use in an aqueous polyurethane dispersion consisting of a glycol, an isocyanate, a diol and 1-hexanol.

5. The prepolymer of any of claims 1, 2, 3 or 4 wherein the isocyanate is dicyclohexylmethane diisocyanate.

6. The prepolymer of any of claims 1, 2, 3 or 4 containing at least 70% glycol, at least 20% isocyanate and at least 2% diol.

7. The prepolymer of claim 2 or claim 4 containing less than 1% 1-hexanol.

8. An aqueous polyurethane dispersion comprising the prepolymer of any of claims 1 through 7 and water, a neutralizer, a surfactant, a defoamer, an antioxidant or a thickener.

9. An aqueous polyurethane dispersion comprising the prepolymer of any of claims 1 through 7 and water, a neutralizer, a surfactant, a defoamer, an antioxidant and a thickener.

10. The aqueous polyurethane dispersion of claim 8 or claim 9 containing at least 30% glycol, at least 10% isocyanate and at least 1% diol.

11. The aqueous polyurethane dispersion of claim 10 further containing at least 50% water, at least 1% surfactant and/or thickener and/or less than 1% neutralizer, antioxidant or defoamer.

12. A method for producing a shaped article comprising applying the aqueous polyurethane dispersion of any of claims 8, 9, 10 or 11 to a substrate.

13. The method of claim 12 wherein the aqueous polyurethane dispersion is applied to the substrate by padding, coating, printing, bonding, spraying or laminating.

14. The method of claim 12 further comprising diluting the aqueous polyurethane dispersion prior to application to the substrate.

15. The method of claim 12 further comprising curing the aqueous polyurethane dispersion to the substrate.

16. The method of claim 12 wherein the substrate is a textile fabric.

17. The method of claim 12 wherein the aqueous polyurethane dispersion is applied as a film, tape or selected pattern of dots, shapes, zigzags or lines to the substrate where stretch and recovery is desired.

18. A shaped article produced by the method of any of claims 12, 13, 14, 15, 16 or 17.

19. The shaped article of claim 18 wherein the article is a garment.

20. The shaped article of claim 19 wherein the aqueous polyurethane dispersion is applied to a seam or support area of the garment.

21. The shaped article of claim 19 wherein the aqueous polyurethane dispersion is resistant to oxidative discoloring.

Description

BRIEF DESCRIPTION OF THE FIGURE

[0022] FIG. 1 shows a comparison of film whiteness retention.

DETAILED DESCRIPTION OF THE INVENTION

[0023] Aqueous polyurethane dispersions falling within the scope of the present invention are provided from particular urethane prepolymers, which also form an aspect of the present invention. The aqueous polyurethane dispersions and prepolymers contain no organic solvent or cosolvent, alkyl ethoxylates or organotin catalyst. The present invention can, in an additional embodiment, provide shaped articles produced by application of the aqueous polyurethane dispersions to substrates including textile fabrics. The dispersion can be applied by padding, coating, printing, bonding, laminating or other treatment methods and then cured with a residence time of about 1 to about 5 minutes. Upon drying, such articles exhibit high stretch and recovery.

[0024] As used herein, the term dispersion refers to a system in which the disperse phase consists of finely divided particles, and the continuous phase can be a liquid, solid or gas.

[0025] As used herein, the term aqueous polyurethane dispersion refers to a composition containing at least a polyurethane or polyurethane urea polymer or prepolymer (such as the polyurethane prepolymer described herein) that has been dispersed in an aqueous medium, such as water, including de-ionized water. The term further relates to such a composition that has been subjected to drying, for example, in the formation of a shaped article.

[0026] As used herein, the term solvent, unless otherwise indicated, refers to a non-aqueous medium, wherein the non-aqueous medium includes organic solvents, including volatile organic solvents (such as acetone) and somewhat less volatile organic solvents (such as MEK, or NMP).

[0027] As used herein, the term essentially solvent-free or essentially solvent-free system refers to a composition or dispersion wherein the bulk of the composition or dispersed components has not been dissolved or dispersed in a solvent.

[0028] As used herein, the term shaped article may refer to one of a number of objects including for example, film, tape, dots, webs, stripes, bead, and foam. A film may describe a sheet material of any shape. A tape may describe a film in narrow strip form. A film may be in the form of a tape. As used herein, the term shaped article refers to a layer comprising an aqueous polyurethane dispersion (such as the aqueous polyurethane dispersion containing the polyurethane prepolymer described herein) that can be directly applied to a substrate or release paper, which can be used for adhesion and/or to form a rigid or an elastic article.

[0029] As used herein, the term article refers to an article which comprises a dispersion or shaped article and a substrate, for example a textile fabric, which may or may not have at least one elastic property, in part, due to the application of a dispersion or shaped article as described herein.

[0030] As used herein, the term textile fabric refers to a knitted, woven or nonwoven material. The knitted fabric may be flat knit, circular knit, warp knit, narrow elastic, and/or lace. The woven fabric may be of any construction, for example sateen, twill, plain weave, oxford weave, basket weave, and/or narrow elastic. The nonwoven material may be meltblown, spun bonded, carded fiber-based staple webs, and the like.

[0031] As used herein, the term substrate refers to any material to which a shaped article can be attached or to which the aqueous polyurethane dispersion can be applied. A substrate can be substantially one dimensional as in a fiber, two dimensional as in a planar sheet, or a three dimensional article or a bumpy sheet. A planar sheet for example may comprise textile fabric, paper, flocked article, and/or web. A three dimensional article for example may comprise leather and/or foam. Other substrates may comprise wood, paper, plastic, metal, and composites such as concrete, asphalt, gymnasium flooring, and plastic chips.

[0032] As used herein, the term hard yarn refers to a yarn which is substantially non-elastic.

[0033] As used herein, the term molded article refers to a process by which the shape of an article or shaped article is changed in response to application of heat and/or pressure.

[0034] As used herein, the term derived from refers to forming a substance out of another object. For example, a shaped article may be derived from a dispersion which can be dried.

[0035] As used herein, the terms a or an may include one or more.

[0036] Prepolymers for use in the aqueous polyurethane dispersions of the present invention comprise a glycol, an isocyanate and a diol compound.

[0037] Glycol components suitable as a starting material for preparing prepolymers according to the invention include polycarbonates, and polyesters, polycarbonate glycols, and polyester glycols.

[0038] Examples of polyether glycols that can be used include, but are not limited to, those glycols with two or more hydroxy groups, from ring-opening polymerization and/or copolymerization of ethylene oxide, propylene oxide, trimethylene oxide, tetrahydrofuran, and 3-methyltetrahydrofuran, or from condensation polymerization of a polyhydric alcohol, preferably a diol or diol mixtures, with less than 12 carbon atoms in each molecule, such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol 1,6-hexanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol and 1,12-dodecanediol. A linear, bifunctional polyether polyol is preferred, and a poly(tetramethylene ether) glycol of molecular weight of about 1,700 to about 2,100, such as Terathane 1800 (Invista) with a functionality of 2, is particularly preferred in the present invention.

[0039] Examples of polyester glycols that can be used include those ester glycols with two or more hydroxy groups, produced by condensation polymerization of aliphatic polycarboxylic acids and polyols, or their mixtures, of low molecular weights with no more than 12 carbon atoms in each molecule. Examples of suitable polycarboxylic acids are malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid and dodecanedicarboxylic acid. Example of suitable polyols for preparing the polyester polyols are ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol 1,6-hexanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol and 1,12-dodecanediol. A linear, bifunctional polyester polyol with a melting temperature of about 5 C. to about 50 C. is preferred.

[0040] Examples of polycarbonate glycols that can be used include those carbonate glycols with two or more hydroxy groups, produced by condensation polymerization of phosgene, chloroformic acid ester, dialkyl carbonate or diallyl carbonate and aliphatic polyols, or their mixtures, of low molecular weights with no more than 12 carbon atoms in each molecule. Example of suitable polyols for preparing the polycarbonate polyols are diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol and 1,12-dodecanediol. A linear, bifunctional polycarbonate polyol with a melting temperature of about 5 C. to about 50 C. is preferred.

[0041] In one nonlimiting embodiment, the prepolymer contains at least 65%, or at least 71%, or at least 72% of the glycol, based upon total weight of the prepolymer.

[0042] The isocyanate component suitable as another starting material for making prepolymers according to the invention is a dicyclohexylmethane diisocyanate. An example of a suitable isocyanate component is a dicyclohexylmethane diisocyanate such as Vestanate H12MD1 (Evonik).

[0043] In one nonlimiting embodiment, the prepolymer contains at least 10%, or at least 22%, or at least 24% of the glycol, based upon total weight of the prepolymer.

[0044] Diol compounds suitable as further starting materials for preparing prepolymers according to the invention, include at least one diol compound with two hydroxy groups capable of reacting with the isocyanate and at least one carboxylic acid group capable of forming salt upon neutralization and incapable of reacting with the isocyanate. Examples of diol compounds having a carboxylic acid group include, but are not limited to, 2,2-dimethylopropionic acid (DMPA) such as Bis-MPA (GEO), 2,2-dimethylobutanoic acid, 2,2-dimethylovaleric acid, and DMPA initiated caprolactones such as CAPA HC 1060 (Solvay). DMPA is preferred in the present invention.

[0045] In one nonlimiting embodiment, the prepolymer contains at least 1%, or at least 2.2%, or at least 2.4% of the diol based upon total weight of the prepolymer.

[0046] In one nonlimiting embodiment, the prepolymer further comprises a monofunctional alcohol including methanols, ethanols, propanols, butanolsand 1-hexanol 1-hexanol. In this embodiment, the prepolymer contains less than 1% or less than 0.5% of the 1-hexanol, based upon total weight of the prepolymer.

[0047] The prepolymer can be prepared by mixing the glycol, isocyanate and diol together in one step and by reacting at temperatures of about 50 C. to about 100 C. for adequate time until all hydroxy groups are essentially consumed and a desired % NCO of the isocyanate group is achieved. Alternatively, this prepolymer can be made by charging molten glycol into a reactor at about 55 C. followed by addition of a DMPA solid powder with agitation and circulation until the diol solid particles are dispersed and dissolved in the glycol. Molten isocyanate is then charged into the reactor with continuous agitation and the capping reaction is allowed to take place at about 90 C. for 240 minutes, still with continuous agitation. The formed viscous prepolymer is then sampled to determine the extent of the reaction by measuring the weight percentage of the isocyanate groups (% NCO) of the prepolymer through a titration method. The theoretical value of the % NCO after the reaction is completed is 2.97 assuming the glycol MW is at 1800. If the determined % NCO value is higher than the theoretical value, the reaction should be allowed to continue until the theoretical value is reached or the % NCO number becomes constant. Once it is determined that the reaction is complete, the prepolymer temperature is maintained between 85 and 90 C. Significantly, the prepolymers are essentially solvent free and contain no alkyl ethoxylates or organotin catalysts. Preferred is that the reaction to prepare the prepolymer be carried out in a moisture-free, nitrogen-blanketed atmosphere to avoid side reactions.

[0048] The prepolymer of the present invention is then used to produce an aqueous polyurethane dispersion comprising the prepolymer and water as well as a neutralizer, a surfactant, a defoamer, an antioxidant and/or a thickener.

[0049] In one nonlimiting embodiment, the prepolymer is added in an amount such that the final dispersion contains at least 30% glycol, at least 10% isocyanate and at least 1% diol, based upon total weight of the dispersion.

[0050] In one nonlimiting embodiment, the aqueous polyurethane dispersion further containing at least 50% water, at least 1% surfactant and/or thickener and/or less than 1% neutralizer, antioxidant or defoamer.

[0051] Neutralizers used in these dispersions must be capable of converting the acid groups to salt groups. Examples include, but are not limited to tertiary amines (such as triethylamine, N,N-diethylmethylamine, N-methylmorpholine, N,N-diisopropylethylamine, and triethanolamine) and alkali metal hydroxides (such as lithium, sodium and potassium hydroxides). Primary and/or secondary amines may be also used as the neutralizers for the acid groups. The degrees of neutralization are generally between about 60% to about 140%, for example, in the range of about 80% to about 120% of the acid groups.

[0052] Examples of surfactants include, but are not limited to, anionic, cationic, or nonionic dispersants or surfactants, such as alkyldiphenyloxide disulfonate, sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, ethoxylated nonyiphenols, and lauryl pyridinium bromide.

[0053] Examples of suitable defoamers include, but are not limited to, mineral oils and/or silicone oils such as BYK 012 and Additive 65 (a silicone additive from Dow Corning), and Surfynol DF 110L (a high molecular weight acetylenic glycol non-ionic surfactant from Air Products & Chemicals).

[0054] Examples of suitable thickeners include, but are not limited to, polyurethanes such as Tafigel PUR 61 by Munzing, hydrophobically-modified ethoxylate urethanes (HEUR), hydrophobically-modified alkali swellable emulsions (HASE), and hydrophobically-modified hydroxy-ethyl cellulose (HMHEC).

[0055] Examples of antioxidants include, but are not limited to hindered phenols such as Irganox 245 (BASF) or Cyanox 1790 (Cytec). Additionally, Diamines including ethylene diamine and similar materials can be used as a diamine chain extender in place of water.

[0056] In one nonlimiting embodiment, the dispersion is prepared by the addition of the prepolymer using a rotor/stator high speed disperser. The prepolymer as made above is transferred directly into the disperser head and dispersed under high shear forces into deionized water preferably containing at least a surfactant, a neutralizer, an anti-oxidant and a foam control agent. Slightly more prepolymer than required by the dispersion recipe is needed to compensate for loss in the transfer line and in the reactor. Once the addition of the prepolymer is complete, a thickener can be added.

[0057] Polyurethane aqueous dispersions falling within the scope of the present invention should be expected to have a solids content of from about 10% to about 50% by weight, for example from about 30% to about 45% by weight. The viscosity of polyurethane aqueous dispersions falling within the scope of the present invention may be varied in a broad range from about 10 centipoises to about 100,000 centipoises depending on the processing and application requirements. For example, in one embodiment, the viscosity is in the range of about 500 centipoises to about 30,000 centipoises. The viscosity may be varied by using an appropriate amount of thickening agent, such as from about 0 to about 5.0 wt %, based on the total weight of the aqueous dispersion.

[0058] It has been found that upon drying, the aqueous polyurethane dispersions of the present invention form a continuous elastic film with high stretch and recovery. Further, the aqueous polyurethane dispersion is resistant to yellowing and hydrolysis. Accordingly, these aqueous polyurethane dispersions are useful in the production of shaped articles. The aqueous polyurethane dispersion can be applied to the substrate by various treatment methods including, but not limited to padding, coating, printing, bonding or laminating. Following application, the aqueous polyurethane dispersion is cured to the substrate. In one nonlimiting embodiment, curing condition comprise heating to about 150 to about 170 C. for 30 seconds to 5 minutes.

[0059] The aqueous polyurethane dispersion can be used alone or with other aqueous dispersions of different polymer. Further the aqueous polyurethane dispersion can be cross-linked with selected crosslinking agents, including polycarbodiimides and polyisocyanates.

[0060] In one nonlimiting embodiment, the aqueous polyurethane dispersion is diluted to a desired solid content prior to application to the substrate.

[0061] The aqueous polyurethane dispersion can be applied directly to the substrate or as a film, a tape or in various selected patterns such as, but not limited to, dots, shapes such as triangles, circles, and rectangles, zigzags and/or lines depending upon where stretch and recovery is desired.

[0062] In one nonlimiting embodiment, the substrate to which the aqueous polyurethane dispersion is applied is a textile fabric or a nonwoven material.

[0063] Accordingly, the aqueous polyurethane dispersions and methods for their application are particularly useful in production of various shaped articles wherein stretch and recovery is desired. In one nonlimiting embodiment, the shaped article is a garment. Examples of garments that can be produced using the dispersions and methods falling within the scope of the present invention, include but are not limited to: disposable undergarments, brassieres, panties, lingerie, swimwear, shapers, camisoles, hosiery, sleepwear, aprons, wetsuits, ties, scrubs, space suits, uniforms, hats, garters, sweatbands, belts, activewear, outerwear, rainwear, cold-weather jackets, pants, shirtings, dresses, blouses, mens and womens tops, sweaters, corsets, vests, knickers, socks, knee highs, dresses, blouses, aprons, tuxedos, bisht, abaya, hijab, jilbab, thoub, burka, cape, costumes, diving suit, kilt, kimono, jerseys, gowns, protective clothing, sari, sarong, skirts, spats, stola, suits, straitjacket, toga, tights, towel, uniform, veils, wetsuit, medical compression garments, bandages, suit interlinings, waistbands, and all components therein. In one nonlimiting embodiment, the aqueous polyurethane dispersion is applied to a seam or support area of the garment.

Analytical Methods

[0064] In the examples that follow, the following analytical methods were used:

[0065] Titration Methods

[0066] Microwave Methods

[0067] RV Spindle methods #3/10 rpm@25 C.

EXAMPLES

[0068] Representative embodiments of the present invention will be described with reference to the following examples that illustrate the principles and practice of the present invention. In no way is the scope of the invention limited to these representative embodiments. In these examples, the following raw materials were used:

TABLE-US-00001 Ingredient Chemical Name CAS # Tradename Vendor Glycol PTMEG 25190-06-1 Terathane INVISTA 1800 Isocyanate Dicyclohexyl- 5124-30-1 Vestanate Evonik methane diiso- H12MDI cyanate DMPA Dimethylolpropi- 4767-03-7 Bis-MPA GEO onic Acid Neutralizer Triethylamine 121-44-8 TEA BASF Surfactant Alkyldiphenyl- 119345-04-9 Dowfax 2A1 Dow oxide Disulfonate Defoamer mineral oil, 3173-53-3 BYK 012 BYK silicone oil Additives & Instru- ments Antioxidant hindered phenols 36443-68-2 Irganox 245 BASF Thickener polyurethane mixture Tafigel PUR Munzing 61

Example 1: Prepolymer Preparation without 1-Hexanol

[0069] A polyurethane prepolymer was made using a polytetramethylene ether glycol, an aliphatic diisocyanate such as PICM (4,4-methylene bis (cyclohexyl isocyanate), a hydrogenated version of 4,4-MDI) and a diol containing a sterically hindered carboxylic acid group. More specifically, the following ingredients and unit quantities were used to make the prepolymer:

TABLE-US-00002 Unit Ingredient CAS Number Quantity Terathane* 1800 251090-06-1 72.7806 1-Hexanol 111-27-3 0.0000 Vestanat* H12MDI 5124-30-1 24.7380 DMPA 4767-03-7 2.4814 Prepolymer 100.0000 total

[0070] The reaction to prepare the prepolymer was carried out in a moisture-free, nitrogen-blanketed atmosphere to avoid side reactions.

[0071] In this example, a 30 gallon reactor, jacketed with hot water and equipped with an agitator, was used. This reactor was heated to a temperature of about 55 C. A pre-determined weight of molten Terathane 1800 glycol was charged into the reactor. Then, DMPA solid powder was added to the reactor with agitation and circulation, under nitrogen blanket, until the DMPA solid particles were dispersed and dissolved in glycol.

[0072] Molten PICM was then charged into the reactor with continuous agitation and the capping reaction was allowed to take place at 90 C. for 240 minutes, still with continuous agitation. The formed viscous prepolymer was then sampled to determine the extent of the reaction by measuring the weight percentage of the isocyanate groups (% NCO) of the prepolymer through a titration method. The theoretical value of the % NCO after the reaction is completed is 2.97 assuming the glycol MW is at 1800. If the determined % NCO value is higher than the theoretical value, the reaction should be allowed to continue until the theoretical value is reached or the % NCO number becomes constant. Once it was determined that the reaction is complete, the prepolymer temperature was maintained between 85 and 90 C.

Example 2: Preparation of Aqueous Polymer Dispersion with Prepolymer of Example 1

[0073] The dispersion was prepared by the addition of prepolymer of Example 1 using a rotor/stator high speed disperser. The prepolymer as made in Example 1 was transferred directly into the disperser head and dispersed under high shear forces into deionized water, containing a surfactant, a neutralizer, an anti-oxidant and a foam control agent. Slightly more prepolymer than required by the dispersion recipe was needed to compensate for loss in the transfer line and in the reactor.

[0074] The ingredients for making the dispersion and the composition of the dispersion are shown below:

TABLE-US-00003 Unit Ingredient CAS Number Quantity Terathane* 1800 251090-06-1 30.1391 Vestanat* H12MDI 5124-30-1 10.2442 DMPA 4767-03-7 1.0276 1-Hexanol 111-27-3 0.0000 DI Water 7732-18-5 54.8093 Dowfax 2A1 119345-04-9 1.2652 Triethylamine 121-44-8 0.7830 Irganox 245 36443-68-2 0.6051 Tafigel PUR 61 Mixture 1.0000 BYK 012 Mixture 0.1265 Other 0.0000 Total 100.0000

[0075] In making a typical batch of 100 kg of the aqueous polymer dispersion, Dowfax 2A1 surfactant (1.2652 kg), an anti-oxidizer Irganox 245 (0.6051 kg), and foam control agent BYK-012 (0.1265 kg) were mixed and dissolved in the deionized water (54.8093 kg). The triethylamine neutralizer (0.783 kg) was added to the above water mixture 5 minutes prior to the addition of the prepolymer. The prepolymer (41.4109 kg) maintained at a temperature between 85 and 90 C. was added into the water mixture with high speed dispersing. The addition rate (typically at about 1.5 kg/min or about 30 minutes) of the prepolymer should be controlled to allow the formation of uniform dispersion, and the temperature of the dispersion should be kept between 40 and 45 C. Once the addition of prepolymer was complete, mixing was continued for 60 minutes. Then, a thickener Tafigel PUR 61 (1.00 kg) was added and allowed to mix for another 60 minutes. The as-made dispersion was continuously agitated at low speed for 8 hours (or overnight) in the container to eliminate foams and to ensure the reaction had reached completion. The finished dispersion typically contains about 42% solids, with viscosity about 4000 centipoises and pH in the range of 7.0 to 8.5.

[0076] The dispersion was then filtered through 100 micron bag filters to remove big particles before packed for shipment. It is recommended to use 55 gallon metal drums with polyethylene liner inside to contain the dispersion for shipment.

[0077] Final product specifications were determined as follows:

TABLE-US-00004 Parameters Aim Limits Method Prepolymer % NCO* 3.00 0.10 Titration Dispersion Solids, % 44.0 2.0 Microwave Dispersion Viscosity, RV Spindle #3/10 cps** 4000 1000 rpm@25 C. Dispersion pH 7.7 0.7 Dispersion Filterability Passing through filter bags no more than 100 microns *Sampled 20-30 minutes before the prepolymer is dispersed. **Sampled and measured 24 hours after the dispersion is thickened.

Example 3: Preparation of Prepolymer with 1-Hexanol

[0078] The polyurethane prepolymer was made using a polytetramethylene ether glycol, 1-Hexanol, an aliphatic diisocyanate such as PICM (4,4-methylene bis (cyclohexyl isocyanate), a hydrogenated version of 4,4-MDI) and a diol containing a sterically hindered carboxylic acid group. More specifically, the following ingredients and unit quantities were used to make the prepolymer:

TABLE-US-00005 Ingredient CAS Number Unit Quantity Terathane* 1800 251090-06-1 72.4492 1-Hexanol 111-27-3 0.4087 Vestanat* H12MDI 5124-30-1 24.6607 DMPA 4767-03-7 2.4814 Prepolymer total 100.0000

[0079] The reaction to prepare the prepolymer was carried out in a moisture-free, nitrogen-blanketed atmosphere to avoid side reactions.

[0080] In this example, a 30 gallon reactor, jacketed with hot water and equipped with an agitator, was used. This reactor was heated to a temperature of about 55 C. A pre-determined weight of molten Terathane 1800 glycol was charged into the reactor. The 1-Hexanol was added second. Then, DMPA solid powder was added to the reactor with agitation and circulation, under nitrogen blanket, until the DMPA solid particles were dispersed and dissolved in glycol.

[0081] Molten PICM was then charged into the reactor with continuous agitation and the capping reaction was allowed to take place at 90 C. for 240 minutes, still with continuous agitation. The formed viscous prepolymer was then sampled to determine the extent of the reaction by measuring the weight percentage of the isocyanate groups (% NCO) of the prepolymer through a titration method. The theoretical value of the % NCO after the reaction is completed is 2.80 assuming the glycol MW is at 1800. If the determined % NCO value is higher than the theoretical value, the reaction should be allowed to continue until the theoretical value is reached or the % NCO number becomes constant. Once it was determined that the reaction is complete, maintain the prepolymer temperature between 85 and 90 C.

Example 4: Preparation of Aqueous Polymer Dispersion with Prepolymer of Example 3

[0082] The dispersion was prepared by the addition of prepolymer of Example 3 using a rotor/stator high speed disperser. The prepolymer as made in Example 3 was transferred directly into the disperser head and dispersed under high shear forces into deionized water, containing a surfactant, a neutralizer, an anti-oxidant and a foam control agent. Slightly more prepolymer than required by the dispersion recipe is needed to compensate for loss in the transfer line and in the reactor.

[0083] The ingredients for making the dispersion and the composition of the dispersion are shown below:

TABLE-US-00006 Ingredient CAS Number Unit Quantity Terathane* 1800 251090-06-1 30.0000 Vestanat* H12MDI 5124-30-1 10.2116 DMPA 4767-03-7 1.0275 1-Hexanol 111-27-3 0.1692 DI Water 7732-18-5 54.8083 Dowfax 2A1 119345-04-9 1.2652 Triethylamine 121-44-8 0.7866 Irganox 245 36443-68-2 0.6051 Tafigel PUR 61 Mixture 1.0000 BYK 012 Mixture 0.1265 Other 0.0000 Total 100.0000

[0084] In making a typical batch of this 100 kg dispersion Dowfax 2A1 surfactant (1.2652 kg), an anti-oxidizer Irganox 245 (0.6051 kg), and foam control agent BYK-012 (0.1265 kg) were mixed and dissolved in the deionized water (54.8083 kg). The triethylamine neutralizer (0.7866 kg) was added to the above water mixture 5 minutes prior to the addition of the prepolymer. The prepolymer (41.4083 kg) maintained at a temperature between 85 and 90 C. was added into the water mixture with high speed dispersing. The addition rate (typically at about 1.5 kg/min or about 30 minutes) of the prepolymer should be controlled to allow the formation of uniform dispersion, and the temperature of the dispersion should be kept between 40 and 45 C. Once the addition of prepolymer was complete, mixing was continued for 60 minutes. Then, a thickener Tafigel PUR 61 (1.00 kg) was added and allowed to mix for another 60 minutes. The as-made dispersion was continuously agitated at low speed for 8 hours (or overnight) in the container to eliminate foams and to ensure the reaction had reached completion. The finished dispersion typically contains about 42% solids, with viscosity about 4000 centipoises and pH in the range of 7.0 to 8.5.

[0085] The dispersion is then filtered through 100 micron bag filters to remove big particles before packed for shipment. It is recommended to use 55 gallon metal drums with vented caps, and with a polyethylene liner inside to contain the dispersion for shipment.

[0086] Final product specifications were determined as follows:

TABLE-US-00007 _Parameters Aim Limits Method Prepolymer 2.80 0.10 Titration % NCO* Dispersion 44.0 2.0 Microwave Solids, % Dispersion 4000 1000 RV Spindle #3/ Viscosity, 10 rpm@25 C. cps** Dispersion 7.7 0.7 pH Dispersion Passing through filter bags no more than 100 microns Filterability *Sampled 20-30 minutes before the prepolymer is dispersed. **Sampled and measured 24 hours after the dispersion is thickened.

Example 5

[0087] The present dispersions have been found to be resistant to oxidative discoloration as compared to other films or dispersions. See results depicted in FIG. 1. This is particularly important for consumer goods as yellowing or discoloration is particularly objectionable for garments and consumer goods.