WO2010039452A2

WO2010039452A2 - Polyurethaneurea foam and articles

Info

Publication number: WO2010039452A2
Application number: PCT/US2009/057414
Authority: WO
Inventors: James Michael Lambert; Charles Frank Iavarone; Sonia Menot; Mary Wahlstrom
Original assignee: Invista Technologies S.A. R.L.
Priority date: 2008-09-23
Filing date: 2009-09-18
Publication date: 2010-04-08
Also published as: WO2010039452A3

Abstract

A composition comprising a polyurethaneurea foam; wherein said polyurethaneurea foam is prepared from a polyurethaneurea solution comprising a solvent and a polyurethaneurea derived from a prepolymer which is the reaction produc of at least one hydroxyl-terminated polymer having a number average molecular weight about 1600 to about 2400; at least one polyisocyanate; and a chain extender.

Description

POLYURETHANEUREA FOAM AND ARTICLES

Cross-reference to Related Applications

This application is a nonprovisional of U.S. Application No. 60/099408 which is a continuation-in-part of U.S. Patent Application No. 11/654,753, filed on January 18, 2007 and claims the benefit of U.S. Provisional Patent Application No. 60/865,091 , filed on November 9, 2006.

Background of the Invention

Field of the Invention

The present invention includes polyurethaneurea foams prepared from polyurethaneurea solutions. The polyurethaneurea foams may be formed into articles that optionally include additives that provide beneficial properties.

Description of the Related Art

Polymers such as polyurethaneureas have historically been used in preparing synthetic fibers. However, these polymers have other properties. that may potentially offer benefits beyond the fiber form. Therefore, there is a need for polymer compositions and methods which emphasize these additional advantages.

One suitable form for a polyurethaneurea is beads. U.S. Patent No. 5,094,914 to Figuly et al. ("Figuly"). The beads are prepared by adding drops of a segmented polyurethane solution (specifically a polyurethaneurea) into a coagulating bath, typically water. The coagulating bath solidifies the bead form. These beads have been noticed to provide no visible pores on the bead surface.

U.S. Patent No. 7,022,746 to Lockwood et al. ("Lockwood") discloses a viscoelastic polyurethane foam from a specified mixture of polyols. Specifically, Lockwood combines a polyoxyethylene with a second polyoxyalkylene based polyol to achieve a softer foam. While these polyurethaneurea foams may be used with conventional methods, the polyols are limited to having a number average molecular weight of about 400 to 1500.

Therefore, there is a need for additional polyurethaneurea foams that provide additional features and have a broader range of utility. Summary of the Invention

In one embodiment is a composition including a polyurethaneurea foam. The polyurethaneurea foam is prepared from a polyurethaneurea solution including a solvent and a polyurethaneurea derived from a prepolymer which is the reaction product of at least one hydroxyl-terminated polymer having a number average molecular weight of about 1600 to about 2400; at least one polyisocyanate; and a chain extender. Examples of hydroxyl-terminated polymers that are useful include glycols such as polyether glycols, copolyether glycols, polyester glycols, copolyester glycols, polycarbonate glycols, copolycarbonate glycols, and mixtures thereof.

In a further embodiment is a composition including a polyurethaneurea foam where the polyurethaneurea foam is prepared from a polyurethaneurea solution including a solvent and a polyurethaneurea derived from a prepolymer which is the reaction product of at least one hydroxyl-terminated polymer having a number average molecular weight of about 1600 to about 2400, where the hydroxyl-terminated polymer includes at least 30% by weight of a polytetramethylene ether glycol; at least one polyisocyanate; and a chain extender.

In another embodiment is an article including a polyurethaneurea foam, wherein the polyurethaneurea foam is prepared from a polyurethaneurea solution including a solvent and a polyurethaneurea derived from a prepolymer which is the reaction product of at least one hydroxyl-terminated polymer having a number average molecular weight of about 1600 to about 2400; at least one polyisocyanate; and a chain extender.

In other embodiments of the present invention are methods of preparing polyurethaneurea foams and shaped articles. One suitable method includes preparing a polyurethaneurea solution by providing a prepolymer which is the reaction product of a hydroxyl-terminated polymer and a polyisocyanate which is subsequently chain extended.

Detailed Description of the Invention

The polyurethaneurea foams of some embodiments are derived from a prepolymer which is a capped glycol. A variety of different hydroxyl-terminated polymers are useful in preparing the prepolymer such as glycols selected from the group consisting of polyether or copolyether glycols, polyester or copolyester glycols, polycarbonate or copolycarbonate glycols, and combinations thereof. This glycol can be a single glycol, such as polytetramethylene ether glycol (PTMEG), or a mixture of different glycols, where polytetramethylene ether glycol is present in an amount greater than 30%. Mixtures of different glycols may also include PTMEG in an amount of 50% or greater, such as 70% or greater PTMEG.

The prepolymer is capped glycol which is the reaction product of a glycol with a polyisocyanate. Examples of polyisocyanates include aromatic diisocyanates selected from the group consisting of phenylenediisocyanate, tolylenediisocyanate (TDI), xylylenediisocyanate, biphenylenediisocyanate, naphthylenediisocyanate, diphenylmethanediisocyanate (MDI), and combinations thereof.

The prepolymer used to prepare the foams has an NCO content of about 1.0% to about 3.0%, including from about 1.3% to about 2.2%, 1.5% to about 2.0%, and about 1.8% to about 2.6%. Additional components of the polyurethaneurea compositions are described hereinbelow.

Polyurethaneurea Beads

Some embodiments of the invention are polyurethaneurea beads. One useful method for preparing such beads is disclosed in U.S. Patent No. 5,094,914 to Figuly et al. ("Figuly"), which is incorporated herein by reference in its entirety. A segmented polyurethaneurea composition, which may be any of those described herein, (such as those based on polyethers or polyesters) can be prepared. A solution including the polyurethaneurea can be prepared with a solvent. A variety of useful solvents may be included such as amide solvents, including but not limited to dimethylacetamide (DMAc), dimethylformamide (DMF), and N-methylpyrrolidone (NMP). The polyurethaneurea solution can then be introduced as droplets into a coagulating bath which solidifies the polymer in bead form. The coagulating bath can include a liquid that extracts the solvent of the polymer solution, but is not a solvent for the polymer, such as water, methanol, acetone, etc.

Thus beads can be prepared having a diameter from about 1 mm to about 4mm, having a void content of 60% to 90%, and having no visible pores on the surface at 500Ox magnification.

Some embodiments of the present invention are polyurethaneurea beads having a broader range of particle sizes, void content, and surface pores than previously disclosed. The void content is based on the density of the beads:

Voids = [1-(bead density/bulk polymer density)]x100%

In some embodiments are polyurethaneurea beads having a void content below 60%. These beads may be prepared by using a higher viscosity solution. For Example, solutions having Brookfield viscosities from about 1000 cps and above and solids content from about 12% and above produce beads that are denser, heavier, and smaller than beads made using the same bead making apparatus, but utilizing solutions having less than lOOOcps. In some embodiments are beads prepared from solutions that have high viscosities (>1000 cps) but have relatively low solids content (i.e. <10%). This can be accomplished by utilizing a polymer with a high average molecular weight, is branched, or a polymer that associates together in the solution through crystallization, hydrogen bonding, hard segment association, etc. For example, polyurethane urea based solutions will become more viscous with age.

Low viscosity solutions with relatively high solids content may be prepared through the use of polymers that shear thin, for example a liquid crystalline polymer or some spandex formulations or by using polymers that have low average molecular weight, or do not associate, hydrogen bond or crystallize in solution.

Another method of preparing smaller, more dense beads is to produce beads from solutions that produce void volumes of 60 to 90%, but in the coagulation and drying process to remove the solvent, some solvent is allowed to remain with the beads. The beads are then dried so that the residual solvent will redissolve and reprecipitate the polymer into a more dense structure, before that solvent is removed.

Beads with void content above 90% may also be prepared. One method is to include polymers with low viscosities. However, as the viscosity is continuously lowered, within the same polymer formulation, a point is reached where the polymer is so dilute that it can not sustain the bead shape in the coagulation process and collapses (This process is disclosed in U.S. Patent No. 5,126,181 for the preparation of flattened microporous disks). On the other hand, it is possible to choose or formulate polymers, in particular polyurethaneureas, which are stiffer in nature so that even when diluted still have enough stiffness to hold the bead shape without collapsing. In particular, it is possible within the family of polyurethaneureas, to synthesize or choose a formulation that is stiffer, but still has the highly desirable elastomeric nature (stretch and recovery) inherent. For example, a polyurethane urea that uses a polyether glycol of low average molecular weight, such as an average molecular weight of less than 1000 or less than 700, as the soft segment will be sufficient to produce a bead having a void content of greater than 90% that maintains a spherical shape.

In addition, other reactants or co-reactants could be used to modify the stiffness of the final polyurethaneurea bead, e.g. different extenders than EDA (ethylene diamine)or coextenders with EDA, or isomers of MDI (4,4'- vs. 2,4-) and mixtures thereof. 1 ,4- phenylene diisocyanate or 1 ,4-phenylene diamine or a combination or mixture thereof will also produce stiffer polyurethaneureas than corresponding polyurethaneureas based on "traditional" MDI and EDA. It should also be appreciated that mixtures of polyurethaneureas having different stiffnesses could also be utilized to tailor or dial in the necessary stiffness required to attain void volumes greater than 90%. Other polymers or additives could be admixed into the solution to achieve the necessary stiffness and other requirements to make higher void volume beads.

In some embodiments are beads with controlled size pores on the surface. A micronized or nano-sized salt or other water-soluble material (e.g. polyethylene glycol) may be combined with the polyurethaneurea solution prior to introduction to a coagulation bath. The water-soluble materials will leave a pore when the bead is coagulated and washed in water.

Also provided are methods for continuously or semi-continuously producing beads. In batch, stirred reactor process, solvent may build up in the water or polymer non-solvent. Excessive build up of solvent may lead to tackiness of the produced beads causing them to stick together or possibly even coalescing them. The buildup of solvent in the non-solvent (or water) may also slow down the coagulation of the beads due to insufficient thermodynamic incentive for the solvent to be "pulled" into or diffuse into the non-solvent. The non-solvent is becoming more and more concentrated and nearly identical to the solvent as the solvent diffuses out of the beads or disks.

Even the semi-continuous process of some embodiments would allow for the production of about 500 grams of beads per 8-hour shift, a 10-fold increase over that of a batch, stirred reactor process, using similar sized bead forming apparati. Beads can be "harvested" anytime after about 2-3 minutes after formation and moved to vessels other than that in which they were formed allowing for the continuous production of beads in the "process apparatus" for at least up to three 8 hour shifts. In another embodiment, water in the "process apparatus" could be continuously flushed and the beads periodically or continuously harvested such that the beads could be produced continuously. A continuous or semi-continuous operation would be industrially favorable in comparison to a batch operation.

Harvesting or moving the beads from where they are formed to a different tank to be soaked and the residual DMAc solvent extracted can be accomplished by numerous methods. One method includes the use of a conveyer system including a conveyor belt. The belt could be a screen or include holes to allow water to pass through them, while retaining the beads thereon. Another method to transfer the beads away from the process apparatus is via a "waterfall." The waterfall method allows for the beads to be collected at one end of the tank away from where they are formed, by allowing some water and a significant number of the beads to spill over the edge of the forming tank into another tank. Since the beads float in the water/solvent mixture, this can be easily accomplished.

The beads have a plethora of useful properties. For example, after having been compressed for 24 hours to a quarter of the original diameter, the beads regain 85% of their volume immediate and about 97% of their volume after 10 minutes. The sizes of the beads may vary. Beads may have a diameter of greater than 0.1 mm to 10 mm, such as from about .05 mm to about 8 mm. Individual beads have been prepared which have diameters of 0.5 mm, 0.8 mm, 1.0 mm, 2.5 mm, 3.0 mm, 4.0 mm, 5.0 mm, and 8.0 mm.

Individual beads may have a density in any suitable range, such as from about 0.05 g/cc to about 0.5 g/cc, including about 0.1 g/cc. Also, the beads have unique absorptions properties. For example, when placed in water, a bead of approximately 3 mm in diameter will absorb approximately 14% of its weight in water. However, when the bead is squeezed and then released in water, the bead will absorb up to about 350% its weight in water. These absorption properties demonstrate additional utility such as a delivery vehicle for substances such as fragrances, ointments, and other fluid compositions.

Polyurethanurea Foams

Non-spherical shapes can also be prepared, for example flat structures having a fairly uniform thickness from end to end and edge to edge. These foams retain the foam characteristics of the beads. Foam structures prepared from polyurethaneurea solutions take on, or retain, the shape of the vessel in which the polyurethaneurea solution is placed in. Foam structure can be made in limitless variety of shapes and sizes including, cups, bottles, and round flat Petri dish, among others. Similar to the beads, the foams are achieved by introducing water to a container including a polyurethaneurea solution. Additionally, the foam structure can be varied by the introduction of the water to only one surface of the polyurethaneurea solution in the container. For example the foam formed from polyurethaneurea solution in a petri dish where water is added to the top (open) of the solution forms a less dense to more dense foam from top to bottom (against the bottom of the glass petri dish).

The foam structures can be molded to a particular size or formed in larger structures that can be cut to an appropriate size. Depending on the use, the foams can have any desired dimensions. This includes substantially planar foams having thickness from about 1 mm to about 50 mm, including about 1 mm to about 5 mm, 1mm to about 3mm and 10mm to 20mm.

The density of the foams may also vary. The bulk polymer itself may have a density of about 0.975 to 1.3 g/cm³, while foams have been prepared that include densities from about 0.1 g/cm³ to about 1 g/cm³, including densities of about 0.3 g/cm³, 0.5 g/cm³, and 0.8 g/cm³. The foam density may be altered depending on the desired end use. Similar to the beads, the non-spherical foams may also include no visible pores at 500Ox magnification. However, salt (e.g., sodium chloride) may be added to the polyurethaneurea solution to create pores on the surface. If enough salt is added, it will create interconnecting pores that will go from the top surface to the bottom surface.

Other means of making polyurethaneurea foams include using "blowing agents" such as entrained air in viscous polyurethaneurea solutions, compressed gasses (air, nitrogen, etc.) that expand when the pressure is released, water soluble materials (salts polyethylene oxide polymer, etc.) that leach out of the polyurethaneurea when immersed in water, chemical agents (sodium bicarbonate, azo compounds, etc.) that release a gas when a certain temperature is reached or when it comes in to contact with water, air or another chemical.

An increase in the number of pores or "bubbles" in the foam can also result by using additional blowing agent/foaming agents including additional "bubbles" that can rise to the surface to become a pore. However, this effect may be altered by other factors such as the co-addition of surface active agents which may "break" the bubbles at the air surface causing open pores. There are also commercially available blowing agents that provide closed cell foams which may be desirable to avoid transmittal of liquids to the interior of the foam (i.e., carpet backing or upholstery foam).

Another manner to introduce more air (reduce density of the foams) is to "whip" in air into the polymer solution before forming the foam under water. This creates a softer foam because there are bigger cells (from the air bubbles) mixed in with the smaller cells formed from the water (removal of the solvent).

Articles

The polyurethaneurea beads and foams of some embodiments have a wide range of applicability. This includes use in textiles, apparel and shoe components, insulation, home furnishings, cosmetics and other household uses. As a bedding material, they may be included as an alternative to fiberfill such as in pillows. In shoes, beads may be included as a cushion for the shoe sole. Additionally, a combination of different size beads or foarn_^s or varying foam densities may be included in the same shoe sole to accommodate for varying pressure points within the sole, as well as in the inner soles, outer and upper shoe portions, particularly where beads are included in a "sandwich" construction in pleated or quilted constructions. Moreover, the polyurethaneurea beads and foams can be used as shock absorber, energy provider, or for its massaging effect, moisture management properties, or perfume release, thermal regulation, antibacterial properties when additives are added. The cushioning effect is also useful for furniture cushions and carpet padding. For example, the beads may be included in fibrous batting materials. Cushioning effects are also beneficial in headgear such as helmets or hats, straps for clothing, straps for luggage, and comfort grip applications such as those found on clubs, ski poles, hammers, bicycles, lawnmowers, steering wheels, etc.

When a self-supporting structure using the beads is desired, i.e, a structure including the beads in a free form, or where the beads are bonded to each other, a variety of constructions may be used. For example, the beads may be adhered by a polyurethaneurea aqueous dispersion or solution or by an adhesive such as a hot melt adhesive or other resin. Alternatively, two separate polymer films of polyurethane, another plastic or a polyurethaneurea (cast from an aqueous dispersion or solution) or a combination of films may be combined and adhered by any suitable method to define an interior space, such as a "pillow" construction, within which polyurethaneurea beads may then be placed and allowed to flow freely, or additionally bonded with polyurethaneurea solution or other adhesive.

Polvurethaneurea Compositions The polyurethaneurea compositions of some embodiments may be in the form of a solution or dispersion. Any of the polyurethaneurea compositions of the present invention may include any glycol, diisocyanate, chain extender, or other component described herein.

In some embodiments, a segmented polyurethaneurea includes: a) at least one hydroxyl-terminated polymer having a number average molecular weight of about 1600 to about 2400; a polyol or a polyol copolymer or a polyol mixture of number average molecular weight between 500 to 5000, including but not limited to polyether glycols, polyester glycols, polycarbonate glycols, polybutadiene glycols or their hydrogenated derivatives, and hydroxy-terminated polydimethylsiloxanes; b) a diisocyanate including aliphatic diisocyanates, aromatic diisocyanates and alicyclic diisocyanates; and c) a chain extender such as water, an aliphatic diamine or a mixture with at least one diamine selected from the group consisting of an aliphatic diamine and an alicyclic diamine, each having 2 to 13 carbon atoms, or an amino-terminated polymer, or an organic compound or a polymer with at least three primary or secondary amine groups; and optionally a monoamine, primary or secondary, as a chain terminator.

Examples of polyether polyols that can be used in some embodiments include 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, for example, 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. For example, a linear, bifunctional polyether polyol may be included, specifically, a poly(tetramethylene ether) glycol of molecular weight of about 1 ,700 to about 2,100, such as Terathane® 1800 (commercially available from INVISTA S. a r.l. of Wichita, KS and Wilmington, DE) with a functionality of 2.

Examples of polyester polyols 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. For example, a linear, bifunctional polyester polyol with a melting temperature of about 5°C to about 50⁰C may be included.

Examples of polycarbonate polyols that can be used include those carbonate glycols with two or more hydroxy groups, produced by condensation polymerization of phosgene, chioroformic 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. For example, a linear, bifunctional polycarbonate polyol with a melting temperature of about 5⁰C to about 50°C may be included.

Examples of suitable diisocyanate components include aliphatic and aromatic diisocyanates such as 1 ,6-diisocyanatohexane, 1 ,12-diisocyanatododecane, isophorone diisocyanate, trimethyl-hexamethylenediisocyanates, 1 ,5-diisocyanato-2-methylpentane, diisocyanato-cyclohexanes, methylene-bis(4-cyclohexyl isocyanate), tetramethyl- xylenediisocyanates, bis(isocyanatomethyl) cyclohexanes, toluenediisocyanates, methylene bis(4-phenyl isocyanate), phenylenediisocyanates, xylenediisocyanates, and a mixture of such diisocyanates. For example the diisocyanate may be an aromatic diisocyanate such phenylenediisocyanate, tolylenediisocyanate (TDI), xylylenediisocyanate, biphenylenediisocyanate, naphthylenediisocyanate, diphenylmethanediisocyanate (MDI), and combinations thereof.

Examples of suitable diamine components (diamine chain extenders) are ethylenediamine, 1 ,2-propanediamine, 1 ,3-propanediamine, 2,2-dimethyl-1 ,3- propanediamine, 1 ,4-butanediamine, 1 ,5-pentanediamine, hexamethylene diamine, 1 ,7- heptanediamine, 1 ,8-octanediamine, 1 ,9-nonanediamine, 1 ,10-decanediamine, 1 ,12- dodecanediamine, 2-methyl-1 ,5-pentanediamine, cyclohexanediamines, cycloheχanebis(methylamine)s, isophorone diamine, xylylenediamines, and methylenebis(cyclohexylamine)s. A mixture of two or more diamines can also be used.

Examples of suitable amine-terminated polymers are bis(3-aminopropyl) terminated polydimethylsiloxane, amine terminated poly(acrylonitrile-co-butadiene), bis(3- aminopropyl) terminated poly(ethylene glycol), bis(2-aminopropyl) terminated poly(propylene glycol), and bis(3-aminopropyl) terminated polytetrahydrofuran.

Examples of suitable organic compounds or polymers with at least three primary or secondary amine groups are tris-2-aminoethyl amine, poly(amido amine) dendrimers, polyethylenimine, poly(vinylamine), and poly(allylamine).

Examples of the suitable monoamine component that can be included with the polyurethaneurea include primary alkylamines such as ethylamine, butylamine, hexylamine, cyclohexylamine, ethanolamine and 2-amino-2-methyl-1-propanol, and secondary dialkylamines such as N,N-diethylamine, N-ethyl-N-propylamine, N₁N- diisopropylamine, N-tert-butyl-N-methylamine, N-tert-butyl-N-benzylamine, N, N- dicyclohexylamine, N-ethyl-N-isopropylamine, N-tert-butyl-N-isopropylamine, N-isopropyl- N-cyclohexylamine, N-ethyl-N-cyclohexylamine, N,N-diethanolamine, and 2,2,6,6- tetramethyipiperidine.

Additives

A wide variety of additives are useful with the polyurethaneurea foams. There are fewer limitations than with typical spandex fibers where certain additives can clog or block filters or small capillaries or spinnerets. Examples of additives include at least one additive selected from the group consisting of antioxidants, pigments, colorants, fragrances, anti-microbial agents, skin care additives, odor absorbers, phase change materials, mica, beeswax (and other oil absorbers), and combinations thereof.

Additives such as antioxidants, pigments, colorants, fragrances, anti-microbial agents (like silver), active ingredients (moisturizers, UV-screens), surfactants, anti- /defoamers, solvents and the like can be blended into the polyurethaneurea solutions prior to forming beads or foams. Encapsulation of the additive may slow the diffusion of the additive out of the polymer matrix providing a delayed or time release of the additive. This delayed release is compared to the relatively faster release of an additive adsorbed on to the surface of a particle. Combinations of encapsulating and surface adsorbed additives may be included to provide quick release of one or more additives from the surface of a particle and a delayed release of the encapsulated additive.

Pigments may also be added to the polyurethaneurea compositions of some embodiments. Pigments may be added in a similar manner to other additives. Examples of pigments include carbon black and TiO₂. For a polyurethaneurea powder, the effect of pigments is shown in Table A below:

Additional examples of pigments are described hereinbelow.

Among the colorants used for some embodiments, including cosmetic compositions are inorganic colorants and organic colorants which include synthetic and natural colorants. Inorganic colorants include TiO2, iron oxides and ultramarines. Synthetic organic colorants include lakes, toners and pigments, such as those described in U.S. Patent No. 4,909,853, herein incorporated by reference. An example of a natural organic colorant is carmine.

Several dyes can be obtained from the major suppliers such as Huntsman (formerly Ciba Textile Effects) and DyStar. See table below for list of commercially available dyes by supplier and class.

Fragrances

There is a range of fragrance materials that deposit well on, or are retained well on, spandex (i.e., segmented polyurethaneurea). Such materials include, but are not limited to, the following two categories, Category A and Category B as set forth below.

Category A: hydroxylic materials which are alcohols, phenols or salicylates, with an octanol/water partition coefficient (P) whose common logarithm (log₁₀ P) is 2.5 or greater, and a gas chromatographic Kovats index (as determined on polydimethylsiloxane as non-polar stationary phase) of at least 1050.

The octanol-water partition coefficient (or its common-logarithm "logP") is well- known in the literature as an indicator of hydrophobicity and water solubility (see Hansch and Leo, Chemical Reviews, 71 , 526-616, (1971); Hansch, Quintan and Lawrence, J. Organic Chemistry, 33, 347-350 (1968). Where such values are not available in the literature they may be measured directly, or estimated approximately using mathematical algorithms. Software providing such estimations is available commercially, for example "LogP" from Advanced Chemistry Design Inc.

Materials having log₁₀ P of 2.5 or more are somewhat hydrophobic.

Kovats indices are calculated from the retention time in a gas chromatographic measurement referenced to the retention time for alkanes [see Kovats, Helv.Chim.Acta 41 , 1915 (1958)]. Indices based on the use of a non-polar stationary phase have been used in the perfumery industry for some years as a descriptor relating to the molecular size and boiling point of ingredients. A review of Kovats indices in the perfume industry is given by T Shibamoto in "Capillary Gas Chromatography in Essential Oil Analysis", P Sandra and C Bicchi (editors), Huethig (1987), pages 259-274. A common non-polar phase which is suitable is 100% dimethyl polysiloxane, as supplied for example under a variety of tradenames such as RP-1 (Hewlett-Packard), CP SiI 5 CB (Chrompack), OV-1 (Ohio Valley) and Rtx-1 (Restek).

Materials of low Kovats index tend to be volatile and are not retained well on many fibers.

Category A includes alcohols of general formula ROH where the hydroxy! group may be primary, secondary or tertiary, and the R group is an alkyl or alkenyl group, optionally branched or substituted, cyclic or acyclic, such that ROH has partition coefficient and Kovats properties as defined above. Alcohols of Kovats index 1050 to 1600 are typically monofunctional alkyl or arylalkyl alcohols with molecular weight falling within the range 150 to 230.

Category A also includes phenols of general formula ArOH, where the Ar group denotes a benzene ring which may be substituted with one or more alkyl or alkenyl groups, or with an ester grouping -CO₂A, where A is a hydrocarbon radical, in which case the compound is a salicylate. ArOH has partition coefficient and Kovats index as defined above. Typically, such phenols with Kovats index 1050 to 1600 are monohydroxylic phenols with molecular weight falling within the range 150 to 210.

Examples of fragrance materials in category A are 1 -(2'-tert-butylcyclohexyloxy)- butan-2-ol, 3-methyl-5-(2',2',3'-trimethylcyclopent-3-enyl)- pentan-2-ol, 4-methyl-3-decen- 5-ol, amyl salicylate, 2-ethyl-4(2',2',3-trimethylcyclopent-3'-enyl)but-2-enol, borneol, carvacrol, citronellol, 9-decenol, dihydroeugenol, dihydrolinalol, dihydromyrcenol, dihydroterpineol, eugenol, geraniol, hydroxycitronellal, isoamyl salicylate, isobutyl salicylate, isoeugenol, linalool, menthol, nerolidol, nerol, para tert-butyl cyclohexanol, phenoxanol, terpineol, tetrahydrogeraniol, tetrahydrolinalol, tetrahydromyrcenol, thymol, 2-methoxy-4-methylphenol, (4-isopropylcyclohexyl)-methanol, benzyl salicylate cyclohexyl salicylate, hexyl salicylate, patchouli alcohol, and famesol.

Category B esters, ethers, nitriles, ketones or aldehydes, with an octanol/water partition coefficient (P) whose common logarithm (log₁₀ P) is 2.5 or greater, and a gas chromatographic Kovats index (as determined on polydimethylsiloxane as non-polar stationary phase) of at least 1300.

Fragrances of Category B are of general formula RX, where X may be in a primary, secondary or tertiary position, and is one of the following groups: -CO₂A, -COA, -OA, -CN or -CHO. The groups R and A are hydrocarbon residues, cyclic or non-cyclic and optionally substituted. Typically, the materials of Category B with Kovats index not exceeding 1600 are monofunctional compounds with molecular weights in the range 160 to 230.

Examples of fragrance materials in category B are 1~methyl-4-(4~methyl-3- pentenyl)-3-cyclohexene-1- carbaldehyde, 1-(5', 5'-dimethylcyclohexenyl)-pent-en-1-one, 2-heptyl cyclopentanone, 2-methyl-3-(4'-tert-butylphenyl)propanal, 2-methylundecanal, 2- undecenal, 2,2-dimethyl-3-(4'-ethylphenyl)-propanal, 3-(4'-isopropylphenyl)-2- methylpropanal, 4-methyl-4-phenylpent-2-yl acetate, allyl cyclohexyl propionate, allyl cyclohexyloxyacetate, amyl benzoate, methyl ethyl ketone trimers, benzophenone, 3-(4'- tert-butylphenyl)-propanal, caryophyllene, cis-jasmone, citral diethyl acetal, citronellal diethyl acetal, citronellyl acetate, phenylethyl butyl ether, alpha-damascone, beta- damascone, delta-damascone, gamma-decalactone, dihydro isojasmonate, dihydrojasmone, dihydroterpinyl acetate, dimethyl anthranilate, diphenyl oxide, diphenylmethane, dodecanal, dodecen-2-al, dodecane nitrile, 1-ethoxy-1-phenoxyethane, 3-(1 '-ethoxyethoxy)-3,7-dimethylocta-1 ,6-diene, 4-(4'-methylpent-3'-enyl)-cyclohex-3-enal, ethyl tricyclo[5.2.1.0-2,6-]decane-2-carboxylate, 1-(7-isopropyl-5-methylbicyclo[2.2.2]oct- 5-en-2-yl)-1- ethanone, allyl tricyclodecenyl ether, tricyclodecenyl propanoate, gamma- undecalactone, n-methyl-n-phenyl-2-methylbutanamide, tricyclodecenyl isobutyrate, geranyl acetate, hexyl benzoate, ionone alpha, ionone beta, isobutyl cinnamate, isobutyl quinoline, isoeugenyl acetate, 2,2,7,7-tetramethyltricycloudecan-5-one, tricyclodecenyl acetate, 2-hexylcyclopentanone, 4-acetoxy-3-pentyltetrahydropyran, ethyl 2- hexylacetoacetate, 8-isopropyl-6-methylbicyclo [2.2.2]oct-5-ene-2- carbaldehyde, methyl 4-isopropyl-1-methylbicyclo[2.2.2]oct-5-ene-2- carboxylate, methyl cinnamate, aipha iso methyl ionone, methyl naphthyl ketone, nerolin, nonalactone gamma, nopyl acetate, para tert-butyl cyclohexyl acetate, 4-isopropyl-1-methyl-2-[1'-propenyl]-benzene, phenoxyethyl isobutyrate, phenylethyl isoamyl ether, phenylethyl isobutyrate, tricyclodecenyl pivalate, phenylethyl pivalate, phenylacetaldehyde hexylene glycol acetal, 2,4-dimethyl-4- phenyltetrahydrofuran, rose acetone, terpinyl acetate, 4-isopropyl-1-methyl-2-[1'- propenyl]-benzene, yara, (4-isopropylcyclohexadienyl)ethyl formate, amyl cinnamate, amyl cinnamic aldehyde, amyl cinnamic aldehyde dimethyl acetal, cinnamyl cinnamate ,1 ,2,3,5,6,7,8,8a-octathyro-1 ,2,8,8-tetramethyl-2-acetyl naphthalene, cyclo- 1 ,13-ethylenedioxytridecan-1 ,13-dione, cyclopentadecanolide, hexyl cinnamic aldehyde, 1 ,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta[g]- 2-benzopyran, geranyl phenyl acetate, 6-acetyl-1-isopropyl-2,3,3,5-tetramethylindane, and 1 ,1 ,2,4,4,7- hexamethyl-6-acetyl-1 ,2,3,4- tetrahydronaphthalene.

While this is an extensive list of fragrances and perfumes that work especially well with polyurethaneurea compositions, it is recognized that a variety of other fragrances are also useful in some embodiments. Fragrances may include a substance or mixture of substances including natural (i.e., obtained by extraction of flowers, herbs, leaves, roots, barks, wood, blossoms or plants), artificial (i.e., a mixture of different nature oils or oil constituents) and synthetic (i.e., synthetically produced) odoriferous substances. A non-limiting examples of fragrances include: hexyl cinnamic aldehyde; amyl cinnamic aldehyde; amyl salicylate; hexyl salicylate; terpineol; 3,7-dimethyl-cis-2,6- octadien-1-ol; 2,6-dimethyl-2-octanol; 2,6~dimethyl-7-octen-2-ol; 3,7-dimethyl-3-octanol; 3,7-dimethyl-trans-2,6-octadien-1-ol; 3,7-dimethyl-6-octen-1-ol; 3,7-dimethyl-1-octanol; 2- methyl-3-(para-tert-butylphenyl)-propionaldehyde; 4-(4-hydroxy-4-methylpentyl)-3- cyclohexene-1-carboxaldehyde; tricyclodecenyl propionate; tricyclodecenyl acetate; anisaldehyde; 2-methyl-2-(para-iso-propylphenyl)-propionaldehyde; ethyl-3-methyl-3- phenyl glycidate; 4-(para-hydroxyphenyl)-butan-2-one; 1-(2,6,6-trimethyl-2-cyclohexen-1- yl)-2-buten-1 -one; para-methoxyacetophenone; para-methoxy-alpha-phenylpropene; methyl-2-n-hexyl-3-oxo-cyclopentane carboxylate; undecalactone gamma, orange oil; lemon oil; grapefruit oil; bergamot oil; clove oil; dodecalactone gamma; methyl-2-(2- pentyl-3-oxo-cyclopentyl) acetate; beta-naphthol methylether; methyl-beta- naphthylketone; coumarin; decylaldehyde; benzaldehyde; 4-tert-butylcyclohexyl acetate; alpha, alpha-dimethylphenethyl acetate; methylphenylcarbinyl acetate; cyclic ethyleneglycol diester of tridecandioic acid; 3,7-dimethyl-2,6-octadiene-1-nitrile; ionone gamma methyl; ionone alpha; ionone beta; petitgrain; methyl cedrylone; 7-acetyl- 1 ,2,3,4,5,6,7,8-octahydro-1 ,1 ,6,7-tetramethyl-naphthalene; ionone methyl; methyl-1 ,6,10- trimethyl^.δ.θ-cyclododecatrien-i-yl ketone; 7-acetyl-1 ,1 ,3,4,4,6-hexamethyl tetralin; A- acetyl-6-tert-butyl-1 ,1 -dimethyl indane; benzophenone; 6-acetyl-1 ,1 ,2,3,3,5-hexamethyl indane; 5-acetyl-3-isopropyl-1 ,1 ,2,6-tetramethyl indane; 1-dodecanal; 7-hydroxy-3,7- dimethyl octanal; 10-undecen-1-al; iso-hexenyl cyclohexyl carboxaldehyde; formyl tricyclodecan; cyclopentadecanolide; 16-hydroxy-9-hexadecenoic acid lactone; 1 Λ4A7,8-hexahydro-4,6,6J,8,8-hexamethylcyclopenta-gamma-2-benzopyran- e; ambroxane; dodecahydro-3a,6,6,9a-tetramethylnaphtho-[2,1b]furan; cedrol; 5-(2,2,3- trimethylcyclopent-3-enyl)-3-methylpentan-2-ol; 2-ethyl-4-(2,2,3-thmethyl-3-cyclopenten- 1-yl)-2-buten-1-ol; caryophyllene alcohol; cedryl acetate; para-tert-butylcyclohexyl acetate; patchouli; olibanum resinoid; labdanum; vetivert; copaiba balsam; fir balsam; hydroxycitronellal and indol; phenyl acetaldehyde and indol; geraniol; geranyl acetate; linalool; linalyl acetate; tetrahydrolinalool; citronellol; citronellyl acetate; dihydromyrcenol; dihydromyrcenyl acetate; tetrahydromyrcenol; terpinyl acetate; nopol; nopyl acetate; 2- phenylethanol; 2-phenylethyl acetate; benzyl alcohol; benzyl acetate; benzyl salicylate; benzyl benzoate; styrallyl acetate; dimethylbenzylcarbinol; trichloromethylphenylcarbinyl methylphenylcarbinyl acetate; isononyl acetate; vetiveryl acetate; vetiverol; 2-methyl-3-(p- tert-butylphenyl)-propanal; 2-methyl-3-(p-isopropylphenyl)-propanal; 3-(p-tert- butylphenyl)-propanal; 4-(4-methyl-3-pentenyl)-3-cyclohexenecarbaldehyde; 4-acetoxy-3- pentyltetrahydropyran; methyl dihydrojasmonate; 2-n-heptylcyclopentanone; 3-methyl-2- pentyl-cyclopentanone; n-decanal; n-dodecanal; 9-decenol-1 ; phenoxyethyl isobutyrate; phenylacetaldehyde dimethylacetal; phenylacetaldehyde diethylacetal; geranonitrile; citronellonitrile; cedryl acetal; S-isocamphylcyclohexanol; cedryl methylether; isolongifolanone; aubepine nitrile; aubepine; heliotropine; eugenol; vanillin; diphenyl oxide; hydroxycitronellal ionones; methyl ionones; isomethyl ionomes; irones; cis-3- hexenol and esters thereof; indane musk fragrances; tetralin musk fragrances; isochroman musk fragrances; macrocyclic ketones; macrolactone musk fragrances; ethylene brassylate, and combinations thereof.

While there have been described what are presently believed to be the preferred embodiments of the invention, those skilled in the art will realize that changes and modifications may be made thereto without departing from the spirit of the invention, and it is intended to include all such changes and modifications as fall within the true scope of the invention.

Claims

What is claimed is:

1. A composition comprising a polyurethaneurea foam; wherein said polyurethaneurea foam is prepared from a polyurethaneurea solution comprising a solvent and a polyurethaneurea derived from a prepolymer which is the reaction product of at least one hydroxyl-terminated polymer having a number average molecular weight of about 1600 to about 2400; at least one polyisocyanate; and a chain extender.

2. The composition of claim 1 , wherein said hydroxyl-terminated polymer comprises a glycol selected from the group consisting of polyether or copolyether glycols, polyester or copolyester glycols, polycarbonate or copolycarbonate glycols, and combinations thereof.

3. The composition of claim 1 , wherein said hydroxyl-terminated polymer comprises greater than 30% polytetramethylene ether glycol.

4. The composition of claim 1 , wherein said polyisocyanate comprises an aromatic diisocyanate selected from the group consisting of phenylenediisocyanate, tolylenediisocyanate (TDI), xylylenediisocyanate, biphenylenediisocyanate, naphthylenediisocyanate, diphenylmethanediisocyanate (MDI), and combinations thereof.

5. The composition of claim 1 , wherein the prepolymer has an NCO content of about 1.3% to about 2.2%.

6. The composition of claim 1 , wherein the prepolymer has an NCO content of 1.5% to 2.0%.

7. The composition of claim 1 , further comprising at least one additive selected from the group consisting of antioxidants, pigments, colorants, fragrances, anti-microbial agents, skin care additives, odor absorbers, phase change materials, beeswax, and combinations thereof.

8. An article comprising a polyurethaneurea foam, wherein said polyurethaneurea foam is prepared from a polyurethaneurea solution comprising a solvent and a polyurethaneurea derived from a prepolymer which is the reaction product of at least one hydroxyl-terminated polymer having a number average molecular weight of about 1600 to about 2400; at least one polyisocyanate; and a chain extender.

9. The article of claim 8, wherein the foam has a substantially uniform thickness from a first end to a second end.

10. The article of claim 9, wherein the article has a thickness of about 1.Omm to about 30.0mm.

11. The article of claim 8, further comprising at least one additive selected from the group consisting of antioxidants, pigments, colorants, fragrances, anti-microbial agents, skin care additives, odor absorbers, phase change materials, beeswax, and combinations thereof.

12. The article of claim 8, wherein said article takes on the shape of the mold in which it was formed.

13. The article of claim 8, wherein said polyurethaneurea foam is in the form of substantially spherical beads.

14. The article of claim 13, further comprising a polyurethaneurea film.

15. The article of claim 14, wherein said polyurethaneurea film contains the polyurethaneurea foam beads by:

(1 ) binding the beads together; or

(2) containing the beads in an interior space defined by at least two separate polyurethaneurea films that are sealed together at edges of the films.

16. The article of claim 8, wherein said article is shoe component.

17. The article of claim 8, wherein said article is an insulator.

18. The article of claim 8, wherein said article includes a surface with no visible pores.

19. The article of claim 8, wherein said article includes pores that extend from a top surface to a bottom surface.