BRPI0706934A2 - fabric care composition, compositions, polyurethane powder, method for extending perfume embodiment into a fabric, method of increasing retention of garment shape, method for increasing the ease of care properties of a fabric, method for providing anti-stain property of a fabric, methods for preparing polyurethaneurea powder, method for dyeing a powder composition and method for prolonging perfume embodiment in a composition - Google Patents

Abstract

TISSUE CARE COMPOSITION, COMPOSITIONS, POLYURETHANEOUS DUST, METHOD FOR THE EXTENSION OF PERFUME CONCRETIZATION IN A TISSUE, METHOD OF INCREASING THE FORMATION OF THE DRESS, METHOD OF INCREASING THE FACILITY OF THE FACILITY OF THE FACILITY OF THE FACILITY SPOTTING PROPERTIES ON A FABRIC, METHODS FOR PREPARING POLYURETHANEOUS DUST, METHOD FOR DYING A COMPOSITION INTO DUST AND METHOD TO EXTEND THE PERFUME INTO A COMPOSITION. The present invention relates to polymeric compositions such as polyurethanureas, polyamides and polyesters. The compositions can be in a variety of forms, such as dispersions, powders, fibers and granules. The compositions are useful in the preparation of many products including health and beauty products, such as cosmetics, paints, household products such as fabric care compositions, clothing! shoes and textiles! furniture.

Description

"TISSUE CARE COMPOSITION, COMPOSITIONS, DEPOLIURETANOURÉIA POWDER, METHOD FOR EXTENSION PERFUME ACCURACY IN A FABRIC, METHOD OF RETENTION OF PROCESS FOR PRODUCT PROCEDURE FOR PROCEDURE TO A FABRIC, METHODS FOR PREPARATION OF POLYLURETANOURÉIA POWDER, METHOD FOR DYING A POWDERPOSITION AND METHOD FOR PROLONGING PERFUME COMPOSITION "

Cross Reference to Related Patent Applications

The present patent application claims the benefit of US Patent Application No. 60 / 865,091 filed on November 9, 2006, claims the benefit of US Patent Application No. 60 / 837,011 filed on August 11, 2006, and claims the benefit of Patent Application No. 60 / 759,853 deposited January 18, 2006, all of which are incorporated herein by reference.

Field of the Invention

The present invention includes polymeric compositions such as aspoliurethanureas, polyamides and polyesters. The compositions may be in a variety of forms, such as dispersions, powders, fibers and granules. Compositions are useful in the preparation of many products including health and beauty products such as cosmetics, paint, household products such as fabric care compositions, apparel / footwear and textiles / furniture.

Background of the Invention

Polymers such as polyurethanureas, polyamides and polyester have historically been used in the preparation of synthetic fibers.

However, these polymers have other properties that may potentially offer benefits beyond the shape of the fiber. Therefore, there is a need for polymeric compositions and methods that emphasize these additional advantages.

An example of a form suitable by different polymers is a powder. Fine powders of synthetic polymers such as polyethylenes, polyamides, polyurethanes and polysiloxanes have been used in stamping, coating and cosmetic applications. Although many particle size reduction techniques (such as solid state shear spraying, cryogenic grinding, gas atomization and high shear mixing and milling) are known in the art and have been applied in the production of polymer powders, there is a need for method improved fine and uniform particle production especially for elastomeric polymers such as segmented polyurethanes and polyurethanureas.

There is a need for improved polymeric compositions which may have additional benefits not only for stamping, coating and cosmetic applications, but also for other applications such as painting and fabric care.

Fabric softeners are often used in detergent additives to provide softness and / or lightness to the washable fabrics. Fabric softeners also soften fabrics, decrease static adhesion, provide a pleasant fragrance, reduce drying time, reduce wrinkles, and make ironing easier. However, the benefits of these properties generally diminish over time after drying. wash.

The most common active components are based on long chain grease molecules called quaternary ammonium compounds, which are cationic in nature. Therefore, in order to avoid unwanted reaction with detergents which may be anionic in nature, fabric softeners are generally introduced during rinsing or drying the fabric.

In order to reduce fabric wash time and costs, there is a need for fabric care compositions that can be added simultaneously with the detergent. There is also a need for tissue care compositions that extend the duration of the benefits of fragrance proving and facilitate care associated with fabric softening compositions.

Brief Description of the Invention

One embodiment features a powdered polyurethaneurea or an aqueous dispersion. These powders or dispersions provide fabric care properties alone or in combination with a detergent or fabric softener composition.

In one embodiment, a fabric care composition is in the form of a nonionic film forming dispersion including a polyurethane and water polymer. The polymer is the product of the reaction of a prepolymer with water as a chain extender where the prepolymer is the reaction product of a glycol or a mixture of glycols and 4,4'-methylenobis (phenylisocyanate).

In another embodiment is a nonionic ionic filming dispersion including water and a polyurethanurea polymer. The polymer is the reaction product of a prepolymer and a chain extender including a diamine and water chain extender, where the polymer is the reaction product of a glycol (polyol) or a mixture of glycols and 4,4'-methylenobis. (phenylisocyanate). The polymer can then be filtered and ground or spray dried to provide a powder.

An additional embodiment provides a method of prolonging the approval of perfume or fragrance on a fabric or garment. The method includes contacting the fabric or garment with a fragrance and a polyurethane urea composition in the form of a powder or an aqueous dispersion. Contact may occur in a variety of ways including, but not limited to, adding fragrance and polyurethane to a softer soapy detergent prior to washing and / or drying the fabric by either adding them directly to the wash water or introducing them during the rinse cycle, either directly or in combination with a fabric softener composition.

A further embodiment presents a method for providing the desired properties to a fabric or garment. The method includes contacting a fabric with a polyurethanurea in the form of a powder or aqueous dispersion. Desired properties that may be provided to the fabric include, but are not limited to, shape retention, ease of care (i.e. ease of ironing) and anti-stain properties.

Segmented polyurethaneureas compositions in the form of fine powders are also provided. Methods for the manufacture of such polyurethane dust powders are also included. Additionally, some embodiments are powders that exhibit water and / or oil absorbing properties.

Other polymeric compositions and forms are presented. These compositions are useful for a variety of compositions including belts, cosmetics and fabric care compositions, among others.

Detailed Description of the InventionAs used herein, the term "powder" means a particulate material consisting of a loss of aggregation of finely divided solid particles. For a fine powder, the maximum dimension is less than 1 millimeter and the average particle size is less than 100 μιτι. However, larger particle sizes are also considered. For example, a coarse powder may have particle sizes larger than 1 millimeter with an average particle size in the range of about 0.5 mm to about 2 mm. As used herein, the term "film former" means that the This material forms a continuous film in the absence of other reagents with the synthetic conditions described herein.

As used herein, the term "non-film forming" means that the material does not form a continuous film in the absence of other reagents with the synthetic conditions described herein.

As used herein, the term "woven" means any nonwoven, knitted, quilted, felt, braided or a combination of fiber and / or yarn bonded material, including, but not limited to, those used in clothing (clothing), sheets , towels, curtains, upholstery and carpets.

As used herein, the term "fabric care composition" refers to any composition that may be applied to a fabric, especially during washing or drying the fabric, to provide beneficial properties to the fabric. These properties include cleaning, removing oily and greasy marks, softening fabrics, decreasing static adhesion, providing a pleasant fragrance, reducing drying time, reducing wrinkling and facilitating ironing.

As used herein, the term "ease of care" with respect to the fabric means that the fabric will have few wrinkles after washing, may not require ironing or will be easier to iron.

Polyurethaneurea Compositions

Polyurethanurea compositions of some embodiments may be in the form of an aqueous dispersion, powder, fiber or granule. Where the powder form is desired, it may be isolated from the aqueous dispersion by filtration, drying and milling or by dry spraying the dispersion. The solids content of the dispersion may vary. For example, the solids content may be from about 5% to about 50%, preferably from about 20% to about 40% by weight of the dispersion. The powders may have an average particle size of less than 100 μm, such as from about 50 to about 80 μm with no particle size greater than 1.0 μm, such as less than about 0.5 mm.

Another suitable method for the preparation of the polyurethanurea powders of some embodiments is in accordance with Roach US 6,475,412, which is incorporated herein by reference. Roach describes a spandex extrusion method with specific process conditions to provide a powder.

To prepare the anionic film-forming aqueous dispersion of some embodiments, a prepolymer is prepared as a protected glycol. The prepolymer is the reaction product of:

- at least one hydroxyl terminated polymer such as opolyether (including copolyethers), polycarbonates or polyol polyester component having an average molecular weight number of about 600 to about 3,500, for example a poly (tetramethylene ether) glycol having a number average molecular weight of from about 1,400 to about 2,400;

- a polyisocyanate, which is a mixture of 4,4'- and 2,4'-methylene bis (phenyl isocyanate) (MDI) isomers, with the ratio of isomers from 4,4'-MDI to 2,4'-MDI from about 65:35 to about 35:65; and

- at least one diol compound with: (i) hydroxy groups capable of reacting with the mixture of polyisocyanate MDI isomers and (ii) at least one carboxylic acid group capable of forming a salt on neutralization, wherein at least one carboxylic acid group is unable to react with the mixture of MDI isomers of polyisocyanates.

The prepolymer is then neutralized to form a salt, for example by the inclusion of triethylamine and finally the common chain extender diamine and water chain extender to form the aqueous dispersion. Additives such as surfactants, defoamers, antioxidants and thickeners may be included.

Mixing MDI isomers for anionic dispersion achieves a reduction in prepolymer viscosity without the addition of a solvent. MDI isomer mixing also serves to reduce the speed of the reaction.

The prepolymer may be prepared in a batch process or in a continuous process.

When included in some embodiments, the diol including hydroxy groups and a carboxylic acid group may be described as a diolacid. Examples of useful acid diols include 2,2-dimethylolacetic acid, 2,2-dimethylolpropionic acid (DMPA) 1 2,2-dimethylolbutanoic acid, 2,2-dimethylolpentanoic acid and combinations thereof.

The nonionic film-forming dispersion of some embodiments includes a prepolymer, which is an isocyanate-terminated polyurethane prepolymer. This prepolymer is the product of the chain reaction of a hydroxyl terminated polymer, such as polyol, such as opoli (tetramethylene-co-ethylene ether) glycol or a mixture of poly (tetramethylene ether) glycol with ethoxylated propylene glycol and a diisocyanate, such as 4,4'-methylenobis (phenyl isocyanate). This prepolymer is then chain extended with water and dispersed in water or dispersed in water followed by chain extension with water.

The nonionic non-film dispersion of some embodiments includes a prepolymer, which is an isocyanate-terminated polyurethane prepolymer. This prepolymer is also the reaction product of a polyol such as polybutadiene glycol or poly (tetramethylene ether) glycol and a diisocyanate such as 4,4'-methylenobis (phenyl isocyanate). This prepolymer can be chain extended with a combination of water and a decade diamine extender such as an ethylene diamine or a functional deamine crosslinker such as polyvinylamine. Either a hydrophilic or hydrophobic glycol may be selected to produce a polymer powder having different water / oil absorbing capacities. Similarly, the powder particle size can be adjusted by adjusting the viscosity of the prepolymer with the use of a diluting solvent.

In some embodiments, a polyurethanurea powder is manufactured by a high shear force dispersion of an isocyanate terminated prepolymer, with or without solvent, in an aqueous medium containing a dispersant, and a chain extension reagent or a crosslinking agent. High shear force is defined as sufficient force to make particles no larger than 500 μιη. The prepolymer may be made by reacting the polyol or a polyol copolymer or a polyol blend such as polyether glycols, polyester glycols, polycarbonate glycols, hydrogenated polybutadiene glycols or derivatives thereof and hydroxy polydimethylsiloxanostermines with a diisocyanate such as methylene bis (4-phenylisocyanate) (MDI) to form an NCO-terminated prepolymer or a "protected glycol". In a polymeric composition, the molar ratio of NCO / OH is in the range of 1.2 to 5.0. An example of a decadeia extender reagent is an aliphatic diamine, such as ethylene diamine (EDA). A chain crosslinking agent is an organic compound or polymer with at least three primary amine or secondary amine functional groups capable of reacting with NCO groups. A water soluble or insoluble organic solvent such as 1-methyl 2-pyrrolidinone (NMP) or xylenes may be used to dilute the prepolymer prior to dispersion. Water dispersed formed polyurethanurea fine particles can be used as such or isolated by filtration and drying in solid powders.

Alternatively, a spray coating process which also has greater particle size control may also be used. The particle size of the powders of some embodiments may vary depending upon the intended use. For example, the average particle size may be less than 1 millimeter (mm), also including an average particle size of less than 100 microns (μιη).

In some embodiments, a segmented polyurethaneurea for the manufacture of an elastomeric powder includes: (a) a polyol or a polyol copolymer or a polyol mixture of an average molecular weight number from 500 to 5,000, including but not limited to polyether glycols, polyester glycol, polycarbonate glycols, polybutadiene glycols or hydroxy-terminated hydrogenated epolidymethylsiloxanes derivatives thereof; (b) a diisocyanate including aliphatic diisocyanates, aromatic diisocyanates and alicyclic diisocyanates; and (c) an aliphatic diamine (i.e. a diamine chain extender) or a mixture of at least one diamine selected from the group consisting of one aliphatic diamine and one alicyclic diamine each having from 2 to 13 carbon atoms or an amino-terminated polymer or an organic compound or polymer with at least three primary or secondary amino groups; and optionally a primary or secondary monoamine as a chain terminator.

Examples of polyester polyols that may be used in some embodiments include those glycols with two or more hydroxy groups, ring opening polymerization and / or copolymerization of ethylene oxide, propylene oxide, trimethylene oxide, tetrahydrofuran and 3-methyl tetrahydrofuran , or from the condensation polymerization of a polyhydric alcohol, for example a diol or mixtures of diols, 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 bifunctional linear polyether polyol may specifically include a pesomolecular poly (tetramethylene ether) glycol of about 1,700 to about 2,100, such as Terathane® 1800 (commercially available from Invista S.à rl de Wichita , KS and Wilmington1DE) with the functionality of 2.

Examples of polyols of polyols which may be used include those glycol esters of two or more hydroxy groups produced by the condensation polymerization of aliphatic polycarboxylic acids and polyols thereof, or mixtures thereof, 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, dodecanodicarboxylic acid and dodecanodicarboxylic acid. Examples of polyols suitable for the preparation of the polyol polyester 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 50 ° C may be included.

Examples of polycarbonate polyols which may be used include those carbonate glycols with two or more hydroxy groups produced by condensation polymerization of phosgene, chloroform acid ester, dialkyl carbonate or diallyl carbonate and mixtures of low molecular weight aliphatic with no more than 12 carbon atoms in each molecule. Examples of polyols suitable for the preparation of polycarbonate polyols are odethylene 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 5 ° C to about 50 ° C may be included.

Examples of suitable diisocyanate components are 1,6-diisocyanatohexane, 1,12-diisocyanatododecane, isophorone diisocyanate, trimethylhexamethylene diisocyanates, 1,5-diisocyanate-2-methylpentane, diisocyanate cyclohexanes, methylenehexis (4-cyclohexane) ), 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 as phenylenediisocyanate, tolylenediisocyanate (TDI) 1 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, cyclohexanobis (methylamine) s, isophorone diamine, xylylenediamines and ethylenebis (cyclohexylamine) s. A mixture of two or more diamines may 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), poly (propylene glycol) bis (2-aminopropyl) terminated, bis (3-aminopropyl) epolitetrahydrofuran.

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

Examples of suitable monoamine components (d) include primary alkylamines such as ethylamine, butylamine, hexylamine, cyclohexylamine, ethanolamine and 2-amino-2-methyl-1-propanol and dialkylamines, such as β, β-diethylamine, N-ethyl-N-propylamine, N-N-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, Δ, β-diethanolamine and 2,2,2,6-tetramethylpiperidine.

In the manufacture of a polyurethanurea powder of some embodiments, a glycol is first reacted with a diisocyanate, optionally with a catalyst present, to form an NCO-terminated prepolymer or a "protected glycol". This reaction is typically performed in a uniformly melt-formed mixture, with heat applied at temperatures of 45 to 98 ° C for a period of 1 hour to 6 hours. Quantities of each reaction component, glycol weight (WgI) and diisocyanate weight (Wdi) are regulated by the protective ratio (CR), which is defined as the mol ratio of diisocyanate to glycol as shown below:

CR = (Wdi / MWdi) / (WgI / MWgl)

Where Mwdi is the molecular weight of diisocyanate and MWgI is the number of average molecular weight of glycol. According to the present invention, the coating ratio is in the range from 1: 2 to 5.0, specifically between 1.5 and 3.0.

Upon completion of the protective reaction, when all the hydroxy (-OH) groups of the glycol molecules have been consumed by the deisocyanate (-NCO) groups from the diisocyanate to form a urethane bond, a viscous polyurethane prepolymer with NCO terminals are formed. This prepolymer is then added and dispersed in an aqueous solution containing surfactants such as dispersants and defoamers and, optionally, chain extenders such as diamines. Alternatively, this prepolymer may be diluted with an organic solvent, such as water-soluble N-methyl pyrrolidone (NMP) or water-soluble xylenesinsoluble before dispersed in aqueous medium. Solid polymer particles are formed under a high shear force during dispersion and under chain extension with water and / or diamine extenders. These polyurethanurea particles can then be filtered and dried.

Additives such as antioxidants, pigments, colorants, fragrances, antimicrobial agents (such as silver), active ingredients (humectants, UV filters), surfactants, anti-defoamers, and similar solvents may be mixed into the polyurethane particles prior to during or after dispersion of the prepolymer. In some cases, it may be beneficial to add the additives during prepolymer dispersion to encapsulate the additive in the polyurethane particles. Encapsulation of the additive may slow the diffusion of the additive outside the polymer matrix by providing a delay in the release time of the additive. This delayed release is compared to the relatively faster release of an additive adsorbed onto the surface of a particle. Encapsulation combinations and surface adsorbed additives may be included to provide rapid release of one or more surface additives of a particle and delayed release of the encapsulated additive.

Pigments may also be added to the polyurethane anurea compositions of some embodiments. Pigments may be added in a similar manner to other additives. Examples of embodiments include carbon black and TiO 2. For a polyurethane powder, the effect of the pigments is shown in Table A below: <table> table see original document page 15 </column> </row> <table>

Additional examples of the pigments are described below.

Polyurethaneurea Beads

Some embodiments of the present invention are polyurethane urea granules. A useful method for preparing such granules is described in US Patent 5,094,914 to Figuly et al. ("Figuly"), which is incorporated herein by reference in its entirety. A segmented polyurethanurea composition, which may be any of those described herein (such as those based on polyethers or polyesters) may be prepared. A solution including polyurethanurea may 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 polyurethane solution can then be introduced as droplets into a coagulation bath that solidifies the polymer in granule form. The coagulation bath may include a liquid which extracts the solvent from the polymer solution, but is not a solvent for the polymer, such as water.

Therefore, the granules may be prepared having an average diameter of from about 1 mm to about 4 mm, having a content ranging from 60% to 90%, and having no visible pores on the surface at 5,000 χ increase.

Some embodiments of the present invention are polyurethanurea granules having a wider range of particle sizes, void content and surface pores than previously described.

The void content is based on the density of the granules:

Voids = [1- (bead density / polymer density)] χ 100%

In some embodiments, the polyurethanurea granules have a void content below 60%. These granules can be prepared by using a higher viscosity solution. For example, solutions that have Brookfield viscosities of about 1,000 cps higher and a solids content of about 12% and larger produce granules which are denser, heavier and smaller than granules manufactured using the same granule making apparatus but using solutions that are less than 1,000 cps. In some embodiments, granules are prepared from solutions have high viscosities (> 1,000cps) but have a relatively low solids content (i.e. <10%). This can be accomplished by the use of a high molecular weight, branched polymer, or a polymer that binds together in solution through crystallization, hydrogen bonding, hard segment association, etc. For example, polyurethane-based solutions will become more viscous over time.

Low viscosity solutions with a relatively high solids content may be prepared by using low shear polymers, for example a liquid crystalline polymer or some spandex formulations, or by using polymers that have a low average molecular weight, or do not associate, bonding. hydrogen or crystallize in solution. Another method for preparing denser and smaller granules is to produce from solutions that produce vacuum volumes of 60 to 90%, but in the coagulation and drying process to remove solvent, some solvent is left to dry. stay with the beads. The granules are then dried such that the residual solvent will redissolve and precipitate the polymer into a denser structure.

Granules with a void content above 90% may also be prepared. One method is to include low viscosity polymers. However, as viscosity is continually decreased within the same polymer formulation, a point is reached where the polymer is so diluted that it cannot maintain the granule shape in the coagulation and collapse process (This process is described in US Patent 5,126,181 to preparation of flattened micropore discs). On the other hand, it is possible to select or formulate polymers, in particular polyurethanureas, which are more rigid in nature such that even when diluted they still have sufficient rigidity to maintain the granule shape without collapsing. In particular, it is possible within the polyurethanurea family to synthesize or select a formulation that is more rigid but still has the inherently highly desirable elastomeric nature (extension and recovery). For example, a polyurethanurea using a low average molecular weight polyether glycol, such as an average molecular weight of less than 1,000 or less than 700, as the soft segment will be sufficient to produce a granule having a void content greater than 90% which is a spherical shape.

In addition, other reagents or co-reagents could be used to modify the stiffness of the final polyurethanurea granule, for example, different EDA (ethylene diamine) extenders or comEDA co-extenders, or MDI isomers (4,4-vs. 2, 4-) and their mixtures. 1,4-Phenylenediisocyanate or 1,4-phenylene diamine or a combination or mixture thereof will also produce the stiffer polyurethanureas than corresponding "traditional" MDI and EDA-based polyurethanureas. It should also be noted that mixtures of polyurethanureas which have different stiffness could also be used to adapt or select the required stiffness required to achieve void volumes greater than 90%. Other polymers or additives could be mixed in the solution to obtain the required stiffness and other requirements to make larger void granules.

Some embodiments are surface-sized pore-controlled granules. A micronized or other water-soluble nano-size salt (e.g., polyethylene glycol) may be combined with the polyureaurethane solution prior to introduction into a coagulation bath. Water soluble materials will leave a pore when the granule is coagulated and washed in water.

Also provided are methods for continuous or semi-continuous production of the granules. In the batch stirring reactor process, the solvent may accumulate in water or non-solvent polymer. Excessive accumulation of solvent can lead to stickiness of the produced granules by causing them to stick together or possibly to coalesce them. Accumulation of solvent in the non-solvent (or water) may also retard granulation coagulation due to insufficient thermodynamic incentive for the solvent to be "pulled" or diffused into the non-solvent. The non-solvent is becoming increasingly concentrated and almost identical to the solvent as the solvent diffuses out of the granules or discs.

Even the semi-continuous process of some embodiments would allow the production of about 500 g of granules for 8 hours shift, a 10-fold increase over that process of the blended stirring reactor. The granules can be "harvested" anytime after about 2-3 minutes after formation and moved to other containers except that they have been formed allowing the granules to be continuously produced in the "process equipment" for at least up to 3-8 hours of formation. shift.

In another embodiment, water in the "process equipment" could be continuously flushed and the granules periodically or continuously harvested, such that the granules could be continuously produced. A continuous or semi-continuous operation would be favorable industrially compared to a batch operation.

Harvesting or moving the granules from where they were formed into a different tank to be wetted and the extracted residual DMAc solvent can be performed by various methods. One method includes the use of a conveyor system including a conveyor belt. The belt could be a filter or include holes to allow water to pass through it while retaining the granules in it. Another method for transferring the granules from process equipment is by a "waterfall". The waterfall method allows granules to be collected at one end of the tank far from where they were formed, allowing some water and a significant number of granules to overflow at the end of the deformation tank into another tank. Since the granules float in the water / solvent mixture, this can easily be accomplished.

Polyurethanurea granules of some embodiments have a wide range of applications. This includes use in textiles, clothing and shoes, home furnishings, cosmetics and other domestic uses. As a bedding material, it can be included as an alternative to padding, such as pillows. In our shoes, the granules can be included as a protection for the sole of the shoes. In addition, a combination of different sized beads may be included in the same shoe sole to accommodate varying depression points within the sole as well as in the inner and outer soles of the shoe portions, particularly where the beads are included in a "like" construction. sandwich "in the pleated or curly buildings. The quilting effect is also useful for furniture upholstery and carpet material. For example, the granules may be included in the fibrous cotton filler materials. The effects of padding are also beneficial in headwear such as helmets or hats, garment straps, luggage straps and comfortable restraint applications such as those found in clubs, ski poles, hammer, bicycles, lawnmowers, steering wheels, etc.

The granules possess a plethora of useful properties. For example, after being compressed for 24 hours to a quarter of the original diameter, the granules regain 85% of their immediate volume and about 97% of their volume after 10 minutes. Granule sizes may vary. The granules have a diameter greater than 0.1 mm to 10 mm, such as from about 0.5 mm to about 8 mm. The individual granules were prepared and had diameters of 0.5mm, 0.8mm, 1.0mm, 2.5mm, 3.0mm, 4.0mm, 5.0mm and 8.0mm.

The individual granules have a density at any appropriate range, such as from about 0.05 g / cc to about 0.5 g / cc, including about 0.1 g / cc. Likewise, the granules have unique absorption properties. For example, when placed in water, a granule about 3 mm in diameter will absorb about 14% of its weight in water. However, when the granule is compressed and then released into water, the granule will absorb about 350% of its weight in water. These absorption properties demonstrate additional utility, such as a vehicle supply for substances such as fragrances, ointments and other fluid compositions.

A variety of different polyamides may be used with some embodiments. Examples of suitable polyamides include Nylon6, Nylon 12 and Nylon 6.6. Polyamide may be present in any desired shape including fibers and powders. A suitable process for the preparation of polyamide powder is described in US Patent 4,831,061 to Hilaire, which is incorporated herein by reference. Such powders are also commercially available under the trade name of Orgasol® by Arkema. From commercially available powders, the size ranges from about 5 μηι to about 20μιη. Polyamide powders can also be supplied in a wider range of sizes, such as having an average particle size in the range of from about 50100 μπα to about 500 μηι, including 100 μιη. Coarser powders are also included, such as those having an average particle size in the range of about 0.5 mm to about 5 mm, including about 1 mm.

Polyester Compositions

A variety of different polyesters are also useful for inclusion in some embodiments. Examples include depolyalkylene terephthalate, polyalkylene naphthalate and polyalkylene isophthalate. Examples of polyalkylene terephthalate are linear fiber-forming condensation polymers having carboxyl-bonding radicals in the polymeric chain, such as polyethylene terephthalate ("2GT" or "PET"), polytrimethylene terephthalate ("3GT" or "PTT") and polytetramethylene terephthalate ("4GT").

The polyester composition may be in any desired shape including fibers, flakes and powders.

In the absence of an indicator to the contrary, the reference to "polyalkylene terephthalate" means to encompass copolyesters, that is, polyolesters made using 3 or more reagents, each having two ester-forming groups. For example, a copoly (ethylene terephthalate) may be used wherein the comonomer used for the manufacture of polyester is selected from the group consisting of linear, cyclic and branched aliphatic dicarboxylic acids having from 4 to 12 carbon atoms (eg acid butanedioic acid, pentanedioic acid, hexanedioic acid, dodecanedioic acid and 1,4-cyclohexanedicarboxylic acid); aromatic dicarboxylic acids other than terephthalic acid and having from 8 to 12 carbon atoms (for example isophthalic acid and 2,6-naphthalenedicarboxylic acid); branched, cyclic aliphatic diols having from 3 to 8 carbon atoms (e.g. 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 3-methyl-1,5-pentanediol, 2,2- dimethyl-1,3-propanediol, 2-methyl-1,3-propanediol and 1,4-cyclohexanediol); and aliphatic and aromatic ether glycols having from 4 to 10 carbon atoms (for example bis (2-hydroxyethyl) ether hydroquinone, or poly (ethylene ether) glycol having a molecular weight below about 460 daltons, including odethylene ether glycol ). Typically, the comonomer may be present at nocopolyester at a level in the range of about 0.5 to about 15 mol%.

Flake

In some embodiments are the polymeric flake compositions. Flake is a very small or fiber-cut precision cut used to produce a velvet as a coating on fabric, rubber, film or paper. The flake can be used as a noplastic filler, paper, rubber or similar compositions to increase impact strength, improve moldability or add a decorative appearance to the finished product. The flake may be a fiber generally in the length of from about 0.040 inch to about 0.250 inch (1 mm to 6.25 mm). The diameter is generally between about 10 and about 100 μηι. Different color flakes can be prepared from a variety of different unnatural synthetic fibers, such as polyamides, polyesters, cotton and rayon.

Dye Information

A variety of different dyes, dyes, and pigment may be used to add color to the compositions of some embodiments. For example, certain dyes are most useful for adding color to polyamide and polyester compositions while pigments may be added to polyurethanurea compositions.

Among the dyes used for some embodiments, including cosmetic compositions, are inorganic dyes and organic dyes including synthetic and natural dyes. Inorganic colorants include TiO2, iron oxides and ultramarines. Synthetic organic colorants include red pigments, toner and pigments, such as those described in US Patent 4,909,853, incorporated herein by reference. An example of an organic natural colorant is carmine.

A suitable method for preparing a colorless nylon powder includes dyeing in a heated dye beaker on an electric plate with a magnetic stirrer. This ensures that the powders will be shaken by the agitators to avoid aggregate formation and ensuring until the dye is absorbed by the batch:

- adjust the dye bath to a pH of 6.0 with phosphate buffers;

- Add 1% (by weight) Levegal SER (anionic leveling agent);

- add the pre-dissolved dye;

- add nylon powder;

- increase to boiling at a speed of 2 ° C / min by increase. Keep the temperature for 30 minutes;

- add 1g / l of Sandacid GBV (acid donor - liberally acid in dye bath to lower pH to pH 5.0 - 5.5);

- keep the temperature for 30 minutes;

- cool;

- pass the dye bath and dust through a fine rinsing filter;

- Collect dust and dry in a heated cabin.

For nylon in any way including fiber, flake and powder, the most commonly used colorants are the nonmetallized acidic dyes. Both of these provide a good shade range and a certain degree of color fastness to both washes and UV. Metallic dyes will provide better UV and wash fastness, but the range of shades is limited to more attenuated colors. Light shades are only obtained with non-metallized acid dyes, which do not perform so well under UV and washes, or there is a limited range of special reactive acid dyes available that offer the best washing performance, but which has a similar solid performance as UV as non-metallized acid dyes. These reactive dyes tend to be much more expensive and the depth of shade is limited depending on the amine ends available in the nylon powder / flake.

For polyester of any shape including fiber, flake and epoxy, dispersed dyes are the only dyes that can dye the standard dispersed dyeable polyesters. However, if cationic polyester is available then basic (cationic) or dispersant dyes may be used.

All these types of dye classes can be obtained from major suppliers such as Huntsman (formerly Ciba Textile Effects) and DyStar. See the Table below for a list of commercially available dyes from suppliers and the class. <table> table see original document page 25 </column> </row> <table>

Fragrances

There is a range of fragrance materials that settle in, or are well retained, in the spandex (ie, segmented polyurethane). These materials include, but are not limited to, the following categories, Category A and Category B as shown below.

Category A: hydroxyl materials which are alcohols, phenols or silicylates, with an octanol / water partition coefficient (P) whose Yogaritmum (Iog10 P) is 2.5 or greater, and a gas chromatographic Kovats index (as determined by polydimethylsiloxane as the nonpolar stationary phase) of at least 1,050.

The octanol - water partition coefficient (or its Yogaritmocomum "log P") is well known in the literature as an indicator of hydrophobicity and water solubility (see Hansch and Leo, ChemicalReviews, 71, 526-616, (1971); Hansch, Quinlan and Lawrence, J. Organic Chemistry, 33, 347-350 (1968)). Where such values are not available in literature, they can be measured directly, or roughly estimated using mathematical algorithms. Software providing such estimates is commercially available, for example, "log P" from Advanced Chemistry Design Inc.

Materials having Iog10 P of 2.5 or greater are, in some ways, hydrophobic.

Kovats indices are calculated from the retention time in a gas chromatography measure with reference to the retention time for alkanes [see Kovats, Helv. Chim. Acts 41, 1915 (1958)]. Indices based on the use of a nonpolar stationary phase have been used in the perfumery industry for a few years as a descriptor with respect to the molecular size and boiling point of the ingredients. A review of Kovats indices in the perfume industry is given by T Shibamotoem Capillary Gas Chromatography in Essential Oil Analysis, P. Sandra and CBicchi (editors), Huethig (1987), pp. 259-274. A common non-polar phase that is appropriate is dimethyl. 100% polysiloxane as supplied, for example, under a variety of trade names, such as RP-1 (Hewlett-Packard), CP Sil 5 CB (Chrompack) 1 OV-1 (Ohio Valley) and Rtx-1 (Restek).

Kovats low index materials tend to be volatile and are not well retained in many fibers.

Category A includes alcohols of formula ROH wherein the hydroxyl group may be primary, secondary or tertiary, and group R is an optionally branched or substituted cyclic or acyclic alkyl or alkenyl group such that ROH has the partition coefficient and the Kovats properties as defined above. Kovats index alcohols 1,050 to 1,600 are typically monofunctional alkyl or arylalkyl alcohols having molecular weights within the range of 150 to 230.

Category A also includes phenols of the formula ArOh, wherein the Ar group denotes a benzene ring which may be substituted with one or more alkyl or alkenyl groups, or with an -CO2A ester group, where A is a hydrocarbon radical, in which case The compound is a salicylate. ArOH has a partition coefficient and a Kovats index as defined above. Typically, such phenols with the Kovats index 1,050 to 1,600 are molecular weight monohydroxyl phenols within the range of 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, 2-ethyl-4- (2 ', 2', 3-trimethylcyclopent-3'-enyl) but-2-enol salicylate , borneol, carvacrol, citronelol, 9-decenol, dihydroeugenol, dihydrolinalol, dihydromyrcenol, dihydroterpineol, eugenol, geraniol, isoamyl salicylate, isobutyl salicylate, isoleugenol, neoolylene menthololene hexylerolene phenoxanol, terpineol, tetrahydrogeraniol, tetrahydrolinalol, tetrahydromyrcenol, thymol, 2-methoxy-4-methylphenol, (4-isopropylcyclohexyl) -methanol, benzyl salicylate, cyclohexyl salicylate, hexyl salicylate, farol and patchouli alcohol.

Category B esters, ethers, nitriles, ketones or aldehydes with an octanol / water partition coefficient (P) whose common Yogarithm (Iog10P) is 2.5 or greater, and a gas chromatographic Kovats index (as determined in polydimethylsiloxane as the non-phase). stationary polar) of at least 1,300.

Category B fragrances are of formula RX1 where X may be in a primary, secondary or tertiary position and is one of the following groups: -CO2A, -COA, -OA1 - CN or -CHO. The R and A groups are cyclic or non-cyclic hydrocarbon residues and optionally substituted. Typically, Category B materials with a Kovats index of not more than 1,600 are monofunctional compounds with molecular weights ranging from 160 to 230.

Examples of Category B fragrance materials are 1-methyl-4- (4-methyl-3-pentenyl) -3-cyclohexene-1-carbaldehyde, 1- (5 ', 5'-dimethyl-cyclohexenyl) -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, demethyl ethyl ketone trimer benzophenone, 3- (4'-tert-butylphenyl) propanal, caryophyllene, cis-jasmon, citral diethyl acetal, citronellal diethyl acetal, citronellal acetate, phenylethylbutyl ether, alpha-damascona, beta-damascona, delta-damascona, gamma- decalactone, dihydro isojasmonate, dihydrojasmona, dihydroterpinyl acetate, dimethylantranylate, 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, allylcyclodecenyl ether, tricyclodecenyl propanoate, gamma -undecalactone, n-methyl-n-phenyl-2-methylbutanamide, tricyclodecenyl isobutyrate, geranyl acetate, hexylbenzoate, alpha ionone, beta ionone, isobutyl cinnamate, deisobutyl quinoline, isoeugenyl acetate, 2,2,7,7-tetramethyltricyclidecan-5 -one, tricyclodecenyl acetate, 2-hexylcyclopentanone, 4-acetoxy-3-pentyl tetrahydropyran, ethyl 2-hexylacetoacetate, 8-isopropyl-6-methylbicyclo [2.2.2] oct-5-eno-2-carbaldehyde, methyl 4-isopropyl 1-methylbicyclo [2.2.2] oct-5-ene-2-carboxylate, methyl cinnamate, alpha iso methyl ionone, methyl naphthyl ketone, nerolin, nonalactone gamma, nopyl acetate, for tert-butyl cyclohexyl acetate, 4-isopropyl 1-methyl-2- [1'-propenyl] benzene, phenoxyethyl isobutyrate, phenylethyl isoamyl ether, phenylethyl isobutyrate, tricyclodecenyl pivalate, phenylethyl pivalate, phenyl acetaldehyde hexylene glycol acetal, 2,4-dimethyl-4-phenylthetrahydrofu rano, rose acetone, terpinylacetate, 4-isopropyl-1-methyl-2- [1'-propenyl] benzene, iara, (4-isopropylcyclohexadienyl) ethyl formate, amyl cinnamate, amyl cinnamic aldehyde, dimethyl acetal amyl aldehyde cinnamic cinnamyl cinnamate 1,2,3,5,6,7,8,8a-octatiro-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.

Although this is an extensive list of fragrances and perfumes that work especially well with spandex 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 odorants (ie, obtained from the extraction of flowers, herbs, leaves, roots, bark, wood, flowers or plants), artificial (ie, a mixture of oils of a different nature or oil constituents) and synthetic (ie synthetically produced).

Non-limiting examples of the fragrances include: dehexyl cinnamic aldehyde; cinnamic amyl aldehyde; amyl salicylate; hexyl salicylate terpineol; 3,7-dimethyl-c / s-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-frans-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-isopropylphenyl) propionaldehyde; ethyl-3-methyl-3-phenyl glycidate; 4- (parahydroxyphenyl) butan-2-one; 1- (2,6,6-trimethyl-2-cyclohexen-1-yl) -2-buten-1-one; para-methoxyacetophenone; para-methoxy-alpha-propylene; 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 methyl ether; methyl beta naphthyl ketone; coumarin; decylaldehyde; benzaldehyde; 4-tert-butylcyclohexyl acetate; alpha.alpha-dimethylphenethyl acetate; methylphenylcarbinyl acetate; tridecandioic acid ethylene glycol cyclic diester; 3,7-dimethyl-2,6-octadiene-1-nitrile; gammamethyl ionone; alpha ionone; ionone beta; petitgrain; methyl cedrilone; 7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethyl naphthalene; methyl ionone; methyl-1,6,10-trimethyl-2,5,9-cyclododecatrien-1-yl ketone; 7-acetyl-1,1,3,4,4,6-hexamethyl tetralin; 4-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; isohexenyl cyclohexylcarboxaldehyde; formyl tricyclodecan; cyclopentadecanolide; 16-hydroxy-9-hexadecenoic acid lactone; 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-gamma-2-benzopyran; 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-trimethyl-3-cyclopenten-1-yl) -2-buten-1-ol; cariopylene alcohol; decedryl acetate; para-tert-butylcyclohexyl acetate; patchouli; frankincan resinoid, labdanum; vetivert; Copaiba resin; balsam spruce; hydroxycitronellal eindole; phenyl acetaldehyde and indole; geraniol; geranyl acetate; linalool; delinalyl acetate; tetrahydrolinalol; citronellol; citronellyl acetate; dihydromyrcenol; dihydromyrcenyl acetate; tetraidromircenol; terpinyl acetate; nopol; nopil acetate; 2-phenylethanol; 2-phenylethyl acetate; benzilic alcohol; benzyl acetate; benzylsalicylate; benzyl benzoate; stiralyl acetate; dimethylbenzylcarbinol; trichloromethylphenylcarbinyl methylphenylcarbinyl acetate; isononyl acetate; vetiverylacetate; 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-pentyl tetrahydropyran; methyldihydrojasmonate; 2-n-heptylcyclopentanone; 3-methyl-2-pentyl-cyclopentanone; n-decanal; n-dodecanal; 9-decenol-1; phenoxyethyl isobutyrate; phenylacetaldehyde dimethylacetal; phenylacetaldehyde diethylacetal; geranenitrile; citronellanitrile; cedrilacetal; 3-isocampylcyclohexanol; cedril methyl ether; isolongifolanone; nitrilaaubepine; aubepine; heliotropin; eugenol; vanillin; diphenyl oxide; hydroxycitronellal ionones; methyl ionones; isomethyl ionomas; ironas; with s-3-hexenole esters thereof; musk indane fragrances; tetralin musk fragrances, isochroman musk fragrances; macrocyclic ketones; macrolactone dealmiscus fragrances; ethylene brassylate and combinations thereof.

Tissue Care CompositionsPolyurethanurea compositions prepared by the methods described above provide the surprisingly improved retention properties of fabrics. In addition, they also provide ease of care or ease of care properties. In other words, fabrics treated with the polyurethane composition have few wrinkles after washing and are easier to iron.

Polyurethanurea compositions of some embodiments also have surprisingly good water and oil absorption, especially when applied to the fabric. This is particularly important for anti-stain properties. After a tissue has been contacted with a polyurethane composition of some embodiments, the polyurethane composition will absorb moisture and oil from the sources causing the stain and thus limit the absorption of the tissue itself.

Due to the absorption properties, the polyurethaneurea compositions also assist in the achievement of fragrance prolongation in a tissue that has been contacted by the composition. This results from the absorption and subsequent gradual release of the fragrance by the polyurethane composition.

The fabric care composition of some embodiments may include a fabric softener or detergent to which the polyurethane composition may be added. These polyurethaneurea compositions may also be in any form, such as a dispersion or powder. Alternatively, the polyurethane composition may be added directly to the fabric, to a washing machine, to wash water (for manual washing) or to an automatic dryer.

In addition, the powder or dispersion may be used as a fabric softener substitute to provide anti-stain properties to the garments through home washing. Fabric softeners are often used to provide tissue perfume or fragrance and secondarily to provide fabric softness. The softening aspect of the fabric is not necessarily required when the tumble drying is used since the damp drying fabrics are already very soft.

Detergent compositions of some embodiments usually contain an anionic, nonionic, amphoteric or anpholitic surfactant or a mixture thereof and often contain, in addition, an inorganic or organic builder.

Fabric softeners will generally include a reactive component such as a quaternary ammonium salt. Examples of non-cyclic ammonium quaternary salts include tallow trimethyl ammonium chloride; deditallow dimethyl ammonium chloride; dithallow dimethyl ammonium methyl sulfate; dihexadecyl dimethyl ammonium chloride; di (tallow hydrogenated) dimethyl ammonium chloride dioctadecyl dimethyl ammonium chloride; deicosyl dimethyl ammonium chloride; didocosyl dimethyl ammonium chloride di (low hydrogenated) dimethylammonium methyl sulfate; dihexadecyl diethyl ammonium chloride; dihexadecyl dimethylammonium acetate; dithallow dipropyl ammonium phosphate; dithallow dimethyl ammonium nitrate; di (coco-alkyl) dimethyl ammonium echloride.

Other optional components of the care compositions contain some conventional embodiments by nature and are generally from about 0.1% to about 10% by weight of the composition. Such optional components include, but are not limited to, dyes, perfumes, bacterial inhibitors, optical brighteners, opacifiers, viscosity modifiers, tissue conditioning agents in solid forms such as clay, tissue absorbance enhancers, emulsifiers, stabilizers, tissue controllers. shrinkage, stain agents, germicides, fungicides, anti-corrosive agents, etc.

The fabric care compositions of some embodiments may be prepared by conventional methods. Homogenization is not necessary. A convenient and satisfactory method is to prepare a pre-mix of water softeners at about 150 ° F which is then added to a hot aqueous solution of the other components. Temperature sensitive components may be added after the fabric conditioning composition has been cooled to about room temperature.

The fabric care compositions of some embodiments may be used by adding to the rinse cycle of conventional household washing operations. Alternatively, the careful fabric compositions may be added to a detergent prior to the wash cycle, either directly to the fabric or by handwashing as part of a detergent or fabric softening composition or directly to the water wash.

Fabric care compositions may be applied in any manner known in the art, such as a powder, liquid, solid tablet, encapsulated liquid (e.g., a polyvinyl alcohol encapsulated composition) or in the case of application to an automatic dryer. , in a non woven sheet.

The fabric care compositions may be added in any amount necessary to obtain the desired properties provided. For example, the fabric care compositions may be added in an amount from about 0.05% to about 1.5%, for example from about 0.2% to about 1% by weight of the rinse bath. wash bath.

When present as an aqueous dispersion, polyurethane anhydride compositions of some embodiments may be present in the fabric care composition of from about 0.1% to about 20% by weight of the fabric care composition, for example, from about 5% to about 10%. about 15%. When present as a powder, polyurethaneurea compositions may be present in the fabric care composition from about 0.1% to about 20% by weight of the fabric care composition, for example from about 0.5% to about from 10% or from about 1% to about 5%.

Alternatively, the polyurethanurea powder or dispersion may be added as a substitute for the fabric care composition rather than as a component of the fabric care composition, where the polyurethane composition may be added as 100%. In this example, the polyurethane composition may be added directly to the wash or rinse water in an amount from about 0.05% to about 1.5%, specifically from about 0.2% to about 1%, weight of rinse water or wash water.

Cosmetic Compositions

Nylon (polyamide) and polyurethaneurea powders have many properties that make them useful for inclusion with cosmetic compositions.

Among these properties are the absorbency of oil, water and sweat. These properties are especially useful for applications such as absorbing sweat to deodorants or antiperspirants when in contact with the skin. These properties are also useful for dosebo control for skin contact products, skin care and decorative cosmetics.

In one embodiment are polymer powders that have antimicrobial activities to reduce bacterial growth and maucheiro. With the addition of an odor absorber such as zinc oxide, it may have greater odor prevention.

The powders of some embodiments have surprisingly good water and oil absorption. In one embodiment, the polyurethane deare powders formed by the method described above, which have a specific particle size and are suitable for application as water or sweat absorbers in deodorant and antiperspirant or oil absorbent (tallow) compositions in skin care or skin compositions. make up. Additional embodiments include powders with antimicrobial additives for improved odor protection, powders with additive fragrance for pleasant aromas, and powders for end use in cosmetics and body care. Non-limiting examples of cosmetic compositions to which powders, granules, fibers and dispersions of some embodiments include deodorants, such as spray, stick or roll-on antiperspirants; makeup and coloring cosmetics, such as powders (blush / tanner / highlighter), foundation, eye shadow, eyeliner, mask, lipstick / gloss and nail polish; careless skin compositions, such as body and facial moisturizers, hair removal and after shaving gels and creams, soaps and cleansers / body wash; careless hair, such as shampoos, conditioners and styling products; and oral care including toothpaste.

The polyamide and polyurethanurea powders of some embodiments have excellent feel and feel properties. For example, they have a smooth glide with a silky smooth feel.

The polyurethanurea powders of the present invention show very high water and sweat absorption by mass properties and at the same time show good oil absorption values. Very high water absorption is defined as values greater than three times higher than NY-6 powder (from Arkema commercially available from Lehmann and Voss & Co. of Hamburg, Germany). Good oil absorption values are defined as comparable to nylon 12 (Arkema) and higher than KOBO's polymethyl, polyethylene and polyurethane omethacrylate (Kobo Products of South Plainfield1 New Jersey and St. Agne France). The polyurethanurea powders of the present invention show that absorption of water or sweat is extremely rapid (immediate). Rapid water absorption is defined as 100 times faster than talc.

The rapid absorption and high mass of water by the depolyurethanurea powders described herein also provide benefits for anti-aging and anti-wrinkle products. The powders can be used as skin wrinkle fillers in anti-aging skin care compositions. The powders are hydrophilic, compressible microspheres with volumetric effects to stretch the skin reducing or eliminating the appearance of wrinkles.

For cosmetic powder applications and body care applications, particles smaller than 100 μηη are suitable for a smooth skin feel and not to be perceived by the user. Ideally, the average particle size should be less than 50 μηι. In one embodiment, the polyurethanurea powders were included were included in 90% of particles smaller than 42 μιτι, which can be obtained by filtration or by the control parameters of a spray drying process.

In one embodiment, the polyurethane beads or powders as exfoliating agents in cleansers, scouring pads, shower gels, etc. Typically, materials such as ground nuts including apricot seeds have been included as exfoliating / rubbing / peeling agents in cosmetic compositions. However, these tend to be hard and have very sharp ends which results in an unpleasant sensation. In contrast, the polyurethanurea granules and powders of some embodiments may have very spherical shapes, rounded surfaces and a silky feel that make them more "skin friendly" while maintaining the effect of a hard material. The powders or granules may be added to a cleaning composition in any amount to achieve the desired effect. Particle sizes may also generally vary by more than about 100 μm to be perceived by the consumer. In another embodiment are dispersions. polyurethane or film forming agents for retention of curls or anti-frizz properties in hair care compositions (gel, spray, shampoo, conditioner, etc.). Pigmented or colored polyurethane powders can be used for non-permanent hair coloring.

Polymeric compositions may be included in any composition up to 100% by weight of the composition. Appropriate ranges of nylon, polyester and inclusion of polyurethane in the composition-based compositions of the composition include from 1 to 20% by weight, from 1 to 15% by weight, from 5 to 10% by weight, and from 25 to 75% by weight. The amount used depends on the application and the desired effect.

Paint Compositions

In some embodiments are compositions which include the polyurethane, polyester and polyamide compositions. The paint may be any of those known in the art including latex, acrylic and oil based paint including primers, sealants and coatings. Apoliurethanurea, polyester and polyamide compositions may be added to the paint in any form to achieve a desired effect.

The addition of the polymer in powder, short fiber or granule form may be included to provide texture to the paint composition. Similarly, if the powders, fibers or granules have been stained or colored, the arrangement also has a different effect of the paint. Such effects are extremely desirable given the recent interest in alternate dyeing techniques and artificial finishes. Compositions of the same embodiments provide alternate surface characteristics such as texture and color without the additional dyeing steps. In addition, the double color effect or the multiple color effect can be achieved by adding color to the base paint and one or more separate colors in the dust / granule / fiber. In addition to the visible effects of color and texture, the addition of Flocones paint compositions have additional benefits. Paint compositions which include these flake fibers provide better coverage of uneven wall / surface areas, greater flexibility and crack resistance.

In addition, they provide a wallpaper effect through an ink application.

In addition to the visible effects of color and texture, the addition of polyurethane dispersion to paint compositions has additional benefits. Paint compositions including these dispersions may provide better coverage, especially on uneven surfaces and crack resistance. This is demonstrated in the examples.

Alternatively, the addition of polymer in powder, fibracurte or granule form may be included to provide anti-slip properties to paint compositions. This is accomplished by increasing the friction of the painted surface compared to a traditional paint composition.

The features and advantages of the present invention are more fully shown by the following examples which are provided for illustration purposes and should not be construed as limiting the present invention in any way.

Examples

Example 1

The protected glycol prepolymer formed from Terathane® E2538 glycol (supplied by Invista, S.à r.l.) and Isonate® 125MDR and with a protection ratio of 1,696 was obtained from the developed LYCRA® spandex production line. Lycra® is a registered trademark of Invista for spandex. This 300 g prepolymer was mixed with 150 grams of NMP solvent in a plastic bottle for 10 minutes to reduce viscosity. The diluted mixture was placed in a steel tube to be injected into a stainless steel container for dispersion.

The vessel contained 2,000 grams of deionized water, 30 grams of T DET N14 surfactant (commercially available from Harcros of Kansas City, Kansas) and 4.5 grams of ethylenediamine chain extender was premixed and cooled to 5 ° C. The diluted pre-polymer was injected. Under air pressure at about 40 psi through a 1/8 inch diameter tube, a high-speed laboratory disperser (model number HSM-100LC commercially available from Charles Ross & SonCompany of Hauppauge1 New York) was operated at 5,000 rpm. Pre-diluted pre-polymer addition was completed within 15 minutes, the formed Milky Dispersion was continued to disperse for an additional 5 minutes. Weighing of the vessel provided the total amount of diluted protected glycol added in the dispersion being 328 grams, equivalent to 218.7 grams of the protected glycol prepolymer added in the dispersion. The 3 gram foam control agent additive 65 (commercially available from Coming of Midland, Michigan) was added to the dispersion, and the dispersion was allowed to mix at 5,000 rpm for another 30 minutes before placing in a plastic bottle.

The average dispersion particle size was determined to be 52.83 μιτι, with 95% of the particles below 202.6 μηι, using a Microtac X 100 particle size analyzer (Leeds, Northrup).

Example 2

The same ingredients and dispersion procedures were used as in Example 1, except that 4.5 grams of ethylenediamine chain extender was added after the diluted prepolymer was dispersed into the water mixture. Weighing the vessel provided the total amount of diluted protected glycol added in the dispersion being 329 grams, equivalent to 219 grams of protected glycol prepolymer added in the dispersion. The average dispersion particle size was determined to be 33.45 μm, with 95% of the particles below 64.91 μm. Solid polymer particles do not form films when isolated.

Example 3

The protected glycol prepolymer was prepared by reacting 500 grams of Krasol® HLB 2000 glycol (supplied by Sartomer Company1 Inc. in Exton, PA) and 105.86 grams of Isonate® 125MDR at 90 ° C for 120 minutes in 2,000 reaction boilers. ml equipped with a heating blanket and a mechanical stirrer. The reaction was performed in a nitrogen-filled dry cabinet. After the reaction, the prepolymer had an NCO group with a weight percent of 2.98 as determined by the titration method. This prepolymer was poured into a steel tube to be injected into a stainless steel container for dispersion. Deionized water (2,000 grams) was mixed at room temperature in the 30 gram T DET N14 surfactant container (commercially available from Harcros of Kansas City, Kansas) and 3 grams of Additive 65 foam control agent (commercially available from Dow Corning of Midland, Michigan). ). The prepolymer was injected at about 80 psi air pressure through a 1/8-inch inner diameter tubing, a high-speed laboratory disperser (model number, HSM-100LC commercially available from Charles Ross & Son Company of Hauppauge). , New York) was operated at 5,000rpm. Addition of diluted prepolymer was completed within 15 minutes, milky dispersion formed was continued to disperse for additional 5 minutes. Weighing the vessel provided the total amount of diluted protected glycol added to the dispersion being 422 grams. The 4.5 grams decadeia ethylenediamine extender was added to the dispersion and allowed to mix at 5,000 rpm for another 30 minutes. The normal disperse average particle size was determined to be 49.81 μιη with 95% of the particles below 309.7 μηι.

Example 4

The procedures were the same as in Example 3 except that a mixture of glycols with 250 grams of Terathane® 1800 glycol and 250 grams of Krasol® HLB 2000 was used to form the prepolymer. A total of 465 grams of prepolymer was dispersed. The average particle size of the dispersion formed was determined to be 13.67 μητι, with 95% of the particles below 38.26 μηι.

Example 5

The prepolymers were prepared in a nitrogen atmosphere glove box. A 2,000mL Pyrex® glass reaction boiler that was equipped with a directed air pressure agitator, a heating blanket and a thermocouple temperature gauge, which was filled with about 382.5 grams of Terathane® 1800 glycol (commercially available from Invest S. R1 from Wichita, KS and Wilmington, DE) and surround 12.5 grams of 2,2-dimethylolpropionic acid (DMPA). This mixture was heated to about 50 ° C with stirring, followed by the addition of about 105 grams of Lupranate® M1 diisocyanate (commercially available from BASF, Wyandotte, Michigan). The reaction mixture was then heated to about 90 ° C with continuous stirring and maintained at about 90 ° C for about 120 minutes, after which time the reaction was terminated as the% NCO of the mixture decreased to a stable value by combining the calculated value (% NCO intent of 1.914) of the prepolymer with the final isocyanate groups. Prepolymer avidity was determined according to the danorma general method ASTM D1343-69 using a DV-8 Falling Ball Viscometer Model (marketed by Duratech Corp., Waynesboro1 VA), operated at about 40 ° C. of total isocyanate, in terms of the weight percentage of the NCO1 groups of the coated glycol prepolymer was measured by the S. Siggia1 Quantitative Orgartic Analysis method via Functional Group, 3rd edition, Wiley & Sons, New York, p. 559-561 (1963), the entire disclosure of which is incorporated herein by reference.

Example 6

A solvent free prepolymer as prepared according to the procedures and compositions described in Example 5 was used to manufacture the aqueous polyurethanurea dispersion of the present invention.

A 2,000 ml stainless steel beaker was charged with about 700 grams of deionized water, about 15 grams of sodium dodecylbenzenesulfonate (SDBS), and about 10 grams of detiethylamine (TEA). This mixture was then cooled with ice / water at about 5 ° C and mixed with a high shear laboratory mixer with the rotor / stator mix (Ross, Model 100LC) at about 5,000 rpm for about 30 seconds. The viscous prepolymer prepared from Example 1 and contained in a metal tubular cylinder was added to the bottom of the mixer end into the aqueous solution by flexible tubing with an applied air pressure. The temperature of the prepolymer was maintained between about 50 ° C and about 70 ° C. The flow of extruded prepolymer was dispersed and stranded with water under the continuous mixing of about 5,000 rpm. Over a period of about 50 minutes, a total amount of about 540 grams of the prepolymer was introduced and dispersed in water. Immediately after the prepolymer was added and dispersed, the dispersed mixture was loaded with about 2 grams of Additive65 (commercially available from Dow Corning®, Midland Michigan). The reaction mixture was then mixed for about another 30 minutes followed by the addition of about 6 grams of diethylamine (DEA) and additional mixing. The resulting solvent free aqueous dispersion was white and stable milky. Dispersion hazard was adjusted by adding and mixing Hauthane HA 900 thickening agent (commercially available from Hauthway, Lynn1 Massachusetts) at a level of about 2.0% by weight of the aqueous dispersion. The viscous dispersion was then filtered through a 40 μιτι Bendix mesh filter and stored at room temperatures for film molding or lamination uses. The dispersion had solid levels of 43% and a viscosity of about 25,000 centipoise.

Example 7

The protected glycol prepolymer formed of Terathane® 1800glycol and Isonate® 125MDR (commercially available from Dow Company1Midland, Michigan) and with a protection ratio of 1,688 was obtained from the commercial LYCRA® spandex production line. Lycra® is an Invista trademark for spandex. This 300 g prepolymer was mixed with 150 grams of NMP solvent in a plastic bottle for 10 minutes to reduce viscosity. The diluted mixture was placed in a sugar tube to be injected into a stainless steel container for dispersion. The container had 2,000 grams of deionized water, 30 grams of T DET N14 surfactant (commercially available from Harcros of Kansas City, Kansas) and 3 grams of ethylenediamine chain extender that was mixed thoroughly and cooled to 5 ° C. The previous diluted polymer was injected under pressure. At about 40 psi through a 1/8-inch inner diameter tube, a high-speed laboratory disperser (model number HSM-100LC commercially available from Charles Ross & SonCompany of Hauppauge, New York) was operated at 5,000 rpm. Addition of the diluted prepolymer was completed within 15 minutes, the formed milk dispersion was continued to disperse for a further 5 minutes. The recipient weighing provided the total amount of dilute protected glycol added to the dispersion being 347 grams, equivalent to 231 grams of protected glycol prepolymer added to the dispersion. The 3 gram foam control agent additive 65 (commercially available from Dow Corning of Midland, Michigan) was added to the dispersion, and the dispersion was allowed to mix at 5,000 rpm for another 30 minutes before placing in a plastic bottle.

The average dispersion particle size was determined to be 32.59 μηι, with 95% of the particles below 65.98 μm, using a Microtac X 100 particle size analyzer (Leeds, Northrup). Solid polymer particles were They were filtered using a Buchner funnel with Whatman® paper filter under reduced pressure, rinsed the filter mass with water 3 times, and dried at 60 - 65 ° C for 4 hours. The particles did not form films during filtration or drying. The filter cake was easily ground into fine powders using a Waring® blender (Blender 700 Model 33BL79 manufactured by Dynamics Inc., NewHartford, Connecticut). In commercial practice, solid particles would be isolated directly from the dispersion using known drying processes such as spray drying. The dry powder had an average molecular weight of 352,550 and an average molecular weight number of 85,200 as determined by the GPC.

Example 8

In Example 8, the same dispersion components and procedures were used as in Example 7, except that the solvent used to dilute the protected glycol prepolymer was changed to xylenes and the amount of ethylenediamine chain extender was increased to 4.5 grams. Weighing the vessel provided the total amount of diluted protected glycol added to the dispersion being 339 grams, equivalent to 226 grams of protected glycol prepolymer added to the dispersion. The average dispersion particle size was determined to be 22.88μm with 95% of the particles below 46.97 μηι. Solid polymer particles do not form films when isolated. Example 9

In Example 9, the same dispersion components and procedures were used as in Example 7, except that the decade-long ethylenediamine extender was replaced by the same amount of a branched polyethyleneimine (Mn of about 600 by GPC by Aldrich). Weighing the vessel provided the total amount of diluted protected glycol added in the dispersion being 340 grams, equivalent to 227 grams of protected glycol prepolymer added in the dispersion.

The average dispersion particle size was determined to be 58.12 μπι with 95% of the particles below 258.5 μτη. Solid polymer particles do not form films when isolated.

Example 10

A dry nitrogen atmosphere glove box was used to prepare the prepolymer. In two separate 2,000 ml Pyrex® glass reaction boilers, which were equipped with an air pressure driven stirrer, a heating mat and a thermostable temperature gauge, each loaded 220.0 grams of Terathane® 1800 glycol. (commercially available from Invista) and 220.0 grams of Pluracol® HP 4000D Glycol (commercially available from BASF). This glycol mixture was heated to 50 ° C with stirring, followed by the addition of 75.03 grams of Isonate®125MDR (commercially available from Dow Chemical). The reaction mixture was then heated to 90 ° C with continuous stirring and kept at 90 ° C for 120 minutes. Samples were taken from the reactor and determined to have 2,170 and 2.169% NCO, respectively, as measured by the S.Siggia1 Quantitative Organic Analysis method via Functional Group, 3rd Edition, Wiley & Sons, New York, pp. 559 - 561 (1963).

A 3,000 ml stainless steel beaker was loaded with 1,600 grams of deionized water, 15 grams of T DET N14 surfactant (commercially available from Harcros of Kansas City, Kansas) and 5 grams of Additive 65 (commercially available from Dow Coming). This mixture was then cooled with ice / water at about 10 ° C and mixed with a high shear scrambler with the rotor / stator blended end (Ross, Model 100LC) at about 5,000 rpm for 30 seconds. The prepolymer-viscous, as prepared above in two reactors, was poured into a metal rotubular cylinder and was added to the bottom of the mixer end in the aqueous solution through flexible tubing with an applied air pressure. The prepolymer temperature was maintained between 50 ° C and 70 ° C. The extruded prepolymer flow was dispersed and stranded with water under the continuous mixing of about 5,000 rpm. Over a period of about 5 minutes, a total amount of about 616 grams of the prepolymer was introduced and dispersed in water. After the prepolymer was added and dispersed, the dispersed mixture was mixed for a further 40 minutes. The resulting solvent-free aqueous dispersion was white to light blue in color, with 28.84% by weight of solids content and 44% viscosity. The dispersion was molded onto a dried polyethylene sheet in a chapel overnight under ambient conditions to form a continuous elastic film. By the GPC measure, this film had an average weight of 127,000 and an average molecular weight of 41,000.

Example 11

The procedures and conditions were essentially the same as mentioned above in Example 10, except that the surfactant was changed to Bio-soft® N 1-9 (commercially available from Stepan of Northfield, Illinois). A total of 640 grams of prepolymer, with 2.156 and 2.136% NCO of the two reactors, was dispersed in water. The formed solvent-free dispersion had a solids content of 26.12% and a viscosity of 51 centipoise. The dry molded elastic film had an average molecular weight of 133,900 and an average molecular weight number of 4,400. Example 12

The solvent free prepolymer, as prepared according to the procedures and composition described in Example 5, was used to fabricate the aqueous polyurethanurea dispersion of the present invention.

A 2,000 mL stainless steel beaker was charged with about 700 grams of deionized water, about 15 grams of sodium dodecylbenzenesulfonate (SDBS), and about 10 grams of detiethylamine (TEA). This mixture was then cooled with ice / water at about 5 ° C and mixed with a high shear laboratory mixer with the rotor / stator mix (Ross, Model 100LC) at about 5,000 rpm for about 30 seconds. The viscous prepolymer prepared from Example 1 and contained in a metal tubular cylinder was added to the bottom of the mixer end into the aqueous solution by flexible tubing with an applied air pressure. The temperature of the prepolymer was maintained between about 50 ° C and about 70 ° C. The flow of extruded prepolymer was dispersed and stranded with water under the continuous mixing of about 5,000 rpm. Over a period of about 50 minutes, a total amount of about 540 grams of the prepolymer was introduced and dispersed in water. Immediately after the prepolymer was added and dispersed, the dispersed mixture was loaded with about 2 grams of Additive65 (commercially available from Dow Corning®, Midland Michigan) and about 6 grams of diethylamine (DEA). The reaction mixture was then mixed for another 30 minutes. The resulting solvent-free aqueous dispersion was white and stable milky. The viscosity of the dispersion was adjusted by adding and mixing Hauthane HA 900 thickening agent (commercially available from Hauthway, Lynn, Massachusetts) at a level of about 2.0% by weight of the aqueous dispersion. The viscous dispersion was then filtered through a 40 μηη Bendix wire mesh filter and stored at room temperature for film molding or lamination uses. The dispersion had 43% solids levels and a viscosity of about 25,000 centipoise. The film molded from this dispersion was soft, sticky and elastomeric.

Example 13

Tissue Test

The compositions of the present invention were tested in combination with cotton / Lycra® fabric (97% cotton / 3% Lycra®spandex). The control for this example was the fabric washed with Unilever's non-concentrated Confort ™ fabric softener. Each of the compositions as shown in Table 1 was used with the cotton / Lycra® fabric by washing with Ariel ™ liquid detergent available from Process and Gamble in program 4 at 40 ° C on a Schulthess® programmable automatic washer using the load fabric. standard to obtain 2.5 kg load and 18 g rinse of fabric softener composition. After tumble drying, the fabrics were evaluated for any deposit on the surface. None of the three fabrics showed any deposition of the dust or film.

The compositions in Table 1 are as follows:

(a) fabric treated with fabric softener only (control),

(b) fabric softener-treated fabric, 1% of the dispersion of example 6, a film-forming anionic polyurethaneurea water, and 2% by weight of Unimer (synthetic wax to improve dispersion),

(c) fabric softener-treated fabric, 1% polyurethanurea powder of Example 5, and 2% by weight of Unimer (synthetic wax to improve dispersion).

Mixtures of compositions (b) and (c) including the trapped softener provided a homogeneous dispersion (no sedimentation, nemagglomeration).

Each tissue was evaluated for ease of care. The AATCC TM 124 / ISO 15487 standard test method was used to determine the durable press ratio ("DP rate") before and after ironing. The "rate of DP" is a measure of the three-dimensional softness of the tissue. Iron slip or ironing was measured as the time for iron to slip over a given length of fabric with the ironing board at an angle of about 20 °. The results of ease of care are shown in Table 1.

Table 1

Care Facility

<table> table see original document page 49 </column> </row> <table>

From the results in Table 1, it is shown that both powder and dispersion-treated sportswear show a greater improvement in the PD rate (1 point gain after ironing) compared to the control (0.5 point gain after ironing). ).

Similarly, fabrics (b) and (c) treated with the compositions of the present invention showed a faster slide of the ferrone tissue surface.

Compositions (a), (b) and (c) were also evaluated for perfume / fragrance embodiment. Three people were left separately to smell each of the tissues. Each of these persons observed a stronger fragrance in the treated tissues (b) and (c) which were treated with the compositions of the present invention. The absorption (moisture control) properties of the tissues including those treated with the compositions of the present invention were also tested. These properties were measured to demonstrate tissue differences after treatment with the powders or dispersions of the present invention as compared to untreated tissues.

For each of the tissues (a), (b) and (c) as described above, one drop (about 30 μΙ) each of the flaxseed oil and water was applied to the tissue surface. The time to complete absorption of each drop was measured and reported in seconds (s) in Table 2. The surface area of the droplet at 60 seconds following complete tissue absorption was also measured and reported in square centimeters (cm2) in Table 2.

Table 2

Humidity Control

<table> table see original document page 50 </column> </row> <table>

As shown in Table 2, the dispersion (b) and powder (c) of the present invention offered improvements compared to control (a) with respect to absorption. The use of the powder of (c) showed a significant improvement.

Example 14

100% Cotton Fabric Test

A 100% cotton fabric was also tested after treatment with a composition of some achievements. The control for this example was a Softian ™ Ultra concentrated fabric softener by ColgatePalmolive. Each of the compositions as shown in Table 3 was used with 100% cotton fabric by washing with Ariel ™ liquid detergent in program 4 and 40 ° C in a Schulthess® programmable automatic washer using standard loading fabric to obtain 2.5 kg load and rinse with 18 g of fabric softener composition. After tumble drying (at moderate temperature), tissues are evaluated for any deposit on the surface. None of the tissues showed any deposition of dust or film.

The compositions in Table 3 are as follows:

(e) fabric treated with fabric softener only (control),

(f) fabric treated with fabric softener and 10% by weight of the dispersion of example 10, a nonionic polyurethaneurea dispersion.

Mixtures of compositions (f) including fabric softener provided a homogeneous dispersion (no sedimentation, nemagglomeration).

In order to test the tissues for growth, the available stretch or maximum stretch was first calculated. The available stretch was determined by first conditioning a tissue specimen followed by the three-fold cycle in a constant-strain tensile tester between 0 and 30 Ν. The maximum stretch was calculated by the following formula:

Maximum Stretch% = (ML - GL) χ 100 / GLWhere: ML is the length in mm at 30 N; and

GL is the gauge length of 250 mm.

Separate specimens from each tissue were then extended to 80% of the "available stretch" and maintained for about 30 minutes. Tissue specimens were then allowed to relax for about 60 min and growth was measured and calculated. According:

Growth% = L2 / L χ 100 where: "growth" is recorded as the percentage after orlaxation;

L2 = the largest length in cm after relaxation; and

L = the original length in cm.

Each of the tissues (e) and (f) were measured for tissue growth. The results are shown in Table 3:

Table 3

<table> table see original document page 52 </column> </row> <table>

Tissue growth is a measure of shape retention. Growth values represent unrecovered elongation during use. A lower growth value shows that the tissue has a better resilience than its initial shape.

Tissues (e) and (f) were also tested for difference in perfume release after a wash and rinse cycle. One to two grams of each tissue sample was placed in a sealed gas sampling container. Stretching of the fabric was performed by shaking with steel ball beads. Volatile compounds released from the sample were removed from the void space of the gas sampling vessel through a Tenex ™ sampling tube using a gas sampling pump operating at 50 cc per minute for 20 minutes. The Tenex ™ tube trapped volatile organic compounds (VOC) for analysis. The Tenex ™ tube was then thermally deflected with volatile organics targeted in a GC / MS for analysis. The results of the VOC measurements in Table 3a show that more perfume was released from the fabric rinse with the fabric softener that contains the dispersion of Example 10, a dispersion of nonionic polyurethane. Table 3a

<table> table see original document page 53 </column> </row> <table>

Example 15

Spandex / Cotton Blend Fabric Test

A spandex / cotton blend fabric was also tested after treatment with a composition of some embodiments. The control for this example was a Softian ™ Ultra concentrated fabric softener by Colgate Palmolive. Each of the compositions as shown in Table 4 was used with despandex / cotton blend fabric by washing with Ariel ™ liquid detergent program 4 and 40 ° C in a Schulthess® programmable automatic washer using standard loading fabric to obtain 2.5 kg load and rinse with 18 g of fabric softener composition. After tumble drying (at moderate temperature), the tissues were evaluated for any deposits on the surface. None of the tissues showed any deposition of dust or film.

The compositions in Table 4 are as follows:

(g) fabric treated with fabric softener only (control),

(h) fabric softener treated fabric and 10% by weight of the dispersion of example 10, a nonionic polyurethaneurea dispersion.

Mixtures of compositions (h) including the trapped softener provided a homogeneous dispersion (no sedimentation, no agglomeration). Each of the tissues (g) and (h) were measured for tissue growth. Results are shown in Table 4: Table 4

Tissue Growth (Weft Direction)

<table> table see original document page 54 </column> </row> <table>

Tissue growth is a measure of shape retention. Growth values represent unrecovered elongation during use. A lower growth value shows that the tissue has a better resilience than its initial shape.

Two Lycra® spandex / cotton blend fabrics were also tested after treatment with a composition of some of the embodiments. The control for this example was a Soupline ™ Ultra fabric softener by Colgate Palmolive. Each of the compositions as shown in Tables 4a and 4b was used with Lycra® spandex / cotton blending fabric by the Dixan® gel detergent wash available from Henkel Corporation at 40 ° C with a standard program on a commercial Miele ™ washer using the standard cargo tissue to obtain 2.5 kg load and rinse with 30 ml of the fabric softener composition. After tumbling drying (at a moderate temperature), the tissues were evaluated for any deposit on the surface. None of the fabrics showed any deposition of the powder or film. For the fabrics below, CK is a 95% cotton -5% Lycra® circular knitting fabric and WOV is a 97% cotton raw yarn stretch fabric. 3% Lycra® spandex.

The compositions in Tables 4a and 4b are as follows: (i) fabric softener treated (control - CK) tissue, (j) fabric softener treated tissue and 10% by weight (3% active ingredient) of the tissue dispersion. example 10, a nonionic (treated - CK)

(k) fabric treated with fabric softener only (-WOV control),

(I) fabric softener treated fabric and 10% by weight (3% doing active ingredient) of the dispersion of example 10, a nonionic polyurethane (WOV) dispersion;

Table 4aCK Tissue Growth

<table> table see original document page 55 </column> </row> <table>

Example 16

<table> table see original document page 55 </column> </row> <table>

Non-slip paint

The compositions of some of the embodiments have been tested for "non-slip" properties. These tests were completed in accordance with ASTM D4518-91 with modification as described below. The test ink (which was also the control) is a commercially available solvent-free matte white vinylacetate base ink from AkzoNobel. Compositions in average particle sizes as shown in the Table below were added for the purpose of increasing static friction. The results are the coefficient of static friction as calculated according to the test method and shown in Table 5.

The procedure for measuring static friction on the coated surface was performed to determine the slip resistance on a coated surface (paint) by measuring static friction. For each sample, one coat of paint was pre-prepared by application with an ink roller. Particles included in the paint are as shown in Table 5. The paint was allowed to dry for a day. This was followed by applying a second coat of paint that was left to dry for a day.

ASTM D4518-91 has been modified by using a round-ended aluminum block instead of a steel block of the same weight and polished surface. The block was placed on the painted surface on an inclined plane. Between measurements, the aluminum block was cleaned with acetone.

To obtain the same constant velocity for the doplane inclination, an Instron dynamometer was used with the following program:

- Absolute slope - At 300% extension at 480 mm / min (about 1,5 ± 0,5 ° / s).

- Kevlar wire has been used to prevent wire extension and provide good reproducibility.

The inclination angle (a) was calculated by the combase trigonometry on the plane height (h) and the plane length (X), which was 30 cm. The coefficient of static friction was measured as:

- static friction = tan a; and

- static friction = tan (sen "1 h / X).

Table 5

Friction Test

<table> table see original document page 56 </column> </row> <table> <table> table see original document page 57 </column> </row> <table>

Table 5 demonstrates that polymeric compositions of some embodiments provide comparable or superior non-slip properties as compared to the rubber control or texturizing agent. Superior results are noted for all inventive compositions at a 5% additive level.

Example 17

Crack in the Paint

The flexibility test of paint compositions was performed on the basis of BS EN ISO 6860: 1995. The paint compositions were prepared as shown in Table 6 including a commercially available matte basecoat paint from Akzo Nobel. Each paint was coated to a thickness of about 30 mils on a cardboard substrate. Then, each substrate was folded over a tapered knurl to determine the minimum curvature diameter that was obtained without cracking the paint.

As can be seen from the results in Table 6, there is significant paint flexibility including dispersions of some embodiments.

Table 6

Paint Crack Test

<table> table see original document page 57 </column> </row> <table> <table> table see original document page 58 </column> </row> <table>

Example 18

Rupture Stress ε Young's Module

The ink samples were mixed according to the compositions described in Tables 7 and 8. The ink compositions were coated onto a release substrate to form films. The samples were cut from these films which were 1 cm wide and 5 cm long for each sample. Three films were tested for each composition using an Instron® dynamometer. Initial tests were performed to measure elongation and distension at rupture for each material. From these data, the limit and Young's modulus (or modulus of elasticity) were calculated. Results are shown in Table 7 and 8.

Table 7

Rupture Distension

<table> table see original document page 58 </column> </row> <table> <table> table see original document page 59 </column> </row> <table>

Table 8

Young's module

<table> table see original document page 59 </column> </row> <table> <table> table see original document page 60 </column> </row> <table>

As can be seen from Tables 7 and 8, the inventive compositions showed improvement over the base control. Specifically, the inventive compositions had a Youngq menormule indicating greater elasticity of the material.

Example 19

Elongation

Each of the 3 ink samples including the dispersers of some embodiments was also tested to determine the maximum 4 N elongation for inks 1 and 3 and 1 N for ink 2 in 3rd cycle using an Instron® Material Testing Machine. The maximum force was selected from the elongation test as shown in Example 18 to be in the elastic domain of the material (flat region of the strain strain curve). The test was to measure the difference in elongation when the same force is applied. Results are shown in Table 9.

Table 9

3rd cycle elongation

<table> table see original document page 61 </column> </row> <table> <table> table see original document page 62 </column> </row> <table>

Table 9 demonstrates that the addition of inventive polyurethanurea dispersions improved the elongation properties of all three base paints. At a minimum, the elongation of the base paint is doubled after the inventive dispersions have been added.

Example 20

Oil and Water Absorption Time

In order to test the absorption properties of inventive powder compositions compared to commercially available powder compositions, several compositions have been tested to determine the time required for the absorption of one drop of each of flaxseed oil, water and artificial perspiration. In each test, a flaxseed oil, water or artificial perspiration was placed in Adaum from the inventive and commercially available powders. The time to drop absorption was noted as shown in Table 10. Table 10

Time for Absorption

<table> table see original document page 63 </column> </row> <table> <table> table see original document page 64 </column> </row> <table>

As shown in Table 10, the inventive powders provided a faster absorption time for oil and water when compared to nylon and silica and provided a similar or improved absorption time compared to commercially available polyurethane powders.

Example 21

Oil - Water - Mass Absorption

In order to test the absorption properties of inventive powder compositions compared to commercially available powder compositions, a number of compositions have been tested to determine linseed oil mass, water and artificial perspiration, which has been absorbed according to the ASTM D281- Test Method. 95 (modified for water and artificial perspiration). Results are shown in Table 11.

Table 11

Absorption Mass

<table> table see original document page 64 </column> </row> <table> <table> table see original document page 65 </column> </row> <table> As shown in Table 11, inventive compositions were capable absorb as well as or better than commercially available powders.

Example 22

Exfoliating Compositions

The incorporation of physical scrubs in cosmetic cleansing preparations is increasingly popular. The anticipated products bear the abrasive effect of broken nutshells from standard basescosmetics and were as appealing to consumers as sandpaper.

Currently, there are many exfoliators available in cosmetic chemistry from both natural and synthetic sources. Particle size and abrasive qualities of each type can be strictly controlled by allowing the desired level of exfoliation to be precisely formulated and a better understanding of rheological properties enables stable and elegant products to be manufactured with evenly distributed scrubs.

Polyethylene (PE) Beads are some of the most common polymer exfoliation agents: they are available in different size ranges. Commercial Polyethylene (PE) Ball samples are available from A&E Connock (Perfumery & Cosmetics) Ltd1 in our following grades:

- 65/100 mesh size (about 150 to 230 μιτι),

- 35/48 mesh size (about 300 to 500 μιτι),

- 24/32 mesh size (about 600 to 700 μιτι),

-14/16 of the mesh size (about 1,200 to 1,400 μητι).

The following polyurethanurea powders with the following particle sizes were prepared to compare with PE beads:

Polyurethane powders prepared by the Roach process: 25 to 200 μιη,

Example 7 polyurethane powders: 300 to 800 μιτι,

Polyurethane powder from Example 3: 500 to 1,000 μιη.

Each powder was added at 15 wt% in a shower gel (Dove's SilkGlow Softening Silk Shower) and compared to an already manufactured exfoliating product containing oxidized polyethylene as an exfoliating agent (Dove's Silk Glow Douche Gommage Quotidienne Soie).

Compositions with Roach process-prepared polyurethaneurea powders provided no real peeling effect as the particle size of the powder is very small. In contrast, the powders of Examples 3 and 7 mixed well with the shower gel and showed an exfoliation effect. Due to the compressibility of polyurethanurea powders, they have a very soft feel and have a milder peeling effect on the skin.

Example 23

Film Forming Polymers

In the cosmetics industry, many film-forming polymers are used especially in nail polish, mascara, eyeliner, face makeup, sunscreen products and hair care formulations. The chemical composition may vary from copolymers of acrylate, polyurethane, polyvinylpyrrolidone vinyl acetate, polyacrylic acid (carbomer). These can be used as modeling polymers or as thickeners and provide transparent flexible films with different levels of gloss, adhesion, abrasion resistance and flexibility. The water-borne polyurethanurea dispersions of Examples 5, 6, and 10 may also be used to provide these effects.

The great advantage of these compositions will be the improved elasticity and flexibility, the soft and smooth feel and the good abrasion resistance. Two commercially available polyurethane polymer dispersions from Noveon: Avalure® UR 425 and UR 450 have been tested and compared to polyurethaneurea compositions as described herein.

The films were cast to 20 mil thickness for commercially available dispersions as well as the dispersion of Example 6. These were compared for elastic properties which are shown in Table 12. Table 12

Elastic Properties of Movies

<table> table see original document page 68 </column> </row> <table>

The Dispersion of Example 6 clearly exhibits very elastic behavior compared to commercially available materials, as Young's modulus is much smaller. This dispersion will enable high elasticity of the formula and will improve following skin movements.

While what is currently believed to have been described as preferred embodiments of the present invention, one skilled in the art will appreciate that changes and modifications may be made thereto without departing from the spirit of the present invention, and are intended to include all changes and modifications that fall within the scope of this invention. in the true scope of the present invention.

Claims (43)

1. TISSUE CARE COMPOSITION, comprising: (a) a fabric softener or detergent composition; and (b) a polyurethanurea in the form of a powder or aqueous dispersion. A composition according to claim 1 in which detergent or fabric softener is compatible for use in the washing machine. COMPOSITION according to claim 1, wherein the detergent or fabric softener is compatible for manual washes. A composition according to claim 1, wherein the detergent or fabric softener is in a form selected from the group consisting of a powder, a liquid, a solid tablet, an encapsulated liquid and a nonwoven sheet. A composition according to claim 1 wherein the polyurethane anhydride comprises a reaction product of an isocyanate terminated depolyurethane prepolymer and a chain extender. A composition according to claim 5 wherein said chain extender is selected from the group consisting of a diamine chain extender, water and combinations thereof. A composition according to claim 1 wherein said polyurethane is in the form of a powder and said prepolymer is a reaction product of: - a hydroxyl terminated polymer selected from the group consisting of a polyether, a polycarbonate, a polyester and its combinations; e- a diisocyanate. A composition according to claim 1 wherein said polyurethanurea is in the form of an aqueous dispersion and said prepolymer is a reaction product of: - a hydroxyl terminated polymer selected from the group consisting of a polyether, a polycarbonate, a polyester and combinations thereof; e- a diisocyanate; and optionally an acid diol. A composition according to claim 8 wherein said aqueous dispersion is selected from the group consisting of an anionic dispersion and a nonionic dispersion. A composition according to claim 8, wherein the hydroxyl-terminated polymer is a polyether polyol, said diisocyanate is an aromatic diisocyanate selected from the group consisting of phenylene diisocyanate, tolylenediisocyanate (biphenocyanate, diphenyldiocyanate, biphenyldiocyanate) ), its combinations, and said acid diol is selected from the group consisting of 2,2-dimethylolacetic acid, 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolpentanoic acid and combinations thereof. A composition according to claim 8 wherein said polymer is a poly (tetramethylene ether) glycol, said diisocyanate is 4,4'-methylene bis (phenyl isocyanate) or a mixture of 4,4'-methylene bis ( phenylisocyanate) and 2,4'-methylene bis (phenyl isocyanate) and said acid glycol is 2,2-dimethylolpropionic acid or is absent. A composition comprising a nonionic film forming dispersion wherein said dispersion comprises water and a polymer; said polymer comprises a reaction product of a prepolymer and water as a chain extender; and said prepolymer consists essentially of the reaction product of a glycol or a mixture of e-4,4'-methylenobis (phenyl isocyanate) glycols. A composition according to claim 12 wherein glycol is selected from the group consisting of poly (tetramethylene-co-ethylene ether) glycol and a mixture of poly (tetramethylene ether) glycol with ethoxylated glycol opolypropylene. The composition of claim 12 further comprising additives selected from the group consisting of surfactants, defoamers, pigments, solvents and combinations thereof. A composition, which comprises a non-ionic film-forming non-dispersion, wherein said dispersion comprises water and polymer; said polymer comprises a reaction product of a prepolymer and the chain extender comprises a diamine and water chain extender, and said prepolymer consists essentially of the reaction product of a 4,4'-methylenobis (phenyl isocyanate) glycol . Composition according to Claim 15, comprising additives selected from the group consisting of surfactants, defoamers, pigments, solvents and combinations thereof. 17. POLYURETHANOURERIA POWDER, derived from a composition comprising a nonionic film-forming dispersion, wherein said dispersion comprises water and polymer; said polymer comprises a reaction product of a prepolymer and the chain extender comprises a diamine and water chain extender; and said prepolymeroconsistently consists of the reaction product of a glycol and 4,4'-methylenobis (phenyl isocyanate). 18. A method for extending the perfuming of a perfume into a tissue comprising contacting said fabric with a composition comprising a fragrance and a polyurethanurea in the form of a powder or an aqueous dispersion. A method according to claim 18, wherein dithotted comprises a garment. A method of increasing retention of the dressing form, which comprises contacting a garment with a polyurethanurea in the form of a powder or an aqueous dispersion. 21. A method of increasing the ease of care of a fabric comprising contacting said fabric with a polyurethanurea in the form of a powder or aqueous dispersion. A method according to claim 21, wherein dithothotide comprises a garment. 23. A method for providing anti-stain properties to a fabric comprising contacting said fabric with a polyurethane powder in the form of a powder or an aqueous dispersion. A method according to claim 23, wherein dithotted comprises a garment. A method for preparing the polyurethaneurea powder comprising: (a) providing an aqueous polyurethanurea dispersion, (b) filtering the dispersion to obtain the polyurethanurea particles, and (c) grinding the particles to a desired size. 26. A method for the preparation of powder polyurethaneurea, comprising: (a) providing an aqueous polyurethaneurea dispersion; and (b) dry spraying the dispersion to obtain a polyurethane powder having a preselected average particle size. A method for dyeing a powder composition comprising: (a) providing a polyamide or polyester composition, (b) adding said powder to a dye bath; and (c) filtering and drying said composition. A composition comprising a paint and at least one of a polyurethane composition, a polyamide composition and a polyester composition. A composition according to claim 28 wherein said polyurethane composition comprises a form selected from the powder, a dispersion, a fiber, a granule and combinations thereof. A composition according to claim 28 wherein said polyamide composition comprises a polyamide in the form of a powder or a flake fiber or a mixture thereof. A composition according to claim 28 wherein said polyamide composition comprises a polyamide in the form of a dyed polyamide powder, a dyed polyamide flake fiber, or mixtures thereof. 32. COMPOSITION, which comprises the polyurethanurea granules, wherein said granule has a void content content of less than -60% or greater than 90%. 33. A composition comprising a cosmetic composition and at least one polyurethane composition, a polyamide composition and a polyester composition. A composition according to claim 33 wherein said polyamide composition is a dyed powder. A composition according to claim 33, wherein said polyurethane composition is a powder. 36. COMPOSITION, which comprises a polyurethanurea powder, said powder comprises a prepolymer terminated in the dispersed isocyanate group and extended in water. A composition according to claim 36, wherein the polyurethane powder has an average particle size of less than 100 μηι. A composition according to claim 37 wherein the polyurethanurea particles are not fiber forming when isolated from the aqueous medium. A composition according to claim 36 which comprises a cosmetic composition. A composition according to claim 36 comprising an antiperspirant composition. 41. Polyurethaneurea powder containing less than 2% of an organic liquid which is substantially inert to polyurethaneurea. 42. A method of extending perfumery into a composition, a cosmetic composition comprising preparing a composition comprising (a) a polyurethane in a form selected from a powder, a dispersion and mixtures thereof; and (b) a fragrance. 43. A method for extending the composition of perfume into a composition for the home comprising preparing a composition comprising (a) a polyurethane in a form selected from a powder, a dispersion and mixtures thereof; and (b) a fragrance.