HK1161890B - Non-textile polymer compositions and methods - Google Patents

Description

Nonwoven polymer compositions and methods

This application is a divisional application of an invention patent application having an application date of 2007, month 1 and 18, application number of 200780009215.8 (international application number of PCT/US2007/001304), entitled "nonwoven polymer composition and method".

Cross Reference to Related Applications

The present invention claims the benefits of U.S. application No. 60/865,091 filed on 9/11/2006, the benefits of U.S. application No. 60/837,011 filed on 11/8/2006, and the benefits of U.S. application No. 60/759,853 filed on 18/1/2006, all of which are incorporated herein by reference.

Background

Technical Field

The present invention includes polymer compositions such as polyurethaneureas (polyurethaneureas), polyamides, and polyesters. The composition may be in various forms, such as dispersions, powders, fibers, and granules (beads). The compositions are useful in the preparation of a number of products, including health and beauty products such as cosmetics; painting; household products such as fabric care compositions, clothing/footwear and textiles/furniture items.

Brief description of the related Art

Polymers, such as polyurethaneureas, polyamides and polyesters, have historically been used to prepare synthetic fibers. However, these polymers have other properties that may provide benefits over fiber forms. Therefore, there is a need to provide polymer compositions and methods that address these additional advantages.

An example of a suitable form of the different polymers is a powder. Fine powders of synthetic polymers (e.g., polyethylene, polyamides, polyurethanes, and silicones) have been used in printing, coating, and cosmetic applications. While there are many particle size reduction techniques known in the art (e.g., solid state shear pulverization, cryogenic grinding, gas atomization, and high shear mixing and milling) and have been used in the production of polymer powders, there remains a need for improved methods to produce fine, uniform particles, particularly for those elastomeric polymers, such as segmented polyurethanes and polyurethaneureas.

There is a need for improved polymer compositions that can provide additional benefits not only in printing, coating and cosmetic applications, but also in other applications such as paint and fabric care.

In addition to detergents, fabric softeners are commonly used to impart softness and/or bulk to washable fabrics. Fabric softeners also smooth the feel of the fabric, reduce electrostatic adsorption, impart a pleasing fragrance, reduce drying time, reduce wrinkling and make ironing easier. However, the benefits of these properties generally diminish over time after washing.

The most common active ingredients are based on long chain fatty molecules, known as quaternary ammonium compounds, which are cationic in nature. Therefore, to prevent unwanted reactions with the detergent (which may be anionic in nature), fabric softeners are typically added during the rinsing or drying of the fabric.

In order to reduce the time and expense of fabric laundering, it is desirable to provide fabric care compositions that can be added simultaneously with detergents. There is also a need to provide fabric care compositions that extend the duration of the fragrance (fragrance) and ease of care benefits associated with fabric softening compositions.

Summary of The Invention

One embodiment provides a polyurethaneurea in powder form or in the form of an aqueous dispersion. These powders or dispersions are provided alone or in combination with detergent or fabric softener compositions to provide fabric care properties.

In one embodiment, the fabric care composition is in the form of a nonionic film-forming dispersion comprising a polyurethaneurea polymer and water. The polymer is the reaction product of a prepolymer, water as a chain extender, wherein the prepolymer is the reaction product of a diol or mixture of diols with 4, 4' -methylenebis (phenyl isocyanate).

Another embodiment is a nonionic non-film forming dispersion comprising water and a polyurethaneurea polymer. The polymer is the reaction product of a prepolymer and a chain extender comprising a diamine chain extender and water, wherein the polymer is the reaction product of a diol (polyol) or mixture of diols with 4, 4' -methylenebis (phenyl isocyanate). The polymer may then be filtered and milled or spray dried to provide a powder.

Another embodiment provides a method of extending the duration of a perfume or fragrance on a fabric or garment. The method comprises the step of contacting the fabric or garment with a fragrance and a polyurethaneurea composition in the form of a powder or an aqueous dispersion. The contacting can be done in a variety of ways, including, but not limited to, adding the perfume and polyurethaneurea to the detergent or fabric softener prior to washing and/or drying the fabric, adding them directly to the wash water (wash water), or adding them directly or with the fabric softener composition during the rinse cycle.

Another embodiment provides a method of providing a desired property to a fabric or garment. The method includes the step of contacting the fabric with a polyurethaneurea in the form of a powder or an aqueous dispersion. The desired properties that may be imparted to the fabric include, but are not limited to, shape retention, ease of care (i.e., ease of ironing), and stain resistance.

The present invention also provides a segmented polyurethaneurea composition in the form of a fine powder. The invention also includes a method of making the polyurethaneurea powder. Additionally, some embodiments provide a powder having water and/or oil absorption.

Other polymer compositions and forms are provided. These compositions are useful in a variety of compositions such as paint, cosmetic and fabric care compositions and the like.

Detailed Description

As used herein, the term "powder" refers to a particulate material comprised of loose agglomerates of finely divided solid particles. For fine powders, the largest dimension is less than 1mm and the average particle size is less than 100 microns. However, larger particle sizes are also included. For example, the coarse powder may have a particle size greater than 1 millimeter with an average particle size in the range of about 0.5mm to about 2 mm.

As used herein, the term "film-forming" means that the material forms a continuous film in the absence of other reagents under the synthesis conditions disclosed 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 under the synthesis conditions disclosed herein.

As used herein, the term "fabric" refers to any woven, nonwoven, knitted, tufted, felt, knit, or bonded material made of an assembly of fibers and/or yarns (assembly), including, but not limited to, those used in clothing (apparel), sheets, towels, curtains, upholstery (upholstery), and carpets.

As used herein, the term "fabric care composition" refers to any composition that can be applied to a fabric, particularly during the laundering or drying of the fabric, to impart beneficial properties to the fabric. These properties include cleaning, removal of oily and greasy stains, smoothing the feel of the fabric, reducing electrostatic adsorption, imparting a pleasing fragrance, reducing drying time, reducing wrinkling and making ironing easier.

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

Polyurethaneurea compositions

The polyurethaneurea composition in some embodiments may be in the form of an aqueous dispersion, a powder, a fiber, or a particle. When a powder form is desired, it can be isolated from the aqueous dispersion by filtration, drying and milling of the dispersion or by spray drying. The solids content of the dispersion may vary. For example, the solids content (by weight) may be from about 5% to about 50% of the dispersion, more specifically from about 20% to about 40% of the dispersion. The powder may have an average particle size of less than 100 microns, such as from about 50 to about 80 microns, with no particle size greater than 1.0mm, such as less than about 0.5 mm.

Another suitable method of making the polyurethaneurea powder of some embodiments is according to U.S. patent No. 6,475,412 to Roach, which is incorporated herein by reference. Roach discloses a method of extruding spandex under specific process conditions to provide a powder.

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

at least one hydroxyl terminated polymer, such as a polyether (including copolyethers), polycarbonate or polyester polyol component having a number average molecular weight of about 600 to about 3500, for example, a poly 1, 4-butanediol ether having a number average molecular weight of about 1400 to about 2400;

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

at least one diol compound having (i) hydroxyl groups capable of reacting with the MDI isomer mixture of the polyisocyanate, and (ii) at least one carboxylic acid group capable of forming a salt upon neutralization, wherein the at least one carboxylic acid group is not capable of reacting with the MDI isomer mixture of the polyisocyanate.

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

The MDI isomer mixture for the anionic dispersion reduces the prepolymer viscosity without the addition of a solvent. The MDI isomer mixture may also 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 containing a hydroxyl group and a carboxylic acid group may be referred to as an acidic diol. Examples of useful acidic diols include 2, 2-dimethylolacetic acid, 2-dimethylolpropionic acid (DMPA), 2-dimethylolbutyric acid, 2-dimethylolpentanoic acid, and combinations thereof.

The nonionic film-forming dispersion in some embodiments comprises a prepolymer that is an isocyanate-terminated polyurethane prepolymer. This prepolymer is the reaction product of a hydroxyl-terminated polymer such as a polyol, e.g., 1, 4-butanediol-ethylene glycol copolyether glycol or a mixture of poly 1, 4-butanediol ether and ethoxylated polypropylene glycol, and a diisocyanate, e.g., 4' -methylenebis (phenyl isocyanate). The chain of this prepolymer is then extended with water and dispersed in water, or dispersed in water and then the chain of this prepolymer is extended with water.

The nonionic non-film forming dispersion in some embodiments comprises a prepolymer that is an isocyanate-terminated polyurethane prepolymer. This prepolymer is also the reaction product of a polyol such as a polybutadiene diol or a poly-1, 4-butanediol ether and a diisocyanate such as 4, 4' -methylenebis (phenyl isocyanate). The chain of this prepolymer can be extended using a combination of water and a diamine chain extender such as ethylenediamine or an amine-functional crosslinker such as polyvinylamine. Hydrophilic or hydrophobic diols may be selected to produce polymer powders with different water/oil absorption capabilities. Also, the powder particle size can be adjusted by adjusting the viscosity of the prepolymer, which is adjusted by using a solvent for dilution.

In some embodiments, the polyurethaneurea powder is made by dispersing an isocyanate-terminated prepolymer with or without a solvent into an aqueous medium containing a dispersant and a chain extender or crosslinker by high shear forces. High shear is defined as a force sufficient to produce particles no larger than 500 microns. The prepolymer can be made by reacting a polyol or polyol copolymer or polyol mixture (e.g., polyether diol, polyester diol, polycarbonate diol, polybutadiene diol or hydrogenated derivatives thereof, and hydroxyl-terminated polydimethylsiloxane) with a diisocyanate (e.g., methylene bis (4-phenyl isocyanate) (MDI)) to form an NCO-terminated prepolymer or "capped diol". The molar ratio of NCO/OH in the polymer composition is from 1.2 to 5.0. An example of a chain extender is an aliphatic diamine, such as Ethylenediamine (EDA). The chain crosslinking agent is an organic compound or polymer having at least three primary or secondary amine functional groups capable of reacting with NCO groups. An organic solvent, soluble or insoluble in water, such as 1-methyl 2-pyrrolidone (NMP) or xylene, may be used to dilute the prepolymer prior to the dispersing step. The resulting fine particles of the polyurethaneurea polymer dispersed in water can be used as such or can be isolated by filtration and dried to a solid powder. Alternatively, spray coating may be used, which also allows for better control of particle size.

The particle size of the powder in some embodiments may vary depending on the desired application. For example, the average particle size may be less than 1 millimeter (mm), including average particle sizes less than 100 micrometers (μm).

In some embodiments, the blocked polyurethaneurea used to make the elastomer powder comprises: a) a polyol or polyol copolymer or polyol blend having a number average molecular weight between 500 and 5000, including but not limited to polyether diols, polyester diols, polycarbonate diols, polybutadiene diols or hydrogenated derivatives thereof, and hydroxyl terminated polydimethylsiloxanes; b) diisocyanates including aliphatic diisocyanates, aromatic diisocyanates and cycloaliphatic diisocyanates; and c) an aliphatic diamine (i.e., a diamine chain extender), or a mixture thereof with at least one diamine selected from the group consisting of aliphatic diamines and cycloaliphatic diamines, both of which have from 2 to 13 carbon atoms, or an amino-terminated polymer, or an organic compound or polymer having at least three primary or secondary amine groups; and optionally a monoamine (primary or secondary) as chain terminator.

Examples of polyether polyols that may be used in some embodiments include those having two or more hydroxyl groups from the ring-opening polymerization and/or ring-opening copolymerization of ethylene oxide, propylene oxide, oxetane, tetrahydrofuran, and 3-methyltetrahydrofuran, or from the polycondensation of polyols, such as diols or diol mixtures, with less than 12 carbon atoms per molecule, for example, 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, linear difunctional polyether polyols, specifically poly-1, 4-butanediol ethers having a molecular weight of about 1700 to about 2100, such as those having a functionality of 2, may be included1800 (commercially available from INVISTA S.a r.l. of Wichiata, KS and Wilmington, DE).

Polyester polyols which may be used include those ester diols (ester diols) containing two or more hydroxyl groups resulting from the polycondensation of aliphatic polycarboxylic acids and diols having a low molecular weight and no more than 12 carbon atoms per molecule, or mixtures thereof. Examples of suitable polycarboxylic acids are malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid and dodecanedicarboxylic acid. Examples of suitable diols for the preparation of the polyester polyols are ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, neopentyl glycol, 3-methyl-1, 5-pentanediol, 1, 7-heptanediol, 1, 8-octanediol, 1, 9-nonanediol, 1, 10-decanediol and 1, 12-dodecanediol. For example, a linear difunctional polyester polyol having a melting temperature of about 5 ℃ to about 50 ℃ may be included.

Examples of polycarbonate polyols which may be used include those carbonate diols having two or more hydroxyl groups resulting from the polycondensation of phosgene, chloroformates, dialkyl or diallyl carbonates and aliphatic polyols, or mixtures thereof, having low molecular weights and no more than 12 carbon atoms per molecule. Examples of suitable diols for preparing the polycarbonate polyols are diethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, neopentyl glycol, 3-methyl-1, 5-pentanediol, 1, 7-heptanediol, 1, 8-octanediol, 1, 9-nonanediol, 1, 10-decanediol and 1, 12-dodecanediol. For example, a linear difunctional polycarbonate polyol having a melting temperature of from about 5 ℃ to about 50 ℃ may be included.

Examples of suitable diisocyanate components are 1, 6-diisocyanatohexane, 1, 12-diisocyanatododecane, isophorone diisocyanate, trimethyl-hexamethylene diisocyanate, 1, 5-diisocyanato-2-methylpentane, diisocyanato-cyclohexane, methylene-bis (4-cyclohexyl isocyanate), tetramethyl-xylene diisocyanate, bis (isocyanatomethyl) cyclohexane, toluene diisocyanate, methylene bis (4-phenyl isocyanate), phenylene diisocyanate, xylene diisocyanate and mixtures of these diisocyanates. For example, the diisocyanate can be an aromatic diisocyanate, such as phenylene diisocyanate, Tolylene Diisocyanate (TDI), xylylene diisocyanate, biphenylene diisocyanate, naphthylene diisocyanate, diphenylmethane diisocyanate (MDI), and combinations thereof.

Examples of suitable diamine components (diamine chain extenders) are ethylenediamine, 1, 2-propylenediamine, 1, 3-propylenediamine, 2-dimethyl-1, 3-propylenediamine, 1, 4-butylenediamine, 1, 5-pentylenediamine, hexylenediamine, 1, 7-heptylenediamine, 1, 8-octylenediamine, 1, 9-nonylenediamine, 1, 10-decyldiamine, 1, 12-dodecylenediamine, 2-methyl-1, 5-pentylenediamine, cyclohexanediamine, isophoronediamine, xylylenediamine and methylenebis (cyclohexylamine). Mixtures of two or more diamines may also be used.

Examples of suitable amine-terminated polymers are bis (3-aminopropyl) -terminated polydimethylsiloxane, amine-terminated acrylonitrile-butadiene copolymer, bis (3-aminopropyl) -terminated polyethylene glycol, bis (2-aminopropyl) -terminated polypropylene glycol and bis (3-aminopropyl) -terminated polytetrahydrofuran.

Examples of suitable organic compounds or polymers having at least three primary or secondary amine groups are tris-2-aminoethylamine, poly (amidoamine) dendrimers, polyethyleneimine, polyvinylamine and polyallylamine.

Examples of suitable monoamine components (d) include primary alkylamines such as ethylamine, butylamine, hexylamine, cyclohexylamine, ethanolamine and 2-amino-2-methyl-1-propanol, and secondary dialkylamines such as N, N-diethylamine, N-ethyl-N-propylamine, N-diisopropylamine, N-tert-butyl-N-methylamine, N-tert-butyl-N-benzylamine, N-dicyclohexylamine, N-ethyl-N-isopropylamine, N-tert-butyl-N-isopropylamine, N-isopropyl-N-cyclohexylamine, N-ethyl-N-cyclohexylamine, N-diethanolamine and 2, 2, 6, 6-tetramethylpiperidine.

In preparing the polyurethaneurea powder of some embodiments, the diol is first reacted with a diisocyanate (optionally in the presence of a catalyst) to form an NCO-terminated prepolymer or "capped diol". The reaction is usually carried out in the form of a melt of the homogeneously mixed mixture and heat is applied at a temperature of 45 to 98 ℃ for 1 to 6 hours. The amount of each of the reaction components, i.e., the weight of the diol (Wgl) and the weight of the diisocyanate (Wdi), is adjusted by the Capping Ratio (CR), which is defined as the molar ratio of diisocyanate to diol as follows:

CR＝(Wdi/MWdi)/(Wgl/MWgl)

where MWdi is the molecular weight of the diisocyanate and MWgl is the number average molecular weight of the diol. According to the invention, the blocking ratio is between 1.2 and 5.0, in particular between 1.5 and 3.0.

After the end-capping reaction is completed, all hydroxyl groups (-OH) on the diol molecules are consumed by isocyanate groups (-NCO) on the diisocyanate to form urethane bonds (urethanebond), thereby forming a viscous polyurethane prepolymer having terminal NCO groups. This prepolymer is then added and dispersed into an aqueous solution containing surfactants, such as dispersants and antifoams/defoamers, and optionally a chain extender, such as a diamine. Alternatively, the prepolymer may be diluted with an organic solvent such as water-soluble N-methylpyrrolidone (NMP) or water-insoluble xylene before being dispersed in an aqueous medium. The solid polymer particles are formed under the action of high shear forces during dispersion and after chain extension with water and/or diamine chain extenders. These polyurethaneurea particles can then be filtered and dried.

Additives such as antioxidants, pigments, colorants, fragrances, antimicrobial agents (e.g., silver), active ingredients (moisturizers, UV-screeners), surfactants, antifoaming/defoaming agents, solvents, and the like may be incorporated into the polyurethaneurea particles before, during, or after dispersion of the prepolymer. In some cases, it may be advantageous to add the additive during dispersion of the prepolymer to encapsulate the additive in the polyurethaneurea particles. Encapsulation of the additive slows diffusion of the additive out of the polymer matrix, thereby providing a delayed or time release (time release) of the additive. This delayed release is relative to the relatively rapid release of the additive adsorbed on the surface of the particles. The invention may include combining the encapsulated additive with the surface adsorbed additive to provide a rapid release of one or more additives from the surface of the particle and a delayed release of the encapsulated additive.

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

pigment type	Colour of powder
		Substrate, without addition of pigment	White colour
Ultramarine blue	Light blue
		Blue pink	Light pink color
Black colourColored oxides	Grey colour
		Orange oxide	Light orange
Yellow oxide	Yellow colour
		Chromium green oxide	Light green

Further embodiments of the pigments are described below.

Polyurethaneurea particles

Some embodiments of the present invention are polyurethaneurea particles. One useful method for preparing such particles is disclosed in U.S. patent No. 5,094,914 to figure et al ("figure"), the entire contents of which are incorporated herein by reference. Segmented polyurea urethane (polyureathane) compositions may be prepared, which may be any of those described herein (e.g., those based on polyether or polyester segmented polyurea urethanes). A solvent may be used to prepare the solution containing the polyurea urethane. 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 polyurea urethane solution may then be introduced in the form of droplets into a coagulating bath (coagulating bath) that coagulates the polymer into particulate form. The coagulation bath may include a liquid, such as water, that extracts the solvent of the polymer solution, but is not a solvent for the polymer.

Particles can be made that are about 1mm to about 4mm in diameter, have 60% to 90% porosity, and have no visible pores (proes) on the surface at 5000X magnification.

Some embodiments of the present invention are polyurea urethane particles having a broader range of particle sizes, voidages, and surface pores than previously disclosed.

The voidage depends on the density of the particles:

voidage ═ 1- (particle density/polymer bulk density) ] x 100%

Some embodiments are polyurea urethane particles having a voidage of less than 60%. These particles can be prepared by using a higher viscosity solution. For example, a solution having a Brookfield viscosity of about 1000cps or greater and a solids content of about 12% or greater produces particles that are denser, heavier, and smaller than those produced using the same particle production apparatus but using a solution less than 1000 cps. In some embodiments, the particles are prepared from high viscosity (> 1000cps) but relatively low solids content (i.e. < 10%). This can be achieved by using polymers with high average molecular weight, branched chains (branched), or by using polymers that associate together in solution by crystallization, hydrogen bonding, hard segment association, and the like. For example, a solution containing a polyurethaneurea will become more viscous with age.

Low viscosity solutions with relatively high solids content can be prepared by using very thin sheared (sheath thin) polymers, such as liquid crystal polymers or some spandex products, or by using polymers that have low average molecular weights or do not associate, hydrogen bond, or crystallize in solution.

Another method of making smaller, denser particles is to make the particles from a solution that yields 60 to 90% void volume, but allows some solvent to remain with the particles during the solidification and drying process to remove the solvent. The particles are then dried such that residual solvent re-dissolves (redissolve) the polymer and re-precipitates into a more dense structure.

Particles having a porosity of greater than 90% may also be prepared. One method involves the use of polymers having low viscosity. However, with a continuous decrease in viscosity, in the same polymer article, a point is reached where the polymer is too dilute to maintain the shape of the particles during the setting process, thereby collapsing (collapse) (this method has been disclosed in U.S. patent No. 5,126,181 for preparing flat microporous discs). On the other hand, it is possible to select or formulate polymers, in particular polyurethaneureas, which are more rigid in nature, so that even when diluted, they still have sufficient hardness to support the particle shape without collapsing. In particular, it is possible to synthesize or select articles in the polyurethaneurea family that are stiffer, but still have very desirable elastic properties (stretch and recovery) inherent. For example, a polyurethaneurea using a low average molecular weight (e.g., average molecular weight less than 1000 or less than 700) polyethylene glycol as the soft segment(s) would be sufficient to produce particles with a void fraction greater than 90% to maintain a spherical shape.

In addition, other reactants or co-reactants may be used to modify the hardness of the final polyurea urethane particles, such as chain extenders other than or in addition to EDA (ethylene diamine), or co-chain extenders with EDA (coextenders), or isomers of MDI (4, 4' and 2, 4-) and mixtures thereof. 1, 4-phenylene diisocyanate or 1, 4-phenylenediamine or combinations or mixtures thereof also produce polyurea urethanes that are harder than corresponding polyurea urethanes based on "traditional" MDI and EDA. It should also be understood that mixtures of polyurea urethanes having different hardnesses may also be used to adjust or tune the necessary hardness to achieve a void volume requirement of greater than 90%. Other polymers or additives may be mixed into the solution to achieve the desired hardness and other requirements for making higher void volume particles.

Some embodiments are particles having controlled size pores on their surface. Micronized or nanosized salts or other water soluble materials (e.g., polyethylene glycol) may be mixed with the polyurea urethane solution prior to introduction into the coagulation bath. The water soluble material will create pores when the particles are coagulated and washed in water.

The invention also provides a method for continuous or semi-continuous production of granules. In a batch, stirred reactor process, the solvent may accumulate in water or a polymer non-solvent (built up). Excessive accumulation of solvent can lead to stickiness of the produced particles, causing them to stick together or possibly even causing them to agglomerate. Solvent accumulation in the non-solvent (or water) may also slow the solidification of the particles because there is not enough thermodynamic incentive (intake) to cause the solvent to be "pulled" or diffused into the non-solvent. As the solvent diffuses out of the particles or disks, the non-solvent becomes more and more concentrated and nearly as solvent.

Even the semi-continuous process of some embodiments may produce about 500 grams of particles per 8 hour shift, a 10-fold increase over batch, stirred reactor processes. The particles may be "harvested" at any time after about 2-3 minutes after formation and moved to a container other than where they were formed, such that continuous production of the particles in a "processing apparatus" reaches at least 38 hour shifts.

In another embodiment, the water in the "processing plant" may be continuously flushed and the particles may be periodically or continuously harvested so that the particles may be continuously produced. The industry would prefer to use continuous or semi-continuous operation over batch operation.

Harvesting of the particles from where they formed and moving to a different tank for soaking can be accomplished by a number of methods to extract residual DMAc solvent. One method includes using a transport system having a transport belt. The conveyor belt may be a screen or have holes to allow water to pass through them while retaining the particles thereon. Another method of transferring the particles from the processing apparatus is by "waterfall". The waterfall method allows some water and a large amount of particles to be spilled from the edge of a trough into another trough, allowing the particles to be collected at the end of the trough remote from where they are formed. This method can be easily implemented because the particles float in the water/solvent mixture.

The polyurethaneurea particles of some embodiments have a wide range of applicability. This includes use in textiles, clothing and shoes, furniture, cosmetics and other household applications. As bedding materials, they may be included in, for example, pillows in place of the fibrous filler. The particles may be incorporated into a shoe for use as a liner for a shoe sole. In addition, combinations of different sized particles may be included in the same sole to accommodate different pressure sites in the sole, in the insole, outside and upper of the shoe, particularly particles may be included in a "sandwich" structure of a pleated or quilted structure. The cushioning effect is also useful for furniture cushions and carpet underlayments. For example, the particles may be included in a fibrous batting material. The damping effect is also beneficial in headwear, such as helmets or hats, straps for clothing, straps for luggage, and comfortable gripping devices (comfort grip applications) that can be found on, for example, clubs, ski poles, hammers, bicycles, lawnmowers, steering wheels, and the like.

The particles have a very large number of useful properties. For example, the particles return to 85% of their volume immediately 24 hours after compression to a diameter of one-fourth of their original diameter, and about 97% of their volume after 10 minutes. The size of the particles may vary. The particles may have a diameter of greater than 0.1mm to 10mm, for example about.05 mm to about 8 mm. The individual particles have been prepared to have diameters of 0.5mm, 0.8mm, 1.0mm, 2.5mm, 3.0mm, 4.0mm, 5.0mm and 8.0 mm.

The density of the individual particles can be in any suitable range, for example, from about 0.05g/cc to about 0.5g/cc, including about 0.1 g/cc. At the same time, the particles have unique absorption properties. For example, when placed in water, a particle about 3mm in diameter will absorb about 14% of its weight in water. However, when the particles are squeezed in water and then released, the particles will absorb up to about 350% of their weight in water. These absorption properties demonstrate additional utility, for example as delivery vehicles for substances such as fragrances, ointments, and other fluid components.

Polyamide composition

A variety of different polyamides may be used with some embodiments. Examples of suitable polyamides include nylon 6, nylon 12 and nylon 6, 6. The polyamide may be present in any desired form, including fiber forms and powder forms. One suitable method for preparing polyamide powders is disclosed in U.S. Pat. No. 4,831,061 to Hilaire, the contents of which are incorporated herein by reference. Such powders are also commercially available (ARKEMA trade name)). The commercially available powders range in size from about 5 microns to about 20 microns. Polyamide powders of a larger size range may also be provided, for example, having an average particle size in the range of about 50100 microns to about 500 microns, including 100 microns. Coarser powders, such as powders having an average particle size of about 0.5mm to about 5mm, including about 1mm, may also be included.

Polyester composition

A variety of different polyesters may also be added in some embodiments. Examples of the polyester include polyalkylene terephthalate, polyalkylene naphthalate and polyalkylene isophthalate. Examples of polyalkylene terephthalates are fiber-forming linear polycondensates with carboxyl linkages in the polymer chain, such as polyethylene terephthalate ("2 GT" or "PET"), polypropylene terephthalate ("3 GT" or "PTT") and polybutylene terephthalate ("4 GT").

The polyester composition may be in any desired form, including fiber, staple fiber (lock), and powder forms.

Unless indicated to the contrary, reference to "polyalkylene terephthalate" is meant to include copolyesters, i.e., polyesters made using 3 or more reactants, each of which has two ester-forming groups. For example, a co-polyethylene terephthalate may be used, wherein the co-monomers used to make the co-polyester are selected from linear, cyclic and branched aliphatic dicarboxylic acids having 4 to 12 carbon atoms (e.g., succinic, glutaric, adipic, dodecanedioic and 1, 4-cyclo-hexanedicarboxylic acids); aromatic dicarboxylic acids other than terephthalic acid having 8 to 12 carbon atoms (e.g., isophthalic acid and 2, 6-naphthalenedicarboxylic acid); linear, cyclic and branched aliphatic diols having 3 to 8 carbon atoms (e.g., 1, 3-propanediol, 1, 2-propanediol, 1, 4-butanediol, 3-methyl-1, 5-pentanediol, 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 (e.g., hydroquinone bis (2-hydroxyethyl) ether, or poly (ethylene ether) glycols having a molecular weight of less than about 460 daltons, including diethylene ether glycol). Typically, the comonomer is present in the copolyester in an amount in the range of from about 0.5 to about 15 mole percent.

Short fiber

In some embodiments in the form of staple fibers. Staple fiber is a very short, precisely cut or comminuted fiber which is used to produce a covering layer like a fleece for clothing, rubber, films or paper. Short fibers may be used as fillers in plastics, paper, rubber or similar compositions to increase impact strength, improve moldability, or add decorative appearance to the finished product. Staple fibers are typically fibers having a length of about 0.040 inch to about 0.250 inch (1mm to 6.25 mm). Typically between about 10 and about 100 microns in diameter. The different colored staple fibers can be made from a variety of different synthetic and natural fibers such as polyamide, polyester, cotton and rayon.

Dye information

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

Colorants useful in some embodiments, including cosmetic compositions, include inorganic colorants, including synthetic and natural colorants, organic colorants, and the like. Inorganic colorants comprising TiO₂Iron oxide and ultramarine. Synthetic organic colorants include lakes, toners, and pigments such as those disclosed in U.S. patent No. 4,909,853, which is incorporated herein by reference. An example of a natural organic colorant is carmine pigment.

One suitable method for preparing colored nylon powder includes dyeing in a dyeing beaker heated on a hot plate with a magnetic stirrer. This ensures that the powder is sufficiently stirred by the stirrer to prevent the formation of lumps and to ensure uniform dyeing throughout the batch:

the bath was adjusted to pH 6.0 with phosphate buffer

1% by weight of Levegal SER (anionic levelling agent) is added

Adding pre-dissolved dye

Adding nylon powder

The temperature was increased to boiling at a rate of 2 ℃/min. The temperature was maintained for 30 minutes.

Add 1g/l Sandacid GBV (acid Donor) -slowly release acid into the bath to bring the pH down to pH 5.0-5.5).

The temperature was maintained for 30 minutes.

And (6) cooling.

The dye bath and powder were poured through a polishing filter and rinsed.

The powder was collected and dried in a hot cabinet.

For nylon in any form, including fiber, staple, and powder forms, the most common dyes are acid dyes that are not metallized and metallized. Both dyes exhibit a good hue range and a certain degree of colour fastness to washing and UV. The metal-treated dyes will exhibit the best fastness to UV and washing, but the hue range is limited to softer hues. Bright shades can be achieved only with non-metallized acid dyes (fastness to UV and washing is not very good) or with a limited range of special reactive acid dyes (which provide the best performance against washing but have similar fastness properties to UV as the non-metallized acid dyes). These reactive dyes tend to be more expensive and depth of shade limited, depending on the available amine ends (amine ends) in the nylon powder/staple.

For any form of polyester including fiber, staple, and powder forms, disperse dyes are the only dyes that can dye standard disperse dyeable polyesters. However, if you have a cationic dyeable polyester, then a basic (cationic) dye or a disperse dye can be used.

All of these types of dye classes are available from larger suppliers, such as Huntsman (formerly Ciba Textile Effects) and DyStar. The following table lists commercially available dyes distinguished by supplier and class.

Perfume

There are a variety of fragrance materials that deposit or remain well on spandex (i.e., segmented polyurea urethane). These materials include, but are not limited to, two species, species a and species B, as set forth below.

Type A: common logarithm (log) of the octanol/water partition coefficient (P) of a hydroxyl material (alcohol, phenol, or salicylate)₁₀P) is 2.5 or more and a gas chromatography faradic index (measured with polydimethylsiloxane as the non-polar stationary phase) of at least 1050.

The octanol-water partition coefficient (or its common logarithm, "logP") is well known in the literature as an indicator of hydrophobicity and water solubility [ see Hansch and Leo, Chemical Reviews, 71, 526-; hansch, Quinlan and Lawrence, J.organic Chemistry, 33, 347-350(1968) ]. When these values are not available from the literature, they can be determined directly or estimated approximately using mathematical algorithms. Software providing such an estimate is commercially available, for example "LogP" from Advanced Chemistry Design Inc.

log₁₀Materials with P of 2.5 or greater have some hydrophobicity.

The Kovat's index is calculated from the retention time in the gas chromatography assay and with reference to the retention time of the alkane [ see Kovats, Helv. Chim. acta 41, 1915(1958) ]. Indices based on the use of a non-polar stationary phase have been used in the fragrance industry as markers (descriptors) for several years, which are related to the molecular size and boiling point of the ingredients. An overview of the Kovat index in the fragrance industry is given by T Shibamoto in "Capillary Gas Chromatography in Essential oil analysis" P Sandra and C Bicchi (eds.), Huethig (1987), pp 259-274. Suitable common non-polar phases are 100% dimethylpolysiloxanes under the trade names RP-1(Hewlett-Packard), CP Sil 5CB (Chrompack), OV-1(Ohio Valley) and Rtx-1 (Restek).

Low kovat's index materials tend to be volatile and not well retained on many fibers.

Species A include alcohols of the general formula ROH, where the hydroxyl group can be a primary, secondary or tertiary hydroxyl group, and the R group can be an alkyl or alkenyl group, optionally branched or substituted, cyclic or acyclic, such that ROH has the partition coefficient and Coffetz characteristics described above. Alcohols having a Kovat's index of 1050 to 1600 are typically monofunctional alkyl or aralkyl alcohols having a molecular weight in the range of 150 to 230.

Class A also includes phenols of the general formula ArOH, in which the Ar group represents a benzene ring which may be substituted by one or more alkyl or alkenyl groups, or by an ester group-CO₂A is substituted wherein a is a hydrocarbyl group, such as a salicylate. ArOH has a partition coefficient and a kovats index as defined above. Typically, such phenols having a Cofferdaz index of 1050 to 1600 are monohydric phenols having a molecular weight of 150 to 210.

Examples of perfume materials in class A are 1- (2 ' -tert-butylcyclohexyloxy) -butan-2-ol, 3-methyl-5- (2 ', 2 ', 3 ' -trimethylcyclopent-3-enyl) -pent-2-ol, 4-methyl-3-decen-5-ol, amyl salicylate, 2-ethyl-4 (2 ', 2 ', 3-trimethylcyclopent-3 ' -enyl) butan-2-enol, camphol, carvacrol, citronellol, 9-decenol, dihydroeugenol, dihydrolinalool, dihydromyrcenol, dihydroterpineol, eugenol, geraniol, hydroxycitronellal, isoamyl salicylate, isobutyl salicylate, isoeugenol, dihydrolinalool, isovaleryl salicylate, isoeugenol, isovaleryl alcohol, and the, Linalool, menthol, nerolidol, nerol, p-tert-butylcyclohexanol, phenoxanol, terpineol, tetrahydrogeraniol, tetrahydrolinalool (tetrahydrolinalol), tetrahydromyrcenol (tetrahydromyrcenol), thymol, 2-methoxy-4-methylphenol, (4-isopropylcyclohexyl) -methanol, phenylmethyl salicylate, cyclohexyl salicylate, hexyl salicylate, patchouli alcohol, and farnesol.

Type B: esters, ethers, nitriles, ketones or aldehydes, having a common logarithm (log)₁₀P) an octanol/water partition coefficient (P) of 2.5 or more and a gas chromatography family Fahrenheit index (measured with polydimethylsiloxane as the non-polar stationary phase) of at least 1300.

Fragrances of class B have the general formula RX, wherein X may beIn a primary, secondary or tertiary position and is one of the following groups: -CO₂A. -COA, -OA, -CN or-CHO. The radicals R and A are cyclic or acyclic hydrocarbon radicals and are optionally substituted. Typically, class B materials having a kovat's index of no more than 1600 are monofunctional compounds having a molecular weight in the range of 160 to 230.

Examples of perfume materials in class B are 1-methyl-4- (4-methyl-3-pentenyl) -3-cyclohexene-1-carbaldehyde (carbaldehyde), 1- (5 ', 5 ' -dimethylcyclohexenyl) -penten-1-one, 2-heptylcyclopentanone, 2-methyl-3- (4 ' -tert-butylphenyl) propanal, 2-methylundecalaldehyde, 2-undecalaldehyde, 2-dimethyl-3- (4 ' -ethylphenyl) -propanal, 3- (4 ' -isopropylphenyl) -2-methylpropanal, 4-methyl-4-phenylpent-2-yl acetate, allylcyclohexylpropionate, allylhexylpropionate, and the like, Allyl cyclohexyl oxyacetate, amyl benzoate, methyl ethyl ketone trimer, benzophenone, 3- (4 '-tert-butylphenyl) -propionaldehyde, caryophyllene, cis-jasmone, citral diethanol, citronellal diethanol, citronellyl acetate, phenethylbutyl ether, alpha-damascone, beta-damascone, delta-damascone, gamma-decalactone, dihydroisojasmone, dihydrojasmone, dihydroterpinyl acetate, dimethyl aminomethylbenzoate, diphenyl oxide, diphenylmethane, dodecanal, dodecene-2-aldehyde, dodecanenitrile, 1-ethoxy-1-phenoxyethane, 3- (1' -ethoxyethoxy) -3, 7-dimethyloct-1, 6-diene, 4- (4 '-methylpent-3' -enyl) -cyclohex-3-enal Tricyclo [5.2.1.0-2, 6- ] decane-2-carboxylic acid ethyl ester, 1- (7-isopropyl-5-methylbicyclo [2.2.2] oct-5-en-2-yl) -1-ethanone (ethanone), allyltricyclodecenyl ether, tricyclodecenyl propionate (tricyclodenyl propionate), gamma-undecanolactone, n-methyl-n-phenyl-2-methylbutylamide, tricyclodecenyl isobutyrate, geranyl acetate, hexyl benzoate, alpha-ionone, beta-ionone, isobutyl cinnamate, isobutylquinoline, isobutyronate, 2, 7, 7-tetramethyltricycloundecan-5-one, tricyclodecenyl acetate, 2-hexylcyclopentanone, 4-acetoacetoxy-3-pentyltetrahydropyran, isopentyl acetate, methyl propionate, ethyl propionate, n-methyl-ethyl propionate, n-2, 7, 7-tetramethyltricycloundecan-5-one, tricyclodecenyl acetate, 2, Ethyl 2-hexyl acetoacetate, methyl 8-isopropyl-6-methylbicyclo [2.2.2] oct-5-ene-2-carbaldehyde, methyl 4-isopropyl-1-methylbicyclo [2.2.2] oct-5-ene-2-carboxylate, methyl cinnamate, alpha-isomethylionone, methylnaphthyl ketone, neryl ether, gamma-nonalactone, nopyl acetate, p-tert-butylcyclohexylacetate, 4-isopropyl-1-methyl-2- [ 1' -propenyl ] -benzene, phenoxyethyl isobutyrate, phenethylisoamyl isovalerate, phenethyl isobutyrate, tricyclodecenyl pivalate, phenethyl acetate, phenylacetaldehyde hexanediol, 2, 4-dimethyl-4-phenyltetrahydrofuran, rose acetone (rose acetone), Terpinyl acetate, 4-isopropyl-1-methyl-2- [ 1' -propenyl ] -benzene, ethyl naphthylmethyl ether (yara), 4-isopropylcyclohexadienyl) ethyl formate, amyl cinnamate, amyl cinnamaldehyde dimethyl acetal, cinnamate, 1, 2, 3, 5, 6, 7, 8, 8 a-octatyro-1, 2, 8, 8-tetramethyl-2-acetonaphthyl, cyclo-1, 13-ethylenedioxytridecane-1, 13-dione, cyclopentadecanolide, hexylcinnamaldehyde, 1, 3, 4, 6, 7, 8-hexahydro-4, 6, 6, 7, 8, 8-hexamethylcyclopenta [ g ] -2-benzopyran, geranylphenyl acetate, 6-acetyl-1-isopropyl-2, 3, 3, 5 tetramethyllindane and 1, 1, 2, 4, 4, 7-hexamethyl-6-acetyl-1, 2, 3, 4-tetrahydronaphthalene.

While this is a broad list of flavors and fragrances that work well with spandex compositions, it is to be appreciated that other flavors may also be useful in some embodiments. Fragrances may include substances or mixtures of substances including natural (i.e., obtained by extracting flowers, herbs, leaves, roots, bark, trees, flowers, or plants), artificial (i.e., mixtures of different natural oils or oil components), and synthetic (i.e., synthetically produced) aromatic substances.

Non-limiting examples of fragrances include: hexyl cinnamic aldehyde; amyl cinnamic aldehyde; amyl salicylate; hexyl salicylate; terpineol; 3, 7-dimethyl-cis-2, 6-octadien-1-ol; 2, 6-dimethyl-2-octanol; 2, 6-dimethyl-7-octen-2-ol; 3, 7-dimethyl-3-octanol; 3, 7-dimethyl-trans-2, 6-octadien-1-ol; 3, 7-dimethyl-6-octen-1-ol; 3, 7-dimethyl-1-octanol; 2-methyl-3- (p-tert-butylphenyl) -propionaldehyde; 4- (4-hydroxy-4-methylpentyl) -3-cyclohexene-1-carbaldehyde; tricyclodecenyl propionate; tricyclodecenyl acetate; anisaldehyde; 2-methyl-2- (p-isopropylphenyl) -propanal; ethyl-3-methyl-3-phenylglycidic acid ester; 4- (p-hydroxyphenyl) -butan-2-one; 1- (2, 6, 6-trimethyl-2-cycloethen-1-yl) -2-buten-1-one; p-methoxyacetophenone; p-methoxy- α -phenylpropylene; methyl-2-n-hexyl-3-oxo-cyclopentane carboxylate; gamma undecalactone, orange oil; lemon oil; grapefruit oil; bergamot oil; clove oil; gamma-dodecalactone; methyl-2- (2-phenyl-3-oxo-cyclopentyl) acetate; beta-naphthol methyl ether; methyl beta-naphthalenone; coumarin; decanal; benzaldehyde; 4-tert-butylcyclohexyl acetate; acetic acid alpha, alpha-dimethyl phenyl ethyl ester; methyl phenyl acetate; ethylene glycol diester of tridecanedioic acid; 3, 7-dimethyl-2, 6-octadiene-1-carbonitrile; gamma-methyl ionone (ionone gamma methyl); alpha-ionone; beta-ionone; grapefruit leaf oil (petitgrain); (ii) cedryl methyl ketone; 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-hexamethyltetralin; 4-acetyl-6-tert-butyl-1, 1-dimethylindan; benzophenone; 6-acetyl-1, 1, 2, 3, 3, 5-hexamethylindane; 5-acetyl-3-isopropyl-1, 1, 2, 6-tetramethylindane; 1-dodecanal; 7-hydroxy-3, 7-dimethyloctanal; 10-undecane-1-aldehyde; isohexylcyclohexylaldehyde; formyl tricyclodecane; cyclopentadecanolide; 16-hydroxy-9-hexadecenoic acid lactone; 1, 3, 4, 6, 7, 8-hexahydro-4, 6, 6, 7, 8, 8-hexamethylcyclopent-gamma-2-benzopyran; ambroxane (ambroxane); dodecahydro-3 a, 6, 6, 9 a-tetramethylnaphtho- [2, 1b ] furan; cedrol; 5- (2, 2, 3-trimethylcyclopent-3-enyl) -3-methylpent-2-ol; 2-ethyl-4- (2, 2, 3-trimethyl-3-cyclopenten-1-yl) -2-buten-1-ol; caryophyllenol; cedryl acetate; p-tert-butylcyclohexyl acetate; patchouli; a mastic resin; rockrose root; cistus oil; vetiver oil; bitter is added to the balsam of the fenugreek; balm canada; hydroxycitronellal and indole (indol); phenylacetaldehyde and indole; geraniol; geranyl acetate; linalool; linalyl acetate; tetrahydrolinalool; citronellol; citronellyl acetate; dihydromyrcenol; dihydromyrcenyl acetate; tetrahydromyrcenol; terpinyl acetate; nopol; nopyl acetate; 2-phenyl ethanol; 2-phenylethyl acetate; benzyl alcohol; benzyl acetate; benzyl salicylate; benzyl benzoate; para-ethyl phenyl acetate (styrallyl acetate; dimethylbenzyl carbinol; trichloromethylphenyl methyl phenyl methyl acetate; isononyl acetate; vetiveryl alcohol; 2-methyl-3- (p-tert-butylphenyl) -propionaldehyde; 2-methyl-3- (p-isopropylphenyl) -propionaldehyde; 3- (p-tert-butylphenyl) -propionaldehyde; 4- (4-methyl-3-pentenyl) -3-cyclohexenecarbaldehyde; 4-acetoxy-3-pentyltetrahydropyran; methyl dihydrojasmonate; n-heptyl cyclopentanone; 3-methyl-2-pentyl-cyclopentanone; n-decanal; n-dodecanal; 9-decenol-1; phenoxyethyl isobutyrate; phenylacetaldehyde dimethyl acetal; phenylacetaldehyde diethyl acetal; geranonitrile; citronellyl nitrile; cedryl acetate; 3-isoborneol cyclohexanol; methyl cedryl ether; isolongifolone; anisaldehyde nitrile; anisaldehyde; piperonal; eugenol; vanillin; a diphenyl oxide; hydroxycitronellal ionone; methyl ionone; iso-methyl ionone; an irone; cis-3-hexenol and its esters; indane type musk perfumes; tetralin type musk fragrances; a musk chamaemelon perfume; a macrocyclic ketone; macrocyclic lactone (macrolactone) musk fragrances; ethylene tridecanedicarboxylate, and combinations thereof.

Fabric care compositions

The polyurethaneurea compositions prepared by the above-described process provide surprisingly improved shape retention to fabrics. Moreover, they also provide ease of care or ease of care (easy care properties) to the fabric. In other words, the fabric treated with the polyurethaneurea composition has less wrinkles after washing and is easier to iron.

The polyurethaneurea compositions of some embodiments also have surprisingly good water and oil absorption, particularly when used on fabrics. This is particularly important for stain resistance. After the fabric is contacted with the polyurethaneurea composition of some embodiments, the polyurethaneurea will absorb and wick moisture from the stain-generating sources (stain-catching sources), thereby limiting the absorption of the fabric itself.

Due to the absorbency, the polyurethaneurea composition also helps to extend the duration of fragrance in a fabric that has been contacted by the composition. This results from the absorption and subsequent gradual release of the fragrance by the polyurethaneurea composition.

The fabric care composition of some embodiments may include a fabric softener or detergent to which the polyurethaneurea composition may be added. These polyurethaneurea compositions can also be in any form, such as a dispersion or powder.

Alternatively, the polyurethaneurea composition can be added directly to the fabric, to a washing machine, to the wash water (for hand washing), or to an automatic dryer.

Furthermore, the powder or dispersion can be used as a replacement for fabric softeners by home laundering (home laundering) to impart soil resistance to clothing. Fabric softeners are often used to impart fragrance or aroma to fabrics and secondly to impart fabric softness. When using drum drying (tumbling drying), a fabric softening operation is not necessarily required, since the drum dried fabric is already soft.

Detergent compositions in some embodiments typically contain anionic, nonionic or amphoteric surfactants or mixtures thereof, and often additionally contain organic or inorganic builders.

Fabric softeners will typically include active ingredients such as quaternary ammonium salts. Examples of the acyclic quaternary ammonium salts include tallow trimethyl ammonium chloride; ditallow dimethyl ammonium chloride; ditallowdimethylammonium methylsulfate; dicetyl dimethyl ammonium chloride (dihexadecyl dimethyl ammonium chloride); bis (hydrogenated tallow) dimethyl ammonium chloride; dioctadecyl dimethyl ammonium chloride; biseicosyldimethylammonium chloride; bisdocosyl dimethyl ammonium chloride; bis (hydrogenated tallow) dimethylammonium methylsulfate; dicetyl diethylammonium chloride; dicetyldimethylammonium acetate; ditallowdimethyl ammonium phosphate; ditallow dimethyl ammonium nitrate; and bis (coconut-alkyl) dimethylammonium chloride.

Other optional ingredients of the fabric care compositions in some embodiments are conventional in nature and typically comprise from about 0.1% to about 10% by weight of the composition. Such optional ingredients include, but are not limited to, colorants, fragrances, bacteriostats, optical brighteners, opacifiers, viscosity modifiers, fabric conditioners in the form of solids such as clays (clay), fabric absorbents (fabric absorbents), emulsifiers, stabilizers, shrinkage control agents (shrinkagecontrollers), anti-spotting agents, bactericides, fungicides, preservatives, and the like.

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 the softening agent in water at about 150F, which is then added to a hot aqueous solution of the other ingredients. After the fabric conditioning composition is cooled to about room temperature, heat sensitive ingredients may be added.

The fabric care compositions of some embodiments may be used by addition to the wash cycle of a conventional home laundering operation. Alternatively, the fabric care composition may be added to the detergent prior to the wash cycle, or directly to the fabric, or when hand washed, as part of the detergent or fabric softening composition, or directly to the wash water.

The fabric care composition may be used in any form known in the art, for example as a powder, liquid, solid tablet (solid tablet), encapsulated liquid (e.g. a composition encapsulated with polyvinyl alcohol), or as a non-woven sheet (non-woven sheet) when used in an automatic dryer.

The fabric care composition in some embodiments can be added in any amount necessary to achieve the desired fabric properties. For example, the fabric care composition may be added in an amount of from about 0.05% to about 1.5%, for example from about 0.2% to about 1%, by weight of the rinse water bath (aqueous ringing bath) or wash water.

When present in the form of an aqueous dispersion, the polyurethaneurea composition in some embodiments may comprise from about 0.1% to about 20%, for example from about 5% to about 15%, by weight of the fabric care composition, in the fabric care composition. When present in powder form, the polyurethaneurea composition can comprise from about 0.1% to about 20%, for example from about 0.5% to about 10%, or from about 1% to about 5%, by weight of the fabric care composition, in the fabric care composition.

Alternatively, the polyurethaneurea powder or dispersion can be added in place of, rather than as an ingredient of, the fabric care composition, in which case the polyurethaneurea composition can be added at a level of 100%. In this case, the polyurethaneurea composition can be added directly to the wash water or rinse water in an amount of from about 0.05% to about 1.5%, specifically, from about 0.2% to about 1%, by weight of the rinse water or wash water.

Cosmetic composition

Nylon (polyamide) and polyurethaneurea powders have many useful properties that make them useful for incorporation into cosmetic compositions. Among these properties are oil absorption, water absorption, and sweat absorption. These properties are particularly useful for perspiration-absorbing applications such as deodorants or antiperspirants when in contact with the skin. These properties are also used for sebum control in skin contact products, skin care and decorative cosmetics.

In one embodiment, the present invention provides a polymer powder having antimicrobial activity to reduce bacterial growth and odor. The powder may have enhanced odor prevention capabilities by the addition of an odor absorbent, such as zinc oxide.

The powder in some embodiments has surprisingly good water and oil absorption. In one embodiment, the polyurethaneurea powder is formed by the process described above, has a particular particle size, and is suitable for use as a water or sweat absorbent in deodorant and antiperspirant compositions, or as an oil (sebum) absorbent in skin care or cosmetic (make-up) compositions. Additional embodiments include powders with antimicrobial additives to enhance odor protection, powders with additional fragrances to provide a pleasing fragrance, and powders for cosmetic or body care end (body end) applications. Non-limiting examples of cosmetic compositions incorporating the powders, granules, fibers and dispersions of some embodiments include deodorants, such as spray, stick or roll-on antiperspirants; cosmetics and color cosmetics such as powders (blush)/bronzer/highlighter), foundations, eye shadows, eyeliners, mascaras, lipsticks/lip glosses; skin care compositions such as body or face moisturizers, shaving gels and creams, after-shave gels and creams, bar soaps and body washes/cleansers (body wash/cleanser); hair care products such as shampoos, conditioners and styling products (styling products); oral care products, including toothpastes.

Some embodiments of the polyamide and polyurethaneurea powders have very good hand and feel (touch property). For example, they are very smooth (slipping), feeling silky (silk) and smooth (smooth) to the touch.

The polyurethaneurea powder of the present invention exhibits very high water and sweat absorption values, determined by a variety of properties, and at the same time exhibits good oil absorption values. Very high water absorption values mean that the absorption values are more than three times greater than those of NY-6 powder (from Arkema, available from Lehmann and Voss & Co. Hamburg, Germany). Good oil absorption values mean comparable to nylon 12(Arkema) and higher than polymethyl methacrylate, polyethylene and polyurethane from KOBO (Kobo Products of South Plainfield, New Jersey and St. Agne France). The polyurethaneurea powders of the present invention exhibit extremely fast (immediate) water absorption or sweat absorption. Fast water absorption means 100 times faster than talc.

The rapid and large water uptake of the polyurethaneurea powders described herein also facilitates anti-aging and anti-wrinkle products. The powder can be used as a filler for skin wrinkles in anti-aging skin care compositions. The powder is hydrophilic, compressible microspheres with a volume change effect (volumizing effect) to stretch the skin and reduce or eliminate the appearance of wrinkles.

For powder applications in cosmetic and body care compositions, particles smaller than 100 microns are suitable to make the skin feel smooth and not noticeable to the user. The desired average particle size should be less than 50 microns. In one embodiment, the polyurethaneurea powder comprises 90% of particles smaller than 42 microns, which can be achieved by filtration or by controlling the parameters of the spray drying process.

Another embodiment is a polyurethaneurea particle or powder as an exfoliant in a cleanser, scrub, shower gel, or the like. Generally, materials such as peanuts (including almonds) have been included in cosmetic compositions as exfoliants/scrubs/peels. However, these substances tend to be hard and have sharp hard edges, resulting in an uncomfortable feeling. In contrast, the polyurethaneurea particles and powders of some embodiments may have a very rounded spherical, rounded surface and silky feel, making them more "skin-friendly" products while maintaining the effect of a hard material. The powder or granules can be added to the detergent composition in any amount to achieve the desired effect. The particle size may also vary, typically greater than about 100 microns, for consumer observation.

Another embodiment is a polyurethaneurea dispersion that can be film formed for hair care compositions (gels, spray, shampoos, conditioners, etc.) for curl retention (curl property) or curl prevention (anti-frizz property). The colored or pigmented polyurethaneurea powder can be used in non-permanent hair dyeing.

The polymer composition may be included in any composition in an amount up to 100% by weight of the composition. Suitable ranges of nylon, polyester and polyurethaneurea content for inclusion in the composition include 1-20%, 1-15%, 5-10% and 25-75% by weight, based on the weight of the composition. The amount used depends on the application and the desired effect.

Paint composition

Some embodiments are paint compositions containing polyurethaneurea, polyester, and polyamide compositions. The paint may be in any form known in the art, including latex, acrylic paint, and oil based paint (oil based paint), including primers, seals, and coatings. The polyurethaneurea, polyester, and polyamide compositions can be added to the paint in any form to achieve the desired effect.

The addition of the polymer in the form of powder, short fibers or particles can be used to provide texture to the paint composition. In addition, if the powders, fibers or particles have been dyed or pigmented, they will also achieve different paint effects. This effect is extremely desirable if interest is given to recent alternative painting techniques (alternate painting techniques) and artificial surfaces (faux finishes). The compositions of some embodiments provide selective (alternative) surface characteristics, such as texture and color, without the need for an additional painting step. Also, a bi-color effect or multi-color effect may be achieved by adding a color to the primer and adding one or more separate colors to the powder/particles/fibers.

In addition to the visual effects of color and texture, the addition of short fibers to paint compositions has additional benefits. Paint compositions containing these short fibers provide better coverage of uneven areas on the walls/surfaces, provide greater flexibility, and provide resistance to cracking. Moreover, they provide a wallpaper effect (wall paper effect) throughout the paint application.

In addition to the visual effects of color and texture, there are additional benefits of adding the polyurethaneurea dispersion to the paint composition. Paint compositions containing these dispersions can provide better coverage (especially on uneven surfaces) and provide resistance to cracking. This is confirmed by the examples.

Alternatively, slip resistance may be provided to the paint composition by adding a polymer in powder, short fiber or particulate form. This is achieved by increasing the friction coated surface (friction coated surface) compared to conventional paint compositions.

The features and advantages of the present invention will be more fully shown by the following description of the examples, which are given by way of illustration only and are not to be construed in any way as limiting the present invention.

Examples

Example 1

From experimentalObtained from spandex in the production lineE2538 diol (supplied by INVISTA, S.a r.l.) and125MDR, the degree of capping was 1.696.Is a registered trademark of the spandex of INVISTA. 300 grams of this prepolymer was mixed with 150 grams of NMP solvent in a plastic bottle for 10 minutes to reduce the viscosity. The diluted mixture was poured into a steel tube to inject it into a stainless steel containerFor dispersion.

The container contained 2000 grams of deionized water, 30 grams of T DET N14 surfactant (available from harcross of Kansas City, Kansas) and 4.5 grams of ethylenediamine chain extender, which were premixed and cooled to 5 ℃. The diluted prepolymer was injected at a pressure of about 40psi through a tube having an inner diameter of 1/8 inches and was run at 5000rpm using a high speed laboratory disperser (model HSM-100LC, available from Charles Ross & Son Company of Hauppauge, N.Y.). The addition of the diluted prepolymer was completed in 15 minutes and the milky white dispersion formed was continued to be dispersed for an additional 5 minutes. Post-weighing (backsweighing) the container showed that the total amount of diluted capped glycol added to the dispersion was 328 grams, corresponding to 218.7 grams of capped glycol prepolymer added to the dispersion. 3 grams of Additive 65(Additive 65) foam control agent (available from Dow Corning of Midland, Michigan) was added to the dispersion and the dispersion was allowed to mix at 5000rpm for an additional 30 minutes before being poured into a plastic bottle.

The dispersion had an average particle size of 52.83 microns as determined using a Microtrac X100 particle size analyser (Leeds, Northrup) with 95% of the particles being smaller than 202.6 microns.

Example 2

The same ingredients and dispersion procedure as in example 1 were used except that 4.5 grams of the ethylenediamine chain extender was added after the diluted prepolymer was dispersed into the water mixture. Post-weighing the container indicated that the total amount of diluted capped glycol added to the dispersion was 329 grams, corresponding to 219 grams of capped glycol prepolymer added to the dispersion. The dispersion was determined to have an average particle size of 33.45 microns with 95% of the particles being less than 64.91 microns. When isolated, the solid polymer particles do not form a film.

Example 3

By mixing 500 g ofHLB 2000 diol (supplied by Sartomer Company, inc. at Exton, PA) and 105.86 grams125MDR was reacted in a 2000ml reaction vessel equipped with a heating mantle and a mechanical stirrer at 90 ℃ for 120 minutes to obtain a capped glycol prepolymer. The reaction was carried out in a dry box filled with nitrogen. After the reaction, the prepolymer had a weight percent NCO groups of 2.98 as determined by titration. This prepolymer was poured into a steel tube to be poured into a stainless steel container for dispersion. Deionized water (2000 grams) was mixed with 30 grams of T DET N14 surfactant (available from harcross of Kansas city, Kansas) and 3 grams of additive 65 foam control agent (available from Dow Corning of midland, Michigan) in the vessel at room temperature. The prepolymer was injected at a pressure of about 80psi through a pipe having an inner diameter of 1/8 inches, high speed laboratory disperser (model HSM-100LC available from Charles Ross&Available from Son Company of Hauppauge, new york) was operated at 5000 rpm. The addition of the diluted prepolymer was completed in 15 minutes and the milky white dispersion formed was continued to be dispersed for an additional 5 minutes. Post-weighing the container showed that the total amount of diluted capped glycol added to the dispersion was 422 grams. To the dispersion was added 4.5 grams of ethylene diamine chain extender and the dispersion was allowed to mix at 5000rpm for an additional 30 minutes. The resulting dispersion was determined to have an average particle size of 49.81 microns with 95% of the particles being smaller than 309.7 microns.

Example 4

The procedure is as in example 3, except that the catalyst used contains 250 g1800 diols and 250 gramsA diol mixture of HLB 2000 diols to form the prepolymer. A total of 465 grams of prepolymer was dispersed. The resulting dispersion was determined to have an average particle size of 13.67 microns with 95% of the particles being smaller than 38.26 microns.

Example 5

The preparation of the prepolymer was carried out in a nitrogen atmosphere glove box. To 2000mlAbout 382.5 grams of a glass reaction kettle equipped with a pneumatically driven stirrer, heating mantle and thermocouple thermometer was charged1800 diols (commercially available from INVISTA, S.a r.l., of Wichiata, KS and Wilmington, DE) and about 12.5 grams of 2, 2-dimethylolpropionic acid (DMPA). The mixture was heated to about 50 ℃ and stirred, followed by the addition of about 105 grams ofMl diisocyanate (commercially available from BASF, Wyandotte, Michigan). The reaction mixture was then heated to about 90 ℃ with constant stirring and maintained at about 90 ℃ for about 120 minutes, after which time the reaction was complete and the% NCO in the mixture dropped to a stable value, consistent with the calculated value for the prepolymer having isocyanate end groups (% NCO target value of 1.914). The viscosity of the prepolymer was determined according to the general method of ASTM D1343-69, operating at about 40 ℃ using a falling ball viscometer model DV-8 (sold by Duratech Corp., Waynesboro, Va.). By S.Siggia, "Quantitative Organic Analysis via functional group (by Quantitative Organic Analysis of functional groups)", third edition, Wiley&The total isocyanate moiety content (in terms of weight percent NCO groups) of the capped glycol prepolymer is determined by the method of Sons, New York, pp.559-561(1963), the entire contents of which are incorporated herein by reference.

Example 6

The aqueous polyurethane urea dispersion of the present invention was made using a solvent-free prepolymer (as prepared according to the procedure and composition described in example 5).

To a 2000ml stainless steel beaker was added about 700 grams of deionized water, about 15 grams of Sodium Dodecylbenzenesulfonate (SDBS), and about 10 grams of Triethylamine (TEA). This mixture was then cooled to about 5 ℃ with ice/water and mixed using a high shear laboratory mixer (Ross, model 100LC) with a rotor/stator mixing head at a speed of about 5000rpm for about 30 seconds. The viscous prepolymer prepared as in example 1 and contained in a metal tubular cylinder was added to the aqueous solution at the bottom of the mixing head through a flexible line to which air pressure was applied. The temperature of the prepolymer is maintained between about 50 ℃ and about 70 ℃. The extruded prepolymer stream was dispersed and chain extended with water under continuous mixing conditions of about 5000 rpm. After about 50 minutes, a total of about 540 grams of prepolymer was added and dispersed in water. Immediately after the prepolymer is added and dispersed, about 2 grams of additive 65 (available from Dow) is added to the dispersed mixtureAvailable from Midland Michigan). The reaction mixture is then stirred for an additional about 30 minutes, after which about 6 grams of Diethylamine (DEA) are added and stirred again. The resulting solvent-free aqueous dispersion was milky white and stable. The viscosity of the dispersion was adjusted by adding and mixing Hauthane HA thickener 900 (available from Hauthway, Lynn, Massachusetts) at about 2.0 wt% of the aqueous dispersion. The viscous dispersion was then filtered with a 40 micron Bendix metal mesh filter and stored at room temperature for film casting or lamination. The dispersion had a solids content of 43% and a viscosity of about 25000 centipoise.

Example 7

From commercializationObtained from spandex in the production line1800 diols andan end-capped glycol prepolymer made from 125MDR (available from Dow Company, Midland, Michigan) had an end-capping ratio of 1.688.Is a registered trademark of the spandex of INVISTA. 300 grams of this prepolymer was mixed with 150 grams of NMP solvent in a plastic bottle for 10 minutes to reduce the viscosity. The diluted mixture was poured into a steel tube to inject it into a stainless steel container for dispersion. The container contained 2000 grams of deionized water, 30 grams of T DET N14 surfactant (available from harcross of Kansas City, Kansas) and 3 grams of ethylenediamine chain extender, which were premixed and cooled to 5 ℃. The diluted prepolymer was injected at a pressure of about 40psi through a line having an inner diameter of 1/8 inches, high speed laboratory disperser (model HSM-100LC available from Charles Ross&Available from Soncompany of Hauppauge, New York) was operated at 5000 rpm. The addition of the diluted prepolymer was completed in 15 minutes and the milky white dispersion formed was continued to be dispersed for an additional 5 minutes. Post-weighing the container indicated that the total amount of diluted capped glycol added to the dispersion was 347 grams, corresponding to 231 grams of capped glycol prepolymer added to the dispersion. To the dispersion was added 3 grams of additive 65 foam control agent (commercially available from dow corning of Midland, Michigan) and the dispersion was allowed to mix for an additional 30 minutes at 5000rpm before being poured into a plastic bottle.

The dispersion had an average particle size of 32.59 microns as determined by using a Microtrac X100 particle size analyser (Leeds, Northrup) with 95% of the particles being less than 65.98 microns. Using a porcelain funnel andthe solid polymer particles were filtered through filter paper under reduced pressure, the filter cake was rinsed 3 times with water and dried at 60-65 ℃ for 4 hours. The particles do not form a film during filtration and drying. For use in laboratoriesA mixer (Blender 700 model 33BL79, manufactured by Dynamics inc., New Hartford, Connecticut) readily ground the dried filter cake to a fine powder. In commercial practice, the solid particles will be isolated directly from the dispersion by known drying methods, such as spray drying. The dry powder had a weight average molecular weight of 352550 and a number average molecular weight of 85200 as determined by GPC.

Example 8

In example 8, the same ingredients and dispersion procedure as in example 7 were used except that the solvent used to dilute the capped glycol prepolymer was changed to xylene and the amount of ethylenediamine chain extender was increased to 4.5 grams. Post-weighing the container indicated that the total amount of diluted capped glycol added to the dispersion was 339 grams, corresponding to 226 grams of capped glycol prepolymer added to the dispersion.

The dispersion was determined to have an average particle size of 22.88 microns with 95% of the particles being smaller than 46.97 microns. When isolated, the solid polymer particles do not form a film.

Example 9

In example 9, the same ingredients and dispersion procedure as in example 7 were used except that the ethylenediamine chain extender was replaced with the same amount of branched polyethylenimine [ Mn determined by GPC about 600 (from Aldrich) ]. Post-weighing the container indicated that the total amount of diluted capped glycol added to the dispersion was 340 grams, corresponding to 227 grams of capped glycol prepolymer added to the dispersion.

The dispersion was determined to have an average particle size of 58.12 microns with 95% of the particles being smaller than 258.5 microns. When isolated, the solid polymer particles do not form a film.

Example 10

The prepolymer was prepared using a glove box under a dry nitrogen atmosphere. To two separate 2000ml220.0 g of each of the glass reaction vessels (equipped with a pneumatically driven stirrer, heating mantle and thermocouple thermometer) was charged1800 diols (available from INVISTA) and 220.0 gramsHP 4000D diol (available from BASF). The diol mixture was heated to 50 ℃ and stirred, after which 75.03 g of water were added125MDR (commercially available from Dow Chemical). The reaction mixture was then heated to 90 ℃ with constant stirring and maintained at 90 ℃ for 120 minutes. Samples were taken from the reactor and determined to have an NCO of 2.170 and 2.169% respectively, by methods such as S.Siggia, "quantitative organic Analysis via Functional Group", third edition, Wiley&Sons, New York, pp.559-561 (1963).

To a 3000ml stainless steel beaker was added 1600 grams of deionized water, 15 grams of TDET N14 surfactant (available from Harcross of Kansas City, Kansas) and 5 grams of additive 65 (available from Dow Corning). This mixture was then cooled to 10 ℃ with ice/water and mixed for 30 seconds at 5000rpm using a high shear laboratory mixer (Ross, model 100LC) with a rotor/stator mixing head. The viscous prepolymer in the two reactors prepared above was poured into a metal tubular cylinder and added to the bottom of the mixing head in an aqueous solution through a flexible tube to which air pressure was applied. The temperature of the prepolymer is maintained between 50 and 70 ℃. The extruded prepolymer stream was dispersed and chain extended with water under continuous mixing conditions of 5000 rpm. After 5 minutes, a total of 616 grams of prepolymer was added and dispersed into water. After the prepolymer is added and dispersed, the dispersed mixture is mixed for an additional 40 minutes. The resulting solvent-free aqueous dispersion was milky to pale blue in color, 28.84 wt% solids, and 44 cps in viscosity. The dispersion was cast (cast) onto polyethylene sheet under ambient conditions and dried overnight in a fume hood to form an elastic continuous film. The weight average molecular weight of the film was 127900 and the number average molecular weight was 41000 by GPC measurement.

Example 11

The procedure and conditions were substantially the same as those of example 10 above except that the surfactant was replaced withN1-9 (commercially available from Stepan of Northfield, Ill.). A total of 640 grams of prepolymer having 2.156 and 2.136% NCO from the two reactors was dispersed in water. The resulting solvent-free dispersion had a solids content of 26.12% and a viscosity of 51 centipoise. The cast and dried elastic film had a weight average molecular weight of 133900 and a number average molecular weight of 44400.

Example 12

The aqueous polyurethane urea dispersion of the present invention was made using a solvent-free prepolymer (as prepared according to the procedure and composition described in example 5).

To a 2000ml stainless steel beaker was added about 700 grams of deionized water, about 15 grams of Sodium Dodecylbenzenesulfonate (SDBS), and about 10 grams of Triethylamine (TEA). This mixture was then cooled to about 5 ℃ with ice/water and mixed using a high shear laboratory mixer (Ross, model 100LC) with a rotor/stator mixing head at a speed of about 5000rpm for about 30 seconds. Such asThe viscous prepolymer prepared in the manner described in example 1 and contained in a metal tubular cylinder was added to the bottom of the mixing head in an aqueous solution through a flexible tube to which air pressure was applied. The temperature of the prepolymer is maintained between about 50 ℃ and about 70 ℃. The extruded prepolymer stream was dispersed and chain extended with water under continuous mixing conditions of about 5000 rpm. After about 50 minutes, a total of about 540 grams of prepolymer was added and dispersed in water. Immediately after the prepolymer is added and dispersed, about 2 grams of additive 65 (available from Dow) is added to the dispersed mixtureAvailable from Midland Michigan) and about 6 grams of Diethylamine (DEA). Subsequently, the reaction mixture was stirred for an additional about 30 minutes. The resulting solvent-free aqueous dispersion was milky white and stable. The viscosity of the dispersion was adjusted by adding and mixing Hauthane HA thickener 900 (available from Hauthway, Lynn, Massachusetts) at about 2.0 wt% of the aqueous dispersion. The viscous dispersion was then filtered with a 40 micron Bendix metal mesh filter and stored at room temperature for film casting or lamination. The dispersion had a solids content of 43% and a viscosity of about 25000 centipoise. Films cast from this dispersion are soft, tacky and elastic.

Example 13 Fabric testing

Composition of the invention and CottonFabric (97% cotton/3%Spandex) were tested together. The control for this example was made with non-concentrated Confort supplied by Unilever^TMFabric softener washed fabrics. By using at 40 deg.CProgramming 4(program 4) of a programmable automatic washing machineAriel available from Procter and Gamble^TMEach of the compositions shown in Table 1 was used for cotton in a liquid detergent wash (standard load fabric) to achieve a load of 2.5 kg) and rinsed with 18g of a fabric softener compositionA fabric. After drum drying, the fabric surface was evaluated for any deposits. None of these three fabrics showed any powder or film deposits.

The compositions in table 1 are as follows:

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

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

(c) Fabric treated with fabric softener, 1% wt of polyurethaneurea powder from example 5 and 2% wt of Unimer (synthetic wax to improve dispersion).

Mixing compositions (b) and (c) comprising the fabric softener yields a homogeneous dispersion (no sedimentation, nor agglomeration).

Each fabric was evaluated for easy care (easy care). The durable pressing rate ("DP rate") was determined before and after ironing using the standard test method AATCCTM 124/ISO 15487. "DP Rate" is a measure of the three-dimensional smoothness of a fabric. Ironing smoothness (ironslipping) or ease of ironing (ease of ironing) is determined as the time for which an iron slips through a certain length of fabric when the angle of the ironing board is about 20 °. The results of ease of care are shown in Table 1.

The results in table 1 show that both fabrics treated with the powder or dispersion show better improvement in DP rate (1 unit increase after ironing) compared to the control (0.5 unit increase after ironing).

Furthermore, fabrics (b) and (c) treated with the composition of the present invention show that the iron slides faster on the fabric surface.

The fragrance/aroma of compositions (a), (b) and (c) were also evaluated. Allowing three people to smell each fabric individually. Everyone perceives a stronger fragrance in the fabrics (b) and (c) treated with the composition of the invention.

The absorbency (moisture management) of fabrics, including those treated with the compositions of the present invention, was also tested. The difference between the fabric treated with the powder or dispersion of the invention and the untreated fabric was confirmed after measuring these properties.

For each of the fabrics (a), (b) and (c) above, a drop (about 30 microliters) of linseed oil and water was applied to the surface of the fabric. The time until complete absorption of each droplet was determined and reported in seconds in table 2. The surface area of the droplets at 60 seconds after complete absorption by the fabric was also determined and measured in square centimeters (cm)²) Are reported in table 2 in units.

As shown in table 2, the dispersion (b) and the powder (c) of the present invention provide improved absorbency compared to the control (a). The use of (c) in powder form shows a considerable improvement.

Examples 14-100% Cotton woven Fabric (cotton woven fabric) testing

Also after treatment with the composition in some embodiments, 100% cotton woven fabrics were tested. The control for this example is a concentrated fabric softener, Softian supplied by Colgate palm olive^TMUltra. Each composition shown in Table 3 was passed at 40 ℃ toProgram for program-controlled automatic washing machine 4, Using Ariel^TMLiquid detergent washes (fabric with standard load to reach a load of 2.5 kg) and rinses with 18g of fabric softener composition for 100% cotton fabric. After drum drying (drying at moderate temperature), the fabric surface was evaluated for any deposits. None of the fabrics showed any powder or film deposits.

The compositions of table 3 are as follows:

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

(f) Fabric treated with a fabric softener and 10% by weight of the dispersion described in example 10 (a nonionic polyurethaneurea dispersion)

Mixing of the composition (f) containing the fabric softener yields a homogeneous dispersion (no sedimentation, nor agglomeration).

To test the amount of growth (growth) of the fabric, the amount of stretch or maximum stretch that can be achieved is first calculated. The amount of stretch achievable is determined by first conditioning a fabric sample and then cycling three times between 0-30N on a constant stretch rate tensile tester. The maximum amount of stretching is calculated by the following formula:

maximum elongation% ((ML-GL) x 100/GL)

Wherein: ML is the length in mm at 30N; and is

GL is a gauge length (gauge length) of 250 mm.

A single sample of each fabric was then stretched to 80% of the "available stretch" and held for about 30 min. The fabric sample was then allowed to relax for about 60min and the amount of growth was determined and calculated according to the following formula:

growth rate%

Wherein: "growth" is expressed as a percentage of the relaxed state;

l2-the length (in cm) that increases after relaxation; and is

L is the original length (in cm).

The amount of fabric growth of each of the fabrics (e) and (f) was measured. The results are shown in table 3.

The amount of web growth is a measure of shape retention. The growth value represents the amount of elongation that is not recoverable during wear. The lower amount of growth demonstrates the fabric has a better ability to recover its original shape.

This example also tested the difference in fragrance release after wash and rinse cycles for fabrics (e) and (f). One to two grams of each fabric sample was placed in a sealed gas sampling vessel. Fabric loading (fabric tensioning) was performed by rocking using a steel ball bearing. Using a gas sampling pump (running at 50cc per minute for 20 minutes), through a Tenex^TMA sampling tube for withdrawing volatile compounds released from the sample from the top of the gas sampling container. The Tenex^TMThe tubes retain the Volatile Organic Compounds (VOCs) for analysis. The Tenex^TMThe tube was then heated to release the volatile organics into the GC/MS for analysis. The VOC measurements in table 3a show that fabrics rinsed with a fabric softener containing the dispersion of example 10 (a nonionic polyurethaneurea dispersion) release more fragrance.

Example 15 Spandex/Cotton blend Fabric test

Spandex/cotton hybrid woven fabrics were also tested after treatment with some embodiments of the compositions. The control for this example was a concentrated fabric softener (Softlan supplied by Colgate palm olive)^TMUltra). Each composition shown in Table 4 was prepared by heating at 40 deg.CProgram for program-controlled automatic washing machine 4, Using Ariel^TMLiquid detergent wash (using standard load fabric to achieve a load of 2.5 kg) and rinse with 18g of fabric softener composition for cotton/spandex blend fabrics. After drum drying (drying at moderate temperature), the fabric surface was evaluated for any deposits. None of the fabrics showed any powder or film deposits.

The compositions of table 4 are as follows:

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

(h) Fabric treated with a fabric softener and the 10 wt% dispersion of example 10 (a nonionic polyurethaneurea dispersion).

Mixing of composition (h) containing the fabric softener produced a homogeneous dispersion (no sedimentation, no agglomeration). The amount of fabric growth was determined for each of fabrics (g) and (h). The results are shown in table 4.

The amount of web growth is a measure of shape retention. The growth value represents the amount of elongation that is not recoverable during wear. The lower amount of growth demonstrates the fabric has a better ability to recover its original shape.

Also after treatment with some embodiments of the compositions, two were testedSpandex/cotton blend fabrics. The control for this example is a concentrated fabric softener (Soupline supplied by ColgatePalmolive)^TMUltra). Each of the compositions shown in tables 4a and 4b was prepared by using Miele at 40 deg.C^TMStandard procedure for commercial washing, useGel detergent (available from Henkel Corporation) wash (using standard loading fabric to achieve a loading of 2.5 kg) and rinse with 30ml of fabric softener composition for cotton andspandex blend fabrics. After drum drying (drying at moderate temperature), the fabric surface was evaluated for any deposits. None of the fabrics showed any powder or film deposits. For the following fabrics, CK is a cotton with 95% cotton-5%Circular knit of spandex, and WOV is 97% cotton-3%Gray weft stretch (wet stretch) woven fabrics of spandex.

The compositions in tables 4a and 4b are as follows:

(i) fabric treated with Fabric softener only (control-CK)

(j) Fabric treated with a fabric softener and a 10 wt% (3% active ingredient) dispersion of example 10 (a nonionic polyurethaneurea dispersion) (treated-CK)

(k) Fabric treated with Fabric softener only (control-WOV)

(l) Fabric treated with a fabric softener and a 10 wt% (3% active) dispersion of example 10 (a nonionic polyurethaneurea dispersion) (treated-WOV)

Example 16 paint anti-slip

This example tests the "skid-resistance" of some embodiments of the compositions. These tests were performed according to ASTM D4518-91 (modified as described below). The paint tested (which is also a control) was a solventless, matte (matte), white vinyl acetate based paint (base paint) available from Akzo Nobel. The compositions and average particle sizes shown in the table below were added for the purpose of increasing static friction. The results produced are static coefficients of friction as calculated according to the test method and shown in table 5.

The procedure of measuring the static friction on the coated surface is carried out to determine the resistance to sliding on the coated surface (paint) by measuring said static friction. For each paint sample, a paint layer was prepared by using a paint roller (paint roller). The paint contained particles as shown in table 5. The paint was then allowed to dry for one day. Thereafter, a second layer of paint was applied and allowed to dry for one day.

A modification to ASTM D4518-91 refers to the replacement of the same weight and polished surface steel block by using a round edge aluminum block (block). The block is placed on the slope of the painted surface. During the measurement, the aluminum block was cleaned with acetone.

To obtain the same constant velocity of the inclined plane, the following procedure was performed using the INSTRON dynamometer:

absolute ramp (absolute ramp) -0 to 300% extension (extension), 480mm/min (. about.1.5 +/-0.5 °/s)

Kevlar yarn was used to avoid yarn elongation and to provide good reproducibility.

The inclination angle (a) is calculated by trigonometry based on the height (h) of the plane and the length (X) (30cm) of the plane. The coefficient of static friction was determined as follows:

static friction is tan a; and is

Static friction tan (sin)^-1h/X)

Table 5 demonstrates that the polymer compositions of some embodiments provide comparable or better slip resistance compared to a control or rubber texturizing agent. For all inventive compositions, an addition of 5% gives better results.

Example 17 paint cracking

Based on BS EN ISO 6860: 1995 to flexibility testing of paint compositions. Paint compositions were prepared as shown in table 6, which included a matte white base paint available from Akzo Nobel. Each paint was applied about 30 mils thick on a paperboard substrate. Each substrate was then folded over a conical mandrel to determine the minimum bend diameter that could be achieved without paint cracking.

As can be seen from the results in table 6, the paint containing some embodiments of the dispersion has considerable flexibility.

Example 18 elongation at break (elongation) and Young's modulus

Paint samples were mixed according to the compositions described in tables 7 and 8. The paint composition is coated on a releasable substrate to form a film. Each sample cut from these films was 1cm wide and 5cm long. Use ofThe force gauge was used to test three membranes for each composition. Initial tests were conducted to determine the elongation and force at break of each material. From this data, the constraint ratio (constraint) and the young's modulus (or elastic modulus) were calculated. The results are shown in tables 7 and 8.

As can be seen from tables 7 and 8, the inventive compositions show an improvement over the control (primer). In particular, the inventive composition has a lower young's modulus, which indicates a higher material elasticity.

Example 19 elongation

And also useA materials testing machine was used to test each of the three paint samples containing some embodiments of the dispersion to determine the maximum elongation at 4N for paints 1 and 3 and the maximum elongation at 1N for paint 2 in the third cycle. The maximum force was selected from the elongation test previously described in example 18 so that it is in the elastic region of the material (horizontal region of the stress-strain curve). This test is used to determine the difference in elongation when the same force is applied. The results are shown in table 9.

Table 9 demonstrates that the addition of the inventive polyurethaneurea dispersion improves the extensibility of all three base paints. The elongation of the base paint increases at least two-fold after addition of the inventive dispersion.

Example 20 absorption of oil and Water-time

In order to test the absorbency of the powder compositions of the present invention compared to commercially available powder compositions, several compositions were tested to determine the time required for each of absorbing a drop of linseed oil, water and artificial sweat. In each test, a drop of linseed oil, water or artificial sweat was placed on each of the inventive and commercially available powders. The time to take up the drop was recorded as shown in table 10.

As shown in table 10, the inventive powder provides faster absorption of oil and water compared to nylon and silica, and similar or improved absorption times compared to commercially available polyurethane powders.

Example 21 absorption of oil and Water-Mass

To test the absorbency of the powder compositions of the present invention compared to commercially available powder compositions, several compositions were tested in this example to determine the mass absorbed by each of linseed oil, water and artificial sweat according to test method ASTM D281-95 (modified for water and artificial sweat). The results are shown in Table 11.

As shown in table 11, the compositions of the present invention can absorb the same or more mass than the commercially available powders.

Example 22 Exfoliating composition (Exfoliating composites)

It has become increasingly common to incorporate physical exfoliants into cosmetic cleansing products. Early products relied on the abrasive effect of breaking up nut shells in standardized cosmetic bases (standard cosmetic bases) and were perceived by consumers as sandpaper. Currently, there are many exfoliating agents available in cosmetic chemicals, both from natural and synthetic sources. The particle size and grinding quality of each type can be tightly controlled so that the desired exfoliation effect can be achieved by precise formulation, and a better understanding of the rheological properties enables the manufacture of a stable, elegant product in which the exfoliating agent is uniformly distributed.

Polyethylene (PE) spheres are the most common polymer release agents. Polyethylene spheres of different size ranges are available. Commercial samples of Polyethylene (PE) spheres of the following grades are available from a & E Connock (Perfumery & Cosmetics) Ltd:

65/100 mesh size (about 150-230 μm),

35/48 mesh size (about 300-500 μm),

24/32 mesh size (about 600-700 μm),

14/16 mesh size (about 1200 and 1400 μm).

The following polyurea urethane powders were prepared having the following particle sizes for comparison with PE spheres:

polyurethaneurea powder prepared by the method of Roach: 25-200 μm

Polyurethaneurea powder of example 7: 300-800 μm

Polyurethaneurea powder of example 3: 500-1000 μm

Each powder was added at 15% (by weight) to a Shower gel (Silk Glow foaming Silk Shower supplied by Dove) and compared with an already manufactured release product (Silk Glow domiche Gommage lotriennesoie, Dove) containing oxidized polyethylene as a release agent.

The composition with the polyurethaneurea powder prepared by the Roach process does not provide any real peeling effect because the particle size of such powder is too small. By contrast, the powders of examples 3 and 7 mixed well with the shower gel and produced a shedding effect. Due to their compressibility, the polyurethaneurea powders have a softer feel and provide a milder skin peeling effect on the skin.

Example 23 film-Forming Polymer

Many film-forming polymers are used in the cosmetics industry, in particular in nail varnishes, mascara-eyeliners, facial make-up, sun protection products and hair care preparations. The chemical composition may be acrylate copolymers, polyurethane, polyvinyl pyrrolidone vinyl acetate, polyacrylic acid (carbomer). These can be used as styling polymers or as thickeners and provide transparent flexible films with varying levels of gloss, adhesion, abrasion resistance and flexibility. The polyurethaneurea aqueous dispersions of examples 5, 6 and 10 can also be used to provide these effects.

The main advantages of these compositions are improved elasticity and flexibility, soft and pleasant tactile sensation and good abrasion resistance. Two polyurethane polymer dispersions available from Noveon were tested as described below:UR 425 and UR 450, and compared to the polyurethaneurea composition.

A 20 mil thick film was cast from the commercial dispersion and the dispersion of example 6. Their elastic properties are compared, which is shown in table 12.

The dispersion of example 6, compared to the commercially available material, clearly shows very good elastic properties, since the young's modulus is much lower. This dispersion will give high formulation elasticity (formula elasticity) and will better conform to the movements of the skin.

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

Claims (2)

1. A composition of matter, said composition of matter comprising,

(a) a polyurethaneurea selected from the group consisting of powders and dispersions; the polyurethaneurea comprises the reaction product of a prepolymer and water as a chain extender;

and the prepolymer consists of the reaction product of a diol or mixture of diols with 4, 4' -methylenebis (phenylisocyanate), and

(b) a fragrance, and

wherein the composition is a cosmetic composition or a household composition.

2. The composition of claim 1, wherein said glycol is selected from the group consisting of 1, 4-butanediol-ethylene glycol copolyether glycol, and a mixture of poly 1, 4-butanediol ether glycol and ethoxylated polypropylene glycol.