JP2009523922A - Non-woven polymer compositions and methods - Google Patents

Abstract

  Includes polymer compositions such as polyurethaneureas, polyamides and polyesters. The form of the composition can vary and can be, for example, dispersions, powders, fibers and beads. The compositions are useful for use in the manufacture of various products, such as health and beauty products such as cosmetics, paints, household products such as fabric care compositions, garments / footwear and textiles / furniture. Etc. are included.

Description

This application claims the benefit of US Application No. 60 / 865,091 filed on Nov. 9, 2006, and is filed with US Application No. 60/837, filed Aug. 11, 2006. No. 60 / 759,853 filed on Jan. 18, 2006, claiming the benefits of 011 and are hereby incorporated by reference in their entirety.

  The present invention includes polymer compositions such as polyurethaneureas, polyamides and polyesters. The form of the composition can be varied, such as dispersions, powders, fibers and beads. The composition is useful in making a variety of products, such as health and beauty products such as cosmetics, paints, household products such as fabric care compositions, clothes / footwear and Includes textile / furniture.

  Polymers such as polyurethaneureas, polyamides and polyesters have historically been used in synthetic fiber production. However, such polymers have other properties that can potentially benefit other than fiber form. Accordingly, there is a need for polymer compositions and methods that highlight such additional advantages.

  One example of a suitable form for various polymers is powder. Fine powders of synthetic polymers such as polyethylene, polyamide, polyurethane and polysiloxane are used in printing, coating and cosmetic applications. Various techniques for reducing particle size (eg, solid state shear grinding, cryogenic grinding, gas spraying and high shear mixing and grinding) are known in the art and applied when trying to produce polymer powders. However, there remains a need for improved methods that are particularly suitable for use with rubber-elastic polymers such as segmented polyurethanes and polyurethaneureas, resulting in fine, uniform particles.

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

  Fabric softeners are often used in addition to detergents to provide softness and / or fluffiness to the washable fabric. Fabric softeners also smooth the feel of the fabric, reduce the degree of static garment clinging, give a pleasant scent, reduce drying time, reduce wrinkles and make ironing easier. However, the benefits of such properties generally decrease over time after washing.

  The most common active ingredient is based on long chain fatty molecules called quaternary ammonium compounds, which are cationic in nature. Thus, fabric softeners are generally introduced during fabric rinsing or drying in order to prevent undesirable reactions with detergents that may be anionic in nature.

  There is a need for a fabric care composition that can be added at the same time as a detergent to reduce fabric wash time and costs. There is also a need for a fabric care composition that increases the period of time during which the benefits of perfume sticking are provided and facilitates the ease of care associated with the fabric softener composition.

SUMMARY OF THE INVENTION In one aspect, a polyurethaneurea in the form of a powder or aqueous dispersion is provided. Such powders or dispersions exhibit fabric care properties when used alone or in combination with a detergent or fabric softener composition.

  The fabric care composition in one embodiment is in the form of a nonionic film-forming dispersion containing a polyurethaneurea polymer and water. The polymer is a reaction product of water as a prepolymer and a chain extender, wherein the prepolymer is a reaction product of glycol or a mixture of glycols and 4,4'-methylenebis (phenylisocyanate).

  In another embodiment, the dispersion is a non-ionic, non-film-forming dispersion containing water and a polyurethaneurea polymer. The polymer is a reaction product of a diamine chain extender, a water-containing chain extender, and a prepolymer, where the polymer is a glycol (polyol) or a mixture of glycols and 4,4′-methylenebis (phenyl). Isocyanate) reaction product. The polymer can then be filtered and then ground or spray dried to produce a powder.

  In a further aspect, a method is provided for prolonging the sticking of a fragrance or fragrance to a fabric or garment. This method involves contacting the fabric or garment with a perfume and a polyurethaneurea composition in the form of a powder or aqueous dispersion. The manner in which the contact occurs can vary, including, but not limited to, adding the perfume and polyurethaneurea to the detergent or fabric softener prior to performing the laundry and / or drying of the fabric. Methods, methods of adding them directly to the wash water, or methods of introducing them directly into the rinse cycle or in combination with the fabric softener composition.

  In a further aspect, a method for imparting desired properties to a fabric or garment is provided. This method involves contacting the fabric with polyurethaneurea in the form of a powder or aqueous dispersion. Desired properties that can be imparted to the fabric include, but are not limited to, shape retention, ease of care (ie ease of ironing) and antifouling properties.

  Also provided is a segmented polyurethaneurea composition in the form of a fine powder. Also included is a method of producing such polyurethaneurea powder. In addition, the powder in some embodiments is a powder that exhibits water and / or oil absorption properties.

  Other polymer compositions and forms are also provided. Such compositions are useful for use in a variety of compositions, such compositions including, inter alia, paints, cosmetics and fabric care compositions.

DETAILED DESCRIPTION OF THE INVENTION The term “powder” as used herein refers to a particulate material composed of loose agglomerates of fine solid particles. The maximum size of the fine powder is less than 1 millimeter and the average particle size is less than 100 microns. However, larger particle sizes are also contemplated. For example, the coarse powder may have a particle size of 1 millimeter or more and an average particle size in the range of about 0.5 mm to about 2 mm.

  The term “film-forming” as used herein means that the material forms a continuous film without the presence of other reactants under the synthetic conditions disclosed herein.

  As used herein, the term “non-film forming” means that the material does not form a continuous film without the presence of other reactants under the synthetic conditions disclosed herein.

  The term “fabric” as used herein means any woven, non-woven, knit, tufted, felted, blaze or bonded material assembled from fibers and / or yarns, including, but not limited to This includes, but is not used in, clothing (clothes), sheets, towels, curtains, upholstery and carpets.

  The term “fabric care composition” as used herein refers to any composition that can be added to a fabric, particularly when the fabric is being washed or dried, for the purpose of imparting beneficial properties to the fabric. Such properties include cleansing, removing oily deposits, smoothing the fabric's feel, reducing the degree of clinging of clothes with static electricity, giving a pleasant scent, shortening drying time, wrinkling Includes lessening and making ironing easier.

  The term “easy care” as used herein with respect to fabric means that the number of wrinkles in the fabric after washing may be reduced, ironing may not be required, or ironing may be easier. means.

Form of polyurethaneurea compositions of some embodiments polyurethaneurea composition aqueous dispersions, powders, may be in the form of fibers or beads. When a powder form is required, the aqueous dispersion may be isolated by filtration, drying and grinding or by subjecting the dispersion to spray drying. The solid content of such dispersions can vary. For example, the solids content of the dispersion may be from about 5 to about 50% by weight, more specifically from about 20 to about 40% by weight. The powder may have an average particle size of less than 100 microns, such as about 50 to about 80 microns, and a particle size of 1.0 mm or less, such as less than about 0.5 mm.

  Another suitable method for producing polyurethaneurea powders of some embodiments is the method according to US Pat. No. 6,475,412 to Roach (incorporated herein by reference). Roach discloses a method for producing a powder by subjecting spandex to extension under specific process conditions.

In some embodiments, the preparation of an anionic film-forming aqueous dispersion results in a prepolymer that is a capped glycol. This prepolymer is:
At least one hydroxyl-terminated polymer, such as a polyether (including copolyether) having a number average molecular weight of about 600 to about 3,500, a polycarbonate or polyester polyol component, such as a number average molecular weight of about 1,400 to about 2,400 With poly (tetramethylene ether) glycol,
A mixture of 4,4'- and 2,4'-methylenebis (phenylisocyanate) (MDI) isomers (ratio of 4,4'-MDI to 2,4'-MDI isomer is about 65:35 to about 35: 65) a polyisocyanate,
(I) a hydroxy group 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 (the at least one carboxylic acid group is At least one diol compound having no ability to react with a mixture of MDI isomers),
The reaction product of

Next, the aqueous dispersion is formed by neutralizing the prepolymer, for example, by adding triethylamine, to form a salt, and finally causing chain extension using a diamine chain extender and water. Cause it to occur. Additives such as surfactants, anti / antifoaming agents, antioxidants and thickeners may be included.

  When the MDI isomer mixture is used in an anionic dispersion, the viscosity of the prepolymer can be reduced without adding a solvent. The MDI isomer mixture also serves to slow the reaction rate. Such prepolymers can be prepared in either a batch process or a continuous process.

  If a diol containing a hydroxy group and a carboxylic acid group is included in some embodiments, it may be described as an acidic diol. Examples of useful acidic diols include 2,2-dimethylolacetic acid, 2,2-dimethylolpropionic acid (DMPA), 2,2-dimethylolbutanoic acid, 2,2-dimethylolpentanoic acid and combinations thereof. included.

  Some embodiments of the nonionic film-forming dispersion contain a prepolymer that is an isocyanate-terminated polyurethane prepolymer. This prepolymer is a hydroxyl-terminated polymer such as a polyol such as poly (tetramethylene-co-ethylene ether) glycol or a mixture of poly (tetramethylene ether) glycol and ethoxylated polypropylene glycol and a diisocyanate such as 4,4′-methylene bis. Reaction products such as (phenyl isocyanate). Next, the prepolymer is subjected to chain extension using water and then dispersed in water, or after being dispersed in water, chain extension using water is performed.

  In some embodiments, the non-ionic, non-film-forming dispersion includes a prepolymer that is an isocyanate-terminated polyurethane prepolymer. This prepolymer is also a reaction product of a polyol such as polybutadiene glycol or poly (tetramethylene ether) glycol and a diisocyanate such as 4,4'-methylenebis (phenylisocyanate). The prepolymer may be subjected to chain extension using a combination of water and a diamine chain extender such as ethylenediamine or an amine functional crosslinker such as polyvinylamine. Either hydrophilic or hydrophobic glycols may be selected to produce polymer powders with various water / oil absorption capabilities. It is also possible to adjust the particle size of the powder by adjusting the viscosity of the prepolymer using a diluent solvent.

In some embodiments, the polyurethaneurea can be dispersed by dispersing the isocyanate-terminated prepolymer in a water medium containing a dispersant and a chain extending reactant or crosslinker with or without a solvent using a high shear force. This gives a powder. A high shear force is defined as a force sufficient to bring the particles below 500 microns. The prepolymer is prepared by polyol or polyol copolymer or polyol mixture such as polyether glycol, polyester glycol, polycarbonate glycol, polybutadiene glycol or hydrogenated derivatives thereof and hydroxy-terminated polydimethylsiloxane and diisocyanate such as methylene bis (4-phenyl). Isocyanate) (MDI) or the like can be reacted to give an NCO-terminated prepolymer or “capped glycol”. The NCO / OH molar ratio in the polymer composition is in the range of 1.2 to 5.0. An example of a chain extending reactant is an aliphatic diamine, such as ethylenediamine (EDA). Chain crosslinkers are organic compounds or polymers having at least three primary amine or secondary amine functional groups that can react with NCO groups. It is also possible to dilute the prepolymer before dispersion using an organic solvent that is soluble or insoluble in water, such as 1-methyl 2-pyrrolidinone (NMP) or xylene. The resulting polyurethaneurea polymer microparticles (dispersed in water) can be used as is, or isolated by filtration and dried to a solid powder. Alternatively, it is also possible to use a spray coating method, which also has a greater degree of control over the particle size.

  The particle size imparted to some embodiments of the powder can vary depending on the desired application. For example, the average particle size may be less than 1 millimeter (mm), which also includes an average particle size of less than 100 microns (μm).

  In some embodiments, segmented polyurethaneureas suitable for producing rubber elastomer powders include: a) a polyol or polyol copolymer or polyol mixture having a number average molecular weight of 500 to 5000, including but not limited to polyethers Glycols, polyester glycols, polycarbonate glycols, polybutadiene glycols or their hydrogenated derivatives and hydroxy-terminated polydimethylsiloxanes] and b) diisocyanates [including aliphatic diisocyanates, aromatic diisocyanates and cycloaliphatic diisocyanates] and c) aliphatics A diamine (ie, a diamine chain extender) or at least one diamine [from the group consisting of aliphatic diamines and alicyclic diamines each having from 2 to 13 carbon atoms Or a segment containing an amino-terminated polymer or a mixture of organic compounds or polymers having at least three primary or secondary amine groups and optionally a mixture of primary or secondary monoamines as chain terminators Polyurethane urea.

  Examples of polyether polyols that can be used in some embodiments include ethylene oxide, propylene oxide, trimethylene oxide, tetrahydrofuran and 3-methyltetrahydrofuran ring-opening and / or copolymerization or polyhydric alcohols, For example, a diol or diol mixture having less than 12 carbon atoms in each molecule, such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neo Such as pentyl glycol, 3-methyl-1,5-pentanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol and 1,12-dodecanediol The number of hydroxy groups generated by condensation polymerization It includes more glycols. For example, linear bifunctional polyether polyols, particularly poly (tetramethylene ether) glycols having a molecular weight of about 1,700 to about 2,100, such as Terathane ™ 1800 [INVISTA S. ar. l (commercially available from Wichita, KS and Wilmington, DE)] and the like.

  Examples of polyester polyols that can be used include those having 2 or more hydroxy groups generated by condensation polymerization of aliphatic polycarboxylic acid and polyol or a mixture thereof (low molecular weight having 12 or less carbon atoms in each molecule). Ester glycol is included. 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 polyols suitable for use in producing such polyester polyols include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neo Pentyl glycol, 3-methyl-1,5-pentanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-dodecanediol and 1,12-dodecanediol . For example, a linear bifunctional polyester polyol having a melting temperature of about 5 ° C. to about 50 ° C. may be included.

Examples of polycarbonate polyols that can be used include condensation polymerization of phosgene, chloroformate esters, dialkyl carbonates or diallyl carbonates and aliphatic polyols or mixtures thereof (low molecular weight with 12 or less carbon atoms in each molecule). Carbonate glycol having 2 or more hydroxy groups is included. Examples of polyols suitable for use in producing such polycarbonate polyols are diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl. Glycol, 3-methyl-1,5-pentanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol and 1,12-dodecanediol. For example, a linear bifunctional polycarbonate polyol having a melting temperature of about 5 ° C. to about 50 ° C. may be included.

  Examples of suitable diisocyanate components are 1,6-diisocyanatohexane, 1,12-diisocyanatododecane, isophorone diisocyanate, trimethyl-hexamethylene diisocyanate, 1,5-diisocyanato-2-methylpentane, diisocyanato-cyclohexane, Methylene-bis (4-cyclohexylisocyanate), tetramethyl-xylene diisocyanate, bis (isocyanatomethyl) cyclohexane, toluene diisocyanate, methylenebis (4-phenylisocyanate), phenylene diisocyanate, xylene diisocyanate and mixtures of such diisocyanates. For example, such diisocyanates may be aromatic diisocyanates 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-propanediamine, 1,3-propanediamine, 2,2-dimethyl-1,3-propanediamine, 1,4-butanediamine. 1,5-pentanediamine, hexamethylenediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-dodecanediamine, 1,12-dodecanediamine, 2-methyl- 1,5-pentanediamine, cyclohexanediamine, cyclohexanebis (methylamine), isophoronediamine, xylylenediamine and methylenebis (cyclohexylamine). It is also possible to use a mixture of two or more diamines.

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

  Examples of suitable organic compounds or polymers having at least three primary or secondary amine groups are tris-2-aminoethylamine, poly (amidoamine) dendrimer, polyethyleneimine, poly (vinylamine) and poly (allylamine). is there.

  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 dialkyls Amines such as N, N-diethylamine, N-ethyl-N-propylamine, N, N-diisopropylamine, Nt-butyl-N-methylamine, Nt-butyl-N-benzylamine, N, N -Dicyclohexylamine, N-ethyl-N-isopropylamine, Nt-butyl-N-isopropylamine, N-isopropyl-N-cyclohexylamine, N-ethyl-N-cyclohexylamine, N, N-diethanolamine and 2, 2,6,6-tetramethylpiperidine and the like are included.

When trying to produce a polyurethaneurea powder of some embodiments, an NCO-terminated prepolymer or “capped glycol” is first formed by reacting glycol and diisocyanate, optionally in the presence of a catalyst. This reaction is typically carried out in the molten form of a homogeneously mixed mixture, and heat at a temperature of 45 to 98 ° C. is applied for 1 to 6 hours. The amount of each reaction component, the weight of glycol (Wgl) and the weight of diisocyanate (Wdi) are capping groups (CR) [below:
CR = (Wdi / MWdi) / (Wgl / MWgl)
As defined by the molar ratio of diisocyanate to glycol]. Where MWdi is the molecular weight of the diisocyanate and MWgl is the number average molecular weight of the glycol. According to the invention, the capping ratio is in the range of 1.2 to 5.0, in particular 1.5 to 3.0.

  When all the hydroxy (—OH) groups derived from the glycol molecule are consumed by the isocyanate (—NCO) groups derived from the diisocyanate to form a urethane bond, and the capping reaction is completed, the viscous terminal NCO group-containing polyurethane prepolymer Occurs. The prepolymer is then added and dispersed in an aqueous solution containing surface active reactants such as dispersants and anti / foaming agents and optionally chain extenders such as diamines. Alternatively, the prepolymer can be diluted with an organic solvent such as water-soluble N-methylpyrrolidone (NMP) or xylene insoluble in water and then dispersed in an aqueous medium. Solid polymer particles are formed when a high shear force is applied during the dispersion and chain extension occurs with water and / or a diamine extender. Next, the polyurethaneurea particles may be filtered and then dried.

  Additives such as antioxidants, pigments, colorants, fragrances, antibacterial agents (such as silver), active materials (humectants, UV screening agents), surfactants before, during or after dispersion of the prepolymer Anti-foaming agents, solvents, etc. may be mixed into the polyurethaneurea particles. In some cases, it may be beneficial to add the additive while dispersing the prepolymer so that the additive is encapsulated in the polyurethaneurea particles. As such, when the additive is encapsulated, the rate at which the additive diffuses out of the polymer matrix may be reduced, resulting in a delayed or sustained release of the additive. Such a slow release rate is in comparison with the relatively early release of the additive adsorbed on the particle surface. By including a combination of additive encapsulation and surface adsorption, one or more additives can be rapidly released from the surface of the particles and the encapsulated additive can be released slowly.

It is also possible to add pigments to the polyurethaneurea compositions of some embodiments. The addition of pigment can be carried out in the same manner as the addition of other additives. Examples of pigments include carbon black and TiO _2. The effect of the pigment in the case of polyurethaneurea powder is shown in Table A below:

  Additional examples of pigments are described herein below.

Polyurethane Urea Beads Some embodiments of the present invention are polyurea urethane beads. One effective method for producing such beads is disclosed in FIG. Et al., US Pat. No. 5,094,914 (“FIGURE”), which is hereby incorporated by reference in its entirety. ing. Segmented polyureaurethane compositions can be prepared, which can be any of those described herein (eg, those based on polyethers or polyesters). A solvent can be used to produce a solution containing the polyureaurethane. Various useful solvents, such as amide solvents, may be included, including but not limited to dimethylacetamide (DMAc), dimethylformamide (DMF) and N-methylpyrrolidone (NMP). Next, the polymer may be solidified in a bead form by introducing the polyureaurethane solution into the coagulation bath as droplets. In the coagulation bath, a solvent that is extracted from the polymer solution but is not a solvent for the polymer, such as water, may be added.

  In this way, a bead can be produced which has a diameter of about 1 mm to about 4 mm, a void content of 60% to 90% and no pores visible on the surface at a magnification of 5000x.

  Some embodiments of the present invention are polyureaurethane beads that have a wider particle size, void content and surface pore range than previously disclosed polyureaurethane beads.

The void content is a content based on the density of the bead:
Void = [1− (bead density / bulk polymer density)] × 100%
In some embodiments, the polyurea urethane bead has a void content of less than 60%. Such a bead can be prepared by using a higher viscosity solution. For example, when a solution having a B-type viscosity of about 1000 cps or more and a solid content of about 12% or more is used, it is denser than a bead produced by using the same bead manufacturing apparatus except that a solution of less than 1000 cps is used. A bead that is heavy and small. In some embodiments, the bead is a bead generated from a solution having a high viscosity (> 1000 cps) but a relatively low solids content (ie, <10%). This can be achieved by using polymers that have a high average molecular weight or are branched, or by using polymers that associate together in solution by crystallization, hydrogen bonding, hard segment association, and the like. For example, polyurethaneurea based solutions will become more viscous as they age.

  The preparation of a low viscosity solution with a relatively high solids content uses a polymer whose viscosity decreases upon shearing, such as a liquid crystal polymer or some spandex formulations, or has a low average molecular weight or is in solution. This can be done by using a polymer that does not cause association, hydrogen bonding or crystallization.

  Another way to produce a smaller, denser bead is to use a solution that results in a porosity of 60-90% but leaves some of the solvent with the bead during the solidification and drying process to remove the solvent. It is a method of generating. The bead is then dried so that the remaining solvent is redissolved and the polymer reprecipitates to a denser structure.

It is also possible to produce beads with a void content greater than 90%. One method is to include a low viscosity polymer. However, since the viscosity is continuously lower within the same polymer formulation, a point is reached where the polymer is too diluted to maintain its bead shape during the coagulation process and to collapse (this process). Is disclosed in US Pat. No. 5,126,181 for the purpose of producing flat microporous disks). On the other hand, it is also possible to select or formulate a polymer exhibiting a substantially higher stiffness, in particular polyurethaneurea, so as to have sufficient stiffness to retain the bead shape without further disintegration even when further diluted. In particular, it is possible to synthesize or select formulations that exhibit the inherently desirable high rubber elasticity (elongation and recovery) even though they are highly rigid within the polyurethaneurea family. For example, a polyurethane urea using a polyether glycol having a low average molecular weight, such as a polyether glycol having an average molecular weight of less than 1000 or less than 700, as a soft segment is a bead that maintains a spherical shape even when the void content is greater than 90%. It will be enough to bring

  In addition, other reactants or co-reactants can be used to change the stiffness of the final polyurea urethane bead, such as different extenders other than EDA (ethylenediamine) or EDA and co-extenders, Alternatively, it is also possible to use isomers of MDI (4,4'-to 2,4-) and mixtures thereof. Also, using 1,4-phenylene diisocyanate or 1,4-phenylenediamine, or combinations or mixtures thereof, a stiffness higher than that exhibited by the corresponding polyureaurethane based on “traditional” MDI and EDA Will result in a polyureaurethane exhibiting It will also be appreciated that mixtures of polyureaurethanes with different stiffnesses can be used to meet the stiffness required to achieve a void volume greater than 90%, or to meet its order. It is also possible to mix other polymers or additives into the solution in order to achieve the rigidity and other requirements necessary to produce higher void volume beads.

  In some embodiments, the bead is a bead with a controlled surface pore size. Micron or nano sized salts or other water soluble materials (eg, polyethylene glycol) may be combined with the polyureaurethane solution prior to introduction into the coagulation bath. With such water soluble materials, the beads will remain when the beads are solidified and washed in water.

  Also provided is a method for producing a bead continuously or semi-continuously. In a process using a batch stirred reactor, the solvent can accumulate in water or be non-solvent for the polymer. The beads that result when the solvent accumulates excessively become sticky so that they stick together or even coalesce. The accumulation of solvent in a non-solvent (or water) can also slow the bead solidification rate because the solvent is "pulled" from the non-solvent or there is not enough thermodynamic incentive to diffuse into it. There is also sex. The concentration of such non-solvents is increasing and becomes nearly the same as the solvent diffuses out of the bead or disk.

  Some embodiments of semi-continuous processes can also produce about 500 grams of beads per 8 hour shift, which is 10 times higher than the production rate of the process using a batch stirred reactor. . The time to “harvest” the beads can be any time about 2-3 minutes after they have occurred and transferred to a container other than the one that produced them, so that within the “process equipment” The bead can be produced continuously with an 8 hour shift of at least 3 shifts.

  In another embodiment, the beads can be produced continuously by continuously draining the water in the “process equipment” and harvesting the beads periodically or continuously. Continuous or semi-continuous operation may be industrially preferred over batch operation.

  This can be accomplished in a variety of ways if the bead is harvested from where it occurs or is transferred to a different tank to be dipped and the remaining DMAc solvent is to be extracted. One method involves the use of a conveyor device with a conveyor belt. The belt may be a screen or a belt that allows water to pass but includes holes to hold the beads. Another way to remove the bead from the process equipment is to use a “waterfall”. With such a waterfall method, some water and a significant number of beads are drained over the edge of the production tank and into another tank so that the bead is far away from where it occurred. It is possible to collect at one end of the. Since the bead floats in the water / solvent mixture, it is easily achievable.

  Some embodiments of polyurethaneurea beads have a wide range of applications. This includes use in textiles, clothes and shoes, household furniture, cosmetics and other household applications. As bedding materials, they may be placed in eg pillows as an alternative to fiber fillers. In the case of shoes, beads may be placed as a sole cushion. In addition, it is possible to adapt various pressure points in the sole by putting combinations of beads of various sizes not only in the same sole but also in the insole, outside and upper part of the shoe. In some cases, the bead is included as a “sandwich” structure in a pleated or quilted structure. Such cushioning effects are also useful for furniture cushions and carpet stuffing. For example, the bead may be placed in a fibrous stuffing material. The cushioning effect is also beneficial for headgear such as helmets or hats, clothing straps, bag straps and comfortable grip applications such as grip applications found in clubs, ski poles, hammers, bicycles, lawn mowers, handles, etc. .

  The bead has a number of beneficial properties. For example, after the bead has been compressed to ¼ of its original diameter over 24 hours, it immediately regains 85% of the volume and regains about 97% of the volume after 10 minutes. The size of the bead can vary. The bead diameter may be from 0.1 mm to 10 mm, for example from about 0.05 mm to about 8 mm. Individual beads with diameters of 0.5 mm, 0.8 mm, 1.0 mm, 2.5 mm, 3.0 mm, 4.0 mm, 5.0 mm and 8.0 mm were produced.

  The density of the individual beads may be in any suitable range, such as from about 0.05 g / cc to about 0.5 g / cc (including about 0.1 g / cc). The beads also have unique absorption characteristics. For example, if a bead with a diameter of about 3 mm is placed in water, it will absorb about 14% of its weight in water. However, if the bead is compressed and placed in water, the bead will absorb up to about 350% of its weight in water. Such absorption properties prove to be useful as additional vehicles, such as delivery vehicles for substances such as perfumes, ointments and other flowable compositions.

Polyamide compositions In some embodiments, a wide variety of polyamides can be used. Examples of suitable polyamides include nylon 6, nylon 12 and nylon 6,6. Such polyamides may be present in any desired form, such forms include fibers and powders. One suitable method of making polyamide powder is disclosed in US Pat. No. 4,831,061 to Hilaire, which is hereby incorporated by reference. Such powders can also be obtained commercially from ARKEMA under the trade name Orgasol ™. Commercially available powder sizes range from about 5 microns to about 20 microns. Polyamide powders can also be supplied in a wider range of sizes, such as powders having an average particle size in the range of about 50100 microns to about 500 microns (including 100 microns). Also included are coarser powders, such as those having an average particle size in the range of about 0.5 mm to about 5 mm (including about 1 mm).

Polyester compositions In some embodiments, it is also useful to include a wide variety of polyesters. Examples include polyalkylene terephthalate, polyalkylene naphthalate and polyalkylene isophthalate. Examples of polyalkylene terephthalates are fiber-forming linear condensation polymers having carboxyl linking groups in the polymer chain, such as polyethylene terephthalate ("2GT" or "PET"), polytrimethylene terephthalate ("3GT" or "PTT"). )) And polytetramethylene terephthalate ("4GT").

  The form of such a polyester composition may be any form desired, such forms including fibers, flocks and powders.

  Unless indicated to the contrary, reference to “polyalkylene terephthalate” is meant to include copolyesters, ie, polyesters formed using three or more reactants each having two ester-forming groups. For example, copoly (ethylene terephthalate) may be used, and the comonomers used for the production of the copolyester may be linear, cyclic and branched aliphatic dicarboxylic acids having 4 to 12 carbon atoms (for example, butanedioic acid, Pentanedioic acid, hexanedioic acid, dodecanedioic acid and 1,4-cyclo-hexanedicarboxylic acid), aromatic dicarboxylic acids having 8 to 12 carbon atoms (other than terephthalic acid) (eg isophthalic acid and 2,6-naphthalene) Dicarboxylic acids), linear, cyclic and branched aliphatic alcohols having 3 to 8 carbon atoms (eg 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 3-methyl- 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol, 2-methyl-1,3-propanediol and 1 4-cyclohexanediol), and aliphatic and aromatic ether glycols having 4 to 10 carbon atoms [eg, hydroquinone bis (2-hydroxyethyl) ether or poly (ethylene ether) glycol (diethylene ether) having a molecular weight of less than about 460 daltons Selected from the group consisting of: The amount of such comonomer present in the copolyester may typically be at a concentration in the range of about 0.5 to about 15 mole percent.

Floe The polymer composition in some embodiments is in the form of floc. Flock is a very short, precisely cut or crushed fiber used to create a velvet-like coating on fabric, rubber, film or paper. Flock can be used as a filler in plastics, paper, rubber or similar compositions to increase the impact strength of the final product, improve moldability, or add a decorative appearance. The flocs can be fibers generally ranging in length from about 0.040 inch to about 0.250 inch (1 mm to 6.25 mm). This diameter is generally in the range of about 10 to about 100 microns. Various colors of floc can be generated from a wide variety of synthetic and natural fibers such as polyamide, polyester, cotton and rayon.

Staining information diverse dyes, can be added to color the compositions of some embodiments with reference to colorants and pigments. For example, specific dyes are most useful when trying to add color to the polyamide and polyester compositions, while pigments may be added to the polyureaurethane composition.

Colorants used in some embodiments (including cosmetic compositions) are inter alia inorganic and organic colorants, which include synthetic and natural colorants. TiO 2 The inorganic colorants _include iron oxide and ultramarine. Synthetic organic colorants include lakes, toners and pigments such as those described in US Pat. No. 4,909,853, incorporated herein by reference. An example of a natural organic colorant is carmine.

One suitable method for producing a colored nylon powder involves heating and dyeing a dye beaker on a hot plate using a magnetic stir bar. Thereby, it is ensured that the powder is sufficiently stirred with a stir bar so that the powder does not clump and that the dye is evenly absorbed throughout the batch:
Set the pH of the dye bath to 6.0 with phosphate buffer,
1% (based on weight) of Levegal SER (anionic leveling agent) is added,
Add the pre-dissolved dye,
Add nylon powder,
Boil at an ascending rate of 2 ° C / min, hold the temperature for 30 minutes,
1 g / l of Sandacid GBV (acid donor-acid is slowly released into the dye bath to lower the pH to pH 5.0-5.5),
Hold the temperature for 30 minutes,
Cool,
Pour and rinse the dyebath and powder through a fine filter,
The powder is collected and dried in a heating cabinet.

  The dyes most commonly used in the case of nylon in any form (including fibers, flocks and powders) are acid free dyes and metal containing acid dyes. Both of them give a good shade range and a specific degree of color fastness to both washing and UV light. Although metal-containing dyes provide the highest fastness to ultraviolet light and laundry, the range of shades is limited to more subdued shades. Shining shades are achieved only with acid-free dyes that do not contain metals (these do not perform very well under UV light and under washing), or the limited range of specials available Only in the presence of any reactive acid dyes, they perform best for laundry, but fastness to ultraviolet light is similar to that exhibited by acid-free dyes. Such reactive dyes tend to be more expensive and the shade depth is limited depending on the effective amine end of the nylon powder / floc.

  In the case of polyesters in any form (including fibers, flocs and powders), the only dyes that have the ability to dye standard dispersible and dyeable polyesters are the only dispersible dyes. However, if a cationic dyeable polyester is available, either basic (cationic) or disperse dyes can be used.

All such types of dyes are available from major suppliers such as Huntsman (formerly Ciba).
Textile Effects) and DyStar. See the table below with suppliers and classes for a list of commercially available dyes.

There are a range of perfumes that adhere well or are well retained to perfume spandex (ie segmented polyureaurethane). Such materials are not limited to these
Includes the following two types, namely type A and type B as shown below.

Type A
Octanol / logarithm water partition coefficient (P) _{(log 10} P) is 2.5 or more gas chromatographic Kovats index (measured using polydimethylsiloxane as non-polar stationary phase) of at least 1050 hydroxyl material (these alcohols, Phenol or salicylic acid ester).

  The octanol-water partition coefficient (or its common logarithm “logP”) is well known in the literature as an index of hydrophobicity and water solubility [Hansch and Leo, Chemical Reviews, 71, 526-616, (1971); Hansch, Quinlan and Lawrence, J.A. Organic Chemistry, 33, 347-350 (1968)]. If such values are not available in the literature, they can be measured directly or estimated approximately using mathematical algorithms. Software that provides such estimates is commercially available, for example, Advanced Chemistry Design Inc. Available as "LogP".

A material with a log ₁₀ P of 2.5 or higher is somewhat hydrophobic.

The Kovats index is calculated from the residence time in the gas chromatographic measurement based on the residence time exhibited by the alkane [Kovats, Helv. Chim. Acta 41, 1915 (1958)]. In the perfume industry, indices based on the use of nonpolar stationary phases have been used for several years as descriptors related to the molecular size and boiling point of materials. A review of the Kovats index in the perfumery industry is T Shibamoto, “Capillary
Gas Chromatography in Essential Oil Analysis, P Sandra and C Bicchi (Editor), Huething (1987), pages 259-274. A suitable general non-polar phase is 100% dimethylpolysiloxane, which includes, for example, various trademarks such as RP-1 (Hewlett-Packard), CP Sil 5 CB (Chrompack), OV-1 (Ohio Valley) and Supplied under Rtx-1 (Restek).

  Materials with low Kovats index tend to be volatile and are not well retained by various dyes.

  Type A includes the general formula ROH [wherein the hydroxyl group can be primary, secondary or tertiary, and the R group is an alkyl or alkenyl group (optionally branched or substituted, cyclic or acyclic, The partition coefficient and Kovats characteristics exhibited by ROH are as defined above. Alcohols with a Kovats index of 1050 to 1600 are typically monofunctional or arylalkyl alcohols with a molecular weight in the range of 150 to 230.

Type A also includes the general formula ArOH {wherein the Ar group is a benzene ring [which is one or more alkyl or alkenyl groups or an ester group —CO ₂ A where A is a hydrocarbon group. And a phenol represented by the above-mentioned formula] is included, and the compound when substituted with an ester group is a salicylic acid ester. The partition coefficient and Kovats index exhibited by ArOH are as defined above. Phenols with a Kovats index of 1050 to 1600 are typically monohydric phenols with a molecular weight in the range of 150 to 210.

  Examples of fragrances falling into type A are 1- (2′-t-butylcyclohexyloxy) -butan-2-ol, 3-methyl-5- (2 ′, 2 ′, 3′-trimethylcyclopent-3- Enyl) -pentan-2-ol, 4-methyl-3-decen-5-ol, amyl salicylate, 2-ethyl-4 (2 ′, 2 ′, 3-trimethylcyclopent-3′-enyl) but-2 Enol, borneol, carvacrol, citronellol, 9-decenol, dihydroeugenol, dihydrolinalol, dihydromyrcenol, dihydroterpineol, eugenol, geraniol, hydroxycitronellal, isoamyl salicylate, isobutyl salicylate, isoeugenol, linalool, menthol , Nerolidol, nerol, para-t-butylcyclohexane Sanol, phenoxanol, terpineol, tetrahydrogeraniol, tetrahydrolinalol, tetrahydromyrsenol, thymol, 2-methoxy-4-methylphenol, (4-isopropylcyclohexyl) -methanol, benzyl salicylate, cyclohexyl salicylate, hexyl salicylate, patchoulialcohol And farnesol.

Type B:
Esters, ethers, nitriles, and ketones having a common logarithm (log ₁₀ P) of octanol / water partition coefficient (P) of 2.5 or more and a gas chromatograph Kovats index (measured using polydimethylsiloxane as a nonpolar stationary phase) of at least 1300 Or an aldehyde.

The perfume of type B has the general formula RX [wherein X may be present in the first, second or third position and this is the group: —CO ₂ A, —COA, —OA, — It is one of CN or -CHO]. The groups R and A are hydrocarbon residues, which can be cyclic or acyclic and optionally substituted. Type B materials with a Kovats index of 1600 or less are typically monofunctional compounds with a molecular weight in the range of 160 to 230.

  Examples of perfumes that fall into type B are 1-methyl-4- (4-methyl-3-pentenyl) -3-cyclohexene-1-carbaldehyde, 1- (5 ′, 5′-dimethylcyclohexenyl) -pentene- 1-one, 2-heptylcyclopentanone, 2-methyl-3- (4′-t-butylphenyl) propanal, 2-methylundecanal, 2-undecenal, 2,2-dimethyl-3- (4 ′ -Ethylphenyl) -propanal, 3- (4'-isopropylphenyl) -2-methylpropanal, 4-methyl-4-phenylpent-2-yl acetate, allyl cyclohexyl propionate, allyl cyclohexyl oxyacetate, benzoic acid Amyl, trimer of methyl ethyl ketone, benzophenone, 3- (4'-t-butylphenyl) -propanal, caryophy Cis-jasmon, citral diethyl acetal, citronellal diethyl acetal, citronellyl acetate, phenyl ethyl butyl ether, alpha-damascon, beta-damascon, delta-damascon, gamma-decalactone, dihydroisojasmonate, dihydrojasmonate, dihydroacetate Terpinyl, dimethyl anthranilate, diphenyl oxide, diphenylmethane, dodecanal, dodecen-2-al, dodecanenitrile, 1-ethoxy-1-phenoxyethane, 3- (1′-ethoxyethoxy) -3,7-dimethylocta- 1,6-diene, 4- (4′-methylpent-3′-enyl) -cyclohex-3-enal, ethyl tricyclo [5.2.1.0-2,6-] decane-2-carboxylate, 1 -(7- Sopropyl-5-methylbicyclo [2.2.2] oct-5-en-2-yl) -1-ethanone, allyltricyclodecenyl ether, tricyclodecenyl propionate, gamma-undecalactone, N -Methyl-N-phenyl-2-methylbutanamide, tricyclodecenyl isobutyrate, geranyl acetate, hexyl benzoate, ionone alpha, ionone beta, isobutyl cinnamate, isobutylquinoline, isoeugenyl acetate, 2,2,7, 7-tetramethyltricycloundecan-5-one, tricyclodecenyl acetate, 2-hexylcyclopentanone, 4-acetoxy-3-pentyltetrahydropyran, ethyl 2-hexylacetoacetate, 8-isopropyl-6-methyl Bicyclo [2.2.2] oct-5-ene-2-carbaldehyde, 4 -Methyl isopropyl-1-methylbicyclo [2.2.2] oct-5-ene-2-carboxylate, methyl cinnamate, alpha isomethyl ionone, methyl naphthyl ketone, neroline, nonalactone gamma, nopylacetate, acetic acid Para-t-butylcyclohexyl, 4-isopropyl-1-methyl-2- [1′-propenyl] -benzene, phenoxyethyl isobutyrate, phenylethyl isoamyl ether, phenylethyl isobutyrate, tricyclodecenyl pivalate, pivalic acid Phenylethyl, phenylacetaldehyde hexylene glycol acetal, 2,4-dimethyl-4-phenyltetrahydrofuran, roseacetone, terpinyl acetate, 4-isopropyl-1-methyl-2- [1′-propenyl] -benzene, Yara, formic acid ( 4-Isopropyl Hexadienyl) ethyl, amyl cinnamate, amyl cinnamamic aldehyde, amyl cinnamic aldehyde dimethyl acetal, cinnamyl cinnamate, 1,2,3,5,6,7,8,8a-octathyro-1,2,8,8- Tetramethyl-2-acetylnaphthalene, cyclo-1,13-ethylenedioxytridecane-1,13-dione, cyclopentadecanolide, hexylcinnamic aldehyde, 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-tetramethylindane and 1 1,2,4,4,7-hexamethyl-6-acetyl-1,2,3,4-tetrahydronaphthalene.

  While this is an extensive list of fragrances and fragrances that work particularly well with spandex compositions, it will be appreciated that in various embodiments, a variety of other fragrances are also useful. Perfumes may include substances or mixtures of substances, including fragrant natural (ie extracted from flowers, herbs, leaves, roots, barks, trees, flowers or plants), artificial (ie various Natural oils or mixtures of oil components) and synthetic (ie synthetically produced) materials.

  Non-limiting examples of fragrances include: hexyl cinnamic aldehyde, amyl cinnamic aldehyde, amyl salicylate, hexyl salicylate, terpineol, 3,7-dimethyl-cis-2,6-octadien-1-ol, 2, 6-dimethyl-2-octanol, 2,6-dimethyl-7-octen-2-ol, 3,7-dimethyl-3-octanol, 3,7-dimethyl-trans-2,6-octadien-1-ol, 3,7-dimethyl-6-octen-1-ol, 3,7-dimethyl-1-octanol, 2-methyl-3- (para-t-butylphenyl) -propionaldehyde, 4- (4-hydroxy-4 -Methylpentyl) -3-cyclohexene-1-carboxaldehyde, tricyclodecenyl propionate, trisyl acetate Lodecenyl, anisaldehyde, 2-methyl-2- (para-iso-propylphenyl) -propionaldehyde, ethyl-3-methyl-3-phenyl glycidate, 4- (para-hydroxyphenyl) -butan-2-one, 1- (2,6,6-trimethyl-2-cyclohexen-1-yl) -2-buten-1-one, para-methoxyacetophenone, para-methoxy-alpha-phenylpropene, methyl-2-n-hexyl- 3-oxo-cyclopentanecarboxylate, undecalactone gamma, orange oil, lemon oil, grapefruit oil, bergamot oil, clove oil, dodecalactone gamma, methyl acetate 2- (2-pentyl-3-oxo-cyclopentyl), Beta-naphthol methyl ether, methyl-beta-naphthylke , Coumarin, decylaldehyde, benzaldehyde, 4-t-butylcyclohexyl acetate, alpha, alpha-dimethylphenethyl acetate, methylphenylcarbyl acetate, cyclic ethyl glycol diester of tridecanedioic acid, 3,7-dimethyl-2,6 Octadiene-1-nitrile, ionone gamma methyl, ionone alpha, ionone beta, petitgrene oil, methyl cedrilone, 7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1 , 6,7-tetramethyl-naphthalene, ionone methyl, 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-dimethylindane 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-undecen-1-al, iso-hexenylcyclohexylcarboxaldehyde, formyltricyclodecane, cyclopentadecanolide, 16-hydroxy-9-hexadecenoic acid lactone, 1,3 4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-gamma-2-benzopyran, ambroxan, dodecahydro-3a, 6,6,9a-tetramethylnaphtho [2,1b] furan, cedrol, 5- (2,2,3-trimethylcyclopent-3-enyl) -3- Tylpentan-2-ol, 2-ethyl-4- (2,2,3-trimethyl-3-cyclopenten-1-yl) -2-buten-1-ol, caryophyllene alcohol, cedolyl acetate, para-t-butyl acetate Cyclohexyl, Patchouli, Oliveranum Resinoid, Labdanum, Vetiverto, Copaiba Balsam, Balsam Fir, Hydroxycitronellal and Indole, Phenylacetaldehyde and Indole, Geraniol, Geranyl Acetate, Linalol, Linalyl Acetate, Tetrahydrolinalol, Citronellol, Citronellyl Acetate, Dihydromyrsenol , Dihydromyrcenyl acetate, tetrahydromyrcenol, terpinyl acetate, nopol, nopyru acetate, 2-phenylethanol, 2-phenylethyl acetate, benzyl alcohol, vinegar Benzyl, benzyl salicylate, benzyl benzoate, styrylyl acetate, dimethylbenzyl carbinol, trichloromethylphenylcarbvinylmethylphenylcarbinyl acetate, isononyl acetate, vetiberyl acetate, tiviberol, 2-methyl-3- (pt-butylphenyl) -Propanal, 2-methyl-3- (p-isopropylphenyl) -propanal, 3- (pt-butylphenyl) -propanal, 4- (4-methyl-3-pentenyl) -3-cyclohexenecarbo Aldehyde, 4-acetoxy-3-pentyltetrahydropyran, methyl dihydrojasmonate, 2-n-heptylcyclopentanone, 3-methyl-2-pentyl-cyclopentanone, n-decanal, n-dodecanal, 9-decenol- 1. Isobutyric acid phenoxy Ethyl, phenylacetaldehyde dimethyl acetal, phenylacetaldehyde diethyl acetal, geranonitrile, citronellonitrile, cedryl acetal, 3-isocamphylcyclohexanol, cedryl methyl ether, isolongifolanone, aubepine nitrile, aubepine, heliotropin, Eugenol, vanillin, diphenyl oxide, hydroxycitronellal ionone, methylionone, isomethylionone, lon, cis-3-hexenol and esters thereof, indane fragrance, tetralin fragrance, isochroman fragrance, macrocyclic ketone, macro Lactone fragrance, ethylene brush rate and combinations thereof.

Fabric Care Composition The polyurethaneurea composition prepared by the method described above gives surprisingly improved shape retention properties to the fabric. In addition, they also provide the fabric with ease of care or easy care characteristics. In other words, treating the fabric with the polyurethaneurea composition results in fewer wrinkles after washing and easier ironing.

  The polyurethaneurea composition of some embodiments also exhibits surprisingly good water and oil absorption, especially when it is added to the fabric. This is particularly important for antifouling properties. When the fabric is contacted with a polyurethaneurea composition of some embodiments, the polyurethaneurea absorbs moisture and oil from sources that cause soiling, thereby limiting the extent to which the fabric itself absorbs it.

  Because the polyurethaneurea composition has absorbent properties, keeping the fabric in contact with the composition also helps prolong the period of time that the perfume remains adhered to the fabric. This is due to the polyurethaneurea composition absorbing the perfume and then gradually releasing it.

  In some embodiments, the fabric care composition may contain a fabric softener or detergent, to which the polyurethaneurea composition may be added. The form of the polyurethaneurea composition may be any form, for example, a dispersion or a powder.

  Alternatively, the polyurethaneurea composition can be added to the fabric, to the washing machine, to the wash water (in the case of hand washing) or directly to the automatic dryer.

  In addition, the present powder or dispersion can be used in place of the fabric softener for the purpose of imparting antifouling properties to the clothes when they are washed at home. Fabric softeners are often used for the purpose of delivering fragrances or fragrances to the fabric and secondarily imparting softness to the fabric. When using tumble drying, the fabric softening surface is not necessarily required because the tumble dried fabric is already very soft.

  Some embodiments of detergent compositions generally contain anionic, nonionic, amphoteric surfactants or mixtures thereof and often additionally contain organic or inorganic materials.

  Fabric softeners generally contain active ingredients such as quaternary ammonium salts. Examples of acyclic quaternary ammonium salts include trimethylammonium chloride, ditallow dimethylammonium chloride, ditallow tallow dimethylammonium sulfate, dihexadecyldimethylammonium chloride, di (hydrogenated tallow) dimethylammonium chloride, didichloride chloride Octadecyldimethylammonium chloride, dieicosyldimethylammonium chloride, didocosyldimethylammonium chloride, dimethylammonium sulfate (hydrogenated tallow) dimethylammonium chloride, dihexadecyldiethylammonium chloride, dihexadecyldimethylammonium acetate, ditallow tallow dipropylammonium phosphate, Di tallow dimethylammonium nitrate and di (coconut-alkyl) dimethylammonium chloride are included.

  Other optional ingredients included in the fabric care composition of some embodiments are virtually conventional ingredients and are generally present in an amount of about 0.1 to about 10% by weight of the composition. Such optional ingredients include, but are not limited to, colorants, fragrances, bacteria inhibitors, optical brighteners, opacifiers, viscosity modifiers, solid form fabric modifiers such as clays, fabrics Absorption enhancers, emulsifiers, stabilizers, shrinkage control agents, spotting agents, bactericides, bactericides, fungicides, anticorrosives and the like are included.

  The preparation of the fabric care composition of some embodiments can be carried out in a conventional manner. Uniformity is not always necessary. The usual satisfactory method is to form a premix produced by placing the softener in about 150 ° F. water and then adding it to the hot aqueous solution containing the other ingredients. Temperature sensitive ingredients may be added after the fabric conditioning composition has cooled to about room temperature.

  Some embodiments of the fabric care composition can be used by adding it to a rinsing cycle of a normal laundry operation performed at home. Alternatively, the fabric care composition can be added to the detergent prior to the wash cycle as part of the detergent or fabric softening composition, added directly to the fabric, at the time of hand washing, or wash water It may be added directly to.

  The fabric care composition can be used in any form known in the art, such as a powder, liquid, solid tablet, encapsulated liquid (eg, a composition encapsulated in polyvinyl alcohol) or an automatic drying device. It can be used as a non-woven sheet or the like when used in.

  The amount of fabric care composition added in some embodiments may be any amount necessary to achieve the desired properties of the fabric. For example, the fabric care composition may be added in an amount of about 0.05 to about 1.5%, such as about 0.2 to about 1% by weight of a water rinsing bath or wash water.

  When the polyurethaneurea composition of some embodiments is present as an aqueous dispersion, it is added to the fabric care composition from about 0.1 to about 20%, such as from about 5 to about 15% by weight of the fabric care composition. May be present in an amount of. When the polyurethaneurea composition is present as a powder, it is added to the fabric care composition from about 0.1 to about 20% by weight of the fabric care composition, such as from about 0.5 to about 10% or from about 1%. It may be present in an amount of about 5% by weight.

  Alternatively, the polyurethaneurea powder or dispersion can be added as an alternative to the fabric care composition rather than as a component of the fabric care composition, in which case the polyurethaneurea composition May be added as 100%. In this case, the polyurethaneurea composition is added directly to the wash water or rinse water in an amount of about 0.05 to about 1.5% by weight, especially about 0.2 to about 1% by weight of rinse water or wash water. May be.

Cosmetic compositions nylon (polyamide) and polyurethaneurea powders have many useful properties for inclusion in cosmetic compositions. Such properties are especially properties that absorb oil, water and sweat. Such properties are particularly useful in applications such as applications where a deodorant or antiperspirant is in contact with the skin to absorb sweat. Such properties are also useful for sebum control for skin contact products, skin care and cosmetic cosmetics.

  The polymer powder in one embodiment is a powder having antibacterial activity that reduces bacterial growth and malodor. This powder can improve odor control when accompanied by the addition of odor absorbers such as zinc oxide.

  Some embodiments of the powder exhibit surprisingly good water and oil absorption. In one embodiment, the method described above is used to provide a specific particle size suitable for use as a water or sweat absorbent in a deodorant and antiperspirant composition or as an oil (sebum) absorbent in a skin care or makeup composition. Resulting in a polyurethaneurea powder having. Additional embodiments include powders with antibacterial additives that improve odor protection, powders with perfumes that are fragrant additives, and cosmetic and body care end use powders. Non-limiting examples of cosmetic compositions to which some embodiments of powders, beads, fibers and dispersions are added include deodorants such as sprays, sticks or roll-on antiperspirants, makeup and color cosmetics such as powders [brush / bronzer ( bronzers / highlighters], foundations, eye shadows, eyeliners, mascara, lipstick / lip gloss and nail polish, skin moisturizers such as body and facial moisturizers, shave and post-shave gels And hair care such as creams, bar soaps and body wash / face wash, such as shampoos, conditioners and styling products, and oral care (including toothpaste).

  Some embodiments of the polyamide and polyurethaneurea powders have excellent feel and feel characteristics. For example, they have a silky smooth feel in addition to good sliding.

  The polyurethaneurea powders of the present invention show very high water and sweat absorption values as well as good oil absorption values due to their mass properties. Very high water absorption values are obtained with NY-6 powder [Lehmann and Voss & Co. Defined as more than three times higher than that of commercially available Arkema (Hamburg, Germany). Good oil absorption values are comparable to nylon 12 (Arkema) and higher than that shown by polymethyl methacrylate, polyethylene and polyurethane [KOBO (Kobo Products of South Plains (New Jersey and St. Agne France)] DEFINITIONS It can be seen that the polyurethaneurea powder of the present invention absorbs water or sweat very quickly (instantaneously), and fast water absorption is defined as 100 times faster than that exhibited by talc.

  The polyurethaneurea powders described herein benefit water fast and in large amounts and also benefit anti-aging and anti-wrinkle products. The powder can be used as a skin wrinkle filler in an anti-aging skin care composition. Since the present powder is a hydrophilic and compressible microsphere, it has the effect of producing a volume for stretching or reducing the appearance of wrinkles.

  When the powder is used in cosmetic and body care applications, particles less than 100 microns are appropriate to provide a smooth feel to the skin and not to be noticed by the wearer. Ideally, the average particle size should be less than 50 microns. In one embodiment, 90% of the particles contained in the polyurethaneurea powder are less than 42 microns, which can be achieved by controlling the parameters of the filtration or spray drying process.

  In another embodiment, a polyurethaneurea bead or powder is present as a exfoliant in facial cleansers, scrubs, shower gels, and the like. Cosmetic compositions typically contain materials such as ground nuts (including apricot kernels) as exfoliating / rubbing / peeling agents. However, they tend to have stiff and very sharp edges and as a result are uncomfortable to the touch. In contrast, the polyurethaneurea beads and powder shapes of some embodiments have a very spherical and round surface and can have a silky feel, so they maintain the effect of a hard material More “skin-friendly”. The amount of the present powder or bead added to the face wash composition may be any amount that achieves the desired effect. The particle size can also vary, but the particle size noticed by consumers is generally about 100 microns or more.

  In another embodiment, the polyurethaneurea dispersion is a film-forming polyurethaneurea dispersion for curl retention or curling prevention properties in hair care compositions (gels, sprays, shampoos, conditioners, etc.). Colored or pigmented polyurethaneurea powders can be used when trying to color the hair non-permanently.

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

Coating composition The composition in some embodiments is a coating composition, which includes polyurethaneurea, polyester and polyamide compositions. The paint may be any paint known in the art, including latex, acrylic and oil based paints, including primer, sealer and coating. The form when the polyurethaneurea, polyester and polyamide composition are added to the paint may be any form that achieves the desired effect.

  The addition of a polymer in powder, short fiber or bead form may be included for the purpose of texturing the coating composition. If the powder, fiber or bead is dyed or colored, the intent is also to achieve various painting effects. Such an effect is highly desirable due to recent interest in alternative coating techniques and counterfeit finishing. Some embodiments of the composition provide alternative surface properties such as texture and color without additional painting steps. In addition, it is also possible to achieve a double color effect or multiple color effects by adding color to the base paint and giving the powder / bead / fiber one or more individual colors.

  Adding floc to the coating composition provides additional benefits in addition to visible color and texture effects. A coating composition containing such floc fibers provides better coverage, non-uniform areas of the wall / surface, provides greater flexibility and resistance to cracking. In addition, they also provide a wallpaper effect through the application of paint.

  Addition of the polyurethaneurea dispersion to the coating composition provides additional benefits in addition to visible color and texture effects. A coating composition containing such a dispersion can give a particularly good coating and crack resistance on a non-uniform surface. This is demonstrated in this example.

  Alternatively, the polymer may be added in powder, short fiber or bead form for the purpose of imparting anti-slip properties to the coating composition. This is achieved by a higher friction on the painted surface compared to traditional paint compositions.

The features and advantages of the present invention are shown in greater detail in the following examples, which are presented for purposes of illustration and are not to be construed as limiting the invention in any way.
[Example]

  Developed a capped glycol prepolymer produced using Terathane ™ E2538 glycol (supplied by INVISTA, S.ar.l.) and Isonate ™ 125MDR to a capping ratio of 1.696. Obtained using the LYCRA ™ spandex production line. LYCRA ™ for spandex is a registered trademark of INVISTA. The viscosity was lowered by mixing this prepolymer (300 grams) in a plastic bottle with 150 grams of NMP solvent for 10 minutes. The diluted mixture was poured into a steel tube and poured into a stainless steel container for dispersion.

  Premixed with 2000 grams of deionized water, 30 grams of T DET N14 surfactant (commercially available from Harcros (Kansas City, Kansas)) and 4.5 grams of ethylenediamine chain extender. It was cooled to 5 ° C. and placed in the container. A model number commercially available from a laboratory high speed disperser [Charles Ross & Son Company (Hauppauge, New York) under an air pressure of about 40 psi through the diluted prepolymer through a 1/8 inch inner diameter pipe This was injected into the HSM-100LC] operating at 5000 rpm. The addition of the diluted prepolymer was completed within 15 minutes and the resulting milky dispersion was continued for another 5 minutes. By measuring the inverse weight of the vessel, it was found that the total amount of dilute capped glycol added to the dispersion was 328 grams, which added 218.7 grams of capped glycol prepolymer to the dispersion. It corresponds to that. 3 grams of Additive 65 foam control agent [commercially available from Dow Corning (Midland, Michigan)] was added to the dispersion and the dispersion was further mixed at 5000 rpm for 30 minutes before being poured into a plastic bottle. .

  When the dispersion was measured using a Microtrac X100 particle size analyzer (Leeds, Northrup), the average particle size was 52.83 microns and 95% of the particles were less than 202.6 microns.

  The same materials and dispersion procedure as in Example 1 were used, except that 4.5 grams of chain extender, ethylenediamine, was added after the dilute prepolymer as shown in Example 1 was dispersed in the water mixture. By measuring the inverse weight of the vessel, the total amount of dilute capped glycol added to the dispersion was found to be 329 grams, which was the addition of 219 grams of capped glycol prepolymer to the dispersion. Equivalent to. The measured average particle size of the dispersion was 33.45 microns and 95% of the particles were less than 64.91 microns. The solid polymer particles do not form a film when isolated.

  500 grams of Krasol ™ HLB 2000 glycol [Sartomer Company, Inc., in a 2000 ml reaction vessel fitted with a heating mantle and mechanical stirrer. (Exton, PA)] and 105.86 grams of Isonate ™ 125MDR were reacted at 90 ° C. for 120 minutes to give a capped glycol prepolymer. The reaction was performed in a nitrogen filled dry box. The weight percent of NCO groups contained in the prepolymer after the reaction was 2.98 as measured by a titration method. The prepolymer was poured into a steel tube and dispersed by pouring it into a stainless steel container. Within the vessel, deionized water (2000 grams) and 30 grams of TDET N14 surfactant (commercially available from Harcros, Kansas City, Kansas) and 3 grams of Additive 65 foam control agent [Dow Corning (Midland Commercially available from Michigan)] at room temperature. The prepolymer is passed through a 1/8 inch inner diameter pipe and under a pressure of about 80 psi under high pressure in the laboratory (model number HSM-, commercially available from Charles Ross & Son Company, Happopage, New York) 100LC] was injected while operating at 5000 rpm. The addition of the diluted prepolymer was completed within 15 minutes and the resulting milky dispersion was continued for another 5 minutes. The total weight of dilute capped glycol added to the dispersion was found to be 422 grams by measuring the inverse weight of the vessel. After adding 4.5 grams of chain extender, which is ethylenediamine, to the dispersion, the dispersion was further mixed for 30 minutes at 5000 rpm. The resulting dispersion had a measured average particle size of 49.81 microns and 95% of the particles were less than 309.7 microns.

  The same procedure as shown in Example 3 was performed except that a mixture of 250 grams of Terathane ™ 1800 glycol and 250 grams of Krasol ™ HLB was used to produce the prepolymer. A total of 465 grams of prepolymer was dispersed. The resulting dispersion had a measured average particle size of 13.67 microns and 95% of the particles were less than 38.26 microns.

  The prepolymer was prepared in a nitrogen atmosphere glove box. Terathane ™ 1800 glycol [INVISTA S., was added to a 2000 ml Pyrex ™ glass reaction vessel equipped with a pneumatically driven stirrer, heating mantle and thermocouple for temperature measurement. ar. 1 (commercially available from Wichita, KS and Wilmington, DE)] was charged about 382.5 grams and about 12.5 grams 2,2-dimethylpropionic acid (DMPA). The mixture was heated to about 50 ° C. with stirring, and then about 105 grams of Lupranate ™ MI diisocyanate (commercially available from BASF (Wyandotte, Michigan)) was added. The reaction mixture is then heated to about 90 ° C. with constant stirring and held at about 90 ° C. for about 120 minutes, after which time the NCO% of the mixture drops to a stable value, The reaction was complete because it met the calculated value of the prepolymer having isocyanate end groups (1.914 which is the target% of NCO). The viscosity of the prepolymer is measured according to the general method of ASTM D1343-69, model DV-8 Falling Ball Viscometer [Duratech Corp. (Waynesboro, VA)] was carried out by operating at about 40 ° C. The measurement of the total isocyanate moiety content (in terms of weight percent of NCO groups) of the capped glycol prepolymer was determined by S.C. Siggia, “Quantitative Organic Analysis via Functional Group”, 3rd edition, Wiley & Sons, New York, pages 559-561 (1963), the disclosure of which is incorporated herein by reference in its entirety. Implemented.

  A polyurethaneurea aqueous dispersion of the present invention was made using the solventless prepolymer as prepared according to the procedure and composition described in Example 5.

  A 2,000 ml stainless steel beaker was charged with about 700 grams of deionized water, about 15 grams of sodium dodecylbenzenesulfonate (SDBS) and about 10 grams of triethylamine (TEA). The mixture is then cooled to about 5 ° C. in an ice / water bath for about 30 seconds using a laboratory high shear mixer (Ross, model 100LC) equipped with a rotor / stator mixing head at about 5,000 rpm. Mixed. A viscous prepolymer (in a metal tubular cylinder) prepared in the same manner as in Example 1 was added as an aqueous solution by passing air through a soft pipe at the bottom of the mixing head. The temperature of the prepolymer was maintained in the range of about 50 ° C to about 70 ° C. The prepolymer stream was extruded and dispersed in water under continuous mixing at about 5,000 rpm and caused chain extension by water. A total amount of about 540 grams of prepolymer was introduced and dispersed in water over about 50 minutes. Immediately after the prepolymer was added and dispersed, about 2 grams of Additive 65 (commercially available from Dow Corning ™ (Midland, Mich.)) Was charged to the dispersed mixture. The reaction mixture was then mixed for about another 30 minutes before adding about 6 grams of diethylamine (DEA) and further mixing. The resulting solventless aqueous dispersion was milky white and stable. The viscosity of the dispersion was adjusted by adding and mixing Hauthane HA thickener 900 [commercially available from Hawthway (Lynn, Massachusetts)] at a concentration of about 2.0% by weight of the aqueous dispersion. . The viscous dispersion was then filtered through a 40 micron Bendix metal mesh filter and stored at room temperature for use in film casting or lamination. The dispersion had a solid concentration of 43% and a viscosity of about 25,000 centipoise.

  Commercially available capped glycol prepolymer produced using Terathane ™ 1800 glycol and Isonate ™ 125 MDR (commercially available from Dow Company, Midland, Michigan) to give a capping ratio of 1.688. LYCRA ™ spandex production line. LYCRA ™ for spandex is a registered trademark of INVISTA. The viscosity was lowered by mixing this prepolymer (300 grams) in a plastic bottle with 150 grams of NMP solvent for 10 minutes. The diluted mixture was poured into a steel tube and poured into a stainless steel container for dispersion. 2000 grams of deionized water, 30 grams of T DET N14 surfactant (commercially available from Harcros (Kansas City, Kansas)) and 3 grams of ethylenediamine chain extender premixed at 5 ° C. And cooled in the container. A model number commercially available from a laboratory high speed disperser [Charles Ross & Son Company (Hauppauge, New York) under an air pressure of about 40 psi through the diluted prepolymer through a 1/8 inch inner diameter pipe This was injected into the HSM-100LC] operating at 5000 rpm. The addition of the diluted prepolymer was completed within 15 minutes and the resulting milky dispersion was continued for another 5 minutes. By measuring the inverse weight of the vessel, the total amount of dilute capped glycol added to the dispersion was found to be 347 grams, which was the addition of 231 grams of capped glycol prepolymer to the dispersion. Equivalent to. 3 grams of Additive 65 foam control agent [commercially available from Dow Corning (Midland, Michigan)] was added to the dispersion and the dispersion was further mixed at 5000 rpm for 30 minutes before being poured into a plastic bottle. .

  When the dispersion was measured using a Microtrac X100 particle size analyzer (Leeds, Northrup), the average particle size was 32.59 microns and 95% of the particles were less than 65.98 microns. The solid polymer particles are filtered under reduced pressure using a Buchner funnel lined with Whatman ™ filter paper, the filter cake is rinsed 3 times with water and then dried at 60-65 ° C. for 4 hours. It was. The particles did not form a film during filtration or drying. The dried filter cake was placed in a laboratory Waring ™ blender [Dynamics Inc. It was easy to grind into a fine powder using a Blender 700 model 33BL79 manufactured by (New Hartford, Connecticut). In commercial practice, the solid particles could be isolated directly from the dispersion using known drying processes such as spray drying. When the dried powder was measured by GPC, the weight average molecular weight was 352,550 and the number average molecular weight was 85,200.

  In Example 8, the components and dispersion procedure shown in Example 7 were used except that the solvent used in the dilution of the capped glycol prepolymer was changed to xylene and the amount of chain extender, ethylenediamine, was increased to 4.5 grams. They used the same. By measuring the inverse weight of the container, the total amount of dilute capped glycol added to the dispersion was found to be 339 grams, which corresponds to 226 grams of capped glycol prepolymer added to the dispersion. To do.

  The measured average particle size of the dispersion was 22.88 microns and 95% of the particles were less than 46.97 microns. The solid polymer particles did not form a film upon isolation.

  Example 9 uses the same components and dispersion procedure as shown in Example 7 except that the chain extender, ethylenediamine, is replaced with the same amount of branched polyethylenimine (Mn by GPC about 600, obtained from Aldrich). It was. By measuring the inverse weight of the container, the total amount of dilute capped glycol added to the dispersion was found to be 340 grams, which corresponds to 227 grams of capped glycol prepolymer added to the dispersion. To do.

The measured average particle size of the dispersion was 58.12 microns and 95% of the particles were less than 258.5 microns. The solid polymer particles did not form a film upon isolation.

  A glove box with a dry nitrogen atmosphere was used to prepare the prepolymer. Terathane ™ 1800 glycol [commercially available from INVISTA] was placed in each of two separate 2000 ml Pyrex ™ glass reactors equipped with a pneumatically driven stirrer, heating mantle and thermocouple for temperature measurement. Available] was charged with 220.0 grams and Pluracol ™ HP 4000D glycol [commercially available from BASF] with 220.0 grams. The glycol mixture was heated to 50 ° C. with stirring and then 75.03 grams of Isonate ™ 125MDR (commercially available from Dow Chemical) was added. The reaction mixture was then heated to 90 ° C. with constant stirring and held at 90 ° C. for 120 minutes. A sample is taken from the reactor and S.P. NCO% measured by using the method of Siggia, “Quantitative Organic Analysis via Functional Group”, 3rd edition, Wiley & Sons, New York, pages 559-561 (1963) is 69.702.1, respectively. Met.

  In a 3000 ml stainless steel beaker, 1600 grams deionized water, 15 grams TDET N14 surfactant (commercially available from Harcros (Kansas City, Kansas)) and 5 grams Additive 65 [commercially available from Dow Corning] Available]. The mixture was then mixed for 30 seconds using a laboratory high shear mixer (Ross, model 100LC) equipped with a rotor / stator mixing head at 5,000 rpm while cooling the mixture to 10 ° C. in an ice / water bath. The viscous prepolymer prepared in the two reaction vessels shown above is poured into a metal tubular cylinder, and then air pressure is applied to the lower part of the mixing head through a soft pipe as an aqueous solution. I added. The prepolymer temperature was maintained in the range of 50-70 ° C. The prepolymer stream was extruded and dispersed into water under continuous mixing at 5,000 rpm and chain extension was caused by water. A total amount of 616 grams of prepolymer was introduced and dispersed in water over 5 minutes. After the prepolymer was added and dispersed, the dispersed mixture was further mixed for 40 minutes. The resulting solventless aqueous dispersion was milky white to light blue in color with a solids content of 28.84% by weight and a viscosity of 44 centipoise. The dispersion was poured onto a single polyethylene sheet and then dried overnight in a fume hood under ambient conditions to produce an elastic continuous film. By GPC measurement, the weight average molecular weight of the film was 127,900, and the number average molecular weight was 41,000.

  Essentially the same procedure and conditions as in Example 10 above were used, except that the surfactant was changed to Bio-soft ™ N1-9 [commercially available from Stepan (Northfield, Illinois)]. From the reactor, prepolymers with NCO% of 2.156 and 2.136 were dispersed in water in a total amount of 640 grams, the solid content of the resulting solventless dispersion was 26.12% and viscosity The elastic film cast and dried had a weight average molecular weight of 133,900 and a number average molecular weight of 44,400.

  A polyurethaneurea aqueous dispersion of the present invention was made using the solventless prepolymer as prepared according to the procedure and composition described in Example 5.

A 2,000 ml stainless steel beaker was charged with about 700 grams of deionized water, about 15 grams of sodium dodecylbenzenesulfonate (SDBS) and about 10 grams of triethylamine (TEA). The mixture is then cooled to about 5 ° C. in an ice / water bath for about 30 seconds using a laboratory high shear mixer (Ross, model 100LC) equipped with a rotor / stator mixing head at about 5,000 rpm. Mixed. A viscous prepolymer (in a metal tubular cylinder) prepared in the same manner as in Example 1 was added as an aqueous solution by passing air through a soft pipe at the bottom of the mixing head. The temperature of the prepolymer was maintained in the range of about 50 ° C to about 70 ° C. The prepolymer stream was extruded and dispersed in water under continuous mixing at about 5,000 rpm and caused chain extension by water. A total amount of about 540 grams of prepolymer was introduced and dispersed in water over about 50 minutes. Immediately after the prepolymer was added and dispersed, the dispersed mixture was added about 65 grams of Additive 65 (commercially available from Dow Corning ™ (Midland, Michigan)) and about 6 grams of diethylamine (DEA). Gram charged. The reaction mixture was then further mixed for about 30 minutes. The resulting solventless aqueous dispersion was milky white and stable. The viscosity of the dispersion was adjusted by adding and mixing Hauthane HA thickener 900 [commercially available from Hawthway (Lynn, Massachusetts)] at a concentration of about 2.0% by weight of the aqueous dispersion. . The viscous dispersion was then filtered through a 40 micron Bendix metal mesh filter and stored at room temperature for use in film casting or lamination. The dispersion had a solid concentration of 43% and a viscosity of about 25,000 centipoise. The film cast from this dispersion was soft, sticky and rubbery.

Fabric Testing A composition of the present invention was tested in combination with a cotton / LYCRA ™ fabric (97% cotton / 3% LYCRA ™ spandex). The control for this example was a fabric laundered using Unilever's non-concentrated Comfort ™ fabric softener. Each of the compositions as shown in Table 1 is used in a cotton / LYCRA ™ fabric and the laundry is programmable using an Ariel ™ liquid detergent available from Procter and Gamble. Was carried out at 40 ° C. with a standard fabric filling reaching 2.5 kg loading with program 4 and rinsing with 18 g of fabric softener composition. The fabric after tumble drying was evaluated for any deposits present on the surface. None of the three fabrics showed any powder or film adhesion.

The compositions in Table 1 are as follows:
(A) Fabric treated with fabric softener only (control)
(B) Fabric softener, fabric treated with the dispersion of Example 6, ie 1% by weight of a film-forming anionic polyurethaneurea water and 2% by weight of Unimer (synthetic wax for improving dispersibility) (c) ) Fabric treated with fabric softener, 1% by weight of the polyurethaneurea powder of Example 5 and 2% by weight of Unimer (a synthetic wax that improves dispersibility).

  Mixing of compositions (b) and (c) containing fabric softener resulted in a uniform dispersion (no settling or coagulation).

  Each fabric was evaluated for easy care. The standard test method AATCC ™ 124 / ISO 15487 was used to determine the durability press grade (“PD grade”) before and after ironing. “DP grade” is a measure of the three-dimensional smoothness exhibited by a fabric. The ease of iron slipping or ironing was measured as the time for the iron to slide over a length of fabric with an ironing board angle of about 20 °. The easy care results are shown in Table 1.

  From the results shown in Table 1, both fabrics treated with powder or dispersion show a good improvement in DP rating (1 point after ironing) compared to the control (0.5 points after ironing). I understand that.

  It can also be seen that in fabrics (b) and (c) treated with the composition of the present invention, the iron slides faster on the surface of the fabric.

  Compositions (a), (b) and (c) were also evaluated for fragrance / fragrance sticking. Three people individually smelled each of the fabrics. These persons observed a strong aroma with the treated fabrics (b) and (c), each treated with the composition of the present invention.

  The absorption properties (moisture management) exhibited by the fabric (including fabrics treated with the composition of the present invention) were also tested. Measuring such properties showed the difference when the fabric after treatment with the powder or dispersion of the present invention was compared to the untreated fabric.

For each of fabrics (a), (b) and (c) as described above, 1 drop (about 30 microliters) of each of linseed oil and water was added to the surface of the fabric. The time until each drop was completely absorbed was measured and reported in seconds in Table 2. The area of the drop surface 60 seconds after the fabric was completely absorbed was also measured and reported in Table 2 as square centimeters (cm ² ).

  As shown in Table 2, the dispersion (b) and powder (c) of the present invention provided an improvement in absorption compared to the control (a). It has been found that there is a significant improvement when using powder form (c).

Testing of 100% Cotton Woven Fabric Tests were also conducted after 100% cotton woven fabric was treated with the composition of some embodiments. The control for this example was Softlan ™ Ultra, a concentrated fabric softener from Colgate Palmolive. Each of the compositions as shown in Table 3 was used in 100% cotton fabric and the laundry was programmable using Ariel ™ liquid detergent and a Schulthes ™ automatic washing machine with a program 4 fill weight of 2.5 kg Was carried out at 40 ° C. using a standard fabric filling reaching 18 and rinsing was carried out with 18 g of fabric softener composition. The fabric after tumble drying (at moderate temperature) was evaluated for any deposits present on the surface. None of the fabrics showed any powder or film adhesion.

The compositions in Table 3 are as follows:
(E) Fabric treated with fabric softener only (control)
(F) Fabric treated with 10% by weight of fabric softener and the dispersion of Example 10, ie nonionic polyurethaneurea dispersion.

  Mixing of composition (f) containing fabric softener resulted in a uniform dispersion (no settling or coagulation).

In order to allow the fabric to be tested for growth, the effective or maximum elongation was first calculated. After first conditioning the fabric specimen, the effective elongation was measured by performing three cycles with a constant speed elongation tensile tester in the range of 0-30N. Maximum elongation was calculated with the following formula:
Maximum elongation% = (ML−GL) × 100 / GL
here,
ML is 30N length (mm) and GL is 250mm gauge length.

The individual specimens of each fabric were then stretched to 80% of the “effective stretch” and held for about 30 minutes. The fabric specimen was then allowed to relax for about 60 minutes before the growth was measured and calculated according to the following.
Growth% = L2 / Lx100
here,
Record "growth" as a percentage after relaxation,
L2 = increased length after relaxation (cm) and L = original length (cm).

  Each of fabrics (e) and (f) was subjected to measurements on fabric growth. The results are shown in Table 3.

  Fabric growth is a measure of shape retention. The growth value corresponds to the unrecovered elongation during wearing. A lower growth value indicates a better ability of the fabric to recover its original shape.

Fabrics (e) and (f) were also tested for differences in perfume release after washing and rinsing cycles. Each fabric sample was placed in a sealed gas sampling vessel in an amount of 1-2 grams. Pressure was applied to the fabric by shaking with a steel ball bearing. By using a gas sampling pump operated at 50 cc per minute, volatile compounds released from the sample were taken out from the top space of the gas sampling vessel through a Tenex ™ sampling tube for 20 minutes. The Tenex ™ tube captured volatile organic compounds (VOC) and analyzed them. Next, analysis was performed by desorbing volatile organic substances from the Tenex (trademark) tube with heat and directing them to GC / MS. The VOC measurement results shown in Table 3a show that the perfume released from the fabric when the fabric is rinsed with the fabric softener containing the dispersion of Example 10, ie, the non-ionic polyurethaneurea dispersion. Shows that the amount of increases.

Testing of Spandex / Cotton Mixed Fabric Tests were also conducted after the spandex / cotton mixed woven fabric was treated with the composition of some embodiments. The control for this example was Softlan ™ Ultra, a concentrated fabric softener from Colgate Palmolive. Each of the compositions as shown in Table 4 was used in a cotton / spandex mixed fabric and the laundry was programmable with an Ariel ™ liquid detergent and a Schutless ™ automatic washing machine programmed with 2.5 kg filling program 4. Standard fabric filling reaching the quantity was performed at 40 ° C. and rinsing was performed with 18 g of fabric softener composition. The fabric after tumble drying (at moderate temperature) was evaluated for any deposits present on the surface. None of the fabrics showed any powder or film adhesion.

The compositions in Table 4 are as follows:
(G) Fabric treated with fabric softener only (control)
(H) Fabric treated with 10% by weight of fabric softener and the dispersion of Example 10, ie nonionic polyurethaneurea dispersion.

  Mixing the composition (h) containing the fabric softener resulted in a uniform dispersion (no settling or coagulation). Each of fabrics (g) and (h) was tested for fabric growth. The results are shown in Table 4.

  Fabric growth is a measure of shape retention. The growth value corresponds to the unrecovered elongation during wearing. A lower growth value indicates a better ability of the fabric to recover its original shape.

  Two LYCRA ™ spandex / cotton blend fabrics were also tested after being treated with the composition of some embodiments. The control for this example was Soupline ™ Ultra, a concentrated fabric softener from Colgate Palmolive. Each of the compositions as shown in Tables 4a and 4b was used in a mixed fabric of cotton and LYCRA ™ spandex, and the laundry was washed in a Mieel ™ commercial laundry using Dixan ™ gel detergent available from Henkel Corporation. The machine was carried out at 40 ° C. with a standard fabric fill reaching a fill of 2.5 kg with a standard program and rinsing was carried out with 30 ml of fabric softener composition. The fabric after tumble drying (at moderate temperature) was evaluated for any deposits present on the surface. None of the fabrics showed any powder or film adhesion. For the fabrics shown below, CK is a circular knitted fabric of 95% cotton and 5% LYCRA ™ spandex and WOV is a gray weft stretch woven fabric of 97% cotton and 3% LYCRA ™ spandex It is.

The compositions in Tables 4a and 4b are as follows:
(I) Fabric treated with fabric softener only (Control-CK)
(J) Fabric treated with 10% by weight (3% active ingredient) of fabric softener and the dispersion of Example 10, ie nonionic polyurethaneurea dispersion (treatment -CK)
(K) Fabric treated with fabric softener only (control-WOV)
(L) Fabric treated with 10% by weight (3% active ingredient) of fabric softener and the dispersion of Example 10, ie nonionic polyurethaneurea dispersion (treatment-WOV)

Non-Slip of Paints Several embodiments of the compositions were tested for “anti-slip” properties. These tests were performed according to ASTM D4518-91 but with modifications as described below. The paint to be tested (which is also a control) is a solventless, matte white vinyl acetate based paint commercially available from Akzo Nobel. A composition having an average particle size as shown in the following table was added to provide the desired static friction improvement. Table 5 shows the results of the coefficient of static friction when calculated according to this test method.

  The procedure for measuring the static friction exhibited by the coated surface was carried out for the purpose of determining the slip resistance exhibited by the coated surface (paint) by static friction measurement. A coating layer was formed by application using a coating roller for each paint sample. The paint contained particles as shown in Table 5. The paint was then dried for 1 day. Then, the 2nd coating layer was made to adhere and it was made to dry for 1 day.

  ASTM D4518-91 was modified by using aluminum blocks with rounded edges instead of building blocks with the same weight and polished surface. The block was placed on the painted surface of the inclined surface. The aluminum block was washed with acetone between measurements.

The INSTRON dynamometer was used in the following program so that the constant speed obtained when tilting the surface was the same:
0 to 300% elongation (-1.5 ± 0.5 ° / sec) at an absolute slope of -480 mm / min
Kevlar yarn was used to avoid yarn elongation and provide good reproducibility.

The tilt angle (a) was calculated by trigonometry based on the surface height (h) and surface length (X) (which was 30 cm). The measurement of the coefficient of static friction was carried out as follows:
Static friction = tan a and static friction = tan (sin ^-1 o'clock / X)

  Table 5 shows that some embodiments of the polymer composition provide anti-slip properties comparable to or better than the control or rubber texturizing agent. Note that all of the compositions of the present invention gave excellent results when the additive concentration was 5%.

Cracking of the coating The flexibility test of the coating composition was carried out on the basis of BS EN ISO 6860: 1995. A paint composition was prepared as shown in Table 6 and included a matte white base paint commercially available from Akzo Nobel. Each paint was coated on a cardboard substrate to a thickness of about 30 mils. The minimum bend diameter achieved without cracking of the coating was then measured through folding each substrate on a conical mandrel.

  As can be seen from the results shown in Table 6, paints containing dispersions of some embodiments exhibit significant flexibility.

Elongation at Break and Young's Modulus Paint samples were mixed according to the compositions described in Tables 7 and 8. These coating compositions were coated on a peelable substrate to produce a coating. Samples having a width of 1 cm and a length of 5 cm were cut from these films for each sample. Three films per composition were tested using an Instron ™ dynamometer. Initial tests were performed to measure the elongation and force at break for each material. Constraints and Young's modulus (or modulus) were calculated from this data. The results are shown in Tables 7 and 8.

  As can be seen from Tables 7 and 8, it has been found that the composition of the present invention provides an improvement over the base paint control. Specifically, the composition of the present invention reduces the Young's modulus, which indicates that the elasticity of the material is higher.

Elongation Also, each of the three paint samples containing dispersions of some embodiments was tested for maximum elongation at 4N for paints 1 and 3 and 1N for paint 2. Taken during the third cycle using an Instron ™ material tester. The maximum force was selected from the elongation test shown in Example 18 above so that the maximum force was in the elastic domain of the material (the flat region of the stress strain curve). A test was conducted to measure the difference in elongation when the same force was applied. The results are shown in Table 9.

  Table 9 shows that when the polyurethaneurea dispersion of the present invention was added to the base paint, the elongation properties of all three types of base paint were improved. When the dispersion of the present invention is added to the base paint, its elongation is at least doubled.

Absorption of oil and water-time absorbs each drop of flaxseed oil, water and artificial sweat for the purpose of testing the absorption characteristics of the powder composition of the present invention in comparison with commercially available powder compositions Several types of compositions were tested to measure the time required to complete. In each of these tests, a drop of linseed oil, water or artificial sweat was placed on each of the powders of the present invention and commercially available powders. The time until the drop was absorbed was recorded and was as shown in Table 10.

  As shown in Table 10, the powder of the present invention absorbs oil and water faster than that of nylon and silica and the absorption time is similar to that of commercially available polyurethane powders or It was better than that.

Oil and Water Absorption-Mass For the purpose of testing the absorption characteristics of the powder composition of the present invention in comparison with commercially available powder compositions, test methods ASTM D281 for linseed oil, water and artificial sweat, respectively. Several compositions were tested to measure mass when subjected to absorption according to -95 (modified with water and artificial sweat). The results are shown in Table 11.

  As shown in Table 11, the compositions of the present invention had the ability to absorb as well as or better than commercially available powders.

Exfoliating compositions It has become increasingly common to mix physical exfoliants in cosmetic cleaning formulations. Early products were like putting ground nut shells into standard cosmetic substrates, relying on the friction effect they showed, and appealing to consumers as sandpaper. Cosmetic chemists currently have a variety of exfoliants, both natural and synthetic. If the particle size and abrasiveness of each type can be strictly controlled, it will be possible to accurately add the necessary concentration of exfoliant and if the rheological properties are better understood, It is possible to produce stable and elegant products that are evenly distributed throughout.

Polyethylene (PE) spheres are the most common exfoliant polymers, several of which are available in a range of sizes. Commercial samples of polyethylene (PE) spheres are available from A & E Connock (Perfumery & Cosmetics) Ltd in the following grades:
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 1200-1400 μm).

The following polyureaurethane powder having the following particle size was prepared for the purpose of comparison with PE spheres: polyurethaneurea powder prepared by the Roach method: 25-200 μm
Polyurethane urea powder of Example 7: 300-800 μm
Polyurethane urea powder of Example 3: 500-1000 μm.

  Each powder is added to a shower gel (Dove's Silk Glow Softening Silk Shower) in an amount of 15% by weight to prepare a ready-to-use exfoliating product (Dove's Silk Glow Douche Somogenene Quotientene Sodene) containing oxidized polyethylene as an exfoliating agent. Compared.

  The composition using the polyurethaneurea powder prepared by the Roach method did not show any actual peeling effect because the particle size of the powder was too small. As a comparison, the powders of Examples 3 and 7 were well mixed with the shower gel and provided an exfoliating effect. Because the polyurethaneurea powders are compressible, their feel is much softer and provides a much gentler peeling effect on the skin.

Film-forming polymers A variety of film-forming polymers are used in the cosmetic industry, especially in nail polishes, mascara eyeliners, facial makeup, sunscreen products and hair care preparations. Its chemical composition can vary from acrylate copolymers to polyurethane, polyvinyl pyrrolidone, vinyl acetate, polyacrylic acid (carbomer). They can be used as styling polymers or thickeners, resulting in transparent soft films with varying degrees of gloss, adhesion, abrasion resistance and flexibility. The water-containing polyurethaneurea dispersions of Examples 5, 6 and 10 can also be used for the purpose of providing such an effect.

  The great advantage of such a composition is that it has improved elasticity and flexibility, has a soft and comfortable feel and good wear resistance. Two polyurethane polymer dispersions commercially available from Noveon: Avalure ™ UR 425 and UR 450 were tested and compared to polyurethane urea compositions as described herein.

  A 20 mil thick film was cast and molded using the dispersion of Example 6 as well as the commercially available dispersion. They are compared in terms of elastic properties and are shown in Table 12.

  The dispersion of Example 6 clearly exhibits very high elastic behavior compared to commercially available materials because the Young's modulus is much lower. This dispersion allows for high formulation flexibility and better follows skin movement.

While embodiments have been described that are presently considered to be preferred embodiments of the invention, it will be appreciated by those skilled in the art that changes and modifications may be made thereto without departing from the spirit of the invention. It will be appreciated that it is intended to embrace all such variations and modifications as would fall within the true scope of the present invention.

Claims (43)

A fabric care composition comprising:
(A) a detergent or fabric softener composition, and (b) a polyurethaneurea in the form of a powder or aqueous dispersion,
A composition comprising:   The composition of claim 1 wherein the detergent or fabric softener is compatible with use in a washing machine.   The composition of claim 1 wherein the detergent or fabric softener is compatible with hand washing.   The composition of claim 1, wherein the detergent or fabric softener is in a form selected from the group consisting of powders, liquids, solid tablets, encapsulated liquids and nonwoven sheets.   The composition of claim 1, wherein the polyurethaneurea comprises a reaction product of an isocyanate-terminated polyurethane prepolymer and a chain extender.   6. The composition of claim 5, wherein the chain extender is selected from the group consisting of diamine based chain extenders, water, and combinations thereof.   The composition of claim 1 wherein the polyurethaneurea is in the form of a powder and the prepolymer is a reaction product of a hydroxyl-terminated polymer selected from the group consisting of polyethers, polycarbonates, polyesters and combinations thereof and a diisocyanate.   The polyurethaneurea is in the form of an aqueous dispersion and the prepolymer is the reaction product of a hydroxyl-terminated polymer selected from the group consisting of polyethers, polycarbonates, polyesters and combinations thereof and diisocyanates and optionally acidic diols. Item 2. The composition according to Item 1.   9. The composition of claim 8, wherein the aqueous dispersion is selected from the group consisting of an anionic dispersion and a nonionic dispersion.   The hydroxyl terminated polymer is a polyether polyol and the diisocyanate is selected from the group consisting of phenylene diisocyanate, tolylene diisocyanate (TDI), xylylene diisocyanate, biphenylene diisocyanate, naphthylene diisocyanate, diphenylmethane diisocyanate (MDI) and combinations thereof; And the acidic diol comprises 2,2-dimethylolacetic acid, 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolpentanoic acid and combinations thereof The composition of claim 8 selected from the group consisting of:   The polymer is poly (tetramethylene ether) glycol and the diisocyanate is 4,4′-methylenebis (phenylisocyanate) or a mixture of 4,4′-methylenebis (phenylisocyanate) and 2,4′-methylenebis (phenylisocyanate). And the acidic glycol is 2,2-dimethylolpropionic acid or is absent. A composition comprising a nonionic film-forming dispersion, wherein the dispersion comprises water and a polymer, wherein the polymer is a reaction product of water as a prepolymer and a chain extender. And wherein the prepolymer consists essentially of the reaction product of glycol or a mixture of glycols and 4,4'-methylenebis (phenylisocyanate).   13. The composition of claim 12, wherein the glycol is selected from the group consisting of poly (tetramethylene-co-ethylene ether) glycol and a mixture of poly (tetramethylene ether) glycol and ethoxylated polypropylene glycol.   13. The composition of claim 12, further comprising an additive selected from the group consisting of surfactants, antifoams, pigments, solvents and combinations thereof.   A composition comprising a nonionic, non-film-forming dispersion, wherein the dispersion comprises water and a polymer, and the polymer comprises a diamine chain extender and water. A composition comprising a reaction product of a chain extender and a prepolymer, wherein the prepolymer consists essentially of the reaction product of glycol and 4,4'-methylenebis (phenylisocyanate).   16. The composition of claim 15, further comprising an additive selected from the group consisting of surfactants, antifoams, pigments, solvents and combinations thereof.   A polyurethaneurea powder produced from a composition comprising a nonionic non-film-forming dispersion, wherein the dispersion comprises water and a polymer, the polymer being a diamine chain extender And a reaction product of a chain extender comprising water and a prepolymer, and said prepolymer is essentially composed of a reaction product of glycol and 4,4'-methylenebis (phenylisocyanate) Polyurethane urea powder.   A method for prolonging perfume sticking to a fabric comprising contacting the fabric with a composition comprising a polyurethane urea in the form of a powder or aqueous dispersion and a perfume.   The method of claim 18, wherein the fabric includes garments.   A method of improving the shape retention of a garment comprising contacting the garment with a polyurethaneurea in the form of a powder or aqueous dispersion.   A method for improving the ease of maintenance properties of a fabric comprising contacting said fabric with polyurethaneurea in the form of a powder or aqueous dispersion.   The method of claim 21, wherein the fabric includes garments.   A method of imparting antifouling properties to a fabric comprising contacting the fabric with polyurethaneurea in the form of a powder or aqueous dispersion.   24. The method of claim 23, wherein the fabric includes garments. A method for producing polyurethaneurea powder, comprising:
(A) preparing an aqueous polyurethaneurea dispersion,
(B) obtaining polyurethaneurea particles by filtering the dispersion, and (c) grinding the particles to the required size.
A method comprising that. A method for producing polyurethaneurea powder, comprising:
(A) preparing an aqueous polyurethaneurea dispersion, and (b) subjecting the dispersion to spray drying to obtain a polyurethaneurea powder having a preselected average particle size,
A method comprising that. A method for dyeing a powder composition comprising:
(A) preparing a polyamide or polyester composition;
(B) adding the powder to the dyebath and (c) filtering and drying the composition;
A method comprising that.   A composition comprising at least one of a polyurethaneurea composition, a polyamide composition, and a polyester composition and a paint.   30. The composition of claim 28, wherein the polyurethaneurea composition comprises a form selected from powders, dispersions, fibers, beads and combinations thereof.   29. The composition of claim 28, wherein the polyamide composition comprises a polyamide in the form of a powder, flock fibers or mixtures thereof.   29. The composition of claim 28, wherein the polyamide composition comprises a polyamide in the form of dyed polyamide powder, dyed polyamide floc fibers or mixtures thereof.   A composition comprising a polyurethaneurea bead, wherein the void content of the bead is less than 60% or greater than 90%.   A composition comprising at least one of a polyurethaneurea composition, a polyamide composition and a polyester composition and a cosmetic composition.   34. The composition of claim 33, wherein the polyamide composition is a dyed powder.   34. The composition of claim 33, wherein the polyurethaneurea composition is a powder.   A composition comprising a polyurethaneurea powder, wherein the powder is formed by dispersing an isocyanate group-terminated prepolymer in water and subjecting it to chain extension.   The composition of claim 36, wherein the polyurethaneurea powder has an average particle size of less than 100 microns.   38. The composition of claim 37, wherein the polyurethaneurea particles are non-film forming when isolated from the aqueous medium.   40. The composition of claim 36, comprising a cosmetic composition.   38. The composition of claim 36, comprising an antiperspirant composition. A polyurethaneurea powder having a content of an organic liquid substantially inert to the polyurethaneurea and less than 2%.   A method of prolonging perfume sticking in a cosmetic composition comprising: (a) preparing a cosmetic composition containing polyurethane urea in a form selected from powders, dispersions and mixtures thereof and (b) perfume. How to be.   A method for prolonging perfume sticking to a household composition, comprising: (a) selecting a polyurethaneurea in a selected form from powders, dispersions and mixtures thereof; and (b) preparing a household composition comprising the perfume. A method comprising: