HK1121478B

HK1121478B - Solvent free aqueous polyurethane dispersions and shaped articles therefrom

Info

Publication number: HK1121478B
Application number: HK08110557.6A
Authority: HK
Inventors: Hong Liu; Carmen A. Covelli; Douglas K. Farmer
Original assignee: Invista Technologies S.À R.L.
Priority date: 2005-02-11
Filing date: 2006-02-10
Publication date: 2014-01-17

Description

Solvent-free aqueous polyurethane dispersion and shaped article thereof

Cross reference to related applications

The present invention claims the present co-pending U.S. applications: priorities of 11/253927, filed on day 19/10/2005, 11/056067, filed on day 11/2/2005, and 11/300229, filed on day 13/12/2005.

Technical Field

The present invention relates to novel aqueous polyurethane dispersions and shaped articles prepared therefrom. In particular, the present invention relates to solvent-free stable dispersions comprising fully formed polyurethaneureas with blocked isocyanate end groups. The dispersion may be prepared by a prepolymer mixing process. The invention also relates to shaped and coated articles prepared from such aqueous dispersions, which articles can be heat and/or pressure activated to bond, laminate and adhere to substrates. The shaped article may remain flexible, elastic after bonding, laminating, or adhering.

Background

Polyurethanes, including polyurethaneureas, are useful adhesives for a variety of substrates, including fabrics. Typically, such polyurethanes are fully formed non-reactive polymers or reactive isocyanate terminated prepolymers. Such reactive polyurethane adhesives often require extended cure times to develop adequate bond strength, which can be a disadvantage during the manufacturing process. Furthermore, the isocyanate groups of polyurethanes are known to be sensitive to moisture, which limits their storage stability and shortens the shelf life of products incorporating such polyurethanes.

Typically, such polymers, when fully formed, are either dissolved in a solvent (solvent-based), dispersed in water (water-based), or processed into thermoplastic solid materials (hot melt). Notably, solvent-based adhesives are subject to increasingly stringent health and environmental laws aimed at reducing Volatile Organic Compounds (VOCs) and Hazardous Air Pollutants (HAPs) emissions. Thus, there is a need for alternatives to conventional solvent-based products.

Hot melt adhesives, while environmentally safe and easy to use as films, typically have a high set and poor recovery over repeated stretching cycles. Therefore, improvements are needed.

Efforts have been made to develop aqueous polyurethane adhesives to overcome these deficiencies.

U.S. patent 5,270,433 discloses "an adhesive composition comprising a substantially clear, solvent-free, aqueous, one-component polyurethane dispersion comprising the reaction product of: (a) a polyol mixture comprising polypropylene glycol, (b) a polyol mixture comprising alpha, alpha¹，α¹-a polyfunctional isocyanate mixture of tetramethylxylene diisocyanate (TMXDI), (c) a functional component capable of forming a salt in aqueous solution and (d) optionally a chain extender ". Because the asymmetric structure and steric hindrance of the isocyanate groups on TMXDI prevents the formation of strong interchain urea hydrogen bonds in the polymer hard segments, the adhesive film recovery of this composition is low and heat resistance is poor.

U.S. patent application publication 2004/0014880 a1 discloses aqueous polyurethane dispersions for adhesive bonding of wet and dry laminates which are said to have excellent coating properties, bond strength and heat resistance. This dispersion contains a large amount of organic solvent, Methyl Ethyl Ketone (MEK).

U.S. patent application publication No. 2003/0220463A 1 discloses a method of preparing polyurethane dispersions that are free of organic solvents such as N-methylpyrrolidone (NMP). However, such compositions are limited to prepolymers with lower free diisocyanate species, such as methylene bis (4-phenyl isocyanate) (4, 4' -MDI). The process for preparing such prepolymers with lower free diisocyanate is complicated (as described in U.S. Pat. No. 5,703,193). This processing also requires short-path distillation of the free diisocyanate and is therefore uneconomical in the preparation of the prepolymer used to prepare the polyurethane dispersion.

U.S. patent 4,387,181 discloses stable aqueous polyurethane dispersions comprising N-methylpyrrolidone (NMP) solvent prepared by the reaction of a carboxyl oxime-blocked isocyanate-terminated prepolymer and a polyamine. The prepolymer is prepared by the reaction of an aromatic diisocyanate, such as 4, 4' -diphenylmethane diisocyanate (MDI) or Toluene Diisocyanate (TDI), with a polyether or polyester polyol and a dihydroxy alkanoic acid. The oxime-blocked isocyanate group can react with polyamine at 60-80 ℃ for 6-18 hours. The dispersions are storage stable and the films formed from the dispersions have good tensile properties. However, such dispersions still have organic solvents present and the long cure times required are not suitable for fabric bonding and lamination practices.

U.S. patent 5,563,208 describes an acetone process for preparing aqueous substantially solvent-free polyurethane dispersions comprising a urethane prepolymer having blocked isocyanate groups and a polyamine having a molecular weight of from 60 to 400, the molar ratio of blocked isocyanate groups to primary and/or secondary amino groups being from 1: 0.9 to 1: 1.5. Such dispersions are stable on storage at room temperature and give rise to heat-resistant adhesives during coating. It requires long curing times (up to 30 minutes), which is still unsuitable for fabric bonding and adhesion. Furthermore, the acetone process requires an additional distillation step to remove the acetone from the dispersion, which makes this process less economical.

Us patent 6,586,523 describes the acetone process for preparing self-crosslinking polyurethane dispersions as sizing agents, which dispersions comprise prepolymers partially blocked and partially chain-extended with isocyanate groups and an excess of polyfunctional compounds having a molecular weight of from 32 to 500, having primary or secondary amino groups and/or hydroxyl groups. Such dispersion compositions reduce the curing time to some extent, but are still deficient because of the additional distillation step required to remove the acetone.

U.S. Pat. No. 6,555,613 describes solvent-free aqueous dispersions of reactive polyurethanes having a number average molecular weight (Mn) of 800 to 14,000, a degree of branching of 0.0 to 3.0mol/kg and an isocyanate functionality of 2.0 to 6.0 per mole. The polyurethanes are prepared from polyester polyols, polyisocyanates and polyisocyanate adducts in which low molecular weight polyols and anion-forming units are incorporated into the polymer chain after neutralization and have blocked isocyanate groups which can be further reacted to effect crosslinking. The result of this dispersion is a hard, glossy and elastic coating, but this coating does not have the elastic characteristics and stretch/recovery properties required for adhesives used with elastic fabrics.

Accordingly, there is a need to provide improved aqueous polyurethane dispersions which overcome one or more of the deficiencies of the prior art.

Summary of The Invention

The first aspect of the present invention may include a prepolymer for an aqueous polyurethane dispersion, the prepolymer comprising:

at least one polyether (including copolyethers), polycarbonate, or polyester polyol component having a number average molecular weight of from about 600 to about 3,500, polytetramethylene ether glycol having a number average molecular weight of from about 1,400 to about 2,400;

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

at least one diol compound having: (i) hydroxyl groups which are capable of reacting with the MDI isomer mixture of component b) and (ii) at least one carboxyl group which is capable of forming a salt upon neutralization, wherein said at least one carboxyl group is not capable of reacting with the MDI isomer mixture of component b).

Another aspect of the present invention may include a method of preparing a prepolymer for an aqueous polyurethane dispersion, wherein the prepolymer comprises:

at least one polyether (including copolyethers), polycarbonate or polyester polyol component having a number average molecular weight of from about 600 to about 3,500, preferably polytetramethylene ether glycol having a number average molecular weight of from about 600 to about 3,500;

at least one diol compound having: (i) a hydroxyl group capable of reacting with the MDI isomer mixture of component b) and (ii) at least one carboxyl group capable of forming a salt upon neutralization, wherein said at least one carboxyl group is not capable of reacting with the MDI isomer mixture of component b);

and the process comprises mixing a), b) and c) in a substantially solvent-free system.

Another aspect of the present invention may include an aqueous polyurethane dispersion comprising a prepolymer comprising components a), b) and c), wherein the aqueous polyurethane dispersion is a substantially solvent-free system, further comprising:

at least one neutralizing agent to form an ionic salt with component c);

at least one monofunctional dialkylamine compound as a capping agent for isocyanate groups;

optionally, at least one diamine chain extending component; and

optionally, at least one polymer component having a molecular weight greater than about 500 and having at least three or more primary and/or secondary amino groups per mole of polymer (with at least one least three or more primary and/or secondary amino groups per mole of polymer).

Another aspect of the invention can include a method of preparing an aqueous polyurethane dispersion, wherein the aqueous polyurethane dispersion comprises: a prepolymer, wherein the aqueous polyurethane dispersion is a substantially solvent-free system, further comprising:

at least one neutralizing agent to form an ionic salt with component c);

and wherein the process comprises dispersing the prepolymer in an aqueous medium, wherein the at least one neutralizing agent is added to the prepolymer or aqueous medium prior to dispersing the prepolymer in the aqueous medium, and the at least one capping agent is added to the aqueous medium during or after dispersing the prepolymer in the aqueous medium.

The dialkylamine component e) is selected to render (i) the blocked isocyanate groups substantially stable during the coating and drying steps and room temperature storage conditions, while (ii) the adhesive film comprising blocked isocyanate groups is heat and/or pressure activatable for fabric bonding and lamination, when the aqueous dispersion is applied to a release paper and converted to a shaped article.

Another aspect of the present invention may comprise a shaped article prepared from an aqueous substantially solvent-free polyurethane dispersion. The present invention may further comprise a garment comprising the shaped article. The present invention may also include an article comprising the at least one shaped article and a substrate to which the shaped article is applied. The invention also includes an article, wherein the article comprises a substrate coated with the aqueous dispersion. The present invention includes molded articles, including shaped articles. The invention includes molded articles comprising a substrate coated with the aqueous polyurethane dispersion. The invention also includes garments made from the above articles.

Another aspect of the present invention can include an article comprising the shaped article and a substrate, wherein the shaped article and the substrate are adhered to produce a laminate such that the resulting elastic laminate has a coefficient of friction that is greater than the coefficient of friction of the substrate alone. Another aspect of the invention is an article comprising a shaped article and a substrate, wherein the modulus of the shaped article varies along the length or width of the article.

The present invention may further include a shaped article which may have the following properties: a set elongation after stretching of about 0 to 10%, such as about 0 to 5%, typically about 0 to about 3%, an elongation of about 400 to about 800% and a toughness of about 0.5 to about 3 Mpa. The present invention may further include a laminate made from the article and the substrate, which may have the following properties: a peel strength after 50 washes, wherein at least 50% of the pre-wash strength is retained; an air permeability of at least about 0 to about 0.5cfm and at least about 0 to about 300g/m for 24 hours²Moisture vapor transmission rate of (c).

Brief Description of Drawings

The present invention will be described in the following detailed description with reference to the following drawings.

FIG. 1 is a flow chart of processing steps that may be used to apply a dispersion or film of the present invention using a coating process;

FIG. 2 is a flow chart of processing steps that may be used to apply the dispersion or film of the present invention using a dipping process;

FIG. 3 is a flow chart of processing steps that may be used to apply the dispersions or films of the present invention using a painting or spraying process;

FIG. 4 is a schematic view of a method of making a laminate using a flat bed laminator;

FIG. 5 is a cross-sectional view of the application of a dispersion or film of the present invention to a substrate using a coating process;

FIG. 6 is a cross-sectional view of the application of the dispersion or film of the present invention to a substrate using a dipping process;

FIG. 7 is a cross-sectional view of the application of a dispersion or film of the present invention to a substrate using a painting or spraying process;

fig. 8 is a diagram of a doctor blade for dispensing a dispersion or film of the invention;

fig. 9 is an exploded view of a portion of the doctor blade of fig. 8;

FIG. 10 is a front view of a feminine bra incorporating the dispersion or shaped article of the present invention;

FIG. 11 is a cross-sectional view of a cup of the brassiere as viewed along line 11-11 of FIG. 10;

FIG. 12 is a partial exploded view of the interface of the bra cup and membrane at the periphery of the cup of FIG. 11;

FIG. 13 is a front view of a feminine pant incorporating the dispersion or shaped article of the invention;

FIG. 14 is a flow chart of the processing steps for making an elastic article according to one embodiment of the present invention

FIG. 15 is a flow chart of the processing steps used to make an elastic article according to one embodiment of the present invention; and

FIG. 16 is a cross-sectional view of a base fabric incorporating an adhesive and an elastic component edge band in accordance with one embodiment of the present invention;

FIG. 17 is a top view of a base fabric incorporating tape and other adhesives according to one embodiment of the present invention.

Detailed Description

The aqueous polyurethane dispersions of the present invention are prepared using specific urethane prepolymers which also form an aspect of the present invention.

Urethane prepolymers or capped diols are generally understood to be the reaction product of a polyol, a polyisocyanate and a compound which, after neutralization, forms a salt, before the prepolymer is dispersed in water or chain extended. Such prepolymers can generally be prepared in one or more steps, with or without the use of solvents. Depending on whether the prepolymer is dissolved in a low volatility solvent (such as MEK or NMP) which will remain in the resulting dispersion; dissolved in a volatile solvent such as acetone, which can be subsequently removed; or dispersed in water without any solvent; the dispersion method can be practically classified into a solvent method, an acetone method or a prepolymer mixing method. The prepolymer mixing process has environmental and economic advantages and is therefore preferably the basic process for preparing the solvent-free aqueous dispersion of the present invention.

In the prepolymer mixing method, important are: the viscosity of the prepolymer is low enough (not diluted by the solvent) to be transferred or dispersed into water. One embodiment of the present invention relates to polyurethane dispersions prepared from such prepolymers that meet such viscosity requirements without any organic solvent in the prepolymer or dispersion. In the present invention, the prepolymer is a reaction product of a polyol a), a diisocyanate b), and a diol compound c).

One embodiment of the present invention can provide novel solvent-free, stable, aqueous polyurethane dispersions that can be processed and used directly as adhesive materials (i.e., without any other adhesive material) for coating, bonding, and laminating to substrates using conventional techniques. The aqueous polyurethane dispersion of the present invention may be provided, wherein: basically no volatile organic matter is discharged; acceptable cure time in preparation; and good adhesive strength, heat resistance and stretch/recovery properties in the final product and in the actual application.

Another embodiment of the present invention may provide a shaped article which may or may not be an adhesive that may be applied to release paper, such that the aqueous dispersion of the present invention may be used for bonding and laminating to substrates, including fabrics. Such adhesives may be activated by heat and/or pressure (dwell time less than 1 minute, e.g., from about 15 seconds to about 60 seconds) on the substrate and resulting adhesive film. The resulting bonded articles have good stretch/recovery properties and are expected to be durable in normal wear and laundering cycles.

The term "dispersion" as used herein refers to a system wherein the dispersed phase consists of highly dispersed particles and the continuous phase can be a liquid, solid or gas.

The term "aqueous polyurethane dispersion" as used herein refers to a composition comprising at least one polyurethane or polyurethaneurea polymer or prepolymer (such as the polyurethane prepolymer described herein) that has been dispersed in an aqueous medium such as water (including deionized water). The term also relates to such compositions that have been dried (e.g., during the manufacture of shaped articles).

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

The term "solvent-free" or "solvent-free system" as used herein refers to a composition or dispersion in which a majority of the composition or dispersed components are not dissolved or dispersed in a solvent.

The term shaped article as used herein may refer to one of many objects including, for example, films, tapes, dots, nets, strips, beads and foams. The film may describe a sheet of any shape. The tape may describe a thin film in the form of a narrow strip. The film may be in the form of a tape. The term "shaped article" as used herein refers to a layer comprising an aqueous polyurethane dispersion (e.g., an aqueous polyurethane dispersion comprising a polyurethane prepolymer as described herein) that can be applied directly to a substrate or release paper, which layer can be used to bond and/or form a rigid or elastic article.

The term "article" as used herein refers to an article comprising a dispersion or shaped article and a substrate (e.g., a fabric), which article may or may not have at least one elasticity, due in part to the use of the dispersion or shaped article described herein.

The term fabric as used herein refers to a knitted, woven or nonwoven material. The knitted fabric may be plain knitted fabric, circular knitted fabric, warp knitted fabric, narrow elastic knitted fabric, and mesh fabric. The woven fabric may be of any construction, such as sateen, twill, plain, oxford, basket and narrow width elastomeric woven fabrics. The nonwoven material may be meltblown, spunbond, wet-laid, carded fiber-based staple fiber webs, and the like.

The term "substrate" as used herein refers to any material to which a shaped article can be adhered or to which the aqueous polyurethane dispersion can be applied. The substrate may be substantially one-dimensional (e.g., fibers), two-dimensional (e.g., planar sheets), or a three-dimensional article or an uneven sheet. Planar sheets may include, for example, fabrics, papers, flocked articles, and nets. Three-dimensional articles may include, for example, skins and foams. Other substrates may include wood, paper, plastic, metal, and composite materials such as concrete, asphalt, stadium flooring, and plastic sheeting.

The term "hard yarn" as used herein refers to a yarn that is substantially inelastic.

The term "molded" article as used herein refers to a process by which the shape of an article or shaped article changes upon the application of heat and/or pressure.

The term "derived from" as used herein refers to the preparation of a substance from another object. For example, the shaped article may be derived from a dryable dispersion.

The term modulus as used herein refers to the ratio of stress acting on an object, expressed as force per unit linear density or area.

The polyol component a) suitable as a starting material for preparing the urethane prepolymers of the present invention may be polyether diols, polycarbonate diols and polyester diols having number average molecular weights of from about 600 to about 3,500.

Examples of polyether polyols which may be used include those having two or more hydroxyl groups resulting from the ring-opening polymerization and/or copolymerization of ethylene oxide, propylene oxide, oxetane, tetrahydrofuran and 3-methyltetrahydrofuran, or polyols, preferably diols or diol mixtures, having less than 12 carbon atoms per molecule, such as ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, neopentyl glycol, 3-methyl-1, 5-pentanediol, 1, 7-heptanediol, 1, 8-octanediol, 1, 9-nonanediol, 1, 10-decanediol and 1, 12-dodecanediol. Linear difunctional polyether polyols are preferred in the present invention, and polytetramethylene ether glycols having a molecular weight of from about 1,700 to about 2,100, such as Terathane having a functionality of 2, are particularly preferred1800(Invista)。

Examples of the polyester polyols which can be used include those ester diols having two or more hydroxyl groups, produced by polycondensation of aliphatic polycarboxylic acids and polyhydric alcohols having low molecular weights and having not more than 12 carbon atoms in each molecule, or mixtures thereof. Examples of suitable polycarboxylic acids are malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid and dodecanedioic acid. Examples of suitable polyols for the preparation of the polyester polyols are ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, neopentyl glycol, 3-methyl-1, 5-pentanediol, 1, 7-heptanediol, 1, 8-octanediol, 1, 9-nonanediol, 1, 10-decanediol and 1, 12-dodecanediol. Linear difunctional polyester polyols having melting temperatures of from about 5 ℃ to about 50 ℃ are preferred.

Examples of polycarbonate polyols which may be used include those carbonate diols having two or more hydroxyl groups, which are produced by polycondensation of phosgene, chloroformates having a low molecular weight and having not more than 12 carbon atoms per molecule, dialkyl or diallyl carbonates and aliphatic polyols or mixtures thereof. Examples of suitable polyols for the preparation of the polycarbonate polyols are diethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, neopentyl glycol, 3-methyl-1, 5-pentanediol, 1, 7-heptanediol, 1, 8-octanediol, 1, 9-nonanediol, 1, 10-decanediol and 1, 12-dodecanediol. Linear difunctional polycarbonate polyols having a melting temperature of from about 5 ℃ to about 50 ℃ are preferred.

The polyisocyanate component b) suitable as another raw material for preparing the urethane prepolymer of the present invention may be a diphenylmethane diisocyanate (MDI) isomer mixture comprising 4, 4 '-methylene bis (phenyl isocyanate) and 2, 4' -methylene bis (phenyl isocyanate) wherein the ratio of the 4, 4 '-MDI to the 2, 4' -MDI isomers is from about 65: 35 to about 35: 65, preferably from about 55: 45 to about 45: 55 and more preferably about 50: 50. Examples of suitable polyisocyanate components include Mondur ML(Bayer)、LupranateMI (BASF) and Isonate50 O，P’(DowChemical)。

Diol compounds c) suitable as further starting materials for the preparation of the urethane prepolymers of the invention comprise at least one diol compound having: (i) two hydroxyl groups which are capable of reacting with the polyisocyanate component b); and (ii) at least one carboxyl group which on neutralization is capable of forming a salt and which is not capable of reacting with the polyisocyanate component b). Common examples of diol compounds c) having one carboxyl group include 2, 2-dimethylolpropionic acid (DMPA), 2-dimethylolbutyric acid, 2-dimethylolpentanoic acid and DMPA-initiated caprolactone (e.g.CAPA)HC 1060 (Solvay)). DMPA is preferred in the present invention.

The prepolymer may be prepared by: the starting materials a), b) and c) are mixed together in one step and reacted at about 50 ℃ to about 100 ℃ for a sufficient time until substantially all hydroxyl groups are consumed and the desired% NCO of the isocyanate groups is obtained. Alternatively, such prepolymers can be prepared in two steps by first reacting the starting materials a) with an excess of b) and then with component c) until the desired final prepolymer% NCO is obtained. For example, the% NCO can be about 1.3 to about 6.5, such as about 1.8 to about 2.6. It is to be noted that no organic solvent is added or mixed with the starting materials before, during or after the reaction. Optionally, a catalyst may be used to promote the formation of the prepolymer.

In one embodiment of the present invention, the prepolymer comprises components a), b) and c), said components being combined and provided in the following weight percent ranges, based on the total weight of the prepolymer:

from about 34% to about 89% of component a);

from about 59% to about 10% of component b); and

from about 7.0% to about 1.0% of component c).

[00065]In another embodiment of the present invention, the prepolymer comprises1800 polyether diols as component a),ML diisocyanate as component b) and 2, 2-dimethylolpropionic acid (DMPA) as component c). In such an embodiment, these components may be, for example, in the following weight percent ranges, based on the total weight of the prepolymer:

1800 polyether diol: from about 61% to about 80%;

ML diisocyanate: from about 35% to about 18%; and

c)2, 2-dimethylolpropionic acid (DMPA): from about 4.0% to about 2.0%.

[00066] The prepolymer prepared from components a), b) and c) has a bulk viscosity (in the absence of any solvent) of less than about 6,000 poise, such as less than about 4,500 poise, for example 500-6,000 poise or 500-4,500 poise, as determined by the falling ball method at 40 ℃. This prepolymer (containing carboxyl groups along the polymer chain) can be dispersed using a high speed dispersing mixer into a deionized water medium containing: at least one neutralizing agent d) to form an ionic salt with the acid; at least one surfactant (ionic and/or non-ionic dispersant or surfactant); and optionally at least one diamine chain extender component f). Alternatively, the neutralizing agent may be mixed with the prepolymer before the prepolymer is dispersed into the aqueous medium. At least one antifoaming and/or defoaming agent and preferably at least one rheology modifier may be added to the aqueous medium before, during or after dispersion of the prepolymer.

[00067] Examples of suitable neutralizing agents d) for converting acid groups into salt groups include: tertiary amines (such as triethylamine, N-diethylmethylamine, N-methylmorpholine, N-diisopropylethylamine and triethanolamine) and alkali metal hydroxides (such as lithium hydroxide, sodium hydroxide and potassium hydroxide). Primary and/or secondary amines may also be used as neutralizing agents for the acid groups. The degree of neutralization is typically from about 60% to about 140%, for example from about 80% to about 120%, of the acid groups.

[00068]Examples of suitable diamine chain extenders f) include: 1, 2-ethylenediamine, 1, 4-butanediamine, 1, 6-hexanediamine, 1, 12-dodecanediamine, 1, 2-propanediamine, 2-methyl-1, 5-pentanediamine, 1, 2-cyclohexanediamine, 1, 4-cyclohexanediamine, 4' -methylenebiscyclohexylamine, isophoronediamine, 2-dimethyl-1, 3-propanediamine, m-tetramethylxylylenediamine and polymers having a molecular weight of less than 500(Texaco)。

Examples of suitable surfactants include: anionic, cationic or nonionic dispersants or surfactants, e.g. sodium dodecyl sulphate, sodium dodecylbenzene sulphonate, ethoxylated nonylphenol and lauryl pyridine bromide。

Examples of suitable antifoams or defoamers or foam control agents include: additive65 and Additive 62 (silicone based additives from Dow Corning), FoamStarI300 (mineral oil based silicone free defoamer from Cognis) and Surfynol^TMDF 110L (from Air Products)&High molecular weight acetylenic diol nonionic surfactant from Chemicals).

Examples of suitable rheology modifiers include: hydrophobically modified ethoxylated urethane (HEUR), hydrophobically modified alkali swellable emulsion (HASE), and hydrophobically modified hydroxyethyl cellulose (HMHEC).

At least one monofunctional dialkylamine compound e) as blocking agent for isocyanate groups is added to the aqueous medium during or after the dispersion of the prepolymer. For example, the end-capping agent may be added to the water mixture immediately after the prepolymer is dispersed. Optionally, at least one polymer component g) (MW > about 500) (with at least 3 or more primary and/or secondary amino groups per mole of polymer) is added to the aqueous medium after the prepolymer is dispersed and the endcapping agent is added.

Examples of suitable monofunctional dialkylamine capping agents e) include: n, N-diethylamine, N-ethyl-N-propylamine, N-diisopropylamine, N-tert-butyl-N-methylamine, N-tert-butyl-N-benzylamine, N-dicyclohexylamine, N-ethyl-N-isopropylamine, N-tert-butyl-N-isopropylamine, N-isopropyl-N-cyclohexylamine, N-ethyl-N-cyclohexylamine, N-diethanolamine and 2, 2, 6, 6-tetramethylpiperidine. The molar ratio of amine blocking agent to isocyanate groups of the prepolymer prior to dispersion in water should generally be from about 0.05 to about 0.50, for example from about 0.20 to about 0.40. A catalyst may be used for the deblocking reaction.

Examples of suitable polymer components g) include: polyethyleneimine, polyvinylamine, polyallylamine, and poly (amide-amine) dendrimers.

Other additives that may optionally be included in the aqueous dispersion or prepolymer include: antioxidants, UV stabilizers, colorants, pigments, crosslinking agents, phase change materials (i.e., Outlast)Available from Outlast Technologies, Boulder, Colorado), antimicrobial agents, minerals (i.e., copper), microencapsulated health (well-bening) additives (i.e., aloe vera, vitamine E gel, aloe vera, seaweed, nicotine, caffeine, perfume or fragrance essential oil), nanoparticles (i.e., silica or carbon), calcium carbonate, flame retardants, anti-tack agents, anti-chlorine degradation agents, vitamine, drugs, fragrances, conductive additives and/or dye adjuvants (i.e., MethacrolFrom e.i. dupont de nemours, Wilmington, Delaware). Other additives that may be added to the prepolymer or aqueous dispersion include: adhesion promoters, antistatic agents, anticratering agents, fluorescent whitening agents, auxiliary film agents, conductive agents, luminescent agents, leveling agents, thawing stabilizers, lubricants, organic and inorganic fillers, preservatives, crimping stabilizers, thermochromic agents, insect repellents and wetting agents.

These optional additives may be added to the aqueous dispersion before, during or after dispersion of the prepolymer, depending on process approval. No organic solvent was added to the aqueous dispersion throughout the process.

It is contemplated that the aqueous polyurethane dispersions of the present invention should have a solids content of from about 10% to about 50% by weight, for example from about 30% to about 45% by weight. The viscosity of the aqueous polyurethane dispersions of the present invention may vary over a wide range from about 10 centipoise to about 100,000 centipoise depending on processing and application requirements. For example, in one embodiment, the viscosity is from about 500 centipoise to about 30,000 centipoise. The viscosity can be varied by employing an appropriate amount of thickener, such as from about 0 to about 2.0 weight percent based on the total weight of the aqueous dispersion.

The solvent-free aqueous polyurethane dispersions of the present invention are particularly suitable for adhesive shaped articles which are useful for fabric bonding, lamination and adhesion when subjected to heat and pressure for relatively short periods of time. Depending on the bonding method used, the pressure may be, for example, from about atmospheric pressure to about 60psi, and the time may be from less than about 1 second to about 30 minutes.

Such shaped articles can be prepared by: the dispersion is coated onto release paper and dried by conventional methods at temperatures below about 100 ℃ to remove the water to form a film on the paper. The prepared film sheet can be cut into strips of desired width and wound into rolls for later use in certain applications to prepare elastic articles, such as fabrics. Examples of such applications include: no sewing or seamless garment construction; a suture seal and reinforcement; labels and patches that are adhered to clothing; and localized stretch/recovery enhancements. The adhesive bond may be formed under the following conditions: the temperature is from about 100 ℃ to about 200 ℃, such as from about 130 ℃ to about 200 ℃, for example from about 140 ℃ to about 180 ℃, and the time is from 0.1 seconds to several minutes, for example less than about 1 minute. Typical bonders are Sew Free (from SewSystems in Leicester, England), Macpi roller (from Macpi group in Brescia, Italy), Framis hot air fusion machine (from Framis Italy, s p.a.in Milano, Italy). Such bonds are expected to be strong and durable in textile garments when subjected to repeated wear, laundering and stretching.

The coating, dispersion or shaped article can be pigmented and, in this regard, can also be used as a design element.

In addition, articles having a laminate film or dispersion can be molded. For example, the fabric may be molded under conditions suitable for the hard yarns in the fabric. Also, molding can be carried out at a temperature that will mold the shaped article or dispersion but below a temperature suitable for molding the hard yarn.

Lamination can be performed by any method for securing the shaped article to the fabric, wherein the laminate surface is heated. Heating methods include, for example, ultrasonic, direct heating, indirect heating, and microwave. Such direct lamination may provide an advantage in that the shaped article may be bonded to the substrate not only by mechanical action but also by chemical bonding, taking into account other methods used in the art. For example, if the substrate has any active hydrogen functional groups, such groups can react with isocyanate and hydroxyl groups on the dispersion or shaped article to provide a chemical bond between the substrate and the dispersion or shaped article. Such chemical bonding of the dispersion or shaped article to the substrate can produce very strong adhesion. This bonding can be carried out in a dry shaped article cured to the substrate or in a wet dispersion dried and cured in one step. Active hydrogen-free materials include polypropylene fabrics and any substance having a fluoropolymer or siloxane-based surface. Materials with active hydrogen include, for example, nylon, cotton, polyester, wool, silk, cellulose, acetate, metals, and acrylics. In addition, articles treated with acid, plasma, or other forms of etching may have active hydrogen for adhesion. The dye molecules may also have binding active hydrogens.

Methods and means for applying the dispersions and shaped articles of the present invention to articles include, but are not limited to: roll coating (including reverse roll coating); casting the dispersion to a uniform thickness using a metal tool or doctor blade (e.g., pouring the dispersion onto a substrate and then distributing it onto the substrate using a metal tool such as a doctor blade); spray coating (e.g., with a pump spray bottle); dip coating; smearing; printing; printing and impregnating the article. These methods can be used to apply the dispersion directly to the substrate without the need for additional adhesive materials and can be repeated if additional/heavier layers are desired. The dispersion can be applied to any knit, woven or nonwoven fabric made of synthetic, natural or synthetic/natural hybrid materials for coating, bonding, laminating and adhering. The water in the dispersion can be removed by drying during processing (e.g., by air drying or oven), leaving a precipitated and coalesced polyurethane layer on the fabric to form an adhesive bond.

At least one coagulant may optionally be used to minimize penetration of the dispersions of the present invention into fabrics or other articles. Examples of coagulants that may be used include calcium nitrate (including calcium nitrate tetrahydrate), calcium chloride, aluminum sulfate (hydrated), magnesium acetate, zinc chloride (hydrated), and zinc nitrate.

One example of a tool that can be used to apply the dispersion of the present invention is a doctor blade as shown in fig. 8 and 9. The doctor blade 100 may be made of metal or any other suitable material. The doctor blade may have a gap of a predetermined width 102 and thickness 104. The gap thickness can be, for example, 0.2mil to 50 mils, such as 5mil, 10mil, 15mil, 25mil, 30mil, or 45mil in thickness.

The thickness of the dispersions and shaped articles of the present invention can vary depending on the application and method of application. If a dry formed article, the final thickness can be, for example, from about 0.1mil to about 250 mils, such as about 0.5mil to about 25mil, including about 1 to about 6mil (1mil to one thousandth of an inch). For aqueous dispersions, the amount used may be, for example, about 2.5g/m²About 6.40kg/m²E.g., about 12.7 to about 635g/m²Including from about 25.4 to about 152.4g/m²。

The types of planar sheets and tapes that can be coated with the dispersions and shaped articles of the invention include, but are not limited to: fabrics (including both woven and knitted fabrics); a nonwoven material; leather (dermis or synthetic leather); paper; metal, plastic and scrims.

Final articles that can be made using the dispersions and shaped articles of the invention include, but are not limited to: garments, including all types of garments or articles of clothing; knitting gloves; indoor decoration; hair accessories, bed sheets; carpet and carpet backing; a conveyor belt; medical applications, such as elastic bandages; personal care products, including incontinence and feminine hygiene products; and footwear. Articles coated with the dispersion or covered with a film or tape can be used as sound suppression articles.

Non-elastic fabrics laminated to shaped articles can have improved stretch and recovery properties and improved molding properties.

Articles comprising shaped articles, films, tapes or aqueous polyurethane dispersions can be molded. The articles can be prepared from multilayer substrates and shaped articles, films, tapes or dispersions. The multilayer article may also be molded. The molded or unmolded article may have different levels of stretch and recovery. The molded article may comprise a body shaping or body protecting garment, such as a brassiere.

Examples of garments or garments that can be made using the dispersions and shaped articles of the present invention include, but are not limited to: intimate apparel, bra, shorts, lingerie, swimwear, body wear, women's intimate apparel, hosiery, pajamas, wetsuit, tie, space suit, hat, thong, sweatband, belt, racing uniform, raincoat, jacket, pants, gown, sweater, corset, lantern, shorts, socks, knee stockings, outerwear, gown, apron, tatami suit, cape (bisht), robe, hood (hijab), islamic garment (covering a person from head to foot with only eyes and hands exposed) (jilbab), loose gown (thoub), muslin lington suit, shawl, suit, wetsuit, scotch skirt, and jersey, protective apparel, sarsa, shack, sarsa, roman suit, robe, suit, body suit, top suit, girl suit, top suit, and jersey suit, top suit, jersey suit, slops, Wetsuits, medical compression garments (gowns), bandages, waistbands, and all components therein.

Fig. 4 is a representative view of a flat bed laminator. A roll of fabric substrate 72 is unwound and preheated at zone 78. The second roll of fabric substrate 76 and film roll 74 are unwound and brought into a laminating heat/pressure zone 80. After heating, the resulting fabric/film/fabric sandwich is cooled in cooling zone 82. Roll 84 represents a rolled-up fabric/film/fabric laminate.

Methods for Reverse Roll Coating and overcoming common problems have been described by Walter et al, "dissolving common Coating rolls in Reverse Roll Coating",AIMCAL Fall Technical Conference(October 26-29, 2003), the entire contents of which are incorporated herein by reference.

The dispersions and shaped articles of the present invention can be applied continuously or selectively to a given substrate. In this regard, FIGS. 5-7 show in cross-sectional views illustrations of the application of the dispersions and shaped articles of the invention. In these figures, the substrate is indicated by a thick black line, and the dispersions and shaped articles of the invention are represented as: (1) two parallel threads, when applied by a spreading method (by using a doctor blade or the like), as shown in fig. 5; (2) the zigzag lines were overlaid onto the thick black lines, when applied by dip coating, as shown in fig. 6; or (3) zigzag lines between or above the thick black lines, when applied by painting or spraying, etc., as shown in fig. 7. The left-hand picture of these figures, indicated by the number followed by the letter "a", indicates the continuous application of the dispersion and shaped article according to the invention, while the right-hand picture of the figures, indicated by the number followed by the letter "b", indicates the selective or segmented application of the dispersion and shaped article according to the invention. Although not shown in fig. 5-7, it is also contemplated that the dispersions and shaped articles of the present invention may be applied continuously and in stages during the same application, such as continuously on or between some layers and in stages on or between other layers.

Figures 10-13 show representative examples of garments that can be made to incorporate the dispersions or shaped articles of the present invention.

Fig. 10 shows a brassiere 110, the brassiere 110 having a fabric brassiere cup 112 formed in a support structure including a peripheral region 114 surrounding the cup 112 and body-engaging side edges 116 terminating in fastening components such as hooks 118 and mating loops 120. Brassiere 110 also includes shoulder straps 122. Bra 110 may incorporate the dispersion or shaped article of the present invention. Such a dispersion or shaped article may be provided to or on any number of locations on the brassiere, including but not limited to shoulder straps 122, peripheral regions 114, and body-wrapping sides 116. Such a dispersion or shaped article may be provided anywhere where a seam is desired to connect one or more pieces of material in a brassiere. As shown in fig. 10, the bra cups 112 and the geometric areas 124 along the wrap around side 116 of the body are free of applied film. All other fabric components comprise the shaped article or dispersion of the present invention. Although not specifically shown in fig. 10, the bra cup 112 can be molded using the dispersion of the present invention.

Fig. 11 shows a cross-sectional view of the breast cup 112. Figure 12 shows an exploded view of the cup rim meeting with the peripheral region 114 surrounding the cup. As shown in fig. 11 and 12, the bra cup 112 is made of fabric without a dispersion or film applied thereto. The peripheral region 114 has a thin film applied and is therefore of greater thickness than the fabric of the cup, including the thickness of the film and fabric together. The peripheral region 114 provides some breast support rigidity and firmness without the uncomfortable stiffness associated with steel supports.

Fig. 13 shows a pair of female pants or briefs 130, which female pants or briefs 130 may be bonded, provided with increased elasticity and/or increased support in combination with the dispersion or shaped article according to the invention. Such a dispersion or shaped article may be provided to or on any number of locations on the female pants or briefs 130, including but not limited to the waist band 132 and leg openings 134.

Another aspect of the present invention is an article that may comprise an adhesive, an elastic component, and a substrate. The adhesive 150 and elastic component 152 can be combined in a first step and adhered to a substrate 154 in a second step to produce an elastic article 156 (fig. 14). Alternatively, the adhesive 162 and elastic component 162 may be applied to the substrate 164 in a single step to produce the elastic article 166 (fig. 15). In both embodiments, heat and pressure may be used to bond the adhesive. Examples of the adhesive may include an adhesive tape prepared from the above-mentioned aqueous polyurethane dispersion or the dispersion itself may be directly used as an adhesive. These adhesives may or may not be elastic. Examples of elastic components may include spandex yarn or tape, rubber thread or tape, woven elastic strips, knitted elastic strips, and the like. One example of the present invention is hemming, wherein a substrate 200 is folded, secured with an adhesive 202 and supported for stretching and recovery by an elastic assembly 204 (fig. 16). The flaps shown in fig. 16 may be used with garments such as underwear or swimwear. Examples of intimate apparel include men's and women's undergarments, brassieres, and body shaping garments.

Another aspect of the invention is an article comprising a shaped article and a substrate, wherein the shaped article and the substrate are adhered together to produce a laminate such that the elastic laminate has a coefficient of friction greater than the coefficient of friction of the substrate alone. Examples of such articles are waistbands with a coating or film comprising an aqueous polyurethane dispersion which prevents the garment from slipping off another garment, such as a blouse or shirt, or the waistband from slipping off the skin of the wearer of the garment.

Another aspect of the invention is an article comprising a shaped article and a substrate, wherein the modulus of the shaped article varies along the length or width of the article. For example, a substrate (e.g., fabric 302) may be treated with a two foot (61cm) shaped article (e.g., one inch (2.5cm) wide tape 304). Additional adhesive layers 306 may be applied by painting three two inch (5cm) by one inch sections along the length of the one inch wide tape to form the composite structure 300 (fig. 17).

Shaped articles, such as films of aqueous polyurethane urea dispersions, can have the following properties:

a permanent set after stretching of about 0 to 10%, for example about 0 to 5%, usually about 0 to about 3%,

an elongation of about 400 to about 800%, and

a tenacity of from about 0.5 to about 3 Mpa.

Laminates made from the article and the substrate may have the following properties:

peel strength after 50 washes, wherein at least 50% of the pre-wash strength is retained,

an air permeability of at least about 0 to about 0.5cfm, and

at least about 0 to about 300g/m for 24 hours²Moisture vapor transmission rate of (c).

Analytical method

In the following examples, the following analytical methods were used:

peel strength of adhesive bond

ASTM D903-93 (which is incorporated herein by reference in its entirety) was adjusted to test film laminated fabrics. The sample size for the test was 1 inch by 6 inches (2.5cm by 15 cm). The separation rate was 2 inches/minute (5 cm/minute). The data is reported as pounds of force per inch of sample width (kg/mm) as shown in tables 2 and 4.

Wash test

The molded breast cups were washed using AATCC test method 150-2001, which is incorporated herein by reference in its entirety. The machine duty cycle was (I) standard/cotton texture. The washing temperature was (III)41 ℃. The drying step was (A) (i) inverting the cotton texture at 66 ℃ for 30 minutes, 10 minutes cooling time.

Moisture penetration

Articles are tested for moisture vapor transmission properties using ASTM E96-00, the entire contents of which are incorporated herein by reference. The data are reported as grams per square meter for a 24 hour period as shown in table 7.

Air permeability

The articles were tested for air permeability performance using ASTM D-737, the entire contents of which are incorporated herein by reference. The data is reported as cubic feet of air per minute per square foot of fabric (cfm, cubic centimeters of air per second per square centimeter of fabric (ccs)) as shown in table 7.

Elongation, toughness and permanent set

The elongation and toughness properties were measured on the film using a dynamic tensile tester Instron. The sample dimensions were 1 × 3 inches (1.5 cm × 7.6 cm), measured along the long dimension. The sample was placed in a jig and stretched at a strain rate of 200% elongation per minute until maximum elongation was reached. Tenacity and elongation were measured just before film break. Likewise, the% set was tested by stretching a 1X 3 inch (1.5 cm. times.7.6 cm) film sample at a strain rate of 200% per minute with five cycles of 0-50% elongation. After the fifth cycle the% permanent set was determined.

Examples

Representative embodiments of the present invention will now be described with reference to the following examples which illustrate the principles and practice of the invention. In these embodiments: reference numerals refer to elements shown in the flow diagrams of fig. 1-3 and, if appropriate, the cross-sectional views of fig. 5-7.

Terathane1800 is a linear polytetramethylene ether glycol (PTMEG) having a number average molecular weight of 1,800 (available from Invista, s. a. r.L, of Wichita, KS and wilmington, DE);

PluracolHP 4000D is a linear primary hydroxyl terminated polypropylene ether glycol (available from BASF, Bruxelles, Belgium) with a number average molecular weight of 400;

MondurML is a diphenylmethane diisocyanate (MDI) isomer mixture (available from Bayer, Baytown, TX) comprising 50-60% of the 2,4 '-MDI isomer and 50-40% of the 4, 4' -MDI isomer;

LupranateMI is a diphenylmethane diisocyanate (MDI) isomer mixture (available from BASF, Wyandotte, Michigan) comprising 45-55% of the 2,4 '-MDI isomer and 55-45% of the 4, 4' -MDI isomer;

Isonate125MDR is a pure mixture of diphenylmethane diisocyanate (MDI) containing 98% of the 4, 4 '-MDI isomer and 2% of the 2, 4' -MDI isomer (available from Dow company, Midland, Michigan); and

DMPA is 2, 2-dimethylolpropionic acid.

Using mixtures of MDI isomers (e.g. Lupranate) containing high levels of 2, 4' -MDIMI and MondurML) the following prepolymer samples were prepared.

Example 1

The prepolymer was prepared in a glove box under nitrogen atmosphere. About 382.5 grams of Terathane1800 diols and about 12.5 grams DMPA to 2000ml PyrexIn the glass reaction kettle, the reaction kettle is provided with: air pressure driven stirrer, heating mantle and thermocouple temperature measurement. The resulting mixture was stirred, heated to about 50 deg.C, and then about 105 grams of Lupranate was addedMI diisocyanate. The reaction mixture was then continuously stirred, heated to about 90 ℃ and held at about 90 ℃ for about 120 minutes, after which the reaction was completed when the% NCO of the mixture had dropped to a stable value which corresponds to the calculated value for the prepolymer with terminal isocyanate groups (% NCO target 1.914). The viscosity of the prepolymer was determined at about 40 ℃ according to the general method ASTM D1343-69 using a Model DV-8 Falling Ball Viscometer (sold by Duratech Corp., Waynesboro, Va.). According to S.Siggia, "Quantitative Organic Analysis via Functional Group", 3rd Edition, Wiley&The total isocyanate moiety content of the capped glycol prepolymer, expressed as a weight percentage of NCO groups, was determined by the method of Sons, New York, pp.559-561(1963), the entire contents of which are incorporated herein by reference.

Example 2

The procedure was as in example 1, except that the following ingredients were used in the reaction mixture:

Terathane1800: about 361 grams;

DMPA: about 19 grams; and

MondurML: about 120 grams.

Example 3

Terathane1800: about 349 grams;

DMPA: about 21 grams; and

MondurML: about 130 grams.

Example 4

Terathane1800: about 329 grams;

PluracolHP 4000D: about 30 grams;

DMPA: about 21 grams; and

MondurML: about 120 grams.

Example 5

Terathane1800: about 331 grams;

PluracolHP 4000D: about 30 grams;

DMPA: about 19 grams; and

MondurML: about 120 grams.

Comparative examples

In the following prepolymer samples, the preparation steps and the type and amount of ingredients remained the same except for the MDI diisocyanate. For comparison, the same amount of Isonate was used in the reaction mixture as shown below125MDR instead of LupranateMI or MondurML：

Example 6C

Terathane1800: about 382.5 grams;

DMPA: about 12.5 grams; and

Isonate125 MDR: about 105 grams.

Example 7C

Terathane1800: about 361 grams;

DMPA: about 19 grams; and

Isonate125 MDR: about 120 grams.

Example 8C

Terathane1800: about 349 grams;

DMPA: about 21 grams; and

Isonate125 MDR: about 130 grams.

Example 9C

Terathane1800: about 329 grams;

PluracolHP 4000D: about 30 grams;

DMPA: about 21 grams; and

Isonate125 MDR: about 120 grams.

Example 10C

Terathane1800: about 331 grams;

PluracolHP 4000D: about 30 grams;

DMPA: about 19 grams; and

Isonate125 MDR: about 120 grams.

The viscosities (measured at 40 ℃ using the falling ball method) of the example prepolymer samples (examples 1-5) and the comparative example samples (examples 6C-10C) are set forth in Table 1 for comparison:

TABLE 1 viscosity (poise) of prepolymer measured at 40 ℃ by falling ball method

Examples	Falling ball viscosity (poise) at 40 DEG C
		1 2 3 4 5 6C 7C 8C 9C 10C	3086 3292 2468 4382 3876 6722 7690 6560 12148 6187

As shown in Table 1, Lupranate was usedMI or MondurViscosity ratio of ML prepared prepolymer (in the absence of any solvent during or after prepolymer preparation) Using IsonateThose made by 125MDR were considerably lower. The prepolymer viscosity of the comparative example sample (without dilution with solvent) is too high to be transported and dispersed in water in downstream processing.

Example 11

Aqueous polyurethane urea dispersions of the present invention were prepared using a solvent-free prepolymer prepared according to the procedure and composition described in example 1.

About 700 grams of deionized water, about 15 grams of Sodium Dodecylbenzenesulfonate (SDBS), and about 10 grams of Triethylamine (TEA) were added to a 2,000ml stainless steel beaker. The resulting mixture was then cooled to about 5 ℃ with ice/water and mixed with a high shear laboratory mixer (Ross, Model 100LC) with a rotor/stator mixing head at about 5,000rpm for about 30 seconds. The viscous prepolymer prepared and stored in the metal tubular cylinder according to the method of example 1 was added to the bottom of the mixing head in an aqueous solution through a hose by applying air pressure. The temperature of the prepolymer is maintained at a temperature of from about 50 ℃ to about 70 ℃. The extruded prepolymer stream was dispersed and chain extended with water under continuous mixing at about 5,000 rpm. A total of about 540 grams of prepolymer was introduced and dispersed in water over about 50 minutes. About 2 grams of Additive65 (from dow corning) was added just after the prepolymer was added and dispersedMidland Michigan) and about 6 grams of Diethylamine (DEA) were added to the dispersion mixture. The reaction mixture was then mixed for about 30 minutes. The resulting solvent-free aqueous dispersion was milky white and stable. The viscosity of the dispersion was adjusted by adding and mixing the aqueous dispersion with HauthhaneHA thickener 900 (available from Hauthway, Lynn, Massachusetts) at a level of about 2.0% by weight. The viscous dispersion was then filtered through a 40 micron Bendix metal mesh filter and stored at room temperature for film casting or lamination. The dispersion had a solids level of 43% and a viscosity of about 25,000 centipoise. Cast films prepared from such dispersions are soft, tacky and elastomeric.

Example 12

About 900 grams of deionized water, about 15 grams of Sodium Dodecylbenzenesulfonate (SDBS), and about 10 grams of Triethylamine (TE)A) Added to a 2,000ml stainless steel beaker. The resulting mixture was then cooled to about 5 ℃ with ice/water and mixed with a high shear laboratory mixer (Ross, Model 100LC) with a rotor/stator mixing head at about 5,000rpm for about 30 seconds. The viscous prepolymer prepared and stored in the metal tubular cylinder according to the method of example 1 was added to the bottom of the mixing head in an aqueous solution through a hose by applying air pressure. The temperature of the prepolymer is maintained at a temperature of from about 50 ℃ to about 70 ℃. The extruded prepolymer stream was dispersed and chain extended with water under continuous mixing at about 5,000 rpm. A total of about 540 grams of prepolymer was introduced and dispersed in water over about 50 minutes. About 2 grams of Additive65 (from dow corning) was added just after the prepolymer was added and dispersedMidland Michigan) and about 6 grams of Diethylamine (DEA) were added to the dispersion mixture. The reaction mixture was then mixed for about 30 minutes. The resulting solvent-free aqueous dispersion was milky white and stable. The viscous dispersion was then filtered through a 40 micron Bendix metal mesh filter and stored at room temperature for film casting or lamination. The dispersion had a solids level of 40% and a viscosity of about 28 centipoise. Cast films prepared from such dispersions are soft, tacky and elastomeric.

Example 13

About 700 grams of deionized water, about 15 grams of Sodium Dodecylbenzenesulfonate (SDBS), and about 10 grams of Triethylamine (TEA) were added to a 2,000ml stainless steel beaker. The resulting mixture was then cooled to about 5 ℃ with ice/water and mixed with a high shear laboratory mixer (Ross, Model 100LC) with a rotor/stator mixing head at about 5,000rpm for about 30 seconds. The viscous prepolymer prepared and stored in the metal tubular cylinder according to the method of example 1 was added to the bottom of the mixing head in an aqueous solution through a hose by applying air pressure. The temperature of the prepolymer is maintained at about 50 ℃ to about 70 DEG C. The extruded prepolymer stream was dispersed and chain extended with water under continuous mixing at about 5,000 rpm. A total of about 540 grams of prepolymer was introduced and dispersed in water over about 50 minutes. About 2 grams of Additive65 (from dow corning) was added just after the prepolymer was added and dispersedMidland Michigan) and about 6 grams of Diethylamine (DEA) were added to the dispersion mixture. The reaction mixture was then mixed for about 30 minutes. The resulting solvent-free aqueous dispersion was milky white and stable. The viscous dispersion was then filtered through a 40 micron Bendix metal mesh filter and stored at room temperature for film casting or lamination. The dispersion had a solids level of 43% and a viscosity of about 28 centipoise. Cast films prepared from such dispersions are soft, tacky and elastomeric.

Example 14C

The procedure was as in example 11, except that DEA was not added to the resulting dispersion after the prepolymer was mixed. Initially, the resulting dispersion appeared to be no different from example 11. However, when the resulting dispersion is aged at room temperature for one week or more, cast films prepared from such dispersions are brittle and not suitable for adhesion or lamination.

Example 15

The silicone coated release paper was coated with the filtered aqueous dispersion prepared according to example 11 by a continuous 12-inch (30 cm) laboratory reverse roll coater. This coater was equipped with a 3-zone drying oven set at about 60 deg.C, 75 deg.C and 120 deg.C, respectively. The total residence time for drying was about 6 minutes. A dry film of about 3 mils thickness was wound up at a speed of about 2 meters per minute. The resulting elastic film 12 can be easily peeled from the release paper and used for lamination.

Example 16

The elastic film 12 was prepared by coating a silicone-coated release paper with the filtered aqueous dispersion prepared according to example 11. Laboratory samples were prepared manually by securing a piece of 12 inch by 12 inch (30 cm by 30 cm) double-sided silicone release paper (Covermount DS from print Mount co., Inc 401-232-0096) to the work surface with masking tape. The aqueous dispersion was poured onto a release paper and cast to uniform thickness using a metal doctor blade tool shown in fig. 8 and 9 having a 6 inch (15cm) wide gap of 5mil thickness to apply the dispersion to the release paper. Excess solution was blotted dry with a paper towel. The cast film was air dried overnight under a fume hood. The resulting film 12 is readily peeled from the release paper for further use.

Example 17

The film 12 on the release paper prepared in example 15 was placed on the back of a 12 inch by 12 inch (30 cm by 30 cm) warp knit nylon and spandex fabric 14. The fabric/film/release paper sandwich was fed into a Hashima HP-400C Belt Oven Laminator (hashimaco., Ltd, Gifu-City Japan, 058-245-4501) and laminated at 165 ℃ with a dwell time of 20 seconds and pressure set at P1, 16 as shown in fig. 1, route 11 a. The release paper is removed leaving the film/fabric laminate elastic article 18 a.

TABLE 2

Examples	Adhesive peel strength (lb/in)	Adhesive peel strength (kg/cm)
			18 19 20 21 25 26 31	2.56 1.71 4.25 1.72 6.17 5.26 4.06	14.38 9.61 23.88 9.66 34.66 29.55 22.81

Example 18

The laminated elastic article 18a was covered with another piece of 12 inch by 12 inch (30 cm by 30 cm) warp knit nylon spandex fabric. The fabric/film/fabric sandwich was fed into a Hashima laminator and laminated at 165 ℃ for 20 seconds at a pressure setting of P ═ 1 to give an elastic article 24 a. The peel strength of example 18 was 2.56lb/in, see Table 2.

Example 19

The film 12 of example 15 was laminated to the fabric under the same conditions as in example 17 except that the laminating temperature was 120 ℃. The release paper is removed leaving the film/fabric laminate elastic article 18 a. The film side of article 18a was covered with another layer of 12 inch by 12 inch (30 cm by 30 cm) warp knit nylon spandex fabric. The fabric/film/fabric sandwich was fed into a Hashima laminator and laminated at 165 ℃ for 20 seconds at a pressure setting of P ═ 1 to give an elastic article 24 a. The peel strength of example 19 was 1.71lb/in, see Table 2.

Example 20

In this embodiment, two 18a elastomeric articles are layered such that the film faces are opposite. The fabric/film/fabric sandwich was fed into a Hashima laminator and laminated at 165 ℃ for 20 seconds at a pressure setting of P ═ 1 to give an elastic article. The peel strength of example 20 was 4.25lb/in, see Table 2.

Example 21

The film 12 of example 15 was carefully removed from the release paper and placed on a 12 inch x 12 inch (30 cm x 30 cm) warp knit nylon and spandex fabric 14. Another 12 inch by 12 inch (30 cm by 30 cm) warp knit nylon spandex fabric was placed over cast film 20. The fabric/film/fabric sandwich 20 was fed into a Hashima laminator and laminated at 165 ℃ for 20 seconds at a pressure setting of P ═ 122 to give the elastic article 24 a. The peel strength of example 21 was 1.72lb/in, see Table 2.

Example 22

The second film was carefully removed from the release paper and placed on the fabric/film/fabric sandwich 24a to make the article 26. Another 12 inch by 12 inch (30 cm by 30 cm) warp knit nylon spandex fabric was placed over the second layer of cast film 28. The fabric/film/fabric sandwich is fed into a Hashima laminator and laminated at 165 ℃ for 20 seconds at a pressure setting of P ═ 1, e.g., 30, to provide an elastic article 32 a.

Example 23

In this example, a piece of warp-knitted nylon spandex fabric (1 inch x 12 inch (2.5cm x 30 cm)) was dipped into the high viscosity aqueous dispersion 10b of example 11 and pulled out, and then the excess was squeezed between the gloved fingers. The second squeeze-off of excess between the gloved fingers results in an impregnated article 34. The resulting coated strip was hung and allowed to air dry overnight under a fume hood to yield an elastomeric article 38a (line 21a in fig. 2).

Example 24

A piece of light weight nonwoven fabric (deformable in the cross direction) was dipped into the low viscosity aqueous dispersion 10b (40% by weight solids and 28 centipoise) prepared according to example 12. The dipped article 34 is dripped to remove excess dispersion liquid and then dried overnight 36 in a fume hood to give an elastic article 38a (line 21a in fig. 2).

Example 25

In this example, the elastic article 38a of example 23 was covered with a warp knit nylon spandex fabric (6 inches by 12 inches (15cm by 30 cm)) 40. The resulting layered article 40 is fed into a Hashima laminator and laminated at 165 ℃ for 20 seconds at a pressure setting P ═ 1, e.g., 42 (scheme 21b in fig. 2), to provide an elastic article 44 a. The peel strength of example 25 was 6.17lb/in, see Table 2.

Example 26

In this example, an elastic article 44a (lane 21c in fig. 2) is covered with a warp knit nylon spandex fabric (6 inches by 12 inches (15cm by 30 cm)) 46. The resulting layered article 46 is fed into a Hashima laminator and laminated at 165 ℃ for 20 seconds at a pressure setting of P ═ 1, e.g., 48, to provide an elastic article 50 a. The peel strength of example 26 was 5.26lb/in, see Table 2.

Example 27

In this example, the filtered solution of the aqueous dispersion prepared in example 12 was poured into a conventional spray bottle. The filtered aqueous dispersion 10c was applied directly to a two-way stretch cotton/spandex twill fabric, as shown at 52 in fig. 3, using a spray bottle. The fabric is air dried 54 to provide an elastic article 56a (path 31a of fig. 3).

Example 28

A piece of elastic twill fabric was pretreated by immersion in a bath containing 20% by weight of an aqueous solution of calcium nitrate tetrahydrate as coagulant and dried in an oven at 100 c for 30 minutes. The aqueous dispersion 10c (40% by weight solids and 28 cps) prepared according to example 12 was uniformly coated onto the back of the pretreated fabric with a doctor blade having a gap thickness of 5mil (as shown in figures 8 and 9). The dispersion coagulated on the fabric surface without immersion. The fabric is then dried 54 in an 80 ℃ oven for 60 minutes to provide an elastic article 56a (line 31a in fig. 3).

Example 29

A piece of elastic twill fabric was coated with the high viscosity dispersion 10c of example 11 (43% by weight solids and 25000 centipoise). The increased viscosity allows the dispersion to be applied to one side of the fabric without saturating the fabric 52. The fabric was dried 54 in an 80 ℃ oven for 60 minutes to give 56a (route 31a of fig. 3).

Example 30

A piece of 12 inch x 12 inch (30 cm x 30 cm) warp knit nylon spandex fabric was secured to the work surface using masking tape (so that the fabric was under less tension in the warp direction). The filtered aqueous dispersion 10c of example 11 (43% by weight solids and 25000 centipoise) was poured onto the fabric 52. The increased viscosity allows the dispersion to be applied to one side of the fabric without saturating the fabric 52. The dispersion was spread onto the fabric using a 6 inch wide gap metal tool (as shown in FIGS. 8 and 9) having a thickness of 10 mils to produce a film of uniform thickness. Excess solution was blotted dry with a paper towel. The coated fabric was allowed to air dry overnight under a fume hood. The article 52 is fed into a Hashima laminator and laminated at 165 ℃ for 20 seconds at a pressure setting of P ═ 1, e.g., 54, to provide an elastic article 56a (fig. 3, line 31 a).

Example 31

A piece of 12 inch x 12 inch (30 cm x 30 cm) warp knit nylon spandex fabric was secured to the work surface using masking tape (so that the fabric was under less tension in the warp direction). The filtered aqueous dispersion 10c of example 11 (43% by weight solids and 25000 centipoise) was poured onto the fabric 52. The dispersion was spread onto the fabric using a 6 inch wide gap metal tool (as shown in FIGS. 8 and 9) having a thickness of 10 mils to produce a film of uniform thickness. Excess solution was blotted dry with a paper towel. Another 12 inch x 12 inch (30 cm x 30 cm) warp knit nylon spandex fabric was laid over the dispersion and lightly pressed to promote adhesion 58 (path 31b in fig. 3). The coated fabric sandwich was allowed to air dry overnight under a fume hood. The layered article 58 is fed into a Hashima laminator and laminated at 165 ℃ for 20 seconds at a pressure setting of P ═ 1, e.g., 60, to provide an elastic article 62 a. The peel strength of example 31 was 4.06lb/in, see Table 2.

TABLE 3 molded bra cup height (cm)

Examples	Molded back height (cm)	2A height after Wash cycle (cm)
			32	7.4	4.2
33C	7.3	1.9
			34	6.7	6.4
35C	6.8	5.9

Example 32

An elastic article 24a (FIG. 1) was prepared according to example 21, except that a 100% cotton circular knit fabric was used as the top and bottom fabric. A12 inch by 12 inch (30 cm by 30 cm) cotton based elastic article 24a was molded into a breast cup using a Texilformung Willi Lehman GmbH Molding machine type 2030 NT with an 8.5cm deep ring shaped elastic mold. The spring, cone mold base was heated to 195 ℃ while the ring clamp was heated to 185 ℃. The fabric was molded for 45 seconds according to standard practice. The cup height after molding was measured immediately and again after one washing and drying cycle according to AATCC Test Method 150-2001. The height of the resulting cotton laminated, molded cup was 7.4 cm. After washing, the height of the cup of example 32 was 4.2 cm.

Example 33C

A piece of 12 inch by 12 inch (30 cm by 30 cm) 100% cotton circular knit was molded in the same manner as in example 32. The cup height was measured immediately after molding and again after one washing and drying cycle according to AATCC Test Method 150-2001. The height of the resulting 100% cotton cylindrical knit molded cup was 7.3 cm. After washing, the height of the cup of example 33C was 1.9 cm.

Example 34

An elastic fabric 24a (fig. 1) was prepared according to example 21 using a warp knit nylon spandex fabric as the top and bottom layer fabrics. A piece of 12 inch by 12 inch (30 cm by 30 cm) tricot nylon spandex base elastomeric article 24a was molded in the same manner as in example 32. The cup height was measured immediately after molding and again after one washing and drying cycle according to AATCC Test Method 150-2001. The height of the resulting laminated, molded cup was 6.7 cm. After washing, the height of the cup of example 34 was 6.4 cm.

Example 35C

A piece of 12 inch x 12 inch (30 cm x 30 cm) 100% warp knit nylon was molded in the same manner as in example 32. The cup height was measured immediately after molding and again after one washing and drying cycle according to AATCC Test Method 150-2001. The height of the resulting laminated, molded cup was 6.8 cm. After washing, the cup height of example 35C was 5.9 cm.

Example 36

From a roll, 4-ply spandex yarn (Lycra) of length 110cm was cut70 denier) and placed side by side. The yarns were placed side by side in a flat bundle and extruded into a tape made from the cast film of example 11 (fig. 14). The resulting tape composite and warp knit fabric were fed to a bonder (available from Sew Systems, Leicester, England) to form a hem on the fabric. The folding was performed at 180 ℃ to produce smooth folds, which were held together with tape and reinforced with spandex yarn (fig. 16).

Example 37

In this example, the hem was performed similarly to example 36, but the spandex yarn was stretched with little to no stretch or tension as the tape was fed to the bonder. This produced a hem similar to example 36, but the hem in this example was gathered.

Example 38

In this example, the fabric of example 36 was coated with the dispersion solution of example 30. The elastic yarn was applied to the fabric and the fabric was hemmed using the bonder in example 36. A flat adhesive hem reinforced with an elastic yarn is formed.

Example 39

In this example, spandex yarn was coated with the dispersion of example 11. The resulting coated yarn was applied to the edge of the fabric. The fabric edges are folded to create hems. The folded hems were glued using a gluing machine as in example 36. A flat adhesive hem is formed which bonds the fabric with the elastic yarn.

Example 40

A laminate prepared similarly to example 17 was subjected to peel strength testing. Samples were washed 5, 10, 20, 30, 40 and 50 times. The data for this example are set forth in Table 4.

EXAMPLE 41

A laminate was prepared as in example 40 (except for the film). The film used in this example was 1mil elastic film #3410 (available from Bemis Associates, inc. of Shirley, Massachusetts). The laminate was tested for peel strength. Samples were washed 5, 10, 20, 30, 40 and 50 times. The data for this example are set forth in tables 4 and 5.

TABLE 4 Peel Strength

	Peel strength (lb/in)	Peel Strength (kg/cm)
					Number of washes	Example 40	EXAMPLE 41	Example 40	EXAMPLE 41
0	1.72	3.07	9.7	17.2
					5	2.42	1.96	13.6	11.0
10	2.11	2.03	11.9	11.4
					20	1.98	1.99	11.1	11.2
30	3.02	1.4	17.0	7.9
					40	2.59	1.24	14.6	7.0
50	2.22	0.86	12.5	4.8

TABLE 5 Peel Strength Retention compared to initial

Number of washes	Example 40	EXAMPLE 41
			5	141％	36％
10	123％	34％
			20	115％	35％
30	176％	54％
			40	151％	60％
50	129％	72％

[0282] Example 42

In this example, a 2mil film was prepared according to example 15 using the dispersion of example 12. A second film was prepared by casting the dispersion of example 12 onto a polypropylene sheet to form a 4.5mil film. Two layers of this film were laminated together by hot oil heated metal rolls (100 ℃) and rubber rolls under 15psi pressure to produce a film thickness of 6.5 mil. The films in this example were tested for tensile properties including tenacity, elongation and permanent set (table 6).

Example 43

In this example, a 3mil film was prepared according to example 15 using the dispersion of example 13. The films in this example were tested for tensile properties including tenacity, elongation and permanent set (table 6).

Example 44

In this example, a film was prepared by casting the dispersion of example 12 onto a polypropylene sheet to form a 4.5mil film. Two layers of this film were laminated together to form a 9mil thick film by hot oil heated metal rolls (100 ℃) and a rubber roll under 15psi pressure. The films in this example were tested for tensile properties including tenacity, elongation and permanent set (table 6).

TABLE 6 film Properties

	Tenacity (Mpa)	Elongation (%)	Permanent deformation%
				Example 42	2 4	945	3.3
Example 43	2.8	496	--
				Example 44	--	--	3.3

Example 45

In this example, the laminate of example 18 was tested for moisture penetration according to the method given above. The data are presented in table 7.

Example 46

In this example, the laminate of example 17 was tested for moisture penetration according to the method given above. The data are presented in table 7.

Example 47

In this example, the laminate of example 18 was subjected to air permeability testing in accordance with the method given above. The data are presented in table 7.

Example 48

In this example, the laminate of example 17 was subjected to air permeability testing in accordance with the method given above. The data are presented in table 7.

The fabric of example 17 was tested for air and moisture permeability alone.

TABLE 7

	MVT (24h g/m)²)	Air permeability (cfm)	Air permeability (ccs)
				Single fabric	1334	196	386
Example 45	247
				Example 46	296
Example 47		0.23	0.45
				Example 48		0.32	0.63

Although the present invention has been described in an illustrative manner, it is to be understood that the terminology which has been used is intended to be in the nature of words of description rather than of limitation. In addition, while the invention has been described with respect to several exemplary embodiments, it is to be understood that one skilled in the art will readily apply these teachings to other possible variations of the invention.

Claims

1. A prepolymer for use in an aqueous polyurethane dispersion, the prepolymer comprising:

a) at least one polyether, polyester, or polycarbonate polyol, wherein the polyether, polyester, or polycarbonate polyol has a number average molecular weight of 600 to 3,500;

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

c) at least one diol compound comprising: (i) a hydroxyl group capable of reacting with the MDI isomer mixture of component b), and (ii) at least one carboxyl group capable of forming a salt upon neutralization, wherein said at least one carboxyl group is not capable of reacting with the MDI isomer mixture of component b);

wherein the prepolymer is solvent free.

2. The prepolymer of claim 1, wherein the at least one polyether, polyester, or polycarbonate polyol of component a) is a polytetramethylene ether glycol having a number average molecular weight of 1400 to 2400.

3. The prepolymer of claim 1, wherein the ratio of 4, 4 '-MDI to 2, 4' -MDI isomers is from 55: 45 to 45: 55.

4. The prepolymer of claim 1, wherein the at least one diol compound is selected from the group consisting of 2, 2-dimethylolpropionic acid (DMPA), 2-dimethylolbutyric acid, and 2, 2-dimethylolpentanoic acid.

5. The prepolymer of claim 2, wherein the ratio of 4, 4 '-MDI to 2, 4' -MDI isomers is from 55: 45 to 45: 55 and the at least one diol compound is 2, 2-dimethylolpropionic acid (DMPA).

6. The prepolymer of claim 1, wherein the weight percent of component a) is from 34% to 89%, based on the total weight of the prepolymer; the weight percentage of the component b) is 10 percent to 59 percent based on the total weight of the prepolymer; and component c) in a weight percentage of 1.0% to 7.0% with respect to the total weight of the prepolymer.

7. The prepolymer of claim 1 having a bulk viscosity of from 500 to 6,000 poise as determined by the falling ball method at 40 ℃.

8. The prepolymer of claim 7 having a bulk viscosity of from 500 to 4,500 poise as determined by the falling ball method at 40 ℃.

9. The prepolymer of claim 1, further comprising at least one additional component selected from the group consisting of: antioxidants, UV stabilizers, colorants, pigments, cross-linking agents, phase change materials, antimicrobial agents, microencapsulated health additives, nanoparticles, flame retardants, anti-tack agents, chlorine-blocking additives, dye-boosters, adhesion promoters, antistatic agents, anti-cratering agents, anti-shrinking agents, optical brighteners, auxiliary film agents, conductive agents, light emitting agents, leveling agents, thawing stabilizers, lubricants, organic and inorganic fillers, preservatives, curl-deforming agents, thermochromic agents, insect repellents, and wetting agents.

10. The prepolymer of claim 1, wherein the at least one polyether, polyester, or polycarbonate polyol of component a) has two hydroxyl end groups or three hydroxyl end groups.

11. The prepolymer of claim 1, wherein the aqueous polyurethane dispersion is a polyurethaneurea.

12. A method of preparing a prepolymer for an aqueous polyurethane dispersion, wherein the prepolymer comprises:

a. at least one polyether, polyester, or polycarbonate polyol, wherein the polyether, polyester, or polycarbonate polyol has a number average molecular weight of 600 to 3,500;

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

c. at least one diol compound comprising: (i) a hydroxyl group capable of reacting with the MDI isomer mixture of component b), and (ii) at least one carboxyl group capable of forming a salt upon neutralization, wherein said at least one carboxyl group is not capable of reacting with the MDI isomer mixture of component b);

and the process comprises mixing components a), b) and c) in a solvent-free system.

13. The process of claim 12 wherein components a), b) and c) are mixed and allowed to react at 50 ℃ to 100 ℃.

14. The process of claim 12 wherein components a), b) and c) are mixed together in one step.

15. The process of claim 12, wherein components a) and b) are reacted in a first step and subsequently mixed with component c).

16. The process of claim 12, further comprising a catalyst.

17. An aqueous polyurethane dispersion comprising:

a prepolymer, the prepolymer comprising:

c) at least one diol compound comprising: (i) a hydroxyl group capable of reacting with the MDI isomer mixture of component b) and (ii) at least one carboxyl group capable of forming a salt upon neutralization, wherein said at least one carboxyl group is not capable of reacting with the MDI isomer mixture of component b);

wherein the aqueous polyurethane dispersion is a solvent-free system, the system further comprising:

d) at least one neutralizing agent to form an ionic salt with the at least one glycol compound; and

e) at least one monofunctional dialkylamine compound as a blocking agent for isocyanate groups.

18. The aqueous polyurethane dispersion of claim 17, further comprising at least one surfactant and at least one antifoaming agent.

19. The aqueous polyurethane dispersion of claim 18, further comprising at least one rheology modifier.

20. The aqueous polyurethane dispersion of claim 19, further comprising:

f) at least one diamine chain extending component, and

g) at least one polymer component having a molecular weight of greater than 500 and at least three primary and/or secondary amino groups per mole of polymer.

21. The aqueous polyurethane dispersion of claim 17, wherein the at least one neutralizing agent is selected from the group consisting of: tertiary amines and alkali metal hydroxides; the at least one capping agent is selected from: n, N-diethylamine, N-ethyl-N-propylamine, N-diisopropylamine, N-tert-butyl-N-methylamine, N-tert-butyl-N-benzylamine, N-dicyclohexylamine, N-ethyl-N-isopropylamine, N-tert-butyl-N-isopropylamine, N-isopropyl-N-cyclohexylamine, N-ethyl-N-cyclohexylamine and 2, 2, 6, 6-tetramethylpiperidine.

22. The aqueous polyurethane dispersion of claim 18, wherein the at least one surfactant is selected from the group consisting of: sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, ethoxylated nonyl phenol and lauryl pyridine bromide

23. The aqueous polyurethane dispersion of claim 19, wherein the at least one rheology modifier is selected from the group consisting of: hydrophobically modified ethoxylated urethane (HEUR), hydrophobically modified alkali swellable emulsion (HASE), and hydrophobically modified hydroxyethyl cellulose (HMHEC).

24. The aqueous polyurethane dispersion of claim 20, wherein the at least one diamine chain extending component is selected from the group consisting of: 1, 2-ethylenediamine, 1, 4-butanediamine, 1, 6-hexanediamine, 1, 12-dodecanediamine, 1, 2-propanediamine, 2-methyl-1, 5-pentanediamine, 1, 2-cyclohexanediamine, 1, 4-cyclohexanediamine, 4' -methylenebiscyclohexylamine, isophoronediamine, 2-dimethyl-1, 3-propanediamine, and m-tetramethylxylylenediamine; the at least one polymer component having a molecular weight greater than 500 is selected from: polyethyleneimine dendrimers, polyvinylamine dendrimers, polyallylamine dendrimers, and poly (amide-amine) dendrimers.

25. The aqueous polyurethane dispersion of claim 17, wherein said at least one polyether, polyester, or polycarbonate polyol of component a) is polytetramethylene ether glycol having a number average molecular weight of 1,700 to 2,100, the ratio of the 4, 4 '-MDI to 2, 4' -MDI isomers is 55: 45 to 45: 55, and said at least one diol compound is 2, 2-dimethylolpropionic acid (DMPA).

26. The aqueous polyurethane dispersion of claim 20, further comprising at least one additional component selected from the group consisting of: antioxidants, UV stabilizers, colorants, pigments, cross-linking agents, phase change materials, antimicrobial agents, microencapsulated health additives, nanoparticles, flame retardants, anti-tack agents, anti-chlorine degradation agents, dye-assist agents, wetting and leveling agents, adhesion promoters, antistatic agents, anti-cratering agents, anti-wrinkling agents, optical brighteners, build-up agents, conductive agents, light emitting agents, leveling agents, thaw stabilizers, lubricants, organic and inorganic fillers, preservatives, curl-deforming agents, thermal discoloration agents, and wetting agents.

27. The aqueous polyurethane dispersion of claim 20, wherein the bulk viscosity is from 10 to 100,000 centipoise as measured by the falling ball method at 40 ℃.

28. The aqueous polyurethane dispersion of claim 27, wherein the bulk viscosity is from 500 to 30,000 centipoise as measured by the falling ball method at 40 ℃.

29. A method of preparing an aqueous polyurethane dispersion, wherein the aqueous polyurethane dispersion comprises:

a prepolymer, wherein the aqueous polyurethane dispersion is a solvent-free system comprising:

e) at least one monofunctional dialkylamine compound as a capping agent for isocyanate groups;

and the method comprises dispersing the prepolymer in an aqueous medium, wherein the at least one neutralizing agent is added to the prepolymer or aqueous medium prior to dispersing the prepolymer in the aqueous medium, and the at least one capping agent is added to the aqueous medium during or after dispersing the prepolymer in the aqueous medium.

30. The method of claim 29, wherein the at least one capping agent is added to the aqueous medium immediately after dispersing the prepolymer in the aqueous medium.

31. The method of claim 30, wherein the at least one neutralizing agent is added to the aqueous medium prior to dispersing the prepolymer in the aqueous medium.

32. The method of claim 30, wherein the at least one neutralizing agent is added to the prepolymer prior to dispersing the prepolymer in the aqueous medium.

33. A shaped article derived from an aqueous solvent-free polyurethane dispersion, wherein said dispersion comprises a prepolymer comprising: a) at least one polyether, polyester, or polycarbonate polyol, wherein the polyether, polyester, or polycarbonate polyol has a number average molecular weight of 600 to 3,500;

wherein the aqueous polyurethane dispersion is a solvent-free system further comprising at least one neutralizing agent to form an ionic salt with the at least one diol compound, and at least one monofunctional dialkylamine compound as a capping agent for isocyanate groups.

34. The shaped article of claim 33 which is non-tacky.

35. The shaped article of claim 33, wherein the shaped article is molded.

36. An article comprising the shaped article of claim 35.

37. An article comprising the shaped article of claim 33.

38. A garment comprising the article of claim 36.

39. The garment of claim 38, wherein the garment is a brassiere.

40. An article comprising at least one shaped article of claim 33 and a substrate, wherein the shaped article is applied to the substrate.

41. The article of claim 40, wherein the substrate is a fabric.

42. The article of claim 40, wherein the article is a garment.

43. The article of claim 40, wherein the shaped article is applied to the substrate after release from a release paper.

44. The article of claim 43, wherein the shaped article is adhered to a substrate comprising a fabric.

45. The article of claim 44 wherein said shaped article is adhered to a seam or a support area of said fabric.

46. The article of claim 44, wherein the article is a garment.

47. The article of claim 42, wherein the garment is selected from the group consisting of: intimate apparel, swimwear, hosiery, pajamas, ties, hats, belts, racing apparel, pants, longuette, sweaters, vests, socks, knee stockings, outerwear garments, headbands, eastern garments, skirts, outfits, camisoles, tights, face yarns, medical body suits, and all components thereof.

48. The article of claim 42, wherein the garment is selected from the group consisting of: brassieres, pants, lady underwear, body suits, women's undershirts, wetsuits, space suits, raincoats, cold weather jackets, bodices, gowns, aprons, tatami robes, cloaks, gowns, blogs, sloppy gowns, muslims' gowns that cover the whole body, capes, scotland shirts, and the harmony, sari, sarong, ancient roman stola shirts, wide gowns, uniforms, garages, sweatbands, bandages, waistbands, tights, and all components thereof.

49. The article of claim 42, wherein the garment is selected from the group consisting of a gown, a suit, an lingerie, and all components thereof.

50. The article of claim 40, wherein the substrate has been pretreated.

51. The article of claim 40, wherein the substrate is pretreated to increase the hydroxyl functionality on the substrate.

52. The article of claim 40, wherein the article is molded.

53. A garment comprising the article of claim 52.

54. The garment of claim 53, wherein the garment is a brassiere.

55. An article, wherein said article comprises a substrate coated with an aqueous solvent-free polyurethane dispersion, wherein said dispersion comprises a prepolymer comprising; a) at least one polyether, polyester, or polycarbonate polyol, wherein the polyether, polyester, or polycarbonate polyol has a number average molecular weight of 600 to 3,500;

wherein the aqueous polyurethane dispersion is a solvent-free system.

56. The article of claim 55, wherein the solvent-free system further comprises:

at least one neutralizing agent to form an ionic salt with component c);

at least one monofunctional dialkylamine compound as a blocking agent for isocyanate groups.

57. The article of claim 55, wherein the solvent-free system further comprises at least one monofunctional dialkylamine compound as a capping agent for isocyanate groups.

58. A method of making the article of claim 55, wherein the method comprises providing the dispersion to the substrate by employing methods of spraying, coating, printing, dipping, and impregnating the dispersion.

59. The article of claim 55, wherein the article is molded.

60. The article of claim 55, wherein the article is a garment.

61. A garment comprising the article of claim 59.

62. The garment of claim 61, wherein the garment is a brassiere.

63. The shaped article of claim 33 wherein said article comprises gloves, condoms, beads, fibers, and film sheets.

64. The shaped article of claim 33 wherein more than one layer of film or tape is applied to the substrate or release paper.

65. The shaped article of claim 33 further comprising at least one layer of an aqueous polyurethane dispersion.

66. The shaped article of claim 33, wherein the shaped article has been printed.

67. The shaped article of claim 33, wherein the shaped article has a thickness of from 0.1mil to 250 mil.

68. The shaped article of claim 67, wherein the shaped article has a thickness of from 0.5mil to 25 mil.

69. The shaped article of claim 68, wherein the shaped article has a thickness of from 1 to 6 mils.

70. The article of claim 55, wherein said aqueous dispersion coating has a basis weight of 2.5g/m²-6.40kg/m²。

71. The article of claim 70, wherein said aqueous dispersion coating has a basis weight of 12.7g/m²-635g/m²。

72. The article of manufacture of claim 71, wherein,wherein the basis weight of the aqueous dispersion coating is 25.4g/m²-152.4g/m²。

73. An article comprising an adhesive, an elastic component, and a substrate, wherein the elastic component is adhered to the substrate in a hem arrangement using the adhesive, and wherein the adhesive is an aqueous polyurethane dispersion comprising a prepolymer comprising:

74. The article of claim 73, wherein the adhesive is a tape.

75. The article of claim 73 wherein the elastic component is spandex.

76. The article of claim 73, wherein the elastic component is rubber.

77. The article in accordance with claim 73, wherein said elastic component is an elastic strip.

78. A method of making the article of claim 73, wherein the adhesive and elastic component are combined in a first step to make an adhesive elastic component and the adhesive elastic component is applied to a substrate in a second step.

79. A method of making the article of claim 73, wherein the adhesive and elastic component are applied to a substrate in one step.

80. A garment comprising the article of claim 73.

81. The garment of claim 80, wherein the garment is a brassiere.

82. The garment of claim 80 wherein the garment is an undergarment.

83. The garment of claim 80, wherein the garment is a swimsuit.

84. The article of claim 33, wherein the article has a% set of 0-10%.

85. The article of claim 33, wherein the article has a% set of 0-5%.

86. The article of claim 33, wherein the article has a% set of 0-3%.

87. The article of claim 33, wherein the article has a maximum elongation of 400% to 800%.

88. The article of claim 33, wherein the article has a toughness of from 0.5 to 3 Mpa.

89. A laminate comprising the shaped article of claim 33 and a substrate, wherein the peel strength of the laminate after 50 washes per AATCC-150-2001 does not decrease to 50% of the initial peel strength value determined per ASTM D093-93.

90. A laminate comprising the shaped article of claim 33 and a substrate, wherein the laminate has a moisture vapor transmission rate of from 0 to 300g/m per 24 hours as measured by ASTM E96-00²。

91. A laminate comprising the shaped article of claim 33 and a substrate, wherein the laminate has an air permeability of 0 to 0.5cfm as measured by ASTM D737-96.

92. An article comprising the shaped article of claim 33 and a substrate, wherein the shaped article and substrate are adhered to produce a laminate such that the laminate has a coefficient of friction that is higher than the coefficient of friction of the substrate.

93. An article comprising the shaped article of claim 33, wherein the article has a modulus and a length, the modulus varying along the length of the article.