BRPI0806288A2 - textiles treated with hyperbranched polyethyleneimine derivatives for odor control properties - Google Patents

Abstract

TEXTILES TREATED WITH HYPER-BRANCHED POLYETHYLENEIMINE DERIVATIVES FOR ODOR CONTROL PROPERTIES. The present invention relates to synthetic textiles treated with derivatives of h-PEI, such derivatives having the general structure shown below: (R) x - h-PEI - (A) y where R is a non-hyper-branched hydrocarbon group said hydrocarbon group has at least one linear portion, and said linear portion has between 5 and 30 carbon atoms; where x is a number from 1 to 10,000; where h-PEI is a hyper-branched polyethyleneimine; where A is an organic compound that has 1 to 4 carbon atoms; where y is a number from 0 to 500; and wherein R is present in an amount between about 0.1% and about 80% by weight of the h-PEI derivative. The chemical treatment provides odor control, softness, wrinkle resistance, and durable moisture absorption to substrates treated with it.

Description

Patent Descriptive Report for "TEXTILE TREATED WITH HYPERAMMORED POLYETHYLENEIMIN DERIVATIVES FOR ODOR CONTROL PROPERTIES".

TECHNICAL FIELD

The present invention relates to the field of hyperbranched polyethylene Lenoimine derivatives useful for the treatment of textile substrates. More specifically, the present invention relates to treatments used to provide durable odor control in textile washes, particularly on synthetic textile substrates or containing synthetic components. Chemical treatment also reduces wrinkling and gives softness and moisture absorption to the treated textile.

The present invention relates to a molecule having a hyperbranched polyethyleneimine core to which it is attached to at least one or more hydrocarbon groups. Optionally, bonding compounds may connect the hydrocarbon groups to the hyperbranched polyethyleneimine core. In addition, other organic compounds may also be used to "cap" the branches of hyperbranched polyethyleneimine that are unreacted with hydrocarbon groups.

In one embodiment, the hydrocarbon groups comprise up to 20% by weight of the hyperbranched polyethyleneimine derivative. In such an embodiment, the resulting treated textile exhibits absorption properties that are desired for textiles used in clothing and other applications. To produce a treated textile whose finish can withstand multiple washes, it is preferable to use a crosslinking agent or compound to attach the hyperbranched polyethyleneimine derivative to the surface of the textile.

In a second embodiment, the hydrocarbon groups comprise from about 20% to about 80% by weight of the hyperbranched polyethyleneimine derivative. In such an embodiment, it has been found that durability can be obtained without the use of a separate crosslinking agent or compound, although one of them may be incorporated if so desired for certain applications. Textiles treated with derivatives that have a larger amount of hydrocarbon groups tend to exhibit finishes that are more water repellent, which may be useful in some circumstances.

BACKGROUND

It has long been desirable to produce a textile substrate having durable odor adsorption capabilities. In particular, reducing human sweat odors is useful in a variety of different applications. For example, hunters are keen to prevent their body odors from reaching the animals being chased. In perhaps a more common application, clothing that can be worn several times before it needs to be washed should confer considerable benefits on its users.

Manufacturers have used a variety of approaches to solve the problem of odor reduction. A first approach is to treat the textile article with microbicidal compounds or incorporate microbicidal compounds into the yarns used to make the substrate, microbicide-treated textiles work to reduce odors by controlling or preventing micro growth. -organisms. When microorganisms grow, they degrade materials such as volatile organic compounds, which often smell bad. Although they prevent the growth of microorganisms, approaches that use microbicides fail to address the issue of odor control as volatile organic compounds are present in textiles.

Another approach to the odor control problem is to incorporate carbon black particles, granules, fibers or cloths into a textile. Depending on the pore size and material chosen, carbon black is generally effective in adsorbing odors when dry, but tends to lose some of its effectiveness when wet (as surface area becomes blocked). water or other aqueous contaminants). A second problem with carbon black is that it must be bonded to the textile by adhesives or other binders, often reducing the breathability of the treated textile. Finally, carbon black gives a black color to the surface of the textile being treated, which is inappropriate in many situations (eg with a lightly colored garment).

Other particles, such as zeolites, have also been used to reduce textile odor. Many of them exhibit the same problems associated with carbon black, although they are functionally less effective.

More recently, manufacturers have been using cyclodextrins and cyclodextrin derivatives in an effort to produce oil-reducing. However, as will be shown herein, cyclodextrins are not particularly effective in reducing the odors associated with human sweat, nor are they particularly durable under repeated washings.

Thus, there is a need for odor-reducing chemistry that preferably confers benefits such as wrinkle resistance, moisture absorption and softness. The present treatment provides a solution to such needs by providing a specific hyperbranched polyethyleneimine structure which is attached to one or more hydrocarbon groups having linear portions of between 5 and 30 carbon atoms and which may additionally be attached to one or more organic "buffering" compounds.

SUMMARY

The present invention relates to treatments for synthetic textiles which impart odor control properties to treated textiles. In addition, chemical treatment provides benefits in terms of reduced drying time, reduced wrinkling, and in some circumstances, increased moisture absorption.

The present treatment comprises a modified hyperbranched polyethyleneimine compound, also referred to herein as "hyperbranched polyethyleneimine derivative". The hyperbranched polyethyleneimine derivative comprises at least one hyperbranched polyethyleneimine (a "hydrophilic component") which has been linked to one or more hydrocarbon groups having from 5 to 30 linearly arranged carbon atoms ("hydrophobic components", which may be attached to the hyperbranched polyethyleneimine using any of a number of different bonds). In another embodiment, the chemical treatment also comprises one or more additional organic "buffering" compounds attached to the core of the hyperbranched polyethyleneimine.

Preferably the hydrophobic components (i.e. the hydrocarbon groups and optional bonding compounds) are electrophilic, so that they react with the nucleophilic hyperbranched polyethyleneimine molecule. Any of a number of acceptable linking groups may be used to link the hydrocarbon groups to the hyperbranched polyethyleneimine as described herein, or the hydrocarbon groups may be directly attached to the hyperbranched polyethyleneimine molecule.

In one embodiment, the hydrocarbon groups comprise up to 20% by weight of the hyperbranched polyethyleneimine derivative. In such an embodiment, the resulting treated textile exhibits abrasion properties that are desired for textiles used in clothing and other applications. To produce a treated textile whose finish can withstand multiple washes, it is preferable to use a crosslinking agent or compound to attach the hyperbranched polyethyleneimine derivative to the textile surface.

In a second embodiment, the hydrocarbon groups comprise from about 20% to about 80% by weight of the hyperbranched polyethyleneimine derivative. In such an embodiment, it has been found that durability can be obtained without the use of a separate cross-linking agent or compound, although it may be incorporated if desired for certain applications. Textiles treated with derivatives that have a larger amount of hydrocarbon groups tend to exhibit finishes that are more water repellent, which may be useful in some circumstances.

The invention also relates to the process for treating textiles with the present chemical treatment, wherein the chemical treatment is applied to at least a portion of the fiber, yarn, textile or compound. In a presently preferred embodiment, the target tissue is placed in chemical treatment (e.g., by dipping), then padded and dried in a single continuous process.

The present invention also relates to dyed fibers, yarns, fabrics, textiles, finished or unbraided products (encompassed herein under the terms "textiles" and "nets") treated with the present hyperethylated polyethyleneimine derivatives. branched. Such textiles and nets exhibit a firmness of color and an extremely improved resistance to fading even after multiple washes. In addition, such treated textiles also require greater softness and reduced wrinkling and drying time.

DETAILED DESCRIPTION

The present chemical treatment is especially well-suited for use with synthetic substrates. The term "synthetic" refers to any type of synthetic fiber, including without limitation polyester, polyamide (e.g. nylon), acrylic, polyethylene, polypropylene, aramides (e.g. NOMEX® and KEVLAR®), and the like. Preferably, the substrate comprises a greater part of the synthetic content and may include a combination of synthetic fiber types or a combination of synthetic and natural fiber types.

Of great utility in the present chemical treatment is the hyperbranched polyethyleneimine (h-PEI) molecule, which may also be indicated herein as the hydrophilic component of the compound. In schematic terms, the h-PEI molecule can be described as having a central nucleus surrounded by a plurality of molecular branches, each branch projecting outward from the nucleus and having a highly reactive end group. Partial branching should be expected to occur frequently. The molecule typically exhibits very high charge density per area, which means that there is a high number of densely packed positive charges clustered around the molecular nucleus. This configuration makes the molecule very capable of interacting with a wide range of other molecules, many of which will be described herein. The number of molecules that can be attached to the h-PEI molecule depends on the numerical average molecular weight (Mn) of h-PEI, which reflects the number of branches available for binding.

For the applications contemplated herein, hyperbranched polyethylene amines having a number average molecular weight (Mn) of from about 300 to about 2 million are preferred, with Mn of from about 1,000 to about 75,000. It is most preferred.

At least one, and preferably more than one, hydrocarbon groups are attached to the h-PEI molecule to increase the hydrophobic capacity of the resulting compound (i.e. the h-PEI derivative). These hydrocarbon groups, together with all the binding compounds that can be used to attach them to the h-PEI molecule, are collectively referred to as the "hydrophobic components" of the dye-reactive molecule. These hydrocarbon groups may be linear molecules or may contain branched or aromatic moieties which have an electrophilic group that may react with nucleophilic h-PEI. Preferably, regardless of the hydrocarbon structure, the linear portion of the hydrocarbon group contains from about 5 to about 30 carbon atoms and more preferably from about 10 to about 24 carbon atoms. Mixtures of hydrocarbons of various lengths can also be used.

Examples of electrophilic hydrocarbons include, without limitation, carboxylic acids, ketene dimers, formates, acetyl halides (such as acetyl chloride), esters, anhydrides, alkyl halides, epoxides, isocyanates, and the like. Preferred examples include stearic acid, stearic hydroxy acid, isostearic acid, and palmitic acid.

In a first embodiment, the weight ratio between h-PEI and hydrophobic groups is from about 1,000: 1 to about 5: 1 and more preferably from about 100: 1 to about 10: 1. . In a second embodiment, the weight ratio between h-PEI and hydrophobic groups is from about 5: 1 to about 1:10 and more preferably from about 2: 1 to about 1 : 5, depending on h-PEI Mn. More preferably, the weight ratios between h-PEI and the hydrophobic group from about 1: 1 to about 1: 4 are employed.

The present h-PEI derivatives have the structure shown below:

(R) x - h-PEI - (A) y

wherein R is a non-hyperbranched hydrocarbon group (for example, such as alkyl, alkenyl, arylalkyl, and arylalkenyl groups, where the number of carbon atoms in the linear portion of the hydrocarbon is from 5 to 30 carbon atoms) , where χ is a number from 1 to about 10,000 (depending on h-PEI Mn), where h-PEI is a hyperbranched polyethyleneimine, where A is a small organic buffering compound, where y is a 0 to 500, and wherein R is present in an amount of from about 0.1% to about 80% by weight of the molecule.

It should be understood that in the synthesis of molecules, such as the adjustment of the overall structure provided above, the actual product exhibits a polydistitude (a ratio distribution) and the molar ratio of each molecule will vary somewhat around the ratio. target.

Optionally, small organic molecules (generally indicated as "A" in the above structure) may be used to "cap" unreacted branches of the hyperbranched polyethyleneimine. Generally speaking, the "A" capping molecule has between one and four carbon atoms. All caps that react with the amine (NH or NH2) portion of the h-PEI molecule may be used, including, without limitation, epoxides, anhydrides, esters, acids, carbonates, sulfates, formats, isocyanates, and mixtures. of these. Specific examples of such caps include, without limitation, ethylene oxide, propylene oxide, methyl bromide, acetic acid, vinyl sulfonates, trifluoroacetic acid, and succinic anhydride. Mixtures of molecules other than "lids" may be used.

Ethylene oxide (EO) or propylene oxide (PO) chains are especially useful as buffering compounds in the present treatment to prevent the treated substrate from turning yellow when exposed to high manufacturing temperatures (e.g. above 176.6 ° C (350 ° F)). The addition of such chains is not required to achieve color firmness and other benefits of the present treatment, but merely to confer additional benefits. For example, it has been found that the addition of EO or PO chains within the h-PEI derivative increases moisture absorption and produces softness in the treated substrate.

A potentially preferred "R" group has a structure C17H35, which in the above structure forms a stearic amide. When using this group R and an h-PEI having a Mn equal to 1,200, the representative molar ratios between h-PEI and R are 1: 2, 1: 4, 1: 6, 1: 8, 1:10 , and 1:12. Similarly, when the Mn of the h-PEI molecule is about 10,000, the representative molar ratios between h-PEI and R are 1:25, 1:60, 1:80, and 1: 100. Finally, when the Mn of the h-PEI molecule is about 75,000, the representative molar ratios between h-PEI and R are 1: 400, 1: 500, and 1: 600.

The chemical synthesis of the present treatment molecules is accomplished by reacting the h-PEI molecule with an electrophilic molecule containing hydrophobic R in the presence of nitrogen. Mechanical agitation of the reagents in a vessel under nitrogen at about 150 ° C has been found to produce the h-PEI derivatives described herein. The time required to complete the reaction depends on the amount of reagents being reacted and the size of the reaction vessel. The resulting compounds, referred to herein as "h-PEI derivatives", are typically in the form of an oily liquid or waxy solid.

In a preferred embodiment, h-PEI derivatives have hydrophobic agents present in an amount of at least 0.1% to about 20% by weight of the h-PEI derivative, and more preferably about 2% to about 15% by weight of the h-PEI derivative. In an alternative embodiment, h-PEI derivatives have hydrophobic agents present in an amount of at least 20% to about 80% by weight of the h-PEI derivative, and more preferably from about 30% to about 75%. % by weight of h-PEI derivative.

To prepare a textile treatment bath using the h-PEI derivatives described herein, it is necessary to heat the h-PEI derivative to its melting point so that it can be poured into a vessel where it is combined by high speed stirring and high shear with hot water. In this case, the term "hot water" refers to water having a temperature at or above the melting point of the h-PEI derivative. Suitable equipment for high speed agitation and high shear includes blade type mixers, Jago® type stirrers, homogenizers, roller mills, ball mills, microfluidizers, and the like.

The dispersion resulting from the forced introduction of the h-PEI derivative into water is aided and stabilized by the addition of a solubilizing agent (e.g., an acid or surfactant), the amount of which depends on the molecular weight of h-PEI. and the molar ratio between h-PEI and hydrophobic components. Acetic acid is a potentially preferred acid for this purpose (excess acid is evaporated during subsequent drying of the treated textile substrate). Amounts of more than 0.1% acid by weight of the solution can be used successfully. Preferably, the amount of acid should be in the range from about 0.1% to about 20% by weight of the h-PEI derivative.

The fiber, yarn, fabric, or finished garment may be dyed by employing conventional processing, after which they are exposed (by methods known in the art such as soaking, spraying, dipping, cushioning, foaming, depletion, and the like) to the aqueous dispersion of the treatment chemistry. In some cases, it may be possible to introduce treatment chemistry into a garment by replacing the softening chemistry (normally applied during the washing process) with the treatment described herein. Alternatively, the treatment chemistry may be applied to a (non-dyed) textile if the textile is to be used in its undyed state.

The treated mesh is then removed from the solution and dried, preferably at temperatures between room temperature and 204.4 ° C (400 ° F), and more preferably at temperatures between about 37.7 ° C (100 ° C). ° F) and about 380 ° F (193.3 ° C). The typical added weight of the h-PEI derivative is about 0.1 wt% to about 10 wt% and preferably about 0.2 wt% to about 5 wt%. % of the weight of the fabric. Treated substrates exhibit durable odor control after multiple washes. In addition, surprisingly, the substrates also have a durable softness, reduced wrinkling after washing / drying, and a higher moisture absorption capacity.

Without wishing to be bound by theory, it is assumed that the h-PEI derivatives disclosed herein have a molecular configuration that facilitates odor adsorption. Specifically, h-PEI derivatives have a hydrophilic core surrounded by a hydrophobic "envelope" that is formed by the plurality of hydrocarbon groups attached to the h-PEI molecule of the core. Such a configuration results in numerous voids within the derivative molecule in which volatile odor molecules having different polarities can be trapped. In addition, secondary interactions such as, for example, Van der Waals forces, hydrogen bonding, and ionic interactions may also contribute to the odor trapping ability exhibited by textiles treated with the present derivatives.

In one embodiment (in particular where hydrocarbon groups are present in an amount of from 0.1% to 20% by weight of the h-PEI derivative), a separate cross-linking agent is incorporated into the aqueous solution or dispersion to intensify the durability of the treatment. Suitable crosslinking agents for this purpose include epoxides, chlorotriazines and their derivatives, azetidines, blocked isocyanates and melamine derivatives, which may further enhance the durability of the treatment chemistry. When used, the crosslinking agent is preferably in an amount from about 0.05% to about 5% by weight of the treated textile. Preferably, the ratio of the h-PEI derivative to the crosslinking agent is from about 1: 0.1 to 1: 1.

Other finishing agents may also be used, such as wetting agents, softeners, dirt release agents, flame retardants, and the like.

In order to further illustrate the derivatives and advantages thereof, the following specific examples are provided and it should be understood that they are provided by way of illustration only and are not present in any limiting manner.

COMPARATIVE EXAMPLE

A 100% polyester knitted fabric was used as a substrate for Comparative Example A. A treatment solution was created which contained 7.5% (by weight) of a propyl beta-cyclodextrin hydroxy (available from Wacker Chemical under the trademark CAVATEX® W7 HPTL) and 2.0% (by weight) of a blocked isocyanate crosslinking agent (available from Clariant Corporation under the trademark ARKOPHOB® DAN). The knitted fabric was dipped into the treatment solution and padded at a pressure of 275.8 kPa (40 psi) to remove excess treatment solution. The treated tissue was then dried at about 187.7 ° C (370 ° F) for about 3 minutes (until dry).

COMPARATIVE EXAMPLE B

A braided fabric containing 52 wt% nylon and 48 wt% cotton was used as a substrate for Comparative Example B. For this comparative example, the fabric was dipped in a bath containing only water and then padded at a pressure of about 275.8 kPa (40 psi) to remove excess water. The tissue was then dried at about 154.4 ° C (310 ° F) for about 10 minutes (until dry).

COMPARATIVE EXAMPLE C

The fabric of Comparative Example B was used in Comparative Example C. For this comparative example, the fabric was dipped into a bath containing 7.5% (by weight) of a hydroxy propyl beta-cyclodextrin (available from Wacker Chemical under CAVATEX® W7 HPTL) and 2.0% (by weight) of a blocked isocyanate crosslinking agent (available from Clariant Corporation under the trademark ARKOPHOB® DAN) and then padded at a pressure of about 275.8 kPa (40 psi) to remove excess. The treatment solution used in Comparative Example C was the same as that used in Comparative Example A. The tissue was dried at about 154.4 ° C (310 ° F) for about 10 minutes (until dry). COMPARATIVE EXAMPLE D

The fabric of Comparative Example B was used in Comparative Example D. For this comparative example, the fabric was dipped into a bath containing about 5.0% (by weight) of a melamine-based repellant material (available from Ciba). Specialty Chemical under the trademark PHOBOTEX® JVA) and 2.0% (by weight) of a blocked isocyanate cross-linking agent (available from Clariant Corporation under the trademark ARKOPHOB® DAN). The tissue was then padded at a pressure of about 275.8 kPa (40 psi) to remove excess, after which the tissue was dried at about 154.4 ° C (310 ° F) for about 10 minutes ( until dry).

COMPARATIVE EXAMPLE AND

A braided fabric containing 52 wt% nylon and 48 wt% cotton was used as a substrate for Comparative Example Ε. The tissue was dipped into a bath containing about 6.0% (by weight) of a propyl beta-cyclodextrin hydroxy (available from Wacker Chemical under the trademark CAVATEX® W7 HPTL) and 1.0% (by weight) of a blocked isocyanate crosslinking agent (available from Claire Corporation under the trademark ARKOPHOB® DAN) and then padded at a pressure of about 275.8 kPa (40 psi) to remove excess. The tissue was then dried at about 165.5 ° C (330 ° F) for about 4 minutes (until dry).

EXAMPLE 1

To a round bottom flask with a mechanical stirrer was added 200.0 grams of hyperbranched polyethyleneimine (sold under the trademark EPOMIN® SP012 by Summit Specialty Chemical, New Jersey) and 94.83 grams of stearic acid (sold by Aldrich, Wisconsin). The hyperbranched polyethyleneimine had an Mn of 1,200. The mixture was heated under nitrogen with stirring at a temperature of about 150 ° C for about 3 hours. At the end of the three hours, an aliquot was removed and analyzed using FT-IR, which indicated that no acid remained present and the reaction was complete. The resulting product was a waxy solid. The h-PEI derivative was dispersed in hot water by high speed stirring and high shear. To solubilize the h-PEI derivative, acetic acid was added to the dispersions to obtain a pH level of about 5. The h-PEI derivative comprised about 3.0% by weight of the dispersion. To the dispersion, about 2.0% by weight of a blocked isocyanate crosslinking agent (available from Clariant Corporation under the trademark ARKOPHOB® DAN) was also added.

The 100% polyester knitted fabric used in Comparative Example A was dipped into the dispersion and padded at a pressure of about 275.8 kPa (40 psi) to remove excess. The tissue was then dried at a temperature of about 187.7 ° C (370 ° F) for about 3 minutes (until dry).

EXAMPLE 2

To a round bottom flask with a mechanical stirrer was added 100.0 grams of hyperbranched polyethyleneimine (sold under the trademark EPOMIN® SP200 by Summit Specialty Chemical, New Jersey) and 170.7 grams of isostearic acid (sold under PRISORINE® trademark by Uniqema, Delaware). The hyperbranched polyethyleneimine had an Mn of about 10,000. The mixture was heated under nitrogen with stirring at a temperature of about 150 ° C for about 3 hours. At the end of the three hours, an aliquot was removed and analyzed using FT-IR, which indicated that no acid remained present and the reaction was complete. The resulting product was a viscous liquid.

The h-PEI derivative was dispersed in hot water by high speed stirring and high shear. To solubilize the h-PEI derivative, acetic acid was added to the dispersions to obtain a pH level of about 5. The h-PEI derivative comprised about 3.0% by weight of the dispersion. To the dispersion was also added about 2.0% by weight of a blocked isocyanate crosslinking agent (available from Clariant Corporation under the trademark ARKOPHOB® DAN).

The 100% polyester knitted fabric used in Comparative Example A was dipped into the dispersion and padded at a pressure of about 275.8 kPa (40 psi) to remove excess. The tissue was then dried at a temperature of about 187.7 ° C (370 ° F) for about 3 minutes (until dry). EXAMPLE 3

To a round bottom flask with a mechanical stirrer was added 100.0 grams of hyperbranched polyethyleneimine (sold under the trademark LUPASOL® WF by BASF, New Jersey) and 284.5 grams of stearic acid (sold by Aldrich, Wisconsin ). The hyperbranched polyethyleneimine had an Mn of about 10,000. The mixture was heated under nitrogen with stirring at a temperature of about 150 ° C for about 3 hours. At the end of the three hours, an aliquot was removed and analyzed using FT-IR, which indicated that no acid remained present and the reaction was complete. The resulting product was a waxy solid.

To a stainless steel reactor with stirrer and temperature controller, 300.0 grams of the h-PEI derivative formed above was added. The h-PEI derivative was heated to about 121.1 ° C (250 ° F), after which 42.0 grams of ethylene oxide was slowly added until all ethylene oxide was reacted as measured. by the number of hydroxyl. The resulting capped h-PEI derivative was a room temperature paste.

The capped h-PEI derivative was dispersed in hot water by high speed stirring and high shear. To solubilize the h-PEI derivative, acetic acid was added to the dispersions to obtain a pH level of about 5. The h-PEI derivative comprised about 5.7% by weight of the dispersion. To the dispersion was also added about 2.0% by weight of a blocked isocyanate crosslinking agent (available from Clariant Corporation under the trademark ARKOPHOB® DAN).

The 100% polyester knitted fabric used in Comparative Example A was dipped into the dispersion and padded at a pressure of about 275.8 kPa (40 psi) to remove excess. The tissue was then dried at a temperature of about 187.7 ° C (370 ° F) for about 3 minutes (until dry).

EXAMPLE 4

To a round bottom flask with a mechanical stirrer was added 200.0 grams of hyperbranched polyethyleneimine (sold under the trademark EPOMIN® SP012 by Summit Specialty Chemical, New Jersey) and 94.83 grams of stearic acid (sold by Aldrich, Wisconsin). The hyperbranched polyethyleneimine had a Mn of 1200. The mixture was heated under nitrogen with stirring at a temperature of about 150 ° C for about 3 hours. At the end of the three hours, an aliquot was removed and analyzed using FT-IR, which indicated that no acid remained present and the reaction was complete. The resulting product was a waxy solid.

The h-PEI derivative was dispersed in hot water by high speed stirring and high shear. To solubilize the h-PEI derivative, acetic acid was added to the dispersions to obtain a pH level of about 5. The h-PEI derivative comprised about 3.0% by weight of the dispersion. To the dispersion was also added about 2.0% by weight of a blocked isocyanate crosslinking agent (available from Clariant Corporation under the trademark ARKOPHOB® DAN). This is the same treatment chemistry that was used in Example 1.

The nylon / cotton braided fabric used in Comparative Examples B-D was dipped into the dispersion and padded at a pressure of about 275.8 kPa (40 psi) to remove excess. The tissue was then dried at a temperature of about 154.4 ° C (310 ° F) for about 10 minutes (until dry).

EXAMPLE 5

To a round bottom flask with a mechanical stirrer, 100.0 grams of hyperbranched polyethyleneimine (sold under the trademark EPOMIN® SP200 by Summit Specialty Chemical, New Jersey) and 24.61 grams of stearic acid (sold by Aldrich, Wisconsin). The hyperbranched polyethyleneimine had an Mn of 10,000. The mixture was heated under nitrogen with stirring at a temperature of about 150 ° C for about 3 hours. At the end of the three hours, an aliquot was removed and analyzed using FT-IR, which indicated that no acid was present and the reaction was complete. The resulting product was a viscous liquid.

The h-PEI derivative was dispersed in hot water by high speed stirring and high shear. To solubilize the h-PEI derivative, acetic acid was added to the dispersions to obtain a pH level of about 5. The h-PEI derivative comprised about 3.0% by weight of the dispersion. To the dispersion was also added about 2.0% by weight of a blocked isocyanate crosslinking agent (available from Clariant Corporation under the trademark ARKOPHOB® DAN).

The nylon / cotton braided fabric used in Comparative Examples B-D was dipped into the dispersion and padded at a pressure of about 275.8 kPa (40 psi) to remove excess. The tissue was then dried at a temperature of about 154.4 ° C (310 ° F) for about 10 minutes (until dry). EXAMPLE 6

To a round bottom flask with a mechanical stirrer was added 100.0 grams of hyperbranched polyethyleneimine (sold under the trademark LUPASOL® WF by BASF, New Jersey) and 14.23 grams of stearic acid (sold by Aldrich, Wisconsin). The hyperbranched polyethyleneimine had an Mn of 10,000. The mixture was heated under nitrogen with stirring at a temperature of about 150 ° C for about 3 hours. At the end of the three hours, an aliquot was removed and analyzed using FT-IR, which indicated that no acid remained present and the reaction was complete. The resulting product was a viscous liquid.

The h-PEI derivative was dispersed in hot water by high speed stirring and high shear. To solubilize the h-PEI derivative, acetic acid was added to the dispersions to obtain a pH level of about 5. The h-PEI derivative comprised about 2.3% by weight of the dispersion. No crosslinking agents were included with this formulation.

The nylon / cotton braided fabric used in Comparative Example E was dipped into the dispersion and padded at a pressure of about 275.8 kPa (40 psi) to remove excess. The tissue was then dried at a temperature of about 165.5 ° C (330 ° F) for about 4 minutes (until dry).

EXAMPLE 7

To a round bottom flask with a mechanical stirrer, 100.0 grams of hyperbranched polyethyleneimine (sold under the trademark LUPASOL® WF by BASF, New Jersey) and 14.23 grams of stearic acid (sold by Aldrich1 Wisconsin) were added. The hyperbranched polyethyleneimine had an Mn of 10,000. The mixture was heated under nitrogen with stirring at a temperature of about 150 ° C for about 3 hours. At the end of the three hours, an aliquot was removed and analyzed using FT-IR, which indicated that no acid remained present and the reaction was complete. The resulting product was a viscous liquid.

The h-PEI derivative was dispersed in hot water by high speed stirring and high shear. To solubilize the h-PEI derivative, acetic acid was added to the dispersions to obtain a pH level of about 5. The h-PEI derivative comprised about 2.3% by weight of the dispersion. To the dispersion was also added about 1.5% by weight of a blocked isocyanate crosslinking agent (available from Clarin Corporation under the trademark ARKOPHOB® DAN).

The nylon / cotton braided fabric used in Comparative Example E was dipped into the dispersion and padded at a pressure of about 275.8 kPa (40 psi) to remove excess. The tissue was then dried at a temperature of about 165.5 ° C (330 ° F) for about 4 minutes (until dry).

EXAMPLE 8

To a round bottom flask with a mechanical stirrer was added 100.0 grams of hyperbranched polyethyleneimine (sold under the trademark LUPASOL® WF by BASF, New Jersey) and 14.23 grams of stearic acid (sold by Aldrich, Wisconsin). The hyperbranched polyethyleneimine had an Mn of 10,000. The mixture was heated under nitrogen with stirring at a temperature of about 150 ° C for about 3 hours. At the end of the three hours, an aliquot was removed and analyzed using FT-IR, which indicated that no acid remained present and the reaction was complete. The resulting product was a viscous liquid.

The h-PEI derivative was dispersed in hot water by high speed stirring and high shear. To solubilize the h-PEI derivative, acetic acid was added to the dispersions to obtain a pH level of about 5. The h-PEI derivative comprised about 2.3% by weight of the dispersion. About 1.5% by weight of a melamine-based crosslinking agent (available from Cytec Industries under the trademark CYMEL® 385) was also added to the dispersion.

The nylon / cotton braided fabric used in Comparative Example E was dipped into the dispersion and padded at a pressure of about 275.8 kPa (40 psi) to remove excess. The tissue was then dried at a temperature of about 165.5 ° C (330 ° F) for about 4 minutes (until dry).

Odor Reduction Test

A tissue sample (typically a 2 inch by 2 inch square) was placed inside a glass vial that has an internal volume of about 20 ml and has a silicone cap . 1 microliter of an odor molecule mixture was injected into the vial. The flask was kept at a temperature of about 40 ° C for about one hour. The chemical composition of the void at the top of the vial (ie the "upper space") was evaluated using samples extracted from the vial and analyzed using a GC / MS. The numbers shown in the following TABLES are relative within each individual table for a given volatile compound. Data are small representations of areas obtained directly from GC peaks for a given compound. The higher numerical values reflect the larger amounts of a particular volatile organic compound in the vapor phase. The lower numerical values reflect tissue samples that have a higher adsorption of odor-causing compounds. For each tissue of the comparative examples and examples, the upper space analysis was performed to determine the presence of three different odor related molecules (isobutyraldehyde, isovaleric acid and limonene) which had been added to the vials in more quantities. or less equal in volume. Tissues were evaluated after initial preparation (ie, after washing) and after multiple washes had taken place (eg after five washes). The term "wash" refers to a washing machine standard when using TIDE® detergent powder according to AATCC method 130 and subsequent drying in a hot air dryer.

TABLE 1: MEASURE OF VOLTAGE COMPOUNDS IN THE UPPER BOTTLE AREA CONTAINING COMPARATIVE EXAMPLE A AND EXAMPLES 1-3 (POLYESTER KNITTED TISSUE)

<table> table see original document page 20 </column> </row> <table>

As shown from the above test data, the fabrics of Examples 1, 2 and 3 adsorbed more volatile compounds from the upper space of their respective vials than Comparative Example A. Treatment chemistry was particularly effective in adsorbing isovanic acid, which is a major component of human sweat odors. The treatment chemistry also worked exceptionally well on isobutyraldehyde adsorption, and performed better than the comparative example on limonene adsorption. It should also be noted that the superior performance of Examples 1-3 was especially evident after the samples had been subjected to multiple washes. TABLE 2: MEASURE OF VOLTAGE COMPOUNDS IN THE UPPER BOTTLE AREA CONTAINING COMPARATIVE EXAMPLES B, C. AND D AND EXAMPLES 4 AND 5 (N-YLON / COTTON FABRIC)

<table> table see original document page 21 </column> </row> <table>

As shown from the above test data, the fabrics of Examples 4 and 5 performed better, or equivalent to, than Comparative Examples B, C and D in the adsorption of volatile compounds from the upper space. their respective vials. The treatment chemistry was particularly effective in adsorbing isovaleric acid. Treatment chemistry also worked well on isobutyraldehyde and limonene adsorption, although the performance was not as drastic as with the polyester fabric samples discussed above. Again, the decrease in odor adsorption with multiple washes was less pronounced with Examples 4 and 5 compared to Comparative Examples B-D.

TABLE 3: MEASURE OF VOLTAGE COMPOUNDS IN THE UPPER SPACE OF BOTTLES CONTAINING COMPARATIVE EXAMPLE AND EXAMPLES 6, 7, AND 8 (N-YLON / COTTON LOCKED FABRIC)

<table> table see original document page 22 </column> </row> <table>

As shown from the above test data, the fabrics of Examples 6, 7 and 8 adsorbed more volatile compounds from the upper space of their respective vials than Comparative Example Ε. The treatment chemistry was particularly effective in adsorbing isoviral acid, and also worked exceptionally well in isobutyraldehyde adsorption. In addition, the treatment chemistry performed better than Comparative Example E, after both had been washed five times in limonene adsorption. It should also be noted that the superior performance of Examples 7 and 8 was especially evident after the samples had been subjected to multiple washes.

The results shown above indicate that the present chemical treatment confers an odor reduction and that the chemical treatment is durable to washes, and both represent a useful advance over the prior art.

Claims (14)

1. Treated textile substrate, said treated textile substrate comprises: (a) a textile substrate containing synthetic components; and (b) a treatment applied to at least one side of said textile substrate, said treatment comprising: (i) a hyperbranched polyethyleneimine derivative of the formula: (R) x -h-PEI - (A) y wherein R is a non-hyperbranched hydrocarbon group, said hydrocarbon group has at least one linear portion, and said linear portion has between 5 and 30 carbon atoms; where χ is a number from 1 to 10,000; where h-PEI is a hyperbranched polyethyleneimine; where A is an organic compound having from 1 to 4 carbon atoms; where y is a number from 0 to 500; and wherein R is present in an amount from about 0.1% to about -20% by weight of said hyperbranched polyethyleneimine derivative; and (ii) a crosslinking agent. A treated textile substrate according to claim 1, wherein said treatment is applied to said substrate at an addition level of from about 0.1% to about 10%, based on the weight of said substrate. A treated textile substrate according to claim 1, wherein said h-PEI has a number average molecular weight (Mn) in the range of from about 1,000 to about 75,000. A treated textile substrate according to claim 1, wherein said linear portion of said group R has from about 10 to about 24 carbon atoms. A treated textile substrate according to claim 1, wherein said h-PEI and said group R are present in a weight ratio of from about 100: 1 to about 10: 1. A treated textile substrate according to claim 1, wherein said group A is at least one compound selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, methyl acetate, vinyl sulfonate. trifluoroacetate, and trialkyl silyl. A treated textile substrate according to claim 1, wherein said group A is ethylene oxide or propylene oxide. A treated textile substrate according to claim 1, wherein said crosslinking agent is selected from the group consisting of isocyanate crosslinking agents, protected isocyanate crosslinking agents, and formaldehyde melamine crosslinking agents. A process for treating a textile substrate, said process comprising: (a) providing a textile substrate containing synthetic components; (b) providing a dispersion comprising a hyperbranched polyethyleneimine derivative and a crosslinking agent, said hyperbranched polyethyleneimine derivative being of the formula: (R) x - h-PEI - N - (A where y is a non-hyperbranched hydrocarbon, said hydrocarbon group has at least one linear portion, said linear portion has between 5 and 30 carbon atoms; where χ is a number from 1 to 10,000; where h-PEI is a hyperbranched polyethyleneimine; where A is an organic compound having from 1 to 4 carbon atoms; where y is a number from 0 to 500; and wherein R is present in an amount from about 0.1% to about 20% by weight of said hyperbranched polyethyleneimine derivative, said dispersion containing said hyperbranched polyethyleneimine derivative being produced by: (i) providing said hyperbranched polyethyleneimine derivative, a solubilizing agent and water, said water has a temperature at least equal to the melting point of said hyperbranched polyethyleneimine derivative; and (ii) subjecting said hyperbranched polyethyleneimine derivative, said solubilizing agent and said water to high speed agitation and high shear; (c) applying said dispersion to said textile substrate; and (d) drying said textile substrate. A process according to claim 9, wherein said solubilizing agent is acetic acid. A process according to claim 9, wherein heat is applied during step (i) or step (ii) to facilitate formation of said dispersion. 12. Treated textile substrate, said treated textile substrate comprises: (a) a textile substrate containing synthetic components; and textile treatment, said treatment comprising: a hyperbranched polyethyleneimine derivative of the formula: wherein R is a non-hyperbranched hydrocarbon group, said hydrocarbon group has at least one linear portion, said linear portion has between -5 and 30 carbon atoms; where χ is a number from 1 to 10,000; where A is an organic compound having 1 to 4 carbon atoms; where y is a number from 0 to 500; where h-PEI is a hyperbranched polyethyleneimine; and wherein R is present in an amount from about 20% to about 80% by weight of said hyperbranched polyethyleneimine derivative. A process for treating a textile substrate, said process comprising: (a) providing a textile substrate containing synthetic components; (b) providing a dispersion comprising a hyperbranched polyethyleneimine derivative and a crosslinking agent, said hyperbranched polyethyleneimine derivative is of the formula: <formula> formula see original document page 26 </formula> where R is a non-hyperbranched hydrocarbon group, said hydrocarbon group has at least one linear portion, said linear portion has between -5 and 30 carbon atoms; where χ is a number from 1 to 10,000; where A is an organic compound having 1 to 4 carbon atoms; where y is a number from 0 to 500; where h-PEI is a hyperbranched polyethyleneimine; and wherein R is present in an amount from about 20% to about 80% by weight of said hyperbranched polyethyleneimine derivative, and said dispersion containing said hyperbranched polyethyleneimine derivative being produced by: ( i) providing said hyperbranched polyethyleneimine derivative, a solubilizing agent and water, said water has a temperature at least equal to the melting point of said hyperbranched polyethyleneimine derivative; and (ii) subjecting said hyperbranched polyethyleneimine derivative, said solubilizing agent and said water to high speed stirring and high shear; (c) applying said dispersion to said textile substrate; and (d) drying said textile substrate. A process according to claim 13 wherein heat is applied during step (i) or step (ii) to facilitate formation of said dispersion.