HK1066036A - Modification of fabric fibers - Google Patents

Description

Fabric fiber modification

Technical Field

The present invention relates to fibrous fabrics or other fibrous substrates coated with amine-containing polymers. These polymers impart durable antimicrobial activity to the fabric surface, recoverable control of certain odors, and the ability to adhere certain materials to the fabric surface.

Background

Fabrics consisting of only natural (e.g., cotton, wool, silk) or synthetic (e.g., polyester, nylon, acrylic) fibers often lack desirable properties. In the textile industry, small amounts of different chemical components are often added to fabrics to impart desired properties; these processes are commonly referred to as "finishing". Such chemical enhancers include dyes, optical brighteners, softeners, water repellents, water/oil repellents, insect repellents, antimicrobial and/or antifungal treatments, antistatic finishes, and hydrophilic finishes.

At the same time, durability is a desirable property and is a significant challenge for any finishing. Even molecules that are slightly volatile will eventually evaporate; sunlight and air will slowly break down other molecules. Cleaning processes such as water washing, dry cleaning and detergent washing are the most significant challenges for fabric finish durability. After only a few washes, much of the finish is removed from the fabric.

Various approaches have been taken to provide durable finishes. One approach is to deposit onto the fabric a chemical agent (typically a polymer) that does not readily dissolve and wash away after precipitation. Alternatively, the reactive components of the finish may be embedded in a layered film that is applied to the fabric; this method often allows for slow release of the reactive ingredients into the surrounding fabric. However, the detergents and mechanical agitation of conventional cleaning processes often eventually remove the polymer or layered film when it is merely deposited onto the fiber surface.

When the textile fibres contain effectively reactive groups, for example in cotton, linen, wool or silk, the finish can be bound to the textile by covalent chemical bonds. This method is very effective, but is limited to the types of fibers and finishes. One disadvantage of rayon (e.g., regenerated cellulose, rayon, or certain non-synthetic polyesters) and synthetic fibers (e.g., acrylic, lycra, polyester, and nylon) is the substantial absence of effective reactive groups; most of these groups are consumed in forming the polymer backbone. Thus, it is difficult to bind a large amount of finish to synthetic fibers by covalent bonding, and thus this effective method of obtaining finish durability is not useful for synthetic fibers.

In polymer coating, it is desirable to provide a method of wrapping textile fibers, particularly synthetic fibers. In this manner, the fibers will provide structural support to the polymer shell and improve the durability of the polymer to conventional cleaning methods such as water washing and dry cleaning. The polymer will provide the desired characteristics to the fabric, potentially including providing reactive groups on the surface of the fiber that can serve as binding sites for further fabric finishing. Some of the "desirable characteristics" that may be imparted by the finish are described below.

US 6,187,856 to Incorvia et al teaches the use of a crosslinked resin formed from a polyamidoamine and a polychlorohydrin crosslinker to form a durable film on a fabric. The resins of this patent are claimed to impart durable antistatic properties to the fabric. In this patent, durability is defined as the manifestation of antistatic properties after soaking the treated fabric in hot water at 80 ℃ for two 20 minute periods.

Antimicrobial finishes are highly desirable for many textile applications. They can be applied to fabrics used in applications where antimicrobial conditions are required, such as in hospitals. They can also be used for old fabrics or fabrics used in the following applications: commercial food, medical facilities, and other areas where exposure of people to infectious bacteria is highly likely.

There are only a few classes of antimicrobial compounds. Durability is a significant problem for most small molecules that evaporate easily or can be washed away. Moreover, many antimicrobial compounds exhibit toxicity to humans. It would be desirable to develop a durable, non-human-harmful antimicrobial textile finish.

A number of short (50 amino acids or less) cytotoxic polypeptides have been identified (Maloy et al, biopolymers (peptide science) 37: 105-122 (1995)). They share the common property of high arginine and lysine residue content and deliver a net positive charge at physiological pH. The mechanism of toxicity appears to be cytolysis mediated by electrostatic coordination of the peptide to the cell wall.

US 5,300,287 to Park teaches derivatizing polyethyleneimines, particularly with polyethylene glycol, to form graft polymers having antimicrobial and antifungal activity. These polymers are particularly suitable for use in ophthalmic products and contact lens care solutions.

US 6,034,129 to Mandeville et al teaches the use of cationic polymers to treat bacterial infections in mammals, particularly humans. The polymers described in this patent have amino or ammonium groups pendant from the polymer backbone.

The ability to eliminate or significantly reduce malodorous axillary and foot odor is a desirable characteristic for apparel fabrics. The chemical component of underarm odor is a waste by-product of certain bacteria that are fed by secretions from human sweat glands. These species of bacteria are called lipophilic diphtheroids (lipophilics). 36 molecules with potential malodour have been identified in body odour (see Preti, G. et al, J.Chem.Ecologies, 1991, 17, 1469; Preti, G. et al, J.Chem.Ecologies, 1992, 18, 1039; Preti, G. et al, J.Chem.Ecologies, 1996, 22, 237; Proc.Nat.Acad.Sci.USA, 1996, 93, 6626). All these are organic acids and the main source of the off-odour has been identified as trans-3-methyl-2-hexenoic acid. The chemical components of foot malodor have similar origins; they are waste products of the bacterium Brevibacterium epidermidis (Brevibacterium epidermidis). These molecules are also organic acids, the most important component being isovaleric acid (see, Kanda, f. et al, brit. j. of dermatology, 1990, 122, 771). It would be desirable to have a durable finish on the fabric that would eliminate or significantly reduce malodorous body odors. One method is to include a germicidal finish. However, these methods do not kill the bacteria living on the skin and thus may still produce an odor. Another approach is to use a finish that absorbs the malodorous organic acids that produce axillary and foot malodors, such that the volatile concentration of the offensive organic acid is below the threshold of detectability. It is highly desirable to be able to recharge the absorbent capacity of such finishes by standard washing methods.

US 4,244,059 to Pflaumer teaches the use of a water-soluble amine-containing polymer Tydex-12(Dow Chemical Co.) as an "odor-absorbent compound". Tydex-12 is applied to a soft, breathable fabric composed of cellulosic fibers, and the treated fabric is then used in the manufacture of a tight-fitting garment. The treated fabric is used to absorb odors emanating from the vagina and surrounding area. This patent does not claim durability nor takes measures to provide durability of the polymer to the fabric during common cleaning methods such as water washing.

WO97/34040 to Koizumi et al teaches the use of polyamines as coatings for acrylic fibers to produce deodorizing fibers. In this patent, wet gel acrylic fibers containing acid genes are contacted with a "nitrogen-based compound" with stoichiometric adjustments made so that the amine groups are in excess. Electrostatic interactions between amine and acid groups are presumably the source of durability. The fibers are already wet spun and not previously dried. After contacting the amine compound, the coated fiber was heated "under wet heat conditions, 100-. The fiber product made of these fibers can remove acidic odor.

Summary of The Invention

The present invention relates to durable finishes for fabrics and other fibrous substrates. The reactive component of the finish is an amine-containing polymer having reactive groups. The polymer crosslinks on the surface of the matrix fibers and forms a soft, wash-resistant resinous coating. The reactive group of the amine-containing polymer can be an amine, but is not limited to only this functional group.

The invention also relates to fibers treated with the amine-containing polymers of the invention; a yarn; woven, knitted or non-woven fabrics and textiles; and finished products (herein, encompassed within the term "fibrous matrix").

The fibrous substrates treated with the finishes described herein have properties not found in natural fabrics, including antimicrobial properties and/or the most unpleasant component of body odor that eliminates or greatly reduces malodor. When applied to synthetic fabrics such as polyester or nylon, the reactive groups of the present invention provide binding sites for other reactive finishes to be added to the amine-containing polymer (either before, simultaneously with, or in a later process) that is resistant to laundering. Durability can be improved by forming ionic or covalent bonds with the reactive groups and/or amine groups of the present invention. Polymer coatings also provide new opportunities for fabric dyeing. For example, reactive dyes can form covalent bonds with amine-containing polymers and are therefore used to dye synthetic fibers.

Detailed Description

As used herein and in the appended claims, "a" and "an" mean one or more, unless stated otherwise.

The term "durable" or "durability" as used herein describes a finished fibrous substrate wherein the desired properties imparted to the substrate by the finish are observed after multiple water washes or dry cleans.

For purposes of this specification and the appended claims, the term "amine-containing polymer" refers specifically to a polymer that contains amine groups located within or pendant from the polymer backbone. For the purposes of this specification, the term "amine group" refers to primary, secondary and/or tertiary amine groups. The polymer may also contain quaternary amine groups, but the inclusion of quaternary amine groups without primary, secondary or tertiary amine groups is insufficient to consider such a polymer as an "amine-containing polymer" as described herein. The amine-containing polymer also contains reactive groups; these reactive groups may be, but are not limited to, amine groups. Examples of other reactive groups include, but are not limited to, hydroxyl, thiol, and carboxylic acid.

The amine-containing polymer can be a homopolymer, copolymer, or terpolymer, which can be derived from natural sources or prepared by synthesis. Examples of amine-containing polymers derived from nature include amine-containing polysaccharides and amine-containing polypeptides. In a preferred embodiment, this natural polymer is chitosan. Examples of synthetic amine-containing polymers include Polyethyleneimine (PEI) and PEI derivatives, polyvinylamine, polydiallylamine, polyallylamine, copolymers and terpolymers of diallylamine and allylamine, copolymers and terpolymers containing diallylamine and/or allylamine, condensation polymers formed from polyamine monomers and monomers having two or more reactive amine groups. Other examples of amine-containing polymers are polyacrylates composed wholly or partially of amine group-containing acrylate monomers, polymethacrylates composed wholly or partially of amine group-containing methacrylate monomers, and copolymers or terpolymers composed of acrylate, methacrylate and/or other vinyl monomers, wherein in the polymer at least some and possibly all of the monomers contain amine groups.

Preferred embodiments of the invention include synthetic polymers PEI and PEI derivatives, polyvinylamine and polymers containing diallylamine or allylamine. PEI can be derivatized with molecules containing reactive groups such as halohydrins, epoxides, organic acids, α, β -unsaturated organic acids, and carbonyl groups. PEI polymers and derivatized PEI polymers are commercially available from Nippon Shokubai and BASF. A preferred polymer is epichlorohydrin grafted PEI available from BASF under the trade designation Lupasol SC-86X.

The term "crosslinker" as used herein refers to a molecule containing two or more functional groups that bond to reactive groups of an amine-containing polymer. The crosslinking agent binds the amine-containing polymers together, thereby forming a coating of the polymer film around the fibers. The reactive functional group-containing fibers can also be reacted with a crosslinking agent to adhere the amine-containing polymer coating directly to the fibers.

In one embodiment, the amine groups of the amine-containing polymer are also reactive groups for forming a durable fiber coating. In this embodiment, primary and/or secondary amine-containing polymers are particularly preferred. One of ordinary skill in the chemical arts will recognize that primary and secondary amines have much greater versatility in bonding than tertiary amines, thereby broadening the variety of potential crosslinking agents. To form a durable coating, the reactive groups in the crosslinker should be present in sufficient amounts, but preferably are present in sub-stoichiometric amounts relative to the amine groups of the polymer, particularly when the subsequent second layer finish is durable by reaction with an amine-containing polymer. In this embodiment, it is particularly desirable that the reactivity of the crosslinking agent be significantly selective to the amine so that the crosslinking agent reacts efficiently to bond the polymers together. In one embodiment, it is desirable (but not required) that the basicity of the nitrogen atoms participating in the crosslinking reaction be substantially unchanged after the reaction. Specific amine-reactive groups include alkyl halides, isothiocyanates, isocyanates, acyl azides, N-hydroxysuccinimide esters, sulfonyl chlorides, aldehydes, dialdehydes, epoxides, oxiranes, carbonates, arylating agents, imidoesters, carbodiimides, anhydrides, and halogenated alcohols. In a preferred embodiment, the crosslinking agent contains halohydrin or epoxide reactive groups. Examples of these crosslinking agents are 1, 3-dichloro-2-propanol and 1, 4-butanediol diglycidyl ether (Sigma-Aldrich).

In another embodiment, the amine-containing polymer also contains non-amine reactive groups. The presence of non-amine reactive groups is particularly valuable when all or almost all of the amine groups of the polymer are tertiary amine groups. Examples of non-amine reactive groups useful in the present invention include hydroxyl, thiol, and carboxylic acid. In a preferred embodiment, the reactive group is a hydroxyl group. It is particularly desirable that the crosslinking reaction does not affect the basicity of the amines in the resulting film. Optionally, a catalyst may be included to promote crosslinking. Reactive hydroxyl functional groups include epoxides, halohydrins, oxiranes, carbonyldiimidazole, N' -disuccinimidyl carbonate or N-hydroxysuccinimidyl chloroformate, alkyl halides, isocyanates, and N-methylol ureas. The thiol group is reacted with haloacetyl and alkyl halide derivatives, maleimide, aziridine, acryloyl derivatives, arylating agents and thiol-disulfide exchange reagents such as pyridyl disulfide, disulfide reductants and 5-thio-2-nitrobenzoic acid. Reactive carboxylate groups include diazoalkanes and diazoacetyl compounds, oxazolines, carbonyldiimidazole, carbodiimides and N-methylol ureas. Preferred crosslinkers are diepoxides (Sigma-Aldrich), N-methylolureas such as dimethyloldihydroxyethyleneurea (DMDHEU) (PatCoRez P-53, BFGoodrich) and blocked polyisocyanates such as Repearl MF (Mitsubishi Chemical).

The finish applied to the fibrous substrate is a solution comprising at least an amine-containing polymer, a crosslinking agent, and a volatile solvent. Desirably, the polymer and crosslinking agent are soluble in the solvent. A particularly preferred solvent is water. The pad solution preferably contains about 0.01 to about 75 wt.%, more preferably about 0.05 to about 50 wt.%, and most preferably about 0.1 to about 40 wt.% of the amine-containing polymer. The padding solution preferably contains about 0.001 to about 40 wt%, more preferably about 0.01 to about 30 wt%, and most preferably about 0.05 to about 20 wt% of a cross-linking agent. The finish solution may also contain other components as described below.

In a particular embodiment of the invention, the amine-containing polymer is partially reacted with the crosslinking agent prior to being placed in the treatment bath, e.g., substantially only one of the two or more reactive groups of the crosslinking agent is pre-reacted with the amine-containing polymer. The resulting graft polymer is then added to the treatment bath and applied to the fabric, after which the fabric is cured to complete the reaction with the crosslinking agent. The graft polymer may be the only component of the treatment bath; or may include other components such as additional cross-linking agents and wetting agents.

The reaction of the amine-containing polymer with certain crosslinker functionalities, such as halohydrins, results in the formation of mineral acids that lower the pH of the finish, and can slow the rate and reduce the degree of crosslinking. To control this detrimental effect, a buffer may be added to the finish solution. Buffers are weak acids or bases that can maintain a solution containing them within ± 1pH of the buffer pKa. One of ordinary skill in the art will appreciate that the optimal buffer solution consists of equimolar portions of the buffer and its corresponding conjugate acid or base, the latter often being formed by the addition of a strong acid or base. An enumeration of buffers can be found in Lange's handbook of Chemistry, 14 th edition, edited by J.A. dean, McGraw-Hill, Inc., Chapter 8, page 103-112. If used, the buffer should be selected such that the pKa of the buffer is within the optimum pH range for the reaction. This pH range depends on the type of reactive groups of the amine-containing polymer and the crosslinker. The buffering agent must also be selected so that it does not react with the crosslinking agent or amine-containing polymer. The amount of buffer should be slightly greater than the theoretical total amount of equimolar acid generated by complete reaction of the crosslinking agent.

The finish solution may also contain other additives. For example, amine groups are susceptible to oxidation, and their by-products are often yellowish brown. The addition of an antioxidant to the finish solution minimizes oxidation both in storage and when the finish is applied and cured on the fabric. A preferred antioxidant of the present invention is phosphoric acid. Optical brighteners (e.g., Leucophor product from Cariant or Uvitex product from Ciba) may be included in the finishing solution. Whitening agents such as sodium tetraborate may also be included in the solution. The finishing solution may also contain wetting agents, such as wetaidinNRW (BFGoodrich) to aid in the even distribution of the finishing agent on the fibers. This is particularly useful when the fibrous material is hydrophobic. Other additives may be added to the solution as desired.

The finish can be applied to the fibrous substrate by exposing the substrate to the finish solution by methods known in the art such as soaking, spraying, dipping, fluid flow, and padding. The exposed fibrous substrate is then heated to remove the volatile solvent and accelerate the reaction of the polymer with the crosslinking agent. Alternatively, the fibers or yarns may be exposed to the finishing solution by soaking, spraying or dipping. After the finish is cured in place, the fibers or yarns can be woven or knitted into a fabric.

The finish solution can be applied to the fibrous substrate at any temperature above the freezing point of the solvent but below the boiling point. In the present embodiment, the coating temperature is preferably 5 to 90 ℃, more preferably 10 to 50 ℃, and most preferably room temperature. The treated fibers should be cured at a temperature high enough to allow the shell to form in a very short time, preferably less than 5 minutes, more preferably 1 minute or less. In embodiments of the present invention, the curing temperature is preferably 100-180 deg.C, more preferably 110-140 deg.C.

The invention also relates to a fibrous substrate treated with the above-mentioned finish. The substrate so treated will have properties not found in the untreated substrate. These properties include antimicrobial properties and the ability to absorb malodorous organic acids through acid-base reaction of the acid with the amine groups of the finish. In the case where the matrix is composed wholly or partially of inert synthetic fibers, the treated fibers provide reactive groups on their surfaces. Further treatment with a second finish containing groups reactive with the modified fiber will impart durability to the second finish. Examples of desirable durable second finishes include dyes, softeners, water repellents, water/oil repellents, insect repellents, antimicrobial and/or antifungal treatments, antistatic finishes, and hydrophilic finishes.

In one embodiment of the invention, the treated fibrous substrate has antimicrobial properties. Fabrics and other fibrous substrates that prevent the growth of, or actively kill bacteria, mold, or fungus are highly desirable, particularly in locations where bio-contaminated fabrics may be a source of infection, such as in hospitals and food preparation facilities. The finish coatings of the present invention have been shown to provide durable, non-leaching antimicrobial properties to the treated fabrics. While not being bound by theory, it is believed that the effect of the finish is due to the cationic charge of the polymer. The cell wall of the microorganism is composed mainly of negatively charged phospholipidic bilayers. In theory, the electrostatic coordination of the lipid bilayer with the finish polymer disrupts the cell wall and kills microorganisms.

Another embodiment of the present invention is to prepare treated fibrous substrates that absorb organic acids and remove their odor, which imparts to such substrates the ability to eliminate or greatly reduce unpleasant body odors. If necessary, the fabric odor absorption capacity can be replenished by conventional washing methods. The molecular source of unpleasant body odor is mainly a waste product of a group of bacteria named lipophilic diphtheroids. This bacterium lives on the surface of the human skin and primarily digests the secretions of the exocrine glands. The malodorous waste products of lipophilic diphtheroids are organic acids, the most important component being 3-methyl-2-hexenoic acid. Generally, volatile organic acids are considered to have an extremely unpleasant odor even at extremely low concentrations. The odor absorbing capacity of the treated fibrous substrate is derived from the basicity of the amine groups of the finish. The acid reacts with the free amine groups of the amine-containing polymer to form a non-volatile ionic complex. The extent to which this ionic complexation occurs depends on the relative strengths of the acid and base. In the case of the present invention, the reaction is biased toward the formation of ionic complexes to the extent that only 1 of a ten thousand acid molecules to only 1 of a hundred thousand acid molecules are found to be non-ionic, possibly volatile forms. Thus, as long as unreacted amine groups are present in the treated fabric, the concentration of volatile organic acids around the treated fabric is reduced to undetectable or nearly undetectable values.

The present invention has an advantage over conventional odor absorbing materials such as activated carbon in that the odor absorbing ability of the fibrous substrate can be replenished. Because amines are weak bases, exposure of the substrate to aqueous solutions at or above the pH of the base pKb will deprotonate most of the amine complex and lead toResulting in the separation of the amine-acid complex. In the laundry detergent, the malodorous organic acids in the form of conjugate bases are washed away, leaving free amine groups on the fiber surface. The pH of 10 is higher than the pKb of most amines, typically laundry detergent solutions such as Tide^Has a pH of this pH or higher. Therefore, conventional washing methods are sufficient to impart odor-absorbing ability to the fabric again.

Another embodiment of the invention is to prepare the fiber surface with reactive amine groups that can participate in bonding other finishes to the fiber substrate in a durable manner. This is particularly useful when the fibers are composed of polymers that do not have many reactive groups, such as in polyesters and nylons. Fibers treated with the amine-containing polymeric finish of the present invention have reactive groups present on their surfaces. Further treatment with a second finish containing groups reactive with the modified fiber will impart durability to the second finish. Examples of desirable durable second finishes include dyes, optical brighteners, softening agents, water repellents, water/oil repellents, insect repellents, antimicrobial and/or antifungal treatments, antistatic finishes, and hydrophilic finishes.

The nature of the reactive functional groups of the second finish as described above depends on the reactive groups of the amine-containing polymer. Examples of reactive amine groups include isothiocyanates, isocyanates, acyl azides, N-hydroxysuccinimide esters, sulfonyl chlorides, aldehydes, dialdehydes, epoxides, oxiranes, carbonates, arylating agents, imidoesters, carbodiimides, anhydrides, and halohydrins. Reactive hydroxyl functional groups include epoxides, halohydrins, oxiranes, carbonyldiimidazole, N' -disuccinimidyl carbonate or N-hydroxysuccinimidyl chloroformate, alkyl halides, isocyanates, and N-methylol ureas. The thiol group is reacted with haloacetyl and alkyl halide derivatives, maleimide, aziridine, acryloyl derivatives, arylating agents and thiol-disulfide exchange reagents such as pyridyl disulfide, disulfide reductants and 5-thio-2-nitrobenzoic acid. Reactive carboxylate groups include diazoalkanes and diazoacetyl compounds, carbonyldiimidazole, carbodiimide and N-methylolurea.

The following examples are for illustrative purposes only. Other embodiments will be recognized by those of ordinary skill in the art, all of which are considered to be part of this invention.

Examples

Example 1

A100.0 gram solution of 10% polyethyleneimine (PEI, molecular weight 70,000, Nippon Shokubai) and 5% 1, 3-dichloro-2-propanol (DCP, Aldrich chemical) at pH 9.0 was prepared by the following procedure: 33.3 g PEI (30% solution) and 50.0 g water were mixed, the pH was adjusted with hydrochloric acid (VWR), additional water was added to reach a mass of 95.0 g, and then 5.0 g DCP was added. Undyed, woven, microdenier polyester fabric swatches were dipped into this solution, processed through a pad-roll or "pad-roll" and cured in a forced air oven at 121 ℃ for 5 minutes. A control swatch (C-1) of the same fabric was immersed in water at pH 9.0 and a second control swatch (C-2) was immersed in 10% PEI at pH 9.0. All control swatches were padded and then cured in a forced air oven at 121 ℃ for 5 minutes. All swatches were cut into four portions. A group of 1/4 portions were rinsed individually with cold tap water for 20 minutes; this group is referred to herein as the zero (0) home wash (HL) sample. The remaining three 1/4 parts were machine washed 5, 10 or 20 times according to method 124 and 1996 of the American Association of Textile Chemists and Colorists (AATCC) as reported in the AATCC technical Manual (1999). When the wash was complete, all 1/4 parts were cut in half. One half was stained as follows and the other half was used for odor absorption analysis.

The sample cloth to be dyed is placed in an aqueous solution of the 0.1% dye acid Red 37 (20: 1, solution: article ratio) for 30 minutes. When dyeing was complete, the samples were removed from the bath and rinsed separately with cold tap water for 1 minute. Note the degree of coloration and is recorded under the heading "color" in fig. 1. The untreated polyester has little or no affinity for acid dyes, while PEI has a strong affinity for acid dyes, and thus this test is a good indicator of the presence of PEI.

The odor analysis was performed as follows: a drop of 0.01% butyric acid solution was placed on each swatch and the drop was allowed to dry. Then, the panelists smell each cloth sample and rated the odor as strong, weak or not noticeable. The overall impression of the referee is recorded under the heading "odor" in table 1.

TABLE 1

Sample (I)	0HL		5HL		10HL		20HL
										Colour(s)	Bad smell	Colour(s)	Bad smell	Colour(s)	Bad smell	Colour(s)	Bad smell
Treated of	Deep red	Is free of	Red wine	Is free of	Red wine	Is free of	Light red	Weak (weak)
									C-1	Red wine	High strength	White colour (Bai)	High strength	White colour (Bai)	High strength	White colour (Bai)	High strength
C-2	Deep red	Is free of	Shallow powder	High strength	White colour (Bai)	High strength	White colour (Bai)	High strength

Example 2

Solutions of 4% PEI (BASF, Mn 60,000), 3% 1, 4-butanediol diglycidyl ether (Sigma-Aldrich) and 0.1% wetaidrw (bfgoodrich) were prepared by mixing 24.0 grams PEI, 0.3 grams WetAid NRW and 2400.0 grams distilled water in a beaker. The pH of this solution was adjusted to 9.0 with 85% phosphoric acid (Baker). Sufficient water was added to achieve a total mass of 291.0 grams, followed by 9.0 grams of 1, 4-butanediol diglycidyl ether. The formulation was then stirred well (formulation a).

Formulation B was a 4% PEI and 0.1% WetAId aqueous solution (300.0 g) at pH 9.0.

Formulation C was 3% 1, 4-butanediol diglycidyl ether and 0.1% WetAId in water (300.0 g).

Formulation D is a 0.1% WetAId aqueous solution (300.0 g) adjusted to pH 9.0 with sodium hydroxide (Aldrich).

Three cloth samples of polyester fabric and a cotton fabric were immersed in each solution. The swatches were then padded to uniform wet pick-up and then dried at 157 deg.C for an additional 15 seconds after the fabric was dried. These samples were then washed 30 times according to AATCC method 124-. Swatches were cut from the fabric before, once and 30 washes. The odor absorption test was performed for each swatch as described in example 1.

The swatches treated with formulation a also smelled after 30 washes, while the other treated swatches did not.

Example 3

A500.0 gram solution of 5% ethoxylated PEI (BASF), 0.1% WetAId NRW (BFGoodrich) and 3% 1, 4-butanediol diglycidyl ether (Sigma-Aldrich) was prepared by mixing 67.5 grams ethoxylated PEI, 0.5 grams WetAId and 417.0 grams water, formulation A. Then 15.0 g of 1, 4-butanediol diglycidyl ether were added and the solution was stirred well.

Formulation B consisted of 500.0 grams of a 0.1% WetAId solution.

Three woven polyester, cotton and 90/10 cotton/lycra fabric swatches were cut and dipped into one of the two formulations. The swatches were then padded to uniform wet pick-up and then dried at 157 deg.C for an additional 15 seconds after the fabric was dried. These samples were then washed 30 times according to AATCC method 124-. Swatches were cut from the fabric before, once and 30 washes.

The cloth samples washed 30 times were subjected to an odor adsorption test using 0.01% butyric acid. The panelists compared the odor of the treated samples to the untreated controls. The value of the control was determined to be 3. If no odor is detected on the treated swatch, it is determined to have a value of 0. Any detectable butyric acid odor on the treated fabric was graded 1-3 relative to the control. Swatches from home washes 30 times were also stained according to the method described in example 1.

The results of the staining and olfactory tests are listed in table 2. The polyester cloth sample is determined to be PET #, the cotton is COT, and the cotton/Lycra mixture is C/L. Suffix T indicates processing with recipe a and suffix U indicates processing with recipe B.

TABLE 2

Sample number judge 1 judge 2 judge 3 average standard deviation dyeing color
					PET1-TPET1-UPET2-TPET2-UPET3-TPET3-UCOT-TCOT-UC/L-TC/L-U	0 0 03 3 31 0 03 3 30 0 03 3 30 0 03 3 30 0 10 3 3	0.003.000.333.000.003.000.003.000.332.00	0.000.000.580.000.000.000.000.000.581.73	White powder, white red powder and red powder

Example 4

100.0 g of 30% PEI (Nippon Shokunai, Mn. 70,000) was mixed with 7.8 g of glycidol (Sigma-Aldrich). Glycidol was reacted with PEI for 1.5 hours at room temperature. It is assumed that the polyethyleneimine has reacted completely with glycidol. Hereinafter, the resulting product, glycidyl grafted polyethyleneimine, is referred to as PEI-g 20. PEI-g20 was used as a 35% aqueous solution without further purification.

A series of padding bath formulations were prepared: all formulations were adjusted to pH 3.5 with hydrochloric acid (VWR). Formulation a consisted of water. Formulation B consisted of 10% PatCoRez P-53(DMDHEU resin, BFGoodrich). Formulation C consisted of 12.6% PEI-g 20. Formulation D consisted of 10% PatCoRezP-53 and 12.6% PEI-g 20. For each formulation, two cotton swatches were dipped, then padded and dried/cured for 3 minutes. One swatch of each formula was then washed 5 times according to AATCC method 124-.

These swatches were then tested for antimicrobial activity according to AATCC test method 100. The results are reported in table 3. The sample number corresponds to the recipe in which the sample is immersed. The term "TMTC" indicates that too many colonies are present to be counted. It is noteworthy that PEI-g20 killed the test bacteria essentially instantaneously at both 0 and 5 home washes (samples C and D). The DMDHEU resin in PatCoRezP-53 also had antimicrobial activity, probably due to its slow release of formaldehyde upon decomposition (sample B); however, the effect is much slower. The untreated control (sample a) had no antimicrobial activity.

TABLE 3

Sample No. HLs colony #
			0 hour 24 hour% kill
A 0 TMTC TMTC 0％5 1589 TMTC 0％B 0 TMTC 0 100％5 TMTC 0 100％C 0 0 0 100％5 423 0 100％D 0 428 0 100％5 0 0 100％

Example 5

A400 liter solution of 25% Lupasol SC-86X (BASF), 1.5% Repearl MF (Mitsubishi chemical) and 0.1% WetAid NRW (Noveon) was prepared and placed in a pad bath on a Montfort frame. 6 (1-6) dried, open width 100% polyester fabric was passed through the solution at a rate of 23.5 yards/minute and then padded by a squeeze roll set at 55psi to obtain an average pick-up of 106%. The fabric was then passed through an oven set at 320 ° F; the fabric was left at this temperature for a period of 14 seconds. The finished fabric was tested for its ability to absorb tart, and each finished swatch was then washed 20 times according to AATCC method 124-96 and tested again. The same 6 swatches untreated were also tested in the same manner for comparison. The results are reported in table 4.

The following tests were performed: 1 drop of diluted butyric acid was placed on a cloth sample, absorbed into the fabric over a period of time, and the cloth sample was then smelled by the members of the referee group. If no odor was detected by any of the judges, a drop of more concentrated butyric acid solution was placed on the fabric and evaluated again. This process was repeated until all judges could smell the butyric acid. Each officials recorded the concentration of butyric acid (in ppm) at which he could detect the odor; this concentration is referred to as the odor score. The odor scores for each swatch were then averaged.

TABLE 4

Average value of parametric odor score

Style processing (Yes/No) 0HL 20HL

1 is 1000600

1 no 133167

2 is 667667

2 no 83117

3 is 867667

No. 3 no 117117

4 is 1000733

4 no 67167

5 is 1000533

No. 5 no 200267

6 is 10001000

6 NO 67467

Claims (18)

1. A finish for a fibrous substrate comprising an amine-containing polymer having reactive groups, a crosslinking agent, and a volatile solvent, wherein the finish is resistant to a cleaning process.

2. A finish according to claim 1 which provides antimicrobial properties to the fibrous substrate.

3. A finish according to claim 1 which imparts to the fibrous substrate the ability to eliminate or greatly reduce unpleasant body odour.

4. A finish according to claim 3 wherein the ability is rechargeable.

5. A fibrous substrate comprising an amine-containing polymer crosslinked on the fiber surfaces of the fibrous substrate to form a resin coating resistant to a cleaning process.

6. A fibrous substrate according to claim 5 which has durable antimicrobial properties.

7. A fibrous substrate according to claim 5 which has the ability to permanently eliminate or greatly reduce unpleasant body odours.

8. The fibrous substrate according to claim 7 wherein the capacity is rechargeable.

9. The fibrous substrate according to any of claims 5 to 8, which is a synthetic fiber further comprising at least one additional finish, wherein the additional finish is resistant to a washing process.

10. The fibrous substrate according to claim 9 wherein the additional finish is a reactive dye.

11. A method of providing antimicrobial properties to a fibrous substrate, the method comprising:

exposing the fibrous substrate to a treatment composition comprising an amine-containing polymer having reactive groups, a crosslinking agent, and a volatile solvent; and

curing the fibrous matrix;

thereby imparting durable antimicrobial properties to the fibrous substrate.

12. A method of providing a fibrous substrate with the ability to eliminate or substantially reduce unpleasant body odor, the method comprising:

exposing the fibrous substrate to a treatment composition comprising an amine-containing polymer having reactive groups, a crosslinking agent, and a volatile solvent; and

curing the fibrous matrix;

thereby providing the treated fibrous substrate with a durable ability to eliminate or greatly reduce unpleasant body odor.

13. A method according to claim 12, further comprising the step of exposing the treated fibrous substrate to an aqueous solution having a pH of 10 or greater to replenish the odor-absorbing capacity of the fibrous substrate.

14. A method of treating a synthetic fiber substrate to provide a durable finish on the synthetic fiber substrate, the method comprising:

exposing the fibrous substrate to a first finish comprising an amine-containing polymer having reactive groups, a crosslinking agent, and a volatile solvent to render the treated fibrous substrate having reactive groups on its surface;

curing the treated fibrous substrate; and

exposing the treated fibrous substrate to a second finish comprising groups reactive with reactive groups on the treated fibrous substrate;

thereby producing a synthetic fiber matrix in which the second finish is resistant to the cleaning process.

15. The method according to claim 14, wherein the synthetic fibrous substrate is exposed to the first and second finishes simultaneously.

16. The method according to claim 14, wherein the synthetic fiber substrate is exposed to the second finish after exposure to the first finish and before or after the curing step.

17. A method according to any of claims 14 to 16, wherein the second finish is a reactive dye.

18. The method of any of claims 11-17, wherein the amine-containing polymer portion is reacted with a crosslinking agent prior to being placed in the volatile solvent.