MXPA99002367A - Durable and regenerable microbiocidal textiles - Google Patents

Abstract

The present invention provides, inter alia, durable and regenerable microbiocidal textiles and methods for preparing such textiles. Such textiles can be readily prepared using a wet finishing process to covalently attach a heterocyclic N- halamine to a cellulose based material or other polymeric material. Once prepared, the textiles of the present invention have a broad spectrum of biocidal activity against pathogenic microorganisms. Moreover, the biocidal activity of such textiles can be regenerated by washing with a halogenated solution.

Description

MICRQBICIDES TEXTILES. DURABLE AND REGENERABLE BACKGROUND OF THE INVENTION An important and growing part of the textile industry is the medical one and in the sectors of health care and hygiene. Textiles used in medicine-related applications include, for example, surgeon's gowns, caps and masks, patient dresses, bandages, cleansers and coverings of various sizes. However, such textile materials are conductive to cross-infection and disease transmission, caused by microorganisms. As such, the possibility of disseminating infections caused by the lethal HIV virus, the insidious hepatitis virus or other epidemic diseases has created a growing interest in the use of protective uniforms and establishments for workers in the medical sectors. of health care / hygiene. Currently, the textile materials used in medical applications are non-woven disposable synthetic fabrics, which are neither biocidal nor reusable. Such textile fabrics provide protection by blocking the transmission of microorganisms, rather than by inhibiting the growth of these microorganisms. Thus, cross-infection through surface contact of contaminated textile fabrics is problematic. As a result, as an effort to prevent cross infection and disease transmission, contaminated materials must be properly sterilized and discarded after use. Unfortunately, such sterilization and discarding procedures result in substantial increases in the cost of health care and in the amount of biohazardous waste that is generated. Therefore, it is desirable that bacterial infections resulting from contact with contaminated textiles be reduced or eliminated, and that the transmission of pathogenic bacteria from one person to another by dressing or using contaminated textiles will be prevented, inhibiting the growth of microorganisms in the fabrics. It is also advisable that surgeon's gowns, hospital carpets and bed materials, underwear, socks and uniforms are biocides, in order to provide the best possible protection. In addition, it is convenient to have biocidal textiles for use, among other places, in hotel towels, bedding materials, socks and other hygienic products as well. Currently, there are two general categories of technologies that can provide protection to medical / health care / hygiene personnel. They are: (1) physical techniques that involve the formation of a physical barrier against microbial infiltration or selected transmission of tissue and coating constructions that are impervious or that are microporous and contain antimicrobial agents; and (2) chemical technologies that involve the incorporation of active functional agents on tissues or fibers by grafting or other chemical methods. Disposable materials are examples of the first category. The coating methods involve the application of impermeable materials on the surface of the tissues, thus blocking the infiltration and permeation of the microorganisms. However, cross infection and spread of diseases through contact of the surface of the coating is still feasible and, thus, have potential threats to the workers who handle the contaminated materials. Also, impervious properties can cause users discomfort and, in turn, become less efficient. As such, the chemical association of antibacterial agents on any surface or completely of the material seems to be more practical in terms of the durability and efficacy of the antibacterial properties. There are two main routes of chemically achieving durable antibacterial effects. In one, the slow release of biocides is used through contact with the processed tissues. On this route, which is widely used around the world, enough chemical agents are impregnated on the fibers by chemical or physical methods. Next, the biocides are slowly released from the processed tissues into the medium, thus making contact and inhibiting the growth of the microorganisms. Unfortunately, such chemical agents can easily wash off if they are not impregnated covalently on the surface of the tissues. Also, antibacterial functions are not regenerable. In the second route, a more innovative technology is used, which involves the chemical modification of textile materials with biocidal or potentially biocidal compounds, in which the antibacterial properties of these compounds are regenerable with a simple wash. Potential antibacterial groups can be made biocides after washing with certain common chemicals, such as diluted bleaching solutions. More than thirty-five years ago, Gagliardi, et al. they first proposed the principle of regenerating antibacterial finishes, hoping to regenerate the function lost by washing the fabrics used with some specific solutions. { see, Am. Dyest. Rep. , 51, 49 (1962)). However, although many efforts have been made, no commercial products have been produced. In view of the foregoing, there is a need in the art for durable and regenerable microbicidal textiles. The present invention remedies such a need for the supply, inter alia, <; μe durable and regenerable microbicide textiles.

COMPENDIUM OF THE INVENTION The present invention provides, among other things, durable and regenerable microbicidal textiles and methods for preparing the same. These textiles can be easily prepared using a classical wet finishing process to covalently link a heterocyclic N-haloamine to a cellulose-based material or other polymeric material. Once prepared, the textiles of the present invention have a broad spectrum of biocidal activity against pathogenic microorganisms. Also, the biocidal activity of these textiles can be regenerated by washing with a halogenated solution. In one embodiment, the present invention provides a process for preparing cellulosic, cellulose / polyester or polyester microbicidal textile precursors, this process comprises: (a) immersing a cellulose, cellulose / polyester or polyester fabric in an aqueous solution of treatment, which comprises a heterocyclic N-haloamine, a soaking agent and a catalyst; (b) removing the excess treatment solution from the cellulose, cellulose / polyester or polyester fabric; (c) drying this cellulose, cellulose / polyester or polyester fabric; (d) curing the dried cellulose, cellulose / polyester or polyester fabric; (c) washing the cured textile of cellulose, cellulose / polyester or polyester, to remove excess reagents; and (f) drying the treated fabric of cellulose, cellulose / polyester or polyester to remove the water. In another embodiment, the present invention provides a process for making a cellulose, cellulose / polyester or polyester fabric microbicide, the process comprising: (a) washing a cellulose, cellulose / polyester or polyester microbicidal textile precursor with a halogenated solution, the microbicidal textile precusor is prepared according to the above method; and (b) drying the treated cellulose, cellulose / polyester or polyester microbicide fabric to remove the water. In the process, the halogenated solution can be a chlorine solution or, alternatively, a bromine solution. In a presently preferred embodiment, the halogenated solution is a chlorine solution (eg, a chlorine bleach solution, such as Clorox). Washing the cellulose, cellulose / polyester or polyester microbicidal precursor with the halogenated solution supplies the textile biocide and, in addition, sterilizes the textile material.

In yet another embodiment, the present invention provides a composition for finishing fabrics, ie an aqueous treatment solution, this composition comprises a soaking agent; and a heterocyclic N-haloamine. In a preferred embodiment, the composition further includes a catalyst. In an even more preferred embodiment, the composition further includes additives (eg, softening and waterproofing agents) to impart composition-friendly characteristics. There are thousands of application areas for the microbicidal textiles of the present invention. For example, microbicidal textile materials can provide biocidal protective gowns to personnel in the medical area, as well as in the areas of health care and related hygiene. In contrast to previously used textiles, these textiles of the present invention are not a barrier to microorganisms, but rather are a disinfectant for them. As such, biocidal, reusable and reusable materials can replace the non-woven, disposable, currently used textiles as medical textiles, thus significantly reducing the costs of hospital maintenance and waste rights. The microbicidal properties of the textiles of the present invention can be advantageously used for clothes worn by women, underwear, socks and for other hygienic purposes. In addition, microbicidal properties can be imparted to carpet materials to create odor-free and germ-free carpets. Likewise, all germ-free environments, such as those required in biotechnology and the pharmaceutical industry, would benefit from the use of the microbicidal textiles of the present invention, to prevent any contamination from the air, and liquid and solid media. Other features, objects and advantages of the invention and their preferred embodiments will become apparent from the detailed description that follows.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 illustrates examples of the heterocyclic N-haloamines, which are suitable for use in the present invention.

Figure 2 illustrates an exemplary reaction scheme, whereby the heterocyclic N-haloamine is covalently bound to cellulose.

DETAILED DESCRIPTION OF THE INVENTION AND THE PREFERRED MODALITIES In one embodiment, the present invention provides a process for preparing a precursor of a microbicidal, cellulose, cellulose / polyester or polyester textile, this process comprises: (a) dipping a cellulose, cellulose textile / polyester or polyester within an aqueous treatment solution, which comprises a heterocyclic N-haloamine, a soaking agent and a catalyst; (b) removing the excess treatment solution from the cellulose, cellulose / polyester or polyester fabric; (c) drying the cellulose, cellulose / polyester or polyester fabric; (d) curing this cellulose, cellulose / polyester or dried polyester fabric; (e) washing the cellulose, cellulose / polyester or polyester fabric to remove excess reagents and (f) drying the cellulose, cellulose / polyester or treated polyester fabric to remove the water.

The "heterocyclic N-haloamine", as used herein, refers to a 4- to 7-membered ring, wherein at least 3 ring members are carbon, and 1 to 3 ring members are nitrogen heteroatoms, and from 0 to 1 ring member is an oxygen heteroatom, wherein from 0 to 2 carbon members comprise a carbonyl group and wherein at least 1 to 3 nitrogen atoms are substituted with a hydroxyalkyl group, such as -CH 2 OH, or an alkoxyalkyl group, such as --CH2OCH. In addition, the ring members may be further substituted with alkyl groups, such as methyl, ethyl, etc. The heterocyclic N-haloamines are generally described in U.S. Patent No. 5,490,983, issued to Worley et al. On February 13, 1996, the teachings of which are incorporated herein by reference for all purposes. The heterocyclic N-haloamines suitable for use in accordance with the present invention include, but are not limited to, the following: monomethylol-5,5-dimethylhydantoin (MDMH), 1,3-dimethylol-5,5-dimethyl- hydantoin (DMDMH); monomethylolated and dimethylolated derivatives of 2, 2, 5, 5-tetramethyl-l, 3-imidazolidin-4-one, 6,6-dimethyl-1,3,5-triazine-2,4-dione, 4,4, 5,5-tetramethyl-1,3-imidazolidin-2-one, cyanuric acid and 5,5-dimethylhydantoin; and monomethoxylated and dimethoxylated derivatives of 2, 2, 5, 5-tetramethyl-1,3-imidazolidin-4-one, 6,6-dimethyl-1,3,5-triazine-2,4-dione, 4, 4 , 5, 5-tetra-methyl-1,3-imidazolidin-2-one, cyanuric acid and 5,5-dimethylhydantoin. Examples of monomethoxylated and dimethoxylated compounds are monomethoxymethyl-5,5-dimethylhydantoin and 1,3-dimethoxymethyl-5,5-dimethylhydantoin, respectively. In a preferred embodiment, the monomethylol-5,5-dimethylhydantoin and the 1,3-dimethylol-5,5-dimethylhydantoin are the heterocyclic N-haloamines used. The heterocyclic N-haloamines used in the present invention are commercially available from a number of different sources. For example, monomethylol-5,5-dimethylhydantoin (MDMH and 1,3-dimethylol-5,5-dimethylolhydantoin (DMDMH) are commercially available under the trade names of DANTOIN® and GLYDANT® XL-1000, respectively from LONZA, INC. (Fair La n, NJ) Likewise, cyanuric acid is commercially available from ALDRICH® (Mil aukee, WI) In addition, those skilled in the art will readily appreciate that the heterocyclic N-haloamines used in the present invention, they can be synthesized in a variety of ways, using conventional techniques of synthetic chemistry In this regard, those skilled in the art will appreciate that dimethoxylated derivatives are prepared from the dimethylated derivatives, while the monomethoxylated derivatives are prepared from any of the derivatives mono- or dimethylated Examples of heterocyclic N-haloamines, suitable for use in the present invention are indicated in Figure 1. It should be noted that many of these heterocyclic N-haloamines are widely used in cosmetic products and their halogenated derivatives are the main disinfectants for use in, for example, ponds of swimming. As such, these compounds will not generate any toxic effect in humans or in the environment, in terms of the finished fabrics or during the finishing process. "Microbicide", as used herein, refers to the ability to kill at least some types of microorganisms, or to inhibit the growth or reproduction of at least some types of microorganisms. The textiles prepared, according to the present invention, have microbicidal activity against a broad spectrum of pathogenic microorganisms. For example, these textiles have microbicidal activity against representative gram-positive bacteria (such as Staphylococcus aureus) and gram-negative bacteria (such as Escherichia coli). Also, very importantly, the microbicidal activity of these textiles is easily regenerable. In step (a) of the above process, the aqueous treatment solution (or, alternatively, the finishing solution or bath) comprises a heterocyclic N-haloamine, as described above, a soaking agent and a catalyst. As used herein, the "soaking agent" refers to a substance that increases the rate at which a liquid spreads across a surface, ie, makes a surface non-repellent to a liquid. Examples of suitable soaking agents include, but are not limited to, Triton X-100 (Sigma Chemical Co., St. Louis, MO), SEQUAWET® (Sequa Chemical Inc., Chester, S, and AM ET® (American Emulsions Co., Dalton, GA.) Other soaking agents suitable for use in the present invention are known and used by those skilled in the art.As used herein, the "catalyst" refers to a substance that increases the rate of A chemical reaction, without being consumed by itself, suitable catalysts for use in the present invention include, but are not limited to, the following: magnesium salts, zinc salts and ammonium salts In presently preferred embodiments, the catalyst employed is one of the following: MgCl2, Mg (N03) 2, Zn (N03) 2 or NH4N03 Those skilled in the art will readily appreciate that the concentration of the various components of the aqueous treatment solution can be varied widely, depending on the the particular components and and the desired results. Typically, the heterocyclic N-haloamine is present at a concentration of at least 0.2%. More typically, the heterocyclic N-haloamine is present in a concentration ranging from about 0.2 to 20%, more preferably at a concentration ranging from about 0.5 to 10% and, especially, at a concentration ranging from about 1 to about 10. to 5%. It will be readily apparent to those skilled in the art that higher concentrations of the heterocyclic N-haloamine (eg, 50%) can be employed, but such higher concentrations are not required to impart the microbicidal activity. Again, the appropriate microbicidal activity can be imparted using a concentration of the heterocyclic N-haloamine as low as 0.2%. The soaking agent is typically present at a concentration ranging from about 0.1 to 3% and, more preferably, at a concentration ranging from about 0.2 to 1%. The concentration of the catalyst used will depend on the concentration of the heterocyclic N-haloamine used. Typically, the ratio of the heterocyclic N-haloamine to the present catalyst will vary from about 10: 1 to 5: 1. The pH of the aqueous treatment solution will typically vary from 2 to 6 and, more preferably, from 2.5 to 4.5, in approximate form. Those skilled in the art will readily appreciate that other additives can be incorporated into the aqueous treatment solution, to impart favorable characteristics to the cellulose, cellulose / polyester or polyester textile. Such additives may include softening and waterproofing agents, which are known and sanctioned by those skilled in the art. Examples of softeners that may be added to the aqueous treatment solution include, but are not limited to, MYKON® and SEQUASOFT®, both commercially available from Sequa Chemical Inc. (Chester, SC). Examples of waterproofing agents, which may be added to the aqueous treatment solution include, but are not limited to, SEQUAPEL® (Sequa Chemical Inc., Chester, SC), SCOTCHGARD (3M, St. Paul, MN) and other water repellent finishing solutions, used by those skilled in the art. In carrying out step (a), the fabric used may be a thread, yarn or fabric, regardless of whether it is spun, knitted or woven, or it may be of non-woven sheets or webs. Also, the textile can be made of cellulose fibers, polyester fibers or mixtures of these fibers. In addition, other polymeric materials having reactive functional groups (e.g., -0H groups) can be used. Such polymer materials include, but are not limited to, polyvinyl alcohol (PVA), starches and proteins. By soaking the textile in the finishing or treatment bath, ordinary textile equipment and methods suitable for the intermittent or continuous passage of strands, threads or tissues through the aqueous solution can be used, at any speed that allows complete soaking and uniform of the textile material.

In step (b), the excess of the aqueous treatment solution is removed by ordinary mechanical methods, such as by passing the textile between tightening rolls, by centrifugation, by draining or by filling. In a preferred embodiment, the excess of the aqueous treatment solution is removed by filler. In step (c), the cellulose, cellulose / polyester or polyester fabric is dried at a temperature ranging from about 50 to 90 ° C and, more preferably, at a temperature ranging from about 75 to 85 ° C. , for a period of time ranging from about 3 to 8 minutes and, more preferably, about 5 minutes. In step (d), the cellulose, cellulose / polyester or dry polyester fabric is cured at a temperature ranging from 120 to 180 ° C and, more preferably, at a temperature ranging from about 140 to 160 ° C. , for a period of time ranging from about 3 to 8 minutes, more preferably about 5 minutes. The heating is carried out in an oven, preferably one having a forced draft of air, directed to the surface of the textile and escaping through ventilation to remove the fumes. In step (e), the cellulose, cellulose / polyester or dry polyester fabric is washed. The washing of the treated textile, that is, step (e), can be done with hot or cold water. The covalent bonds formed are stable, insoluble and durable to mechanical agitation, spraying and rubbing that occur in washing machines or large-scale, continuous or intermittent textile washing equipment. The final drying, that is, step (f), can be carried out by any ordinary means, such as oven drying, line drying or rotary drying in mechanical fabric dryers. A drying temperature of about 80 to 120 ° C, for less than 15 minutes, is particularly preferred. In another embodiment, the present invention provides a process for making a cellulose, cellulose / polyester or microbicidal polyester fabric, this process comprises: (a) washing a precursor of a cellulose, cellulose / polyester or polyester microbicide fabric With a halogenated solution, this precursor of the microbicidal textile is prepared according to the above method; and (b) drying the treated cellulose, cellulose / polyester or polyester fabric to remove the water. In the process, the halogenated solution can be a chlorine solution or, alternatively, a bromine solution. In a presently preferred embodiment, the halogenated solution is a chlorine solution (eg, a chlorine bleach solution, such as Clorox). Washing the precursor of the cellulose, cellulose / polyester or polyester microbicide fabric with the halogenated solution makes the textile biocidal and, in addition, sterilizes this textile. Also, as previously explained, the microbicidal activity, that is, the oxidative properties, of the textiles can be regenerated by periodically washing the textile with a halogenated solution, during regular washings. In yet another embodiment, the present invention provides a composition for finishing fabrics, this composition comprises a soaking agent; and a heterocyclic N-haloamine. In a preferred embodiment, the composition further includes a catalyst. In an even more preferred embodiment, the composition further includes additives (eg, softening and waterproofing agents) to impart favorable characteristics. The discussions pertaining to the heterocyclic N-haloamines, soaking agents, catalysts, additives and their various concentrations are fully applicable to this composition and, thus, such discussions will not be repeated again. The pH of the aqueous treatment solution will typically vary from a pH of 2 to 6 and more preferably of a pH of 2.5 to 4.5, approximately. Those skilled in the art will readily appreciate that the above composition can be prepared in a concentrated form or, alternatively, in a form suitable for immediate use, ie, at appropriate concentrations of the reagent. Considering both the antibacterial and mechanical properties of the finished textiles, prepared using the methods and compositions herein indicated, the skilled artisan will appreciate that such finished textiles can be advantageously used in the preparation of the following articles: gowns, caps, surgeon masks, surgical covers , patient dresses, carpets, bedding materials, underwear, socks, uniforms, etc. Those skilled in the art will readily appreciate that the finished textiles of the present invention can also be advantageously used for a variety of other purposes, such as towels used in hotels, bedding materials, sanitary products, in various fabrics to protect against pesticides and others. toxic chemicals, etc. The invention will be described in greater detail in the form of specific examples. The following examples are offered for illustrative purposes, and are not intended to limit or define the invention in any way. EXAMPLES Example This example illustrates the finishing of the tissues with monomethylol-5, 5-dimethylhydantoin (MDMH or Anti-1). A finishing bath was prepared, containing 24 grams of the monomethylol-5,5-dimethylhydantoin, 4.8 grams of magnesium chloride and 0.6 gram of Triton X-100 (a soaking agent) in 600 milliliters of deionized water. The pH of the finishing bath was adjusted to 3.4 with one milliliter of a 0.1N HCl solution. Then, 140.9 grams of a pure cotton fabric (# 400 Testfabrics, Inc., Middlesex, NJ) and 141.4 grams of a mixed cotton / polyester fabric (35/65) (# 7409, Testfabrics, Inc., Middlesex, NJ ) were immersed in a bath for more than five minutes and were filled through a filling element with a collection rate greater than 80%. The tissues were submerged and re-filled and dried at 80 ° C for 5 minutes. The tissues were then cured at 160 ° C for 5 minutes. Finally, the finished fabrics were machine washed with 90 grams of the American Association of Textile Chemist and Colorist (AATCC) detergent Standard Reference Detergent 124, at a low level of water and at a temperature of about 60 ° C for 30 minutes. The fabrics were dried and weighed, providing 42.8 grams (1.35% aggregate) of the cotton fabric and 142.4 grams (0.71% aggregate) of the cotton / polyester blend fabric. The cotton product exhibited prominent bands of infrared adsorption on pellets of KBr at 1718 and 1770 crrf1. Next, the finished fabrics were washed with a diluted Clorox solution, which contains about 0.01% active chlorine. The antibacterial properties of the tissues were tested against the representative gram-positive bacteria (such as Staphylococcus aureus (ATCC 5368) and gram-negative (such as Escherichia coli (ATCC 2666)) using the protocol outlined in Example III.

Example II This example illustrates the finishing of the fabrics with l, 3-dimethylol-5,5-dimethylhydANTOIN (DMDMH or Anti-2). A finishing bath containing 48 grams of 1,3-dimethylol-5,5-dimethylhydantoin (DMDMH or Anti-2), 9.6 grams of magnesium chloride and 0.8 gram of Triton X-100 (a soaking agent) was prepared. ) in 800 milliliters of deionized water. The pH of the finishing bath was adjusted in 3.1 with 20 milliliters of a 0.01N HCl solution. Then, 144.7 grams of pure cotton fabric (# 400 Testfabrics, Inc., Middlesex, NJ) and 143.2 grams of a mixed cotton / polyester fabric (35/65) (# 7409, Testfabrics, Inc., Middlesex, NJ) they were immersed in the bath for more than five minutes and were filled through a filling element with more than 80% collection rate. The tissues were submerged and re-filled and dried at 80 ° C for 5 minutes. The tissues were then cured at 160 ° C for 5 minutes. Finally, the finished fabrics were machine washed with 90 grams of the AATCC Standard Reference Detergent 124 detergent, at a low level of water and at a temperature of about 60 ° C for 30 minutes. The fabrics were dried and weighed, providing 147.9 grams (2.22% aggregate) of the cotton fabric and 145.5 grams (1.62% aggregate) of the cotton / polyester blend fabric. The cotton product exhibited prominent bands of infrared adsorption on pellets of KBr at 1718 and 1770 cpf1. Next, the finished fabrics were washed with a diluted solution of Clorox, which contains about 0.01% active chlorine. The antibacterial properties of the tissues were tested against the representative gram-positive bacteria (such as Staphylococcus aureus (ATCC 5368) and gram-negative (such as Escherichia coli (ATCC 2666)) using the protocol outlined in Example III.

This example illustrates the qualitative antibacterial study of the finished Anti-1 fabrics, carried out using the AATCC Test Method 147. # 405 tissue samples (pure cotton, Testfabrics, Inc., Middlesex, NJ) and # 7402 ( cotton / polyester 3/65, Testfabrics, Inc., Middlesex, NJ) were finished in a manner similar to that outlined in Example I. The concentration of the finishing agent used was approximately 5 to 15% in the finishing of the Cotton fabrics and approximately 5 to 20% in the cotton / polyester mixed fabric finish (35/65), due to the lower concentration of cellulose in the mix. The final biocidal property was imparted to the finished fabrics by washing it with a diluted solution of Clorox, containing 0.25% chlorine, after each wash cycle. The qualitative antibacterial tests were performed in accordance with the AATCC Test Method # 147. In the AATCC Test Method 147, two pieces of chlorinated tissue, which are 25 mm x 50 mm in size, were placed on a plate of nutrient agar, which had been inoculated by five slats of a diluted solution of bacteria, using a 4 mm inoculation loop. This diluted solution of bacteria was prepared by transferring 1.0 milliliter of a 24-hour broth culture into 9.0 milliliters of sterile distilled water. The agar plate was incubated at 37 ° C for 18-24 hours. The minimum width of the zone of inhibition along a strip, on either side of the test specimen was measured. Table I indicates the qualitative biocidal evaluations of the finished tissues with different concentrations of the Anti-1 agent. Even with a concentration of 5% of the finishing agent and about 1% of the added agents, the processed fabrics exhibited durable and regenerable antibacterial properties.

Table I Results of cotton (# 405) and cotton / polyester 35/65 (# 7402) finished * The biocidal results were tested with the AATCC 147 test method, the minimum disinfection distance in millimeters (mm) was measured. The washing tests were carried out with a washing machine with hot water, according to the AATCC 124 test method and the detergent AATCC Standard Reference Detergent 124 was used.

Four types of fabric materials, namely # 400, # 7402 (35/65, cotton / polyester), sponge cloth and Rayon (all from Testfabrics, Inc., Middlesex, NJ), were chemically finished with the functional agent, followed by the protocol indicated in Example I. The antibacterial results of the different tissues finished with Anti-1 are shown in Table II. The percentage of aggregate of functional agents by tissues is only 1%. However, after the activation of the biocidal properties of the tissues by the dilution of them with diluted Clorox, the areas of bacterial inactivation was relatively large. The results indicate that cellulose-containing materials can be easily incorporated with functional finishing agents and obtain the desired function against microorganisms in a broad spectrum. If complete disinfection is required, the rate of aggregate of the finishing agents can be increased, increasing the concentration of the agents, as discussed above. However, in most applications, only appropriate biocidal properties are necessary, especially in the anti-odor finishes.

Table II. Antibacterial Results of Different Acafeadog Fabrics with Anti-l Example V This example illustrates the quantitative antibacterial study (AATCC Test Method 100) of finished fabrics Anti-1 Quantitative studies of the biocidal properties of the Anti-l finished fabrics indicate that even at a very low concentration of the finishing bath, the biocidal properties in the tissues can be obtained. The AATCC 100 Test method was adopted in this study. According to this test method, four pieces of 4.8 ± 0.1 anchored circular tissue patches (about one gram) were inoculated with 1.0 ± 0.1 milliliter of inoculum in a 250 ml jar. The inoculum was a culture of nutrient broth that contains more than 1.0 x 106 units that form colonies (CFU) of organisms. After the patches were inoculated, they were neutralized by 100 ml of a 0.02% solution of sodium thiosulfate in the jar. The contact time was the time between inoculation and neutralization. The jar was shaken vigorously and the neutralized solution was serially diluted. Dilutions, usually 10 °, 101 and 102, were placed on the nutrient agar and incubated for 18 to 24 hours at 37 ° C. The number of bacteria recovered from the inoculated finished tissues was counted and compared with that of the untreated tissues. The reduction of six logarithms (log) means the total inactivation of the bacteria, and a reduction of one log means that the finished fabrics reduced the bacteria counts from 106 to 105 CFU. The finished fabrics, prepared from solutions containing 1-6% of the monomethylol-5,5-dimethylhdantoin, following the protocol outlined in Example I, with regimes of uptake below 1%, were tested. The biocidal properties of such tissues are indicated in Table III.

Table III. Effects of Anti-l Finishing Concentrations on Bacterial Reduction Regimens # 400 is a flat woven cotton fabric # 7402 is a flat woven polyester / cotton fabric, 65/35. The reduction of six log means the total death of bacteria Table IV illustrates the effects of chlorine concentrations on the biocidal properties of the finished antibacterial tissues with the use of the protocol set forth in Example I. Each regeneration cycle with different concentrations of chlorine will result in slight damage to the grafted heterocyclic rings. A concentration of 4% of monomethylol-5,5-dimethylhydantoin was selected as the finishing bath, and the anti-l uptake rate was 1.29%. The results obtained are somewhat unexpected for fabrics # 7402, limes have more durable biocide properties than cotton fabrics. The regeneration of biocidal properties with lower concentrations of chlorine is preferred.

Table IV. Effects of Chlorine Concentration in Las Biocidal Properties (Bacterial Reduction Regimens) # 400 is 100% cotton and # 7409 is a polyester / cotton blend, 65 &35. Contact time = 60 minutes, a reduction of 6 log means the total death of the bacteria. A reduction of 0 log means some reduction of bacterial growth and prolonged contact causes a further reduction. The washing tests were as follows: AATCC-124 using a washing machine with hot water (140 ° C) for 15 minutes, and 90 grams of the AATCC detergent 124.

Example VI This example illustrates the quantitative antibacterial study (AATCC Test Method 100) of finished Anti-2 fabrics. ejidos finished in accordance with the protocol outlined in Example II with ANti-2, ie 1,3-dimethylol-5,5-dimethylhydantoin, were also tested with the AATCC test method 100, which was briefly described in Example V. In the tests, a diluted Clorox solution containing 0.01% active chlorine was used to chlorinate the finished fabrics. The biocidal properties of the finished Anti-2 fabrics are indicated in Table V. Table V. Durable Antibacterial Properties of the Ejidos Finishes? Oq Anfrí-2 # 400 is 100% cotton and # 7409 is a polyester / cotton blend, 65 &35. Contact time = 60 minutes, a reduction of 6 log means the total death of the bacteria. A reduction of O log means some reduction of bacterial growth and prolonged contact causes a further reduction. The washing tests were as follows: AATCC-124 using a washing machine with hot water (140 ° C) for 15 minutes, and 90 grams of the AATCC detergent 124.

Example VII This example illustrates the durable properties of ironing of fabrics finished with Anti-2. Fabrics finished with Anti-2, according to the protocol indicated in Example II, also exhibited durable ironing properties, which can be understood because the structure of DMDMH is very similar to that of 1,3-dimethylolol- 4, 5-dihydroxylethylene-urea (DMDHEU). Durable ironing properties were tested, according to AATCC test method 66. In these tests, six specimens of twisted and six x-specimens of cotton fabric filling # 400, which have a size of 15 x 40 mm, were conditioned in a room of conditioning (21 ± 1 ° C and 65 ± 2% humidity relative) for more than 24 hours. The wrinkle recovery angles of the twelve samples, which were folded with three specimens of twisting and filling on the side of the face and three specimens of twisting and filling on the posterior side were measured. Table VI shows the average wrinkle recovery angles of the finished fabrics after repeated washings. With a higher concentration of the finishing agent, more functional agents were combined in the tissues. Therefore, most of the entanglements between the cellulose chains were formed and better wrinkle resistance properties of the fabrics are expected. Table VI. Wrinkle Recovery Angles of Pure Cotton Fabrics # 400. Finished with Anti-2 The washing conditions are the same as those in Example III and Example V.

Example VIII This example illustrates the effects of pH and immersion time on the biocidal activity. Based on the proposed reaction mechanism, the modification reaction, ie the coupling reaction, prefers acidic conditions. As such, a lower pH is generally preferred during the finishing process. The reaction time also has an effect on the results of the chemical modification. The reaction time and the H values of the finishing solutions were varied. Acid conditions with lower pH values increase the rate of uptake of the finishing agent by the finished fabrics, a finding that is consistent with the expected reaction mechanism. For example, the pH decrease from 4.6 to 2.5 almost doubled the uptake regimes (Table VII). However, prolonged reaction times generally have no significant real effects on the performance of the finished fabrics.

Table VII. Biocidal Properties of Processed Cotton Products Baio Different PH V Immersion Times In addition, the finished fabrics were also tested in extensive washing tests. Generally, after 5-8 times of machine washing, according to AATCC Test Method 124, the fabrics were recharged with chlorine bleach and tested against bacteria. The disinfection distances of the samples still indicated that finished tissues with a lower pH had strong bactericidal capacities.

Example IX This example illustrates the breaking strength of finished fabrics treated with Anti-l. Table VIII indicates that the retention of the resistance to rupture of the fabrics finished with Anti-l after extensive washes and regenerations of biocidal properties with different concentrations of chlorine. The tissues were finished in a solution with a concentration of 4% of monomethylol-5,5-dimethylhydantoin and the collection regimen of Anti-l in the fabrics was 1.29%. The washing conditions were the same as in Table IV. Tissue tensile strength was tested following test method D1682 of the American Society for Testing and Materials (ASTM). In the tests, a number of unraveled specimens with their long dimension parallel to the filling of the tissues were prepared with a size of 25.4 mm x 152.4 mm. The burst load of the tissues in kilograms (kg) was then recorded.

Table VIII. Retention of the Rupture Resistance of some Fabrics Finished with Anti-l It will be understood that the foregoing description is intended to be illustrative and not restrictive. Many modalities will be apparent to experts in the field of reading the above description. Therefore, the scope of the invention should be determined not with reference to the foregoing description, but, instead, will be determined with reference to the appended claims, together with the full scope of equivalents to which such claims are entitled . Descriptions of all articles and references, including patent applications and publications, will be incorporated herein as a reference for all purposes.

Claims (33)

1. CLAIMS 1. A textile composition, which comprises: a textile material, this textile material is a member of the group consisting of cellulose, cellulose / polyester and polyester; and a covalently linked heterocyclic N-haloamine.
2. 2. The composition of claim 1, wherein the heterocyclic N-haloamine is the halogenated product of a member selected from the group consisting of monomethylol-5,5-dimethylhydantoin (MDMH), 1,3-dimethylol-5,5-dimethylhydantoin ( DMDMH); monomethylolated and dimethylolated derivatives of 2, 2, 5, 5-tetramethyl-l, 3-imidazolidin-4-one, 6,6-dimethyl-1,3,5-triazine-2,4-dione, 4,4, 5,5-tetramethyl-1,3-imidazolidin-2-one, cyanuric acid and 5,5-dimethylhydantoin, and monomethoxylated and dimethoxylated derivatives of the monomethylolated and dimethylolated derivatives of 2, 2, 5, 5-tetramethyl-1, 3-imidazolidin-4-one, 6,6-dimethyl-1,3,5-triazine-2,4-dione, 4,4,5,5-tetramethyl-1,3-imidazolidin-2-one, cyanuric acid , 5,5-dimethylhydantoin, 2,2,5,5-tetramethyl-l, 3-imidazolidin-4-one, 6,6-dimethyl-1,3,5-triazine-2,4-dione, 4,4 , 5,5-tetramethyl-1,3-imidazolidin-2-one, cyanuric acid and 5,5-dimethylhydantoin.
3. 3. The composition of claim 1, wherein the heterocyclic N-haloamine is the halogenated product of monomethyl-5,5-dimethylhydantoin.
4. 4. The composition of claim 1, wherein the heterocyclic N-haloamine is the halogenated product of 1,3, -dimethylol-5,5-dimethylhydantoin.
5. 5. The composition of claim 1, wherein the heterocyclic N-haloamine is a heterocyclic N-chloroamine.
6. 6. The composition of claim 1, wherein the textile material is cellulosic.
7. 7. The composition of claim 2, wherein the heterocyclic N-haloamine is the heterocyclic N-chloroamine.
8. 8. The composition of claim 1, wherein the textile material is cellulosic / polyester.
9. 9. The composition of claim 1, wherein the fabric is a polyester.
10. 10. A process for preparing a microbicidal cellulosic textile precursor, this process comprises: (a) immersing a cellulosic fabric in an aqueous treatment solution, which comprises a catalyst, a soaking agent and a heterocyclic amine; (b) removing the excess treatment solution from the cellulosic textile; (c) drying the cellulosic textile; (d) curing the dry cellulosic textile; (e) washing the cured cellulose fabric to remove excess reagents; and (f) drying the cellulosic textile to remove the water.
11. 11. The process of claim 10, wherein the cellulosic fabric is a cotton fabric.
12. 12. The process of claim 10, wherein the cellulosic textile is paper.
13. 13. The process of claim 10, wherein the N -halocyclic heteroamyl is a member selected from the group consisting of: monomethylol-5,5-dimethylhydantoin (MDMH), 1,3-dimethylol-5,5-dimethylhydantoin (DMDMH); monomethylolated and dimethylolated derivatives of 2,2,5,5-tetramethyl-1,3-imidazolidin-4-one, 6,6-dimethyl-1,3,5-triazine-2, -dione, 4,4,5 , 5-tetramethyl-l, 3-imidazolidin-2-one, cyanuric acid and 5,5-dimethylhydantoin, and monomethoxylated and dimethoxylated derivatives of the monomethylolated and dimethylolated derivatives of 2, 2, 5, 5-tetramethyl-1, 3 -imidazolidin-4-one, 6,6-dimethyl-1,3,5-triazine-2,4-dione, 4, 4, 5, 5-tetramethyl-l, 3-imidazolidin-2-one, cyanuric acid, 5, 5-dimethylhydantoin 2,2,5,5-tetramethyl-l, 3-imidazolidin-4-one, 6,6-dimethyl-1,3,5-triazine-2,4-dione, 4, 4, 5 , 5-tetramethyl-l, 3-imidazolidin-2-one, cyanuric acid and 5,5-dimethylhydantoin.
14. 14. The process of claim 10, wherein the heterocyclic N-haloamine is the halogenated product of monomethylol-5,5-dimethylhydantoin.
15. 15. The process of claim 10, wherein the N-haloamine heterocyclic is 1, 3, -dimethylol-5, 5-dimethylhydantoin (DMDMH) ..
16. 16. The process of claim 10, wherein the soaking agent is a selected member of the soaking agents of the group consisting of Triton X-100, SEQUAWET® and AMWET.
17. 17. The process of claim 10, wherein the catalyst is a member selected from the group consisting of the magnesium salts, zinc salts and ammonium salts.
18. 18. The process of claim 10, wherein the catalyst is a member selected from the group consisting of MgCl, Mg (N03) 2, Zn (N03) 2 and NH4N03.
19. 19. A microbicidal cellulosic textile precursor, this cellulosic textile precursor was prepared by the process of claim 10.
20. 20. A process for making a microbicidal cellulosic textile, this process comprises: (a) washing a microbicidal cellulosic textile precursor with a halogenated solution, this microbicidal cellulosic textile precursor was prepared according to claim 10; and (b) drying the treated microbicidal cellulose fabric to remove the water.
21. 21. As a textile material, the microbicidal cellulosic fabric treated by the process of claim 20.
22. 22. As a textile material, a cotton fabric treated by the process of claim 20.
23. 23. A process for preparing a cellulosic / polyester microbicidal textile precursor, this process comprises: (a) immersing a cellulosic / polyester fabric in an aqueous treatment solution, which comprises a catalyst, a soaking agent and a heterocyclic amine; (b) removing the excess treatment solution from the cellulosic / polyester textile; (c) drying the cellulosic / polyester fabric; (d) curing the dry cellulosic / polyester textile; (e) washing the cured cellulose / polyester fabric to remove excess reagents; and (f) drying the cellulosic / polyester fabric to remove the water.
24. 24. The process of claim 23, wherein the cellulosic / polyester fabric is a cotton / polyester fabric.
25. 25. The process of claim 23, wherein the N-haloamine heterocyclic is a member selected from the group consisting of: monomethylol-5,5-dimethylhydantoin (MDMH), 1,3-dimethylol-5,5-dimethylhydantoin (DMDMH); monomethylolated and dimethylolated derivatives of 2,2,5,5-tetramethyl-1,3-imidazolidin-4-one, 6,6-dimethyl-l, 3,5-triazine-2,4-dione, 4,4, 5,5-tetramethyl-l, 3-imidazolidin-2-one, cyanuric acid and 5,5-dimethylhydantoin, and monomethoxylated and dimethoxylated derivatives of the monomethylolated and dimethylolated derivatives of 2, 2, 5, 5-tetramethyl-1, 3-imidazolidin -one, 6,6-dimethyl-1,3,5-triazine-2,4-dione, 4, 4, 5, 5-tetramethyl-l, 3-imidazolidin-2-one, cyanuric acid, 5, 5-dimethylhydantoin 2,2,5,5-tetramethyl-l, 3-imidazolidin-4-one, 6,6-dimethyl-1,3,5-triazine-2,4-dione, 4, 4, 5 , 5-tetramethyl-l, 3-imidazolidin-2-one, cyanuric acid and 5,5-dimethylhydantoin.
26. 26. The process of claim 23, wherein the heterocyclic N-haloamine is monomethylol-5,5-dimethylhydantoin (MDMH).
27. 27. The process of claim 23, wherein the N-haloamine heterocyclic is 1,3-dimethylol-5,5-dimethylhydantoin (DMDMH).
28. 28. A microbicidal cellulose / polyester textile precursor, this cellulosic / polyester textile precursor was prepared by the process of claim 23.
29. 29. A process for making a cellulosic / polyester microbicidal textile, this process comprises (a) washing a cellulosic / polyester microbicidal textile precursor with a halogenated solution, this cellulosic textile / polyester microbicide precursor was prepared according to claim 23; and (b) drying the treated microbicidal cellulose / polyester fabric, to remove the water.
30. 30. As a textile material, the cellulosic / polyester microbicide fabric treated by the process of claim 29.
31. 31. As a textile material, a cotton / polyester fabric treated by the process of claim 29.
32. 32. A textile material, having a cellulosic surface with a heterocyclic N-haloamine covalently attached thereto.
33. 33. The textile material of claim 32, wherein the heterocyclic N-haloamine is the halogenated product of a member selected from the group consisting of: monomethylol-5,5-dimethylhydantoin (MDMH), 1,3-dimethylol-5, 5 -dimethylhydantoin (DMDMH); monomethylolated and dimethylolated derivatives of 2,2,5,5-tetramethyl-1,3-imidazolidin-4-one, 6,6-dimethyl-1,3,5-triazine-2,4-dione, 4,4, 5,5-tetramethyl-l, 3-imidazolidin-2-one, cyanuric acid and 5,5-dimethylhydantoin, and monomethoxylated and dimethoxylated derivatives of the monomethylolated and dimethylolated derivatives of 2, 2, 5, 5-tetramethyl-1, 3-imidazolidin -one, 6,6-dimethyl-1,3,5-triazine-2,4-dione, 4, 4, 5, 5-tetramethyl-l, 3-imidazolidin-2-one, cyanuric acid, 5, 5-dimethylhydantoin 2,2,5,5-tetramethyl-l, 3-imidazolidin-4-one, 6,6-dimethyl-1,3,5-triazine-2,4-dione, 4, 4, 5 , 5-tetramethyl-l, 3-imidazolidin-2-one, cyanuric acid and 5,5-dimethylhydantoin. Publication Sheet 2 (54) Title: MICROBICIDES, DURABLE AND REGENERABLE TEXTILES 57) Extract: The present invention provides, among other things, microbicidal, durable and regenerable textiles, and methods for preparing these textiles. The textiles can be easily prepared using a wet finishing process, to covalently link a heterocyclic N-haloamine to a material based on cellulose or other polymeric material. Once prepared, the textiles of the present invention have a broad spectrum of biocidal activity against pathogenic microorganisms. Also, this biocide activity of such textiles can be regenerated by washing with a halogenated solution.