US3395212A - Neomycin and organobismuth antibacterial finish for cellulosic material - Google Patents

Description

United States Patent 3,395,212 NEOMYCIN AND ORGANOBISMUTH ANTI- BACTERIAL FINISH FOR CELLULOSIC MATERIAL Frank John Gross, Mountainside, N.J., assignor to American Cyanamid Company, Stamford, Conn., a corporation of Maine No Drawing. Filed Aug. 10, 1964, Ser. No. 388,705 Claims. (Cl. 424-26) ABSTRACT OF THE DISCLOSURE A process for imparting a durable anti-bacterial finish to a cellulosic material, which comprises applying an organobismuth compound and neomycin sulfate to a cellulosic material in an amount suflicient to impart a durable anti-bacterial activity. The invention also relates to a textile fiber having durable anti-bacterial activity against gram-negative bacteria and gram-positive bacteria whereby said fiber retains said activity after washing, including washing in the presence of chlorine.

This invention relates to a process of imparting a durable antibacterial finish to substrates and to the articles treated by the process.

More particularly the process relates to cellulosic text-ile fabrics treated by a process for imparting a durable antibacterial finish whereby the treated cellulosic textile fibers have antibacterial activity against both gram-negative bacteria and gram-positive bacteria both after washing in the absence of chlorine and/ or after washing in the presence of chlorine.

In the particular and preferred aspect, the present invention relates to the impartat-ion of a durable antibacterial finish to cellulosic substrates such as cellulose textile material, paper, wood, and the like, and relates to the above cellulose substrates treated with the finish.

While the invent-ion is described primarily in conjunction with the importation of antibacterial finish for textile substrates, since this is an area of outstanding performance and utility, it should be kept in mind, as will be seen from the examples hereafter, that substrates subject to accumulation or growth of micro-organisms (such as bacteria) are in general contemplated, e.g., plaster, metal, rubber, plastic, painted surfaces, skin (human or animal), leather and the like. It thus becomes evident that articles suh as floors, walls, doorknobs, childrens toys or articles, furniture, bathroom fixtures, school equipment and various other articles may be rendered antibacterial.

In recent years, increased attention has been given to the development of textile finishes which have become known as purifying finishes. Such finishes are maintained to reduce the number of micro-organisms residing on the material whereby such material may be used with less danger from harmful bacteria. These purifying finishes, when applied to articles of clothing worn close to the body, are also helpful in preventing the development of body odors.

A satisfactory purifying finish should be durable and active at low concentrations against a broad spectrum of micro-organisms. The purity should be such that the finish is non-toxic and non-allergenic. It should not have a Ice tendency to sensitize the wearer or person coming in contact therewith and it should not have the property of allowing strains of bacteria to develop which are resistant to the antibacterial agent in said finish. Such purifying finishes should impart little or no color to textile materials finished therewith, and should be stable with respect to color and activity for substantial periods under storage and shipping conditions. It should be resistant to the conditions used in laundering and dry cleaning and should impart little or no modification of the hand of textile materials. It should be substantive to fibers and therefore durable to laundering, with or without chlorine, and compatible with dyes and resins normally found or imprinted in the res-in finishing of textile materials. Additionally, such compounds should be stable to oxidation by air, light, and heat, or remain antibacterially active and effective in an oxidized state.

Many of the purifying finishes available today such as neomycin, the sulfate or other salt thereof, hexachlorophene salts and others can be used in the treatment of textile materials, but are not completely satisfactory therefor, particularly in regard to their durability to washing and laundering.

In this connection, the antibacterial effectiveness of some of these antibacterial finishes is drastically reduced in some cases by mere laundering operations in the absence of chlorine bleach, and in other instances by the use of chlorine bleach during laundering operations.

In the scientific art of textile finishing, it is common knowledge that frequently two or more textile finishes which are individually highly effective in producing a durable finish to the textile materials being treated are incompatible when an attempt is made to combine the finishes or to concurrently apply the finishes to a single substrate, whereby the finished substrate fails to have the commercially acceptable durable characteristic.

It is common knowledge in the textile art, that antibacterial agents which are individually efiective may tend to neutralize or counteract the effectiveness of each other when an attempt is made to combine the agents or to concurrently apply the agents to a common substrate.

It is also common knowledge that antibacterial agents are not equally effective against all forms of bacteria, or other micro-organisms, and that a mixture of two or more such antibacterial agents may well tend to substantially reduce the effectiveness of both antibacterial agents whereby neither agent imparts a commercially satisfactory antibacterial activity.

When a textile finish of one or more antibacterial agents has been found to be durable to a specific set of conditions, it is well known that when the antibacterial agent is altered or diluted by the addition of another agent, the finish may no longer be durable and may no longer be effectively antibacterial.

The above problems associated with the application of antibacterial finishes to textile materials are but a few examples which make clear the fact that the inter-changeability and the combinations of various antibacterial agents for purposes of applying to a substrate such as textile material is far from being simple or predictable insofar as anticipating antibacterial activity and dura bility.

Accordingly, it is an object of this invention to provide a process of applying purifying finish for various substrates and in particular for cellulose substrate and cellulose textile materials in which finishes possessing the described durable characteristics are obtained.

It is a further object of this invention to provide textile materials, particularly cellulosic textile fibers, which have antibacterial properties against both gram-negative bacteria and gram-positive bacteria after repeated laundromat washing 1) in the absence of chlorine bleach, or (2) in the presence of chlorine bleach, or (3) some of which use chlorine bleach.

It is a further object of this invention to provide a process for the treatment of textile material, and the treated product thereof, with two or more antibacterial agents in the form of a textile finish, whereby both antibacterial agents which are of ineffective antibacterial activity when used alone against gram-negative bacteria after laundering with the use of chlorine, are antibacterially effective against gram-negative bacteria when used together.

It is a further object of this invention to provide a process for treating textile material, and for obtaining the product thereof, whereby the textile material acquires a durable antibacterial finish effective against both gramnegative bacteria and gram-positive bacteria, and whereby antibacterial activity remains substantially unaltered as a result of substantially concurrent application of two or more separate antibacterial agents.

A further object is to produce a finish which is durably effective against gram-negative bacteria after washes in the presence of chlorine.

Further objects became apparent from the above and following disclosure.

The objects of this invention are achieved by the use of a particular process for treating a common substrate with a combination of two or more antibacterial agents.

More particularly, triphenylbismuthine and neomycin sulfate are applied in a definite ratio to cellulosic textile material by a specific process whereby the finished textile material has an antibacterial activity of each of the respective antibacterial agents and additionally is effective against gram-negative bacteria after laundering in the presence of chlorine bleach.

Triphenylbismuthine alone is effective against both gram-negative and gram-positive bacteria prior to laundering, but is ineffective against gram-negative bacteria after laundering with or without chlorine bleach. As contrasted to this, neomycin sulfate is effective against both gram-negative and gram-positive bacteria prior to laundering but is ineffective against both gram-negative and grampositive bacteria after laundering in the presence of chlorine. It is seen that neither triphenylbisrnuthine nor neomycin sulfate have commercially effective antibacterial action against gram-negative bacteria after laundering in the presence of chlorine.

-By the process of treatment of this invention, triphenylbismuthine and neomycin sulfate produce a cellulosic textile material which is resistant to both gram-negative and gram-positive bacteria after laundering in the absence of chlorine, and also after laundering in the presence of chlorine, and for a substantial number of repeated launderings. It is seen that where neither the triphenylbismuthine nor the neomycin sulfate produced an effective antibacterial finish after being subjected to laundering in the presence of chlorine, by the process of this invention triphenylbismuthine and neomycin sulfate being used to impart a finish to cellulosic textile material results in a product which, after a substantial number of washes in the presence of chlorine, has antibacterial activity against both gram-negative bacteria and gram-positive bacteria, by the nature of synergistic action. Thus, whereas triphenylbismuthine used alone and neomycin sulfate used alone was ineffective against gram-negative bacteria after laundering with chlorine, after the process of this invention using the combination of triphenyl-bismuthi-ne and neomycin sulfate, the resulting product has substantial antibacterial activity against gram-negative 4. Aryl bacteria particularly which has been subjected to laundering with chlorine bleach.

Neornycin is an antibiotic discovered by Waksman and Le Chevalier and is produced by a strain of Streptomyces closely related to Streptomyces fradiae (ATCC No. 3535). Science, March 25, 1949, vol. 109, pp. 305307. It is a basic compound, freely soluble in water, possesses a wide antibacterial spectrum, is generally non-irritating and nonsensitizing and bacterial resistance to it develops very slowly. The term neomycin is used herein in its ordinary sense to denote the commercially available product which is called neomycin, it actually being a mixture of two very closely related antibiotics known more specifically as neomycin B and neomycin C. The term is also intended to cover neomycin as just defined, the individual components of the complex or its salts of which the sulfate is most generally available. Other salts of neomycin have been used by us in finishing textiles with good results. Among these may be mentioned neomycin para-hydroxybenzoate, neomycin sulfanilate, neomycin tartrate, neomycin propionate, neomycin aconitate, neomycin phthalate, neomycin undecylinate, neomycin palmitate, neomycin stearate, and others, as well as the neomycin sulfate already discussed.

By textile materials, as that term is employed herein, it is meant fibers, filaments or fabrics Whether they be knitted, woven, felted or otherwise formed, prepared from such fibrous material as cotton, rayon, linen, jute, hemp, ramie, silk, acetate, polyamide fibers, polyester fibers, acrylic fibers and various combinations or blends thereof with each other and other textile materials.

By cellulosic textile materials, as the term is enrployed herein it is meant fibers, filaments or fabrics whether they be knitted, woven, felted or otherwise formed prepared from at least about 50% cellulosic fibers such as, for example, cotton, rayon, jute, linen, hemp, ramie, and the like. These cellulosic fibers may be employed alone or in combination with each other or other noncellulosic fibers as for example wool, silk, the polyester fibers, nylon, acrylic fibers and the like.

The organic-bismuth compounds contemplated for use in the present invention are those compounds meeting the classical definition of organometallic compounds, that is, those having at least one carbon-metal bond. Thus, such compounds contemplated for use in the present invention exclude salts of organic acids, i.e., most ionic bondings including metal alkoxides and the like, and compounds where the bonding to carbon is only through heteroatoms such as 0, N or S. Coordination or chelate compounds are also excluded.

Typically the organo-bismuth compounds contemplated for use in the present invention may be classed according to any one of the seven general formulae set forth hereinbelow along with a number of typical illustrative examples of the unknowns Y and X in said formulae 1. Aryl Aryl-Bi Aryl 2. Aryl Aryl-Bi Aryl X A ryl B i-X A ryl A ryl-Bi 7. Aryl X A rylB i In the illustrative formulae above the aryls may be the same or different and typically equal phenyl, tolyl, naphthyl, including substituted aryls where the substituting group is typically halogen (Cl, Br, F, 1), alkoxy, alkyl, hydroxy and the like, Y is a heteroatom such as O, S or N, and the Xs are typically halogen, OH, and the like.

Illustratively, the organo-bismuth compounds contemplated for use in the present invention include: Formula 1-triphenylbismuthine, tri p tolylbismuthine, tris-(pchlorophenyl)bismuthine, tris-(p-bromophenyl)-bismuthine, tris-(p-fluorophenyl)bismuthine, tris-(p methoxyphenyl) bismuthine, bis- (p-chlorophenyl -p-tolylbismuthine, p-hydroxyphenyldiphenylbismuthine, 1 naphthyldiphenylbismuthine; Formula 2phenylbis(phenylthio)- bismuthine, bis(phenylthio)-p-toly1bismuthine, (p-chlorophenyl)bis(phenylthio)bismuthine; Formula 3--diphenyl (phenylthio)bisrnuthine; Formula 4-triphenylbismuthdichloride, diphenyl p tolylbismuth dichloride, triphenyl bismuth dibromide, triphenylbismuth difluoride, triphenylbismuth dinitrate, triphenylbismuth hydroxy chloride, triphenylbismuth carbonate, triphenylbismuth sulfate, triphenylbismuth diacetate, triphenylbismuth dibenzoate; Formula 5chlorodiphenylbismuthine, iodobis(p-chlorophenyl)bismuthine; Formula 6-dichlorophenylbismuthine; Formula 7diphenylbisrnuth trichloride; and the like.

The above illustrative organo-bismuth compounds or their equivalents may be employed singly or in combination with one another in accordance with the present invention.

The organo-bismuth compounds of this invention may be applied to the various substrates and in particular textile materials and paper from organic solvents or from aqueous emulsions or dispersions by conventional application procedures, illustratively either those of the textile finishing industry or those of the paper industry. Thus, with regard to application in accordance with the textile finishing industry these organo-bismuth compounds may be applied by padding, spraying, immersion, dipping and the like.

In general the method of applying the combined finish is accomplished in the following manner.

Stock solutions of neomycin or triphenyl bismuthine are prepared using a diluent, preferably water, for the neomycin and using dimethylformamide as the diluent for the triphenylbismuthine or water where emulsions are used. Solvents for the triphenylbismuthine which are recognized equivalents to dimethylformamide include acetone, benzene, carbontetrachloride, chloroform, toluene, chlorobenzene, and the like, so long as the solvent is not too polar. Water, as noted above, is not a suitable solvent, but is typical of non-solvents Which can be used to prepare emulsions which are within the scope of the method of application of the triphenylbismuthine.

The textile material is first treated with the triphenylbismuthine by padding. The treated fabric is then oven dried followed by the neomycin treatment by padding, drying, and curing.

The concentration of triphenylbismuthine should be in the range of from 90 percent (based on the mixture weight) to about 10 percent. The preferred range being from about percent to about 50 percent.

The concentration of the neomycin sulfate should be in the range of from about 10 percent (based on the mixture weight) to about percent. The preferred range being from about 25 percent to about 50 percent. (In combinations 75% triphenylbismuthine 25% neomycin sulfate is preferred.)

The drying conditions may range from about 70-85 F. up to about 250 F. preferably at from about 200 to about 225 F.

The above conditions may vary somewhat depending upon the type of textile material being employed.

The process of imparting antibacterial properties to a substrate is effective in the treatment of any fabric or material containing a substantial percentage of cellulosic fibers. The percentage range of the representative antibacterial agents in concentration may vary from about 0.25 up to about 0.75% solids, based on the weight of the fabric, where the amount of triphenylbismuthine to the neomycin sulfate, is present in a ratio of from about 1:3 to about 3:1. Superior results are obtained when these antibacterial agents are used in combination where it ranges from about 0.25% to about 0.75% solids, based on the weight of the fabric. The preferred embodiment, rendering the superior results, uses triphenylbismuthine in an amount of about 0.075% to about 0.75% solids, and neomycin sulfate in an amount of about 0.025% to about 0.25%, while maintaining a ratio of about 3:1 of triphenylbismuthine to neomycin sulfate. Within these ranges, triphenylbismuthine is greatly effective when used in an amount from about 0.375% to about 0.75 solids and the neomycin sulfate is from about 0.125% to about 0.25% solids while maintaining the approximate 3 :1 ratio.

In the preparation of the antibacterial finish of this invention, it is critical that the triphenylbismuthine be applied first from a diluent which is preferably dimethylformamide, and then subsequently dried for a sufiicient period of time, about 2 minutes at about a 225 F., the maximum preferred temperature. Subsequently, neomycin sulfate is applied from diluent, preferably from water, and the treated substrate is dried for a sufficient length of time at an effective temperature, about 2 minutes at about 250 C., the maximum preferred temperature. The most critical aspect of the process is the requirement that the triphenylbismuthine be the first applied and that the neomycin sulfate be the subsequently applied.

The organo-bismuth compounds are employable with a wide variety of thermosetting resins of the type normally employed in the crease-proofing of cellulose containing textile materials. As will be evident from the examples hereinafter, the organo-bismuth compounds may be applied simultaneously with the crease-proofing resins, prior to, or subsequent to, the application of such resins to the textile substrates.

Typically the desired thermosetting resin is an aminoplast. As examples of suitable thermosetting aminoplast resins contemplated for use in accordance with this aspect of the present invention, the water soluble melamine formaldehyde resins prepared in accordance with US. Patent No. 2,197,357 and 2,529,856 are contemplated. Examples of such resins are tris(methoxymethyl)melamine, tris(methoxymethyl)dimethylol melamine, hexakis (methoxymethyl)melamine, and the like. In addition to these melamine-formaldehyde resins, the urea and thiourea-formaldehyde condensates are contemplated, as are their alkylated derivatives. Thus, for example, dimethylol urea, methylated dimethylol urea and thiourea, dimethylol ethylene urea, dimethylol 1,2-propylene urea and thiourea, dimethylol 1,3-propylene urea and thiourea and other related homologous compounds are con templated. Additionally, the formaldehyde condensates of dicyandiamide, biuret and the like are contemplated, as are the water soluble formaldehyde condensates of thiobisamides of the type described in U.S. Patent No. 2,887,408.

Guanamine-formaldehyde condensates, as for example, those described in US. Patent No. 2,887,409, including the formaldehyde condensates of methoxy acetoguanamine, ethoxy acetoguanarnine, tertiary butoxy acetoguanamine, and the like are contemplated.

Urons may also be employed with the compounds of this invention as, for example, N,N-bis(methoxymethyl) uron and various other and closely related compounds such as are described in US. Patent No. 2,373,135. Additionally, tetrahydro-s-triazones such as tetrahydro-S-(B- hydroxyethyl)-s-triazone and compounds of the type described in US. Patent No. 2,304,624 are also fully contemplated.

The above and other equivalent crease-proofing resins may be applied to the textile material by any of the Well known techniques as, for example, spraying, dipping, immersing, padding and the like in such amounts as to apply from between 1 and 25% solids and in some instances higher amounts may be applied -based on the dry weight of the material. Preferably the amount (soiids) of the resin applied is from between about 3 and 10% solids based on the weight of the textile material.

Normally, the thermosetting resin is applied with a curing catalyst or accelerator. The catalyst utilized may be a free acid, acid salts, alkanolarnine salts, metal salts and the like. The concentration of catalyst employed may range from about 0.1 to about 25% solids or higher based on the weight of the resin solids, depending upon the particular catalyst type employed. Thus, for example, from between about 0.1 and about 10% solids of a free acid such as phosphoric, tartaric, oxalic and the like may be employed While in the case of ammonium chloride amounts of from between 0.5 and about 10% solids are used. In the case of amine salts including alkanolamine salts such as triethanolamine hydrochloride from about 1.0 to about 10% solids are most useful While with respect to salts such as magnesium chloride, zinc chloride, zinc nitrate, aluminum chloride, amounts of from between 5 and 25% solids may be employed. In all instances the concentration of the catalyst is based on the weight of resin solids employed.

Following the application of the thermosetting resin and curing catalyst to the textile material it is subject to drying and curing operations in order to effect the properties of shrinkage control and Wrinkle resistance. The drying and curing operation may be carried out in a single step or in separate steps. The temperature at which the drying and curing operations are effective varies widely and is influenced to some extent by the type of catalyst employed. Normally the range of temperatures extends from about 180 F. to about 450 F. Generally speaking, the times of drying and/or curing operation is inversely proportional to the temperature employed and of course is influenced by whether or not separate or combined drying and curing steps are employed.

Generally when drying and curing is carried out in a combined operation a time of from about one minute to about ten minutes may be employed at temperatures from about 450 F. to 250 F., respectively. When the material has been dried preliminary to curing, curing times of from the order of five minutes to about A minute at a temperature of from between 250 F. and 450 F., respectively, have been successfully employed.

When the bismuth compounds are applied prior to the thermosetting resin treatment it is preferred that the treated material be first dried prior to the application, drying and curing of the resin treated goods. When the thermosetting creaseproofing resin is first applied, prior to the application of the bismuth compounds, the treated fabric should be dried and cured also. For examples, see abandoned application Ser. No. 120,508.

As noted above, it is Within the scope of this invention to cure with conventional temperatures employed in the applying of wrinkle recovery materials with the textile finishing materials of this invention. It should be noted that cure is not essential to achieve the antibacterial finish of this invention, but that a highly durable finish is obtained where cross-linking is achieved with curing temperatures. The durable finish is superior and therefore preferred.

'In order to illustrate the present invention the following examples are given primarily by way of illustration. No specific details or enumerations contained therein should be construed as limitations on the present invention except insofar as they appear in the appended claims. All parts and percentages are by Weight unless otherwise clearly designated.

The agar plate tests for antibacterial activity are made in accordance to the American Association of Textile Chemicals and Colorists Tent. Test Method 90-159T.

Bacterial inhibition test (agar diffusion method) This test consists of a measurement of the purifying agents activity against a gram-positive type bacteria (Staph. aureus). Discs (11.5 mm.) of the treated fabrics are placed on an agar plate inoculated with the bacteria culture. After several hours contact, the disw are removed, and the plate incubated overnight. The activity of the purifying agent is recorded as the diameter of the clear area (in mm.) at the site of the disc. An effective agent will show a clear area with a diameter greater than the disc itself (11.5 mm.). The larger the clear area, the greater is the activity. The activity under the fabric disc is also noted when there is no zone outside the area covered by the fabric. The area under the disc of the fabric is rated as follows:

C- -Completely clear area underneath the cloth disc. P-At least 75% clear area under the disc.

-Less than 75 clear area under the disc. VSLess than 50% clear area under the disc.

NNo clear area.

Washings were made using a Laundromat Automatic Washer and are reported as (1) LW for washes with soap solutions and (2) LWC for washes containing soap plus sodium hypochloride solution (about 0.02% available chlorine).

EXAMPLE 1 Applications of 0.1% solids (O.W.F.) of either triphenylbismuthine or neomycin sulfate alone or combinations of both, wherein the total amount was 0.1% solids were made on unmercerized x 80 cotton percale. The fabrics were immersed in their respective bath: (1) the triphenylbismuthine alone was applied from dimethylformamide, squeezing on a micro-set padder and drying for 2 minutes at 225 F., (2) the neomycin sulfate alone was applied from water by the same conditions of padding and drying, (3) where the combinations were used, the triphenylbismuthine was applied first, followed by drying for 2 minutes at 225 F. and then repadded through aqueous solution of neomycin sulfate, followed by drying for 2 minutes at 250 F.

Agar diffusion tests were made initially and after 5 Laundromat washes in soap or 5 Laundromat washes in soap plus chlorox. The results of the activity against both E. Coli and .S'taphylococcus aureus are shown in Table I.

TABLE I Treatment Gram Negative (E. colt) Gram Positive (S. omens) Initial 5 L.W. L.W. 5 L.W.C. Initial 5 L.W.O. 15 L.W.O.

TPB (alone):

23.0 18. 7 17. 2 27. 7 N N 21. 0 18. 3 16. 5 25. 3 N N 18. 8 16. 9 15. 3 23. 0 N

NorE.-TPB=Triphenylbismuthine; NS=Neomyein Sulfate; LW=Laundromat Washes (without sodium hypoehlorite); LWC=Laundromat Washes (with sodium hypochlorite) From the above table it is seen that neither the triphenylbismuthine nor the neomycin sulfate produced an effective durable antibacterial activity against gram-negative, (E. coli) Where chlorine bleach was employed in the wash procedures. As contrasted to the lack of durability in the presence of chlorine Washes, of the separately employed antibacterial agents, Table I illustrates that Where the antibacterial agents triphenylbismuthine and neomycin sulfate are used in combination, the treated fabrics continue to be durably antibacterial against gram-negative bacteria after washes in the presence of chlorine, illustrate a form of synergism. Additionally, Table I illustrates that the combination of the antibacterial agents produce an antibacterial activity a high degree of durability against both gram-negative bacteria and gram-positive bacteria, as contrasted to triphenylbismuthine alone which has an ineffective durability to washes, against gram-negative bacteria and as contrasted to neomycin sulfate alone which has an ineffective durability against gram-positive bacteria. Thus Table I illustrates that by the process of this invention, antibacterial durability of both antibacterial agents is retained at an unexpectedly high degree of effectiveness. Table I further illustrates that the relative preferred concentrations and ratios of triphenylbismuthine to neomycin sulfate is in the range of about 0.375 to about 0.75 solids of triphenylbismuthine in combination with about 0.125% to about 0.25% solids of neomycin sulfate in a triphenylbismuthine-neomycin sulfate ratio of about 3:1.

It will be understood that the preceding detailed example is illustrative only, and that minor variations and modifications may be made in the conditions of the processes Without departing from the substance of the invention as herein disclosed and defined in the appended claims.

I claim:

1. A process of imparting a durable antibacterial finish to a cellulosic material, which comprises applying an organobismuth compound having at least one aryl radical attached to the bismuth through a carbon atom of said aryl radical, and neomycin sulfate in the stated order to said material in an amount sufiicient to impart a durable antibacterial activity.

2. A process of imparting a durable antibacterial finish to a cellulosic material, which comprises applying triphenylbismuthine and neomycin sulfate in the stated order to said substrate in an amount sufiicient to impart a durable antibacterial activity.

3. A process of imparting a durable antibacterial finish to cellulosic textile fibers, which comprises applying triphenylbismuthine and neomycin sulfate in the stated order to said substrate in an amount sufiicient to impart a durable antibacterial activity.

4. A process of imparting a durable antibacterial finish to cellulosic textile fibers, which comprises applying from about 0.025% to about 0.75% solids of triphenylbismuthine to said fibers, and subsequently applying from about 0.025% to about 0.75% solids of neomycin sulfate to said fibers, said triphenyl'bismuthine and said neomycin sulfate, respectively being present in a ratio of from about 1:3 to about 3:1, and said percentages being based on the weight of the fabric.

5. A process according to claim 4, in which the ratio of triphenylbismuthine to neomycin sulfate is about 3:1.

6. A process according to claim 5, in which the triphenylbismuthine is from about 0.375% to about 0.75% solids, and the neomycin sulfate is from about 0.125% to about 0.25% solids.

7. A process of imparting a durable antibacterial finish to a cellulosic material, which comprises applying an organobismuth compound having at least one aryl radical attached to the bismuth through a carbon atom of said aryl radical, a liquid diluent and drying, and sub sequently applying neomycin sulfate from an aqueous solvent and drying, said triphenylbismuthine and said neomycin sulfate being employed in an amount sufficient to impart a durable antibacterial activity.

8. A textile fiber having durable antibacterial activity against gram-negative bacteria and gram-positive bacteria whereby said fiber retains said activity after washing in the absence of and continues to retain said activity after washing in the presence of chlorine, said fiber being the product of the method of treatment according to claim 7.

9. A process of imparting a durable antibacterial finish to cellulosic materials, which comprises applying to said material triphenylbismuthine from a non-aqueous solvent and drying, and subsequently applying neomycin sulfate from an aqueous solvent and drying, said triphenylbismuthine and said neomycin sulfate being employed in an amount suflicient to impart a durable antibacterial activity.

10. A process of imparting a durable antibacterial finish to cellulosic textile fibers, which comprises applying to said fibers from about 0.025 to about 0.75 solids of triphenylbismuthine from a non-aqueous solvent and drying from about 0.025 to about 6.75% solids of neomycin sulfate from an aqueous solvent and drying, said triphenylbismuthine and said neomycin sulfate respectively being present in a ratio of from about 1:3 to about 3:1, and said percentages being based on the weight of the fabric.

11. A process of imparting a durable antibacterial finish to cellulosic textile fibers, which comprises applying to said fibers triphenylbismuthine from a solution employ- 11 ing dimethylformamide and drying, and subsequently applying neomycin sulfate from water and drying.

12. A process of imparting a durable antibacterial finish to cellulosic textile fibers, which comprises applying to said fiber triphenylbismuthine from a solution employing a dimethylformamide and drying for about 2 minutes at about 225 F., and subsequently applying neomycin sulfate from water and drying for about 2 minutes at about 250 F.

13. A process according to claim 12, in Which the ratio of triphenylbismuthine to neomycin sulfate is about 3:1.

14. A process according to claim 13, in which the triphenylbismuthine is from about 0.375% to about 0.75% solids, and the neomycin is from about 0.125% to about 0.25% solids, said percentages being based on the Weight of the fabric.

15. A cellulosic material having durable antibacterial activity against gram-negative bacteria and gram-posi tive bacteria comprising said material containing from about 0.025% to about 0.75% solids of triphenylbismuthine and from about 0.025% to about 0.75% solids of neomycin sulfate, respectively, in a ratio of about 1:3 to about 3:1, and said percentages being based on the weight of the material, whereby said material retains said activity after washing.

References Cited FOREIGN PATENTS 1,003,685 9/1965 Great Britain.

ALBERT T. MEYERS, Primary Examiner.

SAM ROSEN, Assistant Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,395,212 July 30, 1968 Frank John Gross It is certified that error appears in the above identified patent and that said Letters Patent are hereby corrected as shown below:

Column 8, line 22, "90-159T" should read 90-19S8T Signed and sealed this 3rd day of March 1970.

(SEAL) Attest:

WILLIAM E. SCHUYLER, JR.

Edward M. Fletcher, Jr.

Attesting Officer Commissioner of Patents