US3173841A - Durable antibacterial textile finish for cellulosic textile material - Google Patents
Durable antibacterial textile finish for cellulosic textile material Download PDFInfo
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- US3173841A US3173841A US218851A US21885162A US3173841A US 3173841 A US3173841 A US 3173841A US 218851 A US218851 A US 218851A US 21885162 A US21885162 A US 21885162A US 3173841 A US3173841 A US 3173841A
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- neomycin
- fabric
- textile
- brightener
- solution
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/70—Carbohydrates; Sugars; Derivatives thereof
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
- Y10S8/916—Natural fiber dyeing
- Y10S8/918—Cellulose textile
Definitions
- This invention relates to durable antibacterial finishes for textile materials in which the active antibacterial agent is neomycin, to methods for applying the same to textile materials, and to the materials so treated.
- a satisfactory purifying finish should be durable and active at low concentrations against a broad spectrum of microorganisms. It should be non-toxic and nonalle-rgenic. It should not have the tendency to sensitize the wearer of the textile material to the material to be finished. It should not have the quality of allowing strains of bacteria to develop, which are resistant to the antibacterial agent of the finish. Still further, it should be resistant to home and co amercial laundering conditions and should impart little or no modification of the hand of the textile.
- Neomycin employed as a purifying finish is highly satisfactory with respect to most of the categories mentioned above, and its use is described fully in US. tatent No. 2,830,011, the subject matter of which is incorporated herein by reference.
- blue pigments or dyes that is, to neutralize the yellow color of the cellulosic material by adding the complementary color, blue.
- blue pigments such as ultramarine or alkali blue or of fugitive blue dyestuffs has long been common practice in fabric and paper manufacture and in laundering operations.
- blue coloring materials are often temporarily effective, they are subject to series disadvantages. For example, the addition of a blue color to a yellow does not produce a pure white, but rather a gray, because both colors are absorbing light and reducing the total amount of reflected light. Further, unless the exact coloring balance is struck, the finished product is not even a gray, but actually may be blue.
- neomycin as an antibacterial agent may be impanted by a single application step to a textile material containing cellulose, so that the material, when laundered, is substantially free from yellowness and/or dullness, which is characteristic of lawn dered neomycin finished cellulose containing textile materials.
- a further object of the present invention is to provide such a process which does not interfere with the antibacterial activity of the neomycin on the fabric, and one which may be accomplished employing conventional finishing equipment and known chemical materials.
- Another object of this invention is to provide novel stable compositions of matter containing neomycin as an antibacterial agent, which when imparted onto cellulose containing textile material by a single application step, yellow less and are less dull than those finishes in accordance with prior art procedures.
- neomycin is a cationic material
- anionic brightener or vice versa
- neomycin solutions are acidic, usually a pH of less than 3 and normally a pH of from about 1 to about 2, even'the addition of alkaline brightener solu- :usnrarsr rais'es'the pH more'than a few units, because ⁇ of the small amounts of brightener employed.
- suitable alkaline agents such as sodium hyd'rox'ide, potassium hydroxide, sodium "carbonate, potassiumgcarbonate, ammonia, organic amines and their equivalents.
- the pH of the treating solution should be above 8.5 and is normally about "9.
- the pH can'certainly' be higher than 9, as for example 10, 11 or more, but addition of amounts of base which are morethan sufiicient to produce clear stable aqueous solutions of 'neomycin and brightener is unnecessary and undesirable in the light-of economic considerations.
- Toprepare a suitable stable solution solutions of the components may-be mixed and the pH adjusted or suit- 'ablebase maybe added to either or both components prior to mixing. If the components are first mixed, the precipitate that is formed and is evidenced initially by'a haze or cloudiness n the solution, may be removed by the herein inits ordinary sense, and as it is defined in US.
- Patent No. 2,830,0ll, above referred'to In general, this refersto a commercially available product which is called 'neomycin, which is actually a'mixt'u're of two very closely related antibiotics known more specifically as neornycin B and neomycin'C.
- the term is also intended to cover 'neomycin as just "defined, the individual components of thewcomplex, or its salts,'of Whichthe sulfate is the most 4 the spectrum, thereby compensating for the slightly yellowish cast of most White fabrics.
- Suitable brighteners for use in this invention may be divided into two types, according to the type of fiber for which they have afinity. There are the cellulosic and all-purpose types, the latter having afiinit-y for both eellulo'sic and non-cellulosic'fibers. Since this invention is restricted to application of solutionsto textile materials containing cellulosic fibers, only such br-ighteners are contemplated.
- Such brighteners may also bedivided into chemical classes.
- the members of the cellulosic type can, for the most part, be assigned to the following classes: acyldiaminostilbene (I), triazinyldiaminostilbenes (II), and acyldiaminodibenzothiophene dioxides (III).
- the members of these classes contain sul'fonic acid groups.
- the allpurpose type comprises the benzimid'azoles (IV) and the triazo'les (V). Only those members of classes IV and V containing one or more sulfonic acid groups are contemplated for use in the instant invention.
- Other salts of neomycin have been usedin finishing textiles with good results, among them may be mentioned neomycin parahydroxybenzoate, neomycin sulfanilate, 'neornycin-N-tartrate, neomycin ipropionate, neomycin aconitate, neomycin phthalate, 'neomycin undecylinate, neomycin palmitate, neomycin stearate, and others.
- cellulosic textilernaterials or cellulose containing textile materials as theseterms are employed herein, it is'meant fibers or'formed fabrics, either woven or felted,-containing at least %fibers of cellulosic origin and preferably composed entirely of cellulose for maximum efiect.
- cellulosic textile materials such as woven or felted,-containing at least %fibers of cellulosic origin and preferably composed entirely of cellulose for maximum efiect.
- R, R, R" and R may be hydrogen, alkyl, aryl, alkoxy, halogen, nitrile, and the like. It should be noted that RR" may be virtually any radical which does not'interfere or significantly reduce the brightening efiect of these dyes.
- Class V Triazoles 2-(4-styryl-3-sulfophenyl -2H-naphtho 1,2] -triazole-5- sulfonic acid
- the fluorescent textile brighteners are applied simultaneously with the neomycin from aqueous solutions containing the same.
- the aqueous solutions containing the fluorescent textile brightener and ne-omycin may be applied to the textile material by any of the known conventional textile finishing techniques, whereby the material is contacted with these components for a sufi'icient period of time to fix them on the material.
- they may be applied by padding, spraying, submersion, exhaustion or the like.
- padding is greatly preferred, in that most finishing plants are adapted to employ this technique, and within certain limits, more uniform control of the process may be achieved.
- the sulfonic groups in the fluorescent textile brighteners employable in this invention impart sutficient solubility or dispersibility to permit their application from aqueous media.
- these groups contribute to the sub stantivity of the brighteners on the cellu-losic fibers.
- neomycin and fluorescent textile brighteners to suitable-textile materials containing cellulose and preferably formed cellulosic fabric, by employing conventional padding techniques.
- the textile material is padded through a bath containing neomycin and a suitable fluorescent textile brightener. Excess of the treating solutions are then removed from the textile material to achieve the desired pick-up by passing the impregnated fabric between rollers and thereafter the textile material is thied, preferably at elevated temperatures, as for example temperatures from between 150 F. to 350 F. Caution should be exercised in the employment of elevated temperature to insure that the textile material is not degraded thereby.
- the concentration of the neomycin in the treating solution may be varied within wide limits, depending upon the use to which the material is intended.
- the solution When applied by padding, the solution should contain from approximately 0.0001% to 4% and more by weight of neomycin as is desired in the dried fabric, since in the padding operation the fabric is usually impregnated with from between about 25 to 150% of the weight of the liquid and then dried.
- the treating solution of neomycin may contain as littleas 0.001 micrograms per milliliter of neomycin when highly absorbent cellulosic fibers are treated. From 5 to 500 micrograms of neomycin per milliliter is considered the preferred range for application by exhaustion.
- sufiicient concentration of neomycin may be substantially adhered to base materials from aqueous treating solutions containing from about 1 microgram to about 400 micrograms per milliliter, with commercial limits lying between about 2 and about 200 micrograms per milliliter.
- the treating solution should normally contain from approximately 0.001% to 4% and more by weight of the fluorescent brightener as is desired in the dried fabric when applied by padding, since in the padding operation the fabric is usually impregnated with from about 25% to about 150% of the weight of the liquid and then dried.
- the concentration of the neomycin applied to the cellulose material may to some extent be varied over wide limits, depending upon the use for which the material is intended. Useful results are obtained when the fabric contains as little as 0.000170 by weight of neomycin on the dry weight of the textile material.
- the preferred range varies from about 0.001% to 1% by weight of neomycin on the dry weight of the treated fabric. For prophylactic purposes, deposition of from about 0.005 microgram up to micrograms per square centimeter has been found satisfactory, with preferred commercial ranges lying between about 0.1 and about 6 micrograms per square centimeter.
- fluorescent organic brightener useful results are obtained in accordance with the present invention when suitable brightener is present on the fabric in an amount of at least 0.001% though preferably the amount based on the dry weight of the fabric is from between about 0.01 to 0.05%. Concentrations of brightener on the fabric of lass than 0.001%, based on the fabrics dry weight, are for the most part impractical.
- the preferred class of cellulose-containing textile materials contemplated by this invention may take any shape, size or form and may clearly include articles which are intended to be reused. Specific illustrations of such articles would include wearing apparel, handkerchiefs, diapers, hand, dish and bath towels, books and book covers, washable cloth toys, dolls and similar playthings, hospital and hotel sheets and pillow cases, hospital and examination room bathrobes, slippers, barbers and beauticians cloths and similar articles.
- the test referred to therein for determination of antibacterial activity is a standard one and the treated fabrics are tested by a standard Agar plate method.
- a convenient test method has been devised on inhibition of the bacterial growth by a piece of textile placed on an Agar plate inoculated with various strains of bacteria.
- the two commonly used strains are E. coli and S. aureus, which are strains usually employed in the evaluation of antibacterial agents for various purposes.
- the effectiveness of the finish may be determined.
- Durability of the finish is determined by subjecting the treated textile to a series of repeated launderings. The number of times the material may be laundered before antibacterial activity decreases below an effective level will give a measure of the durability of the finish.
- discs of treated fabric of a certain size (11.5 millimeters in diameter) are placed on an Agar plate inoculated with the bacterial culture. After two hours contact, the disc is removed and the Agar plate is incubated overnight.
- the degree of inhibition of growth gives an index of the inhibitory effect of the finish on the cloth. This inhibition is easily observed, since the area where the bacterial growth is inhibited remains clear, whereas the remainder of the area where the bacterial growth has taken place becomes cloudy or opaque.
- the area under the disc is observed, and in addition, the total diameter of the area larger than that occupied by the disc is observed.
- Effective finishes show a clear area at least under the disc with more effectively finished materials giving areas having a diameter greater than that of the disc itself. If the area of inhibition is greater than the area of the disc, the activity is given as the diameter of the clear area in millimeters. Otherwise, a rating of C denotes complete inhibition of bacterial growth under the disc; a rating of P denotes partial inhibition; an N rating denotes no inhibition or activity; and S and VS denote slight and very slight inhibition. It should be noted that P is at least 50 to inhibition under the test fabric.
- EXAMPLE 1 125 parts of a solution of neomycin sulfate containing 1% neomycin base was diluted with about five times as much water at room temperature. 0146 part of 4,4- bis[4-anilino-6-bis(Zhydroxyethyl)amino s triazin 2 ylamino] 2,2'-stilbenedisulfonic acid was added and a precipitate formed. A 1% solution of sodium carbonate was then added with stirring until the precipitate just redissolved of 89). This mixture was then diluted with water at room temperature to give a concentration of 0.125% neomycin base and 0.0146% brightener.
- Example 2 The procedure of Example 1 was used with the substitution of dilute aqueous ammonia for the solution of sodium carbonate. A solution was obtained at a pH of 8-9.
- EXAMPLE 3 The procedure of Example 3 was used substituting 0.0027% of 4,4-bis(2,4-dimethoxybenzoylamino)-2,2'-
- stilbenedisulfonic acid for the 4,4-his-(2 ethoxybenzoylamino)-2,2'-stilbenedisulfonic acid.
- the treated fabric contained 0.1% of neornycin and-0.0022% of the brightener on the weight of the fabric.
- EXAMPLE 5 The procedure of Example 3 .was used substituting 0.0325 of dioxide of 3,7-bis-(4 methoxybenzamido)-2,8- dibenzothiophenedisulfonic acid, [4,4'-bis(4-methoxybenz- .oylamino)2,2' sulfonylbiphenyldsulfonic acid].
- the treated fabric contained 0.1% of neomycin and 0.026% of the brightener on the weight of the fabric.
- Example 6 The procedure of Example 5 was used substituting 0.003125% of the same brightener for the 0.0325% used in Example 5.
- the treated fabric contained 0.1% ofneomycin and 0.0026% of the brightener on the weight of the fabric.
- EXAMPLE 7 125 parts of a solution of neomycin sulfate containing 1% of neomycin base was diluted with-water at room temperature to give a concentration of 0.125% neomycin base. Bleached 80 x 80 cotton fabric was passed through the solution, and the excess solution was. removed by passing the fabric through squeeze rolls to .give an 80% expression. The fabric was dried at 225 F.
- EXAMPLE 8 The cotton fabrics to which neornycin and brightener had been applied as described in Examples 2-5 and 7 were tested for antibacterial activity. The fabrics were laundered at 140 F. in hard water. by a standard procedure using a Laundromat washing machine containing 9. gallons of water with 20 cc. of 10% calcium chloride 8 and 0.25% neutral soap added. The antibacterial tests were repeated after the 16th and 25th washes.
- Example7 17.5 12.0 C
- Example2 17.0 VS P'C
- Example 3 I7. 3 0 12-0
- Example 4 17. 6
- Example 5 15.8 C
- Example 7 14.4 VS VS Example 9 14. 4 VS VS Example 3.. .J-.. 13.8 S-P VS Example4 15.2 VS VS Example 5 14. 1 N-VS N-VS EXAMPLE 9
- the cotton fabrics to which neomycin and brightener had been applied as described in Examples 2-7 were tested for durability of whiteness by washing in hard water as described in Example 8. The whiteness of the fabrics were observed visually by daylight, initially and after 16 and 25 washes. The results of these tests are shown in Table I1 hereinbelow.
- Example 4 do do Do.
- Example 5 do do Do.
- Example 6 S1. better than S1. yellower than S1 yellower standard. initially. than initially.
- EXAMPLE 10 Five aqueous solutions containing 2% neomycin sulfate had their pH adjusted by the addition of dilute sodium hydroxide to 4.8, 7.0, 8.0, 9.0 and 10.0.
- the final solutions contained .1% of neomycin sulfate and 0.025% of the anionic brightener identified above.
- EXAMPLE 7 1 1 This solution was then made up to a final volume of 500 cc. so that the solution contained .125 of neornycin and .0375 of 4,4'-bis[4-anilino-6-bis(2-hydroxyethyl) amino s triazin-Z-ylamino]-2,2-stilbenedisulfonic acid. The pH of the final volume of this solution was determined to be 8.7.
- EXAMPLE 12 The above procedure was repeated with the exception that 250 cc. of cold water were added to 6.3 parts of a 1% solution of neomycin sulfate as compared with the 62.5 parts in Example 11.
- EXAMPLE 13 Approximately 250 parts of cold water were added to 62.5 parts of a 1% solution of neomycin sulfate. The pH of this solution was adjusted to 7.5 with a 1% solution of soda ash.
- 0.75 part of a 25% solution of 4 ,4-bis[4-anilino-6-bis (2 hydroxyethyl) amino-s-triazin-Z-ylarnino]2,2-stilbenedisulfonic acid is diluted with approximately 100 parts of Water.
- the pH of this solution is adjusted to 7.5 by the addition of dilute sulfuric acid.
- the brightener solution is then added to the solution of neomycin and the total volume adjusted to 500 cc.
- the pH of the solution is 7.5.
- EXAMPLE 14 Approximately 250 parts of cold water were added to 62.5 parts of a 1% solution of neomycin sulfate. The pH of the solution was adjusted to 9 with a 1% solution of soda ash.
- i0 the like may be incorporated into the treating bath, so long as their presence and function do not inhibit or impair the antibacterial finish and its durability and the brightening etfects achieved in accordance with this invention.
- a process for finishing formed textile fabric containing at least 50% oellulosic fibers to impart a durable antibacterial finish thereto having resistance to discoloration which comprises simultaneously applying thereto an aqueous treating solution having a pH above 8.5 and containing neomycin, an anionic fluorescent brightener containing a sulfonic acid group that is substantive to cellulose fiber, and an alkaline agent, so as to impart at least .0001% of neomycin and at least .00l% of said anionic brightener to the finished fabric, and thereafter drying the fabric.
- neornycin is applied to the fabric in an amount from between about :01 and .05 based on the dry Weight of the fabric and the anionic brightener is applied to the textile material in an amount from between about .01 and 05%, based on the dry Weight of the fabric.
- a composition which comprises in aqueous medium, neomycin, at least 001% of an anionic fluorescent brightener containing a sulfonic acid group, and an alkaline agent, said composition being characterized by a. pH above 8.5.
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Description
United States Patent 3,173,841 DURABZLE ANTIBACTEMAL TEXTHLE FBNESH FOR CELLULQSEC TEXTHJE MATERLaL Philip B. Roth, Somerville, Ni, and Leonard E. Hallows,
Lima, Peru, assignors to American Cyanamid Company, Stamford, Comm, a corporation of Maine N0 Drawing. Filed Aug. 23, 1962, Ser. No. 218,851 8 Claims. (@Cl. 1784) This invention relates to durable antibacterial finishes for textile materials in which the active antibacterial agent is neomycin, to methods for applying the same to textile materials, and to the materials so treated.
In recent years, increased attention has been given to the development of textile finishes of this type, which have become known as purifying finishes. These finishes are intended to reduce the number of microorganisms residing in the materials, whereby such materials 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 the prevention of the development of odor.
A satisfactory purifying finish should be durable and active at low concentrations against a broad spectrum of microorganisms. It should be non-toxic and nonalle-rgenic. It should not have the tendency to sensitize the wearer of the textile material to the material to be finished. It should not have the quality of allowing strains of bacteria to develop, which are resistant to the antibacterial agent of the finish. Still further, it should be resistant to home and co amercial laundering conditions and should impart little or no modification of the hand of the textile.
Neomycin employed as a purifying finish is highly satisfactory with respect to most of the categories mentioned above, and its use is described fully in US. tatent No. 2,830,011, the subject matter of which is incorporated herein by reference. The finish imparted by neomyein employed in accordance with the disclosure of the above eferred to US. patent, insofar as textile materials containing cellulosic fibers are concerned, provides a satisfactory and durable finish, which remains antibacterial after numerous launderings. This dunability is believed to be the result of the neomycin being substantive to the cellulose base material.
While the treatment of cellulosic fibers with neomycin in accordance with the above referred to patent imparts excellent antibacterial properties which remain after the cleaning or processing of the fiber or fabric formed the-refrom, the washing of neomycin treated fabrics, particularly in hard water, with soap, causes the fibers to become yellowish and dull in appearance. This yellowishness or dullness apparently is the result of the formation of neomycin stearate or a mixed salt of calcium or magnesium and neomycin with stearic acid, when finished fabrics are laundered with soap. While laundering with soaps increases the yellowness or dullness of neomyoin finished fabric, laundering with other cleaning agents, as for example, detergents, will also result in yellowing of the finished fabric, although to a lesser degree and at a more gradual rate. The yellowing effect is, of course, very undesirable and any agent or procedure which will minimize or conceal the development of color or dullness is of great importance in the commercialize tion of neomycin as a purifying finish.
While it may be assumed that the yellowing or dullness appearing in neomycin treated fabrics that have been laundered can be corrected by the employment of chemical bleaches, such is not the case. This is true in that in most instances the use of such bleaches, as for eX- ample, those containing chlorine, functions to destroy the antibacterial activity of the neomycin.
ice
For many years it has been the practice to attempt to conceal the yellowish cast of cellulosic materials by the use of blue pigments or dyes, that is, to neutralize the yellow color of the cellulosic material by adding the complementary color, blue. For this purpose, the use of blue pigments, such as ultramarine or alkali blue or of fugitive blue dyestuffs has long been common practice in fabric and paper manufacture and in laundering operations.
While these blue coloring materials are often temporarily effective, they are subject to series disadvantages. For example, the addition of a blue color to a yellow does not produce a pure white, but rather a gray, because both colors are absorbing light and reducing the total amount of reflected light. Further, unless the exact coloring balance is struck, the finished product is not even a gray, but actually may be blue.
Accordingly, it is an object of the present invention to provide a process whereby neomycin as an antibacterial agent may be impanted by a single application step to a textile material containing cellulose, so that the material, when laundered, is substantially free from yellowness and/or dullness, which is characteristic of lawn dered neomycin finished cellulose containing textile materials.
A further object of the present invention is to provide such a process which does not interfere with the antibacterial activity of the neomycin on the fabric, and one which may be accomplished employing conventional finishing equipment and known chemical materials.
It is a further object of the present invention to provide neomycin finished cellulose containing textile materims, which upon repeated launderings manifest substantial improvement with respect to less yellowing and dullness, normally associated with such materials finished in accordance with the prior art procedures.
Another object of this invention is to provide novel stable compositions of matter containing neomycin as an antibacterial agent, which when imparted onto cellulose containing textile material by a single application step, yellow less and are less dull than those finishes in accordance with prior art procedures.
These and other objects and advantages of the present invention will appear more clearly from the detailed description thereof set forth hereinbelow.
It has been discovered in accordance with the present invention that the discoloration or staining (yellowishness or dullness) caused by the laundering or washing of neomycin treated cellulosic textile materials or cellulose containing textile materials can be prevented or at least largely concealed by applying in a single application step anionic fluorescent textile brighteners (optical bleaches) and neomycin fro a stable aqueous solutions containing the same. It will be apparent that the neornycin and brightener must be applied in effective amounts. The stable solutions containing the anionic brighteners and neomycin, to be discussed more fully hereinafter, constitute an essential element of this invention. In view of the fact that neomycin is a cationic material, it will be appreciated that the introduction of such material into an aqueous solution of anionic brightener or vice versa produces a precipitate. Such compositions or suspensions are not suitable for use in conventional application procedures, due to the fact that good quality control is most difficult to maintain when they are employed.
In overcoming this difilculty, we have discovered that if the pH of aqueous solution containing neomycin and a suitable anionic brightener is above 8, these materials are rendered compatible and may be applied in a single application step.
Since most neomycin solutions are acidic, usually a pH of less than 3 and normally a pH of from about 1 to about 2, even'the addition of alkaline brightener solu- :usnrarsr rais'es'the pH more'than a few units, because {of the small amounts of brightener employed. Thus adjustment from the acid side to a pH value above 8 is effected with suitable alkaline agents such as sodium hyd'rox'ide, potassium hydroxide, sodium "carbonate, potassiumgcarbonate, ammonia, organic amines and their equivalents. M
While the pH of the solution should be above 8, we
have found that as apracticalmatter the pH of the treating solution should be above 8.5 and is normally about "9. The pH can'certainly' be higher than 9, as for example 10, 11 or more, but addition of amounts of base which are morethan sufiicient to produce clear stable aqueous solutions of 'neomycin and brightener is unnecessary and undesirable in the light-of economic considerations.
Toprepare a suitable stable solution, solutions of the components may-be mixed and the pH adjusted or suit- 'ablebase maybe added to either or both components prior to mixing. If the components are first mixed, the precipitate that is formed and is evidenced initially by'a haze or cloudiness n the solution, may be removed by the herein inits ordinary sense, and as it is defined in US.
Patent No. 2,830,0ll, above referred'to. In general, this refersto a commercially available product which is called 'neomycin, which is actually a'mixt'u're of two very closely related antibiotics known more specifically as neornycin B and neomycin'C. The term is also intended to cover 'neomycin as just "defined, the individual components of thewcomplex, or its salts,'of Whichthe sulfate is the most 4 the spectrum, thereby compensating for the slightly yellowish cast of most White fabrics.
Suitable brighteners for use in this invention may be divided into two types, according to the type of fiber for which they have afinity. There are the cellulosic and all-purpose types, the latter having afiinit-y for both eellulo'sic and non-cellulosic'fibers. Since this invention is restricted to application of solutionsto textile materials containing cellulosic fibers, only such br-ighteners are contemplated.
Such brighteners may also bedivided into chemical classes. The members of the cellulosic type can, for the most part, be assigned to the following classes: acyldiaminostilbene (I), triazinyldiaminostilbenes (II), and acyldiaminodibenzothiophene dioxides (III). The members of these classes contain sul'fonic acid groups. The allpurpose type comprises the benzimid'azoles (IV) and the triazo'les (V). Only those members of classes IV and V containing one or more sulfonic acid groups are contemplated for use in the instant invention.
Typical general formulae for classes 1-11! are illustrated below:
R R! \:-CONH@CH=CHC NHC o- SOKNa SO3N3, R!
. N N 3-K nmQ-ormornOmnW W-R' N iv l N \I SOsNa SOsNfi IIV I oorrN so N S a a SOz 3 a generally available. Other salts of neomycin have been usedin finishing textiles with good results, among them may be mentioned neomycin parahydroxybenzoate, neomycin sulfanilate, 'neornycin-N-tartrate, neomycin ipropionate, neomycin aconitate, neomycin phthalate, 'neomycin undecylinate, neomycin palmitate, neomycin stearate, and others.
By cellulosic textilernaterials or cellulose containing textile materials, as theseterms are employed herein, it is'meant fibers or'formed fabrics, either woven or felted,-containing at least %fibers of cellulosic origin and preferably composed entirely of cellulose for maximum efiect. Asex'amples of cellulosic textile materials,
the following-are illustrative: cotton, regenerated celllu- *lose,linen, jute, hemp, and the like. Blends of these materials "and combinations of these materials or blends thereof with wool, silk, nylon, acrylic fibers, polyester fibersyand the like, "are also contemplated.
The use-of fluorescent textile brighteners or optical blea'ches in :general'fields of application represent ad- 'vancenient over-prior art techniques attempting to conceal-the yellowish cast on cellulosic materials which employed blue pigments or'dyes. Thus, instead of using a bluerpigment,which absorbs colored light in the yellow range,*their us'e'involves 'the'employment or" a fluorescent si1bstance,'which-emits colored-light'in the blue range.
Thusfithe yellowing eifect is destroyed by'a substance whichemitsthe' blue light.
In r'ecentye'a'rs, the use of these optical bleaching agents or bri-ghteners has'grownenormously. These composi- 'tionsare colorless dyestuiis, exhibiting afiinity for'fabrics,
which when exposed to ultraviolet radiation, such as is contained in daylight, fiuoresce in the blue range of wherein R, R, R" and R, by Way of example, may be hydrogen, alkyl, aryl, alkoxy, halogen, nitrile, and the like. It should be notedthat RR" may be virtually any radical which does not'interfere or significantly reduce the brightening efiect of these dyes.
The following are examples of the various brightener classes which are pertinent'to this invention.
Class V: Triazoles 2-(4-styryl-3-sulfophenyl -2H-naphtho 1,2] -triazole-5- sulfonic acid As noted above, the fluorescent textile brighteners are applied simultaneously with the neomycin from aqueous solutions containing the same.
In general, the aqueous solutions containing the fluorescent textile brightener and ne-omycin may be applied to the textile material by any of the known conventional textile finishing techniques, whereby the material is contacted with these components for a sufi'icient period of time to fix them on the material. Thus, for example, they may be applied by padding, spraying, submersion, exhaustion or the like. Of these suggested techniques, padding is greatly preferred, in that most finishing plants are adapted to employ this technique, and within certain limits, more uniform control of the process may be achieved.
The sulfonic groups in the fluorescent textile brighteners employable in this invention impart sutficient solubility or dispersibility to permit their application from aqueous media. In addition, these groups contribute to the sub stantivity of the brighteners on the cellu-losic fibers.
As indicated above, it is preferred to apply the neomycin and fluorescent textile brighteners to suitable-textile materials containing cellulose and preferably formed cellulosic fabric, by employing conventional padding techniques. Employing such procedure, the textile material is padded through a bath containing neomycin and a suitable fluorescent textile brightener. Excess of the treating solutions are then removed from the textile material to achieve the desired pick-up by passing the impregnated fabric between rollers and thereafter the textile material is thied, preferably at elevated temperatures, as for example temperatures from between 150 F. to 350 F. Caution should be exercised in the employment of elevated temperature to insure that the textile material is not degraded thereby.
The concentration of the neomycin in the treating solution may be varied within wide limits, depending upon the use to which the material is intended. When applied by padding, the solution should contain from approximately 0.0001% to 4% and more by weight of neomycin as is desired in the dried fabric, since in the padding operation the fabric is usually impregnated with from between about 25 to 150% of the weight of the liquid and then dried. When applied by exhausting, the treating solution of neomycin may contain as littleas 0.001 micrograms per milliliter of neomycin when highly absorbent cellulosic fibers are treated. From 5 to 500 micrograms of neomycin per milliliter is considered the preferred range for application by exhaustion. For normally prophylactic purposes, sufiicient concentration of neomycin may be substantially adhered to base materials from aqueous treating solutions containing from about 1 microgram to about 400 micrograms per milliliter, with commercial limits lying between about 2 and about 200 micrograms per milliliter.
The treating solution should normally contain from approximately 0.001% to 4% and more by weight of the fluorescent brightener as is desired in the dried fabric when applied by padding, since in the padding operation the fabric is usually impregnated with from about 25% to about 150% of the weight of the liquid and then dried.
The concentration of the neomycin applied to the cellulose material may to some extent be varied over wide limits, depending upon the use for which the material is intended. Useful results are obtained when the fabric contains as little as 0.000170 by weight of neomycin on the dry weight of the textile material. The preferred range varies from about 0.001% to 1% by weight of neomycin on the dry weight of the treated fabric. For prophylactic purposes, deposition of from about 0.005 microgram up to micrograms per square centimeter has been found satisfactory, with preferred commercial ranges lying between about 0.1 and about 6 micrograms per square centimeter.
With respect to the fluorescent organic brightener, useful results are obtained in accordance with the present invention when suitable brightener is present on the fabric in an amount of at least 0.001% though preferably the amount based on the dry weight of the fabric is from between about 0.01 to 0.05%. Concentrations of brightener on the fabric of lass than 0.001%, based on the fabrics dry weight, are for the most part impractical.
With respect to formed fabrics, the preferred class of cellulose-containing textile materials contemplated by this invention, they may take any shape, size or form and may clearly include articles which are intended to be reused. Specific illustrations of such articles would include wearing apparel, handkerchiefs, diapers, hand, dish and bath towels, books and book covers, washable cloth toys, dolls and similar playthings, hospital and hotel sheets and pillow cases, hospital and examination room bathrobes, slippers, barbers and beauticians cloths and similar articles.
In the subsequent examples and tables of this specification, the test referred to therein for determination of antibacterial activity is a standard one and the treated fabrics are tested by a standard Agar plate method. For evaluating the extent of durability of the antibacterial activity of the textile finish, a convenient test method has been devised on inhibition of the bacterial growth by a piece of textile placed on an Agar plate inoculated with various strains of bacteria. The two commonly used strains are E. coli and S. aureus, which are strains usually employed in the evaluation of antibacterial agents for various purposes.
Thus, by determining the antibacterial activity of cloth treated by the process of this invention before and after a number of laundering treatments, the effectiveness of the finish may be determined. Durability of the finish is determined by subjecting the treated textile to a series of repeated launderings. The number of times the material may be laundered before antibacterial activity decreases below an effective level will give a measure of the durability of the finish.
in the test for antibacterial activity, discs of treated fabric of a certain size (11.5 millimeters in diameter) are placed on an Agar plate inoculated with the bacterial culture. After two hours contact, the disc is removed and the Agar plate is incubated overnight. The degree of inhibition of growth gives an index of the inhibitory effect of the finish on the cloth. This inhibition is easily observed, since the area where the bacterial growth is inhibited remains clear, whereas the remainder of the area where the bacterial growth has taken place becomes cloudy or opaque. The area under the disc is observed, and in addition, the total diameter of the area larger than that occupied by the disc is observed.
Effective finishes show a clear area at least under the disc with more effectively finished materials giving areas having a diameter greater than that of the disc itself. If the area of inhibition is greater than the area of the disc, the activity is given as the diameter of the clear area in millimeters. Otherwise, a rating of C denotes complete inhibition of bacterial growth under the disc; a rating of P denotes partial inhibition; an N rating denotes no inhibition or activity; and S and VS denote slight and very slight inhibition. It should be noted that P is at least 50 to inhibition under the test fabric.
The whiteness of the treated fabric as reported in subsequent examples and tables is judged by visual observation.
In order that the present invention may be more fully understood, the following examples are given primarily by way of illustration. No details or specific enumerations contained therein should be construed as limitations on the present invention, except as they appear in the appended claims. All parts and percentages are by weight unless specifically designated otherwise.
EXAMPLE 1 125 parts of a solution of neomycin sulfate containing 1% neomycin base was diluted with about five times as much water at room temperature. 0146 part of 4,4- bis[4-anilino-6-bis(Zhydroxyethyl)amino s triazin 2 ylamino] 2,2'-stilbenedisulfonic acid was added and a precipitate formed. A 1% solution of sodium carbonate was then added with stirring until the precipitate just redissolved of 89). This mixture was then diluted with water at room temperature to give a concentration of 0.125% neomycin base and 0.0146% brightener.
' Bleached 80 x 80 cotton fabric was passed through the above solution, the excess solution was removed by passing the fabric through squeeze rolls to give an 80% expression, and the treated fabric was dried at 225 F. The fabric contained 0.1% neomycin and 0.0117% brightener on the weight of the fabric.
EXAMPLE 2 The procedure of Example 1 was used with the substitution of dilute aqueous ammonia for the solution of sodium carbonate. A solution was obtained at a pH of 8-9.
EXAMPLE 3 EXAMPLE 4 The procedure of Example 3 was used substituting 0.0027% of 4,4-bis(2,4-dimethoxybenzoylamino)-2,2'-
. stilbenedisulfonic acid for the 4,4-his-(2 ethoxybenzoylamino)-2,2'-stilbenedisulfonic acid. The treated fabric contained 0.1% of neornycin and-0.0022% of the brightener on the weight of the fabric.
EXAMPLE 5 The procedure of Example 3 .was used substituting 0.0325 of dioxide of 3,7-bis-(4 methoxybenzamido)-2,8- dibenzothiophenedisulfonic acid, [4,4'-bis(4-methoxybenz- .oylamino)2,2' sulfonylbiphenyldsulfonic acid]. The treated fabric contained 0.1% of neomycin and 0.026% of the brightener on the weight of the fabric.
EXAMPLE 6 The procedure of Example 5 was used substituting 0.003125% of the same brightener for the 0.0325% used in Example 5. The treated fabric contained 0.1% ofneomycin and 0.0026% of the brightener on the weight of the fabric.
EXAMPLE 7 125 parts of a solution of neomycin sulfate containing 1% of neomycin base was diluted with-water at room temperature to give a concentration of 0.125% neomycin base. Bleached 80 x 80 cotton fabric was passed through the solution, and the excess solution was. removed by passing the fabric through squeeze rolls to .give an 80% expression. The fabric was dried at 225 F.
EXAMPLE 8 The cotton fabrics to which neornycin and brightener had been applied as described in Examples 2-5 and 7 were tested for antibacterial activity. The fabrics were laundered at 140 F. in hard water. by a standard procedure using a Laundromat washing machine containing 9. gallons of water with 20 cc. of 10% calcium chloride 8 and 0.25% neutral soap added. The antibacterial tests were repeated after the 16th and 25th washes.
The resultsare shown in Table I hereinbelow.
Table I Zone of Inhibition Initial t6 Washes 25 Washes S. aureus:
Example7 17.5 12.0 C Example2 17.0 VS P'C Example 3 I7. 3 0 12-0 Example 4 17. 6 O P-C Example 5 15.8 C P-C E. coli:
Example 7 14.4 VS VS Example 9 14. 4 VS VS Example 3.. .J-.. 13.8 S-P VS Example4 15.2 VS VS Example 5 14. 1 N-VS N-VS EXAMPLE 9 The cotton fabrics to which neomycin and brightener had been applied as described in Examples 2-7 were tested for durability of whiteness by washing in hard water as described in Example 8. The whiteness of the fabrics were observed visually by daylight, initially and after 16 and 25 washes. The results of these tests are shown in Table I1 hereinbelow.
Table II Whiteness Initial 16 Washes 25 Washes Example 7 Similar to Yellowcr than Much yellower untreated. initially. than initially. Example 2 Much better V. S]. yellower. V. sl. yellower than than initially. than initially. standard. i Example 3 Better than do Do.
standard. Example 4 do do Do. Example 5 do do Do. Example 6 S1. better than S1. yellower than S1 yellower standard. initially. than initially.
In order to demonstrate that the pH of the aqueous treating solution is a critical element in producing clear stable solutions, the followingillustrative examples are presented.
EXAMPLE 10 Five aqueous solutions containing 2% neomycin sulfate had their pH adjusted by the addition of dilute sodium hydroxide to 4.8, 7.0, 8.0, 9.0 and 10.0.
To this was added a'solution containing approximately 25% of 4,4'-bis [4-anilino-6-bis (2-hydroxyethyl) amino-striazin 2-ylamino] -2,2'-stilbenedisulfonic acid.
The final solutions contained .1% of neomycin sulfate and 0.025% of the anionic brightener identified above.
7 Only the solutions employing the neomycinsulfate solutions having adjusted pHs of 9 and 10 were clear and stable. Those neornycin sulfate solutions having their 'pHs adjusted to 4.8, 7.0 and 8.0 showed the presence of substantial amounts of precipitate.
EXAMPLE 7 1 1 This solution was then made up to a final volume of 500 cc. so that the solution contained .125 of neornycin and .0375 of 4,4'-bis[4-anilino-6-bis(2-hydroxyethyl) amino s triazin-Z-ylamino]-2,2-stilbenedisulfonic acid. The pH of the final volume of this solution was determined to be 8.7.
EXAMPLE 12 The above procedure was repeated with the exception that 250 cc. of cold water were added to 6.3 parts of a 1% solution of neomycin sulfate as compared with the 62.5 parts in Example 11.
The pH at the first point of clarification was 8.9.
EXAMPLE 13 Approximately 250 parts of cold water were added to 62.5 parts of a 1% solution of neomycin sulfate. The pH of this solution was adjusted to 7.5 with a 1% solution of soda ash.
0.75 part of a 25% solution of 4 ,4-bis[4-anilino-6-bis (2 hydroxyethyl) amino-s-triazin-Z-ylarnino]2,2-stilbenedisulfonic acid is diluted with approximately 100 parts of Water. The pH of this solution is adjusted to 7.5 by the addition of dilute sulfuric acid. The brightener solution is then added to the solution of neomycin and the total volume adjusted to 500 cc. The pH of the solution is 7.5.
This identical procedure was repeated to produce solutions having pHs of 8, 8.5 and 9, and the compatibility of these solutions at each of these pH levels was noted. The final solutions having pI-Is of 7.5 and 8 contained substantial precipitate, while that having a pH of 8.5 was turbid. The solution having a pH of 9 was water clear and stable.
EXAMPLE 14 Approximately 250 parts of cold water were added to 62.5 parts of a 1% solution of neomycin sulfate. The pH of the solution was adjusted to 9 with a 1% solution of soda ash.
Approximately 100 parts of water were added to 0.75 part of a 25% solution of 4,4-bis[4-anilino-6-bis(2-hydro- Xyethyl) amino-s-triazin-Lylamino] -2,2'-stilbenedisulfonic acid. No pH adjustment was made in the diluted brightener solution. The brightener solution was added to the solution of neomycin with moderate manual stirring and the final volume of the solution adjusted to 500 parts. The resulting solution was stable and water clear and had a pH of 9.
This example points out that the addition of the alkaline brightener solution, which has a pH of 9.75 when employed in conventional and in efiective amounts, is in amounts insufiicient to afiect the pH of the final solution.
While the present invention relates primarily to the finishing of cellulosic containing textile materials with a purifying finish containing neomycin and a fluorescent organic brightener, it will be apparent that other textile treating agents, lubricants, softeners, wetting agents, and
i0 the like may be incorporated into the treating bath, so long as their presence and function do not inhibit or impair the antibacterial finish and its durability and the brightening etfects achieved in accordance with this invention.
This application is a continuation-in-part of our copending application Serial No. 771,194, filed November 3, 1958, now abandoned.
We claim:
1. A process for finishing formed textile fabric containing at least 50% oellulosic fibers to impart a durable antibacterial finish thereto having resistance to discoloration which comprises simultaneously applying thereto an aqueous treating solution having a pH above 8.5 and containing neomycin, an anionic fluorescent brightener containing a sulfonic acid group that is substantive to cellulose fiber, and an alkaline agent, so as to impart at least .0001% of neomycin and at least .00l% of said anionic brightener to the finished fabric, and thereafter drying the fabric.
2. A process according to claim 1, wherein the brightener is an acyldiaminostilbene.
3. A process according to claim 1, wherein the brightener is a triazinyldiaminostilbene.
4. A process according to claim 1, wherein the brightener is an acyldiarninodibenzothiophene dioxide.
5. A process according to claim 1, in which the neoriycin is applied so as to 'be present on the fabric in an amount of from between .0001 and .l%, based on the dry weight of the fabric, and the anionic fluorescent brightener is present on the fabric in an amount of from between .001 and 0.05%, based on the dry weight of the fabric.
6. A process according to claim 1, in Which the fabric is cotton.
7. A process according to claim 3, in which the neornycin is applied to the fabric in an amount from between about :01 and .05 based on the dry Weight of the fabric and the anionic brightener is applied to the textile material in an amount from between about .01 and 05%, based on the dry Weight of the fabric.
8. A composition which comprises in aqueous medium, neomycin, at least 001% of an anionic fluorescent brightener containing a sulfonic acid group, and an alkaline agent, said composition being characterized by a. pH above 8.5.
References Cited in the tile of this patent UNITED STATES PATENTS 2,468,431 Eberhart Apr. 26, 1949 2,563,493 Scalera Aug. 7, 1951 2,563,795 Scalera Aug. 7, 1951 2,567,796 Ackermann Sept. 11, 1951 2,763,650 Ackermann Sept. 18, 1956 2,830,011 Parker Apr. 8, 1958 OTHER REFERENCES Dorset: Textile Manufacturer, May 1954, pp. 254-258.
Claims (1)
1. A PROCESS FOR FINISHING FORMED TEXTILE FABRIC CONTAINING AT LEAST 50% CELLULOSIC FIBERS TO IMPART A DURABLE ANTIBACTERIAL FINISH THERETO HAVING RESISTANCE TO DISCOLORATION WHICH COMPRISES SIMULTANELUSLY APPLYING THERETO AN AQUEOUS TREATING SOLUTION HAVING A PH ABOVE 8.5 AND CONTAINING NEOMYCIN, AN ANIONIC FLUORESCENT BRIGHTENER COTAINING A SULFONIC ACID GROUP THAT IS SUBSTANTIVE TO CELLULOSE FIBER, AND AN ALKALINE AGENT, SO AS TO IMPART AT LEAST .0001% OF NEOMYCIN AND AT LEAST .001% OF SAID ANIONIC BRIGHTENER TO THE FINISHED FABRIC, AND THEREAFTER DRYING THE FABRIC.
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US218851A US3173841A (en) | 1962-08-23 | 1962-08-23 | Durable antibacterial textile finish for cellulosic textile material |
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US218851A US3173841A (en) | 1962-08-23 | 1962-08-23 | Durable antibacterial textile finish for cellulosic textile material |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3382200A (en) * | 1964-05-11 | 1968-05-07 | American Cyanamid Co | Composition for treating and brightening cellulose fibers |
US3453262A (en) * | 1964-12-18 | 1969-07-01 | Corn Products Co | Composition of matter |
US3650816A (en) * | 1969-05-02 | 1972-03-21 | Lever Brothers Ltd | Additives for clothes dryers |
US5830526A (en) * | 1994-12-28 | 1998-11-03 | Fibermark, Inc. | Light-activated antimicrobial and antiviral materials |
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US2468431A (en) * | 1948-04-29 | 1949-04-26 | American Cyanamid Co | o-alkoxybenzoyl derivatives of 4, 4'-diaminostilbene-2, 2'-disulfonic acid |
US2563493A (en) * | 1951-08-07 | Sulfonated | ||
US2563795A (en) * | 1951-08-07 | Dibenzothiophene derivatives | ||
US2567796A (en) * | 1947-12-12 | 1951-09-11 | Ciba Ltd | Water-soluble aminostilbene derivatives and process |
US2763650A (en) * | 1956-09-18 | Derivatives of x | ||
US2830011A (en) * | 1957-02-07 | 1958-04-08 | American Cyanamid Co | Textile fabrics containing neomycin |
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Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
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US2563493A (en) * | 1951-08-07 | Sulfonated | ||
US2563795A (en) * | 1951-08-07 | Dibenzothiophene derivatives | ||
US2763650A (en) * | 1956-09-18 | Derivatives of x | ||
US2567796A (en) * | 1947-12-12 | 1951-09-11 | Ciba Ltd | Water-soluble aminostilbene derivatives and process |
US2468431A (en) * | 1948-04-29 | 1949-04-26 | American Cyanamid Co | o-alkoxybenzoyl derivatives of 4, 4'-diaminostilbene-2, 2'-disulfonic acid |
US2830011A (en) * | 1957-02-07 | 1958-04-08 | American Cyanamid Co | Textile fabrics containing neomycin |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3382200A (en) * | 1964-05-11 | 1968-05-07 | American Cyanamid Co | Composition for treating and brightening cellulose fibers |
US3453262A (en) * | 1964-12-18 | 1969-07-01 | Corn Products Co | Composition of matter |
US3650816A (en) * | 1969-05-02 | 1972-03-21 | Lever Brothers Ltd | Additives for clothes dryers |
US5830526A (en) * | 1994-12-28 | 1998-11-03 | Fibermark, Inc. | Light-activated antimicrobial and antiviral materials |
WO2000025940A1 (en) * | 1994-12-28 | 2000-05-11 | Fibermark, Inc. | Light-activated antimicrobial and antiviral materials |
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