US3788803A

US3788803A - Method of concurrently dyeing and imparting durable bioactive proper- ties to synthetic textiles

Info

Publication number: US3788803A
Application number: US00195035A
Authority: US
Inventors: S Klein; D Gagliardi; F Gagliardi
Original assignee: Sanitized Inc
Current assignee: Sanitized Inc
Priority date: 1971-11-02
Filing date: 1971-11-02
Publication date: 1974-01-29
Anticipated expiration: 1991-01-29
Also published as: CA985623A

Abstract

DURABLE BIOACTIVE PROPERTIES ARE OBTAINED ON SYNTHETIC TEXTILE FIBERS AND FABRICS BY APPLYING AN AQUEOUS SOLUTION OR DISPERSION OF A COMPOSITION CONTAINING A DYE, A BIOACTIVE MATERIAL AND A CARRIER TO THE TEXTILE BY AN EXHAUSTION TECHNIQUE.

Description

, 3,788,803 METHOD OF CONCURRENTLY DYEING AND IMPARTING DURABLE BIOACTIVE PROPER- TIES TO SYNTHETIC TEXTILES Stewart E. Klein, Harrison, N.Y., and D. Donald Gagliardi, deceased, late of East Greenwich, RJL, by Frances Dodge Gagliardi, executrix, East Greenwich, RL, assignors to sanitized Incorporated, New York, N.Y. No Drawing. Filed Nov. 2, 1971, Ser. No. 195,035 Int. Cl. D06p /18 US. Cl. 8-17 7 Claims ABSTRACT OF THE DISCLOSURE Durable bioactive properties are obtained on synthetic textile fibers and fabrics by applying an aqueous solution or dispersion of a composition containing a dye, a bioactive material and a carrier to the textile by an exhaustion technique.

BACKGROUND OF THE INVENTION Numerous techniques have been proposed for the'treatment of synthetic textile fibers or fabrics with materials having the ability to de-activate or kill microorganisms with which they come into contact. Fibers or fabrics so treated are used in the manufacture of garments in order to prevent odor formation therein, to minimize the risk of skin rashes by contact therewith, and to otherwise inhibit the spread of toxic organisms by such garments. The treated fabrics are particularly useful in hospitals. Such treatments are also widely used for rot-proofing to protect synthetic textiles from attack by fungus, mildew and the like.

In the usual procedure for manufacturing fabrics, the raw fabrics or griege goods are prepared and are thereafter bleached, dyed, and finally finished with water repellants, softeners and/or various resin finishes. Historically, bioactive agents generally have been applied to textile fabrics in the finish bath, along with other specialty finishes (e.g., antistatic agents, softeners, water or stain repellants, etc.). However, when so applied, the bioactive material may be merely superficially deposited on the fabric surface, and when the fabric is subjected to the mechanical manipulation of laundering and the emulsifying action of soap or detergents the bioactive residue may be released, leaving the fabric unprotected. Some bioactive materials applied by such finishing operations may even be leached out by cold water or removed by other weathering factors.

Various attempts have been made to impart improved durability to textiles treated with bioactive materials; see, for example US. Pat. No. 3,547,688. Nevertheless, there still exists a need for a technique for imparting durable, broad spectrum bioactivity to synthetic textiles, which will inhibit gram-positive and gram-negative bacteria, fungi and the like and which will be maintained even after repeated high temperature alkaline washes.

Accordingly, it is the primary object of this invention to provide a process for economically imparting bactericidal, bacteriostatic, fungicidal and/ or fungistatic protection to synthetic textile fibers or fabrics, which bioactive properties persist after the textile is repeatedly exposed to water leaching and subjected to multiple launderings. These and other objects will become apparent to those skilled in the art from the following detailed description.

SUMMARY OF THE INVENTION This invention relates to a method of imparting durable bioactive properties to a synthetic textile, and, more particularly, relates to an improved method of imparting durable bioactive properties to synthetic textile fibers or fabrics by treating the same prior to finishing with an aqueous solution or dispersion of a composition contain- United States Patent O ice ing a bioactive material and a carrier therefor by the exhaustion technique. As distinguished from conventional padding operations, application of the bioactive-carrier composition to the textile by exhaustion involves the use of a closed systemin which the synthetic fibers or fabrics are immersed in the treating bath for an extended period of time and under conditions sufficient to absorb the bioactive material into the textile fibers, effect fixation of the material to the fibers and exhaust the same from the treatment bath. It has been found that by thus treating synthetic textiles with bioactive materials, rather than by applying such materials by conventional padding techniques during textile finishing operations, it is possible to provide bioactive properties of markedly enhanced durability.

PREFERRED EMBODIMENTS OF THE INVENTION In accordance with the present invention, synthetic textile fibers or fabrics are treated with aqueous treating baths, in solution or dispersion form, containing at least one suitable bioactive material and a carrier therefor. By synthetic fibers or fabrics is meant those synthetic fibers, yarns, skeins or fabrics comprised wholly of synthetic polymeric materials, e.g., viscose, cellulose acetate or triacetate; or the nylons, polyesters, or vinyl polymers including polyolefins, acrylics and modacrylics, or the like; or blends of such materials with natural fibers such as cotton or other cellulosics, or wool or other proteinaceous materials.

As used herein, the term bioactive material comprehends those known categories of compounds which exhibit bacteriostatic, bactericidal, fungistatic, and/or fungicidal properties. Bioactive materials so useful for the treatment of textile fabrics include tin salts such as tributyl tin oxide, tributyl tin neodecanoate, tributyl tin acetate, tributyl tin benzoate, or tributyl tin salicylate.

Also useful in the treatment hereof are halophenols, such as para-chloro-meta-xylenol, pentachlorophenol, 2,2- methylene bis(4-chlorophenol), 2,2'-methy1enebis(3,4,6- trichlorophenol), 5 chloro 2(2,4 dichlorophenoxy) phenol, or the alkali metal salts thereof; amines such as anilides, particularly salicylanilide, tribromosalicylanilide, 3,5-dibromo 3 trifiuoromethylsalicylanilide, trichlorocarbanilide, and trifluorochlorocarbanilide; quaternary ammonium compounds such as alkyldimethylbenzyl ammonium chloride and alkyldimethylammonium cyclohexylsulfamate; or thio compounds such as N-trichloromethylthio-4-cyclohexene-1,2-dicarboximide,

bis(dimethylthiocarbamoyl)disulfide,

trans-1,2-bis (n-propylsulfonyl) ethene,

bis(n-propylsulfonyl) ethene,

1,6-bis-(4-ethylmercaptophenylbisguanido)hexane,

hydroxypyridine-Z-thione,

3,5-dimethyl-tetrahydro-1,3,5,ZH-thiadiazine-Z-thione,

and

2,3,5,6-tetrachloro-4-(methylsufonyl) pyridine.

Additional bioactive materials which may be used herein include diphenylstibene Z-ethyl hexoate.

Yet other bioactive materials elfective against bacteria and/or fungi (see, for example, Antiseptics and Disinfectants, Fungicides and Sterilization, edited by C. F. Reddish, 2nd ed., May 1961, chapter 13, pp. 308-313) may comprise the bioactive materials useful in the synthetic textile treatment of the present invention, provided that such materials are compatible with and inert with respect to the synthetic fibers or fabrics and any other additives which may be utilized in connection with the dyeing, finishing, or other treatment thereof.

The carriers whose use is comprehended herein comprises those well-known types of carriers normally employed as adjuvants to dyes in coloring of textile fibers or fabrics. See, e.g., Brown et al., Halogenated Benzenes as Carriers for Dyeing Polyester Fibers, American Dyestuff Reporter, Apr. 22, 1968, p. 49. Carriers useful in the bioactive treatment of the present invention include phenols such as o-phenylphenol, p-phenylphenol, octylphenol, octylcresol and the like; aliphatic or aromatic esters such as butyl benzoate, benzyl benzoate, dimethyl terephthalate, dimethyl phthalate, methyl salicylate, or mixtures of such materials with various additives, e.g., mixtures of butyl benzoate and tripropyl phosphate; dimethyl terephthalate with benzanilide; or mixtures of the benzoic esters of aromatic alcohols, phenols or naphtholswith an ether containing at least one aromatic radical (such as the mixtures of benzyl benzoate and dibenzyl ether). Further useful carriers include halogenated aromatics, particularly halobenzenes such as mono-, di-, and tri-chlorobenzenes, oor p-chlorobromo benzenes, or dibromobenzenes; aryl esters of carbonic acid such as diphenyl carbonate; cyclohexylamides of benzene sulfonic acids; or compounds containing one lactone group and one aromatic nucleus such as the lactone of 2-hydroxynaphthalene-ls-propionic acid. Other carriers useful with bioactive materials suitable for the treatment of synthetic fibers or fabrics in accordance herewith include biphenyl, et-mcthyl-naphthalene or the like.

The bioactive material is admixed with the carrier in the proportion of from about to 35%? bioactive to 65 to 90% carrier, preferably from about 20 to 25% bioactive to 75 to 80% carrier. The combined materials are then incorporated in the synthetic textile treating bath for application prior to finishing of the fabric by an exhaustion technique. As indicated hereinafter, the treatment bath may contain conventional proportions of surfactants, dyestuffs or other materials utilized for the treatment of synthetic textiles.

In particular, the bioactive material-carrier formulation is applied from an aqueous treatment bath, i.e., Water or a mixture of water and a polar solvent, e.g., a lower aliphatic alcohol such as isopropanol. A small amount, for example, up to about 5 weight percent, and preferably from about 1 to 3 weight percent, of a dispersing agent may additionally be incorporated in the bath. Dispersing agents so useful include anionic surfactants such as the alkali metal alkylbenzene sulfonates or long chain (8-20 carbon atoms) alkyl sulfates, e.g., the alkali metal salts of dodecylbenzene sulfonate, lauryl sulfate, heptadecyl sulfate, diethylhexyl sulfate, tetradecyl sulfate, or ethylhexyl sulfate; and non-ionic surfactants such as the alkyland dialkyl-phenoxypoly(ethyleneoxy)ethanols, preferably those having alkyl moieties of from 5 to 12 carbon atoms and l to 20 ethyleneoxy groups, e.g., octyl-, nonyl-, or dodecyl-phenoxypoly(ethyleneoxy)ethanols, fatty acid esters of polyhydric alcohols, e.g., glyceryl monostearate, or the like.

The bioactive material-carrier formulation may additionally incorporate one or more dyestuffs conventionally used for the dyeing of synthetic fibers. In this manner, dyeing and bioactive treatment of the synthetic textiles may be accomplished in a single step and from the same treatment bath. Any dyes conventionally employed for the dyeing of syntheic fibers may be so employed providing, of course, that the particular dyestuff chosen is inert with respect to the bioactive material as well as the other constituents of the treatment bath. Dyestuffs so useful include those disclosed, for example, in Dyeing: Theory and Practice, Dyestuffs, vol. 42, Nos. 5-8, and Dyeing Synthetic Fibers and Blends, 6th ed., General Aniline and Film Corporation.

Textile dyes are defined both by chemical composition and by method of application. Dyes useful in the practice of the present invention may belong to any of the following chemical classes: nitroso, nitro, monoazo, disazo, trisazo, polyazo, azoic, stilbene, diphenylmethane, triphenylmethane, xanthene, acridine, quinoline, methine, thiazole, indamine, indophenol, azine, oxazine, thiazine, sulfur, lactone, aminoketone, hydroxyketone, anthraquinone, indigoid, phthalocyanine, and natural dyes (i.e., obtained from animal or vegetable matter with little or no chemical processing such as curcuma, carmine, litmus, indigo, chlorophyll and walnut oil). Alternatively, the following classes of dyestuffs, defined by mode of application, may be incorporated with the bioactive-carrier materials in the practice of the present invention: vat, sulfur, acid, disperse, developed, basic and reactive dyes. In general, any dyestuffs which may be applied to synthetic textile fibers or fabrics by exhaustion techniques may be used in conjunction with the present treatment so long as they are inert with respect to the other constituents of the treatment bah.

In accordance with the exhaustion technique hereof, the synthetic textile fibers or fabrics are immersed, prior to finishing, in the bioactive-carrier containing treatment bath within a closed system, generally for an extended period of time and under elevated temperature conditions, to eeifct absorption and fixation of the bioactive material within the fibers and thus exhaust the same from the bath. Generally, it has been found necessary for the purposes of this invention to immerse the synthetic textile fibers or fabric within the bioactive material-containing treating bath for periods of from about 20 minutes to 3 hours at elevated temperatures. For such purposes, the use of temperatures of from about 65 to 100 C., and desirably from about to C., is particularly preferred to effect swelling of the textile fibers to facilitate absorption and pick-up of the bioactive material.

The amount of the bioactive materials thus deposited on the textile fibers will vary, depending upon the particular bioactive component, the carrier chosen, and the textile treated. In general, it is preferred to deposit from about 0.5 to 1.5, and most desirably about 0.5, pounds of the bioactive material per square yards of the final fabric product. The bioactive material is thus deposited in amounts of from about 0.1 to 0.5% by weight of the textile substrate. While greater amounts may be employed, such has been found unnecessary to produce the desired bioactive properties and is, of course, economically disadvantageous.

Upon removal of the synthetic textile fibers or fabrics from the exhaustion bath, the treated material may be dried and scoured in accordance with conventional practice, and thereafter further processed in the manner known in the art, i.e., woven, knitted, or otherwise placed into the final piece goods if treated in the fibrous form, and thereafter subjected to finishing operations as usual.

The following examples illustrate various preferred embodiments of the present bioactive-carrier containing treating baths and the method of treating synthetic textile materials therewith. It will be understood that the examples are illustrative and not limiting of the method and compositions of the present invention. All parts and percentages are given by weight and all temperatures are indicated in degrees centigrade throughout the following exampes, the preceding general description and the ensuing claims, unless otherwise specified.

EXAMPLES 1-l9 A first bioactive treatment composition (formulation A) was applied to various fabrics by placing wet-out fabrics by placing wet-out fabric swatches in a bath containing water and, as the bioactive material, 5-chloro- 2-(2,4-dichlorophenoxy) phenol (Geigys Irgasan DP- 300). The bath temperature was about 40-50 C., which was maintained, with agitation, for 5-10 minutes to insure complete dispersion. Thereafter, 3 parts of a mixture of dimethyl phthalate as a carrier, isopropyl alcohol, and a non-ionic surfactant (Triton X-100), per part of bioactive agent, were added and the agitation maintained for an additional 5-10 minutes. The bath temperature was thereafter raised to about 95 100' C. (boiling) and maintained thereat for 1-2 hours. The temperature and period of immersion was such as to provide a pick-up of about 0.5% bioactive material based on the weight of the dry fabric. The resulting treated fabrics were rinsed and dried, and labeled as having been treated with Formulation A.

The foregoing was repeated except that one-half of the 5-chloro-2-(2,4-dichlorophenoxy)phenol was replaced with an additional bioactive material hexachlorophene- [2,2-methylenebis(3,4,6-trichlorophenol)], and the treated fabrics labeled as having been treated with formulation B.

Control formulations corresponding to test formulations A and B but excluding the carrier were prepared by the addition of water, propylene glycol, and Emulphor ON- 870 (a nonionic surfactant comprising a polyoxyethylated fatty alcohol having a melting point of 43 C., a specific gravity at 25 C. of 1.03-1.04, a flash point of 238 C., and a fire point of 343 C.) to the respective bioactive materials. The resulting control formulations had the following compositions.

The control formulations were applied to individual fabric samples, either by the exhaustion technique described hereinabove or by padding with a 2-dip, 2-nip padder. The padding rolls were adjusted so as to provide a pick-up of about 0.5% bioactive material based on the weights of the dry fabrics treated. The samples thus treated were thereafter rinsed and dried in the same manner as the fabric swatches treated as aforesaid by the exhaustion technique.

The resulting fabric samples, treated by exhaustion or padding with bioactive material-containing formulations either incorporating or excluding carrier materials, were thereafter tested for bioactivity by the seeded agar plate test method AATCC 90-1965T, as described in the 1966 Technical Manual of the American Association of Textile Chemists and Colorists, vol. 40, 1968. In accordance with such test method, the various fabric samples were sterilized and thereafter placed on AATCC agar which had previously been seeded with test bacteria. After incubation, the samples were examined for bacterial growth; the examination was repeated after plural launderings to determine the durability of the antibacterial properties imparted to the respective textile samples. The presence of azone or halo. of antibacterial activity (the region in which no growth of the text organism was exhibited) was also determined in each instance.

The antibacterial properties imparted to the various syn- ;thetic textile fabric samples are tabulated in the following Tables IXI. The test fabrics whose antibacterial proper- .materials with the same bioactive compounds in the absence of the carrier by applying the formulation by padding or during finishing of the textile fabrics.

COMPARATIVE ANTIBACTERIAL ACTIVITY Mode of Number of launderings 4 treat- Example or control l ment I 0 5 10 15 TABLE I.RAYON Example I(A) Example 2(B) Control A(I) Control B(I). Control C(II) Control D I) TABLE II.65% POLYESTE R/35% COTTON Example 3(A) E Example 4(B) E Control E(I) E Control F(I) P Control G(II) E $1 Control H(II) E TABLE III.50% WOOL/30% ACRYLIC/20% NYLON Example 5 A) E Control I(I E 1: E

Example 6(A) E Example 7(B) E Control K(I)-. E Control L(I) E-F Control M(II) E Control N(II) E-F TABLE V.--% ACRYLIC/15% NYLON Example 8(A) E Control 0(1) E TABLE VI.70% POLYESTER/30% ACRYLIC Example 9(A)- v o a Control P(I) E Control Q,(I) E-F 4- TABLE VIL-ACETATE Example 10(A) E Example 11 13)-. E e c Control R(I E Control 8(1)-.. P Control 'I(II)- E Control U(II) P TABLE VIII.NYLON Example 12(A) E Example 13(B) E 0 o Control V(I) E 51 P E r? TABLE IX-ACBYLIC Example 14(A) 0 o Example 15(B) 0 a .o Control Z(I) Control AA(I) Control AB(II) Control AC(II) P TABLE X.POLYESTER Example 16(A) Example 17(B) o l The examples are serially numbered from 1 to 19 and the controls are serially lettered from A to Z and AA to AK. The formulations tested in the respective examples and controls are parenthetically referenced after the example or control number as Formulations A and B or Control Formulations I and II as identified above.

I The mode of application of respective formulations is identified by the letters E and P," the former designating treatment of the gtelge goods by exhaustion and the latter designating treatment during finishing by padding. The term E-F in Tables III, IV and VI designates treatment of the test samples in the indicated control experiments by the exhaustion technique during finishing of the samples.

8 In this experiment the treatment composition was applied to the grelge goods by padding.

4 The symbols used to designate the bacterial growth after repeated launderings are as follows:

+= Growth of test organism;

-=N o grqwth of test organism;

#=Imt1al nh1b1tion of growth of test organism; growth after a single laundering of test swatch;

=Sample exhibited zone (halo) of inhibition.

7 EXAMPLES 20-25 Bioactive material-containing formulations are'prepared in the manner described hereinabove by the admixture of 3 parts of the mixture of dimethyl phthalate carrier, isopropanol, and a non-ionic surfactant (Triton X-100) to one part of each of the following bioactive materials.

Example: Bioactive material 20 3',4',5'-tribomosalicylanilide.

21 ch1oro-2-(2,4dichlorophenoxy)phe- 1101 (.4 part).

3',4,5'-tribromosalicylani1ide (.6 part).

22 5 chloro-2-(2,4-dichlorophenoxy)phen01 (.4 part);

3,5 dibromo-3'-trifluoromethy1salicylanilide (.6 part).

23 3,5 dibromo-3'-trifluoromethylsalicylanilide.

24 Zinc pyridmethione-N-oxide (.4 part); 3,4',5' tribromosalicylam'lide (.6 part).

25 Zinc pyridmethione-N-oxide.

It will be understood that various changes and modifications may be made in the method and compositions utilized in accordance with the present invention without departing from the spirit and scope thereof. Accordingly, the preferred embodiments of the invention described hereinabove are solely intended to illustrate the invention and are not limiting thereof.

What is claimed is:

1. In a method of imparting durable bioactive properties to synthetic textile fibers or fabrics, which comprises dyeing the textile, finishing the same, and treating the textile with a bioactive material, the improvement comprising:

treating the textile, concurrently with the dyeing there of, with the bioactive material by immersing the textile in a dyeing bath containing the bioactive material and a carrier therefor; and

maintaining the textile in the dyeing bath within a closed system for an extended period of time and under temperatures sufficient to absorb substantially all of the bioactive materialinto the textile fibers,

etfect fixation of said material to the fibers, and

exhaust the bioactive material from the dyeing bath;

( 1) the bioactive material being a halophenol or an alkali metal salt thereof; and

8 (2) the carrier being an ester of terephthalic or phthalic acid.

2. The method of claim 1, wherein the synthetic textile is maintained in the dyeing bath for a period and at temperatures sufficient to deposit the bioactive material on the synthetic textile in an amount of from 0.1 to 0.5% by weight of the textile.

3. The method of claim 1, wherein the synthetic textile is immersed in the dyeing bath for a period of from 20 minutes to three hours, while maintaining the bath at elevated temperatures.

4. The method of claim 3, wherein the dyeing Bath is maintained during immersion of the synthetic textile therein at temperatures of from to C.

5. The method of claim 1, wherein the bioactive material is parachloro-meta-xylenol, pentachlorophenol, 2,2- methylene bis(4-chlorophenol), 2,2-methylenebis(3,4,6- trichlorophenol), 5-chloro-2(2,4-dichlorophenoxy)phenol or an alkali metal salt thereof; and the carrier is dimethyl terephthalate or dimethyl phthalate.

6. The method of claim 1, wherein the dyeing bath contains 5-chloro-2-(2,4-dichlorophenoxy)phenol as the bioactive material constituent thereof, and dimethyl phthalate as the carrier therefor.

7. The method of claim 1, wherein the dyeing bath contains a mixture of 5-chloro-2-(2,4-dichlorophenoxy) phenol and 2,2'-methylenebis(3,4,6-trichlorophenyl) as the bioactive material constituent thereof, and dimethyl phthalate as the carrier therefor.

References Cited UNITED STATES PATENTS 1,879,351 9/1932 Lehmann 424-308 2,880,129 3/1959 Billings 117--138.5 X 2,957,785 10/1960 Leatherland 117-138.5 2,880,050 3/1959 Fortess et al 8--173 X 2,926,987 3/1960 Freyerrnuth et al. 8-173 X 2,982,597 5/1961 Salvin et al 8-173 X 3,101,236 8/1963 Salvin et a1 8-473 X 3,501,341 3/1970 Spange et a1 117138.5

WILLIAM D. MARTIN, Primary Examiner T. G. DAVIS, Assistant Examiner US. Cl. X.R.

1l7138,5, 138.8 E, 138.8 F, 138.8 N, 138.8 VA