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Publication numberUS3401005 A
Publication typeGrant
Publication dateSep 10, 1968
Filing dateOct 22, 1965
Priority dateOct 22, 1965
Publication numberUS 3401005 A, US 3401005A, US-A-3401005, US3401005 A, US3401005A
InventorsKatz Leon
Original AssigneeGaf Corp
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Germicidal material produced by modifying textile fibers with a methylolated lactam and treating same with iodine
US 3401005 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

United States Patent 3,401,005 GERMICIDAL MATERIAL PRODUCED BY MODI- FYING TEXTILE FIBERS WITH A METHYLOL- ATED LACTAM AND TREATING SAME WITH IODINE Leon Katz, Springfield, N .J assignor to GAF Corporation, a corporation of Delaware No Drawing. Filed Oct. 22, 1965, Ser. No. 502,618 6 Claims. (Cl. 8-1155) The present invention relates to novel germicidal products suitable for use as bandages, surgical dressings and the like.

In the copending application of Randall and Freyermuth, Ser. No. 502,387, filed Oct. 22, 1965, there is disclosed fibrous materials treated with N-hydroxymethyl lactams such as N-hydroxymethylpyrrolidinone. I have discovered that when the thus treated fibrous material is further treated with a halogen containing germicidal agent such a iodine, iodine monochloride or iodine monobromide, the germicidal agent combines with the treated fibrous material in an effective amount so as to produce a germicidal fibrous material suitable for the production of bandages and surgical dressings and the like in which the germicidal activity is retained for substantial periods of time.

The novel germicidal fibrous materials of the present invention are readily prepared by directly applying to the treated fibers, more fully described and claimed in aforesaid application of Randall and Freyermuth, a halogen containing germicidal agent. The germicidal agent can be applied directly to the treated fibers or preferably a solution thereof is applied to the treated fibers. The germicidal agent combines with the treated fibers and renders the fibers germicidically effective for substantial periods of time. The combination of the germicidal agent with the treated fibers can be affected by prolonged contact at ordinary temperatures or preferably may be expedited by the use of elevated temperatures during or immediately following application of the germicidal agent to the treated fibers.

The details of the present invention will be apparent to those skilled in the art from a consideration of the following specific examples of preferred embodiments thereof.

EXAMPLE A Preparation of treated fibers An aqueous solution containing 10% N-hydroxymethylpyrrolidinone and 0.36%, 2-methyl-2-amino-l-propanol hydrochloride was padded on cotton gauze (hospital bandage material). The gauze, padded with N-hydroxymethyl pyrrolidinone, was squeezed through rubber rollers with suflicient pressure to give 100% (by weight) wet pick-up of solution. The fabric in roll form was dried at about 100 C. and then heat cured at ISO-155 C. for three minutes. The roll of guaze was rinsed with warm water on a laboratory jig, squeezed between pressure rollers, and dried. The cloth after this treatment con-v 3,401,005 Patentecl Sept. 10, 1968 ICC EXAMPLE 1.

Three square pieces of cotton fabric each weighing 7.3 g. which had been treated with N-hydroxymethylpyrrolidinone in the manner described above, were rolled up and placed in a wide mouth bottle 6.5 inches high and 2.5 inches in diameter in such a manner that the outer surface of cloth bands touched the surrounding inner curved surface of the bottle. In the center of the roll of the cotton was carefully inserted an inverted 50 ml. beaker, and 10 ml. beaker containing 0.73 g. iodine crystals was placed on the inverted beaker. The bottles were then tightly capped and sealed with a sheet of polyethylene under the cap. The bottles were allowed to stand at room temperature for two weeks during which time the iodine sublimed and reacted with the cloth giving it a reddishbrown color similar in shade to that of the polyvinylpyrrolidinone iodine complex described in US. Patent N. 2,739,922. The treated cloth was then removed from the bottle, rinsed with cold water and dried. It was found to contain 7.5% iodine by analysis.

The thus treated cotton cloth was then evaluated for germicidal activity, along with the following control samples of cotton fabric.

Sample A: x 80 untreated cotton fabric (no treatment with N-hydroxymethylpyrrolidinone) but treated with iodine in the manner described above.

Sample B: 80 x 80 cotton fabric treated as described above with N-hydroxymethylpyrrolidinone and then treated with iodine as described above.

This germicidal activity evaluation was conducted by both a use dilution test .and a zone of inhibition test. The procedures of these tests were as follows:

Use dilution test Ten 2 x 2 cm. swatches of each of the treated cloths were placed in sterile petri dishes. 0.1 cc. of 1:1,000 dilution of a 24 hours broth culture of S. aureus ATCC6538 was placed on each swatch and the petri dishes then placed in an incubator at 37 C. for 15 minutes. At the end of the 15 minutes contact time, the inoculated swatches of cloth were removed to tubes containing 10 cc. of FDA broth using sterile forceps and these tubes incubated at 37 C. for 24 hours at which time they were recorded as positive or negative from the standpoint of turbidity.

To eliminate the possibility of turbidity due to the bacteriocidal agent on the cloth or the possibility of an apparent negative result being bacteriostatic rather than a bacteriocidal effect, transfers of 0.1 cc. were made to new FDA broth tubes from the 24 hour tubes which contained the cloth. These transfers were incubated for an additional 24 hours at 37 C. at which time the final readings were taken from both sets of tubes.

Zone of inhibition test USE DILU'IION TEST Number of tubes negative out of 10 Initial Transfers Sample A 10 10 Sample B 10 10 3 4 Zone of inhibition, average zone size: iodine monobromide will also combine with the N-hydroxyrnethylpyrrolidinone treated fibers and to be retained thereby for a substantial period of time so as to produce a germicidically active fibrous material substantially free of irritating or sensitizing characteristics fre- Sample A, trace Sample B, 3-4 mm.

Conclusions: As tested, both materials exhibit the same degree of biletefioeidal action in the broth Y quently found in the germicidal agent itself or when presever, in the agar system, Cloth B exhibits a much greater m on other b t te, bacteriocidal action than Cloth A. It will also be understood that while fibrous material EXAMPLE 2 treated with l I-hyclroxymethylpyrrolidinone was employed in the foregoing examples and represents a preferred form Samples of both the Cotton gauze matel'lal and of fibrous material for use in the practice of the present the rayon gauze material P p as described above in invention that fibrous materials treated with other N- EXamPIe A, were rolled p and Placed in 16 Wide hydroxymethyl lactams or ethers thereof, more fully demouth glass bottles, aPProXimately inches high and scribed in the above mentioned invention of Randall and 2.5 inches in diameter in such a manner that the outer Freyermuth Sen 502 387 O 22, 1965, may be Surface of a gauze band touched the Surrounding inner used in practicing in the present invention. Thus, there curved Surface of the bottle; in the center of each of the may be used cellulosic materials treated as described in rolls of gallZe was carefully enclosed 10 beaker on said application with an Nhydroxymethyl lactam of the top of which was placed a 5 ml. beaker containing iodine f l crystals. The bottles were then tightly capped and sealed with a small sheet of polyethylene under the cap, and the bottles and their contents were placed in an electric oven CH: 00 and heated to 90 C. for 4 hours. After cooling to room temperatures, the germicidal bandage material was re- A I moved from the bottles and hung on a line in the atmos- Phete for one hour before beginning Stability teStS- The and ring carbon-lower alkyl substituted derivatives there- Peteeht y Weight of iodine, based on the Weight of the of, wherein R represents an alkylene bridge such as, for gauze material, contained in the 5 ml. beaker and also example, ethylene, propylene, butylene, necessary to comthfi precent by weight Of elemental iodine and 21S (16- lete a 5 to '7 membered heterocyclic ring; and R reptefmihed by analysts to be Present in the gaule, both resents hydrogen or lower alkyl such as methyl, ethyl, initially and after storage and is given in the following o yl, isopropyl, butyl, isobutyl, and the like. As exam- Tahle ples of such N-hydroxymethyl lactams may be mentioned,

TABLE I in addition to N-hydroxymethylpyrrolidinone, the following.

Sample 1 2 Pyrrolidones:

N-methoxymethyl pyrrolidinone-Z Mammal Comm Rayon 3,3-dimethyl-N-hydroxymethylpyrrolidinone-Z Percent dine in 5 P 50 50 3,3,5-trimethyl-N-hydroxymethylpyrrolidinone-2 i t Found (mmany) 3132 8; 8 3,3,5 -trimethyl-N-methoxymethylpyrrolidinone-Z Percent HI-aiter 9 days at 40 C. o e bottle 0.29 0. 14 Percent Iz-after 9 days at 40 C. op n oottlm 0.20 0. 09 p top 5 methyl N hydroxymethylpyrrohdmone 2 gerecnt II-fafter go days 0 0 open some--. 22 0. 1e Plp n on ercent ater2 a sa .0 en otte-.- .19 0.07 Percent H I atter 9 da ys at 25 0. s aled bottle..- 0. 76 0. 16 N hydroxymethylp 1? en.d0ne 2 Percent Ihmer 9 days at 25 0. sealed bottle 0. 20 0. 00 N-methoxymethy1p1per1done-2 4,4-dimethyl-N-hydroxymethylprpendone-Z EXAMPLE 3 6-propyl-N-methoxymethylpiperidone-2 4,4-dimethyl-N-ethoxymethylpiperidone-2 Epsilon-caprolactams:

3,3,5-trimethyl-N-hydroxymethyl-E-caprolactam 5O N-hydroxymethyl-E-caprolactam N-methoxymethyl-E-caprolactarn 4,4-dimethyl-N-ethoxymethyl-E-caprolactam 2.5 g. iodine crystals were dissolved in 250 ml. solvent at room temperature with stirring. Cotton gauze (from Example A) was padded with the aforementioned tincture of iodine and squeezed through rubber pressure rollers so that the wet pick-up by the gauze was 66% (by weight). The padded gauze was dried in air at room tem- Petatute 15 minutes and then Was given One of the The N-hydroxymethyl lactam treated fibrous material, following treatments: employed in practicing the present invention, preferrably Heat cured 3 minutes at in an OVeII- contains about 5% by weight of the N-hydroxymethyl lac- Heat Cured ill a Sealed container at fOr 4 tam combined with the fibers. However, the N-hydroxyhours. methyl lactam treated fibrous materials have the prop- (C) Heat cured in an open vessel at 90 C. for 4 erty of combining with halogen containing germicidal hours. agents when the Nhydroxymethyl oxide content thereof The analytical results are indicated on the attached is varied over relatively wide ranges, and effective prod- Table II. ucts have been produced using fibrous materials having TABLE II Heat Wt. percent 12 on Wt. percent I2 Wt. percent HI 0n Sample curing Solvent Wt. percent 12 in Wt. percent in cloth before retained by cloth after treatment solvent pick-up by cloth curing treatment cloth after curing treatment curing treatment A 1 23 65.8 0. 81 0.28 0.59 B 1. 23 65.8 0. 81 0. 30 0. 80 C 1.23 92.0 1 14 0.70 0.27 A 0 02 74.0 0 4e 0. 01 0. 23 B 0. 02 74. 0 0 40 0. 42 0.10 C 0 02 150. 0 0 0. 02 0. 07

While iodine was employed in the foregoing examples combined therewith from about 2% to 10% by weight as a preferred germicidal agent, it should be understood of N-hydroxymethyl lactam. Likewise, the amount of that the interhalogen adducts, iodine monochloride and halogen containing germicidal agent employed in practicing the present invention may be varied at relatively wide ranges. About 0.5% of the germicidal agent by weight is preferred but products containing as low as 0.1% of germicidal agents, have been found to be effective. The maximum amount of germicidal agent which can be combined with the N-hydroxymethyl fibrous treated material will vary substantially directly with the amount of N-hydroxymethyl lactam combined with the fibrous material. An amount of germicidal agent corresponding to of the amount of N-hdroxymethyl lactam combined with the fibrous material can readily be incorporated in the products as illustrated by the foregoing examples. Larger amounts of up to 20 to 25% by weight of the N-hydroxymethyl lactam have, however, been successfully incorporated in the final products.

What is claimed is:

1. A process for producing germicidal fibrous materials which comprises applying a halogen containing germicidal agent selected from the group consisting of iodine, iodine monochloride and iodine monobromide to cellulosic fibrous material obtained by reacting a lactam derivative of the formula I CHnO R and ring carbon-lower alkyl substituted derivatives thereof, and wherein R represents a lower alkylene group necessary to complete a 5 to 7 membered heterocycle and R is selected from the group consisting of hydrogen and lower alkyl, and then drying and curing the fibrous material at a temperature of at least about 120 C.

2. A process as defined in claim 1 wherein the lactam is N-hydroxymethylpyrrolidinone-2.

3. A process as defined in claim 2 wherein the germicidal agent is iodine.

4. A process as defined in claim 3 wherein the fibrous material is heated to a temperature of about C. following the application of iodine thereto.

5. A germicidal fibrous material produced according to the process in claim 1.

6. A germicidal fibrous material produced according to the process in claim 4.

References Cited UNITED STATES PATENTS 3,136,755 6/1964 Grosser et al 167-386 X FOREIGN PATENTS 1,070,588 12/ 1959 Germany.

NORMAN G. TORCHIN, Primary Examiner. I. C. CANNON, Assistant Examiner.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US3136755 *Dec 1, 1960Jun 9, 1964Gen Aniline & Film CorpInsoluble polymeric-iodine complexes
DE1070588B * Title not available
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US4355021 *Oct 29, 1980Oct 19, 1982S. C. Johnson & Son, Inc.Virucidal wipe and method
US4381380 *Nov 3, 1980Apr 26, 1983Leveen Harry HThermoplastic polyurethane article treated with iodine for antibacterial use
US4769013 *Jun 4, 1986Sep 6, 1988Hydromer, Inc.Bio-effecting medical material and device
US5344411 *Nov 3, 1993Sep 6, 1994Leonard BloomMethod and device for inhibiting HIV, hepatitis B and other viruses and germs when using a catheter in a medical environment
US5591350 *Nov 7, 1995Jan 7, 1997Pall CorporationIodine disinfection method using a gaseous iodine treated porous medium
US6077319 *Jun 22, 1998Jun 20, 2000The Regents Of The University Of CaliforniaProcesses for preparing microbiocidal textiles
US6096216 *Mar 7, 1997Aug 1, 2000American National Red CrossIodinated matrices for disinfecting biological fluids
US6106773 *Sep 24, 1998Aug 22, 2000American National Red CrossPathogen inactivating compositions for disinfecting biological fluids
US6241783Oct 8, 1999Jun 5, 2001The Regents Of The University Of CaliforniaFormaldehyde scavenging in microbiocidal articles
US6770287Jun 19, 2000Aug 3, 2004The Regents Of The University Of CaliforniaBiocidal cellulosic material
EP0942649A1 *Sep 12, 1997Sep 22, 1999The Regents Of The University Of CaliforniaDurable and regenerable microbiocidal textiles
EP0942649A4 *Sep 12, 1997Oct 11, 2000Univ CaliforniaDurable and regenerable microbiocidal textiles
WO1982001469A1 *Oct 26, 1981May 13, 1982& Son Inc S C JohnsonVirucidal wipe and method
WO1988002985A1 *Sep 24, 1987May 5, 1988Gaf CorporationQuaternized nitrogen containing compounds
WO2001097617A1 *Jun 14, 2001Dec 27, 2001The Regents Of The University Of CaliforniaBiocidal cellulosic material
U.S. Classification8/189, 514/211.3, 8/115.68, 8/182, 442/123, 8/115.57, 424/723, 514/315, 427/394, 514/424, 424/404, 424/667, 428/907
International ClassificationD06M16/00, D06M13/418, A61L15/18
Cooperative ClassificationA61L15/18, D06M13/418, Y10S428/907, D06M16/00
European ClassificationA61L15/18, D06M16/00, D06M13/418