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Publication numberUS3817702 A
Publication typeGrant
Publication dateJun 18, 1974
Filing dateDec 2, 1970
Priority dateDec 16, 1969
Also published asDE1962899A1, DE1962899B2, DE1962899C3
Publication numberUS 3817702 A, US 3817702A, US-A-3817702, US3817702 A, US3817702A
InventorsW Paulus, O Pauli
Original AssigneeBayer Ag
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Antimicrobial textile materials
US 3817702 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

United States Patent 3,817,702 ANTIMICROBIAL TEXTILE MATERIALS 'Wilfried Paulus, Krefeld-Bockum, and Otto Pauli, Krefeld, Germany, assignors to Bayer Aktiengesellschaft, Leverkusen, Germany No Drawing. Filed Dec. 2, 1970, Ser. No. 94,532 Claims priority, application Germany, Dec. 16, 1969,

Int. Cl. D06m 13/00 vs. C]. 8- 120 16 Claims ABSTRACT OF THE DISCLOSURE Textile materials containing reactive hydrogen sites, e.g. cellulosics such as cotton, are treated with compounds which, through reaction with the reactive hydrogen sites, introduce anion-active sites. These anion-active sites are thereafter chemically combined in salt form With cationactive microbicides. For example, a cotton fabric is reacted with the chlorine atoms of p-N(4,6-dich1oro)-striazinylaminobenzene-carboxylic or -sulfonic acid and the acid group is thereafter reacted with a bactericidal quaternary ammonium salt or an N-chloro-phenyl-alkylene polyamine.

, The resulting products are bactericidal, free from attack by mildew and suitable for autosterile surgical dressings.

The present invention relates to the antimicrobial finishing of textile materials, especially cellulose-containing textile material.

Textile articles are often prone to attack by microorganisms such as mildew, fungi, and the like, resulting in discoloration, odor and, frequently, destruction. Attempts have been made to overcome this problem by impregnation with various agents but this is often attended by a change in hand, e.g. stiffening, by its own change in color, loss of abrasion resistance, etc. Moreover, the treatment is not permanent, the agent being lost in washing or dry cleaning. It is accordingly an object of the present invention to provide textile materials which are resistant to microorganisms but retain all the usual desirable characteristics of textiles and which, further, permanently retain the desired properties.

These. and other objects and advantages are realized in accordance with the present invention which provides a process wherein the textile material is linked chemically with a reactive ionic substance, whereby it is made partially anion-active, and the resulting partially anion-active textile material is finished by treatment with a cationactive microbicide.

Any textile material having a reactive hydrogen may be used for the instant purposes including cotton, rayon, paper, cellulose acetate, polyvinyl alcohol, wool, and the like, the cellulosics being especially preferred.

As examples of reactive ionic substances which can be linked chemically with the textile material, for example cotton, so that a lastingly, partially anion-active textile material is formed, there may be mentioned p-N(4,6-dichloro-)s-triazinyl-aminobenzoic acid and p-N-(4,6-dichloro-)s-triazinyl-aminobenzene-sulfonic acid as well as monochloroacetic acid, chloromethylphosphonic acid and unsaturated aliphatic carboxylic acids, for example haloacrylic acids and acetylenemonoor dicarboxylic acid. Such compounds aifix themselves to the textile base by losing their halogen atoms which react with the reactive hydrogen of the base or by condensation at the unsatu- 3,817,702 Patented June 18, 1974 without loss of anti-microbial effectiveness, bactericidal quaternary ammonium salts and N-chloro-phenyl-alkylenepolyamines are suitable; for example benzyl-dimethyltetradecylammonium chloride, 3,4-dichlorobenzyl-dimethyl-dodecylammonium chloride, N -pentachlorophenyl-N dimethylbenzyltrimethylenediaminium chloride, N -pentachlorophenyl-N -dimethyl-(3,4-dichloro)benzyl trimethylenediaminium chloride (cf. Deutsche Offenlegungschrift (German Published Specification) 1,493,745) and N pentachlorophenyl hexamethylenediamine acetate (cf. Belgian Patent Specification 725,992).

The production of partially anion-active material, for example, cotton fabric, can be effected by treating the fabric with a 2-5 strength alkaline-aqueous solution of the reactive ionic substances concerned, possibly with addition of an electrolyte (for example NaCl, Na SO for 10-40 minutes at 40-60 C. It is also possible to proceed by impregnating the fabric at room temperature with an alkaline-aqueous solution of the reactive ionic substances concerned, subsequently squeezing off and, possibly after a preliminary drying at about 70 C., thermofixing at l50 C.

The subsequent fixation of the cation-active microbicide concerned may be effected by causing it to be absorbed by the alkaline-reacting, partially anion-active textile material from an aqueous solution for about half an hour at 50-60 C.; squeezing off may then be effected and the textile material freed from unfixed portions of active compound by washing. The amounts of cation-active microbicides required for the lasting antimicrobial finishing of partially anion-active textile material are governed by what is demanded of the finish, and can in each case be readily ascertained by preliminary experiments; in general, 0.251% in the treatment bath is sufiicient.

The cation-active microbicides concerned are absorbed better and more lastingly on partially anion-active textile material than on normal textile material; the antimicrobial finish of textile material attainable with the aid of the process according to the invention is therefore distinguished by a particularly high fastness to washing.v

It is quite surprising that the textile materials produced in accordance with the invention are microbicidal since it might have been expected that the agents would lose their potency when tied to the textile material in salt formation. To the contrary, with the aid of the process according to the invention, certain hygiene problems, such as may occur in textile materials, can be successfully solved. The process is useful in the control of pathogenic bacteria and fungi, as well as in avoiding or reducing cross-infections during laundering or other cleaning. The process according to the invention permits the production of autosterile dressings and other microbicidal textile material which can be used in hospitals, for example for wrapping sterilized surgical instruments, or in bacterio EXAMPLE 1 De-sized cotton fabric is treated at 40 C. with a suspension of 2% p-N-( 4,6-dichloro) s triazinylaminobenzoic acid (I) in water which also contains 0.05%

of a non-ionic wetting'agent; liquor ratio 1:20. After 20 minutes a clear solution is formed, in which 1% sodium carbonate and 30% sodium chloride are dissolved; after a further 25 minutes at 40 C., the fabric is taken out, squeezed off and transferred for 30 minutes at 40 C. to a bath which contains 0.75% 3,4-dichlorobenzyldimethyldodecylammonium chloride (II); liquor ratio 1:16. Thefabric is then squeezed off, rinsed, soaped (10 minutes boiling in a 0.1% strength solution of an anion-active detergent, liquor ratio 1:20) and watered (24 hours, 20 C., changes of water per hour, liquor ratio 1: 100). Despite these stresses, the fabric is eminently rot-proof; after 14 days storage in compost soil, the losses of resistance to tearing are less than 3% As against this, fabrics which are treated with (I) or (II) alone in the manner stated above rot completely (loss of resistance to tearing =100%) after these stresses.

EXAMPLE 2 De-sized cotton fabric is treated as stated in Example 1, but instead of (I), p-N-(4,6-dichloro)-s-triazinylaminobenzenesulfonic acid is used, and instead of 0.75% (II),

0.5% (II) is used. After rinsing, the fabric is soapecl at EXAMPLE 3 De-sized cotton fabric is impregnated (2 passages) at room temperature with a freshly prepared solution which, per liter contains 50 g. NaOH, 25 g. chloroacetic acid and 1 g. of a non-ionic wetting agent. The fabric is subsequently dried at 120-140 C. for thermofix-ation and then transferred to a bath having a temperature of 55 C. and containing, per liter, 2.5 g. N -pentachlorophenylhexamethylenediamine acetate; liquor ratio 1: 15. The pH of the bath is adjusted to 8.5 after introduction of the fabric. After 30 minutes, the fabric is squeezed off, rinsed and, in the manner indicated in Example 1, watered twice for 24 hours. Even after this stress, the fabric is still outstandingly rot-proof; after 14 days storage in compost soil, the losses of resistance to tearing are, on average, only about 8% compared with 53% in the case of a not partially carboxymethylated fabric which was treated in the same manner with N -pentachlorophenylhexamethylenediamine acetate.

EXAMPLE 4 De-sized cotton fabric is treated as stated in Example 3, with the difference that N -pentachlorophenyl-N -dimethylbenzyltrimethylene diaminium chloride is used g./liter) as cation-active compolmd and there is no regulation of pH. After rinsing, the fabric is, in the manner indicated in Example 1, watered and tested for resistance to rotting; the losses of resistance to tearing are, on average, 2% compared with 100% and 88% respectively, in the case of a fabric which was only partially carboxymethylated and a fabric which was only treated with the cation-active compound. If the fabric is tested, as stated in Example 2, for anti-bacterial effectiveness, it is shown that, even after soaping 5 times with a non-ionic detergent, the anti-bacterial efliectiveness is retained intact. As against this, a fabric which is not carboxymethylated, but impregnated with the cation-active compound, exhibits no anti-bacterial effectiveness after rinsing and washing.

EXAMPLE 5 De-sized cotton fabric is treated and tested for resistance to rotting in the manner indicated in Example 3 except that, as cation-active compound, N -pentachlorophenyL-N- -dimethyl (3,4-dichloro) benzyltrimethylenediaminium chloride is used (5 g./liter). The losses of resistance to tearing are on average, 4%, compared with 82% in the case of a fabric which was only treated with the cation-active compound.

'4. EXAMPLE 6 De-sized cottom fabric is treated as stated in Example 5, with difference that not 5 g./liter but 10 g./liter of cation-active compound are used. After rinsing and watering, the fabric is 12 times soaped at the boil or washed 12 times with a commercial cold-washing agent and then, in the manner indicated in Example 2, tested for anti-bacterial effectiveness. In both cases, the fabric still possesses a good anti-bacterial effectiveness. A fabric which was not carboxymethylated and was only treated with the cation-active compound, however, no longer shows any anti-bacterial effectiveness after soaping 5 times or cold-washing 5 times.

EXAMPLE 7 De-sized cotton fabric is impregnated (3 passages) at room temperature with a freshly prepared solution which contains per liter, 70 g. NaOH and 50 g. chloromethylphosphonic acid. After squeezing off, drying at ISO-140 C. is effected, followed by thermofixation for a further 5 minutes at 130-140" C., before the fabric is transferred for 30 minutes to a bath which, per liter, contains 10 g. benzyldimethyltetradecylammonium chloride. After rinsing and Watering twice in the manner indicated in Example 1, testing for resistance to rotting is effected: the tear value losses are, on average, 3%. As against this, a fabric treated only with chloromethylphosphonic acid or only with the cation-active compound rots completely loss of resistance to tearing).

EXAMPLE 8 De-sized cotton fabric is impregnated (3 passages) with a solution which, per liter, contains 200 g. NaOH, 50 g. acetylenedicarboxylic acid and 1 g. of a non-ionic wetting agent. After squeezing otf, drying at 100 C. is effected, followed by thermofixation for 10 minutes at 100 C. Treatment with cation-active compound is then carried out in the manner indicated in Example 2.

Before testing for rot resistance as indicated in Example l, the fabric is watered twice for 24 hours. The fabric proves to be so rot-resistant that no measurable loss of rot resistance occurs. Moreover, the fabric is outstandingly anti-bacterially effective, even after soaping 12 times with a non-ionic detergent; 4 times soaping at the boil with an anion-active detergent likewise does not adversely affect the anti-bacterial effectiveness.

As can be seen from the foregoing examples, the textile material can be rendered anion-active by a treatment in fabric form. Alternatively, the treatment can be carried out on the textile in the form of a yarn or staple fibers. In the case of synthetic fibers, it is even posible to carry out the treatment at the resin stage or possible even during the formation of the resin as by copolymerization.

The treatment with the cationic microbicide can similarly be carried out at various stages of processing such as on finished garments, fabrics, yarns, fibers, resins or even monomers. The cationic microbicide treatment can immediately follow the treatment to render the material anion-active or it can be carried out one or more steps later.

The number of anion-active sites can be varied widely and the particular selection will depend upon the type and extent of microbicidal treatment desired. In addition, if it is intended to use the anion-active textile material in the form of a blend, its content of anion-active sites will have to be greater to impart the desired level of activity to the resulting product. The degree of substitution, however, should not be so great that the usual desirable properties of the textile material suffer unduly. The eflicacy and purpose of the microbicidal agent attached to the anionactive site is also significant. Thus stronger agents can be utilized in lesser amounts; if it is merely desired to prevent growth of undesirable organisms a lesser amount is needed than if it is desired that the textile material actively attack undesired microorganisms in the vicinity. In addition, the microbicidal agent need not be employed in such quantity as will form salts with all of the anion-active sites, i.e. the desired level of microbicidal activity may be achieved with only some of the anion-active sites neutralized with microbicide.

It will be appreciated that the instant specification and examples are set forth by way of illustration and not limitation, and that Various modifications and changes may be made without departing from the spirit and scope of the present invention.

What is claimed is:

1. The process for imparting antimicrobial properties to a textile material containing anion-active sites formed by treatment of a textile material selected from the group consisting of cotton, rayon, paper, cellulose acetate, polyvinyl alcohol and wool with an acid having an active site selected from the group consisting of chlormethylphosphonic acid a haloacrylic acid and acetylene monoor dicarboxylic acid, which comprises reacting said textile material with a microbicidal quaternary ammonium salt or an N-chlorophenyl-alkylene polyamine, whereby said rnicrobicide forms a salt with the textile material at said anionactive sites.

' 2. A process according to claim 1 in which the textile material is chemically linked with the reactive compound by treating it with an about 2-S% strength alkaline aqueous solution of the reactive compound for about -40 minutes at about 40-60 C.

3. A process according to claim 2 in which the alkaline aqueous solution contains an electrolyte.

4. A process according to claim 3 in which the electrolyte is sodium chloride or sodium sulfate.

5. A process according to claim 1 in which the textile material is chemically linked with the reactive compound by being impregnated at room temperature with an alkaline aqueous solution of the reactive ionic substance followed by squeezing oflf and thermofixing at about 100- 150 C.

6. A process according to claim 6 in which the material undergoes a preliminary drying at about 70 C. after squeezing OE and before thermofixing.

7. A process according to claim 1 in which the microbicide is fixed to the anion-active textile material by being absorbed thereon from an aqueous solution in which the textile material is maintained at about 50-60" C., followed by squeezing 011 and washing ofi unfixed portions of active material.

8. A process according to claim 7 in which the aqueous solution contains about 0.25 to 1% of the cation-active microbicide.

9. A process according to claim 1 in which the textile material is cellulosic.

10. A process according to claim 9 in which the textile material is a cotton-containing fabric.

11. A process according to claim 1 in which said textile material comprises a cellulosic material and is rendered anionic-active by being impregnated at room temperature with an about 1-5% strength alkaline solution of acid, the solution containing sodium chloride or sulfate, the textile material being treated for about 10-40 minutes at about 40-60 C., then being squeezed oif, thermofixed at about IOU- C., and the cation-active microbicide fixed to the anion-active textile material by being absorbed thereon from an about 0.25 to 1% solution in which the textile material is maintained for about half an hour at about 50-60 C., followed by squeezing oil and washing olf unfixed portions of active material.

12. The textile material produced by the process of claim 1.

13. Textile material according to claim 12 wherein said textile material is cellulosic.

14. The process according to claim 1 wherein the acid having an active site is chlormethyl-phosphonic acid.

15. The process according to claim 1 wherein the compound having an active site is a haloacrylic acid, acetylene monoor di-carboxylic acid.

16. The process of imparting antimicrobial properties to a textile material containing anion-active sites formed by treatment of a textile material selected from the group consisting of cotton, rayon, paper, cellulose acetate, polyvinyl alcohol and wool, with monochloracetic acid, which comprises reacting said textile material with an N-chlorophenyl-alkylene polyamine to form a salt thereof with the textile material at said anion-active sites.

References Cited UNITED STATES PATENTS 3,542,504 11/1970 Schofield et al. 117-1385 2,681,846 6/1954 Guthrie et al. 8120 2,729,535 l/ 1956 Balassa et al 8116 2,979,374 4/1961 Drake et al 81 16 3,294,779 12/ 1966 Bullock et al 8116 3,074,814 1/1963 Sause et al. 117l38.5 2,617,707 11/ 1952 Daul et al 8120 UX 3,227,614 1/ 1966 Scheuer 424-25 OTHER REFERENCES The Merck Index of Chemicals and Drugs, seventh edition, 1960, p. 676.

Gagliardi, American Dyestutf Ref., Ian. 22, 1962, pp. 31-40.

DONALD LEVY, Primary Examiner US. Cl. X.R.

Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US4090844 *Jun 23, 1977May 23, 1978The United States Of America As Represented By The Secretary Of AgricultureProcess of producing high performance durable-press cotton
US4259383 *Jun 26, 1979Mar 31, 1981Sterling Drug Inc.Disinfecting tissue
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US6962608Sep 29, 2003Nov 8, 2005The Regents Of The University Of CaliforniaRegenerable antimicrobial polymers and fibers with oxygen bleaches
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US8962027Jun 19, 2008Feb 24, 2015Rynel Inc.Materials comprising water-soluble polymer particles and methods of making and using them
US20050014436 *Jun 18, 2004Jan 20, 2005Michael BrierProcess for producing fabric articles having water-resistant and/or antimicrobial characteristics
US20090069210 *Feb 8, 2007Mar 12, 2009Henkel Ag & Co. KgaaColour-protecting laundry detergent composition
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Classifications
U.S. Classification8/120, 8/127.1, 424/404, 424/443, 427/354, 424/445, 8/115.59, 427/381, 428/907, 427/369, 8/115.64, 424/414
International ClassificationD06M16/00
Cooperative ClassificationY10S428/907, D06M16/00
European ClassificationD06M16/00