US3437419A

US3437419A - Cellulosics sanitized through reaction with triazone substituted with biologically active quaternary ammonium salt

Info

Publication number: US3437419A
Application number: US426422A
Authority: US
Inventors: Sidney Cohen; Edward Griffin Shay
Original assignee: Millmaster Onyx Corp
Current assignee: Millmaster Onyx Corp; Millmaster Onyx Group Inc
Priority date: 1965-01-18
Filing date: 1965-01-18
Publication date: 1969-04-08
Anticipated expiration: 1986-04-08

Description

United States Patent 3,437 419 CELLULOSICS SANITIZEfi THROUGH REACTION WITH TRIAZONE SUBSTITUTED WITH BIO- LOGICALLY ACTIVE QUATERNARY AMMONI- UM SALT Sidney Cohen, Fair Lawn, and Edward Grifiin Shay, Belle Mead, N.J., assignors to Millmaster Onyx Corporation,

New York, N.Y., a corporation of New York No Drawing. Filed Jan. 18, 1965, Ser. No. 426,422 Int. Cl. A61l13/00, 1/00; D06m 11/00 U.S. Cl. 8116.3 7 Claims This invention relates to durable microbicidal agents for cloth, paper and other fabrics or the fibers from which they are constructed.

An object of the invenion is to synthesize antimicrobial compounds of a nature suitable for application to such materials.

Another object of the invention is to apply the said antimicrobial agents to the fibers in such manner as to fix them thereon so as to resist depletion of the said agents by repeated laundering or dry-cleaning.

A further object of the invention is to obtain fabrics or fibers which are self-sanitizing; that is to say, which will prevent the propagation of microorganisms thereon, and which will kill microorganisms with which they may become contaminated by air-borne matter, or upon being worn in the form of garments, or by handling or by other means.

The agents with which the above objects can be accomplished are of the class of thermosetting cyclic organic compounds of the triazinone type, containing as a part of their structure a germicidally potent quaternary ammonium salt of an integral acid group. These triazinones are derived from 1,3 dimethylol tetrahydro-s-triazin-Z-one which contains in the -position a radical having a terminal acidic group.

They conform, in general, to the following structure:

wherein R is an aliphatic, alicyclic or aromatic radical bearing the residue of an acidic group such as carboxylic, sulfonic, sulfuric, phosphoric and the like, and Z is the cation of a quaternary ammonium salt.

Triazinones are well known to the art, and may be prepared by reacting urea, an aldehyde and a primary amine. A typical preparation is described in Self-Smoothing Fabrics, by J. T. Marsh, p. 77 (Chapman and Hall Ltd., 1962). Triazinones containing an acid radical have also been described as Well as their silver, mercurial and other metal salts.

Germicidal quaternary ammonium salts such as the halides have been found to be substantive to cloth, and particularly to cellulosic fabrics, which are thereby rendered self-sanitizing. Ordinary laundering, however, removes the germicide in one or, at most, a very few washings with either soap or synthetic detergents.

We have now found that we can render a fabric durably self-sanitizing and that this antibacterial effect persists after repeated launderings, by treating it with a quaternary triazinone compound having the structure described above,

and heating it in the presence of a suitable acidic catalyst to fix the triazinone to the cellulose by cross-linking.

Triazinone salts of this type may be prepared by heating urea and formaldehyde or other aldehyde with the alkali-metal salts of organic acids containing a primary amino group such as glycine, aminobutyric acid, sulfanilic acid, aminobenzoic acid and the like. The corresponding microbicidal quaternary ammonium salts may then be prepared by metathesis. Upon reacting them in solution with quaternary ammonium halides or other suitable salts, the quaternary ammonium triazinone salts separate out as a liquid or a solid phase which can be thus isolated and, if desired, further purified; however, such after-treatment is usually unnecessary.

Alternatively, a quaternary ammonium hydroxide or salt may be reacted with an amino-substituted acid or its alkali-metal salt to yield the quaternary ammonium amino-substittued organic salt which can be segregated as described in pending applications, Ser. Nos. 323,598 and 357,281, filed on Nov. 12, 1963 and Apr. 3, 1964, respectively, now Patent Nos. 3,299,073 and 3,361,792, respectively. The resultant amino compound may then be reacted with urea and formaldehyde to form the corresponding substituted triazinone, or with dimethylol urea to form the triazinone compound unsubstituted in the 1,3- positions which may then be further reacted with formaldehyde to form the 1,3-dimethy1o1triazinone compound.

Typical examples of the quaternary ammonium compounds which may be used in this invention are the alkyl trimethyl ammonium chlorides, alkyl-benzyl trimethyl ammonium chlorides, alkyl dimethyl benzyl ammonium chlorides, alkyl dimethyl menaphthyl ammonium chlorides, alkyl dimethyl substituted-benzyl ammonium chlorides in which the benzyl radical is substituted with one or more side chains containing from 1 to 5 carbon atoms such, for example, as methyl, dimethyl, ethyl and the like and in which the carbon atoms may all be in the same or dilferout side chains or in which the benzyl radical bears one, two or more halogen atoms such as chlorine or bromine, alkyl pyridinium chlorides, alkyl isoquinolinium chlorides and bromides, alkyl lower-alkyl pyrrolidinium chlorides, alkyl lower-alkyl morpholinium chlorides in all of which the alkyl group may have from 8 to 22 carbon atoms and the lower-alkyl group may have from 1 to 4 carbon atoms and alkyl phenoxy ethoxy ethyl dimethyl benzyl ammonium chloride in which the akyl radical may be iso-octyl or nonyl and in which the phenyl radical may, if desired, be substituted by a methyl radical. Various other analogs of these quaternaries may also be employed such, for example, as cetyl dimethyl ethyl ammonium bromide or oleyl dimethyl ethyl ammonium bromide.

In general, the quaternary ammonium compounds useful in this invention are the higher alkyl quaternary ammonium hydroxides, halides (chlorides and bromides), sulfates, methosulfates and the like possessing the following formula:

where R is an alkyl or alkaralkyl radical containing from 8 to 22 carbon atoms or an alkyl phenoxy ethoxy ethyl radical in which R is an alkyl radical containing from 8 to 9 carbon atoms and in which the phenyl radical may be substituted by a methyl group; R and R are methyl or ethyl radicals or members of a heterocyclic ring system such as pyridine, isoquinoline, pyrrolidine and morpholine; R' is a methyl radical or a benzyl group or a substituted-benzyl group such, for example, as a monochlorobenzyl radical or a dichlorobenzyl radical or mixture thereof or a methyl benzyl, dimethyl benzyl, ethyl benzyl, diethyl benzyl, isopropyl benzyl, tertiary butyl benzyl or another benzyl radical containing from 1 to carbon atoms as side chains, either as a single side chain or a multiplicity of side chains including mixtures thereof or a menaphthyl group or hydrogenated menaphthyl group. When R and R are members of a morpholine or pyrrolidine ring, R is a methyl, ethyl, propyl or butyl group. When R and R are members of an unsaturated heterocyclic ring such as pyridine or isoquinoline, R' is the same radical as R". X in the above formula corresponds to a halide radical such as chloride, bromide or iodide or to any other water-soluble anion such as methosulfate.

'In general, we prefer to use such quaternary ammonium compounds which have a phenol coeflicient of at least 100 with respect to both Staphylococcus aureus and Salmonella typhosa at 20 C. when determined by the standard method given in the Ofiicial Methods of Analysis of the Association of Ofiicial Agricultural Chemists, ninth edition (1960), p. 63 et seq.

The following examples of methods of preparing, applying and testing the intermediates and the products of this invention are illustrative only, and are not to be considered as limiting the invention, which may be modified or varied within the spirit and scope of the claims.

Example I One mol of urea was dissolved in 400 grams or 3.2 mols of formalin solution in a three-neck flask fitted with an agitator, a reflux condenser and a dropping funnel. The temperature thereupon fell to C. A solution of 75 grams of 0.6 mol of taurine (2-aminoethane sulfonic acid), 60 grams of water and 48 grams or 0.6 mol of 50% sodium hydroxide solution was charged into the dropping funnel, whence it was added gradually to the agitated urea-formaldehyde solution. An exothermic reaction occurred. The reaction was continued for one hour under reflux at about 95 C. until the reaction was essentially complete and the free formaldehyde content was less than 1%. The product contained 0.6 mol of 1,3- dimethylol-tetr'ahydro 5 (sodium sulfoethyl)-s-triazin- 2-one, at a concentration of about 35%. After cooling, the solution was clarified by filtration through paper.

Example II The reaction according to Example I was carried out without excess of urea and formaldehyde. A solution of sodium tauride was prepared by dissolving 125 grams or 1 mol of 2-aminoethane sulfonic acid and 80 grams of 1 mol of 50% sodium hydroxide solution in 400 grams of water. This solution was added gradually to a solution of 60 grams of 1 mole of urea in 324 grams or 4 mols of Formalin solution, with agitation, and at about 60 C. The reaction mixture was then heated at the refluxing temperature for one hour until the free formaldehyde content was 1.45%. The product, 1,3-dimethylol-tetrahydro- S-(sodium sulfoethyl)-s-triazin-2-one of molecular weight 291, was obtained in 30% concentration.

Example III By substituting 173 grams or 1 mol of sulfanilic acid for the taurine of Example II, and conducting the reaction in a similar manner until the residual formaldehyde content was 2.9%, a 30% solution of 1,3-dimethy1ol-tetrahydro-S-(sodium p-sulfophenyl)-s-triazin-2-one of molecular weight 339 was obtained.

Example IV A solution containing 1 mol of sodium m-aminobenzoate was prepared by dissolving 137 grams of m-benzoic acid in 181 grams of water and 80 grams of 50% sodium hydroxide. This was reacted as in Example II with 60 A 40% solution of 1,3-dimethylol-tetrahydro-S-(sodium carboxymethyl)-s-triazin-2-one of molecular weight 241 was prepared in the manner of Example IV, substituting for the sodium aminobenzoate, 218 grams of a solution containing 1 mol of sodium aminoacetate. The filtered product contained 2.8% of unreacted formaldehyde.

Example VI 200 grams of the product of Example I was reacted with an excess of an aqueous solution of alkyl dimethyl ethylbenzyl ammonium chloride (Onyx Chemical Corporations BTC 471 in which the alkyl distribution is 50% C 30% C 17% C 3% C The reaction mixture was shaken in a separatory funnel with 150 ml. of benzene, and the oily layer was removed and dried in a vacuum oven. The product assayed 51% of 1,3-dimethylol-tetrahydro-S-(alkyl dimethyl ethyl-benzyl ammonium sulfoethyl)-s-triazin-2-one, and 48% of alkyl dimethyl ethyl-benzyl ammonium chloride.

Example VII Without further purification, the product of Example VI was applied to x 80 cotton print cloth test fabric as follows:

A 2% aqueous solution of the crude product of Example VI, containing 0.2% by weight of Onyx Chemical Corporations Catalyst ZM (a modified zinc nitrate catalyst containing 20% of zinc nitrate and an organic acid), was applied on a padder to about 75% wet pickup. This solution therefore contained 1% of the alkyl dimethyl ethyl-benzyl ammonium salt of the triazinone and 1% of the alkyl dimethyl ethyl-benzyl ammonium chloride. For a control, the same test fabric was treated with a 1% solution of the alkyl dimethyl ethyl-benzyl ammonium chloride and 0.2% of the Catalyst ZM, applied in the same manner. Both swatches were dried for 2 minutes at 220 F. and cured for 5 minutes at 300 F.

They were then laundered in an automatic washing machine of the household type at 140 F. with Tide (Tide is the registered trademark of the Procter and Gamble Company) and dried in a tumble drier. This process was repeated for ten successive launderings.

The two swatches, and also two corresponding unlaundered swatches, were tested bacteriologically as follows, according to Tentative Test Method No. 100-1961 T of the Technical Manual of the American Association of Textile Chemists and Colorists (1964):

The swatches were inoculated with Staphylococcus aureus according to the requirements of the test, the inoculum load being 214x 10* organisms. The samples were incubated at 37 C. for eighteen hours, after which the swatches were shaken with sterile distilled water. The suspensions were diluted serially and plated in tryptone glucose extract agar and incubated at 37 C. for forty-eight hours. The percentage reduction of the inoculum was calculated in the prescribed manner. A selfsanitizing activity claim calls for a minimum reduction 10f in the number of organisms which were inocuated.

Table I shows the number of organisms recovered; UCT=untreated control fabric; A=unlaundered fabric treated with the product of Example VI and AW=the same after ten launderings; B=unlaundered fabric treated with alkyl dimethyl ethyl-benzyl ammonium chloride and BW=the same after ten launderings; TNC:too numerous to count.

TABLE I Organisms recovered Percent organisms killed 'INO Example VIII Example IX 390 grams of the product of Example II was reacted with an equirnolar amount of an aqueous solution of alkyl dimethyl benzyl ammonium chloride (Onyx Chemical Corporations BTC 824 in which the alkyl distribution is 60% C14, 30% C C 5% C The reaction mixture was shaken in a separatory funnel along with a small quantity of benzene and the organic product layer was separated and vacuum dried. The product, 1,3- dimethylol-tetrahydro-S-(alkyl dimethyl benzyl ammonium sulfoethyl)-s-triazin-2-one, was recovered in 85% of the theoretical yield.

Example X 296 grams of the product of Example 1V was reacted with a molecularly equivalent amount of an aqueous alcohol solution of alkyl isoquinolinium bromide (Onyx Chemical Corporations Isothan Q-75 in which the alkyl distribution is 50% C 30% C 17% C 3% C The reaction mixture was shaken in a separatory funnel with a little benzene and the organic product layer was removed and dried in a vacuum oven. The product, 1,3 dimethylol tetrahydro-S-(alkyl isoquinolinium-mcarboxyphenyl)-striazin-2-0ne, was recovered in substantially the theoretical yield.

Example XI 390 grams of the product of Example V was reacted with an equimolar amount of a solution of the alkyl dimethyl benzyl ammonium chloride of Example IX. The reaction mixture was shaken in a separatory funnel with a little benzene and the organic product layer was removed and dried in a vacuum oven. The product, Lil-dimethyloltetrahydro-S-(alkyl dimethyl benzyl ammonium carboxymethyl-s-triazin-Z-one, was recovered in 82% of the theoretical yield.

The above examples demonstrate the preparation of triazinone compounds containing as an integral part of the molecule a microbicidally active quaternary ammonium group. They also demonstrate that these compounds, like the simpler triazinone compounds from which they are derived, can be permanently aflixed to fabrics and especially to cellulosic fabrics by cross-linking, thus rendering the fabrics self-sanitizing. Furthermore, they show that the germicidal properties of the fabric persist after repeated launderings.

Fabrics and fibers thus self-sanitized may be employed for a number of useful purposes, such as the preservation of the fibers themselves from decay, the prevention of cross-infection and of airor dust-borne infection, the inhibition of odor-forming bacteria and, in general, the killing or stasis of microorganisms which cause disease, putrefaction or deterioration of materials. They find application in such articles as blankets, bedlinens, surgical dressings, hospital uniforms, air filters, curtains and draperies, upholstery stuffing and padding, diapers, undergarments, socks and the like.

We claim:

1. The process of sanitizing cellulosic materials which comprises treating cellulosic material in the presence of an acidic catalyst m'th a triazinone compound having the structure 0 HOCHPN/ NCHzOH H H1 N R I Z wherein R is a radical selected from the group consisting of aliphatic, alicyclic and aromatic radicals bearing the residue of an acidic group, and Z is the cation of a microbiologically active quaternary ammonium salt.

2. The process of sanitizing cellulosic materials as defined in claim 1 wherein the triazinone compound is 1,3- dimethylol-tetrahydro-S-(alkyl dimethyl ethylbenzyl ammonium sulfoethyl)-s-triazin-2-one.

3. The process of sanitizing cellulosic materials as defined in claim 1 wherein the triazinone compound as 1,3- dimethylol-tetrahydro-S-(alkyl dimethyl ethylbenzyl ammonium-p-sulfoethyl) -s-triazin-2-one.

4. The process of sanitizing cellulosic materials as defined in claim 1 wherein the triazinone compound is 1,3- dimethylol tetrahydro 5 (alkyl dimethyl benzyl ammonium sulfoethyl)-s-triazin-2-one.

5. The process of sanitizing cellulosic materials as defined in claim 1 wherein the triazinone compound is 1,3- dimethylol-tetrahydro-S-(alkyl isoquinolinium-m-carboxyphenyl)-s-triazin-2-one.

6. The process of sanitizing cellulosic materials as defined in claim 1 wherein the triazinone compound is 1,3- dimethylol-tetrahydro-S-(alkyl dimethyl benzyl ammonium carboxymethyl)-s-triazin-2-one.

7. Cellulosic textile material cross-linked with a sanitizing agent by the process as defined in claim 1, said material being resistant to depletion of said agent by repeated laundering or dry cleaning.

References Cited UNITED STATES PATENTS 2,763,574 9/1956 Ruperti 8-116.3 X 3,002,859 10/ 1961 Hurwitz 8116.3 X 3,050,419 8/1962 Rupcrti 8-l16.3 X 3,082,118 3/1963 Shaw ct al 8116.3 X 3,085,909 4/1963 Gogliardi ct al. 81l6.3 X 3,130,193 4/1964 Shaw et al 8116.3 X 3,252,751 5/1966 Shaw et a1 8116.3 X 3,317,345 5/1967 Pluck et a1 8-116.3 X

NORMAN G. TORCHIN, Primary Examiner. J. CANNON, Assistant Examiner.

US. Cl. X.R.

U.S. DEPARTMENT OF COMMERCE PATENT OFFICE Washington, D.C. 20231 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,437,419 April 8, 19

Sidney Cohen et al.

It is certified that error appears in the above identified patent and that said Letters Patent are hereby corrected as shown below:

Column 3, line 52, "of", second occurrence, should read or line 5 "of, second occurrence, should read or Column 4, line 58, "214 x 10' should read 214 x 10 Column 6, line 32 "as" should read is line 34, "sulfoethyl" should read sulfophenyl Signed and sealed this 14th day of April 1970.

(SEAL) Attest:

WILLIAM E. SCHUYLER, JR.

Commissioner of Patents Edward M. Fletcher, 11'.

Attesting Officer

Claims

1. THE PROCESS OF SANITIZING CELLULOSIC MATERIALS WHICH COMPRISES TREATING CELLULOSIC MATERIAL IN THE PRESENCE OF AN ACIDIC CATALYST WITH A TRIAZINONE COMPOUND HAVING THE STRUCTURE