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Número de publicaciónUS3482927 A
Tipo de publicaciónConcesión
Fecha de publicación9 Dic 1969
Fecha de presentación24 Ene 1967
Fecha de prioridad24 Ene 1967
Número de publicaciónUS 3482927 A, US 3482927A, US-A-3482927, US3482927 A, US3482927A
InventoresBeachem Michael T, Megson Frederic H, O'brien Samuel J
Cesionario originalUs Army
Exportar citaBiBTeX, EndNote, RefMan
Enlaces externos: USPTO, Cesión de USPTO, Espacenet
Method for imparting antivesicant properties to fabric
US 3482927 A
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United States Patent US. Cl. 8-116.3 3 Claims ABSTRACT OF THE DISCLOSURE A method for imparting antivesicant properties to fabrics comprising the contacting of the fabric with a derivative of 8-quinolinol, and further contacting said treated fabrics with a metal salt.

The present invention relates to an improved method for imparting antivesicant properties to cellulosic fabrics and more particularly to imparting antivesicant properties to cellulosic fabrics by impregnating or modifying them with metal chelates of S-hydroxyquinoline and derivatives thereof.

Vesicant agents, such as mustard gas, attack the skin as well as the respiratory system of exposed personnel. Therefore, a body shield, in addition to a protective mask, is essential to prevent casualties. A fabric impermeable to all fluids would afford complete protection, but would be impractical, especially in warm climates, for extended periods of wear. More preferable is protection built into occupational clothing; thereby permitting air circulation and preventing moisture accumulation.

Mustard gas is the term applied to the well-known vesicant, bis(Z-chloroethyl) sulfide; in its standard form as vapor or as air borne droplets. Various processes and compounds have been suggested and employed to impart finishes to the fabric used for military uniforms which would deactivate mustard gas and would prevent its passage through the cloth. But the efficiency of prior methods leaves much to be desired. For example, among the most commonly used are the N-chloroamides. Once on the fabric, these compounds lose activation by hydrolysis by atmospheric moisture, by perspiration, by thermal decomposition, and by the like.

The present invention is premised on the discovery that cellulosic fabrics treated with metal chelates of 8- hydroxyquinoline have useful and superior characteristics for imparting antivesicant properties to fabrics, especially against mustard gas. Accordingly, it is among the objects of the present invention to provide a treatment for airpermeable cellulosic fabric materials that will prevent passage of vesicant agent vapors through the garment. It is a further object to provide a permanent, noninjurious finish for such fabric materials which requires no further treatment by the wearer for antivesicant protection. It is a final object to provide a vesicant-resistant treatment for textile fabrics that is relatively stable and that does not adversely affect the tensile strength of the fabric. These and other objects and advantages of the instant invention will be fully apparent from the following description and examples.

An antivesicant capacity may be imparted to any fabric by simply padding a solution or dispersion of copper 8-quinolinolate thereon and drying the fabric. The padding process itself involves submerging the fabric in the solution, permitting it to soak for a few minutes, and gently squeezing it between rollers. In such a manner the wet weight of the fabric can be increased by 50%.

3,482,927 Patented Dec. 9, 1969 Fabrics providing a cellulosic substrate are conducive to more permanent protection fixation, In fact, any substrates having active hydrogen atoms are suitable; for example, polyvinyl alcohol, modified starches and the like.

To obtain more durable antivesicant protection, it is desirable to fix catalytically a fiber reactive quinoline derivative to the fabric and treat the thus modified fabric further with a metal salt to form a metal chelate. The metal chelate becomes an integral, chemically-bonded part of the fabric. Especially suitable for the latter process are the S-hydroxymethyl and the 5,7 bis (hydroxymethyl) derivatives of 8-hydroxyquinoline. The process is represented by the following reaction:

(|)H OH alkaline Oi; CHZO out CH OI-I OH OCu+ N i i I CHzOH CHzOstu Where cell designates a portion of the cellulose chain of the fabric. The last configuration may represent any or all of the following structures:

Compounds useful in the process of the invention may be defined as metal chelates of compounds represented by the formula:

where R and R are hydrogen or CH OH or both. The compounds, represented by the last formula, where at least one of the Rs is CHgOH are useful in the method of application wherein the compound is first bonded to the fabric with a catalyst and then chelated with a metal. The hydroxymethylquinoline derivatives are prepared by reaction with formaldehyde.

To accomplish the fixation on the fabric, typical acid catalysts, well known in the textile chemical and textile resin finish arts, are used. Examples are zinc nitrate magnesium chloride and acid salts of amines. Copper nitrate used in excess will catalyze fixation and react to form the chelate in one operation.

Although copper is the preferred metal for chelate formation, other metals known to react with 8-hydroxyquinoline can be used. Found suitable were chromium,

silver, iron, mercury, nickel, zinc, aluminum, and cobalt; some of which may be employed in more than one valence state, e.g. cuprous and cupric. Additionally, compounds of these metals impart to the fabric in durable, fiber-reacted form other useful properties of the metal or of the metal coordination complex. For instance, copper will add fungicidal, aluminum will add antipersperant, and mercury will add bactericidal activity. The 87h}!- droxyquinoline itself is effective to some degree as an antivesicant, although known previously as an antifungal agent.

After bonding the methylol derivatives of 8-hydroxyquinoline to the fabric, copper complexes may be formed using other copper complexes such as copper ethylenediamine nitrate and copper diethanolamine nitrate, depicted structurally below:


1 C ZOnell o z ntu The copper provided by these complexes affords additional antivesicant activity.

Chemically bonding the quinoline moeity to the cellulose affords the durable antivesicant finish unobtainable by simple padding. The structure of the coordination compound can take a variety of forms, provided it is capable of having a fiber reactive group attached to it. Organic coordination compounds which will work are dihydric alcohols, alkanolamines, amino acids acetylacetones, salicylic acids, hydroxybenzoic acids, thiosemicarbazones, guanidines, dicyandiamides, aminothiophenols, hetero-N, -O and -S compounds, azophenols, nitriles, salicylaldehydes, aldimines, oximes, and so on. Any free orbitals remaining after combining the metal atom with the coordination compound are filled by other groups from the substrate (e.g. hydroxyls of cellulose) or by adding on small molecules like NH or H O.

The efiiciency of the mustard-gas barrier is determined by the Dawson Test a measurement of the percent of mustard gas, initially present in an air stream, retained on a fabric after air passage through the fabric. In the examples which follow, the preparations of the antivesicant complexes and treatment of the fabric are described. Table 1, following the last example shown hereinafter, depicts the Dawson Test results. It will be observed that the process whereby 8-hydroxyquinoline-5-methylol derivatives are fixed to the fabric and then topped with a metalcompound solution to form the chelates is significantly more effective than hydroxyquinolinemethanol derivatives alone.

EXAMPLE I A 10% solution of a commercially available fungicidal preparation of copper 8-quinolinolate in a hydrocarbon vehicle is padded onto cellulosic fabric.

EXAMPLE II With the aid of about 0.1 part of 75% solution of a surfactant (Aerosol OT-dioctyl sodium sulfosuccinate), 100 parts of pulverized 8-quinolinol is dispersed in 500 parts of water. Six parts by volume of aqueous sodium hydroxide solution (10 g./ 100 m1. concn.) is added to make the mixture moderately alkaline to phenolphthalein indicator. While stirring the mixture at 2530 C., 230 parts of a 36% aqueous solution of formaldehyde is added over 10-15 minutes. After stirring overnight at 2530 C., the slurry is filtered, and the solid is washed with three portions of 250 parts by volume of water, dried overnight at 5560 C., and ground until the material can be passed through a 60-mesh screen.

The pale orange solid obtained amounts to 117 parts and analyzes C H N indicating it consists of monomethylolated and dimethylolated products in approximately equal molar amounts. On the basis of the known chemistry of 8-quin0linol these products are primarily 8-hydroxy-S-quinolinemethanol, and 8-hydroxy-5,7- quinolinedimethanol and 8-hydroxy 5,7 quinolinemethanol.

Cotton sateen fabric is padded with a dimethylformamide solution containing 20% of the above compound and 2% zinc nitrate (the latter added as an aqueous solution), dried two minutes at 225 F., and curred three minutes at 350 F. The resulting fabric is processed washed one complete cycle (in a typical household washing machine) at 160 F. using 0.1% Tide detergent and 0.1% soda ash, and is air dried.

A portion of the above fabric is topped with copper nitrate by padding it with a 20% solution of Cu(NO in water, air drying it, rewashing it at 160 F. with plain water, and again air drying it. Analysis of the fabric now shows a Cu/N atomic ratio of 0.6 (theory 0.5) and a concentration of metal chelate (based on the Cu content) of 6.7% of the Weight of the fabric.

EXAMPLE III To a mixture of 79.8 parts of 8-quinolinol (pulverized until all passes through a 60-mesh screen), 0.1 part of a surfactant solution (Aerosol OT) and 5 parts by volume of aqueous sodium hydroxide solution (20 g./ ml. concn.) in 500 parts by volume of Water, is added rapidly with good stirring 91.8 parts of 3638% aqueous formaldehyde solution. At this point the pH is about 9. After stirring overnight at 2530 C., the solid is filtered off, washed twice with water, and dried overnight at 5055 C. The cream colored solid amounts to 92.8 parts (96% of theory).

The compound is fixed on cotton sateen fabric, washed, and dried as in Example II. Next, the treated fabric is soaked for about two hours in 20% solution (on an anhydrous basis) of cupric chloride, run through a padder, and air dried.

The above process is repeated exactly with 20% solutions of the following salts substituted for the cupric chloride:

nickel salt cuprous chloride chromium sulfate silver nitrate To 160.0 parts of 8-quinolinol in 1000 parts by volume of water containing 0.2 part by volume of a 25% aqueous solution of a surfactant (Aerosol OT) and 10 parts by volume of aqueous sodium hydroxide solution (20 g./ 100 ml. concn.), is added 184.0 parts of aqueous formaldehyde solution (3638%) and the mixture is stirred for 18 hours. The product filtered off, washed with water and dried at 5055 C., amounts to 192.1 (99% of theory) of cream white solid analyzing C H N (calculated for S-hydroxy-S-quinoline methanoI-C H NO Fabric is padded with a solution containing 20.0 parts of the above and 30.4 parts of Cu(NO '3H O, dried two minutes at 225 F., cured three minutes at 350 F., Washed in plain water and air dried.

EXAMPLE V Fabric is padded with a solution containing 20% 8-hydroxy-S-quinoline methanol (prepared in Example IV) and 2% Zn(NO dried two minutes at 225 F., cured three minutes at 350 F., washed in a household Washing machine at 160 F. using 1% Tide detergent and 1% soda ash, and air dried. A portion of the thus treated fabric is padded with solution of Cu(NO air dried, and washed in plain water. Another portion is padded with 20% solution of Cu(NH CH CH OH) (NO air dried, and washed in plain water. And a third portion is padded with 20% solution of Cu(NH CH CH NH )(NO air dried, but not washed. As a control, a piece of untreated fabric is padded with the last named solution and air dried.

What is claimed is:

1. An improved method for imparting antivesicant properties to cellulosic fabrics comprising the steps of: padding said fabric with a derivative formed by the reaction of 8-quinolinol and an aqueous solution of formaldehyde in the presence of a catalyst in order to fix said derivative to the fabric drying, and further contacting said modified fabric with a metal salt to form a metal chelate.

2. A method in accordance with claim 1 wherein the S-quinolinol derivative is selected from the group consisting of 8-hydroxy 5 quinolinemethanol, 8-hydroxy-5-7- quiriolinemethanol, and 8-hydroxy-5,7-quinolinedimethano TABLE I Percent mustard retention Application Test run Compound applied Method 0-2 hrs. 2-4 hrs. 4-6 hrs.

Example I Copper 8-quin0linolate Padded 88 58 41 Example II 8-hydroxy-5-quinolinemethanol Fixed (no metal) 14 8-hydroxy-5-quinolinemethanol, copper salt Fixe 73 53 51 Example III 8-hydroxy-5-quinolinemethanol, copper salt 49 41 39 (from 011012). s-hydroxy-5-quinolinemethanol, chromium salt do 36 26 24 B-hydroxy-5-qu.in0linemethan01, cerium salt -do 42 33 30 s-hydroxy-5-quin0linernethanol, silver salt 42 33 32 8-hydroxy-5-quinolinemethanol, ferric salt 57 38 s-hydroxy-5-quinolinemethanol, mercuric salt d0 54 51 Example IV 8-hydroxy-Equinolinemcthanol, copper salt, do 51 42 3g fixed with copper nitrate. Example V s-hydroxy'-5-quinolinemethanol, Fixed (no metal) 49 33 31 s-hydroxy-5-quinolinemethanol, copper dietha- Fixed 39 34 nolamine nitrate salt. B-hydroxy-S-quinolinemethanol, copper ethyl- -do 79 61 46 enediarnine nitrate salt. Copper ethylenediamine nitrate Padded 25 While only preferred forms of the invention are described, other forms of the invention are contemplated and numerous changes and modifications may be made 3. A method in accordance with claim 2 wherein the metal salts is selected from the group consisting of: cuprous chloride, copper, nitrate, chromium sulfate, silver therein without departing from the spirit of the invention. 35 nitrate, ferric sulfate, mecuric nitrate and zinc nitrate.

References Cited UNITED STATES PATENTS 2,250,660 7/1941 Straub et a1 260289 2,381,863 8/1945 Benignus 117138.5 2,698,263 12/1954 Weick 117l38.5 2,721,824 10/1955 Feigin et a1 260-270 X 3,033,865 5/1962 Fronmuller et al. 117-138.5 X 3,088,916 5/1963 Roman 252106 WILLIAM D. MARTIN, Primary Examiner T. G. DAVIS, J 11., Assistant Examiner US. Cl. X.R.

Citas de patentes
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US2381863 *1 May 194314 Ago 1945Monsanto ChemicalsMethod of fungusproofing textiles
US2698263 *17 Ago 195028 Dic 1954Pacific MillsMildew resistant textile products and processes for preparing them
US2721824 *1 Ago 195225 Oct 1955Geigy Chem CorpSolubilization of copper-8-quinolinolate
US3033865 *9 Abr 19598 May 1962Augustus S WittnebelSolubilizing copper-8-quinolinolate
US3088916 *11 Ago 19587 May 1963Monsanto ChemicalsBacteriostatic and fungistatic cleansing compositions
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Clasificación de EE.UU.8/182, 427/389.9
Clasificación internacionalD06M16/00
Clasificación cooperativaD06M16/00
Clasificación europeaD06M16/00