US 3227614 A
Description (OCR text may contain errors)
United States Patent Ofi" 3,2216% Patented Jan. 4, 1966 3,227,614 GERNHCIDAL PAPER Fred F. Scheuer, Bronx, N.Y., assignor to Dustllrin Pro-d- ;ctsii Inc., New York, N.Y., a corpuration of New No Drawing. Filed Sept. 29, 1960, Ser. No. 59,150
13 Claims. (Cl. 1167-84) This invention relates to a bacteriostatic or germicidal paper or tissue. More particularly, it relates to a germicidal or bacteriostatic paper or tissue which may be used wet or dry to wipe surfaces to render them germicidal or bacteriostatic.
} It is an object of the present invention to provide a germicidal or bacteriostatic paper which is disposable, economical and effective in rendering surfaces bacteriostatic or germicidal when contacted with this paper. (This is to be contrasted with the common use of untreated paper which may be already contaminated with pathogenic organisms and which transmits these organisms to asurface to be cleaned.)
It is a further object of the present invention to provide a method for preparing such paper.
Other and more detailed objects will be apparent from the following description and claims.
The inexpensive, disposable bacteriostatic paper or tissue of the present invention is of great value both for civilian and military uses.
Dry it is useful in hospitals, doctors offices, laboratories, etc. as dust Wipers, which impart the areas wiped with potential bacteriostatic protection. In this manner the danger of the spread of dust-born infection in hospitals and doctors offices can be reduced. Another use is wiping telephone receivers, keys of typewriters and electronic equipment, industrial safety equipment such as the exposed surfaces of gas masks, goggles, welders and riveters safety masks, respirators, inhalators, safety shoes and boots, etc. in order to render them sanitary.
Wet it is useful in hospitals, doctors ofiices, laboratories and all places where antibiotic protection is required. By simply putting as much water on the paper as can be absorbed, a solution with high bactericidal activity as well as detergent value is instantly produced without the need for measuring water or germicide; There is also no need to wash and rinse the object to be cleaned before using a germicide. For example, an operating table, a toilet seat, etc. can be cleaned and sanitized in one single operation. A soldier, a nurse, a stewardess, etc. can carry a germicide in the pocket in dry form. A two ply wiper size 13" X 18" which weighs only about 7 gms. will absorb about one ounce of water to produce about one ounce of bactericidal solution combined with an efiective alcohol type detergent and provide means of applying a cleaner and sanitizer in one operation.
In the manufacture of germicidal dustcloths made of cotton and the like it has been customary to impregnate the cloth with an aqueous solution containing a germicide which is then air-dried on the colth. Because of the nature of the structure of the cloth it could be subjected to treatment with the aqueous solution for long periods of time without deleterious effect. In attempting to apply these aqueous processes to the treatment of paper it was soon found that the results were not satisfactory. It was found that from an aqueous solution of germicide the paper could not absorb more than 1% water without altering its structure. The absorption of this small amount of water would not result in the deposition of adequate amounts of germicide on the paper. It was thus necessarytodevise a'methodto deposit an adequate amount of germicide on the paper.
It has now been found that paper will absorb sufficient germicide to render it useful as a germicidal or bacteriostatic paper without altering the structure of the paper if the paper is treated with a non-aqueous vehicle in which the germicide is distributed.
A variety of non-aqueous liquid vehicles are known which are useful for the purpose of the present invention. Among these may be mentioned light oils, hydrocarbon distillates, solvents, monohydric alcohols, glycols, naphthas. The preferred liquid vehicles are the normally liquid hydrocarbons, cg. normally light liquid hydrocarbon oils, aliphatic naphthas, Stoddard solvents, kerosenes (refined), paraffinic hydrocarbons, natural mineral oil, pine oil, white mineral oil, etc.
Since the products of the present invention generally come in contact with the skin, the non-aqueous liquid vehicles generally employed are those that are non-toxic or non-irritating when the paper contacts the skin. Furthermore, the said vehicle obviously should be of such a character as not to deleteriously affect the bacteriostatic or germicidal properties of the anti-bacterial agent employed.
All of the ingredients are preferably completely disper sible in the non-aqueous vehicle so that subsequent agitation is not needed to redisperse the ingredients in the vehicle before use. By using the proper percentage of liquid vehicle a total all-side surface treatment is assured. This is especially important when tissue paper is being used which comes in 1, 2, 3, 4-ply or more.
For some purposes it is advantageous to incorporate in the paper certain agents. Thus, for example, there may be added to the liquid vehicle a silicone, wax or other agent which will be adsorbed on the paper when the paper is processed in accordance with this invention.
The germicidal and bacteriostatic agents which are preferably selected for the use in the present invention are the quaternary ammonium compounds which fulfill the requirements of stability, substantivity and low degree of toxity. Of particular interest are the quaternary ammonium compounds of the following general structure wherein R R R and R are selected from the class consisting of alkyl, aryl, aralkyl and heterocyclic radicals and X is a halogen. Of special interest are the alkyl dimethyl benzyl ammonium chloride compounds. The alkyl group in these compounds may be lower or higher alkyl groups.
A variety of water soluble germicidal or bacteriostatic chemicals are known in the prior art which may be used in the present invention. Among these may be mentioned:
(27) (fl-Phenoxyethyl) dimethyl dodecyl ammonium H bromide (28) Octyl phenoxy ethoxy ethyl dimethyl p-chlorobenzyl ammonium chloride (29) Dialkyl dimethyl ammonium chloride (30) Dialkyl dimethyl ammonium bromide (31) Decamethylene-bis (decyl dimethyl ammonium) bromide (32) Trialkyl benzyl ammonium chloride (33) Myristamido propyldimethyl benzyl ammonium chloride (34) Myristyl-Y-picolinium chloride (35 N-N-N-N'-tetramethyl-N-N-didodecyl-fl-hydroxypropylene diammonium bromide With the present invention waxes, high percentage pine alcohols, oils and/or silicones can be added to the required degree and the resulting admixture remains clear indefinitely without separation. This will permit the production of bacteriostatic paper for the many different purposes intended in the invention.
A feature of the present invention is the fact that no separation of the essential constituents of the treating composition occurs. This is true of the treating solution before it is applied to the paper or tissue as well as the treating composition disposed on the paper or tissue. Since the treatment of the paper in accordance with the present invention may involve contacting the paper with a treating solution for several days, it is very important that the components of the treating solution do not separate out. Furthermore, since it may take several days for the treating fluid to reach the deeper plies of paper, it is essential for the proper treatment of these deeper plies that the constituents of the treating solution do not separate out.
This property of stability of the present treating compositions is greatly enhanced by incorporating in the treating solution a detergent of general formula 11 amon -omega wherein R is preferably a long chain alkyl radical and x has an average value of from 10 to 20. The best results are obtained with compounds of Formula 11 above wherein R is a saturated highly branched chain alkyl group of from 11 to 15 carbon atoms and particularly with the polyoxyethylene ethers of tridecyl alcohols. By way of illus tration the following compounds which are useful in the present invention may be mentioned: polyoxyethylene ether of tridecyl alcohol containing 12 oxyethylene groups per mole; polyoxyethylene ether of tetradecyl alcohol containing 16 oxyethylene groups per mole; and polyoxyethylene ether of pentadecyl alcohol containing 14 oxyethylene groups per mole.
The relative proportions of germicide to the other ingredients contained in the treating solution may be varied considerably without departing from the spirit of this invention. In the preferred practice of the invention the ratio of germicide to the weight of treated paper will vary in the range of from 0.3 to 0.6 part by weight of germicide to the treated paper. When a detergent is employed, it is preferably used in the range of l to 5 parts by weight of the liquid vehicle. The other agents, e.g. silicones, oils, waxes or other polishing agents which are employed, are preferably used in the range of about 1 to 5 parts by weight of liquid vehicle.
The following examples are further illustrative of the present invention. It is to be understood, however, that this invention is not limited thereto.
EXAMPLE 1 7 One part by weight of alkyl dimethyl benzyl ammonium chloride in water is mixed with 4 parts by weight of 100% polyoxyethylene tridecyl ether alcohol to form a 10% solution of said alkyl dimethyl benzyl ammonium chloride. This solution is further used to prepare the treating solution. The percentages of the materials indicated below in this example are based on the total weight of the treated paper product made in accordance with the present invention. Three percent of said 10% solution of quaternary ammonium compound was mixed with a solution containing 17% hydrocarbon distillateand 1% silicones. This solution is used in test A below.
EXAMPLE 2 A solution was prepared by diluting one part of a 50% solution of alkyl dimethyl benzyl ammonium chloride in water with 2 parts by weight of 100% polyoxyethylene tridecyl ether alcohol 2 and 2 parts by weight of pine oil containing terpene alcohol to form a 10% solution of said alkyl dimethyl benzyl ammonium chloride. The percentages of materials indicated below in this example are based on the total weight of the treated paper product made in accordance with this invention. Three percent of the 10% solution of quaternary ammonium compound prepared above was mixed with 17% of hydrocarbon distillate and 1% silicones. his solution is used in test B below.
EXAMPLE 3 Three percent of the 10% solution of said quaternary ammonium compound prepared in Example 2 was mixed with a solution containing 5% carnauba wax, 12% hydrocarbon distfllate and 1% silicones. This solution is' used in test C below.
1 50% alkyl (08431 dimethyl benzyl ammonium chloride.
2 Polyoxyethylene tridecyl ether alcohol, viscosity (cp. 25 C.) 80.
3 A colorless, light, non-odorous petroleum distillate, Saybolt viscosity F. 30/35.
4 Siliconcsnon-irritating-20 centistokes viscosity.
Zone of inhibition test results vs. Staph. aureus Average width of zone of inhibition Sample No.
Inner Outer Section, Section, mm. mm.
A typical finish tissue sample contains the following:
C1261%, Cl-22%, GIG-11% related C8 to (118-437 While the invention has been described with particular reference to specific embodiments, it is to be understood that it is not limited thereto, but is to be construed broadly and restricted solely by the scope of the appended claims.
What is claimed is:
1. An article of manufacture useful in rendering surfaces germicidal and bacteriostatic, which comprises paper sfibstantially impre nated with a water soluble germicide distributed in a non-aqueous liquid carrier selected from the group consisting of light oils, hydrocarbon distillates, monohydric alcohols, glycols and naphthas.
2. An article of manufacture useful in wiping surfaces without an aqueous dispenser to render them germicidal and bacterio-static, comprising paper substantially impregnated with a water-soluble germicide distributed in a normally non-aqueous liquid hydrocarbon carrier.
3. An article of manufacture according to claim 2 wherein said liquid hydrocarbon carrier also contains a silicone and Wait.
4. An article of manufacture according to claim 2 wherein said hydrocarbon carrier also contains a detergent of the formula RO(CH -CH O) H, wherein R is long-chain alkyl and x has an average value of from to 20.
5. An article of manufacture according to claim wherein the Water soluble germicide is a quaternary ammonium compound of the formula R2 R -l l-R la wherein R R R and R are selected from the group consisting of alkyl, aryl, aralkyl and heterocyclic, and wherein X represents a halogen.
6. An article of manufacture according to claim 5 wherein said quaternary ammonium compound is alkyl-3- dimethyl benzyl ammonium chloride.
7. An article of manufacture useful in wiping surfaces to render them germicidal and bacteriostatic, comprising paper substantially impregnated with a quaternary ammonium compound of the formula wherein R R R and R are selected from the group consisting of alkyl, aryl, aralkyl and heterocyclic, and wherein X represents a halogen and a polyoxyethylene alkyl ether alcohol of the formula R0 (CH-C18 0) H, wherein R is long-chain alkyl and x has an average value of from 10 to 20 distributed in a non-aqueous liquid hydrocarbon carrier.
8. An article of manufacture according to claim 7 wherein said quaternary ammonium compound is alkyl dimethyl benzyl ammonium chloride and said polyoxyethylene alkyl ether alcohol is polyoxyethylene tridecyl ether alcohol.
9. A method for the impregnation of a paper useful in wiping surfaces without a liquid dispenser to render them germicidal and bacteriostatic which comprises applying to any part of said paper a quantity of non-aqueous liquid vehicle in which is distributed a water soluble and groups germicide selected from the group consisting of light oils, hydrocarbon distillates, monohydric alcohols, glycols, and naphthas, and setting said treated paper aside for a predetermined period of time for said vehicle to penetrate throughout said paper.
10. A composition of matter useful in the treatment of paper to produce an impregnated paper suitable for rendering surfaces germicidal and bacteriostatic, which comprises a non-aqueous liquid hydrocarbon vehicle having distributed therein a quaternary ammonium compound of the formula R -N-R wherein R 1 R and R are selected from the group consisting of alkyl, aryl, aralkyl and heterocyclic and wherein X represents a halogen and a polyoxyethylene alkyl ether alcohol of the formula RO(CH -CH O),,H, wherein R is a long-chain alkyl and x has an average value of from 10 to 20.
11. An article of manufacture useful in wiping surfaces without addition of liquid dispenser to render the wiped surfaces germicidal and bacteriostatic, comprising a paper sheet substantially impregnated with a treating solution containing a water-soluble germicide, a silicone, and a detergent, distributed in a non-toxic, non-aqueous liquid carrier selected from the group consisting of light oil, hydrocarbon distillates, monohydric alcohols, glycols and naphthas, said paper sheet having said germicide substantially uniformly distributed therein and being substantially dry to the touch.
12. An article of manufacture according to claim 11 wherein said treating solution contains about .3 to about .6% of said germicide, no less than 1% of said detergent, and no less than 1% of said silicone, all percentages being by weight of the treated paper.
13. A method of rendering a surface substantially germand bacteria-free, which comprises wiping said surface with a paper impregnated with a non-aqueous liquid vehicle in which is distributed a watersoluble germicide, said vehicle being selected from the group consisting of light oils, hydrocarbon distillates, monohydric alcohols, glycols and naphthas.
References Cited by the Examiner UNITED STATES PATENTS 1,969,900 8/1934 Pickett 252-91 2,093,824 9/ 1937 Woronoff 252-91 2,251,328 8/1941 Ehret 252-91 2,423,262 7/1947 Sowa 167-38.5 2,495,066 1/1950 Jones 252-91 2,544,732 3/1951 Shechmeister 167-84 2,566,092 8/1951 Mayfield 167-42 2,676,987 4/1954 Lewis et al 117-1385 X 2,702,780 2/ 1955 Lerner 167-84 2,756,647 7/1956 Thompson 252-91 2,812,332 3/1957 Pennino 16 7-3 8.5 2,933,431 4/1960 Sperouleas 167-84 2,951,788 9/1960 Lo 167-30 2,973,297 2/ 1961 Bakkeren et a1. 167-84 X 3,138,533 6/1964 Heim et al. 167-84 FOREIGN PATENTS 760,232 10/1956 Great Britain.
OTHER REFERENCES Soap and Sanitary Chemicals, June 1952, p. 159.
JULIAN S. LEVITT, Primary Examiner.
A. WOLMAN, MORRIS O. WOLK, FRANK CACCIA- PAGLIA, 1a., Examiners.