CA2292005A1 - Water-stabilized organosilane compositions and methods for using the same - Google Patents

Abstract

Water stable organosilane products and compositions are disclosed. In particular, organosilane formulations tailored for commercial use are disclosed, as well as articles of manufacture corresponding to said formulations.

Description

..~ CA 02292005 1999-12-10 WATER-STABI .17.R OR ANOSTt.ANF ('.OMPn~TTT(~N~ AND
Field of the Invention:
The invention relates to organosilane compounds and methods for their use. In particular, this invention provides water-stable organosilane products and compositions for treating various substrates, articles treated with the products and compositions, and methods of treatment using the products and compositions. In addition, application of the subject composition to substrates and various articles provides a long-lasting treatment against odors.
Organosilanes of the general formula R"S1X4_~ where n is an integer of from 0 to 3, but more generally from 0 to 2 (where when n is 3 the organosilanes may only dimerize); R
is a nonhydrolizable organic group, such as, but not limited to, alkyl, aromatic, organofunctional,or a combinationthereof, and X is alkoxy, such as methoxy or ethoxy, are prone to self condensationrendering such organosilanesunstable in water over commercially relevant periods of time. Additionally, X can be a halogen, such as Cl, Br; or I, and is similarly liberated as HCI, HBr, or HI. For such organosilanes, the X moiety reacts with various hydroxyl containing molecules in aqueous media to liberate methanol, ethanol, HCI, HBr, HI, HzO, acetic acid, or an unsubstituted or substituted carboxylic acid and to form the hydroxylated, but condensation-prone compound.
For organosilanesR"SiX~", where n is an integer from 0 to 2, hydrolysis of the first two X groups with water produces a species bearing -Si(OH)2- units which can self condense G:lSharelsh-appslBST-1O5C1X.wpd/DNB/sbt 2 BST-lOSCIX
through the hydroxyl moieties to linear and/or cyclic oligomers possessing the partial structure HO-Si-(O-Si)"""O-Si-O-Si-O-Si-OH,where mm is an integer such that an oligomer is formed. For those cases, RSiX3, hydrolysis of the third X group generates a silanetriol (RSi(OH)3) which produces insoluble organosilicon polymers through linear and/or cyclic self condensation of the Si(OH) units. This water induced self condensation generally precludes storage of most organosilanes Rt,SlX4_~, where n ranges from 0 to 2, inclusive, in water. Except for some organosilanes which can be stable in very dilute solutions at specific pH ranges, the use of water solutions of most organosilanes require the use of freshly prepared solutions.
One commercially relevant example of an organosilane suffering from such undesirable self condensation is the antimicrobial Dow Corning 5700 (Dow Corning Corporation, Midland, MI). The literature describes the active ingredient of Dow Corning 5700 as 3-(trimethoxysilyl)propyl-dimethyloctadecyl ammonium chloride.
However, in aqueous media, it is believed that the correct active ingredient is more likely 3-(trihydroxysilyl)propyl-dimethyloctadecyl ammonium chloride. Nonetheless, 3-(trimethoxysilyl)propyl-dimethyloctadecyl ammonium chloride is a water activated antimicrobial integrated system which is capable of binding to a wide variety of natural and synthetic substrates, including fibers and fabrics, to produce a durable surface or fabric coating. 3-(Trimethoxysilyl)propyl-dimethyloctadecyl ammonium chloride is prepared by quaternization of dimethyloctadecylamine with 3-chloropropyl trimethoxysilane.
The C,8 hydrocarbon chain quaternary ammonium portion of the molecule possesses long-acting antimicrobial properties and provides initial association with the surface of the substrate through ionic bonds and/or electrostatic interaction. Preferably, the treated surface becomes permanently coated with a covalently bound octadecylammonium ion, providing a durable, long-acting antimicrobial coating that is able to destroy microbes that come into contact with the surface.
Unfortunately, as noted above, organosilanes in water, such as the activated mixture of 3-(trimethoxysilyl)propyl-dimethyloctadecyl3mmonium chloride and water, are generally unstable and prone to self condensation. For instance, the mixture of 3-GaShare\sh-apps\BST-lOSCiX.wpd/DNB/sbt (trimethoxysilyl)propyl-dimethyloctadecyl ammonium chloride and water begins to lose effectiveness in as little as four to eight hours. Gel formation in this and similar silane formulations in water begins to occur in even shorter times. The limitations of such organosilanes in aqueous media are further described in United States Patent No. 5,411,585, the contents of which are hereby incorporated by this reference. Moreover, such products are notorious for agitation difFculty during the addition of the silane to water. Nevertheless, according to the present invention, clear aqueous gels are considered to be useful compositions.
The use of quaternary ammonium silicon compounds as antimicrobial agents in accordance with the prior art is well known and taught in a wide variety of United States Patents, e.g., 3,560,385; 3,794,736; 3,814,739, the contents of which are hereby incorporated by this reference. It is also taught that these compounds possess certain antimicrobial properties which make them valuable and very useful for a variety of surfaces, substrates, instruments and applications (see, e.g., United States Patent Nos. 3,730,701;
3,794,736;
3,860,709; 4,282,366; 4,504,541; 4,615,937; 4,692,374; 4,408,996; and 4,414,268, the contents of which are hereby incorporated by this reference). While these quaternary ammonium silicon compounds have been employed to sterilize or disinfect many surfaces, their employment is still limited because of their toxicity often as a result of the solvent system used to deliver the compound, the necessity for a solvent solution (for instance, Dow Corning antimicrobial agents contain 50% methanol), short term stability (stability of aqueous silane solutions varies from hours to several weeks only) and poor water solubility.
For instance, while 3-(trimethoxysilyl)propyl-dimethyloctadecyl ammonium chloride does not suffer from water insolubility, it is unstable in water and alse, because it is shipped in 50% methanol, it is overly toxic. Many other antimicrobial organosilanes;
especially quaternary ammonium silicon compounds, also suffer from problems associated with physical health hazards, e.g., precautions must be taken to avoid contact with both skin and eyes, accidental spills to the surrounding area, flammability, and the added manufacturing steps needed in order to incorporate such antimicrobial agents into other articles and surfaces, resulting in much higher manufacturing costs.
G:\Share\stt-apps\BST-1O5C1X.wpd/DNB/sbt r..

Therefore, there exists a need for extended shelf life, water-stable organosilane compounds, products, and compositions whereby, upon application, the active portion of the organosilane is operative for the selected application. Moreover, there exists a need for water-stable, organosilane compounds, products, compositions, and formulations which are simple and economical to formulate and use.
Odor Control A wide variety of deodorizing compositions are known in the art, the most common of which contain perfumes to mask malodor. Odor masking is the intentional concealment of one odor by the addition of another. The control of odor on fabrics, in particular clothes, has been accomplished by using perfumes, colognes, etc. However, preference to perfume is greatly varied and high levels are needed to ensure that the malodor is no longer noticeable.
Odor modification, in which the odor is changed, e.g., by chemical modification, has also been used. Current malodor modification methods known in the art are oxidative degradation, which uses oxidizing agents such as oxygen bleaches, chlorine, chlorinated materials such as sodium hypochlorite, chlorine dioxide, etc., and potassium permanganate to reduce malodor, and reductive degradation which uses reducing agents such as sodium bisulfate to reduce malodor. Both of these methods are unacceptable for general use on fabric because they can damage colored fabrics, specifically, they can bleach and/or discolor fabrics.
Other methods of odor control utilize actives that are targeted to react with malodors having specific chemical filnctional groups. Examples of such actives are:
biguanide polymers, which complex with organic compound containing organically bound N
and/or S atoms and fatty alcohol esters of methyl methacrylic acid which react with thiols, amines, and aldehydes. Such actives are limited in the scope of protection which they afford because they only react with limited types of malodor. A more detailed description of these methods can be found in U. S. Pat. Nos. 2,544,093; 3,074,891; 4,818,524; and 4,946,672; and U. K.
Pat. App. No. 941,1 O5, all of said patents and applications are incorporated herein by reference.
G:\Share\sh-apps\BST-1O5C1X.wpd/DNB/sbt Other types of deodorizing compositions known in the art contain antibacterial and antifungal agents which regulate the malodor-producing microorganisms found on the surface to which the deodorizing composition is directed. Many skin deodorant products use this technology. These compositions are not effective on malodors that have already been 5 produced and malodors that do not come from bacterial sources, such as tobacco or food odors.
Fabric malodor is most commonly caused by environmental odors such as tobacco odor, cooking and/or food odors, or body odor. The unpleasant odors are mainly organic molecules which have different structures and functional groups, such as amines, acids, alcohols, aldehydes, ketones, phenolics, polycyclics, indoles, aromatics, polyaromatics, etc.
They can also be made up of sulfur-containingfunctional groups, such as, thiol, mercaptan, sulfide and/or disulfide groups.
It is preferable to apply an odor absorbing material, preferably a broad spectrum odor absorbing material, to fabrics rather than a masking or chemical reaction material for odor control between washing and dry cleaning operations. As opposed to a masking or chemical reaction material, odor absorbing material can eliminate a broad spectrum of odoriferous molecules and usually does not contribute an odor of its own. The commonly known solid odor absorbers such as activated charcoal and zeolites can be harmful to fabrics and therefore are not preferred as an odor controlling agent under these circumstances.
Activated charcoal easily stains light colored fabrics and zeolites are seen as a light colored stain on dark colored fabris. Furthermore, the zeolites can cause a "harsh" feel if too much is deposited.
There is a need for a quick and efficient treatment of substrates and objects for fighting odors, which is resilient to washing and does not stain or cause a "harsh" feel to the substrate or object.
The present invention fulfills these needs by providing water-stable organosilane products (i. e:, the compounds or compositions formed from performing a specified reaction or mixture), compositions, and formulations; methods for their use; and articles prepared G:\Sharelsh-apps\BST-1O5C1X.wpd/DNB/sbt using the products, compositions, and formulations. The products and compositions of the present invention provide formulations of advantageously extended storage stability.
U.S. patent applications serial nos. 08/852,474 and 08/646,160; and U.S.
applications serial nos. 09/636,101 and 09/118,154; teach methods for stabilizing S organosilanes in water, describe in further detail many of the chemical structures named herein, and their methods of use. The content of these applications is hereby incorporated by this reference.
One embodiment of the present invention comprises the product formed from mixing an organosilane of the formula R,tSiXø~ where n is an integer of from 0 to 3, preferably 0 to 2; each R is, independently,a nonhydrolizableorganic group; and each X is, independently, a hydrolyzable group (hereinafter, "organosilane of interest"); with a polyol containing at least two hydroxy groups wherein at least two hydroxy groups of the at least two hydroxy groups present are separated by less than three intervening atoms (hereinafter, "polyol of interest") . Accordingly, alcohols having at least two hydroxyls;
carbohydrates, including monosaccharides, disaccharides, oligosaccharides, and polysaccharides;
modified carbohydrates, including graft and block co-polymers; partially alkylated, partially acylated or partially acetylated carbohydrates; carbohydrate oxidation products (e.g.
glucuronic acid, mucic acid); reduced carbohydrates; and substituted carbohydrates (e.g.
nucleosides, nucleotides, nucleic acids), are all polyols which are useful according to the instant invention.
Another embodiment of the present invention comprises the product formed from mixing an organosilane of interest with an ether, where the ether is of the formula R-O-R, where R is, independently an organic group and where the ether has either a hydroxy functionality or a carboxylic ester functionality (hereinafter, "ether of interest").
Yet another embodiment of the present invention comprises the product formed from mixing an organosilane of interest with an organic carbonate, preferably propylene carbonate.
Further embodimentsof this inventioninclude advantageousformulationscomprising the products described generically above, and articles of manufacture comprising said G:\Share\sh-apps\BST-1O5C1X.wpd/DNB/sbt advantageous formulations. For example, formulations comprising two or more different organosilanes to increase efficacy. Further, the compositions may comprise other suitable additives such as dyes, solvents, fragrances, or buffers known in the art.
Additional embodiments of this invention include methods for using compositions and formulations comprising an organosilane of interest in a stable aqueous solution, stabilized as taught herein.
In yet other embodiments, the present invention provides methods of treating a substrate, comprising mixing or contacting the substrate with a sufficient amount of the formulations of the invention for a period of time sufficient for treatment of the substrate.
Still a further embodiment of the subj ect invention is directed to a method of fighting odors comprising smelling an odor and applying the subject compositions to the substrate, and objects exuding the odor. Such objects and substrates can include but are not limited to, clothes, furniture, carpet, walls, kitchen counters, and toilets. When using the subject compositions to fight odor, it is preferred that the subject composition not be prone to staining said substrate. Accordingly, compositions for use in fighting odors preferably have a diluted concentration of organosilane. Preferred concentrations are from 0.01 % to 2%
weight percent of the composition.
Additional advantages of the invention will be set forth in part in the description which follows, and in part will be obvious to those skilled in the art from the description, or may be learned by routine practice of the invention as disclosed herein.
The advantages of the invention will be realized and attained by means of the elements and combinations particularly pointed out in the appended claims. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as claimed.
G:\Share\sMapps\BST-1O5C1X.wpd/DNB/sbt Detailed Disclosure of the Invention The present invention may be understood more readily by reference to the following detailed description of preferred embodiments of the invention, including specific examples of compositions and their uses.
The compositions according to the invention comprise the following constituents:
Constituent A: antimicrobial organosilane(s) of interest Constituent B: silane stabilizer Constituent C: water.
The compositions according to the invention may comprise further optional constituents which include cationic surfactants, nonionic surfactants, sequestrants, hydrotropes, detergents, polymers, salts, emulsifiers, fragrances, coloring agents, water softening agents, and/or antimicrobials as well as other conventional additives.
Compositions according to the invention comprise an antimicrobially active silane constituent. In one embodiment, the antimicrobial silane of interest has a general formula selected from the group consisting of ~D)3-a S~'~+R'~~R~~~~Rv X
and R a (I) G:\Share\sh-apps\BST-1O5C1X.wpd/DNB/sbt ~O)3-a S~~ N / \ X
R~a (II) wherein, in each formula:
R is an alkyl radical of 1 to 4 carbon atoms or hydrogen or an ethylene or propylene glycol ether derived group of the formula S R~-(OCHZCHZ)y Or RA-(OCHCH3CH2)y where RA is an alkylene group of 1 to 12 carbon atoms or hydrogen and y representing an average is ranges from 1 to 10;
a has a value of 0, 1 or 2;
R' is an alkylene group of 1 to 26 carbon atoms;
R" is an alkylene group of 1 to 26 carbon atoms;
R"', R"", R" are each independently selected from a group consisting of alkyl radicals of 1 to 26 carbon atoms, with at least one such radical larger than eight carbon atoms, -CHZC6H5, -CHZCHZ OH, -CHZ OH, and -(CHZ ~NHC(O)R''', wherein x has a value of from 2 to 10 and R"' is a perfluoroalkyl radical having from 1 to 12 carbon atoms;
and X is a suitable mono- or di-valent anion such as chloride, bromide, fluoride, iodide, acetate tosylate, formate, sulfate, carbonate, phosphate, phosphonate. Alternatively, (RO) in formulae I and II can represent a halogen fluorine, chlorine, bromine iodine, or carbonic acid with 2 to 26 carbon atoms.
It should be noted that, generally, these materials are quaternary ammonium salts of silanes.
Many of the silanes falling within the scope of this invention are known from the literature, for example U.S. Pat. No. 4,259,103, issued to J. R. Malek and J. L. Speier, on March 31, 1981; Canadian Pat. No. 1,010,782, issued to C. A. Roth; A. J. Isquith, E.A.
Abbott and P.
A. Walters, Applied Microbiology, December, 1972, pages 859-863; P. A. Abbott and A.
J. Isquith, Applied Microbiology, 25, No. 2, p. 253-256, February 1973 and E.
A. Abbott and A. J. Isquith, U.S. Pat. No. 3,794,736 issued February 26, 1974; U.S. Pat.
No.
G:\Share\sh-apps\BST-1O5C1X.wpdIDNB/sbt 4,406,892, issued September 27, 1983, U.S. Patents Numbers 4,282,366, 4,394,378, 3,661,963, among others.
It should be noted that organosilanes described in the herein referenced U. S.
Patents and U. S. patent applications may all be used as the organosilane of interest alone or in 5 addition to the' organosilanes specifically described herein. Further, the organosilane of interest may or may not be a quaternary ammonium compound, and may have one or more amine groups with or without also being an quaternary ammonium compound.
Optimally, the organosilane of interest may also have a carboxylic acid functionality.
Examples of amino containing organosilanes for use in accord with the teachings herein include, but are 10 not restricted to, the following:
3-[N-allyl-N-2-(2aminoethyl)]aminopropyltrimethyoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, N-3-trimethoxysilylpropyl-m-phenylenediamine, N-[(3-trimethoxysilyl)propyl]
diethylenetriamine, p-[N-(2-aminoethyl)aminomethyl] phenethyltrimethoxysilane N-(2-aminoethyl)3-aminopropyltrimethoxysilane, N, N-bis[3-(methyldimethoxysilyl) propyl]ethylenediamine, y-(2-aminoethyl)aminopropyltrimethoxysilane, y-(2-aminoethyl)aminopropylmethyldimethoxysilane.
Of these particularly preferred for use are 'y-(2-aminoethyl) aminopropyltrimethoxysilane, 'y-(2-amino-ethyl) aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, and 3-aminopropyltriethoxysilane.
Constituent A may also comprise a mixture of two or more organosilanes. Those skilled in the art will appreciate from the teachings herein, that the organosilanes can be combined to increase the antimicrobial or odor-fighting efficacy of the subj ect compositions.
Specific silanes of interest within the scope of the invention are represented by the formulae:
(CH3O)3S1(CHz)3N+(CH3)zC1sH37Cl-, (CH3O)3S1(CHz)3N+(CH3)zC18H37Br (CH30)3Si(CHz)3N+(CloHz1)zCH3Cl-, (CH30)3Si(CHz)3N+(CloHz1)zCH3B1'', (CH3O)3S1(CHz)3N+(CH3)3Cl , G:\Sharelsh-apps\BST-105C1X.wpd/DNB/sbt (CH3O)3S1(CHZ)3P+(C6Hs)3C1 s (CH3O)3S1(CHz)aP+(C6Hs)sBr , (CH3O)3S1(CHZ)sP+(CH3)3C1, (CH3O)3S1(CHZ)3P+(C6H13)3Cl , S (CH3O)3S1(CHZ)3N+(CHZ)3CaH9Cl , (CH30)3Si(CHZ)3N+(CHZ)3C,sH3~C1-, (CH30)3Si(CHZ)3N+(CHZ)3CHZC6HsC1-, (CH30)3Si(CHZ)3N+(CHZ)3CHZCHZOHCY, ~O)3S~CH2)3'N+ \ Cl (CH3O)3S1(CHZ)3N+(CH3)2(CHz)3NHC(O)(CFZ)6CFsCl , (CH30)3Si(CHZ)sN+(C2Hs)sCl-, For use of the subject compositions in fighting odors, the percentage of the organosilane of interest is preferably from about 0.01 % - 2% (by weight) of the total composition. This range allows for effective treatment but presents undesired staining of the substrate by the organosilane of interest. More preferably, the percentage of the organosilane of interest is from about 0.08% to about 1.0%
For purposes of this invention the organosilanes of interest can be used neat or in solvent or aqueous-solvent solutions.
Constituent B is a stabilizer of Constituent A, the organosilane of interest.
Examples of silane stabilizers are disclosed in U.S. patent application serial no.
08/852,474 and U.S.
provisional applications, serial nos. 60/016985, 60/053155 and 60/052888, incorporated G:\Share\sh-appslBST-1O5C1X.wpdIDNBJsbt herein by this reference . The stabilizer can be added to the final silane dilution or can be provided together with the silane, especially if the silane is supplied in an aqueous-solvent solution. The use of stabilizers according to the invention is not limited to the stabilizers disclosed in the above patent applications.
' Constituent C
Constituent C is water, in an amount sufficient to theoretically hydrolyze all hydrolyzable groups directly connected to the silicon atom. The formulations according to the invention are water-based cleaning or protecting solutions.
Optionally, the compositions according to the invention may comprise further constituents which include cationic surfactants, nonionic surfactants, sequestrants, hydrotropes, detergents, polymers, salts, emulsifiers, fragrances, coloring agents, water softening agents, antimicrobials, and/or pesticides, as well as other additives. Well known examples of such additives which are useful in the formulations of the subject invention are Accosoft S50-90% HHV, Accosolve DPNP, Amphoterge K-2, Amphoterge LF, Bardac 208M, Barlox 1 Os, Barlox 12, Barlox 12i, Hampene 100, Lonzaine C, Ninol 30-LL, Surfonic L 12-3, Surfonic L 12-6 , Surfonic N-60, and Surfonic N-95. Descriptions of the aforementioned compounds and their equivalents, and example formulations using such compounds, can be found in references well-known and widely available to those of ordinary skill in the art, for example, see "Surfactant Science and Technology" Second Edition, Drew Meyers, 1992, VCH, New York, New York; "Surfactants", a Brochure by Witco Corporation, D 1997; Formulation Guide, Ingredients for the Personal Care Industry and Surfactants for Household and I&I Detergents and Cleaners, by Henkel Corporation, ~ 1996, 1996, and 1995, respectively; "Your Complete Surfactant Source" by Stepan Company, D
1995, Stepan Formulation Guides; "A Complete Guide to the McIntyre Group Product Line"
by McIntyre Group LTD; "A World of Technology, Specialty Chemicals" by Lonza, D
G:\Share\sh-apps\BST-1O5C1X.wpd/DNBlsbt 1996; "The World of Innovation" by Rhone-Poulenc, D 1996; Croda, Inc., "Formulary Update-1996" and "Personal Care, The Croda Product Guide to Innovative Cosmetic Raw Materials," D 1994; "Dow Corning Additives," by Dow Corning, D 1994, Dow Corning Personal Care Formulary and Dow Corning Automotive Care Formulation Guide;
Arco, "Consumer and Institutional Cleaners and Personal Care Products", a guide with sample formulations, D 1996; Huntsman "Surfactants-Surfonic~ Alcohol Ethoxylates", D
1996;
"Neodol-Product Guide for Alcohols, Ethoxylates, and Derivatives," by Shell Chemical Company(SC: 7-94); Lambent Technologies, "Silicone Surfactants, Polymers, Emulsions, Antifoams, Specialties."
As will be readily apparent to the ordinary skilled artisan, in view of the teachings herein, there is a wide variety of aqueous formulations which can be created to achieve the cleaning and antimicrobial effects of the subject invention. The previous listings contain examples of some compounds that are not recommended in combination with aqueous quaternary ammonium compounds, specifically silane quaternary ammonium compounds, as outlined below. However, sample formulations can be modified, as is well-known in the art, to exclude incompatible compounds and to incorporate ingredients according to the invention. The silanes according to the invention can act as surfactants. In addition, the stabilizers) added to the mixture can act as efficient cleaning aids or surfactants or wetting agents. Addition of anionic surfactants or bleach or anionic polyphosphates or sodium polyacrylates is not recommended. If anionic surfactants are added, precipitation of the silane occurs that, only in some cases, can be prevented by addition of large amounts of amine oxide and/or stabilizer. Generally high pH solutions are less stable than lower pH
formulations. The compositions according to the invention are formulations that provide a durable antimicrobial finish to the treated surface at the time of cleaning, or alternatively the compositions are protectant solutions, cosmetics, or treatment products, such as shoe creme or conditioner, leaving a durable antimicrobial finish on the treated material.
It is well known that many commercially available organosilane compositions contain both an active component and an inert component. For example, Dow Corning 5700 contains a mixture of both 3-(Trimethoxysilyl)propyldimethyloctadecyl ammonium chloride G:\Sharelth-apps~BST-1O5C1X.wpdIDNB/sbt and an inert organosilane 3-choropropyl trimethoxysilane. Accordingly, the subject compositions may also contain one or more inert organosilanes. Inert organosilanes suitable for use in accord with the teachings herein may optionally have one or more amine groups or optionally have a carboxylic acid functionality. Alternatively, inert organosilane contains both an amine functionality and a carboxylic acid functionality.
The following examples are based on 3-(trimethoxysilyl)propyl-dimethyloctadecyl ammonium chloride to exemplify an antimicrobial silane of interest. Other silane antimicrobials can be substituted and the utility retained. The silane stabilizer can be any silane stabilizer as taught herein, but is preferably pentaerythritol, glucose, glycol ether DB, or propylene carbonate. All percentages are by weight, unless otherwise indicated. As will be readily apparent to the skilled artisan, the percentage of silane of interest, silane stabilizer, and water in the formulations of the subject invention can widely vary, as the formulations can initially be provided as concentrates for subsequent dilution, if desired.
Generally, the subject formulations will comprise from about 0.01 % to about 15% silane of interest, from about 0.01 % to about 50% silane stabilizer, and from about 1 % to about 99.98% water. In a preferred embodiment, the silane of interest is provided as an aqueous solution with about 5% 3-(trimethoxysilyl)propyl-dimethyloctadecyl ammonium chloride and about 1.9%
pentaerythritol as silane stabilizer. The solution of 5% antimicrobial silane of interest, about 1.9% silane stabilizer, and about 93.1% water is called Aqueous Silane 5.
The following examples are representations of possible formulations that fall within the scope of the invention.
example 1 - Antimicrobial Protectant Concentrate The following formulation provides a preferred antimicrobial protectant concentrate with durable antimicrobial activity:
Aqueous Silane 5 100%
This formulation can be directly applied to many surfaces, including textiles and fibers, to render the treated material antimicrobially active. This solution can be further diluted as G:\Share\sh-apps\BST-1O5C1X.wpd/DNB/sbt desired before application, as is well-known to the ordinarily skilled artisan in view of the teachings herein.
Example 2 - Antimicrobial Protectant Solution The following 'formulation provides a preferred antimicrobial protectant solution with durable activity:
Aqueous Silane 5 20%
DI Water 80%
This formulation can be directly applied to many surfaces, including textiles and fibers, to leave a durable, antimicrobial film.
Example 3 - Antimicrobial Protectant Solution The following formulation provides another preferred antimicrobial protectant solution with durable activity:
Aqueous Silane 5 15%
DI Water 85%
This formulation can be directly applied to many surfaces, including textiles and fibers, to leave a durable, antimicrobial film.
Example 4 - Antimicrobial Protectant Concentrated Solution The following formulation is a yet another preferred antimicrobial protectant concentrate solution with durable activity:
Aqueous Silane 5 30%
DI Water 70%
This formulation can be directly applied to many surfaces, including textiles and fibers, to leave a durable, antimicrobial film. For many applications, this formulated solution should be further diluted before application, as would be apparent to one of ordinary skill in the art.
G:\Share\sh-apps\BST-lOSCIX.wpd/DNB/sbt The following formulation is a preferred carpet cleaning product with antimicrobial activity:
Aqueous Silane 5 5.0%
Barlox 12~ 3.0%
Diethylene glycol butyl ether 5.9%
DI water ' 86.1 This carpet cleaning formulation is applied similar to traditional carpet cleaning products, and provides good cleaning properties in addition to odor and bacterial protection to the treated carpet.
Ex~ple 6 - Antimicrobial Carnet Cleaner A preferred alternative embodiment of antimicrobial carpet cleaner is a formulation according to Example 5, packaged with 5% by weight of a hydrocarbon aerosol propellant.
Example 7 - Antimicrobial Carnet Cleaning Concentrate The following formulation is preferably packaged as a concentrate for carpet cleaning with antimicrobial activity, to preferably be diluted before application in accordance with well-known procedures:

Aqueous Silane 5 30.0%

Isopropyl alcohol 1.0%

Barlox 12~ 4.0%

Diethylene glycol butyl ether5.9%

DI water 59.05%
Fragrance 0.05%
Example 8 - Antimicrobial All-Purn, ose Cleaner The following formulation is a preferred mold and mildew remover and all purpose cleaner:
Aqueous Silane 5 5.0%
Barlox 12~ 1.0%
Diethylene glycol butyl ether 5.9%
G:\Shate\sh-apps\BST-IOSCIX.wpdIDNB/sbt DI water 80.1 Surfonic~ N95 2.0%
Isopropyl alcohol 1.0%

Hydrogen peroxide 5.0%

(50% by weight aqueous solution) Fragrance 0.05%

Dye 2* 10-6%

Example 9 - Antimicrobial Air Freshener The following formulation is a preferred aerosol air freshener formulation:

Aqueous Silane 5 7.5%

Hydrocarbon Propellant 25%

Ethanol 30%

Fragrance 0.01 DI Water 37.5%

Example 10 - Antimicrobial Air Freshener The following formulation is a preferred alternative air freshener formulation:
Aqueous Silane 5 7.5%
Hydrocarbon Propellant 25%
Ethanol 30%
Fragrance 0.01 Propylene glycol 7.5%
DI Water 30%
Example 11 - Antimicrobial Fabric Softener The following formulation is a preferred embodiment of antibacterial fabric softener, suitable for use in amounts of'/4 cup:
G:\Sharelsh-apps\BST-1O5C1X.wpdIDNB/sbt Aqueous Silane 5 34%

Bardac 208M 0.77%

DI Water 54.9%

Fragrance 0.76%

1,2 Propanedio! 1.0%

Accosoft 550-90% HHV 7.6%

Calcium chloride can be added as desired to adjust the viscosity of the formulation, as would be readily known to those of skill in the art.
Example 12 - Antimicrobial Textileand Shoe Cleaner The following formulation is a preferred textile and shoe cleaner:

Surfonic N-95 4.0%

Amphoterge K-2 2.0%

Lonzaine C 1.5%

Ninol 30-LL 1.6%

Barlox 4.0%

Propylene Glycol 2.0%

Surfonic N-60 1.2%

Nino130-LL 2.4%

Citric Acid 0.25%

Hampene 100 0.46%

Silane Mix 1.2%

(36% Active without water:

50% DOW 5772 25% glycol ether DB

25% propylene carbonate) Lemon Fragrance 0.11% (#19669 Atlanta Fragrance Inc.) DI Water 79.3%

G:\Sharelsh-apps\BST-IOSCIX.wpdIDNB/sbt This formulation provides a cleaner having low foam and low-to-medium viscosity characterisitcs.
Example 13 - Antimicrobial Hard-Surface Cleaner The following formulation is a preferred hard surface cleaner:
Amphoterge LF 0.42%

Accosolve DPNP 2.50%

Surfonic N-95 0.34%

Surfonic N-60 0.40%

Barlox lOs 0.39%

Barlox 12i 0.41 Citric Acid 0.50%

Ninol 30-LL 0.15%

Isopropyl Alcohol 4.4%

Aqueous Silane 5 5.0%

DI Water 85.5%

Example 14 - Antimicrobial Hard-Surface Cleaner The following is another preferred formulation for a hard surface cleaner:

Ninol 30-LL 0.18%

Surfonic L 12-6 0.43%

Surfonic L 12-3 0.29%

Accosolve DPNP 2.5%

Aqueous Silane 5.0%

Barlox 12i 0.17%

Barlox lOs 0.53%

Citric Acid 0.30%

Amphoterge LF 0.43%

Isopropyl alcohol 3.0%

G:lShare\sh-apps\BST-1O5C1X.wpd/DNB/sbt DI Water 87.2%
Example 15 - Antimicrobial Hard-Surface Cleaner The following formulation is yet another preferred embodiment of a hard surface cleaner:
Aqueous Silane 5 5.0%

Barlox 12 1.0%

Diethylene glycol butyl5.9%
ether DI Water 85.1 Surfonic N95 2.0%

Isopropyl alcohol 1.0%

Fragrance 0.05%

Dye 2 x 10-6 Example 16 - Odor fig ting Composition 2.0% Aqueous Silane 5 0.1 % fragrance 99.7% water The above composition is encased in a convention spray bottle commonly used in the art which has a label containing instructions for use.
Example 17 - Odor-fighting Composition An aqueous solution containing the following components.
0.1 % 3-(trimethloxysilyl) propyl dimethyloctadecyl ammonium chloride 0.1 % fragrance 0.1 % silane stabilizer 0.05% ethylene glycol 0.2% amine containing organosilane composition containing at least one of the following:
(1) y(2-aminoethyl) aminopropyltrimethloxysilane;
(2) ~-2-aminoethyl) amino propylmethyldimethylsilane;
G:\Share\sh-apps\BST-IOSCIX.wpd/DNB/sbt 21 ~ BST-1O5C1X
(3) 3-amino propylthiethysilane; or (4) N-[3-trimethoxysilyl) propyl] diethyleuetriamine Optionally, the above composition can contain in addition to, or in substitution for, the amino-containing organosilane 0.2% of an acid organosilane. As in Example 16, the above composition is packaged in a conventional spray bottle with a label and instructions.
Ex~ple 18 - Odor-fighting Formulation Aqueous Silane 5 2%
Dow Corning Z 6020 0.05%
Acetic Acid 0.013%
Surfonic N95 0.4%
Fragrance 0.1%
DI Water 97.4%
Example 19 - Odor-fig ting Formulation Aqueous Silane 5 2%
Dow Corning Z 6020 0.05%
Acetic Acid 0.013%
Surfonic N95 0.4%
Fragrance 0.07%
DI Water 97.43%
Ex~ple 20 - Odor-fiE ti Formulation Aqueous Silane 5 2%
Surfonic N95 0.3%
Surflon S-141 0.03%
Fragrance 0.07%
G:\Share\sh-apps\BST-lOSCIX.wpd/DNB/sbt 22 BST-lOSCIX
It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope or spirit of the invention. Other embodiments of the invention will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein. It is intended that the specification and examples be considered as exemplary only, with the true scope and spirit of the invention being indicated by the claims.
G:\Share\sh-apps\BST-1O5C1X.wpd/DNB/sbt

Claims (42)

1. An antimicrobial composition comprising about 5.0% antimicrobial silane of interest and about 1.9% silane stabilizer in an aqueous solution.

2. An antimicrobial composition comprising Aqueous Silane 5 and water.

3. The antimicrobial composition according to claim 2 comprising about 20%
Aqueous Silane 5 and about 80% water.

4. The antimicrobial composition according to claim 2 comprising about 15%
Aqueous Silane 5 and about 85% water.

5. The antimicrobial composition according to claim 2 comprising about 30%
Aqueous Silane 5 and about 70% water.

6. The antimicrobial composition according to claim 2 comprising about 5.0%
Aqueous Silane 5 and about 86.1 % water; and further comprising about 3.0%
amine oxide surfactant and about 5.9% diethylene glycol butyl ether.

7. The antimicrobial composition according to claim 2 comprising about 30%
Aqueous Silane 5 and about 59.05% water; and further comprising about 1.0%
isopropyl alcohol, about 4.0% amine oxide surfactant, about 5.9% diethylene glycol butyl ether, and 0.05% fragrance.

8. The antimicrobial composition according to claim 2 comprising about 5.0%
Aqueous Silane 5 and about 80.1% water; and further comprising about 1.0%
amine oxide surfactant, about 5.9% diethylene glycol butyl ether, about 2.0% ethoxylated nonylphenol, about 1.0% isopropyl alcohol, about 5.0% hydrogen peroxide 50% by weight aqueous solution, about 0.05% fragrance and dye.

9. The antimicrobial composition according to claim 2 comprising about 7.5%
Aqueous Silane 5 and about 37.5% water; and further comprising about 30%
ethanol, about 0.01 % fragrance, and about 25% hydrocarbon propellant.

10. The antimicrobial composition according to claim 2 comprising about 34%
Aqueous Silane 5 and 54.9% water, and further comprising about 0.77%
antimicrobial quaternary ammonium salt, about 0.76% fragrance, about 1.0% 1,2 propanediol, and about 7.6% tallow ammonium salt.

11. The antimicrobial composition according to claim 2 comprising about 7.5%
Aqueous Silane 5 and about 30% water; and further comprising about 25%
hydrocarbon propellant, about 30% ethanol, about 7.5% propylene glycol, and about 0.01%
fragrance.

12. The antimicrobial composition according to claim 2 comprising about 5.0%
Aqueous Silane 5 and about 85.5% water; and further comprising about 4.4%
isopropyl alcohol and at least one constituent selected from the group consisting of cationic surfactants, nonionic surfactants, sequestrants, hydrotropes, detergents, polymers, salts, emulsifiers, fragrances, coloring agents, water softening agents, antimicrobials, and pesticides.

13. The antimicrobial composition according to claim 2 comprising about 5.0%
Aqueous Silane 5 and about 87.2 % water; and further comprising about 3.0%
isopropyl alcohol and at least one constituent selected from the group consisting of cationic surfactants, nonionic surfactants, sequestrants, hydrotropes, detergents, polymers, salts, emulsifiers, fragrances, coloring agents, water softening agents, antimicrobials, and pesticides.

14. The antimicrobial composition according to claim 2 comprising about 5.0%
Aqueous Silane 5 and about 85.1% water; and further comprising about 1.0%
amine oxide surfactant, about 5.9% diethylene glycol butyl ether, about 2.0% ethoxylated nonylphenol, about 1.0% isopropyl alcohol, about 0.05% fragrance and dye.

15. An antimicrobial composition comprising about 1.2% Silane Mix, about 79.3%
water, about 4.0% ethoxylated nonylphenol, about 2.0 propyleneglycol, about 0.25% citric acid, about 0:11 % fragrance and at least one constituent selected from the group consisting of cationic surfactants, nonionic surfactants, sequestrants, hydrotropes, detergents, polymers, salts, emulsifiers, fragrances, coloring agents, water softening agents, antimicrobials, and pesticides.

16. An article of manufacture comprising a container, said container having an antimicrobial composition comprising Aqueous Silane 5 and water contained therein; and instructions for use.

17. The article of manufacture according to claim 16 wherein the antimicrobial composition comprises about 20% Aqueous Silane 5 and about 80% water.

18. The article of manufacture according to claim 16 wherein the antimicrobial composition comprises about 15% Aqueous Silane 5 and about 85% water.

19. The article of manufacture according to claim 16 wherein the antimicrobial composition comprises about 30% Aqueous Silane 5 and about 70% water.

20. The article of manufacture according to claim 16 wherein the antimicrobial composition comprises about 5.0% Aqueous Silane 5 and about 86.1% water; and further comprises about 3.0% amine oxide surfactant and about 5.9% diethylene glycol butyl ether.

21. The article of manufacture according to claim 20 wherein the antimicrobial composition is packed with 5% hydrocarbon propellant.

22. The article of manufacture according to claim 16 wherein the antimicrobial composition comprises 30% Aqueous Silane 5 and about 59.05% water; and further comprises about 1.0% isopropyl alcohol, about 4.0% amine oxide surfactant, about 5.9%
diethylene glycol butyl ether, and 0.05% fragrance.

23. The article of manufacture according to claim 16 wherein the antimicrobial composition comprises about 5.0% Aqueous Silane 5 and about 80.1% water; and further comprising about 1.0% amine oxide surfactant, about 5.9% diethylene glycol butyl ether, about 2.0% ethoxylated nonylphenol, about 1.0% isopropyl alcohol, about 5.0%
hydrogen peroxide 50% by weight aqueous solution, 0.05% fragrance and dye.

24. The article of manufacture according to claim 16 wherein the antimicrobial composition comprises about 7.5% Aqueous Silane 5 and about 37.5% water and further comprising about 30% ethanol, about 0.01 % fragrance and about 25% hydrocarbon propellant.

25. The article of manufacture according to claim 16 wherein the antimicrobial composition comprises about 34% Aqueous Silane 5 and 54.9% water, and further comprising about 0.77% antimicrobial quaternary ammonium salt, about 0.76%
fragrance, about 1.0% 1,2 propanediol, and about 7.6% tallow ammonium salt.

26. The article of manufacture according to claim 16 wherein the antimicrobial composition comprises about 7.5% Aqueous Silane 5 and about 30% water; and further

27 comprising about 25% hydrocarbon propellant, about 30% ethanol, about 7.5%
propylene glycol and about 0.01 % fragrance.
27. The article of manufacture according to claim 16 wherein the antimicrobial composition comprises about 5.0% Aqueous Silane 5 and about 85.5% water; and further comprising about 4.4% isopropyl alcohol and at least one constituent selected from the group consisting of cationic surfactants, nonionic surfactants, sequestrants,hydrotropes, detergents, polymers, salts, emulsifiers, fragrances, coloring agents, water softening agents, antimicrobials, and pesticides.

28. The article of manufacture according to claim 16 wherein the antimicrobial composition comprises about 5.0% Aqueous Silane 5 and about 87.2% water; and further comprising about 3.0% isopropyl alcohol and at least one constituent selected from the group consisting of cationic surfactants, nonionic surfactants, sequestrants, hydrotopes, detergents, polymers, salts, emulsifiers, fragrances, coloring agents, water softening agents, antimicrobials, and pesticides.

29. The article of manufacture according to claim 16 wherein the antimicrobial composition comprises about 5.0% Aqueous Silane 5 and about 85.1% water; and further comprising about 1.0% amine oxide surfactant, about 5.9% diethylene glycol butyl ether, about 2.0% ethoxylated nonylphenol, about 1.0% isopropyl alcohol, about 0.05%
fragrance and dye.

30. An article of manufacture comprising a container, said container having an antimicrobial composition comprising 1.2% Silane Mix, about 79.3% water, about 4.0%
ethoxylated nonylphenol, about 2.0 propyleneglycol, about 0.25% citric acid, about 0.11%
fragrance and at least one constituent selected from the group consisting of cationic surfactants, nonionic surfactants, sequestrants, hydrotropes, detergents, polymers, salts, emulsifiers, fragrances, coloring agents, water softening agents, antimicrobials, and pesticides contained therein; packaging material and instructions for use.

31. An antimicrobial composition comprising from about 0.01 % to about 15%
silane of interest, from about 0.01 % to about 50% silane stabilizer, and from about 1 % to 99.98%
water.

32. The composition according to claim 31 wherein the concentration of silane of interest is from about 0.01 % to about 10%.

33. The composition according to claim 32 wherein the silane concentration is from about 0.01 % to about 2%.

34. The composition of claim 33 wherein the silane concentration is from about 0.25% to about 1.5%.

35. The composition according to claim 31 wherein the stabilizer concentration is from about 0.08% to about 7%.

36. The composition according to claim 35 wherein the stabilizer concentration is from about 0.2% to about 2%.

37. An article of manufacture comprising a container, paid container having the antimicrobial composition of claim 31 contained therein; and instructions for use.

38. The article of manufacture according to claim 37 wherein the concentration of silane is from about 0.01 % to about 10%.

39. The article of manufacture according to claim 37 wherein the concentration of silane is from about 0.01 % to about 2%.

40. The article of manufacture according to claim 37 wherein the concentration of silane is from about 0.25% to about 1.5%.

41. The article of manufacture according to claim 37 wherein the concentration of stabilizer is from about 0.08% to about 7%.

42. The article of manufacture according to claim 37 wherein the concentration of stabilizer is from about 0.2% to about 2%.