JPS625439B2 - - Google Patents

Description

[Detailed description of the invention]

FIELD OF THE INVENTION This invention relates to certain silyl quaternary ammonium salts and methods of using them to inhibit bacterial and fungal growth. In particular, the invention relates to the use of such salts as bactericides or fungicides on textiles or other substrates. It is known in the art that organosilicon quaternary ammonium compounds have bacteriostatic, fungistatic and algistatic and/or bactericidal, fungicidal and algicidal properties (e.g. U.S. Pat. Nos. 3,560,385, 3,730,701;
3794736, 3817739, 3865728 and 4005025 and GB 1386876). US Pat. No. 3,730,701 discloses various silyl quaternary ammonium compounds having one long chain alkyl group of 11 to 22 carbon atoms. For example, one such compound, 3-(trimethoxysilyl)propyloctadecyldimethylammonium chloride, is available from Dow Corning as "Bioguard Q9-5700".
(EPA No. 34292-1) is a commercial antimicrobial product marketed as (EPA No. 34292-1). US Patent No. 3794736
The specification describes several other organosilicon amines and their salts that exhibit antimicrobial activity against a wide variety of organisms. According to the present invention, several silyl quaternary ammonium salts are provided that have antimicrobial activity equal to or greater than known compounds. The present invention provides certain silyl quaternary ammonium salts,
In particular 3-(trimethoxysilyl)propyldidecylmethylammonium salts, such as fluorides, chlorides, bromides, iodides, sulfates, acetates and phosphates, and various substances with reactive surfaces, especially textiles and Concerning their use as fungicides and disinfectants for textiles. As used herein, the term "substance having a reactive surface" or "surface-reactive substrate" means that the surface includes a substance capable of forming a covalent chemical bond with the didecylmethyl-substituted silyl quaternary ammonium compound of the present invention. . These didecylmethyl-substituted ammonium compounds have been found to inhibit the growth of microorganisms, including both various Gram-positive and Gram-negative bacteria, more effectively than their neighboring congeners. Although the specific sites of action of organosilicon quaternary ammonium compounds are still under investigation, these compounds are chemically bound to various reactive surfaces and are not removed from the surfaces by repeated leaching or washing. I know that. Therefore, the compounds of the present invention can be used in natural and synthetic textile fibers, siliceous materials,
For example, glass, stone, and ceramics, metals,
They are also useful in imparting durable bioactivity to surfaces such as leather, wood, plastics, etc. Generally, surface-reactive materials are used by contacting them with biologically active compounds, for example to prevent the growth of microorganisms before the spread of microorganisms, or to kill microorganisms and prevent their new growth. After spreading, the substrate is treated by dipping, spraying, padding, or brushing with the compound of the invention. The compounds of the present invention are active in solution and also when applied to solid surfaces. Accordingly, the antimicrobial compounds can be used as pure compounds, in aqueous solutions or dispersions, or in organic solvent media. The compound of the present invention is preferably dissolved in a suitable water-miscible organic solvent to form a solution containing about 50% of the compound of the present invention as an active ingredient. According to the invention, 3-(trimethoxysilyl)
It has been found that propyldidecylmethylammonium salts exhibit antimicrobial properties superior to those of their known adjacent congeners. Accordingly, such materials are useful in a variety of bactericidal, fungicidal, and similar applications for which the use of silyl quaternary ammonium compounds has been previously proposed. The compounds of the present invention can be produced by known methods.
A tertiary amine, ie, didecylmethylamine, is reacted with a suitable silane, such as 3-chloropropyltrimethoxysilane, with or without the presence of a suitable solvent such as methanol. The alkylation reaction of tertiary amine proceeds smoothly to form chloride 3.
-(trimethoxysilyl)propyldidecylmethylammonium. Of course, other quaternary ammonium halides are within the scope of this invention, such as fluorides, if other silanes are similarly reacted.
Bromide or iodide can be created.
Similarly, silanes containing sulfate or acetate anions can be converted to the corresponding quaternary ammonium salts within the scope of this invention. Alternatively, the salts of the invention can be prepared by reacting didecylamine with trimethoxysilylpropyl halide, sulfate, acetate, or phosphate in the presence of sodium methylate to form the corresponding tertiary amine, followed by the formation of the corresponding tertiary amine. It can be produced by methylating a substance to form an organosilicon quaternary ammonium salt. Yet another method for producing the compound of the present invention is to prepare allyldidecylamine,
The method includes subsequent hydrosilylation of this with trimethoxysilane to produce 3-(didecylamino)propyltrimethoxysilane, which is then treated with an appropriate methyl halide to produce the compound of the present invention. A particularly suitable compound, 3-(trimethoxysilyl)propyldidecylmethylammonium chloride, is
direct contact by spraying or brushing with the surface of the material to be treated;
Alternatively, the surface-reactive substrate may be soaked in the pure antimicrobial compound or in a solution thereof in a suitable solvent. Surface-reactive materials or substrates to which compounds of the present invention can be chemically bound include siliceous materials and metal surfaces. Leather, wood, rubber and plastic have also been shown to have reactive surfaces. In fact, a particularly suitable group of substrates with reactive surfaces to which compounds of the invention can readily be attached include natural and synthetic textile fibers and their corresponding textiles. Such natural fibers include cotton, wool, flax and felt, as well as synthetic fibers that can be combined with entirely synthetic polymeric materials such as viscose, cellulose acetate or cellulose triacetate, or nylon, polyether , vinyl polymers such as polyolefins, acrylics and modacrylics, or blends of such materials with natural fibers. Suitable solvents in which the compounds of the invention may be dissolved for disinfecting, fungicidal or similar applications include water and water-miscible organic solvents, such as alcohols such as methanol, ethanol and butanol, methyl cellosolve and ethyl cellosolve. , ketones such as methyl ethyl ketone. On the other hand, solvents used in commercial dry cleaning processes for textile treatment may also be used, such as hydrocarbons, chlorinated hydrocarbons, ethers and benzene. As mentioned above, the active compounds of the invention can be applied to a variety of surfaces by any suitable means. For example, antimicrobial compounds can be sprayed into shoes to inhibit or prevent the growth of microorganisms therein.
The pure compounds or solutions thereof can be applied to walls to prevent mold and mildew, or added to fillers used in paints to produce paints with antimicrobial properties. To treat textiles, they can be dispersed in the solvents used in commercial dry cleaning processes so that they can readily come into contact with the textiles to be treated. Alternatively,
Closure in which the fibers or fabrics to be treated are immersed in the treatment bath, preferably under somewhat elevated temperature conditions, to effect the absorption and fixation of the bioactive compounds on the textile fibers, thus "exhausting" them from the bath. The active compounds can be applied to fabrics or fibers by exhaustion techniques involving the use of systems. Such techniques are described in detail in, for example, US Pat. No. 3,788,803, which precedes the present invention. Another particularly suitable method of applying the bioactive compounds of the invention to textiles or textile fibers is by padding. The fabric to be treated is immersed in a bath or padder containing a solution of antimicrobial compounds. The concentration of active ingredient in the solution is adjusted depending on the ability of the substrate to pick up the antimicrobial compound from the bath. It goes without saying that finishing agents such as softeners and the like may be added to either the exhaustion bath or the padding bath. Thus, in a particularly suitable embodiment of the invention for applying an antimicrobial compound according to the invention to textile fibers or fabrics, the fibers or fabrics are placed in a bath containing the compound (in pure or dissolved form). During the time, from about 3 to 5 minutes to about 20 to 30 minutes, about 25 minutes
Soak at temperatures between 40° and 95°C, preferably between 40° and 70°C. Therefore, the amount of bioactive compound bound to textile fibers can vary depending on the solvent used and the particular structure of the textile. The active ingredient can be applied in amounts from about 0.1% to 1.0% by weight of the textile substrate. After removal of the textile fibers from such exhaustion or padding baths, the treated material is dried in accordance with common practice in the art and then woven or
It is knitted or otherwise converted into a piece of article (if processed in fiber form) and subjected to normal finishing operations. In the examples below, all parts and percentages are by weight and all temperatures are in degrees Celsius, unless otherwise indicated. Example 1 Preparation of 3-(trimethoxysilyl)propyldidecylmethylammonium chloride In a 12, three-neck round-bottomed flask equipped with a stirrer, thermometer, and condenser, 4746 grams (15.2 moles) of didecylmethylamine and 3-chloro Propyltrimethoxysilane 3160.7 grams (15.9 moles)
Put in. The solution is stirred for 48 hours while heating at 110° C. under nitrogen atmosphere. The dark yellow/orange liquid is then placed under vacuum (5 torr) to remove approximately 135 ml of residual 3-chloropropyltrimethoxysilane. The remaining product is then slowly added to 7750 grams of methanol with stirring to produce a product containing 50% active material. Reaction with other appropriately substituted propyltrimethoxysilanes provides other salts of the desired silyl quaternary ammonium compound, such as the bromide or iodide. Example 2 Preparation of 3-(trimethoxysilyl)propyldidecylmethylammonium chloride in methanol.
804 grams (2.58 moles), 536.5 grams (2.7 moles) of 3-chloropropyltrimethoxysilane and 4500 grams of anhydrous methanol. The reaction mixture is stirred under nitrogen while heating to mild reflux for 48 hours. Cool the reaction to 35°C and add 890 grams of anhydrous methanol. The resulting yellow/
The orange solution contains 50% by weight of active substance. Example 3 Chloride 3 against Gram-positive and Gram-negative bacteria
- Comparison of the antibacterial activity of (trimethoxysilyl)propyldidecylmethylammonium with that of other di-long-chain alkyl-substituted organosilicon quaternary ammonium compounds. and Gram-positive (Klebsiella pneumoniae ATCC 4352) strains with various high and low flanking congeners. Prepare 10 ml of a 10% aqueous solution of each fungicide to be tested.
Four serial dilutions are made by pipetting 1 ml of each 10% solution into a 10 ml volumetric flask and filling to the mark with water. Add 0.1 ml of each serial dilution to 9.9 ml of sterile molten nutrient agar in a tube, which is kept at 47°C in a water bath. Add 0.1 ml of blank water to 9.9 ml of sterile thawed nutrient agar to serve as a control.
A 0.1 ml aliquot of a 24 hour culture of each test organism is pipetted into six sterile Petri dishes prelabeled with 1000, 100, 10, 1 and 0.1 and the control organism. The contents of each tube are then poured into its respective Petri dish, swirled, and allowed to solidify. Incubate the Petri dish at 37°C for 48 hours and invert. The results are as follows:

Table: The compound of Example 1 inhibited the growth of the test bacteria at a concentration of 100 ppm of the test compound, but its higher and lower homologs were unable to prevent bacterial growth at this concentration. Example 4 Comparison of the antibacterial activity of 3-(trimethoxysilyl)propyldidecylmethylammonium chloride and the activity of monolong-chain alkyl-substituted organosilicon quaternary ammonium compounds against Gram-positive and Gram-negative bacteria. A related compound with two long-chain alkyl groups was also compared. The test was conducted according to the procedure of Example 1. I got the following result:

【table】

TABLE The activity of the compound of Example 1 was as great as that of the mono-long chain substituted compound Control D. The compound of Example 1 exhibited antimicrobial activity against the Gram-positive strain tested similar to that of the commercial product (Control E), but greater activity against the Gram-negative strain Klebsiella pneumoniae tested than the commercial product. When the compound of Example 1 and Control E were applied to polyester fabric,
K at a concentration of active ingredient of 0.25-0.5% of the weight of the fabric.
Similar results were obtained against Pneumoniae, whereas on 100% cotton fabrics, the
At a concentration of active ingredient in % by weight, the compound of Example 1 again showed greater activity against K. pneimoniae than the commercial product (Control E). From the foregoing, it can be seen that the present invention provides novel organosilicon quaternary ammonium salts that have improved bactericidal, fungicidal and similar antimicrobial activity and can be applied to a variety of surface-active materials. Dew. It is to be understood that the above particularly suitable embodiments are for illustrative purposes only and should not be considered as limiting the scope of the invention, which is properly delineated in the claims. .

Claims (1)

[Claims] 1 formula 1. A silyl quaternary ammonium compound, wherein X is selected from the group consisting of fluoride, chloride, bromide, iodide, sulfate, acetate and phosphate. 2. The silyl quaternary ammonium compound according to claim 1, wherein X is chloride. 3. In a method for inhibiting the growth of Staph aureus and K. pneumoniae on a surface-reactive substrate, the microorganisms are (wherein X is selected from the group consisting of fluoride, chloride, bromide, iodide, sulfate, acetate and phosphate) and The above method, characterized in that the contact is made in an effective amount. 4. The method of claim 3, wherein the quaternary ammonium compound is 3-(trimethoxysilyl)propyldidecylmethylammonium chloride. 5. The method according to claim 3, wherein the substrate is a siliceous material. 6. The method according to claim 3, wherein the substrate is metal. 7. The method of claim 3, wherein the substrate is selected from the group consisting of leather, wood, rubber and plastic. 8. The substrate is made of natural or synthetic textile fibers;
A method according to claim 3. 9. The method of claim 8, wherein the quaternary ammonium compound is used in an amount of from 0.1 to 1.0% by weight of the textile substrate.