A synergistic antimicrobial composition.
Abstract
An antimicrobial agent and its use together with an acid provides a composition that possesses synergistic effects. More particularly, there is provided a synergistic antimicrobial composition in the form of a quaternary ammonium compound and an acid such as boric, citric and malic.
Term
Term ended
Projected expiry passed 26 April 2009, 17.4 years ago.
- Priority
- Filed
- Published
- Projected expiry
- Today
6 claims: 6 independent, 0 dependent
- 1A synergistic antimicrobial composition comprising:(a) a silane of the general formula Y₃SiRN⁺R′R˝R‴X⁻ where y denotes an organic or a hydrolyzable radical, R denotes a divalent hydrocarbon radical with 1 to 6 carbon atoms, R′, R˝ and R‴ independently denote saturated or unsaturated hydrocarbon radicals containing 1 to 18 carbon atoms, saturated or unsaturated organic radicals consisting of carbon, hydrogen and oxygen;carbon, hydrogen and sulfur;or carbon, hydrogen and nitrogen, and X denotes an anion, and (b) an acid selected from the group consisting of acetic, adipic, anisic, benzoic, boric, butyric, capric, citraconic, citric, cresotinic, elaidic, formic, fumaric, gallic, glutaric, glycolic, lactic, lauric, levulinic, maleic, malic, malonic, oleic, oxalic, palmitic, phthalic, propionic, pyruvic, salicylic, stearic, succinic, tannic and tartaric acids, and where the mole ratio of (a) to (b) is between about 1:1 and about 1:10.
- 2A synergistic antimicrobial composition comprising:(a) a silane of the general formula Y₃SiRN⁺R′R˝R‴X⁻ where y denotes an organic or a hydrolyzable radical, R denotes a divalent hydrocarbon radical with 1 to 6 carbon atoms, R′, R˝ and R‴ independently denote saturated or unsaturated hydrocarbon radicals containing 1 to 18 carbon atoms, saturated or unsaturated organic radicals consisting of carbon, hydrogen and oxygen;carbon, hydrogen and sulfur;or carbon, hydrogen and nitrogen, and X denotes an acid anion, and (b) an acid selected from the group consisting of acetic, adipic, anisic, benzoic, boric, butyric, capric, citraconic, citric, cresotinic, elaidic, formic, fumaric, gallic, glutaric, glycolic, lactic, lauric, levulinic, maleic, malic, malonic, oleic, oxalic, palmitic, phthalic, propionic, pyruvic, salicylic, stearic, succinic, tannic and tartaric acids.
- 3The method of inhibiting the proliferation of potentially destructive microorganisms on a substrate comprising treating the substrate with an effective amount of a synergistic antimicrobial composition formed by combining:(a) a silane of the general formula Y₃SiRN⁺R′R˝R‴X⁻ where y denotes an organic or a hydrolyzable radical, R denotes a divalent hydrocarbon radical with 1 to 6 carbon atoms, R′, R˝ and R‴ independently denote saturated or unsaturated hydrocarbon radicals containing 1 to 18 carbon atoms, saturated or unsaturated organic radicals consisting of carbon, hydrogen and oxygen;carbon, hydrogen and sulfur;or carbon, hydrogen and nitrogen, and X denotes an acid anion, with (b) an acid selected from the group consisting of acetic, adipic, anisic, benzoic, boric, butyric, capric, citraconic, citric, cresotinic, elaidic, formic, fumaric, gallic, glutaric, glycolic, lactic, lauric, levulinic, maleic, malic, malonic, oleic, oxalic, palmitic, phthalic, propionic, pyruvic, salicylic, stearic, succinic, tannic and tartaric acids.
- 4A cellulosic fiber substrate having a surface that inhibits the proliferation of potentially destructive microorganisms present on the substrate, the surface being formed by treating the substrate with an effective amount of a synergistic antimicrobial composition comprising:(a) a silane of the general formula Y₃SiRN⁺R′R˝R‴X⁻ where y denotes an organic or a hydrolyzable radical, R denotes a divalent hydrocarbon radical with 1 to 6 carbon atoms, R′, R˝ and R‴ independently denote saturated or unsaturated hydrocarbon radicals containing 1 to 18 carbon atoms, saturated or unsaturated organic radicals consisting of carbon, hydrogen and oxygen;carbon, hydrogen and sulfur;or carbon, hydrogen and nitrogen, and X denotes an acid anion, and (b) an acid selected from the group consisting of acetic, adipic, anisic, benzoic, boric, butyric, capric, citraconic, citric, cresotinic, elaidic, formic, fumaric, gallic, glutaric, glycolic, lactic, lauric, levulinic, maleic, malic, malonic, oleic, oxalic, palmitic, phthalic, propionic, pyruvic, salicylic, stearic, succinic, tannic and tartaric acids.
- 5A synergistic antimicrobial composition comprising:(a) an organosilane having the general formula selected from the group consisting of wherein, in each formula, R is an alkyl radical of 1 to 4 carbon atoms or hydrogen;a has a value of 0, 1 or 2;R′ is a methyl or ethyl radical;R˝ an alkylene group of 1 to 4 carbon atoms;R‴, R˝˝ and R v are each independently selected from a group consisting of alkyl radicals of 1 to 18 carbon atoms, -CH₂C₆H₅, -CH₂CH₂OH, -CH₂OH and -(CH₂) x NHC(O)R vi , wherein x has a value of from 2 to 10 and R vi is a perfluoroalkyl radical having from 1 to 12 carbon atoms;X is chloride, bromide, fluoride, iodide, acetate or tosylate;and Ph is phenyl;(b) an acid selected from the group consisting of acetic, adipic, anisic, benzoic, boric, butyric, capric, citraconic, citric, cresotinic, elaidic, formic, fumaric, gallic, glutaric, glycolic, lactic, lauric, levulinic, maleic, malic, malonic, oleic, oxalic, palmitic, phthalic, propionic, pyruvic, salicylic, stearic, succinic, tannic and tartaric acids, and where the mole ratio of (a) to (b) is between about 1:1 and about 1:10.
- 6A synergistic antimicrobial composition comprising:(a) an organosilane having the general formula selected from the group consisting of wherein, in each formula, R is an alkyl radical of 1 to 4 carbon atoms or hydrogen;a has a value of 0, 1 or 2;R′ is a methyl or ethyl radical;R˝ is an alkylene group of 1 to 4 carbon atoms;R‴, R˝˝ and R v are each independently selected from a group consisting of alkyl radicals of 1 to 18 carbon atoms, -CH₂C₆H₅, -CH₂CH₂OH, -CH₂OH and -(CH₂) x NHC(O)R vi , wherein x has a value of from 2 to 10 and R vi is a perfluoroalkyl radical having from 1 to 12 carbon atoms;X is chloride, bromide, fluoride, iodide, acetate or tosylate and Ph is phenyl;(b) an acid selected from the group consisting of acetic, adipic, anisic, benzoic, boric, butyric, capric, citraconic, citric, cresotinic, elaidic, formic, fumaric, gallic, glutaric, glycolic, lactic, lauric, levulinic, maleic, malic, malonic, oleic, oxalic, palmitic, phthalic, propionic, pyruvic, salicylic, stearic, succinic, tannic and tartaric acids, and where the mole ratio of (a) to (b) is between about 1:1 and about 1:10.
Independent claims6
36 paragraphs, as filed
0001This invention relates to an antimicrobial agent and its use together with an acid to provide a composition that possesses synergistic effects. More particularly, the invention provides a synergistic antimicrobial composition in the form of a quaternary ammonium compound and an acid such as boric, citric and malic.
0002Antimicrobial agents are chemical compositions that are used to prevent microbiological contamination and deterioration of products, materials and systems. Particular areas of application of antimicrobial agents and compositions are, for example, cosmetics, disinfectants, sanitizers, wood preservation, food, animal feed, cooling water, metalworking fluids, hospital and medical uses, plastics and resins, petroleum, pulp and paper, textiles, latex, adhesives, leather and hides and paint slurries. Of the diverse categories of antimicrobial agents and compositions, quaternary ammonium compounds represent one of the largest of the classes of agents in use. At low concentrations, quaternary ammonium type antimicrobial agents are bacteriostatic, fungistatic, algistatic, sporostatic and tuberculostatic. At medium concentrations they are bactericidal, fungicidal, algicidal and viricidal against lipophilic viruses. Silicone containing quaternary ammonium compounds are well known. What is new and not believed to be taught in the prior art is the concept of combining acids with the particular silanes of the present invention to kill germs synergistically. In accordance with the present invention, it has been found that antimicrobial properties of silicone containing quaternary ammonium compounds can be improved by mixing the antimicrobial agent with an acid to produce a composition that acts synergistically in preventing microbiological contamination and deterioration of products, materials and systems. For example, 3-(trimethoxysilyl)propyldimethyloctadecylammonium chloride is an effective antimicrobial agent in which the active ingredient hydrolyzes in water and reacts with substrates with which it is brought into contact. These substrates demonstrate nonleaching broad spectrum antimicrobial activity. By including an acid component in the antimicrobial composition, such activity of this particular quaternary ammonium compound has been increased substantially against a mixed fungal culture where neither the acid nor the quaternary ammonium compound was effective alone. Hence, the compositions set forth in the present invention possess advantages over existing antimicrobial treating agents and provide improved results thereover, since the combinations disclosed herein of an antimicrobial agent together with an acid provide better results than when either of the individual components are employed separately. Thus, the disadvantages of the prior art are overcome with the present invention wherein improved antimicrobial agents are provided.
0003This invention relates to a synergistic antimicrobial composition formed by combining: <ul id="ul0001" list-style="none"><li>(a) a silane of the general formula Y₃SiRN⁺R′R˝R‴X⁻ where y denotes an organic or a hydrolyzable radical, R denotes a divalent hydrocarbon radical with 1 to 6 carbon atoms, R′, R˝ and R‴ independently denote saturated or unsaturated hydrocarbon radicals containing 1 to 18 carbon atoms, saturated or unsaturated organic radicals consisting of carbon, hydrogen and oxygen; carbon, hydrogen and sulfur; or carbon, hydrogen and nitrogen, and X denotes an anion, with</li><li>(b) an acid selected from the group consisting of acetic, adipic, anisic, benzoic, boric, butyric, capric, citraconic, citric, cresotinic, elaidic, formic, fumaric, gallic, glutaric, glycolic, lactic, lauric, levulinic, maleic, malic, malonic, oleic, oxalic, palmitic, phthalic, propionic, pyruvic, salicylic, stearic, succinic, tannic and tartaric acids, and where the mole ratio of (a) to (b) is between about 1:1 and about 1:10.</li></ul>
0004The preferred acids are citric, boric and malic, and the most desirable mole ratio of (a) to (b) is preferably about 1.5. The silanes are more particularly represented by the formula: Y₃Si(CH₂)<sub>m</sub>N⁺(CH₃)₂(CH₂)<sub>n</sub>CH₃X⁻ where Y denotes an organic or hydrolyzable radical, X denotes an acid anion, and where m + n is 16 to 23, m is 1 to 11 and n is 9 to 17. Specific silanes are, for example, (CH₃O)₃Si(CH₂)₃N⁺(CH₃)₂C₁₈H₃₇Cl⁻ and (CH₃O)₃Si(CH₂)₃N⁺(C₁₀H₂₁)₂(CH₃)Cl⁻.
0005The invention also relates to a method of inhibiting the proliferation of potentially destructive microorganisms on a substrate by treating the substrate with an effective amount of a synergistic antimicrobial composition formed by combining the silane of the general formula indicated above together with an acid of the group set forth previously. The substrate is preferably paper.
0006The invention further relates to a cellulosic fiber substrate having a surface that inhibits the proliferation of potentially destructive microorganisms present on the substrate by treating the substrate with an effective amount of a synergistic antimicrobial composition formed by combining the silane of the general formula indicated previously together with an acid of the group set forth above.
0007It is, therefore, an object of the present invention to provide compositions, methods of treatment and articles of manufacture, wherein there is employed a synergistic antimicrobial agent containing a silane and an acid.
0008It is also an object of the present invention to provide compositions, methods of treatment, and articles of manufacture, wherein there is employed a synergistic antimicrobial agent containing a silane such as 3-(trimethoxysilyl)propyldimethyloctadecylammonium chloride, and an acid such as one of citric, boric and malic, for example.
0009These and other features, objects and advantages, of the present invention will become apparent from the following detailed description of the invention.
0010In order to illustrate the concept of the present invention, tests were conducted as set forth hereinbelow. Results from the tests are set forth in the form of tabular data in order to facilitate an understanding of the invention. Varied samples were prepared some of which acted as control samples, while others contained varied compositions of components selected such that the data could be better interpreted.
0011For example, in Table I, four samples were prepared containing the ingredients shown and in the amounts specified. The sole sample containing the acid component of the invention was Sample No. 4. These four samples were tested one against the other along with a control sample for the prevention of fungal overgrowth and the results of these tests as well as the comparison between the various samples can be seen in Table II. Table II shows that the sole sample providing a zero percent fungal overgrowth was Sample No. 4 which is equivalent to the identically numbered sample in Table I, which is the acid containing composition of the present invention. Thus, it should be apparent that the inclusion of citric acid, for example, along with the antimicrobial quaternary ammonium compound indicated as "B" in the Tables produces a result not obtainable with either the acid component alone or the antimicrobial quaternary ammonium compound when used separately. For example, when used separately in Sample No. 2 in Table I, the quaternary ammonium compound "B" allowed 30% fungal overgrowth as shown in Table II. Sample No. 1 containing a cyclic antimicrobial quaternary ammonium compound of 3-(trimethoxysilyl)propyloctadecyldimethyl ammonium chloride and 3-chloropropyltrimethoxysilane in methanol, was not as effective as the acid containing Sample No. 4, allowing a 75% fungal overgrowth. Sample No. 4 out performed a mixture of two antimicrobial agents in Sample No. 3 where the antimicrobial compound "B" was combined with another quaternary ammonium salt ARQUAD® T2, manufactured by Armour Hess Chemicals, allowing a fungal overgrowth of 75%. The blank control sample in Table II was ineffective allowing a 100% fungal overgrowth.
0012In view of the data obtained and set forth in Tables I and II, additional tests were conducted with samples of citric and boric acid to confirm the results of Table II. Thus, in Table III, varied samples were prepared and tested for the prevention of fungal overgrowth over a two to three week period. It can be seen from Table IV that the citric and boric acid compositions containing the antimicrobial compound "B" again out performed both the acids when employed alone, as well as the quaternary ammonium compound "B", when each were employed individually. Thus, over a two week period, there was no fungal overgrowth with both the mixtures of compound "B" with either citric or boric acid. Over the three week period, the mixture of boric acid and compound "B" outperformed the mixture of compound "B" with citric acid by 20%. In order to demonstrate the durability and the substantivity of the compounds of the present invention, it should be noted that the anion of an aqueous sodium salt of bromphenol blue can be complexed with the cation of a polymerized silane of this invention while it is on a substrate. The blue colored complex, substantive to a water rinse, is qualitatively indicative of the presence of the cation on the substrate thus indicating the extent of antimicrobial agent on a given substrate. A comparison of the intensity of retained blue color to a color standard is used as a check to determine if the treatment has been applied properly.
0013The method consists of preparing a 0.02 to 0.04 weight percent solution of bromphenol blue in distilled water. This solution is made alkaline using a few drops of saturated Na₂CO₃ solution per 100 milliliters of the solution. Two to three drops of this solution are placed on the treated substrate and allowed to stand for two minutes. The substrate is then rinsed with copious amounts of tap water and the substrate is observed for a blue stain and it is compared to a color standard.
0014For a spectrophotometric determination, the following test is used.
0015The sodium salt of bromphenol blue is depleted from a standard solution by complexing with the cations on a treated substrate. The change in bromphenol blue concentration is determined spectrophotometrically or by comparison with color standards whereby the level of substrate treatment by the cationic silane is determinable.
0016The method consists of preparing a 0.02 weight percent standard solution of bromphenol blue in distilled water. It is made alkaline with a few drops of saturated Na₂CO₃ solution per 100 milliliters of bromphenol blue solution. The color of this solution is purple.
0017The blank solution is adjusted to yield a 10 to 12% transmittance reading when measured in 1 cm cells using a spectrophotometer set at 589 nm by the following method.
0018Fill a container 3/4 full of distilled water and add 2 ml of the 0.02% standard bromphenol blue solution for every 50 ml of distilled water. Add 0.5 ml of a 1% Triton® X-100 surfactant (manufactured by Rohm and Haas, Philadelphia, PA, USA) aqueous solution for every 50 ml of water. Mix and, using the spectrophotometer, determine the maximum absorbance. Adjust the upper zero to 100% transmittance with distilled water. Check the percent transmittance of the working bromphenol blue solution at the maximum absorbance setting. Adjust the blank solution to 10 to 12% transmittance with either water or bromphenol blue standard solution as necessary.
0019The samples of treated substrate are tested by placing 0.5 gram samples of the substrate standards in a flask large enough for substantial agitation of the sample and the test solution. Add 50 ml of the working solution. Agitate for 20 minutes on a wrist-action shaker. Fill the test curvette with the test solution. Centrifuge if particulate matter is present. Measure the percent transmittance at the wavelength set forth above. The transmittance is compared against a standard curve prepared by preparing several substrate samples of known concentration of the cationic silane. For example, samples containing a known amount of cationic silane at, for example, 0%, 0.25%, 0.50%, 0.75% and 1% are read spectrophotometrically and a curve is plotted. The data in Tables II and IV was generated using the following technique.
0020The antimicrobial activity of a treated surface was evaluated by shaking a sample weighing 0.75 grams in a 750,000 to 1,500,000 count <u style="single">Klebsiella pneumoniae</u> suspension for a one hour contact time. The suspension was serially diluted, both before and after contact and cultured. The number of viable organisms in the suspensions was determined. The percent reduction based on the original count was determined. The method was intended for those surfaces having a reduction capability of 75 to 100% for the specified contact time. The results are reported as the percent reduction.
0021Media used in this test were nutrient broth, catalog No. 0003-01-6 and tryptone glucose extract agar, catalog No. 0002-01-7 both available from Difco Laboratories, Detroit, Michigan, U.S.A. The microorganism used was <u style="single">Klebsiella pneumoniae</u> American Type Culture Collection; Rockville, Md., U.S.A., catalog No. 4352.
0022The procedure used for determining the zero contact time counts was carried out by utilizing two sterile 250 ml. screw-cap Erlenmeyer flasks for each sample. To each flask was added 70 ml of sterile buffer solution. To each flask was added, aseptically, 5 ml of the organism inoculum. The flasks were capped and placed on a wrist action shaker. They were shaken at maximum speed for 1 minute. Each flask was considered to be at zero contact time and was immediately subsampled by transferring 1 ml of each solution to a separate test tube containing 9 ml of sterile buffer. The tubes were agitated with a vortex mixer and then 1 ml of each solution was transferred to a second test tube containing 9 ml of sterile buffer. Then, after agitation of the tubes, 1 ml of each tube was transferred to a separate sterile petri dish. Duplicates were also prepared. Sixteen ml of molten (42°C.) tryptone glucose extract agar was added to each dish. The dishes were each rotated ten times clockwise and ten times counterclockwise. The dishes were then incubated at 37°C. for 24 to 36 hours. The colonies were counted considering only those between 30 and 300 count as significant. Duplicate samples were averaged. The procedure used for determining the bacterial count after 1 hour was essentially the same as that used to determine the count at the zero contact time. The only difference was that pour plating was performed at the 10⁰ and 10⁻¹ dilutions as well as at the 10⁻² dilution. "Percent reduction" was calculated by the formula<maths id="math0001" num=""><img file="EP0339957A2_D0001.tif" /></maths> where A is the count per milliliter for the flask containing the treated substrate; B is zero contact time count per milliliter for the flask used to determine "A" before the addition of the treated substrate and C is zero contact time count per milliliter for the untreated control substrate. <tables id="tabl0001" num="0001"><table frame="all"><title>TABLE I</title><tgroup cols="5" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="31.50mm" /><colspec colnum="2" colname="col2" colwidth="31.50mm" /><colspec colnum="3" colname="col3" colwidth="31.50mm" /><colspec colnum="4" colname="col4" colwidth="31.50mm" /><colspec colnum="5" colname="col5" colwidth="31.50mm" /><thead valign="top"><row><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col5" align="center"><u style="single">SAMPLE</u></entry></row><row><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="center"><u style="single">I</u></entry><entry namest="col3" nameend="col3" align="center"><u style="single">II</u></entry><entry namest="col4" nameend="col4" align="center"><u style="single">III</u></entry><entry namest="col5" nameend="col5" align="center"><u style="single">IV</u></entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Water(gms.)</entry><entry namest="col2" nameend="col2" align="right">----</entry><entry namest="col3" nameend="col3" align="right">539</entry><entry namest="col4" nameend="col4" align="char" char=".">539</entry><entry namest="col5" nameend="col5" align="char" char=".">533.5</entry></row><row><entry namest="col1" nameend="col1" align="left">Temperature(°C)</entry><entry namest="col2" nameend="col2" align="right">61</entry><entry namest="col3" nameend="col3" align="right">61</entry><entry namest="col4" nameend="col4" align="char" char=".">61</entry><entry namest="col5" nameend="col5" align="char" char=".">61</entry></row><row><entry namest="col1" nameend="col1" align="left">Time(min.)</entry><entry namest="col2" nameend="col2" align="right">30</entry><entry namest="col3" nameend="col3" align="right">30</entry><entry namest="col4" nameend="col4" align="char" char=".">30</entry><entry namest="col5" nameend="col5" align="char" char=".">30</entry></row><row><entry namest="col1" nameend="col1" align="left">Solution(gms.)</entry><entry namest="col2" nameend="col2" align="right">550</entry><entry namest="col3" nameend="col3" align="right">550</entry><entry namest="col4" nameend="col4" align="char" char=".">550</entry><entry namest="col5" nameend="col5" align="char" char=".">550</entry></row><row><entry namest="col1" nameend="col1" align="left">Paper(gms.)</entry><entry namest="col2" nameend="col2" align="right">5</entry><entry namest="col3" nameend="col3" align="right">5</entry><entry namest="col4" nameend="col4" align="char" char=".">5</entry><entry namest="col5" nameend="col5" align="char" char=".">5</entry></row><row><entry namest="col1" nameend="col1" align="left">Temp.Rise(°/min.)</entry><entry namest="col2" nameend="col2" align="right">2</entry><entry namest="col3" nameend="col3" align="right">2</entry><entry namest="col4" nameend="col4" align="char" char=".">2</entry><entry namest="col5" nameend="col5" align="char" char=".">2</entry></row><row><entry namest="col1" nameend="col1" align="left">Compound</entry><entry namest="col2" nameend="col2" align="right">A</entry><entry namest="col3" nameend="col3" align="right">B</entry><entry namest="col4" nameend="col4" align="char" char=".">B</entry><entry namest="col5" nameend="col5" align="char" char=".">B</entry></row><row><entry namest="col1" nameend="col1" align="left">Compound(gms.)</entry><entry namest="col2" nameend="col2" align="right">550</entry><entry namest="col3" nameend="col3" align="right">11</entry><entry namest="col4" nameend="col4" align="char" char=".">5.5</entry><entry namest="col5" nameend="col5" align="char" char=".">5.5</entry></row><row><entry namest="col1" nameend="col1" align="left">Acid</entry><entry namest="col2" nameend="col2" align="right">----</entry><entry namest="col3" nameend="col3" align="right">----</entry><entry namest="col4" nameend="col4" align="char" char=".">----</entry><entry namest="col5" nameend="col5" align="left">Citric</entry></row><row><entry namest="col1" nameend="col1" align="left">Acid(gms.)</entry><entry namest="col2" nameend="col2" align="right">----</entry><entry namest="col3" nameend="col3" align="right">----</entry><entry namest="col4" nameend="col4" align="char" char=".">----</entry><entry namest="col5" nameend="col5" align="char" char=".">11</entry></row><row><entry namest="col1" nameend="col1" align="left">Additive</entry><entry namest="col2" nameend="col2" align="right">----</entry><entry namest="col3" nameend="col3" align="right">----</entry><entry namest="col4" nameend="col4" align="char" char=".">C</entry><entry namest="col5" nameend="col5" align="char" char=".">----</entry></row><row><entry namest="col1" nameend="col1" align="left">Additive(gms.)</entry><entry namest="col2" nameend="col2" align="right">----</entry><entry namest="col3" nameend="col3" align="right">----</entry><entry namest="col4" nameend="col4" align="char" char=".">5.5</entry><entry namest="col5" nameend="col5" align="char" char=".">----</entry></row><row><entry namest="col1" nameend="col5" align="justify">A= Cyclic quaternary ammonium salt</entry></row><row><entry namest="col1" nameend="col5" align="justify">B= (CH₃O)₃Si(CH₂)₃N+(CH₃)₂C₁₈H₃₇Cl-</entry></row><row rowsep="1"><entry namest="col1" nameend="col5" align="justify">C= ARQUAD® T2, a quaternary ammonium salt of Armour Hess Chemicals</entry></row></tbody></tgroup></table></tables><tables id="tabl0002" num="0002"><table frame="all"><title>TABLE II</title><tgroup cols="2" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="78.75mm" /><colspec colnum="2" colname="col2" colwidth="78.75mm" /><thead valign="top"><row><entry namest="col1" nameend="col1" align="left"><u style="single">SAMPLE</u></entry><entry namest="col2" nameend="col2" align="center"><u style="single">FUNGAL</u></entry></row><row><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="center">(% Overgrowth)</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Control</entry><entry namest="col2" nameend="col2" align="right">100</entry></row><row><entry namest="col1" nameend="col1" align="right">1</entry><entry namest="col2" nameend="col2" align="right">75</entry></row><row><entry namest="col1" nameend="col1" align="right">2</entry><entry namest="col2" nameend="col2" align="right">30</entry></row><row><entry namest="col1" nameend="col1" align="right">3</entry><entry namest="col2" nameend="col2" align="right">75</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="right">4</entry><entry namest="col2" nameend="col2" align="right">0</entry></row></tbody></tgroup></table></tables><tables id="tabl0003" num="0003"><table frame="all"><title>TABLE III</title><tgroup cols="4" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="39.37mm" /><colspec colnum="2" colname="col2" colwidth="39.37mm" /><colspec colnum="3" colname="col3" colwidth="39.37mm" /><colspec colnum="4" colname="col4" colwidth="39.37mm" /><thead valign="top"><row><entry namest="col1" nameend="col1" align="center"><u style="single">ACID</u></entry><entry namest="col2" nameend="col2" align="center"><u style="single">ACID</u></entry><entry namest="col3" nameend="col3" align="center"><u style="single">WATER</u></entry><entry namest="col4" nameend="col4" align="center"><u style="single">B</u></entry></row><row><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="center">(gms.)</entry><entry namest="col3" nameend="col3" align="center">(gms.)</entry><entry namest="col4" nameend="col4" align="center">(gms.)</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Citric</entry><entry namest="col2" nameend="col2" align="right">11</entry><entry namest="col3" nameend="col3" align="right">550</entry><entry namest="col4" nameend="col4" align="char" char=".">5.5</entry></row><row><entry namest="col1" nameend="col1" align="left">Citric</entry><entry namest="col2" nameend="col2" align="right">11</entry><entry namest="col3" nameend="col3" align="right">539</entry><entry namest="col4" nameend="col4" align="char" char=".">----</entry></row><row><entry namest="col1" nameend="col1" align="left">Boric</entry><entry namest="col2" nameend="col2" align="right">11</entry><entry namest="col3" nameend="col3" align="right">550</entry><entry namest="col4" nameend="col4" align="char" char=".">5.5</entry></row><row><entry namest="col1" nameend="col1" align="left">Boric</entry><entry namest="col2" nameend="col2" align="right">11</entry><entry namest="col3" nameend="col3" align="right">539</entry><entry namest="col4" nameend="col4" align="char" char=".">----</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">-----</entry><entry namest="col2" nameend="col2" align="right">----</entry><entry namest="col3" nameend="col3" align="right">494</entry><entry namest="col4" nameend="col4" align="char" char=".">55</entry></row></tbody></tgroup></table></tables><tables id="tabl0004" num="0004"><table frame="all"><title>TABLE IV</title><tgroup cols="3" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="52.50mm" /><colspec colnum="2" colname="col2" colwidth="52.50mm" /><colspec colnum="3" colname="col3" colwidth="52.50mm" /><thead valign="top"><row><entry namest="col1" nameend="col1" align="center"><u style="single">SAMPLE</u></entry><entry namest="col2" nameend="col3" align="center"><u style="single">FUNGAL</u></entry></row><row><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col3" align="center">(% Overgrowth)</entry></row><row><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="center"><u style="single">TWO WEEKS</u></entry><entry namest="col3" nameend="col3" align="center"><u style="single">THREE WEEKS</u></entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Blank Control</entry><entry namest="col2" nameend="col2" align="right">100</entry><entry namest="col3" nameend="col3" align="right">100</entry></row><row><entry namest="col1" nameend="col1" align="left">Citric Acid Control</entry><entry namest="col2" nameend="col2" align="right">100</entry><entry namest="col3" nameend="col3" align="right">100</entry></row><row><entry namest="col1" nameend="col1" align="left">Citric Acid + B</entry><entry namest="col2" nameend="col2" align="right">0</entry><entry namest="col3" nameend="col3" align="right">20</entry></row><row><entry namest="col1" nameend="col1" align="left">Boric Acid Control</entry><entry namest="col2" nameend="col2" align="right">10</entry><entry namest="col3" nameend="col3" align="right">10</entry></row><row><entry namest="col1" nameend="col1" align="left">Boric Acid + B</entry><entry namest="col2" nameend="col2" align="right">0</entry><entry namest="col3" nameend="col3" align="right">0</entry></row><row><entry namest="col1" nameend="col1" align="left">Solution B</entry><entry namest="col2" nameend="col2" align="right">90</entry><entry namest="col3" nameend="col3" align="right">90</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">10% Solution B</entry><entry namest="col2" nameend="col2" align="right">90</entry><entry namest="col3" nameend="col3" align="right">90</entry></row></tbody></tgroup></table></tables>
0023The silanes useful in this invention also have the general formula <chemistry id="chem0001" num="0001"><img file="EP0339957A2_D0002.tif" /></chemistry>
0024It should be noted that generically, these materials are quaternary ammonium salts of silanes. Most of the silanes falling within the scope of this invention are known silanes and references disclosing such silanes are numerous. One such reference, United States Patent No. 4,259,103, issued to James R. Malek and John L. Speier, on March 31, 1981, discusses the use of such silanes to render the surfaces of certain substrates antimicrobial. Canadian Patent No. 1,010,782, issued to Charles A. Roth shows the use of fillers treated with certain silanes to be used in paints and the like to give antimicrobial effects.
0025Numerous other publications have disclosed such silanes, namely, A. J. Isquith, E. A. Abbott and P. A. Walters, Applied Microbiology, December, 1972, pages 859-863; P. A. Walters, E. A. Abbott and A. J. Isquith, Applied Microbiology, 25, No. 2, p. 253-256, February 1973 and E. A. Abbott and A. J. Isquith, United States Patent No. 3,794,736 issued February 26, 1974, U.S. Patent 4,406,892, issued September 27, 1983, among others.
0026For purposes of this invention, the silanes can be used neat or they can be used in solvent or aqueous-solvent solutions. When the silanes are used neat, the inventive process is preferably carried out in a system in which some small amount of water is present. If it is not possible to have a system with some small amount of water present, then a water soluble or water-dispersable, low molecular weight hydrolyzate of the silane may be used. What is important is the fact that the durability of any effect produced by the silane as part of a product requires that the silane molecule react with a surface to a certain extent. The most reactive species, as far as the silanes are concerned, is the ≡SiOH that is formed by hydrolysis of the alkoxy groups present on the silane. The ≡SiOH groups tend to react with the surface and bind the silanes to the surface. It is believed by the inventor even though the prime mode of coupling to the surface system is by the route described above, it is also believed by the inventor that the alkoxy groups on the silicon atom may also participate in their own right to bind to the surface.
0027Preferred for this invention is a reactive surface containing some small amount of water. By "reactive", it is meant that the surface must contain some groups which will react with some of the silanols generated by hydrolysis of the silanes of this invention.
0028R in the silanes of this invention are alkyl groups of 1 to 4 carbon atoms. Thus, useful as R in this invention are the methyl, ethyl, propyl and butyl radicals. RO in the above formulas can also be R. R can also be hydrogen thus indicating the silanol form, i.e. the hydrolyzate. The value of <u style="single">a</u> is 0, 1 or 2 and R′ is a methyl or ethyl radical.
0029R˝ for purposes of this invention is an alkylene group of 1 to 4 carbon atoms. Thus, R˝ can be alkylene groups such as methylene, ethylene, propylene and butylene. R‴, R˝˝ and R<sup>v</sup> are each independently selected from a group which consists of alkyl radicals of 1 to 18 carbons, -CH₂C₆H₅ , -CH₂CH₂OH, -CH₂OH and -(CH₂)<sub>x</sub>NHC(O)R<sup>vi</sup>. <u style="single">x</u> has a value of from 2 to 10 and R<sup>vi</sup> is a perfluoroalkyl radical having from 1 to 12 carbon atoms. X is chloride, bromide, fluoride, iodide, acetate or tosylate. Ph is phenyl.
0030Preferred for this invention are the silanes of the general formula <chemistry id="chem0002" num="0002"><img file="EP0339957A2_D0003.tif" /></chemistry> wherein R is methyl or ethyl; <u style="single">a</u> has a value of zero, 1 or 2; R˝ is propylene; R‴ is methyl or ethyl; R˝˝ and R<sup>v</sup> are selected from alkyl groups containing 1 to 18 carbon atoms wherein at least one such group is larger than eight carbon atoms and x is either chloride, acetate or tosylate.
0031Most preferred for this invention are those silanes having the formula (CH₃O)₃Si(CH₂)₃N<sup>⊕</sup>(CH₃)₂C₁₈H₃₇Cl⁻ and (CH₃O)₃Si(CH₂)₃N<sup>⊕</sup>CH₃(C₁₀H₂₁)₂Cl⁻.
0032As indicated above, most of these silanes are known from the literature and methods for their preparation are known as well. See, for example, U.S. Patent 4,282,366, issued August 4, 1981; U.S. Patent 4,394,378, issued July 19, 1983, and U.S. Patent 3,661,963 issued May 9, 1972, among others.
0033Specific silanes within the scope of the invention are represented by the formulae: (CH₃O)₃Si(CH₂)₃N⁺(CH₃)₂C₁₈H₃₇Cl⁻, (CH₃O)₃Si(CH₂)₃N⁺(CH₃)₂C₁₈H₃₇Br⁻, (CH₃O)₃Si(CH₂)₃N⁺(C₁₀H₂₁)₂CH₃Cl⁻, (CH₃O)₃Si(CH₂)₃N⁺(C₁₀H₂₁)₂CH₃Br⁻, (CH₃O)₃Si(CH₂)₃N⁺(CH₃)₃Cl⁻, (CH₃O)₃SiCH₂CH₂CH₂P⁺(C₆H₅)₃Cl⁻, (CH₃O)₃SiCH₂CH₂CH₂P⁺(C₆H₅)₃Br⁻, (CH₃O)₃SiCH₂CH₂CH₂P⁺(CH₃)₃Cl⁻, (CH₃O)₃SiCH₂CH₂CH₂P⁺(C₆H₁₃)₃Cl⁻, (CH₃)₃Si(CH₂)₃N⁺(CH₃)₂C₁₂H₂₅Cl⁻, (CH₃)₃Si(CH₂)₃N⁺(C₁₀H₂₁)₂CH₃Cl⁻, (CH₃)₃Si(CH₂)₃N⁺(CH₃)₂C₁₈H₃₇Cl⁻, (CH₃O)₃Si(CH₂)₃N⁺(CH₃)₂C₄H₉Cl⁻, (C₂H₅O)₃Si(CH₂)₃N⁺(CH₃)₂C₁₈H₃₇Cl⁻, (CH₃O)₃Si(CH₂)₃N⁺(CH₃)₂CH₂C₆H₅Cl⁻, (CH₃O)₃Si(CH₂)₃N⁺(CH₃)₂CH₂CH₂OHCl⁻, (HO)₃Si(CH₂)₃N⁺PhCl⁻, (CH₃O)₃Si(CH₂)₃N⁺PhCl⁻, (CH₃O)₃Si(CH₂)₃N⁺(CH₃)₂(CH₂)₃NHC(O)(CF₂)₆CF₃Cl⁻, (CH₃O)₃Si(CH₂)₃N⁺(C₂H₅)₃Cl⁻.
0034It should be noted that carriers may be employed herein such as gels, powders, creams and lotions, emulsions, microemulsions and solvent solutions, of the active antimicrobial agents. Surfaces that can be treated include carpet; fabrics, for example socks, clothing, shoe inner liners, towels, bedding, upholstery, curtains and draperies; as well as hard surfaces, for example walls, tables, ceilings and furnishings.
0035While the treated substrates of the present invention are of general application, they are especially useful in the preparation of papers employed in conjunction with foodstuffs. Thus, the treated papers and substrates are useful as milk containers and cartons, field transport containers for fruit and vegetables, cardboard fruit containers, consumer foodstuff containers and wrappings, wrapping paper for fruit, vegetables and meat and as wrappers for soap, for example.
0036It will be apparent from the foregoing that many other variations and modifications may be made in the structures, compounds, compositions and methods described herein without departing substantially from the essential concepts of the present invention. Accordingly, it should be clearly understood that the forms of the invention described herein are exemplary only and are not intended as limitations on the scope of the present invention.
5 sheets
Sheet 1 Sheet 2 Sheet 3 Sheet 4 Sheet 5
Every citation, both ways
| Document | Relation | Office | Cited during |
|---|---|---|---|
| WO2014049370A1 | Cited by | World Intellectual Property Organization (WIPO) | International search |
| WO03099006A1 | Cited by | World Intellectual Property Organization (WIPO) | International search |
| US5530024A | Cited by | United States of America | Search report |
| WO9803066A1 | Cited by | World Intellectual Property Organization (WIPO) | International search |
| WO03099006A1 | Cited by | World Intellectual Property Organization (WIPO) | International search |
| US5726206A | Cited by | United States of America | Search report |
| US8940366B2 | Cited by | United States of America | Applicant |
| US7754288B2 | Cited by | United States of America | Applicant |
| EP1286592A4 | Cited by | European Patent Office (EPO) | Search report |
| WO2005079744A1 | Cited by | World Intellectual Property Organization (WIPO) | International search |
| WO9520321A1 | Cited by | World Intellectual Property Organization (WIPO) | International search |
| US7192470B2 | Cited by | United States of America | Applicant |
| US5728730A | Cited by | United States of America | Search report |
| US7128778B2 | Cited by | United States of America | Applicant |
| US7846505B2 | Cited by | United States of America | Applicant |
| WO2005079744A1 | Cited by | World Intellectual Property Organization (WIPO) | International search |
| US7758924B2 | Cited by | United States of America | Applicant |
| US7267714B2 | Cited by | United States of America | Applicant |
| US7838124B2 | Cited by | United States of America | Applicant |
| US8721783B2 | Cited by | United States of America | Applicant |
| EP1286592A1 | Cited by | European Patent Office (EPO) | Search report |
| US7300502B2 | Cited by | United States of America | Applicant |
| US5633278A | Cited by | United States of America | Search report |
| EP0155155A2 | Cites | European Patent Office (EPO) | Search report |
| GB2099301A | Cites | United Kingdom | Search report |
| FR2218052A1 | Cites | France | Search report |
| US4467013A | Cites | United States of America | Search report |
| US4504541A | Cites | United States of America | Search report |
| WO8706470A1 | Cites | World Intellectual Property Organization (WIPO) | Search report |
| WO8800795A1 | Cites | World Intellectual Property Organization (WIPO) | Search report |
14 members in 7 offices
Priority claims4
| Document | Office | Kind | Date |
|---|---|---|---|
| 18715188 | United States of America | A | |
| 187151 | United States of America | – | |
| US19880187151 | – | – | – |
| 187151 | – | – | – |
Members14
| Document | Office | Kind | |
|---|---|---|---|
| US4847088A | United States of America | A | |
| AU3373689A | Australia | A | |
| AU3373689A | Australia | A | |
| EP0339957A2This record | European Patent Office (EPO) | A2 | |
| JPH01313408A | Japan | A | |
| KR900015720A | Republic of Korea | A | |
| EP0339957A3 | European Patent Office (EPO) | A3 | |
| AU624134B2 | Australia | B2 | |
| CA1324955C | Canada | C | |
| EP0339957B1 | European Patent Office (EPO) | B1 | |
| DE68913792D1 | Germany | D1 | |
| DE68913792T2 | Germany | T2 | |
| JPH078767B2 | Japan | B2 | |
| KR970009884B1 | Republic of Korea | B1 |
22 legal events, as 3 offices reported them to INPADOC
Over the term
Point at a mark for the eventEvents
| Event | Code | Office | |
|---|---|---|---|
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Patent expired after termination of 20 yearsExpiredPE20 | PE20 | GB | |
| Patent ceasedCeasedPL | PL | CH | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Name/firm changedPFA | PFA | CH | |
| European patent in force as of 2002-01-01IF02 | IF02 | GB | |
| No opposition filedOpposition26N | 26N | EP | |
| No opposition filed within time limitOppositionORIGINAL CODE: 0009261PLBE | PLBE | EP | |
| Information on the status of an ep patent application or granted ep patentGrantedSTATUS: NO OPPOSITION FILED WITHIN TIME LIMITSTAA | STAA | EP | |
| Fr: translation filedET | ET | EP | |
| Corresponds to:REF | REF | EP | |
| Designated contracting statesAK | AK | EP | |
| (expected) grantORIGINAL CODE: 0009210GRAA | GRAA | EP | |
| First examination report despatched17Q | 17Q | EP | |
| Designated contracting statesAK | AK | EP | |
| Search report despatchedORIGINAL CODE: 0009013PUAL | PUAL | EP | |
| Request for examination filed17P | 17P | EP | |
| Designated contracting statesAK | AK | EP | |
| Public reference made under article 153(3) epc to a published international application that has entered the european phaseORIGINAL CODE: 0009012PUAI | PUAI | EP |
Numbers
- Publication
- 0339957
- Publication, DOCDB
- 0339957
- Publication, EPODOC
- EP0339957
- Application
- 89304141
- Application, DOCDB
- 89304141
- Application, EPODOC
- EP19890304141
Titles6
- German
- Synergistische antimikrobielle Zusammensetzung.
- English
- A synergistic antimicrobial composition.
- French
- Composition antimicrobienne synergique.
- German
- Synergistische antimikrobielle Zusammensetzung
- English
- A synergistic antimicrobial composition
- French
- Composition antimicrobienne synergique
Classification
- CPC, 1
- A01N55/00
- IPC, 11
- A61K8 30
- A01N55 00
- A01N55 10
- A61K8 00
- A61K8 33
- A61K8 36
- A61K8 362
- A61K8 365
- A61K8 368
- A61K8 58
- A61K31 695
Designated states5
- Contracting states, 5
- Switzerland
- Germany
- France
- United Kingdom
- Liechtenstein