Classifications

• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
  • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
  • D21H21/36—Biocidal agents, e.g. fungicidal, bactericidal, insecticidal agents
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
  • A01N35/06—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical containing keto or thioketo groups as part of a ring, e.g. cyclohexanone, quinone; Derivatives thereof, e.g. ketals
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
  • A01N35/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical at least one of the bonds to hetero atoms is to nitrogen
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N61/00—Biocides, pest repellants or attractants, or plant growth regulators containing substances of unknown or undetermined composition, e.g. substances characterised only by the mode of action
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N65/00—Biocides, pest repellants or attractants, or plant growth regulators containing material from algae, lichens, bryophyta, multi-cellular fungi or plants, or extracts thereof
  • A01N65/08—Magnoliopsida [dicotyledons]
• • C—CHEMISTRY; METALLURGY
  • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F1/00—Treatment of water, waste water, or sewage
  • C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
• • C—CHEMISTRY; METALLURGY
  • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
  • C02F2103/02—Non-contaminated water, e.g. for industrial water supply
  • C02F2103/023—Water in cooling circuits
• • C—CHEMISTRY; METALLURGY
  • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
  • C02F2103/26—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof
  • C02F2103/28—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof from the paper or cellulose industry
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
  • D21H17/03—Non-macromolecular organic compounds
  • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
  • D21H17/14—Carboxylic acids; Derivatives thereof
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
  • D21H21/02—Agents for preventing deposition on the paper mill equipment, e.g. pitch or slime control
  • D21H21/04—Slime-control agents

Definitions

• This invention relates to the control of organisms, such as microorganisms, and in particular the inhibition of such organisms by employing hop acids to inhibit the growth of such organisms and/or kill such organisms.
• the invention has particular utility in aqueous systems, such as papermaking systems and process water systems, in particular systems that involve circulating and/or recirculating water systems, such as cooling water systems, etc.
• microorganisms have been a continuing and troublesome problem in aqueous systems, such as systems that involve circulating and/or recirculating water systems, such as such as papermaking systems and process water systems, cooling water systems, etc.
• aqueous systems such as systems that involve circulating and/or recirculating water systems, such as such as papermaking systems and process water systems, cooling water systems, etc.
• Such microorganisms cause bio fouling, such as deposits of microorganisms or products (such as metabolic products) of microorganisms that cause the formation of deposits such as films, mats and other deposits which can result in plugging of pores, reduced flow, reduced heat exchange rates, clogging, etc.
• Slime formation, deposit formation and the formation of filamentous bacteria have been of particular concern, for example.
• filamentous bacteria for example, Sphaerotilus natans
• Sheaths are considered to be a protective structure, and as such, the structure promotes the survival of the organism.
• the sheath structure is thought to protect the organism from biocides, because, for example, getting the biocide into the protective structure poses a problem.
• Filamentous bacterial growth on submerged surfaces in paper process streams can contribute to the formation of large deposits consisting of cells and inert materials (particulates, fines, fiber, etc.) that become enmeshed in the filaments.
• microorganisms which are the cause of such problems are resistant to attempts to control them, such as by inhibiting their growth and/or killing them.
• microorgansims that pose problems in aqueous industrial systems, such as process waters and papermaking systems, are resistant to a broad spectrum of conditions and materials, and thus are able to remain viable in a wide variety of such conditions. Therefore, biocides have been employed in efforts to control such microorganisms.
• hop acids can inhibit the growth of microorganisms that can cause spoilage in beer.
• U.S. Pat. No. 5,082,975 discloses that the hop acid, hexahydrolupulone, can inhibit the growth of certain Lactobacillus.
• This patent further discloses that there has been speculation that hops may have helped control brew house bacterial infections due to the presence of hop acids in the wort and beer.
• hop beta acids are not found in beer, such control, if it indeed existed, was thought to have been due to the hop alpha acids and iso-alpha acids.
• Beta acids are known to be highly unstable, being oxidized in the boiling wort to bitter hulupones and by themselves to deteriorate in a matter of days or hours after crystallization. This lack of stability is now shown to be overcome by conversion to hexahydrolupulone (hexahydro beta acids). There is a vast excess of lupulone available as a result of being discarded in the brewing process, making it a potentially inexpensive raw material.
• U.S. Patent 4,918,240 is a related patent to U.S. Patent No. 5,082,975. Each of these patents is hereby incorporated by reference as though set forth in full herein.
• U.S. Patent No. 5,455,038 discloses that the hop acids, tetrahydroisohummulone and hexahydrocolupulone ( ⁇ and ⁇ hops, respectively), a product of the brewing industry, have been identified as compounds that can inhibit food born pathogens from the genera Listeria, Staphylococcus, Bacillus, and Clostridium.
• U.S. Pat. No. 5,286,506 discloses that solid food products can be protected from food pathogens, including
• U.S. Patent No. 5,370,863 discloses that oral care compositions containing hop acids or their salts are effective in inhibiting Gram positive bacteria, including Streptococcus mutans, which can cause plaque or periodontal disease, which document is hereby inco ⁇ orated by reference as though set forth in full herein.
• a representative composition is a toothpaste containing tetrahydroisohumulone.
• Hop acids have been considered to be selective to Gram-positive bacteria. See, for example, WO 98/11883, inco ⁇ orated by reference above.
• the invention provides a method of controlling organisms, such as microorganisms, particularly bacteria, in aqueous systems or media, such as papermaking systems and process water systems, in particular systems that involve circulating and/or recirculating water systems, such as cooling water systems, etc., which method employs materials which are readily available from renewable resources and which are also effective.
• the invention provides a method of controlling such organisms in such aqueous systems which method employs materials which are relatively inexpensive.
• the invention provides a method of controlling such organisms in such aqueous systems which method is effective against a wide variety of microorganisms but which are also targeted to the microorganisms which affect such aqueous systems.
• the invention provides a method of inhibiting the growth of organisms in an aqueous system selected from a papermaking system, a cooling system or a process water which process water does not contact a final product; or combinations thereof, comprising adding to the aqueous system a hop acid.
• the hop acid comprises a member selected from ⁇ or ⁇ hop acids, and mixtures thereof.
• the method comprises adding a hop acid selected from one or more of a compound of Formula (I): wherein " — " represents an optional double bond;
• R comprises a member selected from OH; and saturated, or unsaturated (containing from about 1 to about 5 double bonds), straight- or branched-chain alkyl or alkenyl of from about 1 to about 20 C atoms, more preferably from about 1 to about 10
• R 5 comprises a ketone of the general formula C(O)C IntelH 2n+1 , wherein n is an integer of from about 2 to about 10, more preferably from about 2 to about 7, and more preferably from about 2 to about 5;
• R ⁇ comprises a member selected from -OH, -SH, and -OOR, wherein R comprises a member selected from C
• C ForceH 2 «+ ⁇
• n is an integer of from about 2 to about 10, more preferably from about 2 to about 7, and more preferably from about 2 to about 5; and H; and
• R 7 comprises a member selected from saturated or unsaturated (containing from about 1 to about 5 double bonds), straight- or branched-chain alkyl or alkenyl of from about 1 to about 20 C atoms, more preferably from about 1 to about 10 C atoms, and more preferably from about 1 to about 5 C atoms;
• R g comprises member selected from saturated or unsaturated (containing from about 1 to about 5 double bonds), straight- or branched-chain alkyl or alkenyl of from about 1 to about 20 C atoms, more preferably from about 1 to about 10 C atoms, and more preferably from about 1 to about 5 C atoms; a ketone of from about 1 to about 20 carbon atoms, more preferably from about 1 to about 10 carbon atoms, and more preferably from about 1 to about 4 carbon atoms, an aldehyde of the general formula C(O)H, or a ketone of the general formula C(O)C ThreadH 2 varnish +1 , where n is an integer of from about 2 to about 10, more preferably from about 2 to about 7, and more preferably about 5; and/or Formula (III):
• R comprises a saturated, or unsaturated (containing from about 1 to about 5 double bonds), straight- or branched-chain alkyl or alkenyl of from about 1 to about 20 C atoms, more preferably from about 1 to about 10 C atoms and more preferably from about 1 to about 5 C atoms; and
• R )0 comprises a member selected from a ketone of from about 1 to about 20 carbon atoms, more preferably from about 1 to about 10 carbon atoms, and more preferably from about 1 to about 4 carbon atoms, an aldehyde of the general formula C(O)H or a ketone of the general formula C(O)C ThreadH 2;)+1 , where n is an integer of from about 2 to about 10, more preferably from about 2 to about 7, and more preferably from about 2 to about 5; and/or Formula (IV):
• R comprises a saturated, or unsaturated (containing from about 1 to about 5 double bonds), straight- or branched-chain alkyl or alkenyl of from about 1 to about 20
• R 12 comprises a member selected from a ketone of from about 1 to about 20 carbon atoms, more preferably from about 1 to about 10 carbon atoms, and more preferably from about 1 to about 4 carbon atoms, an aldehyde of the general formula C(O)H, or a ketone of the C(O)C IntelH 2 consult +1 , where n is an integer of from about 2 to about 10, more preferably from about 2 to about 7, and more preferably from about 2 to about 5.
• R 4 comprises a substituent of the formula
• R 13 comprises a C 3 -C 8 alkyl group.
• R 13 comprises a member selected from -CH 2 CH(CH 3 ) 2 ; -CH(CH 3 ) 2 ; and -CH(CH 3 ) 2 CH 2 CH 3 .
• the method comprises adding a hop acid which comprises a member selected from hexahydrolupulone; hexahydrocolupulone; hexahydroadlupulone, and mixtures thereof.
• a hop acid which comprises a member selected from hexahydrolupulone; hexahydrocolupulone; hexahydroadlupulone, and mixtures thereof.
• the hop acid comprises hexahydrocolupulone.
• R 8 comprises a substituent of the formula
• R 14 comprises a C 3 -C 8 alkyl group.
• R 14 comprises a member selected from CH 2 CH(CH 3 ) 2 ;
• the hop acid comprises tetrahydroisohumulone.
• the organism can comprise a microorganism selected from Gram-negative bacteria, Gram-positive bacteria, and mixtures thereof.
• the microorganism can comprise a member selected from Sphaerotilus natans,
• the microorganism can comprise a Gram-negative bacteria.
• the microorganism can comprise a member selected from Altermonas, Aquaspirillum, Campylobacter, Helicobacter, Acinetobacter, Agrobacterium,
• Alcaligenes Alteromonas, Flavobacterium, Pseudomonas, Xanthomonas, Mycoplasma, Methanococcus mixtures thereof.
• the microorganism can comprise a Gram-positive bacteria.
• the microorganism can comprise a member selected from Bacillus, Enterococcus, Planococcus, Staphylococcus, Streptococcus, Clostridium,
• Lactobacillus Listeria, Actinomyces, Arthrobacter, Corynebacterium, Curtobacterium, Norcardia, Actinoplanes, Mycobacterium and mixtures thereof, mixtures thereof.
• the aqueous system can comprise a papermaking system.
• the aqueous system can comprise a process water.
• the aqueous system can comprise a cooling system.
• the hop acid preferably is present in an amount of from about 0.001 to about 1,000 ppm.
• the hop acid is preferably present in an amount of from about 0.1 to about 250 ppm.
• the hop acid is preferably present in an amount of from about 0.1 to about 100 ppm.
• the hop acid is preferably added with a freezing point depressant.
• the invention also comprises a method of inhibiting the growth of organisms in a papermaking system, comprising adding to the papermaking system a hop acid in accordance with any of the foregoing definitions.
• the invention also provides a composition
• a composition comprising a hop acid in accordance with any of the foregoing definitions and a member selected from a papermaking suspension, a defoamer, an alum, an adhesive, a paper mill coating, a pigment slurry, a starch, a pitch control agent, a scale control agent, a sizing agent, and mixtures thereof.
• the papermaking suspension comprises a member selected from refined or unrefined furnish stock; refined or unrefined pulp; paper making furnish, and combinations thereof.
• the invention also provides a cellulosic product comprising a member selected from paper and paper board.
• the paper can comprise a member selected from stationery paper, paper towel and tissue paper.
• Figure 1 illustrates the growth inhibition of S. natans by hop acid in accordance with the following examples
• Figure 2 illustrates results of experiments with hop acids in the treatment of spore- forming bacteria.
• hop acids can be employed to control organisms such as by inhibiting the growth of and/or killing organisms including both Gram-positive and Gram-negative microorganisms.
• control of organisms and “inhibition of organisms” is intended to include either or both of the inhibition of the growth of organisms and killing organisms, and these terms should be inte ⁇ reted as being interchangeable herein.
• the invention is particularly directed to the control of organisms in aqueous systems such as papermaking systems and process water such as cooling water, as well as any other aqueous system.
• aqueous systems and “aqueous media” are intended include any part of the aqueous system in question and to include the addition of hop acid at any point within or external to the system, especially in cases which result in a hop acid being present in a portion of the aqueous system.
• the invention is expressly intended to cover situations where the hop acid is added upstream of and or downstream of and/or directly and/or indirectly to the aqueous system in question.
• aqueous systems and “aqueous media” are intended to cover any situation or environment in which water is present, including slurries and solutions as illustrative, non-limiting examples.
• the methods of the invention are useful in treating any aqueous system or media in which it may be desired to inhibit the growth of and or kill organisms such as microorganisms.
• the processes of the invention involve adding hop acids to aqueous systems which may come into direct contact with final product, such as aqueous systems associated with papermaking.
• the processes of the invention involve adding hop acids to aqueous systems which do not directly contact final product.
• aqueous system refers to industrial aqueous systems in addition to papermaking systems and are intended to embrace any such aqueous system wherein the water of the system, such as a process water, does not come into contact with the final product.
• Non-limiting examples include cooling water systems, such as internal combustion engine cooling systems, power plant cooling systems; heat exchangers, including radiator coolants, etc.; aqueous systems used in humidifiers; aqueous systems used in heating, ventilating and air conditioning systems; swimming pool water; water used in spas; metal working fluids; petroleum production fluids including drilling muds; paint formulation; disinfectants and sanitizers; plastics processing systems; mixtures of the foregoing; and any other aqueous systems.
• Methods of the invention control organisms in such systems by adding a hop acid to the papermaking system or other aqueous systems.
• hop acid may be employed in the methods of the invention. It has been found that ⁇ and/or ⁇ hop acids are particularly suitable, such as those of Formula (I), (II) (III) and (IV), above. As used herein, whenever reference is made to a compound or component, unless otherwise stated, it includes the individual compound or component by itself as well as mixtures of the compound or component, unless otherwise excluded. Thus, for example, reference to hop acids includes the occurrence of a single hop acid and to mixtures of various hop acids and mixtures with various other materials.
• Compounds of Formulae (I) and (III) are predominately ⁇ hop acids (but also can include some ⁇ hop acids) and compounds of Formula (II) are predominately ⁇ hop acids (but also can include some ⁇ hop acids).
• ⁇ on-limiting examples of ⁇ hop acids include: humulone, isohumulone; cohumulone; adhumulone; tetrahydroisohumulone; tetrahydrodeoxyhumulone.
• ⁇ on-limiting examples of ⁇ hop acids include lupulone; colupulone; hexahydrocolupoulone; and hexahydrolupulone.
• Especially preferred hop acids of Formula (I) include those wherein R 4 comprises
• R 13 comprises a member selected from (C 3 -C 8 ) alkyl, such as - CH 2 CH(CH 3 ) 2 ; -CH(CH 3 ) 2 ; and -CH(CH 3 ) 2 CH 2 CH 3 .
• Hexahydrocolupulone or "HHC” is a particularly preferred compound of Formula (I).
• Especially preferred hop acids of Formula (LT) include those wherein R g comprises
• R 14 is selected from (C 3 -C 8 ) alkyl, such as -CH 2 CH(CH 3 ) 2 ; -CH(CH 3 ) 2 ;
• Particularly preferred compounds of Formula (LT) include those wherein R comprises -(CH 2 ) 2 CH(CH ) j 2 such as tetrahydroisohumulone. Of these, tetrahydroisohumulone is particularly preferred. Particularly preferred compounds of Formula (LTT) include cohumulone.
• Particularly preferred compounds of Formula (IN) include tetrahydrodeoxyhumulone as disclosed in U.S. Patent No. 4,918,240, which document is hereby inco ⁇ orated by reference as though set forth in full herein for this disclosure as well. Further elucidation of the structure and nomenclature of many of the foregoing compounds of Formulae (I) and (LT) may be found in "Investigation of Hop and Beer Bitter Acids by Coupling of High-performance Liquid Chromatography to Nuclear Magnetic Resonance Spectroscopy", Pusecker et al., Journal of Chromatography a. 836 (1999), 245-252, which is hereby inco ⁇ orated by reference as though set forth in full herein.
• n is an integer of from about 1 to about 10, more preferably from about 2 to about 7 and more preferably about 2 to about 5.
• Hop acids may be isolated and prepared in any suitable way by those of ordinary skill in the art, such as those disclosed in the documents inco ⁇ orated by reference above, which are also inco ⁇ orated by reference for their disclosures of how to prepare such hop acids. Among those inco ⁇ orated by reference, WO 98/11883, U.S. Patent No.
• Hop acids useful in accordance with the present invention may also be prepared in accordance with the disclosure of U.S. Patent 4,844,939 to TODD, Jr., which document, as well as all documents cited therein, is hereby inco ⁇ orated by reference as though set forth in full herein for their disclosure of how to prepare hop acids.
• this patent discloses that refined, subsequentlyomerized hop extracts are available in the trade as solutions made according to various U.S.
• Patents such as U.S. Pat. Nos. 3,448,326, 3,798,332, 3,965,188 (Westerman et al); 3,949,092 and 3,973,052 (Mitchell); and 3,486,906 and 4,002,683 (Todd), all of which documents are hereby inco ⁇ orated by reference as though set forth in full herein.
• Todd To overcome the disadvantage of using artificial, organic solvents, the use of liquid and supercritical carbon dioxide for the extraction of hops has been employed. This art is described in Kruger (Monatsschrift fur Brauerei, 33, Nr. 3), which document is hereby inco ⁇ orated by reference as though set forth in full herein.
• methods for the isomerization and separation of the constituents of carbon dioxide hop extracts can also employ organic solvents and/or adso ⁇ tion/extraction processes (Lance U.S. Pat. No. 4,395,431 , which document is hereby inco ⁇ orated by reference as though set forth in full herein or Mueller, Deutsche Auslegeschrift No. 2920765 which document is hereby inco ⁇ orated by reference as though set forth in full herein), or "salt out” impurities (Laws U.S. Pat. No. 4,298,626 which document is hereby inco ⁇ orated by reference as though set forth in full herein), or remove them by filtration using large amounts of adsorbent in dilute solution (Baker U.S. Pat. No. 4,247,183 which document is hereby inco ⁇ orated by reference as though set forth in full herein), all of the foregoing being cited in U.S. Patent 4,844,939 to TODD, inco ⁇ orated by reference above.
• the hop acids may preferably be employed in the form of an aqueous solution, such as disclosed in WO 98/11883, U.S. Patent No. 4,918,240 and U.S. Patent No. 5,082,975 and the solutions can be prepared as disclosed therein, which documents are again specifically inco ⁇ orated by reference herein for this pu ⁇ ose.
• Suitable hop acids are commercially available in the form of an aqueous solution under the trade name "HYDROHOPS” available from Watertown Hops Company, 1224 American Way, Watertown, Wisconsin, 53094.
• Propylene glycol, glycerine, similar stable alcohols and polyols, or mixtures thereof with or without water, may be substituted for the water of the aqueous solution.
• the solubility of the hop acids employed in the present invention can be affected by temperature.
• the hop acids may be subject to crystallization at temperatures lower than room temperature. Therefore, it has been found particularly advantageous to employ one or more freezing point depressive agents.
• the agents are preferably employed in any amount effective to lower the freezing point of the composition so as to inhibit cloudiness and/or crystallization of hop acid.
• Any freezing point depressive agent may employed and may be readily selected by those of ordinary skill in the art. Examples include:
• Glycerol (glycerine); polyglycerols such as diglycerol, triglycerol, tetraglycerol, pentaglycerol, hexaglycerol, and higher oligomers of glycerol;
• Glycols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, and higher oligomers of glycols;
• Polyglycol triols selected from glycerol propoxylate, glycerol ethoxylate, and mixtures thereof;
• Monohydric alcohols which can range for example, from methyl through C 50 alcohols, more preferably C 6 -C 36 , and may include, for example, methanol, ethanol, isopropanol, butanol, isobutanol, amyl alcohol, isoamyl alcohol, hexanol, isohexanol, heptanol, n-octanol, 2-ethylhexanol, iso-octanol, n-nonanol, isononyl alcohol, n-decanol, isodecanol, n-lauryl alcohol, tridecanol, n-myristyl alcohol, n-cetyl alcohol, isocetyl alcohol, n-stearyl alcohol, isostearyl alcohol, oct
• hop acids may be employed in any amount effective to control the organism, as by inhibiting the growth of and/or killing, organisms.
• the hop acid should be employed in amounts of from about 0.001 to about 1,000 ppm, preferably from about 0.1 to about
• the invention is suitable for controlling a wide variety of orgamsms, including microorganisms such as Gram-negative as well as Gram- positive bacteria. It is particularly su ⁇ rising that hop acids can be employed to control
• Gram-negative microorgansims Other microorganisms can be inhibited by the invention as well, including dinoflagellattes, microalgae, microfungi, bacteria, protozoans or mixtures thereof.
• the invention is particularly effective in controlling the vegetative form of microorganisms.
• Gram-negative microorganisms which can be inhibited by the methods of the invention include Genus Altermonas, Genus Aquaspirillum, Genus Campylobactcr, Genus Helicobacter, Genus Acinetobacter, Genus Agrobacterium, Genus Alcaligenes, Alteromonas, Genus Flavobacterium, Genus Pseudomonas, Genus Xanthomonas, Genus Mycoplasma, Genus Methanococcus, and mixtures thereof.
• Gram-positive microorganisms which can be inhibited by the methods of the invention include Genus Bacillus, Genus Enterococcus, Genus Planococcus, Genus Staphylococcus, Genus Streptococcus, Genus Clostridium, Genus Lactobacillus, Genus Listeria, Genus Actinomyces, Genus Arthrobacter, Genus Corynebacterium, Genus Curtobacterium, Genus Norcardia, Genus Actinoplanes,
• the invention is also effective against Family Enter obacteriaceae, including Genus Escherichia, Genus Enterobacter, Genus Klebsiella, and mixtures thereof, as well as Family Vibronacea, including Genus Aeromonas, Genus Vibrio and mixtures thereof.
• Family Enter obacteriaceae including Genus Escherichia, Genus Enterobacter, Genus Klebsiella, and mixtures thereof
• Family Vibronacea including Genus Aeromonas, Genus Vibrio and mixtures thereof.
• the invention is also effective against other bacteria, including Genus
• Group 3 including page 71
• Group 5 including page 175)
• Group 12 including page 427
• Group 14 including page 477
• Group 17 including page 527
• Group 18 including page 559
• Methods of the invention have been found particularly effective in controlling microorganisms selected from Sphaerotilus natans, Clostridium butyricum, Pseudomonas aeruginosa, Curtobacterium flaccumfaciens, Burkholderia cepacia, Pseudomonas glathi, Bacillus cereus, Bacillus maroccanus, Bacillus licheniformis, Bacillus sphaericus, Bacillus subtilis, and mixtures thereof. Whether inhibition of growth or killing of a microorganism has occurred, and the extent to which it has occurred can be measured by those of ordinary skill in the art, such as in accordance with the Examples below.
• hop acids may be added to the aqueous system to be treated in any manner.
• the method of the invention may be conducted by simply adding a commercially available solution of hop acids, such as HYDROHOPS directly to the aqueous system to be treated.
• the hop acid may also be added after being diluted or added to other media to form an admixture or solution, which admixture or solution may then be added to the aqueous system to be treated.
• the hop acid may be added by being added as a component to additives for papermaking or other aqueous systems, the formulation of which additives is otherwise well known to those of ordinary skill in the art. Treatment of Papermaking Systems
• the invention may be applied to any papermaking system at any point in the system and in any manner where additives are typically employed and in any manner that additives used in the paper industry are employed. Solutions, such as aqueous solutions of hop acids may be employed directly and/or indirectly, or in admixture with any papermaking additive, such as those papermaking additives discussed herein.
• Non-limiting examples of suitable aspects for addition include:
• Refined or unrefined furnish stock in stock tanks Pulp refining conducted in a refiner.
• the flow box the point at which the paper making furnish flows at a controlled rate onto the fourdrinier wire. Or any combination of the foregoing, upstream of any of the foregoing locations, or any point in between such locations, or any other suitable location, or combination of locations, concurrently or at different times.
• hop acids in accordance with the invention may be employed in the amounts discussed above.
• a papermaking composition such as a papermaking additive or papermaking pulp or slurry
• the hop acid can become a component of the resultant product.
• the invention also provides cellulosic products such as paper and paper products comprising hop acids.
• hop acids in cellulosic products including paper and paper products provides advantages of effectively controlling organisms in the aqueous systems associated with the production of such products, while not posing safety, toxicity or related concerns, and/or adverse physiological reactions. This is of particular significance with respect to cellulosic products comprising members selected from stationery paper, paper towel and tissue paper.
• the invention may be applied to any process water system at any point in the system and in any manner where additives are typically employed and in any manner that additives used in such industries are employed.
• suitable aspects for addition include addition at the normal fill opening of the system, inco ⁇ oration with or as part of the original liquid added to the system, etc. Any combination of the foregoing may be employed.
• the invention also comprises composition aspects.
• the invention also provides a composition
• a composition comprising a hop acid and an aqueous medium selected from a papermaking systems and other aqueous systems such as emulsions, adhesives, process waters, including cooling water systems, such as internal combustion engine cooling systems, power plant cooling systems; heat exchangers, including radiator coolants, etc.; aqueous systems used in humidifiers; aqueous systems used in heating, ventilating and air conditioning systems; swimming pool water; water used in spas; metal working fluids; petroleum production fluids including drilling muds; paint formulation; disinfectants and sanitizers; plastics; mixtures of the foregoing; and any other aqueous systems.
• a aqueous medium selected from a papermaking systems and other aqueous systems such as emulsions, adhesives, process waters, including cooling water systems, such as internal combustion engine cooling systems, power plant cooling systems; heat exchangers, including radiator coolants, etc.; aqueous systems used in humidifiers; aqueous systems used
• the invention further provides a composition compositions which are preserved for later addition to aqueous systems, such as additives for paper making and water treatment additives.
• the invention also comprises compositions comprising a hop acid and a paper making additive selected from defoamers, alum, adhesives, paper mill coatings, pigment slurries, starches, pitch control agents, scale control products, sizing agents (including alkyl ketene dimer sizing agents (AKD's), and mixtures thereof.
• Papermaking compositions in accordance with the invention comprise Non-limiting examples of suitable composition aspects:
• Refined or unrefined furnish stock in stock tanks Pulp such as that in a refiner. Refined pulp stored, ready for use in stock chests. Paper making furnish drawn from stock chests. The flow box, the point at which the paper making furnish flows at a controlled rate onto the fourdrinier wire.
• This example illustrates that a derivative of a naturally occurring compound in hops can control the growth of S. natans, a filamentous organism.
• S. natans a filamentous organism.
• the results of adding selected concentrations of hop acids to cultures of S. natans are presented below.
• individual flasks containing a dilute culture medium e.g., CYG broth, described in more detail below
• HYDROHOPS from Watertown Hops, diluted to 10, 25, and 50 ppm tetrahydroisohumulone.
• S. natans ATCC cultures 15291, 29329, and 13925
• CYG broth which had the following composition: 0.5 g/1 casitone, 1.0 g/1 glycerol, and 0.1 g/1 yeast extract.
• S. natans strains were grown in 50 ml culture volumes in shake flasks on an orbital shaker at room temperature. Experiments were initiated by inoculating tests flasks with equal amounts of S. natans taken from 48 hour to 72 hour old broth cultures. Selected concentrations of the active were added to flasks containing S. natans. The control used in all experiments were untreated. The effect of hop acid on S. natans was quantitated using ATP measurements. ATP analysis was conducted using reagents and luminometer from Biotrace Ltd (Bridgend, U. K.). ATP extractions and measurements were carried out as follows:
• Test cultures are repeatedly mixed with a 10 ml pipet to break up floes and yield a uniform suspension.
• the graph in Figure 1 indicates that the I 50 value (the concentration of active needed to inhibit 50% of the population) for both strains of microorganisms is ca. 10 ppm.
• Organism Clostridium butyricum (ATCC 3627)
• Tests of the effect of L-alanine and hop acid were conducted as follows. Suspensions of B. cereus spores were added to sterile water to obtain a spore stock having a concentration of about 10 4 to 10 5 spores/ml. The spore stock was then divided into 1.0 ml aliquots for testing. L-alanine was supplied at concentrations of 1 or 2.5 mM. After L-alanine addition, spores were placed at 37°C for one hour. After L-alanine treatment, hop acid (HYDROHOPS from Watertown Hops, Wisconsion) was added to the spores. After a 20 minute exposure, the spore samples were taken through a serial dilution and plated on nutrient agar medium. Plates were incubated at 37°C overnight, and after this period, colonies were counted.
• HYDROHOPS from Watertown Hops, Wisconsion
• a disk diffusion assay using hop acid treatments was used to evaluate the efficacy of controlling the growth of two fungal species-Aspergillus niger and Chaetomium globosum.
• the agar plates used in the experiment were potato dextrose (PDA). Fungal spores were applied as a lawn onto PDA prior to the addition of disks containing hop acid.
• the disk concentrations used in this experiment were 100, 200, 500, and 1000 ppm. Plates were incubated at 35°C, and observations made daily. The experiment was terminated after 8 days, and the results from this study indicated that there was growth observed around each disk after sporulation (i.e., no zones of inhibition). This indicated that the hop acid was ineffective in controlling the growth of these two fungi.
• hop acids may not be effective against some spore- forming bacteria, but are effective against vegetative forms of bacteria.

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