• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    biocidal formulation and method for water treatment. the present invention is related to a biocidal formulation comprising a biocide in a micelle, wherein the micelle comprises a block copolymer having a part soluble in the biocide and a part that is soluble in water, and a quaternary ammonium stabilizing compound. the present invention also provides a method of controlling microorganisms by eliminating and / or preventing biofilm formation in an aqueous environment.
    公开号:BR112015024770B1
    申请号:R112015024770-9
    申请日:2014-03-25
    公开日:2020-08-18
    发明作者:Marko Kolari；Jukka Rautiainen；Hans-Peter Hentze；Hanna-Leena ALAKOMI；Pirkko Forssell
    申请人:Kemira Oyj；
    IPC主号:
    专利说明:

    Field of the Invention
    [001] The present invention is related to a biocidal formulation comprising a biocide in a micelle. More particularly, the micelle comprises a block copolymer and a quaternary ammonium stabilizing compound. The present invention also relates to methods for treating water and controlling biofilms by eliminating microorganisms and / or preventing the growth of microorganisms. Background of the Invention
    [002] Water-intensive processes, such as paper-making and water-cooling processes, offer a fertile environment for microbiological growth. Therefore, biocidal treatments are often necessary in several water-intensive processes. An examination of microbiology in paper making machines and common biocides is presented in chapter 6, "Paper Machine Microbiology", pages 181-198, authored by Marko Kolari, in the Papermaking Chemistry Manual, 2007, Raimo Alen ( Editors), the Association of Paper Engineers of Finland, Helsinki, Finland. The target of treatments using biocide is not always a complete sterilization of the process water, but a contribution to the discovery of a stable and dynamic balance, in order to maintain microbial growth at an acceptable level and in a cost-effective way. . The state of the art refers to a wide variety of biocides in different types of applications within the water intensive industries, where the paper industry is the most consumed. Commonly used techniques are described, for example, in U.S. Patent Nos. 7,285,224 and 6,429,181. It has been estimated that part of the biocidal applications within the high water consumption industries are currently using technologies that could be replaced if a more effective biofilm control technology, based on targeted biocides, could be found.
    [003] A biofilm is an aggregate of microorganisms in which cells adhere to each other, on a surface. These adherent cells are often embedded within a self-produced matrix of extracellular polymeric substance (EPS). An EPS-type biofilm, also referred to as sludge, consists of a polymeric conglomerate that generally comprises extracellular polysaccharides, DNA and proteins. Biofilms can form on surfaces of living or non-living materials, and can predominate in watery natural, industrial and hospital environments. Microbial cells that grow in a biofilm are generally physiologically distinct from planktonic cells in the same organism, which, conversely, are isolated cells that can float or swim in a liquid medium.
    [004] The formation of a biofilm begins with the fixation of microorganisms free from fluctuation on a surface. These first colonizers adhere to the surface, initially, through a weak and reversible adhesion, using van der Waals forces. If colonizers are not immediately separated from the surface, they will be able to self-fix more permanently using cell adhesion structures, such as pili cell structures. Some species are not able to attach to a surface on their own, but are usually able to attach to the EPS matrix or directly to previous colonizers. During this colonization, cells are able to communicate by detecting quorum using signals such as AHL compounds. Once colonization has begun, the biofilm grows through a combination of cell division and reinforcement. The final stage of biofilm formation is known as development, and it is at this stage that the biofilm is established and can only change its shape and size. The development of a biofilm can allow a colony of aggregated cells (or colonies) to become increasingly resistant to antimicrobial agents.
    [005] Biofilms contribute to several problems in aqueous industrial systems, especially in recirculation systems, such as paper machines or cooling systems. The accumulation of biofilms can cause problems, such as, unscheduled downtime of the machines due to cleaning, obstruction of pipes or valves or spray nozzles, poor heat transfer, high energy consumption, corrosion, increased maintenance expenses, shortening of system life, higher operating costs, etc.
    [006] A biocide is an antimicrobial chemical that can prevent, render harmless or exercise effective control over any harmful organism. Biocides are commonly used in industry. An antimicrobial biocide can further be classified, for example, as a germicide, an antibacterial, an antiviral, an antifungal, an antiprotozoal or an antiparasite.
    [007] Most current biocides were originally developed for the control of planktonic bacteria. In low concentrations generally used, these biocides are not very effective against biofilms. The coating or matrix formed by the microorganisms producing EPS makes them tolerate higher dosages of most common biocides. The use of higher dosages of biocides may be economically inadequate or may cause other problems, for example, corrosion of the equipment. In addition, because biocides are idealized for killing living organisms, increased dosages of biocidal products may also increase the health risks of people working with the specific process of intensive water consumption.
    [008] Some biocidal formulations described in the state of the art employ a greater or lesser amount of amphiphilic dispersants, which serve two main functions: (a) the wettability of the biofilm to reduce the biofilm layer (bioumectants), or (b) a delay and prevention of biofilm growth on surfaces (biostabilizer).
    [009] Alternative technologies described in the prior art also include, for example, lipid-based double layer formulations, such as liposomes (patent document WO 2010/107533) or oil-in-water emulsions of biocides to control industrial bio-encrustation (US Patent No. 6,096,225).
    [010] Therefore, there is a need for better biocides and biocidal formulations, which can be used against the presence of biofilms on surfaces. These biocides must be able to target biofilms and also to penetrate said biofilm, to kill biofilm organisms. These biocides must also be effective at low dosages. Summary of the Invention
    [011] The present invention aims at a more effective control of biofilms, through the use of new biocidal formulations, in which the solubilization of the biocide and the formation of micelle by block copolymers are combined with surface adsorption and permeabilization properties. membrane. For this purpose, mixed self-assembled micelles are formed, which contain, in addition to the biocide (s) and block copolymers, also membrane permeabilizers and / or cationic polyelectrolytes, for improved surface adsorption. This allows for a step change in performance (by a factor of about 10), especially when compared to a solvent-based formulation.
    [012] The present invention provides a biocidal formulation comprising a biocide in a micelle, wherein the micelle comprises a block copolymer having a part soluble in the biocide and a part soluble in water, and a quaternary ammonium compound that stabilizes the micelle and , also, possibly improves the permeabilization properties of the formulation.
    [013] The present invention also provides a method for the control of biofilms, by eliminating and / or preventing microorganisms in an aqueous environment, comprising the provision of said biocidal formulation and dosage of said biocidal formulation to the aqueous environment.
    [014] The present invention has advantages with respect to the state of the art, through the use of additional additives to increase the biocidal performance, that is, through additional membrane permeabilizers and through improved surface adsorption (for example, with cationic polyelectrolytes), thus , enabling stage change performances caused by synergistic effects. The biocidal performance was shown to be satisfactory also in hard water and fiber suspensions.
    [015] An advantage of the invention is the fact that it has a surprising biocidal synergistic effect, between the release of the micelle and the permeabilization of the membrane, making it possible to reduce the interruption dosage values (zero viability of planktonic cells and biofilm) by a factor of up to 4-20. Biocides can penetrate the biofilm and attack microorganisms in the biofilm matrix. Despite the potentially higher cost of the formulation, compared to formulations of products known in the prior art, the cost-performance characteristic can potentially be increased by a factor of 2-10. At the same time, the use of less biocide improves the environmental impact and reduces health risks for workers exposed to biocides, making this technology more sustainable.
    [016] It is an advantage of the present invention that biocides can be targeted for biofilms on surfaces.
    [017] It is another advantage of the present invention that it can be implemented with the existing production technology and based on commercially available raw materials.
    [018] It is another advantage of the present invention that the formulations have sufficient shelf life. In addition, that formulations can be pumped through standard industrial chemical pumps. Brief Description of the Figures
    [019] Figure 1 shows results of a biofilm inactivation / death experiment, comparing a biocide containing commercial DBNPA (R20) with the new formulations according to the invention (PD16-01 to PD16-07). All concentrations are expressed in mg / L (PPM) of DBNPA.
    [020] Figure 2 shows results of a biofilm inactivation / death experiment, comparing a biocide containing commercial DBNPA (R20) with the new formulations according to the invention, (PD22-01), and other formulations.
    [021] Figure 3 shows the plot of results from two tests, showing bacterial viability results for pluronic formulations + DBNPA, with a variable concentration of DDAC (biofilm inactivation / death test), versus membrane permeabilization (absorption test similar formulations without DBNPA. Detailed Description of the Invention
    [022] The present invention provides a target release of a biocide on a biofilm surface in an aqueous environment, enabling improved microbe control. In the new formulation, the biocide solubilization and micelle formation by block copolymers are combined with surface adsorption and membrane permeabilization properties.
    [023] An example describes the solubilization of a biocide with low water solubility (eg DBNPA) within a mixed micelle formed by (a) a block copolymer comprising a block soluble in the biocide and a block soluble in water; and (b) an additional stabilizer (for example, DDAC); and / or (c) an additional cationic polyelectrolyte (for example, PDADMAC or PEI), which improves surface adsorption and formulation retention on surfaces.
    [024] In one example, mixed micelles are formed by block copolymers, quaternary ammonium stabilizers and, optionally, additional cationic polyelectrolytes. The function of the latter is to improve the retention of the biocide, of self-assembled aggregates on surfaces (for example, steel). In this way, the treated surface shows a longer protection time and less microbial contamination, even if the dosage of the biocidal formulation is done in a discontinuous way ("shock dosage"), meaning that the aqueous phase can, at some point, time, be free of any biocidal residues. Additional additives to the formulation may also include defoamers, anti-aerators, rheological modifiers, biocidal stabilizers or other chemical process agents.
    [025] The present invention provides a biocidal formulation comprising a biocide (or a mixture of biocides) in a micelle, wherein the micelle comprises a block copolymer having a part soluble in the biocide and a part soluble in water, and a stabilizing compound of quaternary ammonium. In addition to these active ingredients, the formulations may contain other ingredients, such as, for example, stabilizers of the active ingredients and residual amounts or traces of other agents, such as salts, citrate, preservatives, solvents, etc.
    [026] Micelles are aggregates of amphiphilic molecules dispersed in a liquid medium. A typical micelle in aqueous solution is an aggregate, whose hydrophilic portions are in contact with a surrounding solvent, which hijacks the hydrophobic portions in the center of the micelle. The formation of the micellar phase occurs by packaging the hydrophobic molecular entities in a model, which generates interfacial curvature. In this way, different spherical, cylindrical or disc-type aggregates are formed. Normal-phase micelles (oil-in-water micelle) have hydrophobic portions in the center of the micelle, and hydrophilic groups at the micellar interface. The inverse micelles have main groups in the center with terminal portions extending outwards (water-in-oil micelle). Micelles are typically approximately spherical in shape. Other micellar phases, including ellipsoid, cylindrical and double layer formats are also possible. The shape and size of a micelle is a function of the molecular geometry of its surfactant molecules and the conditions of the solution, such as surfactant concentration, temperature, pH and ionic strength. The micelle formation process is known as micellisation and is part of the phase behavior of several lipids and other amphiphilic molecules, according to their polymorphism. Micelles in lipid-water systems are further discussed, for example, by J. M. Seddon and R. H. Templer in the article "Polymorphism of Lipid-Water Systems", contained in the Handbook of Biological Physics, Volume 1, Lipowsky and E. Sackmann. (c) 1995, Elsevier Science B.V. ISBN 0-444-81975-4.
    [027] Micelles form spontaneously in water, and this spontaneous aggregation is due to the amphiphilic nature of the micelle-forming molecules. The attractive interaction of its hydrophobic entities is the basis of its aggregation. When the hydrophobic end portions are not sequestered from the water, the result is the formation of an organized cage around the hydrophobic end portion and the change in entropy is unfavorable. However, when the amphiphilic molecules form the micelles, the hydrophobic end portions interact with each other and this interaction releases water from the hydrophobic end portions, leading to a favorable increase in entropy. Due to the spontaneous formation of the micelles, the simplest way to prepare the biocidal formulation of the invention is to mix the ingredients and let the micelles form.
    [028] Micelles are only formed when the surfactant concentration is greater than the critical micelle concentration (CMC). The surfactant is any surface active material that can form part of the surface after entry. The critical micelle concentration (CMC) is the concentration higher than that of the surfactant when the micelles form spontaneously. The greater the concentration, the greater the number of micelles that will exist. Micelle formation also depends on the temperature of the Kraft process. This temperature is when the surfactants form the micelles. If the temperature is below the temperature of the Kraft process, then there will be no spontaneous micelle formation. As the temperature increases, the surfactant will become a soluble form and will be able to form micelles from a crystalline state.
    [029] The size of the micelles useful in the present invention can be in the range of about 5-30 nm, such as, about 5-20 nm, for example, about 5-15 nm. Generally, the average size of the micelles is about 10 nm. These micelles can also be called nanoparticles or nanospheres, which generally correlate to units of approximately spherical shape, which are self-assembled under appropriate conditions of an amphiphilic material, so that the core is hydrophobic and the crown is hydrophilic. Micelles can be in the form of a nanoemulsion or a nanosuspension in the aqueous solution. These nanoemulsions may be able to cross biological barriers, such as biological membranes. Possible pathways include, for example, phagocytosis, pinocytosis and endocytosis.
    [030] The biocide can be any suitable biocide (antimicrobial agent) capable of killing microorganisms, such as, for example, film-forming microorganisms. In one embodiment, the biocide is present as a mixture of two or more different biocides. The biocide can be soluble in water or have a low solubility in water, or it can even be insoluble in water. It is advantageous that the biocide does not react with the micelle compounds, and that the formulation as a whole is stable. Generally, the biocidal formulation contains at least 2% (weight / weight) of the biocide (antimicrobial agent). In one embodiment, the biocidal formulation contains about 5-50% (weight / weight) of the biocide. In another embodiment, the biocidal formulation contains about 10-25% (weight / weight) of the biocide. In one embodiment, the biocidal formulation contains about 15-25% (weight / weight) of the biocide. In another embodiment, the biocidal formulation contains about 13-17% (weight / weight) of the biocide. In a specific embodiment, the biocidal formulation contains about 15% (weight / weight) of the biocide.
    [031] The terms "insoluble in water" or a compound having "low water solubility", as used herein, refer to compounds having low, including, quite low water solubility. Low solubility can be, for example, a solubility of about 1 gram per 100 grams of water, such as, about 10 grams per 100 grams of water, or about 50 grams per 100 grams of water.
    [032] In general, biocides can be divided into two categories of groups: oxidizing biocides and non-oxidizing (conventional) biocides. Non-oxidizing biocides include biocides, such as DNBPA, glutaraldehyde, isothiazolones, etc. An example of suitable biocides for use in the formulations of the invention includes non-oxidizing biocides. Biocides can also be divided into groups, depending on the mechanisms of operation. The electrophilic group includes oxidizing biocides, such as halogen and peroxy compounds, and electrophilic compounds, such as formaldehyde, formaldehyde releasers, isothiazolones, Bronopol and Cu, Hg and Ag compounds. Active membrane biocides include lithic biocides, such as quaternary ammonium cations (quats), biguanides, phenols and alcohols, and protonophores, such as, for example, weak parabenic acids and pyrithione.
    [033] Examples of non-oxidizing biocides include: glutaraldehyde, 2,2-dibromo-3-nitrilopropionamide (DBNPA), 2-bromo-2-nitropropane-1,3-diol (Bronopol), 5-chloro-2-methyl- 4-isothiazolin-3-one (CMIT), 2-methyl-4-isothiazolin-3-one (MIT), a mixture of CMIT and MIT, 1,2-dibromo-2,4-dicyanobutane, bis (trichloromethyl) sulfone , 2-bromo-2-nitrostyrene, 4,5-dichloro-1,2-dithiol-3-one, 2-n-octyl-4-isothiazolin-3-one, 1,2-benzisothiazolin-3-one, ortho - phthalaldehyde, guanidines, biguanidines, pyrithione, carbamates, 3-iodopropynyl-N-butylcarbamate, phosphonium salts, such as tetrakis-hydroxymethyl phosphonium sulfate (THPS), 3,5-dimethyl-l, 3,5-thiadiazinane- 2-thione (Dazomet), 2- (thiocyanomethylthio) benzothiazole, methylene bistiocyanate (MBT), and a combination thereof.
    [034] Examples of preferred non-oxidizing biocides include: glutaraldehyde, 2,2-dibromo-3-nitrilepropionamide (DBNPA), 5-chloro-2-methyl-4-isothiazolin-3-one (CMIT), 2-methyl-4 -isothiazolin-3-one (MIT), and a mixture of CMIT and MIT; carbamates; and phosphonium salts, such as tetrakis-hydroxymethyl phosphonium sulfate (THPS), 3,5-dimethyl-1, 3,5-thiadiazinane-2-thione (Dazomet), 2- (thiocyanomethylthio) -benzothiazole, methylene bistiocyanate (MBT), and combination thereof. The advantage of using these biocides is that they are commonly used in the pulp and paper industry, and their behavior is well known.
    [035] In one embodiment, non-oxidizing biocides are selected from the group consisting of glutaraldehyde, 2,2-dibromo-3-nitrilepropionamide (DBNPA), 5-chloro-2-methyl-4-isothiazolin-3-one (CMIT ), 2-methyl-4-isothiazolin-3-one (MIT), and a mixture of CMIT and MIT. These biocides have a favorable rate of extermination and provide a preferred mode of action. In addition, the required quantities are reasonably low, which makes the costs bearable.
    [036] Examples of oxidizing biocides include chlorine, alkaline and alkaline earth hypochlorite salts, hypochlorous acid, dorado isocyanurates, bromine, alkaline and earth alkaline hypobromite salts, hypobromous acid, bromine chloride, chlorine dioxide, ozone, hydrogen peroxide , peroxy compounds, such as, peracetic acid, performatic acid, percarbonate or persulfate salts, halogenated hydantoins, e.g. active halogen compounds reacted with other nitrogenous compounds, such as urea, and combinations thereof.
    [037] The most common types of non-oxidizing biocides that are used in pulp and paper making processes include 2-bromo-2-nitropropane-1,3-diol, 5-chloro-2-methyl-4-isothiazolin-3 -one, DBNPA, n-octyl-isothiazolin-3-one, MBT, quaternary ammonium compounds, THPS and glutaraldehyde.
    [038] In one embodiment, the biocide is 2,2-dibromo-2-cyanoacetamide (also called 2,2-dibromo-3-nitrilepropionamide or dibromonitrilepropionamide, DBNPA), which is a white crystalline powder having a melting point of 124 , 5 ° C, water solubility of about 15000 mg / L at 20 ° C and vapor pressure of 9.00 E-4 mm Hg, at 20 ° C. DBNPA hydrolyzes easily under acidic and alkaline conditions. Although DBNPA is compatible with several chemical classes, including oxidizing agents, it will react readily with sulfide-containing nucleophilic agents and reducing agents. DBNPA is a non-oxidizing biocide and is not included as a bromine releasing biocide. DBNPA acts in a similar way to typical halogenated biocides. The reaction of DBNPA with sulfur-containing nucleophilic agents common to microorganisms, such as glutathione or cysteine, is the basis of its mode of antimicrobial action. Unlike other thiol-reactive biocides, their action is such that thiol-based amino acids, such as cysteine, are oxidized, in addition to forming disulfide species. This reaction irreversibly disrupts the functioning of cell surface transport components through cell membranes and inhibits fundamental biological functions.
    [039] The micelle comprises a block copolymer having a part (or portion) soluble in the biocide and a part (or portion) soluble in water. The part that solubilizes in the biocide can be a fat-soluble part or a non-fat-soluble part. In general, poloxamers can be used (available, for example, under the trade names Pluronic or Kolliphor). Poloxamers are three-block non-ionic copolymers, composed of a hydrophobic central chain of polyoxypropylene (poly (propylene oxide)), with two hydrophilic chains of polyoxyethylene (poly (ethylene oxide)) on the flanks. In some cases, the block copolymer can also be called a solubilizer. In one embodiment, the block copolymer is a block copolymer of poly (ethylene oxide) poly (propylene oxide) (PEO-PPO). The content of the block copolymer in the formulation can be 15 to 50% (weight / weight).
    [040] In one embodiment, the content of the block copolymer in the formulation can be in the range of 15-30% (weight / weight), such as, about 20-25% (weight / weight). Specifically, at low or moderate storage temperatures (<30 ° C), it is convenient to use a smaller amount of the block copolymer, thus obtaining an increased efficiency when compared to the solvent-based system.
    [041] In another embodiment, the content of the block copolymer in the formulation is higher, preferably 30-50% (weight / weight), especially when stability under a temperature above 30 ° C is required. More preferably, the content of the block copolymer ranges from 30 to 45% (weight / weight), more preferably, from 34 to 40% (weight / weight), providing excellent stability and a clearly increased effectiveness. The upper limit of the range is restricted in order to optimize the cost of the polymer.
    [042] The quaternary ammonium stabilizing compound (or "stabilizer") can consist, for example, of quaternary ammonium cations, also known as "quats". They are positively charged polyatomic ions, of NR4 + structure, where R is an alkyl group or an aryl group. Unlike ammonium ion (NH4 +) and primary, secondary or tertiary ammonium cations, quaternary ammonium cations are permanently charged, regardless of the pH of their solution. Quaternary ammonium salts or quaternary ammonium compounds (called quaternary amines in the oil field language) are salts of quaternary ammonium cations with an anion.
    [043] In one embodiment of the present invention, the quaternary ammonium stabilizing compound can also show permeabilization properties, thereby having a double effect.
    [044] The quaternary ammonium stabilizing compound can be selected, for example, from n-alkyldimethylbenzyl-ammonium chloride, alkenyldimethylethyl-ammonium chloride, didecyldimethyl-ammonium chloride (or N, N-didecyl-N, N- chloride dimethylammonium, DDAC, available, for example, under the trade name Bardac-22), and dimethyldioctadecyl ammonium bromide (DDAB).
    [045] The content of the quaternary ammonium stabilizing compound in the formulation can be in the range of about 5-30% (weight / weight), such as, about 5-10% (weight / weight).
    [046] The biocidal formulation may further comprise a membrane permeabilizer, such as, for example, cationic polyelectrolytes, or chelating agents. In one embodiment, the cationic polyelectrolyte is selected from poly (diallyldimethylammonium chloride) (PDADMAC) and polyethyleneimine (PEI, available, for example, under the trade name Retaminol®), polyetheramines (for example, polyether diamine or polyether triamine, available, for example) example, by the trade name Jeffamine), or polyamines such as spermidine and spermine. The content of the cationic polyelectrolyte membrane permeabilizer in the formulation can be in the range of 0.5-5% (weight / weight).
    [047] As long as the membrane permeabilizer is present in the biocidal formulation of the present invention, it must not be the same compound as the indicated quaternary ammonium stabilizing compound.
    [048] In one embodiment, chelating agents are selected from the group comprising polyamine polycarboxylic acids, such as TTHA (triethylene tetramino-N, N, N ', N ", N"', N "'- hexa-acetic acid), EDTA (ethylene diamine tetra-acetic acid), DTPA (acid (hydroxyethyl) -ethylenediamine tri-acetic), EDDS (ethylenediamino di-succinic acid); polyamino-polymethylene phosphonic acids, such as DTPMPA (diethylenetriamine pentakis-methylene phosphonic acid) triethylenetriamine hexakis-methylene phosphonic acid), EDTMPA (ethylenediamino tetramethylene phosphonic acid), and AES (N-bis [2- (1,2-dicarboxy-ethoxy) ethyl] aspartic acid). Most preferably, the chelating agent is DTPA.
    [049] Polydialyldimethylammonium chloride (polyDADMAC or polyDDA) is a homydimer of diallyldimethylammonium chloride (DADMAC). The molecular weight of polyDADMAC is typically in the range of hundreds of thousands of grams per mol, up to a million for some products. The polyDADMAC is normally released in the form of a liquid concentrate, having a solid level in the range of 10 to 50%. Said poliDADMAC is a cationic polymer with high charge density.
    [050] Polyethyleneimine is a cationic polymer that can be linear, containing all secondary amines or containing branched primary, secondary or tertiary amino groups.
    [051] The membrane permeabilizer can also be a surfactant. Surfactants are usually organic compounds, which are amphiphilic, meaning that they contain hydrophobic groups (in the terminal portions) and hydrophilic groups (in the initial portions). Therefore, a surfactant contains a water-insoluble (or oil-soluble) component and a water-soluble component. Surfactants will diffuse in water and adsorb at the interfaces between air and water or at the interface between oil and water, in the case where the water is mixed with the oil. The insoluble hydrophobic group can extend out of the aqueous volume phase, into the air phase or into the oil phase, while the main or water-soluble starting group remains in the aqueous phase. This alignment of surfactants on the surface modifies the properties of the water surface at the water / air or water / oil interface.
    [052] In one embodiment, the biocidal formulation also comprises a defoamer. An antifoam (antifoam agent) is a substance generally used to reduce defoaming due to gases, nitrogenous materials or proteins, which can interfere with processing. General examples of defoamers include long-chain fatty alcohols, organic phosphates, silicone fluid, etc.
    [053] In one embodiment, the biocidal formulation contains about 15-23% (weight / weight) of the biocide, such as DBNPA, about 15-25% (weight / weight) of the block copolymer, such as poloxamer , about 5-30% (w / w) of the quaternary ammonium stabilizing compound, such as DDAC. Optionally, the biocidal formulation can also contain 1-5% (weight / weight) of membrane permeabilizer. In one embodiment, the biocidal formulation further comprises a small amount of citrate, such as about 0.2% (weight / weight), which can stabilize the active ingredients. In a specific embodiment, the biocidal formulation contains about 15% (weight / weight) of DBNPA as a biocide, about 15-25% (weight / weight) of PEO-PPO as a block copolymer, and about 20-30 % (weight / weight) of DDAC as a quaternary ammonium stabilizing compound. The percentages used here, in general, refer to the total content of the biocidal formulation as a whole, unless otherwise indicated.
    [054] The formulation can be present as an emulsion or emulsion concentrate, which can contain water in the range of 40-50% (weight / weight), in relation to the total emulsion content. In one example presented, the addition of a cationic polymer or other water-soluble polymer leads to the formation of a water-in-water emulsion, comprising the micellar solution of the biocides.
    [055] In one embodiment, the biocidal formulation is present as a two-component formulation, comprising a first component, which comprises the membrane permeabilizer, and a second component, which comprises the biocide, the block copolymer and the compound quaternary ammonium stabilizer. The second component is usually present as a mixture of ingredients. The first component and / or the second component may contain additional ingredients, such as stabilizing agents of the active ingredients and residual amounts and traces of other agents, such as, salts, citrate, preservatives, solvents, etc. The first component and the second component are arranged to be combined to obtain the final biocidal formulation, prior to addition or dosage to the aqueous environment.
    [056] The present invention further provides a method for targeting a biocide on a biofilm surface in an aqueous environment, comprising the provision of a biocidal formulation and contacting said biofilm surface with said biocidal formulation. The surface can be, for example, a plastic, ceramic, or metal surface, such as, for example, a steel, stainless steel or copper surface. Generally, the formation of colonies by biofilm bacteria is greater on plastic surfaces and less on copper surfaces. The target may also include a controlled release and / or released delivery of the biocide, which provides improved absorption of the biocide to the microbe by means of membrane permeabilization.
    [057] The present invention further provides methods for treating water, comprising providing said biocidal formulation and adding or dosing said biocidal formulation to water. The methods aim to eliminate and / or prevent the formation of biofilms on surfaces, in order to clean and / or remove the formation or the already formed sludge or biofilms. "Dosing" generally refers to the addition or feeding of chemical agents in certain amounts, within a process fluid continuously or at intervals, to provide sufficient time for the chemical to react or show results.
    [058] The biocidal formulation, as used in the methods described here, can be added or dosed in the water to be treated, in biostatic or biocidal amounts. A biostatic amount refers to an amount sufficient to at least inhibit the activity and / or growth of microbes or biofilm. A biocidal amount refers to a more effective activity, such as an amount that is capable of killing most or all microbes.
    [059] The present invention also provides a method for the control of biofilms, by eliminating microorganisms and / or preventing their growth in an aqueous environment, comprising the provision of the biocidal formulation and the addition or dosage of said biocidal formulation to the aqueous environment. The term "aqueous environment", as used herein, refers to a water system, such as an industrial water system, containing an aqueous solution. Elimination and / or prevention refers to any biostatic or biocidal effect, such as extermination, reduction, removal or inhibition of growth, or inactivation or cleaning of the biofilm. The elimination can be total or partial. Prevention refers to any preventive elimination action, which reduces or inhibits the growth of microorganisms and, thus, totally or partially prevents the formation of biofilm.
    [060] The present invention further provides the use of said biocidal formulation to control (for example, eliminate, inactivate and / or prevent) the formation of biofilms or microorganisms in aqueous processes. In one embodiment, microorganisms come in the form of a biofilm. This results in a synergy in the control of fixed microorganisms (biofilms) on the surfaces.
    [061] The present invention further provides the use of additional cationic polyelectrolytes to retain the biocidal formulation (eg micelles) on surfaces (for example, steel surfaces of a pipe or tank for process water), thereby gaining a prolonged protection.
    [062] The term "aqueous solution", as used herein, refers to any solution containing water. Said aqueous solution is generally any solution containing a sufficient amount of aqueous phase to be used in the application in question. Said aqueous solution can be, for example, water, surface water, groundwater, waste water, industrial water, raw industrial water, slurry or solid suspension, pulp suspension or any other suitable aqueous solution.
    [063] The aqueous environment can be an industrial process, such as a water treatment process. The industrial process can be selected from processes such as wood pulp production process, paper production, cardboard, industrial waste water treatment, oil drilling, machining tooling industry, oil cutting tools, hydraulic processes, etc., and the equipment used in these processes. The target application can be, for example, any industrial water system, which generally means a built-in water recirculation system, such as, for example, papermaking system, water cooling systems (for example, cooling towers, open and closed circuit cooling units), industrial raw water systems, drinking water distribution systems, drinking water sanitation system, production or recovery systems (oil field water system, drilling fluids), system fuel storage systems, metal processing systems, heat exchangers, reactors, equipment used for liquid storage and handling, boilers and related steam generation units, radiators, flash evaporation units, refrigeration units, reverse osmosis equipment , gas purification units, blast furnaces, sugar evaporation units, steam power plants, geothermal units as, nuclear cooling units, water treatment units, swimming pool water recirculation units, mining circuits, closed circuit heating units, machining fluids used in operations, such as drilling, boring, milling, widening, stretching, boring, turning, cutting, sewing, polishing, thread cutting, shaping, spinning and rolling, hydraulic fluids, cooling fluids and others.
    [064] The biocidal formulation can be added to the circulating water of a pulp, paper or cardboard production machine. In one example, the biocidal formulation is added or dosed to a pulp and / or paper processing system. In general, the formulation can be used throughout the system to minimize and prevent the formation of biofilm on surfaces of the system. The formulation can be added at any point in the system, to generally maintain microbe control throughout the system. In certain examples, the formulation is added to the system's short water circuit. Other examples of suitable addition points include large storage towers for process water (water circulation towers, filtered water towers), transparent or cloudy filtrate storage tanks, pulping devices or upstream / downstream process streams pulping devices, system or process currents violated upstream / downstream of the vessels present, couch pit process currents (support drain point), upstream / downstream of the couch pit, water recovery section, process streamers wire pit (flow point of the screen) upstream / downstream of the flow point, process currents of the mixing niche of the paper machine upstream / downstream of the niche, and process currents of the upstream / downstream shower water tank the tank.
    [065] In one embodiment, the formulation is added or dosed to raw industrial water, which is usually the incoming water, which can be untreated water or a clarified natural water, originating from surface waters, such as river waters or lakes.
    [066] The formulation of the invention can be added as a solid, such as a dry powder, or in a liquid form, to the liquid or water to be treated. The formulation can be dosed continuously or periodically, as a batch process. Examples of suitable concentrations to be used in the processes are concentrations of about 0.3-50 ppm, more particularly, 0.35-10 ppm, such as, 1-5 ppm. In the batch process, the formulation can be fed for about 3-45 minutes, for 6-24 times a day, or, for example, for about 10-30 minutes, for 12-24 times a day.
    [067] Favorably, the present invention provides a synergistic biocidal effect between micellar release and membrane permeabilization, making it possible to reduce the dosage values of intervals (that is, zero viability of planktonic cells and biofilm) by a factor of 1- 20, preferably in the range of 4-10.
    [068] Despite the potentially higher cost of the formulation, compared to current product formulations, the cost-performance feature can potentially be increased by a factor of 2-10. At the same time, the use of a lower amount of biocide improves the environmental impact, thereby providing a more sustainable technology.
    [069] In the following, the invention will be described in greater detail, with reference to the following non-limiting examples. Examples
    [070] All biofilm inactivation / extermination experiments shown in this document were conducted following the same test method, which consists of: biofilm-forming bacteria (strains of the genera Deinococcus, Meiothermus and Pseudoxanthomonas) were grown at + 50 ° C in a commercial liquid growth medium (R2). Then, 1 mL of this microbial suspension was used to inoculate sterile agar plates (R2A), covered by sterile filter papers. The test organisms were grown on these agar plates covered with filter papers for 1 day. Round stainless steel tapes (also called coupons) were mounted on the filter paper and incubated for 6 days at + 50 ° C. During this incubation time, biofilms were formed on the steel coupons. Each coupon was detached from the filter paper and inserted into the test chamber, then filled with 100 mL of publicly available tap water, adjusted to pH 8 and maintained at +50 ° C. The biocidal formulations were applied in each chamber, according to the test plan, always with three repetition chambers. Chambers with no biocide and chambers with a commercial reference biocide have always been included. At the end of the exposure period, the efficacies of the tested biocidal formulations were quantified through bacterial cultures, using standard liquid chamber plate counting methods (measured by performance against planktonic cells, free from fluctuation) and stainless steel by rubbing the samples (measured by performance against biofilm).
    [071] The experiments shown here used Fennosan R20V as a commercial reference biocide (available from Kemira, Finland). This product consists of a 20% DBNPA solution in polyethylene glycol as a solvent. In the new biocidal formulations shown here, the name "Pluronic" followed by different numbers refers to different grades of PEO-PPO block copolymers, available from BASF GmbH. The product "Bardac-22" refers to a DDAC product available from Lonza Inc. "Retaminol" is the trademark name for a polyethyleneimine (PEI) product, available from Kemira. Example 1: Comparison of Different Biocidal Compositions
    [072] This study was carried out to compare the biocidal performance of different biocidal compositions against bacterial cells in biofilm and liquid. The reference biocide used was a commercial product containing DBNPA (R20V). This product was compared with different new formulations, all containing DBNPA as an active biocidal ingredient. All dosages are shown as a dosage of the biocidal active agent DBNPA (mg / L, PPM). The biofilm test was performed as explained above. The results presented in figure 1 show that 10 ppm of DBNPA demonstrated satisfactory efficacy of planktonic cell extermination, when measured in the form of the product R20V (= free from DBNPA). However, with this dosage, the effectiveness against biofilm was not as strong. The new micellar formulations (PD16-01 to PD16-07) began to show a strong effect against planktonic cells and biofilm already at a dosage level of 1 ppm or less (based on ppm of DBNPA content). Thus, the new formulations were able to improve the biofilm control performance by up to ten times. All new formulations had a DBNPA content of 25%, but with a variation in the Pluronic F68 content (from 20% to 30%), and a variation in the Bardac-22 content (from 10% to 30%). The best performance formulation, PD16-06, contained 25% DBNPA, 20% Pluronic and 20% Bardac-22. The results demonstrated that these new formulations have a clear advantage in the way of increasing biofilm inactivation / extermination. Example 2: Comparison of Different Biocidal Compositions
    [073] This study was carried out for two reasons. First, to assess the impact of adding PEI to the performance of new biocidal formulations. Second, the mixtures were prepared to assess the relative impact of the different components. The compositions Table 1 - Sample of the PD-22 Series

    1) Incomplete solubilization of DBNPA was observed when mixed with DDAC, so it was excluded from the biofilm test.
    [074] The biofilm test was performed as explained above. The results shown in figure 2 show that 5 ppm DBNPA provided a very poor extermination efficacy, and that 10 ppm DBNPA was necessary for a strong extermination efficacy, when DBNPA was dosed as an R2 0V product (free of DBNPA). The formulation PD22-01 ("GMC") showed a very strong extermination efficacy in the concentration of 0.5 ppm, and provided a total sterilization with a dosage of 1.0 ppm. This demonstrates that the micellar formulation of DBNPA with the quaternary ammonium stabilizing compound and PEI as a permeabilization component was highly effective. This composition according to the invention showed an improvement in efficiency greater than 10 times, when compared to the reference compound R20V. The compound PD22-02 ("Pluronic") had no clear extermination effect, demonstrating that the PEO-PPO block copolymer alone was not effective. The PD22-03 mixture ("DBNPA + DDAC") was not soluble and could not be tested. The compound PD22-04 ("PEI") did not show a clear extermination effect, demonstrating that the PEI cationic polymer, alone, was not effective. The mixture of PD22-05 ("DDAC + Pluronic") showed only a small extermination effect (a reduction of about log 0.5 in bacterial quantities), demonstrating that the PEO-PPO block copolymer with the ammonium compound quaternary, but without DBNPA, was not really effective. The mixture of PD22-06 ("R20V + DDAC") showed that the exemption of DBNPA with high relative dose of DDAC quaternary ammonium compound had a clear biocidal effect. However, a higher dosage was required, compared to the composition according to the present invention ("GMC", PD22-01). In addition, the "GMC" composition was considered to be relatively better in biofilm inactivation / extermination properties.
    [075] These results demonstrate that the composition of the present invention has an extermination performance superior to that of the individual components of the composition. It was also observed that the "GMC" formulation showed storage stability of at least 18 weeks, without any phase separations or color changes. Example 3: Permeabilization study
    [076] The biofilm extermination / inactivation tests were conducted with micellar formulations of Pluronic + DBNPA, all with a content of 9% DBNPA, but with a variable content of DDAC. The efficacy of extermination was measured. In addition, a membrane permeabilization study was carried out with the well-known "NPN Absorption Method" (Hancock & Wong, AAC .; Volume 26, No.l, 48-52, July 1984 ; and according to the article by Alakomi et al., Weakening Effect of Cell Permeabilizers on Gram-Negative Bacteria Causing Biodeterioration, Appl. Environ. Microbiol., July 2006; 72 (7): 4695-4703), using bacteria from Pseudomonas aeruginosa as a model organism. In this method, fluorescence is measured after the absorption of 1-N-phenylnaftilamine (NPN), due to membrane permeabilization. The membrane permeabilization effect of the quaternary ammonium compound (DDAC) was studied using similar formulations used in the biofilm extermination test, but excluding DBNPA. Figure 3 shows the results plotted from these two studies. The formulations containing DDAC that provided the strongest response with respect to NPN absorption (strongest permeabilization) also provided the greatest synergistic amplification of the biocidal activity of DBNPA, when used to produce the micellar formulations of Pluronic + DBNPA + DDAC. One of the best performance compositions contained DBNPA 9%, Pluronic 27%, DDAC 4.5% and PEI 2.3% (PD24-01). The biocidal activity increased markedly along with the membrane permeabilization properties, confirming that the quaternary ammonium compound as part of the micellar formulation Pluronic + DBNPA provides the composition of the invention with improved extermination efficacy. Example 4: Comparison of Biocidal Stability and Effectiveness of Different Biocidal Compositions
    [077] This study was carried out in order to compare the stability and efficacy of extermination of different biocidal compositions. The stability was visually monitored at a temperature of +25 ° C and +45 ° C, for five weeks.
    [078] The biocidal compositions were initially homogeneous and colorless; phase formation and / or yellowish color were considered to be poor stability. The stability and compositions of the formulations are shown here in Table 2, below.
    [079] The biocidal efficacy of extermination of the formulations was analyzed using the aforementioned test method. The results are shown in figure 4. Table 2 - Compositions and stability of the PD 46, PD 47 and PD 48 series of samples.

    * the block copolymer was Pluronic L35, L64, PE6800 or PE3500.
    [080] Table 2 shows that biocidal compositions with low block copolymer content (<30%) and low DDAC content (<10%), but with high water content (> 40%) suffer from stability, especially at + 45 ° C storage temperature. In contrast, excellent stability was obtained with compositions containing a high content of block copolymer (> 30%) and a high content of DDAC (> 10%), but with low water concentration (<40%).
    [081] Figure 4 shows that the biocidal efficacy of extermination of the composition PD46-03 (block copolymer content <30%) at 0.5 ppm, and of the compositions PD47-01 and PD47-02 (block copolymer content) > 30%) at 0.5 ppm was markedly better than Fennosan R20 (a solvent-based DBNPA product) at 5 ppm.
    [082] Therefore, the results obtained indicate that all new miscellar biocidal compositions tested with more than 20% block copolymer were more effective than the solvent-based DNBPA product (Fennosan R20). In addition, all formulations showed stability for several days at a temperature of + 25 ° C. Stability with increased temperature was achieved with a high block copolymer content (> 30%), a high DDAC content (> 10%) and a low water content (<40%). This is advantageous for certain industrial applications.
    权利要求:
    Claims (22)
    [0001]
    1. Biocidal formulation comprising a biocide in a micelle, characterized in that the micelle comprises: - a block copolymer, which is a poloxamer; - a quaternary ammonium stabilizing compound; and - a non-oxidizing biocide selected from glutaraldehyde, 2,2-dibromo-3-nitrilepropionamide (DBNPA), 2-bromo-2-nitropropane-1,3-diol, 5-chloro-2-methyl-4-isothiazolin-3 -one (CMIT), 2-methyl-4-isothiazolin-3-one (MIT), a mixture of CMIT and MIT, 1,2-dibromo-2,4-dicianobutane, bis (trichloromethyl) sulfone, 2-bromo- 2-nitrostyrene, 4,5-dichloro-1,2-dithiol-3-one, 2-n-octyl-4-isothiazolin-3-one, 1,2-benzisothiazolin-3-one, ortho-phthalaldehyde, guanidines, biguanidines, pyrithions, carbamates, 3-iodopropynyl-N-butylcarbamate, phosphonium salts such as tetrakis-hydroxymethyl phosphonium sulfate (THPS), 3,5-dimethyl-1, 3,5-thiadiazinane-2-thione, 2- ( thiocyanomethylthio) benzothiazole, methylene bistiocyanate (MBT) and a combination thereof.
    [0002]
    Biocidal formulation according to claim 1, characterized in that it further comprises a membrane permeabilizer.
    [0003]
    Biocidal formulation according to any one of claims 1 and 2, characterized in that the biocide has a low solubility in water.
    [0004]
    Biocidal formulation according to any one of claims 1 and 2, characterized in that the biocide is selected from glutaraldehyde, 2,2-dibromo-3-nitrilepropionamide (DBNPA), 2-bromo-2-nitropropane-1, 3-diol , 5-chloro-2-methyl-4-isothiazolin-3-one (CMIT), 2-methyl-4-isothiazolin-3-one (MIT) and a mixture of CMIT and MIT.
    [0005]
    Biocidal formulation according to claim 1, characterized in that the poloxamer is a block copolymer of poly (ethylene oxide) -poly (propylene oxide) (PEO-PPO).
    [0006]
    Biocidal formulation according to any one of claims 1 and 2, characterized in that the quaternary ammonium stabilizing compound is selected from n-alkyldimethylbenzyl ammonium chloride, alkenyldimethylethyl ammonium chloride, didecyldimethyl ammonium chloride (DDAC) and dimethyldioctadyl ammonium bromide (DDAB).
    [0007]
    7. Biocidal formulation according to claim 2, characterized in that the membrane permeabilizer comprises a cationic polyelectrolyte.
    [0008]
    8. Biocidal formulation, according to claim 7, characterized by the membrane permeabilizer being selected from poly (diallyldimethylammonium chloride) (PDADMAC), polyethyleneimine (PEI), polyetheramines and polyamines.
    [0009]
    Biocidal formulation according to claim 2, characterized in that the membrane permeabilizer comprises a chelating agent.
    [0010]
    Biocidal formulation according to any one of claims 1, 2, 5, 7, 8 and 9, characterized in that it contains from 10% to 25% (w / w) of biocide.
    [0011]
    Biocidal formulation according to any one of claims 1, 2, 5, 7, 8 and 9, characterized in that it contains from 15% to 50% (weight / weight) of the block copolymer.
    [0012]
    Biocidal formulation according to claim 11, characterized in that it contains from 30% to 50% (w / w) of the block copolymer.
    [0013]
    Biocidal formulation according to any one of claims 1, 2, 5, 7, 8, 9 and 12, characterized in that it contains from 5% to 30% (w / w) of the quaternary ammonium stabilizing compound.
    [0014]
    Biocidal formulation according to any one of claims 1, 2, 5, 7, 8, 9 and 12, characterized in that it is present as a two-component formulation, comprising a first component comprising the membrane permeabilizer, and a second component comprising the biocide, the block copolymer and the quaternary ammonium stabilizing compound.
    [0015]
    15. Method for controlling biofilms, by eliminating and / or preventing microorganisms in an aqueous environment, characterized by comprising providing a biocidal formulation, as defined in any of the preceding claims, and administering a dose of said biocidal formulation to the aqueous environment.
    [0016]
    16. Method according to claim 15, characterized in that the aqueous environment is an industrial water system.
    [0017]
    17. Method according to claim 16, characterized in that the industrial water system is selected from a papermaking system, water cooling systems, open and closed circuit cooling units, industrial raw water systems, drinking water distribution, drinking water disinfection system, oil production or recovery systems, drilling fluids, fuel storage system, metal processing systems, heat exchangers, reactors, equipment used for liquid storage and handling , boilers and related steam generation units, radiators, flash type evaporation units, Mb. refrigeration units, reverse osmosis equipment, gas purification units, blast furnaces, sugar evaporation units, steam power plants , geothermal units, nuclear cooling units, water treatment units, water recirculation units baits, mining circuits, closed circuit heating units, machining fluids used in operations such as drilling, boring, milling, widening, stretching, boring, turning, cutting, sewing, polishing, thread cutting, molding, spinning and rolling , hydraulic fluids and cooling fluids.
    [0018]
    18. Method according to claim 17, characterized in that the industrial water system is a cooling tower.
    [0019]
    19. Method according to claim 17, characterized in that the oil production or recovery system is an oil field water system.
    [0020]
    20. Method, according to claim 16, characterized in that the industrial water system is selected from the circulating water of a pulp, paper or cardboard machine and industrial raw water.
    [0021]
    21. Method according to any one of claims 15 to 20, characterized in that the biocidal formulation is dosed in a concentration of 0.3 ppm to 50 ppm.
    [0022]
    22. Method according to claim 21, characterized in that the biocidal formulation is dosed in a concentration of 1 ppm to 5 ppm.
    类似技术:
    公开号 | 公开日 | 专利标题
    BR112015024770B1|2020-08-18|BIOCIDIC FORMULATION AND METHOD FOR WATER TREATMENT
    JP6248331B2|2017-12-20|Biocide composition and water treatment method
    CN1325388C|2007-07-11|Synergistic biocidal mixtures
    RU2523522C2|2014-07-20|Synergic antimicrobial composition
    RU2499387C2|2013-11-27|Synergetic antimicrobial composition
    BR112012019786B1|2020-03-17|PROCESSES TO ATTENUE BIOINCHARISATION
    BR112020007683A2|2020-10-13|compositions that exhibit synergy in biofilm control
    US20150045223A1|2015-02-12|Biocidal compositions and their use in the control of microorganisms in aqueous and water containing systems
    US10640699B2|2020-05-05|Treatment of circulating water systems including well treatment fluids for oil and gas applications
    JP6031522B2|2016-11-24|Biocide compositions and methods of use
    RU2501218C1|2013-12-20|Synergetic antimicrobial composition, containing glutaraldehyde and dimethoxan|
    WO2014144272A1|2014-09-18|Synergistic combinations of monochlorourea and modified monochloroureas
    CA2850505C|2019-12-03|Biocidal compositions and methods of use
    同族专利:
    公开号 | 公开日
    ZA201507915B|2019-01-30|
    KR102148971B1|2020-08-28|
    RU2015126922A|2017-04-27|
    US20150351389A1|2015-12-10|
    CN112655707A|2021-04-16|
    EP2978311B1|2020-06-10|
    JP6501311B2|2019-04-17|
    BR112015024770A2|2017-07-18|
    BR112015024770B8|2021-02-09|
    RU2667076C2|2018-09-14|
    WO2014154946A1|2014-10-02|
    CN105050397A|2015-11-11|
    CA2898842A1|2014-10-02|
    PL2978311T3|2021-01-11|
    CA2898842C|2021-03-16|
    EP2978311A1|2016-02-03|
    JP2016519089A|2016-06-30|
    US10912296B2|2021-02-09|
    ES2805369T3|2021-02-11|
    KR20150135291A|2015-12-02|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    JP2862951B2|1990-04-23|1999-03-03|花王株式会社|Disinfectant composition|
    IL98352A|1991-06-03|1995-10-31|Bromine Compounds Ltd|Process and compositions for the disinfection of water|
    US5312841A|1992-06-15|1994-05-17|Betz Paperchem, Inc.|Water based biocide|
    JP2861951B2|1996-07-19|1999-02-24|日本電気株式会社|Drive circuit for liquid crystal display|
    AU5038299A|1998-07-09|2000-02-01|Rhodia Chimie|Process for the biocidal treatment of surfaces|
    US6096225A|1998-09-11|2000-08-01|Nalco Chemical Company|Method of controlling biofouling in aqueous media using antimicrobial emulsions|
    ES2305055T3|2000-01-31|2008-11-01|Lonza Inc.|HIDANTOINS PARTIALLY HALOGENED FOR LIMO CONTROL.|
    JP2005035900A|2003-07-16|2005-02-10|Hakuto Co Ltd|Emulsion type microbicidal composition|
    GB2433890B|2004-10-09|2009-02-11|Enviroquest Group Ltd|Non-ionic surfactant aggregates|
    CN1836508A|2005-03-25|2006-09-27|黄雅钦|Novel compound o-Phthalaldehyde microemusion sterilization composition|
    DE102006015090B4|2006-03-31|2008-03-13|Advanced Micro Devices, Inc., Sunnyvale|Method for producing different embedded deformation layers in transistors|
    RU2333773C1|2007-06-29|2008-09-20|Автономная некоммерческая организация "Институт нанотехнологий Международного фонда конверсии"|Biocide solution and method for obtaining same|
    CN102355822A|2009-03-20|2012-02-15|通用电气公司|Biodelivery systems|
    JP5210360B2|2009-07-30|2013-06-12|ロームアンドハースカンパニー|Synergistic microbicidal composition|
    US8242176B2|2009-09-09|2012-08-14|Howard Martin|Biocidal aldehyde composition for oil and gas extraction|
    US9113625B2|2009-09-30|2015-08-25|Cjb Industries, Inc.|Adjuvant for agricultural chemicals|
    CN103153290B|2010-10-11|2018-01-16|普渡研究基金会|Contribute to the anti-microbial agents of wound healing|
    WO2013007811A1|2011-07-14|2013-01-17|Lonza Inc.|Method for mic control in oil field applications |DE102015100756A1|2015-01-20|2016-07-21|FAUDI Aviation GmbH|A method for preventing and / or destroying microbial growth in a storage for a liquid hydrocarbon, method for preventing and / or destroying microbial growth in a storage for a liquid hydrocarbon, storage for a liquid hydrocarbon|
    CA3007478C|2015-12-16|2020-11-03|Ecolab Usa Inc.|Peroxyformic acid compositions for membrane filtration cleaning|
    US9781928B2|2016-02-05|2017-10-10|Dow Global Technologies Llc|Microbicidal composition|
    US20170223953A1|2016-02-05|2017-08-10|Dow Global Technologies Llc|Microbicidal composition|
    US9781927B2|2016-02-05|2017-10-10|Dow Global Technologies Llc|Microbicidal composition|
    EP3427060A4|2016-03-07|2019-12-18|CFGenome, LLC|Noninvasive molecular controls|
    US10377792B2|2016-03-16|2019-08-13|The Texas A&M University System|Moisture displacement and simultaneous migration of surface-functionalized algae from water to an extraction solvent using ionic polyelectrolytes|
    WO2017181005A1|2016-04-15|2017-10-19|Ecolab Usa Inc.|Performic acid biofilm prevention for industrial co2 scrubbers|
    WO2018075346A1|2016-10-21|2018-04-26|Ecolab Usa Inc.|Antimicrobial composition for controlling biomass accumulation in so2 scrubbers|
    BR112019010464A2|2016-12-15|2019-09-10|Ecolab Usa Inc|methods for removing microorganisms and mineral deposits and for removing microbial growth and mineral deposits in a membrane system.|
    FI128324B|2017-06-21|2020-03-31|Kemira Oyj|Method for manufacturing a fibrous web|
    WO2019079107A1|2017-10-18|2019-04-25|Solenis Technologies, L.P.|Compositions exhibiting synergy in biofilm control|
    AU2019286654A1|2018-06-13|2020-12-03|A.Y. Laboratories Ltd.|System and method for monitoring process water treated with a biocide using an oxygen sensor|
    CN109761348B|2019-02-28|2021-09-17|北京工业大学|Method for improving matrix impact resistance of anaerobic ammonium oxidation particles|
    EP3711486A1|2019-03-19|2020-09-23|Rhodia Operations|Biocidal compositions including a phosphonium quaternary cationic surfactant and methods for using same|
    CA3143270A1|2019-06-14|2020-12-17|Collidion, Inc.|Compositions, kits, methods and uses for preventing microbial growth|
    CN112586498A|2020-12-18|2021-04-02|湖南幻影三陆零科技有限公司|Compound disinfectant, composition containing disinfectant and application of composition|
    法律状态:
    2018-02-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-05-21| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|
    2020-06-09| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-08-18| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 25/03/2014, OBSERVADAS AS CONDICOES LEGAIS. |
    2020-12-29| B09W| Correction of the decision to grant [chapter 9.1.4 patent gazette]|Free format text: REFERENCIA: RPI 2579 DE 09.06.2020 - CODIGO 9.1 |
    2021-02-09| B16C| Correction of notification of the grant [chapter 16.3 patent gazette]|Free format text: REFERENTE AO DESPACHO 16.1 PUBLICADO NA RPI 2589 DE 18.08.2020, QUANTO AOS DESENHOS |
    优先权:
    申请号 | 申请日 | 专利标题
    FI20135287|2013-03-25|
    FL20135287|2013-03-25|
    PCT/FI2014/050216|WO2014154946A1|2013-03-25|2014-03-25|Biocide formulation and method for treating water|
    [返回顶部]