WO2023012765A1 - A biocidal composition and a process for its preparation - Google Patents
A biocidal composition and a process for its preparation Download PDFInfo
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- WO2023012765A1 WO2023012765A1 PCT/IB2022/057365 IB2022057365W WO2023012765A1 WO 2023012765 A1 WO2023012765 A1 WO 2023012765A1 IB 2022057365 W IB2022057365 W IB 2022057365W WO 2023012765 A1 WO2023012765 A1 WO 2023012765A1
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof
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- 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
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
- A01N25/10—Macromolecular compounds
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- 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
- A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
- A01N33/02—Amines; Quaternary ammonium compounds
- A01N33/12—Quaternary ammonium compounds
Definitions
- the present disclosure relates to a biocidal composition and a process for its preparation.
- Minimum film forming temperature refers to a lowest temperature at which an emulsion will uniformly coalesce when laid on a substrate as a thin film. An accurate minimum film forming temperature value allows the formulation of products that cure correctly under specified application conditions.
- Open time refers to a period of time during which irregularities in a freshly applied coating can be repaired.
- a cationic monomer is incorporated while designing the coating composition, which forms an integral part of coating composition.
- the cationic surfactants such as cetylpyridinium chloride, cetylpyridinium bromide, dialkyl ammonium chloride, and like are added in the surface coating compositions.
- suitable cationic compounds such as substituted pyridinium salts, substituted guanidine salts, tetrasubstituted ammonium salts and the like is incorporated during the coating preparation process.
- incorporation of such cationic compounds in the final coating formulation is widely adopted to achieve anti-microbial efficacy.
- leaching of the cationic compounds over a time period limits the performance of coating composition, with respect to its anti-microbial activity in a long run.
- the use of such cationic compounds shows the anti-microbial efficacy for maximum of 3-4 months.
- combining the cationic surfactant or any cationic molecules during the coating preparation process de-stabilizes the composition due to stringent processing conditions.
- an inorganic material is combined with the final surface coating formulation.
- the most commonly used inorganic material is based on silver ion and its nanoparticles. These silver ion or nanoparticles interact with sodium ion present in the microbes making them inactive.
- the other metals, which have been explored as anti-microbial agents in the coating compositions are copper, copper oxide, zinc oxide and carbon black. However, the anti-microbial effect of these metal oxides is not persisting for longer period because of deactivation and leaching of nano-particles from the coated surface.
- Another object of the present disclosure is to provide a biocidal composition.
- Still another object of the present disclosure is to provide a biocidal composition, which is suitable for coating.
- Another object of the present disclosure is to provide a biocidal composition, which is stable. Yet another object of the present disclosure is to provide a process for the preparation of the biocidal composition.
- Still another object of the present disclosure is to provide a surface coating composition.
- Another object of the present disclosure is to provide a surface coating composition, which is stable at least for 24 months.
- the present disclosure provides a biocidal composition.
- the composition comprising a homogenous mixture of: a polymer backbone, 0.1 to 5% of a plurality of additives, 0.1 to 1% of a biocide, 0.2 to 0.6% of a neutralizer, and 40 to 55% of water.
- the polymer backbone comprises 1 to 5% of at least one cationic monomer, 10 to 30% of at least one alkyl acrylate monomer, 1 to 3% of at least one alkyl methacrylate monomer, 10 to 25% of at least one styrene monomer, 0.1 to 1% of at least one ureido monomer, and 1 to 5% of at least one cross-linking monomer.
- the additives are selected from the group consisting of a methacryloxy silane, an epoxy silane oligomer, and a non-ionic surfactant.
- the at least one of the additives being the non-ionic surfactant.
- the present disclosure further provides a process for preparing a biocidal composition.
- predetermined amounts of at least one alkyl acrylate monomer, at least one alkyl methacrylate monomer, at least one cationic monomer, at least one first non- ionic surfactant, at least one styrene monomer, at least one ureido monomer, and at least one cross-linking monomer are added in water under stirring at a first predetermined stirring speed, at a first predetermined temperature for a first predetermined time period to obtain a pre-emulsion slurry.
- predetermined amounts of at least one second non-ionic surfactant and water are mixed in a second reactor under stirring at a second predetermined stirring speed, at a second predetermined temperature for a second predetermined time period to obtain a first mixture.
- the pre-emulsion slurry is then added to the first mixture in a first predetermined ratio to obtain a second mixture.
- a predetermined amount of a first catalyst is added to the second mixture followed by reacting at a third predetermined temperature for a third predetermined time period under stirring at a third predetermined stirring speed in the second reactor to obtain a first reaction mixture.
- a predetermined amount of a second catalyst is added to the first reaction mixture followed by reacting at a fourth predetermined temperature for a fourth predetermined time period under stirring at a fourth predetermined stirring speed to obtain a second reaction mixture.
- predetermined amounts of a neutralizer, a biocide and a plurality of additives are added in water to obtain a third mixture.
- the additives are selected from the group consisting of methacryloxy silane, an epoxy silane oligomer, and a third non-ionic surfactant. At least one of the additives being the third non-ionic surfactant.
- the third mixture is mixed to the second reaction mixture followed by cooling to a temperature in the range of 25 to 35 °C to obtain the biocidal composition in the form a homogeneous mixture.
- the present disclosure further provides a surface coating composition. It comprises 20 to 25 % of the biocidal composition, 0.05 to 0.15% water softening agent, 0.60 to 1.0% dispersing agent, 0.4 to 0.8% wetting agent, 0.8 to 1.2% open time enhancer, 0.1 to 0.3% defoamer, 0.1 to 0.3% neutralizer, 0.1 to 0.5% cellulose thickner, 8 to 10% pigment, 30 to 35% extender, 0.6 to 1.0% preservatives, 0.2 to 0.6% adhesion promoters, 6 to 10% opaque polymer, 0.5 to 1.5% coalescing agent, and 18 to 22% water. All the percentages are with respect to the total weight of the surface coating composition.
- Figure 1 illustrates a graph of log number of viral particles/percentage viral reduction vs time for the surface coating composition having biocidal composition of trial 1-12 (styrene based).
- Figure 2 illustrates a graph of log number of viral particles/percentage viral reduction vs time for the surface coating composition having biocidal composition of trial 13-14 (pure acrylic based).
- Embodiments are provided so as to thoroughly and fully convey the scope of the present disclosure to the person skilled in the art. Numerous details are set forth, relating to specific components, and methods, to provide a complete understanding of embodiments of the present disclosure. It will be apparent to the person skilled in the art that the details provided in the embodiments should not be construed to limit the scope of the present disclosure. In some embodiments, known processes or well-known apparatus or structures, and well known techniques are not described in detail.
- first, second, third, etc. should not be construed to limit the scope of the present disclosure as the aforementioned terms may be only used to distinguish one element, component, region, layer or section from another component, region, layer or section. Terms such as first, second, third etc., when used herein do not imply a specific sequence or order unless clearly suggested by the present disclosure.
- the conventional surface coating compositions which are used for anti-microbial applications extensively utilizes positively charged surfactants.
- the limitation while using positively charged surfactant is that it leaches out with time when the surface coating is exposed to external environment, and therefore the efficacy of the surface coating composition decreases with time.
- the preparation of surface coating compositions is very critical because of its instability in the surface coatings in long term.
- the present disclosure provides a biocidal composition that would address the above described problem.
- the present disclosure provides a biocidal composition.
- the composition comprising a homogenous mixture of: a polymer backbone, a plurality of additives, a biocide, a neutralizer and water.
- the polymer backbone comprises at least one cationic monomer, at least one alkyl acrylate monomer, at least one alkyl methacrylate monomer, at least one styrene monomer, at least one ureido monomer, and at least one crosslinking monomer.
- the at least one cationic monomer is selected from the group consisting of diallyl dimethyl ammonium chloride, methacryloxy ethyl trimethyl ammonium chloride, acryloxy ethyl trimethyl ammonium chloride, vinyltrimethoxy silane, gamma-methacryloxypropyltrimethoxy silane, and dimethyl aminoethyl acrylate.
- the cationic monomer is a combination of diallyl dimethyl ammonium chloride and vinyltrimethoxy silane.
- the cationic monomer is a combination of diallyl dimethyl ammonium chloride and gammamethacryloxypropyltrimethoxy silane.
- the cationic monomer is a combination of methacryloxy ethyl trimethyl ammonium chloride and vinyltrimethoxy silane. In still another exemplary embodiment, the cationic monomer is a combination of methacryloxy ethyl trimethyl ammonium chloride and gammamethacryloxypropyltrimethoxy silane. In still another exemplary embodiment, the cationic monomer is a combination of acryloxy ethyl trimethyl ammonium chloride and vinyltrimethoxy silane. In still another exemplary embodiment, the cationic monomer is a combination of acryloxy ethyl trimethyl ammonium chloride and gammamethacryloxypropyltrimethoxy silane .
- the amount of at least one cationic monomer is in the range of 1 to 5% with respect to the total weight of the biocidal composition. In an exemplary embodiment, the amount of cationic monomer is 3% with respect to the total weight of the biocidal composition.
- the alkyl acrylate monomer is selected from the group consisting of butyl acrylate, ethyl acrylate, 2-ethyl hexyl acrylate, n-butyl methacrylate.
- the alkyl acrylate monomer is butyl acrylate.
- the alkyl acrylate is ethyl acrylate.
- the alkyl acrylate is 2-ethyl hexyl acrylate.
- the amount of the alkyl acrylate monomer is in the range of 10 to 30% with respect to the total weight of the biocidal composition. In an exemplary embodiment, the amount of the alkyl acrylate monomer is 18%. In another exemplary embodiment, the amount of alkyl acrylate monomer is 23%.
- the alkyl methacrylate monomer is selected from the group consisting of methyl methacrylate, ethyl methacrylate, and butyl methyl acrylate.
- the alkyl acrylate is methyl methacrylate.
- the alkyl acrylate is ethyl methacrylate.
- the alkyl methacrylate monomer is butyl methyl acrylate.
- the amount of alkyl methacrylate monomer is in the range of 1 to 3% with respect to the total weight of the biocidal composition. In an exemplary embodiment, the amount of the alkyl methacrylate monomer is 2% with respect to the total weight of the biocidal composition.
- the amount of styrene monomer is in the range of 10 to 25% with respect to the total weight of the biocidal composition. In an exemplary embodiment, the amount of the styrene monomer is 20%. In another exemplary embodiment, the amount of the styrene monomer is 15%.
- the ureido monomer is N-(2- Methacryloyloxyethyl)-ethylene urea.
- the amount of ureido monomer is in the range of 0.1 to 1 % with respect to the total weight of the composition. In an exemplary embodiment, the amount of ureido monomer is 0.5% with respect to the total weight of the biocidal composition.
- the cross-linking monomer is selected from the group consisting of ethylene glycol dimethacrylate, and N-methylol acrylamide.
- the cross-linking monomer is a combination of ethylene glycol dimethacrylate and 50% acrylamide.
- the amount of the cross-linking monomer is in the range of 1 to 5% with respect to the total weight of the biocidal composition. In an exemplary embodiment, the amount of cross-linking monomer is 2.5% with respect to the total weight of the biocidal composition.
- the additives are selected from the group consisting of a methacryloxy silane, and an epoxy silane oligomer.
- the additive is an epoxy silane oligomer.
- the at least one of the additives being a non-ionic surfactant.
- the amount of the plurality of additives are in the range of 0.1% to 10%. In an exemplary embodiment, the amount of additives is 1 % with respect to the total weight of the biocidal composition.
- the non-ionic surfactant is fatty alcohol ethoxylate having an ethylene oxide mol in the range of 20 to 40 mol. In an exemplary embodiment, the non-ionic surfactant is fatty alcohol ethoxylate having 40 mol ethylene oxide. In another exemplary embodiment, the non-ionic surfactant is fatty alcohol ethoxylate having 30 mol ethylene oxide. In still another exemplary embodiment, the non-ionic surfactant is fatty alcohol ethoxylate having 20 mol ethylene oxide.
- the biocide is selected from the group consisting of 2,2 dibromo-3-nitrilopropionamide (Bruggolite), and disodium octaborate tetrahydrate.
- the biocide is a combination of 2,2 dibromo-3-nitrilopropionamide and disodium octaborate tetrahydrate.
- the amount of the biocide is in the range of 0.1 % to 1 % with respect to the total weight of the biocidal composition. In an exemplary embodiment, the amount of the biocide is 0.5% with respect to the total weight of the biocidal composition.
- the neutralizer is selected from the group consisting of liquid ammonia, sodium hydroxide, potassium hydroxide and ammonium hydroxide.
- the neutralizer is liquid ammonia.
- the amount of neutralizer is in the range of 0.2 to 0.6% with respect to total weight of the biocidal composition. In an exemplary embodiment, the amount of neutralizer is 0.4% with respect to the total weight of the biocidal composition.
- the biocidal composition is characterized by having solids in the range of 40 wt. % to 60 wt. %. In an exemplary embodiment, the biocidal composition has 45.5% of solid. The solids have a particle size is in the range of 200 nm to 250 nm.
- the biocidal composition of the present disclosure has a pH in the range of 7 to 9.
- the biocidal composition of the present disclosure has a viscosity in the range of 0.1 poise to 3.0 poise at 30 °C.
- the biocidal composition of the present disclosure has a minimum film forming temperature is in the range of 16 °C to 22 °C.
- the biocidal composition is cationic.
- the biocidal composition is in the form of an emulsion.
- the composition of the present disclosure is suitable for application in paints, textiles and paper coating.
- the cationic monomers of the composition of the present disclosure which are added in minimal quantities, have the functionality which can contribute to anti-microbial performance. They are covalently attached to the polymer in order to have long term effect as long as the paint or coating remains on the substrate.
- the prepared biocidal composition is very stable when formulated with paint or coatings, which is crucial to achieve.
- the biocidal composition when mixed with paint/coating shows antibacterial and antiviral activity. The extended efficacy is observed when exposed to envelop viruses such as H1N1 and H3N2.
- the biocidal composition of the present disclosure is designed with non-ionic surfactant instead cationic surfactant which provides stability to the paint and coating system.
- the biocidal composition of the present disclosure is styrene based, which improves the antiviral activity when mixed with paints or coatings.
- the biocidal composition of the present disclosure is long acting and suitable for coating.
- the biocidal composition comprises a homogeneous mixture of a polymer backbone, 1 to 3% of a plurality of additives, 0.2 to 0.8% of a biocide, 0.2 to 0.6% of a neutralizer; and 40 to 55% of water. All the percentages are with respect to the total weight of the biocidal composition.
- the polymer backbone comprises 3 to 4% of at least one cationic monomer, 15 to 25% of at least one alkyl acrylate monomer, 1.5 to 2.5% of at least one alkyl methacrylate monomer, 13 to 23% of at least one styrene monomer, 0.2 to 0.7% of at least one ureido monomer, and 2 to 3% of at least one cross-linking monomer.
- the additives are selected from the group consisting of methacryloxy silane, an epoxy silane oligomer, and a non-ionic surfactant; and at least one of the additives are the non-ionic surfactant;
- the present disclosure provides a biocidal coat comprising a biocidal composition and a paint.
- a ratio of the biocidal composition to the paint is in the range of 1:2 to 1:4.
- the present disclosure further provides a process for preparing the biocidal composition.
- a predetermined amount of at least one alkyl acrylate monomer, at least one alkyl methacrylate monomer, at least one cationic monomer, a first non-ionic surfactant, at least one styrene monomer, at least one ureido monomer, and at least one cross-linking monomer are added in water under stirring at a first predetermined stirring speed, at a first predetermined temperature for a first predetermined time period to obtain a pre-emulsion slurry.
- the amount of the alkyl acrylate monomer is in the range of 10 to 30% with respect to the total weight of the biocidal composition. In an exemplary embodiment, the amount of the alkyl acrylate monomer is 18%. In another exemplary embodiment, the amount of alkyl acrylate monomer is 23%
- the amount of alkyl methacrylate monomer is in the range of 1 to 3% with respect to the total weight of the biocidal composition. In an exemplary embodiment, the amount of the alkyl methacrylate monomer is 2% with respect to the total weight of the biocidal composition. In accordance with the present disclosure, the amount of at least one cationic monomer is in the range of 1 to 5% with respect to the total weight of the biocidal composition. In an exemplary embodiment, the amount of cationic monomer is 3% with respect to the total weight of the biocidal composition.
- the amount of styrene monomer is in the range of 10 to 25% with respect to the total weight of the biocidal composition. In an exemplary embodiment, the amount of the styrene monomer is 20%. In another exemplary embodiment, the amount of the styrene monomer is 15%.
- the amount of ureido monomer is in the range of 0.1 to 1% with respect to the total weight of the composition. In an exemplary embodiment, the amount of ureido monomer is 0.5% with respect to the total weight of the biocidal composition.
- the amount of the cross-linking monomer is in the range of 1 to 5% with respect to the total weight of the biocidal composition. In an exemplary embodiment, the amount of cross-linking monomer is 2.5% with respect to the total weight of the biocidal composition.
- the first predetermined stirring speed is in the range of 100 rpm to 250 rpm; the first predetermined temperature is in the range of 25 to 35 °C; and the first predetermined time period is in the range of 5 to 15 minutes.
- the first predetermined stirring speed is 140 rpm; the first predetermined temperature is 30 °C; and the first predetermined time period is 10 minutes.
- predetermined amounts of at least one second non-ionic surfactant and water are mixed under stirring at a second predetermined stirring speed, at a second predetermined temperature for second predetermined time period to obtain a first mixture.
- the predetermined amount of second non-ionic surfactant is in the range of 1 to 5% with respect to total weight of the first mixture. In an exemplary embodiment, the predetermined amount of second non-ionic surfactant is 2.5%.
- the second predetermined stirring speed is in the range of 100 to 250 rpm; the second predetermined temperature is in the range of 25 to 40 °C; and the second predetermined time period is in the range of 10 to 25 minutes.
- the second predetermined stirring speed is 150 rpm; the second predetermined temperature is 35 °C; and the second predetermined time period is 20 minutes.
- the pre-emulsion slurry is then added to the first mixture in a predetermined ratio to obtain a second mixture.
- predetermined ratio of the pre-emulsion slurry to the first mixture is in the range of 1 to 4. In an exemplary embodiment, the predetermined ratio of the pre-emulsion slurry to the first mixture is 2.6.
- a predetermined amount of a first catalyst is then added to the second mixture followed by reacting at a third predetermined temperature for a third predetermined time period under stirring at a third predetermined stirring speed, to obtain a first reaction mixture.
- the predetermined amount of the first catalyst is in the range of 0.5 to 5% with respect to the total weight of the second mixture. In an exemplary embodiment, the predetermined amount of the first catalyst is 2% with respect to the total weight of the second mixture.
- the third predetermined stirring speed is in the range of 100 rpm to 300 rpm; the third predetermined temperature is in the range of 50 to 70 °C; and the third predetermined time period is in the range of 2.5 to 4.0 h.
- the third predetermined stirring speed is 180 rpm; the third predetermined temperature is 55 °C; and the third predetermined time period is 10 minutes.
- a predetermined amount of a second catalyst is added to the first reaction mixture followed by reacting at a fourth predetermined temperature for a fourth predetermined time period under stirring at a fourth predetermined stirring speed to obtain a second reaction mixture.
- the predetermined amount of the second catalyst is in the range of 8 to 18% with respect to the weight of the first reaction mixture. In an exemplary embodiment, the predetermined amount of the second catalyst is 15% with respect to total weight of the first reaction mixture.
- the fourth predetermined stirring speed is in the range of 100 to 250 rpm; the fourth predetermined temperature is in the range of 50 to 70 °C; and the fourth predetermined time period is in the range of 5 to 15 minutes. In an exemplary embodiment, the fourth predetermined stirring speed is 150-200 rpm; the fourth predetermined temperature is 55 °C; the fourth predetermined time period is 10 minutes.
- a neutralizer e.g., a sulfate, a sulfate, a sulfate, a sulfate, a sulfate, a sulfate, a sulfate, a sulfate, a sulfate, a sulfate, a sulfate, a sulfate, a sulfate, a sulfate, a sulfate, a sulfate, a sulfate, a sulfate, a sulfate, a sulfate, a sulfate, a sulfate, a sulfate, a sulfate, a sulfate, a sulfate, a sulfate, a sulfate, a sulfate, a sulfate,
- the neutralizer is at least one selected from the group consisting of liquid ammonia, sodium hydroxide, potassium hydroxide, and ammonium hydroxide.
- the neutralizer is liquid ammonia.
- the predetermined amount of neutralizer is in the range of 0.2 to 0.6% with respect to total weight of the biocidal composition. In an exemplary embodiment, the predetermined amount of neutralizer is 0.5% with respect to the total weight of the biocidal composition.
- the biocide is selected from the group consisting of 2,2 dibromo- 3 -nitrilopropionamide (Mergal 530), and disodium octaborate tetrahydrate.
- the biocide is a combination of 2,2 dibromo- 3- nitrilopropionamide and disodium octaborate tetrahydrate.
- the predetermined amount of biocide is in the range of 0.1 to 1 % with respect to total weight of the biocidal composition. In an exemplary embodiment, the predetermined amount of biocide is 0.5% with respect to the total weight of the biocidal composition.
- the biocidal composition is stable at least for three months.
- the predetermined amount of additives is in the range of 0.1 to 5% with respect to total weight of the biocidal composition. In an exemplary embodiment, the predetermined amount of additives is 1% with respect to the total weight of the biocidal composition.
- the third mixture is added to the second reaction mixture followed by cooling to a temperature in the range of 25 to 35 °C to obtain the biocidal composition in the form a homogeneous mixture.
- the first catalyst is a mixture of 0.1 to 0.3% of an activator, 0.1 to 0.3% of a chelating agent, 0.01 to 0.05% of a first reducing agent, 0.01 to 0.05% of a first oxidizing agent, 0.005 to 0.01% of a fourth non-ionic surfactant and 0.5 to 2 % of water.
- the activator is iron sulphate.
- the chelating agent is ethylenediaminetetraacetic acid sodium salt.
- the second catalyst is a mixture of 0.1 to 0.5% a second reducing agent, 0.5 to 2% of a second oxidizing agent, 0.05 to 0.2% of a fifth non-ionic surfactant, and 8 to 13% of water.
- the first oxidizing agent and the second oxidizing agent are same or different and are independently selected from persulphate and peroxide.
- the persulphate is selected from the group consisting of potassium persulphate, sodium persulphate, and ammonium persulphate.
- the peroxide is selected from the group consisting of tertiary butyl hydroperoxide, hydrogen peroxide, and benzoyl peroxide.
- the oxidizing agent is tertiary butyl hydroperoxide.
- the first reducing agent and the second reducing agent are same or different and are independently selected from sodium formaldehyde sulphoxylate, sodium acetone, sodium meta bisulphite, sodium hydroxymethylsulfinate (Bruggolite), and sodium acetone bisulphite.
- the first reducing agent is a combination of sodium hydroxymethylsulfinate (Bruggolite) and sodium acetone bisulphite.
- the second reducing agent is a combination of sodium hydroxymethylsulfinate (Bruggolite) and sodium acetone bisulphite.
- a weight ratio of the first/second oxidizing agent to the first/second reducing agent is in the range of 0.05% to 2%.
- At least one second cationic monomer, a biocide, a third non-ionic surfactant and at least one neutralizer are mixed with water to obtain a mixture.
- the mixture is then mixed with the second reaction mixture to obtain the biocidal composition.
- the first non-ionic surfactant, the second non-ionic surfactant, the third non-ionic surfactant, the fourth non-ionic surfactant, and the fifth non- ionic surfactant are same or different and are independently selected from fatty alcohol ethoxylate having ethylene oxide in the range 20 mol to 40 Mol.
- the process of the present disclosure is a redox process rather conventional process.
- the redox process incorporates less reactive but better performing specialty cationic monomers in the polymer backbone.
- the combination of cationic monomer and ureido monomer plays a significant role in providing antimicrobial activity along with better adhesion of paint/coating to the substrate.
- the prepared paints and coatings show above 99 % efficacy to antibacterial and antiviral application and at the same to envelop viruses such as H1N1 and H3N2.
- the monomers are fully polymerized.
- the present disclosure further provides a surface coating composition.
- the surface coating composition comprises 20 to 25% of a biocidal composition of the present disclosure, 0.05 to 0.15% water softening agent, 0.60 to 1.0% dispersing agent, 0.4 to 0.8% wetting agent, 0.8 to 1.2% open time enhancer, 0.1 to 0.3% defoamer, 0.1 to 0.3% neutralizer, 0.1 to 0.5% cellulose thickner, 8 to 10% pigment, 30 to 35% extender, 0.6 to 1.0% preservatives, 0.2 to 0.6% adhesion promoters, 6 to 10% opaque polymer, 0.5 to 1.5% coalescing agent, and 18 to 22% water. All the percentages are with respect to the total weight of the surface coating composition.
- the water softening agent is selected from the group consisting of tetrasodium pyrophosphate and ethylene diamine tetra acetic acid.
- the water softening agent is tetrasodium pyrophosphate.
- the dispersing agent is selected from the group consisting of a polyacrylate having a molecular weight in the range of 1000 to 7000 Da.
- the dispersing agent is a poly aery late having a molecular weight ⁇ 5000 Da (Bondex 532).
- the wetting agent is selected from the group consisting of alkyl phenol ethoxylate.
- the wetting agent is nonyl phenol 40 mol ethoxylate (IG Surf 8405).
- the open time enhancer is a glycol.
- the open time enhancer is triethylene glycol.
- the defoamer is selected from the group consisting of mineral oil, polyether, silica and a mixture thereof.
- the defoamer is a mixture of mineral oil, polyether and silica (San Napco SN 1370).
- the neutralizer is 95% aqueous solution of 2-amino-2-methyl-l -propanol (AMP 95).
- the thickener is selected from the group consisting of water soluble non-ionic hydroxyethylcellulose and associative polyurethane.
- the thickner is a mixture of water soluble non-ionic hydroxyethylcellulose (Natrosol 250 HBR) and associative polyurethane (Rheolite 99).
- the pigment is selected from the group consisting of rutile TiCK
- the extender is selected from the group consisting of CaCCh. calcined kaolin, talc powder and a mixture thereof.
- the extender is a mixture of CaCCh. calcined kaolin and talc powder.
- the preservative is benzimidazole carbamate. In an exemplary embodiment, the preservative is Acticide EPW 1.
- the adhesion promoter is 3-(2,3- epoxypropoxypropyl)methyldiethoxysilane. In an exemplary embodiment, the adhesion promoter is 3-(2,3-epoxypropoxypropyl)methyldiethoxysilane (Wetlink 78).
- the opaque polymer is Bondex Opex 90 (styrene based).
- the coalescing agent is a film former selected from texanol and butylcarbitol.
- the coalescing agent (film former) is texanol.
- the biocidal composition acts as a binder.
- the viscosity of the surface coating composition of the present disclosure is in the range of 25 to 35 poise. In an exemplary embodiment, the viscosity of the surface coating composition is 28.4 poise.
- the present disclosure provides a method for treating a surface for biocidal activity.
- the surface is selected from the group consisting of internal wall surface, internal ceiling surface, external wall surface, and external roof surface.
- the surface is internal wall surface.
- a primer coat is applied on the surface and the primer is allowed to dry to obtain a primer coated surface.
- a coat having a uniform thickness in the range of 200 microns to 500 microns is applied on the primer coated surface to obtain a coated surface.
- the coat is carried out by using at least one composition selected from the biocidal composition of the present disclosure, the biocidal coat of the present disclosure, and the surface coating composition of the present disclosure.
- the coat is applied by using at least one appliance selected from a brush and a roller.
- the coated surface is cured for a time period in the range of 2 hours to 6 hours to obtain the treated surface.
- the coated surface is cured for a time period in the range of 2 hours to 3 hours.
- the treated surface has a dry film thickness in the range of 100 microns to 250 microns. In an embodiment of the present disclosure, the treated surface has a dry film thickness in the range of 100 microns to 150 microns.
- the composition of the present disclosure is suitable for application in paints, textiles and paper coating.
- the cationic monomers of the composition of the present disclosure which are added in minimal quantities, have the functionality which can contribute to anti-microbial performance. They are covalently attached to the polymer in order to have long term effect as long as the paint or coating remains on the substrate.
- the prepared biocidal composition is very stable when formulated with paint or coatings, which is crucial to achieve.
- the biocidal composition when mixed with paint/coating shows antibacterial and antiviral activity. The extended efficacy is observed when exposed to envelop viruses such as H1N1 and H3N2.
- EXPERIMENTAL DETAILS Experiment 1: Process for preparing a long lasting biocidal composition in accordance with the present disclosure
- a demineralized water was added in a second reactor.
- a non-ionic surfactant (fatty alcohol ethoxylate) was added to water under stirring at a stirring speed of 150 rpm at 35 °C for 20 minute to obtain a first mixture.
- Table 2 illustrates various combinations of fatty alcohol ethoxylate with demineralized water.
- the pre-emulsion slurry was added to the first mixture in a ratio of 2.6 to obtain a second mixture.
- 1.8 % of first catalyst (with respect to the total weight of second mixture) was added to the second mixture followed by reacting at 55 °C for 10 min under stirring at a stirring speed of 180 rpm (with respect to the weight of pre-emulsion slurry) to obtain a first reaction mixture.
- 5 wt% of seed polymer was added with respect to the total weight of the pre- emulsion slurry to initiate the reaction.
- Table 3 illustrates a composition of the first catalyst.
- the second catalyst also refers to a delayed catalyst that is added slowly over the time period of 3 to 4 hr in the reactor.
- Table 4 discloses a composition of the second catalyst.
- a neutralizer liquid ammonia
- a biocide Mergal 530 and disodium octaborate tetrahydrate
- an additive epoxy silane oligomer and third non-ionic surfactant i.e. fatty alcohol ethoxylate
- the third mixture was then mixed to the second reaction mixture followed by cooling to a temperature in the range of 25 to 35 °C to obtain the biocidal composition in the form a homogeneous mixture.
- Table 5 represents the composition which is added after the polymerization reaction is finished.
- the total weight in each of the trial T1-T14 was 1000 g.
- the pH of the biocidal compositions of T1-T12 were in the range of 7-9.
- the specific gravity of the biocidal compositions (T1-T12) were in the range of 1.02 to 1.09, as measured using ASTM 1475 (see table 6).
- the amount of solid content of the biocidal composition (T1-T12) was 45 to 46%, as determined ASTM D 2369 (see table 6).
- the viscosity of the biocidal compositions was measured using Brookfield RVT Spindle 2, speed 20 at 30 °C, was in the range of 1-2 poise (see table 6).
- Example 4 Determination of minimum film forming temperature (MFFT) of the biocidal composition A standard test method ASTM D2354 was followed for determining MFFT of the biocidal composition.
- the MFFT of the biocidal composition was found to be 18-20 °C (T1-T12). Below 18-20 °C, the biocidal composition did not form a continuous film and it cracks.
- Table 2 illustration of various combinations of non-ionic surfactants with water to prepare the first mixture
- Table 3 A composition of the first catalyst
- Table 5 A composition of a third mixture for post-addition
- the particle sizes of the solid particles were found to be in the range of 200 nm to 250 nm (T1-T12).
- the biocidal composition was prepared as per experiment 1(T1-T12).
- the surface coating composition was prepared by mixing 22 wt% of biocidal composition, 0.1 wt% of tetrasodium pyrophosphate (water softening agent), 0.8 wt% of Bondex 532 (dispersing agent), 0.6 wt% of IG Surf 8405 (wetting agent), 1.0 wt% of triethylene glycol (open time enhancer), 0.2 wt% of San Napco SN 1370 (defoamer), 0.2 wt% of AMP 95 (neutralizer), 0.3 wt% of Natrosol 250 HBR (thickner/cellulose thickner), 9% of Rutile TiCL R 902 (pigment), 17 wt% CaCCh, 12 wt% calcined kaolin, and 4 wt% talk powder 2 p (extenders), 0.20 wt% preventol (In can preservative), 0.6 wt% Acticide EPW 1 (dry film preservative), 0.40 wt% Wetlink 78
- the viscosity of the surface coating composition was found to be 28.4 poise as measured using Brookfield viscometer with spindle 2 at 20 rpm and 30 °C.
- the virus killing activity of the surface coating composition was commercially performed at Centre for Cellular and Molecular Biology Laboratory, Hyderabad, India.
- the surface coating composition having 22 wt% of biocidal compositions which is styrene based was evaluated for the efficacy to kill corona virus (SARS_CoV2) when inoculated at a concentration of 1 x 10 7 viral particles per ml.
- SARS_CoV2 corona virus
- Table 7 Surface coating composition of the present disclosure (white paint @ 22% Bondex AMCAS 46-2)
- the viral assay was performed using (i) viral RNA extraction method using MagMAXTM Viral/Pathogen Extraction Kit from Applied Biosystems (Thermo Fisher), and (ii) qRT-PCR using Q-line Molecular nCOV-19 RT-PCR Detection Kit (Multiplex) manufactured by POCT Services Private Limited. The assays were performed at 5 minute intervals. The experiments were performed in duplicates and the values were averaged to calculate % viral reduction.
- the number of viral particles (x) were calculated using the following equation: — (40.786-CtRdrp.gene at different time points)/3-5442 (2)
- the percentage of viral reduction was calculated using the following equation:
- % viral reduction ((number of viral particles in infection control-number of viral particles exposed to surface (test))/(number of viral particles in infection control))* 100 (3)
- the surface coating composition of the present disclosure showed -99% viral reduction from 25 minutes onward.
- the viral particles number reduced from IxlO 6 ' 9 to IxlO 4 ' 3 (See figure 1).
- the viral assay was performed using (i) viral RNA extraction method using MagMAXTM Viral/Pathogen Extraction Kit from Applied Biosystems (Thermo Fisher), and (ii) qRT-PCR using Meril Covid-19 one-step RT-PCR Kit from Meril Diagnostics Pvt. Ltd.
- the percentage of viral reduction was calculated using equation (3).
- the surface coating composition of the present disclosure showed -94% viral reduction from 45 minutes onward.
- the viral particles number reduced from IxlO 5 ' 7 to IxlO 4 ' 4 (see figure 2). It was found that the surface coating composition prepared using biocidal composition of T1-T12 (styrene based) showed higher efficiency that those prepared using biocidal composition of T13-T14 (pure acrylic based).
- the surface coating composition showed remarkable result in killing the virus on contact due to the cationic nature of the surface developed due to biocidal composition.
- the proposition of killing virus was based on electrostatic force generated by the biocidal composition to the paint which attracts the negative charge virus and thus activated the same due to puncture of cell membrane, and deactived the protein layer.
- One of the objects of the Patent Law is to provide protection to new technologies in all fields and domain of technologies.
- the new technologies shall or may contribute in the country economy growth by way of involvement of new efficient and quality method or product manufacturing in India.
- the applicant submits that the present disclosure will contribute in country economy, which is one of the purposes to enact the Patents Act, 1970.
- the product in accordance with present invention will be in great demand in country and worldwide due to novel technical features of a present invention is a technical advancement in the surface coating technology.
- the technology in accordance with present disclosure will provide product cheaper, saving in time of total process of manufacturing. The saving in production time will improve the productivity, and cost cutting of the product, which will directly contribute to economy of the country.
- the product will contribute new concept in the surface coating compositions wherein patented process/product will be used.
- the present disclosure will replace the whole concept of surface coating being used in this area from decades.
- the product is developed in the national interest and will contribute to country economy.
- the economy significance details requirement may be called during the examination. Only after filing of this Patent application, the applicant can work publically related to present disclosure product/process/method. The applicant will disclose all the details related to the economic significance contribution after the protection of invention.
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Abstract
The present disclosure relates to a biocidal composition, and a process of its preparation. The present disclosure also provides a surface coating composition. The biocidal composition can be used in a surface coating composition. The biocidal composition comprises a polymer backbone, a plurality of additives, a biocide, a neutralizer and water. The composition is prepared using redox polymerization. The composition can kill upto 99% of H1N1 and H3N2 viruses, has a long term anti-microbial effect and is very stable when formulated with the surface coating composition.
Description
A BIOCIDAL COMPOSITION AND A PROCESS FOR ITS PREPARATION
FIELD
The present disclosure relates to a biocidal composition and a process for its preparation.
DEFINITIONS
As used in the present disclosure, the following term are generally intended to have the meaning as set forth below, except to the extent that the context in which they are used to indicate otherwise.
Minimum film forming temperature (MFFT): The term “minimum film forming temperature” refers to a lowest temperature at which an emulsion will uniformly coalesce when laid on a substrate as a thin film. An accurate minimum film forming temperature value allows the formulation of products that cure correctly under specified application conditions.
Open time: The term “open time” refers to a period of time during which irregularities in a freshly applied coating can be repaired.
BACKGROUND
The background information herein below relates to the present disclosure but is not necessarily prior art.
Development of surface coating compositions having anti-microbial and anti-viral activity has drawn significant attention in the recent years. It is highly desirable to have a long term solution for treating the microbial infected surfaces.
There are a few approaches adopted to achieve the long term performance of the surface coating compositions in terms of anti-microbial and anti-viral activity. In an approach, a cationic monomer is incorporated while designing the coating composition, which forms an integral part of coating composition. The cationic surfactants such as cetylpyridinium chloride, cetylpyridinium bromide, dialkyl ammonium chloride, and like are added in the surface coating compositions.
In another approach, suitable cationic compounds such as substituted pyridinium salts, substituted guanidine salts, tetrasubstituted ammonium salts and the like is incorporated
during the coating preparation process. In coating industry, incorporation of such cationic compounds in the final coating formulation is widely adopted to achieve anti-microbial efficacy. However, leaching of the cationic compounds over a time period limits the performance of coating composition, with respect to its anti-microbial activity in a long run. The use of such cationic compounds shows the anti-microbial efficacy for maximum of 3-4 months. Moreover, combining the cationic surfactant or any cationic molecules during the coating preparation process de-stabilizes the composition due to stringent processing conditions.
In still another approach, an inorganic material is combined with the final surface coating formulation. The most commonly used inorganic material is based on silver ion and its nanoparticles. These silver ion or nanoparticles interact with sodium ion present in the microbes making them inactive. The other metals, which have been explored as anti-microbial agents in the coating compositions are copper, copper oxide, zinc oxide and carbon black. However, the anti-microbial effect of these metal oxides is not persisting for longer period because of deactivation and leaching of nano-particles from the coated surface.
Therefore, there is felt a need to provide a biocidal composition that mitigates the drawback mentioned herein above.
OBJECTS
Some of the objects of the present disclosure, which at least one embodiment herein satisfies, are as follows.
It is an object of the present disclosure to ameliorate one or more problems of the prior art or to at least provide a useful alternative.
Another object of the present disclosure is to provide a biocidal composition.
Still another object of the present disclosure is to provide a biocidal composition, which is suitable for coating.
Another object of the present disclosure is to provide a biocidal composition, which is stable.
Yet another object of the present disclosure is to provide a process for the preparation of the biocidal composition.
Still another object of the present disclosure is to provide a surface coating composition.
Another object of the present disclosure is to provide a surface coating composition, which is stable at least for 24 months.
Other objects and advantages of the present disclosure will be more apparent from the following description, which is not intended to limit the scope of the present disclosure.
SUMMARY
The present disclosure provides a biocidal composition. The composition comprising a homogenous mixture of: a polymer backbone, 0.1 to 5% of a plurality of additives, 0.1 to 1% of a biocide, 0.2 to 0.6% of a neutralizer, and 40 to 55% of water. The polymer backbone comprises 1 to 5% of at least one cationic monomer, 10 to 30% of at least one alkyl acrylate monomer, 1 to 3% of at least one alkyl methacrylate monomer, 10 to 25% of at least one styrene monomer, 0.1 to 1% of at least one ureido monomer, and 1 to 5% of at least one cross-linking monomer. All the percentages are with respect to the total weight of the composition. The additives are selected from the group consisting of a methacryloxy silane, an epoxy silane oligomer, and a non-ionic surfactant. The at least one of the additives being the non-ionic surfactant.
The present disclosure further provides a process for preparing a biocidal composition. Initially, in a first reactor, predetermined amounts of at least one alkyl acrylate monomer, at least one alkyl methacrylate monomer, at least one cationic monomer, at least one first non- ionic surfactant, at least one styrene monomer, at least one ureido monomer, and at least one cross-linking monomer are added in water under stirring at a first predetermined stirring speed, at a first predetermined temperature for a first predetermined time period to obtain a pre-emulsion slurry. Separately, predetermined amounts of at least one second non-ionic surfactant and water are mixed in a second reactor under stirring at a second predetermined stirring speed, at a second predetermined temperature for a second predetermined time period to obtain a first mixture. In the second reactor, the pre-emulsion slurry is then added to the first mixture in a first predetermined ratio to obtain a second mixture. A predetermined
amount of a first catalyst is added to the second mixture followed by reacting at a third predetermined temperature for a third predetermined time period under stirring at a third predetermined stirring speed in the second reactor to obtain a first reaction mixture. A predetermined amount of a second catalyst is added to the first reaction mixture followed by reacting at a fourth predetermined temperature for a fourth predetermined time period under stirring at a fourth predetermined stirring speed to obtain a second reaction mixture. Separately, predetermined amounts of a neutralizer, a biocide and a plurality of additives are added in water to obtain a third mixture. The additives are selected from the group consisting of methacryloxy silane, an epoxy silane oligomer, and a third non-ionic surfactant. At least one of the additives being the third non-ionic surfactant. The third mixture is mixed to the second reaction mixture followed by cooling to a temperature in the range of 25 to 35 °C to obtain the biocidal composition in the form a homogeneous mixture.
The present disclosure further provides a surface coating composition. It comprises 20 to 25 % of the biocidal composition, 0.05 to 0.15% water softening agent, 0.60 to 1.0% dispersing agent, 0.4 to 0.8% wetting agent, 0.8 to 1.2% open time enhancer, 0.1 to 0.3% defoamer, 0.1 to 0.3% neutralizer, 0.1 to 0.5% cellulose thickner, 8 to 10% pigment, 30 to 35% extender, 0.6 to 1.0% preservatives, 0.2 to 0.6% adhesion promoters, 6 to 10% opaque polymer, 0.5 to 1.5% coalescing agent, and 18 to 22% water. All the percentages are with respect to the total weight of the surface coating composition.
BRIEF DESCRIPTION OF THE ACCOMPANYING DRAWING
The present disclosure will now be described with the help of the accompanying drawing, in which:
Figure 1 illustrates a graph of log number of viral particles/percentage viral reduction vs time for the surface coating composition having biocidal composition of trial 1-12 (styrene based); and
Figure 2 illustrates a graph of log number of viral particles/percentage viral reduction vs time for the surface coating composition having biocidal composition of trial 13-14 (pure acrylic based).
DETAILED DESCRIPTION
Embodiments, of the present disclosure, will now be described with reference to the accompanying drawing.
Embodiments are provided so as to thoroughly and fully convey the scope of the present disclosure to the person skilled in the art. Numerous details are set forth, relating to specific components, and methods, to provide a complete understanding of embodiments of the present disclosure. It will be apparent to the person skilled in the art that the details provided in the embodiments should not be construed to limit the scope of the present disclosure. In some embodiments, known processes or well-known apparatus or structures, and well known techniques are not described in detail.
The terminology used, in the present disclosure, is only for the purpose of explaining a particular embodiment and such terminology shall not be considered to limit the scope of the present disclosure. As used in the present disclosure, the forms "a,” "an," and "the" may be intended to include the plural forms as well, unless the context clearly suggests otherwise. The terms "comprises," "comprising," “including,” and “having,” are open ended transitional phrases and therefore specify the presence of stated features, integers, steps, operations, elements, modules, units and/or components, but do not forbid the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof. The particular order of steps disclosed in the method and process of the present disclosure are not to be construed as necessarily requiring their performance as described or illustrated. It is also to be understood that additional or alternative steps may be employed.
The terms first, second, third, etc., should not be construed to limit the scope of the present disclosure as the aforementioned terms may be only used to distinguish one element, component, region, layer or section from another component, region, layer or section. Terms such as first, second, third etc., when used herein do not imply a specific sequence or order unless clearly suggested by the present disclosure.
As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed elements.
The conventional surface coating compositions which are used for anti-microbial applications extensively utilizes positively charged surfactants. The limitation while using positively charged surfactant is that it leaches out with time when the surface coating is exposed to
external environment, and therefore the efficacy of the surface coating composition decreases with time. The preparation of surface coating compositions is very critical because of its instability in the surface coatings in long term.
The present disclosure provides a biocidal composition that would address the above described problem.
In an aspect, the present disclosure provides a biocidal composition. The composition comprising a homogenous mixture of: a polymer backbone, a plurality of additives, a biocide, a neutralizer and water.
In accordance with the present disclosure, the polymer backbone comprises at least one cationic monomer, at least one alkyl acrylate monomer, at least one alkyl methacrylate monomer, at least one styrene monomer, at least one ureido monomer, and at least one crosslinking monomer.
In accordance with the present disclosure, the at least one cationic monomer is selected from the group consisting of diallyl dimethyl ammonium chloride, methacryloxy ethyl trimethyl ammonium chloride, acryloxy ethyl trimethyl ammonium chloride, vinyltrimethoxy silane, gamma-methacryloxypropyltrimethoxy silane, and dimethyl aminoethyl acrylate. In an exemplary embodiment, the cationic monomer is a combination of diallyl dimethyl ammonium chloride and vinyltrimethoxy silane. In another exemplary embodiment, the cationic monomer is a combination of diallyl dimethyl ammonium chloride and gammamethacryloxypropyltrimethoxy silane. In still another exemplary embodiment, the cationic monomer is a combination of methacryloxy ethyl trimethyl ammonium chloride and vinyltrimethoxy silane. In still another exemplary embodiment, the cationic monomer is a combination of methacryloxy ethyl trimethyl ammonium chloride and gammamethacryloxypropyltrimethoxy silane. In still another exemplary embodiment, the cationic monomer is a combination of acryloxy ethyl trimethyl ammonium chloride and vinyltrimethoxy silane. In still another exemplary embodiment, the cationic monomer is a combination of acryloxy ethyl trimethyl ammonium chloride and gammamethacryloxypropyltrimethoxy silane .
In accordance with the present disclosure, the amount of at least one cationic monomer is in the range of 1 to 5% with respect to the total weight of the biocidal composition. In an
exemplary embodiment, the amount of cationic monomer is 3% with respect to the total weight of the biocidal composition.
In accordance with the present disclosure, the alkyl acrylate monomer is selected from the group consisting of butyl acrylate, ethyl acrylate, 2-ethyl hexyl acrylate, n-butyl methacrylate. In an exemplary embodiment, the alkyl acrylate monomer is butyl acrylate. In another exemplary embodiment, the alkyl acrylate is ethyl acrylate. In still another exemplary embodiment, the alkyl acrylate is 2-ethyl hexyl acrylate. The amount of the alkyl acrylate monomer is in the range of 10 to 30% with respect to the total weight of the biocidal composition. In an exemplary embodiment, the amount of the alkyl acrylate monomer is 18%. In another exemplary embodiment, the amount of alkyl acrylate monomer is 23%.
In accordance with the present disclosure, the alkyl methacrylate monomer is selected from the group consisting of methyl methacrylate, ethyl methacrylate, and butyl methyl acrylate. In an exemplary embodiment, the alkyl acrylate is methyl methacrylate. In another exemplary embodiment, the alkyl acrylate is ethyl methacrylate. In still another exemplary embodiment, the alkyl methacrylate monomer is butyl methyl acrylate. The amount of alkyl methacrylate monomer is in the range of 1 to 3% with respect to the total weight of the biocidal composition. In an exemplary embodiment, the amount of the alkyl methacrylate monomer is 2% with respect to the total weight of the biocidal composition.
The amount of styrene monomer is in the range of 10 to 25% with respect to the total weight of the biocidal composition. In an exemplary embodiment, the amount of the styrene monomer is 20%. In another exemplary embodiment, the amount of the styrene monomer is 15%.
In accordance with an embodiment of the present disclosure, the ureido monomer is N-(2- Methacryloyloxyethyl)-ethylene urea. The amount of ureido monomer is in the range of 0.1 to 1 % with respect to the total weight of the composition. In an exemplary embodiment, the amount of ureido monomer is 0.5% with respect to the total weight of the biocidal composition.
In accordance with the present disclosure, the cross-linking monomer is selected from the group consisting of ethylene glycol dimethacrylate, and N-methylol acrylamide. In an exemplary embodiment, the cross-linking monomer is a combination of ethylene glycol
dimethacrylate and 50% acrylamide. The amount of the cross-linking monomer is in the range of 1 to 5% with respect to the total weight of the biocidal composition. In an exemplary embodiment, the amount of cross-linking monomer is 2.5% with respect to the total weight of the biocidal composition.
In accordance with the present disclosure, the additives are selected from the group consisting of a methacryloxy silane, and an epoxy silane oligomer. In an exemplary embodiment, the additive is an epoxy silane oligomer. The at least one of the additives being a non-ionic surfactant. The amount of the plurality of additives are in the range of 0.1% to 10%. In an exemplary embodiment, the amount of additives is 1 % with respect to the total weight of the biocidal composition.
In accordance with the present disclosure, the non-ionic surfactant is fatty alcohol ethoxylate having an ethylene oxide mol in the range of 20 to 40 mol. In an exemplary embodiment, the non-ionic surfactant is fatty alcohol ethoxylate having 40 mol ethylene oxide. In another exemplary embodiment, the non-ionic surfactant is fatty alcohol ethoxylate having 30 mol ethylene oxide. In still another exemplary embodiment, the non-ionic surfactant is fatty alcohol ethoxylate having 20 mol ethylene oxide.
In accordance with the present disclosure, the biocide is selected from the group consisting of 2,2 dibromo-3-nitrilopropionamide (Bruggolite), and disodium octaborate tetrahydrate. In an exemplary embodiment, the biocide is a combination of 2,2 dibromo-3-nitrilopropionamide and disodium octaborate tetrahydrate. The amount of the biocide is in the range of 0.1 % to 1 % with respect to the total weight of the biocidal composition. In an exemplary embodiment, the amount of the biocide is 0.5% with respect to the total weight of the biocidal composition.
In accordance with the present disclosure, the neutralizer is selected from the group consisting of liquid ammonia, sodium hydroxide, potassium hydroxide and ammonium hydroxide. In an exemplary embodiment, the neutralizer is liquid ammonia. The amount of neutralizer is in the range of 0.2 to 0.6% with respect to total weight of the biocidal composition. In an exemplary embodiment, the amount of neutralizer is 0.4% with respect to the total weight of the biocidal composition.
In accordance with the present disclosure, the biocidal composition is characterized by having solids in the range of 40 wt. % to 60 wt. %. In an exemplary embodiment, the biocidal
composition has 45.5% of solid. The solids have a particle size is in the range of 200 nm to 250 nm.
The biocidal composition of the present disclosure has a pH in the range of 7 to 9.
The biocidal composition of the present disclosure has a viscosity in the range of 0.1 poise to 3.0 poise at 30 °C.
The biocidal composition of the present disclosure has a minimum film forming temperature is in the range of 16 °C to 22 °C.
In accordance with an embodiment of the present disclosure, the biocidal composition is cationic.
In accordance with another embodiment of the present disclosure, the biocidal composition is in the form of an emulsion.
The composition of the present disclosure is suitable for application in paints, textiles and paper coating. The cationic monomers of the composition of the present disclosure, which are added in minimal quantities, have the functionality which can contribute to anti-microbial performance. They are covalently attached to the polymer in order to have long term effect as long as the paint or coating remains on the substrate. The prepared biocidal composition is very stable when formulated with paint or coatings, which is crucial to achieve. The biocidal composition when mixed with paint/coating, shows antibacterial and antiviral activity. The extended efficacy is observed when exposed to envelop viruses such as H1N1 and H3N2.
The biocidal composition of the present disclosure is designed with non-ionic surfactant instead cationic surfactant which provides stability to the paint and coating system. The biocidal composition of the present disclosure is styrene based, which improves the antiviral activity when mixed with paints or coatings.
The biocidal composition of the present disclosure is long acting and suitable for coating.
In accordance with an embodiment of the present disclosure, the biocidal composition comprises a homogeneous mixture of a polymer backbone, 1 to 3% of a plurality of additives,
0.2 to 0.8% of a biocide, 0.2 to 0.6% of a neutralizer; and 40 to 55% of water. All the percentages are with respect to the total weight of the biocidal composition.
The polymer backbone comprises 3 to 4% of at least one cationic monomer, 15 to 25% of at least one alkyl acrylate monomer, 1.5 to 2.5% of at least one alkyl methacrylate monomer, 13 to 23% of at least one styrene monomer, 0.2 to 0.7% of at least one ureido monomer, and 2 to 3% of at least one cross-linking monomer.
The additives are selected from the group consisting of methacryloxy silane, an epoxy silane oligomer, and a non-ionic surfactant; and at least one of the additives are the non-ionic surfactant;
In another aspect, the present disclosure provides a biocidal coat comprising a biocidal composition and a paint.
In accordance with the present disclosure, a ratio of the biocidal composition to the paint is in the range of 1:2 to 1:4.
In still another aspect, the present disclosure further provides a process for preparing the biocidal composition.
Initially, a predetermined amount of at least one alkyl acrylate monomer, at least one alkyl methacrylate monomer, at least one cationic monomer, a first non-ionic surfactant, at least one styrene monomer, at least one ureido monomer, and at least one cross-linking monomer are added in water under stirring at a first predetermined stirring speed, at a first predetermined temperature for a first predetermined time period to obtain a pre-emulsion slurry.
In accordance with the present disclosure, the amount of the alkyl acrylate monomer is in the range of 10 to 30% with respect to the total weight of the biocidal composition. In an exemplary embodiment, the amount of the alkyl acrylate monomer is 18%. In another exemplary embodiment, the amount of alkyl acrylate monomer is 23%
The amount of alkyl methacrylate monomer is in the range of 1 to 3% with respect to the total weight of the biocidal composition. In an exemplary embodiment, the amount of the alkyl methacrylate monomer is 2% with respect to the total weight of the biocidal composition.
In accordance with the present disclosure, the amount of at least one cationic monomer is in the range of 1 to 5% with respect to the total weight of the biocidal composition. In an exemplary embodiment, the amount of cationic monomer is 3% with respect to the total weight of the biocidal composition.
The amount of styrene monomer is in the range of 10 to 25% with respect to the total weight of the biocidal composition. In an exemplary embodiment, the amount of the styrene monomer is 20%. In another exemplary embodiment, the amount of the styrene monomer is 15%.
In an exemplary embodiment, the amount of ureido monomer is in the range of 0.1 to 1% with respect to the total weight of the composition. In an exemplary embodiment, the amount of ureido monomer is 0.5% with respect to the total weight of the biocidal composition.
In accordance with the present disclosure, the amount of the cross-linking monomer is in the range of 1 to 5% with respect to the total weight of the biocidal composition. In an exemplary embodiment, the amount of cross-linking monomer is 2.5% with respect to the total weight of the biocidal composition.
In accordance with the present disclosure, the first predetermined stirring speed is in the range of 100 rpm to 250 rpm; the first predetermined temperature is in the range of 25 to 35 °C; and the first predetermined time period is in the range of 5 to 15 minutes. In an exemplary embodiment, the first predetermined stirring speed is 140 rpm; the first predetermined temperature is 30 °C; and the first predetermined time period is 10 minutes.
Separately, in a second reactor, predetermined amounts of at least one second non-ionic surfactant and water are mixed under stirring at a second predetermined stirring speed, at a second predetermined temperature for second predetermined time period to obtain a first mixture.
In accordance with the present disclosure, the predetermined amount of second non-ionic surfactant is in the range of 1 to 5% with respect to total weight of the first mixture. In an exemplary embodiment, the predetermined amount of second non-ionic surfactant is 2.5%.
In accordance with the present disclosure, the second predetermined stirring speed is in the range of 100 to 250 rpm; the second predetermined temperature is in the range of 25 to 40 °C;
and the second predetermined time period is in the range of 10 to 25 minutes. In an exemplary embodiment, the second predetermined stirring speed is 150 rpm; the second predetermined temperature is 35 °C; and the second predetermined time period is 20 minutes.
The pre-emulsion slurry is then added to the first mixture in a predetermined ratio to obtain a second mixture.
In accordance with the present disclosure, predetermined ratio of the pre-emulsion slurry to the first mixture is in the range of 1 to 4. In an exemplary embodiment, the predetermined ratio of the pre-emulsion slurry to the first mixture is 2.6.
A predetermined amount of a first catalyst is then added to the second mixture followed by reacting at a third predetermined temperature for a third predetermined time period under stirring at a third predetermined stirring speed, to obtain a first reaction mixture.
In accordance with the present disclosure, the predetermined amount of the first catalyst is in the range of 0.5 to 5% with respect to the total weight of the second mixture. In an exemplary embodiment, the predetermined amount of the first catalyst is 2% with respect to the total weight of the second mixture.
In accordance with the present disclosure, the third predetermined stirring speed is in the range of 100 rpm to 300 rpm; the third predetermined temperature is in the range of 50 to 70 °C; and the third predetermined time period is in the range of 2.5 to 4.0 h. In an exemplary embodiment, the third predetermined stirring speed is 180 rpm; the third predetermined temperature is 55 °C; and the third predetermined time period is 10 minutes.
A predetermined amount of a second catalyst is added to the first reaction mixture followed by reacting at a fourth predetermined temperature for a fourth predetermined time period under stirring at a fourth predetermined stirring speed to obtain a second reaction mixture.
In accordance with the present disclosure, the predetermined amount of the second catalyst is in the range of 8 to 18% with respect to the weight of the first reaction mixture. In an exemplary embodiment, the predetermined amount of the second catalyst is 15% with respect to total weight of the first reaction mixture.
In accordance with the present disclosure, the fourth predetermined stirring speed is in the range of 100 to 250 rpm; the fourth predetermined temperature is in the range of 50 to 70 °C; and the fourth predetermined time period is in the range of 5 to 15 minutes. In an exemplary embodiment, the fourth predetermined stirring speed is 150-200 rpm; the fourth predetermined temperature is 55 °C; the fourth predetermined time period is 10 minutes.
Separately, predetermined amounts of a neutralizer, a biocide and a plurality of additives are added in water to obtain a third mixture. The additives are selected from the group consisting of methacryloxy silane, and an epoxy silane oligomer, wherein at least one of the additives being a third non-ionic surfactant.
In accordance with the present disclosure, the neutralizer is at least one selected from the group consisting of liquid ammonia, sodium hydroxide, potassium hydroxide, and ammonium hydroxide. In an exemplary embodiment, the neutralizer is liquid ammonia.
In accordance with the present disclosure, the predetermined amount of neutralizer is in the range of 0.2 to 0.6% with respect to total weight of the biocidal composition. In an exemplary embodiment, the predetermined amount of neutralizer is 0.5% with respect to the total weight of the biocidal composition.
In accordance with the present disclosure, the biocide is selected from the group consisting of 2,2 dibromo- 3 -nitrilopropionamide (Mergal 530), and disodium octaborate tetrahydrate. In an exemplary embodiment, the biocide is a combination of 2,2 dibromo- 3- nitrilopropionamide and disodium octaborate tetrahydrate.
In accordance with the present disclosure, the predetermined amount of biocide is in the range of 0.1 to 1 % with respect to total weight of the biocidal composition. In an exemplary embodiment, the predetermined amount of biocide is 0.5% with respect to the total weight of the biocidal composition.
Even with the small amount of biocide, the biocidal composition is stable at least for three months.
In accordance with the present disclosure, the predetermined amount of additives is in the range of 0.1 to 5% with respect to total weight of the biocidal composition. In an exemplary
embodiment, the predetermined amount of additives is 1% with respect to the total weight of the biocidal composition.
Then, the third mixture is added to the second reaction mixture followed by cooling to a temperature in the range of 25 to 35 °C to obtain the biocidal composition in the form a homogeneous mixture.
In accordance with the present disclosure, the first catalyst is a mixture of 0.1 to 0.3% of an activator, 0.1 to 0.3% of a chelating agent, 0.01 to 0.05% of a first reducing agent, 0.01 to 0.05% of a first oxidizing agent, 0.005 to 0.01% of a fourth non-ionic surfactant and 0.5 to 2 % of water.
In accordance with an exemplary embodiment of the present disclosure, the activator is iron sulphate.
In accordance with an exemplary embodiment of the present disclosure, the chelating agent is ethylenediaminetetraacetic acid sodium salt.
The second catalyst is a mixture of 0.1 to 0.5% a second reducing agent, 0.5 to 2% of a second oxidizing agent, 0.05 to 0.2% of a fifth non-ionic surfactant, and 8 to 13% of water.
In accordance with the present disclosure, the first oxidizing agent and the second oxidizing agent are same or different and are independently selected from persulphate and peroxide. The persulphate is selected from the group consisting of potassium persulphate, sodium persulphate, and ammonium persulphate. The peroxide is selected from the group consisting of tertiary butyl hydroperoxide, hydrogen peroxide, and benzoyl peroxide. In an exemplary embodiment, the oxidizing agent is tertiary butyl hydroperoxide.
In accordance with the present disclosure, the first reducing agent and the second reducing agent are same or different and are independently selected from sodium formaldehyde sulphoxylate, sodium acetone, sodium meta bisulphite, sodium hydroxymethylsulfinate (Bruggolite), and sodium acetone bisulphite. In an exemplary embodiment, the first reducing agent is a combination of sodium hydroxymethylsulfinate (Bruggolite) and sodium acetone bisulphite. In an exemplary embodiment, the second reducing agent is a combination of sodium hydroxymethylsulfinate (Bruggolite) and sodium acetone bisulphite.
In accordance with the present disclosure, a weight ratio of the first/second oxidizing agent to the first/second reducing agent is in the range of 0.05% to 2%.
Separately, at least one second cationic monomer, a biocide, a third non-ionic surfactant and at least one neutralizer are mixed with water to obtain a mixture. The mixture is then mixed with the second reaction mixture to obtain the biocidal composition.
In accordance with the present disclosure, the first non-ionic surfactant, the second non-ionic surfactant, the third non-ionic surfactant, the fourth non-ionic surfactant, and the fifth non- ionic surfactant are same or different and are independently selected from fatty alcohol ethoxylate having ethylene oxide in the range 20 mol to 40 Mol.
The process of the present disclosure is a redox process rather conventional process. The redox process incorporates less reactive but better performing specialty cationic monomers in the polymer backbone. The combination of cationic monomer and ureido monomer plays a significant role in providing antimicrobial activity along with better adhesion of paint/coating to the substrate. The prepared paints and coatings show above 99 % efficacy to antibacterial and antiviral application and at the same to envelop viruses such as H1N1 and H3N2.
In accordance with another embodiment of the present disclosure, the monomers are fully polymerized.
In yet another aspect, the present disclosure further provides a surface coating composition. The surface coating composition comprises 20 to 25% of a biocidal composition of the present disclosure, 0.05 to 0.15% water softening agent, 0.60 to 1.0% dispersing agent, 0.4 to 0.8% wetting agent, 0.8 to 1.2% open time enhancer, 0.1 to 0.3% defoamer, 0.1 to 0.3% neutralizer, 0.1 to 0.5% cellulose thickner, 8 to 10% pigment, 30 to 35% extender, 0.6 to 1.0% preservatives, 0.2 to 0.6% adhesion promoters, 6 to 10% opaque polymer, 0.5 to 1.5% coalescing agent, and 18 to 22% water. All the percentages are with respect to the total weight of the surface coating composition.
In accordance with the present disclosure, the water softening agent is selected from the group consisting of tetrasodium pyrophosphate and ethylene diamine tetra acetic acid. In an exemplary embodiment, the water softening agent is tetrasodium pyrophosphate.
In accordance with the present disclosure, the dispersing agent is selected from the group consisting of a polyacrylate having a molecular weight in the range of 1000 to 7000 Da. In an exemplary embodiment, the dispersing agent is a poly aery late having a molecular weight <5000 Da (Bondex 532).
In accordance with the present disclosure, the wetting agent is selected from the group consisting of alkyl phenol ethoxylate. In an exemplary embodiment, the wetting agent is nonyl phenol 40 mol ethoxylate (IG Surf 8405).
In accordance with the present disclosure, the open time enhancer is a glycol. In an exemplary embodiment, the open time enhancer is triethylene glycol.
In accordance with the present disclosure, the defoamer is selected from the group consisting of mineral oil, polyether, silica and a mixture thereof. In an exemplary embodiment, the defoamer is a mixture of mineral oil, polyether and silica (San Napco SN 1370).
In accordance with an embodiment of the present disclosure, the neutralizer is 95% aqueous solution of 2-amino-2-methyl-l -propanol (AMP 95).
In accordance with the present disclosure, the thickener is selected from the group consisting of water soluble non-ionic hydroxyethylcellulose and associative polyurethane. In an exemplary embodiment, the thickner is a mixture of water soluble non-ionic hydroxyethylcellulose (Natrosol 250 HBR) and associative polyurethane (Rheolite 99).
In accordance with the present disclosure, the pigment is selected from the group consisting of rutile TiCK
In accordance with the present disclosure, the extender is selected from the group consisting of CaCCh. calcined kaolin, talc powder and a mixture thereof. In an exemplary embodiment, the extender is a mixture of CaCCh. calcined kaolin and talc powder.
In accordance with the present disclosure, the preservative is benzimidazole carbamate. In an exemplary embodiment, the preservative is Acticide EPW 1.
In accordance with the present disclosure, the adhesion promoter is 3-(2,3- epoxypropoxypropyl)methyldiethoxysilane. In an exemplary embodiment, the adhesion promoter is 3-(2,3-epoxypropoxypropyl)methyldiethoxysilane (Wetlink 78).
In an exemplary embodiment, the opaque polymer is Bondex Opex 90 (styrene based).
In accordance with the present disclosure, the coalescing agent is a film former selected from texanol and butylcarbitol. In an exemplary embodiment, the coalescing agent (film former) is texanol.
In the surface coating composition, the biocidal composition acts as a binder.
The viscosity of the surface coating composition of the present disclosure is in the range of 25 to 35 poise. In an exemplary embodiment, the viscosity of the surface coating composition is 28.4 poise.
In yet another aspect, the present disclosure provides a method for treating a surface for biocidal activity.
Initially a surface is cleaned.
In accordance with the present disclosure, the surface is selected from the group consisting of internal wall surface, internal ceiling surface, external wall surface, and external roof surface. In an exemplary embodiment, the surface is internal wall surface.
A primer coat is applied on the surface and the primer is allowed to dry to obtain a primer coated surface.
A coat having a uniform thickness in the range of 200 microns to 500 microns is applied on the primer coated surface to obtain a coated surface.
In accordance with the present disclosure, the coat is carried out by using at least one composition selected from the biocidal composition of the present disclosure, the biocidal coat of the present disclosure, and the surface coating composition of the present disclosure.
In accordance with the present disclosure, the coat is applied by using at least one appliance selected from a brush and a roller.
The coated surface is cured for a time period in the range of 2 hours to 6 hours to obtain the treated surface.
In accordance with an embodiment of the present disclosure, the coated surface is cured for a time period in the range of 2 hours to 3 hours.
In accordance with the present disclosure, the treated surface has a dry film thickness in the range of 100 microns to 250 microns. In an embodiment of the present disclosure, the treated surface has a dry film thickness in the range of 100 microns to 150 microns.
The composition of the present disclosure is suitable for application in paints, textiles and paper coating. The cationic monomers of the composition of the present disclosure, which are added in minimal quantities, have the functionality which can contribute to anti-microbial performance. They are covalently attached to the polymer in order to have long term effect as long as the paint or coating remains on the substrate. The prepared biocidal composition is very stable when formulated with paint or coatings, which is crucial to achieve. The biocidal composition when mixed with paint/coating, shows antibacterial and antiviral activity. The extended efficacy is observed when exposed to envelop viruses such as H1N1 and H3N2.
The foregoing description of the embodiments has been provided for purposes of illustration and not intended to limit the scope of the present disclosure. Individual components of a particular embodiment are generally not limited to that particular embodiment, but, are interchangeable. Such variations are not to be regarded as a departure from the present disclosure, and all such modifications are considered to be within the scope of the present disclosure.
The present disclosure is further illustrated herein below with the help of the following experiments. The experiments used herein are intended merely to facilitate an understanding of the ways in which the embodiments herein may be practiced and to further enable those of skill in the art to practice the embodiments herein. Accordingly, the experiments should not be construed as limiting the scope of embodiments herein. These laboratory scale experiments can be scaled up to industrial/commercial scale and the results obtained can be extrapolated to industrial/commercial scale.
EXPERIMENTAL DETAILS:
Experiment 1: Process for preparing a long lasting biocidal composition in accordance with the present disclosure
Preparation of a pre-emulsion slurry
Water was added in a monomer mix tank (a first reactor). Then, an alkyl acrylate monomer, an alkyl methacrylate monomer, a first cationic monomer, a first non-ionic surfactant, a styrene monomer, an ureido monomer, and a cross-linking monomer were added in water under stirring at a speed of 140 rpm, at 30 °C for 10 minutes to obtain a pre-emulsion slurry. The amounts and different combinations of the various monomers in water are provided in table 1.
Preparation of a first mixure (aqueous phase mixture):
Separately, a demineralized water was added in a second reactor. A non-ionic surfactant (fatty alcohol ethoxylate) was added to water under stirring at a stirring speed of 150 rpm at 35 °C for 20 minute to obtain a first mixture. Table 2 illustrates various combinations of fatty alcohol ethoxylate with demineralized water.
Preparation of a first reaction mixture:
The pre-emulsion slurry was added to the first mixture in a ratio of 2.6 to obtain a second mixture. 1.8 % of first catalyst (with respect to the total weight of second mixture) was added to the second mixture followed by reacting at 55 °C for 10 min under stirring at a stirring speed of 180 rpm (with respect to the weight of pre-emulsion slurry) to obtain a first reaction mixture. 5 wt% of seed polymer was added with respect to the total weight of the pre- emulsion slurry to initiate the reaction.
Table 3 illustrates a composition of the first catalyst.
Preparation of a second reaction mixture:
15% of second catalyst (with respect to the weight of the first reaction mixture) was added to the first reaction mixture followed by reacting at 55 °C for 3 hours under stirring at a speed of 180 rpm to obtain a second reaction mixture. The second catalyst, also refers to a delayed catalyst that is added slowly over the time period of 3 to 4 hr in the reactor.
Table 4 discloses a composition of the second catalyst.
Preparation affinal composition:
A neutralizer (liquid ammonia), a biocide (Mergal 530 and disodium octaborate tetrahydrate), and an additive (epoxy silane oligomer and third non-ionic surfactant i.e. fatty alcohol ethoxylate) were added in water to obtain a third mixture. The third mixture was then mixed to the second reaction mixture followed by cooling to a temperature in the range of 25 to 35 °C to obtain the biocidal composition in the form a homogeneous mixture.
Table 5 represents the composition which is added after the polymerization reaction is finished.
The total weight in each of the trial T1-T14 was 1000 g.
Experiment 2: Characterization of the biocidal composition of the present disclosure
Example 1: Determination of pH and specific gravity
The pH of the biocidal compositions of T1-T12 (styrene based) were in the range of 7-9.
The specific gravity of the biocidal compositions (T1-T12) were in the range of 1.02 to 1.09, as measured using ASTM 1475 (see table 6).
Example 2: Determination of solid content of the biocidal composition
The amount of solid content of the biocidal composition (T1-T12) was 45 to 46%, as determined ASTM D 2369 (see table 6).
Example 3: Determination of viscosity of the biocidal composition
The viscosity of the biocidal compositions (T1-T12) was measured using Brookfield RVT Spindle 2, speed 20 at 30 °C, was in the range of 1-2 poise (see table 6).
Example 4: Determination of minimum film forming temperature (MFFT) of the biocidal composition
A standard test method ASTM D2354 was followed for determining MFFT of the biocidal composition. The MFFT of the biocidal composition was found to be 18-20 °C (T1-T12). Below 18-20 °C, the biocidal composition did not form a continuous film and it cracks.
Table 1: Different combinations of the various monomers in water for the preparation of preemulsion slurry
Table 2: illustration of various combinations of non-ionic surfactants with water to prepare the first mixture
Table 3: A composition of the first catalyst
Example 5: Determination of particle size
The particle sizes of the solid particles were found to be in the range of 200 nm to 250 nm (T1-T12).
Experiment 3: Preparation of a surface coating composition
The biocidal composition was prepared as per experiment 1(T1-T12).
The surface coating composition was prepared by mixing 22 wt% of biocidal composition, 0.1 wt% of tetrasodium pyrophosphate (water softening agent), 0.8 wt% of Bondex 532 (dispersing agent), 0.6 wt% of IG Surf 8405 (wetting agent), 1.0 wt% of triethylene glycol (open time enhancer), 0.2 wt% of San Napco SN 1370 (defoamer), 0.2 wt% of AMP 95 (neutralizer), 0.3 wt% of Natrosol 250 HBR (thickner/cellulose thickner), 9% of Rutile TiCL R 902 (pigment), 17 wt% CaCCh, 12 wt% calcined kaolin, and 4 wt% talk powder 2 p (extenders), 0.20 wt% preventol (In can preservative), 0.6 wt% Acticide EPW 1 (dry film preservative), 0.40 wt% Wetlink 78 (adhesion propmoter), 8 wt% of Bondex Opex 90 (opaque polymer), 1 wt% of texanol (coalescing agent), 0.2 wt% of Rheol 99 (PU thickner) and 22.4% water (see table 7).
The viscosity of the surface coating composition was found to be 28.4 poise as measured using Brookfield viscometer with spindle 2 at 20 rpm and 30 °C.
Experiment 4: Virus killing activity of the surface coating composition of the present application
The virus killing activity of the surface coating composition was commercially performed at Centre for Cellular and Molecular Biology Laboratory, Hyderabad, India.
Example 1
The surface coating composition having 22 wt% of biocidal compositions which is styrene based (as shown in table 7), was evaluated for the efficacy to kill
corona virus (SARS_CoV2) when inoculated at a concentration of 1 x 107 viral particles per ml.
Table 7: Surface coating composition of the present disclosure (white paint @ 22% Bondex AMCAS 46-2)
The viral assay was performed using (i) viral RNA extraction method using MagMAX™ Viral/Pathogen Extraction Kit from Applied Biosystems (Thermo Fisher), and (ii) qRT-PCR using Q-line Molecular nCOV-19 RT-PCR Detection Kit (Multiplex) manufactured by POCT Services Private Limited. The assays were performed at 5 minute intervals. The experiments were performed in duplicates and the values were averaged to calculate % viral reduction.
The regression equation for viral particles vs Ct value of the N-gene specific to SARS-CoV2 virus was: y=-3.5442x + 40.786 (1) wherein x=number of viral particles, and y=Ct value, and regression co-efficient obtained was R =0.99.
The number of viral particles (x) were calculated using the following equation: — (40.786-CtRdrp.gene at different time points)/3-5442 (2)
The percentage of viral reduction was calculated using the following equation:
% viral reduction=((number of viral particles in infection control-number of viral particles exposed to surface (test))/(number of viral particles in infection control))* 100 (3)
The surface coating composition of the present disclosure showed -99% viral reduction from 25 minutes onward. The viral particles number reduced from IxlO6'9 to IxlO4'3 (See figure 1).
Example 2
Similarly, another surface coating composition having 22 wt% of biocidal compositions (prepared using T13 or T14), which are pure acrylic based (Bondex AMCA 46-2) was evaluated for the efficacy to kill corona virus
(SARS_CoV2) when inoculated at a concentration of 1 x 107 viral particles per ml.
The viral assay was performed using (i) viral RNA extraction method using MagMAX™ Viral/Pathogen Extraction Kit from Applied Biosystems (Thermo Fisher), and (ii) qRT-PCR using Meril Covid-19 one-step RT-PCR Kit from Meril Diagnostics Pvt. Ltd.
The regression equation for viral particles vs Ct value of the N-gene specific to SARS-CoV2 virus was: y=-3.8424x + 40.364 (4) wherein x=number of viral particles, and y=Ct value, and regression co-efficient obtained was R2=0.999.
The number of viral particles (x) were calculated using the following equation: x=(40.364-CtN -gene at different time points)/3.8424 (5)
The percentage of viral reduction was calculated using equation (3).
The surface coating composition of the present disclosure showed -94% viral reduction from 45 minutes onward. The viral particles number reduced from IxlO5'7 to IxlO4'4 (see figure 2). It was found that the surface coating composition prepared using biocidal composition of T1-T12 (styrene based) showed higher efficiency that those prepared using biocidal composition of T13-T14 (pure acrylic based).
Clinically, on the wall surface, the surface coating composition showed remarkable result in killing the virus on contact due to the cationic nature of the surface developed due to biocidal composition.
The proposition of killing virus was based on electrostatic force generated by the biocidal composition to the paint which attracts the negative charge virus and
thus activated the same due to puncture of cell membrane, and deactived the protein layer.
TECHNICAL ADVANCEMENTS AND ECONOMICAL SIGNIFICANCE
The present disclosure described herein above has several technical advantages including, but not limited to, the realization of, a biocidal composition that:
• is able to kill virus selected from H1N1 and H3N2 upto 99%;
• have a long term effect with respect to anti-microbial effect upto 24 months and more
• is suitable for application in paints, textile and paper coating; and
• is very stable when formulated with a surface coating composition; the process of preparing the biocidal composition:
• incorporates less reactive with better performing speciality monomers;
• is simple and economical; and
• is environment friendly; the surface coating composition:
• is having an antiviral activity upto 24 months or more.
The embodiments herein and the various features and advantageous details thereof are explained with reference to the non-limiting embodiments in the following description. Descriptions of well-known components and processing techniques are omitted so as to not unnecessarily obscure the embodiments herein. The examples used herein are intended merely to facilitate an understanding of ways in which the embodiments herein may be practiced and to further enable those of skill in the art to practice the embodiments herein. Accordingly, the examples should not be construed as limiting the scope of the embodiments herein.
The foregoing description of the specific embodiments so fully reveal the general nature of the embodiments herein that others can, by applying current knowledge, readily modify and/or adapt for various applications such specific embodiments without departing from the generic concept, and, therefore, such adaptations and modifications should and are intended to be comprehended within the meaning and range of equivalents of the disclosed embodiments. It is to be understood that the phraseology or terminology employed herein is for the purpose of description and not of limitation. Therefore, while the embodiments herein have been described in terms of preferred embodiments, those skilled in the art will recognize that the embodiments herein can be practiced with modification within the spirit and scope of the embodiments as described herein.
The use of the expression “at least” or “at least one” suggests the use of one or more elements or ingredients or quantities, as the use may be in the embodiment of the disclosure to achieve one or more of the desired objects or results.
Any discussion of documents, acts, materials, devices, articles or the like that has been included in this specification is solely for the purpose of providing a context for the disclosure. It is not to be taken as an admission that any or all of these matters form a part of the prior art base or were common general knowledge in the field relevant to the disclosure as it existed anywhere before the priority date of this application.
The numerical values mentioned for the various physical parameters, dimensions or quantities are only approximations and it is envisaged that the values higher/lower than the numerical values assigned to the parameters, dimensions or quantities fall within the scope of the disclosure, unless there is a statement in the specification specific to the contrary.
While considerable emphasis has been placed herein on the components and component parts of the preferred embodiments, it will be appreciated that many embodiments can be made and that many changes can be made in the preferred embodiments without departing from the principles of the disclosure. These and
other changes in the preferred embodiment as well as other embodiments of the disclosure will be apparent to those skilled in the art from the disclosure herein, whereby it is to be distinctly understood that the foregoing descriptive matter is to be interpreted merely as illustrative of the disclosure and not as a limitation.
One of the objects of the Patent Law is to provide protection to new technologies in all fields and domain of technologies. The new technologies shall or may contribute in the country economy growth by way of involvement of new efficient and quality method or product manufacturing in India.
To provide the protection of new technologies by patenting the product or process will contribute significant for innovation development in the country. Further by granting patent the patentee can contribute in manufacturing the new product or new process of manufacturing by himself or by technology collaboration or through the licensing.
The applicant submits that the present disclosure will contribute in country economy, which is one of the purposes to enact the Patents Act, 1970. The product in accordance with present invention will be in great demand in country and worldwide due to novel technical features of a present invention is a technical advancement in the surface coating technology. The technology in accordance with present disclosure will provide product cheaper, saving in time of total process of manufacturing. The saving in production time will improve the productivity, and cost cutting of the product, which will directly contribute to economy of the country.
The product will contribute new concept in the surface coating compositions wherein patented process/product will be used. The present disclosure will replace the whole concept of surface coating being used in this area from decades. The product is developed in the national interest and will contribute to country economy. The economy significance details requirement may be called during the examination. Only after filing of this Patent application, the applicant can work
publically related to present disclosure product/process/method. The applicant will disclose all the details related to the economic significance contribution after the protection of invention.
Claims
CLAIMS:
1) A biocidal composition comprising a homogeneous mixture of: a. a polymer backbone comprising: i. 1 to 5% of at least one cationic monomer; ii. 10 to 30% of at least one alkyl acrylate monomer; iii. 1 to 3% of at least one alkyl methacrylate monomer; iv. 10 to 25% of at least one styrene monomer; v. 0.1 to 1 % of at least one ureido monomer; vi. 1 to 5% of at least one cross-linking monomer; b. 0.1 to 5% of a plurality of additives; wherein said additives are selected from the group consisting of methacryloxy silane, an epoxy silane oligomer, and a non-ionic surfactant; and at least one of the additives being said non-ionic surfactant; c. 0.1 to 1% of a biocide; d. 0.2 to 0.6% of a neutralizer; and e. 40 to 55% of water; wherein all the percentages are with respect to the total weight of the biocidal composition.
2) A biocidal coat comprising the biocidal composition as claimed in claim 1 and a paint; wherein a ratio of said biocidal composition to said paint is in the range of 1:2 to 1:4.
3) A biocidal composition as claimed in claim 1 comprising a homogeneous mixture of: a. a polymer backbone comprising: i. 3 to 4% of at least one cationic monomer; ii. 15 to 25% of at least one alkyl acrylate monomer; iii. 1.5 to 2.5% of at least one alkyl methacrylate monomer; iv. 13 to 23% of at least one styrene monomer; v. 0.2 to 0.7% of at least one ureido monomer; and vi. 2 to 3% of at least one cross-linking monomer; b. 1 to 3% of a plurality of additives; wherein said additives are selected from the group consisting of methacryloxy silane, an epoxy silane oligomer, and a non-
36 ionic surfactant; and at least one of the additives being said non-ionic surfactant; c. 0.2 to 0.8% of a biocide; d. 0.2 to 0.6% of a neutralizer; and e. 40 to 55% of water; wherein all the percentages are with respect to the total weight of the biocidal composition. ) The composition as claimed in claim 1 , wherein said composition is characterized by having o solids in an amount in the range of 40 to 60 wt.%, wherein a particle size of said solids is in the range of 200 nm to 250 nm. o a pH in the range of 7 to 9; o a viscosity in the range of 0.1 poise to 3.0 poise at 30°C; and o a minimum film forming temperature is in the range of 16 °C to 22 °C.) The composition as claimed in claim 1, wherein said composition is cationic. ) The composition as claimed in claim 1, said composition is in the form of an emulsion. ) The composition as claimed in claim 1, wherein said cationic monomer is selected from the group consisting of diallyl dimethyl ammonium chloride, methacryloxy ethyl trimethyl ammonium chloride, acryloxy ethyl trimethyl ammonium chloride, vinyltrimethoxy silane, gamma-methacryloxypropyltrimethoxy silane, and dimethyl aminoethyl acrylate. ) The composition as claimed in claim 1, wherein said alkyl acrylate monomer is selected from the group consisting of butyl acrylate, ethyl acrylate, 2-ethyl hexyl acrylate, and n-butyl methacrylate. ) The composition as claimed in claim 1, wherein said alkyl methacrylate monomer is selected from the group consisting of methyl methacrylate, ethyl methacrylate, and butyl methyl acrylate. 0) The composition as claimed in claim 1, wherein said non-ionic surfactant is fatty alcohol ethoxylate having an ethylene oxide mol in the range of 20 to 40 mol; wherein
said neutralizer is a base selected from the group consisting of liquid ammonia, sodium hydroxide, potassium hydroxide, and ammonium hydroxide. 1) The composition as claimed in claim 1, wherein said biocide is selected from the group consisting of 2, 2 dibromo-3-nitrilopropionamide and disodium octaborate tetrahydrate; wherein said ureido monomer is N-(2-Methacryloyloxyethyl)-ethylene urea. 2) A process for preparing a biocidal composition, said process comprising the following steps: a. mixing, in a first reactor, predetermined amounts of at least one alkyl acrylate monomer, at least one alkyl methacrylate monomer, at least one cationic monomer, at least one first non-ionic surfactant, at least one styrene monomer, at least one ureido monomer, and at least one cross-linking monomer in water under stirring at a first predetermined stirring speed, at a first predetermined temperature for a first predetermined time period to obtain a pre-emulsion slurry; b. separately, mixing, in a second reactor, predetermined amounts of at least one second non-ionic surfactant and water under stirring at a second predetermined stirring speed, at a second predetermined temperature for a second predetermined time period to obtain a first mixture; c. adding said pre-emulsion slurry to said first mixture in said second reactor in a first predetermined ratio to obtain a second mixture; d. adding a predetermined amount of a first catalyst to said second mixture followed by reacting at a third predetermined temperature for a third predetermined time period under stirring at a third predetermined stirring speed in said second reactor to obtain a first reaction mixture; e. adding a predetermined amount of a second catalyst to said first reaction mixture followed by reacting at a fourth predetermined temperature for a fourth predetermined time period under stirring at a fourth predetermined stirring speed to obtain a second reaction mixture; f. separately, adding predetermined amounts of a neutralizer, a biocide and a plurality of additives in water to obtain a third mixture; wherein said additives are selected
from the group consisting of methacryloxy silane, an epoxy silane oligomer, and a third non-ionic surfactant; wherein at least one of the additives being said third nonionic surfactant; and g. mixing said third mixture to said second reaction mixture followed by cooling to a temperature in the range of 25 to 35 °C to obtain the biocidal composition in the form a homogeneous mixture. ) The process as claimed in claim 12, wherein said predetermined amount of the alkyl acrylate monomer is in the range of 10 to 30%; said predetermined amount of the alkyl methacrylate monomer is in the range of 1 to 3%, said at least one cationic monomer is in the range of 1 to 5%; said first non-ionic surfactant is in the range of 0.1 to 0.5%, said styrene monomer is in the range of 10 to 25%, said ureido monomer is in the range of 0.1 to 1%, and said cross-linking monomer is in the range of 1 to 5% with respect to total weight of the biocidal composition. ) The process as claimed in claim 12, wherein said first predetermined stirring speed is in the range of 100 rpm to 250 rpm; said first predetermined temperature is in the range of 25 °C to 35 °C; and said first predetermined time period is in the range of 5 to 15 minutes.) The process as claimed in claim 12, wherein said alkyl acrylate monomer is selected from the group consisting of butyl acrylate, ethyl acrylate and 2-ethyl hexyl acrylate; said alkyl methacrylate monomer is selected from the group consisting of methyl methacrylate, ethyl methacrylate, and butyl methyl acrylate. ) The process a claimed in claim 12, wherein said cationic monomer is selected from the group consisting of diallyl dimethyl ammonium chloride, methacryloxy ethyl trimethyl ammonium chloride, acryloxy ethyl trimethyl ammonium chloride, vinyltrimethoxy silane, gamma-methacryloxypropyltrimethoxy silane, and dimethyl aminoethyl acrylate.) The process as claimed in claim 12, said ureido monomer is N-(2-Methacryloyloxyethyl)- ethylene urea; and said cross-linking monomer is selected from the group consisting of ethylene glycol dimethacrylate, and N-methylol acrylamide. ) The process as claimed in claim 12, wherein said predetermined amount of second non- ionic surfactant is in the range of 1 to 5% with respect to the total weight of the first mixture.
39 ) The process as claimed in claim 12, wherein said second predetermined stirring speed is in the range of 100 rpm to 250 rpm; said second predetermined temperature is in the range of 25 to 40 °C; and said second predetermined time period is in the range of 10 to 25 minutes. ) The process as claimed in claim 12, wherein said predetermined ratio is in the range of 1 to 4; and said predetermined amount of the first catalyst is in the range of 0.5 to 5% with respect to the total weight of the second mixture. ) The process as claimed in claim 12, wherein said third predetermined stirring speed is in the range of 100 to 300 rpm, said third predetermined temperature is in the range of 50 °C to 70 °C, and said third predetermined time period is in the range of 5 to 15 minutes.) The process as claimed in claim 12, wherein said predetermined amount of second catalyst is in the range of 8 to 18% with respect to the weight of the first reaction mixture; wherein said fourth predetermined stirring speed is in the range of 100 to 250 rpm; said fourth predetermined temperature is in the range of 50 to 70 °C; and said fourth predetermined time period is in the range of 2 hours to 5 hours. ) The process as claimed in claim 12, wherein said predetermined amount of neutralizer is in the range of 0.2 to 0.6%, said predetermined amount of additives are in the range of 0.1 to 5%, and said predetermined amount of biocide is in the range of 0.1 to 1% with respect to total weight of the biocidal composition. ) The process as claimed in claim 12, wherein said neutralizer is a base selected from the group consisting of liquid ammonia, sodium hydroxide, potassium hydroxide, and ammonium hydroxide; and wherein said biocide is selected from the group consisting of 2,2-dibromo-3,3-nitrilopropionamide, and disodium octaborate tetrahydrate. ) The process as claimed in claim 12, wherein said first catalyst is a mixture of 0.1 to 0.3% of an activator, 0.1 to 0.3% of a chelating agent, 0.01 to 0.05% of a first reducing agent, 0.01 to 0.05% of a first oxidizing agent, 0.005 to 0.01% of a fourth non-ionic surfactant and 0.5 to 2 % of water; wherein said activator is iron sulphate, and said chelating agent is ethylene diamine tetraacetic acid sodium salt.
40 ) The process as claimed in claim 12, wherein said second catalyst is a mixture of 0.1 to 0.5% a second reducing agent, 0.5 to 2% of a second oxidizing agent, 0.05 to 0.2% of a fifth non-ionic surfactant, and 8 to 13% of water. ) The process as claimed in claims 12, 25 and 26, wherein said first oxidizing agent and said second oxidizing agent are same or different and are independently selected from the group consisting of persulphate and peroxide; wherein said persulphate is selected from the group consisting of potassium persulphate, sodium persulphate, and ammonium persulphate; and said peroxide is selected from the group consisting of tertiary butyl hydroperoxide, hydrogen peroxide, and benzoyl peroxide. ) The process as claimed in claims 12, 25 and 26, wherein said first reducing agent and said second reducing agent are same or different and are independently selected from sodium formaldehyde sulphoxylate, Bruggalite, sodium acetone, sodium meta bisulphite, sodium hydroxymethylsulfinate, and sodium acetone bisulphite; and wherein a weight ratio of said first/second oxidizing agent to said first/second reducing agent is in the range of 0.05 to 2%. ) The process as claimed in claims 12, 25 and 26, wherein said first non-ionic surfactant, said second non-ionic surfactant, said third non-ionic surfactant, said fourth non-ionic surfactant, and said fifth non-ionic surfactant are same or different and are independently selected from fatty alcohol ethoxylate having ethylene oxide in the range of 20 to 40 mol.) A surface coating composition comprising: a) 20 to 25 % of the biocidal composition as claimed in claim 1 ; b) 0.05 to 0.15% water softening agent; c) 0.60 to 1.0% dispersing agent; d) 0.4 to 0.8% wetting agent; e) 0.8 to 1.2% open time enhancer; f) 0.1 to 0.3% defoamer; g) 0.1 to 0.3% neutralizer; h) 0.1 to 0.5% thickner; i) 8 to 10% pigment; j) 30 to 35% extender; k) 0.6 to 1.0% preservatives;
41 l) 0.2 to 0.6% adhesion promoter; m) 6 to 10% opaque polymer; n) 0.5 to 1.5% coalescing agent; and n) 18 to 22% water; wherein all the percentages are with respect to the total weight of the surface coating composition. ) The surface coating composition as claimed in claim 30, wherein said water softening agent is selected from the group consisting of tetrasodium pyrophosphate and ethylene diamine tetra acetic acid sodium salt; said dispersing agent is selected from the group consisting of a polyacrylate having a molecular weight in the range of 1000 to 7000 Da; said wetting agent is alkyl phenol ethoxylate; said open time enhancer is a glycol; said defoamer is selected from the group consisting of mineral oil, polyether, silica, and a mixture thereof; said neutralizer is 95% aqueous solution of 2-amino-2-methyl-l- propanol; said thickner is selected from the group consisting of water soluble non-ionic hydroxyethylcellulose and associative polyurethane; said pigment is rutile TiCh; said extender is selected from the group consisting of CaCCh. calcined kaolin, talc powder and a mixture thereof; said preservative is benzimidazole carbamate; said adhesion promoter is 3-(2,3-epoxypropoxypropyl) methyldiethoxy silane; and said coalescing agent is a film former selected from texanol and butylcarbitol. ) A method for treating a surface for biocidal activity, said method comprises the following steps:
(i) cleaning the surface;
(ii) applying a primer coat on the surface and allowing the primer to dry to obtain a primer coated surface;
(iii) applying a coat having a uniform thickness in the range of 200 microns to 500 microns on said primer coated surface to obtain a coated surface; and
(iv) curing said coated surface for a time period in the range of 2 hours to 6 hours to obtain said treated surface; wherein said surface is selected from the group consisting of an internal wall surface, an internal ceiling surface, an external wall surface, and an external roof surface.
42 ) The method as claimed in claim 32, wherein said coat is applied by using at least one appliance selected from a brush and a roller. ) The method as claimed in claim 32, wherein said coat in step (iii) is carried out by using at least one composition selected from o said biocidal composition as claimed in claim 1 ; o said biocidal coat as claimed in claim 2; and o said surface coating composition as claimed in claim 30. ) The method as claimed in claim 32, wherein said treated surface has a dry film thickness in the range of 100 microns to 250 microns.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IN202121035663 | 2021-08-06 | ||
| IN202121035663 | 2021-08-06 |
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| Publication Number | Publication Date |
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| WO2023012765A1 true WO2023012765A1 (en) | 2023-02-09 |
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| PCT/IB2022/057365 Ceased WO2023012765A1 (en) | 2021-08-06 | 2022-08-08 | A biocidal composition and a process for its preparation |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011150001A2 (en) * | 2010-05-25 | 2011-12-01 | 3M Innovative Properties Company | Antimicrobial coatings |
| EP2778195A1 (en) * | 2013-03-15 | 2014-09-17 | Rohm and Haas Company | Redox polymers for improved dirt and water resistance for elastomeric wall and roof coatings |
| WO2020187606A1 (en) * | 2019-03-19 | 2020-09-24 | Rhodia Operations | Synergistic biocidal compositions and methods for using same |
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2022
- 2022-08-08 WO PCT/IB2022/057365 patent/WO2023012765A1/en not_active Ceased
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011150001A2 (en) * | 2010-05-25 | 2011-12-01 | 3M Innovative Properties Company | Antimicrobial coatings |
| EP2778195A1 (en) * | 2013-03-15 | 2014-09-17 | Rohm and Haas Company | Redox polymers for improved dirt and water resistance for elastomeric wall and roof coatings |
| WO2020187606A1 (en) * | 2019-03-19 | 2020-09-24 | Rhodia Operations | Synergistic biocidal compositions and methods for using same |
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