CN105419530A - Graphene nano-silver antibacterial coating and preparation method thereof - Google Patents
Graphene nano-silver antibacterial coating and preparation method thereof Download PDFInfo
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- CN105419530A CN105419530A CN201610021032.9A CN201610021032A CN105419530A CN 105419530 A CN105419530 A CN 105419530A CN 201610021032 A CN201610021032 A CN 201610021032A CN 105419530 A CN105419530 A CN 105419530A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
- C09D125/02—Homopolymers or copolymers of hydrocarbons
- C09D125/04—Homopolymers or copolymers of styrene
- C09D125/08—Copolymers of styrene
- C09D125/14—Copolymers of styrene with unsaturated esters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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Abstract
The invention belongs to the field of chemical coatings, and particularly relates to a graphene nano-silver antibacterial coating and a preparation method thereof. The graphene nano-silver antibacterial coating comprises water, cellulose, a wetting agent, an antifreezing agent, a thickening agent, a defoaming agent, titanium dioxide slurry, filler slurry, a multifunctional amine auxiliary, emulsion, a sterilizing agent, a coalescing agent, a flatting agent, a formaldehyde-resistant auxiliary, and a silver-bearing antibacterial agent, and the silver-bearing antibacterial agent is graphene nano-silver dispersion liquid. According to the graphene nano-silver antibacterial coating and the preparation method thereof, a traditional formula is improved, the specially-made graphene nano-silver dispersion liquid is added to the formula, and the antibacterial effect is achieved. Nano silver can further destroy a microorganism electron transmission system, a respiratory system and a material transfer system. When the activity of thalli is lost, the nano silver can be dissociated out of the thalli and repeatedly conducts sterilization activities, and therefore the long-acting antibacterial function of the coating can be maintained. The nano silver can exert the lasting antibacterial effect by slowly releasing Ag<+>.
Description
Technical field
The invention belongs to chemistry painting industry field, particularly relate to a kind of graphene nano silver antibiotic paint and preparation method thereof.
Background technology
Silver can be traced back to B.C. in antibacterial applications, and people at that time just know that silver can accelerate wound healing, control is infected, purified water and preservation and antisepsis, can prevent bacterial growth, food and extend shelf lives with silverware storing food.The Ming Dynasty of China physician LI Shi-Zhen describes in Compendium of Material Medica: silver bits have five viscera settling, centering god, only palpitation with fear, except effects such as perverse trends, clothes can be made light of one's life by commiting suicide and be prolonged life for a long time, and raw silver-colored taste is pungent cold, nontoxic.Also more than 100 years were had with the record of silver-colored diagnosis and treatment diseases related in doctor trained in Western medicine.
Silver element has so-called oligodynamic effect, only needs the silver ions of minute quantity, just can kill contact with it bacterium, mould, the microorganism such as spore and fungi.The ion of various metals all has anti-microbial effect, and their antibacterial ability size order is:
Ag>Hg>Cu>Cd>Cr>Ni>Pd>Co>Zn>Fe，
The security sequence of conventional metallic element to human body is:
Ag>Co>Ni>Al>Zn>Cu＝Fe>Mn>Sn>Ba>Mg>Ca，
Because the size of Argent grain diminishes, the atomic quantity of particle surface significantly increases, and even more than the atomic quantity of granule interior, thus shows a series of excellent properties being different from block silver, is widely applied in sides such as electrocondution slurry, sterilization, catalysis.Modern study shows, the Graphene with two-dimentional laminated structure has certain anti-microbial effect equally.
Summary of the invention
The present invention is directed to the technical problems such as existing antibiotic paint discomposing effect is bad, decomposition efficiency is low, propose to fill a prescription rationally, technique is simple, discomposing effect good and the graphene nano that decomposition efficiency is high silver antibiotic paint and preparation method thereof.
In order to achieve the above object, the present invention adopts following scheme,
A kind of graphene nano silver antibiotic paint, comprises following composition according to parts by weight:
Wherein, described Antibacterial accessory ingredient is graphene nano silver dispersion liquid, and the mass ratio of Graphene and nanometer silver is 1:50 ~ 50:1.
As preferably, described Mierocrystalline cellulose is sodium carboxymethyl-cellulose fibrid element; Described wetting agent is any one in alkyl aryl polyether, glass amber acid di-isooctyl hydrochlorate; Described frostproofer is any one in ethylene glycol, propylene glycol; Described thickening material is at least one in association type alkali swollen thickener or polyurethane thickener; Described defoamer is mineral hydrocarbon polymer defoamer and/or non-ionic type alkyl copolymer defoamer; Described flow agent is polydimethylsiloxane, any one in alkyl-modified organo-siloxane, fluorin modified crylic acid ester.
As preferably, film coalescence aid is TEXANOL ester alcohol, and extender paste is at least one in water-ground limestone slurry, kaolin, ultra-fine calcite in powder, diatomite, barium sulfate, mica powder.
As preferably, described emulsion is any one in AA emulsion, pure third polymkeric substance, benzene emulsion.
Prepare the method for graphene nano silver antibiotic paint, comprise the following steps:
(1) water, Mierocrystalline cellulose, film coalescence aid, defoamer, sterilant, flow agent, Antibacterial accessory ingredient, frostproofer to be added in mixing kettle and be stirred to and mix, obtain mixed solution a;
(2) in mixed solution a, drop into titanium dioxide slurry, high-gravity filler slurry, emulsion successively, and be stirred to and mix, obtain mixed solution b;
(3) slowly in mixed solution b, add thickening material, and be stirred to mix and namely obtain nano-silver antibacterial paint finished product.
As preferably, in described step (1), churning time is 30min, and stir speed (S.S.) is 600 ~ 800 turns/min.
As preferably, in described step (2), churning time is 30min, and stir speed (S.S.) is 400 ~ 600 turns/min.
As preferably, in described step (3), churning time is 30min, and stir speed (S.S.) is 400 ~ 600 turns/min.
Compared with prior art, advantage of the present invention and positively effect are,
The present invention, by improving traditional formula, adds special graphene nano silver dispersion liquid, when the nanometer silver of trace arrives microorganism cells film, slowly releases Ag in formula
+, because cytolemma is electronegative, rely on Coulomb's force, Ag
+the sulfydryl of zymoprotein in bacterial cell membrane or strong absorption bacterial body can be destroyed at very low concentrations, and combine rapidly, reduce the activity of protista organized enzyme, the active cells destroying cell synthetic enzyme loses division growth ability and dead, has anti-microbial effect.Nanometer silver can also destroy microorganisms electric transmission system, respiratory system and substance delivery system.Out repeat fungicidal property when nanometer silver after thalline loses activity can dissociate again from thalline, therefore it can keep long acting antibiotic.Thus by slowly-releasing Ag
+, nanometer silver can play lasting antibacterial effect.On the other hand, due to Graphene two dimension laminated structure, can bacterial cell membrane be penetrated, kill bacterium, reach antibacterial effect.In addition, graphene nano silver antibacterial agent, due to the huge specific surface area of Graphene, can strengthen the contact area of antiseptic-germicide and bacterium, thus improves antibiotic rate, reaches the antibacterial effect of high-efficient and lasting.
Embodiment
In order to more clearly understand above-mentioned purpose of the present invention, feature and advantage, below in conjunction with embodiment, the present invention will be further described.It should be noted that, when not conflicting, the feature in the embodiment of the application and embodiment can combine mutually.
Set forth a lot of detail in the following description so that fully understand the present invention, but the present invention can also adopt and be different from other modes described here and implement, and therefore, the present invention is not limited to the restriction of the specific embodiment of prospectus below.
Embodiment 1, the present embodiment provides graphene nano silver massfraction to be nano-silver antibacterial paint of 1 ‰ and preparation method thereof.Mark comprises following composition by weight: 18 parts, water; Sodium carboxymethyl-cellulose 0.1 part; Alkyl aryl polyether 0.1 part; Propylene glycol 0.5 part; Association type alkali swollen thickener (CHECOATVT-183) 0.2 part; Polyurethane thickener (CHECOATVT-903) 0.2 part; Mineral hydrocarbon polymer defoamer (CHECOATDF6684) 0.1 part; Titanium dioxide slurry 5 parts; Water-ground limestone starches 50 parts; Multifunction amine auxiliary agent (AMP-95) 0.1 part; AA emulsion 10 parts; Film coalescence aid (TEXANOL ester alcohol) 0.2 part; 0.1 part, sterilant (Clariant HF-I); Polydimethylsiloxane 0.1 part; Antibacterial accessory ingredient 0.1 part.
Preparation method is: the water first dropping into 13g in stirred pot, then sodium carboxymethyl-cellulose 0.1g is added successively by stirring, film coalescence aid (TEXANOL ester alcohol) 0.2g, mineral hydrocarbon polymer defoamer (CHECOATDF6684) 0.1g, sterilant (Clariant HF-I) 0.1g, polydimethylsiloxane 0.1g, Antibacterial accessory ingredient 0.1g (mass ratio of Graphene and nanometer silver is 50:1), propylene glycol 0.5g, according to the rotating speed of 600 turns/min, after stirring 30min, obtain the mixed solution mixed.Then be delivered to by mixed solution in larger stirred pot, then in mixed solution, add titanium dioxide slurry 5g successively, water-ground limestone slurry 50g, AA emulsion 10g, according to the rotating speed of 400 turns/min, after stirring 30min, obtain the mixed solution mixed.According to the ratio (thickening material and water) of 1:1, the polyurethane thickener (CHECOATVT-903) of 0.2g is diluted, then slowly add in mixed solution, stir, the rotating speed of stirring is constant, to be mixed evenly after, according to the ratio of 1:2, the polyurethane thickener (CHECOATVT-903) of 0.2g is diluted, then slowly adds in mixed solution, stir, the rotating speed of stirring is constant.After canister before remaining water is rinsed, be delivered to large tank, stir, to be mixed evenly after, namely obtain finished product graphene nano silver antibiotic paint.
Embodiment 2, the present embodiment provides a kind of graphene nano silver dispersion liquid massfraction to be nano-silver antibacterial paint of 3 ‰ and preparation method thereof.Mark comprises following composition by weight: 20 parts, water; Sodium carboxymethyl-cellulose 0.2 part; Glass amber acid di-isooctyl acid hydrochlorate 0.2 part; Ethylene glycol 1 part; Association type alkali swollen thickener (CHECOATVT-183) 0.1 part; Polyurethane thickener (CHECOATVT-903) 0.4 part; Non-ionic type alkyl copolymer defoamer (CHECOATDF9000) 0.1 part; Titanium dioxide slurry 10 parts; 60 parts, diatomite; Multifunction amine auxiliary agent (AMP-95) 0.2 part; Pure 10 parts, third polymkeric substance; Film coalescence aid (TEXANOL ester alcohol) 1 part; 0.2 part, sterilant (Clariant HF-I); Alkyl-modified organo-siloxane 0.2 part; Antibacterial accessory ingredient 0.3 part.
Preparation method is: the water first dropping into 14g in stirred pot, then sodium carboxymethyl-cellulose 0.1g is added successively by stirring, film coalescence aid (TEXANOL ester alcohol) 1g, non-ionic type alkyl copolymer defoamer (CHECOATDF9000) 0.1g, sterilant 0.2g, alkyl-modified organo-siloxane 0.2g, Antibacterial accessory ingredient 0.3g (mass ratio of Graphene and nanometer silver is 1:50), ethylene glycol 1g, according to the rotating speed of 800 turns/min, after stirring 30min, obtain the mixed solution mixed.Then mixed solution is delivered in larger stirred pot, then in mixed solution, adds titanium dioxide slurry 10g successively, diatomite 60g, pure third polymkeric substance 10g, according to the rotating speed of 400 turns/min, after stirring 30min, obtain the mixed solution mixed.According to the ratio (thickening material and water) of 1:1, the polyurethane thickener (CHECOATVT-903) of 0.4g is diluted, then slowly add in mixed solution, stir, the rotating speed of stirring is constant, to be mixed evenly after, according to the ratio of 1:2, the polyurethane thickener (CHECOATVT-903) of 0.1g is diluted, then slowly adds in mixed solution, stir, the rotating speed of stirring is constant.After canister before remaining water is rinsed, be delivered to large tank, stir, to be mixed evenly after, namely obtain finished product graphene nano silver antibiotic paint.
Embodiment 3, the present embodiment provides a kind of graphene nano silver dispersion liquid massfraction to be graphene nano silver antibiotic paint of 5 ‰ and preparation method thereof.Be 15 parts, water according to each material composition of weight fraction; Sodium carboxymethyl-cellulose 0.2 part; Glass amber acid di-isooctyl acid hydrochlorate 0.2 part; Propylene glycol 1 part; Association type alkali swollen thickener (CHECOATVT-183) 0.2 part; Polyurethane thickener (CHECOATVT-903) 0.2 part; Non-ionic type alkyl copolymer defoamer (CHECOATDF9000) and mineral hydrocarbon polymer defoamer (CHECOATDF6684) totally 0.4 part; Titanium dioxide slurry 10 parts; Ultra-fine calcite in powder 55 parts; Multifunction amine auxiliary agent (AMP-95) 0.2 part; Benzene emulsion 10 parts; Film coalescence aid (TEXANOL ester alcohol) 1 part; 0.2 part, sterilant; Fluorin modified crylic acid ester 0.5 part; Antibacterial accessory ingredient 0.5 part.
Preparation method is: the water first dropping into 12g in stirred pot, then sodium carboxymethyl-cellulose 0.2g is added successively by stirring, film coalescence aid (TEXANOL ester alcohol) 1g, non-ionic type alkyl copolymer defoamer (CHECOATDF9000) and mineral hydrocarbon polymer defoamer (CHECOATDF6684) 0.4g altogether, sterilant 0.2g, fluorin modified crylic acid ester 0.5g, Antibacterial accessory ingredient 0.5g (mass ratio of Graphene and nanometer silver is 1:1), propylene glycol 1g, according to the rotating speed of 800 turns/min, after stirring 30min, obtain the mixed solution mixed.Then mixed solution is delivered in larger stirred pot, then in mixed solution, adds titanium dioxide slurry 10g successively, ultra-fine calcite in powder 55g, benzene emulsion 10g, according to the rotating speed of 400 turns/min, after stirring 30min, obtain the mixed solution mixed.According to the ratio (thickening material and water) of 1:1, the polyurethane thickener (CHECOATVT-903) of 0.2g is diluted, then slowly add in mixed solution, stir, the rotating speed of stirring is constant, to be mixed evenly after, according to the ratio of 1:2, the polyurethane thickener (CHECOATVT-903) of 0.2g is diluted, then slowly adds in mixed solution, stir, the rotating speed of stirring is constant.After canister before remaining water is rinsed, be delivered to large tank, stir, to be mixed evenly after, namely obtain finished product graphene nano silver antibiotic paint.
In the performance of the graphene nano silver antibiotic paint provided embodiment 1 ~ 3 and coating, Harmful ingredient content detects, salient features test is with reference to GB/T9756-2009 interior wall coating national standard, the I generic request that purifying formaldehyde rate testing method execution JC/T1074-2008 " function of purifying indoor air coating material purification function " specifies is tested, and germ resistance method performs with reference to GB/T21866-2008 " antibiotic paint (paint film) germ resistance assay method and antibacterial effect ".Detected result is as shown in table one and table two.
The Performance Detection of the graphene nano silver antibiotic paint of preparation in table one embodiment 1 ~ 3
Result
The Harmful ingredient content detected result of the graphene nano silver antibiotic paint that table two embodiment 1 ~ 3 provides
From the detected result of above-mentioned table one and table two, no matter graphene nano silver antibiotic paint provided by the invention all reaches, exceedes national standard on single performance and over-all properties, wherein, the purification efficiency of formaldehyde and washability number of times considerably beyond national standard, purifying formaldehyde Be very effective.
The above; it is only preferred embodiment of the present invention; it is not restriction the present invention being made to other form; the Equivalent embodiments that any those skilled in the art may utilize the technology contents of above-mentioned announcement to be changed or be modified as equivalent variations is applied to other field; but everyly do not depart from technical solution of the present invention content; according to any simple modification, equivalent variations and remodeling that technical spirit of the present invention is done above embodiment, still belong to the protection domain of technical solution of the present invention.
Claims (8)
1. a graphene nano silver antibiotic paint, is characterized in that, comprise following composition according to parts by weight:
Wherein, described Antibacterial accessory ingredient is graphene nano silver dispersion liquid, and the mass ratio of Graphene and nanometer silver is 1:50 ~ 50:1.
2. graphene nano silver antibiotic paint according to claim 1, is characterized in that, described Mierocrystalline cellulose is sodium carboxymethyl-cellulose fibrid element; Described wetting agent is any one in alkyl aryl polyether, glass amber acid di-isooctyl hydrochlorate; Described frostproofer is any one in ethylene glycol, propylene glycol; Described thickening material is at least one in association type alkali swollen thickener or polyurethane thickener; Described defoamer is mineral hydrocarbon polymer defoamer and/or non-ionic type alkyl copolymer defoamer; Described flow agent is polydimethylsiloxane, any one in alkyl-modified organo-siloxane, fluorin modified crylic acid ester.
3. graphene nano silver antibiotic paint according to claim 1, it is characterized in that, described film coalescence aid is TEXANOL ester alcohol, and extender paste is at least one in water-ground limestone slurry, kaolin, ultra-fine calcite in powder, diatomite, barium sulfate, mica powder.
4. graphene nano according to claim 1 silver antibiotic paint, is characterized in that, described emulsion is any one in AA emulsion, pure third polymkeric substance, benzene emulsion.
5. the method for the graphene nano silver antibiotic paint of preparation described in Claims 1 to 4, is characterized in that, comprise the following steps:
(1) water, Mierocrystalline cellulose, film coalescence aid, defoamer, sterilant, flow agent, Antibacterial accessory ingredient, frostproofer to be added in mixing kettle and be stirred to and mix, obtain mixed solution a;
(2) in mixed solution a, drop into titanium dioxide slurry, high-gravity filler slurry, emulsion successively, and be stirred to and mix, obtain mixed solution b;
(3) slowly in mixed solution b, add thickening material, and be stirred to mix and namely obtain nano-silver antibacterial paint finished product.
6. the method preparing graphene nano silver antibiotic paint according to claim 5, it is characterized in that, in described step (1), churning time is 30min, and stir speed (S.S.) is 600 ~ 800 turns/min.
7. the method preparing graphene nano silver antibiotic paint according to claim 5, it is characterized in that, in described step (2), churning time is 30min, and stir speed (S.S.) is 400 ~ 600 turns/min.
8. the method preparing graphene nano silver antibiotic paint according to claim 5, it is characterized in that, in described step (3), churning time is 30min, and stir speed (S.S.) is 400 ~ 600 turns/min.
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| CN106364066A (en) * | 2016-08-29 | 2017-02-01 | 佛山市高明区尚润盈科技有限公司 | Preparation method of deodorizing fiberglass packaging box |
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| CN116716014A (en) * | 2023-06-26 | 2023-09-08 | 江门市皇宙实业有限公司 | Nano-silver graphene composite antibacterial coating material and preparation method thereof |
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