CN113214716A - Anti-ultraviolet bacteriostatic coating and preparation method thereof - Google Patents

Anti-ultraviolet bacteriostatic coating and preparation method thereof Download PDF

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Publication number
CN113214716A
CN113214716A CN202110565168.7A CN202110565168A CN113214716A CN 113214716 A CN113214716 A CN 113214716A CN 202110565168 A CN202110565168 A CN 202110565168A CN 113214716 A CN113214716 A CN 113214716A
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shell
stirring
starch
acrylate
ultraviolet
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林燕娟
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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
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/062—Copolymers with monomers not covered by C09D133/06
    • C09D133/064—Copolymers with monomers not covered by C09D133/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
    • 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
    • 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
    • C09D7/63—Additives non-macromolecular organic
    • 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
    • C09D7/65—Additives macromolecular

Abstract

The invention discloses an anti-ultraviolet bacteriostatic coating and a preparation method thereof, and relates to the field of new materials. The preparation method comprises the steps of firstly carrying out lactic acid copolymerization on methacryloyloxyethyl trimethyl ammonium chloride, methyl methacrylate, butyl acrylate and acrylic acid to obtain acrylate copolymer emulsion, calcining shell powder at high temperature, mixing the shell powder and the acrylate copolymer emulsion by adopting a coprecipitation method to obtain a shell acrylate compound, and then modifying the shell acrylate compound by using a sodium stearate starch compound to obtain a modified shell acrylate compound, namely the uvioresistant antibacterial coating. The anti-ultraviolet bacteriostatic coating prepared by the invention has the effects of sterilization, hydrophilicity, impact resistance and wear resistance.

Description

Anti-ultraviolet bacteriostatic coating and preparation method thereof
Technical Field
The invention relates to the technical field of new materials, in particular to an anti-ultraviolet bacteriostatic coating and a preparation method thereof.
Background
With the enhancement of living conditions, more and more people like going to holidays at sea and enjoy leisure time, the swimsuit worn by people is fully irradiated by ultraviolet rays on the beach, the skin is damaged by continuous strong ultraviolet irradiation, burns, blisters, induced dermatitis and even skin cancer are caused, the swimsuit soaked in seawater for a long time can deform, the swimsuit is easy to be damaged by coral in the sea, and the swimsuit serving as close-fitting clothes can carry various harmful substances in the seawater for a long time, so that the swimsuit enters the human body, allergy, disease infection and the like can be caused, and inconvenience is brought to people. Therefore, it is necessary to design antibacterial, hydrophilic, wear-resistant, and impact-resistant anti-uv bacteriostatic coatings.
Disclosure of Invention
The invention aims to provide an anti-ultraviolet bacteriostatic coating and a preparation method thereof, and aims to solve the problems in the background art.
In order to solve the technical problems, the invention provides the following technical scheme: an anti-ultraviolet bacteriostatic coating and a preparation method thereof, which comprises the following raw materials by weight:
60-90 parts of shell acrylate compound, 30-50 parts of sodium stearate starch compound and 5-10 parts of auxiliary agent.
Preferably, the auxiliary agent is one of an ultraviolet light absorber UV-O and an ultraviolet light absorber UV-P.
Preferably, the sodium stearate starch complex is prepared by mixing and stirring starch after gelatinization with sodium stearate at a certain temperature.
Preferably, the shell acrylate compound is prepared by calcining shell powder at high temperature and then coprecipitating the calcined shell powder and acrylate copolymer emulsion.
Preferably, the acrylate copolymer emulsion is prepared by lactic acid copolymerization of methacryloyloxyethyl trimethyl ammonium chloride, methyl methacrylate, butyl acrylate and acrylic acid.
The invention provides an anti-ultraviolet bacteriostatic coating and a preparation method thereof, which comprises the following specific steps:
(1) preparation of acrylic ester copolymer emulsion: mixing polyvinyl alcohol and deionized water to obtain a dispersion, heating, adding methacryloyloxyethyl trimethyl ammonium chloride, methyl methacrylate, butyl acrylate, acrylic acid and deionized water, continuously heating, stirring, keeping the temperature, reacting, and cooling to room temperature to obtain an acrylate copolymer emulsion;
(2) preparation of shell acrylate complex: washing shells, soaking the shells in a sodium hydroxide solution to remove impurities, washing, drying, crushing, calcining in a muffle furnace, grinding to obtain a shell powder carrier, mixing an acrylate copolymer emulsion and the shell powder carrier, stirring at a constant temperature, and taking out to obtain a shell acrylate compound;
(3) preparation of sodium stearate starch complex: preparing starch into starch suspension, gelatinizing, mixing with a certain amount of sodium stearate at high temperature, and stirring;
(4) preparing the anti-ultraviolet bacteriostatic coating: heating and mixing the shell acrylate compound and the sodium stearate starch compound, adding the auxiliary agent, and uniformly stirring to obtain the anti-ultraviolet bacteriostatic coating.
Preferably, in the step (1): soaking polyvinyl alcohol and deionized water at room temperature for 20-24 h according to the mass ratio of 1: 3-1: 5, heating to 95-100 ℃, stirring and refluxing for 1.5-2 h to completely dissolve polyvinyl alcohol to obtain a polyvinyl alcohol dispersion, adding the polyvinyl alcohol dispersion and the deionized water into a flask according to the mass ratio of 2: 3-2: 5, stirring for 30-40 min, heating to 65-70 ℃, dropwise adding methacryloyloxyethyl trimethyl ammonium chloride, methyl methacrylate, butyl acrylate and acrylic acid according to the mass ratio of 1:2:1: 1-3: 2:3:3, dropwise adding the mixture for about 1.5-2 h, keeping the temperature at 65-70 ℃ after dropwise adding, reacting for 4-5 h, and cooling to room temperature to obtain the acrylic ester copolymer emulsion.
Preferably, in the step (2): cleaning a shell, soaking the shell in a sodium hydroxide solution with the mass fraction of 8% for 1-5 hours, removing impurities on the surface by alkali washing, washing the shell with distilled water with the mass of 8-10 times that of the shell, drying the shell in an air-blast drying oven at 100-110 ℃ for 20-24 hours, then putting the dried shell in a crusher for crushing, sieving, calcining the crushed shell in a muffle furnace at 1000-1100 ℃ for 2-2.5 hours, grinding the crushed shell by a mortar to obtain a shell powder carrier, mixing the shell powder carrier and an acrylate copolymer emulsion according to the mass ratio of 2: 3-4: 3, stirring and reacting at the constant temperature of 90-100 ℃ for 1.5-2 hours, and taking out the mixture to obtain the shell acrylate compound.
Preferably, in the step (3): preparing starch suspension with the mass fraction of 5% in a three-neck flask, firstly dispersing in cold water for 10-15 min, and then placing in a water bath kettle for 200-220 r.min-1Heating at the stirring speed, gelatinizing at 95-100 ℃ for 30-40 min, continuously mixing and stirring the gelatinized starch solution and sodium stearate solution uniformly according to the mass ratio of 1: 2-1: 3, and cooling to room temperature to obtain the sodium stearate-starch compound.
Preferably, in the step (4): heating, mixing and stirring the shell acrylate compound and the sodium stearate starch compound uniformly at 70-80 ℃ according to the mass ratio of 3: 2-7: 2, adding an ultraviolet absorbent UV-O with the mass of 0.05-0.1 time of that of the sodium stearate starch compound, mixing and stirring for 2-3 h, and cooling to room temperature to obtain the anti-ultraviolet bacteriostatic coating.
Compared with the prior art, the invention has the following beneficial effects:
the uvioresistant bacteriostatic coating prepared by the invention is applied to beach swimwear.
Firstly, carrying out lactic acid copolymerization on methacryloyloxyethyl trimethyl ammonium chloride, methyl methacrylate, butyl acrylate and acrylic acid to prepare acrylate copolymer emulsion, calcining shell powder at high temperature, mixing the shell powder and the acrylate copolymer emulsion by adopting a coprecipitation method to obtain a shell acrylate compound, wherein the biocompatibility of the shell powder can enable the acrylate copolymer emulsion to be firmly loaded on the shell powder, and corners of the original cubic structure of the shell powder are smooth, so that the shell powder has good compatibility with a coating and is beneficial to uniform dispersion, the aperture of the shell powder is large, the shell powder has certain adsorption capacity and can adsorb bacteria in the sea and light on the sea surface, when the bacteria enter a system, the acrylate copolymer emulsion in the shell powder and the shell powder are subjected to photocatalysis under the combined action to oxidize internal hydroxyl groups and surface water molecules into hydroxyl radicals with strong oxidizing property, the coating can block and kill bacteria in a system to play a role in sterilization, and ionic groups in the methacryloyloxyethyl trimethyl ammonium chloride are compatible with shell powder and then have strong hydrophilicity, so that the interaction force between the surface of the coating and a water interface is enhanced, the coating can be smoother in seawater when applied to swimwear, and substances such as seaweed and the like are difficult to wind.
Sodium stearate and starch are synthesized and then used for modifying the shell acrylate compound to obtain a modified shell acrylate compound, the sodium stearate can react with calcium ions in the shell acrylate compound to form insoluble salt calcium stearate which is deposited on the surface of the coating, a starch deposition film is formed on the surface of the coating, when the coating is applied to swimwear, the film coating firmness of a starch layer on the surface of the coating can be improved, the hydrogen bond combination between starch molecule hydroxyl in the modified shell acrylate compound and swimwear fiber molecule hydroxyl is enhanced, the physical performance of the swimwear is improved, the impact resistance of the swimwear is enhanced, when the coating is coated with a sodium stearate starch compound, the contact with bacteria can be hindered or weakened, the sterilization effect is not facilitated, but the sodium stearate is a salt containing carboxyl, the carboxyl is easy to dissociate in an aqueous solution, and strong interaction can be generated between the carboxyl and the starch molecule hydroxyl, selectively occupy the growth points on the surface of the coating, and the butyl acrylate component in the shell acrylate compound can cause the two to grow towards different directions and be communicated with each other to form a net structure, thereby increasing the contact surface, enhancing the wear resistance and being beneficial to the sterilization effect of the coating.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides the technical scheme that: an anti-ultraviolet bacteriostatic coating and a preparation method thereof, which comprises the following raw materials by weight:
60-90 parts of shell acrylate compound, 30-50 parts of sodium stearate starch compound and 5-10 parts of auxiliary agent.
Preferably, the auxiliary agent is one of an ultraviolet light absorber UV-O and an ultraviolet light absorber UV-P.
Preferably, the sodium stearate starch complex is prepared by mixing and stirring starch after gelatinization with sodium stearate at a certain temperature.
Preferably, the shell acrylate compound is prepared by calcining shell powder at high temperature and then coprecipitating the calcined shell powder and acrylate copolymer emulsion.
Preferably, the acrylate copolymer emulsion is prepared by lactic acid copolymerization of methacryloyloxyethyl trimethyl ammonium chloride, methyl methacrylate, butyl acrylate and acrylic acid.
The invention provides an anti-ultraviolet bacteriostatic coating and a preparation method thereof, which comprises the following specific steps:
(1) preparation of acrylic ester copolymer emulsion: mixing polyvinyl alcohol and deionized water to obtain a dispersion, heating, adding methacryloyloxyethyl trimethyl ammonium chloride, methyl methacrylate, butyl acrylate, acrylic acid and deionized water, continuously heating, stirring, keeping the temperature, reacting, and cooling to room temperature to obtain an acrylate copolymer emulsion;
(2) preparation of shell acrylate complex: washing shells, soaking the shells in a sodium hydroxide solution to remove impurities, washing, drying, crushing, calcining in a muffle furnace, grinding to obtain a shell powder carrier, mixing an acrylate copolymer emulsion and the shell powder carrier, stirring at a constant temperature, and taking out to obtain a shell acrylate compound;
(3) preparation of sodium stearate starch complex: preparing starch into starch suspension, gelatinizing, mixing with a certain amount of sodium stearate at high temperature, and stirring;
(4) preparing the anti-ultraviolet bacteriostatic coating: heating and mixing the shell acrylate compound and the sodium stearate starch compound, adding the auxiliary agent, and uniformly stirring to obtain the anti-ultraviolet bacteriostatic coating.
Preferably, in the step (1): soaking polyvinyl alcohol and deionized water at room temperature for 20-24 h according to the mass ratio of 1: 3-1: 5, heating to 95-100 ℃, stirring and refluxing for 1.5-2 h to completely dissolve polyvinyl alcohol to obtain a polyvinyl alcohol dispersion, adding the polyvinyl alcohol dispersion and the deionized water into a flask according to the mass ratio of 2: 3-2: 5, stirring for 30-40 min, heating to 65-70 ℃, dropwise adding methacryloyloxyethyl trimethyl ammonium chloride, methyl methacrylate, butyl acrylate and acrylic acid according to the mass ratio of 1:2:1: 1-3: 2:3:3, dropwise adding the mixture for about 1.5-2 h, keeping the temperature at 65-70 ℃ after dropwise adding, reacting for 4-5 h, and cooling to room temperature to obtain the acrylic ester copolymer emulsion.
Preferably, in the step (2): cleaning a shell, soaking the shell in a sodium hydroxide solution with the mass fraction of 8% for 1-5 hours, removing impurities on the surface by alkali washing, washing the shell with distilled water with the mass of 8-10 times that of the shell, drying the shell in an air-blast drying oven at 100-110 ℃ for 20-24 hours, then putting the dried shell in a crusher for crushing, sieving, calcining the crushed shell in a muffle furnace at 1000-1100 ℃ for 2-2.5 hours, grinding the crushed shell by a mortar to obtain a shell powder carrier, mixing the shell powder carrier and an acrylate copolymer emulsion according to the mass ratio of 2: 3-4: 3, stirring and reacting at the constant temperature of 90-100 ℃ for 1.5-2 hours, and taking out the mixture to obtain the shell acrylate compound.
Preferably, in the step (3): preparing starch suspension with the mass fraction of 5% in a three-neck flask, firstly dispersing in cold water for 10-15 min, and then placing in a water bath kettle for 200-220 r.min-1Heating at the stirring speed, gelatinizing at 95-100 ℃ for 30-40 min, continuously mixing and stirring the gelatinized starch solution and sodium stearate solution uniformly according to the mass ratio of 1: 2-1: 3, and cooling to room temperature to obtain the sodium stearate-starch compound.
Preferably, in the step (4): heating, mixing and stirring the shell acrylate compound and the sodium stearate starch compound uniformly at 70-80 ℃ according to the mass ratio of 3: 2-7: 2, adding an ultraviolet absorbent UV-O with the mass of 0.05-0.1 time of that of the sodium stearate starch compound, mixing and stirring for 2-3 h, and cooling to room temperature to obtain the anti-ultraviolet bacteriostatic coating.
Example 1: anti-ultraviolet bacteriostatic coating I
An anti-ultraviolet bacteriostatic coating comprises the following raw materials in parts by weight:
60-90 parts of shell acrylate compound, 30-50 parts of sodium stearate starch compound and 5-10 parts of auxiliary agent.
An anti-ultraviolet bacteriostatic coating and a preparation method thereof, comprising the following steps:
(1) preparation of acrylic ester copolymer emulsion: mixing polyvinyl alcohol and deionized water to obtain a dispersion, heating, adding methacryloyloxyethyl trimethyl ammonium chloride, methyl methacrylate, butyl acrylate, acrylic acid and deionized water, continuously heating, stirring, keeping the temperature, reacting, and cooling to room temperature to obtain an acrylate copolymer emulsion;
(2) preparation of shell acrylate complex: washing shells, soaking the shells in a sodium hydroxide solution to remove impurities, washing, drying, crushing, calcining in a muffle furnace, grinding to obtain a shell powder carrier, mixing an acrylate copolymer emulsion and the shell powder carrier, stirring at a constant temperature, and taking out to obtain a shell acrylate compound;
(3) preparation of sodium stearate starch complex: preparing starch into starch suspension, gelatinizing, mixing with a certain amount of sodium stearate at high temperature, and stirring;
(4) preparing the anti-ultraviolet bacteriostatic coating: heating and mixing the shell acrylate compound and the sodium stearate starch compound, adding the auxiliary agent, and uniformly stirring to obtain the anti-ultraviolet bacteriostatic coating.
Preferably, in the step (1): soaking polyvinyl alcohol and deionized water at room temperature for 24 hours according to the mass ratio of 1:5, heating to 100 ℃, stirring and refluxing for 2 hours to completely dissolve polyvinyl alcohol to obtain polyvinyl alcohol dispersion, adding the polyvinyl alcohol dispersion and the deionized water into a flask according to the mass ratio of 2:5, stirring for 40 minutes, heating to 70 ℃, dropwise adding methacryloyloxyethyl trimethyl ammonium chloride, methyl methacrylate, butyl acrylate and acrylic acid according to the mass ratio of 3:2:3:3, completing dropwise addition for about 2 hours, keeping the temperature at 70 ℃ for reaction for 5 hours after the dropwise addition is completed, and cooling to room temperature to obtain the acrylate copolymer emulsion.
Preferably, in the step (2): cleaning and soaking a shell, soaking the shell in a sodium hydroxide solution with the mass fraction of 8% for 5 hours, removing impurities on the surface by alkali washing, washing the shell with distilled water with the mass of 10 times that of the shell, drying the shell in an air-blast drying oven at 110 ℃ for 24 hours, then putting the dried shell in a crusher for crushing, sieving, putting the crushed shell in a muffle furnace for calcining at 1100 ℃ for 2.5 hours, grinding the crushed shell in a mortar to obtain a shell powder carrier, mixing the shell powder carrier and an acrylate copolymerization emulsion according to the mass ratio of 4:3, stirring and reacting at the constant temperature of 100 ℃ for 2 hours, and taking out the mixture to obtain the shell acrylate composite.
Preferably, in the step (3): preparing starch suspension with mass fraction of 5% in a three-neck flask, dispersing in cold water for 15min, and placing in a water bath at 220 r.min-1Heating under stirring, gelatinizing at 100 deg.C for 40min, and mixing with starch solution and sodium stearate solutionAnd continuously mixing and stirring uniformly according to the mass ratio of 1:3, and cooling to room temperature to obtain the sodium stearate-starch compound.
Preferably, in the step (4): heating, mixing and stirring the shell acrylate compound and the sodium stearate starch compound according to the mass ratio of 7:2 at 80 ℃, adding an ultraviolet absorbent UV-O with the mass of 0.1 time that of the sodium stearate starch compound, mixing and stirring for 3 hours, and cooling to room temperature to obtain the anti-ultraviolet bacteriostatic coating.
Example 2: anti-ultraviolet bacteriostatic coating II
An anti-ultraviolet bacteriostatic coating comprises the following raw materials in parts by weight:
60 parts of shell acrylate compound, 30 parts of sodium stearate starch compound and 5 parts of auxiliary agent.
An anti-ultraviolet bacteriostatic coating and a preparation method thereof, comprising the following steps:
(1) preparation of acrylic ester copolymer emulsion: mixing polyvinyl alcohol and deionized water to obtain a dispersion, heating, adding methacryloyloxyethyl trimethyl ammonium chloride, methyl methacrylate, butyl acrylate, acrylic acid and deionized water, continuously heating, stirring, keeping the temperature, reacting, and cooling to room temperature to obtain an acrylate copolymer emulsion;
(2) preparation of shell acrylate complex: washing shells, soaking the shells in a sodium hydroxide solution to remove impurities, washing, drying, crushing, calcining in a muffle furnace, grinding to obtain a shell powder carrier, mixing an acrylate copolymer emulsion and the shell powder carrier, stirring at a constant temperature, and taking out to obtain a shell acrylate compound;
(3) preparation of sodium stearate starch complex: preparing starch into starch suspension, gelatinizing, mixing with a certain amount of sodium stearate at high temperature, and stirring;
(4) preparing the anti-ultraviolet bacteriostatic coating: heating and mixing the shell acrylate compound and the sodium stearate starch compound, adding the auxiliary agent, and uniformly stirring to obtain the anti-ultraviolet bacteriostatic coating.
Preferably, in the step (1): soaking polyvinyl alcohol and deionized water at room temperature for 20h according to the mass ratio of 1:3, heating to 95 ℃, stirring and refluxing for 1.5h to completely dissolve polyvinyl alcohol to obtain polyvinyl alcohol dispersion, adding the polyvinyl alcohol dispersion and the deionized water into a flask according to the mass ratio of 2:3, stirring for 30min, heating to 65 ℃, dropwise adding methacryloyloxyethyl trimethyl ammonium chloride, methyl methacrylate, butyl acrylate and acrylic acid according to the mass ratio of 1:2:1:1, dropwise adding for about 1.5h, keeping the temperature and reacting for 4h at 65 ℃ after the dropwise adding is finished, and cooling to room temperature to obtain the acrylic ester copolymer emulsion.
Preferably, in the step (2): cleaning and soaking a shell in a sodium hydroxide solution with the mass fraction of 8% for 1h, removing impurities on the surface by alkali washing, washing with distilled water with the mass of 8 times that of the shell, drying at 100 ℃ for 20h in an air-blast drying oven, then placing the dried shell in a grinder for grinding, sieving, calcining at 1000 ℃ in a muffle furnace for 2h, grinding by a mortar to obtain a shell powder carrier, mixing the shell powder carrier and an acrylate copolymerization emulsion according to the mass ratio of 2:3, stirring at the constant temperature of 90 ℃ for reaction for 1.5h, and taking out to obtain the shell acrylate composite.
Preferably, in the step (3): preparing starch suspension with mass fraction of 5% in a three-neck flask, dispersing in cold water for 10min, and placing in a water bath at 200 r.min-1Heating up under stirring speed, gelatinizing at 95 ℃ for 30min, continuously mixing and stirring the gelatinized starch solution and sodium stearate solution uniformly according to the mass ratio of 1:2, and cooling to room temperature to obtain the sodium stearate starch compound.
Preferably, in the step (4): heating, mixing and stirring the shell acrylate compound and the sodium stearate starch compound according to the mass ratio of 3:2 at 70 ℃, adding an ultraviolet absorbent UV-O with the mass of 0.05 time of that of the sodium stearate starch compound, mixing and stirring for 2 hours, and cooling to room temperature to obtain the anti-ultraviolet bacteriostatic coating.
Comparative example 1:
preparation of a common coating: heating, mixing and stirring the acrylic emulsion, the dispersing agent, the defoaming agent and other auxiliaries uniformly to obtain the common coating.
Comparative example 2:
comparative example 2 was formulated as in example 1. The preparation method of the anti-ultraviolet bacteriostatic coating is different from that of the example 1 only in that the preparation of the step (2) is not carried out, and the rest of the preparation steps are the same as those of the example 1.
Comparative example 3:
the formulation of ratio 3 was the same as in example 1. The preparation method of the anti-ultraviolet bacteriostatic coating is different from that of the example 1 only in that the preparation of the step (3) is not carried out, and the rest of the preparation steps are the same as those of the example 1.
Test example 1
The same gram of swimwear was coated with the coatings prepared in example 1, comparative example 1 and comparative example 3, respectively, the wear resistance of the swimwear was measured, the same force was controlled at normal temperature and pressure, and the swimwear was torn, with the following breakage degrees:
degree of breakage (%)
Example 1 20
Comparative example 1 80
Comparative example 3 40
It can be seen from the above data that the damage degree of example 1 is the lowest, this is because when the sodium stearate starch compound is applied to the swimsuit, the film-coating firmness of the starch layer on the surface of the coating can be improved, the hydrogen bond bonding between the starch molecule hydroxyl group and the swimsuit fiber molecule hydroxyl group in the modified shell acrylate compound is enhanced, the physical properties of the swimsuit are improved, and the anti-impact property of the swimsuit is enhanced, and the sodium stearate starch compound is easy to dissociate carboxyl group in the aqueous solution, the carboxyl group and the starch molecule hydroxyl group can generate strong interaction, selectively occupy the growth point on the surface of the coating, and the butyl acrylate component in the shell acrylate compound can cause the two to grow towards different directions and communicate with each other to form a network structure, thereby achieving the purposes of increasing the contact surface and enhancing the wear resistance.
Test example 2
Two marine common bacteria, namely vibrio natriegens and bacillus, are selected for carrying out a bacteriostatic circle experiment, the swimsuits coated with the coatings prepared in example 1, comparative example 1 and comparative example 3 and having the same gram weight are placed in a bacteria incubator, and are taken out after 24 hours, the survival rate of the bacteria is observed by a microscope, and the measured data are as follows:
bacterial survival Rate (%)
Example 1 22
Comparative example 1 85
Comparative example 2 46
The bacteria survival rate of the comparative example 1 is the highest, and the other two bacteria survival rates are relatively low, because the biocompatibility of the shell powder in the shell acrylate compound can enable the acrylate copolymerization emulsion to be firmly loaded on the shell powder, the edges and corners of the original cubic structure of the shell powder are smooth, the shell powder has good compatibility with the coating, the dispersion is uniform, the aperture of the shell powder is large, the shell powder has certain adsorption capacity, the bacteria in the sea and the light on the sea surface can be adsorbed, when the bacteria enter a system, the acrylate copolymerization emulsion in the shell powder and the shell powder perform photocatalysis under the combined action, the internal hydroxyl groups and surface water molecules are oxidized into hydroxyl radicals with strong oxidizing property, the bacteria in the system can be blocked and killed, and the sterilization effect is achieved.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. The anti-ultraviolet bacteriostatic coating is characterized by comprising the following raw materials in parts by weight: 60-90 parts of shell acrylate compound, 30-50 parts of sodium stearate starch compound and 5-10 parts of auxiliary agent.
2. The anti-ultraviolet bacteriostatic coating according to claim 1, wherein the auxiliary agent is one of ultraviolet absorbers UV-O and UV-P.
3. The anti-ultraviolet bacteriostatic coating according to claim 2, wherein the sodium stearate-starch complex is prepared by mixing and stirring starch and sodium stearate at a certain temperature after being gelatinized.
4. The anti-ultraviolet bacteriostatic coating according to claim 2, wherein the shell acrylate compound is prepared by calcining shell powder at high temperature and then co-precipitating the calcined shell powder and acrylate copolymer emulsion.
5. The anti-ultraviolet bacteriostatic coating according to claim 4, wherein the acrylate copolymer emulsion is prepared by lactic acid copolymerization of methacryloyloxyethyl trimethyl ammonium chloride, methyl methacrylate, butyl acrylate and acrylic acid.
6. An anti-ultraviolet bacteriostatic coating and a preparation method thereof are characterized by comprising the following steps:
(1) preparation of acrylic ester copolymer emulsion: mixing polyvinyl alcohol and deionized water to obtain a dispersion, heating, adding methacryloyloxyethyl trimethyl ammonium chloride, methyl methacrylate, butyl acrylate, acrylic acid and deionized water, continuously heating, stirring, keeping the temperature, reacting, and cooling to room temperature to obtain an acrylate copolymer emulsion;
(2) preparation of shell acrylate complex: washing shells, soaking the shells in a sodium hydroxide solution to remove impurities, washing, drying, crushing, calcining in a muffle furnace, grinding to obtain a shell powder carrier, mixing an acrylate copolymer emulsion and the shell powder carrier, stirring at a constant temperature, and taking out to obtain a shell acrylate compound;
(3) preparation of sodium stearate starch complex: preparing starch into starch suspension, gelatinizing, mixing with a certain amount of sodium stearate at high temperature, and stirring;
(4) preparing the anti-ultraviolet bacteriostatic coating: heating and mixing the shell acrylate compound and the sodium stearate starch compound, adding the auxiliary agent, and uniformly stirring to obtain the anti-ultraviolet bacteriostatic coating.
7. The anti-ultraviolet bacteriostatic coating and the preparation method thereof according to claim 6, characterized in that in the step (1): soaking polyvinyl alcohol and deionized water at room temperature for 20-24 h according to the mass ratio of 1: 3-1: 5, heating to 95-100 ℃, stirring and refluxing for 1.5-2 h to completely dissolve polyvinyl alcohol to obtain a polyvinyl alcohol dispersion, adding the polyvinyl alcohol dispersion and the deionized water into a flask according to the mass ratio of 2: 3-2: 5, stirring for 30-40 min, heating to 65-70 ℃, dropwise adding methacryloyloxyethyl trimethyl ammonium chloride, methyl methacrylate, butyl acrylate and acrylic acid according to the mass ratio of 1:2:1: 1-3: 2:3:3, dropwise adding the mixture for about 1.5-2 h, keeping the temperature at 65-70 ℃ after dropwise adding, reacting for 4-5 h, and cooling to room temperature to obtain the acrylic ester copolymer emulsion.
8. The anti-ultraviolet bacteriostatic coating and the preparation method thereof according to claim 6, characterized in that in the step (2): cleaning a shell, soaking the shell in a sodium hydroxide solution with the mass fraction of 8% for 1-5 hours, removing impurities on the surface by alkali washing, washing the shell with distilled water with the mass of 8-10 times that of the shell, drying the shell in an air-blast drying oven at 100-110 ℃ for 20-24 hours, then putting the dried shell in a crusher for crushing, sieving, calcining the crushed shell in a muffle furnace at 1000-1100 ℃ for 2-2.5 hours, grinding the crushed shell by a mortar to obtain a shell powder carrier, mixing the shell powder carrier and an acrylate copolymer emulsion according to the mass ratio of 2: 3-4: 3, stirring and reacting at the constant temperature of 90-100 ℃ for 1.5-2 hours, and taking out the mixture to obtain the shell acrylate compound.
9. The anti-ultraviolet bacteriostatic coating and the preparation method thereof according to claim 6, characterized in that in the step (3): preparing starch with the mass fraction of 5% in a three-neck flaskDispersing the suspension in cold water for 10-15 min, and placing in a water bath at 200-220 r.min-1Heating at the stirring speed, gelatinizing at 95-100 ℃ for 30-40 min, continuously mixing and stirring the gelatinized starch solution and sodium stearate solution uniformly according to the mass ratio of 1: 2-1: 3, and cooling to room temperature to obtain the sodium stearate-starch compound.
10. The anti-ultraviolet bacteriostatic coating and the preparation method thereof according to claim 6, characterized in that in the step (4): heating, mixing and stirring the shell acrylate compound and the sodium stearate starch compound uniformly at 70-80 ℃ according to the mass ratio of 3: 2-7: 2, adding an ultraviolet absorbent UV-O with the mass of 0.05-0.1 time of that of the sodium stearate starch compound, mixing and stirring for 2-3 h, and cooling to room temperature to obtain the anti-ultraviolet bacteriostatic coating.
CN202110565168.7A 2021-05-24 2021-05-24 Anti-ultraviolet bacteriostatic coating and preparation method thereof Pending CN113214716A (en)

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Publication number Priority date Publication date Assignee Title
EP1326929A2 (en) * 2000-09-27 2003-07-16 Unilever House Process for coating a water-soluble package and package coated by that process
KR100994148B1 (en) * 2010-07-14 2010-11-15 (주)아팩 Cationic resin composition for aqueous gravure printing and a production method
CN104789154A (en) * 2015-05-08 2015-07-22 南通启秀门窗有限公司 Wood window
CN106566191A (en) * 2016-10-14 2017-04-19 华蓥市盈胜电子有限公司 Mainboard surface protection treating method
CN108046657A (en) * 2017-12-25 2018-05-18 广州瓷添乐装饰材料有限公司 A kind of preparation and application of multifunctional nano shell powder paint
CN108822599A (en) * 2018-07-11 2018-11-16 合肥择浚电气设备有限公司 A kind of Corrosion resistant heat radiation paint and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1326929A2 (en) * 2000-09-27 2003-07-16 Unilever House Process for coating a water-soluble package and package coated by that process
KR100994148B1 (en) * 2010-07-14 2010-11-15 (주)아팩 Cationic resin composition for aqueous gravure printing and a production method
CN104789154A (en) * 2015-05-08 2015-07-22 南通启秀门窗有限公司 Wood window
CN106566191A (en) * 2016-10-14 2017-04-19 华蓥市盈胜电子有限公司 Mainboard surface protection treating method
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