CN111423696B - Antibacterial and antiviral toilet cover and preparation method thereof - Google Patents
Antibacterial and antiviral toilet cover and preparation method thereof Download PDFInfo
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- CN111423696B CN111423696B CN202010311899.4A CN202010311899A CN111423696B CN 111423696 B CN111423696 B CN 111423696B CN 202010311899 A CN202010311899 A CN 202010311899A CN 111423696 B CN111423696 B CN 111423696B
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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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
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- A—HUMAN NECESSITIES
- A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
- A47K—SANITARY EQUIPMENT NOT OTHERWISE PROVIDED FOR; TOILET ACCESSORIES
- A47K13/00—Seats or covers for all kinds of closets
- A47K13/02—Seats or covers for all kinds of closets of plastic materials
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
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- C08K3/36—Silica
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- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
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- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C—CHEMISTRY; METALLURGY
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- C08K2201/011—Nanostructured additives
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Abstract
The invention relates to an antibacterial and antiviral toilet cover and a preparation method thereof, wherein the antibacterial and antiviral toilet cover is prepared from the following components in parts by weight: 60-70 parts of resin material, 10-20 parts of flame-retardant filler, 1.0-5.0 parts of dispersing agent, 1.0-2.0 parts of antioxidant and 0.5-1.0 parts of modified antibacterial and antiviral treatment agent; the modified antibacterial and antiviral treatment agent adopts an organosilicon modified photocatalyst, and the organosilicon modified photocatalyst is obtained by modifying an inorganic photocatalyst antibacterial agent by an organosilicon release agent. In addition, the preparation method is also disclosed. The invention greatly reduces the dosage of the antibacterial agent on the premise of ensuring the antibacterial, antiviral and anti-mite effects of the toilet cover.
Description
Technical Field
The invention belongs to the field of bathroom, and particularly relates to an antibacterial and antiviral toilet cover and a preparation method thereof.
Background
The toilet bowl is closely related to the life of people, so that great convenience is brought to people, but various tiny microorganisms which cannot be seen by naked eyes are often present on the toilet bowl cover and the gasket particularly in public areas due to the influence of the use environment of the toilet bowl. According to the investigation and discovery of the relevant public health authorities: the shigella is arranged on 32% of the toilet cover and the toilet pad, and some of the shigella can survive on the toilet pad for up to 17 days; when the closestool is flushed, the instant cyclone in the closestool can bring germs to the height of 6 meters at the highest, suspend for a plurality of hours, and then fall on the wall, the toothbrush, the tooth glass and the towel of the bathroom, so that the closestool is polluted by bacteria and viruses, and especially when people in families have diseases, the germs can be increased by hundreds of times, and the health of people is seriously endangered. Therefore, the toilet cover with the antibacterial and antiviral functions is urgently needed to be developed, and on one hand, bacteria and viruses brought out by instant cyclone when the toilet is flushed can be killed through the toilet cover; on the other hand, bacteria and viruses contacted with the toilet can be killed by the toilet cover, so that a cleaner space is formed, and the possibility of cross infection of the bacteria and the viruses is reduced.
At present, the preparation methods of the antibacterial toilet cover mainly comprise two methods, wherein the first method is to spray an antibacterial agent on the surface of the toilet cover, then bake the surface of the toilet cover at a high temperature of 200-250 ℃ to form an antibacterial layer on the surface of the toilet cover, the problem of the method is that the high-temperature baking accelerates the aging speed of the toilet cover and reduces the service life of the toilet cover, the second method is to add the antibacterial agent into the raw materials for preparing the toilet cover, and the main problem of the method is that the antibacterial agent is diluted by the raw materials, and the toilet cover has a certain thickness, so that most of the antibacterial agent is positioned in the toilet cover and the surface is less, thereby causing most of the antibacterial agent in the toilet cover to not exert the antibacterial effect and causing great waste of the antibacterial agent.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide an antibacterial and antiviral toilet cover and a preparation method thereof, which greatly reduce the dosage of antibacterial agents on the premise of ensuring the antibacterial, antiviral and anti-mite effects of the toilet cover.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the technical scheme is as follows:
an antibacterial and antiviral toilet cover is prepared from the following components in parts by weight:
the modified antibacterial and antiviral treatment agent adopts an organosilicon modified photocatalyst, and the organosilicon modified photocatalyst is obtained by modifying an inorganic photocatalyst antibacterial agent by an organosilicon release agent.
Further, the inorganic photocatalyst antibacterial agent is one or more selected from nano titanium dioxide, nano zinc oxide, nano silicon oxide, nano bismuth tungstate and nano bismuth molybdate;
the organic silicon release agent is selected from one or two of polyorganosiloxane, siloxane compound, silicone oil, methyl silicone resin and methyl phenyl silicone resin.
Further, the process for modifying the inorganic photocatalyst antibacterial agent by the organic silicon specifically comprises the following steps:
step 1, vacuum drying inorganic photocatalyst powder in an oven at 60-100 ℃ for 4-6 hours, and cooling for standby;
step 2, preparing an ethanol solution according to 3-8wt%, adding the inorganic light touch mould powder subjected to the drying treatment in the step 1 into the ethanol solution according to the amount of 50-80wt%, uniformly dispersing the mixed solution by high-speed shearing of a high-speed emulsifying machine, and vibrating for 20-50min by using an ultrasonic vibration instrument to uniformly disperse the solution;
step 3, adding an organosilicon release agent into the solution uniformly dispersed in the step 2 according to the amount of 2-5 wt%, and then carrying out reflux reaction for 2-4h at 50-80 ℃;
and 4, after the reflux reaction is finished, centrifuging the reaction solution to obtain a precipitate, washing the obtained precipitate with absolute ethyl alcohol for 3-6 times, and then drying in vacuum at 50-80 ℃ to obtain the organosilicon modified photocatalyst, namely the modified antibacterial and antiviral treatment agent.
Further, the resin material comprises one or more of urea resin, acrylic resin, PP resin, PVC resin and ABS resin.
Further, the flame-retardant filler comprises one or more of aluminum hydroxide, magnesium hydroxide, calcium carbonate, silicon dioxide and zinc oxide.
Further, the dispersing agent comprises one or more of ethylene bis stearamide, stearic acid monoglyceride, oleamide, barium stearate, polyethylene wax and polypropylene wax.
Further, the antioxidant comprises one or two of pentaerythritol tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (antioxidant 1010), N-stearyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (antioxidant 1076), N-diphenyl-p-phenylenediamine, di-tert-butyl-methylphenol, dilauryl thiodipropionate and bis (octadecyl) pentaerythritol diphosphite.
The second technical scheme is as follows:
the preparation method of the antibacterial and antiviral toilet cover specifically comprises the following steps:
step (1), putting the modified antibacterial antiviral agent and the resin material into a high-speed stirrer, stirring at a high speed for 5-10min at 95-115 ℃, and pre-dispersing uniformly;
and (2) adding the flame-retardant filler, the antioxidant and the dispersing agent into the material which is pre-dispersed uniformly in the step (1), continuously stirring for 10-30min to obtain a pre-mixed material, then carrying out melt mixing on the pre-mixed material in a double-screw extruder, injecting the mixture into a die cavity, and opening the die after cooling and taking out.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, the inorganic photocatalyst antibacterial agent is added into the raw materials for preparing the toilet cover, so that the toilet cover has antibacterial and antiviral effects, and bacteria and viruses brought out by instant cyclone during flushing of the toilet can be killed; on the other hand, bacteria and viruses contacted with the toilet can be killed by the toilet cover, so that a cleaner space is formed, and the possibility of cross infection of the bacteria and the viruses is reduced.
2. According to the invention, the organic silicon release agent can be separated out from the inside in the cooling process of resin and uniformly distributed on the surface of the toilet cover, so that a lubricating layer is formed on the surface of the toilet cover, a resin material cannot adhere to a mold, and the mold release is convenient, before the inorganic photocatalyst is added into a resin raw material, the inorganic photocatalyst is modified by the organic silicon release agent, in the process of modifying the photocatalyst by the organic silicon release agent, a Si-O-Si structure can be formed between the organic silicon release agent and the inorganic nanometer photocatalyst through a silicon-oxygen bond, and meanwhile, an alkoxy in the organic silicon release agent can abstract protons on the surfaces of the photocatalyst nanoparticles and react with chemical groups on the surfaces of the nanoparticles to form chemical bonds, so that the modified molecular layer is covered on the surfaces of the photocatalyst nanoparticles; the modified antibacterial and antiviral treatment agent has lower specific surface energy, so that the inorganic photocatalyst nano particles have better dispersibility under the high-temperature melting condition, and the dispersing effect is improved; under the action of chemical bonds between inorganic photocatalyst nano particles and an organic silicon release agent, the inorganic photocatalyst nano particles can be quickly migrated to the surface of the toilet cover along with exudation of the organic silicon release agent in the low-temperature cooling process of resin, so that a lubricating layer with inorganic photocatalyst antibacterial agent is formed on the surface of the toilet cover, the antibacterial agent is concentrated on the surface of the toilet cover instead of the inside of the material of the toilet cover, and compared with the traditional production process of simply doping the antibacterial agent into a resin raw material, the antibacterial antiviral agent concentration on the surface of a product is increased under the same antibacterial agent dosage, and the antibacterial antiviral efficiency of the product is further improved; under the same antibacterial and antiviral effects of the toilet cover, the dosage of the antibacterial and antiviral treatment agent is greatly reduced, and in addition, the problem of aging acceleration of the toilet cover caused by high-temperature baking is also avoided.
3. According to the invention, the organic silicon is used for modifying the inorganic photocatalyst by adopting a reflux method, and the modification rate is greatly improved by strictly controlling modification parameters, so that after the modified antibacterial antiviral agent is doped into the preparation raw material of the toilet cover, the inorganic photocatalyst nano particles can migrate to the surface of the toilet cover under the action of the organic silicon release agent, and a temperature antibacterial agent film layer is formed on the surface of the toilet cover.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1
A first part:
an antibacterial and antiviral toilet cover is prepared from the following components in parts by weight:
the organic silicon modified photocatalyst is obtained by modifying inorganic photocatalyst antibacterial agent nano titanium dioxide by organic silicon release agent methyl phenyl silicone resin,
the specific operation method for modifying the photocatalyst by the organosilicon release agent comprises the following steps:
step 1, vacuum drying inorganic photocatalyst powder in an oven at 80 ℃ for 4 hours, and cooling for standby;
step 2, preparing an ethanol solution according to 7wt%, adding the inorganic light touch mould powder subjected to the drying treatment in the step 1 into the ethanol solution according to 80wt%, uniformly dispersing the mixed solution by high-speed shearing of a high-speed emulsifying machine, and vibrating for 30min by using an ultrasonic vibration instrument to uniformly disperse the solution;
step 3, adding an organosilicon release agent methyl phenyl silicone resin into the solution uniformly dispersed in the step 2 according to the amount of 5wt%, and then carrying out reflux reaction for 3 hours at 60 ℃;
and step 4, after the reflux reaction is finished, centrifuging the reaction solution to obtain a precipitate, washing the obtained precipitate with absolute ethyl alcohol for 5 times, and then drying the washed precipitate in vacuum at 75 ℃ to obtain the organosilicon modified photocatalyst, namely the modified antibacterial and antiviral treatment agent.
A second part:
the preparation method of the antibacterial and antiviral toilet cover specifically comprises the following steps:
step (1), putting the modified antibacterial antiviral agent and the resin material into a high-speed stirrer, stirring at a high speed for 5min at 100 ℃, and pre-dispersing uniformly;
and (2) adding the flame-retardant filler, the antioxidant and the dispersing agent into the material which is pre-dispersed uniformly in the step (1), continuously stirring for 15min to obtain a pre-mixed material, then carrying out melt mixing on the pre-mixed material in a double-screw extruder at 150 ℃, injecting the mixture into a die cavity, and opening the die after cooling and taking out.
Example 2
A first part:
an antibacterial and antiviral toilet cover is prepared from the following components in parts by weight:
the organic silicon modified photocatalyst is obtained by modifying inorganic photocatalyst antibacterial agent nano bismuth tungstate by organic silicon release agent siloxane compound,
the specific operation method for modifying the photocatalyst by the organosilicon release agent comprises the following steps:
step 1, vacuum drying inorganic photocatalyst powder in a baking oven at 75 ℃ for 5 hours, and cooling for standby;
step 2, preparing an ethanol solution according to 5wt%, adding the inorganic photocatalyst powder subjected to the drying treatment in the step 1 into the ethanol solution according to 75wt%, uniformly dispersing the mixed solution by high-speed shearing of a high-speed emulsifying machine, and vibrating for 35min by using an ultrasonic vibration instrument to uniformly disperse the solution;
step 3, adding an organosilicon release agent siloxane compound into the solution uniformly dispersed in the step 2 according to the amount of 4wt%, and then carrying out reflux reaction for 4 hours at 57 ℃;
and 4, after the reflux reaction is finished, centrifuging the reaction solution to obtain a precipitate, washing the obtained precipitate with absolute ethyl alcohol for 4 times, and then drying the washed precipitate in vacuum at 65 ℃ to obtain the organosilicon modified photocatalyst, namely the modified antibacterial and antiviral treatment agent.
A second part:
the preparation method of the antibacterial and antiviral toilet cover specifically comprises the following steps:
step (1), putting the modified antibacterial antiviral agent and the resin material into a high-speed stirrer, stirring at a high speed for 8min at a temperature of 95 ℃, and pre-dispersing uniformly;
and (2) adding the flame-retardant filler, the antioxidant and the dispersing agent into the material which is pre-dispersed uniformly in the step (1), continuously stirring for 20min to obtain a pre-mixed material, then carrying out melt mixing on the pre-mixed material in a double-screw extruder at 190 ℃, injecting the mixture into a die cavity, and opening the die after cooling and taking out.
Example 3
A first part:
an antibacterial and antiviral toilet cover is prepared from the following components in parts by weight:
the organosilicon modified photocatalyst is obtained by modifying inorganic photocatalyst antibacterial agent nano silicon oxide by organosilicon release agent polyorganosiloxane,
the specific operation method for modifying the photocatalyst by the organosilicon release agent comprises the following steps:
step 1, vacuum drying inorganic photocatalyst powder in a 65 ℃ oven for 6 hours, and cooling for standby;
step 2, preparing an ethanol solution according to 6wt%, adding the inorganic light touch mould powder subjected to the drying treatment in the step 1 into the ethanol solution according to the amount of 7wt%, uniformly dispersing the mixed solution by high-speed shearing of a high-speed emulsifying machine, and vibrating for 25min by using an ultrasonic vibration instrument to uniformly disperse the solution;
step 3, adding organosilicon release agent polyorganosiloxane into the solution uniformly dispersed in the step 2 according to the amount of 5wt%, and then carrying out reflux reaction for 4 hours at 55 ℃;
and step 4, after the reflux reaction is finished, centrifuging the reaction solution to obtain a precipitate, washing the obtained precipitate with absolute ethyl alcohol for 3 times, and then drying the washed precipitate in vacuum at 75 ℃ to obtain the organosilicon modified photocatalyst, namely the modified antibacterial and antiviral treatment agent.
A second part:
the preparation method of the antibacterial and antiviral toilet cover specifically comprises the following steps:
step (1), putting the modified antibacterial antiviral agent and the resin material into a high-speed stirrer, stirring at a high speed for 10min at 110 ℃, and pre-dispersing uniformly;
and (2) adding the flame-retardant filler, the antioxidant and the dispersing agent into the material which is pre-dispersed uniformly in the step (1), continuously stirring for 20min to obtain a pre-mixed material, then carrying out melt mixing on the pre-mixed material in a double-screw extruder at 210 ℃, injecting the mixture into a die cavity, and opening the die after cooling and taking out.
Example 4
A first part:
an antibacterial and antiviral toilet cover is prepared from the following components in parts by weight:
the organic silicon modified photocatalyst is obtained by modifying inorganic photocatalyst antibacterial agent nano zinc oxide by organic silicon release agent methyl silicone resin,
the specific operation method for modifying the photocatalyst by the organosilicon release agent comprises the following steps:
step 1, vacuum drying inorganic photocatalyst powder in a baking oven at 70 ℃ for 5 hours, and cooling for standby;
step 2, preparing an ethanol solution according to 8wt%, adding the inorganic light touch mould powder subjected to the drying treatment in the step 1 into the ethanol solution according to 69wt%, uniformly dispersing the mixed solution by high-speed shearing of a high-speed emulsifying machine, and vibrating for 20min by using an ultrasonic vibration instrument to uniformly disperse the solution;
step 3, adding an organosilicon release agent methyl silicone resin into the solution uniformly dispersed in the step 2 according to the amount of 4wt%, and then carrying out reflux reaction for 3 hours at 65 ℃;
and step 4, after the reflux reaction is finished, centrifuging the reaction solution to obtain a precipitate, washing the obtained precipitate with absolute ethyl alcohol for 3 times, and then drying the washed precipitate in vacuum at 60 ℃ to obtain the organosilicon modified photocatalyst, namely the modified antibacterial and antiviral treatment agent.
A second part:
the preparation method of the antibacterial and antiviral toilet cover specifically comprises the following steps:
step (1), putting the modified antibacterial antiviral agent and the resin material into a high-speed stirrer, stirring at a high speed for 6min at 115 ℃, and pre-dispersing uniformly;
and (2) adding the flame-retardant filler, the antioxidant and the dispersing agent into the material which is pre-dispersed uniformly in the step (1), continuously stirring for 25min to obtain a pre-mixed material, then carrying out melt mixing on the pre-mixed material in a double-screw extruder at 160 ℃, injecting the mixture into a die cavity, and opening the die after cooling and taking out.
Example 5
A first part:
an antibacterial and antiviral toilet cover is prepared from the following components in parts by weight:
the organic silicon modified photocatalyst is obtained by modifying inorganic photocatalyst antibacterial agent nano bismuth molybdate by organic silicon release agent emulsified silicone oil,
the specific operation method for modifying the photocatalyst by the organosilicon release agent comprises the following steps:
step 1, vacuum drying inorganic photocatalyst powder in an oven at 85 ℃ for 4 hours, and cooling for standby;
step 2, preparing an ethanol solution according to 7wt%, adding the inorganic light touch mould powder subjected to the drying treatment in the step 1 into the ethanol solution according to 7wt%, uniformly dispersing the mixed solution by high-speed shearing of a high-speed emulsifying machine, and vibrating for 25min by using an ultrasonic vibration instrument to uniformly disperse the solution;
step 3, adding the organosilicon release agent emulsified silicone oil into the solution uniformly dispersed in the step 2 according to the amount of 2wt%, and then carrying out reflux reaction for 2 hours at 70 ℃;
and 4, after the reflux reaction is finished, centrifuging the reaction solution to obtain a precipitate, washing the obtained precipitate with absolute ethyl alcohol for 4 times, and then drying the precipitate in vacuum at 70 ℃ to obtain the organosilicon modified photocatalyst, namely the modified antibacterial and antiviral treatment agent.
A second part:
the preparation method of the antibacterial and antiviral toilet cover specifically comprises the following steps:
step (1), putting the modified antibacterial antiviral agent and the resin material into a high-speed stirrer, stirring at a high speed for 5min at 100 ℃, and pre-dispersing uniformly;
and (2) adding the flame-retardant filler, the antioxidant and the dispersing agent into the material which is pre-dispersed uniformly in the step (1), continuously stirring for 25min to obtain a pre-mixed material, then carrying out melt mixing on the pre-mixed material in a double-screw extruder at 240 ℃, injecting the mixture into a die cavity, and opening the die after cooling and taking out.
Comparative example 1
An antibacterial and antiviral toilet cover is prepared from the following components in parts by weight:
the amounts of the silicone release agent methylphenyl silicone resin and the inorganic photocatalyst antibacterial agent nano titanium dioxide used in this comparative example were the same as in example 1.
The preparation method of the antibacterial and antiviral toilet cover specifically comprises the following steps:
step (1), placing an inorganic photocatalyst, an organosilicon release agent and a resin material into a high-speed stirrer, stirring at a high speed for 5min at a temperature of 100 ℃, and pre-dispersing uniformly;
and (2) adding the flame-retardant filler, the antioxidant and the dispersing agent into the material which is pre-dispersed uniformly in the step (1), continuously stirring for 15min to obtain a pre-mixed material, then carrying out melt mixing on the pre-mixed material in a double-screw extruder at 150 ℃, injecting the mixture into a die cavity, and opening the die after cooling and taking out.
Comparative example 2
An antibacterial and antiviral toilet cover is prepared from the following components in parts by weight:
the same as comparative example 1, except that the amount of the inorganic photocatalyst antibacterial agent nano titanium dioxide was increased from 0.8 parts to 3 parts in comparative example 1.
The preparation method of the antibacterial and antiviral toilet cover specifically comprises the following steps: the same as in comparative example 1.
Comparative example 3
A first part:
an antibacterial and antiviral toilet cover is prepared from the following components in parts by weight:
the same as in example 2.
The specific operation method for modifying the photocatalyst by the organosilicon release agent comprises the following steps:
step 1, vacuum drying inorganic photocatalyst powder in a baking oven at 45 ℃ for 8 hours, and cooling for standby;
step 2, preparing an ethanol solution according to 9wt%, adding the inorganic photocatalyst powder subjected to the drying treatment in the step 1 into the ethanol solution according to 75wt%, uniformly dispersing the mixed solution by high-speed shearing of a high-speed emulsifying machine, and vibrating for 10min by using an ultrasonic vibration instrument to uniformly disperse the solution;
step 3, adding an organosilicon release agent siloxane compound into the solution uniformly dispersed in the step 2 according to the amount of 4wt%, and then carrying out reflux reaction for 6 hours at 40 ℃;
and 4, after the reflux reaction is finished, centrifuging the reaction solution to obtain a precipitate, washing the obtained precipitate with absolute ethyl alcohol for 4 times, and then drying the washed precipitate in vacuum at 65 ℃ to obtain the organosilicon modified photocatalyst, namely the modified antibacterial and antiviral treatment agent.
A second part:
the preparation method of the antibacterial and antiviral toilet cover specifically comprises the following steps: the same as in example 2.
Comparative example 4
A first part:
an antibacterial and antiviral toilet cover is prepared from the following components in parts by weight:
the same as in example 2.
The specific operation method for modifying the photocatalyst by the organosilicon release agent comprises the following steps:
step 1, vacuum drying inorganic photocatalyst powder in a baking oven at 120 ℃ for 2 hours, and cooling for standby;
step 2, preparing an ethanol solution according to 2wt%, adding the inorganic light touch mould powder subjected to the drying treatment in the step 1 into the ethanol solution according to 75wt%, uniformly dispersing the mixed solution by high-speed shearing of a high-speed emulsifying machine, and vibrating for 15min by using an ultrasonic vibration instrument to uniformly disperse the solution;
step 3, adding organosilicon release agent polyorganosiloxane into the solution uniformly dispersed in the step 2 according to the amount of 4wt%, and then carrying out reflux reaction for 5 hours at 85 ℃;
and 4, after the reflux reaction is finished, centrifuging the reaction solution to obtain a precipitate, washing the obtained precipitate with absolute ethyl alcohol for 4 times, and then drying the washed precipitate in vacuum at 65 ℃ to obtain the organosilicon modified photocatalyst, namely the modified antibacterial and antiviral treatment agent.
A second part:
the preparation method of the antibacterial and antiviral toilet cover specifically comprises the following steps: the same as in example 2.
Effect test
The toilet covers prepared in each example and each comparative example were subjected to antibacterial, antiviral and mildew-proof tests, respectively, according to the following methods, and the results are shown in table 1;
antiviral test: the products obtained in each example and comparative example were tested for their antiviral activity rates of H1N1 and H3N2 according to the standard ISO21702-2019 determination of antiviral activity of plastics and other non-porous surfaces.
Antibacterial test: the products obtained in each example and comparative example were tested for antimicrobial according to the standard of GB/T31402-2015 test method for antimicrobial Performance of Plastic surface.
Mildew resistance test: the mildew-proof test is carried out on the products obtained in each example and comparative example according to GB/T24128-2009 method for testing mildew-proof performance of plastics.
Experimental strain: aspergillus niger AS3.315, aureobasidium pullulans AS3.837, penicillium funiculosum AS3.3875, mucor sphaeroides AS3.3601, scopularium viridis AS3.3987.
Remarks: according to the measurement of GB/T24128-2009 method for testing mildew resistance of plastics, the observed growth of mould on the surface of a sample is evaluated as follows:
0-no growth
1-Trace growth (long mould area <10% observed under microscope)
2-growth in small amounts (mould growth area > 10% and < 30%)
3-moderate growth (mould growth area is greater than or equal to 30% and less than 60%)
4-severe growth (mould growth area is more than or equal to 60% and less than or equal to 100%)
TABLE 1
The data in the table shows that: the toilet cover provided by each embodiment has good antibacterial and antiviral functions, the antibacterial rate of staphylococcus aureus and escherichia coli reaches more than 99%, and the mildew-proof level is 0; and the quick-acting effect on the influenza virus is good, and the antiviral activity rate reaches more than 99%. In comparative example 1, the inorganic photocatalyst and the organic silicon release agent are added as separate components instead of being added after modification, so that the inorganic photocatalyst of the antibacterial component is uniformly dispersed in the toilet cover material, and thus the photocatalyst on the surface of the toilet cover is extremely small under the condition that the same photocatalyst antibacterial agent and the same amount are adopted as those in example 1, so that the antibacterial, antiviral and mildew-proof effects of the toilet cover product are poor, and in comparative example 2, after the amount of the photocatalyst is increased from 0.8 part to 3 parts, the prepared toilet cover surface can have a sufficient amount of photocatalyst antibacterial agent component, so that the antibacterial, antiviral and mildew-proof effects equivalent to those in example 1 are achieved. In comparative examples 3 and 4, the modification rate of the antibacterial agent was seriously affected by adjusting the drying temperature and time of the photocatalyst powder, the concentration of the ethanol solution, the time of ultrasonic vibration, and the reflux temperature under the condition that the raw materials and the amounts thereof were the same as those of example 2, so that the antibacterial, antiviral and mildew-proof effects of the prepared toilet lid product were remarkably deteriorated.
The applicant states that the detailed method of the present invention is illustrated by the above examples, but the present invention is not limited to the detailed method described above, i.e. it does not mean that the present invention must be practiced in dependence upon the detailed method described above. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (8)
1. The antibacterial and antiviral toilet cover is characterized by being prepared from the following components in parts by weight:
the modified antibacterial and antiviral treatment agent is prepared by modifying an inorganic photocatalyst antibacterial agent by an organosilicon release agent;
the organic silicon release agent is selected from one or two of polyorganosiloxane, siloxane compound, methyl silicone resin and methyl phenyl silicone resin;
the preparation method of the antibacterial and antiviral toilet cover is characterized by comprising the following steps of:
step (1), putting the modified antibacterial antiviral agent and the resin material into a high-speed stirrer, stirring at a high speed for 5-10min at 95-115 ℃, and pre-dispersing uniformly;
and (2) adding the flame-retardant filler, the antioxidant and the dispersing agent into the material which is pre-dispersed uniformly in the step (1), continuously stirring for 10-30min to obtain a pre-mixed material, then carrying out melt mixing on the pre-mixed material in a double-screw extruder, injecting the mixture into a die cavity, and opening the die after cooling and taking out.
2. The antibacterial and antiviral toilet lid according to claim 1, wherein the inorganic photocatalyst antibacterial agent is one or more selected from the group consisting of nano titanium dioxide, nano zinc oxide, nano silicon oxide, nano bismuth tungstate and nano bismuth molybdate.
3. The antibacterial and antiviral toilet lid according to claim 1, wherein the process for modifying the inorganic photocatalyst antibacterial agent by the organic silicon comprises the following steps:
step 1, vacuum drying inorganic photocatalyst powder in an oven at 60-100 ℃ for 4-6 hours, and cooling for standby;
step 2, preparing an ethanol solution according to 3-8wt%, adding the inorganic photocatalyst powder subjected to the drying treatment in the step 1 into the ethanol solution according to the amount of 50-80wt%, uniformly dispersing the mixed solution by high-speed shearing of a high-speed emulsifying machine, and vibrating for 20-50min by using an ultrasonic vibration instrument to uniformly disperse the solution;
step 3, adding an organosilicon release agent into the solution uniformly dispersed in the step 2 according to the amount of 2-5 wt%, and then carrying out reflux reaction for 2-4h at 50-80 ℃;
and 4, after the reflux reaction is finished, centrifuging the reaction solution to obtain a precipitate, washing the obtained precipitate with absolute ethyl alcohol for 3-6 times, and then drying in vacuum at 50-80 ℃ to obtain the organosilicon modified photocatalyst, namely the modified antibacterial and antiviral treatment agent.
4. The antibacterial and antiviral toilet lid according to claim 1, wherein the resin material comprises one or more of urea formaldehyde resin, acryl resin, PP resin, PVC resin, and ABS resin.
5. The antibacterial and antiviral toilet lid according to claim 1, wherein the flame-retardant filler comprises one or more of aluminium hydroxide, magnesium hydroxide, calcium carbonate, silica, zinc oxide.
6. The antibacterial and antiviral toilet lid according to claim 1, wherein the dispersant comprises one or more of ethylene bis stearamide, glyceryl monostearate, oleamide, barium stearate, polyethylene wax and polypropylene wax.
7. An antibacterial and antiviral toilet lid according to claim 1 wherein the antioxidant comprises one or two of pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], N-stearyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, N-diphenyl-p-phenylenediamine, di-tert-butyl-methylphenol, dilauryl thiodipropionate, bis (octadecyl) pentaerythritol diphosphite.
8. A method for preparing an antibacterial and antiviral toilet cover according to any one of claims 1 to 7, comprising the following steps:
step (1), putting the modified antibacterial antiviral agent and the resin material into a high-speed stirrer, stirring at a high speed for 5-10min at 95-115 ℃, and pre-dispersing uniformly;
and (2) adding the flame-retardant filler, the antioxidant and the dispersing agent into the material which is pre-dispersed uniformly in the step (1), continuously stirring for 10-30min to obtain a pre-mixed material, then carrying out melt mixing on the pre-mixed material in a double-screw extruder, injecting the mixture into a die cavity, and opening the die after cooling and taking out.
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