CN111423696A

CN111423696A - Antibacterial and antiviral toilet lid and preparation method thereof

Info

Publication number: CN111423696A
Application number: CN202010311899.4A
Authority: CN
Inventors: 陈广川; 于红光; 孙小娟
Original assignee: Tongxi Group Co ltd
Current assignee: Tongxi Group Co ltd
Priority date: 2020-04-20
Filing date: 2020-04-20
Publication date: 2020-07-17
Anticipated expiration: 2040-04-20
Also published as: CN111423696B

Abstract

The invention relates to an antibacterial and antiviral toilet lid and a preparation method thereof, wherein the antibacterial and antiviral toilet lid 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 dispersant, 1.0-2.0 parts of antioxidant and 0.5-1.0 part of modified antibacterial and antiviral treating agent; the modified antibacterial and antiviral treating agent is organic silicon modified photocatalyst, and the organic silicon modified photocatalyst is obtained by modifying an inorganic photocatalyst antibacterial agent with an organic silicon release agent. In addition, a preparation method thereof 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

Antibacterial and antiviral toilet lid and preparation method thereof

Technical Field

The invention belongs to the field of bathrooms, and particularly relates to an antibacterial and antiviral toilet lid and a preparation method thereof.

Background

The closestool is closely related to the life of people and brings great convenience to people, but various tiny microorganisms which cannot be seen by naked eyes often exist on the closestool cover and the gasket particularly in public areas due to the influence of the use environment of the closestool. According to the survey findings of relevant public health authorities: 32% of the toilet cover and the toilet cushion are provided with dysentery bacillus, and some of the dysentery bacillus can even survive on the toilet cushion for 17 days; when the closestool is flushed, germs can be carried to the air with the height of 6 meters at the highest by the instant cyclone in the closestool and suspended for several hours, and then the germs fall on the wall of a toilet, a toothbrush, a tooth mug and a towel, so that the germs and the viruses are polluted, and particularly when a person is ill in a family, the number of the germs is increased by hundreds, and the health of the person is seriously harmed. Therefore, the development of a toilet lid with antibacterial and antiviral functions is urgently needed, and on one hand, bacteria and viruses brought out by instant cyclone when a toilet is flushed can be killed through the toilet lid; on the other hand, bacteria and viruses in the toilet which are contacted with the toilet can be killed through 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 method of the antibacterial toilet lid mainly comprises two methods, wherein the first method is to spray an antibacterial agent on the surface of the toilet lid, and then bake the surface of the toilet lid at a high temperature of 200-.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provides an antibacterial and antiviral toilet lid and a preparation method thereof, which greatly reduce the dosage of an antibacterial agent on the premise of ensuring the antibacterial, antiviral and anti-mite effects of the toilet lid.

In order to achieve the purpose, the technical scheme adopted by the invention is as follows:

the first technical scheme is as follows:

an antibacterial and antiviral toilet lid is prepared from the following components in parts by weight:

the modified antibacterial and antiviral treating agent is organic silicon modified photocatalyst, and the organic silicon modified photocatalyst is obtained by modifying an inorganic photocatalyst antibacterial agent with an organic silicon release agent.

Further, the inorganic photocatalyst antibacterial agent is selected from one or more of 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 polysiloxane, siloxane compound, silicone oil, methyl silicone resin and methyl phenyl silicone resin.

Further, the process for modifying the inorganic photocatalyst antibacterial agent by using the organic silicon specifically comprises the following steps:

step 1, drying inorganic photocatalyst powder in an oven at 60-100 ℃ for 4-6 hours in vacuum, and cooling for later use;

step 2, preparing an ethanol solution according to 3-8 wt%, adding the dried inorganic photothyrophosis powder obtained in the step 1 into the ethanol solution according to the amount of 50-80 wt%, uniformly dispersing the mixed solution by high-speed shearing of a high-speed emulsifying machine, and vibrating for 20-50min by an ultrasonic oscillator to uniformly disperse the solution;

step 3, adding an organic silicon release agent into the uniformly dispersed solution obtained in the step 2 according to the amount of 2-5 wt%, and then carrying out reflux reaction at 50-80 ℃ for 2-4 h;

and 4, after the reflux reaction is finished, centrifuging the reaction solution to obtain a precipitate, cleaning the precipitate for 3-6 times by using absolute ethyl alcohol, and drying in vacuum at 50-80 ℃ to obtain the organic silicon modified photocatalyst, namely the modified antibacterial and antiviral treating agent.

Furthermore, the resin material comprises one or more of urea-formaldehyde 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-based bis-stearamide, stearic acid monoglyceride, oleamide, barium stearate, polyethylene wax and polypropylene wax.

Further, the antioxidant comprises one or two of pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (antioxidant 1010), N-octadecyl β - (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:

a preparation method of an antibacterial and antiviral toilet lid specifically comprises the following steps:

putting the modified antibacterial antiviral agent and the resin material into a high-speed stirrer, and stirring at a high speed of 95-115 ℃ for 5-10min to obtain uniform pre-dispersion;

and (2) adding the flame-retardant filler, the antioxidant and the dispersing agent into the uniformly pre-dispersed material obtained in the step (1), continuously stirring for 10-30min to obtain a premixed material, then melting and mixing the premixed material in a double-screw extruder, injecting the premixed material into a mold cavity, cooling, opening the mold, and taking out the mold.

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 material for preparing the toilet lid, so that the toilet lid has antibacterial and antiviral effects, and not only can bacteria and viruses brought out by instant cyclone when a toilet is flushed be killed; on the other hand, bacteria and viruses in the toilet which are contacted with the toilet can be killed through 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 organosilicon release agent can be separated out from the inside in the cooling process of resin and is uniformly distributed on the surface of the toilet lid, so that a lubricating layer is formed on the surface of the toilet lid, so that a resin material cannot be adhered to a mold, and the demolding is convenient; the modified antibacterial and antiviral treatment agent has lower specific surface energy, and not only can enable the inorganic photocatalyst nanoparticles to have better dispersibility under the high-temperature melting condition, but also can improve the dispersion effect; under the action of chemical bonds between the inorganic photocatalyst nano particles and the organic silicon release agent, the inorganic photocatalyst nano particles can rapidly migrate to the surface of the toilet lid along with the seepage of the organic silicon release agent in the process of low-temperature cooling of resin, so that a lubricating layer with an inorganic photocatalyst antibacterial agent is formed on the surface of the toilet lid, the antibacterial agent is concentrated on the surface of the toilet lid but not in the interior of the material of the toilet lid, and compared with the traditional production process of simply mixing the antibacterial agent into the resin raw material, the concentration of the antibacterial agent and the antiviral agent on the surface of a product is increased under the same antibacterial agent dosage, so that the antibacterial and antiviral efficiency of the product is further improved; under the condition that the toilet lid has the same antibacterial and antiviral effects, the using amount of the antibacterial and antiviral treating agent is greatly reduced, and in addition, the problem of accelerated aging of the toilet lid caused by high-temperature baking is also avoided.

3. According to the invention, the inorganic photocatalyst is modified by the organic silicon through a reflux method, and the modification rate is greatly improved by strictly controlling the modification parameters, so that after the modified antibacterial and antiviral agent is doped into the preparation raw material of the toilet lid, the inorganic photocatalyst nano particles can migrate to the surface of the toilet lid under the action of the organic silicon release agent, and a temperature antibacterial agent film layer is formed on the surface of the toilet lid.

Detailed Description

The present invention will be described in further detail with reference to examples.

Example 1

A first part:

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 using the organic silicon release agent is as follows:

step 1, drying inorganic photocatalyst powder in an oven at 80 ℃ for 4 hours in vacuum, and cooling for later use;

step 2, preparing an ethanol solution according to 7 wt%, adding the dried inorganic photottouch mildew powder obtained in the step 1 into the ethanol solution according to 80 wt%, uniformly dispersing the mixed solution by high-speed shearing of a high-speed emulsifying machine, and vibrating for 30min by an ultrasonic oscillator to uniformly disperse the solution;

step 3, adding an organic silicon release agent methyl phenyl silicone resin into the uniformly dispersed solution obtained in the step 2 according to the amount of 5 wt%, and then carrying out reflux reaction at 60 ℃ for 3 hours;

and 4, after the reflux reaction is finished, centrifuging the reaction solution to obtain a precipitate, cleaning the precipitate for 5 times by using absolute ethyl alcohol, and drying in vacuum at 75 ℃ to obtain the organic silicon modified photocatalyst, namely the modified antibacterial and antiviral treating agent.

A second part:

putting the modified antibacterial antiviral agent and the resin material into a high-speed stirrer, and stirring at a high speed of 100 ℃ for 5min to pre-disperse uniformly;

and (2) adding the flame-retardant filler, the antioxidant and the dispersing agent into the uniformly pre-dispersed material obtained in the step (1), continuously stirring for 15min to obtain a premixed material, then melting and mixing the premixed material in a double-screw extruder at 150 ℃, injecting the premixed material into a mold cavity, cooling, opening the mold, and taking out.

Example 2

A first part:

the organic silicon modified photocatalyst is obtained by modifying inorganic photocatalyst antibacterial agent nano bismuth tungstate by an organic silicon release agent siloxane compound,

step 1, drying inorganic photocatalyst powder in a 75 ℃ oven for 5 hours in vacuum, and cooling for later use;

step 2, preparing an ethanol solution according to 5 wt%, adding the dried inorganic photocatalyst powder obtained in the step 1 into the ethanol solution according to 75 wt%, uniformly dispersing the mixed solution by high-speed shearing of a high-speed emulsifying machine, and vibrating for 35min by an ultrasonic oscillator to uniformly disperse the solution;

step 3, adding an organic silicon release agent siloxane compound into the uniformly dispersed solution obtained in the step 2 according to the amount of 4 wt%, 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, cleaning the precipitate for 4 times by using absolute ethyl alcohol, and drying in vacuum at 65 ℃ to obtain the organic silicon modified photocatalyst, namely the modified antibacterial and antiviral treating agent.

A second part:

putting the modified antibacterial antiviral agent and the resin material into a high-speed stirrer, and stirring at a high speed of 95 ℃ for 8min to obtain uniform pre-dispersion;

and (2) adding the flame-retardant filler, the antioxidant and the dispersing agent into the uniformly pre-dispersed material obtained in the step (1), continuously stirring for 20min to obtain a premixed material, then melting and mixing the premixed material in a double-screw extruder at 190 ℃, injecting the premixed material into a mold cavity, cooling, opening the mold, and taking out.

Example 3

A first part:

the organic silicon modified photocatalyst is obtained by modifying inorganic photocatalyst antibacterial agent nano silicon oxide with organic silicon release agent polyorganosiloxane,

step 1, drying inorganic photocatalyst powder in a 65 ℃ oven for 6 hours in vacuum, and cooling for later use;

step 2, preparing an ethanol solution according to 6 wt%, adding the dried inorganic photottouch mildew powder obtained in the step 1 into the ethanol solution according to 76 wt%, uniformly dispersing the mixed solution by high-speed shearing of a high-speed emulsifying machine, and vibrating for 25min by an ultrasonic oscillator to uniformly disperse the solution;

step 3, adding organic silicon release agent polyorganosiloxane into the uniformly dispersed solution in the step 2 according to the amount of 5 wt%, and then carrying out reflux reaction for 4 hours at 55 ℃;

and 4, after the reflux reaction is finished, centrifuging the reaction solution to obtain a precipitate, cleaning the precipitate for 3 times by using absolute ethyl alcohol, and drying in vacuum at 75 ℃ to obtain the organic silicon modified photocatalyst, namely the modified antibacterial and antiviral treating agent.

A second part:

putting the modified antibacterial antiviral agent and the resin material into a high-speed stirrer, and stirring at a high speed of 110 ℃ for 10min to obtain uniform pre-dispersion;

and (2) adding the flame-retardant filler, the antioxidant and the dispersing agent into the uniformly pre-dispersed material obtained in the step (1), continuously stirring for 20min to obtain a premixed material, then melting and mixing the premixed material in a double-screw extruder at 210 ℃, injecting the premixed material into a mold cavity, cooling, opening the mold, and taking out.

Example 4

A first part:

the organic silicon modified photocatalyst is obtained by modifying inorganic photocatalyst antibacterial agent nano zinc oxide with organic silicon release agent methyl silicone resin,

step 1, drying inorganic photocatalyst powder in an oven at 70 ℃ for 5 hours in vacuum, and cooling for later use;

step 2, preparing an ethanol solution according to 8 wt%, adding the dried inorganic photottouch mildew powder obtained in the step 1 into the ethanol solution according to 69 wt%, uniformly dispersing the mixed solution by high-speed shearing of a high-speed emulsifying machine, and vibrating for 20min by an ultrasonic oscillator to uniformly disperse the solution;

step 3, adding organosilicon release agent methyl silicone resin into the uniformly dispersed solution in the step 2 according to the amount of 4 wt%, and then carrying out reflux reaction for 3 hours at 65 ℃;

and 4, after the reflux reaction is finished, centrifuging the reaction solution to obtain a precipitate, cleaning the precipitate for 3 times by using absolute ethyl alcohol, and drying in vacuum at 60 ℃ to obtain the organic silicon modified photocatalyst, namely the modified antibacterial and antiviral treating agent.

A second part:

putting the modified antibacterial antiviral agent and the resin material into a high-speed stirrer, and stirring at a high speed of 115 ℃ for 6min to pre-disperse uniformly;

and (2) adding the flame-retardant filler, the antioxidant and the dispersing agent into the uniformly pre-dispersed material obtained in the step (1), continuously stirring for 25min to obtain a premixed material, then melting and mixing the premixed material in a double-screw extruder at 160 ℃, injecting the premixed material into a mold cavity, cooling, opening the mold, and taking out.

Example 5

A first part:

the organic silicon modified photocatalyst is obtained by modifying inorganic photocatalyst antibacterial agent nano bismuth molybdate with organic silicon release agent emulsified silicone oil,

step 1, drying inorganic photocatalyst powder in an oven at 85 ℃ for 4 hours in vacuum, and cooling for later use;

step 2, preparing an ethanol solution according to 7 wt%, adding the dried inorganic photottouch mildew powder obtained in the step 1 into the ethanol solution according to 76 wt%, uniformly dispersing the mixed solution by high-speed shearing of a high-speed emulsifying machine, and vibrating for 25min by an ultrasonic oscillator to uniformly disperse the solution;

step 3, adding 2 wt% of organosilicon release agent emulsified silicone oil into the uniformly dispersed solution in the step 2, and then carrying out reflux reaction at 70 ℃ for 2 hours;

and 4, after the reflux reaction is finished, centrifuging the reaction solution to obtain a precipitate, cleaning the obtained precipitate for 4 times by using absolute ethyl alcohol, and drying in vacuum at 70 ℃ to obtain the organic silicon modified photocatalyst, namely the modified antibacterial and antiviral treating agent.

A second part:

and (2) adding the flame-retardant filler, the antioxidant and the dispersing agent into the uniformly pre-dispersed material obtained in the step (1), continuously stirring for 25min to obtain a premixed material, then melting and mixing the premixed material in a double-screw extruder at 240 ℃, injecting the premixed material into a mold cavity, cooling, opening the mold, and taking out.

Comparative example 1

the dosage of the organic silicon release agent methyl phenyl silicone resin and the inorganic photocatalyst antibacterial agent nano titanium dioxide in the comparative example is the same as that of the example 1.

putting an inorganic photocatalyst, an organic silicon release agent and a resin material into a high-speed stirrer, and stirring at a high speed of 100 ℃ for 5min to obtain uniform pre-dispersion;

Comparative example 2

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.

A preparation method of an antibacterial and antiviral toilet lid specifically comprises the following steps: same as in comparative example 1.

Comparative example 3

A first part:

same as in example 2.

step 1, drying inorganic photocatalyst powder in a 45 ℃ oven for 8 hours in vacuum, and cooling for later use;

step 2, preparing an ethanol solution according to 9 wt%, adding the dried inorganic photocatalyst powder obtained in the step 1 into the ethanol solution according to 75 wt%, uniformly dispersing the mixed solution by high-speed shearing of a high-speed emulsifying machine, and vibrating for 10min by an ultrasonic oscillator to uniformly disperse the solution;

step 3, adding an organic silicon release agent siloxane compound into the uniformly dispersed solution obtained in the step 2 according to the amount of 4 wt%, and then carrying out reflux reaction at 40 ℃ for 6 hours;

A second part:

a preparation method of an antibacterial and antiviral toilet lid specifically comprises the following steps: same as in example 2.

Comparative example 4

A first part:

same as in example 2.

step 1, drying inorganic photocatalyst powder in a 120 ℃ oven for 2 hours in vacuum, and cooling for later use;

step 2, preparing an ethanol solution according to 2 wt%, adding the dried inorganic photottouch mildew powder obtained in the step 1 into the ethanol solution according to 75 wt%, uniformly dispersing the mixed solution by high-speed shearing of a high-speed emulsifying machine, and vibrating for 15min by an ultrasonic oscillator to uniformly disperse the solution;

step 3, adding organic silicon release agent polyorganosiloxane into the uniformly dispersed solution obtained in the step 2 according to the amount of 4 wt%, and then carrying out reflux reaction at 85 ℃ for 5 hours;

A second part:

Effect test

The toilet lids prepared in the examples and the comparative examples were respectively subjected to antibacterial, antiviral and antifungal tests as follows, and the results are shown in table 1;

antiviral testing: the antiviral activity rates of H1N1 and H3N2 were determined for the products obtained in each example and comparative example according to the ISO21702-2019 test for antiviral activity on plastics and other non-porous surfaces.

And (3) antibacterial testing: antibacterial detection is carried out on the products obtained in each example and comparative example according to the standard of GB/T31402-2015 plastic surface antibacterial property test method.

And (3) mildew resistance test: according to the GB/T24128-2009 plastic mildew resistance test method, the mildew resistance test is carried out on the products obtained in each example and comparative example.

Experimental strains: aspergillus niger AS3.315, Aureobasidium pullulans AS3.837, Penicillium funiculosum AS3.3875, Chaetomium globosum AS3.3601, Gliocladium virens AS 3.3987.

Remarking: according to the determination of GB/T24128-2009 plastic mildew resistance test method, the growth of the mold observed on the surface of the sample is evaluated as follows:

0-no growth

1-Trace growth (microscopic observation, mold growth area < 10%)

2-little growth (area of mold growth is more than or equal to 10% and less than 30%)

3-moderate growth (mold growth area is more than or equal to 30% and less than 60%)

4-severe growth (area of mold growth is more than or equal to 60% and less than or equal to 100%)

TABLE 1

The data in the table show that: the toilet lid 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 grade is 0; and has good quick-acting effect on influenza virus, and the antiviral activity rate reaches over 99 percent. In the comparative example 1, since the inorganic photocatalyst and the organic silicon release agent are added as separate components rather than being added after modification, the antibacterial component of the inorganic photocatalyst is uniformly dispersed in the toilet lid material, so that in the case of using the same photocatalyst antibacterial agent and the amount thereof as those in the example 1, the amount of the photocatalyst on the surface of the toilet lid is extremely small, and thus the antibacterial, antiviral and antifungal effects of the toilet lid product are poor, and in the comparative example 2, when the amount of the photocatalyst is increased from 0.8 parts to 3 parts, the enough amount of the photocatalyst component can be present on the surface of the prepared toilet lid, and thus the antibacterial, antiviral and antifungal effects equivalent to those in the example 1 are achieved. In comparative examples 3 and 4, when the raw materials and the amounts thereof are the same as those in example 2, the modification rate of the antibacterial agent is 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, so that the antibacterial, antiviral and antifungal effects of the prepared toilet lid product are remarkably deteriorated.

The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims

1. An antibacterial and antiviral toilet lid is characterized by being prepared from the following components in parts by weight:

2. The antibacterial and antiviral toilet lid according to claim 1, wherein 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;

3. The antibacterial and antiviral toilet lid as claimed in claim 1, wherein the process of modifying the inorganic photocatalyst antibacterial agent by the organic silicon specifically comprises the following steps:

4. The toilet lid with antibacterial and antiviral effects as claimed in claim 1, wherein the resin material comprises one or more of urea-formaldehyde resin, acrylic 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 aluminum hydroxide, magnesium hydroxide, calcium carbonate, silica, and zinc oxide.

6. The antibacterial and antiviral toilet lid according to claim 1, wherein the dispersant comprises one or more of ethylene bis stearamide, stearic acid monoglyceride, oleamide, barium stearate, polyethylene wax, polypropylene wax.

7. The 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-octadecyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, N-diphenyl-p-phenylenediamine, di-tert-butyl-methylphenol, dilauryl thiodipropionate, and bis (octadecyl) pentaerythritol diphosphite.

8. The preparation method of the antibacterial and antiviral toilet lid as claimed in any one of claims 1 to 7, comprising the following steps: