CN113773569B - Antibacterial bath ball and preparation method thereof - Google Patents
Antibacterial bath ball and preparation method thereof Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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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
- A47K7/00—Body washing or cleaning implements
- A47K7/02—Bathing sponges, brushes, gloves, or similar cleaning or rubbing implements
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- C08K2003/2241—Titanium dioxide
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Abstract
The invention relates to the technical field of bath product production, in particular to an antibacterial bath ball and a preparation method thereof; the antibacterial bath ball consists of 93 to 95 weight percent: 4 to 6:0.07 to 0.1 of low-density polyethylene, low-density polyethylene antibacterial master batch and PE toner; the low-density polyethylene antibacterial master batch comprises the following raw materials in parts by weight: 93 to 97 parts of low-density high-pressure polyethylene, 2.5 to 3.6 parts of high-efficiency antibacterial agent, 2.0 to 4.0 parts of nano zinc oxide and 3.2 to 4.5 parts of silver-loaded antibacterial agent; the antibacterial bath ball prepared by the invention not only has good antibacterial and bacteriostatic properties, but also has good ageing resistance, so that the service life of the antibacterial bath ball is effectively prolonged, and the quality of the antibacterial bath ball is ensured; meanwhile, the prepared bath ball also has the advantages of safety, innocuity and difficult fading.
Description
Technical Field
The invention relates to the technical field of bath product production, in particular to an antibacterial bath ball and a preparation method thereof.
Background
Bath balls are also called bath balls and bath flowers, and the English name is bat or bat. When steaming or bathing, the bath cream is put on the bath ball to foam and lightly wipe the skin to generate a large amount of foam, and Polyethylene (PE) is generally used as a raw material. The bath ball is often needed to be used in bath, a small amount of bath cream is squeezed on the bath ball during bath, then a small amount of water is added, and the bath ball is gently rubbed to generate a large amount of foam immediately.
However, since the bath ball is often contacted with water, the surface of the bath ball can generate peculiar smell due to the breeding of microorganisms for a long time and even erode the structure of the bath ball, thereby influencing the service life and quality of the bath ball. Furthermore, aging phenomena of different degrees can appear after the bath ball produced by the prior art is used for a long time, and the service life of the bath ball is affected to a certain extent. Therefore, providing an antibacterial bath ball and a preparation method thereof becomes a technical problem to be solved urgently by those skilled in the art.
Disclosure of Invention
The invention aims to provide an antibacterial bath ball and a preparation method thereof, and the prepared antibacterial bath ball not only has good antibacterial and bacteriostatic properties, but also has good ageing resistance, so that the service life of the antibacterial bath ball is effectively prolonged, and the quality of the antibacterial bath ball is ensured; meanwhile, the prepared bath ball also has the advantages of safety, innocuity and difficult fading.
In order to achieve the above purpose, the present invention provides the following technical solutions:
an antibacterial bath ball comprises the following components in percentage by weight: 4 to 6:0.07 to 0.1 of low-density polyethylene, low-density polyethylene antibacterial master batch and PE toner; the low-density polyethylene antibacterial master batch comprises the following raw materials in parts by weight: 93 to 97 portions of low-density high-pressure polyethylene, 2.5 to 3.6 portions of high-efficiency antibacterial agent, 2.0 to 4.0 portions of nano zinc oxide and 3.2 to 4.5 portions of silver-carrying antibacterial agent.
Further, the preparation method of the efficient antibacterial agent comprises the following steps:
1. modification of the inorganic porous substrate;
according to the solid-liquid ratio of 0.06-0.1 g/mL, the inorganic porous substrate is put into the mixed solvent; under the condition of ultrasonic dispersion, adding a silane coupling agent with the mass of 8-15% of the inorganic porous substrate into the mixed solvent; dispersing for 30-40 min by ultrasonic; then reacting for 3-5 h under the stirring condition; after the reaction is finished, filtering, washing and drying the obtained generated product in sequence; the obtained solid powder is preserved for standby;
2. preparing a high-efficiency antibacterial agent;
adding solid powder into proper amount of ethanol according to the solid-liquid ratio of 0.08-0.15 g/mL, and then adding 2, 6-dimethyl-2, 6-octadienal with the mass of 10-20% of that of the solid powder into the ethanol under the stirring condition; and the mixture is stirred and reacts for 5 to 8 hours at the temperature of 30 to 50 ℃; and after the reaction is finished, sequentially filtering, washing and drying to obtain the solid powder which is the finished product of the efficient antibacterial agent.
Further, the preparation method of the inorganic porous substrate comprises the following steps:
weighing a proper amount of tetrabutyl titanate, dripping the tetrabutyl titanate into ethanol with the volume of 4-6 times of that of the tetrabutyl titanate, uniformly dispersing the tetrabutyl titanate by ultrasonic waves, slowly dripping the obtained mixed component into deionized water with the volume of 20-30 times of that of the tetrabutyl titanate, mixing and stirring for 30-40 min, and fully hydrolyzing the tetrabutyl titanate;
ii, after tetrabutyl titanate is completely hydrolyzed, the obtained mixed solution is transferred into reaction equipment after being washed by ethanol, a proper amount of ethanol is added to enable the volume of the mixed solution to be 65-75% of that of a reaction kettle, ammonium bicarbonate with the dosage of 2-3% of deionized water is added into the reaction kettle, after being uniformly mixed and stirred, the temperature of the reaction kettle is set to 170-190 ℃, and the reaction is carried out for 40-50 hours under the temperature;
iii, naturally cooling the generated liquid in the reaction kettle to room temperature after the reaction is finished; then the generated liquid is respectively washed for 2 to 3 times by deionized water and ethanol; and then placing the obtained solid matter into a drying oven for drying treatment, wherein the obtained solid matter is the inorganic porous substrate finished product.
Further, the mixed solvent consists of 40-60% ethanol water solution, 8-15% dodecyl trimethyl ammonium chloride, 15-20% 2-hydroxy-4-methoxybenzophenone-5-sodium sulfonate and 2.5-3.8% surfactant.
Further, the surfactant is selected from any one of octyl phenol polyoxyethylene ether and nonylphenol polyoxyethylene ether.
Further, the silane coupling agent is selected from any one of 3-aminopropyl triethoxysilane and 3-aminopropyl trimethoxysilane.
Further, the average particle diameter of the prepared inorganic porous substrate is 150-165 nm, and the pore diameter of the surface micropores is 4-6 nm.
Further, the preparation method of the silver-loaded antibacterial agent comprises the following steps: mixing shell powder with the particle size of 20-50 nm and distilled water with the mass of 8-12 times of the shell powder, and uniformly stirring to form turbid suspension electrolyte; then, silver is taken as an anode to carry out electrolysis in electrolyte so as to dissolve and separate silver ions out of the anode silver, and after the electrolysis is finished, the anode silver is sequentially filtered, separated and dried; then carrying out heat treatment on the obtained solid powder for 3-13 h in nitrogen atmosphere at the temperature of 350-650 ℃; and (3) heating and decomposing the silver oxide and the silver hydroxide adsorbed on the surface of the powder material into elemental silver, naturally cooling the elemental silver to room temperature, and obtaining solid powder which is a finished product of the silver-carrying antibacterial agent.
Further, the anode current density in the electrolytic process is 50-10000A/m 2 The electrolysis time is set to 10-60 min.
The preparation method of the antibacterial bath ball comprises the following steps:
firstly, accurately weighing the raw materials, and then uniformly mixing and stirring the low-density polyethylene, the low-density polyethylene antibacterial master batch and the PE toner at the rotating speed of 180-230 r/min, wherein the obtained mixture is marked as a mixed material;
II, melt blending the mixed material obtained in the step I, and extruding the melt blended mixed material at 220-250 ℃ to obtain a net-shaped semi-finished product;
III, cooling, traction, draining, secondary traction and rolling the obtained net-shaped semi-finished product; and then sequentially cutting and embossing the stretched semi-finished product to obtain the antibacterial bath ball finished product.
Compared with the prior art, the invention has the beneficial effects that:
the invention takes tetrabutyl titanate, ammonium bicarbonate and the like as raw materials for preparing the inorganic porous substrate, and finally prepares the inorganic porous substrate with a hollow porous structure and a larger specific surface area. Then, the inorganic porous substrate is put into an ethanol water solution containing dodecyl trimethyl ammonium chloride, 2-hydroxy-4-methoxybenzophenone-5-sodium sulfonate and a surfactant, and the dodecyl trimethyl ammonium chloride and the 2-hydroxy-4-methoxybenzophenone-5-sodium sulfonate are fully dispersed on the surface, the inner wall and the pores of the inorganic porous substrate through ultrasonic dispersion. And then carrying out chemical modification on the inorganic porous substrate through the silane coupling agent, so that the silane coupling agent is connected with the inorganic porous substrate through chemical bonds. And the modified inorganic porous substrate and 2, 6-dimethyl-2, 6-octadienal undergo a grafting reaction, and finally the 2, 6-dimethyl-2, 6-octadienal is successfully grafted on the surface, the inner wall and the pores of the inorganic porous substrate. Under the dual actions of a silane coupling agent and 2, 6-dimethyl-2, 6-octadienal, dodecyl trimethyl ammonium chloride and 2-hydroxy-4-methoxybenzophenone-5-sodium sulfonate are effectively locked on the surface and the inner wall of an inorganic porous substrate.
The prepared efficient antibacterial agent contains a certain amount of dodecyl trimethyl ammonium chloride and 2, 6-dimethyl-2, 6-octadienal, and the two are mutually cooperated with the silver-loaded antibacterial agent, so that the prepared efficient antibacterial agent has good antibacterial performance. In addition, the high-efficiency antibacterial agent is made of nano titanium dioxide, and can be mutually cooperated with 2-hydroxy-4-methoxyl benzophenone-5-sodium sulfonate and nano zinc oxide, so that the prepared high-efficiency antibacterial agent has good ultraviolet resistance and ageing resistance, and the service life of the prepared antibacterial bath ball is prolonged to a certain extent.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
An antibacterial bath ball comprises the following components in percentage by weight: 6:0.07 of low-density polyethylene, low-density polyethylene antibacterial master batch and PE toner; the low-density polyethylene antibacterial master batch consists of the following raw materials in parts by weight: 93 parts of low-density high-pressure polyethylene, 2.5 parts of high-efficiency antibacterial agent, 2.0 parts of nano zinc oxide and 3.2 parts of silver-loaded antibacterial agent.
The preparation method of the efficient antibacterial agent comprises the following steps:
1. modification of the inorganic porous substrate;
adding the inorganic porous substrate into the mixed solvent according to the solid-to-liquid ratio of 0.06 g/mL; under the condition of ultrasonic dispersion, adding a silane coupling agent with the mass of 8% of the inorganic porous substrate into the mixed solvent; dispersing for 30min by ultrasonic; then reacting for 3h under stirring; after the reaction is finished, filtering, washing and drying the obtained generated product in sequence; the obtained solid powder is preserved for standby;
2. preparing a high-efficiency antibacterial agent;
adding the solid powder into a proper amount of ethanol according to the solid-to-liquid ratio of 0.08g/mL, and then adding 2, 6-dimethyl-2, 6-octadienal with the mass accounting for 10% of the solid powder into the ethanol under the stirring condition; and the mixture is stirred and reacts for 5 hours at the temperature of 30 ℃; and after the reaction is finished, sequentially filtering, washing and drying to obtain the solid powder which is the finished product of the efficient antibacterial agent.
The preparation method of the inorganic porous substrate comprises the following steps:
weighing a proper amount of tetrabutyl titanate, dripping the tetrabutyl titanate into ethanol with the volume of 4 times of that of the tetrabutyl titanate, uniformly dispersing the tetrabutyl titanate by ultrasonic waves, slowly dripping the obtained mixed component into deionized water with the volume of 20 times of that of the tetrabutyl titanate, mixing and stirring for 30min, and fully hydrolyzing the tetrabutyl titanate;
ii, after tetrabutyl titanate is completely hydrolyzed, the obtained mixed solution is transferred into reaction equipment after being washed by ethanol, a proper amount of ethanol is added to enable the volume of the mixed solution to be 65 percent of that of a reaction kettle, ammonium bicarbonate with the dosage of 2 percent of deionized water is added into the reaction kettle, after the mixed solution is uniformly mixed and stirred, the temperature of the reaction kettle is set to 170 ℃, and the reaction is carried out for 40 hours under the temperature;
iii, naturally cooling the generated liquid in the reaction kettle to room temperature after the reaction is finished; then the generated liquid is respectively washed for 2 times by deionized water and ethanol; and then placing the obtained solid matter into a drying oven for drying treatment, wherein the obtained solid matter is the inorganic porous substrate finished product.
The mixed solvent consists of 40% ethanol water solution, 8% dodecyl trimethyl ammonium chloride, 15% 2-hydroxy-4-methoxybenzophenone-5-sodium sulfonate and 2.5% surfactant.
The surfactant is selected from octyl phenol polyoxyethylene ether.
The silane coupling agent is 3-aminopropyl triethoxy silane.
The average particle diameter of the prepared inorganic porous substrate is 150nm, and the pore diameter of the surface micropores is 4nm.
The preparation method of the silver-loaded antibacterial agent comprises the following steps: mixing shell powder with the particle size of 20nm and distilled water with the mass of 8 times of the shell powder, and uniformly stirring to form turbid suspension electrolyte; then, silver is taken as an anode to carry out electrolysis in electrolyte so as to dissolve and separate silver ions out of the anode silver, and after the electrolysis is finished, the anode silver is sequentially filtered, separated and dried; then carrying out heat treatment on the obtained solid powder for 3 hours in a nitrogen atmosphere at the temperature of 350 ℃; and (3) heating and decomposing the silver oxide and the silver hydroxide adsorbed on the surface of the powder material into elemental silver, naturally cooling the elemental silver to room temperature, and obtaining solid powder which is a finished product of the silver-carrying antibacterial agent.
The anode current density in the electrolysis process is 50A/m 2 The electrolysis time was set to 60min.
The preparation method of the antibacterial bath ball comprises the following steps:
firstly, accurately weighing all raw materials, and then uniformly mixing and stirring the low-density polyethylene, the low-density polyethylene antibacterial master batch and the PE toner at the rotating speed of 180r/min, wherein the obtained mixture is recorded as a mixed material;
II, melt blending the mixed material obtained in the step I, and extruding the melt blended mixed material at 220 ℃ to obtain a net-shaped semi-finished product;
III, cooling, traction, draining, secondary traction and rolling the obtained net-shaped semi-finished product; and then sequentially cutting and embossing the stretched semi-finished product to obtain the antibacterial bath ball finished product.
Example 2
The main differences between this example and example 1 are that the specific proportions of the raw materials are different, specifically: the antibacterial bath ball comprises the following components in percentage by weight: 5:0.09, low density polyethylene antibacterial master batch and PE toner; the low-density polyethylene antibacterial master batch consists of the following raw materials in parts by weight: 95 parts of low-density high-pressure polyethylene, 3.2 parts of high-efficiency antibacterial agent, 3.0 parts of nano zinc oxide and 4.0 parts of silver-loaded antibacterial agent.
The preparation method of the efficient antibacterial agent comprises the following steps:
1. modification of the inorganic porous substrate;
adding the inorganic porous substrate into the mixed solvent according to the solid-to-liquid ratio of 0.08 g/mL; under the condition of ultrasonic dispersion, adding a silane coupling agent with the mass of 12% of that of the inorganic porous substrate into the mixed solvent; dispersing for 35min by ultrasonic; then reacting for 4 hours under the stirring condition; after the reaction is finished, filtering, washing and drying the obtained generated product in sequence; the obtained solid powder is preserved for standby;
2. preparing a high-efficiency antibacterial agent;
adding solid powder into proper amount of ethanol according to the solid-liquid ratio of 0.12g/mL, and then adding 2, 6-dimethyl-2, 6-octadienal with the mass of 15% of that of the solid powder into the ethanol under the stirring condition; and the mixture is stirred and reacts for 6 hours at the temperature of 40 ℃; and after the reaction is finished, sequentially filtering, washing and drying to obtain the solid powder which is the finished product of the efficient antibacterial agent.
The preparation method of the inorganic porous substrate comprises the following steps:
weighing a proper amount of tetrabutyl titanate, dripping the tetrabutyl titanate into ethanol with the volume of 5 times of that of the tetrabutyl titanate, uniformly dispersing the tetrabutyl titanate by ultrasonic waves, slowly dripping the obtained mixed component into deionized water with the volume of 25 times of that of the tetrabutyl titanate, and mixing and stirring for 35min to fully hydrolyze the tetrabutyl titanate;
ii, after tetrabutyl titanate is completely hydrolyzed, the obtained mixed solution is transferred into reaction equipment after being washed by ethanol, a proper amount of ethanol is added to enable the volume of the mixed solution to be 70 percent of that of a reaction kettle, ammonium bicarbonate with the dosage of 2.5 percent of deionized water is added into the reaction kettle, after the mixed solution is uniformly mixed and stirred, the temperature of the reaction kettle is set to 180 ℃, and the reaction is carried out for 45 hours under the temperature;
iii, naturally cooling the generated liquid in the reaction kettle to room temperature after the reaction is finished; then the generated liquid is respectively washed for 2 times by deionized water and ethanol; and then placing the obtained solid matter into a drying oven for drying treatment, wherein the obtained solid matter is the inorganic porous substrate finished product.
The mixed solvent consists of 45% ethanol water solution, 10% dodecyl trimethyl ammonium chloride, 18% 2-hydroxy-4-methoxybenzophenone-5-sodium sulfonate and 3.0% surfactant.
The surfactant is selected from polyoxyethylene nonylphenol ether.
The silane coupling agent is 3-aminopropyl trimethoxy silane.
The average particle diameter of the prepared inorganic porous substrate is 160nm, and the pore diameter of the surface micropores is 5nm.
The preparation method of the silver-loaded antibacterial agent comprises the following steps: mixing and stirring shell powder with the particle size of 35nm and distilled water with the mass of 10 times of the shell powder uniformly to form turbid suspension electrolyte; then, silver is taken as an anode to carry out electrolysis in electrolyte so as to dissolve and separate silver ions out of the anode silver, and after the electrolysis is finished, the anode silver is sequentially filtered, separated and dried; then carrying out heat treatment on the obtained solid powder for 8 hours in a nitrogen atmosphere at the temperature of 500 ℃; and (3) heating and decomposing the silver oxide and the silver hydroxide adsorbed on the surface of the powder material into elemental silver, naturally cooling the elemental silver to room temperature, and obtaining solid powder which is a finished product of the silver-carrying antibacterial agent.
Anode current density of 5000A/m in electrolysis process 2 The electrolysis time was set to 30min.
Example 3
The main differences between this example and example 1 are that the specific proportions of the raw materials are different, specifically: the antibacterial bath ball comprises the following components in percentage by weight: 4:0.1 of low-density polyethylene, low-density polyethylene antibacterial master batch and PE toner; the low-density polyethylene antibacterial master batch consists of the following raw materials in parts by weight: 97 parts of low-density high-pressure polyethylene, 3.6 parts of high-efficiency antibacterial agent, 4.0 parts of nano zinc oxide and 4.5 parts of silver-loaded antibacterial agent.
The preparation method of the efficient antibacterial agent comprises the following steps:
1. modification of the inorganic porous substrate;
adding the inorganic porous substrate into the mixed solvent according to the solid-to-liquid ratio of 0.1 g/mL; under the condition of ultrasonic dispersion, adding a silane coupling agent with the mass of 15% of that of the inorganic porous substrate into the mixed solvent; dispersing for 40min by ultrasonic; then reacting for 5h under stirring; after the reaction is finished, filtering, washing and drying the obtained generated product in sequence; the obtained solid powder is preserved for standby;
2. preparing a high-efficiency antibacterial agent;
adding the solid powder into a proper amount of ethanol according to the solid-to-liquid ratio of 0.15g/mL, and then adding 2, 6-dimethyl-2, 6-octadienal with the mass accounting for 20% of the solid powder into the ethanol under the stirring condition; and the mixture is stirred and reacts for 8 hours at the temperature of 50 ℃; and after the reaction is finished, sequentially filtering, washing and drying to obtain the solid powder which is the finished product of the efficient antibacterial agent.
The preparation method of the inorganic porous substrate comprises the following steps:
weighing a proper amount of tetrabutyl titanate, dripping the tetrabutyl titanate into ethanol with the volume of 6 times of that of the tetrabutyl titanate, uniformly dispersing the tetrabutyl titanate by ultrasonic waves, slowly dripping the obtained mixed component into deionized water with the volume of 30 times of that of the tetrabutyl titanate, mixing and stirring for 40min, and fully hydrolyzing the tetrabutyl titanate;
ii, after tetrabutyl titanate is completely hydrolyzed, the obtained mixed solution is transferred into reaction equipment after being washed by ethanol, a proper amount of ethanol is added to enable the volume of the mixed solution to be 75 percent of that of a reaction kettle, ammonium bicarbonate with the dosage of 3 percent of deionized water is added into the reaction kettle, after the mixed solution is uniformly mixed and stirred, the temperature of the reaction kettle is set to 190 ℃, and the reaction is carried out for 50 hours under the temperature;
iii, naturally cooling the generated liquid in the reaction kettle to room temperature after the reaction is finished; then the generated liquid is respectively washed for 3 times by deionized water and ethanol; and then placing the obtained solid matter into a drying oven for drying treatment, wherein the obtained solid matter is the inorganic porous substrate finished product.
The mixed solvent consists of 60% ethanol water solution, 15% dodecyl trimethyl ammonium chloride, 20% 2-hydroxy-4-methoxybenzophenone-5-sodium sulfonate and 3.8% surfactant.
The surfactant is selected from octyl phenol polyoxyethylene ether.
The silane coupling agent is 3-aminopropyl triethoxy silane.
The average particle diameter of the prepared inorganic porous substrate is 165nm, and the pore diameter of the surface micropores is 6nm.
The preparation method of the silver-loaded antibacterial agent comprises the following steps: mixing shell powder with the particle size of 50nm and distilled water with the mass of 12 times of the shell powder, and uniformly stirring to form turbid suspension electrolyte; then, silver is taken as an anode to carry out electrolysis in electrolyte so as to dissolve and separate silver ions out of the anode silver, and after the electrolysis is finished, the anode silver is sequentially filtered, separated and dried; then carrying out heat treatment on the obtained solid powder for 13h under a nitrogen atmosphere at the temperature of 650 ℃; and (3) heating and decomposing the silver oxide and the silver hydroxide adsorbed on the surface of the powder material into elemental silver, naturally cooling the elemental silver to room temperature, and obtaining solid powder which is a finished product of the silver-carrying antibacterial agent.
The anode current density in the electrolytic process is 10000A/m 2 The electrolysis time was set to 10min.
Comparative example 1: the main difference between this embodiment and embodiment 1 is that: replacing the high-efficiency antibacterial agent with an equal amount of inorganic porous base materials with similar particle size grades;
comparative example 2: the main difference between this embodiment and embodiment 1 is that: the raw materials do not contain silver-carrying antibacterial agents;
performance testing
Antibacterial bath balls prepared by using examples 1 to 3 and comparative examples 1 to 2 were respectively referred to as experimental examples 1 to 3 and comparative examples 1 to 2; the antibacterial performance, the ageing resistance and other relevant performances of each group of antibacterial bath balls are detected respectively; the data obtained are recorded in table 1 and table 2:
1. and (3) stretch breaking performance test: determination of tensile Properties of plastics according to GB/T1040.3-2006 section 3: test conditions for films and sheets the tensile strength (N) was tested; then respectively carrying out ultraviolet aging test on each group of samples to be tested, and then testing the tensile strength of each group of samples to be tested; wherein, the ultraviolet aging condition is: irradiating with ultraviolet rays at 60deg.C for 8 hr; the illumination intensity was 0.89w/m 2 The method comprises the steps of carrying out a first treatment on the surface of the Lamp type, UVA-340;
2. fading experiment: rubbing and washing for 40 times by using daily washing products, and observing whether fading occurs or not;
3. safety experiment: according to GB 18401-2010 national basic safety Specification for textile products, safety and sanitation requirements of bath balls are detected, and whether adverse reactions exist or not is observed;
4. antibacterial test: the antibacterial property of the bath ball is detected according to GB/T31420-2015 method for testing antibacterial property of plastic surface;
TABLE 1
TABLE 2
As can be seen from the relevant data in tables 1 and 2, the antibacterial bath ball prepared by the invention not only has good antibacterial and bacteriostatic properties, but also has good ageing resistance, so that the service life of the antibacterial bath ball is effectively prolonged, and the quality of the antibacterial bath ball is also ensured. Meanwhile, the prepared bath ball also has the advantages of safety, innocuity and difficult fading. Therefore, the bath ball product prepared by the invention has wider market prospect and is more suitable for popularization.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The preferred embodiments of the invention disclosed above are intended only to assist in the explanation of the invention. The preferred embodiments are not exhaustive or to limit the invention to the precise form disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best understand and utilize the invention. The invention is limited only by the claims and the full scope and equivalents thereof.
Claims (7)
1. An antibacterial bath ball, which is characterized in that: the antibacterial bath ball consists of 93 to 95 weight percent: 4 to 6:0.07 to 0.1 of low-density polyethylene, low-density polyethylene antibacterial master batch and PE toner; the low-density polyethylene antibacterial master batch comprises the following raw materials in parts by weight: 93 to 97 parts of low-density high-pressure polyethylene, 2.5 to 3.6 parts of high-efficiency antibacterial agent, 2.0 to 4.0 parts of nano zinc oxide and 3.2 to 4.5 parts of silver-loaded antibacterial agent;
the preparation method of the efficient antibacterial agent comprises the following steps:
1. modification of the inorganic porous substrate;
according to the solid-liquid ratio of 0.06-0.1 g/mL, the inorganic porous substrate is put into the mixed solvent; under the condition of ultrasonic dispersion, adding a silane coupling agent with the mass of 8-15% of the inorganic porous substrate into the mixed solvent; dispersing for 30-40 min by ultrasonic; then reacting for 3-5 h under the stirring condition; after the reaction is finished, filtering, washing and drying the obtained generated product in sequence; the obtained solid powder is preserved for standby;
2. preparing a high-efficiency antibacterial agent;
adding solid powder into proper amount of ethanol according to the solid-liquid ratio of 0.08-0.15 g/mL, and then adding 2, 6-dimethyl-2, 6-octadienal with the mass of 10-20% of that of the solid powder into the ethanol under the stirring condition; and the mixture is stirred and reacts for 5 to 8 hours at the temperature of 30 to 50 ℃; after the reaction is finished, sequentially filtering, washing and drying the reaction product to obtain solid powder which is the finished product of the efficient antibacterial agent;
the preparation method of the inorganic porous substrate comprises the following steps:
weighing a proper amount of tetrabutyl titanate, dripping the tetrabutyl titanate into ethanol with the volume of 4-6 times of that of the tetrabutyl titanate, uniformly dispersing the tetrabutyl titanate by ultrasonic waves, slowly dripping the obtained mixed component into deionized water with the volume of 20-30 times of that of the tetrabutyl titanate, mixing and stirring for 30-40 min, and fully hydrolyzing the tetrabutyl titanate;
ii, after tetrabutyl titanate is completely hydrolyzed, the obtained mixed solution is transferred into reaction equipment after being washed by ethanol, a proper amount of ethanol is added to enable the volume of the mixed solution to be 65-75% of that of a reaction kettle, ammonium bicarbonate with the dosage of 2-3% of deionized water is added into the reaction kettle, after being uniformly mixed and stirred, the temperature of the reaction kettle is set to 170-190 ℃, and the reaction is carried out for 40-50 hours under the temperature;
iii, naturally cooling the generated liquid in the reaction kettle to room temperature after the reaction is finished; then the generated liquid is respectively washed for 2 to 3 times by deionized water and ethanol; then placing the obtained solid matter into a drying oven for drying treatment, wherein the obtained solid matter is the inorganic porous substrate finished product;
the mixed solvent consists of 40-60% ethanol water solution, 8-15% dodecyl trimethyl ammonium chloride, 15-20% 2-hydroxy-4-methoxybenzophenone-5-sodium sulfonate and 2.5-3.8% surfactant.
2. An antibacterial bath ball according to claim 1, wherein: the surfactant is selected from any one of octyl phenol polyoxyethylene ether and nonylphenol polyoxyethylene ether.
3. An antibacterial bath ball according to claim 1, wherein: the silane coupling agent is selected from any one of 3-aminopropyl triethoxy silane and 3-aminopropyl trimethoxy silane.
4. An antibacterial bath ball according to claim 1, wherein: the average grain diameter of the prepared inorganic porous base material is 150-165 nm, and the pore diameter of the surface micropore is 4-6 nm.
5. The antibacterial bath ball according to claim 1, wherein the preparation method of the silver-loaded antibacterial agent comprises the following steps: mixing shell powder with the particle size of 20-50 nm and distilled water with the mass of 8-12 times of the shell powder, and uniformly stirring to form turbid suspension electrolyte; then, silver is taken as an anode to carry out electrolysis in electrolyte so as to dissolve and separate silver ions out of the anode silver, and after the electrolysis is finished, the anode silver is sequentially filtered, separated and dried; then carrying out heat treatment on the obtained solid powder for 3-13 h in nitrogen atmosphere at the temperature of 350-650 ℃; and (3) heating and decomposing the silver oxide and the silver hydroxide adsorbed on the surface of the powder material into elemental silver, naturally cooling the elemental silver to room temperature, and obtaining solid powder which is a finished product of the silver-carrying antibacterial agent.
6. An antibacterial bath ball according to claim 1, wherein: the anode current density is 50-10000A/m in the electrolytic process 2 The electrolysis time is set to 10-60 min.
7. A method of preparing an antibacterial bath ball according to any one of claims 1 to 6, comprising the steps of:
firstly, accurately weighing the raw materials, and then uniformly mixing and stirring the low-density polyethylene, the low-density polyethylene antibacterial master batch and the PE toner at the rotating speed of 180-230 r/min, wherein the obtained mixture is marked as a mixed material;
II, melt blending the mixed material obtained in the step I, and extruding the melt blended mixed material at 220-250 ℃ to obtain a net-shaped semi-finished product;
III, cooling, traction, draining, secondary traction and rolling the obtained net-shaped semi-finished product; and then sequentially cutting and embossing the stretched semi-finished product to obtain the antibacterial bath ball finished product.
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