CN114656762A - Antibacterial transparent material, preparation method thereof, water storage container and dish washing machine - Google Patents
Antibacterial transparent material, preparation method thereof, water storage container and dish washing machine Download PDFInfo
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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
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/45—Heterocyclic compounds having sulfur in the ring
- C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
- C08K5/47—Thiazoles
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- A—HUMAN NECESSITIES
- A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
- A47L—DOMESTIC WASHING OR CLEANING; SUCTION CLEANERS IN GENERAL
- A47L15/00—Washing or rinsing machines for crockery or tableware
- A47L15/42—Details
- A47L15/4214—Water supply, recirculation or discharge arrangements; Devices therefor
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
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- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/19—Quaternary ammonium compounds
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- 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
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- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
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- 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
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
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- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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- C08L2201/00—Properties
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- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
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Abstract
The invention relates to the field of high polymer materials, and provides an antibacterial transparent material, a preparation method thereof, a water storage container and a dish washing machine. The raw materials of the antibacterial transparent material comprise transparent plastic particles and an antibacterial agent, wherein the antibacterial agent is one or more of polyhexamethylene guanidine hydrochloride, polyhexamethylene biguanide hydrochloride, isothiazolinone and quaternary ammonium salt antibacterial agents. According to the invention, a specific kind of antibacterial agent is selected, and specifically the antibacterial agent is at least one of polyhexamethylene guanidine hydrochloride, polyhexamethylene biguanide hydrochloride, isothiazolinone and quaternary ammonium salt antibacterial agents, so that the light transmittance of the original transparent plastic particles is hardly reduced while long-acting antibacterial effect is achieved.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to an antibacterial transparent material and a preparation method thereof, a water storage container and a dish washing machine.
Background
With the rapid development of the household appliance industry and the continuous improvement of the quality of life, the dish washing machine is more and more popular. Wherein, the transparent plastic water storage container in the dishwasher stores the softened water to supply to the dishwasher to complete the washing work. However, bacteria are very easy to breed on the surface of the transparent plastic water storage container for storing water, which can cause the softened water stored in the water storage container to exceed standard and generate peculiar smell, and great adverse effect is generated on the washing and sanitation of the tableware.
In order to solve the above problems, the currently adopted measures are to add antibacterial materials, such as zeolite-loaded silver and zinc oxide, into the transparent plastic, but these antibacterial materials can improve the antibacterial performance of the surface of the transparent plastic water tank, but also can greatly reduce the transparency of the water storage container, and are not beneficial to observing the working conditions and subsequent maintenance of other parts in the water storage container.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention provides an antibacterial transparent material, which realizes the compatibility of long-acting antibacterial performance and good transparency by adding a specific type of antibacterial agent into transparent plastic particles.
The invention also provides a preparation method of the antibacterial transparent material.
The invention also provides a water storage container.
The invention also provides a dishwasher.
According to the antibacterial transparent material provided by the embodiment of the first aspect of the invention, the raw materials comprise transparent plastic particles and an antibacterial agent, wherein the antibacterial agent is one or more of polyhexamethylene guanidine hydrochloride, polyhexamethylene biguanide hydrochloride, isothiazolinone and quaternary ammonium salt antibacterial agent.
According to the antibacterial transparent material provided by the embodiment of the invention, a specific type of antibacterial agent is added into the transparent plastic particles, specifically at least one of polyhexamethylene guanidine hydrochloride, polyhexamethylene biguanide hydrochloride, isothiazolinone and quaternary ammonium salt antibacterial agents, instead of the existing antibacterial materials such as zeolite silver-loaded and zinc oxide, so that both long-acting antibacterial performance and good transparency are realized.
According to some embodiments of the invention, the antibacterial agent is present in an amount of 0.5-5% by mass of the transparent plastic particles.
According to some embodiments of the invention, the transparent plastic particles include, but are not limited to, one or more of polypropylene, acrylonitrile-butadiene-styrene copolymer, polymethyl methacrylate, acrylonitrile-styrene copolymer, styrene-methyl methacrylate copolymer, polyethylene terephthalate-1, 4-cyclohexanedimethanol ester copolymer, polystyrene.
According to some embodiments of the present invention, the antibacterial agent is a composite antibacterial agent composed of polyhexamethylene guanidine hydrochloride and isothiazolinone, the mass ratio of the polyhexamethylene guanidine hydrochloride in the composite antibacterial agent is 20% -80%, and the mass of the composite antibacterial agent is 0.5-1% of the mass of the transparent plastic particles.
The preparation method of the antibacterial transparent material according to the second aspect of the invention comprises the step of mixing the raw materials and granulating by a double-screw extruder.
According to the preparation method provided by the embodiment of the invention, the target antibacterial transparent material particles are obtained through raw material blending and extrusion granulation, and can be further processed into the required transparent plastic finished product.
According to some embodiments of the present invention, the mixing of the raw materials is performed using mechanical agitation at a rate of 100-400 rpm.
According to some embodiments of the present invention, the temperature range during the pelletization of the twin-screw extruder is 160-240 ℃. The method is specifically determined according to the types of the transparent plastic particles:
the transparent plastic particles are polypropylene or polyethylene terephthalate-1, 4-cyclohexane dimethanol ester copolymer, and the process parameters of the double-screw extruder granulation are as follows: temperature in the first zone: 160 ℃ and 180 ℃, and the temperature of the second zone: 170 ℃ and 190 ℃, and the temperature of the three zones: 180 ℃ and 200 ℃, four-zone temperature: 180 ℃ and 200 ℃, and the temperature of the five zones: 180 ℃ and 200 ℃, and the temperature of the six zones: 180 ℃ and 200 ℃, and the temperature of the seventh zone: 180 ℃ and 200 ℃, and the temperature of the eight zones: 180 ℃ and 200 ℃, die temperature: 190 ℃ and 210 ℃, and the rotating speed of the main screw: 300-500rpm, feed rate: 500-1000 kg/h.
The transparent plastic particles are acrylonitrile-butadiene-styrene copolymer or polystyrene, and the process parameters of granulation by a double-screw extruder are as follows: temperature in the first zone: 170 ℃ and 190 ℃, and the temperature of the second zone: 180 ℃ and 200 ℃, and the temperature of the three zones: 180 ℃ and 200 ℃, four-zone temperature: 180 ℃ and 200 ℃, and the temperature of the five zones: 180 ℃ and 200 ℃, and the temperature of the six zones: 190 ℃ to 210 ℃, and the temperature of the seven zones: 190 ℃ and 210 ℃, and the temperature of the eight zones: 190 ℃ to 210 ℃, die temperature: 200 ℃ and 220 ℃, main screw rotation speed: 300-500rpm, feed rate: 500-800 kg/h.
The transparent plastic particles are acrylonitrile-styrene copolymer, styrene-methyl methacrylate copolymer or polymethyl methacrylate, and the process parameters of the double-screw extruder granulation are as follows: temperature in the first zone: 180 ℃ and 200 ℃, and the temperature of the second zone: 190 ℃ to 210 ℃, and the temperature of the three zones: 190 ℃ to 210 ℃, and the temperature of the four zones: 200 ℃ and 220 ℃, and the temperature of the five zones: 200 ℃ and 220 ℃, and the temperature of the six zones: 210 ℃ and 230 ℃, and the temperature of the seven zones: 210 ℃ and 230 ℃, temperature of eight zones: 210 ℃ 230 ℃, die temperature: 220 ℃ and 240 ℃, main screw rotation speed: 300-500rpm, feed rate: 500-800 kg/h.
According to the third aspect of the present invention, the water container is made of the above-mentioned antibacterial transparent material.
The water storage container made of the antibacterial transparent material (such as injection molding) can realize long-acting antibacterial, and compared with the water storage container without the antibacterial agent, the transparency of the water storage container is not obviously reduced.
The dishwasher according to the fourth aspect of the present invention is provided with the above-described water storage container. In essence, the water tank of the dish washer is made of the antibacterial transparent material.
One or more technical solutions in the embodiments of the present invention have at least one of the following technical effects:
by selecting a specific kind of antibacterial agent, in particular at least one of polyhexamethylene guanidine hydrochloride, polyhexamethylene biguanide hydrochloride, isothiazolinone and quaternary ammonium salt antibacterial agents, the light transmittance of the original transparent plastic particles is hardly reduced while long-acting antibacterial is realized.
Further, the invention also develops a more effective antibacterial agent combination, which can realize equivalent or even more excellent long-acting antibacterial property and good transparency with less addition amount.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Detailed Description
The following examples further describe embodiments of the present invention in detail. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., 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 an embodiment of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
The embodiment of the invention provides an antibacterial transparent material, which comprises transparent plastic particles and an antibacterial agent, wherein the antibacterial agent is one or more of polyhexamethylene guanidine hydrochloride, polyhexamethylene biguanide hydrochloride, isothiazolinone and a quaternary ammonium salt antibacterial agent.
Wherein the chemical formula of the polyhexamethylene guanidine hydrochloride is (C)7H15N3) n.xHCl, abbreviated as PHMG. PHMG is an environment-friendly multipurpose novel cationic polymer, is colorless transparent liquid in appearance, has no special odor, has extremely strong capability of killing bacteria and viruses, has good biocompatibility and is nontoxic.
The polyhexamethylene biguanide hydrochloride has the formula (C)8H17N5)nxHCl, n-12-16, with an average molecular weight of 1100-1800, abbreviated as PHMB, is a colorless or yellowish transparent liquid broad-spectrum antimicrobial agent.
The isothiazolinone antibacterial agent is brown yellow transparent liquid, and has the excellent properties of broad-spectrum sterilization, low toxicity, no pollution, better compatibility, wider pH application range and natural biodegradation. Common isothiazolinone antibacterial agents are: 1, 2-benzisothiazolin-3-one (BIT), 2-n-octyl-4-isothiazolin-3-One (OIT), 2-methyl-4-isothiazolin-3-one (MIT), 5-chloro-2-methyl-4-isothiazolin-3-one (CMIT).
The quaternary ammonium salt antibacterial agent is a colorless to yellowish liquid. Commonly used are 3- [ trimethoxysilyl ] propyldimethyloctadecyl ammonium chloride, dodecyltrimethyl ammonium chloride, dodecyldimethylbenzyl ammonium bromide, bis (dodecyldimethyl) bromide, dodecyldimethylethyleneoxyethyl ammonium bromide, didecyldimethylammonium bromide, and the like.
According to the invention, a specific type of antibacterial agent, specifically at least one of polyhexamethylene guanidine hydrochloride, polyhexamethylene biguanide hydrochloride, isothiazolinone and quaternary ammonium salt antibacterial agents is added into the transparent plastic particles, instead of the existing antibacterial materials such as zeolite silver-loaded and zinc oxide, so that both long-acting antibacterial performance and good transparency are realized.
Further, the mass of the antibacterial agent is 0.5-5% of the mass of the transparent plastic particles.
The transparent plastic particles of the present invention include, but are not limited to, one or more of polypropylene (PP), acrylonitrile-butadiene-styrene copolymer (ABS), polymethyl methacrylate (PMMA), acrylonitrile-styrene copolymer (AS), styrene-methyl methacrylate copolymer (MS), polyethylene terephthalate-1, 4-cyclohexanedimethanol ester copolymer (PCTG), and Polystyrene (PS). The transparent plastic particles are generally cylindrical particles with a diameter of 2-4mm and a length of 4-6 mm.
Further, the invention provides an antibacterial agent combination with a better effect, and particularly provides a composite antibacterial agent consisting of polyhexamethylene guanidine hydrochloride and isothiazolinone antibacterial agents, wherein the mass ratio of the polyhexamethylene guanidine hydrochloride in the composite antibacterial agent is 20-80%, and the mass of the composite antibacterial agent is 0.5-1% of the mass of the transparent plastic particles.
When the antibacterial agent combination is adopted, equivalent or even better long-acting antibacterial property and good transparency can be realized under the condition of less adding amount.
In a preferred embodiment of the invention, the composite antibacterial agent consists of polyhexamethylene guanidine hydrochloride and 2-n-octyl-4-isothiazolin-3-one, and the mass ratio of the polyhexamethylene guanidine hydrochloride to the 2-n-octyl-4-isothiazolin-3-one is 0.3:0.2, namely the mass ratio of the polyhexamethylene guanidine hydrochloride in the composite antibacterial agent is 60%.
In another preferred embodiment of the invention, the composite antibacterial agent consists of polyhexamethylene guanidine hydrochloride and 5-chloro-2-methyl-4-isothiazolin-3-one, and the mass ratio of the polyhexamethylene guanidine hydrochloride to the 5-chloro-2-methyl-4-isothiazolin-3-one is 0.3:0.5, namely the mass ratio of the polyhexamethylene guanidine hydrochloride in the composite antibacterial agent is 37.5%.
In a second aspect, the embodiment of the present invention provides a preparation method of the above antibacterial transparent material.
The preparation method provided by the embodiment of the invention comprises the step of mixing the raw materials and then granulating by using a double-screw extruder.
Further, the raw materials are mixed by mechanical stirring, the stirring speed is 100-400rpm, and the stirring time is 2-5 min.
Further, the temperature range is controlled to be 160-240 ℃ in the granulation process of the double-screw extruder.
The method is specifically determined according to the types of the transparent plastic particles:
when the transparent plastic particles are polypropylene or polyethylene terephthalate-1, 4-cyclohexane dimethanol ester copolymer, the technological parameters of the double-screw extruder granulation are as follows: temperature in the first zone: 160 ℃ and 180 ℃, and the temperature of the second zone: 170 ℃ and 190 ℃, and the temperature of the three zones: 180 ℃ and 200 ℃, four-zone temperature: 180 ℃ and 200 ℃, and the temperature of the five zones: 180 ℃ and 200 ℃, and the temperature of the six zones: 180 ℃ and 200 ℃, and the temperature of the seventh zone: 180 ℃ and 200 ℃, and the temperature of the eight zones: 180 ℃ and 200 ℃, die temperature: 190 ℃ and 210 ℃, and the rotating speed of the main screw: 300-500rpm, feed rate: 500-1000 kg/h;
when the transparent plastic particles are acrylonitrile-butadiene-styrene copolymer or polystyrene, the process parameters of the double-screw extruder granulation are as follows: temperature in the first zone: 170 ℃ and 190 ℃, and the temperature of the second zone: 180 ℃ and 200 ℃, and the temperature of the three zones: 180 ℃ and 200 ℃, four-zone temperature: 180 ℃ and 200 ℃, and the temperature of the five zones: 180 ℃ and 200 ℃, and the temperature of the six zones: 190 ℃ to 210 ℃, and the temperature of the seven zones: 190 ℃ and 210 ℃, and the temperature of the eight zones: 190 ℃ to 210 ℃, die temperature: 200 ℃ and 220 ℃, main screw rotation speed: 300-500rpm, feed rate: 500-800 kg/h;
when the transparent plastic particles are acrylonitrile-styrene copolymer, styrene-methyl methacrylate copolymer or polymethyl methacrylate, the technological parameters of the double-screw extruder granulation are as follows: temperature in the first zone: 180 ℃ and 200 ℃, and the temperature of the second zone: 190 ℃ to 210 ℃, and the temperature of the three zones: 190 ℃ to 210 ℃, and the temperature of the four zones: 200-220 ℃, and the temperature of the five zones: 200-220 ℃, and the temperature of the six zones: 210 ℃ and 230 ℃, and the temperature of the seven zones: 210 ℃ and 230 ℃, temperature of eight zones: 210 ℃ 230 ℃, die temperature: 220 ℃ and 240 ℃, main screw rotation speed: 300-500rpm, feed rate: 500-800 kg/h.
In a third aspect, an embodiment of the invention provides a water storage container, which is made of the above antibacterial transparent material.
The water storage container made of the antibacterial transparent material (such as injection molding) can realize long-acting antibacterial, and compared with the water storage container without the antibacterial agent, the transparency of the water storage container is not obviously reduced. When the water storage container needs to meet the requirements of long-acting antibiosis and transparency and visibility, the antibacterial transparent material can be adopted. The water storage container may be a dishwasher tank, a drinking water bottle or a drinking water bucket, or the like.
In a fourth aspect, an embodiment of the present invention provides a dishwasher, which is provided with the above water storage container. Namely, the dishwasher is provided with a water tank which is arranged in a matching way and is used for storing water for washing the tableware.
Example 1
The embodiment provides an antibacterial transparent material, which comprises transparent plastic particles PP and an antibacterial agent 2-n-octyl-4-isothiazoline-3-ketone, wherein the weight ratio of the 2-n-octyl-4-isothiazoline-3-ketone to the PP is 0.8: 100.
the embodiment also provides a preparation method of the antibacterial transparent material, which comprises the following steps:
accurately weighing 2-n-octyl-4-isothiazoline-3-ketone and PP according to the proportion, transferring the mixture to a high-speed stirrer, stirring at the speed of 100rpm for 3min, uniformly stirring and mixing, transferring the mixture to a double-screw extruder feeding hopper for preparing extrusion granulation;
the parameters of the twin-screw extrusion granulation process are as follows: temperature in the first zone: 170 ℃, temperature in zone two: 180 ℃, three zone temperature: 180 ℃, four zone temperature: 190 ℃, five zone temperature: 190 ℃, six zone temperature: 200 ℃, temperature in seven zones: 200 ℃, eight zone temperature: 200 ℃, die temperature: 200 ℃, main screw rotation speed: 400rpm, feed rate: 600 kg/h.
The embodiment also provides the antibacterial transparent PP water tank prepared from the materials, and the specific injection molding process comprises the following steps: the injection temperature is 210 ℃, the pressure maintaining cooling time is 25s, and the mold temperature is 60 ℃.
Example 2
The embodiment provides an antibacterial transparent material, which is prepared from transparent plastic particles PCTG and an antibacterial agent polyhexamethylene guanidine hydrochloride, wherein the weight ratio of the polyhexamethylene guanidine hydrochloride to the PCTG is 1.0: 100.
the embodiment also provides a preparation method of the antibacterial transparent material, which comprises the following steps:
accurately weighing polyhexamethylene guanidine hydrochloride and PCTG according to the proportion, transferring the mixture to a high-speed stirrer, stirring at the speed of 300rpm for 4min, uniformly stirring and mixing, transferring the mixture to a double-screw extruder feeding hopper for preparing extrusion granulation;
the parameters of the twin-screw extrusion granulation process are as follows: temperature in the first zone: 180 ℃, temperature in zone two: 190 ℃, three zone temperature: 190 ℃, four zone temperature: 190 ℃, five zone temperature: 190 ℃, six zone temperature: 200 ℃, temperature in seven zones: 200 ℃, eight zone temperature: 200 ℃, die temperature: 210 ℃, main screw rotation speed: 500rpm, feed rate: 800 kg/h.
The embodiment also provides the antibacterial transparent PCTG water tank prepared from the materials, and the specific injection molding process comprises the following steps: the injection temperature is 210 ℃, the pressure maintaining cooling time is 20s, and the mold temperature is 50 ℃.
Example 3
The embodiment provides an antibacterial transparent material, which comprises transparent plastic particles of ABS and an antibacterial agent of polyhexamethylene biguanide hydrochloride, wherein the weight ratio of the polyhexamethylene biguanide hydrochloride to the ABS is 1.5: 100.
the embodiment also provides a preparation method of the antibacterial transparent material, which comprises the following steps:
accurately weighing polyhexamethylene biguanide hydrochloride and ABS according to the proportion, transferring the polyhexamethylene biguanide hydrochloride and the ABS to a high-speed stirrer, stirring at the speed of 200rpm for 5min, uniformly stirring and mixing, transferring the mixture to a double-screw extruder feeding hopper for preparing extrusion granulation;
the parameters of the twin-screw extrusion granulation process are as follows: temperature in the first zone: 180 ℃, temperature in zone two: 180 ℃, three zone temperature: 190 ℃, four zone temperature: 190 ℃, five zone temperature: 190 ℃, six zone temperature: 200 ℃, temperature in seven zones: 200 ℃, eight zone temperature: 200 ℃, die temperature: 210 ℃, main screw rotation speed: 400rpm, feed rate: 800 kg/h.
The embodiment also provides the antibacterial transparent ABS water tank prepared from the materials, and the specific injection molding process is as follows: the injection temperature is 230 ℃, the pressure maintaining cooling time is 15s, and the mold temperature is 50 ℃.
Example 4
The present embodiment provides an antibacterial transparent material, which is prepared from transparent plastic particles of acrylonitrile-styrene copolymer and antibacterial agent dodecyl dimethyl benzyl ammonium chloride, wherein a weight ratio of dodecyl dimethyl benzyl ammonium chloride to acrylonitrile-styrene copolymer is 1.2: 100.
the embodiment also provides a preparation method of the antibacterial transparent material, which comprises the following steps:
accurately weighing dodecyl dimethyl benzyl ammonium chloride and acrylonitrile-styrene copolymer according to the proportion, transferring the mixture to a high-speed stirrer, stirring at the speed of 300rpm for 3min, uniformly stirring and mixing, transferring the mixture to a double-screw extruder feeding hopper for preparing extrusion granulation;
the granulation process parameters of the double-screw extruder are as follows: temperature in the first zone: 180 ℃, temperature in zone two: 190 ℃, three zone temperature: 190 ℃, four zone temperature: 200 ℃, five zone temperature: 200 ℃, six zone temperature: 210 ℃, seven zone temperature: 210 ℃, eight zone temperature: 220 ℃, die temperature: 220 ℃, main screw rotation speed: 450rpm, feed rate: 600 kg/h.
The embodiment also provides an antibacterial transparent acrylonitrile-styrene copolymer water tank prepared from the materials, and the specific injection molding process comprises the following steps: the injection temperature is 230 ℃, the pressure maintaining cooling time is 30s, and the mold temperature is 60 ℃.
Example 5
The embodiment provides an antibacterial transparent material, which comprises transparent plastic particles PS and an antibacterial agent 5-chloro-2-methyl-4-isothiazolin-3-one (CMIT), wherein the weight ratio of the 5-chloro-2-methyl-4-isothiazolin-3-one (CMIT) to the PS is 2.0: 100.
the embodiment also provides a preparation method of the antibacterial transparent material, which comprises the following steps:
accurately weighing 5-chloro-2-methyl-4-isothiazoline-3-ketone (CMIT) and PS according to the proportion, transferring the mixture to a high-speed stirrer, stirring at the speed of 200rpm for 3min, uniformly stirring and mixing, transferring the mixture to a double-screw extruder feeding hopper for preparing extrusion granulation;
the parameters of the twin-screw extrusion granulation process are as follows: temperature in the first zone: 180 ℃, temperature in zone two: 190 ℃, temperature: 190 ℃, four zone temperature: 200 ℃, five zone temperature: 200 ℃, six zone temperature: 200 ℃, temperature in seven zones: 210 ℃, temperature in eight zones: 210 ℃, die temperature: 210 ℃, main screw rotation speed: 400rpm, feed rate: 500 kg/h.
The embodiment also provides the antibacterial transparent PS water tank prepared from the materials, and the specific injection molding process comprises the following steps: the injection temperature is 220 ℃, the pressure maintaining cooling time is 25s, and the mold temperature is 50 ℃.
Example 6
The embodiment provides an antibacterial transparent material, which is prepared from transparent plastic particles PMMA and an antibacterial agent 1, 2-benzisothiazolin-3-one (BIT), wherein the weight ratio of the 1, 2-benzisothiazolin-3-one (BIT) to the PMMA is 1.0: 100.
the embodiment also provides a preparation method of the antibacterial transparent material, which comprises the following steps:
accurately weighing isothiazolinone and PMMA according to the proportion, transferring the isothiazolinone and PMMA to a high-speed stirrer, stirring at the speed of 400rpm for 2min, uniformly stirring and mixing, transferring the mixture to a double-screw extruder feeding hopper to prepare for extrusion granulation;
the parameters of the twin-screw extrusion granulation process are as follows: temperature in the first zone: 190 ℃, second zone temperature: temperature at 200 ℃, temperature: 210 ℃, four zone temperature: 220 ℃, five zone temperature: 220 ℃, six zone temperature: 220 ℃, temperature in seven zones: 230 ℃, eight zone temperature: 230 ℃, die temperature: 230 ℃, main screw rotation speed: 500rpm, feed rate: 600 kg/h.
The embodiment also provides the antibacterial transparent PMMA water tank prepared by the materials, and the specific injection molding process comprises the following steps: the injection temperature is 230 ℃, the pressure maintaining cooling time is 25s, and the mold temperature is 60 ℃.
Example 7
The embodiment provides an antibacterial transparent material, which comprises transparent plastic particles PP, antibacterial agent polyhexamethylene guanidine hydrochloride and 2-n-octyl-4-isothiazoline-3-ketone, wherein the weight ratio of the polyhexamethylene guanidine hydrochloride, the 2-n-octyl-4-isothiazoline-3-ketone and the PP is 0.3: 0.2: 100.
the embodiment also provides a preparation method of the antibacterial transparent material, which comprises the following steps:
accurately weighing the antibacterial agent and the PP according to the proportion, transferring the antibacterial agent and the PP to a high-speed stirrer, stirring at the speed of 100rpm for 3min, uniformly stirring and mixing, transferring the mixture to a double-screw extruder feeding hopper for preparing extrusion granulation;
the parameters of the twin-screw extrusion granulation process are as follows: temperature in the first zone: 170 ℃, temperature in zone two: 180 ℃, three zone temperature: 180 ℃, four zone temperature: 190 ℃, five zone temperature: 190 ℃, six zone temperature: 200 ℃, temperature in seven zones: 200 ℃, eight zone temperature: 200 ℃, die temperature: 200 ℃, main screw rotation speed: 400rpm, feed rate: 600 kg/h.
The embodiment also provides the antibacterial transparent PP water tank prepared from the materials, and the specific injection molding process comprises the following steps: the injection temperature is 210 ℃, the pressure maintaining cooling time is 25s, and the mold temperature is 60 ℃.
Example 8
The embodiment provides an antibacterial transparent material, which comprises transparent plastic particles PS, antibacterial agent polyhexamethylene guanidine hydrochloride and 5-chloro-2-methyl-4-isothiazoline-3-ketone (CMIT), wherein the weight ratio of the polyhexamethylene guanidine hydrochloride, the 5-chloro-2-methyl-4-isothiazoline-3-ketone (CMIT) to the PS is 0.3: 0.5: 100.
the embodiment also provides a preparation method of the antibacterial transparent material, which comprises the following steps:
accurately weighing the antibacterial agent and the PS according to the proportion, transferring the antibacterial agent and the PS to a high-speed stirrer, stirring at the speed of 200rpm for 3min, uniformly stirring and mixing, transferring the mixture to a double-screw extruder feeding hopper for preparing extrusion granulation;
the parameters of the twin-screw extrusion granulation process are as follows: temperature in the first zone: 180 ℃, temperature in zone two: 190 ℃, temperature: 190 ℃, four zone temperature: 200 ℃, five zone temperature: 200 ℃, six zone temperature: 200 ℃, temperature in seven zones: 210 ℃, eight zone temperature: 210 ℃, die temperature: 210 ℃, main screw rotation speed: 400rpm, feed rate: 500 kg/h.
The embodiment also provides the antibacterial transparent PS water tank prepared from the materials, and the specific injection molding process comprises the following steps: the injection temperature is 220 ℃, the pressure maintaining cooling time is 25s, and the mold temperature is 50 ℃.
Comparative example 1
This comparative example provides a transparent water tank directly injection molded from a transparent PP starting material (without any antimicrobial agent) under the same injection molding conditions as in example 1.
Comparative example 2
This comparative example provides a water tank prepared from a transparent PP raw material and a zinc oxide antibacterial agent, the zinc oxide: the PP weight ratio is 0.8: 100, mechanical mixing, twin-screw extrusion granulation and injection molding conditions were the same as in example 1.
Comparative example 3
This comparative example provides a water tank prepared from a transparent PCTG raw material with a silver-loaded zeolite antimicrobial, the silver-loaded zeolite: PCTG weight ratio 1.0: 100. mechanical mixing, twin-screw extrusion granulation and injection molding conditions were the same as in example 2.
Performance testing
The antibacterial performance test refers to an appendix A film pasting method in GB 21551.2-2010 Special requirements for antibacterial materials with antibacterial, degerming and purifying functions of household and similar appliances, wherein an experimental sample is an antibacterial transparent water tank prepared in each embodiment of the invention and a comparative example, and a reference sample is a transparent water tank without an antibacterial agent.
The light transmittance test adopts GB/T2410 2008 determination of light transmittance and haze of transparent plastic.
The test results are shown in table 1.
TABLE 1
The results show that the antibacterial rate of the plastic water tanks of the examples to escherichia coli and staphylococcus aureus is more than 99.9%, while the antibacterial rate of the water tank of the comparative example 1 without the antibacterial agent to escherichia coli and staphylococcus aureus is only 20.3% and 12.5%. As can be seen from comparative example 1 and example 1, the light transmittance of the antibacterial transparent PP water tank and the light transmittance of the transparent PP water tank have no obvious difference, which shows that the antibacterial agent added in example 1 greatly improves the antibacterial performance of the material, and has little influence on the transparency. The zinc oxide antibacterial agent is added in the comparative example 2, the antibacterial performance is improved to a certain extent, but the light transmittance is only 56.6%, which is obviously lower than 82.4% of that of the example 1. In comparative example 3, after 1.0% of the silver-loaded zeolite antibacterial agent is added to the transparent PCTG, although the antibacterial rates of the transparent PCTG on Escherichia coli and Staphylococcus aureus are both more than 99.9%, the light transmittance of the water tank is only 27.3%, which is far lower than that of the antibacterial transparent PCTG water tank in example 2.
In the embodiment 7, after the polyhexamethylene guanidine hydrochloride and the 2-n-octyl-4-isothiazoline-3-ketone compound antibacterial agent are adopted, the antibacterial rate is still more than 99.9%, and the light transmittance of the antibacterial water tank is greatly improved to 84.7% compared with that of the embodiment 1, and is close to that of a pure transparent PP raw material. In the embodiment 8, after the polyhexamethylene guanidine hydrochloride and the 5-chloro-2-methyl-4-isothiazoline-3-ketone compound antibacterial agent are adopted, the light transmittance of the antibacterial PS water tank is greatly improved to 91.3% compared with that of the embodiment 5, and the antibacterial PS water tank is close to a pure transparent PS raw material. Moreover, the antibacterial rate of the antibacterial water tank of the embodiment 8 to escherichia coli and staphylococcus aureus is still more than 99.9%, and meanwhile, the excellent performances of high antibacterial rate and high transparency are considered.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. The antibacterial transparent material is characterized in that raw materials comprise transparent plastic particles and an antibacterial agent, wherein the antibacterial agent is one or more of polyhexamethylene guanidine hydrochloride, polyhexamethylene biguanide hydrochloride, isothiazolinone and a quaternary ammonium salt antibacterial agent.
2. The antibacterial transparent material according to claim 1, wherein the mass of the antibacterial agent is 0.5-5% of the mass of the transparent plastic particles.
3. The antibacterial transparent material according to claim 2, wherein the transparent plastic particles comprise one or more of but not limited to polypropylene, acrylonitrile-butadiene-styrene copolymer, polymethyl methacrylate, acrylonitrile-styrene copolymer, styrene-methyl methacrylate copolymer, polyethylene terephthalate-1, 4-cyclohexane dimethanol ester copolymer, polystyrene.
4. The antibacterial transparent material according to any one of claims 1 to 3, wherein the antibacterial agent is a composite antibacterial agent consisting of polyhexamethylene guanidine hydrochloride and isothiazolinone, the mass ratio of the polyhexamethylene guanidine hydrochloride in the composite antibacterial agent is 20-80%, and the mass ratio of the composite antibacterial agent is 0.5-1% of the mass of the transparent plastic particles.
5. A method for preparing the antibacterial transparent material as claimed in any one of claims 1 to 4, characterized by comprising the step of mixing the raw materials and granulating by a twin-screw extruder.
6. The method as claimed in claim 5, wherein the mixing of the raw materials is performed by mechanical stirring at a speed of 100-400 rpm.
7. The method as claimed in claim 5, wherein the temperature range during the granulation process of the twin-screw extruder is 160-240 ℃.
8. The preparation method according to claim 7, wherein the transparent plastic particles are polypropylene or polyethylene terephthalate-1, 4-cyclohexanedimethanol ester copolymer, and the process parameters of the twin-screw extruder granulation are as follows: temperature in the first zone: 160-180 ℃, temperature of the second zone: 170 ℃ and 190 ℃, and the temperature of the three zones: 180 ℃ plus 200 ℃, four-zone temperature: 180 ℃ and 200 ℃, and the temperature of the five zones: 180 ℃ plus 200 ℃, and the temperature of the six zones: 180 ℃ and 200 ℃, and the temperature of the seventh zone: 180 ℃ and 200 ℃, and the temperature of the eight zones: 180 ℃ and 200 ℃, die temperature: 190 ℃ plus 210 ℃, main screw rotation speed: 300-500rpm, feed rate: 500-1000 kg/h;
and/or the transparent plastic particles are acrylonitrile-butadiene-styrene copolymer or polystyrene, and the process parameters of the double-screw extruder granulation are as follows: temperature in the first zone: 170 ℃ and 190 ℃, and the temperature of the second zone: 180 ℃ and 200 ℃, and the temperature of the three zones: 180 ℃ and 200 ℃, four-zone temperature: 180 ℃ and 200 ℃, and the temperature of the five zones: 180 ℃ and 200 ℃, and the temperature of the six zones: 190 ℃ to 210 ℃, and the temperature of the seven zones: 190 ℃ and 210 ℃, and the temperature of the eight zones: 190 ℃ and 210 ℃, die temperature: 200-220 ℃, main screw rotation speed: 300-500rpm, feed rate: 500-800 kg/h;
and/or the transparent plastic particles are acrylonitrile-styrene copolymer, styrene-methyl methacrylate copolymer or polymethyl methacrylate, and the process parameters of the double-screw extruder granulation are as follows: temperature in the first zone: 180 ℃ and 200 ℃, and the temperature of the second zone: 190 ℃ to 210 ℃, and the temperature of the three zones: 190 ℃ to 210 ℃, and the temperature of the four zones: 200 ℃ and 220 ℃, and the temperature of the five zones: 200 ℃ and 220 ℃, and the temperature of the six zones: 210 ℃ and 230 ℃, and the temperature of the seven zones: 210 ℃ and 230 ℃, temperature of eight zones: 210 ℃ 230 ℃, die temperature: 220 ℃ and 240 ℃, main screw rotation speed: 300-500rpm, feed rate: 500-800 kg/h.
9. A water storage container, characterized in that, the material is the antibacterial transparent material of any one of claims 1-4.
10. A dishwasher, characterized in that it is provided with a water storage container as claimed in claim 9.
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