CN114656762B - 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
- C08K5/16—Nitrogen-containing compounds
- 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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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 antibacterial transparent material 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 quaternary ammonium salt antibacterial agents. The invention realizes long-acting antibiosis and hardly reduces the transmittance of original transparent plastic particles by selecting a specific type of antibiosis agent, specifically at least one of polyhexamethylene guanidine hydrochloride, polyhexamethylene biguanidine hydrochloride, isothiazolinone and quaternary ammonium salt antibiosis agent.
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 home appliance industry and the continuous improvement of the quality of life, dish washers are becoming more popular. Wherein, the transparent plastic water storage container in the dish-washing machine stores softened water to supply the dish-washing machine to complete washing work. However, bacteria are extremely easy to multiply on the surface of a transparent plastic water storage container storing water, which causes excessive bacteria and off-flavor generation of softened water stored in the water storage container, and has a great adverse effect on washing and sanitation of tableware.
Aiming at the problems, the common measures are to add antibacterial materials such as zeolite silver and zinc oxide into the transparent plastic, but the antibacterial materials can improve the antibacterial performance of the surface of the transparent plastic water tank, but the transparency of the water storage container can be greatly reduced, so that the water storage container is not beneficial to observing the working condition and subsequent maintenance of other parts in the water storage container.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems existing in the prior art. Therefore, the invention provides an antibacterial transparent material, which realizes both 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 further provides a water storage container.
The invention also provides a dish-washing machine.
According to the antibacterial transparent material of 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, isothiazolinone and quaternary ammonium salt antibacterial agents.
According to the antibacterial transparent material provided by the embodiment of the invention, the specific types of antibacterial agents, particularly at least one of polyhexamethylene guanidine hydrochloride, polyhexamethylene biguanidine hydrochloride, isothiazolinone and quaternary ammonium salt antibacterial agents, are added into the transparent plastic particles, and the antibacterial materials such as silver, zinc oxide and the like are not carried by the existing zeolite, so that the long-acting antibacterial performance and good transparency are achieved.
According to some embodiments of the invention, the antimicrobial agent is 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 invention, the antibacterial agent is a composite antibacterial agent composed of polyhexamethylene guanidine hydrochloride and isothiazolinone, wherein the mass ratio of the polyhexamethylene guanidine hydrochloride in the composite antibacterial agent ranges from 20% to 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 embodiment of the second aspect of the invention comprises the steps of mixing raw materials and granulating by a double-screw extruder.
According to the preparation method of the embodiment of the invention, the target antibacterial transparent material particles are obtained through raw material blending, extrusion granulation, and can be further processed into a required transparent plastic finished product.
According to some embodiments of the invention, the mixing of the raw materials is performed using mechanical stirring at a rate of 100-400rpm.
According to some embodiments of the invention, the temperature range during pelletization of the twin screw extruder is 160-240 ℃. Depending on the type of transparent plastic particles:
the transparent plastic particles are polypropylene or polyethylene glycol terephthalate-1, 4-cyclohexanedimethanol ester copolymer, and the technological parameters of granulating by a double-screw extruder are as follows: a zone temperature: 160-180 ℃, two-zone temperature: 170-190 ℃, three-zone temperature: 180-200 ℃, four zone temperature: 180-200 ℃, five-zone temperature: 180-200 ℃, six zone temperature: 180-200 ℃, seven zone temperature: 180-200 ℃, eight zone temperature: 180-200 ℃, die temperature: 190-210 ℃, main screw rotation speed: 300-500rpm, feeding speed: 500-1000kg/h.
The transparent plastic particles are acrylonitrile-butadiene-styrene copolymer or polystyrene, and the technological parameters of granulating by a double-screw extruder are as follows: a zone temperature: 170-190 ℃, two-zone temperature: 180-200 ℃, three-zone temperature: 180-200 ℃, four zone temperature: 180-200 ℃, five-zone temperature: 180-200 ℃, six zone temperature: 190-210 ℃, seven zone temperature: 190-210 ℃, eight zone temperature: 190-210 ℃, die temperature: 200-220 ℃, main screw rotating speed: 300-500rpm, feeding speed: 500-800kg/h.
The transparent plastic particles are acrylonitrile-styrene copolymer, styrene-methyl methacrylate copolymer or polymethyl methacrylate, and the technological parameters of granulating by a double-screw extruder are as follows: a zone temperature: 180-200 ℃, two-zone temperature: 190-210 ℃, three zone temperature: 190-210 ℃, four zone temperature: 200-220 ℃, five-zone temperature: 200-220 ℃, six zone temperature: 210-230 ℃, seven zone temperature: 210-230 ℃, eight zone temperature: 210-230 ℃, die temperature: 220-240 ℃, main screw rotation speed: 300-500rpm, feeding speed: 500-800kg/h.
According to the water storage container of the embodiment of the third aspect of the invention, the water storage container is made of the antibacterial transparent material.
The water storage container made of the antibacterial transparent material (such as injection molding) can realize long-acting antibacterial effect, and has no obvious reduction in transparency compared with a water storage container without antibacterial agent.
A dishwasher according to a fourth aspect of the present invention is provided with the above-described water storage container. In particular, the water tank of the dish washer is made of the antibacterial transparent material.
The above 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, specifically at least one of polyhexamethylene guanidine hydrochloride, polyhexamethylene biguanide hydrochloride, isothiazolinone and quaternary ammonium salt antibacterial agent, the long-acting antibacterial effect is realized, and the transmittance of the original transparent plastic particles is hardly reduced.
Further, the present invention has developed an antimicrobial combination with better effect, which can achieve quite even better long-lasting antimicrobial properties and good transparency with a smaller amount of addition.
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
Embodiments of the present invention are described in further detail below with reference to examples. The following examples are illustrative of the invention but are not intended to limit the scope of the invention.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means 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 embodiments of the present invention. In this specification, schematic representations of the above terms are not necessarily directed 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, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those 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, isothiazolinone and quaternary ammonium salt antibacterial agents.
Wherein the chemical formula of polyhexamethylene guanidine hydrochloride is (C 7 H 15 N 3 ) n.xHCl, abbreviated PHMG. PHMG is an environment-friendly multipurpose novel cationic polymer, is colorless transparent liquid in appearance, has no special smell, has extremely strong capability of killing bacteria and viruses, has good biocompatibility and is nontoxic.
Polyhexamethylene biguanide hydrochloride has the formula (C) 8 H 17 N 5 ) n xHCl, n=12-16, average molecular weight 1100-1800, abbreviated PHMB, is a broad spectrum antimicrobial agent in colorless or pale yellow transparent liquid form.
The isothiazolinone antibacterial agent is brown transparent liquid, and has the excellent performances of broad-spectrum sterilization, low toxicity, no pollution, good compatibility, wide 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. As the conventional method, 3- [ trimethoxysilyl ] propyl dimethyl octadecyl ammonium chloride, dodecyl trimethyl ammonium chloride, dodecyl dimethyl benzyl ammonium bromide, bis (dodecyl dimethyl) bromide, dodecyl dimethyl ethylbenzene oxyethyl ammonium bromide, didecyl dimethyl ammonium bromide and the like are used.
According to the invention, specific types of antibacterial agents, particularly at least one of polyhexamethylene guanidine hydrochloride, polyhexamethylene biguanide hydrochloride, isothiazolinone and quaternary ammonium salt antibacterial agents, are added into transparent plastic particles, and the antibacterial agents are not the conventional antibacterial materials such as zeolite silver-loaded and zinc oxide, so that both long-acting antibacterial performance and good transparency are achieved.
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 copolymer (PCTG), 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 better effect, in particular to a composite antibacterial agent composed 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 ratio of the composite antibacterial agent is 0.5-1% of the mass of the transparent plastic particles.
With this antimicrobial combination, a considerably even better long-acting antimicrobial property and good transparency can be achieved with a smaller amount of addition.
In a preferred embodiment of the invention, the composite antibacterial agent consists of polyhexamethylene guanidine hydrochloride and 2-n-octyl-4-isothiazolin-3-ketone, wherein the mass ratio of the polyhexamethylene guanidine hydrochloride to the 2-n-octyl-4-isothiazolin-3-ketone 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, wherein 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, an embodiment of the present invention provides a method for preparing the antimicrobial transparent material.
The preparation method provided by the embodiment of the invention comprises the steps of mixing raw materials and granulating by a double-screw extruder.
Further, the raw materials are mixed by mechanical stirring, the stirring speed is 100-400rpm, and the stirring time is 2-5min.
Further, in the granulating process of the double-screw extruder, the temperature range is controlled between 160 ℃ and 240 ℃.
Depending on the type of transparent plastic particles:
when the transparent plastic particles are polypropylene or polyethylene glycol terephthalate-1, 4-cyclohexanedimethanol ester copolymer, the technological parameters of granulating by a double screw extruder are as follows: a zone temperature: 160-180 ℃, two-zone temperature: 170-190 ℃, three-zone temperature: 180-200 ℃, four zone temperature: 180-200 ℃, five-zone temperature: 180-200 ℃, six zone temperature: 180-200 ℃, seven zone temperature: 180-200 ℃, eight zone temperature: 180-200 ℃, die temperature: 190-210 ℃, main screw rotation speed: 300-500rpm, feeding speed: 500-1000kg/h;
when the transparent plastic particles are acrylonitrile-butadiene-styrene copolymer or polystyrene, the technological parameters of granulating by a double-screw extruder are as follows: a zone temperature: 170-190 ℃, two-zone temperature: 180-200 ℃, three-zone temperature: 180-200 ℃, four zone temperature: 180-200 ℃, five-zone temperature: 180-200 ℃, six zone temperature: 190-210 ℃, seven zone temperature: 190-210 ℃, eight zone temperature: 190-210 ℃, die temperature: 200-220 ℃, main screw rotating speed: 300-500rpm, feeding speed: 500-800kg/h;
when the transparent plastic particles are acrylonitrile-styrene copolymer, styrene-methyl methacrylate copolymer or polymethyl methacrylate, the technological parameters of granulating by a double-screw extruder are as follows: a zone temperature: 180-200 ℃, two-zone temperature: 190-210 ℃, three zone temperature: 190-210 ℃, four zone temperature: 200-220 ℃, five-zone temperature: 200-220 ℃, six zone temperature: 210-230 ℃, seven zone temperature: 210-230 ℃, eight zone temperature: 210-230 ℃, die temperature: 220-240 ℃, main screw rotation speed: 300-500rpm, feeding speed: 500-800kg/h.
In a third aspect, an embodiment of the present 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 effect, and has no obvious reduction in transparency compared with a water storage container without antibacterial agent. When the water storage container needs to meet the requirements of long-acting antibiosis and transparency visualization, the antibiosis transparent material can be adopted. The water storage container may be a dishwasher water 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 provided with the above-described water storage container. I.e. the dishwasher has a water tank arranged in cooperation for storing water for washing tableware.
Example 1
The embodiment provides an antibacterial transparent material, which comprises transparent plastic particles PP and antibacterial agent 2-n-octyl-4-isothiazolin-3-ketone, wherein the weight ratio of the 2-n-octyl-4-isothiazolin-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-isothiazolin-3-ketone and PP according to the proportion, transferring to a high-speed stirrer, stirring at 100rpm for 3min, and transferring to a feeding hopper of a double-screw extruder for extrusion granulation after uniform stirring and mixing;
the technological parameters of the twin-screw extrusion granulation are as follows: a zone temperature: 170 ℃, two-zone temperature: 180 ℃, three zone temperature: 180 ℃, four zone temperature: 190 ℃, five zone temperature: 190 ℃, six zone temperature: 200 ℃, seven zone temperature: 200 ℃, eight zone temperature: 200 ℃, die temperature: 200 ℃, main screw rotation speed: 400rpm, feed rate: 600kg/h.
The embodiment also provides an antibacterial transparent PP water tank prepared from the materials, and the specific injection molding process is as follows: the injection temperature was 210℃and the dwell cooling time was 25s, the mold temperature was 60 ℃.
Example 2
The embodiment provides an antibacterial transparent material, which comprises transparent plastic particles PCTG and 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 to a high-speed stirrer, stirring at 300rpm for 4min, uniformly stirring and mixing, and transferring to a feeding hopper of a double-screw extruder for preparing extrusion granulation;
the technological parameters of the twin-screw extrusion granulation are as follows: a zone temperature: 180 ℃, two-zone temperature: 190 ℃, three zone temperature: 190 ℃, four zone temperature: 190 ℃, five zone temperature: 190 ℃, six zone temperature: 200 ℃, seven zone temperature: 200 ℃, eight zone temperature: 200 ℃, die temperature: 210 ℃, main screw rotational speed: 500rpm, feed rate: 800kg/h.
The embodiment also provides an antibacterial transparent PCTG water tank prepared from the materials, and the specific injection molding process is as follows: the injection temperature was 210℃and the dwell cooling time was 20s, the mold temperature was 50 ℃.
Example 3
The embodiment provides an antibacterial transparent material, which comprises transparent plastic particles ABS and antibacterial agent 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 to a high-speed stirrer, stirring at 200rpm for 5min, and transferring to a feeding hopper of a double-screw extruder for extrusion granulation after uniform stirring and mixing;
the technological parameters of the twin-screw extrusion granulation are as follows: a zone temperature: 180 ℃, two-zone temperature: 180 ℃, three zone temperature: 190 ℃, four zone temperature: 190 ℃, five zone temperature: 190 ℃, six zone temperature: 200 ℃, seven zone temperature: 200 ℃, eight zone temperature: 200 ℃, die temperature: 210 ℃, main screw rotational speed: 400rpm, feed rate: 800kg/h.
The embodiment also provides an antibacterial transparent ABS water tank prepared from the materials, and the specific injection molding process is as follows: the injection temperature was 230 ℃, the dwell cooling time was 15s, and the mold temperature was 50 ℃.
Example 4
The embodiment provides an antibacterial transparent material, which comprises transparent plastic particles of acrylonitrile-styrene copolymer and antibacterial agent dodecyl dimethyl benzyl ammonium chloride, wherein the weight ratio of the dodecyl dimethyl benzyl ammonium chloride to the 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 the dodecyl dimethyl benzyl ammonium chloride and the acrylonitrile-styrene copolymer according to the proportion, transferring to a high-speed stirrer, stirring at 300rpm for 3min, and transferring to a feeding hopper of a double-screw extruder for extrusion granulation after uniform stirring and mixing;
the technological parameters of the granulation of the double-screw extruder are as follows: a zone temperature: 180 ℃, two-zone temperature: 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 rotational speed: 450rpm, feed rate: 600kg/h.
The embodiment also provides an antibacterial transparent acrylonitrile-styrene copolymer water tank prepared from the materials, and the specific injection molding process is as follows: the injection temperature was 230 ℃, the dwell cooling time was 30s, and the mold temperature was 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-isothiazolin-3-one (CMIT) and PS according to the proportion, transferring to a high-speed stirrer, stirring at 200rpm for 3min, and transferring to a feeding hopper of a double-screw extruder for extrusion granulation after uniform stirring and mixing;
the technological parameters of the twin-screw extrusion granulation are as follows: a zone temperature: 180 ℃, two-zone temperature: 190 ℃, temperature: 190 ℃, four zone temperature: 200 ℃, five zone temperature: 200 ℃, six zone temperature: 200 ℃, seven zone temperature: 210 ℃, eight zone temperature: 210 ℃, die temperature: 210 ℃, main screw rotational speed: 400rpm, feed rate: 500kg/h.
The embodiment also provides an antibacterial transparent PS water tank prepared from the materials, and the specific injection molding process is as follows: the injection temperature was 220 ℃, the dwell cooling time was 25s, and the mold temperature was 50 ℃.
Example 6
The embodiment provides an antibacterial transparent material, which comprises transparent plastic particles PMMA and antibacterial agent 1, 2-benzisothiazolin-3-one (BIT), wherein the weight ratio of 1, 2-benzisothiazolin-3-one (BIT) to 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 to a high-speed stirrer, stirring at 400rpm for 2min, and transferring to a feeding hopper of a double-screw extruder for extrusion granulation after uniform stirring and mixing;
the technological parameters of the twin-screw extrusion granulation are as follows: a zone temperature: 190 ℃, two zone temperature: 200 ℃, temperature: 210 ℃, four zone temperature: 220 ℃, five zone temperature: 220 ℃, six zone temperature: 220 ℃, seven zone temperature: 230 ℃, eight zone temperature: 230 ℃, die temperature: 230 ℃, main screw rotational speed: 500rpm, feed rate: 600kg/h.
The embodiment also provides an antibacterial transparent PMMA water tank prepared from the materials, and the specific injection molding process is as follows: the injection temperature was 230℃and the dwell cooling time was 25s, the mold temperature was 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-isothiazolin-3-ketone, wherein the weight ratio of the polyhexamethylene guanidine hydrochloride to the 2-n-octyl-4-isothiazolin-3-ketone to 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 to a high-speed stirrer, stirring at 100rpm for 3min, and transferring to a feeding hopper of a double-screw extruder for extrusion granulation after uniform stirring and mixing;
the technological parameters of the twin-screw extrusion granulation are as follows: a zone temperature: 170 ℃, two-zone temperature: 180 ℃, three zone temperature: 180 ℃, four zone temperature: 190 ℃, five zone temperature: 190 ℃, six zone temperature: 200 ℃, seven zone temperature: 200 ℃, eight zone temperature: 200 ℃, die temperature: 200 ℃, main screw rotation speed: 400rpm, feed rate: 600kg/h.
The embodiment also provides an antibacterial transparent PP water tank prepared from the materials, and the specific injection molding process is as follows: the injection temperature was 210℃and the dwell cooling time was 25s, the mold temperature was 60 ℃.
Example 8
The embodiment provides an antibacterial transparent material, which comprises transparent plastic particles PS, antibacterial agents polyhexamethylene guanidine hydrochloride and 5-chloro-2-methyl-4-isothiazolin-3-one (CMIT), wherein the weight ratio of the polyhexamethylene guanidine hydrochloride to the 5-chloro-2-methyl-4-isothiazolin-3-one (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 PS according to the proportion, transferring to a high-speed stirrer, stirring at 200rpm for 3min, and transferring to a feeding hopper of a double-screw extruder for extrusion granulation after uniform stirring and mixing;
the technological parameters of the twin-screw extrusion granulation are as follows: a zone temperature: 180 ℃, two-zone temperature: 190 ℃, temperature: 190 ℃, four zone temperature: 200 ℃, five zone temperature: 200 ℃, six zone temperature: 200 ℃, seven zone temperature: 210 ℃, eight zone temperature: 210 ℃, die temperature: 210 ℃, main screw rotational speed: 400rpm, feed rate: 500kg/h.
The embodiment also provides an antibacterial transparent PS water tank prepared from the materials, and the specific injection molding process is as follows: the injection temperature was 220 ℃, the dwell cooling time was 25s, and the mold temperature was 50 ℃.
Comparative example 1
This comparative example provides a transparent water tank directly injection molded from a transparent PP material (without any antimicrobial agent) under the same injection molding conditions as example 1.
Comparative example 2
The comparative example provides a water tank prepared by adding zinc oxide antibacterial agent into transparent PP raw material, zinc oxide: the weight ratio of PP is 0.8:100, mechanical mixing, twin-screw extrusion pelletization and injection molding conditions were the same as in example 1.
Comparative example 3
The comparative example provides a water tank prepared by adding zeolite silver-carrying antibacterial agent into transparent PCTG raw material, wherein the zeolite silver-carrying antibacterial agent comprises: the weight ratio of PCTG was 1.0:100. mechanical mixing, twin screw extrusion pelletization and injection molding conditions were the same as in example 2.
Performance testing
The antibacterial performance test refers to an annex A film coating method in GB 21551.2-2010 special requirements for antibacterial, degerming and purifying function antibacterial materials of household and similar-purpose electric appliances, wherein an experimental sample is an antibacterial transparent water tank prepared by each embodiment and comparative example of the invention, and a control sample is a transparent water tank without an antibacterial agent.
The light transmittance test adopts GB/T2410-2008 'determination of transparent Plastic light transmittance and haze'.
The test results are shown in Table 1.
TABLE 1
The results show that the plastic water tanks of the examples have an antibacterial rate of greater than 99.9% against both E.coli and Staphylococcus aureus, while the water tank of comparative example 1, without added antibacterial agent, has an antibacterial rate of only 20.3% and 12.5% against E.coli and Staphylococcus aureus. As can be seen from comparative example 1 and example 1, there is no significant difference in the transmittance of the antibacterial transparent PP water tank and the transparent PP water tank, indicating that the addition of the antibacterial agent in example 1 greatly improves the antibacterial performance of the material with little impact on the transparency. The comparative example 2 added with the zinc oxide antibacterial agent improved antibacterial performance to some extent, but the light transmittance was only 56.6%, which is significantly lower than the light transmittance of 82.4% of example 1. After 1.0% of zeolite-loaded silver antibacterial agent was added to the transparent PCTG of comparative example 3, the antibacterial rate against both escherichia coli and staphylococcus aureus was more than 99.9%, but the light transmittance of the water tank was only 27.3%, which is far lower than that of the antibacterial transparent PCTG water tank of example 2.
In the embodiment 7, after the polyhexamethylene guanidine hydrochloride and the 2-n-octyl-4-isothiazolin-3-ketone are adopted to compound the antibacterial agent, the antibacterial rate is still more than 99.9%, the light transmittance of the antibacterial water tank is greatly improved as compared with that of the embodiment 1, and the antibacterial water tank reaches 84.7% and is close to that of a pure transparent PP raw material. In example 8, after the polyhexamethylene guanidine hydrochloride and 5-chloro-2-methyl-4-isothiazolin-3-ketone are adopted to compound the antibacterial agent, the light transmittance of the antibacterial PS water tank is greatly improved to 91.3 percent compared with that of example 5, and the antibacterial PS water tank is close to a pure transparent PS raw material. Moreover, the antibacterial water tank of example 8 still has an antibacterial rate of more than 99.9% against both escherichia coli and staphylococcus aureus, while having both high antibacterial rate and excellent transparency.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the 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 scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (8)
1. The antibacterial transparent material is characterized by comprising transparent plastic particles and an antibacterial agent, 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 of the composite antibacterial agent is 0.5-1% of the mass of the transparent plastic particles.
2. The antimicrobial transparent material of claim 1, wherein the transparent plastic particles comprise 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.
3. A method for producing the antibacterial transparent material according to claim 1 or 2, characterized by comprising the step of granulating the raw materials by a twin-screw extruder after mixing them.
4. A method of preparation according to claim 3, wherein the mixing of the raw materials is carried out by mechanical stirring at a rate of 100-400rpm.
5. A method of preparation according to claim 3, wherein the temperature during pelletisation in the twin screw extruder is in the range 160-240 ℃.
6. The method according to claim 5, wherein the transparent plastic particles are polypropylene or polyethylene terephthalate-1, 4-cyclohexanedimethanol ester copolymer, and the technological parameters of the granulation by a twin-screw extruder are as follows: a zone temperature: 160-180 ℃, two-zone temperature: 170-190 ℃, three-zone temperature: 180-200 ℃, four zone temperature: 180-200 ℃, five-zone temperature: 180-200 ℃, six zone temperature: 180-200 ℃, seven zone temperature: 180-200 ℃, eight zone temperature: 180-200 ℃, die temperature: 190-210 ℃, main screw rotation speed: 300-500rpm, feeding speed: 500-1000kg/h;
and/or the transparent plastic particles are acrylonitrile-butadiene-styrene copolymer or polystyrene, and the technological parameters of granulating by a double-screw extruder are as follows: a zone temperature: 170-190 ℃, two-zone temperature: 180-200 ℃, three-zone temperature: 180-200 ℃, four zone temperature: 180-200 ℃, five-zone temperature: 180-200 ℃, six zone temperature: 190-210 ℃, seven zone temperature: 190-210 ℃, eight zone temperature: 190-210 ℃, die temperature: 200-220 ℃, main screw rotating speed: 300-500rpm, feeding speed: 500-800kg/h;
and/or the transparent plastic particles are acrylonitrile-styrene copolymer, styrene-methyl methacrylate copolymer or polymethyl methacrylate, and the technological parameters of granulating by a double-screw extruder are as follows: a zone temperature: 180-200 ℃, two-zone temperature: 190-210 ℃, three zone temperature: 190-210 ℃, four zone temperature: 200-220 ℃, five-zone temperature: 200-220 ℃, six zone temperature: 210-230 ℃, seven zone temperature: 210-230 ℃, eight zone temperature: 210-230 ℃, die temperature: 220-240 ℃, main screw rotation speed: 300-500rpm, feeding speed: 500-800kg/h.
7. A water storage container, characterized in that the material is the antibacterial transparent material as claimed in claim 1 or 2.
8. A dishwasher, characterized in that it is provided with a water reservoir according to claim 7.
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