CN115785609B - Transparent ABS resin composition, and preparation method and application thereof - Google Patents
Transparent ABS resin composition, and preparation method and application thereof Download PDFInfo
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- CN115785609B CN115785609B CN202310044795.5A CN202310044795A CN115785609B CN 115785609 B CN115785609 B CN 115785609B CN 202310044795 A CN202310044795 A CN 202310044795A CN 115785609 B CN115785609 B CN 115785609B
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- butadiene
- styrene copolymer
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- methyl methacrylate
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- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 title claims abstract description 118
- 239000011342 resin composition Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
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- 229920001577 copolymer Polymers 0.000 claims abstract description 58
- 230000000844 anti-bacterial effect Effects 0.000 claims abstract description 49
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims abstract description 43
- 238000002156 mixing Methods 0.000 claims abstract description 28
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- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000002245 particle Substances 0.000 claims abstract description 19
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- 206010011409 Cross infection Diseases 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 206010029803 Nosocomial infection Diseases 0.000 description 1
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- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
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- 208000037797 influenza A Diseases 0.000 description 1
- 239000002054 inoculum Substances 0.000 description 1
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- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
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- 150000007523 nucleic acids Chemical group 0.000 description 1
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 1
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Images
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
- C08J3/2053—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the additives only being premixed with a liquid phase
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2355/00—Characterised by the use of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08J2323/00 - C08J2353/00
- C08J2355/02—Acrylonitrile-Butadiene-Styrene [ABS] polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/04—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses a transparent ABS resin composition, a preparation method and application thereof, wherein the raw materials comprise acrylonitrile-butadiene-styrene copolymer, nanometer platinum, methyl methacrylate-butadiene-styrene copolymer, pentaerythritol and diphenyl dimethoxy silane in a specific mass ratio, the nanometer platinum is added in the form of nanometer platinum solution, and the methyl methacrylate-butadiene-styrene copolymer is in the form of powder particles with the particle size smaller than 12 mu m; preparation: uniformly mixing the nano platinum solution with the powdery granular methyl methacrylate-butadiene-styrene copolymer, and drying to form an intermediate of the nano platinum attached to the powdery granular methyl methacrylate-butadiene-styrene copolymer; the intermediate is mixed with the rest of other raw materials, and the mixture is melt extruded, and the composition has the advantages of high transparency, strong antibacterial and antiviral capability, good durability and the like, and is suitable for being applied to antibacterial transparent products.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a high polymer material with high transparency, strong antibacterial and antiviral capability and long-term stable performance, and particularly relates to a transparent ABS resin composition and a preparation method and application thereof.
Background
An acrylonitrile-butadiene-styrene copolymer (ABS resin for short) is a thermoplastic polymer material having high strength, good toughness and excellent processability, and thus is widely used in the fields of automobile industry, home appliances, packaging, construction, medical care, and the like. In the environment filled with microorganisms, part of pathogenic bacteria such as mould, bacteria, viruses and the like seriously endanger the health of human beings and even endanger life. In the field of application of ABS resin products, ABS resin products are often contacted with human bodies or food, and after long-term use, ABS resin products inevitably get infected with and grow various pathogenic bacteria on the surfaces of ABS resin products, so that cross infection caused by contact with ABS resin products is likely to be caused to the health of users, and development of ABS resin with antibacterial and antiviral effects is extremely important in reducing the risk of spreading pathogenic bacteria. However, ABS resin itself does not have antibacterial and antiviral properties, and is a vehicle for the transmission of pathogenic bacteria and viruses, thereby causing harm to the health of users.
The existing preparation methods of the antibacterial ABS resin materials are relatively more, but in practice, it is found that the transparency of the materials is reduced or destroyed when the common antibacterial agents are added, for example, the common antibacterial agents of silver series, copper series and zinc series can not only greatly reduce the transparency of the materials, but also introduce metallic variegates into the materials, and the antiviral grade cannot be achieved, for example, for influenza A H1N1 virus, the existing antibacterial ABS resin materials are difficult to realize effective resistance. And the ABS resin material added with silver series, copper series and zinc series antibacterial agents can continuously migrate and separate out silver, copper and zinc in the using process, and has poor stability.
Disclosure of Invention
The invention aims to overcome one or more defects in the prior art and provide a novel transparent ABS resin composition which has the advantages of high transparency, strong antibacterial and antiviral capability, good durability, good mechanical (mechanical) property and the like.
The invention also provides a preparation method of the transparent ABS resin composition.
The invention also provides application of the transparent ABS resin composition in preparation of an antibacterial transparent product, which can be a transparent water tank and the like, and is not only beneficial to the health of water quality, but also convenient to know the water level of the water tank in time under the condition of meeting antibacterial and antiviral and transparency.
In order to achieve the above purpose, the invention adopts a technical scheme that: a transparent ABS resin composition comprises acrylonitrile-butadiene-styrene copolymer and additive, wherein the additive comprises nano platinum, methyl methacrylate-butadiene-styrene copolymer, pentaerythritol and diphenyl dimethoxy silane; the nanometer platinum is added in the form of nanometer platinum solution, the nanometer platinum solution comprises the nanometer platinum and a solvent for dispersing the nanometer platinum, and the methyl methacrylate-butadiene-styrene copolymer is in powder particles with the particle size smaller than 12 mu m;
the transparent ABS resin composition is prepared by the following method: uniformly mixing the nano platinum solution with the powdery granular methyl methacrylate-butadiene-styrene copolymer, and drying to form an intermediate of the nano platinum attached to the powdery granular methyl methacrylate-butadiene-styrene copolymer;
mixing the intermediate with the rest other raw materials, and carrying out melt extrusion;
the mass ratio of the acrylonitrile-butadiene-styrene copolymer to the methyl methacrylate-butadiene-styrene copolymer to the pentaerythritol to the diphenyl dimethoxy silane to the nano platinum is 1:0.0001-0.0012:0.0003-0.0009:0.002-0.009:0.0001-0.0008.
According to some preferred and specific aspects of the invention, the methyl methacrylate-butadiene-styrene copolymer has a particle size of 4-10 μm.
According to some preferred and specific aspects of the invention, the nano platinum has a particle size of 3-8nm.
According to some preferred aspects of the invention, the feeding mass ratio of the methyl methacrylate-butadiene-styrene copolymer to the nano platinum is 1:0.2-1.2.
According to some preferred aspects of the present invention, the acrylonitrile-butadiene-styrene copolymer, the methyl methacrylate-butadiene-styrene copolymer, the pentaerythritol, the diphenyldimethoxysilane, and the nano platinum are fed in a mass ratio of 1:0.0002 to 0.0012:0.0005 to 0.00085:0.002 to 0.0065:0.0001 to 0.0008.
According to some preferred aspects of the invention, the acrylonitrile-butadiene-styrene copolymer has a melt index of 10-25g/10min. In some embodiments of the invention, the acrylonitrile-butadiene-styrene copolymer has a melt index of 12 to 25g/10min. In some embodiments of the invention, the acrylonitrile-butadiene-styrene copolymer has a melt index of 15 to 25g/10min.
According to some preferred aspects of the invention, the methyl methacrylate-butadiene-styrene copolymer has a melt index of 17-27g/10min. In some embodiments of the invention, the methyl methacrylate-butadiene-styrene copolymer has a melt index of 20 to 27g/10min.
In the present invention, the melt index of the acrylonitrile-butadiene-styrene copolymer was measured at a temperature of 220℃under a load of 10kg, and the melt index of the methyl methacrylate-butadiene-styrene copolymer was measured at a temperature of 240℃under a load of 3.8 kg.
According to some preferred aspects of the present invention, the transparent ABS resin composition comprises, in mass%, 90% to 99.7% of acrylonitrile-butadiene-styrene copolymer, 0.01% to 1% of methyl methacrylate-butadiene-styrene copolymer, 0.03% to 0.85% of pentaerythritol, 0.2% to 8% of diphenyldimethoxysilane and 0.01% to 0.08% of nano platinum in raw materials. Further, in the raw materials of the transparent ABS resin composition, the acrylonitrile-butadiene-styrene copolymer accounts for 95 to 99.7 percent, the methyl methacrylate-butadiene-styrene copolymer accounts for 0.02 to 0.5 percent, the pentaerythritol accounts for 0.05 to 0.5 percent, the diphenyl dimethoxy silane accounts for 0.2 to 6 percent and the nano platinum accounts for 0.01 to 0.08 percent. Further, in terms of mass percent, the transparent ABS resin composition comprises 97% -99.7% of acrylonitrile-butadiene-styrene copolymer, 0.02% -0.3% of methyl methacrylate-butadiene-styrene copolymer, 0.05% -0.2% of pentaerythritol, 0.2% -3% of diphenyl dimethoxy silane and 0.01% -0.08% of nano platinum.
In some preferred embodiments of the present invention, the transparent ABS resin composition comprises, in mass%, 99.1% to 99.7% of acrylonitrile-butadiene-styrene copolymer, 0.02% to 0.1% of methyl methacrylate-butadiene-styrene copolymer, 0.05% to 0.1% of pentaerythritol, 0.2% to 0.8% of diphenyldimethoxysilane and 0.01% to 0.08% of nano platinum.
According to some preferred aspects of the invention, the feeding mass ratio of the methyl methacrylate-butadiene-styrene copolymer, the pentaerythritol and the diphenyl dimethoxy silane is 1:1-2:8-12.
According to some preferred aspects of the invention, the preparation method of the nano platinum solution comprises the following steps: under the protection of protective gas, potassium chloroplatinate, sodium borohydride, citric acid and lactic acid are reacted in water under the existence of polyvinylpyrrolidone and heating condition to generate nanometer platinum precursor particles, the nanometer platinum precursor particles are separated, dispersed by a solvent, vibrated ultrasonically, and then irradiated by ultraviolet light with the wavelength of 200-350nm to obtain nanometer platinum solution.
According to some preferred and specific aspects of the invention, the potassium chloroplatinate, the sodium borohydride, the citric acid, the lactic acid and the polyvinylpyrrolidone are added in a mass ratio of 1:10-16:25-35:10-20:20-30.
In some embodiments of the invention, the heating conditions are such that the reaction is carried out at a temperature of 55-65 ℃. In some embodiments of the invention, the shielding gas may be nitrogen, helium, or the like.
According to some preferred aspects of the present invention, the nano platinum solution contains 0.001% -0.5% by mass of nano platinum.
The invention provides another technical scheme that: the preparation method of the transparent ABS resin composition comprises the following steps:
uniformly mixing a powdery granular methyl methacrylate-butadiene-styrene copolymer with a nano platinum solution, and drying to form an intermediate of attaching nano platinum to the powdery granular methyl methacrylate-butadiene-styrene copolymer, wherein the nano platinum solution comprises nano platinum and a solvent for dispersing the nano platinum; mixing the intermediate with other raw materials except acrylonitrile-butadiene-styrene copolymer and drying; then adding the acrylonitrile-butadiene-styrene copolymer, uniformly mixing, and carrying out melt extrusion at 190-220 ℃.
In some embodiments of the invention, the solvent is water. In some embodiments of the invention, the melt extrusion is performed using a twin screw extruder at a screw speed of 200-300r/min.
The invention provides another technical scheme that: the application of the transparent ABS resin composition in preparing antibacterial transparent products.
According to some preferred and specific aspects of the invention, the antimicrobial transparent article is a transparent water tank.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
the inventor of the invention has conducted intensive researches on the problems of insufficient antibacterial and antiviral capability, negative influence on transparency after addition of additives and the like existing in the actual use process of the existing ABS resin, and has unexpectedly found that after a large number of experimental researches, nanometer platinum is adopted as an antibacterial and antiviral additive, and simultaneously methyl methacrylate-butadiene-styrene copolymer, pentaerythritol and diphenyldimethoxysilane are compounded as a mixing modifier, and when the ABS resin is prepared, the methyl methacrylate-butadiene-styrene copolymer and nanometer platinum are firstly mixed to prepare an intermediate and then are mixed with other raw materials for extrusion, so that the ABS resin composition has excellent antibacterial and antiviral capability, especially the antibacterial and antiviral capability can be kept for a long time, and unexpected and surprising high transparency is also obtained;
based on this finding, the inventors thought that by further research analysis: the antibacterial and antiviral ability is strong and the long-acting performance is good, because the nano platinum is attached to the powdery granular methyl methacrylate-butadiene-styrene copolymer in a solid form, can be distributed in the whole material system in an excellent dispersity, and is fully embedded into the resin surface layer after re-melt extrusion, is not easy to agglomerate and aggregate, is not easy to migrate and separate out, can continuously maintain the functions of nano effect and the like in the system, and simultaneously, the pentaerythritol and the diphenyl dimethoxy silane are added, hydroxyl and methoxy in the system are hopefully activated by the nano platinum, so that the functional groups have the effects of damaging the outer membrane structure of microorganisms and blocking the synthesis of nucleic acid sequences, and cooperate with the antibacterial and antiviral ability of the nano platinum, so that the ABS resin composition has excellent and long-acting antibacterial and antiviral ability; in addition, although the nano platinum is in a semitransparent state, the system has good combination compatibility, good and uniform dispersion of each particle, small pores in the system, basically no bubbles exist, light refraction is reduced, and the formula system can reduce selective absorption of visible light after being combined, so that the transparency is improved. Therefore, the invention solves the problem that the transparency is reduced for improving the antibacterial capability in the prior art by adjusting the formula system and the process, and the whole process is simple and easy to realize.
Drawings
FIG. 1 is a photograph of a sample wafer molded by injection molding a transparent ABS resin composition of example 1 of the present invention.
Detailed Description
The above-described aspects are further described below in conjunction with specific embodiments; it should be understood that these embodiments are provided to illustrate the basic principles, main features and advantages of the present invention, and that the present invention is not limited by the scope of the following embodiments; the implementation conditions employed in the examples may be further adjusted according to specific requirements, and the implementation conditions not specified are generally those in routine experiments.
All starting materials are commercially available or prepared by methods conventional in the art, not specifically described in the examples below.
In the following, the melt index of the acrylonitrile-butadiene-styrene copolymer was 21g/10min, which was purchased from Toli 920 of Japan; the melt index of the methyl methacrylate-butadiene-styrene copolymer was 24.6g/10min, which was obtained from brillouin M722 of japan, and the particle size thereof was measured to be about 6.5 μm.
The nano platinum solution used in the following examples was prepared by the following method: potassium chloroplatinate (1 g), sodium borohydride (12 g), polyvinylpyrrolidone (25 g, purchased from Shanghai Ala, K29-32), citric acid (30 g) and lactic acid (15 g) are added into deionized water (1L) and stirred to react for 2.5 hours under the heating condition of 60 ℃ to generate nano platinum precursor particles, nitrogen is continuously added as inert protective gas in the reaction process, then the heated solution is purified by a column chromatography mode to remove reaction impurities, the purified nano platinum precursor particles are dispersed by a proper amount of deionized water, and are placed in ultrasonic waves to vibrate for 30 minutes by 30kHz ultrasonic waves, then are irradiated by ultraviolet light with the wavelength of 300nm for 10 minutes to prepare nano platinum solution, the average particle size of the nano platinum prepared by the method is about 5nm, and the mass percentage of the nano platinum is about 0.02%.
Example 1: the present example provides a transparent ABS resin composition and a method for preparing the same, the transparent ABS resin composition comprising, in mass percent: 99.33% of acrylonitrile-butadiene-styrene copolymer, 0.06% of methyl methacrylate-butadiene-styrene copolymer, 0.06% of pentaerythritol, 0.5% of diphenyl dimethoxy silane and 0.05% of nano platinum;
the preparation method of the transparent ABS resin composition comprises the following steps: uniformly mixing the powder granular methyl methacrylate-butadiene-styrene copolymer and a nano platinum solution (the addition mass of the nano platinum solution is 2.5 times of the total mass of the transparent ABS resin composition), and drying to form an intermediate of the nano platinum attached to the powder granular methyl methacrylate-butadiene-styrene copolymer; mixing the intermediate with other raw materials except acrylonitrile-butadiene-styrene copolymer and drying at 60 ℃; then adding the acrylonitrile-butadiene-styrene copolymer, uniformly mixing, and adopting a double-screw extruder to melt and extrude to obtain the transparent ABS resin composition, wherein the screw speed of the double-screw extruder is 220r/min, and the working temperature of the double-screw extruder is as follows: a region: 200 ℃; two areas: 205 deg.c; three regions: 210 ℃; four regions: 215 ℃; five regions: 215 ℃; six areas: 215 ℃; and (3) a die head: 205 ℃.
Example 2: the present example provides a transparent ABS resin composition and a method for preparing the same, the transparent ABS resin composition comprising, in mass percent: 99.42% of acrylonitrile-butadiene-styrene copolymer, 0.04% of methyl methacrylate-butadiene-styrene copolymer, 0.08% of pentaerythritol, 0.4% of diphenyl dimethoxy silane and 0.06% of nano platinum;
the preparation method of the transparent ABS resin composition comprises the following steps: uniformly mixing the powdery granular methyl methacrylate-butadiene-styrene copolymer with a nano platinum solution (the addition mass of the nano platinum solution is 3 times of the total mass of the transparent ABS resin composition), and drying to form an intermediate of the nano platinum attached to the powdery granular methyl methacrylate-butadiene-styrene copolymer; mixing the intermediate with other raw materials except acrylonitrile-butadiene-styrene copolymer and drying at 60 ℃; then adding the acrylonitrile-butadiene-styrene copolymer, uniformly mixing, and adopting a double-screw extruder to melt and extrude to obtain the transparent ABS resin composition, wherein the screw speed of the double-screw extruder is 220r/min, and the working temperature of the double-screw extruder is as follows: a region: 200 ℃; two areas: 205 deg.c; three regions: 210 ℃; four regions: 215 ℃; five regions: 215 ℃; six areas: 215 ℃; and (3) a die head: 205 ℃.
Example 3: the present example provides a transparent ABS resin composition and a method for preparing the same, the transparent ABS resin composition comprising, in mass percent: 99.23% of acrylonitrile-butadiene-styrene copolymer, 0.05% of methyl methacrylate-butadiene-styrene copolymer, 0.07% of pentaerythritol, 0.6% of diphenyl dimethoxy silane and 0.05% of nano platinum;
the preparation method of the transparent ABS resin composition comprises the following steps: uniformly mixing the powder granular methyl methacrylate-butadiene-styrene copolymer and a nano platinum solution (the addition mass of the nano platinum solution is 2.5 times of the total mass of the transparent ABS resin composition), and drying to form an intermediate of the nano platinum attached to the powder granular methyl methacrylate-butadiene-styrene copolymer; mixing the intermediate with other raw materials except acrylonitrile-butadiene-styrene copolymer and drying at 60 ℃; then adding the acrylonitrile-butadiene-styrene copolymer, uniformly mixing, and adopting a double-screw extruder to melt and extrude to obtain the transparent ABS resin composition, wherein the screw speed of the double-screw extruder is 220r/min, and the working temperature of the double-screw extruder is as follows: a region: 200 ℃; two areas: 205 deg.c; three regions: 210 ℃; four regions: 215 ℃; five regions: 215 ℃; six areas: 215 ℃; and (3) a die head: 205 ℃.
Example 4: the present example provides a transparent ABS resin composition and a method for preparing the same, the transparent ABS resin composition comprising, in mass percent: 98.95% of acrylonitrile-butadiene-styrene copolymer, 0.08% of methyl methacrylate-butadiene-styrene copolymer, 0.1% of pentaerythritol, 0.8% of diphenyl dimethoxy silane and 0.07% of nano platinum;
the preparation method of the transparent ABS resin composition comprises the following steps: uniformly mixing the powder granular methyl methacrylate-butadiene-styrene copolymer and a nano platinum solution (the addition mass of the nano platinum solution is 3.5 times of the total mass of the transparent ABS resin composition), and drying to form an intermediate of the nano platinum attached to the powder granular methyl methacrylate-butadiene-styrene copolymer; mixing the intermediate with other raw materials except acrylonitrile-butadiene-styrene copolymer and drying at 60 ℃; then adding the acrylonitrile-butadiene-styrene copolymer, uniformly mixing, and adopting a double-screw extruder to melt and extrude to obtain the transparent ABS resin composition, wherein the screw speed of the double-screw extruder is 220r/min, and the working temperature of the double-screw extruder is as follows: a region: 200 ℃; two areas: 205 deg.c; three regions: 210 ℃; four regions: 215 ℃; five regions: 215 ℃; six areas: 215 ℃; and (3) a die head: 205 ℃.
Example 5: the present example provides a transparent ABS resin composition and a method for preparing the same, the transparent ABS resin composition comprising, in mass percent: 98.87% of acrylonitrile-butadiene-styrene copolymer, 0.075% of methyl methacrylate-butadiene-styrene copolymer, 0.095% of pentaerythritol, 0.9% of diphenyl dimethoxy silane and 0.06% of nano platinum;
the preparation method of the transparent ABS resin composition comprises the following steps: uniformly mixing the powdery granular methyl methacrylate-butadiene-styrene copolymer with a nano platinum solution (the addition mass of the nano platinum solution is 3 times of the total mass of the transparent ABS resin composition), and drying to form an intermediate of the nano platinum attached to the powdery granular methyl methacrylate-butadiene-styrene copolymer; mixing the intermediate with other raw materials except acrylonitrile-butadiene-styrene copolymer and drying at 60 ℃; then adding the acrylonitrile-butadiene-styrene copolymer, uniformly mixing, and adopting a double-screw extruder to melt and extrude to obtain the transparent ABS resin composition, wherein the screw speed of the double-screw extruder is 220r/min, and the working temperature of the double-screw extruder is as follows: a region: 200 ℃; two areas: 205 deg.c; three regions: 210 ℃; four regions: 215 ℃; five regions: 215 ℃; six areas: 215 ℃; and (3) a die head: 205 ℃.
Comparative example 1: substantially the same as in example 1, the only difference is that: pentaerythritol was replaced with equal quality of dimer glycerol.
Comparative example 2: substantially the same as in example 1, the only difference is that: pentaerythritol was replaced with an equivalent mass of stearic acid amide.
Comparative example 3: substantially the same as in example 1, the only difference is that: pentaerythritol was replaced with talc of equivalent quality.
Comparative example 4: substantially the same as in example 1, the only difference is that: methyl methacrylate-butadiene-styrene copolymer was replaced with polyethylene wax of equivalent quality.
Comparative example 5: substantially the same as in example 1, the only difference is that: methyl methacrylate-butadiene-styrene copolymer was replaced with an equivalent mass of calcium stearate.
Comparative example 6: substantially the same as in example 1, the only difference is that: in the preparation process, all the raw materials are uniformly mixed at the same time and then are subjected to melt extrusion.
Comparative example 7: substantially the same as in example 1, the only difference is that: the acrylonitrile-butadiene-styrene copolymer is adjusted to 97.39 percent, the pentaerythritol is adjusted to 2 percent, and the formula system after adjustment is as follows: the transparent ABS resin composition comprises the following raw materials in percentage by mass: 97.39% of acrylonitrile-butadiene-styrene copolymer, 0.06% of methyl methacrylate-butadiene-styrene copolymer, 2% of pentaerythritol, 0.5% of diphenyl dimethoxy silane and 0.05% of nano platinum.
Performance test: (1) antiviral test, the experimental procedure is as follows:
1. experiment preparation: the test is used for sterilizing all the test instruments so as to avoid test pollution;
2. preparation of test samples: preparing a sample to be tested and a blank control sample into a plurality of squares with the sizes of (50+/-2) mm and X (50+/-2) mm and the thicknesses of not more than 10 mm; and (3) injection: the blank control group is a sample of the same material without any antibacterial, antiviral, mildewproof and preservative;
3. preparation of test virus: the cryopreserved host cells were placed in a 37℃water bath, quickly thawed, and the thawed host cells were transferred to a new flask and cell culture was performed using 20mL of medium. Flasks were incubated at 37℃for 24.+ -. 2 hours in a carbon dioxide incubator. Then, the cells were observed under a microscope to see whether the cells were attached to the bottom of the flask. If cells are observed, the next step of the assay is entered. If not, continuing to place the flask in the incubator;
the medium was removed from the flask of host cells and 20mL of fresh medium was added to the flask. Flasks were incubated at 37℃for 48.+ -. 2 hours in a carbon dioxide incubator. The cells were examined under a microscope to confirm whether they were cultured as a fused cell monolayer at the bottom of the flask. Then, the medium was removed from the flask, and the cell monolayer was washed twice with 5mL of PBS solution (phosphate buffer solution). After the PBS solution was removed, 0.5mL of trypsin-EDTA (ethylenediamine tetraacetic acid) solution was added to the flask, and the whole flask surface was smeared. The flask was incubated at 37℃for 10min to 20min in a carbon dioxide incubator. Then, it was observed whether or not the cells on the flask surface began to fall off, and the sides of the flask were tapped and the cells were dispersed. 5mL of medium was added to the flask, and the cell suspension was gently removed with a pipette to avoid damaging the cells. 1mL of the cell suspension was transferred to a new flask, and 20mL of the culture solution was added to perform cell culture. Culturing the flask in a carbon dioxide incubator at 37 ℃ for 3 to 5 days until cell monolayer fusion is confirmed;
the medium in the flask was removed, inoculated with influenza virus, and the flask was incubated in a carbon dioxide incubator at 34℃for 1 hour to allow virus to adsorb on the cells. 20mL of medium and 30 μl of trypsin and PBS solution were again added to the flask. The flasks were incubated in a carbon dioxide incubator at 34 ℃ for 1 to 3 days until about 80% of the monolayers observed under the microscope showed virus-induced cytopathic effects. The contents of the flask were transferred to a centrifuge tube. The mixture was centrifuged at 4℃for 15min to separate cell debris. After centrifugation, the supernatant, i.e., influenza virus suspension, is removed from the centrifuge tube. The suspension was suitably divided into fresh test tubes and stored frozen in a refrigerator at-80 ℃; the frozen influenza virus suspension is placed in a water bath at 37deg.C for use, and thawed rapidly. Adjusting the concentration of the virus suspension to 1X 10 8 PFU/mL to 5X 10 8 PFU/mL. Then, diluting the adjusted virus suspension with purified water to obtain a 10-fold diluted virus suspension, which is the test inoculum;
4. test: dripping 0.4mL of virus suspension on all samples to be tested respectively, covering the samples to be tested respectively by using a sterile film, spreading the bacteria uniformly in contact with the samples without bubbles, placing the bacteria in a sterilization plate, and culturing for 24 hours under the conditions of 25+/-1 ℃ and the relative humidity RH of more than 90%; taking out a sample cultured for 24 hours, respectively adding 10mL of eluent, repeatedly eluting the sample to be tested and the covering film, fully eluting, taking the lotion, inoculating the lotion into a culture medium, culturing for 72 hours at a proper temperature of 37+/-1 ℃, measuring and calculating the infection log value of viruses on cells by a Reed-Muench two-step method, and further calculating the antiviral activity value, wherein the specific result is as follows:
the viruses and host cells are: influenza a H1N1 and MDCK cells;
blank control group: viral infection log value, 0 hours: 5.48 24 hours: 5.38
Example 1: viral infection log value, 0 hours: 5.48 24 hours: 1.06, an antibacterial activity value of 4.32, and an antiviral rate of more than 99.99 percent;
example 2: viral infection log value, 0 hours: 5.48 24 hours: 1.02, an antibacterial activity value of 4.36, and an antiviral rate of more than 99.99%;
example 3: viral infection log value, 0 hours: 5.48 24 hours: 1.13, an antibacterial activity value of 4.25, and an antiviral rate of more than 99.99%;
example 4: viral infection log value, 0 hours: 5.48 24 hours: 0.98, an antibacterial activity value of 4.40, and an antiviral rate of more than 99.99%;
example 5: viral infection log value, 0 hours: 5.48 24 hours: 1.00, an antibacterial activity value of 4.38, and an antiviral rate of more than 99.99%;
comparative example 1: viral infection log value, 0 hours: 5.48 24 hours: 2.98, an antibacterial activity value of 2.40, and an antiviral rate of 99.60%;
comparative example 2: viral infection log value, 0 hours: 5.48 24 hours: 4.17, an antibacterial activity value of 1.21 and an antiviral rate of 93.83%;
comparative example 3: viral infection log value, 0 hours: 5.48 24 hours: 5.17, an antibacterial activity value of 0.21, and an antiviral rate of 38.34%;
comparative example 4: viral infection log value, 0 hours: 5.48 24 hours: 4.00, an antibacterial activity value of 1.38 and an antiviral rate of 95.83%;
comparative example 5: viral infection log value, 0 hours: 5.48 24 hours: 4.05, an antibacterial activity value of 1.33, and an antiviral rate of 95.32%;
comparative example 6: viral infection log value, 0 hours: 5.48 24 hours: 4.33, an antibacterial activity value of 1.05 and an antiviral rate of 91.08%;
comparative example 7: viral infection log value, 0 hours: 5.48 24 hours: 2.68, an antibacterial activity value of 2.70, and an antiviral rate of 99.80%;
antiviral activity value = control 24 hour viral infection log value-test group (i.e. inventive example) 24 hour viral infection log value;
antiviral Rate= [ 1-1/(10++antiviral Activity value) ] × 100% note: of the 10 antiviral activity values, the antiviral activity value is the power of 10, e.g., the antiviral activity value is 4, then it is 4 to the power of 10.
After the materials prepared in examples 1 to 5 and comparative examples 1 to 7 were left for half a year, the above antiviral test was performed again, and specific results are as follows:
the viruses and host cells are: influenza a H1N1 and MDCK cells;
blank control group: viral infection log value, 0 hours: 5.50 24 hours: 5.45;
example 1: viral infection log value, 0 hours: 5.50 24 hours: 1.20, an antibacterial activity value of 4.25, and an antiviral rate of more than 99.99%;
example 2: viral infection log value, 0 hours: 5.50 24 hours: 1.12, an antibacterial activity value of 4.33, and an antiviral rate of more than 99.99%;
example 3: viral infection log value, 0 hours: 5.50 24 hours: 1.30, an antibacterial activity value of 4.15, and an antiviral rate of more than 99.99%;
example 4: viral infection log value, 0 hours: 5.50 24 hours: 1.06, an antibacterial activity value of 4.39, and an antiviral rate of more than 99.99 percent;
example 5: viral infection log value, 0 hours: 5.50 24 hours: 1.10, an antibacterial activity value of 4.35, and an antiviral rate of more than 99.99%;
comparative example 1: viral infection log value, 0 hours: 5.50 24 hours: 3.75, an antibacterial activity value of 1.70, and an antiviral rate of 98%;
comparative example 2: viral infection log value, 0 hours: 5.50 24 hours: 4.55, an antibacterial activity value of 0.9 and an antiviral rate of 87.41%;
comparative example 3: viral infection log value, 0 hours: 5.50 24 hours: 5.25, an antibacterial activity value of 0.20 and an antiviral rate of 36.90%;
comparative example 4: viral infection log value, 0 hours: 5.50 24 hours: 4.50, an antibacterial activity value of 0.95 and an antiviral rate of 88.78%;
comparative example 5: viral infection log value, 0 hours: 5.50 24 hours: 4.53, an antibacterial activity value of 0.92 and an antiviral rate of 88%;
comparative example 6: viral infection log value, 0 hours: 5.50 24 hours: 4.40, an antibacterial activity value of 1.05 and an antiviral rate of 91.09%;
comparative example 7: viral infection log value, 0 hours: 5.50 24 hours: 3.00, the antibacterial activity value is 2.45, and the antiviral rate is 99.65%;
from the above, the formulation system and the corresponding preparation process of the invention play a key role in the antibacterial and antiviral ability of the product, especially in the persistent antibacterial and antiviral ability.
(2) Other Performance test
The materials prepared in examples 1-5 and comparative examples 1-7 were tested for clarity, impact strength, and tensile strength, and the specific results are shown below:
pure ABS resin: the transparency was 88% and the impact strength was 9kJ/m 2 The tensile strength is 48MPa;
example 1: the transparency is 86%, and the impact strength is 11 kJ/m 2 The tensile strength is 49MPa;
example 2: a transparency of 85% and an impact strength of 11 kJ/m 2 Tensile strength was 47MPa;
example 3: the transparency is 86%, and the impact strength is 10 kJ/m 2 The tensile strength is 48MPa;
example 4: the transparency is 85%, and the impact strength is 10 kJ/m 2 The tensile strength is 48MPa;
example 5: a transparency of 85% and an impact strength of 11 kJ/m 2 The tensile strength is 48MPa;
comparative example 1: the transparency was 70%, and the impact strength was 8 kJ/m 2 The tensile strength is 45MPa;
comparative example 2: the transparency was 62%, and the impact strength was 8 kJ/m 2 The tensile strength is 46MPa;
comparative example 3: transparency of 50% and impact strength of 9kJ/m 2 The tensile strength is 45MPa;
comparative example 4: transparency of 35%, impact strength of 8 kJ/m 2 The tensile strength is 45MPa;
comparative example 5: the transparency is 28 percent, and the impact strength is 9kJ/m 2 The tensile strength is 46MPa;
comparative example 6: the transparency is 80 percent, and the impact strength is 10 kJ/m 2 The tensile strength is 48MPa;
comparative example 7: the transparency is 86%, and the impact strength is 10 kJ/m 2 The tensile strength is 49MPa;
test standard, transparency was determined by GB/T2410-2008; impact strength was determined by GB/T1843-2008; tensile strength was determined by GB/T1040-2018;
from the above, it is clear that although some comparative examples have good transparency, they do not satisfy the requirements of antibacterial and antiviral ability, and some comparative examples have slightly high antibacterial ability, but the transparency is severely degraded, and it is difficult to achieve both performance and compatibility, which has a problem in that they are considered to be out of date.
(3) The material of the embodiment 1 of the invention is injection molded into a water tank (injection molding temperature: 220 ℃ and injection molding pressure: 110 MPa), and the picture is as shown in figure 1, so that the material of the invention has good transparency, and is convenient for intuitively observing the internal water level condition.
The above embodiments are provided to illustrate the technical concept and features of the present invention and are intended to enable those skilled in the art to understand the content of the present invention and implement the same, and are not intended to limit the scope of the present invention. All equivalent changes or modifications made in accordance with the spirit of the present invention should be construed to be included in the scope of the present invention.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
Claims (14)
1. The transparent ABS resin composition comprises an acrylonitrile-butadiene-styrene copolymer and an additive, and is characterized in that the additive comprises nano platinum, methyl methacrylate-butadiene-styrene copolymer, pentaerythritol and diphenyl dimethoxy silane; the nanometer platinum is added in the form of nanometer platinum solution, the nanometer platinum solution comprises the nanometer platinum and a solvent for dispersing the nanometer platinum, and the methyl methacrylate-butadiene-styrene copolymer is in powder particles with the particle size smaller than 12 mu m;
the transparent ABS resin composition is prepared by the following method: uniformly mixing the nano platinum solution with the powdery granular methyl methacrylate-butadiene-styrene copolymer, and drying to form an intermediate of the nano platinum attached to the powdery granular methyl methacrylate-butadiene-styrene copolymer;
mixing the intermediate with other raw materials except acrylonitrile-butadiene-styrene copolymer and drying;
then adding the acrylonitrile-butadiene-styrene copolymer, uniformly mixing, and carrying out melt extrusion at 190-220 ℃;
the mass ratio of the acrylonitrile-butadiene-styrene copolymer to the methyl methacrylate-butadiene-styrene copolymer to the pentaerythritol to the diphenyl dimethoxy silane to the nano platinum is 1:0.0001-0.0012:0.0003-0.0009:0.002-0.009:0.0001-0.0008.
2. The transparent ABS resin composition according to claim 1, wherein the mass ratio of the methyl methacrylate-butadiene-styrene copolymer to the nano platinum is 1:0.2 to 1.2.
3. The transparent ABS resin composition according to claim 1, wherein the particle size of the methyl methacrylate-butadiene-styrene copolymer is 4 to 10 μm and the particle size of the nano platinum is 3 to 8nm.
4. The transparent ABS resin composition according to claim 1, wherein the mass ratio of the acrylonitrile-butadiene-styrene copolymer, the methyl methacrylate-butadiene-styrene copolymer, the pentaerythritol, the diphenyldimethoxysilane and the nano platinum is 1:0.0002 to 0.0012:0.0005 to 0.00085:0.002 to 0.0065:0.0001 to 0.0008.
5. The transparent ABS resin composition according to claim 1, wherein the melt index of the acrylonitrile-butadiene-styrene copolymer is 10 to 25g/10min.
6. The transparent ABS resin composition according to claim 1, wherein the melt index of the methyl methacrylate-butadiene-styrene copolymer is 17 to 27g/10min.
7. The transparent ABS resin composition according to claim 1, wherein the raw materials of the transparent ABS resin composition comprise, by mass, 90% to 99.7% of acrylonitrile-butadiene-styrene copolymer, 0.01% to 1% of methyl methacrylate-butadiene-styrene copolymer, 0.03% to 0.85% of pentaerythritol, 0.2% to 8% of diphenyldimethoxysilane and 0.01% to 0.08% of nano platinum.
8. The transparent ABS resin composition according to claim 7, wherein the raw materials of the transparent ABS resin composition comprise, by mass, 99.1 to 99.7% of acrylonitrile-butadiene-styrene copolymer, 0.02 to 0.1% of methyl methacrylate-butadiene-styrene copolymer, 0.05 to 0.1% of pentaerythritol, 0.2 to 0.8% of diphenyldimethoxysilane and 0.01 to 0.08% of nano platinum.
9. The transparent ABS resin composition according to any one of claims 1 to 8, wherein the mass ratio of the methyl methacrylate-butadiene-styrene copolymer, the pentaerythritol, the diphenyldimethoxysilane is 1:1 to 2:8 to 12.
10. The transparent ABS resin composition according to claim 1, wherein the preparation method of the nano platinum solution comprises: under the protection of protective gas, in the presence of polyvinylpyrrolidone and under the heating condition, potassium chloroplatinate, sodium borohydride, citric acid and lactic acid are reacted in water to generate nanometer platinum precursor particles, the nanometer platinum precursor particles are separated, dispersed by a solvent, subjected to ultrasonic vibration, and then irradiated by ultraviolet light with the wavelength of 200-350nm to obtain nanometer platinum solution; wherein the feeding mass ratio of the potassium chloroplatinate to the sodium borohydride to the citric acid to the lactic acid to the polyvinylpyrrolidone is 1:10-16:25-35:10-20:20-30, and the heating condition enables the reaction to be carried out at the temperature of 55-65 ℃.
11. The transparent ABS resin composition according to claim 1 or 10, wherein the nano platinum solution has a mass percentage of nano platinum of 0.001% to 0.5%.
12. A method for producing the transparent ABS resin composition according to any one of claims 1 to 11, wherein the method for producing the transparent ABS resin composition comprises:
uniformly mixing a powdery granular methyl methacrylate-butadiene-styrene copolymer with a nano platinum solution, and drying to form an intermediate of attaching nano platinum to the powdery granular methyl methacrylate-butadiene-styrene copolymer, wherein the nano platinum solution comprises nano platinum and a solvent for dispersing the nano platinum;
mixing the intermediate with other raw materials except acrylonitrile-butadiene-styrene copolymer and drying;
then adding the acrylonitrile-butadiene-styrene copolymer, uniformly mixing, and carrying out melt extrusion at 190-220 ℃.
13. Use of the transparent ABS resin composition according to any one of claims 1 to 11 for the preparation of an antibacterial transparent article.
14. The use according to claim 13, wherein the antimicrobial transparent article is a transparent water tank.
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| PCT/CN2024/084673 WO2024160305A1 (en) | 2023-01-30 | 2024-03-29 | Transparent abs resin composition, preparation method therefor, and use thereof |
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| CN103073832B (en) * | 2011-10-26 | 2015-02-11 | 中国石油化工股份有限公司 | Antibacterial ABS composition and preparation method thereof |
| CN104927331A (en) * | 2015-06-30 | 2015-09-23 | 上海磐树新材料科技有限公司 | Polycarbonate resin composition as well as preparation method and application thereof |
| CN104987648A (en) * | 2015-07-28 | 2015-10-21 | 苏州荣昌复合材料有限公司 | Antibacterial ABS modified plastic |
| CN106084609B (en) * | 2016-06-22 | 2018-09-14 | 武汉纺织大学 | A kind of transparent plastic and preparation method thereof with antibacterial and mouldproof ability |
| JP2020041094A (en) * | 2018-09-13 | 2020-03-19 | 東レ株式会社 | Antibacterial-antifungal resin composition and molding thereof |
| CN111320855A (en) * | 2020-03-30 | 2020-06-23 | 安徽精卫医用材料科技有限公司 | Preparation method of PC/ABS alloy for medical apparatus |
| CN111872410A (en) * | 2020-07-07 | 2020-11-03 | 开贝纳米科技(苏州)有限公司 | Preparation method of nano platinum |
| CN117500376A (en) * | 2021-06-15 | 2024-02-02 | Dic株式会社 | Antibacterial and antiviral agent, antibacterial and antiviral coating composition, laminated body, antibacterial and antiviral resin composition and molded article |
| CN114133695B (en) * | 2021-12-31 | 2024-01-12 | 广东圆融新材料有限公司 | Antibacterial and antiviral master batch, ABS material and preparation method thereof |
| CN114656762B (en) * | 2022-04-15 | 2023-08-22 | 佛山市顺德区美的洗涤电器制造有限公司 | Antibacterial transparent material, preparation method thereof, water storage container and dish-washing machine |
| CN115044162A (en) * | 2022-06-27 | 2022-09-13 | 安徽赤诚塑胶科技有限公司 | Production method of high-transparency ABS plastic masterbatch |
| CN116656075A (en) * | 2023-01-30 | 2023-08-29 | 开贝科技(苏州)有限公司 | Application of transparent ABS resin composition in preparation of antibacterial transparent product and antibacterial transparent product |
-
2023
- 2023-01-30 CN CN202310612201.6A patent/CN116656075A/en active Pending
- 2023-01-30 CN CN202310044795.5A patent/CN115785609B/en active Active
-
2024
- 2024-03-29 WO PCT/CN2024/084673 patent/WO2024160305A1/en unknown
- 2024-03-29 WO PCT/CN2024/084672 patent/WO2024160304A1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CN115785609A (en) | 2023-03-14 |
| CN116656075A (en) | 2023-08-29 |
| WO2024160304A1 (en) | 2024-08-08 |
| WO2024160305A1 (en) | 2024-08-08 |
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