CN102558747B - Acrylonitrile-butadiene-styrene (ABS) material with excellent antibacterial performance and preparation method thereof - Google Patents
Acrylonitrile-butadiene-styrene (ABS) material with excellent antibacterial performance and preparation method thereof Download PDFInfo
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- CN102558747B CN102558747B CN201110433779.2A CN201110433779A CN102558747B CN 102558747 B CN102558747 B CN 102558747B CN 201110433779 A CN201110433779 A CN 201110433779A CN 102558747 B CN102558747 B CN 102558747B
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Abstract
The invention discloses an acrylonitrile-butadiene-styrene material with an excellent antibacterial performance and a preparation method thereof. The steps include: subjecting nanometer TiO2 particles to a doping process so as to obtain doped nanometer TiO2 particles, obtaining modified nanometer TiO2 particles through a coupling modified process, further performing a melt extrusion of the modified nanometer TiO2 particles and the acrylonitrile-butadiene-styrene to prepare the ABS material with the excellent antibacterial performance, wherein the ABS material with an excellent antibacterial performance consists of the following raw materials of, by weight, 93-97% of the ABS, 1-5% of the modified nanometer TiO2 particles, 0.2-1% of dispersing agents, 0.1-1% of antioxygens and 0-3% of other additives. The acrylonitrile-butadiene-styrene material with the excellent antibacterial performance and the preparation method thereof attach a certain antibacterial performance to the ABS material on the basis of guaranteeing the original performances of the ABC material, and have a good application prospect.
Description
Technical field
The present invention relates to a kind of acrylonitrile-butadiene-styrene copolymer (ABS) material with excellent anti-microbial property and preparation method thereof, more particularly pass through nano-TiO
2particle carries out doping treatment and coupling modification obtains modified Nano TiO
2particle, melt extrudes and prepares the ABS material with excellent anti-microbial property with ABS, belongs to polymer modification and manufacture field.
Background technology
Acrylonitrile-butadiene-styrene copolymer (ABS) is a kind of important general synthetic resin, it has the advantages such as good heat resistance, resistance to chemical attack, surface hardness are high, easy forming process, is widely used in the fields such as electronic apparatus, automobile component, body-building apparatus, office appliance, medicine equipment and sanitary ware.In the today of advocating health, environmental protection, by ABS for directly contact with people the parts such as daily living article time, because ABS plastic surface may grow a large amount of harmful microorganisms, when therefore requiring ABS material to there is fine use properties, also require material environment friendly, health, there is good antimicrobial property.
The method of the antibacterial ABS material of preparation is that antiseptic-germicide is directly added in ABS material at present, because of antiseptic-germicide and matrix phase capacitive, bad that antiseptic-germicide is disperseed is inhomogeneous, occur to reunite and make the antibacterial effect can not be lasting, the easy variable color of ABS goods simultaneously obtaining, even can affect its mechanical property.Therefore, need to improve the dispersiveness of antiseptic-germicide in ABS matrix.
Titanium dioxide (TiO
2) as a kind of novel anti-biotic material, enjoy in recent years the features such as people pay close attention to, and it has nontoxic, tasteless, nonirritant, and stability is strong.Due to nano-TiO
2bactericidal property be mainly to utilize the ultraviolet excitation in sunlight, head light to make electronics generation transition, it is not high to light utilization efficiency, particularly in the environment that light lacks, its anti-microbial effect a little less than, therefore need to carry out modification and optimization to it.The method generally adopting is at present silver-doped, as Chinese patent CN 200410017349.2, although the method can make anti-microbial activity increase, because silver exists high, the allochroic problem of cost, has limited to a certain extent its application.
Summary of the invention
The object of the present invention is to provide a kind of ABS material with excellent anti-microbial property and preparation method thereof, wherein antimicrobial particle is uniformly dispersed, and the anti-biotic material antibacterial effect making is long-acting lasting, to meet better the requirement of material to anti-microbial property.
The present invention by the following technical solutions to achieve these goals.
An ABS material with excellent anti-microbial property, is comprised of the raw material of following weight percent:
Wherein, described ABS is the general ABS with different heat-resisting, different shock resistances, and to production company and kind, without strict demand, its rubber content is 5-30% (massfraction).
Described modified Nano TiO
2particle is the dopen Nano TiO through coupling modification
2particle, wherein coupling agent is one or more in silane coupling agent, titanate coupling agent and aluminate coupling agent.
Described dopen Nano TiO
2particle is with anatase type nano TiO
2particle is matrix, and 5% nano zine oxide (ZnO) that adulterates adopts ball milled to make itself and TiO
2mix particles evenly obtains.
Described dispersion agent is one or both combinations in polyethylene wax and Poly Propylene Wax.
Described oxidation inhibitor is Hinered phenols primary antioxidant and phosphorous acid esters auxiliary antioxidant.
Other described additive is shades of colour additive or Masterbatch.
The preparation method of the above-mentioned ABS material with excellent anti-microbial property is as follows:
(4) take by weight ratio raw material;
(5) by ABS, modified Nano TiO
2particle, dispersion agent, oxidation inhibitor and other additive are dry mixed 5～15 minutes in super mixer;
(6) mixed raw material is added in twin screw extruder, after melt extruding, cooling granulation makes, and its technique is: 205～215 ℃, 200～210 210～220 210～220 ℃， 4th district, ℃， 3rd district, ℃， 2nd district, a district; The residence time of whole extrusion is 1～2 minute, and pressure is 12～18MPa.
In order to improve the anti-microbial property of ABS material, technical scheme of the present invention is first to nano-TiO
2particle carries out ZnO doping processing, reduces the energy gap of its transition of electron, makes it absorb light wave generation red shift, increases the responding range of light, thereby improves the photocatalytic activity under sunlight or illumination light; Again particle is carried out to coupling modification and improve the consistency between particle and matrix, increase its degree of scatter in matrix, finally improve the anti-microbial property of material.
Advantage of the present invention is:
1, the present invention is to nano-TiO
2particle carries out doping treatment, has improved it and has lacked the antibacterial ability in environment at light, just has very strong anti-microbial effect, thereby prepare the ABS material with excellent anti-microbial property under weak visible ray effect.
2, to nano-TiO
2particle carries out coupling modification, can improve TiO
2dispersiveness in ABS matrix, keeps TiO well
2photocatalytic activity.
3, the ABS material that the present invention proposes can keep, on the basis of the original mechanical property of ABS material, having excellent anti-microbial property.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail:
In embodiment and comparative example composite-material formula, the ABS that ABS selects Taiwan Qi Mei company to produce, trade names are 747.Nano-TiO
2particle is selected anatase titania, its particle diameter≤5nm, specific surface area > 200m
2/ g.Dopen Nano TiO
2particle: use ball milled at nano-TiO
25% nano zine oxide (production of ZnO， Shanghai Chemical Co., Ltd.) and obtaining adulterates in particle.Modified Nano TiO
2particle: by dopen Nano TiO
2particle makes through silane coupling agent (KH550, commercially available) modification.Dispersion agent is selected polyethylene wax (commercially available).Primary antioxidant is 1076 of Ciba company product, and trade names are Irganox 1076, and chemical name is the positive octadecanol ester of β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid.Auxiliary anti-oxidant is 168 of Ciba company product, and trade names are Irgafos 168, and chemical name is three (2,4-di-tert-butyl-phenyl) phosphorous acid ester.Comprise in addition black masterbatch.
By ABS, modified Nano TiO
2particle, dispersion agent, oxidation inhibitor and other additive are dry mixed 5～15 minutes in super mixer; The raw material mixing is added in twin screw extruder, and through melt extruding, cooling granulation obtains ABS material, and its technique is: 205～215 ℃, 200～210 210～220 210～220 ℃， 4th district, ℃， 3rd district, ℃， 2nd district, a district; The residence time of whole extrusion is 1～2 minute, and pressure is 12～18MPa.
performance evaluation mode and implementation standard:
By the particulate material of preparing as stated above, in the convection oven of 90～100 ℃, be dried 2～3 hours, and then dried particle carried out on injection moulding machine to injection molding sample preparation.
Tensile property test: undertaken by ISO 527-2 standard, specimen size is 170*10*4mm, and draw speed is 50mm/min.
Bending property test: undertaken by ISO 178 standards, specimen size is 80*10*4mm, and rate of bending is 2mm/min, and span is 64mm.
Simple beam impact strength test: undertaken by ISO 179 standards, specimen size is 80*10*4mm, notch depth is sample thickness 1/3rd.
Vicat softening temperature is undertaken by ISO 306, and specimen size is 10*10*4mm, and load is 5kg.
Anti-microbial property test: with reference to GB15981-1995, Q/02GZS001 detection method and standard; Bacterial classification on probation: intestinal bacteria, streptococcus aureus.Concrete steps: after sample sterilization and drying to be checked, 0.2mL bacterium liquid to be measured is evenly dripped on sample respectively, with film, cover, be placed in container, place 24h under 36 ℃ of temperature, humidity 90%RH after, add respectively 20ml elutriant, fully vibration wash-out, carries out live bacterial count, with the recovery bacterium of antibacterial sample and blank sample, calculates its bacteriostasis rate.
The comprehensive mechanical property of material is passed judgment on by the numerical value of tensile strength, flexural strength, notched Izod impact strength and the vicat softening temperature of test gained.
The formula of embodiment and comparative example and properties test result are shown in lower each table:
Table 1 embodiment 1～3 and comparative example 1～7 material prescription table (% by weight)
Table 2 embodiment 1～3 and comparative example 1～7 test result
From the contrast of embodiment 1～3, comparative example 2～7 and comparative example 1, can find out, fill TiO
2aBS material after particle improves greatly to the bacteriostasis rate of intestinal bacteria and streptococcus aureus, has good antimicrobial property, can keep original mechanical property simultaneously.From the contrast of comparative example 2～4 and comparative example 5～7, can find out nano-TiO
2particle, after doping vario-property is processed, can obviously improve the anti-microbial property of ABS material to intestinal bacteria and streptococcus aureus.From the contrast of embodiment and comparative example, can find out filling-modified nano-TiO
2the ABS material of particle has excellent anti-microbial property, and the bacteriostasis rate of intestinal bacteria and streptococcus aureus is reached more than 90%, and when particularly addition is greater than 3%, its bacteriostasis rate reaches more than 96%, has excellent anti-microbial property.
Claims (6)
1. an ABS material with excellent anti-microbial property, is characterized in that: the raw material by following weight percent forms:
Described modified Nano TiO
2particle is the dopen Nano TiO through coupling modification
2particle, wherein coupling agent is one or more in silane coupling agent, titanate coupling agent and aluminate coupling agent; Described dopen Nano TiO
2particle is with anatase type nano TiO
2particle is matrix, and 5% nano zine oxide that adulterates adopts ball milled to make itself and TiO
2mix particles evenly obtains.
2. the ABS material with excellent anti-microbial property according to claim 1, is characterized in that: the rubber content of described ABS is 5-30%.
3. the ABS material with excellent anti-microbial property according to claim 1, is characterized in that: described dispersion agent is one or both combinations in polyethylene wax and Poly Propylene Wax.
4. the ABS material with excellent anti-microbial property according to claim 1, is characterized in that: described oxidation inhibitor is Hinered phenols primary antioxidant and phosphorous acid esters auxiliary antioxidant.
5. the ABS material with excellent anti-microbial property according to claim 1, is characterized in that: other described additive is shades of colour additive or Masterbatch.
6. prepare a method described in claim 1 with the ABS material of excellent anti-microbial property, it is characterized in that:
The steps include:
(1) take by weight ratio raw material;
(2) by ABS, modified Nano TiO
2particle, dispersion agent, oxidation inhibitor and other additive are dry mixed 5～15 minutes in super mixer;
(3) mixed raw material is added in twin screw extruder, after melt extruding, cooling granulation makes, and its technique is: 205～215 ℃, 200～210 210～220 210～220 ℃， 4th district, ℃， 3rd district, ℃， 2nd district, a district; The residence time of whole extrusion is 1～2 minute, and pressure is 12～18MPa.
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| CN102558747B true CN102558747B (en) | 2014-02-26 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103044795A (en) * | 2012-12-17 | 2013-04-17 | 上海普利特复合材料股份有限公司 | Antibacterial transparent polystyrene material and preparation method thereof |
| CN103146133A (en) * | 2013-04-10 | 2013-06-12 | 苏州旭光聚合物有限公司 | Anti-photoaging nano TiO2/ABS (acrylonitrile-butadiene-styrene) composite material and preparation method thereof |
| CN106317755A (en) * | 2016-08-29 | 2017-01-11 | 合肥会通新材料有限公司 | Long-acting, anti-bacterial and mould-proof ABS (acrylonitrile butadiene styrene) functional material and preparation method thereof |
| CN117866373A (en) * | 2024-03-13 | 2024-04-12 | 上海罗克环控节能科技股份有限公司 | Antibacterial composite material for air conditioner and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1563183A (en) * | 2004-03-31 | 2005-01-12 | 华东理工大学 | Method for preparing antibiosis ABS products |
| CN101056505A (en) * | 2006-04-14 | 2007-10-17 | 郭春樱 | Abrasion-proof portable electronic device casing |
| CN101402777A (en) * | 2008-11-14 | 2009-04-08 | 广州市申万电子科技有限公司 | ABS/vinyl cyanide-styrene resin composite material with function of generating negative ion, far-infrared ray or antimicrobial mildew resistant function |
| CN102190855A (en) * | 2011-05-31 | 2011-09-21 | 王剑伟 | Formula and manufacture process for ABS (acrylonitrile-butadiene-styrene copolymer) antibacterial board |
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- 2011-12-21 CN CN201110433779.2A patent/CN102558747B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1563183A (en) * | 2004-03-31 | 2005-01-12 | 华东理工大学 | Method for preparing antibiosis ABS products |
| CN101056505A (en) * | 2006-04-14 | 2007-10-17 | 郭春樱 | Abrasion-proof portable electronic device casing |
| CN101402777A (en) * | 2008-11-14 | 2009-04-08 | 广州市申万电子科技有限公司 | ABS/vinyl cyanide-styrene resin composite material with function of generating negative ion, far-infrared ray or antimicrobial mildew resistant function |
| CN102190855A (en) * | 2011-05-31 | 2011-09-21 | 王剑伟 | Formula and manufacture process for ABS (acrylonitrile-butadiene-styrene copolymer) antibacterial board |
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Address after: 201703 12th Floor, Lane 1, 2855, Shanghai Qingping Highway, Zhaoxiang Town, Qingpu District, Shanghai Patentee after: Shanghai Pret Compound Material Co., Ltd. Address before: 200081 2nd Floor, 421 Lane, Siping Road, Hongkou District, Shanghai Patentee before: Shanghai Pret Compound Material Co., Ltd. |