CN103073784A - Antibacterial polypropylene composition and preparation method thereof - Google Patents
Antibacterial polypropylene composition and preparation method thereof Download PDFInfo
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- CN103073784A CN103073784A CN2011103305309A CN201110330530A CN103073784A CN 103073784 A CN103073784 A CN 103073784A CN 2011103305309 A CN2011103305309 A CN 2011103305309A CN 201110330530 A CN201110330530 A CN 201110330530A CN 103073784 A CN103073784 A CN 103073784A
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Abstract
The invention provides an antibacterial polypropylene composition comprising blended materials of polypropylene resin and a load-type antibacterial agent. Calculated with the weight of the polypropylene resin as 100 parts, the composition comprises 0.1-30 parts of the load-type antibacterial agent. The load-type antibacterial agent is an antibacterial agent loaded by butylbenzene powder rubber. The load-type antibacterial agent comprises an organic antibacterial agent and butylbenzene power rubber. The antibacterial agent is loaded on the butylbenzene powder rubber. An organic antibacterial agent which is in a liquid state in normal temperature or an organic antibacterial agent solution is well mixed with the butylbenzene powder rubber, and the mixture is subjected to standing, until the butylbenzene powder rubber absorbs the organic antibacterial agent which is in a liquid state in normal temperature or the organic antibacterial agent solution, such that the load-type antibacterial agent is obtained. With the method, the obtained antibacterial polypropylene composition has the advantages such as good antibacterial effect, good color, low cost, high safety, and the like. The preparation process is simple and is easy to operate. The method is suitable for industrialized application.
Description
Technical field
The present invention relates to the acrylic plastering manufacture field, say further, relate to a kind of antibacterial polypropylene composition and method of making the same.
Background technology
Along with the raising of people's living standard, healthy and health consciousness constantly strengthens, and many plastics have been proposed antibiotic requirement.Polypropylene is widely used in the daily life articles for use as one of kind maximum in the general-purpose plastics, therefore, polyacrylic antibacterial modified be the focus of antibiotic area research always.
The preparation of antibacterial polypropylene mainly is to realize by add a certain amount of antiseptic-germicide in the polypropylene granulation process.The kind of antiseptic-germicide is a lot, mainly comprises mineral-type antiseptic-germicide, organic antiseptic-germicide two large classes, and mineral-type comprises Ag, Zn-zeolite, Ag, Zn-phosphate laminate, Ag, Zn-water-soluble glass etc., organic comprise quaternary ammonium salts, season phosphonium salt class, imidazoles, pyridines, organo-metallic class etc.The characteristics of inorganic antiseptic are that security, thermotolerance, weather resistance are better, and weak point is the late effect property that price is higher and antibiotic, can not be as organic antibacterial agent rapid kill bacteria.Organic antibacterial agent has the advantages such as sterilization speed is fast, antibacterial range is wide, but also have poor heat resistance, easily ooze out, the problem such as wash resistant, working life be not short, with the inorganic and composite use of organic antibacterial agent, comprehensive the two advantage, remedying weak point that their use separately, is one of antibiotic plastic study hotspot in recent years.
At present, inorganic antiseptic mainly is with Ag, the Zn ion is main sterilization element, it is carried on zeolite, zirconium phosphate, glass, hydroxyapatite, polynite, in the inorganic carriers such as diatomite, because Ag, the Zn ion is supported on the porous of carrier, in the amorphous matrix of stratiform or solubility, therefore in the finished product, can be discharged lentamente, therefore, preferably security and weather resistance are arranged, for example, patent US4775585, US4906464, US4911898 etc. have introduced zeolite-loaded Ag, the antiseptic-germicide of Zn ion, patent US4025608, US4059678, US5296238 etc. have introduced the zirconium phosphate loaded Ag, the Zn antiseptic-germicide, patent US6939820, CN1323588C, CN1318500C etc. have introduced glass-loaded Ag, the Zn antiseptic-germicide, patent US5009898 and US5268174 etc. has introduced Hydroxyapatite-Supported Ag, the Zn antiseptic-germicide.
Organic antibacterial agent normally has the compound of certain molecular structure, kind is more, for example, thiabendazole, m-tetrachlorophthalodinitrile, derosal, Zinc Pyrithione, 2-n-octyl-4-isothiazole-3 ketone (OIT), 4,5-two chloro-Kathons (DCOIT), 10,10 '-oxygen Lian phenoxarsine (OBPA), normal-butyl benzo isothiazolinone (BBIT), 3-iodo-2-propargyl butyl carbamate (IPBC) etc., most of organic antibacterial agent, have the poor characteristics of wetting ability, with general inorganic carrier (for example, zeolite, zirconium phosphate, glass, hydroxyapatite, polynite, diatomite etc.) consistency is bad, therefore, in the structures such as the relatively difficult porous that is supported on inorganic carrier or stratiform, generally directly added in the plastics in use, therefore unlike the Ag in the inorganic antiseptic, the Zn ion, be stored in the hole of inorganic carrier, the sheet interlayer, or in the unformed matrix, can be released slowly, thereby have grow ageing, organic antibacterial agent can be in plastic prod can be separated out with speed faster, therefore, may exist than being easier to and ooze out, wash resistant not, the shortcoming that working life is short.
Summary of the invention:
Therefore, for the problems of the prior art, one of purpose of the present invention provides a kind of antibacterial polypropylene composition, and this antibacterial polypropylene composition has good antimicrobial efficiency, good water tolerance, and have long antibiotic ageing.
Another object of the present invention provides the preparation method of described antibacterial polypropylene composition.This preparation method's technique is simple, easy handling, is suitable for industrial applications.
A kind of antibacterial polypropylene composition of the present invention includes acrylic resin and the loading type antiseptic-germicide of blend, and wherein take acrylic resin as 100 weight parts, the loading type antiseptic-germicide is 0.1～30 part, is preferably 0.3～10 part.
The above loading type antiseptic-germicide is the antiseptic-germicide of powdered rubber load, comprises organic antibacterial agent and butylbenzene powdered rubber, and wherein antiseptic-germicide loads on the butylbenzene powdered rubber.This loading type antiseptic-germicide and acrylic resin consistency are good, can improve the antimicrobial efficiency to acrylic resin, prolong antibiotic ageing and water tolerance.
The above butylbenzene powdered rubber is the powdered rubber with crosslinking structure, and its rubber particles is equal phase structure, and gel content is more than or equal to 60%wt, be preferably more than or equal 75%wt, more preferably greater than or equal 80%wt; Its rubber particles median size is 20～500nm, and more preferably 30～200nm most preferably is 50～150nm.
The above loading type antiseptic-germicide is got by the preparation of one of following methods:
(1) leaves standstill after being mixed to the liquid organic antibacterial agent of normal temperature and butylbenzene powdered rubber evenly, until powdered rubber is with the liquid organic antibacterial agent absorption of normal temperature.
The liquid organic anti-bacterial agent content of described normal temperature is excessively low, the germ-killing efficiency of the antiseptic-germicide of gained butylbenzene powdered rubber load is lower, if the liquid organic antibacterial agent too high levels of normal temperature can cause the butylbenzene powdered rubber to absorb fully, and cause the powdered rubber of load antiseptic-germicide to unite, be unfavorable for that it is in the processed and applied of antibiotic plastic.Therefore, the weight ratio of butylbenzene powdered rubber and organic antibacterial agent is 100: 0.3～100: 50 in the method, is preferably 100: 5～100: 30, more preferably 100: 10～100: 20.
(2) leave standstill after organic anti-bacterial agent solution and described butylbenzene powdered rubber being mixed to evenly, until powdered rubber is with the organic antibacterial agent solution absorption.
Organic antibacterial agent is normal temperature when solid-state, owing to can't be adsorbed in pulverous butylbenzene powdered rubber particle, is convenient to absorption so it need to be prepared into solution; Also can as required it be dissolved in softening agent as for the organic antibacterial agent of normal temperature liquid state and support that solution loads on the powdered rubber.Therefore, the agent solution of organic anti-bacterial described in present method is that normal temperature liquid state and/or the solid-state organic antibacterial agent of normal temperature are dissolved in the solution that softening agent obtains.If the organic antibacterial agent solution usage is excessively low, antiseptic-germicide content is excessively low in the antiseptic-germicide of the butylbenzene powdered rubber load for preparing like that, cause its germ-killing efficiency lower, if the organic antibacterial agent solution usage is too high, can cause powdered rubber to absorb fully, and cause the butylbenzene powdered rubber after the load to unite, be unfavorable for that it uses in the processing of antibiotic plastic.Therefore, the weight ratio of butylbenzene powdered rubber and organic anti-bacterial agent solution is 100: 1～100: 50 in the method, is preferably 100: 10～100: 40, more preferably 100: 20～100: 30.
When described organic anti-bacterial agent solution is the solid-state organic antibacterial agent of normal temperature when being dissolved in the solution that softening agent obtains, the organic anti-bacterial agent content is excessively low, can cause it to be carried in the butylbenzene powdered rubber after, content is lower, antimicrobial efficiency descends; If the too high levels of organic antibacterial agent can cause can't dissolving too much antiseptic-germicide in the softening agent, be unfavorable for the load of antiseptic-germicide in the butylbenzene powdered rubber.Therefore, the weight ratio of wherein said normal temperature SOLID ORGANIC antiseptic-germicide and softening agent is 1: 100～15: 100, is preferably 5: 100～10: 100.
When described organic anti-bacterial agent solution is that the liquid organic antibacterial agent of normal temperature is when being dissolved in the solution that softening agent obtains, weight ratio between wherein said organic antibacterial agent and the softening agent is 1: 100～100: 1, preferred 20: 100～100: 50, more preferably 30: 100～100: 100.
More specifically, be that the liquid and solid-state organic antibacterial agent of normal temperature of normal temperature is when being dissolved in the solution that softening agent obtains at organic anti-bacterial agent solution described in the method (2), be first the solid-state organic antibacterial agent of normal temperature to be dissolved in softening agent, the more liquid organic antibacterial agent adding of normal temperature mixed and gets.
Among the preparation method of the above loading type antiseptic-germicide, with the liquid organic antibacterial agent of butylbenzene powdered rubber and normal temperature or the organic anti-bacterial agent solution mixes, owing to the highly cross-linked structure of butylbenzene powdered rubber, can under the effect of concentration gradient, organic antibacterial agent be absorbed inside and the surface of butylbenzene powdered rubber.Thereby obtain the antiseptic-germicide of this special butylbenzene powdered rubber load.
Butylbenzene powdered rubber described in the loading type antiseptic-germicide of anti-bacterial thermoplastic composite of the present invention can be selected and meet the various butylbenzene powdered rubbers that above-mentioned parameter requires in the prior art, the preferred disclosed full sulfuration butylbenzene powdered rubber of Chinese patent CN1402752A.The full sulfuration of this kind butylbenzene powdered rubber refers to that gel content reaches 60wt% or higher, more preferably 75wt% or higher, and need not with separant after the drying is free flowable rubber micro mist.Should entirely vulcanize the particle diameter of butylbenzene powdered rubber within 20nm～2000nm.Should complete each particulate that vulcanizes in the butylbenzene powdered rubber be homogeneous phase, namely single particulate all be homogeneous on forming.Under the observation of existing microtechnique, do not find the phenomenon of layering, minute equal uneven phase in the particulate.This butylbenzene powdered rubber is by fixing the styrene butadiene rubber latex cross-linking radiation with the styrene-butadiene rubber(SBR) particle diameter.
Described full sulfuration butylbenzene powdered rubber has more surface functional group because itself being organic material, has therefore possessed the condition as some organic anti-bacterial agent carrier.More particularly, entirely vulcanize the butylbenzene powdered rubber, its rubber is the polymkeric substance that is formed by divinyl and styrene monomer copolymerization, and most of organic antibacterial agent is the compound that contains phenyl ring or heterocycle structure, therefore has good consistency with the butylbenzene powdered rubber.The full sulfuration of this kind butylbenzene powdered rubber is little except the particle diameter of rubber particles, specific surface area is large, outside the good advantage of acrylic resin consistency, the crosslinking structure that it is inner, be that latex produces under the effect of the series of process such as irradiation, this and common vulcanization of rubber goods need to add the crosslinking structure that vulcanizing agent could produce in the post-treatment process completely different.The inventor finds by research, because the crosslinking structure of the rubber particles of this butylbenzene powdered rubber can well load to organic antibacterial agent its surface and inner, and behind the complete organic antibacterial agent of load, still can keep its original nano level or near nano level particle diameter, because its nano-scale benefit, large specific surface area, can improve the germ-killing efficiency of organic antibacterial agent, and because the part organic antibacterial agent is supported on its inside, therefore after the organic antibacterial agent on surface is separated out, its inner organic antibacterial agent can continue to separate out outward under the effect of concentration gradient, and it is antibiotic long-lasting thereby improve.
The above organic antibacterial agent can be selected of the prior art various for the antibiotic organic antibacterial agent of plastics, and wherein the solid-state organic antibacterial agent of normal temperature is preferred 4,5-two chloro-Kathons (DCOIT); The organic antibacterial agent of described normal temperature liquid state is at least a in 2-n-octyl-4-isothiazole-3 ketone (OIT), normal-butyl benzo isothiazolinone (BBIT) preferably.
The above softening agent can be selected in the prior art existing various liquid plasticizers in the field of plastics processing, preferably includes at least a in the following material: dioctyl phthalate (DOP), dibutyl phthalate, Di Iso Decyl Phthalate, epoxy soybean oil, epoxyoleic acid butyl ester, Octyl adipate, dioctyl sebacate or Tritolyl Phosphate.
Described in the anti-bacterial thermoplastic composite of the present invention among the preparation method of loading type antiseptic-germicide, the liquid organic antibacterial agent of normal temperature or organic anti-bacterial agent solution mixed with described butylbenzene powdered rubber can adopt various mixing means of the prior art, such as stirring etc.For organic antibacterial agent is loaded on the butylbenzene powdered rubber fully as far as possible, after being mixed to the organic antibacterial agent of normal temperature liquid state or organic anti-bacterial agent solution and described butylbenzene powdered rubber evenly, leaving standstill to be absorbed fully by the butylbenzene powdered rubber to described normal temperature liquid antibacterial agent or organic anti-bacterial agent solution and get final product.Describedly absorb fully, namely take the butylbenzene powdered rubber that has absorbed antiseptic-germicide away after, do not have the visible fluent meterial of naked eyes in the mixing vessel.
Contained loading type antiseptic-germicide in the antibacterial polypropylene composition of the present invention efficiently solves the problem that organic antibacterial agent and common inorganic carrier consistency are poor, be difficult to load.And the butylbenzene powdered rubber in load still can keep the original characteristics of butylbenzene powdered rubber after the organic antibacterial agent, comprise that particle diameter is little, specific surface area is large, the advantage good with the acrylic resin consistency.Therefore, it is added in the acrylic resin, can play the raising antimicrobial efficiency, prolong the effect of antibiotic ageing and water tolerance.
Acrylic resin is selected from various acrylic resin of the prior art described in the antibacterial polypropylene composition of the present invention.Comprise at least a in homo-polypropylene, the Co-polypropylene.
Antibacterial polypropylene composition of the present invention can use separately above-mentioned loading type antiseptic-germicide, can also be with it with the composite use of auxiliary antiseptic-germicide.With the antibiotic broad spectrum of further raising and long-lasting.Described auxiliary antiseptic-germicide comprises inorganic antiseptic and/or organic antibacterial agent.Described inorganic antiseptic is of the prior art take the sterilization metallic element as bactericidal component, the antiseptic-germicide take zeolite, zirconium phosphate or glass as carrier; The wherein preferred Ag ion of sterilization metallic element, Zn ion, Cu ion etc.Inorganic antiseptic preferably includes at least a in the following material: zeolite carries Ag antiseptic-germicide, zeolite and carries Zn antiseptic-germicide, zirconium phosphate and carry Ag antiseptic-germicide, zirconium phosphate and carry Zn antiseptic-germicide, silicate glass and carry Ag antiseptic-germicide, silicate glass and carry Zn antiseptic-germicide, phosphate glass and carry that Ag antiseptic-germicide, phosphate glass carry the Zn antiseptic-germicide, hydroxyapatite carries the Ag antiseptic-germicide and hydroxyapatite carries the Zn antiseptic-germicide.Described organic antibacterial agent is to be usually used in the antibiotic organic antibacterial agent of plastics in the prior art, preferably include thiabendazole, m-tetrachlorophthalodinitrile, derosal, Zinc Pyrithione, poly (hexamethylene) hydrochloride, 2,4,4 '-three chloro-2 '-dihydroxy diphenyl ether, orthoxenol, 10,10 '-in the oxygen connection phenoxarsine (OBPA), 3-iodo-2-propargyl butyl carbamate (IPBC) one or more.Because the loading type antiseptic-germicide in the polypropene composition of the present invention, wherein the inner and area load of butylbenzene powdered rubber described organic antibacterial agent, in the course of processing, have better flowability and oilness, with other auxiliary antiseptic-germicides together, may produce synergistic effect, the antiseptic-germicide total amount that needs to add is reduced, reduce cost.Described auxiliary antiseptic-germicide is take thermoplastics as 100 weight parts, and 0.01～2 part, preferred 0.05～1.0 part.
Antibacterial polypropylene composition of the present invention also can add a certain amount of other plastic processing additives, such as softening agent, toughener, fire retardant, static inhibitor, nucleator, toughner, weighting agent, lubricant, pigment etc. according to concrete needs.Its consumption is conventional amount used, or adjusts according to the requirement of practical situation.
The preparation method of antibacterial polypropylene composition of the present invention comprises the step that the component of described acrylic resin and loading type antiseptic-germicide is got described antibacterial polypropylene composition by described consumption melt blending.
Specifically, first the above each component is mixed according to quantity, and then carry out melt blending, granulation etc.Mixing equipment can adopt used various mixing equipments in the existing processing technology, such as stirrer, kneading machine etc.The equipment of melt blending can adopt various twin screw extruder of the prior art, single screw extrusion machine, Banbury mixer, mill etc., preferred twin screw extruder.
Material melt blending temperature is blending temperature used in the common plastic working among the preparation method of antibacterial polypropylene composition of the present invention, can decide according to the melt temperature of different plastics, should select not only guaranteeing the complete melting of matrix plastic but also can not make in the scope of its decomposition.
Antibacterial polypropylene composition provided by the invention adopts the loading type antiseptic-germicide to carry out antibacterial modified.The loading type antiseptic-germicide adopts has the butylbenzene powdered rubber of crosslinking structure as carrier, because the crosslinked special construction of butylbenzene powdered rubber internal height, and it is good that the butylbenzene powdered rubber has advantages of with the organic antibacterial agent consistency, make it become a kind of good organic anti-bacterial agent carrier, antiseptic-germicide can be carried on it inner and surperficial, efficiently solve organic antibacterial agent and common inorganic carrier consistency poor, the problem that is difficult to load, and the butylbenzene powdered rubber in load still can keep the original characteristics of powdered rubber after the organic antibacterial agent, comprise that particle diameter is little, specific surface area is large, the advantage good with resin compatible, it is added in the acrylic resin, antimicrobial efficiency that can the Effective Raise organic antibacterial agent prolongs that it is ageing, water tolerance.
The preparation method of the antibacterial polypropylene composition that the invention provides can realize the disposable blending extrusions of component such as acrylic resin and loading type antiseptic-germicide can be increased work efficiency greatly, realizes simultaneously good mixing dispersion effect and antibacterial effect.
The antibacterial polypropylene composition of the present invention's preparation has the advantages such as color is good, cost is low, security is high, and its preparation technology is simple, easy handling, is suitable for industrial applications.
Embodiment:
Further describe the present invention below in conjunction with embodiment.Scope of the present invention is not subjected to the restriction of these embodiment, and scope of the present invention proposes in claims.
Following examples and comparative example Raw and equipment are as follows:
One, in the preparation of loading type antiseptic-germicide:
(1) entirely vulcanize butylbenzene powdered rubber: trade(brand)name Narpow, trade mark VP101, gel content (80%wt, 85%wt, 90%wt), median size 100nm, the Sinopec Beijing Chemical Research Institute produces
(2) organic antibacterial agent:
2-n-octyl-4-isothiazole-3 ketone: normal temperature is liquid, trade(brand)name OIT, and Dalian Bio-Chem Co., Ltd. produces.
Normal-butyl benzo isothiazolinone: normal temperature is liquid, trade(brand)name BBIT, and fine jade difficult to understand company produces.
4,5-, two chloro-Kathons: normal temperature is solid-state, trade(brand)name DCOIT, and Dalian Bio-Chem Co., Ltd. produces.
(3) softening agent:
Dioctyl phthalate (DOP): trade(brand)name DOP, commercially available.
Didecyl phthalate: trade(brand)name DIDP, commercially available.
Tritolyl Phosphate: trade(brand)name TCP, commercially available.
Two, in the preparation of antibacterial polypropylene composition:
Pp material:
PP 7726, Sinopec Yanshan Petrochemical, the molten 26g/10min that refers to
PP 9012, Sinopec Maoming Petrochemical, the molten 12g/10min that refers to
PP HHP8, Sinopec Maoming Petrochemical, the molten 8g/10min that refers to
PP F280Z, Sinopec Zhenghai refinery, the molten 2.8g/10min that refers to
PP 9015, and Sinopec is raised sub-petrochemical industry, the molten 15g/10min that refers to
PP M800E, Sinopec oil of SPC, the molten 8g/10min that refers to
Ethylene bis stearamide (EBS), the Shanghai Long March the second chemical plant
Antioxidant 1010, irgasfos 168, Switzerland's Ciba-Geigy is produced
Maleic anhydride inoculated polypropylene, PP-g-MAH, Beijing Chemical Research Institute's percentage of grafting 2%
Ag-silicate glass antiseptic-germicide, SR-104, Beijing Ai Sier company
The Ag-Phosphate Glasses Antibacterial Agents, S-100, the Industrial Co., Ltd. of upper seamount
Zinc Pyrithione, ZPT, Hangzhou Wan Jing company
10,10 '-oxygen Lian phenoxarsine, OBPA, the lofty nanometer in Beijing company limited
The Ag-zirconium phosphate, KWAg, the antibiotic limited-liability company of Xi'an Kang Wang
Carry the zinc zeolite, JYZN, Bei Jingji grinds scientific ﹠ technical corporation
Carry the agent of Zn-antibacterial glass, AMPZ, the lofty nanometer in Beijing company limited
Sodium Benzoate, the Beijing Chemical Plant
The organophosphate nucleator, NA21, Japanese Asahi Denka Kogyo K. K
Calcium stearate, polyethylene wax, commercially available
Twin screw: ZSK-40, German WP company;
Antibiotic print: utilize injection moulding machine (Hai Tian) to make 50mm * 50mm print, in order to antibiotic detection.
Antibiotic examination criteria and operation steps:
1, antibacterial test standard: QB/T 2591-2003A " antibiotic plastic anti-microbial property test method and antibacterial effect "; Detect and use bacterium: staphylococcus aureus (Staphylococcus aureus) ATCC 6538; Intestinal bacteria (Escherichia coli) ATCC 25922.
2, antibacterial test step is tested with reference to antibiotic plastic examination criteria QB/T 2591-2003A, and concrete steps are as follows: testing sample is processed with 75% ethanol disinfection and dried, and bacterial classification is for subsequent use with the bacteria suspension that sterilized water is diluted to proper concn.The bacteria suspension of getting 0.2mL drops in sample surfaces, and (4.0cm * 4.0cm) cover thereon makes bacteria suspension form uniform liquid film between sample and film with the thick polyethylene film of 0.1mm.Keep relative humidity 90% to cultivate 18～24 hours at 37 ℃.With sterilized water bacterium liquid is washed, dilution is got 0.1mL and is uniformly coated on the aseptic nutrient agar that has prepared.Cultivated observations 18～24 hours in 37 ℃.Negative control replaces with aseptic plate, and other operations are identical.
One, the preparation of loading type antiseptic-germicide:
Embodiment 1-1:
Take by weighing full sulfuration butylbenzene powdered rubber (VP101, gel content 80%wt) 100g, 2-n-octyl-4-isothiazole-3 ketone (OIT) 30g, it is stirred in stirrer mixes, take out after leaving standstill 2h, entirely vulcanized the antiseptic-germicide (VP101KJ-1) of butylbenzene powdered rubber load OIT.Each composition weight umber or weight ratio see Table 1.
Embodiment 1-2:
Take by weighing full sulfuration butylbenzene powdered rubber (VP101, gel content 80%wt) 95g, normal-butyl benzo isothiazolinone (BBIT) 5g, it is stirred in stirrer mixes, take out after leaving standstill 3h, entirely vulcanized the antiseptic-germicide (VP101KJ-2) of butylbenzene powdered rubber load BBIT.Each composition weight umber or weight ratio see Table 1.
Embodiment 1-3:
Take by weighing 4,5-, two chloro-Kathon (DCOIT) 10g, it is dissolved among plasticizer phthalic acid dioctyl ester (DOP) 90g, fully stirring makes it become clear solution, is referred to as DCOIT/DOP-1#.
Take by weighing DCOIT/DOP-1#40g, full sulfuration butylbenzene powdered rubber (VP101, gel content 85%wt) 100g stirs it in stirrer, take out after leaving standstill 3h, entirely vulcanized the antiseptic-germicide (VP101KJ-3) of butylbenzene powdered rubber load DCOIT.Each composition weight umber or weight ratio see Table 1.
Embodiment 1-4:
Take by weighing full sulfuration butylbenzene powdered rubber (VP101, gel content 90%wt) 100g, normal-butyl benzo isothiazolinone (BBIT) 50g, it is stirred in stirrer mixes, take out after leaving standstill 4h, entirely vulcanized the antiseptic-germicide (VP101KJ-4) of butylbenzene powdered rubber load BBIT.Each composition weight umber or weight ratio see Table 1.
Embodiment 1-5:
Take by weighing full sulfuration butylbenzene powdered rubber (VP101, gel content 90%wt) 90g, normal-butyl benzo isothiazolinone (BBIT) 10g, it is stirred in stirrer mixes, take out after leaving standstill 4h, entirely vulcanized the antiseptic-germicide (VP101KJ-5) of butylbenzene powdered rubber load BBIT.Each composition weight umber or weight ratio see Table 1.
Embodiment 1-6:
Take by weighing 4,5-, two chloro-Kathon (DCOIT) 10g, it is dissolved among plasticizer phthalic acid didecyl ester (DIDP) 70g, fully stirring makes it become clear solution, is referred to as DCOIT/DIDP-1#.
Take by weighing DCOIT/DIDP-1#30g, full sulfuration butylbenzene powdered rubber (VP101, gel content 90%wt) 70g stirs it in stirrer, take out after leaving standstill 3h, entirely vulcanized the antiseptic-germicide (VP101KJ-6) of butylbenzene powdered rubber load DCOIT.Each composition weight umber or weight ratio see Table 1.
Embodiment 1-7:
Take by weighing 2-n-octyl-4-isothiazole-3 ketone (OIT) 0.3g, full sulfuration butylbenzene powdered rubber (VP101, gel content 90%wt) 100g, it is stirred in stirrer, take out after leaving standstill 1h, entirely vulcanized the antiseptic-germicide (VP101KJ-7) of butylbenzene powdered rubber load OIT.Each composition weight umber or weight ratio see Table 1.
Embodiment 1-8:
Take by weighing normal-butyl benzo isothiazolinone (BBIT) 100g, softening agent Tritolyl Phosphate (TCP, commercially available) 100g, fully stirring mixes it, is referred to as BBIT/TCP-1#.
Take by weighing BBIT/TCP-1#10g, full sulfuration butylbenzene powdered rubber (VP101, gel content 90%wt) 90g stirs it in stirrer, take out after leaving standstill 1h, entirely vulcanized the antiseptic-germicide (VP101KJ-8) of butylbenzene powdered rubber load BBIT.Each composition weight umber or weight ratio see Table 1.
Embodiment 1-9:
Take by weighing normal-butyl benzo isothiazolinone (BBIT) 400g, softening agent Tritolyl Phosphate (TCP) 100g, fully stirring mixes it, is referred to as BBIT/TCP-2#.
Take by weighing BBIT/TCP-2#30g, full sulfuration butylbenzene powdered rubber (VP101, gel content 90%wt) 70g stirs it in stirrer, take out after leaving standstill 1h, entirely vulcanized the antiseptic-germicide (VP101KJ-9) of butylbenzene powdered rubber load BBIT.Each composition weight umber or weight ratio see Table 1.
Embodiment 1-10:
Take by weighing normal-butyl benzo isothiazolinone (BBIT) 90g, softening agent Tritolyl Phosphate (TCP) 10g, fully stirring mixes it, is referred to as BBIT/TCP-3#.
Take by weighing BBIT/TCP-3#1g, full sulfuration butylbenzene powdered rubber (VP101, gel content 90%wt) 99g stirs it in stirrer, take out after leaving standstill 1h, entirely vulcanized the antiseptic-germicide (VP101KJ-10) of butylbenzene powdered rubber load BBIT.
Embodiment 1-11
Take by weighing normal-butyl benzo isothiazolinone (BBIT) 20g, softening agent Tritolyl Phosphate (TCP) 100g, fully stirring mixes it, is referred to as BBIT/TCP-4#.
Take by weighing BBIT/TCP-3#10g, full sulfuration butylbenzene powdered rubber (VP101, gel content 90%wt) 90g stirs it in stirrer, take out after leaving standstill 1h, entirely vulcanized the antiseptic-germicide (VP101KJ-11) of butylbenzene powdered rubber load BBIT.Each composition weight umber or weight ratio see Table 1.
Table 1
Two, the preparation of antibacterial polypropylene composition
Embodiment 2-1:
With 100 parts of polypropylene (PP, 7726); VP101KJ-1:0.65 part is put into low speed mixer and is stirred, and then mixture is passed through the twin screw extruder melt blending, and extruding pelletization, extruder temperature are 190 ℃～220 ℃, and rotating speed is 350r.p.m.The pellet of extruding is dried 3hr in 90 ℃ of constant temperature ovens, then become the sample of 50mm * 50mm at 200～220 ℃ of hemostasis of injection temperature, carry out antibacterial test.The part print is positioned in 50 ℃ of hot water and soaks 16h before antibacterial test.
The anti-bacterial result:
Before the poach: staphylococcus aureus: 99.9%; Intestinal bacteria: 99.9%
Behind the poach: staphylococcus aureus: 99.9%; Intestinal bacteria: 99.9%
Comparative example 2-1
VP101KJ-10.65 part among the embodiment 2-1 is replaced with 0.15 part of the 2-n-octyl identical with content among the embodiment 2-1-4-isothiazole-3 ketone (OIT), and other steps are made into print with embodiment 2-1, carry out antibacterial test.
The anti-bacterial result:
Before the poach: staphylococcus aureus: 97.3%; Intestinal bacteria: 92.0%
Behind the poach: staphylococcus aureus: 75.5%; Intestinal bacteria: 63.2%
From above-mentioned comparative example, as seen for acrylic plastering, in the situation that identical organic antibacterial agent OIT content, before and after the poach, utilize the antibacterial effect of VP101KJ-1 modified polypropene all to be better than the effect of independent use OIT, the VP101KJ-1 antibacterial effect will be significantly better than the effect of independent use antiseptic-germicide OIT behind the poach, this may be because OIT is supported on the surperficial and inner of butylbenzene fully vulcanized powder rubber, dispersiveness is improved, also play the effect of slowly-releasing OIT, therefore, germ resistance, water tolerance and long-lasting being improved.
Embodiment 2-2:
With 100 parts of polypropylenes (PP, 7726); VP101KJ-2:2.0 part, ethylene bis stearamide (EBS): 0.2 part; Antioxidant 1010: 0.1 part; Irgasfos 168: 0.1 part; PP-g-MAH:3 part, 0.05 part of calcium stearate; Putting into low speed mixer stirs, then mixture is passed through the twin screw extruder melt blending, extruder temperature is 190 ℃～220 ℃, rotating speed is the 350r.p.m extruding pelletization, roving glass fiber in the extrusion (state-run 251 factories), by material blend in glass charging opening and the screw rod on the twin screw, add-on is 32%wt approximately.The pellet of extruding is dried 3hr in 90 ℃ of constant temperature ovens, then become the sample of 50mm * 50mm at 200～220 ℃ of hemostasis of injection temperature, carry out antibacterial test.The part print is positioned in 50 ℃ of hot water and soaks 16h before antibacterial test.
The anti-bacterial result:
Before the poach: staphylococcus aureus: 99.9%; Intestinal bacteria: 99.9%
Behind the poach: staphylococcus aureus: 99.9%; Intestinal bacteria: 99.9%
Comparative example 2-2
VP101KJ-2 among the embodiment 2-2 is replaced with 0.1 part of the normal-butyl benzo isothiazolinone (BBIT) identical with content among the embodiment 2-2, and other steps are made into print with embodiment 2-2, carry out antibacterial test.
The anti-bacterial result:
Before the poach: staphylococcus aureus: 98.9%; Intestinal bacteria: 95.0%
Behind the poach: staphylococcus aureus: 62.7%; Intestinal bacteria: 60.8%
From above-mentioned comparative example, as seen for fiber glass reinforced polypropylene, in the situation that identical BBIT content, utilizing the glass of VP101KJ-2 modification to strengthen the antibacterial effect of PP will be significantly better than the effect of independent use BBIT.
Embodiment 2-3:
With 100 parts of polypropylene (PP, 9012); VP101KJ-3:3.5 part, 0.1 part of polyethylene wax, putting into low speed mixer stirs, then mixture is passed through the twin screw extruder melt blending, extruder temperature is 190 ℃～200 ℃, and rotating speed is the 350r.p.m extruding pelletization, and the pellet of extruding is dried 3hr in 90 ℃ of constant temperature ovens, then become the sample of 50mm * 50mm at 200～210 ℃ of hemostasis of injection temperature, carry out antibacterial test.The part print is positioned in 50 ℃ of hot water and soaks 16h before antibacterial test.
The anti-bacterial result:
Before the poach: staphylococcus aureus: 99.9%; Intestinal bacteria: 99.9%
Behind the poach: staphylococcus aureus: 99.9%; Intestinal bacteria: 99.9%
Comparative example 2-3
VP101KJ-3 among the embodiment 2-3 is replaced with identical with content among the embodiment 2-3 4,0.1 part of 5-two chloro-Kathon (DCOIT), other steps are made into print with embodiment 2-3, carry out antibacterial test.
The anti-bacterial result:
Before the poach: staphylococcus aureus: 97.8%; Intestinal bacteria: 93.5%
Behind the poach: staphylococcus aureus: 89.2%; Intestinal bacteria: 86.7%
From above-mentioned comparative example, in the situation that identical DCOIT content, utilize the antibacterial effect of VP101KJ-3 MODIFIED PP will be significantly better than the effect of independent use DCOIT.
Embodiment 2-4:
Get 100 parts of polypropylene (PP, 7726), antiseptic-germicide: VP101KJ-40.1 part; Auxiliary antiseptic-germicide: 0.2 part of Ag-silicate glass antiseptic-germicide (Beijing Ai Sier SR-104 of company), material is put into low speed mixer stir.Then mixture is passed through the twin screw extruder melt blending, extrusion temperature is 200～210 ℃, and the pellet of extruding is dried 3hr in 90 ℃ of constant temperature ovens, then becomes the sample of 50mm * 50mm at 190～220 ℃ of hemostasis of injection temperature, carries out antibacterial test.The part print is positioned in 50 ℃ of hot water and soaks 16h before antibacterial test.
The anti-bacterial result:
Before the poach: staphylococcus aureus: 99.9%; Intestinal bacteria: 99.9%
Behind the poach: staphylococcus aureus: 99.9%; Intestinal bacteria: 99.9%
Comparative example 2-4.1
VP101KJ-4 among the embodiment 2-4 is replaced with 0.033 part of the normal-butyl benzo isothiazolinone (BBIT) that content is identical among the embodiment 2-4, and other steps are made into print with embodiment 2-4, carry out antibacterial test.
The anti-bacterial result:
Before the poach: staphylococcus aureus: 96.3%; Intestinal bacteria: 95.5%
Behind the poach: staphylococcus aureus: 90.6%; Intestinal bacteria: 89.4%
By relatively can finding out of embodiment 2-4 and comparative example 2-4.1, in the situation that identical BBIT content, before and after the poach, utilize the antibacterial effect of VP101KJ-4 and the composite modified PP of Ag-silicate glass antiseptic-germicide SR-104 will be significantly better than using BBIT and the composite effect of SR-104.
Comparative Examples 2-4.2
VP101KJ-4 among the embodiment 2-4 is replaced with 0.1 part of full sulfuration butylbenzene powdered rubber (VP101, gel content 90%wt), and other steps are made into print with embodiment 2-4, carry out antibacterial test.
The anti-bacterial result:
Before the poach: staphylococcus aureus: 92.1%; Intestinal bacteria: 90.6%
Behind the poach: staphylococcus aureus: 87.4%; Intestinal bacteria: 82.9%
By relatively can finding out of embodiment 2-4 and Comparative Examples 2-4.2, utilization contains the composite antibacterial effect of the VP101KJ of BBIT and SR-104 will be significantly better than the composite effect of pure powdered rubber and SR-104, because the effect of organic BBIT and inorganic antiseptic Synergistic antimicrobial on the one hand, may be that to contain the butylbenzene powdered rubber surface lubrication of BBIT good on the other hand, inorganic antiseptic SR-104 has been played better dissemination.
Embodiment 2-5:
Get 100 parts of polypropylene (PP, HHP8); VP101KJ-50.5 part; Auxiliary antiseptic-germicide: 0.2 part of Ag-Phosphate Glasses Antibacterial Agents (S-100 of Industrial Co., Ltd. of upper seamount); 0.5 part of calcium stearate, 0.2 part of nucleator (Sodium Benzoate), mixture is passed through the twin screw extruder melt blending, extruder temperature is 190 ℃～210 ℃, rotating speed is 350r.p.m melt blending extruding pelletization, the pellet of extruding is dried 9hr in 80 ℃ of constant temperature ovens, then become the sample of 50mm * 50mm at 250～260 ℃ of hemostasis of injection temperature, carry out antibacterial test.The part print is positioned in 50 ℃ of hot water and soaks 16h before antibacterial test.
The anti-bacterial result:
Before the poach: staphylococcus aureus: 99.9%; Intestinal bacteria: 99.9%
Behind the poach: staphylococcus aureus: 99.9%; Intestinal bacteria: 99.9%
Comparative example 2-5
VP101KJ-51 part among the embodiment 2-5 is replaced with 0.05 part of the normal-butyl benzo isothiazolinone (BBIT) that content is identical among the embodiment 2-5, and other steps are made into print with embodiment 2-5, carry out antibacterial test.
The anti-bacterial result:
Staphylococcus aureus: 92.6%; Intestinal bacteria: 89.3%
Staphylococcus aureus: 88.2%; Intestinal bacteria: 83.7%
From above-mentioned comparative example, in the situation that same amount BBIT and inorganic antiseptic S-100, utilize the composite modified PP antibacterial effect of VP101KJ-5 and SR104 will be significantly better than using antiseptic-germicide BBIT and the composite effect of S-100.
Embodiment 2-6:
Get 100 parts of polypropylene (PP, F280Z); VP101KJ-6:1.0 part; Auxiliary antiseptic-germicide: 0.05 part of Zinc Pyrithione (the Hangzhou Wan Jing ZPT of company); 0.3 part of calcium stearate; Passing through the twin screw extruder melt blending after mixing, extruder temperature is 190 ℃～200 ℃, rotating speed is 350r.p.m melt blending extruding pelletization, the pellet of extruding is dried 5hr in 90 ℃ of constant temperature ovens, then become the sample of 50mm * 50mm at 200 ℃ of injection temperatures～210 ℃ of hemostasis, carry out antibacterial test.The part print is positioned in 50 ℃ of hot water and soaks 16h before antibacterial test.
The anti-bacterial result:
Before the poach: staphylococcus aureus: 99.9%; Intestinal bacteria: 99.9%
Behind the poach: staphylococcus aureus: 99.9%; Intestinal bacteria: 99.9%
Comparative example 2-6
With the VP101KJ-6 among the embodiment 2-6 replace with content among the embodiment 2-6 identical 4,0.035 part of 5-two chloro-Kathon (DCOIT), other steps are made into print with embodiment 2-6, carry out antibacterial test.
The anti-bacterial result:
Before the poach: staphylococcus aureus: 99.2%; Intestinal bacteria: 94.4%
Behind the poach: staphylococcus aureus: 84.7%; Intestinal bacteria: 82.3%
From above-mentioned comparative example, in the situation that identical DCOIT and Zinc Pyrithione content, utilize the antibacterial effect of VP101KJ-6 and the composite post-modification of Zinc Pyrithione will be significantly better than using DCOIT and the composite effect of Zinc Pyrithione.
Embodiment 2-7:
Get 100 parts of polypropylene (PP, 9012); VP101KJ-7:30 part; Auxiliary antiseptic-germicide: 10,10 '-0.03 part of oxygen Lian phenoxarsine (OBPA); Ethylene bis stearamide (EBS): 0.3 part; Antioxidant 1010: 0.1 part; Irgasfos 168: 0.1 part; Putting into low speed mixer stirs, then mixture is passed through the twin screw extruder melt blending, extruder temperature is 190 ℃～210 ℃, rotating speed is the rotating speed melt blending extruding pelletization of 350r.p.m, the pellet of extruding is dried 5hr in 90 ℃ of constant temperature ovens, then become the sample of 50mm * 50mm at 190～200 ℃ of hemostasis of injection temperature, carry out antibacterial test.The part print is positioned in 50 ℃ of hot water and soaks 16h before antibacterial test.
The anti-bacterial result:
Before the poach: staphylococcus aureus: 99.9%; Intestinal bacteria: 99.9%
Behind the poach: staphylococcus aureus: 99.9%; Intestinal bacteria: 99.9%
Comparative example 2-7
VP101KJ-7 among the embodiment 2-7 is replaced with 0.09 part of the 2-n-octyl that content is identical among the embodiment 2-7-4-isothiazole-3 ketone (OIT), and other steps are made into print with embodiment 2-7, carry out antibacterial test.
The anti-bacterial result:
Before the poach: staphylococcus aureus: 96.2%; Intestinal bacteria: 92.8%
Behind the poach: staphylococcus aureus: 91.5%; Intestinal bacteria: 89.2%
From above-mentioned comparative example, in the situation that identical OIT and OBPA content, utilize VP101KJ-7 and
The antibacterial effect of the composite post-modification of OBPA will be significantly better than using antiseptic-germicide OIT and the composite effect of OBPA.
Embodiment 2-8:
Get 100 parts of polypropylene (PP, 9015); VP101KJ-8:1.0 part, auxiliary antiseptic-germicide: 0.6 part of Ag-zirconium phosphate (Xi'an Kang Wang, KWAg); Antioxidant 1010: 0.2 part; Putting into low speed mixer stirs, then mixture is passed through the twin screw extruder melt blending, extruder temperature is 190 ℃～210 ℃, rotating speed is the 350r.p.m extruding pelletization, the pellet of extruding is dried 3hr in 100 ℃ of constant temperature ovens, then become the sample of 50mm * 50mm at 190～210 ℃ of hemostasis of injection temperature, carry out antibacterial test.The part print is positioned in 50 ℃ of hot water and soaks 16h before antibacterial test.
The anti-bacterial result:
Before the poach: staphylococcus aureus: 99.9%; Intestinal bacteria: 99.9%
Behind the poach: staphylococcus aureus: 99.9%; Intestinal bacteria: 99.9%
Comparative example 2-8
VP101KJ-8 among the embodiment 2-8 is replaced with 0.054 part of the normal-butyl benzo isothiazolinone (BBIT) that content is identical among the embodiment 2-8, and other steps are made into print with embodiment 2-8, carry out antibacterial test.
The anti-bacterial result:
Before the poach: staphylococcus aureus: 89.3%; Intestinal bacteria: 86.8%
Behind the poach: staphylococcus aureus: 74.5%; Intestinal bacteria: 70.1%
From above-mentioned comparative example, in the situation that identical BBIT and Ag-zirconium phosphate (KWAg) content, utilize the antibacterial effect of VP101KJ-8 and the composite post-modification of KWAg will be significantly better than using antiseptic-germicide BBIT and the composite effect of KWAg.
Embodiment 2-9:
Get 100 parts of polypropylene (PP, M800E); VP101KJ-9,0.2 part; Auxiliary antiseptic-germicide carries 0.3 part in zinc zeolite (Bei Jingji grinds the JYZN of scientific ﹠ technical corporation); Putting into low speed mixer stirs, then mixture is passed through the twin screw extruder melt blending, extruder temperature is 190 ℃～210 ℃, rotating speed is the 350r.p.m extruding pelletization, the pellet of extruding is dried 3hr in 100 ℃ of constant temperature ovens, then become the sample of 50mm * 50mm at 200～210 ℃ of hemostasis of injection temperature, carry out antibacterial test.The part print is positioned in 50 ℃ of hot water and soaks 16h before antibacterial test.
The anti-bacterial result:
Before the poach: staphylococcus aureus: 99.9%; Intestinal bacteria: 99.9%
Behind the poach: staphylococcus aureus: 99.9%; Intestinal bacteria: 99.9%
Comparative example 2-9
The VP101KJ-9 of embodiment 2-9 is replaced with 0.05 part of the normal-butyl benzo isothiazolinone (BBIT) that content is identical among the embodiment 2-9, and other steps are made into print with embodiment 2-9, carry out antibacterial test.
The anti-bacterial result:
Before the poach: staphylococcus aureus: 99.3%; Intestinal bacteria: 98.7%
Behind the poach: staphylococcus aureus: 92.5%; Intestinal bacteria: 89.7%
From above-mentioned comparative example, in the situation that identical BBIT and carry a zinc zeolite JYZN, utilizing VP101KJ-9 and carry the antibacterial effect of the composite post-modification of zinc zeolite JYZN will be significantly better than using BBIT and the composite effect of JYZN.
Embodiment 2-10:
Get 100 parts of polypropylene (PP, 9015); VP101-10,1.0 parts; Auxiliary antiseptic-germicide: carry 0.4 part of Zn-antibacterial glass agent (the lofty nanometer AMPZ of company limited in Beijing), 0.2 part of Sodium Benzoate, 0.1 part of organophosphate nucleator (Japanese rising sun electrification NA21), putting into low speed mixer stirs, then mixture is passed through the twin screw extruder melt blending, extruder temperature is 190 ℃～210 ℃, rotating speed is the 350r.p.m extruding pelletization, the pellet of extruding is dried 3hr in 100 ℃ of constant temperature ovens, then become the sample of 50mm * 50mm at 200～210 ℃ of hemostasis of injection temperature, carry out antibacterial test.The part print is positioned in 50 ℃ of hot water and soaks 16h before antibacterial test.
The anti-bacterial result:
Before the poach: staphylococcus aureus: 99.9%; Intestinal bacteria: 99.9%
Behind the poach: staphylococcus aureus: 99.9%; Intestinal bacteria: 99.9%
Comparative example 2-10
The VP101KJ-10 of embodiment 2-10 is replaced with 0.01 part of the normal-butyl benzo isothiazolinone (BBIT) that content is identical among the embodiment 2-10, and other steps are made into print with embodiment 2-10, carry out antibacterial test.
The anti-bacterial result:
Before the poach: staphylococcus aureus: 97.5%; Intestinal bacteria: 95.6%
Behind the poach: staphylococcus aureus: 90.2%; Intestinal bacteria: 87.3%
From above-mentioned comparative example, in the situation that identical BBIT and carry a zinc glass AMPZ, utilizing VP101KJ-10 and carry the antibacterial effect of the composite post-modification of zinc glass AMPZ will be significantly better than using BBIT and the composite effect of AMPZ.
Embodiment 2-11
Get 100 parts of polypropylene (PP, 9015); VP101-11,1.5 parts; Auxiliary antiseptic-germicide: carry 0.5 part of Zn zeolite antibacterial agent (Bei Jingji grinds the JYZN of Science and Technology Ltd.), 0.2 part of Sodium Benzoate, putting into low speed mixer stirs, then mixture is passed through the twin screw extruder melt blending, extruder temperature is 190 ℃～210 ℃, and rotating speed is the 350r.p.m extruding pelletization, and the pellet of extruding is dried 3hr in 100 ℃ of constant temperature ovens, then become the sample of 50mm * 50mm at 200～210 ℃ of hemostasis of injection temperature, carry out antibacterial test.The part print is positioned in 50 ℃ of hot water and soaks 16h before antibacterial test.
The anti-bacterial result:
Before the poach: staphylococcus aureus: 99.9%; Intestinal bacteria: 99.9%
Behind the poach: staphylococcus aureus: 99.9%; Intestinal bacteria: 99.9%
Comparative example 2-11
The VP101KJ-11 of embodiment 2-10 is replaced with 0.027 part of the normal-butyl benzo isothiazolinone (BBIT) that content is identical among the embodiment 2-11, and other steps are made into print with embodiment 2-11, carry out antibacterial test.
The anti-bacterial result:
Before the poach: staphylococcus aureus: 98.2%; Intestinal bacteria: 96.4%
Behind the poach: staphylococcus aureus: 93.5%; Intestinal bacteria: 91.7%
From above-mentioned comparative example, in the situation that identical BBIT and carry a Zn zeolite, utilizing VP101KJ-11 and carry the antibacterial effect of the composite post-modification of zinc zeolite JYZN will be significantly better than using BBIT and the composite effect of JYZN.
Claims (15)
1. antibacterial polypropylene composition includes acrylic resin and the loading type antiseptic-germicide of blend, and wherein take acrylic resin as 100 weight parts, the loading type antiseptic-germicide is 0.1～30 part; Described loading type antiseptic-germicide is the antiseptic-germicide of butylbenzene powdered rubber load, comprises organic antibacterial agent and butylbenzene powdered rubber, and wherein antiseptic-germicide loads on the butylbenzene powdered rubber; It is got by the preparation of one of following methods:
(1) leaves standstill after being mixed to the liquid organic antibacterial agent of normal temperature and butylbenzene powdered rubber evenly, until the butylbenzene powdered rubber is with the liquid organic antibacterial agent absorption of normal temperature; Wherein the weight ratio of butylbenzene powdered rubber and organic antibacterial agent is 100: 0.3～100: 50;
(2) leave standstill after organic anti-bacterial agent solution and described butylbenzene powdered rubber being mixed to evenly, until the butylbenzene powdered rubber is with the organic antibacterial agent solution absorption; Described organic anti-bacterial agent solution is that normal temperature liquid state and/or the solid-state organic antibacterial agent of normal temperature are dissolved in the solution that softening agent obtains; The weight ratio of butylbenzene powdered rubber and organic anti-bacterial agent solution is 100: 1～100: 50; Wherein the weight ratio of the solid-state organic antibacterial agent of normal temperature and softening agent is 1: 100～15: 100; The weight ratio of the liquid organic antibacterial agent of normal temperature and softening agent is 1: 100～100: 1;
The butylbenzene powdered rubber is the butylbenzene powdered rubber with crosslinking structure described in the above method, and its rubber particles is equal phase structure, and gel content is more than or equal to 60%wt, and median size is 20～500nm.
2. antibacterial polypropylene composition according to claim 1 is characterized in that:
Among the preparation method of described loading type antiseptic-germicide (1), the weight ratio of the liquid organic antibacterial agent of butylbenzene powdered rubber and normal temperature for be preferably 100: 5～100: 30, be preferably 100: 10～100: 20.
3. antibacterial polypropylene composition according to claim 1 is characterized in that:
Among the preparation method of described loading type antiseptic-germicide (2), the weight ratio of butylbenzene powdered rubber and organic anti-bacterial agent solution is 100: 10～100: 40, is preferably 100: 20～100: 30.
4. antibacterial polypropylene composition according to claim 1 is characterized in that:
Among the preparation method of described loading type antiseptic-germicide (2), the weight ratio of the solid-state organic antibacterial agent of normal temperature and softening agent is 5: 100～10: 100.
5. antibacterial polypropylene composition according to claim 1 is characterized in that:
Among the preparation method of described loading type antiseptic-germicide (2), the weight ratio of the liquid organic antibacterial agent of normal temperature and softening agent is 20: 100～100: 50, is preferably 30: 100～100: 100.
6. antibacterial polypropylene composition according to claim 1 is characterized in that:
The rubber particles gel content of butylbenzene powdered rubber is more than or equal to 75%wt in the described loading type antiseptic-germicide.
7. antibacterial polypropylene composition according to claim 1 is characterized in that:
The rubber particles median size of butylbenzene powdered rubber is 30～200nm in the described loading type antiseptic-germicide.
8. anti-bacterial thermoplastic composite according to claim 1 is characterized in that:
Described acrylic resin comprises at least a in the following material: homo-polypropylene, Co-polypropylene.
9. antibacterial polypropylene composition according to claim 1 is characterized in that:
Wherein take acrylic resin as 100 weight parts, the loading type antiseptic-germicide is 0.3～10 part.
10. antibacterial polypropylene composition according to claim 1 is characterized in that:
Comprise take acrylic resin as 100 weight parts, 0.01～2 part, be preferably 0.05～1.0 part auxiliary antiseptic-germicide; Described auxiliary antiseptic-germicide comprises inorganic antiseptic and/or organic antibacterial agent; Described inorganic antiseptic is take the sterilization metallic element as bactericidal component, the antiseptic-germicide take zeolite, zirconium phosphate or glass as carrier; Described organic antibacterial agent comprises thiabendazole, m-tetrachlorophthalodinitrile, derosal, Zinc Pyrithione, poly (hexamethylene) hydrochloride, 2,4,4 '-three chloro-2 '-dihydroxy diphenyl ether, orthoxenol, 10,10 '-in the oxygen connection phenoxarsine, 3-iodo-2-propargyl butyl carbamate one or more.
11. antibacterial polypropylene composition according to claim 10 is characterized in that:
Described inorganic antiseptic comprises at least a in the following material: zeolite carries Ag antiseptic-germicide, zeolite and carries Zn antiseptic-germicide, zirconium phosphate and carry Ag antiseptic-germicide, zirconium phosphate and carry Zn antiseptic-germicide, silicate glass and carry Ag antiseptic-germicide, silicate glass and carry Zn antiseptic-germicide, phosphate glass and carry that Ag antiseptic-germicide, phosphate glass carry the Zn antiseptic-germicide, hydroxyapatite carries the Ag antiseptic-germicide and hydroxyapatite carries the Zn antiseptic-germicide.
12. the described antibacterial polypropylene composition of according to claim 1～11 each is characterized in that:
The solid-state organic antibacterial agent of normal temperature in the described loading type antiseptic-germicide is 4,5-, two chloro-Kathons; The liquid organic antibacterial agent of normal temperature in the described loading type antiseptic-germicide is selected from least a in 2-n-octyl-4-isothiazole-3 ketone, the normal-butyl benzo isothiazolinone.
13. antibacterial polypropylene composition according to claim 12 is characterized in that:
The butylbenzene powdered rubber is full sulfuration butylbenzene powdered rubber in the described loading type antiseptic-germicide.
14. antibacterial polypropylene composition according to claim 12 is characterized in that:
Softening agent in the described loading type antiseptic-germicide comprises at least a in the following material: dioctyl phthalate (DOP), dibutyl phthalate, Di Iso Decyl Phthalate, epoxy soybean oil, epoxyoleic acid butyl ester, Octyl adipate, dioctyl sebacate or Tritolyl Phosphate.
15. the preparation method of the described antibacterial polypropylene composition of according to claim 1～14 each is characterized in that the component that will comprise described acrylic resin and loading type antiseptic-germicide gets described antibacterial polypropylene composition by described consumption melt blending.
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| CN103524887A (en) * | 2013-09-27 | 2014-01-22 | 广东聚石化学股份有限公司 | Flame-retardant air conditioner filter screen material with long-acting antibacterial and mosquito repelling effects |
| CN103524887B (en) * | 2013-09-27 | 2015-11-04 | 广东聚石化学股份有限公司 | A kind of Flame-retardant air conditioner filter screen material with long acting antibiotic, mosquito repellent |
| CN104893099A (en) * | 2015-05-28 | 2015-09-09 | 安徽同丰橡塑工业有限公司 | Medical bite device and processing technique thereof |
| CN105111386A (en) * | 2015-09-23 | 2015-12-02 | 江苏蓝湾生物科技有限公司 | Method for preparing medical antibacterial material |
| CN108384181A (en) * | 2017-01-12 | 2018-08-10 | Toto株式会社 | Resin-formed body and with water place component |
| CN108384181B (en) * | 2017-01-12 | 2021-04-23 | Toto株式会社 | Resin molded article and water-use site member |
| CN109485994A (en) * | 2018-09-18 | 2019-03-19 | 青岛国恩科技股份有限公司 | A kind of antibacterial antimildew polyacrylic and preparation method thereof for outer drum for drum washing machine |
| CN109485994B (en) * | 2018-09-18 | 2022-02-01 | 青岛国恩科技股份有限公司 | Antibacterial and mildewproof polypropylene for outer barrel of drum washing machine and preparation method thereof |
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