CN102453317B - Antibacterial polylactic acid composition and preparation method thereof - Google Patents
Antibacterial polylactic acid composition and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an antibacterial polylactic acid composition and a preparation method thereof. The composition comprises mixed polylactic acid, a composite antibacterial agent, and a dispersant; on a basis of 100 parts by weight of polylactic acid, the composition comprises 0.3-2 parts by weight of composite antibacterial agents, and 0.1-0.5 parts by weight of dispersants; wherein, the composite antibacterial agent is a polyguanidine/polysilicate composite antibacterial agent which is obtained by mixing an aqueous solution of water-soluble polyguanidine inorganic acid salts or organic acid salts and an aqueous solution of water-soluble silicate, and then adding an aqueous solution of water-soluble metal salts; the molar ratio of the water-soluble polyguanidine inorganic acid salts or organic acid salts and the water-soluble silicate is 10:1-1:50; the molar ratio of the water-soluble silicate and the water-soluble metal salts is 5:1-1:3. Therefore a polylactic acid product prepared by the composition is not easy to discolor, has a bactericidal rate for escherichia coli and staphylococcus aureus of up to above 99.9%, still maintains good antibacterial effect after water boiling, and has good water resistance.
Description
Technical field
The present invention relates to a kind of antimicrobial compound, further, relate to a kind of poly (lactic acid) composition with long acting antibiotic performance and preparation method thereof.
Background technology
Poly(lactic acid) (PLA) is a kind of Biodegradable material, makes through polycondensation by obtaining lactic acid after the fermentations such as starch or corn again, and its application prospect is extensive, comprises people's articles for daily use, wrapping material, fibrous woven etc.In recent years, along with improving constantly of people's environmental consciousness, the research of poly(lactic acid) (PLA) and production have all caused the interest of each big scientific research of the world and company.
Poly(lactic acid) has biodegradability, can produce the small molecules segment in its degradation process, easily by microorganisms such as bacteriums as food, be conducive to the breeding of microorganisms such as bacterium.Along with the enhancing of health of people and health consciousness, some have been suggested antibiotic requirement with the poly-lactic acid products that human body contacts closely, for example, and medical device, tableware, medicine box, public transport cutting ferrule, toothpick etc.
The preparation of antibacterial polylactic acid needs to realize by the method that adds antiseptic-germicide, and antiseptic-germicide of a great variety comprises mineral-type antiseptic-germicide, organic class antiseptic-germicide two big classes.Mineral-type comprises Ag, Zn-zeolite, Ag, Zn-phosphoric acid zirconates, Ag, Zn-water-soluble glass etc.; Organic class comprises quaternary ammonium salts, season phosphonium salt class, imidazoles, pyridines, organo-metallic class etc.Mineral-type and organic class antiseptic-germicide respectively have relative merits, and the mineral-type thermotolerance is higher, but have the allochroic shortcoming of Ag series antibacterial agent, and consumption is relatively large, and cost is higher; Shortcomings such as organic class antiseptic-germicide germ-killing efficiency is higher, and addition is less, but has poor heat resistance, easily separates out, and security is low.
Guanidine salt polymer is a kind of positively charged ion bactericidal polymer, is a kind of wide spectrum, efficient, nontoxic, non-stimulated good stability, the higher new type bactericide of heat decomposition temperature, and it has very strong killing action to Gram-positive and negative bacterium and part mould.The kind of guanidine salt polymer is more, and common has: polyhexamethylene (two) guanidinesalt hydrochlorate, polyhexamethylene (two) guanidine propionic salt, polyhexamethylene (two) guanidine stearate, polyoxyethylene groups guanidinesalt hydrochlorate etc.
Because guanidine radicals is hydrophilic radical, therefore most of poly-guanidinesalt is water-soluble stronger, mainly with the form of its aqueous solution, is used for the environment in fields such as agricultural, food, hospital, food and drink or the surface sterilization of goods and handles during use; In addition, poly-guanidine also is mainly used in the back arrangement of textiles, makes it have the fungus and mildew resistance function.For example, GB 2182245, and JP 05209195, and US 4891423, CN 1390876A, and CN 1227219C, patents such as CN101156586A are mainly introduced the synthetic of water-soluble poly guanidine and are used.
Document Synthesis and antimicrobial activity of polymeric guanidine andbiguanidine salts, Polymer 40 (1999) 6189-6198 have reported the preparation method of poly (hexamethylene) hydrochloride and polyhexamethylene guanidine stearate, find that it is after 280 ℃ Temperature Treatment, various bacteria and fungi are still had the good sterilization effect, therefore can be used for the antimicrobial treatment of thermoplastic polymers such as polypropylene, nylon.
At present, the antibacterial application that poly-guanidine is used for fields such as plastics, rubber has become a research focus gradually.Industrially can successfully guanidine salt polymer be made powdery product, the application of using it for plastics is also arranged.For example, patent CN 101037503A, invented a kind of production method for preparing polyhexamethylene guanidine propionic salt powder, this invention utilizes the ion isolation exchange membrane, successfully the polyhexamethylene guanidine propionic salt is separated from the aqueous solution, make powdered samples, make it can be used for the antibiotic auxiliary agent of plastics, rubber.But this Powdered polyhexamethylene guanidine propionic salt is easy to the moisture absorption, after in adding plastics to, if often contact with water, can from plastics, separate out gradually after long-time, antimicrobial efficiency can reduce, even disappear, be difficult to satisfy the requirement of the antibacterial plastic product that water tolerance is had relatively high expectations, and this patent is not mentioned antibacterial modified for poly(lactic acid).
Patent CN 1569923A, CN 1445270A and US 7282538B2 have introduced a kind of elder generation the guanidine radicals polymkeric substance and the matrix resin that have the groups such as amide group, alkyl, acyl group, amido of active group on the molecular chain have been made antibacterial matrices by reaction, then with the working method of its preparation antibiotic plastic.This method can help guanidine radicals polymkeric substance better must dispersion in plastics, and guanidine radicals is combined more firmly with matrix resin, is not easy to run off.But, these patents at first will prepare the guanidine salt polymer of special construction earlier, make its grafting different active group, comprise acid anhydrides, two keys, epoxide group etc., utilize scorification then, solution method or solid phase method are made antibacterial matrices with compound and the resin of this poly-guanidine according to higher ratio, preparation process is comparatively loaded down with trivial details, relate to and use more organic solvent, acid anhydrides, isocyanic ester etc., and the color of antibacterial matrices product is yellow, color to end article has certain influence, and does not mention the antibacterial matrices that is applicable to that poly(lactic acid) is antibacterial modified in these patents.
Patent CN 100410323C has introduced a kind of preparation method of antibacterial and mouldproof foaming poly(lactic acid), and the antibacterial components that this method is used is Ag
+, Cu
2+, Zn
2+Ion, TiO
2In a kind of or wherein several, the mildew-resistant component is a kind of of thiabendazole, m-tetrachlorophthalodinitrile, No. 75 mould inhibitors, derosal or multiple mixture wherein.But concrete in this patent working example what use is antibacterial matrices, does not mention commercially available or own preparation, and the matrix of antibacterial matrices is poly(lactic acid) or other matrix resins, and specifically recipe ingredient is not quite clear.Oxidation takes place and causes variable color in its antibacterial and mouldproof proximate analysis of introducing in specification sheets according to this patent, Ag ion antibacterial component easily in the course of processing, perhaps through after the long-time illumination metachromatism takes place easily also, and Ag
+Cost is higher, Cu
2+Itself has color ion, causes the poly(lactic acid) variable color of modification easily; No. 75 mould inhibitors are the organoarsenic antiseptic-germicide in the mildew-resistant component, toxicity is bigger, is restricted in a lot of the application, and other thiabendazoles, m-tetrachlorophthalodinitrile and derosal are heterocyclic pesticide class antiseptic-germicide, comparatively speaking, the security of the guanidine salt polymer of linear molecule chain wants high a lot.
Summary of the invention
Application present situation in conjunction with present inorganic antiseptic and organic antibacterial agent, one of purpose of the present invention provides a kind of have high-efficiency antimicrobial and antibiotic persistent antibacterial polylactic acid composition, goods apparent colour with its preparation is good, not easy to change, can be applied to the field that water tolerance is had relatively high expectations.
A kind of antibacterial polylactic acid composition of the present invention includes the following component of blend: poly(lactic acid), complex antimicrobials, dispersion agent;
Wherein, in poly(lactic acid) by 100 weight parts, complex antimicrobials 0.3～2 weight part, preferred 0.6～1.2 weight part; Dispersion agent 0.1～0.5 weight part, preferred 0.1～0.3 weight part.
In antibacterial polylactic acid composition of the present invention, described poly(lactic acid) is selected from disclosed various types of polylactic resin in the prior art.
In the antibacterial polylactic acid composition of the present invention, described complex antimicrobials is poly-guanidine/polysilicate complex antimicrobials, be a kind of water, particle diameter is little, germ-killing efficiency is high antiseptic-germicide of being insoluble in, after the aqueous solution by the aqueous solution of water-soluble poly guanidine inorganic acid salt or organic acid salt and water-soluble silicate, add water that the aqueous solution of soluble metal salts obtains.
Specifically, be to be raw material with poly-guanidine, silicate and water-soluble metal salt three, via the method preparation that includes following steps and get: will gather the guanidine aqueous solution and mix with aqueous silicate solution; Add water the aqueous solution of soluble metal salts then in the aqueous solution of poly-guanidine/silicate, poly-guanidine/polysilicate is separated out from solution through flocculating settling, the throw out drying, pulverize after, obtain the Powdered complex antimicrobials of water-insoluble solid.
Wherein silicate can hydrolysis gradually after water-soluble, aggregate into certain intermediate product, when the aqueous solution of itself and poly-guanidine inorganic acid salt or organic acid salt, because poly-silicic acid molecular weight is very high, have very strong bonding ability of aggregation and adsorption bridging effect, and twine mutually with the high molecular molecular chain of poly-guanidine; After adding metal-salt, molecular chain and metal ion that poly-silicic acid and poly-guanidine twine in water solution system mutually play chelatropic reaction, produce flocculation, make the molecular chain of poly-guanidine be difficult to from the system of poly-guanidine/polysilicate of forming, shake off out like this, thereby form the poly-guanidine/polysilicate complex antimicrobials of hydrophobe.
In this complex antimicrobials, described water-soluble poly guanidine inorganic acid salt or organic acid salt are selected from and comprise at least a of following material: salt of the water-soluble poly guanidine of the mineral acid of water miscible polyhexamethylene guanidine or organic acid salt or other structure etc.; Wherein the mineral acid of preferred water miscible polyhexamethylene guanidine or organic acid salt comprise: polyhexamethylene (two) guanidinesalt hydrochlorate, polyhexamethylene (two) guanidine nitrate, polyhexamethylene (two) guanidine carbonate, polyhexamethylene (two) guanidine propionic salt.
Described water-soluble silicate is selected from and comprises at least a of water glass, potassium silicate, water glass potassium.
Described water-soluble metal salt is selected from water miscible Zn
2+Salt, Ca
2+Salt, Al
3+Salt, Cu
2+Salt, Fe
2+Salt, Ag
+Salt, Ce
3+At least a in the salt, such as: Zn (NO
3)
2, ZnSO
4, Ca (NO
3)
2, Al (NO
3)
3, Cu (NO
3)
2, Fe (NO
3)
2, AgNO
3, Ce (NO
3)
3Deng.Consider the color problem of goods, the metal-salt of preferred light color, as: Zn
2+Salt, Ca
2+Salt, Al
3+Salt, Ce
3+Salt etc.In use, can add wherein a kind of, perhaps add wherein two or more simultaneously.
This complex antimicrobials more specifically preparation process is: (1) is dissolved in a certain amount of water-soluble poly guanidine inorganic acid salt or organic acid salt in a certain amount of water, is called solution A; (2) take by weighing a certain amount of soluble silicate, it is soluble in water, be called solution B; (3) solution A and solution B are mixed, form solution C, and stir the regular hour; (4) take by weighing a certain amount of water-soluble metal salt, it is soluble in water, be called solution D; (5) with solution D, join gradually in the solution C, namely there is cotton-shaped infusible precipitate to generate, with the throw out pumping rate, washing, drying can obtain poly-guanidine/polysilicate complex antimicrobials after the pulverizing.
In preparation process, poly-guanidine: silicate: water-soluble metal salt three's ratio can be regulated as required at this complex antimicrobials.
Wherein, the molar ratio of water-soluble poly guanidine inorganic acid salt or organic acid salt and water-soluble silicate can be regulated in wideer scope, and the preferred molar ratio example is 10: 1～1: 50.If ratio is greater than 10: 1, namely poly-guanidine consumption is excessive, and then the productive rate that is converted into the poly-guanidine/polysilicate of hydrophobe of the poly-guanidine in the poly-guanidine aqueous solution can reduce, and most of poly-guanidine still can keep water soluble state to be present in the aqueous solution, causes productive rate to reduce; If ratio is lower than 1: 50, be that the silicate consumption is excessive, can make the effective antimicrobial component in the poly-guanidine/polysilicate of preparation, namely poly-guanidine content is too low, cause antimicrobial efficiency low excessively, when preparation antibacterial polylactic acid composition of the present invention, addition is excessive, thereby can have influence on performances such as processing, mechanics and surface property, cause practicality to reduce.Therefore, consider from point of view of practicability that preferred ratio is poly-guanidine: the silicate molar ratio is 2: 1～1: 5.
The molar ratio of water-soluble silicate and water-soluble metal salt also can be regulated in a big way, and the preferred molar ratio example is 5: 1～1: 3.If ratio was greater than 5: 1, the relative proportion that is metal-salt is low excessively, can cause the productive rate of poly-guanidine/polysilicate to reduce, can be interpreted as there are not enough metal-salts, reduced throwing out, the poly-silicic acid macromolecular chain system of gathering guanidine and hydrolyzed silicate formation in the aqueous solution is precipitated out from water; If ratio is lower than 1: 3, namely the ratio of metal-salt is excessive relatively, then can cause unnecessary waste, because add-on too much also is difficult to improve productive rate.
In synthesis step (3), be about to A solution (the poly-guanidine aqueous solution) and B solution (silicate solutions) and mix and stir, in the process of formation solution C, the time of stirring is preferably 5 minutes～and 2 hours.Certainly churning time is not confined to this scope, but churning time is too short, B solution is difficult to that whole hydrolysis become poly-silicic acid or the polymerization degree is big inadequately, poly-like this silicic acid and poly-guanidine winding degree in the aqueous solution are not enough, also can make poly-guanidine to detest the water degree not enough, if and overlong time surpasses 2 hours, then cause temporal waste.More preferred churning time is 20min～1h.
In synthesis step (4), solution D slowly should be poured in the mixed solution C of poly-guanidine and silicate, and vigorous stirring, can make the particle diameter of poly-guanidine/polysilicate particle of generation littler like this.
In addition, the preparation process of this complex antimicrobials can at room temperature be carried out, and certainly, also can heat and carry out, and it is faster to make hydrolyzed silicate be polymerized to the speed of silicic acid, the quickening reaction process.Reacting the last infusible precipitate that forms can purify by suction filtration, also can place for some time, and throw out can be deposited to container bottom from water, and upper water liquid is drained, and lower sediment collection oven dry, pulverizing are got final product.Therefore, among the present invention, the preparation method of this complex antimicrobials is simple, and the reaction conditions gentleness is easy to suitability for industrialized production.
In composition, add the dispersion that certain amount of dispersant helps to improve auxiliary agent and matrix resin, various other auxiliary agents evenly are coated on the material grain of matrix resin, thereby make the physical mixed of material in homogenizer more effective.Antibacterial polylactic acid composition of the present invention also comprises dispersion agent, can select the various dispersion agents commonly used of plastic working in the prior art, at least a in preferred stearic acid, Zinic stearas, the white oil, more preferably Zinic stearas.Dispersion agent can make poly-guanidine/polysilicate complex antimicrobials dispersed better in poly(lactic acid), can also play certain lubrication simultaneously, makes poly(lactic acid) when granulation, diminishes in the shearing force of screw feed section, and granulation is carried out smoothly.
In addition, in the course of processing of antibacterial polylactic acid composition, the needs of the concrete processing of available basis, in the blend material, add processing aid commonly used in the poly (lactic acid) composition modification technology, for example: toughner, oxidation inhibitor etc., its consumption is conventional amount used, or adjusts according to practical requirements.
Two of purpose of the present invention provides this preparation method with poly (lactic acid) composition of anti-microbial property, is achieved through the following technical solutions:
Comprise that the each component that will include described poly(lactic acid), complex antimicrobials, dispersion agent mixes by described content, melt blending makes described antibacterial polylactic acid composition.
In the course of processing of antibacterial polylactic acid composition of the present invention, material melt blending temperature is used blending temperature in the processing of common poly(lactic acid), should select not only guaranteeing the complete fusion of matrix but also can not make in the scope of its decomposition, and be 160～230 ℃.Consider the low excessively melt blending that is unfavorable for poly(lactic acid) and antiseptic-germicide and other component of temperature, the too high degraded that causes poly(lactic acid) easily of temperature causes the mechanical properties decrease of antibacterial polylactic acid, and more preferred processing temperature is 180～200 ℃.In addition, in the course of processing of antibacterial polylactic acid, the concrete needs of available basis add other auxiliary agents, and for example: polynite, glass fibre, sisal hemp, pigment, toughner etc., its consumption is conventional amount used, or adjusts according to practical requirements.
The blending equipment of mixing of materials can adopt various mixing equipments used in the prior art in the preparation method of the invention described above, as stirrer, kneading machine etc.Employed melt blending equipment is the general blending equipment in the rubber and plastic processing industry in the method for the invention described above, can be twin screw extruder, single screw extrusion machine, mill or Banbury mixer etc.
Antibacterial polylactic acid composition of the present invention, its characteristics are: poly-guanidine/polysilicate complex antimicrobials that employed antiseptic-germicide is a kind of low cost, be insoluble in water, particle diameter is little, germ-killing efficiency is high, overcome the shortcoming of the easy moisture absorption of common guanidine salt polymer, and success this complex antimicrobials is used for the antibacterial modified of poly(lactic acid), the antibacterial polylactic acid goods of preparation are not easy to change, sterilizing rate to intestinal bacteria and staphylococcus aureus can reach more than 99.9%, and still can keep good antibacterial effect after poach, water-wash resistance is good.Preparation method's technology of the present invention is simple, easy handling, is suitable for industrial applications.
Embodiment
The present invention will be further described below in conjunction with specific embodiment.But the present invention is not limited in following embodiment.
Raw material in following examples and the comparative example is:
Poly(lactic acid) (PLA): Naturework company, the trade mark: Ingeo
TM3051, Ingeo
TM3001D;
The positive Biomatera Inc. in sea, the trade mark: REVODE201201, REVODE101;
Dispersion agent: white oil: the real magnificent limited-liability company of Maoming petrochemical industry;
Zinic stearas: chemical pure, commercially available;
Stearic acid: chemical pure, commercially available;
Antiseptic-germicide: poly-guanidine/polysilicate, self-control;
Twin screw: ZSK-40, German WP company;
Antibiotic print: utilize injection moulding machine (Hai Tian) to make 50mm * 50mm print.
One, the preparation of complex antimicrobials
Embodiment 1
(1) takes by weighing polyhexamethylene guanidine propionic salt (the high poly-F3000 in Shanghai) 100.0g (0.465mol), join in the 300mL deionized water solution, stir and make its dissolving, be called solution A; (2) claim water glass (chemical pure, commercially available) 70.0g (0.246mol) in addition, join in the 300mL deionized water, stir and make its dissolving, be called solution B; (3) at room temperature (about 25 ℃) mix solution A and solution B, and fully stirred 30 minutes, form solution C; (4) take by weighing zinc sulfate ZnSO
4(chemical pure, commercially available) 180.0g (0.626mol) slowly pours in the solution C, and vigorous stirring 5min, and throw out is filtered, and drying is pulverized, and obtains polyhexamethylene guanidine propionic salt/zinc polysilicate complex antimicrobials (complex antimicrobials one).
Embodiment 2:
(1) takes by weighing polyhexamethylene guanidine propionic salt (the high poly-F3000 in Shanghai) 100.0g (0.465mol), join in the 300mL deionized water solution, stir and make its dissolving, be called solution A; (2) claim water glass (chemical pure, commercially available) 100.0g (0.352mol) in addition, join in the 500mL deionized water, stir and make its dissolving, be called solution B; (3) solution A and solution B are mixed, fully stir 1h down at 50 ℃, form solution C; (4) take by weighing zinc sulfate ZnSO
4(chemical pure, commercially available) 120.0g (0.417mol) slowly pours in the solution C, and vigorous stirring 10min, and throw out is filtered, and drying is pulverized, and obtains polyhexamethylene guanidine propionic salt/zinc polysilicate complex antimicrobials (complex antimicrobials two).
Embodiment 3:
(1) takes by weighing poly (hexamethylene) hydrochloride (the high poly-F1000 in Shanghai) 100.0g (0.635mol), join in the 300mL deionized water solution, stir and make its dissolving, be called solution A; (2) claim water glass (chemical pure, commercially available) 150.0g (0.528mol) in addition, join in the 600mL deionized water, stir and make its dissolving, be called solution B; (3) at room temperature (about 25 ℃) mix solution A and solution B, and fully stir 1.5h, form solution C; (4) take by weighing nitrocalcite Ca (NO
3)
2(chemical pure, commercially available) 120.0g (0.508mol) slowly pours in the solution C, and vigorous stirring 10min, and throw out is filtered, and drying is pulverized, and obtains poly (hexamethylene) hydrochloride/calcium polysilicate complex antimicrobials (complex antimicrobials three).
Embodiment 4:
(1) takes by weighing poly (hexamethylene) hydrochloride (the high poly-F1000 in Shanghai) 100.0g (0.635mol), join in the 300mL deionized water solution, stir and make its dissolving, be called solution A; (2) claim water glass (chemical pure, commercially available) 480.0g (1.689mol) in addition, join in the 300mL deionized water, stir and make its dissolving, be called solution B; (3) solution A and solution B are mixed, fully stirred 20 minutes down at 80 ℃, form solution C; (4) take by weighing aluminum nitrate Al (NO
3)
3(chemical pure, commercially available) 900.0g (2.4mol) slowly pours in the solution C, and vigorous stirring 5min, and throw out is filtered, and drying is pulverized, and obtains poly (hexamethylene) hydrochloride/aluminium silicate polymer complex antimicrobials (complex antimicrobials four).
Embodiment 5:
(1) takes by weighing hexamethylene (going up the PHMB of Industrial Co., Ltd. of seamount) 100.0g (0.456mol), join in the 300mL deionized water solution, stir and make its dissolving, be called solution A; (2) claim water glass (chemical pure, commercially available) 600.0g (2.11mol) in addition, join in the 300mL deionized water, stir and make its dissolving, be called solution B; (3) solution A and solution B are mixed, under 75 ℃, fully stirred 30 minutes, form solution C; (4) take by weighing zinc sulfate ZnSO
4(chemical pure, commercially available) 800.0g (2.784mol) slowly pours in the solution C, and vigorous stirring 5min, and throw out is filtered, and drying is pulverized, and obtains hexamethylene/zinc polysilicate complex antimicrobials (complex antimicrobials five).
Two, the preparation of antibiotic PLA:
Embodiment 6:
With 100 parts of PLA resins (IngeoTM3051); One 0.3 parts of complex antimicrobials, 0.1 part of white oil; Put into low speed mixer and stir, then mixture is passed through the twin screw extruder melt blending, extruder temperature is 180～200 ℃, and rotating speed is the 350r.p.m extruding pelletization, and the pellet of extruding is dried 5hr in 90 ℃ of constant temperature ovens.Under 180～200 ℃ of injection temperatures, be injected into the sample of 50mm * 50mm then, carry out antibacterial test.
Before carrying out antibacterial test, elder generation in 50 ℃ of water, boils 16 hours with a part of poly(lactic acid) sample, and is standby.
1, antibacterial test standard: QB/T 2591-2003A " antibiotic plastic anti-microbial property test method and antibacterial effect ", detect and use bacterium: intestinal bacteria (Escherichia coli) ATCC 25922, staphylococcus aureus (Staphylococcus aureus) ATCC 6538.
2, antibacterial test step is tested with reference to antibiotic plastic examination criteria QB/T 2591-2003, and concrete steps are as follows: testing sample is handled with 75% ethanol disinfection and dried, it is standby that bacterial classification is diluted to bacteria suspension with sterilized water.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, be diluted to suitable concentration gradient, get 0.1mL and be 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.
The anti-bacterial result (sterilizing rate %):
Before the poach: staphylococcus aureus: 99.9%; Intestinal bacteria: 99.9%;
Behind the poach: staphylococcus aureus: 99.9%; Intestinal bacteria: 99.9%.
Comparative Examples 1
Antiseptic-germicide among the embodiment 6 is replaced with 0.3 part of pure polyhexamethylene guanidine propionic salt, and all the other conditions all with embodiment 6, are made into print, carry out antibacterial test.
The anti-bacterial result (sterilizing rate %):
Before the poach: staphylococcus aureus: 43.8%; Intestinal bacteria: 39.1%;
Behind the poach: staphylococcus aureus: 0; Intestinal bacteria: 0.
From above-mentioned comparative result, can see that the poach front and back utilize the antibacterial effect of the poly(lactic acid) of polyhexamethylene guanidine propionic salt/zinc polysilicate complex antimicrobials modification all to be better than the antibacterial modified effect of pure poly-guanidine propionic salt.0.3 a part pure poly-guanidine propionic salt polydactyl acid has not almost had anti-microbial property after poach.
Embodiment 7:
With PLA resin (Ingeo
TM3001D) 100 parts; 2 0.6 parts of complex antimicrobials, 0.2 part of stearic acid; Put into low speed mixer and stir, then mixture is passed through the twin screw extruder melt blending, extruder temperature is 180～200 ℃, and rotating speed is the 350r.p.m extruding pelletization, and the pellet of extruding is dried 5hr in 90 ℃ of constant temperature ovens.Under 180～200 ℃ of injection temperatures, be injected into the sample of 50mm * 50mm then, carry out antibacterial test.
The anti-bacterial result (sterilizing rate %):
Before the poach: staphylococcus aureus: 99.9%; Intestinal bacteria: 99.9%;
Behind the poach: staphylococcus aureus: 99.9%; Intestinal bacteria: 99.9%.
Comparative Examples 2
Antiseptic-germicide among the embodiment 7 is replaced with 0.6 part of pure polyhexamethylene guanidine propionic salt, and all the other conditions all with embodiment 7, are made into print, carry out antibacterial test.
The anti-bacterial result (sterilizing rate %):
Before the poach: staphylococcus aureus: 66.3%; Intestinal bacteria: 59.1%;
Behind the poach: staphylococcus aureus: 18.4%; Intestinal bacteria: 21.0%.
From above-mentioned comparative result, can see that the poach front and back utilize the antibacterial effect of the poly(lactic acid) of polyhexamethylene guanidine propionic salt/zinc polysilicate complex antimicrobials modification all to be better than the antibacterial modified effect of pure poly-guanidine propionic salt.
Embodiment 8:
With 100 parts of PLA resins (REVODE201); 3 0.8 parts of complex antimicrobials, 0.2 part of Zinic stearas; Put into low speed mixer and stir, then mixture is passed through the twin screw extruder melt blending, extruder temperature is 180～200 ℃, and rotating speed is the 350r.p.m extruding pelletization, and the pellet of extruding is dried 5hr in 90 ℃ of constant temperature ovens.Under 180～200 ℃ of injection temperatures, be injected into the sample of 50mm * 50mm then, carry out antibacterial test.
The anti-bacterial result (sterilizing rate %):
Before the poach: staphylococcus aureus: 99.9%; Intestinal bacteria: 99.9%;
Behind the poach: staphylococcus aureus: 99.9%; Intestinal bacteria: 99.9%.
Comparative Examples 3
Antiseptic-germicide among the embodiment 8 is replaced with 0.8 part of pure poly (hexamethylene) hydrochloride, and all the other conditions all with embodiment 8, are made into print, carry out antibacterial test.
The anti-bacterial result (sterilizing rate %):
Before the poach: staphylococcus aureus: 85.3%; Intestinal bacteria: 80.4%;
Behind the poach: staphylococcus aureus: 38.4%; Intestinal bacteria: 34.7%.
From above-mentioned comparative result, can see that the poach front and back utilize the antibacterial effect of the poly(lactic acid) of poly (hexamethylene) hydrochloride/calcium polysilicate complex antimicrobials modification all to be better than the antibacterial modified effect of pure poly (hexamethylene) hydrochloride.
Embodiment 9:
With 100 parts of PLA resins (REVODE201); 4 1.2 parts of complex antimicrobials, 0.3 part of Zinic stearas; Put into low speed mixer and stir, then mixture is passed through the twin screw extruder melt blending, extruder temperature is 180～200 ℃, and rotating speed is the 350r.p.m extruding pelletization, and the pellet of extruding is dried 5hr in 90 ℃ of constant temperature ovens.Under 180～200 ℃ of injection temperatures, be injected into the sample of 50mm * 50mm then, carry out antibacterial test.
The anti-bacterial result (sterilizing rate %):
Before the poach: staphylococcus aureus: 99.9%; Intestinal bacteria: 99.9%;
Behind the poach: staphylococcus aureus: 99.9%; Intestinal bacteria: 99.9%.
Comparative Examples 4
Antiseptic-germicide among the embodiment 9 is replaced with 1.2 parts of pure poly (hexamethylene) hydrochlorides, and all the other conditions all with embodiment 9, are made into print, carry out antibacterial test.
The anti-bacterial result (sterilizing rate %):
Before the poach: staphylococcus aureus: 94.5%; Intestinal bacteria: 91.3%;
Behind the poach: staphylococcus aureus: 54.2%; Intestinal bacteria: 49.8%.
From above-mentioned comparative result, can see that the poach front and back utilize the antibacterial effect of the poly(lactic acid) of poly (hexamethylene) hydrochloride/calcium polysilicate complex antimicrobials modification all to be better than the antibacterial modified effect of pure poly (hexamethylene) hydrochloride.
Embodiment 10:
With 100 parts of PLA resins (REVODE101); 52 parts of complex antimicrobials, 0.5 part of Zinic stearas; Put into low speed mixer and stir, then mixture is passed through the twin screw extruder melt blending, extruder temperature is 180～200 ℃, and rotating speed is the 350r.p.m extruding pelletization, and the pellet of extruding is dried 5hr in 90 ℃ of constant temperature ovens.Under 180～200 ℃ of injection temperatures, be injected into the sample of 50mm * 50mm then, carry out antibacterial test.
The anti-bacterial result (sterilizing rate %):
Before the poach: staphylococcus aureus: 99.9%; Intestinal bacteria: 99.9%;
Behind the poach: staphylococcus aureus: 99.9%; Intestinal bacteria: 99.9%.
Comparative Examples 5
Antiseptic-germicide among the embodiment 10 is replaced with 2.0 parts of pure hexamethylene, and all the other conditions all with embodiment 10, are made into print, carry out antibacterial test.
The anti-bacterial result (sterilizing rate %):
Before the poach: staphylococcus aureus: 99.9%; Intestinal bacteria: 99.9%;
Behind the poach: staphylococcus aureus: 87.2%; Intestinal bacteria: 83.4%.
From above-mentioned comparative result, utilize hexamethylene/zinc polysilicate complex antimicrobials and pure hexamethylene can reach good antibacterial effect before can seeing poach, illustrate that hexamethylene reaches and to reach 99.9% sterilization effect after a certain amount of; But after the poach, can see that still the antibacterial effect of poly (hexamethylene) hydrochloride/calcium polysilicate complex antimicrobials all is better than pure hexamethylene.
Claims (9)
1. antibacterial polylactic acid composition includes the following component of blend: poly(lactic acid), complex antimicrobials, dispersion agent;
In poly(lactic acid) by 100 weight parts, complex antimicrobials 0.3～2 weight part;
Wherein, described complex antimicrobials is poly-guanidine/polysilicate complex antimicrobials, after being the aqueous solution by the aqueous solution of water-soluble poly guanidine inorganic acid salt or organic acid salt and water-soluble silicate, add water that the aqueous solution of soluble metal salts obtains, the molar ratio of described water-soluble poly guanidine inorganic acid salt or organic acid salt and water-soluble silicate is 10:1～1:50, and the molar ratio of described water-soluble silicate and water-soluble metal salt is 5:1～1:3.
2. poly (lactic acid) composition as claimed in claim 1 is characterized in that, includes the following component of blend:
In poly(lactic acid) by 100 weight parts, complex antimicrobials 0.6～1.2 weight part, dispersion agent 0.1～0.5 weight part.
3. poly (lactic acid) composition as claimed in claim 1 is characterized in that:
Described water-soluble poly guanidine inorganic acid salt or organic acid salt are selected from least a in poly (hexamethylene) hydrochloride, hexamethylene, polyhexamethylene guanidine nitrate, poly hexamethylene biguanide nitrate, polyhexamethylene guanidine carbonate, poly hexamethylene biguanide carbonate, polyhexamethylene guanidine propionic salt, the poly hexamethylene biguanide propionic salt.
4. poly (lactic acid) composition as claimed in claim 1 is characterized in that:
Described water-soluble silicate is selected from least a of water glass, potassium silicate, water glass potassium.
5. poly (lactic acid) composition as claimed in claim 1 is characterized in that:
Described water-soluble metal salt is selected from water miscible Zn
2+Salt, Ca
2+Salt, Al
3+Salt, Cu
2+Salt, Fe
2+Salt, Ag
+Salt, Ce
3+At least a in the salt.
6. poly (lactic acid) composition as claimed in claim 5 is characterized in that:
Described water-soluble metal salt is selected from water miscible Zn
2+Salt, Ca
2+Salt, Al
3+Salt, Ce
3+At least a in the salt.
7. poly (lactic acid) composition as claimed in claim 1 is characterized in that:
The molar ratio of described water-soluble poly guanidine inorganic acid salt or organic acid salt and water-soluble silicate is 2:1～1:5.
8. as the arbitrary described poly (lactic acid) composition of claim 1～7, it is characterized in that:
Described poly (lactic acid) composition contains dispersion agent, is 100 weight parts in poly(lactic acid), dispersion agent 0.1～0.3 weight part; Described dispersion agent is selected from least a in stearic acid, Zinic stearas, the white oil.
9. as the arbitrary described antibacterial polylactic acid preparation of compositions method of claim 1～8, it is characterized in that:
Comprise that the each component that will include described poly(lactic acid), complex antimicrobials mixes by described content, melt blending makes described antibacterial polylactic acid composition.
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| CN114292391A (en) * | 2022-03-01 | 2022-04-08 | 辽宁东盛塑业有限公司 | Polyhexamethylene guanidine modified antibacterial degradation material and preparation method thereof |
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| CN1904159A (en) * | 2006-07-13 | 2007-01-31 | 苏州大学 | Anti bacteria natural silk composite nano-fiber material and its preparation method |
| CN101735636A (en) * | 2008-11-12 | 2010-06-16 | 福建恒安集团有限公司 | Biodegradation time controlled plastic film and preparation method thereof |
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| CN101735636A (en) * | 2008-11-12 | 2010-06-16 | 福建恒安集团有限公司 | Biodegradation time controlled plastic film and preparation method thereof |
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