CN102453316A - Antibacterial biaxially-oriented polylactic acid (BOPLA) film and preparation method thereof - Google Patents
Antibacterial biaxially-oriented polylactic acid (BOPLA) film and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an antibacterial biaxially-oriented polylactic acid (BOPLA) film and a preparation method thereof. The polylactic acid film comprises the following components in parts by weight: 100 parts of a material special for a biaxially-oriented polylactic acid film and 0.4-3 parts of an antibacterial agent, wherein the film is prepared with a biaxial orientation method, and is 10-100 mum in thickness; the antibacterial agent is a poly-guanidine/polysilicate compound antibacterial agent, and is prepared by mixing a water-soluble poly-guanidine inorganic acid salt or an aqueous solution of an organic acid salt and an aqueous solution of water-soluble silicate, and adding an aqueous solution of a water-soluble metal salt; the molar ratio of the water-soluble poly-guanidine inorganic acid salt or the organic acid salt to the water-soluble silicate is 10:1-1:50; and the molar ratio of the water-soluble silicate to the water-soluble metal salt is 5:1-1:3. The antibacterial BOPLA film has the characteristics of high antibacterial efficiency, small using amount, good antibacterial effect and high water stability, and has a wide application prospect.
Description
Technical field
The present invention relates to a kind of poly (lactic acid) composition, more specifically, the present invention relates to a kind of biodegradable antibacterial polylactic acid film.
Background technology
POLYACTIC ACID is through will making lactic acid as raw material by the starch that corn, taro etc. obtains, and further through chemosynthesis prepare polymkeric substance.In recent years; Improving constantly of Along with people's environmental consciousness; Each big scientific research institution of the world and company have all increased the research of POLYACTIC ACID (PLA) and the input of production, and POLYACTIC ACID has been applied to fields such as people's articles for daily use, wrapping material, fibrous woven, foam material.
Because POLYACTIC ACID has advantages such as biodegradability, mechanical property and the transparency are good, resistance oxygen property is good; POLYACTIC ACID (PLA) film has become the focus of domestic and international research in the application of packaging field; Many companies such as Japan, America and Europe, for example Heploh-Cargilldow, pula gram, Naturework, Leca-Mitsui Chemicals, Heplon-U.S. Chronopol company etc. have released the PLA trade mark that can utilize multiple working method (blowing, curtain coating, two-way stretch etc.) preparation film.Wherein, biaxially stretched polylactic acid (BOPLA) is stretched in horizontal and vertical direction because its special complete processing makes POLYACTIC ACID in film process, and polylactic acid molecule is orientated, and mechanical properties such as the tensile strength of film are excellent.At present; Naturework company has released POLYACTIC ACID (BOPLA) trade mark material that can use stretch processes; In the future good application prospects is arranged, can partly replace the market of BOPP Biaxially oriented polypropylene film (BOPP) and two-way stretch polyethylene terephthalate (BOPET) at packaging field.
Because POLYACTIC ACID has degradable characteristics, is accompanied by the degraded of POLYACTIC ACID, the small molecules segment in the degraded product; Easily by mikrobes such as bacteriums as food, help the breeding of part unwanted bacteria, be unfavorable for people's health; At some application of special occasions BOPLA films; For example articles for use packing etc. in food, menu, photograph album, the music of song and the hospital if give its antibacterial, will have the quality guaranteed period of improving wrap food; Reduce the probability that public place unwanted bacterias intersections such as hospital and dining room are propagated, be beneficial to people's health.But, seldom see report about the document and the patent of antibiotic biaxially stretched polylactic acid (BOPLA) at present.
The preparation of antibiotic BOPLA film can be inorganic through in the BOPLA raw material, adding, organic antibacterial agent realizes.BOPLA has thin thickness, characteristics that transparency is high, therefore requires the inorganic antiseptic particle diameter little, otherwise can cause the BOPLA film hole to occur, the influence transparency and processibility etc.A lot of so common inorganic antiseptics can not be applied in the BOPLA film, for example, and common antibacterial glass agent; Its particle diameter is thicker, and the particle size distribution range broad arrives between the hundreds of micron at several microns; If be used for the antibacterial modified of BOPLA film, just must carry out careful pulverizing, and carry out strict classification it; Classification goes out narrow diameter distribution, and particle diameter is lower than several microns product.Simultaneously, some Ag series antibacterial agents also exist the shortcoming that adds easy to change and weather stain in man-hour; In addition, some nanometer grade inorganic antibacterial agent, for example nano-TiOs
2Though particle diameters such as ZnO are thinner, there is the low shortcoming of anti-microbial property.Organic antibacterial agent, most of fusing point is lower, is usually less than the processing temperature of BOPLA, does not have the problem of size, and is also less to the transparency influence of BOPLA film; But most of organic antibacterial agent thermotolerance is low, be prone in the course of processing decompose, molecular weight is low, the shortcoming of from the BOPLA film, separating out easily, and also the toxicity of many organic antibacterial agents is bigger, and safety in utilization is low, for example, organoarsenic antiseptic-germicide (OBPA) etc.
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, so major part gathers the water-soluble stronger of guanidinesalt, 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, gather the back arrangement that guanidine also is mainly used in textiles, make it have the fungus and mildew resistance function.For example, GB2182245, JP05209195, US4891423, CN1390876A, 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; Reported the preparation method of poly (hexamethylene) hydrochloride and polyhexamethylene guanidine stearate among Polymer 40 (1999) 6189-6198; 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 Vestolen PP 7052, nylon.At present, will gather the antibacterial application that guanidine is used for fields such as plastics, rubber and become a research focus gradually.
At present, can successfully guanidine salt polymer be made powdery product in the industry, the application of using it for plastics is also arranged.For example; Patent CN101037503A; Invented a kind of working 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; Process 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, easy moisture absorption caking in a humid environment, in adding plastics to after; In the water of being everlasting, soak or often with after water contact, for a long time after meeting from plastics, separate out gradually, 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 do not mention and be used for the antibacterial modified of POLYACTIC ACID, more do not mention the application on BOPLA.
Patent CN 1569923A, CN 1445270A and US 7282538B2 have introduced a kind of elder generation the guanidine radicals polymkeric substance and the matrix resin of groups such as the carboxamido-group that has reactive group on the molecular chain, alkyl, acyl group, amido have been processed antibacterial matrices through reaction, prepare the working method of antibiotic plastic then with it.This method can help guanidine radicals polymkeric substance better must dispersion in plastics, and guanidine radicals and matrix resin binding ratio are more firm, are not easy to run off.But; These patents at first will prepare the guanidine salt polymer of special construction earlier; Make its grafting different reactive group, comprise acid anhydrides, two key, epoxide group or the like, utilize scorification, solution method or solid phase method that this compound and the resin that gathers guanidine processed antibacterial matrices according to higher ratio then; Preparation process is comparatively loaded down with trivial details; Relate to and use more organic solvent, acid anhydrides, isocyanic ester etc., and do not mention the antibacterial matrices that is applicable to that POLYACTIC ACID is antibacterial modified in these patents, more do not mention the application on BOPLA.
Patent US6031119 improves its wash durability through gathering the alkoxysilane groups side chain of introducing special construction on the molecular chain of guanidine.But its preparation process need add a large amount of organic solvents usually, and the preparation process is more complicated also.And this patent is not mentioned the purposes of using it for the BOPLA film.
Summary of the invention
To the defective that prior art exists, the invention provides a kind of antibiotic biaxially stretched polylactic acid (BOPLA) film based on guanidine salt polymer and preparation method thereof.Antibiotic BOPLA film of the present invention has the antimicrobial efficiency height, and antibacterial components is difficult for from film, separating out, water-tolerant, and transparency is high, is difficult for taking place the advantage of xanthiochromatic, can be applicable in the future.
One of the object of the invention is to provide this kind antibiotic biaxially stretched polylactic acid film, includes following component: biaxially stretched polylactic acid film PP Pipe Compound, antiseptic-germicide, dispersion agent;
Be 100 weight parts wherein in biaxially stretched polylactic acid film PP Pipe Compound, antiseptic-germicide 0.4～3 weight part, preferred 0.6～2 weight part; Film is through the preparation of two-way stretch method, and thickness is 10～100 μ m, preferred 15～30 μ m.This thickness can be decided according to the requirement of concrete wrapped product.
In antibiotic biaxially stretched polylactic acid film of the present invention, all can be used for the polylactic resin of two-way stretch in its matrix resin employing prior art, are commonly called as to be " biaxially stretched polylactic acid film (BOPLA) PP Pipe Compound ".The BOPLA PP Pipe Compound is meant and can adopts the tensile polylactic resin of specific drawing process at the vertical and horizontal both direction that the tensile film has certain intensity and deflection, and industriallization membrane speed can reach certain requirement.At present; Domestic and international most of POLYACTIC ACID trade mark is injection grade, extrusion grade and fibre-grade product; The company that worldwide can produce biaxially stretched polylactic acid film (BOPLA) PP Pipe Compound is very few, and the resin dedicated molecular weight of this BOPLA, comonomer, molten finger, melt strength etc. all have the characteristics of oneself.Because biaxially stretched polylactic acid advance technically, abroad the constructional feature to biaxially stretched polylactic acid does not have full disclosure.At present, be known that the BOPLA PP Pipe Compound that Naturework company releases, it mentions trade mark Ingeo in introducing
TM4032D, Ingeo
TM4042D can be used for biaxially oriented film, and Ingeo
TM4060D can extrude simultaneously with other BOPLA trade mark resin and carry out two-way stretch again, can not influence the performance of two-way stretch PLA, for example the mist degree and the transparency etc.The poly-lactic acid products of other companies; In its description of product, do not stress can two-way stretch the POLYACTIC ACID trade mark; Also might be through auxiliary agents such as adding chainextenders; Its molecular weight is increased; Thereby melt strength increases the performance that possesses two-way stretch; For example; The trade mark that A.Shulman Inc company releases is
PLA308AS,
PLA5AB,
PLA8757 POLYACTIC ACID master batch; Wherein add some auxiliary agent, can help the POLYACTIC ACID of other trade mark to realize the two-way stretch function.
In antibiotic biaxially stretched polylactic acid film of the present invention; Described antiseptic-germicide is for gathering 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 that the aqueous solution of water-soluble metal salt obtains.
Specifically, be to be raw material, via the method preparation that includes following steps and get: will gather the guanidine aqueous solution and mix with aqueous silicate solution to gather guanidine, silicate and water-soluble metal salt three; In the aqueous solution that gathers guanidine/silicate, add the aqueous solution of water-soluble metal salt then, gather guanidine/polysilicate and separate out from solution through flocculating settling, throw out obtains the Powdered complex antimicrobials of water-insoluble solid after drying, pulverizing.
Wherein silicate can hydrolysis gradually after water-soluble, aggregate into certain intermediate product; When its when gathering the aqueous solution of guanidine inorganic acid salt or organic acid salt; Because it is very high to gather the silicic acid molecular weight; Have very strong bonding ability of aggregation and adsorption bridging effect, and with gather the high molecular molecular chain of guanidine and twine mutually; After adding metal-salt; The molecular chain and the metals ion of winding play chelatropic reaction each other in water solution system with gathering guanidine to gather silicic acid; Produce flocculation; Make the molecular chain that gathers guanidine be difficult to from the system of gathering guanidine/polysilicate that forms, to shake off out like this, thus form hydrophobe gather guanidine/polysilicate complex antimicrobials.
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 or the like.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.
The more concrete preparation process of this complex antimicrobials 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, promptly there is cotton-shaped infusible precipitate to generate, throw out is taken out rate, washing, drying can obtain gathering guanidine/polysilicate complex antimicrobials after the pulverizing.
In the preparation process, gather guanidine at this complex antimicrobials: silicate: water-soluble metal salt three's ratio can be regulated as required.
Wherein, the molar ratio of water-soluble poly guanidine inorganic acid salt or organic acid salt and water-soluble silicate can be regulated in the scope of broad, and the preferred molar ratio example is 10: 1～1: 50.If ratio was greater than 10: 1, it is excessive promptly to gather the guanidine consumption, then gathers gathering the productive rate that gathers guanidine/polysilicate that guanidine is converted into hydrophobe and can reduce in the guanidine aqueous solution, and major part is gathered guanidine and still can be kept water soluble state to be present in the aqueous solution, causes productive rate to reduce; If ratio is lower than 1: 50, promptly the silicate consumption is excessive, can make the effective antimicrobial component in guanidine/polysilicate that gathers of preparation; It is too low promptly to gather guanidine content; Cause antimicrobial efficiency low excessively, when preparation antibacterial polylactic acid compsn 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 that from point of view of practicability preferred ratio is for gathering 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; The productive rate that can cause gathering guanidine/polysilicate reduces; Can be interpreted as does not have enough metal-salts, has reduced throwing out, and the silicic acid macromolecular chain system of gathering of gathering guanidine and hydrolyzed silicate formation in the aqueous solution is precipitated out from water; If ratio is lower than 1: 3, promptly 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 (gathering the guanidine aqueous solution) and mix with B solution (silicate solutions) 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, and B solution is difficult to whole hydrolysis to be become and gather silicic acid or the polymerization degree is big inadequately, gathers silicic acid like this and to gather guanidine winding degree in the aqueous solution not enough; Also can make gather guanidine to detest the water degree not enough; And if overlong time surpasses 2 hours, then cause temporal waste.More preferred churning time is 20min～1h.
In synthesis step (4), should solution D slowly be poured in the mixed solution C of gathering guanidine and silicate, and vigorous stirring, can make the particle diameter that gathers 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, accelerates reaction process.Reacting the infusible precipitate of last formation can purify through 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 antiseptic-germicide is simple, and reaction conditions is gentle, is easy to suitability for industrialized production.
In compsn, 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 impeller more effective.Employed dispersion agent among the present invention can be selected the various dispersion agents commonly used of plastic working in the prior art, at least a in preferred Triple Pressed Stearic Acid, Zinic stearas, the white oil, more preferably Zinic stearas.Dispersion agent can make that to gather guanidine/polysilicate complex antimicrobials dispersed better in POLYACTIC ACID, can also play certain lubrication simultaneously, makes POLYACTIC ACID when granulation, diminishes in the shearing force of screw feed section, and granulation is carried out smoothly.In biaxially stretched polylactic acid film PP Pipe Compound is 100 weight parts, dispersion agent 0～0.5 weight part, preferred 0.1～0.3 weight part.
In addition, in the course of processing of this antibiotic biaxially stretched polylactic acid film, the concrete needs of available basis add other auxiliary agents, and for example: toughner, pigment polynite, lime carbonate etc., its consumption is conventional amount used, or adjusts according to practical requirements.
Two of the object of the invention provides the preparation method of this antibiotic biaxially stretched polylactic acid film, realizes through following technical scheme:
Comprise that the each component that will include said biaxially stretched polylactic acid film PP Pipe Compound, antiseptic-germicide mixes by said content, melt blending, again through curtain coating after the two-way stretch method makes described antibiotic biaxially stretched polylactic acid film.
More concrete preparation process can be divided into two approach:
(1) will include said biaxially stretched polylactic acid film PP Pipe Compound, antiseptic-germicide earlier mixing device such as stirs by said content through height at interior each component and mixes; Prepare antibiotic BOPLA material through melt blending devices such as twin screws then; Again antibiotic BOPLA material is become sheet material through casting films device curtain coating; Through the biaxially oriented film device sheet material is stretched at last and become antibiotic BOPLA film.
(2) will include said biaxially stretched polylactic acid film PP Pipe Compound, antiseptic-germicide earlier mixing device such as stirs by said content through height at interior each component and mixes; Then mixed material is gone out sheet material through casting films device curtain coating; Through the biaxially oriented film device sheet material is stretched at last and become antibiotic BOPLA film.
First kind of working method gathered guanidine/polysilicate antiseptic-germicide and BOPLA raw material through the melt blending process, and antiseptic-germicide disperses better in plastics, and antibacterial effect is better, therefore, and preferred first kind of working method.
In the course of processing of antibiotic biaxially stretched polylactic acid film of the present invention; Material melt blending temperature is used blending temperature in the common POLYACTIC ACID processing; Should select not only guaranteeing the complete fusion of matrix but also can not make in the scope of its decomposition, be 160～230 ℃.Consider the low excessively melt blending that is unfavorable for POLYACTIC ACID and antiseptic-germicide and other component of temperature; The too high degraded that causes POLYACTIC ACID easily of temperature; The curtain coating and the biaxially oriented film that are unfavorable for POLYACTIC ACID; Also can cause simultaneously the mechanical properties decrease of antibacterial polylactic acid, more preferred processing temperature is 180～200 ℃.For the process of curtain coating BOPLA sheet material, the heating zone temperature of casting films device is provided with and can be 170～230 ℃, and based on the consideration same with the front, preferred heating zone temperature is 190～200 ℃.
In preparation method of the present invention, the concrete steps of two-way stretch are: the BOPLA sheet material that at first curtain coating is gone out carries out preheating, and preheating temperature is 75～120 ℃, preferred 78～83 ℃; Then the BOPLA sheet material is stretched in vertical (MD) direction, stretching ratio is 2～6 times, and draft temperature is: 75～120 ℃, preferred temperature is 80～85 ℃, and rate of extension is 100～700%/s, preferred 100～300%; Film is stretched in horizontal (TD) direction, stretching ratio is 2～6 times again, and rate of extension is 100～700%/s, preferred 100～300%/s; With the typing that bounces back of BOPLA film, eliminate stress at last, setting temperature is 85～100 ℃, preferred 90 ℃.
In the preparation method of the invention described above, the mixing equipment of mixing of materials can adopt various mixing equipments used in the prior art, like stirrer, kneading machine etc.Employed melt blending equipment is the general blending equipment in the rubber and plastic processing industry, can be twin screw extruder, single screw extrusion machine, mill or Banbury mixer etc.Employed casting apparatus can adopt in the prior art general various casting apparatus, like cast film machine etc.Employed stretcher is general various stretchers, as: biaxial orientation stretching machine etc.
Antibiotic biaxially stretched polylactic acid film of the present invention, its characteristics are that the antiseptic-germicide that uses is a kind of guanidine/polysilicate complex antimicrobials that gathers, this complex antimicrobials have particle diameter little, be insoluble in water, germ-killing efficiency advantages of higher.Utilization of the present invention becomes sheet material through the casting device curtain coating earlier based on this antibiotic BOPLA plastics that gather guanidine/polysilicate for antibacterial components, and utilizing two-way film drawing device to stretch with certain rate of extension and stretching ratio again becomes antibiotic BOPLA film.Utilize the antibiotic BOPLA film of this method preparation to have the antimicrobial efficiency height, under the less situation of antiseptic-germicide consumption, can reach better anti-bacterial effect; Antibioticly reach 99.9%, antibacterial components is difficult for from film, separating out, and water-resistant stability is good; Behind poach, still keep better anti-bacterial effect, transparency is high, is difficult for taking place xanthiochromatic; And production stage is simple, has a good application prospect.
Embodiment
Below in conjunction with specific embodiment the present invention is further specified.But the present invention is not limited in following embodiment.
Raw material is in following examples and the comparative example:
POLYACTIC ACID (PLA): Naturework company, the trade mark: Ingeo
TM4032D, Ingeo
TM4042D;
Dispersion agent: white oil, the real magnificent limited-liability company of Maoming petrochemical industry;
Zinic stearas: CP, commercially available;
Triple Pressed Stearic Acid: CP, commercially available;
Antiseptic-germicide: gather guanidine/polysilicate, self-control;
Twin screw: ZSK-40, German WP company;
Three-layer co-extruded cast film machine: homemade;
Film biaxial tensile test machine: Kero IV Germany Bruckner;
Antibacterial test standard: QB/T 2591-2003A " antibiotic plastic anti-microbial property TP and antibacterial effect ";
Detect and use bacterium: intestinal bacteria (Escherichia coli) ATCC 25922;
Staphylococcus aureus (Staphylococcus aureus) ATCC 6538.
One, the preparation of complex antimicrobials
Embodiment 1:
(1) takes by weighing polyhexamethylene guanidine propionic salt (the Shanghai height gathers F3000) 100.0g (0.465mol), join in the 300mL deionized water solution, stir and make its dissolving, be called solution A; (2) claim water glass (CP, 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(CP, 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 Shanghai height gathers F3000) 100.0g (0.465mol), join in the 300mL deionized water solution, stir and make its dissolving, be called solution A; (2) claim water glass (CP, 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, form solution C at 50 ℃; (4) take by weighing zinc sulfate ZnSO
4(CP, 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 Shanghai height gathers F1000) 100.0g (0.635mol), join in the 300mL deionized water solution, stir and make its dissolving, be called solution A; (2) claim water glass (CP, 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(CP, 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 Shanghai height gathers F1000) 100.0g (0.635mol), join in the 300mL deionized water solution, stir and make its dissolving, be called solution A; (2) claim water glass (CP, commercially available) 160.0g (0.563mol) 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, form solution C at 80 ℃; (4) take by weighing aluminum nitrate Al (NO
3)
3(CP, commercially available) 300.0g (0.8mol) 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 (CP, commercially available) 60.0g (0.211mol) 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(CP, commercially available) 100.0g (0.348mol) 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 B0PLA film:
Embodiment 6:
With POLYACTIC ACID Ingeo
TM100 parts of 4032D; One 0.6 parts of complex antimicrobials, 0.1 part of white oil, Zinic stearas is put into low speed mixer for 0.1 part and is stirred; 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.
The antibiotic BOPLA raw material of preparation is passed through casting films equipment, and 190～200 ℃ of temperature, curtain coating becomes sheet material.Utilize two-way stretch equipment that sheet material is drawn into the BOPLA film according to condition in the table 1, thickness is about 35 μ m.
BOPLA film stretching condition among table 1 embodiment 6～10
Before carrying out antibacterial test, elder generation in 50 ℃ of water, boils 16 hours with a part of BOPLA sample, and is subsequent use.
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 is replaced with 0.6 part of pure polyhexamethylene guanidine propionic salt (the Shanghai height gathers F3000), and all the other conditions are all with embodiment 6, it is drawn into film after, carry out antibacterial test.
The anti-bacterial result (sterilizing rate %):
Before the poach: staphylococcus aureus: 42.7%; Intestinal bacteria: 31.9%;
Behind the poach: staphylococcus aureus: 0%; Intestinal bacteria: 0%.
From above-mentioned comparative example, can see before and after poach, utilize the BOPLA film antibacterial effect that gathers guanidine/zinc polysilicate complex antimicrobials preparation will get well much than the pure guanidine propionic salt that gathers.
Embodiment 7:
With POLYACTIC ACID Ingeo
TM4032D100 part; 2 1.2 parts of complex antimicrobials; Zinic stearas is put into low speed mixer for 0.3 part and is stirred, and then mixture is passed through the twin screw extruder melt blending, and extruder temperature is 190～200 ℃; Rotating speed is the 350r.p.m extruding pelletization, and the pellet of extruding is dried 3hr in 90 ℃ of constant temperature ovens.
The antibiotic BOPLA raw material of preparation is passed through casting films equipment, and 190～200 ℃ of temperature, curtain coating becomes sheet material.Utilize two-way stretch equipment that sheet material is become the BOPLA film according to condition two-way stretch in the table 1, thickness is about 26 μ m.
Before carrying out antibacterial test, elder generation in 50 ℃ of water, boils 16 hours with a part of BOPLA sample, and is subsequent use.
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 is replaced with 1.2 parts of pure polyhexamethylene guanidine propionic salts (the Shanghai height gathers F3000), and all the other conditions are all with embodiment 7, it is drawn into film after, carry out antibacterial test.
The anti-bacterial result (sterilizing rate %):
Before the poach: staphylococcus aureus: 64.4%; Intestinal bacteria: 61.0%;
Behind the poach: staphylococcus aureus: 28.6%; Intestinal bacteria: 23.5%.
From above-mentioned comparative example, can see before and after poach, utilize the BOPLA film antibacterial effect that gathers guanidine/zinc polysilicate complex antimicrobials preparation will get well much than the pure guanidine propionic salt that gathers.
Embodiment 8:
With POLYACTIC ACID Ingeo
TM100 parts of 4042D; 3 1.5 parts of complex antimicrobials; Triple Pressed Stearic Acid is put into low speed mixer for 0.3 part and is stirred, and then mixture is passed through the twin screw extruder melt blending, and extruder temperature is 190～200 ℃; Rotating speed is the 350r.p.m extruding pelletization, and the pellet of extruding is dried 3hr in 90 ℃ of constant temperature ovens.
The antibiotic BOPLA raw material of preparation is passed through casting films equipment, and 190～200 ℃ of temperature, curtain coating becomes sheet material.Utilize two-way stretch equipment that sheet material is become the BOPLA film according to condition two-way stretch in the table 1, thickness is about 32 μ m.
Before carrying out antibacterial test, elder generation in 50 ℃ of water, boils 16 hours with a part of BOPLA sample, and is subsequent use.
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 is replaced with 1.5 parts of pure poly (hexamethylene) hydrochlorides (the Shanghai height gathers F1000), and all the other conditions are all with embodiment 8, it is drawn into film after, carry out antibacterial test.
The anti-bacterial result (sterilizing rate %):
Before the poach: staphylococcus aureus: 93.6%; Intestinal bacteria: 91.4%;
Behind the poach: staphylococcus aureus: 37.3%; Intestinal bacteria: 35.2%.
From above-mentioned comparative example, can see before and after poach, utilize the BOPLA film antibacterial effect that gathers guanidine/calcium polysilicate complex antimicrobials preparation will get well much than the pure guanidinesalt hydrochlorate that gathers.
Embodiment 9:
With POLYACTIC ACID Ingeo
TM4042D100 part; 4 1.6 parts of complex antimicrobials; Zinic stearas is put into low speed mixer for 0.4 part and is stirred, and then mixture is passed through the twin screw extruder melt blending, and extruder temperature is 190～200 ℃; Rotating speed is the 350r.p.m extruding pelletization, and the pellet of extruding is dried 3hr in 90 ℃ of constant temperature ovens.
The antibiotic BOPLA raw material of preparation is passed through casting films equipment, and 190～200 ℃ of temperature, curtain coating becomes sheet material.Utilize two-way stretch equipment that sheet material is become the BOPLA film according to condition two-way stretch in the table 1, thickness is about 20 μ m.
Before carrying out antibacterial test, elder generation in 50 ℃ of water, boils 16 hours with a part of BOPLA sample, and is subsequent use.
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 is replaced with 1.6 parts of pure poly (hexamethylene) hydrochlorides, and all the other conditions are all with embodiment 9, it is drawn into film after, carry out antibacterial test.
The anti-bacterial result (sterilizing rate %):
Before the poach: staphylococcus aureus: 96.3%; Intestinal bacteria: 94.2%;
Behind the poach: staphylococcus aureus: 68.2%; Intestinal bacteria: 61.9%.
From above-mentioned comparative example, can see before and after poach, utilize the BOPLA film antibacterial effect that gathers guanidine/aluminium silicate polymer complex antimicrobials preparation will get well much than the pure guanidinesalt hydrochlorate that gathers.
Embodiment 10:
With POLYACTIC ACID Ingeo
TM100 parts of 4042D; 5 2.0 parts of complex antimicrobials; Zinic stearas is put into low speed mixer for 0.5 part and is stirred, and then mixture is passed through the twin screw extruder melt blending, and extruder temperature is 190～200 ℃; Rotating speed is the 350r.p.m extruding pelletization, and the pellet of extruding is dried 3hr in 90 ℃ of constant temperature ovens.
The antibiotic BOPLA raw material of preparation is passed through casting films equipment, and 190～200 ℃ of temperature, curtain coating becomes sheet material.Utilize two-way stretch equipment that sheet material is become the BOPLA film according to condition two-way stretch in the table 1, thickness is about 20 μ m.
Before carrying out antibacterial test, elder generation in 50 ℃ of water, boils 16 hours with a part of BOPLA sample, and is subsequent use.
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 is replaced with pure 2.0 parts of the six methylene biguanide hydrochlorides that gather, and all the other conditions are all with embodiment 10, it is drawn into film after, 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: 78.9%; Intestinal bacteria: 72.6%.
From above-mentioned comparative example; Utilize the BOPLA of hexamethylene/zinc polysilicate complex antimicrobials and pure hexamethylene modification that good antibacterial effect is all arranged before can seeing poach, explain 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.
Embodiment 11:
With POLYACTIC ACID Ingeo
TM100 parts of 4042D; 4 2.5 parts of complex antimicrobials; Zinic stearas is put into low speed mixer for 0.5 part and is stirred, and then mixture is passed through the twin screw extruder melt blending, and extruder temperature is 190～～200 ℃; Rotating speed is the 350r.p.m extruding pelletization, and the pellet of extruding is dried 3hr in 90 ℃ of constant temperature ovens.
The antibiotic BOPLA raw material of preparation is passed through casting films equipment, and 190～200 ℃ of temperature, curtain coating becomes sheet material.Utilize two-way stretch equipment that sheet material is become the BOPLA film according to condition two-way stretch in the table 1, thickness is about 100 μ m.
Before carrying out antibacterial test, elder generation in 50 ℃ of water, boils 16 hours with a part of BOPLA sample, and is subsequent use.
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 6:
Antiseptic-germicide is replaced with 2.5 parts of pure poly (hexamethylene) hydrochlorides, all same additional embodiment of all the other conditions, it is drawn into film after, 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: 90.8%; Intestinal bacteria: 89.6%.
From above-mentioned comparative example; Utilize the BOPLA of poly (hexamethylene) hydrochloride/aluminium silicate polymer complex antimicrobials and pure poly (hexamethylene) hydrochloride modification that good antibacterial effect is all arranged before can seeing poach, explain that poly (hexamethylene) hydrochloride 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/aluminium silicate polymer complex antimicrobials all is better than pure poly (hexamethylene) hydrochloride.
Claims (9)
1. an antibiotic biaxially stretched polylactic acid film includes following component: biaxially stretched polylactic acid film PP Pipe Compound, antiseptic-germicide;
Be 100 weight parts wherein in biaxially stretched polylactic acid film PP Pipe Compound, antiseptic-germicide 0.4～3 weight part; Film is through the preparation of two-way stretch method, and thickness is 10～100 μ m;
Described antiseptic-germicide is for gathering guanidine/polysilicate complex antimicrobials; After being aqueous solution by the aqueous solution of water-soluble poly guanidine inorganic acid salt or organic acid salt and water-soluble silicate; The aqueous solution of adding water-soluble metal salt 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. antibiotic biaxially stretched polylactic acid film as claimed in claim 1 is characterized in that including following component:
In biaxially stretched polylactic acid film PP Pipe Compound is 100 weight parts, antiseptic-germicide 0.6～2 weight part.
3. antibiotic biaxially stretched polylactic acid film 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 polyhexamethylene (two) guanidinesalt hydrochlorate, polyhexamethylene (two) guanidine nitrate, polyhexamethylene (two) guanidine carbonate, polyhexamethylene (two) the guanidine propionic salt.
4. antibiotic biaxially stretched polylactic acid film 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. antibiotic biaxially stretched polylactic acid film 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. antibiotic biaxially stretched polylactic acid film 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. antibiotic biaxially stretched polylactic acid film 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. like the described antibiotic biaxially stretched polylactic acid film of claim 1～7, it is characterized in that:
Comprise dispersion agent; In biaxially stretched polylactic acid film PP Pipe Compound is 100 weight parts, dispersion agent 0～0.5 weight part;
Described dispersion agent is selected from least a in Triple Pressed Stearic Acid, Zinic stearas, the white oil.
9. like the preparation method of the arbitrary described antibiotic biaxially stretched polylactic acid film of claim 1～8, it is characterized in that:
Comprise that the each component that will include said biaxially stretched polylactic acid film PP Pipe Compound, antiseptic-germicide mixes by said content, melt blending, again through curtain coating after the two-way stretch method makes described antibiotic biaxially stretched polylactic acid film.
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| CN104151792A (en) * | 2014-08-06 | 2014-11-19 | 南京神奇生物技术有限公司 | Non-migration and degradable antimicrobial polyester film and preparation method thereof |
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| KR20010100067A (en) * | 2001-08-30 | 2001-11-14 | 김권 | Biodegradable resin composition combined with starch |
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| KR20010100067A (en) * | 2001-08-30 | 2001-11-14 | 김권 | Biodegradable resin composition combined with starch |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104151792A (en) * | 2014-08-06 | 2014-11-19 | 南京神奇生物技术有限公司 | Non-migration and degradable antimicrobial polyester film and preparation method thereof |
| CN104151792B (en) * | 2014-08-06 | 2016-01-20 | 南京神奇生物技术有限公司 | A kind of non-migratory and degradable antibacterial polyester film and preparation method thereof |
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