CN103755991B - A kind of Antibiotic Membrane - Google Patents
A kind of Antibiotic Membrane Download PDFInfo
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- CN103755991B CN103755991B CN201410037095.4A CN201410037095A CN103755991B CN 103755991 B CN103755991 B CN 103755991B CN 201410037095 A CN201410037095 A CN 201410037095A CN 103755991 B CN103755991 B CN 103755991B
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Abstract
The present invention relates to a kind of Antibiotic Membrane, it is characterized in that, comprise dope layer and substrate layer successively, the thickness of described dope layer is 0.1-2um, and the thickness of substrate layer is 10-50um.Make the nanoparticle of film inside also can play the effect of absorption and catalysis, be also conducive to the orderly release of antimicrobial substance simultaneously, thus make coating have effect of long-acting absorption degradation objectionable impurities and long acting antibiotic.
Description
Technical field
The invention belongs to nano material technology, be specifically related to a kind of Antibiotic Membrane.
Background technology
Along with improving constantly of development in science and technology and people's Living Water skin, the packaging film of germ resistance also applies to industry widely.Because nanoparticle has quantum size effect, small-size effect, surface effects and macro quanta tunnel effect, thus show much special character.When these materials are added among traditional coating, just can good effect be produced, as long acting antibiotic performance, uv-shielding capacity, photocatalysis performance etc., and some inherent naturies simultaneously increasing coating, as film snappiness, coating hardness, sticking power, petrol-resistance, performances such as alkali-resistivity etc.Porous material of the present invention is the three-dimensional open-framework that carbon coated copper/metal oxide has nano-scale, product morphology is homogeneous, controlled, and preparation method is simple, with low cost, environmental friendliness, and it can be used as a component to add in coating, nanoparticle can easily be adsorbed and not easily absorption is agglomerating mutually by porous mass.The existence of porous mass, effective micro channel can be formed in coating, make the nanoparticle of film inside also can play the effect of absorption and catalysis, be also conducive to the orderly release of antimicrobial substance simultaneously, thus make coating have effect of long-acting absorption degradation objectionable impurities and long acting antibiotic.
Summary of the invention
The object of the present invention is to provide a kind of Antibiotic Membrane, it is characterized in that, comprise dope layer and substrate layer successively, described dope layer thickness be 0.1-2um, the thickness of substrate layer is 10-50um.
Described substrate layer is selected from Biaxially oriented polypropylene film (BOPP) (BOPP) film or biaxial stretching polyester (PET) film.
Described dope layer comprises following component:
(1) porous material, the content of described porous material is 1-40%.
(2) nanoparticle, content is 1-40%, described nanoparticle be selected from nano-titanium oxide, nanometer silver, nano aluminum or its composition.
(3) filmogen, content is 5-80%, and described filmogen is acrylic resin.
(4) additive, described additive comprises the thickening material of 1-2% dispersion agent, 1-2% defoamer and 1-3%, and described thickening material is selected from, and molecular weight is the Natvosol of 3-10 ten thousand.
(5) deionized water, the content of described deionized water is 5-15%.
Described porous material is prepared by following methods:
Step one, chooses nanometal mixture
Described nanometal mixture is made up of nanometer zinc acetate and nanometer venus crystals powder, and the mol ratio of described zinc acetate and venus crystals is 2:1.
Step 2, the preparation of the first solution
The nanometal mixture of step one is mixed with tensio-active agent and ethylene glycol solution, mass ratio is: nanometal mixture: tensio-active agent: ethylene glycol solution=(4-6): (3-5): 300, mixed solution is stirred 10-30 minute with the speed of 600-1000r/min in 60-90 DEG C of oil bath, and naturally cooling obtains the first solution.
Step 3: the preparation of the second solution
Ethylene glycol and oxalic acid are mixed under normal temperature, obtained second solution, the mass ratio of described ethylene glycol and oxalic acid is 100:3.
Step 4: the preparation of composite precursor
By the dripping in fast the first solution instilled obtained by step 2 with 3-10mL/min of the second solution obtained by step 3, stir 4h with the speed 60-100 of 600-1000r/min DEG C of constant temperature; After reaction terminates, resultant of reaction is respectively washed 3 times, collected by centrifugation with deionized water and dehydrated alcohol respectively, and in baking oven, 80 DEG C of dry 6h, namely obtain composite precursor.The mass ratio of described second solution and the first solution is: 1:3-4.
Step 5: the preparation of the coated Cu/ZnO composite porous material of carbon
By composite precursor obtained by step 4 as in tube furnace, pass to the X/H2 atmosphere that hydrogen volume content is 1-10%, with the ramp to 200 DEG C of 5 DEG C/min, constant temperature keeps 2h, then rise to 500 DEG C with 5 DEG C/min, constant temperature keeps 2h, obtains the coated Cu/ZnO composite porous material of carbon, described X is nitrogen, argon gas, the one in helium that purity is not less than 99.9%, and the volume content of hydrogen is at 1%-10%.
2. a kind of Antibiotic Membrane as claimed in claim 1, is characterized in that the particle diameter of described nanometer zinc acetate and nanometer venus crystals powder is 1-50nm, and the porosity of obtained porous material is more than 86%, and the size of hole is 1-25nm.
3. a kind of Antibiotic Membrane as claimed in claim 1, it is characterized in that described tensio-active agent be selected from a kind of in polyvinylpyrrolidone (PVP), cetyl trimethylammonium bromide (CTAB), chlorination trimethylcetylammonium (CTAC), polyethylene oxide-poly(propylene oxide)-polyethylene oxide triblock copolymer (P123), polyoxyethylene-poly-oxypropylene polyoxyethylene triblock polymer (F127) or with arbitrarily than mixture.
4. a kind of Antibiotic Membrane as claimed in claim 1, is characterized in that the particle diameter of described nanoparticle is 1-10nm.
Porous material of the present invention is the three-dimensional open-framework that carbon coated copper/metal oxide has nano-scale, product morphology is homogeneous, controlled, and preparation method is simple, with low cost, environmental friendliness, and it can be used as a component to add in coating, nanoparticle can easily be adsorbed and not easily absorption is agglomerating mutually by porous mass.The existence of porous mass, effective micro channel can be formed in coating, make the nanoparticle of film inside also can play the effect of absorption and catalysis, be also conducive to the orderly release of antimicrobial substance simultaneously, thus make coating have effect of long-acting absorption degradation objectionable impurities and long acting antibiotic.
Embodiment
A kind of Antibiotic Membrane, is characterized in that, comprise dope layer and substrate layer successively, described dope layer thickness be 0.1-2um, the thickness of substrate layer is 10-50um.
The surface of this substrate layer needs to carry out corona treatment, afterwards prepared dope layer is applied to substrate surface, dries and photocuring formation dry film under the environment of anaerobic.Described dope layer can be positioned at one side or the two sides of base material.
Described substrate layer is selected from Biaxially oriented polypropylene film (BOPP) (BOPP) film or biaxial stretching polyester (PET) film.
Described dope layer comprises following component:
(1) porous material, the content of described porous material is 1-40%.
(2) nanoparticle, content is 1-40%, described nanoparticle be selected from nano-titanium oxide, nanometer silver, nano aluminum or its composition.
(3) filmogen, content is 5-80%, and described filmogen is acrylic resin.
(4) additive, described additive comprises the thickening material of 1-2% dispersion agent, 1-2% defoamer and 1-3%, and described thickening material is selected from, and molecular weight is the Natvosol of 3-10 ten thousand.
(5) deionized water, the content of described deionized water is 5-15%.
Described porous material is prepared by following methods:
Step one, chooses nanometal mixture
Described nanometal mixture is made up of nanometer zinc acetate and nanometer venus crystals powder, and described zinc acetate and venus crystals are respectively 0.02mol and 0.01mol.
Step 2, the preparation of the first solution
Mixed with 4g tensio-active agent and 300ml ethylene glycol solution by the nanometal mixture of step one, mixed solution is stirred 15 minutes with the speed of 800r/min in 80 DEG C of oil baths, naturally cooling obtains the first solution.
Step 3: the preparation of the second solution
100 ethylene glycol and 0.03mol oxalic acid are mixed under normal temperature, obtained second solution.
Step 4: the preparation of composite precursor
By the second solution obtained by step 3 with in the first solution obtained by a speed instillation step 2 of 5mL/min, stir 4h with speed 80 DEG C of constant temperature of 800r/min; After reaction terminates, resultant of reaction is respectively washed 3 times, collected by centrifugation with deionized water and dehydrated alcohol respectively, and in baking oven, 80 DEG C of dry 6h, namely obtain composite precursor.The mass ratio of described second solution and the first solution is: 1:3-4.
Step 5: the preparation of the coated Cu/ZnO composite porous material of carbon
By composite precursor obtained by step 4 as in tube furnace, pass to the X/H2 atmosphere that hydrogen volume content is 1-10%, with the ramp to 200 DEG C of 5 DEG C/min, constant temperature keeps 2h, then rise to 500 DEG C with 5 DEG C/min, constant temperature keeps 2h, obtains the coated Cu/ZnO composite porous material of carbon, described X is nitrogen, argon gas, the one in helium that purity is not less than 99.9%, and the volume content of hydrogen is at 1%-10%.
The particle diameter of described nanometer zinc acetate and nanometer venus crystals powder is 1-50nm, and the porosity of obtained porous material is more than 86%, and the size of hole is 1-25nm.
Described tensio-active agent be selected from a kind of in polyvinylpyrrolidone (PVP), cetyl trimethylammonium bromide (CTAB), chlorination trimethylcetylammonium (CTAC), polyethylene oxide-poly(propylene oxide)-polyethylene oxide triblock copolymer (P123), polyoxyethylene-poly-oxypropylene polyoxyethylene triblock polymer (F127) or with arbitrarily than mixture.
The particle diameter of described nanoparticle is 1-10nm.
Choose 800 object 40g porous materials, 16g nano-titanium oxide, 4 grams of nano-silver powders, 80g acrylic resin, 3g dispersion agent and 3g defoamer, 4g Natvosol and 30g deionized water, as in container, adopt mechanical stirring to mix, form stable coating.Described coating has more micro channel, has long-acting absorption, the organic obnoxious flavour of catalyzed degradation and bactericidal property.Described coating water at normal temperature contact angle is greater than 120 degree.
The water-fast experimental results of GB/T1733-93 is 360 hours nothing difference;
Alcohol resistance (60% ethanolic soln) test result of GB1727-79 is 100 hours nothing difference.
Below in conjunction with specific embodiment technical scheme of the present invention done and introduce in detail further; but protection scope of the present invention is not limited thereto; those skilled in the art makes some nonessential improvement and adjustment according to the content of the invention described above, all belongs to scope.
Claims (4)
1. an Antibiotic Membrane, is characterized in that, comprises dope layer and substrate layer successively,
Described dope layer thickness be 0.1-2um, the thickness of substrate layer is 10-50um;
Described substrate layer is selected from BiOriented Polypropylene Films or biaxially oriented polyester film;
Described dope layer comprises following component:
(1) porous material, the content of described porous material is 1-40%;
(2) nanoparticle, content is 1-40%, described nanoparticle be selected from nano-titanium oxide, nanometer silver, nano aluminum or its composition;
(3) filmogen, content is 5-80%, and described filmogen is acrylic resin;
(4) additive, described additive comprises the thickening material of 1-2% dispersion agent, 1-2% defoamer and 1-3%, and described thickening material is selected from, and molecular weight is the Natvosol of 3-10 ten thousand;
(5) deionized water, the content of described deionized water is 5-15%;
Described porous material is prepared by following methods:
Step one, chooses nanometal mixture
Described nanometal mixture is made up of nanometer zinc acetate and nanometer venus crystals powder, and the mol ratio of described zinc acetate and venus crystals is 2:1;
Step 2, the preparation of the first solution
The nanometal mixture of step one is mixed with tensio-active agent and ethylene glycol solution, mass ratio is: nanometal mixture: tensio-active agent: ethylene glycol solution=4-6:3-5:300, mixed solution is stirred 10-30 minute with the speed of 600-1000r/min in 60-90 DEG C of oil bath, and naturally cooling obtains the first solution;
Step 3: the preparation of the second solution
Ethylene glycol and oxalic acid are mixed under normal temperature, obtained second solution, the mass ratio of described ethylene glycol and oxalic acid is 100:3;
Step 4: the preparation of composite precursor
By the dripping in fast the first solution instilled obtained by step 2 with 3-10mL/min of the second solution obtained by step 3, stir 4h with the speed 60-100 of 600-1000r/min DEG C of constant temperature; After reaction terminates, resultant of reaction is respectively washed 3 times, collected by centrifugation with deionized water and dehydrated alcohol respectively, and in baking oven, 80 DEG C of dry 6h, namely obtain composite precursor; The mass ratio of described second solution and the first solution is: 1:3-4;
Step 5: the preparation of the coated Cu/ZnO composite porous material of carbon
Composite precursor obtained by step 4 is placed in tube furnace, passes to the X/H that hydrogen volume content is 1-10%
2atmosphere, with the ramp to 200 DEG C of 5 DEG C/min, constant temperature keeps 2h, then rise to 500 DEG C with 5 DEG C/min, constant temperature keeps 2h, obtains the coated Cu/ZnO composite porous material of carbon, described X is nitrogen, argon gas, the one in helium that purity is not less than 99.9%, and the volume content of hydrogen is at 1%-10%.
2. a kind of Antibiotic Membrane as claimed in claim 1, is characterized in that the particle diameter of described nanometer zinc acetate and nanometer venus crystals powder is 1-50nm, and the porosity of obtained porous material is more than 86%, and the size of hole is 1-25nm.
3. a kind of Antibiotic Membrane as claimed in claim 1, it is characterized in that described tensio-active agent be selected from a kind of in polyvinylpyrrolidone, cetyl trimethylammonium bromide, chlorination trimethylcetylammonium, polyethylene oxide-poly(propylene oxide)-polyethylene oxide triblock copolymer or with arbitrarily than mixture.
4. a kind of Antibiotic Membrane as claimed in claim 1, is characterized in that the particle diameter of described nanoparticle is 1-10nm.
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