CN103756589B - A kind of preparation method of nanometer functional film - Google Patents
A kind of preparation method of nanometer functional film Download PDFInfo
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- CN103756589B CN103756589B CN201410038684.4A CN201410038684A CN103756589B CN 103756589 B CN103756589 B CN 103756589B CN 201410038684 A CN201410038684 A CN 201410038684A CN 103756589 B CN103756589 B CN 103756589B
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Abstract
The present invention relates to a kind of preparation method of nanometer functional film; it is characterized in that; comprise dope layer, substrate layer, tack coat and protective layer successively; the thickness of described dope layer is 0.1-2um; the thickness of substrate layer is 10-50um; the thickness of tack coat is 0.5-5um, and the thickness of protective layer is 10-50um.Make the nano particle of film inside also can play the effect of absorption and catalysis, be also conducive to the orderly release of antibacterial material simultaneously, thus make coating have effect of long-acting absorption degradation harmful substance and long acting antibiotic.
Description
Technical field
The invention belongs to nano material technology, be specifically related to a kind of preparation method of nanometer functional film.
Background technology
Along with improving constantly of development in science and technology and people's Living Water skin, nano material has started to have had in coating to apply widely.Because nano particle has quantum size effect, small-size effect, skin effect 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 intrinsic properties simultaneously increasing coating, as film pliability, coating hardness, adhesive force, petrol-resistance, performances such as alkali resistance 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, nano particle 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 nano particle of film inside also can play the effect of absorption and catalysis, be also conducive to the orderly release of antibacterial material simultaneously, thus make coating have effect of long-acting absorption degradation harmful substance and long acting antibiotic.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of nanometer functional film, this film comprises dope layer, substrate layer, tack coat and protective layer successively,
Described dope layer thickness be 0.1-2um, the thickness of substrate layer is 10-50um, and the thickness of tack coat is 0.5-5um, and the thickness of protective layer is 10-50um.
Described substrate layer is selected from Biaxially oriented polypropylene (BOPP) film or biaxial stretching polyester (PET) film.The material of described tack coat is selected from acrylic binders, and described protective layer is PET type mould release membrance.
It is characterized in that the preparation of described film comprises the following steps:
The first step: the process of substrate layer, chooses base material as substrate layer, and sided corona treatment is carried out on the surface of described substrate layer.
Second step, the preparation of dope layer, is coated on dope layer on a surface of the substrate layer that the first step is handled well, and under the environment of anaerobic, solidify photocureable coating layer formation dry film.
3rd step, by tack coat even spread to the another side of substrate layer;
4th step, is placed in the another side of tack coat by protective layer.
Described dope layer comprises following component:
(1) porous material, the content of described porous material is 1-40%.
(2) nano particle, content is 1-40%, described nano particle be selected from nano-titanium oxide, Nano Silver, nano aluminum or its composition.
(3) film forming matter, content is 5-80%, and described film forming matter is acrylic resin.
(4) additive, described additive comprises the thickener of 1-2% dispersant, 1-2% defoamer and 1-3%, and described thickener is selected from, and molecular weight is the hydroxyethylcellulose 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 manganese acetate and nanometer copper chloride powder, and the mol ratio of described manganese acetate and copper chloride is 2: 1.
Step 2, the preparation of the first solution
The nanometal mixture of step one is mixed with surfactant and ethylene glycol solution, mass ratio is: nanometal mixture: surfactant: ethylene glycol solution=(5-7): (3-5): 300, mixed liquor is stirred 10-30 minute with the speed of 600-1000r/min in 60-90 DEG C of oil bath, naturally obtained first solution of cooling.
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, reaction product is respectively washed 3 times, collected by centrifugation with deionized water and absolute ethyl 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/Mn2O 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 450 DEG C with 5 DEG C/min, constant temperature keeps 2h, obtains the coated Cu/Mn2O 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. the preparation method of a kind of nanometer functional film as claimed in claim 1, is characterized in that the particle diameter of described nanometer manganese acetate and nanometer copper chloride powder is 1-50nm, and the porosity of obtained porous material is more than 86%, and the size of hole is 1-25nm.
3. the preparation method of a kind of nanometer functional film as claimed in claim 1, it is characterized in that described surfactant be selected from a kind of in polyvinylpyrrolidone (PVP), softex kw (CTAB), chlorination trimethylcetylammonium (CTAC), PEO-PPOX-PEO triblock copolymer (P123), polyoxyethylene-poly-oxypropylene polyoxyethylene triblock polymer (F127) or with arbitrarily than mixture.
4. the preparation method of a kind of nanometer functional film as claimed in claim 1, is characterized in that the particle diameter of described nano particle 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, nano particle 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 nano particle of film inside also can play the effect of absorption and catalysis, be also conducive to the orderly release of antibacterial material simultaneously, thus make coating have effect of long-acting absorption degradation harmful substance and long acting antibiotic.
Detailed description of the invention
A preparation method for nanometer functional film, this film comprises dope layer, substrate layer, tack coat and protective layer successively,
Described dope layer thickness be 0.1-2um, the thickness of substrate layer is 10-50um, and the thickness of tack coat is 0.5-5um, and the thickness of protective layer is 10-50um.
Described substrate layer is selected from Biaxially oriented polypropylene (BOPP) film or biaxial stretching polyester (PET) film.The material of described tack coat is selected from acrylic binders, and described protective layer is PET type mould release membrance.During use, protective layer is peeled off, affix to required surface.
It is characterized in that the preparation of described film comprises the following steps:
The first step: the process of substrate layer, chooses base material as substrate layer, and sided corona treatment is carried out on the surface of described substrate layer.
Second step, the preparation of dope layer, is coated on dope layer on a surface of the substrate layer that the first step is handled well, and under the environment of anaerobic, solidify photocureable coating layer formation dry film.
3rd step, by tack coat even spread to the another side of substrate layer;
4th step, is placed in the another side of tack coat by protective layer.
Described dope layer comprises following component:
(1) porous material, the content of described porous material is 1-40%.
(2) nano particle, content is 1-40%, described nano particle be selected from nano-titanium oxide, Nano Silver, nano aluminum or its composition.
(3) film forming matter, content is 5-80%, and described film forming matter is acrylic resin.
(4) additive, described additive comprises the thickener of 1-2% dispersant, 1-2% defoamer and 1-3%, and described thickener is selected from, and molecular weight is the hydroxyethylcellulose 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 0.02mol nanometer manganese acetate and 0.01mol nanometer copper chloride powder.
Step 2, the preparation of the first solution
The nanometal mixture of step one is mixed with 4g surfactant and 200ml ethylene glycol solution, mixed liquor is stirred 15 minutes with the speed of 800r/min in 80 DEG C of oil baths, naturally obtained first solution of cooling.
Step 3: the preparation of the second solution
100ml ethylene glycol and 0.03ml 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 3-10mL/min, stir 4h with speed 80 DEG C of constant temperature of 800r/min; After reaction terminates, reaction product is respectively washed 3 times, collected by centrifugation with deionized water and absolute ethyl alcohol respectively, and in baking oven, 80 DEG C of dry 6h, namely obtain composite precursor.
Step 5: the preparation of the coated Cu/Mn2O 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 450 DEG C with 5 DEG C/min, constant temperature keeps 2h, obtains the coated Cu/Mn2O 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 manganese acetate and nanometer copper chloride powder is 1-50nm, and the porosity of obtained porous material is more than 86%, and the size of hole is 1-25nm.
Described surfactant be selected from a kind of in polyvinylpyrrolidone (PVP), softex kw (CTAB), chlorination trimethylcetylammonium (CTAC), PEO-PPOX-PEO triblock copolymer (P123), polyoxyethylene-poly-oxypropylene polyoxyethylene triblock polymer (F127) or with arbitrarily than mixture.
The particle diameter of described nano particle is 1-10nm.
Choose 800 object 40g porous materials, 16g nano-titanium oxide, 4 grams of nano-silver powders, 80g acrylic resin, 3g dispersant and 3g defoamer, 4g hydroxyethylcellulose and 30g deionized water, as in container, adopt mechanical agitation to mix, form stable coating.Described coating has more micro channel, has long-acting absorption, the organic pernicious gas of catalytic 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 solution) 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. a preparation method for nanometer functional film, this film comprises dope layer, substrate layer, tack coat and protective layer successively,
The thickness of described dope layer is 0.1-2um, and the thickness of substrate layer is 10-50um, and the thickness of tack coat is 0.5-5um, and the thickness of protective layer is 10-50um;
Described substrate layer is selected from bidirectional stretching polypropylene film or biaxially oriented polyester film; The material of described tack coat is selected from acrylic binders, and described protective layer is PET type mould release membrance;
It is characterized in that the preparation of described film comprises the following steps:
The first step: the process of substrate layer, chooses base material as substrate layer, and sided corona treatment is carried out on the surface of described substrate layer;
Second step, the preparation of dope layer, is coated on dope layer on a surface of the substrate layer that the first step is handled well, and under the environment of anaerobic, solidify photocureable coating layer formation dry film;
3rd step, by tack coat even spread to the another side of substrate layer;
4th step, is placed in the another side of tack coat by protective layer;
Described dope layer comprises following component:
(1) porous material, the content of described porous material is 1-40%;
(2) nano particle, content is 1-40%, and described nano particle is selected from nano-titanium oxide, Nano Silver, nano aluminum or its composition;
(3) film forming matter, content is 5-80%, and described film forming matter is acrylic resin;
(4) additive, described additive comprises the thickener of 1-2% dispersant, 1-2% defoamer and 1-3%, and described thickener is selected from, and molecular weight is the hydroxyethylcellulose 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 manganese acetate and nanometer copper chloride powder, and the mol ratio of described manganese acetate and copper chloride is 2:1;
Step 2, the preparation of the first solution
The nanometal mixture of step one is mixed with surfactant and ethylene glycol solution, mass ratio is: nanometal mixture: surfactant: ethylene glycol solution=5-7:3-5:300, mixed liquor is stirred 10-30 minute with the speed of 600-1000r/min in 60-90 DEG C of oil bath, naturally obtained first solution of cooling;
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, reaction product is respectively washed 3 times, collected by centrifugation with deionized water and absolute ethyl 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 coated Cu/Mn of carbon
2the preparation of O composite porous material
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 rises to 450 DEG C with 5 DEG C/min, and constant temperature keeps 2h, obtains the coated Cu/Mn of carbon
2o composite porous material, 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. the preparation method of a kind of nanometer functional film as described in claim 1, is characterized in that the particle diameter of described nanometer manganese acetate and nanometer copper chloride powder is 1-50nm, and the porosity of obtained porous material is more than 86%, and the size of hole is 1-25nm.
3. the preparation method of a kind of nanometer functional film as described in claim 1, it is characterized in that described surfactant be selected from a kind of in polyvinylpyrrolidone, softex kw, chlorination trimethylcetylammonium, polyoxyethylene-poly-oxypropylene polyoxyethylene triblock polymer or with arbitrarily than mixture.
4. the preparation method of a kind of nanometer functional film as described in claim 1, is characterized in that the particle diameter of described nano particle is 1-10nm.
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| CN104263274B (en) * | 2014-10-20 | 2016-08-24 | 江门新时代胶粘科技有限公司 | Antimildew and antibacterial adhesive tape and preparation method thereof |
| CN104984762A (en) * | 2015-06-30 | 2015-10-21 | 苏州博利迈新材料科技有限公司 | Carbon monoxide catalysis nanometer film and a preparation method thereof |
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| CN1191126C (en) * | 2002-03-22 | 2005-03-02 | 深圳市尊业纳米材料有限公司 | Microporous nano composite material |
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