CN105735049B - A kind of ultra-smooth nanometer paper of high transparency and its fast preparation method - Google Patents
A kind of ultra-smooth nanometer paper of high transparency and its fast preparation method Download PDFInfo
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- CN105735049B CN105735049B CN201610199891.7A CN201610199891A CN105735049B CN 105735049 B CN105735049 B CN 105735049B CN 201610199891 A CN201610199891 A CN 201610199891A CN 105735049 B CN105735049 B CN 105735049B
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/001—Modification of pulp properties
- D21C9/002—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives
- D21C9/004—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives inorganic compounds
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/001—Modification of pulp properties
- D21C9/002—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives
- D21C9/005—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives organic compounds
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/001—Modification of pulp properties
- D21C9/007—Modification of pulp properties by mechanical or physical means
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21F—PAPER-MAKING MACHINES; METHODS OF PRODUCING PAPER THEREON
- D21F13/00—Making discontinuous sheets of paper, pulpboard or cardboard, or of wet web, for fibreboard production
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
- D21H11/02—Chemical or chemomechanical or chemothermomechanical pulp
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
- D21H11/12—Pulp from non-woody plants or crops, e.g. cotton, flax, straw, bagasse
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
- D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
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Abstract
The invention discloses a kind of ultra-smooth nanometer paper of high transparency and its fast preparation methods, belong to nanometer environmental protection material and pulp technology for making paper.Preparation method is as follows：1）Using plant fiber as raw material, nano-cellulose dispersion liquid is prepared with mechanical treatment after chemical pretreatment；2）Thin-film material is fitted tightly over to the bottom of flat rigid container, prepares the casting film container of nano-cellulose dispersion liquid；3）Nano-cellulose homogeneous dispersion is poured into casting film vessel surface；4）The casting film container for filling nano-cellulose dispersion liquid is positioned over casting film in climatic chamber to dry, prepares nano-cellulose/film composite material；5）By the thin-film material stripping in nano-cellulose/film composite material, the ultra-smooth nanometer paper of high transparency is made.Compared to the ultra-smooth nanometer paper preparation method of other high transparencies, preparation method preparation process of the invention is simple, takes short, prepared nanometer paper transparency is high, surface roughness is low, tensile strength is high, flatness is high etc..
Description
Technical field
The present invention relates to nanometer environmental protection material and pulp technology for making paper, and in particular to a kind of ultra-smooth nanometer of high transparency
Paper and its fast preparation method.
Technical background
The thin-film material that nanometer paper is made of nano-cellulose dispersion.In recent years, because of its unique characteristic exhibition
Its application prospect in flexible electronic device field is showed.The various flexible electronic devices prepared using nanometer paper as substrate material are such as
Electrode, Flied emission transistor, organic solar batteries and antenna are reported in media in succession, cause government, scientific research institution and enterprise
The extensive concern of industry.But the characteristic of the one-dimensional nano-scale and high water retention value of nano-cellulose limits the height of nanometer paper
The preparation of efficiency；And existing nanometer paper technology of preparing, while realizing efficiently preparation but it is difficult to take into account high transparency and surpasses
Smooth performance requirement.Therefore, the quick preparation that can realize nanometer paper and nanometer paper high transparency, super flat are developed
The manufacturing technology of sliding characteristic, becomes the Main way of nanometer paper preparation research.
Currently, the quick preparation for nanometer paper, mainly around accelerated filtration speed and/or acceleration rate of drying etc.
Expansion research.Sehaqui et al. reports a kind of method that filtering adds vacuum drying realization quickly to prepare nanometer paper, entire preparation
Process takes 1-2 hours.[Sehaqui H et.al. Fast preparation procedure for large, flat
cellulose and cellulose/inorganic nanopaper structures. Biomacromolecules
2010;11:2195-2198].Compared to other methods for preparing nanometer paper, although the efficiency of this method significantly improves, but should
There is following two aspect in nanometer paper prepared by method：（1）Because using porous membrane, the surface roughness of nanometer paper to be more than 20
Nanometer, cannot meet requirement of the flexible electronic device to substrate surface performance；（2）Using vacuum drying, lead to the saturating of nanometer paper
Light rate is only 42%（Under 600nm wavelength）.Finland scientist develops a kind of squeeze and filter and high-pressure drying is combined quick preparation
The method of nanometer paper, whole preparation process take 1-2h.[Österberg M et.al. A fast method to
produce strong nfc films as a platform for barrier and functional materials.
ACS Applied Materials & Interfaces 2013;5:4640-4647].But nanometer paper obtained is for soft
When property electronic device substrate, there is also following deficiencies：（1）43% nano-cellulose is lost in the squeeze and filter stage, and is prepared
Nanometer paper shape it is uncontrollable；(2) it during hot-pressing drying, needs to be related to accurate pressure control, otherwise can make wet
Nanometer paper is crushed；（3）In order to improve rate of drying, is dried using 100 DEG C of temperature, lead to the water of nano-cellulose network internal
Divide rapid evaporation, reduces the tightness of nanometer paper（Tightness is only 0.5g/cm3)；（4）The use of large aperture filter membrane, leads to nanometer paper
Rough surface.Method used in Beneventi et al., it is first that spraying to for 2% nano-cellulose dispersion homogeneous is hydrophilic
On nylon wire, it then is prepared into nanometer paper by vacuum filter, squeezing, vacuum drying, whole process, which takes, is less than 40min
[Beneventi D et. al. Rapid nanopaper production by spray deposition of
concentrated microfibrillated cellulose slurries. Industrial Crops and
Products 2015, 72: 200-205].But the surface of the nanometer paper of this method preparation is same very coarse, no
The requirement of flexible electronic device can be met.The above method is shown, although combining pressurization or vacuum drying mode can by filtering
To significantly improve the preparation efficiency of nanometer paper, still, high surface roughness（>20nm）With low light transmittance（<70%) it constrains
The application of nanometer paper prepared by these methods in flexible electronic device field.
American researcher forms nanometer paper filter cake by way of filtering, then during pressurizeing air drying,
Filter cake is close to smooth PET to prepare rough surface to be 3nm-10nm, the nanometer paper that transparency is about 90% without filter membrane face
[Huang J et.al Highly transparent and flexible nanopaper transistors. ACS
Nano 2013, 7: 2106-2113].Although the nanometer paper gasket that performance is suitable for flexible transistor is successfully made in this method
Bottom, still, preparation time are up to 30h, and high-pressure drying is needed to prevent nanometer paper from deforming.Fujisaki et al. is by a concentration of 1%
Nano-cellulose dispersion is applied to acrylic resin substrate, is then dried to also obtain and be put down with excellent light transmittance and surface
Sliding nanometer paper [Fujisaki Y, et.al. Transparent nanopaper-based flexible organic
thin-film transistor array. Advanced Functional Materials 2013, 24: 1657-
1663].But the preparation process takes and is also up to for 24 hours, and the thickness of the nanometer paper of gained is only 20 μm.The above method is aobvious
Show, by being dried after nano-cellulose homogeneous dispersion is distributed in ultra-smooth material surface, can assign nanometer paper excellent table
Face smoothness and translucency, but this kind of preparation process takes more than for 24 hours.
Invention content
It is an object of the invention to overcome the deficiencies in the prior art and disadvantage, provide a kind of ultra-smooth nanometer paper of high transparency and
Its fast preparation method.
The purpose of the present invention is achieved through the following technical solutions.
A kind of fast preparation method of the ultra-smooth nanometer paper of high transparency, the preparation method comprises the following steps：
（1）Using plant fiber as raw material, nano-cellulose dispersion liquid is prepared with mechanical treatment after chemical pretreatment；
（2）Thin-film material is fitted tightly over to the bottom of flat rigid container, prepares the casting film of nano-cellulose dispersion liquid
Container；
（3）Nano-cellulose homogeneous dispersion is poured into casting film inner surface of container；
（4）The casting film container for filling nano-cellulose dispersion liquid is positioned over casting film in climatic chamber to dry, preparation is received
Rice cellulose/film composite material；
（5）By the thin-film material stripping in nano-cellulose/film composite material, the ultra-smooth nanometer of high transparency is made
Paper.
It advanced optimizes, step（1）The plant fiber be bleaching needle-point leaf pulp, bleached hardwood pulp, bleaching it is non-wood
One or more in slurry, bleached waste paper slurry, Time of Fluff Slurry and cotton pulp.
It advanced optimizes, step（1）The chemical pretreatment is pre- using NaOH pretreatment method, cellulose enzyme process
One or more in facture, TEMPO oxidation systems method for pretreating and acidic treatment；The mechanical treatment is using high
Press the one or more in microjet method, high pressure homogenization method, highly concentrated mill method and high strength supersonic crush method.
It advanced optimizes, the substance used in the acidic treatment is sulfuric acid or phosphoric acid.
It advanced optimizes, step（1）The mass concentration of the nano-cellulose dispersion liquid is 1% -2%, and viscosity is
100cp - 2000cp。
It advanced optimizes, step（2）The thin-film material is copper foil, polyethylene terephthalate macromolecule membrane
Material（PET）, aluminium foil, polypropylene film, polyethylene film, leaching membrane paper, BOPP（Bidirectional stretching polypropylene film）It is thin with nylon
One kind in film；Film thickness is 15 μm ~ 200 μm, and surface roughness is 1-20nm；The material of the flat rigid container
For one kind in glass, silica, marble, timber, metal, resin, ceramics, plastics, cardboard and combination board material, put down
The shape of bottom rigid container depends on preparing the shape of sample, and surface roughness is less than 1000nm.
It advanced optimizes, step（3）The nano-cellulose dispersion liquid, which need to uniformly topple over and be paved with entire casting film, to be held
Device mustn't generate bubble in dispersion liquid, and liquid level is less than 40mm, and liquid level is both needed to holding level with bottom surface.
It advanced optimizes, step（4）The casting film container for filling nano-cellulose dispersion liquid is put in climatic chamber
In be dried, humidity be 30% -60%, temperature be 30 DEG C -50 DEG C, drying time be less than 10 hours.
It advanced optimizes, step（5）Nano-cellulose/the film composite material can be removed mutually, nanometer paper with
The peeling force of thin-film material is less than 50mN/m.
A kind of ultra-smooth nanometer paper of high transparency made from above-mentioned preparation method, surfacing is smooth, wrinkle resistant no gas
Bubble；Nanometer paper transparency is more than 85%, and surface roughness is 1.5-20nm, and tightness is 1.0-1.2g/cm3, tensile strength is
100 - 200MPa。
Compared with prior art, the invention has the advantages that and technique effect：
The ultra-smooth nanometer paper technology of preparing of high transparency proposed by the present invention, which significantly shortens, prepares the ultra-smooth nanometer of high transparency
Time needed for paper, from being shortened to more than 24 hours less than 10 hours, efficiency improves 2 times or more；Prepared nanometer paper is transparent
Degree is high, surface roughness is low, smooth bubble-free, tightness is big, intensity is good, can be used as substrate material and is applied to flexible electronic device such as
The structure of solar cell, thin film transistor (TFT), transparent conductive electrode etc..
Specific implementation mode
The specific implementation of the present invention is further described with reference to example, but implementation and the protection domain of the present invention
It is without being limited thereto.In following embodiments, nanometer paper thickness is measured with density measurement using JIS P8118-1998 national standards；It receives
Rice paper transparency is according to GB/T2679.1-1993 standard tests；Tensile strength test is using GB/T20671.7-2006 countries
Standard testing.
Embodiment 1
It is prepared by nano-cellulose：Using bleached eucalyptus pulp as raw material, 5% is used first（Quality, similarly hereinafter）Sodium hydroxide solution
Bleached eucalyptus pulp is pre-processed, the specific steps are bleached eucalyptus pulp is weighed in flask, addition mass concentration is 5% hydrogen-oxygen
Change sodium solution and adjust stock quality a concentration of 1.0%, 1h is stirred to slurry with the rotating speed of 500r/min, taking-up is filtered,
Washing adds water to adjust stock quality a concentration of 1.0%, then handles pretreated slurry high pressure homogenizer 3 times（1 time
D10,2 D5）, it is prepared into nano-cellulose dispersion.The viscosity of nano-cellulose dispersion is 970cp, mass concentration 1%.
It is prepared by casting film container：The PET film for being 38 μm by thickness（Surface roughness is 3nm）It is fitted tightly over by glass plate
The bottom of the flat rigid container prepared（Surface roughness is 10nm）.
The preparation of nanometer paper/PET film composite material：The nano-cellulose dispersion homogeneous of gained is poured into casting film
Inner surface of container is simultaneously placed on casting film drying in the climatic chamber that temperature is 40 DEG C, humidity is 60%, is obtained by 7 hours
To nano-cellulose/PET film composite material.
The preparation of the ultra-smooth nanometer paper of high transparency：Nanometer paper is detached with PET film, peeling force 30mN.
The ultra-smooth nanometer paper of high transparency is obtained by above step, the thickness of the nanometer paper is 30 μm, tightness 1.1g/cm3,
Transparency is 88%, tensile strength 114Mpa, surface roughness 20nm.
Embodiment 2
It is prepared by nano-cellulose：Using the northern wood pulp of bleaching as raw material, it is located in advance using TEMPO oxidation systems first
Reason, processing procedure press 0.1mol/g（Oven dry stock）Weigh 2,2,6,6- tetramethyl piperidines-nitrogen-oxide (TEMPO) in beaker,
100ml is added water to, with magnetic force oscillator stirring and dissolving；By 1mmol/g（Oven dry stock）Claim sodium bromide in beaker, adds water to
100ml, with glass bar stirring and dissolving；For use.The bleaching north wood pulp that 400g mass concentrations are 10% is transferred in round-bottomed flask,
Add water 1000g, slurry is stirred with the rotating speed of 500r/min.The sodium bromide that front prepares is sequentially added after stirring 30min
Solution, TEMPO solution, then claim 8mmol/g again（Oven dry stock）Liquor natrii hypochloritis slowly adds and is gone in flask, water is added to adjust
Slurry concentration is 2.0%, measures the pH of slurry in flask in real time, and entire reaction process pH value maintains 10.5.When pH variations are slow
Or do not change for a long time, it indicates that reaction is basically completed, is stirred for 30min, then takes out and washed, until washing outflow
Until liquid is detected with silver nitrate solution without precipitation generation, adds water to adjust stock quality a concentration of 1.0% and then penetrated using micro-
It flows the slurry after nanometer homogenizer aoxidizes TEMPO and carries out homogeneous 2 times, obtain nano-cellulose dispersion, nano-cellulose point
The viscosity of granular media is 1000cp, mass concentration 1%.
It is prepared by casting film container：The PET film for being 50 μm by thickness（Surface roughness is 2.5nm）It is fitted tightly over by stainless
The bottom of flat rigid container prepared by steel plate（Surface roughness is 500nm）.
The preparation of nanometer paper/PET film composite material：The nano-cellulose dispersion homogeneous of gained is poured into casting
Film container inner surface was simultaneously placed on casting film drying in the climatic chamber that temperature is 30 DEG C, humidity is 30%, by 6 hours
Obtain nano-cellulose/PET film composite material.
The preparation of the ultra-smooth nanometer paper of high transparency：Nanometer paper is detached with PET film, peeling force 45mN.
The ultra-smooth nanometer paper of high transparency is obtained by above step, the thickness of the nanometer paper is 35 μm, tightness 1.15g/
cm3, transparency 89%, tensile strength 198Mpa, surface roughness 3.2nm.
Embodiment 3
It is prepared by nano-cellulose：Using bagasse pulp as raw material, using 64%（Quality）Sulfuric acid it is pre-processed, weigh
Bagasse slurry is air-dried in flask, the sulfuric acid that mass fraction is 64% is added and adjusts stock quality a concentration of 2.0%, with 500r/min
Rotating speed slurry is stirred, while then 60 DEG C of heating water bath, processing time 30min are filtered slurry, wash,
Extra sulfuric acid is removed, adds water to adjust stock quality a concentration of 2.0%, later with ultrasonic grinder to pretreated slurry
It is ultrasonically treated, is prepared into nano-cellulose dispersion, the viscosity of nano-cellulose dispersion is 100cp, and mass concentration is
2%。
It is prepared by casting film container：The polyethylene film (surface roughness 2nm) that thickness is 30 μm is fitted tightly over by glass
The bottom of flat rigid container prepared by glass plate（The thickness of glass plate is 1000 μm, surface roughness 5nm）.
The preparation of nanometer paper/polyethylene film composite material：By being poured into for the nano-cellulose dispersion homogeneous of gained
Casting film inner surface of container is simultaneously placed on casting film drying in the climatic chamber that temperature is 30 DEG C, humidity is 30%, small by 4
When obtain nano-cellulose/polyester film compound material.
The preparation of the ultra-smooth nanometer paper of high transparency：Nanometer paper is detached with polyester film, peeling force 35mN.
The ultra-smooth nanometer paper of high transparency is obtained by above step, the thickness of the nanometer paper is 38 μm, tightness 1.2g/cm3,
Transparency is 90%, tensile strength 200Mpa, surface roughness 1.5nm.
Embodiment 4
It is prepared by nano-cellulose：Using bleached eucalyptus pulp as raw material, it is located in advance using TEMPO oxidation systems first
Reason, processing procedure press 0.1mol/g（Oven dry stock）Weigh 2,2,6,6- tetramethyl piperidines-nitrogen-oxide (TEMPO) in beaker,
100ml is added water to, with magnetic force oscillator stirring and dissolving；By 1mmol/g（Oven dry stock）Claim sodium bromide in beaker, adds water to
100ml, with glass bar stirring and dissolving；For use.The bleached eucalyptus pulp that 400g mass concentrations are 10% is transferred in round-bottomed flask,
Add water 1000g, slurry is stirred with the rotating speed of 500r/min.The sodium bromide that front prepares is sequentially added after stirring 30min
Solution, TEMPO solution, then claim 10mmol/g again（Oven dry stock）Liquor natrii hypochloritis slowly adds and is gone in flask, water is added to adjust
Slurry concentration is 2.0%, measures the pH of slurry in flask in real time, and entire reaction process pH value maintains 10.5.When pH variations are slow
Or do not change for a long time, it indicates that reaction is basically completed, is stirred for 30min, then takes out and washed, until washing outflow
Until liquid is detected with silver nitrate solution without precipitation generation, water is added to adjust stock quality a concentration of 1.2%, then, using high pressure
Slurry after nanometer homogenizer aoxidizes TEMPO carries out homogeneous 6 times（1 time D10,5 times D5）, it is prepared into nano-cellulose dispersion
The viscosity of body, nano-cellulose dispersion is 150cp, mass concentration 1.2%.
It is prepared by casting film container：The PET film for being 200 μm by thickness（Surface roughness is 1 nm）It is fitted tightly over by glass
The bottom of flat rigid container prepared by plate（Surface roughness is 5nm）.
The preparation of nanometer paper/polyethylene film composite material：By being poured into for the nano-cellulose dispersion homogeneous of gained
Casting film inner surface of container is simultaneously placed on casting film drying in the climatic chamber that temperature is 35 DEG C, humidity is 40%, by 5.5
Hour obtains nano-cellulose/PET film composite material.
The preparation of the ultra-smooth nanometer paper of high transparency：Nanometer paper is detached with PET film, peeling force 40mN.
The ultra-smooth nanometer paper of high transparency is obtained by above step, the thickness of the nanometer paper is about 40 μm, tightness 1.2g/
cm3, transparency 91%, tensile strength 166Mpa, surface roughness 1.82nm.
Embodiment 5
It is prepared by nano-cellulose：Using the northern wood pulp of bleaching as raw material, it is located in advance using TEMPO oxidation systems first
Reason, processing procedure press 0.1mol/g（Oven dry stock）Weigh 2,2,6,6- tetramethyl piperidines-nitrogen-oxide (TEMPO) in beaker,
100ml is added water to, with magnetic force oscillator stirring and dissolving；By 1mmol/g（Oven dry stock）Claim sodium bromide in beaker, adds water to
100ml, with glass bar stirring and dissolving；For use.The bleaching north wood pulp that 400g mass concentrations are 10% is transferred in round-bottomed flask,
Add water 1000g, slurry is stirred with the rotating speed of 500r/min.The sodium bromide that front prepares is sequentially added after stirring 30min
Solution, TEMPO solution, then claim 10mmol/g again（Oven dry stock）Liquor natrii hypochloritis slowly adds and is gone in flask, water is added to adjust
Slurry concentration is 2.0%, measures the pH of slurry in flask in real time, and entire reaction process pH value maintains 10.5.When pH variations are slow
Or do not change for a long time, it indicates that reaction is basically completed, is stirred for 30min, then takes out and washed, until washing outflow
Until liquid is detected with silver nitrate solution without precipitation generation, water is added to adjust stock quality a concentration of 1.0%, then, using high pressure
Slurry after nanometer homogenizer aoxidizes TEMPO carries out homogeneous 1 time（1 D10）, ultrasonic grinder ultrasound 2h is then used,
It is prepared into nano-cellulose dispersion, the viscosity of nano-cellulose dispersion is 2000 cp, mass concentration 1%.
It is prepared by casting film container：The PET film for being 60 μm by thickness（Surface roughness is 3nm）It is fitted tightly over by stainless steel
The bottom of flat rigid container prepared by plate（Surface roughness is 1000nm）.
The preparation of nanometer paper/PET film composite material：The nano-cellulose dispersion homogeneous of gained is poured into casting film
Inner surface of container is simultaneously placed on casting film drying in the climatic chamber that temperature is 50 DEG C, humidity is 50%, is obtained by 5 hours
To nano-cellulose/PET film composite material.
The preparation of the ultra-smooth nanometer paper of high transparency：Nanometer paper is detached with PET film, peeling force 30mN.
The ultra-smooth nanometer paper of high transparency is obtained by above step, the thickness of the nanometer paper is about 33 μm, tightness 1.0g/
cm3, transparency 87%, tensile strength 100Mpa, surface roughness 3.2nm.
Claims (8)
1. a kind of fast preparation method of the ultra-smooth nanometer paper of high transparency, which is characterized in that the preparation method includes following step
Suddenly：
（1）Using plant fiber as raw material, nano-cellulose dispersion liquid is prepared with mechanical treatment after chemical pretreatment；The Nanowire
The mass concentration of the plain dispersion liquid of dimension is 1% -2%, and viscosity is 100cp -2000cp；
（2）Thin-film material is fitted tightly over to the bottom of flat rigid container, prepares the casting film container of nano-cellulose dispersion liquid；
（3）Nano-cellulose homogeneous dispersion is poured into casting film inner surface of container；The nano-cellulose dispersion liquid needs equal
Even topples over and is paved with entire casting film container, and bubble mustn't be generated in dispersion liquid, and liquid level is less than 40mm, and liquid level is equal with bottom surface
It need to keep horizontal；
（4）The casting film container for filling nano-cellulose dispersion liquid is positioned over casting film in climatic chamber to dry, prepares Nanowire
Tie up element/film composite material；The casting film container for filling nano-cellulose dispersion liquid, which is put in climatic chamber, to be dried,
Humidity is 30% -60%, and temperature is 30 DEG C -50 DEG C, and drying time is less than 10 hours；
（5）By the thin-film material stripping in nano-cellulose/film composite material, the ultra-smooth nanometer paper of high transparency is made；
The time needed for the ultra-smooth nanometer paper of high transparency is prepared from being shortened to more than 24 hours less than 10 hours, efficiency improves 2 times
More than；Prepared nanometer paper surfacing is smooth, wrinkle resistant bubble-free；Nanometer paper transparency is more than 85%, and surface roughness is
1.5-20nm, tightness are 1.0-1.2g/cm3, tensile strength is 100-200MPa.
2. a kind of fast preparation method of the ultra-smooth nanometer paper of high transparency according to claim 1, it is characterised in that：Step
（1）The plant fiber is bleaching needle-point leaf pulp, bleached hardwood pulp, the non-wood pulp of bleaching, bleached waste paper slurry, Time of Fluff Slurry and cotton pulp
One or more of.
3. a kind of fast preparation method of the ultra-smooth nanometer paper of high transparency according to claim 1, it is characterised in that：Step
（1）The chemical pretreatment is located in advance using NaOH pretreatment method, cellulose enzyme process method for pretreating, TEMPO oxidation systems
One or more of logos and acidic treatment；The mechanical treatment is using high pressure microjet method, high pressure homogenization method, highly concentrated mill
One or more of method and high strength supersonic crush method.
4. a kind of fast preparation method of the ultra-smooth nanometer paper of high transparency according to claim 3, it is characterised in that：It is described
Substance used in acidic treatment is sulfuric acid or phosphoric acid.
5. a kind of fast preparation method of the ultra-smooth nanometer paper of high transparency according to claim 1, it is characterised in that：Step
（2）The thin-film material is copper foil, polyethylene terephthalate high molecular film material, aluminium foil, polypropylene film, poly- second
One kind in alkene film, leaching membrane paper and nylon film；Film thickness is 30 μm ~ 200 μm, and surface roughness is 1-20nm；
The material of the flat rigid container is one kind in silica, marble, timber, metal, resin, ceramics, cardboard, flat
The shape of rigid container depends on preparing the shape of sample, and surface roughness is less than 1000nm.
6. a kind of fast preparation method of the ultra-smooth nanometer paper of high transparency according to claim 5, it is characterised in that：It is described
Thin-film material is BOPP；The material of the flat rigid container is one kind in glass, plastics, combination board material.
7. a kind of fast preparation method of the ultra-smooth nanometer paper of high transparency according to claim 1, it is characterised in that：Step
（5）Nano-cellulose/the film composite material can be removed mutually, and the peeling force of nanometer paper and thin-film material is less than 50mN/
m。
8. a kind of ultra-smooth nanometer paper of high transparency, feature made from claim 1-7 any one of them preparation methods exist
In：Prepared nanometer paper surfacing is smooth, wrinkle resistant bubble-free；Nanometer paper transparency is more than 85%, and surface roughness is
1.5-20nm, tightness are 1.0-1.2g/cm3, tensile strength is 100-200MPa.
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| CN107170831A (en) * | 2017-06-14 | 2017-09-15 | 华南理工大学 | A kind of nanometer paper substrate film transistor and preparation method thereof |
| CN107705884A (en) * | 2017-09-04 | 2018-02-16 | 华南理工大学 | A kind of electrically conducting transparent paper based on nano silver wire and preparation method thereof |
| CN108004829B (en) * | 2017-11-01 | 2019-11-15 | 华南理工大学 | A kind of high intensity nano fibre sill and the preparation method and application thereof |
| CN110551300A (en) * | 2018-05-30 | 2019-12-10 | 华南理工大学 | Water-resistant transparent cellulose-based film and preparation method thereof |
| CN110551301A (en) * | 2018-05-30 | 2019-12-10 | 华南理工大学 | Water-resistant nano cellulose film and preparation method thereof |
| CN109137598B (en) * | 2018-06-22 | 2021-03-30 | 华南理工大学 | Transparent paper and production method thereof |
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| CN110241647A (en) * | 2019-06-21 | 2019-09-17 | 江西农业大学 | A kind of preparation method of high-strength transparence nano-cellulose paper |
| CN112482092B (en) * | 2020-11-25 | 2022-12-30 | 牡丹江恒丰纸业股份有限公司 | Production process of transparent hand cigarette paper |
| CN112663377B (en) * | 2020-12-22 | 2021-09-14 | 阿尔诺维根斯(衢州)特种纸有限公司 | Preparation method of natural flexible transparent paper |
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