CN106012652B - A kind of nanofiber composite air filter paper and preparation method thereof - Google Patents
A kind of nanofiber composite air filter paper and preparation method thereof Download PDFInfo
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- CN106012652B CN106012652B CN201610371040.6A CN201610371040A CN106012652B CN 106012652 B CN106012652 B CN 106012652B CN 201610371040 A CN201610371040 A CN 201610371040A CN 106012652 B CN106012652 B CN 106012652B
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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
- D21H27/08—Filter paper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B29/00—Layered products comprising a layer of paper or cardboard
- B32B29/002—Layered products comprising a layer of paper or cardboard as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B29/005—Layered products comprising a layer of paper or cardboard as the main or only constituent of a layer, which is next to another layer of the same or of a different material next to another layer of paper or cardboard layer
-
- 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
-
- 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
- D21H11/20—Chemically or biochemically modified fibres
-
- 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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
-
- 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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
- D21H17/06—Alcohols; Phenols; Ethers; Aldehydes; Ketones; Acetals; Ketals
-
- 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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/66—Salts, e.g. alums
-
- 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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
- D21H17/675—Oxides, hydroxides or carbonates
-
- 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
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/12—Coatings without pigments applied as a solution using water as the only solvent, e.g. in the presence of acid or alkaline compounds
-
- 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
- D21H27/30—Multi-ply
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/26—All layers being made of paper or paperboard
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- Filtering Materials (AREA)
- Paper (AREA)
Abstract
The invention discloses a kind of nanofiber composite air filter paper and preparation method thereof.The nanofiber composite air filter paper includes upper filter layer, lower filter layer and the nano-cellulose composite coating located at the upper filter layer upper surface；Composite mortar includes following material：Nano-cellulose, titania aerogel particle, phenoxy resin, dimethylformamide, water；The raw material of upper filter layer includes following material：Mercerization fiber, sisal fiber, akund, ethylene glycol diglycidylether, dispersant and water；The raw material of lower filter layer includes following material：Broad-leaved wood fiber, titania aerogel particle, beta cyclodextrin, carboxymethyl cellulose, ethylene glycol diglycidylether and water.The filter layer of the nanofiber composite air filter paper of the present invention on the premise of paper permeability and filter efficiency is ensured, improves the water resistance, weatherability and bursting strength of filter paper provided with gas permeability height, the nano-cellulose composite coating of water-tolerant.
Description
Technical field
The present invention relates to filter paper preparing technical field, more particularly to a kind of nanofiber composite air filter paper and its preparation side
Method.
Background technology
Air paper is the key building block in air cleaner, decides the performance of air cleaner.Air paper
The filter layer of a kind of papery for wanting composition to be made based on common wood pulp is generally included, due to common wood pulp cellulose relatively thin, tightness
Height, therefore made air paper generally existing is the shortcomings of tightness height, low filter efficiency, short life, its filter efficiency one
As below 90%, and the air paper also generally existing curability of papery is poor, the inadequate shortcoming of water resistance, weatherability, when
When air humidity changes, paper is easily deformed, and then influences filter effect.
Also there is the Application No. of filter paper, such as the applicant's earlier application that one layer of resin bed is coated with its surface at present
CN201220523227.0 Chinese patent discloses the thermosetting air paper applied in a kind of air cleaner；The air filter
Paper includes filter layer made of paper, and the surface also even spread of filter layer one layer of resin bed, and resin bed is thermosetting phenolic resin
Layer.
The filter paper improves air paper to a certain extent by being designed with resin bed in the upper and lower surface of filter layer
Curability, water resistance and weatherability, when air humidity is raised, the hygroscopic deformation of paper is small, and service life is long.But
There is also defect：Due to being provided with resin bed on the two sides of air paper, and the coated weight of resin bed is larger, causes thickness thicker,
The air permeability and filter efficiency of air paper are had a strong impact on.
The content of the invention
In order to solve the above-mentioned technical problem, the invention provides a kind of nanofiber composite air filter paper and its preparation side
Method.Nano-cellulose of the filter layer of the nanofiber composite air filter paper of the present invention provided with gas permeability height, water-tolerant is answered
Coating is closed, on the premise of paper permeability and filter efficiency is ensured, the water resistance of filter paper, weatherability and resistance to broken is improved
Degree.
The present invention concrete technical scheme be：A kind of nanofiber composite air filter paper, including upper filter layer, lower filter layer
With the nano-cellulose composite coating located at the upper filter layer upper surface；The nano-cellulose composite coating is by composite mortar
Solidification is formed, and the composite mortar includes the material of following mass parts：10-20 parts of nano-celluloses, 30-50 parts of titanium dioxide gas
Gel particles, 10-20 parts of phenoxy resins, 15-25 parts of dimethylformamides, 5-15 parts of water；The raw material of the upper filter layer include with
The material of lower mass parts：20-40 parts of mercerization fiber, 10-20 parts of sisal fiber, 10-20 parts of akund, ethylene glycol two contracts
0.5-1.5 parts of water glycerin ether, 0.2-0.4 parts of dispersant and the desired amount of water；The raw material of the lower filter layer includes following quality
The material of part：50-70 parts of broad-leaved wood fiber, 1-3 parts of titania aerogel particle, 1-3 parts of beta-schardinger dextrin, carboxymethyl cellulose
0.5-1.5 parts, 0.5-1.5 parts of ethylene glycol diglycidylether and the desired amount of water.
Difference of the invention with traditional filter paper is：Traditional filter paper is in order to improve the water resistance of filter paper and resistance to broken
Degree, resin bed is equipped with the two sides of filter paper, although two-sided resin bed can greatly improve the water resistance of filter paper, weatherability and resistance to
Broken degree, increases the service life, but it has had a strong impact on the air permeability of filter paper, not only reduces ventilation efficiency, and cause filter
Paper easily puts aside heat, so as to cause temperature to raise, has higher requirement to the heat endurance of filter paper.And the present invention is only making
The upper filter layer for flowing into face for air is provided with individual layer nano-cellulose composite coating, can effectively reduce paper sheet thickness, improves
Air permeability.And upper and lower filter layer itself has preferable bursting strength and water resistance, subtracting because of resin bed can be effectively made up
The defect brought less.And the nano-cellulose composite coating of the present invention is with nano-cellulose, titania aerogel particle
With phenoxy resin as main component, wherein, nano-cellulose light weight, specific surface area are big, porosity is high, energization enough suspensions by force
Grain improves filter efficiency in the deposition probability on composite coating surface；Nano-cellulose is easily crosslinked simultaneously, with higher-strength,
It is improved the bursting strength of filter paper.Itself specific surface area of titania aerogel particle is big, is handed over complicated three-dimensional network
It is coupled structure, compared with traditional resin-cured layer, air permeability and filter efficiency are higher.On the one hand phenoxy resin is deposited as binding agent
The conjugation of composite mortar and filter layer is being improved, on the other hand, phenoxy resin can improve nano-cellulose composite coating
Water resistance, resistance to shrinkage, resistance to acids and bases and bursting strength.
In upper filter layer, primary raw material, mercerising chemical fibre are used as using mercerization fiber, sisal fiber and akund
Dimension table face is smooth, and washing shrinkage is low, good stability of the dimension, and surface-active is high, and chemical reaction ability is strong, easily multiple with other fibers
Crosslink, and high adsorption capacity, increase dust containing capacity；Sisal fiber quality is harder, and length-width ratio is big, and modulus of elasticity is big, antifriction
Wipe, humidity, intensity is high, and with outstanding air permeability and adsorption capacity, it is possible to increase dust containing capacity, and fiber interweaving ability is strong；
Akund high mechanical strength, water resistance and heat endurance are good.Above-mentioned three kinds of fibers are passing through mashing, defibrination and manufactured paper with pulp
After shaping, by fibre length control in certain length so that the aperture of the fibrous layer after crosslinking is larger mutually, and porosity is big,
Therefore with preferable dust absorbing ability, dust containing capacity is improved.In addition, the strand two ends of ethylene glycol diglycidylether have
Active group, its two ends can serve bridge beam action, so as to further increase fiber respectively with fiber is carried out into " bonding "
Between cross-link intensity, improve the bursting strength and water resistance of fibrous layer.
Lower filter layer uses broad-leaved wood fiber as fibrous layer primary raw material, and is combined with titania aerogel grain
Son, beta-schardinger dextrin, carboxymethyl cellulose and ethylene glycol diglycidylether.Wherein, broad-leaved wood fiber is wider, after mashing, defibrination
Control its fibre length so that the fibrous layer aperture after shaping is smaller, can be miscellaneous through the fine particle of upper filter layer to some
Matter is filtered.Itself specific surface area of titania aerogel particle is big, with intensive tiny hole, it is possible to increase filtering essence
While spending, the air permeability of fibrous layer is not influenceed, and the addition of titania aerogel particle can improve the machine of fibrous layer
Tool intensity；And also there is cavity inside beta-schardinger dextrin, it may have preferable absorption property；Improve filtering accuracy, carboxymethyl cellulose
Element serves not only as dispersant herein, and together with beta-schardinger dextrin, ethylene glycol diglycidylether, can also improve the friendship of fibrous layer
Join intensity.Lift bursting strength and water resistance.
The filter paper of the present invention operationally, is flowed into by filtering fluid media (medium) from thick and porosity gap upper filter layer, from fine and closely woven
The lower filter layer outflow of hole, impurity is mainly intercepted in the macrovoid of filter layer, because upper filter layer interstitial space is big,
With huge dust capaciting ability, so that filtration members service life is greatly prolonged, and filtration resistance is low, and lower filter layer is close and thin
Fine pore is further intercepted to less and minute impurities particulate in upper filter layer filtered fluid medium.Filtering essence has been effectively ensured
Degree, has given full play to the combination property of each fibrous layer.
Further, since by large quantity of air in filter paper, after the impurity such as dust are by a large amount of adsorbed, air by when can occur
Friction, produces noise, and the nano-cellulose composite coating of the present invention, up and down filter layer each possess the hole of different pore size,
Air permeability is high, and lower filter layer is due to the presence of TiO 2 particles and beta-schardinger dextrin, with a large amount of tiny holes, up and down
Filter layer is worked in coordination down, can play Noise Reduction.
Preferably, the composite mortar includes the material of following mass parts：15 parts of nano-celluloses, 40 parts of titanium dioxide
Aerogel particles, 15 parts of phenoxy resins, 20 parts of dimethylformamides, 10 parts of water；The raw material of the upper filter layer includes following quality
The material of part：30 parts of mercerization fiber, 15 parts of sisal fiber, 15 parts of akund, 1 part of ethylene glycol diglycidylether, point
0.3 part of powder and the desired amount of water；The raw material of the lower filter layer includes the material of following mass parts：60 parts of broad-leaved wood fiber,
2 parts of titania aerogel particle, 2 parts of beta-schardinger dextrin, 1 part of carboxymethyl cellulose, 1 part of ethylene glycol diglycidylether and required
The water of amount.
Preferably, the length of the nano-cellulose is 400-600nm, a diameter of 30-50nm；The phenoxy resin
Molecular weight is between 100000-150000.Phenoxy resin between the molecular weight area is for filter layer, aerogel particles in the present invention
Caking property chamber, and water resistance, resistance to shrinkage are good.
Preferably, the thickness of the nanofiber composite air filter paper is 0.28-0.36mm, the thickness of the upper filter layer
Spend for 0.10-0.15mm, the thickness of the lower filter layer is 0.16-0.20mm.
Preferably, the quantification of 105-115g/m of the nanofiber composite air filter paper2, nano-cellulose is compound to be applied
Layer accounts for the 6-10% of nanofiber composite air filter paper gross mass.
Preferably, the dispersant is sodium pyrophosphate or calgon.
A kind of preparation method of above-mentioned nanofiber composite air filter paper, is carried out according to the following steps：
A. the preparation of upper filter layer uncoated paper：To being beaten after mercerization fiber, sisal fiber, akund mixing,
Slurry concentration is 1.9-2.5wt%, after mashing to slurry beating degree is 12-14 ° of SR, then carries out defibrination, until beating degree is 16-
20 ° of SR, are made slurry a；Ethylene glycol diglycidylether is added in the slurry a, slurry b is made after stirring；Will
Dispersant is added in the slurry b, and slurry c is made to 1.5-1.9wt% in the regulation slurry concentration that added water after being uniformly dispersed；It is right
Slurry c progress online is manufactured paper with pulp after shaping, and upper filter layer uncoated paper is made.
B. the preparation of filter layer uncoated paper is descended：Broad-leaved wood fiber is beaten, slurry concentration is 2.5-3.0%, mashing is extremely
After slurry beating degree is 16-18 ° of SR, then defibrination is carried out, until beating degree is 26-30 ° of SR, slurry A is made；Ethylene glycol two is contracted
Water glycerin ether is added in the slurry A, and slurry B is made after stirring；By titania aerogel particle, beta-schardinger dextrin and
Carboxymethyl cellulose is added in the slurry B, and slurry is made to 1.3-1.7wt% in the regulation slurry concentration that added water after being uniformly dispersed
Expect C, slurry C progress online is manufactured paper with pulp after shaping, lower filter layer uncoated paper is made.
C. the laminating of upper and lower filter layer：The upper filter layer uncoated paper and lower filter layer uncoated paper are fitted, then passed through
Vacuumize the upper filter layer and lower filter layer that laminating is made after squeezing, drying.
D. composite mortar solidifies：Composite mortar is prepared by proportioning, the upper surface of filter layer is coated with or is sprayed onto, vacuum is done
It is dry to solidify to form after nano-cellulose composite coating, that is, nanofiber composite air filter paper is made.
Preferably, after mashing, defibrination, the mercerization fiber, sisal fiber, the length of akund are
2.4-2.6mm, the length of the broad-leaved wood fiber is 2.0-2.2mm.
Preferably, the preparation method of the titania aerogel particle is as follows：By butyl titanate, absolute ethyl alcohol, first
Benzene in mass ratio 1:15-25:0.02-0.04 is mixed, obtained solution a；By absolute ethyl alcohol, 1-2mol/L glacial acetic acid and water
10-20 in mass ratio:3-5:1 is mixed, obtained solution b；Supersonic oscillations processing is carried out at 55-65 DEG C to solution a, will
Solution b is added drop-wise to 1-2mL/s speed in the solution a of 2-3 times of quality；It is solution a's to add quality into solution a simultaneously
0.04-0.06 times of aluminium hydroxide, continues to stir after 2-3h, colloidal sol is made；The colloidal sol is stood into aging 24-48h, then made
Solvent displacement 24-48h is carried out to colloidal sol with excessive n-hexane, then removes n-hexane, gel is obtained, finally by gel in 300-
The titania aerogel particle of micron-scale is made after dry at 500 DEG C, crushing.
The titania aerogel particle of the present invention carries out toluene and carries out a pore, then select in preparation process
Aluminium hydroxide carries out secondary pore, and various sizes of hole can be made, and voidage is high, and specific surface area is big, and air permeability is good.And
During the pore of aluminium hydroxide, aluminium hydroxide is thermally decomposed into aluminum oxide and water, and water is by thermal evaporation pore, and aluminum oxide is residual
Stay in titania aerogel particle, it is possible to increase intensity.
Preferably, after the gel is made, gel passes through modification before it is dried：Using trim,ethylchlorosilane with
The mixed liquor of n-hexane modified 16-36h at 55-65 DEG C to gel；The wherein quality of trim,ethylchlorosilane, n-hexane and gel
Than for 30-50:50:8-12.
After being modified to gel, with preferable hydrophobic ability, prevent titania aerogel particle from largely adsorbing water
Point.Therefore it is modified to improve the filter capacity and water resistance of filter paper.
It is compared with the prior art, the beneficial effects of the invention are as follows：The filtering of the nanofiber composite air filter paper of the present invention
Layer is provided with gas permeability height, the nano-cellulose composite coating of water-tolerant, before paper permeability and filter efficiency is ensured
Put, improve the water resistance, weatherability and bursting strength of filter paper.
Brief description of the drawings
Fig. 1 is the structural representation of the nanofiber composite air filter paper of the present invention.
Reference is：Upper filter layer 1, lower filter layer 2, nano-cellulose composite coating 3.
Embodiment
With reference to embodiment, the invention will be further described.
Embodiment 1
As shown in figure 1, a kind of nanofiber composite air filter paper, including upper filter layer 1, lower filter layer 2 and it is coated on institute
State the nano-cellulose composite coating 3 of filter layer upper surface.
Wherein, the thickness of the upper filter layer is 0.11-0.12mm, and the thickness of the lower filter layer is 0.18-0.19mm.
A kind of preparation method of nanofiber composite air filter paper, is carried out according to the following steps：
A. the preparation of upper filter layer uncoated paper：To 30 parts of mercerization fibers, 15 parts of sisal fibers, 15 parts of akund mixing
It is beaten afterwards, slurry concentration is 2.2wt%, after mashing to slurry beating degree is 13 ° of SR, then defibrination is carried out, until beating degree
For 18 ° of SR, slurry a is made；1 part of ethylene glycol diglycidylether is added in the slurry a, slurry is made after stirring
b；0.3 part of sodium pyrophosphate is added in the slurry b, slurry is made to 1.7wt% in the regulation slurry concentration that added water after being uniformly dispersed
Expect c；Mercerization fiber described in slurry c, sisal fiber, the length of akund are 2.4-2.6mm.
Slurry c progress online is manufactured paper with pulp after shaping, upper filter layer uncoated paper is made.
B. the preparation of filter layer uncoated paper is descended：60 parts of broad-leaved wood fibers are beaten, slurry concentration is 2.75%, mashing is extremely
After slurry beating degree is 17 ° of SR, then defibrination is carried out, until beating degree is 28 ° of SR, slurry A is made；1 part of ethylene glycol two is shunk
Glycerin ether is added in the slurry A, and slurry B is made after stirring；By 2 parts of titania aerogel particles, 2 parts of β-ring pastes
Essence and 1 part of carboxymethyl cellulose are added in the slurry B, and the regulation slurry concentration that added water after being uniformly dispersed is made to 1.5wt%
Slurry c, the length of broad-leaved wood fiber described in slurry C is 2.0-2.2mm.Online is carried out to slurry C to manufacture paper with pulp after shaping, under being made
Filter layer uncoated paper.
Wherein, the preparation method of the titania aerogel particle is as follows：Butyl titanate, absolute ethyl alcohol, toluene are pressed
Mass ratio 1:20:0.03 is mixed, obtained solution a；By absolute ethyl alcohol, 1.5mol/L glacial acetic acid and water in mass ratio 15:
4:1 is mixed, obtained solution b；Supersonic oscillations processing is carried out at 60 DEG C to solution a, by solution b with 1.5mL/s speed
Rate is added drop-wise in the solution a of 2.5 times of quality；It is solution a 0.05 times of aluminium hydroxide times to add quality into solution a simultaneously
Sodium bicarbonate powder, continues to stir after 2.5h, colloidal sol is made；The colloidal sol is stood into aging 36h, then using it is excessive just oneself
Alkane carries out solvent displacement 36h to colloidal sol, then removes n-hexane, obtains gel.Use the mixing of trim,ethylchlorosilane and n-hexane
Liquid modified 24h at 60 DEG C to gel；Wherein the mass ratio of trim,ethylchlorosilane, n-hexane and gel is 40:50:10.Finally
Modified gel is made to the titania aerogel particle of micron-scale at 400 DEG C after dry, crushing.
C. the laminating of upper and lower filter layer：The upper filter layer uncoated paper and lower filter layer uncoated paper are fitted, then passed through
Vacuumize the upper filter layer and lower filter layer that laminating is made after squeezing, drying.
D. composite mortar solidifies：It is 400-600nm, a diameter of 30-50nm nano-cellulose, 40 part two by 15 parts of length
Titania aerogel particle, phenoxy resin of 15 parts of molecular weight between 100000-150000,20 parts of dimethylformamides, 10 parts
The proportioning of water prepares composite mortar, is applied to the upper surface of filter layer, and vacuum drying solidify to form the compound painting of nano-cellulose
After layer, that is, nanofiber composite air filter paper is made.
Embodiment 2
A kind of nanofiber composite air filter paper, including upper filter layer, lower filter layer and located at the upper filter layer upper table
The nano-cellulose composite coating in face.
Wherein, the thickness of the upper filter layer is 0.10-0.11mm, and the thickness of the lower filter layer is 0.18-0.19mm.
A kind of preparation method of nanofiber composite air filter paper, is carried out according to the following steps：
A. the preparation of upper filter layer uncoated paper：To 20 parts of mercerization fibers, 10 parts of sisal fibers, 10 parts of akund mixing
It is beaten afterwards, slurry concentration is 1.9wt%, after mashing to slurry beating degree is 12 ° of SR, then defibrination is carried out, until beating degree
For 16 ° of SR, slurry a is made；0.5 part of ethylene glycol diglycidylether is added in the slurry a, slurry is made after stirring
Expect b；0.2 part of calgon is added in the slurry b, the regulation slurry concentration that added water after being uniformly dispersed is made to 1.5wt%
Obtain slurry c；Mercerization fiber described in slurry c, sisal fiber, the length of akund are 2.4-2.6mm.
Slurry c progress online is manufactured paper with pulp after shaping, upper filter layer uncoated paper is made.
B. the preparation of filter layer uncoated paper is descended：50 parts of broad-leaved wood fibers are beaten, slurry concentration is 2.5%, mashing is extremely
After slurry beating degree is 16 ° of SR, then defibrination is carried out, until beating degree is 26 ° of SR, slurry A is made；0.5 part of ethylene glycol two is contracted
Water glycerin ether is added in the slurry A, and slurry B is made after stirring；By 1 part of titania aerogel particle, 1- parts of β-
Cyclodextrin and 0.5 part of carboxymethyl cellulose are added in the slurry B, added water after being uniformly dispersed regulation slurry concentration to
1.3wt%, is made slurry C, the length of broad-leaved wood fiber described in slurry C is 2.0-2.2mm.Online is carried out to slurry C to manufacture paper with pulp
After shaping, lower filter layer uncoated paper is made.
Wherein, the preparation method of the titania aerogel particle is as follows：Butyl titanate, absolute ethyl alcohol, toluene are pressed
Mass ratio 1:15:0.02 is mixed, obtained solution a；By absolute ethyl alcohol, 1mol/L glacial acetic acid and water in mass ratio 10:3:1
Mixed, obtained solution b；Supersonic oscillations processing is carried out at 55 DEG C to solution a, solution b is added dropwise with 1mL/s speed
Into the solution a of 2 times of quality；0.04 times of the aluminium hydroxide that quality is solution a is added into solution a simultaneously, continues to stir 2h
Afterwards, colloidal sol is made；The colloidal sol is stood into aging 24h, solvent displacement 24h is then carried out to colloidal sol using excessive n-hexane,
N-hexane is removed again, obtains gel.36h is modified at 55 DEG C to gel using the mixed liquor of trim,ethylchlorosilane and n-hexane；
Wherein the mass ratio of trim,ethylchlorosilane, n-hexane and gel is 30:50:8.Finally modified gel is done at 300 DEG C
The titania aerogel particle of micron-scale is made after dry, crushing.
C. the laminating of upper and lower filter layer：The upper filter layer uncoated paper and lower filter layer uncoated paper are fitted, then passed through
Vacuumize the upper filter layer and lower filter layer that laminating is made after squeezing, drying.
D. composite mortar solidifies：It is 400-600nm, a diameter of 30-50nm nano-cellulose, 50 part two by 10 parts of length
Titania aerogel particle, phenoxy resin of 10 parts of molecular weight between 100000-150000,25 parts of dimethylformamides, 15 parts
The proportioning of water prepares composite mortar, is sprayed onto the upper surface of filter layer, and vacuum drying solidify to form the compound painting of nano-cellulose
After layer, that is, nanofiber composite air filter paper is made.
Embodiment 3
A kind of nanofiber composite air filter paper, including upper filter layer, lower filter layer and located at the upper filter layer upper table
The nano-cellulose composite coating in face.
Wherein, the thickness of the upper filter layer is 0.14-0.15mm, and the thickness of the lower filter layer is 0.19-0.20mm.
A kind of preparation method of nanofiber composite air filter paper, is carried out according to the following steps：
A. the preparation of upper filter layer uncoated paper：To 40 parts of mercerization fibers, 20 parts of sisal fibers, 20 parts of akund mixing
It is beaten afterwards, slurry concentration is 2.5wt%, after mashing to slurry beating degree is 14 ° of SR, then defibrination is carried out, until beating degree
For 20 ° of SR, slurry a is made；1.5 parts of ethylene glycol diglycidylethers are added in the slurry a, slurry is made after stirring
Expect b；0.4 part of calgon is added in the slurry b, the regulation slurry concentration that added water after being uniformly dispersed is made to 1.9wt%
Obtain slurry c；Mercerization fiber described in slurry c, sisal fiber, the length of akund are 2.4-2.6mm.
Slurry c progress online is manufactured paper with pulp after shaping, upper filter layer uncoated paper is made.
B. the preparation of filter layer uncoated paper is descended：70 parts of broad-leaved wood fibers are beaten, slurry concentration is 3.0%, mashing is extremely
After slurry beating degree is 18 ° of SR, then defibrination is carried out, until beating degree is 30 ° of SR, slurry A is made；1.5 parts of ethylene glycol two are contracted
Water glycerin ether is added in the slurry A, and slurry B is made after stirring；By 3 parts of titania aerogel particles, 3 parts of β-rings
Dextrin and 1.5 parts of carboxymethyl celluloses are added in the slurry B, are added water after being uniformly dispersed and are adjusted slurry concentration to 1.7wt%,
Slurry C is made, the length of broad-leaved wood fiber described in slurry C is 2.0-2.2mm.Slurry C progress online is manufactured paper with pulp after shaping, made
Filter layer uncoated paper must be descended.
Wherein, the preparation method of the titania aerogel particle is as follows：Butyl titanate, absolute ethyl alcohol, toluene are pressed
Mass ratio 1:25:0.04 is mixed, obtained solution a；By absolute ethyl alcohol, 2mol/L glacial acetic acid and water in mass ratio 20:5:1
Mixed, obtained solution b；Supersonic oscillations processing is carried out at 65 DEG C to solution a, solution b is added dropwise with 2mL/s speed
Into the solution a of 3 times of quality；0.06 times of the aluminium hydroxide that quality is solution a is added into solution a simultaneously, continues to stir 3h
Afterwards, colloidal sol is made；The colloidal sol is stood into aging 48h, solvent displacement 48h is then carried out to colloidal sol using excessive n-hexane,
N-hexane is removed again, obtains gel.16h is modified at 65 DEG C to gel using the mixed liquor of trim,ethylchlorosilane and n-hexane；
Wherein the mass ratio of trim,ethylchlorosilane, n-hexane and gel is 50:50:12.Finally modified gel is done at 500 DEG C
The titania aerogel particle of micron-scale is made after dry, crushing.
C. the laminating of upper and lower filter layer：The upper filter layer uncoated paper and lower filter layer uncoated paper are fitted, then passed through
Vacuumize the upper filter layer and lower filter layer that laminating is made after squeezing, drying.
D. composite mortar solidifies：It is 400-600nm, a diameter of 30-50nm nano-cellulose, 30 part two by 20 parts of length
Titania aerogel particle, phenoxy resin of 20 parts of molecular weight between 100000-150000,15 parts of dimethylformamides, 5 parts
The proportioning of water prepares composite mortar, is sprayed onto the upper surface of filter layer, and vacuum drying solidify to form the compound painting of nano-cellulose
After layer, that is, nanofiber composite air filter paper is made.
Embodiment 4
A kind of nanofiber composite air filter paper, including upper filter layer, lower filter layer and located at the upper filter layer upper table
The nano-cellulose composite coating in face.
Wherein, the thickness of the upper filter layer is 0.11-0.12mm, and the thickness of the lower filter layer is 0.19-0.20mm.
A kind of preparation method of nanofiber composite air filter paper, is carried out according to the following steps：
A. the preparation of upper filter layer uncoated paper：To 25 parts of mercerization fibers, 16 parts of sisal fibers, 16 parts of akund mixing
It is beaten afterwards, slurry concentration is 2.3wt%, after mashing to slurry beating degree is 13 ° of SR, then defibrination is carried out, until beating degree
For 19 ° of SR, slurry a is made；1.25 parts of ethylene glycol diglycidylethers are added in the slurry a, are made after stirring
Slurry b；0.35 part of calgon is added in the slurry b, added water after being uniformly dispersed regulation slurry concentration to
1.8wt%, is made slurry c；Mercerization fiber described in slurry c, sisal fiber, the length of akund are 2.4-2.6mm.
Slurry c progress online is manufactured paper with pulp after shaping, upper filter layer uncoated paper is made.
B. the preparation of filter layer uncoated paper is descended：50-70 parts of broad-leaved wood fibers are beaten, slurry concentration is 2.8%, be beaten
After being 16-18 ° of SR to slurry beating degree, then defibrination is carried out, until beating degree is 28 ° of SR, slurry A is made；By 1 part of ethylene glycol two
Glycidol ether is added in the slurry A, and slurry B is made after stirring；By 2 parts of titania aerogel particles, 1-3 parts
Beta-schardinger dextrin and 1 part of carboxymethyl cellulose are added in the slurry B, added water after being uniformly dispersed regulation slurry concentration to
1.6wt%, is made slurry C, the length of broad-leaved wood fiber described in slurry C is 2.0-2.2mm.Online is carried out to slurry C to manufacture paper with pulp
After shaping, lower filter layer uncoated paper is made.
Wherein, the preparation method of the titania aerogel particle is as follows：Butyl titanate, absolute ethyl alcohol, toluene are pressed
Mass ratio 1:22:0.035 is mixed, obtained solution a；By absolute ethyl alcohol, 1.6mol/L glacial acetic acid and water in mass ratio 16:
4:1 is mixed, obtained solution b；Supersonic oscillations processing is carried out at 60 DEG C to solution a, by solution b with 1.6mL/s speed
Rate is added drop-wise in the solution a of 2.5 times of quality；0.045 times of the aluminium hydroxide that quality is solution a is added into solution a simultaneously, after
After continuous stirring 3h, colloidal sol is made；The colloidal sol is stood into aging 36h, solvent then is carried out to colloidal sol using excessive n-hexane
36h is replaced, then removes n-hexane, gel is obtained.Using the mixed liquor of trim,ethylchlorosilane and n-hexane to gel at 60 DEG C
Modified 30h；Wherein the mass ratio of trim,ethylchlorosilane, n-hexane and gel is 45:50:11.Finally modified gel is existed
The titania aerogel particle of micron-scale is made after dry at 350 DEG C, crushing.
C. the laminating of upper and lower filter layer：The upper filter layer uncoated paper and lower filter layer uncoated paper are fitted, then passed through
Vacuumize the upper filter layer and lower filter layer that laminating is made after squeezing, drying.
D. composite mortar solidifies：It is 400-600nm, a diameter of 30-50nm nano-cellulose, 35 part two by 16 parts of length
Titania aerogel particle, phenoxy resin of 15 parts of molecular weight between 100000-150000,20 parts of dimethylformamides, 10 parts
The proportioning of water prepares composite mortar, is applied to the upper surface of filter layer, and vacuum drying solidify to form the compound painting of nano-cellulose
After layer, that is, nanofiber composite air filter paper is made.
Embodiment 5
A kind of nanofiber composite air filter paper, including upper filter layer, lower filter layer and located at the upper filter layer upper table
The nano-cellulose composite coating in face.
Wherein, the thickness of the upper filter layer is 0.13-0.14mm, and the thickness of the lower filter layer is 0.18-0.19mm.
A kind of preparation method of nanofiber composite air filter paper, is carried out according to the following steps：
A. the preparation of upper filter layer uncoated paper：To 36 parts of mercerization fibers, 15 parts of sisal fibers, 17 parts of akund mixing
It is beaten afterwards, slurry concentration is 2.2wt%, after mashing to slurry beating degree is 14 ° of SR, then defibrination is carried out, until beating degree
For 20 ° of SR, slurry a is made；1 part of ethylene glycol diglycidylether is added in the slurry a, slurry is made after stirring
b；0.3 part of calgon is added in the slurry b, the regulation slurry concentration that added water after being uniformly dispersed is made to 1.8wt%
Slurry c；Mercerization fiber described in slurry c, sisal fiber, the length of akund are 2.4-2.6mm.
Slurry c progress online is manufactured paper with pulp after shaping, upper filter layer uncoated paper is made.
B. the preparation of filter layer uncoated paper is descended：67 parts of broad-leaved wood fibers are beaten, slurry concentration is 2.6%, mashing is extremely
After slurry beating degree is 18 ° of SR, then defibrination is carried out, until beating degree is 30 ° of SR, slurry A is made；1 part of ethylene glycol two is shunk
Glycerin ether is added in the slurry A, and slurry B is made after stirring；By 2 parts of titania aerogel particles, 2 parts of β-ring pastes
Essence and 1 part of carboxymethyl cellulose are added in the slurry B, and the regulation slurry concentration that added water after being uniformly dispersed is made to 1.6wt%
Slurry C, the length of broad-leaved wood fiber described in slurry C is 2.0-2.2mm.Online is carried out to slurry C to manufacture paper with pulp after shaping, under being made
Filter layer uncoated paper.
Wherein, the preparation method of the titania aerogel particle is as follows：Butyl titanate, absolute ethyl alcohol, toluene are pressed
Mass ratio 1:21:0.03 is mixed, obtained solution a；By absolute ethyl alcohol, 1.5mol/L glacial acetic acid and water in mass ratio 15:
4:1 is mixed, obtained solution b；Supersonic oscillations processing is carried out at 60 DEG C to solution a, by solution b with 1.5mL/s speed
Rate is added drop-wise in the solution a of 2.5 times of quality；0.055 times of the aluminium hydroxide that quality is solution a is added into solution a simultaneously, after
After continuous stirring 2.5h, colloidal sol is made；The colloidal sol is stood into aging 36h, then colloidal sol carried out using excessive n-hexane molten
36h is replaced in agent, then removes n-hexane, obtains gel.Using the mixed liquor of trim,ethylchlorosilane and n-hexane to gel at 60 DEG C
Lower modified 24h；Wherein the mass ratio of trim,ethylchlorosilane, n-hexane and gel is 40:50:11.Finally by modified gel
The titania aerogel particle of micron-scale is made after dry at 450 DEG C, crushing.
C. the laminating of upper and lower filter layer：The upper filter layer uncoated paper and lower filter layer uncoated paper are fitted, then passed through
Vacuumize the upper filter layer and lower filter layer that laminating is made after squeezing, drying.
D. composite mortar solidifies：It is 400-600nm, a diameter of 30-50nm nano-cellulose, 45 part two by 18 parts of length
Titania aerogel particle, phenoxy resin of 18 parts of molecular weight between 100000-150000,20 parts of dimethylformamides, 10 parts
The proportioning of water prepares composite mortar, is applied to the upper surface of filter layer, and vacuum drying solidify to form the compound painting of nano-cellulose
After layer, that is, nanofiber composite air filter paper is made.
The technical indicator of nanofiber composite air filter paper is as shown in the table made from embodiment 1-5：
(quantitative measure uses GB/T451.2-2002 paper and the quantitative assay method of cardboard；Bursting strength uses GB/
The measure of T454-2002 paper bursting strengths.)
Raw materials used in the present invention, equipment, is the conventional raw material, equipment of this area unless otherwise noted；In the present invention
Method therefor, is the conventional method of this area unless otherwise noted.
It is described above, only it is presently preferred embodiments of the present invention, not the present invention is imposed any restrictions, it is every according to the present invention
Any simple modification, change and equivalent transformation that technical spirit is made to above example, still fall within the technology of the present invention side
The protection domain of case.
Claims (10)
1. a kind of nanofiber composite air filter paper, it is characterised in that：Including upper filter layer（1）, lower filter layer（2）With located at institute
State the nano-cellulose composite coating of filter layer upper surface（3）；The nano-cellulose composite coating is solidified by composite mortar
Form, the composite mortar by following mass parts material composition：10-20 parts of nano-celluloses, 30-50 parts of titanium dioxide airsettings
Micelle, 10-20 parts of phenoxy resins, 15-25 parts of dimethylformamides, 5-15 parts of water；The upper filter layer is by following mass parts
Material composition：20-40 parts of mercerization fiber, 10-20 parts of sisal fiber, 10-20 parts of akund, ethylene glycol diglycidyl
0.5-1.5 parts of ether, 0.2-0.4 parts of dispersant and the desired amount of water；The lower filter layer by following mass parts material composition：It is wealthy
50-70 parts of leaf wood-fibred, 1-3 parts of titania aerogel particle, 1-3 parts of beta-schardinger dextrin, 0.5-1.5 parts of carboxymethyl cellulose,
0.5-1.5 parts of ethylene glycol diglycidylether and the desired amount of water.
2. a kind of nanofiber composite air filter paper as claimed in claim 1, it is characterised in that the composite mortar is by following
The material composition of mass parts：15 parts of nano-celluloses, 40 parts of titania aerogel particles, 15 parts of phenoxy resins, 20 parts of diformazans
Base acid amides, 10 parts of water；The upper filter layer by following mass parts material composition：30 parts of mercerization fiber, 15 parts of sisal fiber,
15 parts of akund, 1 part of ethylene glycol diglycidylether, 0.3 part of dispersant and the desired amount of water；The lower filter layer by with
The material composition of lower mass parts：60 parts of broad-leaved wood fiber, 2 parts of titania aerogel particle, 2 parts of beta-schardinger dextrin, carboxymethyl is fine
1 part of dimension element, 1 part of ethylene glycol diglycidylether and the desired amount of water.
3. a kind of nanofiber composite air filter paper as claimed in claim 1, it is characterised in that the length of the nano-cellulose
Spend for 400-600nm, a diameter of 30-50nm；The molecular weight of the phenoxy resin is between 100000-150000.
4. a kind of nanofiber composite air filter paper as claimed in claim 1, it is characterised in that the nanofiber compound air
The thickness of air filter paper is 0.28-0.36mm, and the thickness of the upper filter layer is 0.10-0.15mm, the thickness of the lower filter layer
For 0.16-0.20mm.
5. a kind of nanofiber composite air filter paper as claimed in claim 4, it is characterised in that the nanofiber compound air
The quantification of 105-115g/m of air filter paper2, nano-cellulose composite coating accounts for the 6- of nanofiber composite air filter paper gross mass
10%。
6. a kind of nanofiber composite air filter paper as claimed in claim 1, it is characterised in that the dispersant is pyrophosphoric acid
Sodium or calgon.
7. a kind of a kind of preparation method of nanofiber composite air filter paper as described in one of claim 1-6, its feature exists
Carried out according to the following steps：
A. the preparation of upper filter layer uncoated paper：To being beaten after mercerization fiber, sisal fiber, akund mixing, slurry
Concentration is 1.9-2.5wt%, after mashing to slurry beating degree is 12-14 ° of SR, then carries out defibrination, until beating degree is 16-20 °
SR, is made slurry a；Ethylene glycol diglycidylether is added in the slurry a, slurry b is made after stirring；Will be scattered
Agent is added in the slurry b, and slurry c is made to 1.5-1.9wt% in the regulation slurry concentration that added water after being uniformly dispersed；To slurry c
Progress online is manufactured paper with pulp after shaping, and upper filter layer uncoated paper is made；
B. the preparation of filter layer uncoated paper is descended：Broad-leaved wood fiber is beaten, slurry concentration is 2.5-3.0%, mashing to slurry
After beating degree is 16-18 ° of SR, then defibrination is carried out, until beating degree is 26-30 ° of SR, slurry A is made；Ethylene glycol two is shunk sweet
Oily ether is added in the slurry A, and slurry B is made after stirring；By titania aerogel particle, beta-schardinger dextrin and carboxylic first
Base cellulose is added in the slurry B, and slurry C is made to 1.3-1.7wt% in the regulation slurry concentration that added water after being uniformly dispersed, right
Slurry C progress online is manufactured paper with pulp after shaping, and lower filter layer uncoated paper is made；
C. the laminating of upper and lower filter layer：The upper filter layer uncoated paper and lower filter layer uncoated paper are fitted, it is then true by taking out
The upper filter layer and lower filter layer of laminating are made after pneumatics squeezing, drying；
D. composite mortar solidifies：Composite mortar is prepared by proportioning, the upper surface of filter layer is coated with or is sprayed onto, is dried in vacuo
It solidify to form after nano-cellulose composite coating, that is, nanofiber composite air filter paper is made.
8. a kind of preparation method of nanofiber composite air filter paper as claimed in claim 7, it is characterised in that by beating
After slurry, defibrination, the mercerization fiber, sisal fiber, the length of akund are 2.4-2.6mm, the broad-leaved wood fiber
Length be 2.0-2.2mm.
9. a kind of preparation method of nanofiber composite air filter paper as claimed in claim 7, it is characterised in that the dioxy
The preparation method for changing titanium aerogel particles is as follows：By butyl titanate, absolute ethyl alcohol, toluene in mass ratio 1:15-25:0.02-
0.04 is mixed, obtained solution a；By absolute ethyl alcohol, 1-2mol/L glacial acetic acid and water 10-20 in mass ratio:3-5:1 is carried out
Mixing, obtained solution b；Supersonic oscillations processing is carried out at 55-65 DEG C to solution a, solution b is dripped with 1-2mL/s speed
In the solution a for being added to 2-3 times of quality；0.04-0.06 times of the aluminium hydroxide that quality is solution a is added into solution a simultaneously, after
After continuous stirring 2-3h, colloidal sol is made；The colloidal sol is stood into aging 24-48h, then colloidal sol carried out using excessive n-hexane
Solvent replaces 24-48h, then removes n-hexane, obtains gel, and gel finally is made into micro- after dry, crushing at 300-500 DEG C
The titania aerogel particle of meter ruler cun.
10. a kind of preparation method of nanofiber composite air filter paper as claimed in claim 9, it is characterised in that be made
After the gel, gel passes through modification before it is dried：Mixed liquor using trim,ethylchlorosilane and n-hexane exists to gel
Modified 16-36h at 55-65 DEG C；Wherein the mass ratio of trim,ethylchlorosilane, n-hexane and gel is 30-50:50：8-12.
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| CN202809390U (en) * | 2011-12-30 | 2013-03-20 | 东莞市海莎过滤器有限公司 | Oil-saving filter paper used for fuel oil filter |
| CN104420400A (en) * | 2013-08-30 | 2015-03-18 | 珠海市红旌发展有限公司 | Preparation method of air filtering paper containing nanocellulose |
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| CN202809390U (en) * | 2011-12-30 | 2013-03-20 | 东莞市海莎过滤器有限公司 | Oil-saving filter paper used for fuel oil filter |
| CN104420400A (en) * | 2013-08-30 | 2015-03-18 | 珠海市红旌发展有限公司 | Preparation method of air filtering paper containing nanocellulose |
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Denomination of invention: Nanofiber composite air filter paper and production method thereof Effective date of registration: 20191108 Granted publication date: 20170915 Pledgee: Hengfeng Bank Co., Ltd. Hangzhou Fuyang sub branch Pledgor: Hangzhou Special Paper Industry Co., Ltd. Registration number: Y2019990000488 |