CN110305540A - A kind of aqueous high-obstructing coating liquid and preparation method thereof - Google Patents
A kind of aqueous high-obstructing coating liquid and preparation method thereof Download PDFInfo
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- C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
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Abstract
The invention discloses a kind of aqueous high-obstructing coating liquid and preparation method thereof, the aqueous high-obstructing coating liquid includes 0.01~10 part of 0.1~15 part of 0.5~15 part of water-soluble polymer, nano-oxide, the graphene of hydroxyl, 0.01~5 part of organosiloxane class coupling agent, 0.1~30 part of 0.1mol/L dilute hydrochloric acid and 30~95 parts of solvent.The present invention loads the reunion that can inhibit between graphene on the surface of graphene using nanometer oxide particle made from sol-gel method as small size polymerization inhibitor by way of physical absorption, solves the problems, such as that graphene dispersion is bad；Using the crosslinked action of nano-oxide and water-soluble polymer, the barrier action that graphene/polymer enhances gas associating has been given full play to.In addition, present invention process is simple and easy, prepared thin-film material also has both good mechanical performance and packages printing performance, can be widely applied to the fields such as medicine, food, electronic product packaging, encapsulation.
Description
Technical field
The present invention relates to a kind of aqueous high-obstructing coating liquids that can satisfy medicine, food, electronic product and pack, and belong to film
Technical field.
Background technique
In order to avoid the content of packaging is rotten, Shelf-life, the high-quality for guaranteeing product, it is desirable that be used for food, medicine
The packaging material of product and electronic article can effectively separate extraneous oxygen, vapor etc., reduce due to barrier property is bad
Lead to the intermediate loss of product, therefore, the barrier property for improving packing film has become a urgent problem to be solved.
Sufficient barrier properties for gases and water resistance in order to obtain can disperse inorganic nano-particle in barrier resin composition
The inorganic fillers such as son or lamellar compound, wherein what is be most widely used is to be added to resin using graphene as barrier property filler
Laminated film is prepared in composition.Different from other lamellar compounds such as mica, montmorillonite,
Graphene is a kind of two-dimensional slice material of the honeycomb framework of single layer of carbon atom composition, the graphite of structural integrity
Alkene has a natural gas impermeability, this special construction also determine it without intercalator expand interlamellar spacing or
Mechanical stress realizes splitting state completely, is the ideal filler of separating polymer composite material.But the graphite of complete structure
It is prone to stack phenomenon in the dispersion process of alkene in the polymer, weakens with the interface interaction of polymer, affect its barrier
The performance of performance.
Chinese patent CN101812194A proposes a kind of graphene-based barrier composite material and preparation method thereof, specifically
Functionalization first is carried out to graphene oxide with coupling agent, then the graphene oxide after functionalization is restored, followed by
Solvent will modify redox graphene carried out in polyolefin solution it is evenly dispersed, while be added initiator promote graphene with
The crosslinking of polyolefin, which is bonded, is made nanocomposite.However, prepared by the approach for restoring graphene chemical oxidation
There are certain faults of construction for graphene, this will be unfavorable for graphene and plays natural water and oxygen barrier property, while a large amount of preparations are held
Waste liquor contamination easily is brought, is restricted its industrialized production.
Chinese patent CN106221179A proposes a kind of graphene-silicon dioxide hybrid materials and prepares polyurethane nanometer
The method of composite material, specifically, using functional 3-aminopropyltriethoxysilane monomer as link silica with
Graphene-silicon dioxide hybrid materials are made in the intermediate bridge of graphene oxide, and using the hybrid material as filler, with poly- third
Olefine resin is matrix, and polyurethane nanocomposite is made through melt-blending process.The method is by playing graphene-dioxy
The mutual blocking effect of SiClx improves the dispersibility of graphene, but there is also what is easily reunited to show for the silicon-dioxide powdery being added
As not only can not achieve the effect for inhibiting graphene to reunite in this way, also will affect the barrier property of matrix resin.
To sum up, it plays polymer matrix graphene composite material to the maximum extent the key of water oxygen barrier property is to solve now
There is in technology graphene dispersed bad problem in a polymer matrix.
Summary of the invention
The purpose of the present invention is to provide a kind of aqueous high-obstructing coating liquid, the coating fluid to oxygen and vapor simultaneously
With superior barrier properties, it can inhibit the reunion of graphene itself, solve the problems, such as that its dispersibility is bad, meanwhile, using receiving
Rice oxide is bonded with crosslinking between water-soluble polymer, while improving the compactness of coating, is given full play to and graphene
Synergistic effect, increases substantially the barrier property to gas.
The purpose of the present invention is what is be achieved through the following technical solutions:
A kind of aqueous high-obstructing coating liquid, the coating fluid are made using the raw material of following component:
0.5~15 parts by weight of water-soluble polymer of hydroxyl
0.1~15 parts by weight of nano-oxide
0.01~5 parts by weight of graphene
0.01~5 parts by weight of organosiloxane class coupling agent
0.1~30 parts by weight of dilute hydrochloric acid 0.1mol/L
30~95 parts by weight of solvent.
Above-mentioned aqueous high-obstructing coating liquid, the nano-oxide are urged using sol-gel method in acid by metal alkoxide
It is prepared under the conditions of change by hydrolysis-condensation.
Above-mentioned aqueous high-obstructing coating liquid, the metal alkoxide are selected from tetramethoxy-silicane, tetraethoxysilane, trimethoxy
Base aluminium, aluminium ethoxide, aluminium isopropoxide, three n-butylaluminums, titanium tetramethoxide, purity titanium tetraethoxide, tetraisopropoxy titanium, four
At least one of normal-butyl titanium, tetraethoxy zirconium or zirconium tetraisopropoxide.
Above-mentioned aqueous high-obstructing coating liquid, the hydroxyl water-soluble polymer be selected from polyvinyl alcohol, starch, cellulose,
One of chitosan is a variety of；The degree of polymerization of the hydroxyl water-soluble polymer be 500~3000, alcoholysis degree be 80%~
99.99%.
Above-mentioned aqueous high-obstructing coating liquid, the graphene are intrinsic graphene, graphene oxide or sulfonated graphene
At least one of, and the removing of the graphene, having a size of 0.5~8nm, lamella size is 3~70 μm.
Above-mentioned aqueous high-obstructing coating liquid, the general structure of the organosiloxane class coupling agent are YR3Si(OR2)3,
Middle R2For methyl or ethyl, R3For the alkyl chain with 0-4 carbon, Y is vinyl, epoxy group, glycidoxy, metering system
At least one of acyloxy, urea groups, amino or isocyanate functional group.
A method of aqueous high-obstructing coating liquid as described above being prepared, preparation carries out as follows:
1) hydrolyzate of sol-gel method preparing metal alkoxide under acid catalysed conditions is advanced with, is stirred under normal temperature and pressure
40~60min is mixed, nano-oxide solution is obtained after standing；
2) graphene is added in Xiang Suoshu nano-oxide solution, is persistently stirred under normal temperature and pressure, stirring rate be 600~
800 turns/min, 1~2h is stirred, stands and obtains the graphene dispersing solution of load nanometer oxide particle；
3) stirring rate is down to 300~400 turns/min, is slowly added into the graphene dispersing solution in step 2 water-soluble
Property polymer solution, continues 20~40min of stirring while organosiloxane class coupling agent hydrolyzate is added, stir under normal temperature and pressure
1~2h is stored at room temperature, and obtains the aqueous high-obstructing coating liquid.
Above-mentioned preparation method, the aqueous high-obstructing coating liquid are used as barrier layer in the coating of inorganic deposition layer surface, will
A repetitive unit is set as comprising the stepped construction including the inorganic deposition layer and the barrier layer, settable 1 or more
Repetitive unit.
Above-mentioned preparation method, the liquid measure being coated with should make the film thickness as dry coating be 0.05~3 μm；The basement membrane
Layer with a thickness of 5~300 μm, inorganic deposition layer with a thickness of 10~100nm.
Compared with prior art, the invention has the advantages that and the utility model has the advantages that
1, the nanometer oxide particle of present invention distribution on the surface of graphene is to be existed by metal alkoxide using sol-gel method
The homogeneous system being prepared under acid catalysed conditions by hydrolysis-condensation, can be avoided after being directly added into nano-oxide particles
Issuable secondary agglomeration phenomenon, dramatically improve graphene in a polymer matrix bad dispersibility the problem of.
2, the present invention is same to inhibit to reunite each other in the mutual blocking effect for giving full play to graphene and nano-oxide
When, water-soluble polymer is further added, it can be made to generate crosslinking with the nano-oxide of load on the surface of graphene and be bonded
Effect, further increases the compactness of coating, significantly enhances the barrier property to oxygen especially vapor.
3, preparation is simple by the present invention, and practicability is good, can be realized low-cost industrial production, prepared is thin
Membrane material also has both good mechanical performance and packages printing performance, can be widely used in medicine, food, electronic product packaging
Equal fields.
Detailed description of the invention
Fig. 1 is the knot that inorganic deposition layer provided by the invention and coating barrier layer are constituted transparent barrier layer in the form of pairs of
Structure schematic diagram；
Fig. 2 is inorganic deposition layer and the structural schematic diagram for being coated with the transparent barrier layer that barrier layer is formed with multilayered structure.
Each label respectively indicates in figure are as follows: 1- base membrane layer；2- transparent barrier layer；21- inorganic deposition layer；22- coating resistance
Interlayer.
Specific embodiment
Below in conjunction with specific embodiment, present invention is further described in detail.
The aqueous high-obstructing coating liquid that barrier layer (22) in the present invention uses is by the water-soluble poly of graphene, hydroxyl
Object, nano-oxide, organosiloxane class coupling agent, 0.1mol/L hydrochloric acid and solvent is closed to be made.The barrier layer utilizes load
Graphene uniform is dispersed therein while nano-oxide on the surface of graphene is bonded with water-soluble polymer crosslinking, is changed
The dispersibility of graphene has been apt to it, the compactness of coating is also promoted, in addition the synergistic effect of water-soluble polymer high-barrier, institute
There is very excellent water and oxygen barrier property with the barrier layer.
It can be any in intrinsic graphene, graphene oxide either sulfonated graphene about the type of graphene
One kind, but preferably intrinsic graphene.The surfaces such as graphene graphene oxide or sulfonated graphene by surface modification because
There are functional groups, dispersibility will be substantially better than intrinsic graphene, but it may generate surface defect during the preparation process,
Space compactness is destroyed, so functionalization graphene is not as good as intrinsic graphene in terms of the barrier property to water oxygen.To obtain more
Good barriering effect, the preferably intrinsic graphene of the present invention.
The graphene added in the present invention can be single layer or multilayered structure, remove size preferably in 0.5~8nm range
It is interior, and lamella size control is at 3~70 μm.Lamella size is too small to limit its barrier because not becoming fine and close tiling lamination
The performance of effect, and lamella size is excessive, the uniformity dispersed in the solution is easy to be deteriorated, and causes in damage graphene lamination
While close property, the barriering effect of water-soluble polymer itself can be also destroyed.
The additive amount of graphene of the present invention is preferably 0.01 weight % or more, 5 weight % or less.If additional amount is less than 0.01
Weight %, there will be the tendencies that barrier properties for gases reduces, and decline when especially using for a long time in the harsh environments such as high temperature and humidity
Trend will become more apparent.If additional amount is greater than 5 weight %, can have an adverse effect to the dispersion effect in graphene solution, nothing
Method guarantees to obtain abundant gas barrier property, at the same also will appear film layer flexibility reduce or light transmission be deteriorated the case where.
Nano-oxide of the present invention is prepared in acid condition by sol-gel method by metal alkoxide, should
The nano-oxide of method preparation has the characteristics that granularity is small, activity is high.It is nano oxidized play connection water-soluble polymer with
On the one hand the function served as bridge of graphene is loaded nano-oxide by way of physical absorption on the surface of graphene；Separately
One side nano-oxide can also carry out hybrid cross-linked with the water-soluble object that depolymerizes；Two aspect synergistic effect to reach by
Graphene uniform is distributed to the purpose in water-soluble polymer.Nano-oxide and graphene are added in water-soluble polymer can be with
Further improve the barrier property and moisture resistance properties of coating.
In addition, graphene can be added in nano-oxide as the method for mixing graphene with nano-oxide
Powder, the method for being stirred for thus dispersing it, or the dispersion liquid of pre-prepd graphene is mixed with nano-oxide
The method of conjunction is stirred in acid condition furthermore it is also possible to which metal alkoxide and graphene powder are added in solvent simultaneously
The method for mixing, while being hydrolyzed and dispersing.In the above-mentioned methods, it is contemplated that the controllable difficulty or ease journey of graphene dispersion state
Degree, it is preferred to use the method mixed after the dispersion liquid of preparation of nano oxide and graphene respectively.
As the decentralized medium of graphene, water can be, be also possible to water Combination organic solvent.Have as water Combination
The concrete example of solvent, can enumerate methanol, ethyl alcohol, propyl alcohol, ethylene glycol, propylene glycol, methyl formate, methyl acetate, ethyl acetate,
Acetone etc..For above-mentioned decentralized medium, different dispersion can be properly selected according to different purposes.But it is aqueous utilizing
When high-obstructing coating liquid, from the aspect of the dispersibility of graphene, furthermore examined in terms of the uniformity of formed coating
Consider, it is preferable to use water is as decentralized medium.
The present invention prepares nano oxidized metal alkoxide used and preferably is selected from tetramethoxy-silicane, tetraethoxysilane, front three
Oxygroup aluminium, aluminium ethoxide, aluminium isopropoxide, three n-butylaluminums, titanium tetramethoxide, purity titanium tetraethoxide, tetraisopropoxy titanium,
One of tetra-n-butyl titanium, tetraethoxy zirconium, zirconium tetraisopropoxide etc., wherein more preferable tetramethoxy-silicane, tetraethoxy
Silane.It is considered herein that element silicon is metallic element.
The pH value that the present invention prepares the system of nano-oxide is preferably 2~5.The pH value of system is greater than 5, then metal alkoxide
It is unable to complete hydrolysis, and hydrolysis time is longer；And system pH is less than 2, it will cause the acidity of prepared coating fluid is too high,
It is also uneconomical to cause the corrosion to equipment.
One of the preferred polyvinyl alcohol of water-soluble polymer, starch, cellulose, chitosan in the present invention are a variety of,
More preferable vinol series polymer (hereinafter referred to as PVA).The degree of polymerization of PVA controls alcoholysis in the range of 500~3000
Degree control is between 80%~99.99%, and the degree of polymerization is higher, and coating film forming is better, and alcoholysis degree is higher, the gas barrier property of coating
It can be more excellent.The additional amount of water-soluble polymer is preferably 0.5~15 weight % of coating fluid weight, more preferably 1~10 weight
Measure %.
The general formula of organosiloxane class coupling agent selected by the present invention is YR3Si(OR2)3, wherein R2For methyl or ethyl, R3
For the alkyl chain with 0~4 carbon, Y should be preferably hydrophobic functional groups such as vinyl, epoxy group, glycidoxy, methyl-prop
One of alkene acyloxy, urea groups, amino or isocyanate group.This kind of organosiloxane class coupling agents can by hydrolysis with
The nano-oxide and water-soluble polymer of graphene surface load form hydrogen bond, advanced optimize the crosslinking between resin combination
Degree inhibits the reunion of graphene itself, improves the compactness of coating, can also improve the adhesive force between coating and basement membrane,
The hydrophobic group being had in coupling agent simultaneously additionally aids the water resistance of strengthened coat.Specifically, organosiloxane
Class coupling agent includes n-propyl trimethoxy silane, methyltrimethoxysilane, γ-(the third oxygen of 2,3- epoxy) propyl trimethoxy
Silane (A187), vinyltrimethoxysilane (A171), γ-methacryloxypropyl trimethoxy silane (A174),
Vinyltriethoxysilane (A151), 1,3,5- tri- (3- trimethoxy-silylpropyl) isocyanuric acid ester etc..Described
In aqueous high-obstructing coating liquid, the additional amount of organosiloxane class coupling agent is preferably 0.01~5 weight % of coating fluid weight.
The additional amount of organosiloxane class coupling agent it is excessive or it is very few be unfavorable for improve coating barrier property.
Dissolubility is poor in aqueous solution for the organosiloxane class coupling agent with hydrophobic group, is added directly into
It can be scattered in coating fluid with oily drop in coating fluid, influence the performance of its effect, therefore it is preferable to use organosiloxane class idols
Coupling agent, i.e., be first hydrolyzed in acid condition, expose hydrophilic " Si-OH " therein by the hydrolyzate for joining agent
Come, in this way, coupling agent solubility in an aqueous solvent not only can be improved, while the barrier property of coating will not also be generated not
It influences sharply.
Meanwhile to improve Painting effect, improving coating appearance can be to institute under the premise of not damaging the purpose of the present invention
It states in high-obstructing coating liquid and is added well known to wetting agent, levelling agent, adhesion promoter, antistatic agent, plasticizer, anti-wear agent etc.
The additive types of additive, addition are not particularly limited, and can arbitrarily be selected from each additive according to purpose.Described aqueous
In high-obstructing coating liquid, the additional amount of each additive is preferably 0.01 weight % or more, 1 weight % or less.
The structure of barrier film of the present invention is preferably the laminated construction of inorganic deposition layer and barrier layer.Because inorganic
On the one hand object sedimentary (22) and the barrier layer (2) of aqueous high-obstructing coating liquid coating can have expected synergistic effect, into one
Barrier property of the step optimization to gas；On the other hand the thickness requirement to barrier layer also can be effectively reduced, meet packaging field
Requirement to packaging film slimming, flexibility.
For inorganic deposition layer (21), it is preferable to use transparent compound deposition layer, specifically have aluminium oxide, silica,
One of silicon nitride, titanium oxide, zirconium oxide are a variety of, more preferably use silica.The thickness of sedimentary preferably 10~
Within the scope of 100nm.If deposit thickness is less than 10nm, it is not enough to be completely covered membrane surface bumps that may be present；If heavy
The case where lamination thickness is greater than 100nm, is easy to film layer cracking occur, and flexibility reduces.Therefore, the thickness of sedimentary should be limited preferably
Determine within the above range.For deposited inorganic layers and barrier layer stackup when thickness be not particularly limited, from cost, operability with
And from the aspect of the barrier property of stack membrane, preferably in 0.05~3 μ m, and then preferably in 0.1~2 μ m.Such as
Fruit thickness cannot obtain expected barrier property less than 0.05 μm；On the other hand, it if thickness has been more than 3 μm, does not obtain not only
Obtain the improvement with its comparable barrier properties for gases, it is also possible to which it is insufficient that there are coated film dry solidifications, and coating brittleness increases etc.
Problem.
Inorganic deposition layer (21) of the present invention can either physically or chemically be deposited by well known, specifically
Including such as vacuum thermal evaporation, electron beam evaporation plating (EBPVD), magnetron sputtering, plasma activated chemical vapour deposition (PECVD) etc..
Basement membrane (1) of the present invention be transparent resin film, including selected from ethylene glycol terephthalate film (PET),
Poly (ethylene naphthalate) film (PEN), polypropylene screen (PP), PA membrane (PA), any one in polyethylene film (PE),
But it is not limited to this.Basement membrane is needed using corona and/or plasma treatment technique before plated film or coating to resin film substrate
Surface is activated.By as above handling, resin film surfacing surface can be higher than 36dyn/cm.Do not have for the thickness of basement membrane
It is particularly limited to.But consider that basement membrane thickness is preferably in 5~300 μ ms, more preferably 10 from practicability and processability angle
In~250 μ ms.
The coating method of aqueous high-obstructing coating liquid of the present invention is not particularly limited.As long as according to the viscous of coating fluid
Degree or coating weight etc., use, such as can use print roll coating, intaglio plate from the coating method of well known aqueous coating fluid
Be coated with, scrape roller coating cloth, blade coating, the coating of item seam, extrusion coated, airblade coating, dip coated, spraying etc..
For a further understanding of the present invention, combined with specific embodiments below to aqueous high-obstructing coating liquid provided by the invention
Preparation and in barrier film application be described in detail, protection scope of the present invention is not limited by the following examples.
First to the preparation method of poly-vinyl alcohol solution A, nano silicon oxide dispersion liquid B and silane coupling agent hydrolyzate D into
Row explanation, detailed process include:
The preparation of poly-vinyl alcohol solution A:
50 parts by weight PVA (alcoholysis degree 99%, the degree of polymerization 2400) are added in the water and 50 parts by weight Methanol of 900 parts by weight
In the mixed solvent is sufficiently swollen in 50 DEG C of water-bath first, is then warming up to 95 DEG C under stiring, constant temperature stirring
0.5h obtains the PVA solution A of solid content 5.0% wait be completely dissolved and after cooled to room temperature.
The preparation of nano silicon oxide dispersion liquid B:
360 parts by weight TEOS (purity 99.9%) are added to the in the mixed solvent of 170 parts by weight Methanol, 468 parts by weight water,
And then add 2 parts by weight hydrochloric acid (mass fraction 0.1%) and condensation is hydrolyzed in stirring at normal temperature, about 1h is reacted, thus
To solid content 10.4% nano silicon oxide dispersion liquid B (with SiO2Meter).
The preparation of silane coupling agent hydrolyzate D:
By 30 parts by weight A187 (purity 99.9%), 400 parts by weight of isopropyl alcohol, 569 parts by weight water and 1 parts by weight hydrochloric acid
(mass fraction 0.1%) mixing, stirring at normal temperature 1h is hydrolyzed, obtain the coupling agent of solid content 2.5% hydrolyzate D (with
YR3Si(OH)3Meter).
Embodiment 1
By the graphene aqueous solution of 2.0 parts by weight, (product type " FNG-C100 ", high pass new material system, solid content are
10%) it is added in the nano silicon oxide dispersion liquid B of 68.6 parts by weight, 1h is stirred under normal temperature and pressure keeps its evenly dispersed；Then
The PVA solution A of 19.6 parts by weight is added in above-mentioned dispersion liquid, and then addition while above-mentioned mixed solution is sufficiently stirred
The hydrolyzate D of 9.8 parts by weight coupling agents, it is to be mixed uniformly after, be eventually adding 1.0 parts by weight Delay Action Crosslinker sodium sulphate, 0.5
The levelling agent Silok8000 of the parts by weight and adhesion promoter Silok628 of 0.5 parts by weight, continues the stirring of 0.5h
Thus mixed processing obtains high-obstructing coating liquid TC-1.
Using micro- gravure coater, done in a manner of thickness is 0.3 μm by coated film in the silica of deposition 30nm thickness
Be coated above-mentioned TC-1 coating fluid on 12 μm of PET basement membranes of coating, obtained after 85 DEG C of hot settings inorganic deposition layer with
Obstruct layer stacked structure barrier film NO.1.
Embodiment 2
Other than graphene aqueous solution additive amount is changed to 0.5 parts by weight, other operations are same as Example 1,
Obtain high-obstructing coating liquid TC-2.It using the coating fluid, carries out similarly to Example 1, obtains inorganic deposition layer and barrier
Layer stacked structure barrier film NO.2.
Embodiment 3
Other than graphene aqueous solution additive amount is changed to 20.0 parts by weight, other operations are same as Example 1,
Obtain high-obstructing coating liquid TC-3.It using the coating fluid, carries out similarly to Example 1, obtains inorganic deposition layer and barrier
Layer stacked structure barrier film NO.3.
Embodiment 4
In addition to PVA solution A, nano silicon oxide dispersion liquid B additive amount are changed to 28.8 parts by weight PVA solution A, 57.6 weights
It measures other than part nano silicon oxide dispersion liquid B, other operations are same as Example 1, obtain high-obstructing coating liquid TC-4.Using institute
Coating fluid is stated, is carried out similarly to Example 1, inorganic deposition layer and barrier layer stacked structure barrier film NO.4 are obtained.
Embodiment 5
In addition to PVA solution A, nano silicon oxide dispersion liquid B additive amount are changed to 38.4 parts by weight PVA solution A, 48.0 weights
It measures other than part nano silicon oxide dispersion liquid B, other operations are same as Example 1, obtain high-obstructing coating liquid TC-5.Using institute
Coating fluid is stated, is carried out similarly to Example 1, inorganic deposition layer and barrier layer stacked structure barrier film NO.5 are obtained.
Embodiment 6
In addition to by graphene dispersion medium replace with ethylene glycol (product type " FNG-D111 ", high pass new material system, admittedly contain
Amount is 10%) outside, other operations are same as Example 1, obtain high-obstructing coating liquid TC-6.Using the coating fluid, with reality
It applies example 1 equally to carry out, obtains inorganic deposition layer and barrier layer stacked structure barrier film NO.6.
Comparative example 1
In addition to not having addition graphene aqueous solution, other operations are consistent with embodiment 1, obtain high-obstructing coating liquid TC-
7.It using the coating fluid, carries out similarly to Example 1, obtains inorganic deposition layer and barrier layer stacked structure barrier film
NO.7。
Comparative example 2
In addition to the intrinsic graphene in graphene aqueous solution is replaced with graphene oxide, other operation with embodiment 1
Unanimously, high-obstructing coating liquid TC-8 is obtained.Using the coating fluid, carry out similarly to Example 1, obtain inorganic deposition layer with
Obstruct layer stacked structure barrier film NO.8.
Comparative example 3
Nano silica powder in addition to nano silicon oxide dispersion liquid B to be replaced with to 7.13 parts by weight, other operation with
Embodiment 1 is consistent, obtains high-obstructing coating liquid TC-9.Using the coating fluid, carries out similarly to Example 1, obtain inorganic matter
Sedimentary and barrier layer stacked structure barrier film NO.9.
Respectively to the stability of high-obstructing coating liquid used in above embodiments and comparative example, prepared barrier film
It blocks water and is tested with oxygen resistance, concrete outcome is detailed in following table:
1. embodiment and comparative example barrier film performance of table summarizes
Using aqueous high-obstructing coating liquid of the invention as barrier in one side Examples 1 to 6 it can be seen from upper table
When layer is used cooperatively with sedimentary, oxygen permeability and moisture-vapor transmission are lower, can realize respectively less than 0.5cc/m2.d and it is small
In 1.0g/m2.d requirement.Surface can be above 50dyn/cm simultaneously, show excellent surface printing performance.
Comparative example 1 is the situation that graphene aqueous solution is not added in aqueous coating fluid, and comparative example 2 is by the sheet in dispersion liquid
Sign graphene replaces with the situation of graphene oxide, and comparative example 3 is that nano silicon oxide dispersion liquid is replaced with nano oxidized silicon powder
The situation of body, their oxygen permeability and moisture-vapor transmission are above Examples 1 to 6, and oxygen transmission rate is above 0.5cc/m2.d,
And permeability rate is also in 1.0g/m2.d more than.
For industrial applicibility angle, it is prepared into using the present invention containing the high-obstructing coating liquid for the graphene that is uniformly dispersed
The gas barrier film arrived has excellent water oxygen barrier property, while packages printing performance is preferable, can be widely applicable for curing
Medicine, food, package of electronic products way.
The method of the performance test of above embodiments and comparative example:
1, theoretical solid content
With the quality of the water-soluble polymer of addition, the quality of nano-oxide, the quality of graphene and coupling agent quality
Summation and coating fluid gross mass ratio calculation.
2, coating fluid pH value is tested
It is tested according to standard GB/T/T 6368-2008 " the measurement potentiometry of aqueous surfactant solution pH value ".
3, surface can measure
A membrane surface energy is tested using dyne pen, test according to GB/T 14216-2008 " plastic foil and piece wetting tension
Measurement ".
4, thickness of coating measures
According to national standard, " the optical functional film Surface hardened layer film cures layer thickness measurement side GB/T 33051-2016
Method " pass through refraction reflection interference spectrum principle measurement.
5, coating thickness determination
According to " the optical functional film Surface hardened layer film cures layer thickness measurement side standard GB/T/T 33051-2016
Method ", pass through refraction reflection interference spectrum principle measurement.
6, coating adhesion measures
Adhesive force is tested using baige method, " furniture surface paint film physicochemical property tests the 4th to GB/T 4893.4-2013
Point: adhesive force cross-cut measuring method ".
7, air blocking thin film oxygen transmission rate measures
Test is according to standard GB/T/T 19789-2005 " packaging material plastic film and the test of thin slice permeability
Coulomb meter detection method ".
8, air blocking thin film permeability rate measures
According to standard GB/T/T 21529-2008, " measurement of plastic film and thin slice moisture-vapor transmission is electrolysed sensing
Device method " measurement.
Claims (9)
1. a kind of aqueous high-obstructing coating liquid, which is characterized in that the coating fluid is made using the raw material of following component:
2. aqueous high-obstructing coating liquid according to claim 1, which is characterized in that the nano-oxide is by metal alkoxide
It is prepared under acid catalysed conditions by hydrolysis-condensation using sol-gel method.
3. aqueous high-obstructing coating liquid according to claim 2, which is characterized in that the metal alkoxide is selected from tetramethoxy
Silane, tetraethoxysilane, aluminium methoxide, aluminium ethoxide, aluminium isopropoxide, three n-butylaluminums, titanium tetramethoxide, four
At least one of ethanolato-titanium, tetraisopropoxy titanium, tetra-n-butyl titanium, tetraethoxy zirconium or zirconium tetraisopropoxide.
4. aqueous high-obstructing coating liquid according to claim 1, which is characterized in that the hydroxyl water-soluble polymer choosing
From one of polyvinyl alcohol, starch, cellulose, chitosan or a variety of；The degree of polymerization of the hydroxyl water-soluble polymer is
500~3000, alcoholysis degree is 80%~99.99%.
5. aqueous high-obstructing coating liquid according to claim 1, which is characterized in that the graphene be intrinsic graphene,
At least one of graphene oxide or sulfonated graphene, and the removing of the graphene is having a size of 0.5~8nm, lamella ruler
Very little is 3~70 μm.
6. aqueous high-obstructing coating liquid according to claim 1, which is characterized in that the organosiloxane class coupling agent
General structure is YR3Si(OR2)3, wherein R2For methyl or ethyl, R3For the alkyl chain with 0-4 carbon, Y is vinyl, epoxy
At least one of base, glycidoxy, methacryloxy, urea groups, amino or isocyanate functional group.
7. a kind of method for preparing the aqueous high-obstructing coating liquid as described in any one of claim 1-6 right, which is characterized in that
Preparation carries out as follows:
1) hydrolyzate of sol-gel method preparing metal alkoxide under acid catalysed conditions is advanced with, stirs 40 under normal temperature and pressure
~60min obtains nano-oxide solution after standing；
2) graphene is added in Xiang Suoshu nano-oxide solution, is persistently stirred under normal temperature and pressure, stirring rate is 600~800
Turn/min, stir 1~2h, stands and obtain the graphene dispersing solution of load nanometer oxide particle；
3) stirring rate is down to 300~400 turns/min, is slowly added to water-soluble poly into the graphene dispersing solution in step 2
Polymer solution continues 20~40min of stirring while organosiloxane class coupling agent hydrolyzate is added, under normal temperature and pressure stir 1~
2h is stored at room temperature, and obtains the aqueous high-obstructing coating liquid.
8. preparation method according to claim 7, which is characterized in that the aqueous high-obstructing coating liquid is in inorganic deposition layer
(21) surface coating is used as barrier layer (22), will include the stacking knot including the inorganic deposition layer (21) and barrier layer (22)
Structure is set as a repetitive unit, settable 1 or more repetitive unit.
9. preparation method according to claim 8, which is characterized in that the liquid measure being coated with should make the film as dry coating
Thickness is 0.05~3 μm；The base membrane layer (1) with a thickness of 5~300 μm, inorganic deposition layer (21) is with a thickness of 10~100nm.
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