CN103692743B - A kind of graphene composite film material and preparation method thereof - Google Patents
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Abstract
The present invention relates to a kind of graphene composite film material and preparation method thereof, described graphene composite film material is: between two-layer macromolecule transparent membrane, be provided with at least graphene layer of one deck, between described macromolecule transparent membrane and graphene layer, be connected by Photocurable adhesive or hot setting adhesive between adjacent graphene layer. The present invention overcome the shortcoming of in the past preparing in Graphene barrier composite performance, prepared the nano compound film of high barrier, high permeability. The Graphene macromolecule composite film material that the present invention is prepared, combination of flexibility and high transparent, the transmitance of visible region can reach more than 85%. In addition, this laminated film has excellent barrier property to steam and oxygen, has solved prior art and has prepared the not good problem of graphene/polymer composite material water oxygen barrier performance, can meet OLED device package, the application demands such as medicine, packaging for foodstuff, have very large practical and popularizing value.
Description
Technical field
The present invention relates to a kind of graphene composite film material and preparation method thereof, belong to composite Materials DesignPreparing technical field.
Background technology
Organic Light Emitting Diode (organiclightemittingdiode, OLED) has spontaneousThe advantage such as light, wide viewing angle, super fast response, high efficiency, low-voltage, device are ultra-thin and in large size, quiltThink to have the display and lighting technology of future generation of application prospect. Flexibility is sending out of following electronic deviceExhibition direction is also the distinctive advantage of OLED. It is good that the organic material that OLED uses has itselfFlexibility, is produced on the flexible transparent plastic base material of shock-resistant, frivolous cheapness, just can realizeFlexible device is manufactured.
Can be used to do the transparent plastic film of flexible substrate, as polyethylene (PE), poly terephthalic acidGlycol ester (PET), polyethylene naphthalate (PEN) etc. are the large of master by linear structureStrand composition, interchain is model ylid bloom action power, adhesion intensity and compact structure degree are far below inorganicAnd metal material, there is larger free volume. This multilevel hierarchy feature has given polymer some spiesSome performances, as light weight, pliable and tough, easy processing etc., but also greatly reduce it to steam, oxygen simultaneouslyDeng the barrier property of gas. Research shows, the steam and the oxygen that penetrate into device inside are impactsThe principal element in OLED life-span. The cathodic metal of low work function, as aluminium, magnesium, calcium etc., and luminous meritErgosphere easily reacts with steam and oxygen that infiltration is come in, reduces luminous efficiency, forms stain, finalCause component failure.
For the life-span that makes OLED device reaches real requirement, conventionally require the steam of device package materialInfiltration rate (WVTR) is less than 10-6g/(m224hr), oxygen infiltration rate (OTR) is less than10-5cc/(m224hr). And the WVTR of macromolecular material and OTR are conventionally respectively 10-1～40g/(m224hr) He 10-2～102cc/(m224hr) in scope. Therefore, use in pliabilityGood transparent plastic film, as OLED substrate, must increase considerably its gas barrier property. ProtectingDemonstrate,prove under the prerequisite of certain transparency and improve barrier property, a kind of feasible method is by Graphene and macromoleculeMaterial cladding. Graphene is a kind of carbon nanomaterial of two dimension, by SP2Hydridization carbon atom hexagon keyed jointingForm, on each carbon atom, remain single electron 2P track and overlap, form the large π key of delocalization conjugation.Single-layer graphene is greater than 97% to visible light transmissivity, and thickness is only 0.34nm, and that width can reach is several micro-Even tens of centimetres, rice. This ultimate attainment depth-width ratio, adds interior fine and close π bonding electron cloud above, Yi JigaoLight transmittance, makes Graphene become optimal nano-filled barrier material.
At present, the method for utilizing Graphene to improve polymer barrier property is mainly taking graphite as starting materialThe graphene oxide (GO) obtaining or redox graphene (RGO) they are Modification material, by means ofSolvent and mixed with polymers, then by curtain coating, mold pressing, build, the forming method such as blowing prepares compoundFilm. For example: application publication number is CN102115566A, patent name is " high barrier oxidation stoneThe preparation method of China ink alkene and polymer nanocomposite membrane ", a kind of graphene oxide with high barrier/poly-is disclosedThe preparation method of compound nano composite material: GO is scattered in solvent under ultrasonic dispersion condition to shapeBecome GO colloid. Then add polymer, ultrasonicly add dissolve polymer under mechanical agitation condition, remove gasAfter bubble, adopt curtain coating or blowing to obtain GO/ polymer composite film; Application publication number is CN101812194A, patent name " a kind of graphene-based barrier composite material and preparation method thereof ", providesA kind of function modified RGO and polyolefin polymer complex method. Specifically first with coupling agent, GO is enteredRow function of surface is modified, then by the GO reduction after modifying. RGO will be modified by means of solvent dispersedIn polyolefin solution, under initator effect, crosslinked bonding obtains nano composite material; Application publication numberFor CN102173145A, patent name is " a kind of preparation method of oxidized graphene coated film ", public affairsOpen a kind of simple Graphene/thin polymer film complex method. Concrete steps are first by graphene oxideUltrasonic processing is distributed in water and obtains even soliquid, by the mode of spraying or roll-in, GO is coated withOverlay on general purpose film surface, after being dried, apply again several times, finally cover one deck general purpose film, obtain GOCoated film. Similarly also have: application publication number is CN10327368A, and patent name is " machineryThe method of graphene oxide/white carbon/rubber nano composite material is prepared in blend "; Application publication number is CN102532629A, patent name is the " system of graphene oxide/rubber nano composite material of peeling off completelyPreparation Method "; Application publication number is CN102827386A, and patent name is " a kind of polyether-ether-ketone/oxidationThe preparation method of graphene nano laminated film "; Application publication number is CN103265714A, proprietary termBe called " a kind of preparation method of polyvinyl alcohol/graphene composite thin film "; Application publication number is CN102604175, patent name is for " to prepare the side of graphene oxide/white carbon/rubber nano composite materialMethod ". Difference is polymeric system difference or the GO/ polymer composite forming method difference of selecting.
Above-mentioned open method has been included multiple polymers, has contained multiple GO or RGO/ polymer is combined intoType technology, but the water oxygen transmission rates approximately 10 of prepared composite-1～10-2Magnitude, is far from reachingTo the requirement of OLED encapsulating material.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of graphene composite film material and preparation thereofMethod, using large area single-layer graphene as gas barrier functional layer, macromolecular material is as transparent supportLayer, is mutually compounded to form bi-material by means of fluid binder and has high transparent and superior in gas resistanceEvery the composite of property.
The technical scheme that the present invention solves the problems of the technologies described above is as follows: a kind of graphene composite film material,Between two-layer macromolecule transparent membrane, be provided with at least graphene layer of one deck, described macromolecule transparent membraneAnd between graphene layer, between adjacent graphene layer by Photocurable adhesive or hot setting adhesive phaseConnect.
On the basis of technique scheme, the present invention can also do following improvement.
Further, described macromolecule transparent membrane is polypropylene (PP), polyethylene (PE), poly-to benzene twoFormic acid glycol ester (PET), polybutylene terephthalate (PBT) (PBT), PEN (PEN)In one.
Further, described graphene layer is the large area mono-layer graphite with vapour deposition process (CVD) growthAlkene. CVD (ChemicalVaporDeposition, chemical vapour deposition (CVD)), refers to containing formation filmThe gaseous reactant of element or the steam of liquid reactants and react required other gas and introduce reative cell,The process of substrate surface generation chemical reaction film former. The present invention's graphene layer used be thickness onlyThe large area single-layer graphene of 0.34nm, length and width reach tens of centimetres, the ratio of long or wide and thickness > 107。
Further, described Photocurable adhesive comprises the material of following weight portion: light-cured resin 50～80Part, 5～35 parts of activated monomers, 0.5～5 part of light trigger.
Further, described light-cured resin is urethane acrylate or methacrylate, and its soft section isPolybutadiene polyol, polyisoprene polyalcohol, hydrogenated butadiene polymer polyalcohol, the poly-isoamyl two of hydrogenationOne or more in alkene polyalcohol. Soft section, be also soft chain segment, easily change allosteric polymer segment.As contained carbon-to-carbon (C-C) strand, contain isolated double bond (C=C) and containing heteroatomic singly-bound [carbon-oxygen (C-O), carbon-nitrogen (C-N) and silicon-oxygen (Si-O) etc.] segment etc. be soft chain segment.
Further, described activated monomer is by two parts component, and a part is maleic anhydride and methacrylic acidA kind of formation in hydroxyl ethyl ester, hydroxy propyl methacrylate, hydroxy-ethyl acrylate, hydroxypropyl acrylateTransparent and homogeneous mixture, another part is 2(2-ethoxy ethoxy) ethyl propylene acid esters, acrylic acidNorborneol ester, benzene oxygen ethyl propylene acid esters, lauryl methacrylate, isodecyl methacrylate, thirdThe mixing of one or more in olefin(e) acid lauryl, isodecyl acrylate.
Further, described light trigger is 2,4,6-trimethylbenzoyl-diphenyl phosphate oxidation.
Further, described hot setting adhesive comprises the material of following percetage by weight: multi-thiol 1～30%, conjugated diene prepolymer 50～95%, free radical thermal initiator 1～5%, functional monomer 1～5%.
Further, described multi-thiol contains 2～6 uncle's sulfydryls or secondary sulfydryl.
Further, described multi-thiol is Thiodiglycol, glycol dimercaptosuccinate, trihydroxy methylPropane three-3 mercaptan propionic esters, pentaerythrite four-3 mercaptan propionic esters, trimethylolpropane tris-3 mercaptanThe mixing of one or more in butyrate, pentaerythrite four-3 mercaptan butyrates.
Further, described conjugated diene prepolymer is polybutadiene or polyisoprene, or poly-fourth twoAlkene or polyisoprene and acrylonitrile or cinnamic block copolymer; The number of described conjugated diene prepolymerAverage molecular weight is 1000～8000. Number-average molecular weight (Number-averageMolecularWeight):Polymer is the homology compositions of mixtures that do not waited by the identical and degree of polymerization of chemical composition, by molecular chain lengthSpend different high polymers and mix composition. Conventionally adopt average molecular weight characterization bulk of molecule. Press moleculeNumber statistical is average, is called number-average molecular weight, and symbol is (MN).
Further, described free radical thermal initiator is azo-bis-isobutyl cyanide, isopropyl benzene hydroperoxide, peroxideThe mixing of one or more in change benzoyl, cumyl peroxide, peroxidized t-butyl perbenzoate.
Further, described functional monomer is maleic anhydride and hydroxyethyl methacrylate, acrylic acid hydroxyl secondThe monoester derivates of a kind of formation in ester, hydroxypropyl acrylate.
Cure adhesive of the present invention (Photocurable adhesive or hot setting adhesive) material of main partHave hydrophobicity and flexibility concurrently, curing shrinkage internal stress is little. In addition the radical initiator adding in formula, andMaleic acid monoester derivates can react with Graphene pi-pi bond in solidification process, increases interface combinationIntensity.
Another technical scheme that the present invention solves the problems of the technologies described above is as follows: a kind of graphene composite film materialThe preparation method of material, comprises the following steps:
(1) preparation of cure adhesive: Photocurable adhesive, the light that is 50～80 parts by weight portion is consolidatedChange resin, the activated monomer of 5～35 parts, the light trigger of 0.5～5 part mix, and stirAfter to remove bubble for subsequent use; Or, multi-thiol that hot setting adhesive is 1～30% by percetage by weight,50～95% conjugated diene prepolymer, 1～5% free radical thermal initiator, 1～5% functional monomerMix, after stirring, remove bubble for subsequent use;
(2) preparation of graphene layer: with the large area single-layer graphene of vapour deposition process growth;
(3) bonding between graphene layer: the diaphragm of graphene layer one side is thrown off, be coated with lighting solidChange adhesive or hot setting adhesive, then another sheet graphene layer one side diaphragm is thrown off, and by thisSide pressurization is close on the cure adhesive of coating, guarantees without after bubble cure adhesive layer; According to upperThe method of stating is bonded together all graphene layers; If graphene layer only has one deck, skip this step;
(4) graphene layer and macromolecule transparent membrane is bonding: by bonding good graphene layer orThe upper surface of single-layer graphene layer and the diaphragm of lower surface are thrown off, coating Photocurable adhesive or heat cureAdhesive, pressurizes the macromolecule transparent membrane of the activated processing in surface to be close to the cure adhesive of coatingUpper, guarantee that without after bubble cure adhesive layer finally obtains described graphene composite film material.
On the basis of technique scheme, the present invention can also do following improvement.
Further, in described step (3) and step (4), if adopt Photocurable adhesive, solidify stickyThe actual conditions of mixture layer is 1000W medium pressure mercury lamp, 20cm lamp distance, time for exposure 10～30s; If adoptWith hot setting adhesive, the actual conditions of cure adhesive layer is for being first heated to 60～80 DEG C of curing 5hr,Be heated to again 75～110 DEG C and solidify 2～3hr.
Further, in described step (4), the mode of macromolecule transparent membrane surface activation process is coronaOr Cement Composite Treated by Plasma.
The invention has the beneficial effects as follows: the present invention has overcome and prepares Graphene barrier composite performance in the pastOn shortcoming, prepared the nano compound film of high barrier, high permeability. The present invention is preparedGraphene macromolecule composite film material, combination of flexibility and high transparent, the transmitance of visible region canReach more than 85%. In addition, this laminated film has excellent barrier property to steam and oxygen, has solved existingThere is technology to prepare the not good problem of graphene/polymer composite material water oxygen barrier performance, can meet OLEDDevice package, the application demands such as medicine, packaging for foodstuff, have very large practical and popularizing value.
Detailed description of the invention
Below principle of the present invention and feature are described, example is only for explaining the present invention, andNon-for limiting scope of the present invention.
Embodiment 1
(1) Photocurable adhesive preparation: add successively maleic anhydride 1g, methyl-prop to 500mL containerOlefin(e) acid hydroxyl ethyl ester 3g, 2,4,6-trimethylbenzoyl-diphenyl phosphate oxidation 0.5g, 2-hydroxyl-2-Methyl isophthalic acid-phenyl-1-acetone 1g, methacrylic acid norborneol ester 10g, lauryl methacrylate14.5g, stirs and makes to add polyurethane acrylate resin (soft section is polybutadiene) after dissolution of solid again70g, removes bubble after stirring for subsequent use;
(2) with the large area single-layer graphene of vapour deposition process growth, get one deck for subsequent use;
(3) diaphragm of the upper surface of single-layer graphene layer and lower surface is thrown off, coating photocuring is stickyMixture, pressurizes the macromolecule transparent membrane of the activated processing in surface to be close to the Photocurable adhesive of coatingUpper, guarantee without after bubble, cure adhesive layer, wherein macromolecule transparent membrane used is transparent PP film,Photocurable adhesive condition of cure is 1000W medium pressure mercury lamp, 20cm lamp distance, time for exposure 10s.
Finally obtain described graphene composite film material, its structure is: PP/ Photocurable adhesive/graphiteAlkene/Photocurable adhesive/PP, the mean transmissivity of visible region is 92%, water vapor transmittance 4.9 × 10-5g/(m224hr), OTR oxygen transmission rate is 6.3 × 10-3cc/(m2·24hr)。
Embodiment 2
(1) Photocurable adhesive preparation: add successively maleic anhydride 3.5g, propylene to 500mL containerAcid hydroxyl ethyl ester 2g, hydroxyethyl methacrylate 3g, the oxidation of 2,4,6-trimethylbenzoyl-diphenylPhosphorus 0.5g, 2-hydroxyl-2-cyclohexyl-1-phenyl-1-acetone 1g, benzene oxygen ethyl propylene acid esters 8g, propyleneAcid isodecyl ester 22g, stirs and makes to add polyurethane acrylate resin after dissolution of solid again (soft section is hydrogenationPolybutadiene) 60g, after stirring, remove bubble for subsequent use;
(2) with the large area single-layer graphene of vapour deposition process growth, get two-layer for subsequent use;
(3) first the diaphragm of graphene layer one side is thrown off, coating Photocurable adhesive, then by anotherSheet graphene layer one side diaphragm is thrown off, and this side pressurization is close to the Photocurable adhesive of coatingUpper, guarantee without after bubble, cure adhesive layer, wherein Photocurable adhesive condition of cure is in 1000WPressure mercury lamp, 20cm lamp distance, time for exposure 15s;
(4) the upper surface of bonding good graphene layer and the diaphragm of lower surface are thrown off to coatingPhotocurable adhesive, the light that the macromolecule transparent membrane pressurization of the activated processing in surface is close to coating is solidChange on adhesive, guarantee without after bubble, cure adhesive layer, wherein macromolecule transparent membrane used isBright PP film, Photocurable adhesive condition of cure is identical with upper step.
Finally obtain described graphene composite film material, its structure is: PE/ Photocurable adhesive/graphiteAlkene/Photocurable adhesive/Graphene/Photocurable adhesive/PE, the mean transmissivity of visible region is 91%,Water vapor transmittance 3.8 × 10-5g/(m224hr), OTR oxygen transmission rate is 8.2 × 10-3cc/(m2·24hr)。
Embodiment 3
(1) Photocurable adhesive preparation: add successively maleic anhydride 0.5g, methyl to 500mL containerHydroxy-ethyl acrylate 3g, 2,4,6-trimethylbenzoyl-diphenyl phosphate oxidation 1g, 2-hydroxyl-2-Cyclohexyl-1-phenyl-1-acetone 1g, benzene oxygen ethyl propylene acid esters 18g, lauryl methacrylate26.5g, 2(2-ethoxy ethoxy) ethyl propylene acid esters 5g, stir make to add again after dissolution of solid poly-Chlorinated polyethylene (soft section is polyisoprene and polybutadiene) 45g, removes after stirringBubble is for subsequent use;
(2) with the large area single-layer graphene of vapour deposition process growth, get three layers for subsequent use;
(3) first the diaphragm of graphene layer one side is thrown off, coating Photocurable adhesive, then by anotherSheet graphene layer one side diaphragm is thrown off, and this side pressurization is close to the Photocurable adhesive of coatingUpper, guarantee without after bubble, cure adhesive layer, wherein Photocurable adhesive condition of cure is in 1000WPressure mercury lamp, 20cm lamp distance, time for exposure 30s; According to the method described above the graphene layer of three layers is bonded inTogether;
(4) the upper surface of bonding good graphene layer and the diaphragm of lower surface are thrown off to coatingPhotocurable adhesive, the light that the macromolecule transparent membrane pressurization of the activated processing in surface is close to coating is solidChange on adhesive, guarantee without after bubble, cure adhesive layer, wherein macromolecule transparent membrane used isBright pen film, Photocurable adhesive condition of cure is identical with upper step.
Finally obtain described graphene composite film material, its structure is: PEN/ Photocurable adhesive/stoneChina ink alkene/Photocurable adhesive/Graphene/Photocurable adhesive/Graphene/Photocurable adhesive/PEN, canThe mean transmissivity in Jian Guang district is 86%, water vapor transmittance 2.7 × 10-6g/(m224hr), oxygen sees throughRate is 2.3 × 10-5cc/(m2·24hr)。
Embodiment 4
(1) Photocurable adhesive preparation: add successively maleic anhydride 0.5g, methyl to 500mL containerHydroxy-ethyl acrylate 3g, 2,4,6-trimethylbenzoyl-diphenyl phosphate oxidation 1g, 2-hydroxyl-2-Methyl isophthalic acid-phenyl-1-acetone 1g, Isooctyl acrylate monomer 10g, lauryl methacrylate 20g, 2(2-Ethoxy ethoxy) ethyl propylene acid esters 5g, stirs and makes to add urethane acrylate after dissolution of solid againResin (soft section is polyisoprene) 66g, removes bubble after stirring for subsequent use;
(2) with the large area single-layer graphene of vapour deposition process growth, get two-layer for subsequent use;
(3) first the diaphragm of graphene layer one side is thrown off, coating Photocurable adhesive, then by anotherSheet graphene layer one side diaphragm is thrown off, and this side pressurization is close to the Photocurable adhesive of coatingUpper, guarantee without after bubble, cure adhesive layer, wherein Photocurable adhesive condition of cure is in 1000WPressure mercury lamp, 20cm lamp distance, time for exposure 20s;
(4) the upper surface of bonding good graphene layer and the diaphragm of lower surface are thrown off to coatingPhotocurable adhesive, the light that the macromolecule transparent membrane pressurization of the activated processing in surface is close to coating is solidChange on adhesive, guarantee without after bubble, cure adhesive layer, wherein macromolecule transparent membrane used isBright PBT film, Photocurable adhesive condition of cure is identical with upper step.
Finally obtain described graphene composite film material, its structure is: PBT/ Photocurable adhesive/stoneChina ink alkene/Photocurable adhesive/Graphene/Photocurable adhesive/PBT, the mean transmissivity of visible region is88%, water vapor transmittance 5.8 × 10-5g/(m224hr), OTR oxygen transmission rate be 3.5 ×10-4cc/(m2·24hr)。
Embodiment 5
(1) hot setting adhesive preparation: add successively maleic anhydride 0.5g, methyl to 500mL containerHydroxy-ethyl acrylate 2g, dibenzoyl peroxide 2g, methacrylic acid norborneol ester 5g, the equal molecule of numberAmount is 3000 polybutadiene 96g, removes bubble for subsequent use after stirring;
(2) with the large area single-layer graphene of vapour deposition process growth, get two-layer for subsequent use;
(3) first the diaphragm of graphene layer one side is thrown off, coated heat cure adhesive, then by anotherSheet graphene layer one side diaphragm is thrown off, and this side pressurization is close to the hot setting adhesive of coatingUpper, guarantee without after bubble, cure adhesive layer, wherein hot setting adhesive condition of cure is for being first heated to80 DEG C of curing 5hr, then be heated to 110 DEG C of curing 2hr;
(4) the upper surface of bonding good graphene layer and the diaphragm of lower surface are thrown off to coatingHot setting adhesive, is close to the macromolecule transparent membrane pressurization of the activated processing in surface the thermosetting of coatingChange on adhesive, guarantee without after bubble, cure adhesive layer, wherein macromolecule transparent membrane used isBright pen film, hot setting adhesive condition of cure is identical with upper step.
Finally obtain described graphene composite film material, its structure is: PEN/ hot setting adhesive/stoneChina ink alkene/hot setting adhesive/Graphene/hot setting adhesive/PEN, the mean transmissivity of visible region is83%, water vapor transmittance 1.3 × 10-7g/(m224hr), OTR oxygen transmission rate be 8.1 ×10-5cc/(m2·24hr)。
Embodiment 6
(1) hot setting adhesive preparation: add successively pentaerythrite four-3-sulfydryl fourth to 500mL containerAcid esters 7g, azodiisobutyronitrile 2g, dibenzoyl peroxide 1g, methacrylic acid norborneol ester 10g,After dissolution of solid, adding number-average molecular weight is 4700 hycar 98g, stirs allAfter even, remove bubble for subsequent use;
(2) with the large area single-layer graphene of vapour deposition process growth, get two-layer for subsequent use;
(3) first the diaphragm of graphene layer one side is thrown off, coated heat cure adhesive, then by anotherSheet graphene layer one side diaphragm is thrown off, and this side pressurization is close to the hot setting adhesive of coatingUpper, guarantee without after bubble, cure adhesive layer, wherein hot setting adhesive condition of cure is for being first heated to60 DEG C of curing 5hr, then be heated to 75 DEG C of curing 3hr;
(4) the upper surface of bonding good graphene layer and the diaphragm of lower surface are thrown off to coatingHot setting adhesive, is close to the macromolecule transparent membrane pressurization of the activated processing in surface the thermosetting of coatingChange on adhesive, guarantee without after bubble, cure adhesive layer, wherein macromolecule transparent membrane used isBright PET film, hot setting adhesive condition of cure is identical with upper step.
Finally obtain described graphene composite film material, its structure is: PET/ hot setting adhesive/stoneChina ink alkene/hot setting adhesive/Graphene/hot setting adhesive/PET, the mean transmissivity of visible region is85%, water vapor transmittance 4.3 × 10-7g/(m224hr), OTR oxygen transmission rate be 3.6 ×10-5cc/(m2·24hr)。
Embodiment 7
(1) hot setting adhesive preparation: add successively maleic anhydride 1g, methyl-prop to 500mL containerOlefin(e) acid hydroxyl ethyl ester 3g, azodiisobutyronitrile 2g, dibenzoyl peroxide 1g, methacrylic acid norborneolEster 10g adds trimethylolpropane tris-3-sulfydryl butyrate 6g, number-average molecular weight after dissolution of solidBe isoprene-styrol copolymer 98g of 3500, after stirring, remove bubble for subsequent use;
(2) with the large area single-layer graphene of vapour deposition process growth, get three layers for subsequent use;
(3) first the diaphragm of graphene layer one side is thrown off, coated heat cure adhesive, then by anotherSheet graphene layer one side diaphragm is thrown off, and this side pressurization is close to the hot setting adhesive of coatingUpper, guarantee without after bubble, cure adhesive layer, wherein hot setting adhesive condition of cure is for being first heated to70 DEG C of curing 5hr, then be heated to 95 DEG C of curing 3hr; According to the method described above that the graphene layer of three layers is stickyBe combined;
(4) the upper surface of bonding good graphene layer and the diaphragm of lower surface are thrown off to coatingHot setting adhesive, is close to the macromolecule transparent membrane pressurization of the activated processing in surface the thermosetting of coatingChange on adhesive, guarantee without after bubble, cure adhesive layer, wherein macromolecule transparent membrane used isBright pen film, hot setting adhesive condition of cure is identical with upper step.
Finally obtain described graphene composite film material, its structure is: PEN/ hot setting adhesive/stoneChina ink alkene/hot setting adhesive/Graphene/hot setting adhesive/Graphene/hot setting adhesive/PEN, canThe mean transmissivity in Jian Guang district is 83%, water vapor transmittance 2.6 × 10-7g/(m224hr), oxygen sees throughRate is 8.8 × 10-5cc/(m2·24hr)。
The foregoing is only preferred embodiment of the present invention, in order to limit the present invention, not all in the present inventionSpirit and principle within, any amendment of doing, be equal to replacement, improvement etc., all should be included in thisWithin bright protection domain.
Claims (13)
1. a graphene composite film material, is characterized in that, two-layer macromolecule transparent membrane itBetween be provided with at least graphene layer of one deck, between described macromolecule transparent membrane and graphene layer, adjacentBetween graphene layer, be connected by Photocurable adhesive or hot setting adhesive; Described Photocurable adhesive bagDraw together the material of following weight portion: 50～80 parts of light-cured resins, 5～35 parts of activated monomers, light-initiated0.5～5 part of agent; Described activated monomer is made up of two parts, and a part is maleic anhydride and metering systemOne in acid hydroxyl ethyl ester, hydroxy propyl methacrylate, hydroxy-ethyl acrylate, hydroxypropyl acrylate formsTransparent and homogeneous mixture, another part is 2 (2-ethoxy ethoxy) ethyl propylene acid esters, propyleneAcid norborneol ester, benzene oxygen ethyl propylene acid esters, lauryl methacrylate, isodecyl methacrylate,The mixing of one or more in lauryl acrylate, isodecyl acrylate; Described hot setting adhesive bagDraw together the material of following percetage by weight: multi-thiol 1～30%, conjugated diene prepolymer 50～95%, fromBy base thermal initiator 1～5%, functional monomer 1～5%.
2. graphene composite film material according to claim 1, is characterized in that described high scoreSub-transparent membrane is polypropylene, polyethylene, PETG, poly terephthalic acid fourth twoOne in alcohol ester or PEN.
3. graphene composite film material according to claim 1, is characterized in that described graphiteAlkene layer is the large area single-layer graphene with vapour deposition process growth.
4. graphene composite film material according to claim 1, is characterized in that, described light is solidChange resin is urethane acrylate, its soft section be polybutadiene polyol, polyisoprene polyalcohol,One or more in hydrogenated butadiene polymer polyalcohol, hydrogenated polyisoprene polyalcohol.
5. graphene composite film material according to claim 1, is characterized in that, described light drawsSending out agent is 2,4,6-trimethylbenzoyl-diphenyl phosphine oxide.
6. graphene composite film material according to claim 1, is characterized in that, described polynaryMercaptan contains 2～6 uncle's sulfydryls or secondary sulfydryl.
7. graphene composite film material according to claim 1, is characterized in that, described polynaryMercaptan be Thiodiglycol, glycol dimercaptosuccinate, trimethylolpropane tris-3 mercaptan propionic ester,Pentaerythrite four-3 mercaptan propionic esters, trimethylolpropane tris-3 mercaptan butyrate, pentaerythrite four-3The mixing of one or more in mercaptan butyrate.
8. graphene composite film material according to claim 1, is characterized in that described conjugationDiene prepolymer is polybutadiene or polyisoprene, or polybutadiene or polyisoprene and propyleneNitrile or cinnamic block copolymer; The number-average molecular weight of described conjugated diene prepolymer is 1000～8000。
9. graphene composite film material according to claim 1, is characterized in that described freedomBase thermal initiator is that azo-bis-isobutyl cyanide, isopropyl benzene hydroperoxide, benzoyl peroxide, peroxidating two are differentThe mixing of one or more in propyl benzene, peroxidized t-butyl perbenzoate.
10. graphene composite film material according to claim 1, is characterized in that described functionProperty monomer is in maleic anhydride and hydroxyethyl methacrylate, hydroxy-ethyl acrylate, hydroxypropyl acrylateA kind of monoester derivates of formation.
The preparation method of 11. 1 kinds of graphene composite film materials, is characterized in that, comprises the following steps:
(1) preparation of cure adhesive: Photocurable adhesive, the light that is 50～80 parts by weight portion is consolidatedChange resin, the activated monomer of 5～35 parts, the light trigger of 0.5～5 part mix, and stirAfter to remove bubble for subsequent use; Or, multi-thiol that hot setting adhesive is 1～30% by percetage by weight,50～95% conjugated diene prepolymer, 1～5% free radical thermal initiator, 1～5% functional monomerMix, after stirring, remove bubble for subsequent use;
(2) preparation of graphene layer: with the large area single-layer graphene of vapour deposition process growth;
(3) bonding between graphene layer: the diaphragm of graphene layer one side is thrown off, be coated with lighting solidChange adhesive or hot setting adhesive, then another sheet graphene layer one side diaphragm is thrown off, and by thisSide pressurization is close on the cure adhesive of coating, guarantees without after bubble cure adhesive layer; According to upperThe method of stating is bonded together all graphene layers; If graphene layer only has one deck, skip this step;
(4) graphene layer and macromolecule transparent membrane is bonding: by bonding good graphene layer orThe upper surface of single-layer graphene layer and the diaphragm of lower surface are thrown off, coating Photocurable adhesive or heat cureAdhesive, pressurizes the macromolecule transparent membrane of the activated processing in surface to be close to the cure adhesive of coatingUpper, guarantee that without after bubble cure adhesive layer finally obtains described graphene composite film material.
12. according to the preparation method of graphene composite film material described in claim 11, and its feature existsIn, in described step (3) and step (4), if adopt Photocurable adhesive, cure adhesive layerActual conditions is 1000W medium pressure mercury lamp, 20cm lamp distance, time for exposure 10～30s; If employing heat cureAdhesive, the actual conditions of cure adhesive layer is for being first heated to 60～80 DEG C of curing 5hr, then is heated to75～110 DEG C solidify 2～3hr.
13. according to the preparation method of graphene composite film material described in claim 11 or 12, itsBe characterised in that, in described step (4) mode of macromolecule transparent membrane surface activation process be corona orCement Composite Treated by Plasma.
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| CN104538562B (en) * | 2015-01-15 | 2017-04-26 | 京东方科技集团股份有限公司 | OLED device and packaging method and packaging device thereof |
| CN104760362B (en) * | 2015-03-25 | 2017-09-19 | 东莞前沿技术研究院 | Stratosphere aerostatics covering and preparation method thereof |
| CN105425463A (en) * | 2015-12-16 | 2016-03-23 | 青岛海信电器股份有限公司 | Display device, backlight module, quantum dot optical diaphragm and preparation method thereof |
| CN106335235B (en) * | 2016-08-18 | 2019-01-29 | 常州二维碳素科技股份有限公司 | A kind of graphene gas barrier stacking film and preparation method thereof |
| KR102596292B1 (en) | 2016-09-01 | 2023-10-31 | 엘지전자 주식회사 | Apparatus for graphene heating |
| CN106674569A (en) * | 2016-12-09 | 2017-05-17 | 深圳八六三计划材料表面技术研发中心 | PLA environment-friendly composite membrane and preparation method thereof |
| CN107142547B (en) * | 2017-06-26 | 2019-07-23 | 杭州高烯科技有限公司 | A kind of fire-retardant UV resistance polyester fiber and preparation method thereof that graphene is modified |
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| CN108530690A (en) * | 2018-05-02 | 2018-09-14 | 合肥市晨雷思建筑材料科技有限公司 | A kind of high molecular film material and preparation method thereof |
| CN109096517B (en) * | 2018-09-03 | 2021-02-19 | 四川汇利实业有限公司 | Medicine packaging film and preparation method thereof |
| CN109206650B (en) * | 2018-09-03 | 2021-02-19 | 四川汇利实业有限公司 | Film for medicine packaging and preparation method thereof |
| CN110253971A (en) * | 2019-04-12 | 2019-09-20 | 中山市旭森涂层材料有限公司 | A kind of digital intelligent patch and its production technology |
| CN111716852A (en) * | 2020-06-06 | 2020-09-29 | 湖北富思特材料科技集团有限公司 | Antistatic superstrong printing cigarette membrane |
| CN112895656B (en) * | 2021-01-29 | 2023-03-24 | 中国工程物理研究院材料研究所 | Water vapor barrier composite membrane and preparation method and application thereof |
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