CN103626909B - Weather-proof barrier coating and its application - Google Patents

Weather-proof barrier coating and its application Download PDF

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CN103626909B
CN103626909B CN201310633905.8A CN201310633905A CN103626909B CN 103626909 B CN103626909 B CN 103626909B CN 201310633905 A CN201310633905 A CN 201310633905A CN 103626909 B CN103626909 B CN 103626909B
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weather
barrier coating
monomer
proof barrier
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CN103626909A (en
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杨楚峰
汤建成
潘建军
周光大
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SUZHOU FOSTER PV MATERIAL CO Ltd
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SUZHOU FOSTER PV MATERIAL CO Ltd
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Abstract

The present invention relates in a kind of polyvinylidene emulsions, preparation method and formula containing the weather-proof barrier coating of this polyvinylidene emulsions and the application of this coating.The composition of raw materials of polyvinylidene emulsions comprises the component of following parts by weight: deionized water 40 ~ 50 parts, vinylidene 30 ~ 40 parts, acrylate monomer 2 ~ 10 parts, be rich in polar group monomer 5 ~ 20 parts, initiator 0.1 ~ 5 part, emulsifying agent 0.5 ~ 1.5 part, wherein, the described polar group monomer that is rich in is 2, 2-dimethyl-4-amylene alcohol ester, dihydromyrcene alcohol ester, the mixture of one or more compositions in cellulose acetate, polar group monomer is rich in by introducing in composition of raw materials, the content of polymer polarity group in polyvinylidene emulsions can be increased, improve its sticking power on intermediate structure enhancement layer.

Description

Weather-proof barrier coating and its application
Technical field
The invention belongs to polymeric material field, be specifically related to the application of a kind of weather-proof barrier coating and this weather-proof barrier coating.
Background technology
At packaging field, with single-material as wrapping material, often performance does not reach service requirements, if paper is due to cheap and easy to get, and there is oil absorbency, be widely used for wrap food, but the food of sheet package can not be fresh-keeping, because the non-constant of the barrier property of paper, steam and oxygen can freely enter in packing material by paper product, make food spoilage.So, as wrapping material, need it to have excellent barrier property often.At present, the barrier packaging material of widespread use mainly contains polyvinylidene chloride and (or is called polyvinylidene dichloride, be called for short PVDC), ethylene-propylene alcohol copolymer (EVOH) and aluminium foil etc., wherein, PVDC is the one that wherein materials with high barrier property is best, and its moisture barrier property does not reduce with the increase of humidity.According to reports, just can well solve the problem of paper barrier difference with the coating of PVDC latex, have outstanding resistance to air loss with the converted paper of PVDC multipolymer coating.
The molecular structural formula of PVDC is such as formula shown in I, and its symmetrical configuration, repeating unit is little, close structure, and is rich in C1 in molecule -ion, superpolymer the cohesive energy ratio is higher, and molecular chain not easily moves, the easy crystallization of molecule and crystallization degree is high, and molecular structure feature determines the barrier property of its excellence;
PVDC homopolymer and PVC (polyvinyl chloride) have very big-difference, and its melt fluidity is poor, directly can not bring and melt extrude film forming or melt coating film forming.Therefore, what generally select is PVDC multipolymer instead of homopolymer.PVDC multipolymer can be used for melt-shaping processing, solution coat and dispersion coating etc.And by changing kind and the ratio of comonomer, PVDC performance of copolymer can be designed, some special applications can be met.
Although PVDC has excellent barrier property as wrapping material, but there are some familiar lacunas, as sticking power is not high, before the coating of PVDC emulsion, need first be coated with one deck primer, increase PVDC coating to the cohesive force of base material.Also have weathering resistance not good enough, cannot use out of doors, containing a large amount of ultraviolet in outdoors sunlight, under uviolizing, easily HCl is decomposited in PVDC resin, the easy xanthochromia efflorescence of PVDC coating, and in the polyvinylidene emulsions utilizing conventional method obtained, polyvinylidene dichloride molecular weight is lower, and major part is 5 × 10 4below, the barrier coat Tc utilizing such polyvinylidene emulsions to prepare is lower, these drawbacks limit application of PVDC at some special dimension: such as photovoltaic solar cell assembly backboard outermost material should provide weather resistance and water vapor rejection performance for backboard, and want the high temperature that can bear more than 130 DEG C.
Publication number is that the Chinese invention patent of CN101875254 has related to a kind of polyvinyl dichloride coating film of resistance to ultraviolet, it is by adding anti ultraviolet agent triazine derivative, and be cross-linked with polyvinylidene dichloride in the curing process, evenly be distributed in enduringly in coating, make coating have resistance to ultraviolet function.
Publication number is the PVDC coating that the Chinese invention patent of CN1977009 describes a kind of resistance to bond, by adding the resin micropowders such as HDPE, LLDPE in coating, reducing contact surface area, realizing the not viscosity in film manufacturing process.
Summary of the invention
The present invention seeks to provide a kind of can improve PVDC sticking power and containing the polyvinylidene emulsions of higher molecular weight PVDC multipolymer to overcome the deficiencies in the prior art.
For achieving the above object, the technical solution used in the present invention is: a kind of polyvinylidene emulsions, and its composition of raw materials comprises the component of following parts by weight:
Wherein, the mixture that polar group monomer is one or more compositions in 2,2-dimethyl-4-amylene alcohol ester, dihydromyrcene alcohol ester, cellulose acetate is rich in described in.
Optimally, described acrylate monomer is the mixture of one or more compositions in methyl methacrylate, β-dimethyl-aminoethylmethacrylate, butyl methacrylate, described initiator is di-isopropyl peroxydicarbonate, di-cyclohexylperoxy dicarbonate, peroxidized t-butyl perbenzoate or peroxidation trimethylacetic acid tertiary butyl ester, and described emulsifying agent is sodium laurylsulfonate or sodium cetanesulfonate.
The present invention also provides a kind of preparation method of polyvinylidene emulsions, comprises the following steps:
(a) pre-reaction: first reaction vessel vacuumized and pass into rare gas element, then add deionized water, the initiator of described formula ratio successively, be rich in polar group monomer, acrylate monomer, emulsifying agent, then 140 ~ 160 DEG C are warming up under agitation, keep that reaction vessel internal pressure is constant to be 0.2 ~ 1.2MPa and to pass into the vinylidene of described formula ratio, continue reaction 20 ~ 40min;
(b) hypothermic response: temperature in reaction vessel is down to 110 ~ 125 DEG C and continues stirring reaction 10 ~ 30 hours.
Optimally, the time that passes into of described vinylidene is 1.5 ~ 3 hours; In step (a), described stirring velocity is 80 ~ 120 revs/min, in step (b), and described stirring velocity is 180 ~ 300 revs/min.
Because technique scheme is used, the present invention compared with prior art has following advantages: polyvinylidene emulsions of the present invention, polar group monomer is rich in by introducing in composition of raw materials, effectively can carry out modification to polymkeric substance in polyvinylidene emulsions, increase the content of its polar group, improve its sticking power on intermediate structure enhancement layer; The preparation method of polyvinylidene emulsions of the present invention, by passing into vinylidene under a constant and carry out hypothermic response after pre-reaction, effectively can suppress the carrying out of side reaction, make the PVDC multipolymer of pbz polymer amount in the polyvinylidene emulsions prepared, its molecular weight reaches as high as 2 × 10 5.
Another object of the present invention is to provide a kind of weather-proof barrier coating, and its composition of raw materials comprises the component of following parts by weight:
The weather-proof barrier coating of the present invention, by adding hydrophilic modifying tetrafluoroethylene (PTFE) powder in its composition of raw materials, can be scattered in polyvinylidene emulsions preferably, in weathering resistance barrier coating coating process, PTFE powder is uniformly coated on membrane surface equally, along with the volatilization of moisture, hydrophilic modifying PTFE powder can gather coatingsurface and form PTFE powder layer, plays the effect that weather-proof, surperficial anti-soil does not glue; Simultaneously PVDC multipolymer also part seed dormancy in PTFE powder gap, carry out determining anchor supporting role to PTFE powder, under PTFE powder layer, define PVDC resin layer, play the effect of barrier.
Optimally, described modified Teflon powder be with tetrafluoroethylene powder be acceptor, enol acid esters for grafted monomer adopt radiation or uv irradiation grafting after be hydrolyzed and make.Enol acid esters is grafted to through hydrolysis on tetrafluoroethylene powder, produces the hydroxyl of some amount, makes tetrafluoroethylene powder have excellent hydrophilic, improves its degree of scatter in polyvinylidene emulsions.
Optimally, the composition of raw materials of described weather-proof barrier coating also includes mineral filler and dispersion agent, and the parts by weight of described mineral filler are 5 ~ 30 parts, and the parts by weight of described dispersion agent are 0.1 ~ 0.5 part.Hydrolysis-resisting agent and oxidation inhibitor can improve the performance of weathering resistance barrier coat.
Optimally, the composition of raw materials of described weather-proof barrier coating also includes mineral filler and dispersion agent, and the parts by weight of described mineral filler are 5 ~ 30 parts, and the parts by weight of described dispersion agent are 0.1 ~ 0.5 part; Further, described mineral filler is titanium dioxide, carbon powder, polynite or silicon-dioxide, and described dispersion agent is alkaline polyurethane copolymer solution.By adding mineral filler and dispersion agent in the composition of raw materials of weathering resistance barrier coating, the performances such as the physical strength of weather-proof barrier coat can be improved, make coating have certain color simultaneously.
Another object of the present invention is to provide the application of a kind of weather-proof barrier coating in preparation weathering resistance barrier coat.
Owing to comprising the modification PVDC multipolymer of high molecular in weather-proof barrier coating, the Tc being coated on weathering resistance barrier coat prepared by basement membrane is made to be 80 ~ 170 DEG C; And owing to being rich in the modification of polar group monomer to polymkeric substance in polyvinylidene emulsions, make this coating outstanding at epilamellar sticking power; The PTFE micro mist layer on surface is that coating provides remarkable weathering resistance, can be used as solar cell backboard outermost material, for solar cell backboard provides weather resistance and water vapor rejection performance.
Embodiment
The composition of raw materials of polyvinylidene emulsions of the present invention comprises deionized water, initiator, emulsifying agent, vinylidene, acrylate monomer, is rich in polar group monomer, and their parts by weight are specific as follows: deionized water 40 ~ 50 parts, vinylidene 30 ~ 40 parts, acrylate monomer 2 ~ 10 parts, be rich in polar group monomer 5 ~ 20 parts, initiator 0.1 ~ 5 part, emulsifying agent 0.5 ~ 1.5 part.Wherein, the mixture that polar group monomer is one or more compositions in 2,2-dimethyl-4-amylene alcohol ester, dihydromyrcene alcohol ester, cellulose acetate is rich in described in.Polar group monomer is rich in by adding in the composition of raw materials of polyvinylidene emulsions, and select and be different types ofly rich in polar group monomer, the content of multipolymer polar group in polyvinylidene emulsions can be increased, improve its sticking power on intermediate structure enhancement layer.
Described acrylate monomer is preferably methacrylate-based monomer, the mixture of such as, one or more compositions in methyl methacrylate, β-dimethyl-aminoethylmethacrylate, butyl methacrylate; Described initiator is preferably peroxide initiator, such as di-isopropyl peroxydicarbonate, di-cyclohexylperoxy dicarbonate, peroxidized t-butyl perbenzoate or peroxidation trimethylacetic acid tertiary butyl ester; Described emulsifying agent is preferably alkyl sodium sulfonate, such as sodium laurylsulfonate or sodium cetanesulfonate.
In polyvinylidene emulsions, the molecular weight of polyvinylidene chloride copolymer free radical activity corresponding to it, temperature of reaction, reactant concn, reaction vessel pressure (because vinylidene is gas), stirring velocity are closely connected.Therefore, in order to prepare containing ultra-high molecular weight (1.5 × 10 5the polyvinylidene emulsions of polyvinylidene chloride copolymer above), the preparation method of polyvinylidene emulsions of the present invention, comprise the following steps: (a) pre-reaction: first reaction vessel vacuumized and pass into rare gas element, then add deionized water, the initiator of described formula ratio successively, be rich in polar group monomer, acrylate monomer, emulsifying agent, then 140 ~ 160 DEG C are warming up under agitation, keep that reaction vessel internal pressure is constant to be 0.2 ~ 1.2MPa and to pass into the vinylidene of described formula ratio, continue reaction 20 ~ 40min; (b) hypothermic response: temperature in reaction vessel is down to 110 ~ 125 DEG C and continues stirring reaction 10 ~ 30 hours.When reacting, the change of reactor pressure can affect the speed of response of whole system, therefore need slowly to pass into vinylidene under a constant, and hypothermic response is carried out after pre-reaction, be down to 110 ~ 125 DEG C by temperature by 140 ~ 160 DEG C, effectively can suppress the carrying out of side reaction like this.
The time that passes into of vinylidene is 1.5 ~ 3 hours, and slowly the passing into of vinylidene is conducive to it and fully reacts and to maintain reaction vessel internal pressure constant.Along with the carrying out of reaction, in polyvinylidene emulsions, the molecular weight of polymkeric substance constantly increases, and its system viscosity also increases gradually, therefore in step (b), preferably improves stirring velocity, to improve the degree of uniformity of material in reaction vessel, sufficient reacting is carried out.Such as: in step (a), stirring velocity is preferably 80 ~ 120 revs/min, in step (b), stirring velocity is preferably 180 ~ 300 revs/min.
The feature of polyvinylidene dichloride ultra-high molecular weight in the sticking power utilizing above-mentioned polyvinylidene emulsions to improve on intermediate structure enhancement layer and polyvinylidene emulsions, weathering resistance barrier coating can be prepared into, and this weathering resistance barrier coating be coated on the upper drying of matrix (material such as basement membrane, substrate) and make weathering resistance barrier coat.
Weathering resistance barrier coating of the present invention, its composition of raw materials comprises the component of following parts by weight: polyvinylidene emulsions 80 ~ 120 parts; Hydrophilic modifying tetrafluoroethylene powder 5 ~ 20 parts; Flow agent 0.5 ~ 1.5 part; Defoamer 0.1 ~ 1 part.By adding hydrophilic modifying tetrafluoroethylene (PTFE) powder in the composition of raw materials of weathering resistance barrier coating, can be scattered in polyvinylidene emulsions preferably, in weathering resistance barrier coating coating process, PTFE powder is uniformly coated on membrane surface equally, along with the volatilization of moisture, hydrophilic modifying PTFE powder can gather coatingsurface and form PTFE powder layer, plays the effect that weather-proof, surperficial anti-soil does not glue; Simultaneously PVDC multipolymer also part seed dormancy in PTFE powder gap, carry out determining anchor supporting role to PTFE powder, and define PVDC resin layer under PTFE powder layer, play the effect of barrier; And due to the PVDC multipolymer of high molecular in polyvinylidene emulsions, the Tc making the weathering resistance barrier coat prepared is 80 ~ 170 DEG C, the requirement of the special dimensions such as solar cell can be met up to the temperature of 170 DEG C, and owing to being rich in the modification of polar group monomer to polymkeric substance in polyvinylidene emulsions, this coating is outstanding at epilamellar sticking power, solar cell backboard outermost material can be used as, for solar cell backboard provides weather resistance and water vapor rejection performance; Flow agent in formula, defoamer, can improve the coating performance of coating on matrix.
Flow agent, defoamer usually can with of the prior art those, wherein flow agent is preferably polyacrylic ester, and defoamer is preferably polyether silicone.
Modified Teflon powder be with tetrafluoroethylene powder be acceptor, enol acid esters for grafted monomer adopt radiation or uv irradiation grafting after be hydrolyzed and make, enol acid esters is preferably vinylcarbinol acetic ester, vinylcarbinol butyric ester or vinylcarbinol propionic ester.Enol acid esters is grafted to through hydrolysis on tetrafluoroethylene powder, produces the hydroxyl of some amount, makes tetrafluoroethylene powder have excellent hydrophilic, improves its degree of scatter in polyvinylidene emulsions.
The composition of raw materials of weathering resistance barrier coating also includes oxidation inhibitor and hydrolysis-resisting agent, the parts by weight of described oxidation inhibitor are 0.2 ~ 2 part, and the parts by weight of described hydrolysis-resisting agent are 0.5 ~ 3 part, and wherein oxidation inhibitor is preferably 2,6-ditertbutylparacresol, hydrolysis-resisting agent is polycarbodiimide.By adding oxidation inhibitor in the composition of raw materials of weathering resistance barrier coating, hydrolysis-resisting agent can give weathering resistance barrier coat antioxidant, resistance to hydrolysis, improves its performance, extends its work-ing life.
The composition of raw materials of weathering resistance barrier coating also includes mineral filler and dispersion agent, and the parts by weight of described mineral filler are 5 ~ 30 parts, and the parts by weight of described dispersion agent are 0.1 ~ 0.5 part; Mineral filler is preferably titanium dioxide, carbon powder, polynite or silicon-dioxide, and dispersion agent is preferably alkaline polyurethane copolymer solution.By adding mineral filler and dispersion agent in the composition of raw materials of weathering resistance barrier coating, the performances such as the physical strength of weathering resistance barrier coat can be improved, make coating have certain color simultaneously.
In the present invention, oxidation inhibitor, hydrolysis-resisting agent, flow agent, defoamer select 2 respectively, 6-ditertbutylparacresol (BHT), bright hundred million HyMax1010 in Shanghai, enlightening height TEGO Flow425, enlightening height TEGO Wet270, dispersion agent is enlightening height TEGODispers750W.
Below will the present invention is described in detail by specific embodiment.
Embodiment 1
Polyvinylidene emulsions composition of raw materials: deionized water 50kg, vinylidene 40kg, methyl methacrylate 10kg, di-isopropyl peroxydicarbonate 0.1kg, sodium laurylsulfonate 0.5kg, cellulose acetate 0.5kg, dihydromyrcene alcohol ester monomer 5kg.
The preparation of polyvinylidene emulsions:
(a) pre-reaction: be first that the withstand voltage reactor of 100L vacuumizes and passes into nitrogen by volume, then the deionized water of above-mentioned quality, di-isopropyl peroxydicarbonate, cellulose acetate, dihydromyrcene alcohol ester monomer, methyl methacrylate, sodium laurylsulfonate is added successively, be be warming up to 160 DEG C under the agitation condition of 120 revs/min again with speed, maintenance reaction vessel internal pressure is constant to be 0.2MPa and to pass into 40kg vinylidene (time of passing into is 1.5 ~ 3 hours), continues reaction 20min;
B () hypothermic response: temperature in reaction vessel is down to 125 DEG C is continue reaction 30 hours under the agitation condition of 300 revs/min in speed.
The hydrophilic modifying of tetrafluoroethylene powder:
Add common tetrafluoroethylene powder 5kg, vinylcarbinol acetic ester 20kg and methyl alcohol 50kg in a kettle., with nitrogen to after reactor displacement deoxidation, at room temperature carry out radiation grafting with the gamma-rays that Co60 produces, product, through filtering extracting, obtains the PTFE micro mist of preliminary modification; Preliminary modified ptfe micro mist is immersed in acid solution again, stirs and carries out ester decomposition in 2 hours, obtain the PTFE powder of the rich surface hydroxyl of further modification.
The preparation of weathering resistance barrier coating and weathering resistance barrier coat:
To in above-mentioned obtained 80kg polyvinylidene emulsions, add the PTFE powder of 0.5kg flow agent TEGO Flow425,0.1kg defoamer TEGO Wet270,5kg hydrophilic modifying, 0.5kg hydrolysis-resisting agent HyMax1010 and 0.3kg antioxidant BHT, to stir to obtain weathering resistance barrier coating with the speed of 1000 revs/min; With the polyethylene terephthalate film (PET film) of 250 micron thickness for basement membrane, coating machine is coated with above-mentioned coating, by Infrared heaters, heat drying is carried out to wet film coating again, through 80 DEG C of hot blast drying tunnel finish-dryings, after rolling in 100 DEG C of curing chambers slaking more than crystallization 72h, coat-thickness is 35 microns.
Embodiment 2
Polyvinylidene emulsions composition of raw materials: deionized water 40kg, vinylidene 30kg, β-dimethyl-aminoethylmethacrylate 2kg, di-cyclohexylperoxy dicarbonate 5kg, sodium cetanesulfonate 1.5kg, cellulose acetate 0.5kg, dihydromyrcene alcohol ester monomer 5kg, 2,2-dimethyl-4-amylene alcohol ester 10kg.
The preparation of polyvinylidene emulsions:
(a) pre-reaction: be first that the withstand voltage reactor of 100L vacuumizes and passes into argon gas by volume, then the deionized water of above-mentioned quality, di-cyclohexylperoxy dicarbonate, cellulose acetate, dihydromyrcene alcohol ester monomer, 2 is added successively, 2-dimethyl-4-amylene alcohol ester, β-dimethyl-aminoethylmethacrylate, sodium cetanesulfonate, be be warming up to 140 DEG C under the agitation condition of 80 revs/min again with speed, maintenance reaction vessel internal pressure is constant to be 1.2MPa and to pass into 30kg vinylidene (time of passing into is 1.5 ~ 3 hours), continues reaction 40min;
B () hypothermic response: temperature in reaction vessel is down to 125 DEG C is continue reaction 10 hours under the agitation condition of 180 revs/min in speed.
The hydrophilic modifying of tetrafluoroethylene powder: identical with embodiment 1.
The preparation of weathering resistance barrier coating and weathering resistance barrier coat:
To in above-mentioned obtained 120kg polyvinylidene emulsions, add 10kg titanium dioxide, 0.2kg dispersion agent TEGODispers750W, twice is ground with moderate speed in sand mill, titanium dioxide is made to be dispersed in emulsion, add 0.5kg flow agent TEGO Flow425,0.1kg defoamer TEGO Wet270,0.5kg hydrolysis-resisting agent HyMax1010 and 0.3kg antioxidant BHT again, and add the PTFE micro mist of the final modification of 5kg, to stir to obtain weathering resistance barrier coating with the speed of 1000 revs/min; With the BiOriented Polypropylene Films of 150 micron thickness (BOPP film) for basement membrane, on coating machine, first be coated with weathering resistance barrier layer coating, by Infrared heaters, heat drying is carried out to wet film coating again, through 80 DEG C of hot blast drying tunnel finish-dryings, after rolling in 140 DEG C of curing chambers slaking more than crystallization 72h, coat-thickness is 25 microns.
Embodiment 3
Polyvinylidene emulsions composition of raw materials: deionized water 45kg, vinylidene 35kg, butyl methacrylate 10kg, peroxidized t-butyl perbenzoate 2kg, sodium laurylsulfonate 1kg, cellulose acetate 0.5kg, dihydromyrcene alcohol ester monomer 10kg.
The preparation of polyvinylidene emulsions:
(a) pre-reaction: be first that the withstand voltage reactor of 100L vacuumizes and passes into nitrogen by volume, then the deionized water of above-mentioned quality, peroxidized t-butyl perbenzoate, cellulose acetate, dihydromyrcene alcohol ester monomer, butyl methacrylate, sodium laurylsulfonate is added successively, be be warming up to 155 DEG C under the agitation condition of 100 revs/min again with speed, keep the constant 0.8MPa of reaction vessel internal pressure and pass into 35kg vinylidene (time of passing into is 1.5 ~ 3 hours), continuing reaction 30min;
B () hypothermic response: temperature in reaction vessel is down to 120 DEG C is continue reaction 20 hours under the agitation condition of 200 revs/min in speed.
The hydrophilic modifying of tetrafluoroethylene powder: identical with embodiment 1.
The preparation of weathering resistance barrier coating and weathering resistance barrier coat: substantially the same manner as Example 2 is the polyamide membrane (PA film) of 200 micron thickness unlike matrix.
Embodiment 4
In the present embodiment, the preparation method of polyvinylidene emulsions composition of raw materials and component concentration thereof, polyvinylidene emulsions is substantially the same manner as Example 3, is peroxidation trimethylacetic acid tertiary butyl ester unlike initiator
The preparation of polyvinylidene emulsions:
(a) pre-reaction: be first that the withstand voltage reactor of 100L vacuumizes and passes into nitrogen by volume, then the deionized water of above-mentioned quality, peroxidation trimethylacetic acid tertiary butyl ester, cellulose acetate, dihydromyrcene alcohol ester monomer, butyl methacrylate, sodium laurylsulfonate is added successively, be be warming up to 145 DEG C under the agitation condition of 100 revs/min again with speed, maintenance reaction vessel internal pressure is constant to be 0.4MPa and to pass into 35kg vinylidene (time of passing into is 1.5 ~ 3 hours), continues reaction 30min;
B () hypothermic response: temperature in reaction vessel is down to 120 DEG C is continue reaction 24 hours under the agitation condition of 200 revs/min in speed.
The hydrophilic modifying of tetrafluoroethylene powder:
Add common polytetrafluoroethylpowder powder 5kg, benzophenone 0.3kg and methyl alcohol 50kg in a kettle., then after deoxidation being replaced to reactor with nitrogen, then at room temperature with the ultraviolet that xenon lamp produces, pre-treatment is carried out after 2 hours to material, add grafted monomer vinylcarbinol butyric ester 20kg, proceed uv irradiation, make vinylcarbinol butyric ester monomer-grafted to PTFE surface, product, through filtering extracting, obtains the PTFE micro mist of modification; Finally modified ptfe micro mist is immersed in acid solution, stirs and carry out ester decomposition in 2 hours, obtain the PTFE micro mist of the rich surface hydroxyl of further modification.
The preparation of weathering resistance barrier coating and weathering resistance barrier coat:
5kg carbon black, 0.2kg dispersion agent TEGODispers750W is added in above-mentioned obtained 100kg polyvinylidene emulsions, twice is ground with moderate speed in sand mill, titanium dioxide is made to be dispersed in emulsion, add PTFE micro mist, the 5kg aerosil ED-2 of 0.5kg flow agent TEGO Flow425,0.1kg defoamer TEGO Wet270,5kg hydrophilic modifying again, to stir to obtain weathering resistance barrier coating with the speed of 1000 revs/min; With the PEN of 200 micron thickness (pen film) for basement membrane, coating machine is coated with weathering resistance barrier coating, by Infrared heaters, heat drying is carried out to wet film coating again, through 80 DEG C of hot blast drying tunnel finish-dryings, after rolling in 100 DEG C of curing chambers slaking more than crystallization 72h, coat-thickness is 35 microns.
Test example 1
Weathering resistance barrier coat obtained for embodiment 1 to 4 is carried out weathering resistance, water vapor barrier property, sticking power three performance tests respectively, and test result is listed in table 1 as follows:
(1) weathering resistance
According to standard IEC 61215, the air surface of back veneer material accepts ultraviolet light irradiation, and ultraviolet wavelength range is 280 ~ 400nm, irradiation time 1000h, the yellowness index of test sample after completing, and characterizes the weather resistance of weather-proof barrier layer sample.
(2) water vapor barrier property
Perform according to standard A STM F1249, test condition is humidity 100%RH & temperature 37.8 DEG C, carrys out the water vapor barrier property of exosyndrome material with 24h steam transit dose in unit surface.
(3) sticking power on base material
Perform according to standard A STM D3359, adopt hundred lattice method test sticking power, sticking power highest ranking is 5B, and minimum is 0B, compares test before and after hydrothermal aging (temperature 85 DEG C of & humidity 85%RH) 1000h.
The performance data of the weathering resistance barrier coat that table 1 embodiment 1 to 4 is obtained
As shown in Table 1, the weathering resistance barrier coat that embodiment 1 to 4 obtains, after the hydrothermal aging process of 1000h, still has the sticking power of highest ranking; After ultraviolet ageing test, its xanthochromia degree only slightly increases, and illustrates that it has good weather resistance; And their water vapor rejection performance is also very outstanding.
In sum, at the weather-proof barrier coating that the present invention utilizes polyvinyl dichloride emulsion to obtain for matrix resin, be coated on (PET on structure enhancement layer base material, BOPP, PA, PEN), the coating obtained has good weathering resistance, barrier property, surface contamination resistance and the sticking power to base material, and due to the Tc of weathering resistance barrier coat of the present invention be 80 ~ 170 DEG C, the requirement of the special dimensions such as solar cell can be met up to the temperature of 170 DEG C, solar cell backboard outermost material can be used as, for solar cell backboard provides weather resistance and water vapor rejection performance.
Above-described embodiment is only for illustrating technical conceive of the present invention and feature; its object is to person skilled in the art can be understood content of the present invention and implement according to this; can not limit the scope of the invention with this; all equivalences done according to spirit of the present invention change or modify, and all should be encompassed within protection scope of the present invention.

Claims (6)

1. a weather-proof barrier coating, is characterized in that: its composition of raw materials comprises the component of following parts by weight:
Polyvinylidene emulsions 80 ~ 120 parts;
Enol acid esters graft modification tetrafluoroethylene powder 5 ~ 20 parts;
Flow agent 0.5 ~ 1.5 part;
Defoamer 0.1 ~ 1 part;
The composition of raw materials of described polyvinylidene emulsions comprises the component of following parts by weight:
Deionized water 40 ~ 50 parts;
Vinylidene 30 ~ 40 parts;
Acrylate monomer 2 ~ 10 parts;
Be rich in polar group monomer 5 ~ 20 parts;
Initiator 0.1 ~ 5 part;
Emulsifying agent 0.5 ~ 1.5 part,
Wherein, mixtures that polar group monomer is one or both compositions in 2,2-dimethyl-4-amylene alcohol ester and dihydromyrcene alcohol ester are rich in described in.
2. weather-proof barrier coating according to claim 1, is characterized in that: described enol acid esters graft modification tetrafluoroethylene powder be with tetrafluoroethylene powder be acceptor, enol acid esters for grafted monomer adopt radiation or uv irradiation grafting after be hydrolyzed and make.
3. weather-proof barrier coating according to claim 1, it is characterized in that: in the composition of raw materials of described weather-proof barrier coating, also include oxidation inhibitor and hydrolysis-resisting agent, the parts by weight of described oxidation inhibitor are 0.2 ~ 2 part, and the parts by weight of described hydrolysis-resisting agent are 0.5 ~ 3 part.
4. weather-proof barrier coating according to claim 1, it is characterized in that: in the composition of raw materials of described weather-proof barrier coating, also include mineral filler and dispersion agent, the parts by weight of described mineral filler are 5 ~ 30 parts, and the parts by weight of described dispersion agent are 0.1 ~ 0.5 part.
5. weather-proof barrier coating according to claim 4, is characterized in that: described mineral filler is titanium dioxide, carbon powder, polynite or silicon-dioxide, and described dispersion agent is alkaline polyurethane copolymer solution.
6. the application of the weather-proof barrier coating according to any one of claim 1 to 5 in preparation weathering resistance barrier coat.
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