CN103626909A - Polyvinylidene chloride (PVDC) emulsion and preparation method thereof as well as weather-proof barrier coating and application thereof - Google Patents
Polyvinylidene chloride (PVDC) emulsion and preparation method thereof as well as weather-proof barrier coating and application thereof Download PDFInfo
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Abstract
The invention relates to polyvinylidene chloride (PVDC) emulsion, a preparation method of the emulsion, a weather-proof barrier coating including the polyvinylidene chloride emulsion, and the application of the coating. The PVDC emulsion comprises the following components in parts by weight: 40-50 parts of deionized water, 30-40 parts of a vinylidene chloride monomer, 2-10 parts of an acrylic ester monomer, 5-20 parts of a monomer rich in polar groups, 0.1-5 parts of an initiator and 0.5-1.5 parts of an emulsifier, wherein the monomer rich in polar groups is one or more of 2, 2-dimethyl-4-pentene alcohol ester, dihydromyrcene alcohol ester and cellulose acetate; the monomer rich in polar groups is introduced in the raw material formula, so that the content of polar groups of the polymer in the PVDC emulsion can be increased, and the adhesion on the enhancement layer of the intermediate structure is improved.
Description
Technical field
The invention belongs to polymeric material field, be specifically related to the preparation method of a kind of polyvinylidene dichloride emulsion, polyvinylidene dichloride emulsion and utilize weather-proof barrier coating prepared by polyvinylidene dichloride emulsion and the application of 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 often it to have good barrier property.At present, the barrier packaging material of widespread use mainly contains polyvinylidene chloride and (or is called polyvinylidene dichloride, abbreviation PVDC), ethene-polyvinyl alcohol copolymer (EVOH) and aluminium foil etc., wherein, PVDC is best a kind of of materials with high barrier property wherein, and its moisture barrier property does not reduce with the increase of humidity.According to reports, with the coating of PVDC latex, just can well solve the poor problem of paper barrier, with the converted paper of PVDC multipolymer coating, have outstanding resistance to air loss.
The molecular structural formula of PVDC is suc as formula shown in I, its symmetrical configuration, and repeating unit is little, close structure, and in molecule, be rich in C1
-ion, superpolymer the cohesive energy ratio is higher, and molecular chain is difficult for motion, and the easy crystallization of molecule and crystallization degree are high, and molecular structure feature has determined the barrier property that it is excellent.
PVDC homopolymer and PVC (polyvinyl chloride) have very big-difference, and its melt fluidity is poor, can not directly bring and melt extrude film forming or melt coating film forming.What therefore, one was selected is PVDC multipolymer rather than homopolymer.PVDC multipolymer can be used for melt-shaping processing, solution coat and dispersion coating etc.And can PVDC performance of copolymer be designed by changing kind and the ratio of comonomer, can meet some special applications.
Although PVDC has excellent barrier property as wrapping material, but there are some familiar lacunas, as not high in sticking power, before the coating of PVDC emulsion, need first be coated with one deck primer, increase the cohesive force of PVDC coating to base material.Also have weathering resistance not good enough, cannot use out of doors, in outdoor sunlight, contain a large amount of ultraviolet rays, under uviolizing, in PVDC resin, easily decomposite HCl, the easy xanthochromia efflorescence of PVDC coating, and utilize in the polyvinylidene dichloride emulsion that conventional method makes polyvinylidene dichloride molecular weight lower, most of 5 * 10
4below, the barrier coat Tc of utilizing such polyvinylidene dichloride emulsion to prepare is lower, these drawbacks limit the application of PVDC at some special dimension: for example photovoltaic solar cell assembly backboard outermost material should provide weather resistance and water vapor rejection performance for backboard, and wants to bear 130 ℃ of above high temperature.
Publication number is the polyvinyl dichloride coating film that the Chinese invention patent of CN101875254 has related to a kind of resistance to ultraviolet, it is by adding anti ultraviolet agent triazine derivative, and crosslinked with polyvinylidene dichloride in solidification process, evenly be distributed in enduringly in coating, make coating there is resistance to ultraviolet function.
Publication number is the PVDC coating that the Chinese invention patent of CN1977009 has been described a kind of resistance to bond, by adding the resin micropowders such as HDPE, LLDPE in coating, reduces Surface Contact area, realizes the not viscosity in processing film process.
Summary of the invention
The present invention seeks to provide in order to overcome the deficiencies in the prior art a kind of polyvinylidene dichloride emulsion that can improve PVDC sticking power and contain higher molecular weight PVDC multipolymer.
For achieving the above object, the technical solution used in the present invention is: a kind of polyvinylidene dichloride emulsion, and its composition of raw materials comprises the component of following parts by weight:
Wherein, described in, being rich in polar group monomer is the mixture of one or more compositions in 2,2-dimethyl-4-amylene alcohol ester, dihydromyrcene alcohol ester, cellulose acetate.
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 dichloride emulsion, comprises the following steps:
(a) pre-reaction: first reaction vessel is vacuumized and passed into rare gas element, then add successively described formula ratio deionized water, initiator, be rich in polar group monomer, acrylate monomer, emulsifying agent, then under agitation condition, be warming up to 140～160 ℃, keeping reaction vessel internal pressure constant is 0.2～1.2MPa the vinylidene that passes into described formula ratio, continues reaction 20～40min;
(b) hypothermic response: temperature in reaction vessel is down to 110～125 ℃ 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, and in step (b), described stirring velocity is 180～300 revs/min.
Because technique scheme is used, the present invention compared with prior art has following advantages: polyvinylidene dichloride emulsion of the present invention, by introducing and be rich in polar group monomer in composition of raw materials, can effectively to polymkeric substance in polyvinylidene dichloride emulsion, carry out modification, increase the content of its polar group, improved its sticking power on intermediate structure enhancement layer; The preparation method of polyvinylidene dichloride emulsion of the present invention, by passing into vinylidene and carry out hypothermic response under constant pressure after pre-reaction, can effectively suppress the carrying out of side reaction, the PVDC multipolymer of pbz polymer amount in the polyvinylidene dichloride emulsion that makes to prepare, 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 add hydrophilic modifying tetrafluoroethylene (PTFE) powder in its composition of raw materials, can be scattered in preferably in polyvinylidene dichloride emulsion, 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 not sticky effect of weather-proof, surperficial anti-soil; While PVDC multipolymer also part seed dormancy, in PTFE powder gap, carries out determining anchor supporting role to PTFE powder, has formed PVDC resin layer under PTFE powder layer, plays the effect of barrier.
Optimally, described modified Teflon powder is to take tetrafluoroethylene powder as acceptor, enol acid esters as grafted monomer, to adopt after radiation or uv irradiation grafting and be hydrolyzed and make.Enol acid esters is grafted on tetrafluoroethylene powder through hydrolysis, produces the hydroxyl of some amount, makes tetrafluoroethylene powder have excellent hydrophilic, has improved its degree of scatter in polyvinylidene dichloride emulsion.
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 at weathering resistance barrier coating, can improve the performances such as physical strength of weather-proof barrier coat, 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.
Due to the modification PVDC multipolymer that comprises high molecular in weather-proof barrier coating, the Tc that makes to be coated on the weathering resistance barrier coat of preparing on basement membrane is 80～170 ℃; And owing to being rich in the modification of polar group monomer to polymkeric substance in polyvinylidene dichloride emulsion, make this coating outstanding at epilamellar sticking power; The PTFE micro mist layer on surface, for 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 dichloride emulsion 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: 40～50 parts of deionized waters, 30～40 parts of vinylidene, 2～10 parts of acrylate monomers, be rich in 5～20 parts of polar group monomers, 0.1～5 part of initiator, 0.5～1.5 part of emulsifying agent.Wherein, described in, being rich in polar group monomer is the mixture of one or more compositions in 2,2-dimethyl-4-amylene alcohol ester, dihydromyrcene alcohol ester, cellulose acetate.By adding and be rich in polar group monomer in the composition of raw materials in polyvinylidene dichloride emulsion, and select different types of polar group monomer that is rich in, can increase the content of multipolymer polar group in polyvinylidene dichloride emulsion, improve its sticking power on intermediate structure enhancement layer.
Described acrylate monomer is preferably methyl acrylic ester monomer, for example the mixture of one or more compositions in methyl methacrylate, β-dimethyl-aminoethylmethacrylate, butyl methacrylate; Described initiator is preferably peroxide initiator, for example 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, for example sodium laurylsulfonate or sodium cetanesulfonate.
In polyvinylidene dichloride emulsion, the molecular weight of polyvinylidene chloride copolymer free radical activity corresponding with it, temperature of reaction, reactant concn, reaction vessel pressure (because vinylidene is gas), stirring velocity are closely connected.Therefore, in order to prepare, contain ultra-high molecular weight (1.5 * 10
5the polyvinylidene dichloride emulsion of polyvinylidene chloride copolymer above), the preparation method of polyvinylidene dichloride emulsion of the present invention, comprise the following steps: (a) pre-reaction: first reaction vessel is vacuumized and passed into rare gas element, then add successively described formula ratio deionized water, initiator, be rich in polar group monomer, acrylate monomer, emulsifying agent, then under agitation condition, be warming up to 140～160 ℃, keeping reaction vessel internal pressure constant is 0.2～1.2MPa the vinylidene that passes into described formula ratio, continues reaction 20～40min; (b) hypothermic response: temperature in reaction vessel is down to 110～125 ℃ and continues stirring reaction 10～30 hours.When reaction, the variation of reactor pressure can affect the speed of response of whole system, therefore need under constant pressure, slowly pass into vinylidene, and after pre-reaction, carry out hypothermic response, be about to temperature and be down to 110～125 ℃ by 140～160 ℃, can effectively 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.Carrying out along with reaction, in polyvinylidene dichloride emulsion, 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.For example: in step (a), stirring velocity is preferably 80～120 revs/min, in step (b), stirring velocity is preferably 180～300 revs/min.
Utilize the feature of polyvinylidene dichloride ultra-high molecular weight in sticking power that above-mentioned polyvinylidene dichloride emulsion improves on intermediate structure enhancement layer and polyvinylidene dichloride emulsion, can be prepared into weathering resistance barrier coating, and this weathering resistance barrier coating is coated on to the upper drying of matrix materials such as () basement membrane, substrates makes 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: 80～120 parts of polyvinylidene dichloride emulsions; 5～20 parts of hydrophilic modifying tetrafluoroethylene powders; 0.5～1.5 part of flow agent; 0.1～1 part of defoamer.By adding hydrophilic modifying tetrafluoroethylene (PTFE) powder in the composition of raw materials at weathering resistance barrier coating, can be scattered in preferably in polyvinylidene dichloride emulsion, in weathering resistance barrier coating coating process, PTFE powder is uniformly coated on membrane surface equally, volatilization along with moisture, hydrophilic modifying PTFE powder can gather coatingsurface and form PTFE powder layer, plays the not sticky effect of weather-proof, surperficial anti-soil; While PVDC multipolymer also part seed dormancy, in PTFE powder gap, carries out determining anchor supporting role to PTFE powder, and under PTFE powder layer, has formed PVDC resin layer, plays the effect of barrier; And due to the PVDC multipolymer of high molecular in polyvinylidene dichloride emulsion, making the Tc of the weathering resistance barrier coat of preparation is 80～170 ℃, up to the temperature of 170 ℃, can meet the requirement of the special dimensions such as solar cell, and owing to being rich in the modification of polar group monomer to polymkeric substance in polyvinylidene dichloride emulsion, this coating is outstanding at epilamellar sticking power, can be used as solar cell backboard outermost material, 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 conventionally can with of the prior art those, wherein flow agent is preferably polyacrylic ester, defoamer is preferably polyether silicone.
Modified Teflon powder is to take tetrafluoroethylene powder as acceptor, enol acid esters as grafted monomer, to adopt after radiation or uv irradiation grafting and be hydrolyzed and make, and enol acid esters is preferably vinylcarbinol acetic ester, vinylcarbinol butyric ester or vinylcarbinol propionic ester.Enol acid esters is grafted on tetrafluoroethylene powder through hydrolysis, produces the hydroxyl of some amount, makes tetrafluoroethylene powder have excellent hydrophilic, has improved its degree of scatter in polyvinylidene dichloride emulsion.
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 at weathering resistance barrier coating, hydrolysis-resisting agent can be given 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 at weathering resistance barrier coating, can improve the performances such as physical strength of weathering resistance barrier coat, make coating have certain color simultaneously.
In the present invention, oxidation inhibitor, hydrolysis-resisting agent, flow agent, defoamer select respectively 2,6-ditertbutylparacresol (BHT), bright hundred million HyMax1010 in Shanghai, the high TEGO Flow425 of enlightening, the high TEGO Wet270 of enlightening, dispersion agent is the high TEGO Dispers750W of enlightening.
Below will by specific embodiment, the present invention is described in detail.
Embodiment 1
Polyvinylidene dichloride emulsion materials formula: 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 dichloride emulsion:
(a) pre-reaction: the withstand voltage reactor that is first 100L by volume vacuumizes and pass into nitrogen, then the deionized water, di-isopropyl peroxydicarbonate, cellulose acetate, dihydromyrcene alcohol ester monomer, methyl methacrylate, the sodium laurylsulfonate that add successively above-mentioned quality, the speed of take is again warming up to 160 ℃ under the agitation condition of 120 revs/min, keep the constant 0.2MPa of being of reaction vessel internal pressure and pass into 40kg vinylidene (time of passing into is 1.5～3 hours), continuing reaction 20min;
(b) hypothermic response: temperature in reaction vessel is down to 125 ℃, is to continue reaction 30 hours under the agitation condition of 300 revs/min in speed.
The hydrophilic modifying of tetrafluoroethylene powder:
In reactor, add common tetrafluoroethylene powder 5kg, vinylcarbinol acetic ester 20kg and methyl alcohol 50kg, with nitrogen, reactor is replaced after deoxidation, at room temperature with the gamma-rays that Co60 produces, carry out radiation grafting, 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, obtains the PTFE powder of the rich surface hydroxyl of further modification.
The preparation of weathering resistance barrier coating and weathering resistance barrier coat:
In the above-mentioned 80kg polyvinylidene dichloride emulsion making, add PTFE powder, 0.5kg hydrolysis-resisting agent HyMax1010 and the 0.3kg antioxidant BHT of 0.5kg flow agent TEGO Flow425,0.1kg defoamer TEGO Wet270,5kg hydrophilic modifying, with the speed of the 1000 revs/min weathering resistance barrier coating that stirs to obtain; The polyethylene terephthalate film (PET film) of 250 micron thickness of take is basement membrane, on coating machine, be coated with above-mentioned coating, by Infrared heaters, wet film coating is carried out to heat drying again, through 80 ℃ of hot blast drying tunnel finish-dryings, after rolling, in 100 ℃ of curing chambers more than slaking crystallization 72h, coat-thickness is 35 microns.
Embodiment 2
Polyvinylidene dichloride emulsion materials formula: 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 dichloride emulsion:
(a) pre-reaction: the withstand voltage reactor that is first 100L by volume vacuumizes and pass into argon gas, then the deionized water, di-cyclohexylperoxy dicarbonate, cellulose acetate, the dihydromyrcene alcohol ester monomer, 2 that add successively above-mentioned quality, 2-dimethyl-4-amylene alcohol ester, β-dimethyl-aminoethylmethacrylate, sodium cetanesulfonate, the speed of take is again warming up to 140 ℃ under the agitation condition of 80 revs/min, keep the constant 1.2MPa of being of reaction vessel internal pressure and pass into 30kg vinylidene (time of passing into is 1.5～3 hours), continuing reaction 40min;
(b) hypothermic response: temperature in reaction vessel is down to 125 ℃, is to 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:
In the above-mentioned 120kg polyvinylidene dichloride emulsion making, add 10kg titanium dioxide, 0.2kg dispersion agent TEGODispers750W, in sand mill, with moderate speed, grind twice, titanium dioxide is dispersed in emulsion, add again 0.5kg flow agent TEGO Flow425,0.1kg defoamer TEGO Wet270,0.5kg hydrolysis-resisting agent HyMax1010 and 0.3kg antioxidant BHT, and add the PTFE micro mist of the final modification of 5kg, with the speed of the 1000 revs/min weathering resistance barrier coating that stirs to obtain; The BiOriented Polypropylene Films (BOPP film) of 150 micron thickness of take is basement membrane, on coating machine, first be coated with weathering resistance barrier layer coating, by Infrared heaters, wet film coating is carried out to heat drying again, through 80 ℃ of hot blast drying tunnel finish-dryings, after rolling, in 140 ℃ of curing chambers more than slaking crystallization 72h, coat-thickness is 25 microns.
Embodiment 3
Polyvinylidene dichloride emulsion materials formula: 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 dichloride emulsion:
(a) pre-reaction: the withstand voltage reactor that is first 100L by volume vacuumizes and pass into nitrogen, then the deionized water, peroxidized t-butyl perbenzoate, cellulose acetate, dihydromyrcene alcohol ester monomer, butyl methacrylate, the sodium laurylsulfonate that add successively above-mentioned quality, the speed of take is again warming up to 155 ℃ under the agitation condition of 100 revs/min, 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 ℃, is to 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, different is that matrix is the polyamide membrane (PA film) of 200 micron thickness.
Embodiment 4
In the present embodiment, the preparation method of polyvinylidene dichloride emulsion materials formula and component concentration thereof, polyvinylidene dichloride emulsion is substantially the same manner as Example 3, and different is that initiator is peroxidation trimethylacetic acid tertiary butyl ester
The preparation of polyvinylidene dichloride emulsion:
(a) pre-reaction: the withstand voltage reactor that is first 100L by volume vacuumizes and pass into nitrogen, then the deionized water, peroxidation trimethylacetic acid tertiary butyl ester, cellulose acetate, dihydromyrcene alcohol ester monomer, butyl methacrylate, the sodium laurylsulfonate that add successively above-mentioned quality, the speed of take is again warming up to 145 ℃ under the agitation condition of 100 revs/min, keep the constant 0.4MPa of being 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 ℃, is to continue reaction 24 hours under the agitation condition of 200 revs/min in speed.
The hydrophilic modifying of tetrafluoroethylene powder:
In reactor, add common polytetrafluoroethylpowder powder 5kg, benzophenone 0.3kg and methyl alcohol 50kg, then with nitrogen, reactor is replaced after deoxidation, then at room temperature with the ultraviolet ray that xenon lamp produces, material was carried out to pre-treatment after 2 hours, 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:
In the above-mentioned 100kg polyvinylidene dichloride emulsion making, add 5kg carbon black, 0.2kg dispersion agent TEGODispers750W, in sand mill, with moderate speed, grind twice, titanium dioxide is dispersed in emulsion, add again 0.5kg flow agent TEGO Flow425,0.1kg defoamer TEGO Wet270, the PTFE micro mist of 5kg hydrophilic modifying, 5kg aerosil ED-2, with the speed of the 1000 revs/min weathering resistance barrier coating that stirs to obtain; The PEN (pen film) of 200 micron thickness of take is basement membrane, on coating machine, be coated with weathering resistance barrier coating, by Infrared heaters, wet film coating is carried out to heat drying again, through 80 ℃ of hot blast drying tunnel finish-dryings, after rolling, in 100 ℃ of curing chambers more than slaking crystallization 72h, coat-thickness is 35 microns.
Test example 1
The weathering resistance barrier coat that embodiment 1 to 4 is made carries out respectively weathering resistance, water vapor barrier property, three performance tests of sticking power, 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 is accepted ultraviolet light irradiation, and ultraviolet wavelength scope is 280～400nm, irradiation time 1000h, and the xanthochromia index of specimen after completing, characterizes the weather resistance of weather-proof barrier layer sample.
(2) water vapor barrier property
According to standard A STM F1249, carry out, test condition is 37.8 ℃ of humidity 100%RH & temperature, carrys out the water vapor barrier property of exosyndrome material with 24h steam transit dose in unit surface.
(3) sticking power on base material
According to standard A STM D3359, carry out, adopt hundred lattice method test sticking power, sticking power highest ranking is 5B, and minimum is OB, compares test before and after hydrothermal aging (85 ℃ of & humidity 85%RH of temperature) 1000h.
The performance data of the weathering resistance barrier coat that table 1 embodiment 1 to 4 makes
As shown in Table 1, the weathering resistance barrier coat that embodiment 1 to 4 makes, after the hydrothermal aging of 1000h is processed, 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, the weather-proof barrier coating that utilizes polyvinyl dichloride emulsion to make for matrix resin in the present invention, be coated on (PET on structural reinforcing layer base material, BOPP, PA, PEN), the coating obtaining has good weathering resistance, barrier property, surface contamination resistance and the sticking power to base material, and because the Tc of weathering resistance barrier coat of the present invention is 80～170 ℃, up to the temperature of 170 ℃, can meet the requirement of the special dimensions such as solar cell, can be used as solar cell backboard outermost material, for solar cell backboard provides weather resistance and water vapor rejection performance.
Above-described embodiment is only explanation technical conceive of the present invention and feature; its object is to allow person skilled in the art can understand content of the present invention and implement according to this; can not limit the scope of the invention with this; all equivalences that spirit is done according to the present invention change or modify, within all should being encompassed in protection scope of the present invention.
Claims (10)
1. a polyvinylidene dichloride emulsion, is characterized in that: its composition of raw materials comprises the component of following parts by weight:
40 ~ 50 parts of deionized waters;
30 ~ 40 parts of vinylidene;
2 ~ 10 parts of acrylate monomers;
Be rich in 5 ~ 20 parts of polar group monomers;
0.1 ~ 5 part of initiator;
0.5 ~ 1.5 part of emulsifying agent,
Wherein, described in, being rich in polar group monomer is the mixture of one or more compositions in 2,2-dimethyl-4-amylene alcohol ester, dihydromyrcene alcohol ester, cellulose acetate.
2. polyvinylidene dichloride emulsion according to claim 1, it is characterized in that: 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.
3. a method of preparing polyvinylidene dichloride emulsion described in claim 1 or 2, is characterized in that: it comprises the following steps:
(a) pre-reaction: first reaction vessel is vacuumized and passed into rare gas element, then add successively described formula ratio deionized water, initiator, be rich in polar group monomer, acrylate monomer, emulsifying agent, then under agitation condition, be warming up to 140 ~ 160 ℃, keeping reaction vessel internal pressure constant is 0.2 ~ 1.2MPa the vinylidene that passes into described formula ratio, continues reaction 20 ~ 40min;
(b) hypothermic response: temperature in reaction vessel is down to 110 ~ 125 ℃ and continues stirring reaction 10 ~ 30 hours.
4. the preparation method of polyvinylidene dichloride emulsion according to claim 3, is characterized in that: the time that passes into of described vinylidene is 1.5 ~ 3 hours; In step (a), described stirring velocity is 80-120 rev/min, and in step (b), described stirring velocity is 180 ~ 300 revs/min.
5. a weathering resistance barrier coating that comprises polyvinylidene dichloride emulsion described in claim 1 in composition of raw materials, is characterized in that: its composition of raw materials comprises the component of following parts by weight:
80 ~ 120 parts of polyvinylidene dichloride emulsions;
5 ~ 20 parts of hydrophilic modifying tetrafluoroethylene powders;
0.5 ~ 1.5 part of flow agent;
0.1 ~ 1 part of defoamer.
6. weather-proof barrier coating according to claim 5, is characterized in that: described hydrophilic modifying tetrafluoroethylene powder is to take tetrafluoroethylene powder after grafted monomer adopts radiation or uv irradiation grafting, to be hydrolyzed and to make as acceptor, enol acid esters.
7. weather-proof barrier coating according to claim 5, is characterized in that: in its composition of raw materials, 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.
8. weather-proof barrier coating according to claim 5, is characterized in that: in its composition of raw materials, 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.
9. weather-proof barrier coating according to claim 8, 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.
10. the application of the weather-proof barrier coating described in any one in preparation weathering resistance barrier coat in claim 6 to 9.
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| CN112266653A (en) * | 2020-10-28 | 2021-01-26 | 厦门奈福新材料股份有限公司 | Printing ink adopting LED-UV light curing on PVC (polyvinyl chloride) base material and preparation method thereof |
| CN114989473A (en) * | 2022-06-01 | 2022-09-02 | 成都福全新材料有限公司 | Modified PVDC coating film and preparation method thereof |
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