CN104530852B - A kind of preparation method of photovoltaic component back plate with high hydrophobic fluorocarbon coating - Google Patents
A kind of preparation method of photovoltaic component back plate with high hydrophobic fluorocarbon coating Download PDFInfo
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- CN104530852B CN104530852B CN201410819548.9A CN201410819548A CN104530852B CN 104530852 B CN104530852 B CN 104530852B CN 201410819548 A CN201410819548 A CN 201410819548A CN 104530852 B CN104530852 B CN 104530852B
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract
The invention provides a kind of preparation method of photovoltaic component back plate with high hydrophobic fluorocarbon coating, it is adaptable to outdoor coating, application type photovoltaic back is particularly well-suited to.The fluorocarbon coating is made up of two component of first, second, and first component is 1 ~ 5 with the mass ratio of component B：1, wherein first component includes fluorocarbon resin, the nano-particle of hydrophobically modified, tin catalyst and anhydrous diluents A；Component B includes isocyanate curing agent and anhydrous diluents B.The nano-particle of the present invention can be uniformly dispersed in matrix resin Jing after coupling agent hydrophobically modified, compatibility is good, and after being coated on base material, form micro-nano rough grain structure, with reference to the low-surface-energy of fluorocarbon resin itself, make its surface that there is the high hydrophobicity of " lotus leaf effect ", good antifouling effect, and greatly reduce impact of the water droplet to component.Meanwhile, obtained fluororine-carbon coating, weather-proof, chemicals-resistant, salt spray resistance are excellent, are a kind of fluorocarbon coatings of application type photovoltaic component back plate function admirable.
Description
Technical field
The present invention relates to a kind of preparation method of high hydrophobic fluorocarbon coating, is particularly useful for making the application type photovoltaic module back of the body
Plate, belongs to material surface resist technology field.
Background technology
Photovoltaic industry is used as green, the important component part of regenerative resource, it has also become solve the master of global energy crisis
Want method.After large-sized photovoltaic power plant runs 3 or four years, photovoltaic module is asked because of the quality that component internal penetrates into the impact appearance of moisture
Topic is received more and more attention.Support and protection materials of the solar cell backboard as rear surface of solar cell, which blocks water
Performance is gradually paid attention to by industry, if its surface has high hydrophobicity, can reduce the enrichment of back plate surface moisture, in certain journey
The moisture that penetrated into by backboard of component internal is reduced on degree, from component internal can more effectively being protected from the impact of steam.
Mainly based on fluorocarbon resin, prepared fluorocarbon coating has low surface energy to application type backboard, so at present
And its intrinsic hydrophobic angle is 90 ° ~ 110 °, still there is a certain distance compared with hydrophobic requirement.Patent CN102925015A is disclosed
A kind of self-cleaning four fluorine-type fluorocarbon coating, which to surface migration and can be hydrolyzed by adding fluorine richness siloxanes to be used as in coating
Compound automatically cleaning auxiliary agent to increase its hydrophobicity, but which simply reduces coating surface from chemical composition of paint
Can, but it is fairly limited that its hydrophobicity is improved to reduce the free energy of coating surface, water contact angle is less than 120 °.Specially
Sharp CN1903961A discloses a kind of lotus leaf effect self cleaning fluorocarbon paint, and nano fumed silica is directly added into the painting of fluorine carbon
Material, but nano particle is poor with fluorocarbon radical compatability, and the big surface energy of nano particle causes its easy reunion.Recent patent
CN103992701A is proposed by adding coupling agent modified nano-particle building material surface in fluoropolymer emulsion
Micro-nano structure, obtains up to 140 ° of hydrophobic angle, but which is suitable for and is coated in metal surface and solidification temperature height, and energy consumption is big.
Haze was serious in recent years, and in air, impurity is more, and high hydrophobic backboard has anti-fouling effect simultaneously.Therefore it is comprehensive real
The pluses and minuses of demand and existing patented product, develop a kind of preparation process is simple, and group partition inter-capacitive is good, hydrophobic with height
Property, antifouling backboard, while the aspect such as weather-proof, chemicals-resistant, salt fog resistance all show excellent combination property fluorine carbon apply
Material, has certain practical significance in photovoltaic component back plate industry.
The content of the invention
The present invention seeks to be directed to the deficiencies in the prior art, there is provided a kind of photovoltaic component back plate is with high hydrophobic fluorocarbon coating
Preparation method, to improve the hydrophobicity of back plate surface, reduces the enrichment of back plate surface moisture, and reduction is led by backing plate outer residual moisture
The component of cause loses.
The invention discloses a kind of preparation method of high hydrophobic fluorocarbon coating, comprises the following steps：
（1）By coupling agent, hydrolytic accelerating agent and deionized water according to volume ratio 0.1 ~ 2:0.5~5:In normal temperature after 10 mixing
0.5 ~ 8 h of hydrolysis, adds inorganic nano-particle, and the inorganic nano-particle is 0.1 ~ 0.3 with the mass ratio of deionized water:1；
Under mechanical agitation, 60 ~ 100 DEG C of 0.5 ~ 6 h of reaction, Jing after suction filtration, washing, being dried, are milled and with 150 mesh sieve net filtrations, are obtained
The nano-particle of hydrophobically modified；
（2）Weigh 15 ~ 35 weight portion anhydrous diluents A to pour in sand mill, add in anhydrous diluents A successively under stirring
Enter fluorocarbon resin, 2 ~ 25 weight portion steps of 30 ~ 45 weight portions（1）The nano-particle of the hydrophobically modified for obtaining and 0.1 ~ 1.5 weight
The tin catalyst of amount part, the wetting dispersing agent of 0 ~ 5 weight portion, the levelling agent of 0 ~ 1 weight portion, the polyester resin of 0 ~ 10 weight portion
With 0 ~ 25 parts of filler material by weight, after being well mixed, grain fineness≤5 micron are milled to, add anhydrous diluents A viscosity to be adjusted to 10
~ 30 PaS, filter, and first component is obtained, deposit in be dried it is stand-by in sealing container；
（3）Weigh the isocyanate curing agent of 40 ~ 65 weight portions to be well mixed with the anhydrous diluents B of 35 ~ 60 weight portions,
Filter, component B be obtained, deposit in be dried it is stand-by in sealing container；
（4）During use, it is 1 ~ 5 according to mass ratio by first component and component B:1 is well mixed, continuous by automation
Shaping or batch process are coated uniformly on by gluing base material, solidify 0.5 ~ 20 min at 120 DEG C ~ 200 DEG C.
Further, the coupling agent is by γ-mercaptopropyl trimethoxysilane, N- (β-aminoethyl)-γ-aminopropyl three
Methoxy silane, dodecyl triethoxysilane, γ-aminopropyl triethoxysilane, γ-glycidyl ether oxygen propyl three
Methoxy silane, γ-（Methacryloxypropyl）Propyl trimethoxy silicane, isopropyl three（Isostearoyl base）It is titanate esters, complete
（13）Fluorine octyltri-ethoxysilane, isopropoxy three（Dioctylphosphoric acid ester）Titanium, three contracting acyl titanate of isopropoxy, two
（Dioctylphosphato）Metatitanic acid second diester, two（Dioctyl pyrophosphoryl epoxide）Glycolic titanium, two（The poly- ethene of itching of octyl phenol
Ether）One or more in the different stearic metatitanic acid of phosphatide, isopropoxy, methacryloxypropyl trimethoxy silane according to appoint
Meaning proportioning mixing composition；
The hydrolytic accelerating agent is carbon tetrachloride, methyl alcohol, isopropanol, propane diols, diesel oil or toluene；
The inorganic nano-particle particle diameter is 5 ~ 100 nm, by silica, titanium dioxide, nano aluminium oxide, three oxidations
One or more in two aluminium, zinc oxide, zirconium oxide is constituted according to the mixing of any proportioning.
Further, the fluorocarbon resin is solvent soluble type fluorocarbon resin, and hydroxyl value is 45 ~ 60 mgKOH/g, and acid number is 2
~ 12 mgKOH/g, solid content >=50%, Oil repellent are 20% ~ 30%.
Further, the tin catalyst is by stannous octoate, tin dilaurate dioctyl tin, monobutyltin oxide, only son
One or more in three isooctyl acid tin of base, dibutyl tin laurate is constituted according to the mixing of any proportioning.
Further, the isocyanate curing agent is by IPDI（IPDI）Tripolymer, isophorone
Diisocyanate（IPDI）Addition product, hexamethylene diisocyanate（HDI）Biuret, hexamethylene diisocyanate（HDI）
One or more of addition product is constituted according to the mixing of any proportioning.
Further, aromatic hydrocarbon of the diluent A and diluent B by C7 ~ C10, the ester type compound of C3 ~ C8, C1 ~
The alcohol compound of C5, one or more in the ketone compounds of C2 ~ C6 are constituted according to the mixing of any proportioning.
Further, the wetting dispersing agent is molten by the block copolymer of the copolymerization liquid solution containing acidic-group, polyamine
Liquid, acrylic block copolymers class dispersant, height branched structure polyesters wetting dispersing agent, hydroxy functional group carboxylic acid esters profit
One or more in hygroscopic water powder is constituted according to the mixing of any proportioning；
The levelling agent is polyether siloxane copolymer class, reactive polyether modified fluoro-silicone oxygen alkanes, polyether-modified poly- has
The mixture that one or more in organic siloxane class, polyacrylate is constituted according to any proportioning；
The polyester resin is the linear hydroxyl polyester with ester group and ether, and acid number≤4.0 mg KOH/g, hydroxyl contain
Measure 1.0 % ~ 5.0 %, water content≤0.1 %；
Described filler is by titanium dioxide, calcium carbonate, white fused alumina, magnesium sulfate, iron oxide black, copper is black, press for one or more in carbon black
Constitute according to the mixing of any proportioning.
The beneficial effects are mainly as follows：The invention provides a kind of preparation process is simple, it is adaptable to industrialize
Production, nano-particle can be uniformly dispersed in matrix resin Jing after coupling agent hydrophobically modified, and compatibility is good, and is coated in base material
Formed after upper it is micro--receive rough grain structure, with reference to the low-surface-energy of fluorocarbon resin itself so as to which surface has " lotus leaf effect "
High hydrophobicity, has the water contact angle for being not less than 120 ° at 25 DEG C, shows high hydrophobicity, it is to avoid dewdrop, rainwater and water
Adhesion of the vapour in back plate surface, improves the anti-hydrolytic performance of backboard, and good antifouling effect.Hydrophobic silica is significantly reduced simultaneously
The water vapor transmittance of backboard, reduces the moisture that component is penetrated into by backboard.
Specific embodiment
A kind of preparation method of photovoltaic component back plate with high hydrophobic fluorocarbon coating, obtained fluorocarbon coating have at 25 DEG C
120 ° of water contact angle is not less than, high hydrophobicity is shown, and the water vapor transmittance of backboard is significantly reduced.The preparation side of the coating
Method method is comprised the following steps：
（1）By coupling agent, hydrolytic accelerating agent and deionized water according to volume ratio 0.1 ~ 2:0.5~5:In normal temperature after 10 mixing
0.5 ~ 8 h of hydrolysis, adds inorganic nano-particle, and the inorganic nano-particle is 0.1 with the mass ratio of deionized water:1；, machine
Under tool stirring, 60 ~ 100 DEG C of 0.5 ~ 6 h of reaction, Jing after suction filtration, washing, being dried, are milled and with 150 mesh sieve net filtrations, are dredged
The modified nano-particle of water；
（2）Weigh 15 ~ 35 weight portion anhydrous diluents A to pour in sand mill, add in anhydrous diluents A successively under stirring
Enter 30 ~ 45 weight portion fluorocarbon resins, 2 ~ 25 weight portion steps（1）The nano-particle of the hydrophobically modified for obtaining and 0.1 ~ 1.5 weight
Part tin catalyst.Meanwhile, can use optional additive as needed in coating composition, such additive includes 0 ~
5 weight portion wetting dispersing agents, 0 ~ 1 weight portion levelling agent, 0 ~ 10 weight of polyester resin and 0 ~ 25 parts of filler material by weight.It is well mixed
Afterwards, grain fineness≤5 micron are milled to, anhydrous diluents A adjusts viscosity to 10 ~ 30 PaS as needed plus in right amount, filters,
Prepared first component, deposit in be dried it is stand-by in sealing container；
（3）Weigh 40 ~ 65 weight portion isocyanate curing agents to be well mixed with 35 ~ 60 weight portion anhydrous diluents B, mistake
Filter, is obtained component B, deposit in be dried it is stand-by in sealing container；
（4）During use, it is 1 ~ 5 according to the ratio of quality consumption by first component and component B:1 is well mixed, by automation
Continuously shaped or batch process is coated uniformly on by gluing base material, solidifies 0.5 ~ 20 min at 120 DEG C ~ 200 DEG C.
Coupling agent of the present invention is the modified coupling agent of hydrosulphonyl silane, the modified coupling agent of vinyl silanes, amino silane change
Property coupling agent, the modified coupling agent of silicon fluoride and titanate coupling agent, can be specifically γ-mercaptopropyl trimethoxysilane, N-
(β-aminoethyl)-γ-aminopropyltrimethoxysilane, dodecyl triethoxysilane, γ-aminopropyl triethoxysilane,
γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-（Methacryloxypropyl）Propyl trimethoxy silicane, isopropyl three
（Isostearoyl base）It is titanate esters, complete（13）Fluorine octyltri-ethoxysilane, isopropoxy three（Dioctylphosphoric acid ester）Titanium, isopropyl oxygen
Three contracting acyl titanate of base, two（Dioctylphosphato）Metatitanic acid second diester, two（Dioctyl pyrophosphoryl epoxide）Glycolic titanium, two
（The poly- vinethene of itching of octyl phenol）The different stearic metatitanic acid of phosphatide, isopropoxy, methacryloxypropyl trimethoxy silane
In one or more according to any proportioning mixing constitute；
Hydrolytic accelerating agent of the present invention is carbon tetrachloride, methyl alcohol, isopropanol, propane diols, diesel oil or toluene；
The preferred silica dioxide granule of inorganic nano-particle of the present invention, its preferred particle diameter with 5 ~ 100nm, as city
The powder-product sold, silica is cheap and can be easily obtained.Although silica dioxide granule is preferred, but it is also possible to use which
He can carry out coupling agent hydrophobically modified and can make the material with sufficiently small particle size, such as titanium dioxide, nanometer
At least one in aluminum oxide, alundum (Al2O3), zinc oxide, zirconium oxide, particle diameter are 5 ~ 100 nm；
Fluorocarbon resin of the present invention is the fluorine carbon of fluoroolefins and alkyl vinyl ether or alkyl vinyl base ester copolymerization
Resin（FEVE）.The fluorocarbon resin of the fluorocarbon resin for solvent soluble type of the present invention is suitable for, and the hydroxyl value of fluorocarbon resin is 45 ~ 60
MgKOH/g, acid number are 2 ~ 12 mgKOH/g, and solid content >=50%, Oil repellent are 20% ~ 30%；Can be vinylidene type, trifluoro
Chloroethene ene-type, fluorocarbon resin of tetrafluoroethene type etc..
Tin catalyst of the present invention is stannous octoate, tin dilaurate dioctyl tin, monobutyltin oxide, monobutyl three
The mixture that one or more in isooctyl acid tin, dibutyl tin laurate is constituted according to any proportioning；
Aliphatic isocyanates of the isocyanate curing agent of the present invention for color inhibition, to adapt to outdoor environment, preferably
IPDI（IPDI）Tripolymer, IPDI（IPDI）Addition product, two isocyanide of hexa-methylene
Acid esters（HDI）Biuret, hexamethylene diisocyanate（HDI）One or more of addition product is according to mixing that any proportioning is constituted
Compound；
Anhydrous diluents A of the present invention or anhydrous diluents B each stand alone as following one or more according to arbitrarily matching somebody with somebody
Than the mixture for constituting：The aromatic hydrocarbon of C7 ~ C10, the ester type compound of C3 ~ C8, the alcohol compound of C1 ~ C5, the ketone of C2 ~ C6
Compound.For example：Toluene, dimethylbenzene, n-butyl acetate, propylene glycol methyl ether acetate, ethyl acetate, butyl acetate, ethylene glycol,
Methyl alcohol, n-butanol, butanone, MEK, cyclohexanone etc.；The mixing for constituting according to any proportioning for preferably following one or more
Thing：Toluene, dimethylbenzene, ethyl acetate, butyl acetate, propylene glycol methyl ether acetate, butanone；
Wetting dispersing agent of the present invention be the copolymerization liquid solution containing acidic-group, the block copolymer solution of polyamine,
In acrylic block copolymers class dispersant, height branched structure polyesters dispersant, hydroxy functional group carboxylic acid esters dispersant
One or more according to any proportioning constitute mixture；
Levelling agent of the present invention is polyether siloxane copolymer class levelling agent, reactive polyether modified fluoro-silicone oxygen alkanes stream
Flat agent, polyether-modified poly organo siloxane levelling agent, one or more in polyacrylate levelling agent according to arbitrarily matching somebody with somebody
Than the mixture for constituting；
Polyester resin of the present invention is the linear hydroxyl polyester with ester group and ether, its acid number≤4.0 mg KOH/
G, 1.0 % ~ 5.0 % of hydroxy radical content, water content≤0.1 %；
Filler of the present invention is that titanium dioxide, calcium carbonate, white fused alumina, iron oxide black, copper is black, one or more in carbon black according to
Arbitrarily the mixture of proportioning composition, can improve covering power of the coating to base material, while avoiding ultraviolet from reaching substrate, carry
The weatherability of high backboard；
The commercially available acquisition of above-mentioned each component raw material.
Coating method of the present invention is routine techniques, including brushing, dip-coating, roller coating, spraying etc..When application and solidification
When, the thickness of coating composition be it is controllable in 2 ~ 35 μm, preferably 8 ~ 25 μm；Solidification temperature is adjustable in 120 DEG C ~ 200 DEG C, solidification
Time is variable between 0.5 ~ 20min.
The invention further relates to application of the fluorocarbon coating on photovoltaic component back plate, specifically, fluorocarbon coating can be coated in
On base material, base material is protected.It, with certain mechanical property and electric insulating quality, can be poly- terephthaldehyde that the base material is
Sour glycol ester, PEN, polybutylene terephthalate (PBT) and safety glass, are coated in safety glass
Air surface carries out protection and makes solar double-glass assemblies to which, or and the air surface of the polyester material containing EVA compound adhesives prepares glue
Film integration backboard, can also be that the air surface of the polyester material for being compounded with fluorine film prepares TPC class backboards.It should be noted that
For ease of contrast and experiment, the base material in following examples adopts PET.
With reference to embodiment, the invention will be further described, and wherein embodiment is not provided to limit claim
Scope, preferably specific embodiment only of the invention, but protection scope of the present invention is not limited to this, and it is any to be familiar with book
, in the technical scope of present disclosure, technology according to the present invention scheme its inventive concept is in addition for those skilled in the art
Equivalent or change, should all be included within the scope of the present invention.
Sample property indices are being measured by following method：
1. coating hardness
Method of testing reference standard GB/T 6739-2006《Hardness of film pencil determination method》.
Method of testing：Hand-held pencil inclines about 45 °, with pencil not degree of breaking into, by pencil with uniformly about 5 mm/s
Speed moves horizontally 5 mm or so on sample, and the pencil of same label repeats 5 roads, is defined so that cut is high-visible, according to drawing
Trace, records hardness values.
2. water contact angle test
Using video optics contact angle（OCA20, German DATAPHYSICS companies）Determine the water contact angle of coating.Normal temperature
Under take the deionized water that volume is 6 μ L 5 diverse locations tested in coating respectively, take its mean value.
3. constant wet and heat ageing resistant performance
Hydrothermal aging test is carried out by GB/T2423.3 test methods.
Experimental condition：+ 85 DEG C, relative humidity 85%.
Test is forward and backward to sample yellowness index（ΔYI）By GB GB 2409《Plastics yellow colour index test method》Determine；
Adhesive force test is carried out according to according to ISO-2409-2007 standards to sample after experiment.
Embodiment 1
（1）Nano-particle hydrophobically modified
By 50 mL γ-aminopropyl triethoxysilane（KH550, Noah's ark chemical material Co., Ltd）In 250 mL first
Alcohol（Hangzhou chemical reagent Co., Ltd）With 2 h of ordinary-temp hydrolysis in 500 ml deionized waters, in the lower 80 DEG C of water-baths of mechanical agitation, plus
Enter silica（Particle diameter be 15 ± 5 nm, Aladdin reagent Co., Ltd）50 g modified-reactions, 3 h, be cooled to room temperature suction filtration,
Mill after washing, 120 DEG C of 12 h of drying and obtain hydrophobically modified nano grade silica particles, powder is crossed Jing after 150 mesh sieve net filtrations
Preserve stand-by；
（2）Weigh 15g butanone（Hangzhou chemical reagent Co., Ltd）Pour in sand mill, under stirring at low speed, sequentially add 45
G (44.2 mmol OH groups) fluorocarbon resin ZHM-2（East fluorination work）, 17 g steps（1）The titanium dioxide of the hydrophobically modified for obtaining
Silicon and 1.5g monobutyls three isooctyl acid tin catalysts (Shanghai Shi Feng bio tech ltd), 17g titanium dioxide R960（The U.S.
E.I.Du Pont Company）, 1g carbon black N550（German goldschmidt chemical corporation）, it is pre-dispersed to be ground to grain fineness≤5 micron, add 0.5 g streams
Flat agent BYK310（German Bick Chemical Co., Ltd.）, after being well mixed, adjustment viscosity to 10 ~ 30 PaS is filtered, and first is obtained
Component face is starched, and is deposited in stand-by in dry hermetically sealed can；
（3）By 55g（155.81 mmol NCO groups）IPDI（IPDI）Tripolymer Z4470BA
（NCO content is 37.5%, Bayer Bitterfeld GmbH）With 20 g anhydrous dimethyl benzene（Hangzhou chemical reagent Co., Ltd）With 25 g anhydrous acetic acids
Butyl ester（Hangzhou chemical reagent Co., Ltd）It is well mixed, filters, make component B, deposits in stand-by in dry hermetically sealed can；
（4）During use, it is 3 according to the ratio of quality consumption by first component and component B:1 is well mixed, by the company of automation
Continuous shaping or batch process are coated uniformly on PET, and coating dry film thickness is 20 microns, and solidification temperature is 150 DEG C, during solidification
Between be 8 min.
Embodiment 2
（1）Nano-particle hydrophobically modified
By 100 mL γ-（Methacryloxypropyl）Propyl trimethoxy silicane（KH570, the Shanghai sea limited public affairs of Qu Huagong
Department）In 50 mL carbon tetrachloride（Jinan Jia Yu Chemical Co., Ltd.s）With 8 h of ordinary-temp hydrolysis in 1000 ml deionized waters, machinery stirs
Mix in lower 60 DEG C of water-baths, add nano aluminium oxide（Particle diameter be 10 ± 5 nm, Aladdin reagent Co., Ltd）100 g modified-reactions
6 h, are cooled to room temperature suction filtration, washing, milling after 120 DEG C of 12 h of drying obtains hydrophobically modified Nano-sized Alumina Powder, powder Jing
Preserve stand-by after 150 mesh sieve net filtrations；
（2）Weigh 20 g propylene glycol methyl ether acetates（Hangzhou chemical reagent Co., Ltd）Pour in sand mill, low speed is stirred
Mix down and sequentially add 40 g (42.8 mmol OH groups) fluorocarbon resin GK570（Daikin）, 5 g polyester
DESMOPHEN1652（Bayer A.G）, 20 g steps（1）The hydrophobically modified nano aluminium oxide for obtaining and 0.8g zinc Isoocatanoates
Catalyst (the far and near Chemical Co., Ltd. in Nantong), 4.2g wetting dispersing agent BYK-9010（German Bick Chemical Co., Ltd.）, 10
G titanium dioxide R960（Du pont company）, it is pre-dispersed to be ground to grain fineness≤5 micron afterwards, after being well mixed, adjustment is viscous
Spend to 10 ~ 30 PaS, filter, component B face slurry is obtained, deposit in stand-by in dry hermetically sealed can；
（3）50g（228.6 mmol NCO groups）Hexamethylene diisocyanate addition product curing agent HXT（The poly- ammonia of Japan
Ester Industrial Co., Ltd）With 25 g anhydrous dimethyl benzene（Hangzhou chemical reagent Co., Ltd）With the anhydrous butanone of 25 g（Hangzhou chemistry
Reagent Co., Ltd）It is well mixed, filters, make first component, deposits in stand-by in dry hermetically sealed can；
（4）During use, it is 5 according to the ratio of quality consumption by first component and component B:1 is well mixed, by the company of automation
Continuous shaping or batch process are coated uniformly on PET, and coating dry film thickness is 10 microns, and solidification temperature is 120 DEG C, during solidification
Between be 15 min.
Embodiment 3
（1）Nano-particle hydrophobically modified
Will be 100 mL complete（13）Fluorine octyltri-ethoxysilane（Jinan Lang Hua Chemical Co., Ltd.s）In 150 mL toluene
（Hangzhou chemical reagent Co., Ltd）With 1 h of ordinary-temp hydrolysis in 500 ml deionized waters, in the lower 120 DEG C of water-baths of mechanical agitation, plus
Enter titanium dioxide（Particle diameter be 40 ± 5 nm, Aladdin reagent Co., Ltd）50 g modified-reactions, 0.5 h, is cooled to room temperature and takes out
Filter, washing, milling after 120 DEG C of 12 h of drying obtains hydrophobically modified nano titanium dioxide powder, and powder is protected Jing after 150 screen filtrations
Deposit stand-by；
（2）Weigh 29g anhydrous dimethyl benzene（Hangzhou chemical reagent Co., Ltd）It is placed in container, adds under stirring at low speed successively
Enter 30 g (32.14 mmol OH groups) fluorocarbon resin GK570（Daikin）, 10 g polyester DESMOPHEN1652（Germany
Beyer Co., Ltd）, 25 g steps（1）The titanium dioxide of the hydrophobically modified for obtaining and 0.1 g tin dilaurate dioctyl tin catalyst (gold
Field raw material Co., Ltd), 5 g wetting dispersing agent BYK-9010（German Bick Chemical Co., Ltd.）, it is pre-dispersed to be ground to afterwards
Grain fineness≤5 micron, add 0.9 g levelling agents, and after being well mixed, adjustment viscosity to 10 ~ 30 PaS is filtered, and first is obtained
Component face is starched, and is deposited in stand-by in dry hermetically sealed can；
（3）By 65g (303.5 mmol NCO groups) hexamethylene diisocyanate trimer curing agent HT-90BS
（NCO content is 19.6%, Wanhua Chemical Group Co., Ltd.）With 20 g dry toluenes（Hangzhou chemical reagent Co., Ltd）
With 15 g anhydrous ethyl acetates（Hangzhou chemical reagent Co., Ltd）It is well mixed, filters, make component B, deposit in dry
It is stand-by in hermetically sealed can；
（4）During use, it is 1 according to the ratio of quality consumption by first component and component B:1 is well mixed, by the company of automation
Continuous shaping or batch process are coated uniformly on PET, and coating dry film thickness is 25 microns, and solidification temperature is 150 DEG C, during solidification
Between be 20 min.
Embodiment 4
（1）Nano-particle hydrophobically modified
By 10 mL isopropyls three（Isostearoyl base）Titanate esters（Nanjing Xu Yang Chemical Co., Ltd.s）In 400 mL methyl alcohol
（Hangzhou chemical reagent Co., Ltd）With 0.5 h of ordinary-temp hydrolysis in 1000 ml deionized waters, in the lower 60 DEG C of water-baths of mechanical agitation,
Add alundum (Al2O3)（Particle diameter be 95 ± 5 nm, Aladdin reagent Co., Ltd）15 g modified-reactions, 6 h, is cooled to room temperature and takes out
Filter, washing, milling after 120 DEG C of 12 h of drying obtains hydrophobically modified nano-aluminium oxide powder, 150 mesh sieve net filtrations of powder Jing
After preserve stand-by；
（2）Weigh 26g ethyl acetate（Hangzhou chemical reagent Co., Ltd）It is placed in container, adds under stirring at low speed successively
Enter 45g (52.2 mmol OH groups) fluorocarbon resin L101（Huambo painting Co., Ltd）, 2g steps（1）What is obtained dredges
The modified alundum (Al2O3) of water and 0.82 g stannous octoate catalysts (Aladdin reagent), 0.96g is containing acid group copolymer analog
Dispersant B YK9076（German Bi Ke chemical companies）, 23g titanium dioxide R960（Du pont company）, 2g carbon black #960（Japan three
Water chestnut chemistry）, it is pre-dispersed to be ground to grain fineness≤5 micron afterwards, add 0.22 g levelling agent YCK-1020（YCK companies）Mixing
After uniform, adjustment viscosity to 10 ~ 30 PaS is filtered, and first component face slurry is obtained, and is deposited in stand-by in dry hermetically sealed can；
（3）By 40g（206.56 mmol NCO groups）Hexamethylene diisocyanate trimer curing agent TKA100（The rising sun
Chemical conversion KCC）With 30 g anhydrous dimethyl benzene（Yong Wang Chemical Co., Ltd.s of Shenzhen）With 30 g anhydrous acetic acid butyl esters
（Hangzhou chemical reagent Co., Ltd）It is well mixed, filters, make component B, deposits in stand-by in dry hermetically sealed can；
（4）During use, it is 2.5 according to the ratio of quality consumption by first component and component B:1 is well mixed, by automation
Continuously shaped or batch process is coated uniformly on PET, and coating dry film thickness is 8 microns, and solidification temperature is 175 DEG C, solidification
Time is 0.5min.
Comparative example 1：
（1）Weigh 30 g butanone（Hangzhou chemical reagent Co., Ltd）Pour in sand mill, sequentially add under stirring at low speed
40 g (39.29 mmol OH groups) fluorocarbon resin ZHM-2（East fluorination work）, the not hydrophobically modified silica of 20 g（Grain
Footpath be 15 ± 5 nm, Aladdin reagent Co., Ltd）And 0.6g monobutyls three isooctyl acid tin catalysts (the limited public affairs of Taixing City's Shinning
Department), while adding 1.4g wetting dispersing agent BYK-163（German Bick Chemical Co., Ltd.）, 7 g carbon black 2429G（The black treasure in Anhui
Pigment new material Co., Ltd）, it is pre-dispersed to be ground with sand mill afterwards, to grain fineness≤5 micron, add 1 g levellings
Agent BYK310（German Bick Chemical Co., Ltd.）, after being well mixed, adjustment viscosity to 10 ~ 30 PaS is filtered, and first group is obtained
Point face slurry, deposits in stand-by in dry hermetically sealed can；
（3）By 55g（259.34 mmol NCO groups）Hexamethylene diisocyanate trimer curing agent HT-90BS
（NCO content is 19.6%, Wanhua Chemical Group Co., Ltd.）With 20 g anhydrous dimethyl benzene（The limited public affairs of Hangzhou chemical reagent
Department）With 25 g anhydrous acetic acid butyl esters（Bo Yang Chemical Companies of Suzhou City）It is well mixed, filters, make component B, deposits
It is stand-by in dry hermetically sealed can；
（4）During use, it is 3 according to the ratio of quality consumption by first component and component B:1 mechanical mixture is uniform, by automatic
Change continuously shaped or batch process to be coated uniformly on PET, coating dry film thickness is 15 microns, solidification temperature is 160 DEG C, Gu
The change time is 3 min.
Comparative example 2：
（1）Weigh 30 g butyl acetates（Hangzhou chemical reagent Co., Ltd）Pour in sand mill, under stirring at low speed successively
Add 40 g (42.8 mmol OH groups) fluorocarbon resin SW-5570（Shanghai Sheng Wei trade Co., Ltds）, 15 g are unmodified
Nano zircite and 1.0g zinc Isoocatanoate catalyst (Nanjing An Jing drier Co., Ltd http://
Shop1370710529412.1688.com/), 3.6g wetting dispersing agents BYK-9010（German Bick Chemical Co., Ltd.）, 10
G titanium dioxide R960（Du pont company）, it is pre-dispersed to be ground to grain fineness≤5 micron afterwards, add 0.4g levelling agents
BYK310（German Bick Chemical Co., Ltd.）, after being well mixed, adjustment viscosity to 10 ~ 30 PaS is filtered, and component B is obtained
Face is starched, and is deposited in stand-by in dry hermetically sealed can；
（3）By 40g（206.56 mmol NCO groups）Hexamethylene diisocyanate trimer curing agent TKA100（The rising sun
Chemical conversion KCC）With the anhydrous butanone of 30 g（Bo Yang Chemical Companies of Suzhou City）With 30 g anhydrous acetic acid butyl esters
（Hangzhou chemical reagent Co., Ltd）It is well mixed, filters, make component B, deposits in stand-by in dry hermetically sealed can；
（4）During use, it is 4 according to the ratio of quality consumption by first component and component B:1 is well mixed, by the company of automation
Continuous shaping or batch process are coated uniformly on PET, and coating dry film thickness is 20 microns, and solidification temperature is 160 DEG C, during solidification
Between be 5 min.
Performance detection is carried out to embodiment 1,2,3,4 and application type backboard obtained in comparative example 1,2, as a result as shown in table 1.
The performance parameter of 1 application type backboard of table
| Performance parameter | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 | Comparative example 2 |
| Hardness | 4H | 4H | 4H | 4H | 3H | 3H |
| Dwell angle | 139° | 141° | 138° | 130° | 101° | 95° |
| Adhesive force | 0 grade | 0 grade | 0 grade | 0 grade | 0 grade | 0 grade |
| Hydrothermal aging 2000h yellowness index（ΔYI） | 2.2 | 2.3 | 2.0 | 2.8 | 3.0 | 2.6 |
| Hydrothermal aging 2000h outward appearances | Without cracking, bubble-free, without powder Change | Without cracking, bubble-free, without powder Change | Without cracking, bubble-free, without powder Change | Without cracking, bubble-free, without powder Change | Without cracking, bubble-free, without powder Change | Without cracking, bubble-free, nothing Efflorescence |
The photovoltaic back fluorocarbon coating prepared from data in table, the present invention, it is with higher hydrophobicity and resistance to old
Change excellent performance, be a kind of fluorocarbon coating composition of the excellent performance that can adapt to outdoor environment.
Claims (7)
1. preparation method of a kind of photovoltaic component back plate with high hydrophobic fluorocarbon coating, it is characterised in that comprise the following steps：
(1) by coupling agent, hydrolytic accelerating agent and deionized water according to volume ratio 0.1～2:0.5～5:In normal-temperature water after 10 mixing
0.5～8h of solution, adds inorganic nano-particle, and the inorganic nano-particle is 0.1 with the mass ratio of deionized water:1；Machinery is stirred
Mix down, 60～100 DEG C of 0.5～6h of reaction, Jing after suction filtration, washing, being dried, mill and with 150 mesh sieve net filtrations, obtain hydrophobic changing
The nano-particle of property；
(2) 15～35 weight portion anhydrous diluents A are weighed to pour in sand mill, is sequentially added in anhydrous diluents A under stirring
The nano-particle and 0.1～1.5 weight of the hydrophobically modified that the fluorocarbon resin of 30～45 weight portions, 2～25 weight portion steps (1) are obtained
The tin catalyst of amount part, the wetting dispersing agent of 0～5 weight portion, the levelling agent of 0～1 weight portion, the polyester of 0～10 weight portion
Resin and 0～25 parts of filler material by weight, after being well mixed, are milled to grain fineness≤5 micron, add anhydrous diluents A adjustment
Viscosity is filtered to 10～30PaS, and first component is obtained, deposit in be dried it is stand-by in sealing container；
(3) the anhydrous diluents B of the isocyanate curing agent and 35～60 weight portions of 40～65 weight portions is weighed, is well mixed,
Filter, component B be obtained, deposit in be dried it is stand-by in sealing container；
(4), when using, it is 1～5 according to mass ratio by first component and component B:1 is well mixed, continuously shaped by automating
Or batch process is coated uniformly on by gluing base material, solidifies 0.5～20min at 120 DEG C～200 DEG C.
2. preparation method of a kind of photovoltaic component back plate according to claim 1 with high hydrophobic fluorocarbon coating, its feature exist
In, the coupling agent by γ-mercaptopropyl trimethoxysilane, N- (β-aminoethyl)-γ-aminopropyltrimethoxysilane, 12
Alkyl triethoxysilane, γ-aminopropyl triethoxysilane, γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-
(methacryloxypropyl) propyl trimethoxy silicane, isopropyl three (isostearoyl base) titanate esters, complete three second of (13) fluorine octyl group
One kind in TMOS, two (dioctylphosphato) metatitanic acid second diester, methacryloxypropyl trimethoxy silane
Or it is various according to any proportioning mixing composition；
The hydrolytic accelerating agent is carbon tetrachloride, methyl alcohol, isopropanol, propane diols, diesel oil or toluene；
The inorganic nano-particle particle diameter is 5～100nm, by silica, titanium dioxide, nano aluminium oxide, zinc oxide, oxidation
One or more in zirconium is constituted according to the mixing of any proportioning.
3. preparation method of a kind of photovoltaic component back plate according to claim 1 with high hydrophobic fluorocarbon coating, its feature exist
In, the fluorocarbon resin is solvent soluble type fluorocarbon resin, and hydroxyl value is 45～60mgKOH/g, and acid number is 2～12mgKOH/g, Gu
Content >=50%, Oil repellent are 20%～30%.
4. preparation method of a kind of photovoltaic component back plate according to claim 1 with high hydrophobic fluorocarbon coating, its feature exist
In, the tin catalyst by stannous octoate, tin dilaurate dioctyl tin, monobutyltin oxide, three isooctyl acid tin of monobutyl, two
One or more in dibutyl tin laurate is constituted according to the mixing of any proportioning.
5. preparation method of a kind of photovoltaic component back plate according to claim 1 with high hydrophobic fluorocarbon coating, its feature exist
In the isocyanate curing agent is by IPDI (IPDI) tripolymer, IPDI
(IPDI) addition product, hexamethylene diisocyanate (HDI) biuret, the one of hexamethylene diisocyanate (HDI) addition product
Plant or various according to any proportioning mixing composition.
6. preparation method of a kind of photovoltaic component back plate according to claim 1 with high hydrophobic fluorocarbon coating, its feature exist
In, aromatic hydrocarbon of the diluent A and diluent B by C7～C10, the ester type compound of C3～C8, the alcohols of C1～C5
Compound, one or more in the ketone compounds of C2～C6 are constituted according to the mixing of any proportioning.
7. preparation method of a kind of photovoltaic component back plate according to claim 1 with high hydrophobic fluorocarbon coating, its feature exist
In the wetting dispersing agent is common by the copolymerization liquid solution containing acidic-group, the block copolymer solution of polyamine, acrylic acid block
In polymers class dispersant, height branched structure polyesters wetting dispersing agent, hydroxy functional group carboxylic acid esters wetting dispersing agent one
Plant or various according to any proportioning mixing composition；
The levelling agent is by polyether siloxane copolymer class, reactive polyether modified fluoro-silicone oxygen alkanes, polyether-modified poly-organosilicon
One or more in oxygen alkanes, polyacrylate is constituted according to the mixing of any proportioning；
The polyester resin is the linear hydroxyl polyester with ester group and ether, acid number≤4.0mg KOH/g, hydroxy radical content
1.0%～5.0%, water content≤0.1%；
Described filler is by titanium dioxide, calcium carbonate, white fused alumina, magnesium sulfate, iron oxide black, copper is black, one or more in carbon black according to appointing
Meaning proportioning mixing composition.
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| CN106243798B (en) * | 2016-07-28 | 2018-04-17 | 河北科技大学 | A kind of dual cure F-Si hydrophobic coating material and preparation method thereof |
| CN106366791B (en) * | 2016-08-29 | 2018-11-09 | 苏州福斯特光伏材料有限公司 | A kind of backboard that can delay failure under dry wet alternating environment |
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| US9221076B2 (en) * | 2010-11-02 | 2015-12-29 | Ut-Battelle, Llc | Composition for forming an optically transparent, superhydrophobic coating |
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| CN103242718A (en) * | 2013-04-03 | 2013-08-14 | 广东电网公司电力科学研究院 | Titanate coupling agent modified pollution-flashover-preventing fluorocarbon paint and preparation method thereof |
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