CN106010414A - High-cohesiveness fluorocarbon coating and application - Google Patents

Abstract

The invention discloses a high-cohesiveness fluorocarbon coating. The high-cohesiveness fluorocarbon coating is adopted as a bonding layer of a solar cell backing plate. The fluorocarbon coating is formed by mixing a component A and a component B, wherein the component A contains an isocyanate curing agent adopted as a cross-linking agent; the component B is prepared from fluorocarbon resin, modified polyolefin and inorganic filler A modified by a functional coupling agent. The inorganic filler treated by the functional coupling agent plays a bridge role in the bonding layer and an EVA interface, and cohesive force between the coating and the EVA is effectively improved; meanwhile, the modified polyolefin introduced in the bonding layer and a polyester supporting body obtained after corona treatment with the surface containing a polar group and achieve the excellent sealing performance. According to the obtained fluorocarbon coating, the bonding layer can achieve the cohesiveness with a packaging material and the polyester supporting body, the packaging material peel strength is high, the adhesive force is good, the bonding durability and excellent weather resistance are achieved under the damp, hot and optical environment, and the high-cohesiveness fluorocarbon coating can be prepared with low cost.

Description

A kind of high-adhesion fluorocarbon coating and purposes

Technical field

The present invention relates to a kind of coating, particularly relate to one and be applicable to prepare application type solar cell backboard, be used for changing The fluorocarbon coating of kind cohesive between encapsulating material and backboard.

Background technology

The application of solar energy is mainly converted into electric energy by solar module and is used, and does not arranges during generating Go out carbon dioxide and the little generation mode of environmental pressure, be the representative of green energy resource.At present, in conventional solar module too Positive electricity pool unit is sandwiched between the face glass of sunlight light incident side and the so-called backboard being placed in opposition side (rear side), Wherein, between face glass and solar battery cell and between solar battery cell and backboard, it is utilized respectively encapsulating material (logical Often for vinyl-vinyl acetate copolymer (EVA) resin) seal.In order to reach the solar module use of 25 years Life-span, it is important that protection solar battery cell and encapsulant are not affected by wind and rain, dampness, high temperature, sand and dust etc., therefore it is required that Backboard have long durability and and EVA between there is high sealing.

Polyester film is with thermostability, mechanical property and the chemical proofing of its excellence, and is favourable becoming present aspect, logical Often it is selected as the supporter of backboard, different from the composition of encapsulating material EVA yet with polyester support, therefore, it is difficult to incite somebody to action both Directly bonding, needs both to be engaged by intermediate adhesive layer.Cohesive between encapsulating material and backboard includes polyester support The two interface, interface between interface and tack coat and encapsulating material between body and tack coat, thereby ensure that assembly sealing Need to improve the two interface performance simultaneously.The main product of backboard has compound (TPT, KPK) and application type at present, due to multiple Mould assembly backboard manufacturing cost is high, and fluorine film as tack coat in addition to the bad adhesion of EVA, prop up with polyester also by glue Support body carries out boning and easily occurs aging stripping after humid heat treatment.

Patent CN105097971 A makes fluorocarbon resin have with the EVA in encapsulating material by the addition of function coupling agent Good caking property, the fluorocarbon coating described in this patent only has fluorocarbon resin and firming agent in addition to function coupling agent, it is impossible to enough Ensure internally coated reflectance, and the xanthochromia after tropical deterioration processes is relatively big, poor adhesive force, simultaneously its described firming agent Containing aromatic isocyanate, strengthen xanthochromia further, affect backboard weatherability and outward appearance.Patent JP-A 2006-152013 With the technology described in JP-A 2003-060218 can improve the initial adhesion between encapsulant and backboard, but in phase To in hot and humid environment, poor durability.Patent CN 102792462 A uses polyolefin, polyester, acrylic polymer And polyurethane is as binding agent, adds fine inorganic particle composition adhesive linkage and be coated in polyester support surface, improve backboard with close Closure material durability in hygrothermal environment, but its described binding agent weatherability is the best, and aging post yellowing is serious, it is impossible to full Podoscutum was service life of outdoor 25 years.Patent CN 105102228 A is by arranging stacked film, institute on polyester support Stating stacked film is double-layer structure, and ground floor is ethylene and (methyl) acrylate and the improved polyalkene tree of the copolymer of anhydride Fat, the second layer is olefin-based resin, has effectively had the caking property to EVA and tack to polyester support concurrently, but its Complex manufacturing technology, it is desirable to high, described stacking thickness as little as 0.05 μm, there is certain challenge in industrialized production.

In view of the above circumstances, it is provided that while a kind of and encapsulating material has excellent adhesion, also have and polyester support The tack coat that body tack is excellent becomes important, and especially, this tack coat is excellent the most at normal temperatures and pressures, and wet Heat, luminous environment have adhesive durability and excellent weather resistance, it is possible to prepared by low cost, for the guarantor of solar module Protect particularly important.

Summary of the invention

Present invention aims to the deficiency that prior art exists, it is provided that a kind of high-adhesion fluorocarbon coating.

It is an object of the invention to be achieved through the following technical solutions: a kind of high-adhesion fluorocarbon coating, it is by first, second Two component compositions；Described first component is cross-linking agent, including isocyanate curing agent and 35～60 weight portions of 40～65 weight portions Anhydrous diluents A；Described component B contains the fluorocarbon resin of 35～50 weight portions, the improved polyalkene of 2～15 weight portions, and 5 ～25 weight portion through the coupling agent modified inorganic filler A, the anhydrous diluents B of 15～35 weight portions of function；During use, by first group Part and component B be 0.4～1.5 to mix by the ratio of the NCO in first component with the amount of the material of the hydroxyl in component B, Obtain high-adhesion fluorocarbon coating.

Further, described component B may also include 0～15 fluorocarbon resins, 0.1～2 part by weight of catalyst, 0～20 weight Part inorganic filler B, 0～0.5 one or more of weight portion levelling agent and 0.2～2 weight portion wetting dispersing agents；

Described catalyst is metal compound as catalyst；

Described inorganic filler B is Rutile type titanium dioxide；

Described wetting dispersing agent is by the copolymer solution containing acidic-group, the block copolymer solution of polyamine, acrylic acid One or more in block copolymerization species, highly branched structure polyesters, hydroxy functional group carboxylic acid esters are mixed by any proportioning It is combined into；

Described anhydrous diluents A, anhydrous diluents B each stand alone as one or more mixing by any proportioning following Close: the aromatic hydrocarbon of C7～C10, the ester type compound of C3～C8, the alcohol compound of C1～C5, the ketone compounds of C2～C6.

Further, described component B is prepared by the following method and obtains: weighs anhydrous diluents B and pours in sand mill, In diluent B, it is sequentially added into fluorocarbon resin, improved polyalkene, inorganic filler A under stirring under 1500-3500rpm rotating speed, divides in advance After Saning, it is milled to fineness of the particles≤5 micron；Add polyester resin, wetting dispersing agent, catalyst, levelling agent, inorganic filler B In one or more, mechanical mixture is uniform, adds anhydrous diluents B and adjusts viscosity to 500～2000m Pa S, filters, deposit In dry sealing container stand-by.

Further, the amount of the material of the NCO (NCO) in described first component and the hydroxyl (OH) in component B Ratio be preferably 0.5～1.2, more preferably 0.8～1.0.

Further, described isocyanate curing agent is aliphatic isocyanates；Described fluorocarbon resin is by solvent soluble type Vinylidene type, CTFE type, tetrafluoroethene type fluorocarbon resin one or both by any proportioning mixing composition, The hydroxyl value of fluorocarbon resin is 45～60mgKOH/g, and acid number is 2～12mgKOH/g, solid content >=50%, and Oil repellent is 20wt% ～30wt%；

Further, described modified polyolefin hydrocarbon content is preferably the 5%～30% of fluorocarbon resin, more preferably 10%～ 25%, can be grafting polyolefin, esters modification polyolefin, terminal hydroxy group polyolefin, including Low Density Polyethylene and acrylic acid Ester and the terpolymer of maleic anhydride, ethylene-(methyl) acrylate-maleic anhydride multipolymer, ethylene-propylene-(first Base) acrylate-maleic anhydride multipolymer, end hydroxy butadiene, hydrogenation end hydroxy butadiene, maleic anhydride grafting Polybutadiene, maleic anhydride inoculated polypropylene, ene-propylene-butene-(methyl) acrylate-maleic anhydride multipolymer, It it is the most preferably ethylene-(methyl) acrylate-maleic anhydride multipolymer.

Further, described inorganic filler A is through function coupling agent treatment, and inorganic filler A is by silicon dioxide, calcium carbonate, carbon Acid magnesium, zinc oxide, aluminium oxide, Pulvis Talci, wax powder, Kaolin, white fused alumina, barium sulfate, ceramic, white carbon black in one or Multiple by any proportioning mixing composition；Described functional type coupling agent is by titanate coupling agent, aluminate coupling agent, silicon fluoride modification One or more in coupling agent, zirconium ester coupling agent, Lü Zuqian and aluminum-titanium composite coupler press any proportioning Mixing composition；

Further, first described function coupling agent treatment particularly as follows: join 30 by the inorganic filler A of 100 weight portions ～80 weight portion anhydrous diluents A or B in, ultrasonic disperse 0.5h～3h at a temperature of 30 DEG C～50 DEG C, after being uniformly dispersed, then Add the function coupling agent of 0.1～10 weight portions, then supersound process 1h～3h at 50 DEG C～60 DEG C, obtain coupling agent treatment Inorganic filler A；The consumption of function coupling agent preferably 0.3～5 weight portion.

A kind of above-mentioned high-adhesion fluorocarbon coating on solar components purposes, this purposes particularly as follows: by fluorine carbon be coated with On material coated polyester supporter, prepare high-adhesion backboard；Again high-adhesion backboard is laminated with encapsulating material；Described poly- The average thickness of ester supporter is 50～300 μm, and carboxyl-content is 0.5 equivalent/t to 35 equivalents/t, for poly terephthalic acid second Diol ester (PET), PEN (PEN), polybutylene terephthalate (PBT) (PBT), poly terephthalic acid third The single or multiple lift thin film that diol ester (PTT) is constituted；Described encapsulating material is vinyl-vinyl acetate copolymer (EVA).

Further, described polyester support carries out surface reason before coating fluorocarbon coating, and described surface processes and is selected from The process of sided corona treatment, flame treatment, low pressure plasma, atmospheric plasma treatment, UV treatment etc.；Preferably at corona Reason, the described sided corona treatment time is 0.5s～100s；Described coating method is selected from brushing, dip-coating, roller coating, spraying；Paint thickness Being 3～30 μm, solidification temperature is 150 DEG C～200 DEG C, hardening time 1min to 15min.

The invention has the beneficial effects as follows: the present invention provides a kind of high-adhesion fluorocarbon coating, as solar panel Tack coat, in tack coat, the inorganic filler surface of function coupling agent treatment contains and active function groups generation chemistry in fluorocarbon resin The group of reaction, the radical reaction that simultaneously can produce with EVA in lamination process forms chemical bond, plays " bridge at interface Beam " effect, effectively raise the cohesive force between coating and EVA, macroscopically show as high peel strength.PET simultaneously After treatment, substantial amounts of hydroxyl, carboxyl are contained in surface, react with the cross-linking agent in first component in solidification process, form chemical bond Keyed jointing, improves the adhesiveness of tack coat and polyester support, and the polyester that polar group is contained on the surface that sided corona treatment is crossed simultaneously props up Support body and improved polyalkene show the adhesion of excellence, and macro manifestations is good adhesive force.Fluorine carbon prepared by the present invention Paint adhesion layer can take into account the caking property with encapsulating material and polyester support simultaneously, high with the peel strength of encapsulating material, Adhesive force is high, and has adhesive durability and excellent weather resistance under damp and hot, luminous environment, and can low cost prepare.

Detailed description of the invention

Hereinafter the present invention is described in detail, wherein, this specification uses "～" numerical range that represents refers to Comprise "～" before and after described numerical value as lower limit and the scope of higher limit, and as long as no particularly pointing out, occurred " part " and " % " is on the basis of quality.

High-adhesion fluorocarbon coating of the present invention, is made up of first, second two component；Described first component is the cross-linking agent of tack coat, It is prepared from by the isocyanate curing agent of 40～65 weight portions and the anhydrous diluents A mix homogeneously of 35～60 weight portions, deposits It is put in dry sealing container stand-by；Described component B at least contains the fluorocarbon resin of 35～50 weight portions, 2～15 weight portions Improved polyalkene, the inorganic filler A that 5～25 weight portion functions are coupling agent modified, the anhydrous diluents B of 15～35 weight portions.

For improving the adhesive property of tack coat further, improve the reaction rate of first and second liang of components, increase the covering of coating Power and improve the combination property of coating, the most described component B may also include 0～15 fluorocarbon resins, 0.1～2 weight portion urge Agent, 0～20 parts by weight of inorganic filler B, 0～0.5 weight portion levelling agent, 0.2～2 weight portion wetting dispersing agents, the most excellent Elect as including at least catalyst, wetting dispersing agent.

The preparation process of described component B is: weighing 15～35 weight portion anhydrous diluents B and pour in sand mill, low speed stirs Mix the lower 35～50 weight portion fluorocarbon resins that are sequentially added in diluent B, the improved polyalkene of 2～15 weight portions, 0.2～2 weights Amount part wetting dispersing agent, the inorganic filler A of 5～25 weight portions, pre-dispersed after, be milled to fineness of the particles≤5 micron, as required Can use optional additive in coating composition, although not necessarily, such additive includes 0.1～2 weight portions Catalyst, 0～0.5 weight portion levelling agent, 0～15 polyester resin, 0～20 parts by weight of inorganic filler B, mechanical mixture is uniform, root Add appropriate anhydrous diluents A according to needs and adjust viscosity to 500～2000m Pa S, filter, prepare first component, deposit in dry Seal in container stand-by.

Described high-adhesion fluorocarbon coating is according to the NCO (NCO) in first component and the hydroxyl in component B (OH) ratio of the amount of material is 0.4～1.5 (preferably 0.5～1.2, more preferably 0.8～1.0), first component and component B is entered Row proportioning, mechanical mixture is uniform, prepares compo, or batch process continuously shaped by automatization is coated uniformly on polyester On supporter, after solidification, obtain described high-adhesion backboard.

In described first component, the amount of NCO (NCO) can be calculated according to the consumption of isocyanate curing agent, different Cyanate firming agent solid content is typically shown in commodity packaging, or can detect voluntarily.

In described component B, the amount of hydroxyl (OH) can be calculated according to the hydroxyl value in the fluorocarbon resin contained in component B, The hydroxyl value of fluorocarbon resin is similarly the parameter of commodity sign, or can detect voluntarily.

Described isocyanate curing agent is not yellowing, the aliphatic isocyanates protecting gloss, preferably isophorone two isocyanide Acid esters (IPDI) trimer, isophorone diisocyanate (IPDI) addition product, hexamethylene diisocyanate (HDI) contract two Urea, one or more mixture of hexamethylene diisocyanate (HDI) addition product.

Described fluorocarbon resin is fluoroolefins and alkyl vinyl ether or the fluorocarbon resin of alkyl vinyl ester copolymerization (FEVE).The fluorocarbon resin being suitable for the present invention is solvent soluble type vinylidene type, CTFE type, tetrafluoroethene type fluorine carbon One or both mixture of resin, the hydroxyl value of preferred fluorocarbon resin is 45～60mgKOH/g, acid number be 2～ 12mgKOH/g, solid content >=50%, Oil repellent is 20%～30%.

Described improved polyalkene can be can be grafting polyolefin, esters modification polyolefin, terminal hydroxy group polyolefin, bag Include and include Low Density Polyethylene and acrylate and the terpolymer of maleic anhydride, ethylene-(methyl) acrylic acid ester-maleic Anhydride multipolymer, ethylene-propylene-(methyl) acrylate-maleic anhydride multipolymer, end hydroxy butadiene, hydrogenation End hydroxy butadiene, maleic anhydride grafted polybutadiene, maleic anhydride inoculated polypropylene, ene-propylene-butene-(methyl) Acrylate-maleic anhydride multipolymer, is the most preferably that ethylene-(methyl) acrylate-maleic anhydride is common Polymers, the form of copolymer can be any one of trackless copolymer, block copolymer, graft copolymer etc., is easy for obtaining Aspect for, preferably random copolymer, graft copolymer.

The content of described improved polyalkene is preferably the 5%～30% of fluorocarbon resin, more preferably 10%～25%, contains Amount may insure that the tack coat caking property for EVA more than 5%, if content is less than 30%, then can obtain as target resistance to The raising effect of time property.

With component B further be the catalyst of cross-linking agent, by the catalyst containing cross-linking agent, can promote main Body resin and the reaction of firming agent, it is achieved the raising of solvent resistance, and, cross-link good carrying out, bonding can be improved further The intensity of layer, dimensional stability, thus can improve the adhesion of tack coat.

Described catalyst is metal compound as catalyst, and concrete can be one of the following or two or more mixing Thing: zinc Isoocatanoate, stannous octoate, tin dilaurate dioctyl tin, monobutyltin oxide, monobutyl three isooctyl acid stannum, tin dilaurate Dibutyl tin etc..

Described diluent A or diluent B can improve coating adhesion and final coating performance, is suitable for the diluent of the present invention A or diluent B each stands alone as one or more mixing following: the aromatic hydrocarbon of C7～C10, the esters chemical combination of C3～C8 Thing, the alcohol compound of C1～C5, the ketone compounds of C2～C6.Further, described diluent A or diluent B is each independent For one or more mixing following: toluene, dimethylbenzene, n-butyl acetate, propylene glycol methyl ether acetate, ethyl acetate, Butyl acetate, ethylene glycol, methanol, n-butyl alcohol, butanone, butanone, Ketohexamethylene；One or more mixed more preferably the most following Close: toluene, dimethylbenzene, ethyl acetate, butyl acetate, propylene glycol methyl ether acetate, butanone.

Described wetting dispersing agent is the copolymer solution containing acidic-group, the block copolymer solution of polyamine, acrylic acid One or more mixture in block copolymerization species, highly branched structure polyesters, hydroxy functional group carboxylic acid esters.

Described levelling agent is polyether siloxane copolymer class, reactive polyether modified fluoro-silicone oxygen alkanes, has polyether-modified gathering Organic siloxane class, one or both mixture of polyacrylate apoplexy due to endogenous wind.

Further, described tack coat comprises the inorganic filler A that at least one function is coupling agent modified.

Described inorganic filler A includes silicon dioxide, calcium carbonate, magnesium carbonate, zinc oxide, aluminium oxide, Pulvis Talci, wax powder, height Ridge soil, white fused alumina, barium sulfate, ceramic, white carbon black, select white carbon black as inorganic filler herein, solar energy backboard can be made to have Disguise, wherein, from the point of view of the adhesiveness when being exposed to heat and humid atmosphere reduces, preferably talc powder and wax powder； The particle diameter of described inorganic filler A is 0.1～5 μm, preferably 0.5～3 μm, when particle diameter in this range, it is possible to obtain more satisfied Easy adhesiveness.

Described inorganic filler A is through function coupling agent treatment.

Described functional type coupling agent is titanate coupling agent, aluminate coupling agent, silicon fluoride modification coupling agent, zirconate idol One or more in connection agent, Lü Zuqian and aluminum-titanium composite coupler.

The method of described function coupling agent treatment inorganic filler A is: first joined by the inorganic filler A of 100 weight portions In anhydrous diluents A or B of 30～80 weight portions, after at a temperature of 30 DEG C～50 DEG C, ultrasonic disperse 0.5h～3h is uniformly dispersed, It is slow added into the function coupling agent of 0.1～10 weight portions, then supersound process 1～3h at 50 DEG C～60 DEG C, obtains coupling agent The inorganic filler A processed.

Described functional type coupling agent accounts for 0.1%～10% into inorganic filler weight portion, preferably 0.3%～5%, if adding Amount is less than 0.1%, it is impossible to ensures that inorganic filler processes completely, does not has good cementation, if addition is more than 10%, residual The function coupling agent stayed will lower the adhesive force of bonding coat and base material, and performance is that EVA packaging adhesive film carries out peel test Time bonding coat remain on EVA packaging adhesive film, coupling agent consumption within the above range, can significantly improve fluorocarbon resin with Peeling force between EVA packaging adhesive film, it is not necessary to the tack coat being cured is done subsequent treatment, in the premise ensureing high-adhesion Under, simplify preparation technology.

Content based on tack coat component B, the content of described inorganic filler A, in the range of 15～50%, is filled out if inorganic The content of material is less than 15%, then when cruelly leaking the adhesiveness that can not keep satisfied in heat and humid atmosphere, if content is more than When 50%, tie layer surface state can be deteriorated, preferably in the range of 20～40%.

Described inorganic filler B is titanium dioxide, has rutile-type, Detitanium-ore-type, brockite in the system of crystallization of titanium dioxide Type, based on tack coat reflectance, the requirement of the weatherability under the experiment of long term high temperature high humidity and UV senile experiment, preferably rutile-type Titanium dioxide, can improve coating simultaneously and to the covering power of polyester support and improve further and the adhesion of other critical layers.

In described first component, in isocyanate groups and component B, the mol ratio of hydroxyl is 0.4～1.5, preferably 0.5～ 1.2, most preferably 0.8～1.0, if the mol ratio of isocyanate groups and hydroxyl is less than 0.4, the hydroxyl reaction in fluorocarbon resin is not Completely, the crosslink density causing bonding coat is low, and the filming performance of bonding coat is poor, reduces the wet and heat ageing resistant of backboard Energy；If isocyanate groups is higher than 1.5 with the mol ratio of hydroxyl, the most unreacted isocyanates can occur with the moisture in air Reaction, causes bonding coat solidification crosslink density high, and bonding coat is harder, causes tack coat attachment on polyester support Power reduces.

The invention still further relates to fluorocarbon coating application on photovoltaic component back plate, concrete, fluorocarbon coating can coat poly- On ester supporter.

Described polyester support can be polyethylene terephthalate (PET), PEN (PEN) single or multiple lift that, polybutylene terephthalate (PBT) (PBT), PTT (PTT) etc. are constituted is thin Film, evaluates from heat stability, cost etc., and preferably polyethylene terephthalate (PET), can select not according to purposes difference The polyester support of stack pile different colours；Described polyester support surface tension be more than 10dyn/cm, carboxyl-content be 0.5 work as Amount/t to 35 equivalents/t.

The average thickness of described polyester support is 50～300 μm, thickness be more than 50 μm, for backboard mechanical strength, Insulating properties and high voltage performance aspect are favourable, should be less than 300 μm, particularly polyester support tool for cost consideration thickness Have along with thickness increases and hydrolytic resistance can be deteriorated, thus durability reduces during life-time service, therefore polyester support Average film thickness is preferably below 300 μm.

Described polyester support carries out sided corona treatment, flame treatment, low pressure plasma process, atmospheric pressure etc. before coating The surfaces such as gas ions process or UV treatment process, increase surface polarity, sided corona treatment increase surface functional group (-OH ,- COOH) content, coated after, solidification process reacts with the cross-linking agent in first component, formed chemical bond keyed jointing, improve tack coat With the adhesiveness of polyester support, polyester support and the improved polyalkene of polar group is contained on the surface that sided corona treatment is crossed simultaneously Show the adhesion of excellence.

The described sided corona treatment time is preferably 0.5s～100s, more preferably 1～50s, is processing deficiency of time 0.5s's In the case of, there is the situation that adherence improved effect is insufficient, if contrary more than 100s, then exist produce processed film deformation or Person's coloring problem.

Described coating method uses known coating method, including brushing, dip-coating, roller coating, spraying etc..When applying and solidifying Time, the thickness of the coating composition of the typical present invention is 3～30 μm, and when the thickness of tack coat is more than 3 μm, bonding coat can Fully obtain the raising of durability, weatherability, it is ensured that coating reflectivity, and tack coat and polyester support and the caking property of EVA, When the thickness of tack coat is less than 30 μm, controllable costs increases, the deterioration of suppression planar, it is ensured that adhesiveness, preferred thickness In being 5 μm～25 μ m.

The condition of cure of described tack coat is: solidification temperature is adjustable, general 150 DEG C～200 DEG C, and preferably 160 DEG C～ 190℃；Hardening time is variable, typically 1min to 15min, and preferably 2min to 10min.

Present invention additionally comprises the application on solar components of the described high-adhesion backboard, carry out being laminated with encapsulating material and Become.

Described encapsulating material is vinyl-vinyl acetate copolymer (EVA) resin.

Below in conjunction with specific embodiment, the present invention is described further, but protection scope of the present invention is not limited to these Specific embodiment and the content of embodiment, and described base material is also not necessarily limited to polyethylene terephthalate.

Embodiment 1:

Prepared by first component: by 55g (155.81mmol NCO group) isophorone diisocyanate (IPDI) trimer Z4470BA (NCO content is 37.5%, Bayer Bitterfeld GmbH) and 20g anhydrous dimethyl benzene (Hangzhou chemical reagent company limited) and 25g without Water butyl acetate (Hangzhou chemical reagent company limited) mix homogeneously, filters, makes first component, deposit in dry hermetically sealed can Stand-by.

Prepared by component B: be placed in container by 15g butanone (Hangzhou chemical reagent company limited), add successively under stirring at low speed Enter 50g (49.1mmol OH group) fluorocarbon resin ZHM-2 (east fluorination work), 2g improved polyalkene CHEMIPEARLS (trade name, Manufactured by Mitsui Chemicals, Inc.), 0.65g wetting dispersing agent BYK-163 (Bick Chemical Co., Ltd. of Germany), 15g (good luck source, Shanghai chemical industry is limited for the calcium carbonate that titanium dioxide (good luck source, Shanghai Chemical Co., Ltd.) and 5g titanate coupling agent process Company) pre-dispersed after be ground with sand mill, to fineness of the particles≤5 micron, add 0.2g levelling agent BYK310 (Germany ratio Gram Chemical Co., Ltd.), 0.1g catalyst zinc Isoocatanoate (Shinning company limited of Taixing City), after mix homogeneously, adjust viscosity, mistake Filter, prepares second component face slurry, deposits in dry hermetically sealed can stand-by.

Prepared by a kind of solar cell backboard fluororine-carbon coating: be 1.2 by first, second two component by the mol ratio of NCO/OH: 1.0 mix, or batch process continuously shaped by automatization is coated uniformly on the PET polyester support of corona cleaning On body, solidify 5min at 170 DEG C, obtain 20 μ m-thick tack coat solar components backboards, be denoted as S1.

Embodiment 2:

Prepared by first component: by 50g (233.5mmolNCO group) hexamethylene diisocyanate trimer firming agent HT- (Hangzhou chemical reagent is limited with 20g dry toluene for 90BS (NCO content is 19.6%, Wanhua Chemical Group Co., Ltd.) Company) and 30g anhydrous ethyl acetate (Hangzhou chemical reagent company limited) mix homogeneously, filter, make first component, deposit in dry In dry hermetically sealed can stand-by.

Prepared by component B: by 10g ethyl acetate (Hangzhou chemical reagent company limited) and 25g propylene glycol methyl ether acetate (PMA) (Kunshan sincerity chemical industry) is placed in container, is sequentially added into 35g (37.49mmolOH group) fluorocarbon resin under stirring at low speed GK570 (Daikin), 15g improved polyalkene S-75N (is manufactured by Mitsui Chemicals, Inc.), 3g fluorocarbon resin DESMOPHEN1652 (Bayer A.G), 1.2g wetting dispersing agent BYK-9010 (Bick Chemical Co., Ltd. of Germany), 25g The BHS8860 Pulvis Talci (Quanzhou Xu Feng powder material company limited) of silicon fluoride coupling agent treatment, pre-dispersed after use sand mill It is ground, to fineness of the particles≤5 micron, adds 0.2g levelling agent BYK310 (Bick Chemical Co., Ltd. of Germany), 0.48g bis- Dioctyltin laurate catalyst (Jin Tian raw material company limited), after mix homogeneously, adjusts viscosity, filters, prepare second component face Slurry, deposits in dry hermetically sealed can stand-by.

Prepared by a kind of solar cell backboard fluororine-carbon coating: be 0.4 by first, second two component by the mol ratio of NCO/OH: 1.0 mix, or batch process continuously shaped by automatization is coated uniformly on the PET polyester support of corona cleaning On body, solidify 10min at 145 DEG C, obtain 10 μ m-thick tack coat solar components backboards, be denoted as S2.

Embodiment 3:

Prepared by first component: by 40g (206.56mmol NCO group) hexamethylene diisocyanate trimer firming agent TKA100 (Asahi Chemical Corp) and anhydrous two butanone of 20g (Hangzhou chemical reagent company limited) and 30g anhydrous acetic acid Butyl ester (Hangzhou chemical reagent company limited) mix homogeneously, filters, makes first component, deposit in dry hermetically sealed can stand-by.

Prepared by component B: be placed in container, under stirring at low speed successively by 23g dimethylbenzene (Hangzhou chemical reagent company limited) Add 40g (46.4mmol OH group) fluorocarbon resin L101 (Huambo painting company limited), 2g improved polyalkene Hai Teke (Hitech) S3121 (east nation chemistry manufactures), 15g fluorocarbon resin DESMOPHEN2200B (Bayer A.G), 2g moistening divides Powder BYK-9010 (Bick Chemical Co., Ltd. of Germany), wax powder PTFE0101 (sky, the Nanjing poem that 18g zirconium ester coupling agent processes Wax powder), pre-dispersed after be ground with sand mill, to fineness of the particles≤5 micron, add the polyether-modified poly-organosilicon of 0.22g Oxygen alkanes levelling agent 505 (Wei Bo Chemical Co., Ltd. of Shenzhen), (the far and near chemical industry in Nantong is limited for 0.82g stannous octoate catalyst Company), after mix homogeneously, adjust viscosity, filter, prepare second component face slurry, deposit in dry hermetically sealed can stand-by.

Prepared by a kind of solar cell backboard fluororine-carbon coating: be 0.9 by first, second two component by the mol ratio of NCO/OH: 1.0 mix, or batch process continuously shaped by automatization is coated uniformly on the PET polyester support of corona cleaning On body, solidify 8min at 155 DEG C, obtain 15 μ m-thick tack coat solar components backboards, be denoted as S3.

Embodiment 4:

Prepared by first component: by 60g (228.6mmol NCO group) hexamethylene diisocyanate addition product firming agent HXT (Nippon Polyurethane Industry Co., Ltd.) and 15g anhydrous dimethyl benzene (Hangzhou chemical reagent company limited) and the anhydrous butanone of 25g (Hangzhoupro State chemical reagent company limited) mix homogeneously, filters, makes first component, deposit in dry hermetically sealed can stand-by.

Prepared by component B: be placed in container, low speed by 20g propylene glycol methyl ether acetate (Hangzhou chemical reagent company limited) 45g (48.15mmolOH group) it is sequentially added under stirring) fluorocarbon resin SW-5570 (Shanghai Sheng Wei trade Co., Ltd), 12g End hydroxy butadiene (Hangzhou Tianyuan grinds institute), 5g fluorocarbon resin DESMOPHEN1652 (Bayer A.G), 0.2g moistening Dispersant B YK-163 (Bick Chemical Co., Ltd. of Germany), white carbon black (the huge Thailandization of Dongguan City that 5g Lü Zuqian processes Work company limited), pre-dispersed after be ground with sand mill, to fineness of the particles≤5 micron, add 0.3g levelling agent BYK310 (Bick Chemical Co., Ltd. of Germany), 0.82g stannous octoate catalyst (the far and near Chemical Co., Ltd. in Nantong), after mix homogeneously, Adjust viscosity, filter, prepare second component face slurry, deposit in dry hermetically sealed can stand-by.

Prepared by a kind of solar cell backboard fluororine-carbon coating: be 1.0 by first, second two component by the mol ratio of NCO/OH: 1.0 mix, or batch process continuously shaped by automatization is coated uniformly on the PET polyester support of corona cleaning On body, solidify 3.5min at 175 DEG C, obtain 12 μ m-thick tack coat solar components backboards, be denoted as S4.

Embodiment 5:

Prepared by first component: by 50g (141.65mmol NCO group) isophorone diisocyanate (IPDI) trimer Z4470BA (NCO content is 37.5%, Bayer Bitterfeld GmbH) and 30g anhydrous dimethyl benzene (Hangzhou chemical reagent company limited) and 20g Anhydrous acetic acid butyl ester (Hangzhou chemical reagent company limited) mix homogeneously, filters, makes first component, deposit in dry hermetically sealed can In stand-by.

Prepared by component B: 20g ethyl acetate (Hangzhou chemical reagent company limited) be placed in container, depend under stirring at low speed Secondary addition 40g (42.8mmolOH group)) fluorocarbon resin SW-5570 (Shanghai Sheng Wei trade Co., Ltd), 8g improved polyalkene (Bayer Bitterfeld GmbH is public for sieve's Ah bass (Arrowbase) SE-1013N (You Nijika manufacture), 4g fluorocarbon resin DESMOPHEN1652 Department), 0.59g wetting dispersing agent BYK-163 (Bick Chemical Co., Ltd. of Germany), the pottery that 9g aluminum-titanium composite coupler processes Micropowder (Henan Xing Yu ceramic company limited), 6g titanium dioxide R790 (E.I.Du Pont Company), pre-dispersed after carry out with sand mill Grind, to fineness of the particles≤5 micron, add 0.2g levelling agent BYK310 (Bick Chemical Co., Ltd. of Germany), 1.22g monobutyl Three isooctyl acid tin catalysts (the far and near Chemical Co., Ltd. in Nantong), after mix homogeneously, adjust viscosity, filter, prepare second component face Slurry, deposits in dry hermetically sealed can stand-by.

Prepared by a kind of solar cell backboard fluororine-carbon coating: be 1.5 by first, second two component by the mol ratio of NCO/OH: 1.0 mix, or batch process continuously shaped by automatization is coated uniformly on the PET polyester support of corona cleaning On body, solidify 4min at 165 DEG C, obtain 15 μ m-thick tack coat solar components backboards, be denoted as S5.

Embodiment 6:

Prepared by first component: by 65g (247.65mmol NCO group) hexamethylene diisocyanate addition product firming agent HXT (Nippon Polyurethane Industry Co., Ltd.) and 15g anhydrous dimethyl benzene (Hangzhou chemical reagent company limited) and the anhydrous butanone of 20g (Hangzhoupro State chemical reagent company limited) mix homogeneously, filters, makes first component, deposit in dry hermetically sealed can stand-by.

Prepared by component B: by 16 ethyl acetate (Hangzhou chemical reagent company limited), (Hangzhou chemical reagent has with 8g toluene Limit company) it is placed in container, (Japan is big to be sequentially added into 45g (48.21mmolOH group) fluorocarbon resin GK570 under stirring at low speed Gold), 8g improved polyalkene sieve's Ah bass (Arrowbase) SE-1013N (You Nijika manufacture), 12g fluorocarbon resin DESMOPHEN2200B (Bayer A.G), 1.68g are containing acid group copolymer analog dispersant B YK9076 (Germany's Bi Keization Company), silicon dioxide that 9g aluminum-titanium composite coupler processes (Dongguan City Ju Tai Chemical Co., Ltd.), 9g titanium dioxide R793 (Luohe Xing Mao Tai Ye limited company), pre-dispersed after be ground with sand mill, to fineness of the particles≤5 micron, add 0.22g levelling agent BYK310 (Bick Chemical Co., Ltd. of Germany), (gold field raw material has 0.1g tin dilaurate dioctyl tin catalyst Limit company), after mix homogeneously, adjust viscosity, filter, prepare second component face slurry, deposit in dry hermetically sealed can stand-by.

Prepared by a kind of solar cell backboard fluororine-carbon coating: be 0.9 by first, second two component by the mol ratio of NCO/OH: 1.0 mix, or batch process continuously shaped by automatization is coated uniformly on the PET polyester support of corona cleaning On body, solidify 2.5min at 180 DEG C, obtain 25 μ m-thick tack coat solar components backboards, be denoted as S6.

Comparative example 1:

Prepared by first component: same as in Example 1；

Prepared by component B: identical with embodiment 1 manufacture method, makes raw material and is added without the carbonic acid that titanate coupling agent processes Calcium；

Prepared by a kind of solar cell backboard fluororine-carbon coating: same as in Example 1, is denoted as B1.

Comparative example 2:

Prepared by first component: the same as in Example 4；

Prepared by component B: identical with embodiment 4 manufacture method, makes raw material and is added without end hydroxy butadiene；

Prepared by a kind of solar cell backboard fluororine-carbon coating: the same as in Example 4, is denoted as B2.

Comparative example 3:

Prepared by first component: same as in Example 5；

Prepared by component B: identical with embodiment 5 manufacture method, makes raw material and is i.e. added without improved polyalkene sieve's Ah bass (Arrowbase) SE-1013N, is also added without the ceramic that aluminum-titanium composite coupler processes；

Prepared by a kind of solar cell backboard fluororine-carbon coating: same as in Example 5, is denoted as B3.

The high-adhesion application type backboard preparing embodiment 1～6 and the application type backboard of comparative example 1～3 preparation enter Row performance detects, and evaluation result is listed in table 1.Wherein, peel strength test assembly, the high-adhesion provided except the present invention is coated with Cover outside type backboard, also need to use other materials, comprise energy ultrawhite figured glass (Nan Bo group), EVA adhesive film F406, F806 (Hangzhou Foster photovoltaic) carry out laminated.

Available lamination is: laminating temperature 140 DEG C～165 DEG C, evacuation 2min～8min, lamination times is 8min～20min, makes assembly；Wherein, contrast test for convenience, the present invention uses identical preparation condition, specially layer Pressure temperature is 150 DEG C, and evacuation 3.5min, lamination times is 10min.

It should be noted that every related performance indicators of the coating obtained by above-described embodiment and application type backboard is It is evaluated through following method of testing,.

1, coating hardness

Hardness according to GB/T6739 " hardness of film pencil algoscopy " standard testing coating: by pencil with 0.5mm/s speed Degree moves horizontally 3mm on sample and measures hardness, according to cut, records hardness values.

2, wet and heat ageing resistant performance

Hydrothermal aging test is carried out by GB/T2423.3 test method.

Experiment condition :+85 DEG C, relative humidity 85%.

Before and after experiment, sample adhesive force is tested according to ISO-2409-2007 standard；To sample yellowness index (△ YI) it is measured according to GB GB2409-80 " plastics yellow colour index test method ".

3, backboard and the peel strength of EVA adhesive film

Method of testing is according to standard GB/T/T2790-1995 " 180 ° of peel strength experimental technique flexible materials of adhesive To rigid material " test, record peel strength numerical value.

Table 1: each embodiment and comparative example performance test results

In comparison sheet, data understand, application type solar battery back prepared by high-adhesion fluorocarbon coating of the present invention Plate, coating hardness is high, high with the peel strength of encapsulating material, still keep after 2500h after tropical deterioration processes 80% with On peel strength, adhesive force 90% and more than, yellowness index (Δ YI) is within 3.Fluorocarbon coating prepared by the present invention Tack coat can take into account the caking property with encapsulating material and polyester support simultaneously, and it is resistance to have bonding under damp and hot, luminous environment Property and excellent weather resistance for a long time, and can low cost prepare.

Claims (10)

1. a high-adhesion fluorocarbon coating, it is characterised in that it is made up of first, second two component；

Described first component is cross-linking agent, anhydrous dilute including the isocyanate curing agent of 40～65 weight portions and 35～60 weight portions Release agent A；

Described component B contains the fluorocarbon resin of 35～50 weight portions, the improved polyalkene of 2～15 weight portions, 5～25 weight portions Through the inorganic filler A that function is coupling agent modified, the anhydrous diluents B of 15～35 weight portions；

During use, by first component and component B by the amount of the NCO in first component and the material of the hydroxyl in component B it Than being 0.4～1.5 mixing, obtain high-adhesion fluorocarbon coating.

2. high-adhesion fluorocarbon coating as claimed in claim 1 a kind of, it is characterised in that described component B may also include 0～ 15 fluorocarbon resins, 0.1～2 part by weight of catalyst, 0～20 parts by weight of inorganic filler B, 0～0.5 weight portion levelling agent and 0.2～2 One or more of weight portion wetting dispersing agent；

Described catalyst is metal compound as catalyst；

Described inorganic filler B is Rutile type titanium dioxide；

Described wetting dispersing agent is by the copolymer solution containing acidic-group, the block copolymer solution of polyamine, acrylic acid block One or more in copolymer analog, highly branched structure polyesters, hydroxy functional group carboxylic acid esters press any proportioning mixing group Become；

Described anhydrous diluents A, anhydrous diluents B each stand alone as following one or more by the mixing of any proportioning: The aromatic hydrocarbon of C7～C10, the ester type compound of C3～C8, the alcohol compound of C1～C5, the ketone compounds of C2～C6.

3. a kind of high-adhesion fluorocarbon coating as claimed in claim 2, it is characterised in that described component B is by the following method Prepare: weigh anhydrous diluents B and pour in sand mill, under stirring under 1500-3500rpm rotating speed in diluent B successively Add fluorocarbon resin, improved polyalkene, inorganic filler A, pre-dispersed after, be milled to fineness of the particles≤5 micron；Add polyester tree One or more in fat, wetting dispersing agent, catalyst, levelling agent, inorganic filler B, mechanical mixture is uniform, adds anhydrous diluents B adjustment viscosity, to 500～2000m Pa S, filters, and deposits in dry sealing container stand-by.

4. a kind of high-adhesion fluorocarbon coating as claimed in claim 1, it is characterised in that the isocyanates in described first component Base (NCO) is preferably 0.5～1.2 with the ratio of the amount of the material of the hydroxyl (OH) in component B, more preferably 0.8～1.0.

5. a kind of high-adhesion fluorocarbon coating as claimed in claim 1, it is characterised in that described isocyanate curing agent is fat Fat race isocyanates；Described fluorocarbon resin is by the vinylidene type of solvent soluble type, CTFE type, tetrafluoroethene type fluorine carbon Resin one or both by any proportioning mixing composition, the hydroxyl value of fluorocarbon resin is 45～60mgKOH/g, acid number be 2～ 12mgKOH/g, solid content >=50%, Oil repellent is 20wt%～30wt%.

6. a kind of high-adhesion fluorocarbon coating as described in claims 1 to 3, it is characterised in that described modified polyolefin hydrocarbon content Being preferably the 5%～30% of fluorocarbon resin, more preferably 10%～25%, can be that grafting polyolefin, esters modification are poly- Alkene, terminal hydroxy group polyolefin, including Low Density Polyethylene and acrylate and the terpolymer of maleic anhydride, ethylene-(first Base) acrylate-maleic anhydride multipolymer, ethylene-propylene-(methyl) acrylate-maleic anhydride multipolymer, end Hydroxyl polybutadiene, hydrogenation end hydroxy butadiene, maleic anhydride grafted polybutadiene, maleic anhydride inoculated polypropylene, ethylene- Propene-1-butene-(methyl) acrylate-maleic anhydride multipolymer, is the most preferably ethylene-(methyl) acrylic acid Ester-maleic anhydride multipolymer.

7. a kind of high-adhesion fluorocarbon coating as described in claims 1 to 3, it is characterised in that described inorganic filler A is through function Coupling agent treatment, described inorganic filler A is by silicon dioxide, calcium carbonate, magnesium carbonate, zinc oxide, aluminium oxide, Pulvis Talci, wax powder, height One or more in ridge soil, white fused alumina, barium sulfate, ceramic, white carbon black are by any proportioning mixing composition；

Described functional type coupling agent is by titanate coupling agent, aluminate coupling agent, silicon fluoride modification coupling agent, zirconate coupling One or more in agent, Lü Zuqian and aluminum-titanium composite coupler are by any proportioning mixing composition.

8. a kind of high-adhesion fluorocarbon coating as claimed in claim 7, it is characterised in that described function coupling agent treatment is concrete For: first the inorganic filler A of 100 weight portions is joined in anhydrous diluents A or B of 30～80 weight portions, at 30 DEG C～50 Ultrasonic disperse 0.5h～3h at a temperature of DEG C, after being uniformly dispersed, adds the function coupling agent of 0.1～10 weight portions, then at 50 DEG C ～supersound process 1h～3h at 60 DEG C, obtain the inorganic filler A of coupling agent treatment；The consumption of function coupling agent preferably 0.3～5 weight Amount part.

9. high-adhesion fluorocarbon coating described in a claim 1 on solar components purposes, it is characterised in that this use Way is particularly as follows: by fluorocarbon coating coated polyester supporter, prepare high-adhesion backboard；Again by high-adhesion backboard and encapsulation material Material is laminated；

The average thickness of described polyester support is 50～300 μm, and carboxyl-content is 0.5 equivalent/t to 35 equivalents/t, for poly-right PET (PET), PEN (PEN), polybutylene terephthalate (PBT) (PBT), poly-right The single or multiple lift thin film that benzene dicarboxylic acid trimethylene glycol ester (PTT) is constituted；

Described encapsulating material is vinyl-vinyl acetate copolymer (EVA).

10. a kind of high-adhesion fluorocarbon coating as described in claim 1～9, it is characterised in that described polyester support is being coated with Carry out surface reason before covering fluorocarbon coating, described surface process process selected from sided corona treatment, flame treatment, low pressure plasma, Atmospheric plasma treatment, UV treatment etc.；Preferably sided corona treatment, the described sided corona treatment time is 0.5s～100s；

Described coating method is selected from brushing, dip-coating, roller coating, spraying；Paint thickness is 3～30 μm, solidification temperature be 150 DEG C～ 200 DEG C, hardening time 1min to 15min.