CN105505183A - Preparation method of high-performance fluorocarbon coating - Google Patents
Preparation method of high-performance fluorocarbon coating Download PDFInfo
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- CN105505183A CN105505183A CN201510997912.5A CN201510997912A CN105505183A CN 105505183 A CN105505183 A CN 105505183A CN 201510997912 A CN201510997912 A CN 201510997912A CN 105505183 A CN105505183 A CN 105505183A
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
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- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6275—Polymers of halogen containing compounds having carbon-to-carbon double bonds; halogenated polymers of compounds having carbon-to-carbon double bonds
- C08G18/6279—Polymers of halogen containing compounds having carbon-to-carbon double bonds; halogenated polymers of compounds having carbon-to-carbon double bonds containing fluorine atoms
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
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- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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Abstract
The invention relates to a preparation method of a high-performance fluorocarbon coating. The fluorocarbon coating is composed of a component A and a component B. The component A is composed of an isocyanate-capped polyol oligomer and an anhydrous diluent A, and the component B consists of fluorocarbon resin, dispersant, inorganic filler, catalysts and anhydrous diluents. The component A and the component B are mixed in accordance with the molar ratio of isocyanate to hydroxyl value being (0.6-1.5): 1 to obtain the fluorocarbon coating. The polyol oligomer contains polyester polyol and polyether polyol, endows the coating with outstanding mechanical performance, good low-temperature flexibility and hydrolysis resistance and is capped by isocyanate to be reacted with fluorocarbon resin, and soft segments formed by the polyol oligomer and the fluorocarbon resin and isocyanate hard segments are distributed regularly in the coating to form a three-dimensional network interpenetration structure. The prepared fluorocarbon coating has the advantages of ageing resistant and wind and sand resistant performance and is applicable in preparation of coating type solar cell back plates used in areas with adverse environments.
Description
Technical field
The present invention relates to a kind of preparation method of fluorocarbon coating, belong to material surface resist technology field.
Background technology
Nearly ten years; country is in the development of new forms of energy, building, machinery, automobile, railway etc.; drive the development of the coatings industry matched with it; by application, decoration and provide protection are played to outdoor steel structure, aluminum curtain walls, wind power installation, solar cell backboard etc.; effectively can resist their erosion of outer bound pair, increase the service life.Some are large-scale, emphasis Steel Structure Work Project design requires that corrosion protection coating weather resistance reaches 20 years, aluminium-plastic panel also require 20 years colour-fast, the backboard as solar module back-protective material requires the work-ing life reaching 25 years especially.Fluorocarbon resin introduces the large fluorine element of electronegativity, and fluorine carbon bond can be strong, makes it have outstanding ageing resistance, corrosion-resistant and anti-stain characteristic, is applicable to very much making long-acting weather-resistant coating, particularly in the Northwest that dust storm overall situation is comparatively severe.
Traditional fluorocarbon resin is linear structure, after isocyanate curing agent reaction, form two dimensional surface reticulated structure, coating adhesion, the erosion performance of resistance to dust storm and physical strength more weak, stand will agingly to come off for about 15 years, strong for adapting to sunshine, dust storm is large, haze is many, the large grade of the four seasons temperature difference comparatively rugged environment condition, need to start with from formulation for coating material, increase coating cross-linking density, form tridimensional network, introduce the resistance to low temperature that flexible group improves coating simultaneously, for increase coating to the provide protection of material and extend working life significant.
Patent CN102664204A provides a kind of application type solar cell backboard of novel texture, its wear resistance is improved by adding epoxy resin in its fluororine-carbon coating, epoxy resin and the good consistency of fluoro-resin make coating abrasion performance be largely increased, but because their molecular chain is by physical force combination, intensity is little, and adding of epoxy resin, cause coating xanthochromia serious, patent CN101792639A discloses a kind of wear-resisting scratch-resisting weather-proof polyurethane coating, it mainly adopts hydroxyl ester acrylic resin, fluorocarbon resin and vibrin are as matrix resin, add all kinds of nanometer inorganic filler to fill, react obtained afterwards with polyisocyanate curing agent, be applicable to bullet train, the surface daub on a wall of automobile big bus etc., wherein because the introducing of hydroxyl acrylic and vibrin can weaken the ageing-resistant performance of coating to a certain extent, nano-sized filler is just filled in resin matrix simultaneously, both consistencies are poor, difficulties in dispersion in matrix resin, if process bad, the drawbacks such as coating be full of cracks can be caused, patent CN104194599A discloses a kind of two component coating of fluorine carbon of excellent property, wherein first component is primarily of compositions such as fluorine carbon base polyurethane prepolymer for use as, nanometer inorganic fillers, component B is primarily of Hydroxylated acrylic resin, isocyanate curing agent composition, obtain high crosslink density fluororine-carbon coating, there is excellent wear resistance, but its manufacture craft relative complex.
Therefore, be necessary to invent a kind of preparation technology simple, each group partition inter-capacitive is good, has excellent color inhibition, resistance to ultraviolet, the erosion performance of resistance to dust storm, the coating of weathering resistance for 25 years, to meet the application type solar cell backboard that ruthless area uses.
Summary of the invention
The technical problem to be solved in the present invention is, overcomes deficiency of the prior art, provides a kind of preparation method of high performance fluorine carbon coating.
For technical solution problem, solution of the present invention is: a kind of preparation method of high performance fluorine carbon coating, comprises the following steps:
(1), after the oxidation inhibitor of 100 weight polyol oligopolymer, 0 ~ 2.5 weight part, the acid stopper of 0 ~ 0.5 weight part being mixed, dewater 2.5 ~ 4.5 hours under 100 ~ 150 DEG C of conditions; Temperature is down to 45 ~ 95 DEG C, add isocyanate curing agent and anhydrous diluents A insulation reaction 5 ~ 8 hours, then add catalyst A, after mixing, keep 1 ~ 3 hour under vacuum condition, obtained first component (isocyanate-terminated polyol oligomer performed polymer); Wherein, the OH of polyol oligomer and the NCO mol ratio of isocyanate curing agent are 1:2.0 ~ 4.5, and anhydrous diluents A is equal with the quality of isocyanate curing agent, and the consumption of catalyst A is 0 ~ 0.5% of isocyanate curing agent quality;
(2) in the diluent B of 20 ~ 35 weight parts, add the fluorocarbon resin of 35 ~ 65 weight parts under agitation, add the mineral filler of the dispersion agent of 0 ~ 1.6 weight part, 0 ~ 40 weight part again, grind with sand mill after pre-dispersed, to particle fineness≤5 micron, add the catalyst B of 0.1 ~ 1.5 weight part, the flow agent of 0 ~ 0.5 weight part, the defoamer of 0 ~ 1.2 weight part, the flatting silica of 0 ~ 5 weight part, after mixing, adjustment viscosity, filter, obtained component B (fluorocarbon coating host);
During coating, according to institute's hydroxyl (OH) in the isocyanate group (NCO) in first component and component B mole ratio be that 0.6 ~ 1.5:1.0 carries out proportioning;
Described polyol oligomer is one or both mixtures formed according to any proportioning in polyether glycol, polyester polyol, and described polyether glycol comprises polyoxypropylene polyol, polymer graft polyether glycol, polytetrahydrofuran diol homopolymerization, polytetrahydrofuran polyol, tetrahydrofuran (THF)-propylene oxide copolymer glycols, polyoxyethylated polyols; Polyester polyol comprises hexanodioic acid system polyester glycol, aromatic polyester polyol, polycaprolactone polyol, polycarbonate polyol; As preferably, polyol oligomer functionality can be 2 or 3, and molecular weight is 200 ~ 1300, and hydroxyl value is 100 ~ 700mgKOH/g, acid number≤1.0mgKOH/g, moisture content≤0.2%.
Further, described isocyanate curing agent is one of following or two kinds of mixtures formed according to any proportioning: hexamethylene diisocyanate (HDI) tripolymer, hexamethylene diisocyanate (HDI) biuret, hexamethylene diisocyanate (HDI) affixture, isophorone diisocyanate (IPDI) tripolymer, isophorone diisocyanate (IPDI) affixture.
Further, described fluorocarbon resin is made up of according to any proportioning one or more in vinylidene type fluorocarbon resin, trifluorochloroethylene type fluorocarbon resin, tetrafluoroethylene type fluorocarbon resin, as preferably, the hydroxyl value of fluorocarbon resin is 45 ~ 60mgKOH/g, acid number is 2 ~ 12mgKOH/g, solid content >=50%, Oil repellent is 20% ~ 30%.
Further, described oxidation inhibitor is Hinered phenols antioxidant; Described acid stopper is tosic acid; Described catalyst A or catalyst B are metal catalyst, comprise one or more mixtures formed according to any proportioning in isocaprylic acid zinc, stannous octoate, tin dilaurate dioctyl tin, monobutyltin oxide, monobutyl three isocaprylic acid tin, dibutyl tin laurate.
Further, described dispersion agent is by containing the segmented copolymer class dispersion agent of pigment affinity groups, acrylic block copolymers class dispersion agent, height branched structure polyester dispersion agent, form according to any proportioning containing one or more in acidic-group copolymer analog dispersion agent, hydroxy functional group carboxylic acid esters dispersion agent.
Further, described flow agent is made up of according to any proportioning one or more in polyether siloxane copolymer class flow agent, polyether-modified poly organo siloxane flow agent, polyacrylate(s) flow agent.
Further, described mineral filler by titanium dioxide, carbon black, calcium carbonate, aluminum oxide, barium sulfate one or more form according to any proportioning.
Further, described thinner A, diluent B form according to any proportioning by one or more in toluene, dimethylbenzene, n-butyl acetate, 1-Methoxy-2-propyl acetate, ethyl acetate, butylacetate, ethylene glycol, methyl alcohol, propyl carbinol, butanone, methylethylketone, pimelinketone.
Further, described defoamer be polyoxyethylene polyoxypropylene tetramethylolmethane ether, polyoxyethylene polyoxy propyl alcohol amidogen ether, polypropylene glycerol aether, polyoxyethylene polyoxypropylene glyceryl ether, fluorine-carbon modified acrylate type one or more form according to any proportioning.
Further, described flatting silica be silicon-dioxide, talcum powder a kind of or both form according to any proportioning.
Beneficial effect of the present invention is mainly reflected in: the invention provides a kind of preparation technology relatively simple, the fluorocarbon coating that between each component, consistency is good, wherein polyol oligomer and long-chain fluorocarbon resin form soft section, isocyanic ester agent forms hard section, hydroxy-end capped polyol oligomer provides chain extension effect simultaneously, by reaction, soft section and hard section rule are distributed in the coating, improve coating cross-linking density, form three-dimensional netted interpenetrating structure.Wherein polyester polyol gives the mechanical property of coating excellence, thermotolerance and hardness, and polyether glycol gives the good low temperature flexibility of coating and anti-hydrolytic performance, and fluorocarbon resin gives weathering resistance and the erosion resistance of coating excellence.Made fluorocarbon coating high-strength and high ductility height attachment is a kind of high-performance coating inside material surface protection field, can be applicable to the application type solar cell backboard being prepared in the larger ruthless area use of dust storm.
Embodiment
Below in conjunction with specific embodiment, the present invention is described further, but protection scope of the present invention is not limited to the content of these concrete embodiments and embodiment.
It should be noted that, height branched structure polyester dispersion agent described in the present invention is the matured product of this area, " highly " and non-limiting degree of grafting, height branched structure polyester is this area common technology term, the BYK2151 of such as German Bick Chemical Co., Ltd., 2152 etc.
Embodiment 1
A kind of high performance fluorine carbon coating, is made up of first and second liang of components.
The preparation of first component: by 1000g (3.04molOH group) PTMG-propylene oxide copolymer glycols (Shanghai Yi Qing trade Co., Ltd) under 150 DEG C of conditions, add 15g Hinered phenols antioxidant 1076 (Dongguan City Hui Yi chemical materials company limited) as required, add 5g tosic acid (Mike woods reagent) and dewater 2.5 hours; Temperature of reaction is down to 95 DEG C afterwards, PTMG after dehydration-propylene oxide copolymer glycols adds 2932g (9.12molNCO group) hexamethylene diisocyanate trimer solidifying agent HT-90BS (Wanhua Chemical Group Co., Ltd.), 2932g anhydrous acetic acid butyl ester (Zhejiang chemical company) joins in reactor successively, insulation reaction 8 hours, then vacuum keeps 1 hour, obtained isocyanate-terminated PTMG-propylene oxide copolymerization performed polymer, obtain first component, after cooling, sealing is for subsequent use;
The preparation of component B:
200g butanone (Hangzhou chemical reagent company limited) is placed in container, 400g (0.39molOH group) fluorocarbon resin ZHM-2 (eastern fluorine chemical) is added successively under stirring at low speed, 6.5g is containing pigment affinity groups polymer copolymerization body wetting dispersing agent BYK-163 (German Bick Chemical Co., Ltd.), 230g titanium dioxide R793 (Luohe Xing Mao Tai Ye limited-liability company), grind with sand mill after 10g carbon black MA100 (Mitsubishi) is pre-dispersed, to particle fineness≤5 micron, add 11.5g monobutyl three isocaprylic acid tin catalyst (the far and near Chemical Co., Ltd. in Nantong), 2g polyester modification polydimethylsiloxane flow agent BYK310 (German Bick Chemical Co., Ltd.), after mixing, adjustment viscosity, filter, obtained second component, deposit in dry sealed can stand-by,
The preparation of high performance fluorine carbon coating: before coating, by first component and component B according to mole ratio be 0.6 carry out proportioning, mix, obtained fluorocarbon coating.
Embodiment 2
The preparation of first component: by 1000g (9.6molOH group) polycaprolactone polyol PCL303 (Japanese Daicel) under 100 DEG C of conditions, add 5g Hinered phenols antioxidant 1076 (Dongguan City Hui Yi chemical materials company limited) as required, dewater 3.5 hours; Temperature of reaction is down to 75 DEG C afterwards, add 3717g (19.2molNCO group) hexamethylene diisocyanate trimer solidifying agent TKA100 (Asahi Chemical Corp) in polycaprolactone polyol PCL303 after dehydration, 18g dibutyl tin laurate, the anhydrous positive butanone of 3717g (Zhejiang chemical company) to join in reactor insulation reaction 6 hours successively, then vacuum keeps 2 hours, obtained isocyanate-terminated polycaprolactone polyol performed polymer, obtain first component, after cooling, sealing is for subsequent use;
The preparation of component B:
Anhydrous for 230g butanone (Hangzhou chemical reagent company limited) is placed in container, 400g (0.46molOH group) fluorocarbon resin L101 (Huambo painting company limited) is added successively under stirring at low speed, 16g is containing acid pigment affinity groups polymer copolymerization body class dispersant B YK111 (German Bi Ke chemical company), 400g titanium dioxide r902 (Dupont), grind with sand mill after pre-dispersed, to particle fineness≤5 micron, add the polyether-modified poly organo siloxane flow agent 505 (Wei Bo Chemical Co., Ltd. of Shenzhen) of 2.2g, 8.2g stannous octoate catalyst (the far and near Chemical Co., Ltd. in Nantong), after mixing, adjustment viscosity, filter, obtained second component face slurry, deposit in dry sealed can stand-by,
The preparation of high performance fluorine carbon coating: before coating, by first component and component B according to mole ratio be 1.5 carry out proportioning, mix, obtained fluorocarbon coating.
Embodiment 3
A kind of high performance fluorine carbon coating, is made up of first and second liang of components.
The preparation of first component: 1000g PCDL T5651 (1.96molOH group) (Guangzhou Hao Yi Chemical Industry Science Co., Ltd) is dewatered 4.5 hours under 130 DEG C of conditions, temperature of reaction is down to 45 DEG C afterwards, polycarbonate polyol T5651 after dehydration adds the different Buddhist isophorone diisocyanate trimer Z4470BA (Bayer Bitterfeld GmbH) of 1557g (4.41molNCO group), 854g (4.41molNCO group) hexamethylene diisocyanate trimer solidifying agent TKA100 (Asahi Chemical Corp), 2411g anhydrous ethyl acetate (Zhejiang chemical company) joins in reactor successively, insulation reaction 5 hours, then vacuum keeps 3 hours, obtained isocyanate-terminated PCDL performed polymer, obtain first component, after cooling, sealing is for subsequent use,
The preparation of component B:
350g anhydrous dimethyl benzene (Hangzhou chemical reagent company limited) is placed in container, 650g (1.7molOH group) fluorocarbon resin GK570 (Daikin) is added successively under stirring at low speed, the polyester wetting dispersing agent BYK-2151 (German Bick Chemical Co., Ltd.) of 16g highly branched structure, 160g carbon black (Dongguan City Ju Tai Chemical Co., Ltd.), grind with sand mill after 60g calcium carbonate (good luck source, Shanghai Chemical Co., Ltd.) is pre-dispersed, to particle fineness≤5 micron, mend 8g polymer based defoamer BYK8801 (German Bick chemical company) and add 1g tin dilaurate dioctyl tin catalyzer (Jin Tian raw material company limited), 5g is with the multipolymer flow agent BYK4510 (German Bick Chemical Co., Ltd.) of acidic-group, 50g Degussa flatting silica OK520 (the triumphant mattress chemical industry in Shanghai), after mixing, adjustment viscosity, filter, obtained second component, deposit in dry sealed can stand-by,
The preparation of high performance fluorine carbon coating: before coating, by first component and component B according to mole ratio be 1.0 carry out proportioning, mix, obtained fluorocarbon coating.A kind of high performance fluorine carbon coating, is made up of first and second liang of components.
Embodiment 4
A kind of high performance fluorine carbon coating, is made up of first and second liang of components.
The preparation of first component: prepared by first component: by 1000g (2.36molOH group) aromatic polyester polyol AK3080 (Foshan is with moral Chemical Co., Ltd.) under 105 DEG C of conditions, add 25g Hinered phenols antioxidant 1076 (Dongguan City Hui Yi chemical materials company limited), dewater 2.5 hours; Temperature of reaction is down to 55 DEG C afterwards, aromatic polyester polyol AK3080 after dehydration adds 2023g (6.08molNCO group) hexamethylene diisocyanate trimer solidifying agent HT-90BS (Wanhua Chemical Group Co., Ltd.), 2023g anhydrous acetic acid butyl ester (Zhejiang chemical company) joins in reactor successively, insulation reaction 8 hours, then vacuum keeps 1 hour, obtained isocyanate-terminated PTMG-propylene oxide copolymerization performed polymer, obtain first component, after cooling, sealing is for subsequent use;
The preparation of component B:
200g 1-Methoxy-2-propyl acetate (Hangzhou chemical reagent company limited) is placed in container, 350g (0.37molOH group) is added successively under stirring at low speed) fluorocarbon resin SW-5570 (Shanghai Sheng Wei trade Co., Ltd), 2g wetting dispersing agent BYK-163 (German Bick Chemical Co., Ltd.), grind with sand mill after pre-dispersed, to particle fineness≤5 micron, add 3g acrylate interpolymer flow agent BYK350 (German Bick Chemical Co., Ltd.), 15g isocaprylic acid zinc catalyst (the far and near Chemical Co., Ltd. in Nantong), 12g polymer based defoamer BYK8801 (German Bick Chemical Co., Ltd.), after mixing, adjustment viscosity, filter, obtained component B face slurry, deposit in dry sealed can stand-by,
The preparation of high performance fluorine carbon coating: before coating, by first component and component B according to mole ratio be 0.9 carry out proportioning, mix, obtained fluorocarbon coating.
Comparative example 1
The preparation of first component: 1303g (6.08molNCO group) hexamethylene diisocyanate trimer solidifying agent HT-90BS (Wanhua Chemical Group Co., Ltd.) is mixed with 1303g anhydrous acetic acid butyl ester (Zhejiang chemical company), filter, make first component, deposit in dry sealed can stand-by.
The preparation of component B: identical with embodiment 1;
The preparation of high performance fluorine carbon coating: before coating, by first component and component B according to mole ratio be 0.6 carry out proportioning, mix, obtained fluorocarbon coating.
Comparative example 2
The preparation of first component: by 1000g (9.6molOH group) polycaprolactone polyol PCL303 (Japanese Daicel) under 100 DEG C of conditions, add 5g Hinered phenols antioxidant 1076 (Dongguan City Hui Yi chemical materials company limited) as required, dewater 3.5 hours; Temperature of reaction is down to 75 DEG C afterwards, add 1858g (9.6molNCO group) hexamethylene diisocyanate trimer solidifying agent TKA100 (Asahi Chemical Corp) in polycaprolactone polyol PCL303 after dehydration, the anhydrous butanone of 1858g (Zhejiang chemical company) to join in reactor insulation reaction 6 hours successively, then vacuum keeps 2 hours, obtained isocyanate-terminated polycaprolactone polyol performed polymer, obtain first component, after cooling, sealing is for subsequent use;
The preparation of component B: identical with embodiment 2;
The preparation of high performance fluorine carbon coating: before coating, by first component and component B according to mole ratio be 0.6 carry out proportioning, mix, obtained fluorocarbon coating.
The making method of the sample in the present embodiment is the common technology means of this area, specifically continuously shaped or batch process evenly can be coated in by gluing substrate surface by automatization, coating dry film thickness is 5 ~ 60 microns, and solidification value is 145 DEG C ~ 200 DEG C, and set time is 2 ~ 30min.Bonded base material can be structural steel, aluminium, PET substrate's film, polybutylene terephthalate basilar membrane, PEN basilar membrane, PBN basilar membrane, poly-11 lactam group counterdies, nylon 12 basilar membrane, polypropylene-base counterdie, polyvinyl counterdie, toughened glass etc.
Coating prepared by the fluorocarbon coating prepared embodiment 1 ~ 4 and comparative example 1,2, and carry out Performance Detection and burn-in test, it should be noted that, every related performance indicators of sample prepared by the coating obtained by above-described embodiment evaluates through following testing method, and evaluation result lists in table 1.
1. coating hardness
Hardness according to GB/T6739 " hardness of film pencil assay method " standard testing coating: pencil is moved horizontally 3mm with 0.5mm/s speed on sample and measures hardness, test 5 times, according to occurring cut situation, record hardness values.
2. testing method reference standard GB/T23988 " coating wear resistance measure knockout method ": sample in advance 25 DEG C, place 24h under 50% humidity environment, then test, standard sand is highly fallen the sample of 45° angle, according to eroded area from 914mm, calculate knockout amount, wear resistance by formulae discovery testing sample: A=V/T, in formula: A wear resistance, unit is for rising every micron (L/ μm), V abrasive material usage quantity, unit is for rise L, and T is coat-thickness, and unit is μm.
3. 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 sticking power is tested according to ISO-2409-2007 standard; Sample yellowness index (△ YI) is measured according to GB GB2409-80 " plastics yellowness index test method ".
The performance perameter of the fluororine-carbon coating sample that table 1 is obtained
In the preparation method of embodiment 1 ~ 4 fluorocarbon coating, the polyol oligomer of use is respectively polyether glycol, polycaprolactone polyol, polycarbonate polyol, aromatic polyester polyol prepare isocyanate-terminated prepolymer; Be normal experiment formula in comparative example 1, use conventional solidified dose, do not use polyol oligomer to carry out performed polymer preparation; Comparative example 2 polyol oligomer performed polymer is prepared by 1:1 according to the OH of polyol oligomer and the NCO mol ratio of isocyanate curing agent.From data in table, embodiment 1 ~ 4 fluororine-carbon coating, effectively can improve the wear resistance of coating, hardness is high, and relatively little through burin-in process after yellowing index, and ageing-resistant performance is excellent.Visible fluorocarbon coating provided by the invention has excellent weather-proof, resistance to knockout performance, is a kind of high performance fluorine carbon coating, is a kind of high performance fluorine carbon coating of the application type solar cell backboard used for the preparation of the ruthless area larger at dust storm.
Claims (10)
1. a preparation method for high performance fluorine carbon coating, is characterized in that, comprises the following steps:
(1), after the oxidation inhibitor of 100 weight polyol oligopolymer, 0 ~ 2.5 weight part, the acid stopper of 0 ~ 0.5 weight part being mixed, dewater 2.5 ~ 4.5 hours under 100 ~ 150 DEG C of conditions; Temperature is down to 45 ~ 95 DEG C, add isocyanate curing agent and anhydrous diluents A insulation reaction 5 ~ 8 hours, then add catalyst A, after mixing, keep 1 ~ 3 hour under vacuum condition, obtained first component (isocyanate-terminated polyol oligomer performed polymer); Wherein, the OH of polyol oligomer and the NCO mol ratio of isocyanate curing agent are 1:2.0 ~ 4.5, and anhydrous diluents A is equal with the quality of isocyanate curing agent, and the consumption of catalyst A is 0 ~ 0.5% of isocyanate curing agent quality;
(2) in the diluent B of 20 ~ 35 weight parts, add the fluorocarbon resin of 35 ~ 65 weight parts under agitation, add the mineral filler of the dispersion agent of 0 ~ 1.6 weight part, 0 ~ 40 weight part again, grind with sand mill after pre-dispersed, to particle fineness≤5 micron, add the catalyst B of 0.1 ~ 1.5 weight part, the flow agent of 0 ~ 0.5 weight part, the defoamer of 0 ~ 1.2 weight part, the flatting silica of 0 ~ 5 weight part, after mixing, adjustment viscosity, filter, obtained component B (fluorocarbon coating host);
During coating, according to institute's hydroxyl (OH) in the isocyanate group (NCO) in first component and component B mole ratio be that 0.6 ~ 1.5:1.0 carries out proportioning;
Described polyol oligomer is one or both mixtures formed according to any proportioning in polyether glycol, polyester polyol, and described polyether glycol comprises polyoxypropylene polyol, polymer graft polyether glycol, polytetrahydrofuran diol homopolymerization, polytetrahydrofuran polyol, tetrahydrofuran (THF)-propylene oxide copolymer glycols, polyoxyethylated polyols; Polyester polyol comprises hexanodioic acid system polyester glycol, aromatic polyester polyol, polycaprolactone polyol, polycarbonate polyol; As preferably, polyol oligomer functionality can be 2 or 3, and molecular weight is 200 ~ 1300, and hydroxyl value is 100 ~ 700mgKOH/g, acid number≤1.0mgKOH/g, moisture content≤0.2%.
2. the preparation method of a kind of high performance fluorine carbon coating as claimed in claim 1, is characterized in that: described isocyanate curing agent is one of following or two kinds of mixtures formed according to any proportioning: hexamethylene diisocyanate (HDI) tripolymer, hexamethylene diisocyanate (HDI) biuret, hexamethylene diisocyanate (HDI) affixture, isophorone diisocyanate (IPDI) tripolymer, isophorone diisocyanate (IPDI) affixture.
3. the preparation method of a kind of high performance fluorine carbon coating as claimed in claim 1, it is characterized in that: described fluorocarbon resin is made up of according to any proportioning one or more in vinylidene type fluorocarbon resin, trifluorochloroethylene type fluorocarbon resin, tetrafluoroethylene type fluorocarbon resin, as preferably, the hydroxyl value of fluorocarbon resin is 45 ~ 60mgKOH/g, acid number is 2 ~ 12mgKOH/g, solid content >=50%, Oil repellent is 20% ~ 30%.
4. the preparation method of a kind of high performance fluorine carbon coating as claimed in claim 1, is characterized in that: described oxidation inhibitor is Hinered phenols antioxidant; Described acid stopper is tosic acid; Described catalyst A and catalyst B are metal catalyst, comprise one or more mixtures formed according to any proportioning in isocaprylic acid zinc, stannous octoate, tin dilaurate dioctyl tin, monobutyltin oxide, monobutyl three isocaprylic acid tin, dibutyl tin laurate.
5. the preparation method of a kind of high performance fluorine carbon coating as claimed in claim 1, is characterized in that: described dispersion agent is by containing the segmented copolymer class dispersion agent of pigment affinity groups, acrylic block copolymers class dispersion agent, height branched structure polyester dispersion agent, form according to any proportioning containing one or more in acidic-group copolymer analog dispersion agent, hydroxy functional group carboxylic acid esters dispersion agent.
6. the preparation method of a kind of high performance fluorine carbon coating as claimed in claim 1, is characterized in that: described flow agent is made up of according to any proportioning one or more in polyether siloxane copolymer class flow agent, polyether-modified poly organo siloxane flow agent, polyacrylate(s) flow agent.
7. the preparation method of a kind of high performance fluorine carbon coating as claimed in claim 1, is characterized in that: described mineral filler by titanium dioxide, carbon black, calcium carbonate, aluminum oxide, barium sulfate one or more form according to any proportioning.
8. the preparation method of a kind of high performance fluorine carbon coating as claimed in claim 1, is characterized in that: described thinner A, diluent B form according to any proportioning by one or more in toluene, dimethylbenzene, n-butyl acetate, 1-Methoxy-2-propyl acetate, ethyl acetate, butylacetate, ethylene glycol, methyl alcohol, propyl carbinol, butanone, methylethylketone, pimelinketone.
9. the preparation method of a kind of high performance fluorine carbon coating as claimed in claim 1, is characterized in that: described defoamer is polyoxyethylene polyoxypropylene tetramethylolmethane ether, polyoxyethylene polyoxy propyl alcohol amidogen ether, polypropylene glycerol aether, polyoxyethylene polyoxypropylene glyceryl ether, fluorine-carbon modified acrylate type one or more form according to any proportioning.
10. the preparation method of a kind of high performance fluorine carbon coating as claimed in claim 1, is characterized in that: described flatting silica is silicon-dioxide, talcum powder a kind of or both form according to any proportioning.
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