CN102838906A - Fluoropolymer coating solution and weather-resistant coating obtained therefrom - Google Patents
Fluoropolymer coating solution and weather-resistant coating obtained therefrom Download PDFInfo
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Abstract
The invention relates to a fluoropolymer coating solution and a weather-resistant coating obtained therefrom. Fluoroplastics have excellent dielectric property and chemical corrosion resistance, high and low temperature resistance, and other excellent weatherability. At the same time, fluoroplastics also have the properties of waterproofness, no stickness, low friction coefficient, and good self-lubricating performance, etc. Currently, fluoroplastics are widely used in chemicals, electronics, electrical engineering, aviation, aerospace, semiconductors, machinery, textiles, construction, medicines, automobiles and other industrial fields. However, due to the intrinsic characteristics of fluoroplastics, the processing difficulty is very large. After long-term in-depth study, the inventor of the invention finds that the fluoropolymer coating solution provided in the invention can overcome the above disadvantages in the prior art. The coating obtained from the fluoropolymer coating solution provided in the invention has the characteristics of high fluorocarbon content, room temperature curing, good bonding strength with various substrates, no need of adhesive, convenient use and the like. The coating solution can be subjected to on-site construction under a variety of circumstances, and while improving the using performance, the use cost is reduced.
Description
Technical field:
The present invention relates to a kind of fluoropolymer coated liquid, particularly relate to a kind of solvent-borne type fluoropolymer coated liquid.By this coating fluid can obtain to have high-weatherability, high resistance to chemicals medicine property and all gases that comprises water vapour had the coating of good barrier properties.
Background technology:
Fluroplast-4 have excellent dielectric properties and splendid weathering resistance such as resistance to chemical attack, high-low temperature resistant.Also have waterproof simultaneously, not sticking, low-friction coefficient, good performances such as self lubricity.At present, Fluroplast-4 have been widely used in chemical industry, and electronics is electric, aviation, space flight, semi-conductor, machinery, weaving, building, medicine, industrial circles such as automobile.But because the Fluroplast-4 self characteristics, difficulty of processing is very big.Because its fusing point and decomposition temperature are very approaching, so when film extrusion, need add latent solvent or it is carried out modification by copolymerization.This just all has higher requirement for the process control of film forming link and the assurance of film quality.And the employing coating process, still there are many deficiencies in prior art.Because the kind tetrafluoroethylene that most fluorine carbon contents are high, pvdf etc.; All need carry out hot setting; Promptly adopt 370 ℃-400 ℃ high-sintering process; Therefore coating is sintered on the base material, is difficult in heatproof less than making coating on 370 ℃ the base material, big limitations its range of application.In addition, though the fluorine material of some kind can adopt organic solvent, water etc. to be coated with as solvent, all must could realize through hot setting (370 ℃-400 ℃) or intermediate temperature setting (170 ℃).In addition, though there is the fluorine material of minority kind can carry out ambient cure,, therefore can not fully satisfy in the use demand to multiple performances such as its weathering resistancies because its fluorine carbon content when copolymerization is lower.Simultaneously, because the not viscosity of fluorine material itself, it is sticking and and realize good stripping strength with other materials that it is difficult in the ordinary course of things.Therefore; Present Application Areas (except the sintering process) at all kinds of fluorine materials; All need adopt all kinds of tackiness agents to fluorine material and base material glue with, and the performance of most tackiness agent at aspects such as weathering resistance, chemical resistances can't be equal to the fluorine material at all.So, the performance of tackiness agent has also just restricted the performance of fluorine material property, make at present as: numerous fluorine material Application Areass such as solar energy back film, lithium electricity peplos, pesticides packaging film, the excellent characteristic of fluorine material itself can not obtain the expection realization.
Therefore, this area still need provide a kind of easy processing, ambient cure; Can realize the cementability outstanding with various base materials, high fluorine carbon content has excellent weathering resistance, chemical proofing; Water-repellancy, high performance fluoropolymer coated liquid such as preservative property and coating thereof.
Summary of the invention:
The inventor finds through secular further investigation, according to fluoropolymer coated liquid of the present invention, can overcome the above-mentioned shortcoming of prior art.Obtain coating by fluoropolymer coated liquid of the present invention, have high fluorine carbon content, characteristic such as ambient cure all has good bonding strength with all kinds of base materials, need not tackiness agent, and is easy to use.Can under multiple environment, carry out site operation, when improving use properties, reduce use cost again.
According to an aspect of the present invention, provide a kind of high fluorine carbon content, the especially coating can ambient cure, need not to use any tackiness agent can all have the coating fluid and the coating of very good bonding strength simultaneously with all kinds of base materials.Advantageously this coating fluid use is convenient especially, only need adopt conventional printing press just can accomplish coating when on plastic film substrate, being coated with.Surface covered can reach 100m/min.When on other base materials, using, can under multiple environment, carry out site operation.And can be widely used in solar energy back film, terminal box, lithium electricity peplos, pesticides packaging, wiring board electrically conductive ink, marine finish; Trade sales coating, military all kinds of coating, space flight coating, electronics, electric, semi-conductor; Machinery, weaving, food medicine, iron and steel, fields such as automobile.Have good cost performance, thereby can prolong the work-ing life of all kinds of base materials greatly, practiced thrift resource simultaneously, be very beneficial for environment protection.
Said fluoropolymer coating is obtained by following solvents type fluoropolymer coated liquid, and it comprises: fluoropolymer; Solvent; With crosslinked tackifier.
All numerical value or the expression of the expression composition that uses at this paper unless otherwise prescribed,, reaction conditions etc. are considered to can use in all cases word " approximately " to modify.
Many numerical ranges are disclosed in this application.Because these scopes are successive, so they have been included in each value between minimum value and the peak.Except the practical implementation exception, do not having under the situation about clearly stipulating in addition, specified in this application various numerical ranges are approximations.
The fluoropolymer that is applicable to fluoropolymer coated liquid of the present invention comprises: polytetrafluoroethylene (PTFE), the multipolymer of tetrafluoroethylene and perfluoroalkyl vinyl ether (PFA), the multipolymer of tetrafluoroethylene and R 1216 (FEP); Tetrafluoroethylene and ethylene copolymer (ETFE), daiflon (PCTFE), low molecular weight polytetrafluoroethylene; Pvdf (PVDF), PVF (PVF), ethene trifluoro-ethylene copolymer (F30); Tetrafluoroethylene vinylidene fluoride copolymer (F-24), trifluorochloroethylene-inclined to one side fluo-copolymer (F-23), FEVE; All kinds of fluorochemical monomers and/or other monomer, the multipolymer of polymkeric substance and blend, and the modified product of above-mentioned polymkeric substance.The term " polymer " of here using " comprise homopolymer, multipolymer, and comprise prepolymer and oligopolymer.
In fluoropolymer coated liquid of the present invention, solvent is preferably selected from: chloroform, acetone, butanone, ETHYLE ACETATE; N-butyl acetate, DMSO 99.8MIN., tetramethylene sulfone, N, dinethylformamide; N,N-DIMETHYLACETAMIDE, ethanamide, methane amide, N-Methyl pyrrolidone, isocyanic ester; Toluene, quadrol, ammoniacal liquor, water.Above-mentioned each kind solvent can use separately, also can be with two kinds or more kinds of being used in combination.
In fluoropolymer coated liquid of the present invention, crosslinked tackifier are preferably selected from: the chemical structural formula of product is expressed as:
And the modified product of above-mentioned product.The term " product " that here uses comprises multipolymer, compound, prepolymer and oligopolymer.
According to a specific embodiments of the present invention, fluoropolymer coated liquid of the present invention comprises: the fluoropolymer of 1%-50%wt%; The solvent of 5%-98.9%wt%; The crosslinked tackifier of 0.1%-45%wt%; Gross weight meter based on coating fluid.
As required, also can also contain organic/inorganic substance in the fluoropolymer coated liquid of the present invention, for example, but be not limited to: silver, silver suboxide, aluminium; Aluminum oxide, copper, cupric oxide, zinc oxide, Natural manganese dioxide, silicon oxide; Ceramics powder, graphite, carbon black, white titanium pigment, REE, lime carbonate; Permanent white, kaolin, mica, glass microballon, talcum powder, and they two or more mixture.Particle diameter can be micron-sized and/or be nano level.Above-mentioned inorganics can account for about 0%-20%wt% of coating fluid total amount; Preferred 2%-10%wt%.
As required, can also contain functional additive in the fluoropolymer coated liquid of the present invention, include but not limited to: ROHM and ester thereof, vinylformic acid and ester thereof, methyl acrylate; Ethyl propenoate, Bing Xisuandingzhi, third Hydroxyethyl acrylate, Propylene glycol monoacrylate, sodium acrylate; Polymethyl acrylic acid and ester thereof, methylacrylic acid and ester thereof, TEB 3K, Jia Jibingxisuanyizhi; Thanomin, diethylolamine, trolamine, polymine; Quadrol, ethyleneimine, acrylic amide, propylene is fine.Anti UV agent, oxidation inhibitor, inorganic dyestuff, organic dye, light reflecting material, and they two or more mixture, multipolymer.
According to a non-limiting embodiments of the present invention, fluoropolymer coated liquid of the present invention comprises: the fluoropolymer of 1%-20%wt%; The crosslinked tackifier of 0.1%-20%wt%; The inorganics of 0%-20%wt%; The functional additive of 0%-30%wt%; The solvent of 10%-98.9%wt%; Gross weight meter based on coating fluid.
Fluoropolymer coated liquid of the present invention also can add materials such as tensio-active agent, antiseptic-germicide, tinting material, electro-conductive material as required therein.
The method of manufacture of fluoropolymer coated liquid of the present invention includes but are not limited to: adopt heatable container, adding solvent, fluoropolymer stir, and are heated to 40 ℃-80 ℃ earlier.After fluoropolymer is fully dissolved, be cooled to normal temperature.Then add crosslinked tackifier, and fully stir, promptly get the present invention's fluoropolymer coated liquid.
The present invention also method of manufacture of the fluoropolymer coated liquid of a scheme includes but not limited to: adopt heatable container, adding solvent, fluoropolymer, inorganics, additive stir, and are heated to 40 ℃-80 ℃ earlier.After fluoropolymer is fully dissolved, be cooled to normal temperature.Then add crosslinked tackifier, and fully stir, promptly get the present invention's fluoropolymer coated liquid.
The needs fluoropolymer coated liquid according to the present invention; Also can adopt all kinds of fluorochemical monomers and other monomer, and/or compound, with crosslinked tackifier, carry out copolymerization through the known all kinds of polymerization methods of prior art.Also can obtain fluoropolymer coated liquid of the present invention.
Fluoropolymer coated liquid of the present invention can be coated on all kinds of base materials, includes, but are not limited to: Vilaterm (PE), Vestolen PP 7052 (PP), polyester (PET), polycarbonate (PC), SE (PVC); Polyamide (PA), PS (PS), ethene-vinyl acetate copolymer (EVA), Z 150PH (PVA), polymethylmethacrylate (PMMA), timber, ABS resin; Glass, aluminium, iron, steel, copper, cement, stone material; Rubber, paper, and the film of processing with them, sheet material, sheet material, hollow piece.Its coat-thickness is 0.2-100 μ m.
Preferably printing press coating of fluoropolymer coated liquid of the present invention, the coating machine coating, the dry compound machine coating, the casting machine coating is brushed, spraying, roller coat, dipping is coated with, and known coating processes such as reticulate pattern roller coat are coated on the base material, can repeat repeatedly to be coated with.And non-essentially can between this base material and fluoropolymer coating, use undercoat.
Fluoropolymer coating of the present invention has very light of outward appearance, and weathering resistance is very good, can keep out of doors 25 years and the characteristic that do not change.Fabulous chemical proofing is arranged simultaneously, can anti-strong acid, highly basic and most organic solvent.Water-fast, self-cleaning is good, and low-friction coefficient is not sticking, high-low temperature resistant, good self lubricity etc.And has a very low WVTR water vapor trausmission rate.
Below, further specify the present invention with non-limiting example.
But it should be noted that it is limitation of the present invention that these embodiment should not be regarded as.In present specification, unless expressly stated otherwise,, all parts and per-cent are all based on weight.
Embodiment 1:
According to following proportioning, pvdf (PVDF) and DMSO 99.8MIN. are joined in the heatable container, and under agitation be heated to 50 ℃-60 ℃, fully dissolving.After treating near 50 ℃-20 ℃ of temperature, add crosslinked tackifier structural formula product 1., obtain coating fluid (1) after fully mixing.This coating fluid is deposited at 10 ℃-40 ℃ and was not produced gelatin phenomenon in 180 days, and storage stability is good.
Adopt spraying method to be applied on the aluminium sheet ambient cure 30 minutes, coat-thickness 10 μ m coating fluid (1).Adopt cutter that coating is divided into the grid of 1cm, use adhesive tape to peel off.
Embodiment 2:
According to following proportioning, tetrafluoroethylene and ethylene copolymer (ETFE) and dinethylformamide are joined in the heatable container, and under agitation be heated to 50 ℃-60 ℃, fully dissolving.After treating near 50 ℃-20 ℃ of temperature, add crosslinked tackifier structural formula product 2., obtain coating fluid (2) after fully mixing.This coating fluid is deposited at 10 ℃-40 ℃ and was not produced gelatin phenomenon in 180 days, and storage stability is good.
Adopt printing press to be applied on polyester (PET) base material coating fluid (2), on-line velocity 100m/min, coat-thickness 20 μ m behind the following machine, use adhesive tape to peel off.
Embodiment 3:
According to following proportioning, with pvdf (PVDF) and N-Methyl pyrrolidone, ETHYLE ACETATE, (mixed weight was than 1: 1); White titanium pigment, oxidation inhibitor join in the heatable container, and under agitation are heated to 70 ℃-80 ℃, fully dissolving.After treating near 30 ℃-20 ℃ of temperature, add crosslinked tackifier structural formula product 3., obtain coating fluid (3) after fully mixing.This coating fluid is deposited at 10 ℃-40 ℃ and was not produced gelatin phenomenon in 180 days, and storage stability is good.
Adopt rolling method to be applied on the steel plate ambient cure 30 minutes, coat-thickness 35 μ m coating fluid (3).Adopt cutter that coating is divided into the grid of 1cm, use adhesive tape to peel off.
Embodiment 4:
According to following proportioning, the multipolymer (FEP) and the n-butyl acetate of tetrafluoroethylene and R 1216 joined in the heatable container, and under agitation be heated to 50 ℃-60 ℃, fully dissolving.After treating near 50 ℃-20 ℃ of temperature, add crosslinked tackifier structural formula product 1., obtain coating fluid (4) after fully mixing.This coating fluid is deposited at 10 ℃-40 ℃ and was not produced gelatin phenomenon in 180 days, and storage stability is good.
Adopt pickling process to be applied on the terminal box coating fluid (4), ambient cure 30 minutes, coat-thickness 30 μ m use adhesive tape to peel off.
Embodiment 5:
According to following proportioning, with PVF (PVF) and N, isocyanic ester, (mixed weight was than 1: 1); Titanium silver powder, anti UV agent join in the heatable container, and under agitation are heated to 60 ℃-70 ℃, fully dissolving.After treating near 30 ℃-20 ℃ of temperature, add crosslinked tackifier structural formula product 3., obtain coating fluid (5) after fully mixing.This coating fluid is deposited at 10 ℃-40 ℃ and was not produced gelatin phenomenon in 180 days, and storage stability is good.
Adopt spread coating to be applied on the cement plate ambient cure 30 minutes, coat-thickness 40 μ m coating fluid (5).Adopt cutter that coating is divided into the grid of 1cm, use adhesive tape to peel off.
Embodiment 6:
According to following proportioning, polytetrafluoroethylene (PTFE) and dinethylformamide are joined in the heatable container, and under agitation be heated to 50 ℃-60 ℃, fully dissolving.After treating near 50 ℃-20 ℃ of temperature, add crosslinked tackifier structural formula product 2., obtain coating fluid (6) after fully mixing.This coating fluid is deposited at 10 ℃-40 ℃ and was not produced gelatin phenomenon in 180 days, and storage stability is good.
Adopt coating machine to be applied on Vestolen PP 7052 (PP) base material coating fluid (6), on-line velocity 80m/min, coat-thickness 20 μ m behind the following machine, use adhesive tape to peel off.
Embodiment 7:
According to following proportioning, daiflon (PCTFE) and tetramethylene sulfone are joined in the heatable container, and under agitation be heated to 40 ℃-60 ℃, fully dissolving.After treating near 30 ℃-20 ℃ of temperature, add crosslinked tackifier structural formula product 3., obtain coating fluid (7) after fully mixing.This coating fluid is deposited at 10 ℃-40 ℃ and was not produced gelatin phenomenon in 180 days, and storage stability is good.
Adopt the solution casting coating method to be applied on the paper coating fluid (7), coat-thickness 0.8 μ m behind the following machine, uses adhesive tape to peel off.
Embodiment 8:
According to following proportioning, with ethene trifluoro-ethylene copolymer (F30) and N,N-DIMETHYLACETAMIDE, acetone, (mixed weight was than 1: 1); Aluminum oxide, light reflecting material join in the heatable container, and under agitation are heated to 70 ℃-80 ℃, fully dissolving.After treating near 50 ℃-30 ℃ of temperature, add crosslinked tackifier structural formula product 1., obtain coating fluid (8) after fully mixing.This coating fluid is deposited at 10 ℃-40 ℃ and was not produced gelatin phenomenon in 180 days, and storage stability is good.
Adopt the reticulate pattern rolling method to be applied on the PS (PS) coating fluid (8), ambient cure 30 minutes, coat-thickness 15 μ m use adhesive tape to peel off.
Embodiment 9:
According to following proportioning, trifluorochloroethylene-inclined to one side fluo-copolymer (F-23) and ETHYLE ACETATE are joined in the heatable container, and under agitation be heated to 40 ℃-60 ℃, dissolving fully.After treating near 30 ℃-20 ℃ of temperature, add crosslinked tackifier structural formula product 1., obtain coating fluid (9) after fully mixing.This coating fluid is deposited at 10 ℃-40 ℃ and was not produced gelatin phenomenon in 180 days, and storage stability is good.
It is on glass to adopt spraying method to be applied to coating fluid (9), ambient cure 30 minutes, coat-thickness 15 μ m.Adopt cutter that coating is divided into the grid of 1cm, use adhesive tape to peel off.
Embodiment 10:
According to following proportioning, with the multipolymer (PFA) and the butanone of tetrafluoroethylene and perfluoroalkyl vinyl ether, isocyanic ester, (mixed weight was than 1: 1); Glass microballon, organic dye join in the heatable container, and under agitation are heated to 50 ℃-70 ℃, fully dissolving.After treating near 40 ℃-30 ℃ of temperature, add crosslinked tackifier structural formula product 3., obtain coating fluid (10) after fully mixing.This coating fluid is deposited at 10 ℃-40 ℃ and was not produced gelatin phenomenon in 180 days, and storage stability is good.
Adopt dry compound machine to be applied on the polycarbonate (PC) coating fluid (10), ambient cure 30 minutes, coat-thickness 20 μ m use adhesive tape to peel off.
Claims (12)
1. fluoropolymer coated liquid, its component comprises: fluoropolymer; Solvent; With crosslinked tackifier.
2. the fluoropolymer coated liquid of claim 1, wherein said fluoropolymer is selected from polytetrafluoroethylene (PTFE), the multipolymer of tetrafluoroethylene and perfluoroalkyl vinyl ether (PFA); The multipolymer of tetrafluoroethylene and R 1216 (FEP), tetrafluoroethylene and ethylene copolymer (ETFE), daiflon (PCTFE); Low molecular weight polytetrafluoroethylene, pvdf (PVDF), PVF (PVF); Ethene trifluoro-ethylene copolymer (F30); Tetrafluoroethylene vinylidene fluoride copolymer (F-24), trifluorochloroethylene-inclined to one side fluo-copolymer (F-23), one or more of FEVE and composition thereof.
3. the fluoropolymer coated liquid of claim 1, wherein said solvent is selected from: chloroform, acetone, butanone, ETHYLE ACETATE; N-butyl acetate, DMSO 99.8MIN., tetramethylene sulfone, N, dinethylformamide; N,N-DIMETHYLACETAMIDE, ethanamide, methane amide, N-Methyl pyrrolidone, isocyanic ester; Toluene, quadrol, ammoniacal liquor, water, and composition thereof one or more.
4. the fluoropolymer coated liquid of claim 1, wherein said crosslinked tackifier are preferably selected from: the chemical structural formula of product is expressed as: 1.
Above-mentioned three kinds one or more.
5. the fluoropolymer coated liquid of claim 1, it comprises:
The fluoropolymer of 1%-50%wt%; The solvent of 5%-98.9%wt%; The crosslinked tackifier of 0.1%-45%wt%; Gross weight meter based on coating fluid.
6. the fluoropolymer coated liquid of claim 1 also contains organic/inorganic substance, is preferably selected from: silver, silver suboxide, aluminium, aluminum oxide; Copper, cupric oxide, zinc oxide, Natural manganese dioxide, silicon oxide, ceramics powder; Graphite, carbon black, white titanium pigment, REE, lime carbonate, permanent white; Kaolin, mica, glass microballon, talcum powder, and they two or more mixture.
7. the fluoropolymer coated liquid of claim 1 also contains functional additive, is preferably selected from: ROHM and ester thereof, vinylformic acid and ester thereof, methyl acrylate, ethyl propenoate; Bing Xisuandingzhi, third Hydroxyethyl acrylate, Propylene glycol monoacrylate, sodium acrylate, polymethyl acrylic acid and ester thereof, methylacrylic acid and ester thereof; TEB 3K, Jia Jibingxisuanyizhi, thanomin, diethylolamine, trolamine; Polymine, quadrol, ethyleneimine, acrylic amide, propylene is fine.Anti UV agent, oxidation inhibitor, inorganic dyestuff, organic dye, light reflecting material, and they two or more mixture, multipolymer.
8. the fluoropolymer coated liquid of claim 6-7 comprises:
The fluoropolymer of 1%-20%wt%; The crosslinked tackifier of 0.1%-20%wt%; The inorganics of 0%-20%wt%; The functional additive of 0%-30%wt%; The solvent of 10%-98.9%wt%; Gross weight meter based on coating fluid.
9. the method for manufacture of the fluoropolymer coated liquid of claim 1-5 is:
Adopt heatable container, adding solvent, fluoropolymer stir, and are heated to 40 ℃-80 ℃ earlier.After fluoropolymer is fully dissolved, be cooled to normal temperature.Then add crosslinked tackifier, and fully stir, promptly get the present invention's fluoropolymer coated liquid.
10. the method for manufacture of the fluoropolymer coated liquid of claim 6-8 is:
Adopt heatable container, adding solvent, fluoropolymer, inorganics, additive stir, and are heated to 40 ℃-80 ℃ earlier.After fluoropolymer is fully dissolved, be cooled to normal temperature.Then add crosslinked tackifier, and fully stir, promptly get the present invention's fluoropolymer coated liquid.
11. by the fluorine coating that each fluoropolymer coated liquid of claim 1-8 obtains, its base material is preferably selected from: Vilaterm (PE), Vestolen PP 7052 (PP), polyester (PET), polycarbonate (PC), SE (PVC), polyamide (PA); PS (PS), ethene-vinyl acetate copolymer (EVA), Z 150PH (PVA), polymethylmethacrylate (PMMA), timber, ABS resin, glass; Aluminium, iron, steel, copper, cement, stone material; Rubber, paper, and the film of processing with them, sheet material, sheet material, hollow piece.Its coat-thickness is 0.2-100 μ m.
12. by the coating that the fluoropolymer coated liquid of claim 1-8 item obtains, its coating process is preferably selected from: adopt coating machine, dry compound machine, printing press coating, the solution casting coating is brushed, roller coat, dipping is coated with, spraying, reticulate pattern roller coat.Can repeat repeatedly to be coated with.
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