CN1278285A - Fluoropolymer dispersion coatings from modified thermoplastic vinylidene fluoride based resins - Google Patents
Fluoropolymer dispersion coatings from modified thermoplastic vinylidene fluoride based resins Download PDFInfo
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- CN1278285A CN1278285A CN98800901A CN98800901A CN1278285A CN 1278285 A CN1278285 A CN 1278285A CN 98800901 A CN98800901 A CN 98800901A CN 98800901 A CN98800901 A CN 98800901A CN 1278285 A CN1278285 A CN 1278285A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F259/00—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00
- C08F259/08—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00 on to polymers containing fluorine
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
Abstract
A paint base for dispersion coatings substrates comprising an acrylic modified fluoropolymer, paints and varnishes derived therefrom, coatings derived therefrom and articles coated with said coatings are disclosed. The coatings have improved gloss, flex, crack resistance and other improved use properties.
Description
It is the U.S. Provisional Application sequence number No.60/051 on July 2nd, 1997 that the application requires the applying date, 642 right of priority.
FIELD OF THE INVENTION
The present invention relates to be classified as in the chemical field material of seed polymer with based on vinylformic acid, esters of acrylic acid, the composition of the polymkeric substance of methacrylic acid and/or methyl acrylic ester (acrylic polymers), the described material that is classified as seed polymer is a fluoropolymer system, described fluoropolymer is the homopolymer of vinylidene fluoride (VDF) and the multipolymer of vinylidene fluoride and comonomer more particularly, and described comonomer is selected from R 1216 (HFP), tetrafluoroethylene (TFE), trifluorochloroethylene (CTFE), trifluoro-ethylene (TrFE) and/or vinyl fluoride (VF).The present invention relates to contain the composition of above-mentioned these materials, relate to contain the liquid coating composition of above-mentioned these materials more specifically.The invention still further relates to the seed polymer that contains fluoropolymer and the preparation of compositions and the using method of acrylic polymers, and using method of fluoropolymer and acrylic polymers their itself combination.
The background of invention
Known, the coating that uses the paint adhesive that is mixed with by polyvinylidene difluoride (PVDF) (PVDF) fluoropolymer resin and paint vehicle to make has good solvent resistance, chemical resistant properties, weathering resistance, thermostability, intensity and rebound resilience.Yet its performance need improves further, especially the outside durabitity under severe rugged environment.In addition, the membrane formation mechanism of the dispersion paint (dispersion coating) of conventional polyvinylidene difluoride (PVDF) (PVDF) base and the industrial condition of using these coating obtain the coating of medium gloss, and observed value is 30 to 40 under 60 degree glossiness condition determinations.Conventional PVDF dispersion paint well as if discrete PVDF particle homogeneous propylene acids polymers soln in mutually mixture or discrete PVDF particle and discrete acrylic polymers particle at the mixture of aqueous phase.These systems can contain or not contain pigment and other additive.Known in this area, PVDF must mix between film stage to obtain the optimum performance of this class coating system mutually with acrylic polymers.Apply under the situation of (it is a kind of common coating method of this class coating system) film formation time normally 30 to 60 seconds at coiled material.The storing time weak point makes PVDF and complete blended time of acrylic polymers lack.
Have been found that the glossiness of mixing the paint vehicle that is used for coating and varnish (varnishes) that obtains and adhesive formula gained coating with acrylic polymers (hereinafter can describe in more detail) by PVDF homopolymer and multipolymer is higher than the glossiness of conventional prior art PVDF acrylic acid or the like blending resin coating system.In addition, under certain prescription and baking condition, the mechanically flexible of coating provided by the present invention increases than prior art co-mixing system, acceleration ultraviolet light (UV) test shows of carrying out with standard method, coating provided by the present invention has improved ultraviolet light performance than the blending resin system of prior art, and this can increase from the gloss retention and show.
Prior art
The whole world has many disclosed patents and patent application to describe with the particle in the latex of polyvinylidene fluoride homopolymer or multipolymer as being used for multiple acrylic acid monomers polymeric seed to form latex, directly form water-based paint and other coating by this latex, and need not polymkeric substance is separated from latex.For example, referring to United States Patent (USP) 5,439,980,4,946,889,5,034,460; European patent application 0 670 353 A2,0 736 583 A1,0 360 575 A2; Japanese patent application 6-335005 (8-170045), 4-97306 (5-271359), 3-355973 (5-170909), 3-124997 (4-325509), 7-63193 (8-259773); PCT applies for WO 95/08582, and following digest: chemical abstracts 1994:702216, chemical abstracts 1993:474687, Derwent 93:278324, Derwent 91:329278, Derwent 90:317958, Derwent 87:082345, Derwent 86:213626, Derwent 94:107015/13, Derwent 93:365288/46, Derwent 93:365461/46, Derwent 96:049627, Derwent 93:397686, Derwent 94:808169, and the reference quoted of these publications.All not mentioned and point out solid is separated from seeding polymerization latex in all these publications, subsequently with the solid redispersion of these recovery in water-based or the non-aqueous solvent to form dispersing coating and varnish.
Have many patents and publication to describe dispersing coating and clear coat composition, these compositions are to carry out the polyvinylidene fluoride polymer of physical mixed and copolymerization system with acrylic polymers.For example, referring to United States Patent (USP) 3,324,069, United States Patent (USP) 4,128,519, PCT application WO 93/13178 and european patent application 0 670353 A2 and the reference of wherein being quoted.These reference show that all the coating property that invention composition at that time is used to paint with the varnish gained improves to some extent.
Definition
The composition that used term " paint binder (paint base) " or " paint vehicle (paint vehicle) " are interpreted as paint adhesive and thinner in this specification sheets and the appending claims is to wherein having sneaked into pigment to form coating.Term " varnish " used in this specification sheets and the appending claims is interpreted as a kind of fluid composition, and its coating is can become transparent solid after the skim.Not containing the paint binder or the paint vehicle that add pigment is varnish.
The non-volatile part that used term " tackiness agent " or " paint adhesive " are interpreted as paint binder or paint vehicle in this specification sheets and the appending claims.It keeps together granules of pigments, and will film and remain on its material that applies as an integral body.
Used " thinner " is interpreted as evaporable coating (or varnish) part in drying process in this specification sheets and the appending claims.It comprises any solvent (water or non-water).
" fluoropolymer of acrylic acid or the like modification " (acrylicmodified fluoropolymer in this specification sheets and the appending claims; " AMF ") be meant solid resin (particle or aggregate); this solid resin is following to be made: polymerization is selected from the ethylenically unsaturated monomers of vinylformic acid, esters of acrylic acid, methacrylic acid, methyl acrylic ester and composition thereof in the presence of the latex of foraflon or multipolymer (hereinafter can describe in more detail); if necessary, resin is separated from the latex of this preparation gained.
Used " dispersion paint " is meant a kind of like this coating in this specification sheets and the appending claims, paint binder wherein or paint vehicle are by isolating dried resin basically from the latex of above-mentioned preparation gained, and it is dissolved or suspended in the thinner makes.
Therefore, the paint binder that is used for dispersion paint only contains the resin of separating from the latex of initial this resin of formation substantially, and if necessary, this resin is exsiccant basically.
The general introduction of invention
The present invention is in the first aspect of composition, a kind of paint binder or paint vehicle that is used for dispersion paint is provided, it comprises the fluoropolymer resin of acrylic acid or the like modification, and the content of the fluoropolymer dried resin of this acrylic acid or the like modification (dry resin content) is 10%-90% (weight).
What specifically mention is the embodiment of present composition first aspect, and the thinner that wherein is used for paint binder or paint vehicle is non-water basically.
The embodiment of specifically mentioning that also has present composition first aspect, the thinner that wherein is used for paint binder or paint vehicle is water base.
The present invention provides a kind of coating in the second aspect of composition, and it comprises paint binder or the paint vehicle and the pigment of sneaking into wherein of present composition first aspect.
The present invention provides a kind of coating in the third aspect of composition, this coating obtains with the following method: will be applied on the surface that needs coating as defined coating of present composition second aspect or the varnish of being made up of paint binder or paint vehicle (being defined as present composition first aspect) basically, and evaporate solvent contained in described coating or the varnish.
The present invention provides a kind of goods in the fourth aspect of composition, and these goods comprise it and are attached with goods as the defined coating of the third aspect of the present composition on one side at least.
The present invention provides a kind of coating that will contain the fluoropolymer adhesive of improved acrylic acid or the like modification to be applied in lip-deep method aspect method, it comprises on the surface as described in being applied in as the defined coating of present composition second aspect or the varnish be made up of paint binder or paint vehicle (being defined as present composition first aspect) basically, evaporates thinner contained in described coating or the varnish.
The detailed description of invention
Those skilled in the art refer now to preferable embodiment of the present invention and come describe, in general terms the present invention, so that can prepare and use.
As the foraflon of raw material and copolymer emulsion and preparation method thereof is known.For example, referring to the vinylidene fluoride polymer of Humphrey and Dohany, polymer science and engineering complete works (Encyclopedia of Polymer Science and Engineering), second edition, volume 17, page or leaf 532 to 548,
1989, John Wiley and Sons, and the reference of wherein being quoted.Also can be referring to United States Patent (USP) 3,857,827; 4,360,652; 4,569,978; 3,051,677; 3,178,399; 5,093,427; 4,076,929; 5,543,217; The polymkeric substance communique of Moggi etc. (Polymer Bulletin),
7, the 115th to 122 page, (1982), the polymkeric substance of Bonardelli etc. (Polymer)
27, 905-909 page or leaf (1986), the polymkeric substance of Pianca etc. (Polymer),
28, the european patent application No.650 of 224-230 page or leaf (1987) and Abusleme etc., 982A1.The latex that so makes can be PVDF homopolymer or PVDF and be suitable for multipolymer with the monomer (being selected from HFP, TFE, TrFE, VF or their mixture) of VDF copolymerization.HFP is preferable comonomer.
One or more comonomers of about 30% (weight) can add in the PVDF multipolymer at most, are preferably about 25% (weight) of 0%-.
It is preferably for the present invention that Tg is lower than 25 ℃ seed grain.The technology that is used for controlling Tg is to know in this area, itself is not a part of the present invention.For fluo-copolymer, the prevailing method of control Tg is the composition of control fluo-copolymer.
Be preferably, the size of seed grain should be lower than 250 nanometers, in order that obtain final AMF polymer particles particle size less than 350 nanometers.
The present invention adopts letex polymerization or suspension polymerization, in vertical reactor or horizontal reactor with intermittently, semicontinuous or continuous mode carries out.
The acrylic acid or the like and the methacrylic monomer that carry out seeding polymerization in the presence of fluoropolymer latex are vinylformic acid, alkyl acrylate, methacrylic acid and alkyl methacrylate, wherein the alkyl of the ester moiety of molecule contains 1 to about 10 carbon atoms, is preferably to contain 1 to about 4 carbon atoms.
Suitable esters of acrylic acid includes, but not limited to ethyl propenoate, methyl acrylate, butyl acrylate, propyl acrylate, isobutyl acrylate, vinylformic acid pentyl ester, 2-EHA and Ethyl acrylate.Suitable methyl acrylic ester comprises, but be not limited to Jia Jibingxisuanyizhi, methyl methacrylate, butyl methacrylate, propyl methacrylate, Propenoic acid, 2-methyl, isobutyl ester, methacrylic acid pentyl ester, methacrylic acid 2-ethylhexyl and methacrylic acid hydroxyethyl ester.Preferable monomer is vinylformic acid, methacrylic acid, ethyl propenoate, methyl acrylate, butyl acrylate, methyl methacrylate and glycidyl methacrylate.Acrylate and methacrylate monomer can be used separately or be used in combination.
In order to finely tune the film performance of final formation, can carry out copolymerization with the monomer of a spot of other copolymerisable monomer and/or oligopolymer and vinylformic acid and/or methacrylic acid and ester thereof.These other copolymerisable monomers and/or oligopolymer comprise; but be not limited to; vinyl cyanide, conjugated diolefine (as 1,3-butadiene and isoprene), fluoroalkyl acrylate, methacrylic acid fluoropropenes acyl group alkyl ester, aromatics alkenyl compound (as vinylbenzene, alpha-methyl styrene, vinylbenzene halogenide) and divinyl hydrocarbon compound (Vinylstyrene).Can use reactive emulsifier, as the product of commercially available commodity Burenna, Eliminol by name, NK ester.
The total amount of vinylformic acid, esters of acrylic acid, methacrylic acid, methyl acrylic ester or its mixture should account for 80% (weight) of whole monomer mixture or higher, is preferably 90% (weight) or higher.
It is 10 to 200 weight parts that the whole monomer mixture that is used in the presence of fluoropolymer seed grain polymerization or copolymerization should be per 100 weight part seed grains, is 20 to 80 weight parts preferably.
Seeding polymerization can carry out under the condition identical with conventional emulsion polymerization.In seed latex, add required acrylic monomer and/or methacrylic monomer and initiators for polymerization, and optional tensio-active agent, chain-transfer agent, pH regulator agent, can randomly finally add solvent and sequestrant in addition, under barometric point, 20-90 ℃ (being advisable), react 0.5 to 6 hours with 40-80 ℃.
Carrying out letex polymerization with fluoropolymer as seed can be undertaken by standard method:
Batchwise polymerization adds one or more monomers, initiator and other component (if necessary) at the very start in the water dispersion of fluoropolymer in this polymerization;
Semi-continuous polymerzation adds part or all of every kind of component continuously or off and in reaction process in this polymerization;
Successive polymerization adds all components and aqueous fluoropolymer dispersion simultaneously in reactor in this polymerization.
Component can be added in the reactor, solubilising in suitable solvent (organic or water) is perhaps as the dispersion in suitable solvent.
The present invention uses all types of polymerization reactors (stirring tank, pipe, endless tube).Convenient and handiness becomes preferable reactor to the stirred-tank reactor of operating under semicontinuous state owing to it.
The method that is used for preparing product of the present invention comprises two steps at least.The letex polymerization of fluoropolymer needs at least one step, and the inoculation letex polymerization of acrylic monomer (seeded emulsion polymerization) needs at least one step.
These steps can be carried out in same reactor or different reactor.Each step can comprise its distinctive monomer, tensio-active agent, initiator, chain-transfer agent, pH regulator agent, solvent and/or sequestrant.Be preferably a plurality of steps and use same reactor.
Final latex is made up of single-size and the discrete particles formed, perhaps is made up of multiple size and/or the discrete particles formed.Be preferably and have the latex that homogeneous is formed the discrete particles that distributes.And the particle size distribution of broad or multimodal particle size distribution can be carried out particulate effectively and filled, and would rather use these particles and without the particle size distribution of homogeneous.
Final latex particle can be by the single-phase, two-phase or heterogeneous composition of variform, described form such as single-phase form, nuclear-shell, first quarter moon, antinucleus-shell, strawberry, snowball people (snow ball men), interpenetrating(polymer)networks etc., all these are technology that obtain latex particle of knowing in this area.Preferable form is fluoropolymer nuclear/acrylic polymers shell, latex particle and homogeneous latex particle.Monophasic latex particle form can with mixable fluoropolymer/acrylic polymers to or obtain with interpenetrating(polymer)networks.
The available tensio-active agent comprises anion surfactant, cats product, nonionogenic tenside and amphoterics.They can use separately or two or more are used in combination, and condition is that obvious inconsistent type can not be used in combination.They can mix with seed latex or with monomer mixture, perhaps form the composition of any appropriate with other polymeric component.Anion surfactant comprises the vitriol (esters of higher alcohol sulfates) (as the sodium salt of alkylsulphonic acid, the sodium salt of alkyl benzene sulphonate (ABS), the sodium salt of Succinic Acid, the sodium salt of succinic acid dialkyl ester sulfonic acid, the sodium salt of alkyl diphenyl ether disulphonic acid) of high alcohol ester.Suitable cationic surfactants is kelene yl pyridines and chlorination alkylammonium.Ionic surfactant pack is drawn together polyoxyethylene alkyl phenyl ether, Voranol EP 2001, polyxyethylated ester, polyoxyethylene alkylphenyl ester, glyceryl ester, sorbitan alkyl ester and their derivative thereof.Suitable amphoterics is the lauryl betaine.Can also use can with the reactive emulsifier of above-mentioned monomer copolymerization, as Sodium styrene sulfonate, alkyl sodium sulfonate, arylalkyl sulfonic acid sodium.The common consumption of tensio-active agent is that per 100 weight part particles of fluoropolymer total amounts are the 0.05-5 weight part.
Any initiator that can produce the free radical be suitable for the Raolical polymerizable in 20-100 ℃, aqueous medium can be used as initiators for polymerization.They can use separately or be used in combination with reductive agent (as sodium bisulfite (sodium hydrogenobisulfite), L-sodium ascorbate, Sulfothiorine, V-Brite B (sodiumhydrogenosulfite)).For example, persulphate, hydrogen peroxide can be used as water soluble starter, cumene hydroperoxide, peroxidation carbonic acid diisopropyl ester, benzoyl peroxide, 2,2 '-azo nitrile dimethyl, 2,2 '-Diisopropyl azodicarboxylate, 1,1 '-azo bicyclohexane-1-nitrile, isopropyl benzene hydroperoxide can be used as oil-soluble initiator.Be preferably initiator and be 2,2 '-azo nitrile dimethyl and 1,1 '-azo bicyclohexane-1-nitrile.If necessary, oil-soluble initiator may be dissolved in a spot of solvent.The consumption of initiator is that the monomer mixture that per 100 weight parts are added is 0.1 to 2 weight part.
For the type of spendable chain-transfer agent without limits, as long as these chain-transfer agents can exceedingly not make reaction not slow down.The available chain-transfer agent for example comprises, mercaptan (as dodecyl mercaptans, octyl mercaptan), halohydrocarbon (as tetracol phenixin, chloroform), xanthan (as curing dimethyl xanthan).It is the 0-5 weight part that the consumption of chain-transfer agent is generally the monomer mixture that per 100 weight parts are added.
In reaction process, can add a small amount of solvent to help the seed grain swelling.The quantity of solvent that is added should be in the scope that does not weaken application property, environmental safety, production security, anti-fire.
It is 0-2 weight part and 0-0.1 weight part that the consumption of the consumption of pH regulator agent (as yellow soda ash, salt of wormwood, sodium bicarbonate) and sequestrant (as ethylenediamine tetraacetic acid (EDTA), glycine, L-Ala) is respectively per 100 monomer mixtures that weight part adds.
The tensio-active agent or the pH regulator agent that can in final latex, add additional content.This helps to improve package stability usually.
Used monomeric further describing seen European patent 0 360 575 B1 and Japanese patent application 4-97306 in the preferred approach of synthetic AMF polymkeric substance and the synthetic AMF polymkeric substance.
The fluoropolymer resin of separation of propylene acids modification can be finished with standard method well known in the art from seed polymer latex, these standard methods as latex is carried out drying, with high shear mixing solidify, centrifugal and/or change ionic equilibrium and/or freezing, then filter and optional washing etc.
Paint binder or paint composition can be not painted to form varnish, perhaps can mix forming coating with one or more pigment.The pigment that is used for other PVDF base coating can be used for the present invention's practice equally satisfactorily.These pigment for example comprise, U.S. Patent No. 3,340,222 specified pigment.This pigment is organic or inorganic.According to an embodiment, this pigment can comprise the mixture (wherein titanium dioxide accounts for the major portion of this mixture) of titanium dioxide or titanium dioxide and one or more other mineral dyes.Can use separately or for example comprise silicon-dioxide, versicolor ferric oxide, cadmium, lead titanate and various silicate (for example talcum, diatomite, asbestos, mica, clay and lead silicate white) with titanium dioxide blended mineral dye.Can for example comprise zinc oxide, zinc sulphide, zirconium white, white lead, carbon black, lead chromate, floating and non-floating shaped metal pigment, molybdenum red, lime carbonate and barium sulfate with titanium dioxide blended pigment.
Preferable pigment classification is the pigment of ceramic metal oxide type, and these pigment are through incinerating.The chromic oxide of calcining type and some oxide compounds of iron also can use satisfactorily.For the occasion that needs white coating, recommend the rutile titanium dioxide of not efflorescence, not yellowing.Lithopones etc. are not enough, because they have the shortcoming that lacks resistance to chalking and/or hiding lack.Anatase type (anastase) TiO
2Equally also be unfavorable.
If there is pigment component, the amount of pigment component is preferably per 100 parts of resin Compositions and is about the 0.1-50 weight part in the composition.Though for most of purposes preferred range are the per 100 parts of about 25-35 weight part of resin Composition pigment, but for white and light pigment, the consumption of pigment in higher preferable weight range, can be 35 weight parts or higher up to per 100 parts by weight resin components usually.
The coating of transparent metallic pigment has the pigment of considerably less weight.
As paint binder or paint vehicle, the present composition is a liquid form.The tackiness agent that will contain fluoropolymer resin and wherein contained optional any other resin disperses, partly or entirely is dissolved in the thinner, and described thinner can comprise water base or non-water-based solvent.These solvents can be the mixtures of single solvent or multiple solvent.Suitable water-based solvent is described in United States Patent (USP) 4,128,519.Suitable non-water-based solvent is described in WO 93/13178 and United States Patent (USP) 3,324,069.Solvent for use itself is not a part of the present invention, and the solvent of any routine or solvent mixture (comprising the latent solvent that is generally used for PVDF resin base coating) all are considered to be applicable to the present invention.
Can also add other conventional coating composition in paint binder of the present invention or paint vehicle and coating and the clear coat composition, as tensio-active agent, dispersion agent, wax, linking agent, UV light absorber, flatting agent, thickening material etc.
Standard technique well known to those skilled in the art can be used to mix contained component in paint binder that the present invention thinks or paint vehicle and coating and the clear coat composition.
Coating of the present invention and clear coat composition can be applied over the wide variety of substrates of a wider range, comprise plastics, timber, metal, pottery, glass etc., available conventional coating process applies, as spraying, brushing, dip-coating, cast, scraper coating, coiled material coating, inverse roller coating, blade coating and other method as known in the art.
After applying, make solvent based coating and varnish (containing resin in its solution) at room temperature carry out dry air to remove thinner (comprising solvent) in 15 ℃-50 ℃.The coating of other water-based and non-aqueous solvent base and varnish are toasted or heats with evaporation thinner (comprising solvent), coalescent coating.Heating temperature about 125 ℃ to about 300 ℃ scope, about preferably 175 ℃ to about 275 ℃.Obviously, for coated substrates, should use consoluet solvent based coating of resin and varnish to the comparatively high temps range-sensitive.
Though by the dry polymeric film that forms of coating and clear coat composition the sticking power of ground has been exceeded suitable value usually, can by on substrate surface at first the compatible coating of primary coat one deck improve sticking power.For example, for timber, the available undercoat is the painted acrylic ester polymer of one deck, as United States Patent (USP) 3,234, and 039 and United States Patent (USP) 3,037, described in 881.For metallic coating, for water-based paint and clear coat composition, preferable undercoat is described in United States Patent (USP) 3,111, in 426, is one deck epoxy group(ing) undercoat.In general, the undercoat of acrylic based (as United States Patent (USP) 3,526, described in 532) and (see United States Patent (USP) 4 based on the undercoat of the mixture of partially fluorinated vinyl halide polymers, Resins, epoxy, powdery metal pigment and wet ground mica, 179,542) also can be used for metal.For the coating on glass and woven fiber glass, glass fibre or other flexible substrates (weave or non-woven), can use known tackifier.Especially glass fibre is handled with silane coupling agent earlier, as I.L.Fan and R.G.Shaw, the rubber world (Rubber World), in June, 1971, the 56th page is described.
Solvent-based coating of the present invention on the dry air ground (as paper, glass fibre, woven fiber glass and supatex fabric) and varnish (containing resin in its solution) can at room temperature carry out, and are about 3 to 24 hours time of drying.Yet with forcing air in about 50 ℃ of dryings, this is filmed can be at 10 to 15 minutes inner dryings.60 ℃ use down force dry airs carry out about 5 to 10 minutes just enough.After applying, other water base or non-aqueous based systems is heated with evaporation thinner (comprising solvent), carry out coalescent polymkeric substance.As mentioned above, Heating temperature about 125 ℃ to about 300 ℃ scope, between about 175 ℃ and 275 ℃, be preferably between about 215 ℃ and 250 ℃ preferably.
Perhaps, can pour into a mould and heat, obtain the free film (freefilm) of composition coating of the present invention and varnish.In all cases, coating all be smooth, glossy, evenly and securely be bonded on the ground.These films and coating also have hardness, creep resistance (being dimensional stability), flexible, chemical resistant properties and weathering resistance.These films and coating also have antibiosis cigarette and hydrophobicity.
Following examples further illustrate the enforcement best mode of the present invention that the contriver thinks, these embodiment should be understood that it is illustrative, rather than limitation of the present invention.
Following examples have shown that the glossiness of AMF coating that resin forms is higher than conventional PVDF/ acrylic acid or the like blend coating system.In addition, under certain prescription and baking condition, the flexible co-mixing system that is better than of AMF coating.The accelerating ultraviolet test shows, the ultraviolet light performance of AMF base coating is better than co-mixing system, and this can increase by its gloss retention and embody.
Embodiment 1: white coating (PVDF/ acrylic polymers ratio is 70/30)
Preparation contains preparation A, B and the C of the listed component of Table I.For each preparation, component is added in the grinding container, adding consumption in every kind of preparation is 4 millimeters granulated glass spherees of 1.25 times of total formulation weight amounts.Ground coating formulation 1 hour.Used matrix resin is that the weight ratio that contains PVDF and acrylic polymers (acrylic) is 80/20 AMF among the preparation A, and preparation B has used two kinds of different PVDF homopolymer with C.In every kind of preparation, add second kind of acrylic resin, so that the final weight ratio of fluoropolymer and acrylic polymers is 70/30 in all preparations.Only note that in preparation A, to add toluene, to constitute with the toluene among Acryloid B-44S adding preparation B and the C.
Table I
| The weight percentage of formulation component | |||
| Preparation A | Preparation B | Formulation C | |
| Matrix resin | (25.6 AMF1@PVDF/ acrylic polymers=80/20) | ??20.5 ??(PVDF?1) | ??20.5 ??(PVDF?2) |
| ??Ti-pure?R-960 ** | ???15.8 | ??15.8 | ??15.8 |
| ??Acryloid?B-44S *(40% solid in the toluene) | ???9.1 | ??21.9 | ??21.9 |
| Toluene | ???7.7 | ??-- | ??-- |
| Isophorone | ???41.8 | ??41.8 | ??41.8 |
| The ratio of total fluoropolymer/acrylic polymers | ???70/30 | ??70/30 | ??70/30 |
*The multipolymer of methyl methacrylate and ethyl propenoate (Rohm and Hass Co., Phila., PA)
*Ti-pure is the registered trademark of DuPont company, is the trade mark of its titanium dioxide.
With wire bar applicator every kind of coating is applied on the aluminium sheet, the plate through applying was toasted 90 seconds in 525 °F.After the baking, this plate immersed the quenching-in water of room temperature immediately or this plate toasted 140 ℃ of second time and carried out aftertreatment with annealing in 24 hours.Table II shows the glossiness and the flexure test result of these plates.The glossiness of AMF preparation A all is higher than PVDF preparation B and C after quenching or annealing.And, have only the quenching coating of preparation A to keep high flexible.Preparation B and C have lost to a certain degree flexible once annealing.Observed the surperficial SEM photo of the quenching coating that makes by preparation A and C.The SEM photo clearly illustrates that the surface of AMF coating is more smooth than PVDF/ acrylic polymers blend coating significantly.This glossiness with the AMF coating is higher also to be consistent.
Table II
| Coating performance | |||
| Preparation A | Preparation B | Formulation C | |
| 60 degree glossiness of quenching coating | ??68 | ??41 | ??45 |
| 60 degree glossiness of annealing coating | ??42 | ??37 | ??35 |
| The T type model alternating bending (T-bend Flexibility) of quenching coating | ??0-T | ??0-T | ??0-T |
| The T type model alternating bending of annealing coating | ??0-T | ??4-T | ??2-T |
Embodiment 2: white coating (PVDF/ acrylic polymers ratio is 80/20)
Preparation contains the preparation D and the E of the listed component of Table III.For each preparation, component is added in the grinding container, adding consumption in every kind of preparation is 4 millimeters granulated glass spherees of 1.25 times of total formulation weight amounts.Ground coating formulation 1 hour.Used matrix resin is that the weight ratio that contains PVDF and acrylic polymers is 80/20 AMF among the preparation D, and the matrix resin of preparation E is the PVDF homopolymer.In preparation E, add second kind of acrylic resin, so that the final weight ratio of fluoropolymer and acrylic polymers is 80/20 in two kinds of preparations.Only note that in preparation D, to add toluene, to constitute with the toluene among the Acryloid B-44S adding preparation E.
Table III
| The weight percentage of component | ||
| Preparation D | Preparation E | |
| Resin | (29.2 AMF1@PVDF/ acrylic polymers=80/20) | ????23.4 ????(PVDF?2) |
| ??Ti-pure?R-960 | ???15.8 | ????15.8 |
| Acryloid B-44S (40% solid in the toluene) | ???-- | ????14.6 |
| Toluene | ???8.8 | ????-- |
| Isophorone | ???46.2 | ????46.2 |
| The ratio of total fluoropolymer/acrylic polymers | ???80/20 | ????80/20 |
(wire wound drawdown applicator) is applied in every kind of coating on the aluminium sheet with wire bar applicator, and the plate through applying was toasted 90 seconds in 525 °F.After the baking, this plate immersed the quenching-in water of room temperature immediately or this plate toasted 140 ℃ of second time and carried out aftertreatment with annealing in 24 hours.Table IV shows the glossiness and the flexure test result of these plates.The glossiness of AMF preparation D all is higher than PVDF preparation E after quenching or annealing.In this case, two kinds of preparations have all kept the high flexible of coating under two kinds of post-treatment conditions.
Table IV
| Coating performance | ||
| Preparation D | Preparation E | |
| 60 degree glossiness of quenching coating | ????68 | ????34 |
| 60 degree glossiness of annealing coating | ????47 | ????28 |
| The T type model alternating bending of quenching coating | ????0-T | ????0-T |
| The T type model alternating bending of annealing coating | ????0-T | ????0-T |
Embodiment 3
Preparation contains the preparation F and the G of the listed component of Table V.For each preparation, component is added in the grinding container, adding consumption in every kind of preparation is 4 millimeters granulated glass spherees of 1.25 times of total formulation weight amounts.Ground coating formulation 1 hour.Used matrix resin is that the weight ratio that contains PVDF and acrylic polymers is 70/30 AMF among the preparation F, and the matrix resin of preparation G is the PVDF homopolymer.In preparation G, add second kind of acrylic resin, so that the final weight ratio of fluoropolymer and acrylic polymers is 70/30 in two kinds of preparations.
Table V
| The weight percentage of component | ||
| Preparation F | Preparation G | |
| Resin | (29.2 AMF2@PVDF/ acrylic polymers=70/30) | ???20.5 ?(PVDF?3) |
| Ti-pure?R-960 | ????15.8 | ???15.8 |
| Acryloid B-44S (40% solid in the toluene) | ????-- | ???21.9 |
| Isophorone | ????55.0 | ???41.8 |
| The ratio of total fluoropolymer/acrylic polymers | ????70/30 | ???70/30 |
| The 60 initial degree glossiness of quenching coating | ????56 | ???36 |
| QUV-B is 60 degree glossiness of exposure coating after 15,000 hours down | ????58 | ???22 |
| QUV-B is the gloss retention percentage ratio of exposure coating after 15,000 hours down | ????104 | ???61 |
With wire bar applicator every kind of coating is applied on the aluminium sheet, plate that will be through applying is in 550 bakings 90 seconds, then immediately at the quenching-in water of room temperature.As shown in Table V, the original gloss of AMF preparation F is higher than PVDF preparation G.After exposing 15,000 hours under the fluorescence UV-B, the AMF coating has also kept higher original gloss percentage ratio.
The water base dispersion paint of embodiment 4:VDF-HFP base AMF
The component 1 to 6 that adds ratio shown in the Table VI in the grinding container that 4 millimeters glass grinding pearls of 100 grams are housed makes the 100 coating batch of materials that restrain by preparation H.Mixture was ground 2 hours, filter by coarse filter, to remove grinding medium.In filtered mixture, add component 7 and 8, this mixture was slowly rolled about 2 hours.On this coating paint aluminium sheet, select used wire bar applicator to obtain the dry coating of 20-25 micron.Aluminium sheet that will be through applying obtains the coating of smooth and continuous in 450 bakings 10 minutes.This coating is impacted and can not split (60 in-lbs are maximum loads that ground does not produce fracture) by the front or the reverse side of 0-T alternating bending test, 100% cross-hatching sticking power (crosshatch adhesion) and 60 in-lbs.
Table VI: preparation H
| Component | Weight percentage |
| 1) AMF resin | 44.0 (the VDF-HFP/ acrylic polymers=62-8/30) |
| 2) deionized water | ????44.0 |
| 3) dipropylene glycol | ????3.5 |
| 4) 3 third glycol methyl ethers (tripropylene glycol methyl ether) | ????3.5 |
| 5) ethylene glycol monobutyl ether | ????1.0 |
| 6)Rhone-Poulenc?Colloid 643 * | ????0.5 |
| 7) N-Methyl pyrrolidone | ????3.5 |
| 8) dimethylaminoethanol | The pH value is adjusted to the required amount of 8-9 |
*=dedicated defoamer
T-bending forming (T-bend formability) can according to ASTM D 4145-83 (rehear fixed 1990) for measuring through the standard test methods of precoating sheet material coating flexible.In this test, will increase the thickness of metal or the diameter of mould rod (dies) gradually through the plate of precoating around crooked 180 ° of metal or mould rod, when no longer fracture taking place, reach terminal point.After each bending, with coating failure (cracking) that hangs down ratio of enlargement (5 to 10 times) access panel and the loss (pulling off) of checking sticking power with adhesive tape pull-off test (tape pull off test).
60 ° of glossiness are measured in standard test methods according to the mirror surface luster of ASTM D523-89.This test is reflected with reference to measuring minute surface (mirror) as a comparison with the black glass standard.60 ° angle is the sample that is used for medium gloss, is used for the specimen test that this purposes is reported.
Sticking power and shock-resistance use standard test methods and NCCA technical bulletin (Technical Bulletin) II-6 with the tape test measurement sticking power that are determined by ASTM D 3359-90 to measure about the explanation of using " cross-hatching (Cross Hatch) " tape test evaluation film sticking power after reverse side impacts respectively.In ASTM test, make the lattice that each direction has 6 or 11 secants in the film on ground, be applied in Pressuresensitive Tape on the grid and throw off.In NCCA technical bulletin II-6 test, with the variable shock-testing machine of Gardner the sample that scribbles coating to be carried out reverse side and impact, used surging force is up to the required power of sample ground cracking that makes.#610 is applied on the strained zone with the Scotch sealing tape, removes bubble by friction, and sample is adjusted to return room temperature (but being no more than 10 minutes).To pull the band that removes photoresist fast for the vertical angle of specimen surface.
Embodiment 5: the dispersion paint of highly filled non-diluent water base
Table VII
| Component | Weight percentage |
| AMF resin (PVDF/ acrylic polymers=80/20) | ????39.6 |
| Ti-Pure?R-960 | ????19.8 |
| Tripropionin | ????19.8 |
| VM?&?P?Naphtha ** | ????19.8 |
| BYK 182 (45% activity) * | ????1.0 |
| Total weight of solids | ????59.9 |
*BYK 182 is the dispersion agents from BYK-Chemie
*The aliphatic hydrocarbon solvent, boiling range is at 119 ℃ to 139 ℃
All components are mixed, add and be equipped with in the grinding container of 4 millimeters glass grinding pearls, ground said preparation 1 hour.The coating of gained is low viscosity (＜1000cps) homogeneous phase particulate dispersion.With wire bar applicator coating is applied on the chromium plating aluminium sheet.In 550 bakings 45 seconds, in 450 bakings 10 minutes with in 350 bakings 20 minutes, these baking process processes can both make the film of smooth and continuous, have 100% cross-hatching sticking power.
In the above-described embodiment, be used for preparing the vinylidene fluoride polymer of used paint vehicle and the following expression of fluoropolymer of acrylic acid or the like modification:
The PVDF polymkeric substance all is Elf Atochem North America, and Inc. is with trade mark KYNAR
Commercially available VDF homopolymer.
PVDF 1 is KYNAR 500+
PVDF 2 is KYNAR 500
PVDF 3 is KYNAR 500
The AMF polymkeric substance all is a PVDF polymer latex base, and described PVDF polymer latex is according to ElfAtochem North America, and Inc. synthesizes with the commercially available used preparation method of PVDF polymkeric substance of trade mark KYNAR.The AMF polymkeric substance is according to being prepared of illustrating in the specification sheets.PVDF type polymkeric substance in the seed polymer latex and acrylic monomer and corresponding weight percentage thereof are as follows:
| ????AMF | The PVDF seed | Acrylic monomer | The ratio of acrylic monomer |
| ????AMF?1 | ?KYNAR?730 | ????M.A./EA | ????70/30 |
| ????AMF?2 | ?KYNAR?500 | ????MMA/EMA/BMA | ????50/40/10 |
| AMF (embodiment 4) | ?KYNAR?Flex?2800 | ????MMA/EA/MAA | ????65/32/3 |
| AMF (embodiment 5) | ?KYNAR?730 | ????MMA/EA | ????70/30 |
The abbreviation of acrylate monomer:
The MMA=methyl methacrylate
EA=ethyl propenoate (ethylacrylate)
The EMA=Jia Jibingxisuanyizhi
The BMA=butyl methacrylate
The MAA=methacrylic acid
The applicant specifically notes the main points of its invention and these main points are proposed appended claim clearly:
Claims (8)
1. paint binder that is used for dispersion paint, it comprises the fluoropolymer resin of acrylic acid or the like modification, and the content of the fluoropolymer dried resin of this acrylic acid or the like modification is 10%-90% (weight).
2. paint binder as claimed in claim 1, the thinner in the wherein said paint binder are non-water basically.
3. paint binder as claimed in claim 1, the thinner in the wherein said paint binder is water base.
4. a coating comprises and the described paint binder blended of claim 1 pigment.
5. coating, it is to obtain by the thinner that is applied in the described coating of claim 4 on the surface that needs coating and evaporate described coating.
6. coating, it is to obtain by the thinner that is applied in the described paint binder of claim 1 on the surface that needs coating as varnish and evaporate described paint binder.
7. goods comprise the goods that it is attached with the described coating of claim 5 at least on one side.
8. goods comprise the goods that it is attached with the described coating of claim 6 at least on one side.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US5164297P | 1997-07-02 | 1997-07-02 | |
| US60/051,642 | 1997-07-02 | ||
| US10876498A | 1998-07-01 | 1998-07-01 | |
| US09/108,764 | 1998-07-01 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1278285A true CN1278285A (en) | 2000-12-27 |
Family
ID=26729669
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98800901A Pending CN1278285A (en) | 1997-07-02 | 1998-07-02 | Fluoropolymer dispersion coatings from modified thermoplastic vinylidene fluoride based resins |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP0932645A4 (en) |
| JP (1) | JP2002513442A (en) |
| KR (1) | KR20000068392A (en) |
| CN (1) | CN1278285A (en) |
| AU (1) | AU735801B2 (en) |
| BR (1) | BR9806106A (en) |
| CA (1) | CA2264719A1 (en) |
| EA (1) | EA001802B1 (en) |
| NZ (1) | NZ335012A (en) |
| WO (1) | WO1999001505A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100393826C (en) * | 2006-06-01 | 2008-06-11 | 江苏兰陵化工集团有限公司 | Water fluorine carbon emulsion paint and preparation process thereof |
| WO2018145263A1 (en) * | 2017-02-08 | 2018-08-16 | Akzo Nobel Coatings International B.V. | A coating composition, the preparation method therefore and use thereof |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2804440A1 (en) * | 1999-09-14 | 2001-08-03 | Atofina | LATEX FLUORINATED IN MINIDISPERSION IN WATER WITHOUT SURFACTANT OR ORGANIC SOLVENT |
| US6761431B2 (en) | 1999-12-13 | 2004-07-13 | Canon Kabushiki Kaisha | Polymer film, polymeric compound for forming the same, method of manufacturing such polymeric compound, liquid-repellency treatment solution using such polymeric compound, surface-modifying method using such treatment solution and surface-modified article |
| US6340720B1 (en) | 2000-02-14 | 2002-01-22 | Ausimont Usa, Inc. | Process for making polyvinylidene fluoride power coatings and coating formulations |
| US7803867B2 (en) | 2005-05-19 | 2010-09-28 | Arkema Inc. | Highly weatherable roof coatings containing aqueous fluoropolymer dispersions |
| ME02121B (en) * | 2006-01-17 | 2014-06-30 | Abbvie Ireland Unlimited Co | Combination therapy with parp inhibitors |
| US20130089671A1 (en) * | 2011-10-05 | 2013-04-11 | Honeywell International Inc. | Polymers formed from 2,3,3,3-tetrafluoropropene and articles and uses thereof |
| WO2022055472A1 (en) * | 2020-09-08 | 2022-03-17 | Hewlett-Packard Development Company, L.P. | Housings for electronic devices |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5439980A (en) * | 1990-11-29 | 1995-08-08 | Daikin Industries | Process for preparing polymer |
| US5646201A (en) * | 1993-09-22 | 1997-07-08 | Daikin Industries, Ltd. | Aqueous dispersion of fluorine-containing copolymer |
-
1998
- 1998-07-02 KR KR1019997001699A patent/KR20000068392A/en not_active Application Discontinuation
- 1998-07-02 EA EA199900181A patent/EA001802B1/en not_active IP Right Cessation
- 1998-07-02 CA CA002264719A patent/CA2264719A1/en not_active Abandoned
- 1998-07-02 EP EP98933065A patent/EP0932645A4/en not_active Withdrawn
- 1998-07-02 JP JP50735699A patent/JP2002513442A/en active Pending
- 1998-07-02 BR BR9806106-2A patent/BR9806106A/en active Search and Examination
- 1998-07-02 WO PCT/US1998/013734 patent/WO1999001505A1/en not_active Application Discontinuation
- 1998-07-02 CN CN98800901A patent/CN1278285A/en active Pending
- 1998-07-02 AU AU82817/98A patent/AU735801B2/en not_active Ceased
- 1998-07-02 NZ NZ335012A patent/NZ335012A/en unknown
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100393826C (en) * | 2006-06-01 | 2008-06-11 | 江苏兰陵化工集团有限公司 | Water fluorine carbon emulsion paint and preparation process thereof |
| WO2018145263A1 (en) * | 2017-02-08 | 2018-08-16 | Akzo Nobel Coatings International B.V. | A coating composition, the preparation method therefore and use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| AU735801B2 (en) | 2001-07-12 |
| EA001802B1 (en) | 2001-08-27 |
| CA2264719A1 (en) | 1999-01-14 |
| EP0932645A4 (en) | 2000-09-13 |
| EP0932645A1 (en) | 1999-08-04 |
| NZ335012A (en) | 2000-01-28 |
| AU8281798A (en) | 1999-01-25 |
| EA199900181A1 (en) | 1999-12-29 |
| JP2002513442A (en) | 2002-05-08 |
| KR20000068392A (en) | 2000-11-25 |
| BR9806106A (en) | 1999-08-31 |
| WO1999001505A1 (en) | 1999-01-14 |
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