CN1312842A - Sprayable powder composition for use as underbody protection or sealant - Google Patents
Sprayable powder composition for use as underbody protection or sealant Download PDFInfo
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- CN1312842A CN1312842A CN99809511A CN99809511A CN1312842A CN 1312842 A CN1312842 A CN 1312842A CN 99809511 A CN99809511 A CN 99809511A CN 99809511 A CN99809511 A CN 99809511A CN 1312842 A CN1312842 A CN 1312842A
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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
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/03—Powdery paints
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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
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
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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
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
- C09K2200/0615—Macromolecular organic compounds, e.g. prepolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09K2200/0617—Polyalkenes
- C09K2200/062—Polyethylene
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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
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
- C09K2200/0615—Macromolecular organic compounds, e.g. prepolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09K2200/0625—Polyacrylic esters or derivatives thereof
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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
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
- C09K2200/0645—Macromolecular organic compounds, e.g. prepolymers obtained otherwise than by reactions involving carbon-to-carbon unsaturated bonds
- C09K2200/0647—Polyepoxides
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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
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
- C09K2200/0645—Macromolecular organic compounds, e.g. prepolymers obtained otherwise than by reactions involving carbon-to-carbon unsaturated bonds
- C09K2200/065—Polyurethanes
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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
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
- C09K2200/0645—Macromolecular organic compounds, e.g. prepolymers obtained otherwise than by reactions involving carbon-to-carbon unsaturated bonds
- C09K2200/0667—Polyamides, polyimides
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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
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
- C09K2200/068—Containing also other elements than carbon, oxygen or nitrogen in the polymer main chain
- C09K2200/0685—Containing silicon
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Sealing Material Composition (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to powdery thermoplastic polymer compositions on the basis of polymers with polar, functional groups, which are suitable for the preparation of sprayable powdery compositions for use as underbody protection or sealants. The compositions are substantially free of water, volatile organic solvents and/or liquid plasticizers and are deposited on the substrates to be coated or sealed using known powder-coating technology. The compositions are used in motor vehicle construction as underbody protection or as sealant for joint seams.
Description
The present invention relates to sprayable powder composition based on powders of thermoplastic polymers, and preparation and be applied to object foot guard or sealing agent.
For increasing the service life, comprise that in vehicle manufacturing, mechanical engineering and instrument manufacturing many article of metallic weapon all need to use coating to improve antiwear property.In the vehicle manufacturing, especially in the automobile making, these article are particularly including car body bottom and wheel bow-shaped structural and so-called beam.In addition.Be necessary to seal to prevent the infiltration of dust and water for seam with spot welding or other mechanical fixation.In vehicle was made, past, mainly by using plastisol to carry out, soon organic polymer was dispersed in the softening agent, and it is heated to gel and cooling curing behind the relative comparatively high temps.The plastisol that is used for this purpose is homopolymer and the multipolymer that is dispersed in the methacrylic ester of softening agent, the dispersion of styrol copolymer and especially polyvinyl chloride homopolymer and/or multipolymer.Usually, these plastisols also comprise the so-called supplement that exist with the high-boiling hydrocarbons form except that these components.Although the volatility of above-mentioned plastisol and supplement is very low, always follow the volatilization of a spot of two kinds of components in the peptization course in the spraying furnace of automotive industry.This can cause emission problem and coagulation problems in the spraying furnace.In addition,, but still can not prevent known overspray phenomenon fully although modern machining control is arranged, for example spray to use the chamber around.This so-called overspray must be avoided or the process for subsequent treatment by complexity is recycled to material in the product circulation.
Thereby, be necessary to provide the car body foot guard composition or the sealing material that do not contain any solvent and softening agent especially for the vehicle manufacturing.The composition that contains water-soluble emulsion or dispersion is used in past suggestion, but can cause application problem in common vehicle production process because in producing time of drying very short, water can not evaporate fully, perhaps the evaporation back forms bubble on coating.In addition, even always water-soluble dispersion and emulsion also comprise a small amount of volatile organic solvent as so-called homogenizing auxiliary agent and/or membrane-forming agent.
Thereby the purpose of this invention is to provide and do not contain solvent and softening agent also water-free object foot guard composition and/or sealing compositions.
According to the present invention, use the Powdered composition that sprays can reach this purpose based on the powdery thermoplastic polymkeric substance, these compositions are not moisture substantially, be the softening agent of liquid under volatile organic solvent and/or the room temperature.These compositions contain one or more powdery thermoplastic polymkeric substance, and wherein partial polymer contains polar functional group at least.In addition, these mixtures also can further contain other organic or inorganic pulverulent solids.These compositions are sprayed on undressed metallic surface by electrostatic methods, perhaps handle and the metallic surface of coating through organic or inorganic.Charged like this result is, particle at once and also can be after several hours, even on also can be attached to metal on the vertical surface.Behind the contact comparatively high temps, the powder bed fusion forms film subsequently securely attached on the base material.
Like powder shape composition once disclosed, and was called as powder material spray.
For example, US-A-4865882 has described the method for powder spraying metal.The powder spraying composition contains the modified polypropene powder of 80-97% and the low-down polyethylene powders of density of 20-3%.Mix after these material fusions, and granulation in forcing machine, these particles are obtained the powder that median size is approximately 150 microns through cryogrinding.Metal, as basket, plate or car accessories are preheating to about 200-250 ℃ after spraying, immerse subsequently in the fluidized-bed contain Powdered spray composition to arrive several minutes in several seconds.As a result, the veneer of powdered composition is on the thermometal article.After the spraying, metal is heated to 160-230 ℃ and stops one long period, makes the even fusion of gained coatingsurface.This document does not disclose foot guard spraying and joint seal.
US-A-5498783 has described the powder spraying composition of heat cross-linking, and it comprises the powder mixture of vibrin, and vibrin on average contains two or more carboxyls; First linking agent, its carboxyl to vibrin has reactive behavior; Also has reactive acrylate's multipolymer; With second linking agent, it mainly has reactivity to the reactive functional groups of acrylate copolymer.But because their very strong crosslinked actions, these compositions needing only to be suitable for the paint application of strong hardness.For the snappiness that the protection of article bottom is used and joint seal need be high, these compositions are improper.
The powder material spray disclosed for EP-A-404960 also has similar evaluation, and these materials are substantially by ethylene copolymer, and Resins, epoxy and curing agent for epoxy resin are formed.In the case, the heavy % of the 0.5-10 that the skeleton of ethylene copolymer is formed comes the comonomer of self-contained carboxylic acid anhydride, the carboxylic acid monomer that the heavy % of 3-40 comes the two keys of self-contained unsaturated olefin.According to the explanation of this document, be suitable for the corrosion of protection to defend to cause of metal matrix in the Powdered spray composition of this disclosure by splinter of stone.According to the explanation of this document, because thermoplastic resin is relatively poor to the adhesion property of matrix, the ordinary hot thermoplastic resin composition that the heat cross-linking degree is lower is not suitable for forming the coating of defence splinter of stone.
The powder spraying composition that WO 87/02043 discloses comprises the solid-state solidifying agent of powder epoxy resin solid and this Resins, epoxy, and wherein the average epoxidation functionality of Resins, epoxy per molecule is higher than 2.Solid epoxy is the polyfunctional group polyglycidyl ether of bisphenol cpd, or the polyfunctional group polyglycidyl ether of poly ethyldiol modified bis-phenol.Document discloses powder composition and can be painted on phosphatization, chromaking or the galvanized steel or the persistent coating of formation on the chromated aluminum.But do not provide such composition whether to be fit to the information that foot guard is used.
WO 95/03344 has described a kind of preparation method who can be used as the plastics of powder material spray and/or hot melt adhesives.For this purpose, use range of frequency in the Low Temperature Plasma Treating of 30 kHz polyolefine to 10 GHz.According to this document description, be 160 ℃ in processing temperature, in this way, use powder material spray, the Clear coating with well attached performance can be used on glass.And then claim that again this composition is suitable for generating base coat or shell coating in automobile making.But this type of material only has good adhesion property to metal sheet in the very short and limited time.
That be used in the automobile making spray or the matrix of carrying out joint seal is steel plate normally, it can be for anticorrosion through phosphatization and/or chromate treating, or also can be steel plate galvanized and the steel plate that scribbles the above description type of electrodeposited coating, electrodeposited coating is known as the cathode electric coating material.Nearest application has comprised the sheet material made from aluminium, aluminium alloy and magnesium alloy, so spray composition or sealing agent require that above all matrix is had good adhesion property.
The polymer powder of using according to the present invention is thermoplastic.These thermoplastic materials require melting ranges between 50-180 ℃, and at least suitably contain the polar group of obvious dipolar nature and lower space tap density, make itself and previous coating and/or metallic surface form enough adhesivepropertieies.Find to use the polymkeric substance that contains the polar nitrogen-containing group as basic polymkeric substance or multipolymer, as urethane or polymeric amide, epoxide is made main component or mixes formed coating with powder mixture that (negative electrode) electropaining matrix or other priming paint are had excellent adhesion property.The multipolymer of methacrylic acid or methacrylic ester can obtain the result of similarly good adhesion property.In addition, contain the basic polymkeric substance or the multipolymer of vinyl acetate,, above matrix is formed similar tack as polyvinyl acetate copolymer or polyethylene vinyl acetate ester copolymer.
Can use the thermoplastic powder shaped polymer manufacturing of polar functionalities although mentioned bottom group compound of the present invention or encapsulant composition, but still might use the mixture of two kinds or multiple thermoplastic polymer, wherein partial polymer polar functionalities at least.Polar functional group can be selected from hydroxyl, amino, epoxy group(ing), carboxyl, ester, acid amides, urethanum, isocyanuric acid ester, biuret, allophanate, blocked isocyanate, silicon hydroxyl, or group such as alcoxyl silane.Extremely might mention that the thermoplastic polymer of polar group mixes mutually with the homopolymer and/or the multipolymer of poly-alpha olefins more than more with containing, poly-alpha olefins makes after preferably using corona or plasma body pre-treatment in these situations.Coating of the present invention polymer beads in the process of curing must form effective and non-leakage connection; Therefore have only above-mentioned thermoplastic material just suitable.If use powdered mixture, mixture as urethane or polyamine and epoxide, mass phenomena explanation polymeric matrix crosslinking reaction each other is not topmost reaction, and main reaction occurs between polymeric matrix and cathode electric coating matrix (cathaphoretic deposited coatings) or the metal matrix.Therefore the adhesion property of foot guard compound of the present invention and matrix is fine; In addition, this has guaranteed that also the crosslinking degree of foot guard composition itself is not very high, because high crosslinking degree can cause coating more crisp.
Usually the main adhesive component in the powder material spray is extremely important for the powder spraying application, is used as linking agent, but for above-mentioned reasons, need not to add these linking agents for composition of the present invention, or only adds seldom amount.D.A.Bate in " powder coating, chemistry are made and are used ", SITA Technology, London, 1990, especially in the 2-4 chapter, provide the example of other this type of bonding system especially.For example, especially the system of Shi Yonging includes, softening temperature is higher than 50 ℃ single-component epoxy powder material spray, melting range is between 80-100 ℃, melting index (MFI 190/2.16 is according to DIN 53735) is/10 minutes the powder spraying caking agent based on urethane of 30-40 gram, melting index is polyethylene-acrylate copolymer powder of/10 minutes of 5-15 gram, thermoplastic polyurethane, melting index is/10 minutes a polymeric amide of 15-40 gram, ethylene-vinyl acetate copolymer powder and through pretreated LDPE (new LDPE (film grade)).
Remove above-mentioned polymeric constituent, composition of the present invention also comprises finely disseminated inorganic and/or organic (polymeric) filler, pigment and/or antiaging agent.The example of suitable mineral filler comprises the finely disseminated lime carbonate that exists with multiple Wingdale ore or precipitation Wingdale form, and barite, aluminum oxide, silicate.Tinting pigment can use carbon black, ferric oxide, titanium dioxide, zinc oxide and the similar known material that has pigment characteristics itself.In this case, use surface treated material proper for filler and pigment.Antiaging agent can use polymkeric substance antiaging agents all on the traditional sense like this, the UV stabilizer that prevents the light-initiated or photo-oxidative degradation of polymkeric substance is arranged, prevent the antioxidant of thermal destruction or thermooxidative degradation, with the stablizer that prevents to degrade, or resist the ozone protective agent of ozone attack because of hydrolysis.Ageing-resistant kind and consumption are according to the chemical structure decision of use polymkeric substance.
For composition of the present invention can be sprayed when the powder material spray smoothly, importantly the median size of all powder component will be lower than 700 microns, preferably is lower than 200 microns, more preferably less than 80 microns.Guarantee that simultaneously the surface that is lower than powdery components between 30-40 ℃ in temperature does not have stickiness, can prevent powder particle caking before paint application like this.
The suitability that studies show that common utilisation technology has direct dependency to particle diameter.The throughput of suitability representation unit time and on the metallic surface enough dried adhesive ability.Therefore composition must satisfy following requirement:
-good fluidizing performance in fluidized-bed
The low consumption of-conveying air
The throughput height of-unit time
-corresponding, short spray time
Carrying the low consumption of air is the prerequisite that obtains homogeneous coat-thickness pattern, and can prevent that the powder that has sprayed is blown away.
For the preparation of powdered mixture, must select a kind of method can avoid the segregation of the mixture in the process of using and reclaim the overspray powder.
The fluidisation of powdery components when a kind of appropriate means is based on temperature in the hot blast a little less than main polymer melting temperature.Can select different temperature according to auxiliary agent with second polymkeric substance.A kind of possible method is that fluidisation is carried out between the melt temperature 2-20 that is lower than main polymkeric substance ℃.Optimum obtains the melting range 5-10 that is lower than main polymkeric substance ℃ temperature range.The sintering slight by polymer surfaces can prevent cohering of polymer beads, polymer powder fluidisation, transmission and spraying at any time like this.In preferred manufacturing procedure, process is as follows: the powder that is pre-mixed is blown in the reactor and fluidisation under the effect of hot blast; Subsequently, this powder/air mixture sprays by nozzle, and cools off in cold air flow.Use the polyolefine of plasma body and corona pre-treatment also unsatisfactory, because the matrix that these polymkeric substance will be coated with for them can not reach enough and secular powder sticking power as the result that unique basic polymeric constituent is used for foot guard coating gained.In addition, the film adhesive ability after curing is also unsatisfactory.Research thinks as using the plasma body pre-treatment to have only the polymer chain of particle surface to be converted into polar functional group, and that these a spot of electric charges are not enough to obtain is satisfied, enough at least in other words powder tacks and/or film tack.But can use the part auxiliary agent of the pretreated polymkeric substance of this method as other polymkeric substance.
Except that the dip-coating method that begins to describe, powder coating can spray with the method for spraying, and the two all can use corona discharge and rubbing method.Two kinds of methods that composition of the present invention has just been mentioned more than can using, but particularly preferred rubbing method are because use this means can make powder enter the corner better and obtain good coating.For making the application efficiency maximization of coating composition, the device of use, powder circulation and powder quality must suitably mate mutually, make not relevant with system operation be interrupted.Except that the above good fluidizing performance of having mentioned, powder must produce minimum triboelectric charge when adopting rubbing method under specific air velocity.The testing apparatus that the tribo-charging performance is measured in existing suitable being used to has, as electric current-electric charge-time meter (I-Q-T meter).Purpose is that at air velocity be 1.8m herein
3Obtaining minimum discharging current during/h (s.t.p) (under standard temperature and pressure (STP) per hour cubic meter) is the 1.7-2.5 microampere.
Known in spraying method, air is as transmission medium; Air is not only for transmission, and for metering with to produce triboelectric charge also be necessary.From the economic consideration of using, the consumption that is used to transmit, measure and produce the air of triboelectric charge should be as much as possible little, can not surpass 7.5m
3/ h.Be transmission, spraying and the discharge that makes the enough powder of total air velocity, should make the thin component of powder, as be lower than 8 microns component, few as much as possible.Wish to reduce air velocity, especially transmit air velocity, like this can be so that the minimise wear of application apparatus.Fluidisation can obtain the powderject effect of homogeneous efficiently in the powder supplies container.
Do directly contrast with existing very high-quality bottom protection effect based on the polyvinyl chloride plastisol, the attrition value of the bottom supercoat that obtains according to the present invention is far above existing level.Therefore can obviously reduce the thickness of coating.In addition, the proportion of coating composition of the present invention descends obviously with respect to the polyvinyl chloride plastisol, therefore owing to these two factors, can reach the purpose of obvious reduction vehicle weight.
Using above-mentioned powder composition of the present invention to protect as the bottom, i.e. vehicle bottom section, as wheel shelf structure, or under the situation of the protection of beam, the thickness of coating is between the 100-900 micron, between the preferred 150-400 micron.According to the general sequence that vehicle is made, these coatings are converted into film in paint drying oven.Here be used for film forming temperature usually between 120-180 ℃,, dried by the fire 15-30 minute preferably up to 160 ℃.
Application for the sealing material of seam is used for vehicle inside with respect to these materials of other material, and the sealing material of seam can solidify under the help of laser.
According to the world wide automaker the existing particular requirement of bottom protection composition is carried out tack test, condensation test or salt spray test and low-temperature test, powdered material of the present invention meets the requirements.
Below further set forth the present invention by some embodiment.
Embodiment 1
Powdered mixture is made by following component: polyepoxide powder (softening range is higher than 50 ℃) 49.7 heavy % polyethylene powders, low density 48.5 heavy % carbon blacks, the sedimentary gluing of Printex XE1 (Degussa) 0.1 heavy % weighs % with Wingdale Winofil SPT 0.5 heavy % alumina powder 1
Above-mentioned powdered mixture is ground to the different-grain diameter scope, and in hot blast a little less than fluidisation under the main polymer melting temperature, be ejected in the cold air flow by nozzle subsequently and cool off.For obtaining the best applications effect, the particle size range that research is following:
| Embodiment | Particle diameter (micron) | Transmit air (m 3(s.t.p.)) | Metering air (m 3(s.t.p.)) | Fluidisation | Throughput (restraining/30 seconds) |
| ????2 | ?0-80 | ????1.7 | ????1.5 | ????0.5 | ????150 |
| ????3 | ?0-200 | ????2.3 | ????1.0 | ????1.0 | ????100 |
| ????4 | ?0-400 | ????3.0 | ????0.7 | ????1.5 | ????80 |
| ????5 | ?80-200 | ????3.4 | ????0.5 | ????1.6 | ????80 |
| ????6 | ?100-400 | ????4.0 | ????0.5 | ????2.0 | ????35 |
The throughput that obtains when optimizing minimum transmission air finds that size distribution≤200 micron are suitable.Particle diameter≤80 micron obtain optimum.
The comparing result of different bottoms supercoat
| Characteristic | The pretreated polyolefine of prior art ionic medium body | Powder material spray in the prior art | Powder of the present invention bottom protecting materials among the embodiment 1 |
| Do tack | Satisfied | Satisfied | Satisfied |
| Cure postadhesion (20 min./160 ℃) | Dissatisfied | Satisfied | Satisfied |
| Available maximum coat-thickness (micron) | ????200 | ????300 | ????700 |
| Abrasion resistance (Sablux 200 μ, sec) | ????15 | ????20 | ????128 |
| Tack behind the constant condensation condition | Dissatisfied | Satisfied | Satisfied |
| Low-temperature flexibility property testing (40 ℃) | Dissatisfied | Dissatisfied | Satisfied |
These comparing results clearly illustrate and can not satisfy except that doing tack any to foot guard coating important criterion very all according to the pretreated polyolefin powder of the plasma body of prior art (being similar to WO 95/0344).In the prior art traditional powder material spray as bottom protection composition in that can to get maximum coat-thickness, abrasion resistance and low temperature flexibility unsatisfactory aspect several.
Be similar to embodiment 1, adopt different caking agents to prepare powdered mixture.These powdered mixture are used on the cathode electric coating metal sheet, and cure at 150 ℃ or 170 ℃.Subsequently from the quality of aspect evaluated for film such as outward appearance, swelling property and tack.In addition, test abrasion resistance.For ease of contrast, the high-quality thin film that the Terotex 3028 polyvinyl chloride plastisols of Henkel Terson are obtained carries out identical test.Gained is the result provided by following table.
| Embodiment | The polymer bonding agent | Particle diameter | Melting range (℃) | Film quality | Stretchiness | 150 ℃ of tacks | 170 ℃ of tacks | Tack after the condensation | Coating (micron) | Abradability (kilogram) |
| ????7 | Urethane | ＜200 | ??80-100 | Slightly coarse | Pliable and tough | ????10 | ????10 | ????10 | ????281 | ????20.84 |
| ????8 | Polyethylene and ethylene copolymers | ＜500 | ????100 | Coarse/ripple | Pliable and tough | ????10 | ????10 | ????10 | ????930 | ????16.66 |
| ????9 | Urethane | ＜200 | ????70 | Coarse | Pliable and tough | ????10 | ????10 | ????10 | ????280 | ????22.54 |
| Contrast | Terotex ?3028 | ??- | ?????- | Smooth | Pliable and tough | ????10 | ????10 | ????10 | ????230 | ????12.28 |
| ????10 | Polyethylene and ethylene copolymers | ＜500 | ????100 | Coarse/ripple | Pliable and tough | ????10 | ????10 | ????10 | ????250 | ????8.33 |
| ????11 | Epoxide | ＜80 | ????120 | Smooth | Crisp | ????10 | ????10 | ????10 | ????250 | ????8.33 |
| ????12 | Copolyamide | ＜200 | ?115-120 | Smooth | Hard | ????10 | ????10 | ????250 | ????6.94 |
The parameter of the caking agent that uses: embodiment 7 polyurethane powder MFI:35 restrain/10 minutes embodiment 8 polyethylene-acrylate copolymers, MFI:8 restrains/10 minutes embodiment 9 polyurethane powders 2,90-100 ℃ of embodiment 10 polyethylene of melting range (Kofler)-acrylate copolymer powder, MFI:9 restrains/10 minutes embodiment 11 epoxide powder, melting range＞50 ℃ (DSC method, differential calorimetric scanning method) embodiment 12 copolyamides, MFI:18 gram/10 minutes
All coating can both obtain being applicable to the continuous film of bottom protection, wherein are pliable and tough and tensile mostly.All coating, not only 150 ℃ cure after, and cure the back and show the excellent result's (rating, 10=is fine, 0=is not suitable for fully) that adheres at condensation climatic test (condensation irradiation, 14 days/40 ℃) afterwards at 170 ℃.
In order to use the BMW method to measure abrasion resistance, adopt spray composition to produce metal sheet according to the coat-thickness of statement in the table.Measure the amount (in kilogram) that penetrates the required gravel of bottom supercoat fully.Attrition value illustrates that clearly the result of all bottom protection prescriptions is good, even also the result with high-quality plastisol coating is suitable for the attrition value that low-down coat-thickness obtains.
Claims (8)
1. but based on the protection of dusty spray shape object bottom or the encapsulant composition of powdery thermoplastic polymkeric substance, it is characterized in that it is substantially anhydrous, non-volatility organic solvent and/or liquid plasticizer.
2. according to the composition of claim 1, it is characterized in that the median size of its powdery components is lower than 700 microns, preferably be lower than 200 microns, especially be lower than 80 microns.
3. according to the composition of claim 1 or 2, the melting range that it is characterized in that thermoplastic polymer is between 50-180 ℃.
4. according at least one composition in the above claim, it is characterized in that using the mixture of thermoplastic polymer.
5. according at least one composition in the above claim, it is characterized in that polymkeric substance or polymeric blends contain polar functional group, this polar functional group is selected from hydroxyl, amino, epoxy group(ing), carboxyl, ester, acid amides, urethanum, isocyanuric acid ester, biuret, allophanate, blocked isocyanate, silicon hydroxyl, or alcoxyl silylation.
6. according at least one composition in the above claim, it is characterized in that except that thermoplastic polymer, also containing thin filler, pigment and/or antiaging agent.
According among the claim 1-6 at least one based on the application in the sealing agent of the spray material of the composition of the powdery thermoplastic polymkeric substance protection zone, object bottom in Motor vehicles are made or butt seam and joint sealing.
8. the method that bottom section in Motor vehicles or the Motor vehicles part or wheel shelf structure are sprayed is characterized in that following basic procedure of processing:
-will be according at least one be sprayed on the stromal surface that selectivity in advance handles with cathode electric coating by corona or friction apparatus for coating among the claim 1-6 based on the composition of powdery thermoplastic polymkeric substance,
-subsequently coating was cured between 110-180 ℃ 15-30 minute,
-obtain the film thickness of coating between the 100-900 micron.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19836491.1 | 1998-08-12 | ||
| DE19836491A DE19836491C1 (en) | 1998-08-12 | 1998-08-12 | Sprayable powdered undercoat or jointing composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1312842A true CN1312842A (en) | 2001-09-12 |
Family
ID=7877275
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99809511A Pending CN1312842A (en) | 1998-08-12 | 1999-08-03 | Sprayable powder composition for use as underbody protection or sealant |
Country Status (12)
| Country | Link |
|---|---|
| EP (1) | EP1123356A1 (en) |
| JP (1) | JP2002522619A (en) |
| KR (1) | KR20010072433A (en) |
| CN (1) | CN1312842A (en) |
| AR (1) | AR021761A1 (en) |
| AU (1) | AU5419099A (en) |
| BR (1) | BR9913642A (en) |
| DE (1) | DE19836491C1 (en) |
| PL (1) | PL346135A1 (en) |
| TR (1) | TR200100473T2 (en) |
| WO (1) | WO2000009618A1 (en) |
| ZA (1) | ZA200101108B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114316754A (en) * | 2021-12-24 | 2022-04-12 | 老虎表面技术新材料（清远）有限公司 | Antiskid powder coating composition and coating thereof |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19962020A1 (en) * | 1999-12-22 | 2001-07-05 | Volkswagen Ag | Protectively coating a part particularly in the automobile industry comprises applying different layers of PVC powder and drying |
| DE102012210529A1 (en) * | 2012-06-21 | 2013-12-24 | Röchling Automotive AG & Co. KG | Casing e.g. underbody casing, for motor vehicle to e.g. minimize sound emission due to stone impact, has protectors including plastic material coated on external surfaces of casing, where surfaces are provided with synthetic material |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4211691A (en) * | 1977-02-23 | 1980-07-08 | E. I. Du Pont De Nemours And Company | Thermoplastic powder coating systems |
| ES2002379A6 (en) * | 1985-09-27 | 1988-08-01 | Dow Chemical Co | Epoxy resin powder coating composition. |
| JPS62149753A (en) * | 1985-12-25 | 1987-07-03 | Toyobo Co Ltd | Thermoplastic resin composition |
| JPH01297174A (en) * | 1988-05-26 | 1989-11-30 | Sumitomo Seika Chem Co Ltd | Method for powder coating on metal product |
| EP0404960A4 (en) * | 1988-11-11 | 1992-05-06 | Shinto Paint Company, Limited | Thermosetting resin composition and powder coating material comprising same |
| DE4325377C1 (en) * | 1993-07-26 | 1995-08-17 | Gvu Ges Fuer Verfahrenstechnik | Process for producing a plastic that can be used as powder coating material and / or hot melt adhesive |
| US5498783A (en) * | 1994-08-22 | 1996-03-12 | Basf Corporation | Powder coating composition resistant to overspray incompatibility defects |
-
1998
- 1998-08-12 DE DE19836491A patent/DE19836491C1/en not_active Revoked
-
1999
- 1999-08-03 AU AU54190/99A patent/AU5419099A/en not_active Abandoned
- 1999-08-03 PL PL99346135A patent/PL346135A1/en unknown
- 1999-08-03 KR KR1020017001833A patent/KR20010072433A/en not_active Application Discontinuation
- 1999-08-03 WO PCT/EP1999/005623 patent/WO2000009618A1/en not_active Application Discontinuation
- 1999-08-03 TR TR2001/00473T patent/TR200100473T2/en unknown
- 1999-08-03 JP JP2000565057A patent/JP2002522619A/en active Pending
- 1999-08-03 BR BR9913642-2A patent/BR9913642A/en not_active Application Discontinuation
- 1999-08-03 CN CN99809511A patent/CN1312842A/en active Pending
- 1999-08-03 EP EP99939784A patent/EP1123356A1/en not_active Withdrawn
- 1999-08-11 AR ARP990104010A patent/AR021761A1/en unknown
-
2001
- 2001-02-08 ZA ZA200101108A patent/ZA200101108B/en unknown
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114316754A (en) * | 2021-12-24 | 2022-04-12 | 老虎表面技术新材料（清远）有限公司 | Antiskid powder coating composition and coating thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| DE19836491C1 (en) | 2000-01-27 |
| BR9913642A (en) | 2001-06-05 |
| KR20010072433A (en) | 2001-07-31 |
| AU5419099A (en) | 2000-03-06 |
| WO2000009618A1 (en) | 2000-02-24 |
| PL346135A1 (en) | 2002-01-28 |
| TR200100473T2 (en) | 2001-07-23 |
| JP2002522619A (en) | 2002-07-23 |
| EP1123356A1 (en) | 2001-08-16 |
| ZA200101108B (en) | 2002-07-31 |
| AR021761A1 (en) | 2002-08-07 |
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| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |