CN101534965A - Process for coating a substrate with a coating - Google Patents
Process for coating a substrate with a coating Download PDFInfo
- Publication number
- CN101534965A CN101534965A CNA2007800416814A CN200780041681A CN101534965A CN 101534965 A CN101534965 A CN 101534965A CN A2007800416814 A CNA2007800416814 A CN A2007800416814A CN 200780041681 A CN200780041681 A CN 200780041681A CN 101534965 A CN101534965 A CN 101534965A
- Authority
- CN
- China
- Prior art keywords
- substrate
- thermal sense
- resin
- sense material
- priming paint
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
-
- 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
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
- B05D3/0254—After-treatment
- B05D3/029—After-treatment with microwaves
-
- 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
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
Landscapes
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Plasma & Fusion (AREA)
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
The present invention pertains to a process for coating a substrate comprising the steps of providing a substrate the outer layer of which comprises an electroheat- susceptible material,applying a powder coating composition onto the substrate, and curing the powder coating composition using electroheat radiation. The electroheat-susceptible material may be a microwave-susceptible material with the curing being effected using microwave radiation. It may also be a radio frequency-susceptible material, in which case the curing is effected using radio frequency radiation. The substrate may be provided with an outer layer which comprises an electroheat-susceptible material by contacting the substrate with a primer comprising an electroheat-susceptible material or by coating the inside of a mould with a primer layer, filling the mould with a curable resin that will form the substrate, curing the resin, and releasing the substrate the outer layer of which comprises an electroheat-susceptible material from the mould. The process is particular suitable for coating heat-senstive substrates, where it will allow electroheat curing of conventional powder coating compositions.
Description
The present invention relates to method, also relate to the substrate of method acquisition thus with the powdery paints coated substrate.
Powder paint compositions is the field that is increasing in the coating market.Shown in its title, powder paint compositions is the coating composition of powder type.Powdered thermosetting compositions for coatings comprises resin and curing agent.They for example are administered in the substrate via electrostatic method, in electrostatic method, produce the electric charge difference between particle and substrate, so that particle is attached in the substrate.Can easily reclaim unnecessary coating, to obtain economic method.Owing to there is not solvent, it also is the method for environmental protection.Make the substrate that has this coating stand heating steps, so that particle fusion is together forming coating, and stands curing schedule, wherein the reaction of this resin and curing agent forms crosslinked polymer network.If stand heating once more, have cured and the not fusion and mobile again of crosslinked thermosetting powder.
The variety of way that powder paint compositions is solidified is as known in the art.In modal solidification method, this coating is solidified in substrate by applying heat (baking).Hardening time and temperature be according to the composition therefor prescription and interrelated, and be about 280 ℃ following 10 seconds to not waiting in following 40 minutes at about 100 ℃.The shortcoming of this solidification method is, for effective solidification method, should use high temperature, but is not that all substrates can both be born this high temperature.In addition, in conventional method, make coated substrate, this means that coating and substrate and its ambient air all are heated and cooling then by stove.Even this does not influence substrate, the unnecessary heating and cooling of substrate and air also are the invalid utilizations to energy.
Radiant energy, for example infrared or ultraviolet, the application in powder coating solidification also is known.
The ultraviolet curing of powdery paints requires to have light trigger, and the character of the character of light trigger and other component of resin, curing agent and powder paint compositions (for example pigment) is complementary.Compare with baking, can significantly reduce hardening time with the ultraviolet curing powdery paints.But the UV powder formulation beyond the transparent and translucent coating is difficult to be cured to bases downwards always.
The infrared ray cured of powdery paints may have attraction, because less energy dissipation is in heating substrate or its ambient air.In addition, heating coating this means with the tradition curing of using stove and compares that less heat is born in thermally sensitive substrate from outside to inside.But, especially when thermally sensitive suprabasil coating is solidified, be difficult to when not influencing substrate, coating fully heated to realize that completely crued mode controls this process.In addition, in the conventional red outside line is solidified, use the infrared waves with multi-wavelength, some of them heating powder coating flows and solidifies realizing, and other are absorbed by substrate and with the substrate heating, or by absorption of air, so that effectively do not utilize energy.
It also is known in the art using the microwave radiation to make resin solidification.
DE 3511654 has described the resin that contains microwave susceptor that uses microwave curing, and this receptor is heated by catching microwave and causing curing reaction.
US 5,234, and 760 have described with the substrate of powdery paints coating temperature-sensitive, make this coating film forming by electromagnetic radiation then.This substrate should at most can only be very slightly by microwave-excitation.But this coating is based on the polymer of microwave-excitation.
In these two lists of references, must regulate powdery paints specially to be applicable to microwave curing.At US 5,234, in 760, this coating must be based on the polymer of particular type, and this causes cost to improve.In DE 3511654, the thermal sense material is added in the conventional polymeric resin.This requirement must be prepared and the testing tree oil/fat composition again, and is unaffected to guarantee its character.
But for many reasons, the microwave curing of powdery paints is still attractive.The using of microwave causes very fast, the almost instantaneous heating of powdery paints, therefore very rapidly obtains fusion and condition of cure.This method can be carried out in a controlled manner, has wherein prevented the unwanted heating of substrate.In addition, although most substrate absorbs infrared waves with more or less amount, less substrate is a microwave-absorbing body.Therefore, the energy of importing this method can more effectively be utilized, because it is less not to be used for the trap that flows and solidify of powdery paints.
Therefore, method that need to use microwave (or in broad aspect more, electrical heating) that powder paint compositions is solidified, it can be flexible and can uses the heat-setting powder paint compositions of any traditional type to be used.The invention provides such method.
The present invention relates to the aspect of coated substrate, comprise the steps:
Zero provides substrate, and the skin of this substrate comprises the thermal sense material,
Zero is administered to powder paint compositions in the described substrate,
Zero uses electrical heating that described powder paint compositions is solidified.
It is to be noted, as known in the artly be, for nonconducting substrate provides conductive material, so that can use powder paint compositions via electrostatic method.
With reference to US 6,296,939, it has been described by following step powder paint compositions has been administered to method in the temperature-sensitive substrate (for example timber): by the microwave radiation substrate is heated, use powder paint compositions, heat and solidify this paint vehicle.For responsive especially substrate, preferably at first with conduction water-based paints coated substrate, this water-based paints can be via the microwave radiant drying.Mentioned the possibility of the coating that uses radiation-hardenable, for example can be via the coating of ultra-violet radiation or electronic radiation solidifying, but clearly mention, electromagnetic radiation is not suitable for solidifies powder paints.
US 4,587, and 160 have described the skin that graphitiferous is provided can carry out electrostatic painting with acquisition surface conductivity values on thermosetting polymer.As if but this list of references relates to the electrostatic painting of liquid lacquer.Do not consider in the document to use graphite as the thermal sense material that can carry out the microwave curing of powdery paints.
In this manual, the term electrical heating is meant that frequency of utilization is the radiation heating of 10MHz to 3GHz.Frequency is that the radiation of 10MHz to 100MHz is known as radio frequency or RF radiation, is known as the microwave radiation and frequency is the radiation of 100MHz to 3GHz.In business practice, distribute specific wavelength for the heating purposes.For the U.S., the radio frequency of distribution is 13.56MHz ± 6.68kHz, 27.12MHz ± 160.00kHz and 40.68MHz ± 20.00kHz.The microwave frequency of distributing is 915MHz ± 13MHz, 2450MHz ± 50MHz, 5800MHz ± 75MHz and 24125MHz ± 125MHz.In other country, may distribute different frequency to be used for heating; Especially, beyond the U.S., distributed the frequency of 433.92MHz, 896MHz and 2375MHz.In a preferred embodiment of the invention, use to have and divide the radiation of the frequency that is used in heating to carry out this method in the country that carries out this method.
Relate to two kinds of mechanism with microwave and radio frequency heating, i.e. ionic conduction and dielectric heating.Ionic conduction mainly takes place in the RF scope.In this mechanism, apply electromagnetic field and cause ion to vibrate along with the field vibration.If there is any resistance in the conductor, then this ion motion can produce heat.In microwave range, exist the use of uniting of ionic conduction and dielectric heating, wherein dielectric is heated to be main mechanism.Add in dielectric and to pine for, the molecule with dipole character or magnetic property is along with the electromagnetic field vibration and vibrate, so that heating.
Method of the present invention originates in substrate, and the skin of this substrate comprises the thermal sense material.
The thermal sense material is meant that the radiation of its frequency of absorption in the electrical heating scope and its change into the material of heat.They normally are dispersed in the particulate solid material in the priming paint, this particle be conduction and/or magnetic.Suitable conductive material comprises carbon black, graphite, metal (for example aluminium), conductive oxide (for example tin oxide of indium tin oxide target, fluorine doping) etc.Suitable magnetic material comprises ferrite.Also can use multiple mixtures of material, for example the mixture of conduction and magnetic material.
In one embodiment, the thermal sense material is mainly radiosensitive to microwave.This further is known as microwave susceptor material.In another embodiment, the thermal sense material is mainly to the radio-frequency radiation sensitivity.This further is known as the RF sensitive material.
Generally speaking, conductive material, comprise listed above those, be microwave susceptor material, and magnetic material, comprise listed above those, be the RF sensitive material.
The substrate that its skin comprises the thermal sense material can obtain by substrate is contacted with the priming paint that comprises the thermal sense material.This contact can be carried out in every way.
In one embodiment of the invention, with the priming paint coated substrate that comprises the thermal sense material.In this embodiment, priming paint can be liquid or solid (determining spreading under the temperature).Liquid primer can be used with any way that is used for applicating liquid coating known in the art, for example uses brush, sprayer, roller, dip coating, curtain coating method etc.Solid priming paint is particulate form.They can be administered in the substrate via the powder spraying process.If substrate allows, can use static to be coated with and excute a law, electrostatic fluidized bed form or electrostatic spray form all can.Use for the static bed, and for non-conductive substrate and the relatively poor substrate of conduction, with reference to WO 99/30838, WO 02/098577, WO 2004/052558 and WO 2004/052557.
In another embodiment of the present invention, substrate is carried out with contacting in the substrate molding process of priming paint.More particularly, in this embodiment, following carrying out and the contacting of priming paint: apply mould inside with prime coat, in mould, pack into, make this resin solidification, and from mould, deviate from the substrate that its skin comprises the thermal sense material with forming the curable resin of substrate.In addition, in this embodiment, this priming paint can be solid or liquid, and solid priming paint is preferred.
Priming paint preferably also contains resin except the thermal sense material.
The existence of resin has improved the cohesive of thermal sense material and substrate.It also can improve the cohesive of powder paint compositions and substrate.Exist another advantage of resin to be that it can serve as hot dispersant in the priming paint.It helps heat to distribute in whole coating, and the risk that consequently forms focus is less.
The existence of curable resin also helps to make the thermal sense material to be fixed to by on the material of its coating, and this material is substrate or mould.
In an embodiment of method of the present invention, with the priming paint coated substrate that comprises curable resin and thermal sense material, and partially or completely make this solidifying priming paint to help the thermal sense material is fixed in the substrate, provide its skin to comprise the substrate of thermal sense material thus.
In another embodiment of method of the present invention, mould inside is coated prime coat, partially or completely made this solidifying priming paint the thermal sense material is fixed on the mould to help making, the curable resin that will form substrate of packing in mould, makes this resin solidification and deviate from the substrate that its skin comprises the thermal sense material from mould, provide its skin to comprise the substrate of thermal sense material thus.
Based on the thermal sense material that exists in the priming paint and the calculation of total of resin, the thermal sense material is present in the priming paint with the amount of 100 to 2 weight % usually.If add resin obtaining one or more above-mentioned advantageous effects, it preferably adds with at least 10%, more preferably at least 20% amount of thermal sense material and resin total amount.Interpolation thermal sense material very little may cause the curing efficiency deficiency of the powder paint compositions that will solidify.Therefore, the thermal sense material preferably constitutes at least 10 weight % of resin and thermal sense total amount of material.
If priming paint is solid priming paint, then wherein used resin then is a hard resin.Priming paint can comprise the resin particle with the mix particles of thermal sense material, but priming paint also can comprise not only resinous but also contain the particle of thermal sense material.Correspondingly, this priming paint can followingly obtain: with resin particle and thermal sense material mix particles; Resin particle and thermal sense material mix particles are carried out thermal sense material particle is adhered to step on the resin particle then; Or the thermal sense material mixed with liquid form with resin, then for example by with this mixture solidified with grind this mixture is changed into particle.
If use solid priming paint by coated substrate, then appropriate resin comprises the hereinafter described resin that is used for powder paint compositions of this specification.In one embodiment, this base coat comprises the traditional powder coating composition, wherein added the thermal sense material, for example mix by itself and existing powder paint compositions are done, add by it is adhered on the existing powder paint compositions or by its certain stage in the powder paint compositions manufacture process is added in the powder paint compositions, this causes the thermal sense material to merge in the powder paint compositions particle.For example, can before extruding, this thermal sense material be added in the powdery paints.These powder paint compositions and this specification hereinafter described to be applied on the priming paint those identical.
If priming paint will be administered on the mould, the character that can select resin with the resin compatible that will become substrate.
If solid priming paint is administered on the mould, it has 1 to 300 micron, preferred 10 to 200 microns granularity usually.Preferably, 95 volume % are lower than 120 microns.In some embodiments, possibility is attractive is that 95% particle is lower than 50 microns, or even is lower than 20 microns.When having the small-particle of big percentage, it may be attractive adding dried flow improver additives in priming paint.These compounds are known in the powdery paints manufacturing field.
If solid priming paint is administered in the substrate, it has 1 to 200 micron granularity usually; The particle of preferred at least 95 volume % has maximum 120 microns diameters.Equally, in some embodiments, possibility is attractive to be that 95% particle is lower than 50 microns, or even is lower than 20 microns.Equally, when having the small-particle of big percentage, it may be attractive adding dried flow improver additives in priming paint.
If priming paint is liquid, it contains liquid-carrier usually, and this carrier can be water base or solvent based.For environment reason, preferably use aqueous based carrier.
Available resin can be the dispersed particle form in the liquid primer.Also can use the solute resin.In one embodiment, this resin is to be selected from the resin that is applicable to the resin in the powdery paints.In aqueous priming paint, this can produce resin dispersion.Dry liquid prime coat in a conventional manner.For example, they can be at room temperature, under the temperature of the rising of using hot-air, stand the microwave radiation or use the IR drying.For the above reasons, IR may be preferred.
Prepare suitable liquid primer fully in technical staff's limit of power, for example prepare by the thermal sense particle is added in the traditional liquid priming paint formulation.
The amount of available thermal sense material should be for carrying out the effective dose of powder paint compositions electrothermal solidifying on the substrate surface.According to following criterion, use traditional experiment and error, determining of this effective dose is complete in technical staff's limit of power.Use relatively large thermal sense material to improve curing rate, but too much the thermal sense material can make curing break away from control, may cause the temperature-sensitive substrate impaired.The thermal sense material that adds conduction also can be used for improving the surface conductivity of substrate, and this powdery paints that has improved again via electrostatic method adds, and produces more all powder coatings of even unanimity thus.This has prevented that also suprabasil electric charge from gathering, thereby produces more level and smooth coating.
The amount that is present in suprabasil thermal sense material be generally 0.5 gram/square metre to 100 grams/square metre, preferred 1 gram/square metre to 10 grams/square metre.
For resiniferous priming paint, the thickness of prime coat (after the dried/cured) is generally 10 to 200 microns.When using priming paint by coated substrate, thickness is generally 10 to 100 microns, preferred 15 to 80 microns.When being administered to priming paint on the mould, thickness is generally 20 to 300 microns, preferred 50 to 200 microns.This priming paint can be used with one or more layers form.For not resiniferous priming paint, prime coat (after the cure/dry) can be thinner, and for example 1 to 50 micron, more special 1 to 10 micron.
The granularity of thermal sense material should adapt to the desired thickness of prime coat.If prime coat is thicker relatively, for example be used for mold cured, can use the thermal sense material that has than coarsegrain.If prime coat is thinner, should correspondingly reduce the size of thermal sense material.If the granularity of thermal sense material is too big, the final character of coating is undesirable.
Thermal sense material particle has 30 microns or littler, preferred 10 microns or littler d (v, 90) usually.D (v, 90) is generally at least 0.5 micron.
The technical staff it is evident that, for described granularity (d), (v x) is meant that the percentage (x) of overall particle in long-pending is lower than described granularity to d; The percentage of the gross area (100-x) is equal to or higher than described granularity.Therefore, for example, d (v, 90)=7 microns is meant that 90% particle (calculating this percentage based on particle volume) is lower than 7 microns and 10% and is higher than this granularity.Granularity is measured by laser diffraction technology, for example measures by Malvern Mastersizer, unless and indicate separately, described granularity is measured refraction index 1.45, absorption index 0.01 by Mastersizer 2000.
This priming paint can contain other traditional in coating manufacturing field component, as stabilizing agent, thickener, dispersing aid, wetting agent, tackifier etc.
This priming paint can contain or not contain pigment.As a rule, the powder paint compositions that will use contains pigment afterwards, and does not require pigment is mixed in the priming paint.But in some cases, it may be attractive in the priming paint that pigment is added to, does not especially have in the system of strong color at the thermal sense material.
In one embodiment of the invention, the thermal sense material is embedded in the substrate.This provides the cohesive of the raising of powder coating and substrate.
The thermal sense material is embedded in the substrate surface.First method is by via said method the thermal sense material being merged in the plastic-substrates surface in the substrate molding process.
But other method is to have the outer field substrate of thermal deformation by applying with the priming paint that comprises the thermal sense material, heats this prime coat then.This will make thermal sense material particle be embedded in the substrate.In this embodiment, attractive is that based on the calculation of total of resin and priming paint, priming paint contains the thermal curable resin of the amount of 10 to 90 weight %.Be used for that the thermal sense material is embedded in the heating process of substrate, this thermal curable resin solidification, and help to make the thermal sense material to be fixed in the substrate.In this manual, if the particle of at least 50% (in number) meets following requirement, then a material is regarded as being embedded in another material: on the direction vertical with substrate surface, at least 25% of their maximum cross-section diameters are embedded in the substrate.
The suitable plastic substrate is that the technical staff is conspicuous.In one embodiment, use the plastic-substrates that is fit to the inside and outside application in the auto industry, these application comprise for example air bag cover, bumper, instrument board, dashboard, rearview mirror, door-plate, engine cover plate (panel hood), top board (panel roof) and boot-lid panel (panel trunk lids).
Another embodiment of the present invention is the coating of medium density fibre board (MDF) (MDF).The surface smoothing of MDF plate also has low porosity.When they provide powdery paints, obtain smooth surface thus easily.But, the relative porous in the edge of MDF and coarse.The conventional method that powdery paints is administered on the edge can cause the powder coating resin of fusion to be adsorbed in the hole, and this causes the out-of-flatness coating on the edge surface.On the MDF edge often with the direction of edge-perpendicular on the rough wearing fiber of projection aggravated this effect.When in the method for the invention with comprising the thermal sense material and during based on the prime treatment MDF substrate of 30 to 90% resin of thermal sense material and resin calculation of total, this resin can stop up the hole at MDF edge, so that the resin of the powder paint compositions that provides afterwards can not sink to hole.In addition, can be after the priming paint drying sand milling any projection fiber of breaking off the base and forming in the lacquer application, thereby produce the level and smooth pore-free surface that is fit to very much use powdery paints.
Powder paint compositions is administered in the substrate that its skin comprises the thermal sense material.It is as known in the art that powder paint compositions is administered to suprabasil method.
In one embodiment, powder paint compositions is administered in the substrate via electrostatic method.Can use any static application method known in the powdery paints technical field, for example, electrostatic spraying (corona charging or frictional electrification) or electrostatic fluidized bed method (corona charging or frictional electrification).These are fully in those skilled in the art's general knowledge and do not require and further describe.This powder paint compositions usually with 5 to 200 microns, preferred 10 to 100 microns, more preferably 15 to 80 microns film thickness is used.
In another embodiment, powder paint compositions is administered in the substrate via heated fluidized bed.In this method, substrate work piece is preheated (being heated to 200 ℃ to 400 ℃ usually), and immerse in the fluid bed of powder paint compositions.The powder particle fusion that contacts with pre-heated surface also adheres on the workpiece.Under the situation that is powdered thermosetting compositions for coatings, can impose further heating, the curing of the coating of being used to finish to the workpiece of initial application.Under the situation that is the thermoplastic powder coating composition, may not need to heat after this class.
Usually, powdery paints is powder type and gains the name thus.But, in recent years, developed the powdery paints slurry.The powdery paints slurry is included in the resiniferous solids in the liquid medium.When using the powdery paints slurry in the present invention, they can be used by traditional application process of liquid lacquer, for example use brush, sprayer, roller, dip coating, curtain coating method etc.
Powdery paints slurry and manufacturing thereof are as known in the art.About the further information of these materials, with reference to EP1559751 and US 2003/092799.
After using powder paint compositions, the lining substrate is imposed electric radiation so that powder paint compositions solidifies.As implied above, in this manual, the term electrical heating is meant the radiation heating of frequency of utilization 10MHz to 3GHz.The radiation of frequency 10MHz to 100MHz is known as radio frequency or RF radiation, and the radiation of frequency 100MHz to 3GHz is known as the microwave radiation.In business practice, distribute specific wavelength for the heating purposes.For the U.S., the radio frequency of distribution is 13.56MHz ± 6.68kHz, 27.12MHz ± 160.00kHz and 40.68MHz ± 20.00kHz.The microwave frequency of distributing is 915MHz ± 13MHz, 2450MHz ± 50MHz, 5800MHz ± 75MHz and 24125MHz ± 125MHz.In other country, may distribute different frequency to be used for heating; Especially, beyond the U.S., distributed the frequency of 433.92MHz, 896MHz and 2375MHz.In a preferred embodiment of the invention, use to have and divide the radiation of the frequency that is used in heating to carry out this method in the country that carries out this method.
Be generally 0.5 second to 40 minutes hardening time, particularly 10 seconds to 30 minutes.The energy that applies is generally 10W to 4kW.As the technical staff understands, solidify existence relation between the required time in the energy and the realization of supply, lower energy level needs longer hardening time.Can in solidification process, change energy level.For example, in one embodiment, starting curing with high energy pulse and flow to guarantee coating, is repeatedly more low-energy pulse then, guarantees to solidify necessary duration so that coating keeps fusion to reach.
As the technical staff was conspicuous, institute's selected frequency will mate with the character of thermal sense material.If the thermal sense material is mainly radiosensitive to RF, the RF radiation that then is used under the RF frequency is cured.Perhaps, if the thermal sense material is mainly radiosensitive to microwave, the microwave radiation that then is used under the microwave frequency is cured.If the thermal sense material is all responsive to RF and microwave radiation, can use the frequency in arbitrary scope.
Method of the present invention can be used on conduction, weakly conducting with nonconducting substrate on.For this specification, non-conductive substrate is meant the substrate of sheet resistance greater than 10^11 ohm/square, the weakly conducting substrate is that sheet resistance is the substrate of 10^3 ohm/square to 10^11 ohm/square, and conductive substrates is the substrate of sheet resistance less than 10^3 ohm/square.Measure sheet resistance according to ASTM-D257-93 applying under the situation of 2KkV.
For conductive substrates, need to use mainly to the radiosensitive thermal sense material of RF, as ferrite.This also is applicable to own weakly conducting or non-conductive but contain the substrate of current-carrying part.
Method of the present invention is specially adapted to apply non-conductive and substrate (electrical conductivity is to measure under the situation that does not have the thermal sense material) weakly conducting.
Suitable non-conductive substrate and weakly conducting substrate comprise medium density fibre board (MDF) (MDF), timber, woodwork, plastics, the plastics that comprise conductive additive, polyamide, high ambroin, for example Merlon.
The MDF substrate can have the sheet resistance of about 10^3 ohm/square to 10^11 ohm/square according to its moisture content, and wherein higher moisture content can cause lower sheet resistance.
Timber and woodwork estimate to have the sheet resistance of about 10^3 ohm/square to 10^11 ohm/square according to timber type and moisture content thereof.
The various plastics that comprise the plastics of conductive additive and do not contain conductive additive can and comprise the sheet resistance that has about 10^3 to 10^11 ohm/square under the situation of additive according to additive according to material.
High ambroin comprises for example polyamide and Merlon, estimates to have the sheet resistance of about 10^11 ohm/square.
If desired, before using powdery paints the known method of operation technique personnel chemistry or mechanically cleaning have the substrate of thermal sense material.If use priming paint that the thermal sense material is administered in the substrate, can advantageously before using priming paint, carry out chemistry or physics cleaning.
For example, according to the character of substrate, can be with its washing or sand milling before using.Also can use powdery paints to use the preliminary treatment of other known in field type.For example, if substrate contains moisture, as MDF or timber, may be with the substrate preheating before using powder paint compositions, to reduce moisture content, because the existence of moisture may throw into question in the powder paint compositions solidification process.Be to contain under the situation of substrate of moisture, it may be attractive using RF to solidify, because moisture is radiosensitive to microwave, cause the substrate heating, and the specific aim of RF radiation is lower.On the other hand, when suitably implementing, can the method according to this invention in the substrate that contains moisture, use microwave curing.
One of advantage of method of the present invention is, solidifies with traditional hot and compares, and only the very specific zone of substrate is heated, i.e. the thermal sense material.The heat that generates in the thermal sense material has been guaranteed powder paint compositions curing, and base body keeps at a lower temperature.Correspondingly, in the specific embodiments of method of the present invention, substrate is the temperature-sensitive substrate.In this manual, the temperature-sensitive substrate is the substrate that can not bear the dominance condition in the powder paint compositions curing process.
Another advantage of the inventive method is, because the nonjoinder of thermal sense material in powder paint compositions, therefore can use all traditional thermal curable powder paint compositions to utilize this method.The thermal curable powder paint compositions is as known in the art.
Suitable powder paint compositions comprises one or more film-forming resins and its curing agent.This resin serves as adhesive, and have wetting pigment and the ability of cohesive strength is provided between pigment particles, and wetting or be adhered to suprabasil ability, and being administered in the substrate back fusion and flowing in solidification process, to form homogeneous film.
This film-forming resin can be one or more resins that are selected from carboxyl-functional polyester resin, hydroxyl-functional mylar, epoxy resin and the functional acrylic resins.
For example, the carboxyl-functional polyester film-forming resin can with the coupling of polyepoxide curing agent.This class carboxyl-functional polyester system is the most widely used powdery paints at present.This polyester has 10 to 100 acid number usually, 1,500 to 10,000 number-average molecular weight Mn and 30 ℃ to 85 ℃, preferred at least 40 ℃ glass transition temperature Tg.Polyepoxide can for example be the low molecular weight epoxy compound, for example the compound of the glycidol ether of the bisphenol-A of triglycidyl isocyanurate (TGIC), the condensation of for example terephthalic acid diglycidyl ester or light stabilizing ring epoxy resins.Perhaps, this class carboxyl-functional polyester film-forming resin can with two (beta-hydroxy alkylamide) curing agent for example four (2-ethoxy) adipamide use.
Perhaps, the hydroxyl-functional polyester can with the isocyanate-functional curing agent of end-blocking or amine-formaldehyde condensation products (for example melmac, urea-formaldehyde resins or glycol ural formaldehyde resin, the for example material " Powderlink 1174 " of Cyanamid Company supply, or hexamethylolmelamine) uses together.The blocked isocyanate curing agent that is used for the hydroxyl-functional polyester can for example be interior end-blocking, as urea diketone type, maybe can be caprolactam blocking type, for example IPDI.
As another possibility, epoxy resin can use by curing agent (for example dicyandiamide) with the amine official.Can use phenolic material, preferably the material (that is the poly-phenol of making by adduction bisphenol-A and epoxy resin) that is formed by the reaction of chloropropylene oxide and excessive bisphenol-A replaces the amine official of used for epoxy resin can curing agent.Functional acrylic resins, for example carboxyl-functional, hydroxyl-functional or epoxy functionalized resin can use with suitable curing agent.
Can use the mixture of film forming polymer, for example carboxyl-functional polyester can and be used to solidify the curing agent of these two kinds of polymer with the carboxyl-functional acrylic resin, and for example two (beta-hydroxy alkylamide) uses together.In addition, for the mixed adhesive system, carboxyl-functional, hydroxyl-functional or epoxy functional acrylic resin can use with epoxy resin or mylar (carboxyl-functional or hydroxyl-functional).Can select the combination of this resinoid so that co-curing, for example carboxyl-functional acrylic resin and epoxy resin co-curing, or carboxyl-functional polyester and glycidyl functional acrylic resin co-curing.But, more generally, prepare this class mixed adhesive system so that solidify (the cured with isocyanates hydroxy-functional acrylic resins and the hydroxyl-functional polyester that for example, use end-blocking) with single curing agent.Another optimization formula comprises that each adhesive to the mixture of two kinds of polymeric binders uses different curing agent (for example, the hydroxy-functional acrylic resins coupling of the cured with isocyanates of the epoxy resin of amine curing and end-blocking).
Other film forming polymer that can mention comprises functionalized fluoropolymer polymer, sense fluorine-chlorine polymer and functionalized fluoropolymer acrylate copolymer, they can be hydroxyl-functional or carboxyl-functional separately, and can be used as unique film forming polymer and use or, use with the curing agent that is applicable to these functional polymers together with one or more functional acrylics, polyester and/or epoxy resin.
Other curing agent that can mention comprises epoxy linear phenol-aldehyde resin and epoxy cresol linear phenol-aldehyde resin; With the isocyanate curing agent of oxime end-blocking, for example with the IPDI of methyl ethyl ketone oxime end-blocking, with the tetramethylene XDI of acetoxime end-blocking with the Desmodur W (dicyclohexyl methyl hydride diisocyanate curing agent) of methyl ethyl ketone oxime end-blocking; Light stabilizing ring epoxy resins, for example " the Santolink LSE 120 " of Monsanto supply; With alicyclic polyepoxide, " EHPE-3150 " of Daicel supply for example.
Powder paint compositions used according to the invention can not contain the colouring agent that adds, but contains one or more this class reagent (pigment or dyestuff) usually.The example of available pigment is an inorganic pigment, as titanium dioxide, red and yellow ferric oxide, chromium pigment and carbon black, and organic pigment, for example color lake, alkalescence and the mordant dye of phthalocyanine, azo, anthraquinone, thioindigo, isodibenzanthrone, triphendioxane and quinacridone pigment, vat dyestuffs pigment and acid.Can use dyestuff to replace pigment, or not only use dyestuff but also use pigment.
Composition of the present invention can also comprise one or more extenders or filler, and it especially helps opacity, makes cost minimization simultaneously, or more generally as diluent.
Composition of the present invention can also comprise one or more performance additive, for example, glidant, plasticizer, stabilizing agent, for example stabilizing agent of UV degradation, or anti-gas agent as benzoin, maybe can use two or more this class additives.
If desired, can help the stream additive to mix in the powder paint compositions one or more by doing to mix, for example among the WO 94/11446 disclosed those, especially disclosed preferable additives combination in this list of references, comprise aluminium oxide and aluminium hydroxide, preferably with the ratio of 30:70 to 70:30.Based on the gross weight of the composition of disregarding additive, the amount that helps the stream additive of going into by dried blending can be for example 0.05 or 0.1 to 5 weight %.
The invention still further relates to and have the prime coat that contains the thermal sense material and the substrate of powder paint compositions layer.About the specific embodiments of the character of for example base property, priming paint and powder paint compositions etc., with reference to content mentioned above.
The many specific embodiments of various details.Be noted that they in no case are to limit the present invention by any way.
In one embodiment of the invention, with the priming paint coating plastic substrate that contains thermal sense material and resin.This thermal sense material constitutes 30 to 90 weight % of thermal sense material and resin total amount.Resin is the aforesaid solid powder paint resin that is dispersed in the aqueous priming paint.This priming paint is used via traditional application method of liquid lacquer.Make the prime coat drying.Then, powder paint compositions is administered in the substrate via electrostatic powder coating composition method.Handle coated substrate so that powder paint compositions solidifies with batch microwave radiation outburst.
In the variant of above-mentioned embodiment, the plastic-substrates that scribbles priming paint is heated to the temperature that is enough to make substrate surface softening.This temperature is high enough to make the thermal sense material to be embedded in the substrate surface.This heating also causes the resin solidification in the priming paint, and this helps to make the thermal sense material to be fixed in the substrate.Behind solidifying priming paint, handle substrate surface removing loose material, and use powder paint compositions as mentioned above and its curing.
In another embodiment of the present invention, apply the MDF substrate with the priming paint that contains thermal sense material and resin.This thermal sense material constitutes 10 to 40 weight % of thermal sense material and resin total amount.Resin is the aforesaid solid powder paint resin that is dispersed in the aqueous priming paint.This priming paint is used via traditional application method of liquid lacquer.Make the prime coat drying.For guaranteeing to use the thermal sense material of capacity, can use prime coat more than one deck.After the prime coat drying, by sanded treatment substrate for example to remove surface irregularity.Then, powder paint compositions is administered in the substrate via electrostatic powder coating composition method.Handle the lining substrate so that powder paint compositions solidifies with batch microwave radiation outburst.
In another embodiment of the present invention, handle mould with the solid paint base composition that contains thermal sense material and resin.This thermal sense material constitutes 10 to 40 weight % of thermal sense material and resin total amount.Select resin with the resin compatible that constitutes substrate.Priming paint is added in the mould in a conventional manner, for example via electrostatic gun (wherein priming paint is powder type) or via wet paint spray gun (wherein priming paint is liquid form) or by as disclosed method among the EP-A 1486311.Back one method is used the carrier gas under the pressure of for example 3 to 100, more preferably 20 to 60 crust, for example nitrogen or carbon dioxide, and in about 1 to 5 second, inject priming paint.
Mold heated is fully solidified to guarantee resin, thereby guarantee that primer adhesion is on mould in the process of adding liquid base resin.Liquid base resin is added in the mould, and with mold heated so that base resin solidify.Then, from mould, deviate to have to comprise the substrate of the superficial layer of thermal sense material.The thermal sense material is embedded in the substrate surface.Powder paint compositions is administered in the substrate, for example uses via electrostatic powder coating composition method.Handle the lining substrate so that powder paint compositions solidifies with batch microwave radiation outburst.
Embodiment
Embodiment 1: the coating of polypropylene board
Paint base composition A is the thermal sense material slurry that is dispersed in the water.
| Carbon black thermal sense material | 5 grams |
| Wetting agent (Dynwet 800) | 3 grams |
| Dispersant (Byk 190) | 3 grams |
| Water | 89 grams |
Use hand-held compressed-air sprayer to spray above-mentioned paint base composition A, so that (size 15cm * 10cm * 3mm H * W * D) goes up the even covering that produces priming paint at polypropylene board.Make this priming paint at room temperature dry.Then substrate was kept before heat lamp 3 seconds, this is enough to make the polypropylene board melt surface, and carbon black thermal sense particle is embedded in the substrate.In heating process, substrate body remains below the temperature of its deformation temperature.Make this plate cooling, use standard powdery paints corona spray gun to carry out powder coated then with commercially available heat-setting epoxy novolac powder paint compositions.This coating is to cover by the uniform powder deposition layer of priming paint regions coated.
Then this plate is placed standard 800W household microwave oven, and, continue 10 minutes microwave " unlatching " time, 20 minute total time with total power outburst heating in 5 seconds.In this process, the lower surface of plate reaches 90 ℃, and the top coat surface temperature of plate is measured as maximum 130 ℃.Temperature survey is by stopping heating using microwave, opening door for microwave oven and measure sample temperature with Thermal Imaging Camera and carry out.Powder paint compositions fusing, fusion are also solidified, and shown in DSC (differential scanning calorimetry) analyzed, powder paint compositions solidified fully.Coating on the whole plate is level and smooth and even, has high gloss and does not have variable color.
Embodiment 2: the coating of polypropylene board-2
Use hand-held compressed-air sprayer to spray above-mentioned paint base composition A, so that (size 15cm * 10cm * 3mm H * W * D) goes up the even covering that produces priming paint at polypropylene board.Make this priming paint at room temperature dry.
Then this plate is placed microwave cavity, make primer coating on the plate directly towards the waveguide of deriving microwave from microwave source.The position of this plate makes can be maximum in the heating using microwave of plate surface.Applied the 150W microwave power onboard 1 to 2 second.Be enough to heat time heating time make carbon black thermal sense particle to be embedded in the substrate, substrate body keeps below 40 ℃ simultaneously.
This plate is carried out powder coated and makes its curing with commercially available thermal curable epoxy novolac powder paint compositions in the mode described in the embodiment 1 then.Shown in DSC (differential scanning calorimetry) analyzed, powder paint compositions solidified fully.Coating on the whole plate is level and smooth and even.
The coating of embodiment 3:ABS plate
Priming paint B is the powdery paints that mixes with the thermal sense material slurry with following composition:
| Charcoal blacks | 4 grams |
| The polyester powder slurry | 20 grams |
| Wetting agent (Dynwet 800) | 2.4 gram |
| Water | 71.2 gram |
The prescription of contained powder slurry is as follows in this priming paint:
| Mylar | 56.8 gram |
| Carbon black thermal sense material | 37.5 gram |
| Curing agent (primid) | 2 grams |
| Catalyst (Irganox) | 0.2 gram |
| Flow control agent (benzoin) | 0.4 gram |
| Glidant (Acronal low molecular weight propylene acids) | 1.6 gram |
| Filler barite (barium sulfate) | 2 grams |
Use hand-held compressed ir spray gun that paint base composition B is sprayed onto the ABS plate (on the size 15cm * 10cm * 3mm).Make this priming paint at room temperature dry.Then substrate was kept before heat lamp 3 seconds, this is enough to make the polypropylene board surface melting, and carbon black thermal sense particle is embedded in the substrate.In heating process, substrate body remains below the temperature of its deformation temperature.Make this plate cooling, use epoxy polyester hybrid powder coatings composition to carry out powder coated then.This coating is to cover by the uniform powder deposition layer of priming paint regions coated.
Then this plate is placed standard 800W household microwave oven, and, continue 15 minutes microwave " unlatching " time, 30 minute total time with total power outburst heating 5 to second.In this process, the lower surface of plate reaches 90 ℃, and the top coat surface temperature of plate is measured as maximum 130 ℃.Temperature survey is by stopping heating using microwave, opening door for microwave oven and measure sample temperature with Thermal Imaging Camera and carry out.Powder paint compositions fusing, fusion are also solidified, and have the level and smooth coating uniformly of good fluency and outward appearance with generation.
The coating of embodiment 4:MDF plate
With MDF plate of priming paint formulation B spraying (size 15cm * 10cm * 3mm H * W * D) to produce the even covering of priming paint.Shown in the composition of priming paint B is as above shown.
Priming paint is dry under heat lamp.Then this plate is placed standard 800W household microwave oven, and use microwave energy to be heated to be no more than 140 ℃ temperature, and under this temperature, keep 2 minutes microwave times of contact.Carry out this processing removing some surface moistures on the slave plate, otherwise they can destroy the appearance of final curing powder coating.
Use standard powdery paints corona spray gun to apply this plate then with commercially available thermal curable epoxy novolac powder paint compositions.Then this plate is placed standard 800W household microwave oven and be heated to 110 ℃ maximum surface temperature, and under this temperature, kept 20 minutes so that powder coating solidifies fully.This powder coating is all smoothly had no time on whole surface, and the edge scribbles and do not show porous smooth finish.
Embodiment 5: use priming paint via the in-mould coating method
By using the corona spray gun that powder primer formulation C is administered to mould inside, prepare testing mould.Priming paint formulation C's is composed as follows.
Priming paint C
| Mylar | 83 weight % |
| Organic peroxide | 2 weight % |
| Carbon black thermal sense material | 11.5 weight % |
| Zinc stearate as releasing agent | 2 weight % |
| Flowing additive | 1.5 weight % |
At 149 ℃ this coating was solidified 3 minutes.The sheet molding synthetic material (SMC) of in mould, packing into.Use heat and pressure, SMC is pressed into the plain film of the face coat that has priming paint formulation C.From mould, take out this sheet material.
Owing to there is priming paint, the surface conductivity of this substrate is enough high, can carry out the electrostatic coating of this substrate.Use standard powdery paints corona spray gun to apply this substrate thus with commercially available thermal curable epoxy novolac powder paint compositions.Then this plate is placed 30 minute total time in standard 800W household microwave oven, and heated, be no more than its deformation temperature to guarantee the SMC temperature with the short outburst of microwave power.Completely crued final coating is level and smooth, does not show the visible surface breakdown phenomenon that is caused by the volatile matter of overflowing.
Claims (17)
1. the method for coated substrate comprises the steps:
A., substrate is provided, and the skin of this substrate comprises the thermal sense material,
B. powder paint compositions is administered in the described substrate and
C. use electric radiation that described powder paint compositions is solidified.
2. according to the process of claim 1 wherein powder paint compositions is administered on the skin that comprises the thermal sense material of substrate.
3. according to the method for claim 1 or 2, wherein, provide the skin that comprises the thermal sense material for this substrate by substrate is contacted with the priming paint that comprises the thermal sense material.
4. according to the method for claim 3, wherein said is by carrying out with the priming paint coated substrate that comprises the thermal sense material with contacting of priming paint.
5. according to the method for claim 3, wherein saidly carry out: apply mould inside with prime coat with contacting of priming paint is following, in mould, pack into forming the curable resin of substrate,, and from mould, deviate from the substrate that its skin comprises the thermal sense material this resin solidification.
6. according to each method of claim 3 to 5, wherein said priming paint also comprises resin except the thermal sense material.
7. according to the method for claim 6, wherein said priming paint contains the thermal sense material of 10 to 90 weight % and the resin of 90 to 10 weight %, and the two is all based on the calculation of total of thermal sense material and resin.
8. claim 6 or 7 method, the resin that exists in the wherein said priming paint is the curable resin that was cured before using powder paint compositions.
9. each method of aforementioned claim, the amount of the thermal sense material that wherein exists in the substrate be 0.5 gram/square metre to 100 grams/square metre, preferred 1 gram/square metre to 10 grams/square metre.
10. each method of aforementioned claim, wherein said thermal sense material is embedded in the substrate surface.
11. each method of aforementioned claim, wherein said thermal sense material is a microwave susceptor material, and described curing is to use the microwave radiation to realize.
12. each method of claim 1 to 10, wherein said thermal sense material is the radio frequency sensitive material, and described curing is to use radio-frequency radiation to realize.
13. each method of claim 3 to 12, wherein said priming paint is liquid.
14. each method of claim 3 to 12, wherein said priming paint is powder.
15. according to each method of aforementioned claim, wherein said powdery paints is a dry powder form.
16. according to each method of claim 1 to 14, wherein said powdery paints is the powdery paints slurry.
17. the substrate that can obtain by each method of claim 1 to 16.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP06123770 | 2006-11-09 | ||
| EP06123770.7 | 2006-11-09 | ||
| US60/873,679 | 2006-12-07 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101534965A true CN101534965A (en) | 2009-09-16 |
Family
ID=37873138
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007800416814A Pending CN101534965A (en) | 2006-11-09 | 2007-11-07 | Process for coating a substrate with a coating |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101534965A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104640357A (en) * | 2014-11-14 | 2015-05-20 | 无锡信大气象传感网科技有限公司 | Method for manufacturing large mechanical and electronic circuit board by using microwave curing method |
| CN104981735A (en) * | 2012-09-18 | 2015-10-14 | Ev集团E·索尔纳有限责任公司 | Method and device for embossing |
| CN108368387A (en) * | 2015-10-27 | 2018-08-03 | 康茂股份公司 | For on automobile body assembly line by two component assemblings to together system and corresponding process |
| CN108940792A (en) * | 2018-10-10 | 2018-12-07 | 安徽科纳家居饰材有限公司 | A kind of powder coating process on wood furniture surface |
| CN114761493A (en) * | 2019-10-16 | 2022-07-15 | 斯泰尔控股有限公司 | Method for coating a workpiece |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6296939B1 (en) * | 1996-06-07 | 2001-10-02 | Basf Coatings Ag | Heat-sensitive material coated with powder paint |
| US20020024170A1 (en) * | 2000-07-11 | 2002-02-28 | Nippon Liner Co., Ltd. | Curing method to cure epoxy resins in a short time, and a method for absorbing electromagnetic wave through cured epoxy resins obtained by said curing method |
-
2007
- 2007-11-07 CN CNA2007800416814A patent/CN101534965A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6296939B1 (en) * | 1996-06-07 | 2001-10-02 | Basf Coatings Ag | Heat-sensitive material coated with powder paint |
| US20020024170A1 (en) * | 2000-07-11 | 2002-02-28 | Nippon Liner Co., Ltd. | Curing method to cure epoxy resins in a short time, and a method for absorbing electromagnetic wave through cured epoxy resins obtained by said curing method |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104981735A (en) * | 2012-09-18 | 2015-10-14 | Ev集团E·索尔纳有限责任公司 | Method and device for embossing |
| CN104640357A (en) * | 2014-11-14 | 2015-05-20 | 无锡信大气象传感网科技有限公司 | Method for manufacturing large mechanical and electronic circuit board by using microwave curing method |
| CN108368387A (en) * | 2015-10-27 | 2018-08-03 | 康茂股份公司 | For on automobile body assembly line by two component assemblings to together system and corresponding process |
| CN108368387B (en) * | 2015-10-27 | 2021-05-28 | 康茂股份公司 | System and corresponding process for assembling two parts together on a vehicle body assembly line |
| CN108940792A (en) * | 2018-10-10 | 2018-12-07 | 安徽科纳家居饰材有限公司 | A kind of powder coating process on wood furniture surface |
| CN114761493A (en) * | 2019-10-16 | 2022-07-15 | 斯泰尔控股有限公司 | Method for coating a workpiece |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0806459B2 (en) | method of forming textured epoxy powder coatings on heat-sensitive substrates | |
| AU620171B2 (en) | Process for coating plastic substrates with powder coating compositions | |
| US5338578A (en) | Method for achieving a smooth powder coated finish on a low density compression-molded plastic article | |
| JP7555370B2 (en) | Dual-coated single-cured powder coating | |
| AU2005311948B2 (en) | Powder coating composition for coating surfaces of heat-sensitive substrates | |
| PL193008B1 (en) | Method for producing powder coatings | |
| CN102690588A (en) | Powder coating compound for coating thermal sensitive substrate and coating method | |
| CN101534965A (en) | Process for coating a substrate with a coating | |
| US6531189B1 (en) | Method for hardening powder coatings | |
| US20100009210A1 (en) | Process for coating a substrate with a coating | |
| US20170190919A1 (en) | Microwave Bonding For Coating Compositions | |
| WO2008055923A1 (en) | Process for coating a substrate with a coating | |
| JP2004262988A (en) | Method for forming highly white, pearly-tone multilayered coating film | |
| US20080103224A1 (en) | Near infrared radiation curable powder coating composition having enhanced flow characteristics | |
| CN1950157B (en) | Pulsed heating process for curing substrates with near infrared radiation | |
| US3321329A (en) | Method of forming a traffic line | |
| CN103443212B (en) | There is the soft feeling powder coating of anodizing outward appearance | |
| WO2008055926A1 (en) | Process for coating a substrate with a liquid coating | |
| US20030207026A1 (en) | Sprayable powderous composition for underbody protection or sealant | |
| CN1312842A (en) | Sprayable powder composition for use as underbody protection or sealant | |
| MXPA97003116A (en) | Coating compositions in epoxitexturized powder for wooden substrates and metodopara revestira wood with mis | |
| EP1572378B1 (en) | Process for the application of powder coatings | |
| MXPA01001623A (en) | Sprayable powder composition for use as underbody protection or sealant | |
| CS233628B1 (en) | Method of creating of plastic coating of absorber of solar collector |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20090916 |