CN1826392A - Powder coating precursors and the use thereof in powder coating compositions - Google Patents
Powder coating precursors and the use thereof in powder coating compositions Download PDFInfo
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- CN1826392A CN1826392A CN 200480020721 CN200480020721A CN1826392A CN 1826392 A CN1826392 A CN 1826392A CN 200480020721 CN200480020721 CN 200480020721 CN 200480020721 A CN200480020721 A CN 200480020721A CN 1826392 A CN1826392 A CN 1826392A
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Abstract
A laminar pigment which has hydrolyzed silane coupling agent treated surface is used as a pigment for a powder coating composition. By combining the pigment with a powdery film-forming polymer, a film-forming composition, which can be applied by electrostatic coating is produced. With the addition of leveling agent to the silane treated products, the spray properties of effect pigments are improved. The products of this invention are useful in all types of automotive and industrial paint applications.
Description
Present patent application has required the right of priority of the unsettled US60/488366 of submission on July 18th, 2003.
Background of invention
The electrostatic applications method that applies coloured coating in various substrates is well-known.In described method, use a kind of composition, but described composition is film-forming polymer and the charged powder mixture with pigment of required color.Regrettably, in the past, the preparation of this powder paint compositions that applies with the powder spraying device has brought the problem relevant with lamellar pigment.
Pearly pigment or pearl shape pigment have been simulated the effect of natural peral and have been made of platelet transparent in the spectrographic visibility region.Platelet is very smooth and make the luminous reflectance and the part of part irradiation platelet pass through the platelet transmission.Make of the layer reflection of the light of part transmission subsequently by other platelet.Multiple reflection takes place from many layers in the result, and this causes gloss to be deepened because eyes can not concentrate on the specific layer.
Because input angle equals reflection angle, the reflection that is taken place is a minute surface.Catoptrical amount is little and reduce fast with the catoptrical amount of the disappearance of mirror angle under the nonspecular surface angle.The result is that pearly pigment is extremely responsive to the visual angle.In order to reflect the light of maximum, platelet must be extremely smooth.Any surface irregularity causes light to be scattered in the mode of nonspecular surface and has reduced luster effect.
Platelet must be arranged in parallel with each other and be parallel to substrate to obtain maximum reflectivity.If do not arrange like this, light will reflect and make once more gloss reduction randomly.Catoptrical amount depends on refractive index, and along with refractive index increases, catoptrical amount increases.
The lamellar pigment of metallic substance depends on its laminate structure that obtains best appearance effect.Described thin slice for example comprises tinsel for example aluminium, bronze and stainless steel substrates and natural or synthetic pearly pigment, for example natural peral powder or the substrate that is coated with metal oxide for example be coated with titanium dioxide mica, be coated with ferric oxide mica, be coated with titanium dioxide glass, be coated with the glass of ferric oxide and be coated with the aluminum slice of iron.Destroyed in extruding that the laminate structure of described metallic pigment or pearly pigment is used in the coating composition that makes powder or the process of lapping, the appearance of coat that the result obtains demonstrates the luster effect of reduction.
The industrial trial is about to polymer support and the pigment mechanically mixing is avoided the problems referred to above by pigment and polymer powder being done mix.Regrettably, pigment and powder particle produce the different quantities of electric charge usually, and this is producing the powder paint compositions electrostatic spraying to substrate the time application problems and colour-change.In addition, pigment is tending towards separating from polymer powder, and its reason is not adhere in the substrate and the volume of the powder spraying composition that is recovered subsequently.As a result, the material of the excessive spraying of recovery is difficult to utilize again.
In order to overcome the problem that causes owing to dry mix, as United States Patent (USP) 5,187, described in 220, researched and developed a kind of dry mix, wherein powder base and pigment have been mixed, being heated to then is enough to make the surperficial remollescent temperature of powder particle so that pigment is adhered on the described particulate surface.Although this method is applicable to corona electro-static charge (corona electrostatic charging) and has alleviated the problem of utilizing the powder of excessive spraying again that it is a kind of more expensive method well.
Technical significant an improvement is described in United States Patent (USP) 5,824, in 144, at this its content is introduced with for referencial use.Provide the sticky table surface layer of polymkeric substance or other viscous liquid material to described metallic platelet pigment.But when the pigment that will handle mixes with powder paint compositions, powder adherence to the surface of pigment, thereby color separated is minimized.The also available powder encapsulate of pigment, thus single surface is provided.Also can realize the better charging of the granules of pigments that those do not adhere to powdered material.
Be with in powder paint compositions, using the relevant major issue of metallic platelet pigment, limited the concentration of the pigment that can add.Although spendable amount of pigment is up to about 10% or higher in the environment that single applies or in the laboratory, when needed as industry, when carrying out fairly large operation, concentration limit is about 3%.Being higher than under about 3% the level, produce many problems.These problems comprise that spray gun stops up and nozzle accumulation, spotted plate outward appearance and color separation.
Find, provide premium properties in a kind of treatment process aspect the scope of powder coating, former having developed of described treatment process is used for the outside pearly pigment that uses improved wet fastness and whole weathering resistance to be provided and to be used for the motor vehicle coating system (for example colored primer and clear finish) that the liquid coating system is for example carried by solvent or water.Surprisingly, when joining it in powder coating, the outside pigment that uses is handled the performance that applies of having improved pigment.Described improvement comprises that pigment is at the less accumulation in the port of electrostatic gun, improved conveying through feeding line, improved pigment transport efficiency and more uniform appearance of coat.License to same patentee's United States Patent (USP) 6,524,661 have instructed a kind of improved pearly pigment powder paint compositions, described composition comprises the mixture of particulate resin carrier and granular pigments, wherein pigment is stratiform containing metal pigment, its have first coating of hydrated aluminum oxide or hydrous ceria and aluminum oxide and hydrolysising silane coupling agent or with the first coating blended coating.The image of the scanning electron imaging microscope (SEM) of described product is shown in Fig. 4.SEM graphical representation is 5 at ratio of enlargement, 500x and 33, the mica platelet of employing silane surface-treated titanium oxide coating under the 000x.The powder coating compositions that comprises the pigment of external treatment has the advantage that makes the pigment minimizing separation in gun nozzle, in case but powder curing can influence the quality of the film of coated portion.We believe, do not have aluminium hydroxide on the outside surface of silane coating.Also referring to United States Patent (USP) 6,176,918.Therefore, because the pearly pigment of silane coating and the surface energy between the resin is poor, the powder coated film of solidified has the outward appearance of reticulate pattern outward appearance or orange peel shape.
Industrial known by with aluminum oxide and resin premixed, then pre-composition is mixed with pearly pigment, or similarly aluminum oxide, resin and pearly pigment are mixed simultaneously and aluminum oxide is joined in the powder paint compositions.Referring to Nargiello, Fumed Metallic Oxides ImprovePowder Processing and Application rolls up 4 (3) the 16th to 20 pages (in June, 1993).Shown in following comparative example 5, the mixture of preparation simultaneously sprayed to does not provide any outward appearance to improve on the sheet material.
Summary of the invention
The present invention relates to a kind of improved pearly pigment powder paint compositions and powder coated method.
More particularly, the present invention relates to a kind of powder paint compositions, described powder paint compositions comprises the particulate resin carrier; Granular pigments; With the mixture of levelling agent, pigment is stratiform containing metal pigment in described granular pigments, and it contains the hydrolysising silane coupling agent.Use the panel appearance of this powder paint compositions when in powder ejection process, having eliminated the pigment separation problem and significantly having improved powder curing that a kind of improved application of powder coatings method is provided.Aluminum oxide is joined changed the surface energy of pigment on the surface of pearly pigment of silane coating and in solidification process, provide and powdex system consistency preferably.
Therefore, the present invention relates to a kind of powder coating precursors, described precursor comprises: the pearly pigment that (a) is coated with at least a silane coupling agent; (b) be present in levelling agent on the outside surface of pearly pigment (a) of silane coating.
The present invention also provides a kind of preparation method of powder paint compositions, described method comprise the steps: (a) with (i) be coated with the pearly pigment of at least a silane coupling agent and (ii) levelling agent mix to form powder coating precursors, wherein levelling agent is present on the outside surface of pearly pigment of silane coating; (b) resin is joined in the described powder coating precursors (a).
The accompanying drawing summary
Fig. 1 has shown a kind of pearly pigment.
Fig. 2 has shown a type of pearly pigment of silane coating.
Fig. 3 has shown an embodiment of powder coating precursors of the present invention.
Fig. 4 is the SEM of the product of prior art.
Fig. 5 is the SEM of an embodiment of powder coating precursors of the present invention.
Invention is described
Powder paint compositions of the present invention is to derive from the conventional powder paint compositions that static applies that is used for that is dry mixed, wherein pigment as described below the processing. Therefore, employed any known particulate resin carrier also can be used in the compositions and methods of the invention so far. Because the improved pigment that utilizes in the present invention, pigment concentration can be up to about 15% of total powder usually. Usually, according to needed effect, pigment can consist of about 1 to 8% of composition.
Pearlescent pigment:
Pigment of the present invention is layered substrate, and namely it is the crystalline pigment of sheet. Platelet can be made or can also is any natural or synthetic pearlescent pigment by the reflective metal that is sheet form such as aluminium, bronze or stainless steel. Other useful base material comprises natural mica, synthetic mica, aluminium oxide, bismoclite, boron nitride, silica, copper foil, copper alloy thin slice, zinc thin slice, kirsite thin slice, enamel, potter's clay and pottery. Useful glass flake is disclosed in the United States Patent (USP) 6,045,914 that licenses to same patentee, is incorporated herein by reference at this. Glass flake is flexible and optional also attractive. Useful glass flake is disclosed in the United States Patent (USP) 6,045,914 that licenses to same patentee, is incorporated herein by reference at this. Useful synthetic mica substrate is disclosed in United States Patent (USP) 5,741, in 355, is incorporated herein by reference at this. Preferred substrate length be about 2.5 microns to about 200 microns and thickness be about 0.05 micron to about 5 microns.
Can also use the mixture of substrate. In substrate mixture, the different materials that uses among the present invention and/or substrate can have any form, comprise platelet, sphere, cube, needle-like, palpus shape or fibrous. The example of useful flaky material comprises tabular alumina, foliated glass, aluminium, mica, bismoclite, flake ferric oxide, flake graphite, flaky silicon dioxide, bronze, stainless steel, natural peral, boron nitride, silica, copper foil, copper alloy thin slice, zinc thin slice, kirsite thin slice, zinc oxide, enamel, potter's clay and pottery etc. Can use any combination of aforementioned flaky material or any combination of at least a aforementioned flaky material and at least a non-flaky material.
The example of useful metal oxide includes but not limited to titanium dioxide (comprising anatase octahedrite and rutile form), ferric oxide (Fe
2O
3And Fe
3O
4), silicon-dioxide, zinc oxide and zirconium white.Can use a plurality of coatings of different metal oxides.
Natural pearlescent pigments comprises that natural peral and synthetic dyestuff comprise metal oxide coated pigments, mica, metal oxide coated glass flake, the aluminum slice of iron coating and the mica of reductive titanium coating.The plate-like titanium dioxide that lamellar pigment for example is disclosed in the common mandate United States Patent (USP) 4,192,691 or 5,611,691 also can be used among the present invention.In Fig. 1, pearly pigment 10 comprises the substrate 12 that is coated with metal oxide 14.
Pearly pigment of the present invention adopts the mixture process of hydrolysising silane coupling agent or these reagent in addition.Known these coupling agents are to strengthen the compound of avidity between the two as the interface between organic materials and the inorganic materials.Therefore, silane coupling agent contains organo-functional group usually and directly or indirectly is keyed to functionalized silicon group on the silicon.Functionalized silicon group is generally alkoxyl group, and preferred C
1-4Alkoxyl group.Useful especially organo-functional group is epoxy group(ing) and aminoalkyl group.
The example that can be used for silane coupling agent of the present invention is γ-(2-amino-ethyl) TSL 8330, aminopropyl trimethoxysilane, γ-An Jibingjisanyiyangjiguiwan, γ-(2-amino-ethyl) aminopropyl methyl dimethoxysilane, γ-methacryloxypropyl methyltrimethoxy silane, γ-methacryloxypropyl trimethoxy silane, γ-glycidoxypropyltrimewasxysilane, γ-Qiu Jibingjisanjiayangjiguiwan, vinyltriacetoxy silane, γ-r-chloropropyl trimethoxyl silane, vinyltrimethoxy silane, trimethylchlorosilane, γ-isocyanate group propyl-triethoxysilicane or the like.
Should select so that be applicable to and any organic materials of used pigment bonded silane coupling agent.
Pigment adopts silane coupling agent to handle by dry type or wet mixing.For example, the aqueous solution of the reagent in the mixture of water or water and organic solvent can be joined in the aqueous slurries of pigment.Preferably silane is for example passed through coupling agent is stirred appropriate time hydrolysis in advance in water.Can also when mixing, realize hydrolysis.Usually,, use about 0.1 to 10 weight %, preferred about 0.25 to 5 weight % silane coupling agent based on the pending pigment of 100 weight parts.Coupling agent combines the time that is enough to react with pigment, common sustainable several minutes of this time extremely several hours or more, preferred about 3 to 24 hours.Then, can adopt usual manner for example pigment to be reclaimed and drying by filtration, centrifugation or the like.If desired, can also coupling agent treatment combine with aluminium/cerium processing.Also, be incorporated herein by reference at this referring to the United States Patent (USP) 5,759,255 that licenses to same patentee.
Term " pearly pigment of the silane coating " meaning is that also therefore silane be formed up to the small part coating around pearly pigment, and pearly pigment can partially or completely be coated with by silane.As an example, in Fig. 2, adopt the pearly pigment 18 of silane 16 coatings formation silane coating fully from the pearly pigment 10 of Fig. 1.The silane surface that does not herein contact with pearly pigment is called " outside surface ".Outside surface 17 is shown in the accompanying drawing 2.
The pigments, mica itself that adopts aqueous alumina coating metal oxide coatings is known and optional can the use on pearly pigment before adopting the silane coating.It is described in the United States Patent (USP) 5,091,011 that for example licenses to same patentee, at this it is introduced in full with for referencial use.In brief, with pigment by dispersed with stirring in water, then with aluminum compound for example aluminum chloride, Tai-Ace S 150 or potassium aluminium sulfate and neutralizing agent for example sodium hydroxide, potassium hydroxide, ammonia and urea add as the aqueous solution simultaneously.The hydrolysis that causes thus causes hydrous oxide to deposit in the substrate.As described in this article, coating and speed that aluminum compound must enough add lentamente to form smooth and continuous on platelet should fall into about 0.03 to 0.1mg Al/min/g pigment, in the scope of preferred about 0.005 to 0.07mg Al/min/g pigment.Use a certain amount of aluminum compound solution so that production based on the total amount of pigment, contains 0.05 to 1.2% aluminium of having an appointment, and the oxidizing aqueous aluminum coating of preferred about 0.1 to 0.8% aluminium.Wherein aluminum concentration be about 1.2% pigment aspect stable not as the pigment of the aluminium that contains low concentration effective.After deposited coatings, product can be filtered, wash with water under the how easily temperature also in office dry.Should avoid using the temperature that is enough to calcine aqueous alumina.As mentioned above aforesaid silane is applied to then on the pearly pigment of aluminium hydroxide coating.
The main coating coating pigment that is made of the composition of hydrous ceria and aluminum oxide of employing itself also is known and can chooses wantonly before adopting the silane coating and use on pearly pigment.It is described in the United States Patent (USP) 5,423,912 that for example licenses to same patentee, at this it is introduced in full with for referencial use.In brief, in liquid, cerium and aluminium can easily be deposited on the surface of pigment from this liquid with colo(u)rant dispersion.This liquid easily and be preferably water dispersion.In dispersion, solid pigment accounts for about 5 to 30%, preferred about 10 to 20% usually; And cerium and aluminium all join in the dispersion with the form that dissolves in the salt in the liquid medium.Although can use other salt, preferably nitrate.Also preferred deposition is about 0.1 to 1.5%, more preferably 0.2 to 0.6% cerous hydroxide (with the cerium weight percent meter) and about 0.1 to 1%, and more preferably 0.2 to 0.6% aluminium hydroxide (with the aluminium weight percent meter) is based on the weight of pigment.Can separately add in slurry with random order salt and make its precipitation or preferably add simultaneously and make its precipitation.By pH being increased to the value greater than about 5, preferred about value of 5.5 to 7.5 is controlled precipitation.After settling step is finished, the product handled to be separated from dispersion by for example filtration of method easily, centrifugation or sedimentation arbitrarily, washing is also dry.As mentioned above aforesaid silane is applied to then on the pearly pigment of cerous hydroxide and aluminium hydroxide coating.
Useful preferred pearly pigment is commercially available from Engelhard Corporation and be described below:
| ENGELHARD pigment | Form |
| MAGNAPEARL 1103 pearly pigments | Mica platelet (61 to 77 weight %), it is coated with TiO 2(22 to 34 weight %), be coated with cerous hydroxide/polymer network (1 to 4 weight %) and stannic oxide (being less than 1 weight %) |
| MAGNAPEARL 2103 pearly pigments | Mica platelet (50 to 66 weight %), it is coated with TiO 2(33 to 45 weight %), be coated with cerous hydroxide/polymer network (1 to 4 weight %) and stannic oxide (being less than 1 weight %) |
| MAGNAPEARL 3103 pearly pigments | Mica platelet (43 to 58 weight %), it is coated with TiO 2(41 to 51 weight %), be coated with cerous hydroxide/polymer network (1 to 4 weight %) and stannic oxide (being less than 0.3 weight %) |
| LUMIN pearly pigment | Mica platelet (28.3 to 40.3 weight %), it is coated with TiO 2(58.7 to 66.7 weight %), be coated with cerous hydroxide/polymer network (1 to 4 weight %) and stannic oxide (being less than 1 weight %) |
| The super copper pearly pigment of MEARLIN | Mica platelet (46 to 65 weight %), it is coated with ferric oxide (34 to 50 weight %), is coated with cerous hydroxide/polymer network (1 to 4 weight %) |
| MEARLIN oyster pearl pearly pigment | Mica platelet (53 to 64 weight %), it is coated with TiO 2(34 to 41 weight %), be coated with cerous hydroxide/polymer network (1 to 4 weight %) and stannic oxide (being less than 1 weight %) |
| MEARLIN silver lustre pearly pigment | Mica platelet (66 to 75 weight %), it is coated with TiO 2(24 to 30 weight %), be coated with cerous hydroxide/polymer network (1 to 4 weight %) and stannic oxide (being less than 1 weight %) |
| The super red pearly pigment of MEARLIN | Mica platelet (43 to 57 weight %), it is coated with TiO 2(42 to 52 weight %), be coated with cerous hydroxide/polymer network (1 to 4 weight %) and stannic oxide (being less than 1 weight %) |
Levelling agent
Especially, levelling agent is selected from aluminum oxide, carbon nanotube, titanium oxide, zinc oxide and zirconium white.
The pearly pigment physical mixed of levelling agent and silane coating.As an example, aforementioned mixture can place in the Lacquered Tin Plate Can with baffle plate and it is shaken until aluminum oxide on coating vibrator and disperse well.The result obtains containing the pearly pigment of the silane coating of levelling agent on the outside surface of silane.Based on physical mixed, levelling agent can be the form of island or agglomerate on the silane outside surface.Result of the present invention is opposite with industrial practice, in described industrial practice,, then pre-composition is mixed with pearly pigment or simultaneously aluminum oxide, resin and pearly pigment is mixed that aluminum oxide is joined in the powder paint compositions by making aluminum oxide and resin premixed.We believe, described industrial practice does not cause that levelling agent exists as the present invention's degree on the outside surface of silane.The pearly pigment that contains levelling agent silane coating of the present invention on this will the outside surface at silane is called " powder coating precursors ".As non-limiting example, in Fig. 3, the pearly pigment 18 of the silane of Fig. 2 coating contains levelling agent 20 to form powder coating precursors 22 on the silane outside surface.Fig. 5 is the SEM of the product of the present invention that obtained by following embodiments of the invention 2.Fig. 5 represents to adopt silane treatment, adds the titanium oxide mica platelet of aluminum oxide subsequently.Compare with the zone that does not exist bunch, be present on the surface of pigments bunch on use the X-ray ultimate analysis of energy-dispersive spectroscopy (EDS) technology to show the increase of aluminium content.Above-mentioned analysis clearly illustrates that on the surface of pigment and has aluminum oxide.The tridimensional electronic microscopic inspection of two Photomicrographs shows that some alumina particles can be embedded in the titan oxide particles.
Preferably, the pyrogene aluminum oxide exists with about 0.5 to about 2.5 weight % of the pigment of aforementioned processing.The primary particle size that aluminum oxide among the present invention has is that 13nm and surface-area are 100 ± 15 meters
2/ gram.In addition, also can use surface-area among the present invention is 55 meters
2The alumina particle of/gram.
Carbon nanotube is that diameter is nano level microscopic fibers pipe.Carbon nanotube comprises around the single shaft of the central column sigmoid of pipe or co-axial monatomic and the cylindrical center space or the cylinder type hollow that are surrounded by sheet.Monatomic comprises monatomic of graphite carbon.Described carbon pipe is that diameter is nano level carbon fiber as thin as a wafer.With single monatomic arranged in co-axial alignment with the spaced radial certain distance.The micron order carbon fiber has been known in the prior art.Nano-scale carbon fiber reported first is in Natrue, in 354 the 56th to 68 pages of the volumes in 1991.Carbon nano-tube coating can make the electric-charge-dissipating that accumulates on the pigment in it is transported to process in the spray gun.Nano particle can have attendant advantages as levelling agent by the surface energy that changes pigment.
Resin:
Aforementioned mixture placed to shake until aluminum oxide in the Lacquered Tin Plate Can with baffle plate and on coating vibrator disperse well.Aluminum oxide also can use and can produce mixer instance such as Patterson-Kally or the Littleford Day mixer disperses of shearing.Then with resulting dispersion or powder coating precursors and powder coating resin preparation and shook 5 to 10 minutes.Useful powder coating resin comprises polyester TGIC-polyester TGIC-free, and urethane.Usually, contain 1 to the about 8 weight % rosin products of the present invention of having an appointment in the powdered mixture.Powder uses desk-top corona spray gun of Gema or gravity feed type gun to spray and resulting spray coating plate is solidified down at about 400 °F.
Purposes:
Composition of the present invention can be used for having used so far in any application of pearly pigment.Therefore, product of the present invention particularly has unlimited purposes in organic colo(u)r coating of the dark colouring intensity of needs and printing ink in various motor vehicles and factory coatings apply.For example, these pigment can be used for spraying paint to give various motor vehicles and bicycle in the mass-tone or as style reagent (styling agent).Similarly, they can use on all clay/formica/wood/glass/enamel/ceramic and non-porous or porous surface.
Analysis test method:
Scanning electron imaging microscope (SEM): the instrument that is used to obtain the SEM image is that JEOL 100CXII and operating voltage with ASID4D sweep attachment are 100KV.Sample powder is dispersed in the water, manually stirs, its paint is had on the grid of support membrane with dropper, and air-dry.
Energy-dispersive spectroscopy (EDS): EDS uses the Kevex Sigma 2 with angle ultra-thin window under 30 degree to obtain.The subtense angle that obtains same area is the tridimensional electronic Photomicrograph of 10 two Photomicrographs of spending and uses by Alan Gordon Enterprises that the F-71 type mirror stereoscope that Inc makes obtains stereoeffect.
For the present invention that further explains, various indefiniteness embodiment have below been provided.In these embodiments, if not indicated otherwise, in whole specification sheets and claims, all umbers and percentage all by weight and all temperature all in ℃.
Comparative example 1
Use (contains mica (64 to 77 weight %), TiO by Exterior MEARLIN MAGNAPEARL 1109 products of Engelhard Corporation supply
2(22 to 34 weight %), Cr (OH)
3(0.5 to 1 weight %) and SnO
2(0.2 to 1.0 weight %)) as pearly pigment; Described pearly pigment does not contain silane coupling agent.We do not join aluminum oxide in the pearly pigment.Use polyester TGIC resin; This resin does not contain aluminum oxide.Pearly pigment uses under 8% heap(ed) capacity in polyester TGIC resin system, causes producing pigment in gun nozzle in spraying process and separates.Then, the pigment of piling up at the nozzle place is ejected into powder coated part, and this produces defective parts.Add aluminum oxide subsequently and be helpless to the pigment separation problem.
Comparative example 2
Use the surface-treated titanium dioxide-coated mica that constitutes by aluminium hydroxide, phenylalanine and lauric acid according to having of the United States Patent (USP) 6,245,323 that licenses to same patentee as pearly pigment.This pearly pigment does not contain silane coating.Pearly pigment is mixed with polyester TGIC-free is dried at 8% time, in spraying process, still have pigment and pile up problem in gun nozzle.Resin does not contain aluminum oxide.Add aluminum oxide and be helpless to the spraying problem.
Comparative example 3
In polyester TGIC-free resin system, adopt the pigment that is purchased of silane treatment not spray well at 8% time.This resin does not contain aluminum oxide.Product under the situation of adding or not adding aluminum oxide all has pigment in gun nozzle to be separated.
Comparative example 4
Have silane treatment to be purchased the mean particle size that pearly pigment has be about 20 microns.We do not join aluminum oxide in the described pearly pigment.This pearly pigment mixes with vibrin under 8% heap(ed) capacity and powder is sprayed onto on the plate.Described resin does not contain any aluminum oxide.In the process of powder ejection, after the nozzle place of spray gun observes the accumulation of pearly pigment and is solidifying, the outward appearance that spray coating plate has similar " tangerine peel ".When pearly pigment is at first mixed with 2% aluminum oxide, when mixing with vibrin then, the outward appearance of observing powder coated plate has remarkable improvement.
Comparative example 5
To have the surface-treated titanium dioxide-coated mica that is made of cerous hydroxide/polymer network and aluminum oxide and polyester TGIC-free resin system mixes.The powder spraying of 3-mixture shows that the plate that solidifies coating does not afterwards improve.Powder coated surface lacked to improve when 3 all components mixed proves and must carry out modification to surface of pigments before adding resin system.Only the existence of aluminum oxide can not cause the improvement of powder coated plate.
Inventive embodiments 1
The pearly pigment that EXTERIOR CFSMEARLIN MAGNAPEARL 1103 products (contain mica platelet (61 to 77 weight %), it is coated with titanium dioxide (22 to 34 weight %), is coated with cerous hydroxide/polymer network (1 to 4 weight %) and stannic oxide (being less than 1 weight %)) of selecting 197 grams to be supplied by Engelhard Corporation are coated with as silane.Silane coating is made of two kinds of silane with different organo-functional groups.With the pearly pigment and the 3 gram primary particle size of silane coating is that 13nm and surface-area are 100 meters
2The pyrogene aluminum oxide of/gram mixes 20 minutes to form powder coating precursors in 5 quarts of Lacquered Tin Plate Cans with baffle plate.The mean particle size of resultant product is 17 to 20 μ m.
Use following resin: polyester TGIC, polyester TGIC-free and urethane.These resins do not contain aluminum oxide.To in each aforementioned resin system, use the corona spray gun to be sprayed onto on the plate by the powder coating precursors under 8% heap(ed) capacity.The outward appearance that powder coating precursors separation and plate do not take place is good in general.
Inventive embodiments 2
The pearly pigment that Exterior CFSMEARLIN MAGNAPEARL 2103 products (contain mica platelet (50 to 66 weight %), it is coated with titanium dioxide (33 to 45 weight %), is coated with cerous hydroxide/polymer network (1 to 4 weight %) and stannic oxide (being less than 1 weight %)) of selecting 197 grams to be supplied by Engelhard Corporation are coated with as silane.Silane coating is made of two kinds of silane with different organo-functional groups.With the pearly pigment and the 3 gram primary particle size of silane coating is that 13nm and surface-area are 100 meters
2The pyrogene aluminum oxide of/gram mixes to form powder coating precursors.The mean particle size of resultant product is 8 to 10 μ m.The powder coating precursors that sprays under 8% powder coating precursors heap(ed) capacity in the listed resin in inventive embodiments 1 does not demonstrate the separation or the accumulation of powder coating precursors in gun nozzle.The outward appearance of plate is slick and has high quality after solidifying.
Inventive embodiments 3
The pearly pigment that Exterior CFSMEARLIN MAGNAPEARL 3103 products (contain mica platelet (43 to 58 weight %), it is coated with titanium dioxide (41 to 51 weight %), cerous hydroxide/polymer network (1 to 4 weight %) and stannic oxide (0.3 to 0.8 weight %)) that use 197 grams to be supplied by Engelhard Corporation are coated with as silane.Silane coating is made of two kinds of silane with different organo-functional groups.With the pearly pigment and the 3 gram primary particle size of silane coating is that 13nm and surface-area are 100 meters
2The pyrogene aluminum oxide of/gram mixes to form powder coating precursors.The mean particle size of resultant product is 3.5 to 6.5 μ m.The powder coating precursors that sprays under 8% powder coating precursors heap(ed) capacity in the listed resin in above inventive embodiments 1 does not demonstrate the separation or the accumulation of powder coating precursors in gun nozzle.The outward appearance of plate is slick and high quality with outward appearance of metalloid lacquer after solidifying.
Inventive embodiments 4
The pearly pigment that the Exterior LUMINA Turquoise T303D product (contain mica platelet (28.3 to 40.3 weight %), it is coated with titanium dioxide (58.7 to 66.7 weight %), is coated with cerous hydroxide/polymer network (1 to 4 weight %) and stannic oxide (0.3 to 0.8 weight %)) that uses 197 grams to be supplied by Engelhard Corporation is coated with as silane.Silane coating is made of two kinds of silane with different organo-functional groups.With the pearly pigment and the 3 gram primary particle size of silane coating is that 13nm and surface-area are 100 meters
2The pyrogene aluminum oxide of/gram mixes to form powder coating precursors.The mean particle size that described powder coating precursors has is 16.5 μ m.
Use following resin: polyester TGIC-free and urethane.These resins do not contain aluminum oxide.In each aforementioned resin system under 8% powder coating precursors heap(ed) capacity the spray coating powder paint precursor.Do not exist the accumulation of powder coating precursors and plate outward appearance to have good quality in gun nozzle.Add aluminum oxide and produce the bright powder coated plate that has than high chroma.The plate that is coated with powder coating precursors is in increase by 12% aspect the colourity and in increase by 21% aspect the brightness under 110 ° in measured angular.Under contiguous reflection angle, brightness increase by 20% and colourity increase by 12%.
Inventive embodiments 5
The pearly pigment that the Exterior CFSMEARLIN Super Copper 3503Z product (mica platelet (46 to 65 weight %), it is coated with ferric oxide (34 to 50 weight %) and is coated with cerous hydroxide/polymer network (1 to 4 weight %)) that uses 197 grams to be supplied by Engelhard Corporation is coated with as silane.Silane coating is made of two kinds of silane with different organo-functional groups.With the pearly pigment and the 3 gram primary particle size of silane coating is that 13nm and surface-area are 100 meters
2The pyrogene aluminum oxide of/gram mixes to form powder coating precursors.The mean particle size that described powder coating precursors has is 16.4 to 19.4 μ m.
Use following resin: polyester TGIC-free and urethane.These resins do not contain aluminum oxide.The powder coating precursors that sprays under 8% powder coating precursors heap(ed) capacity in each aforementioned resin system has good quality in the outward appearance that gun nozzle does not demonstrate accumulation and plate.
Inventive embodiments 6
The pearly pigment that the Exterior CFSMEARLIN Fine Pearl 1303V product (mica platelet (53 to 64 weight %), it is coated with titanium dioxide (34 to 41 weight %), is coated with cerous hydroxide/polymer network (1 to 4 weight %) and stannic oxide (being less than 1 weight %)) that uses 197 grams to be supplied by Engelhard Corporation is coated with as silane.Silane coating is made of two kinds of silane with different organo-functional groups.With the pearly pigment and the 3 gram primary particle size of silane coating is that 13nm and surface-area are 100 meters
2The pyrogene aluminum oxide of/gram mixes to form powder coating precursors.The mean particle size that described powder coating precursors has is 9.4 to 12.4 μ m.
Used resin is polyester TGIC-free and does not contain aluminum oxide.The powder coating precursors that sprays in the polyester TGIC-free resin system demonstrates in gun nozzle does not have the accumulation of powder coating precursors and the outward appearance of plate to have good quality.
Inventive embodiments 7
The pearly pigment that the Exterior CFSMEARLIN Bright Silver 1303Z product (mica platelet (65 to 75 weight %), it is coated with titanium dioxide (24 to 30 weight %), is coated with cerous hydroxide/polymer network (1 to 4 weight %) and stannic oxide (being less than 1 weight %)) that uses 197 grams to be supplied by Engelhard Corporation is coated with as silane.Silane coating is made of two kinds of silane with different organo-functional groups.With the pearly pigment and the 3 gram primary particle size of silane coating is that 13nm and surface-area are 100 meters
2The pyrogene aluminum oxide of/gram mixes to form powder coating precursors.The mean particle size that described powder coating precursors has is 17.3 to 20.3 μ m.
Use following resin: polyester TGIC-free and urethane.These resins do not contain aluminum oxide.The powder coating precursors that sprays under 8% powder coating precursors heap(ed) capacity in each aforementioned resin system demonstrates in gun nozzle does not have the accumulation of powder coating precursors and the plate outward appearance of good quality.
Inventive embodiments 8
The pearly pigment that the Exterior CFSMEARLIN Super Red 4303Z product (mica platelet (43 to 57 weight %), it is coated with titanium dioxide (42 to 52 weight %), is coated with cerous hydroxide/polymer network (1 to 4 weight %) and stannic oxide (being less than 1 weight %)) that uses 197 grams to be supplied by Engelhard Corporation is coated with as silane.Silane coating is made of two kinds of silane with different organo-functional groups.With the pearly pigment and the 3 gram primary particle size of silane coating is that 13nm and surface-area are 100 meters
2The pyrogene aluminum oxide of/gram mixes to form powder coating precursors.The mean particle size of powder coating precursors is 15.3 to 20.3 μ m.
Used resin is polyester TGIC-free and does not contain aluminum oxide.The powder coating precursors that sprays under 8% powder coating precursors in polyester TGIC-free resin system demonstrates extraordinary spraying property.Do not exist the accumulation of powder coating precursors and whole plate outward appearance to have good quality in gun nozzle.
Comparative example 6 and inventive embodiments 9
With 400 gram MAGNAPEARL 2100 pigment (56.5 to 64.5 weight % micas, 35.5 to 41.5 weight % rutile titanium dioxides and 0.2 to 2.0 weight % stannic oxide) mean particle sizes is that the titanium coated mica of 7.8 to 10.9 microns reflective white is dispersed in 2.6 liters of distilled water and is heated to 78 ℃.With the pH regulator to 6.5 of slurry, under 0.15ml/min, add two kinds of silane subsequently with different organo-functional groups.Then product is filtered, washs and dry 2 hours pearly pigments under 120 ℃ with the coating of formation silane.The pearly pigment of 2 gram aluminum oxide with 100 gram silane coatings mixed to form powder coating precursors.
Used resin is polyester TGIC-free and does not contain aluminum oxide.The powder formulation of preparation powder coating precursors of 8% in polyester TGIC-free resin.The powder that ejection is estimated does not demonstrate the accumulation of powder coating precursors in spray gun.Will be in the existence of aluminum oxide or the powder coated plate of micaceous of the titanium coating of silane treatment not compare.Add aluminum oxide significant improvement is being provided aspect the outward appearance of plate.
100 gram MAGNAPEARL 2100 pigment (56.5 to 64.5 weight % micas, 35.5 to 41.5 weight % rutile titanium dioxides and 0.2 to 2.0 weight % stannic oxide) are mixed as pearly pigment and with each of 4% following material: 2-amino-ethyl-3-TSL 8330,3-aminopropyltriethoxywerene werene and isocyanate group propyl-triethoxysilicane.In sieve (below 40 microns) classification of under 120 ℃ each drying of three kinds of mixtures also being passed through 325 sieve meshes.Part fractionated powder is mixed with 2.0% aluminum oxide and another part is used for the comparison purpose.In polyester TGIC resin system under 8% heap(ed) capacity to exist at aluminum oxide and not in the presence of the pearly pigment of each silane coating estimate.The powder coated plate that has aluminum oxide on the MAGNAPEARL 2100 of silane coating shows the improvement of ejecting plate outward appearance.
In method of the present invention and product, can carry out various changes and improvements, and not depart from its spirit and scope.This paper has described, and the various embodiments of the present invention that are used to explain do not mean it are limited.
Claims (10)
1, a kind of powder coating precursors, described precursor comprises:
(a) be coated with the pearly pigment of at least a silane coupling agent; (b) be present in levelling agent on the outside surface of pearly pigment (a) of described silane coating.
2, the powder coating precursors of claim 1, wherein said pearly pigment (a) is metal oxide coated substrate.
3, the powder coating precursors of claim 1, wherein said levelling agent (b) is an aluminum oxide.
4, the powder coating precursors of claim 1, wherein, based on the pearly pigment (a) of described silane coating, described levelling agent (b) exists with about 1.5 to about 2.5 weight %.
5, the powder coating precursors of claim 1, the surface-area of wherein said aluminum oxide are about 50 meters
2/ gram is to about 120 meters
2/ gram.
6, the powder coating precursors of claim 1, described precursor comprise (c) polymkeric substance in addition.
7, a kind of preparation method of powder paint compositions comprises the steps: that (a) mixes following material
(i) be coated with the pearly pigment of at least a silane coupling agent; With
(ii) levelling agent,
Forming powder coating precursors, wherein said levelling agent is present on the outside surface of pearly pigment of described silane coating; With
(b) resin is added in the described powder coating precursors (a).
8, the method for claim 7, wherein said levelling agent is an aluminum oxide.
9, the method for claim 7, wherein, based on the pearly pigment of described silane coating, described levelling agent exists with about 1.5 amounts to about 2.5 weight %.
10, the method for claim 8, the surface-area of wherein said aluminum oxide are about 50 meters
2/ gram is to about 120 meters
2/ gram.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US48836603P | 2003-07-18 | 2003-07-18 | |
| US60/488,366 | 2003-07-18 | ||
| US10/879,661 | 2004-06-29 |
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| CN1826392A true CN1826392A (en) | 2006-08-30 |
| CN100439456C CN100439456C (en) | 2008-12-03 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102939343A (en) * | 2010-05-20 | 2013-02-20 | 萨克特本化学有限责任公司 | Functionalized particles and use thereof |
| CN103305104B (en) * | 2013-07-01 | 2016-01-06 | 上海纪森商贸有限公司 | A kind of method preparing Dry powder type thermal radiation coating |
| CN105967658A (en) * | 2016-03-23 | 2016-09-28 | 马鞍山金晟工业设计有限公司 | Wear-resistant composite coating material |
| CN108250662A (en) * | 2018-01-12 | 2018-07-06 | 北京慧缘有限责任公司 | Colorful is exempted to spray ABS compositions and its production technology and ABS safety caps |
| CN111117299A (en) * | 2020-01-14 | 2020-05-08 | 长乐力恒锦纶科技有限公司 | Titanium dioxide delustering agent for relieving fouling of prepolymerization tower |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4308312A (en) * | 1979-07-24 | 1981-12-29 | General Electric Company | Dielectric films with increased voltage endurance |
| US5314723A (en) * | 1992-06-09 | 1994-05-24 | Gte Products Corporation | Method of coating phosphors on fluorescent lamp glass |
| US5759255A (en) * | 1996-02-07 | 1998-06-02 | Engelhard Corporation | Pearlescent pigment for exterior use |
| US6325846B1 (en) * | 2000-06-20 | 2001-12-04 | Engelhard Corporation | Powder coating composition and method |
-
2004
- 2004-07-16 CN CNB2004800207213A patent/CN100439456C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102939343A (en) * | 2010-05-20 | 2013-02-20 | 萨克特本化学有限责任公司 | Functionalized particles and use thereof |
| CN102939343B (en) * | 2010-05-20 | 2014-11-19 | 萨克特本化学有限责任公司 | Functionalized particles and use thereof |
| CN103305104B (en) * | 2013-07-01 | 2016-01-06 | 上海纪森商贸有限公司 | A kind of method preparing Dry powder type thermal radiation coating |
| CN105967658A (en) * | 2016-03-23 | 2016-09-28 | 马鞍山金晟工业设计有限公司 | Wear-resistant composite coating material |
| CN108250662A (en) * | 2018-01-12 | 2018-07-06 | 北京慧缘有限责任公司 | Colorful is exempted to spray ABS compositions and its production technology and ABS safety caps |
| CN111117299A (en) * | 2020-01-14 | 2020-05-08 | 长乐力恒锦纶科技有限公司 | Titanium dioxide delustering agent for relieving fouling of prepolymerization tower |
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| CN100439456C (en) | 2008-12-03 |
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