CN101326221A - Methods for reducing the time to produce a mar and/or scratch resistant coating on a substrate - Google Patents

Abstract

Disclosed are methods for reducing the time required to produce a mar and/or scratch resistant coating on a substrate. The methods comprise (a) applying a coating composition to the substrate, then (b) partially crosslinking crosslinkable components in the composition, and then (c) allowing the coating composition to post cure, wherein, between steps (b) and (c), and after step (c), a mar and/or scratch resistant coating is present on the substrate. Also disclosed are substrates, such as plastic substrates, at least partially coated with a coating produced by such methods as well as related articles of manufacture.

Description

Shortening produces the time method of the coating of scuff resistance and/or scratch resistant on base material

The cross reference of related application

The application has required the U.S. Provisional Patent Application sequence number No.60/748 of submission on December 9th, 2005,866 right, and its full content is hereby incorporated by reference.

Technical field

The present invention relates to shorten the time method of the coating requirement that on base material such as plastic basis material, produces scuff resistance and/or scratch resistant.More particularly, method of the present invention comprises that (a) is coated in coating composition on the base material, it is partial cross-linked that (b) makes the crosslinkable component in the composition then, (c) allows the coating composition after fixing then, wherein, step (b) and (c) between, and in step (c) afterwards, on base material, have the coating of scuff resistance and/or scratch resistant.The invention still further relates to the base material that is coated with the coating of producing to small part with these class methods, as plastic basis material, and correlated product.

Background technology

Various products, for example exterior automotive parts and element, usually handle by laminated coating, these coatings can not only be improved the outward appearance of product, and can prevent impaired, the ultraviolet radiation cracked as burn into of product, acid rain and the infringement that other envrionment conditionss caused.The challenge that many manufacturerss of these products face is to find to shorten the time that deposition protective coating system requires.

Many coatings are to come drying and solidified by hot baking method, wherein the goods that apply are passed through to set baking oven at high temperature.Had and manyly be suggested about the drying of quickening this type coating and the suggestion of solidification process.Yet, wherein many suggestions comprise may be nonconforming fast, the high temperature drying method, this is because these technology can cause holiday, as cracking, bubbling or foaming.In addition, some material, as TPO (" TPO ") type product, to temperature sensitive so that can't use high temperature drying and curing technology.This material is used to construct exterior automotive parts and element usually.

Other coating can be come rapid drying and curing by radiation curing technology, as coating is exposed in ultraviolet (" UV ") radiation.Yet the enforcement of ultraviolet radiation usually needs a large amount of capital investments that is difficult to accept.

The result is, is desirable to provide a kind of method that can shorten the cycling time of the coating that produces scuff resistance and/or scratch resistant on base material such as plastic basis material, and this method does not need to adopt high temperature drying technology or radiation curing technology.

Summary of the invention

In some aspects, the present invention relates to a kind of shortening produces the coating requirement of scuff resistance and/or scratch resistant on base material time method, this method comprises that (a) is coated in coating composition on the base material, it is partial cross-linked that (b) makes the crosslinkable component in the composition then, (c) allows the coating composition after fixing then, wherein, step (b) and (c) between, and in step (c) afterwards, on base material, there is the coating of scuff resistance and/or scratch resistant.

The invention still further relates to the base material that is coated with the coating of producing to small part, as plastic basis material with these class methods.

On the other hand, the present invention relates to surface to small part and be coated with scuff resistance and/or the scratch resistant coating is the goods of partial cross-linked film.

Embodiment

For the purpose of following detailed description, except that special opposite regulations, be appreciated that the present invention can suppose different alternative variation and sequence of steps.In addition, remove in any operation embodiment, perhaps indication in addition, all numerals of for example expressing the component of using in specification sheets and claims are understood that all " approximately " to limit with term under all situations.Therefore, unless indication in contrast, the numerical parameter that proposes in following specification sheets and claims all is the approximation that the performance that can want according to the present invention to obtain changes.Minimally and be not the application of attempting to limit claim protection domain doctrine of equivalents, each numerical parameter should be to determine according to the number and the application method of rounding up of the significant figure of report at least.Although illustrating the numerical range and the parameter of wide region of the present invention is approximation, the numerical value of Ti Chuing can as far as possible accurately be reported in a particular embodiment.Yet because their standard differences in the test determination separately, any numerical value itself certainly exists some mistake.

Similarly, be to be understood that any numerical range of mentioning comprises that all are included in interior subrange herein.For example, the scope of " 1 to 10 " comprises all subranges that (comprise 1 and 10) between minimum value 1 and the maximum value 10, promptly minimum value be equal to, or greater than 1 and maximum value be equal to or less than 10.

Among the application, unless specify that in addition the use of odd number comprises that plural number and plural number comprise plural number.For example, still without limits, the application mentions and comprises the method for coating " coating composition " to the step of base material." coating composition " herein is meant and comprises the method that wherein single coating composition is coated on the base material and two or more coating compositions are coated to method on the base material.In addition, in this application, unless other special indicating, " or " the use meaning be meant " and/or ", even " and/or " may be clearly used as some situation.

As show, in certain embodiments, the present invention relates to shorten the time method of the coating requirement that on base material, produces scuff resistance and/or scratch resistant.Scuffing that those skilled in the art can learn, term " scratch " and " " is meant the physical deformation that is produced by machinery or chemical abrasion." scuff resistance " is the measurement yardstick that a kind of material is resisted the appearance degradation capability that is caused by the small-scale mechanical stress." scratch resistance " is meant that the material opposing can cause more obviously, the ability of the more havoc of darker or wideer groove.Therefore, scratch and to be considered to more serious usually than the scratch of in technology, mentioning, and in the art they two be considered to different.Be understandable that scratch and scuffing can and be passed through normal the use by manufacturing and environmental factors and produce.Here the term of using " scuff resistance and/or scratch resistant coating " is meant that after abrasion under following take place coatingsurface coating can keep 30 at least percent its initial 20 ° of gloss.In certain embodiments, remain with at least initial 20 ° of gloss of percent 40 and, in other cases, after coatingsurface produces abrasion, remain with initial 20 ° of gloss of percent 60 at least.Can use 20 ° of NOVO-GLOSS statistics glossmeters of a kind of Gardner instrument company to measure according to 20 ° of gloss of curing coated substrate of the present invention.The CM-5 type Atlas AATCC scratch tester that provides with the Atlas electrical equipment company in Chicago, Illinois makes coated substrate stand to bear a heavy burden 10 double rub of sand paper.Described sand paper is commercially available St.Paul, the 3M 281Q WETORDRY of the 3M company of Minnesota ^TMPRODUCTION ^TM9 microns polishing sand paper sheets.Then with tap water clean plate face and carefully dry with paper handkerchief.20 ° of gloss are to measure on the abrasion zone of test panel face.The numerical value of being reported is the percentage ratio of the original gloss that keeps after the scratch hardness test, that is, 100%x scratches gloss/initial gloss.

Term used herein " base material " is meant that the surface can scribble any material of film, comprises naked base material and has deposited cated base material thereon.In certain embodiments of the present invention, described base material comprises plastic basis material.Here the term of Shi Yonging " plastic basis material " is meant and comprises any base material that is made of as especially TPO, acrylonitrile-butadiene-styrene (ABS) (" ABS "), polycarbonate, thermoplastic elastomer, polyurethanes and thermoplastic polyurethanes thermoplastics or thermoset synthetic materials to small part, these thermoplasticss or thermoset synthetic materials are to be used for injection or reaction molding, sheet molding or other similar methods, thus parts formed.

As shown, some method of the present invention comprises coating composition is coated on the base material.In certain embodiments, coating composition exists with liquid state, and promptly it is water-based or solvent-based system.The organic solvent that can be used for this type of coating composition comprises, for example, and alcohol, ketone, aromatic hydrocarbon, glycol ethers, ester or their mixture.In solvent-based compositions, solvent exists with 5 to 80wt% the amount that accounts for composition total weight usually, as 30 to 50wt%.Comprise that at aqueous composition and those solvent can exist with higher weight percent in composition of mixture of water/solubility promoter.

In certain embodiments, composition comprises the thermoset film-forming resin.Here the term of Shi Yonging " thermoset " is meant that resin is when solidifying or when crosslinked irreversibly " sclerosis ", wherein the polymer chain of polymeric constituent is connected together by covalent linkage.This performance is relevant with the crosslinking reaction of composition component usually.Referring to Hawley, Gessner G., The CondensedChemical Dictionary, the 9th edition, 856 pages; Surface Coatings, vol.2, Oiland Colour Chemists ' Association, Australia, TAFE EducationalBooks (1974).In case solidify or crosslinked, thermosetting resin no longer melts when heating and is insoluble to solvent.

In certain embodiments, the thermoset film-forming resin comprises the polymkeric substance that (i) contains reactive functional, and (ii) has the respond solidifying agent of active functional group of reactive functional to polymkeric substance.In certain embodiments, polymkeric substance is selected from the acrylic copolymer that contains hydroxyl and/or carboxylic acid, the polyester polymers that contains hydroxyl and/or carboxylic acid, oligopolymer and contain isocyanic ester and/or the polyether polyols with reduced unsaturation of hydroxyl, the polyureas that contains amine and/or isocyanic ester, perhaps their mixture.U.S. Patent No. 5,939,491, the 7 hurdles the 7th row further is described these polymkeric substance in the 8th hurdle the 2nd row; This patent and the patent of wherein quoting are herein by incorporated by reference.Proper curing agents includes but not limited to, patent ' 491 the 6th hurdles the 6th row is to those of the 62nd line description.The combination of solidifying agent can be used.

In certain embodiments, film-forming resin with based on the composition solid gross weight greater than about 20wt%, as greater than about 40wt%, and the amount that is lower than 90wt% is present in the coating composition.For example, the weight percentage of resin can be between 20 to 80wt%.When using solidifying agent, its usage quantity is at most 50wt% usually; The weight percentage here is based on the total weight of solids of coating composition equally.

In certain embodiments, coating composition comprises curing catalysts, promptly quickens (ii) catalyst for reaction of polymkeric substance (i) and solidifying agent.Appropriate catalyst comprises, for example, and organo-tin compound such as dibutyl tin oxide, dioctyltin oxide, dibutyl tin laurate or the like.Those skilled in the art can use the appropriate catalyst that is used for other linking agent in case of necessity.In certain embodiments, the gross weight of resin solid in the coating based composition, catalyzer exists as 0.05 to 2.0wt% amount with 0.01 to 5.0wt% amount.

In certain embodiments, coating composition comprises a large amount of particles that are dispersed in the film-forming resin.Be used for particle of the present invention and can have mean particle size from the nanometer to the micrometer range.Between size range 2.0 to 500 nanometers, can be used as " nanoparticle " between about 5 to 200 nanometers.About 0.5 to 100 micron of size range, as greater than 1 micron to 50 microns, " micron particle " between 0.5 to 30 micron or 0.5 to 10 micron can be used.

Can decide granularity according to method well known in the art, as passing through the regular particle size analyser.For example, can use laser scattering technology during greater than 1 micron when mean particle size.For example, this type of particulate mean particle size can use Horiba LA 900 type laser diffraction granularity instruments to measure, this instrument uses wavelength to measure particle size as the helium-neon laser of 633nm and the supposition particle has sphere, and promptly " granularity " is meant the ball that surrounds the particulate minimum fully.Wherein when mean particle size during less than 1 micron, mean particle size can be passed through the electron photomicrograph of visual inspection transmission electron microscope (" TEM ") image, particulate diameter in the measurement image, and be that benchmark calculates mean particle size and determines with the magnification of TEM image.Those skilled in the art will appreciate that how to prepare this TEM image and U.S. Patent No. 6,610,777 the 29th hurdles the 64th row discloses the description of appropriate method to 30 hurdle eighth rows, will quote part herein as with reference to introducing.

Coating of particles (perhaps form) can change according to selected individual particle or a plurality of particulate kind.For example, usually, can use spherical particle, as crystalline material, solid bead, microballon grain or hollow spheres, particle also can be tabular, cubical or acicular (that is to say, elongated or fibrous).Particle can also have random or uneven form.In addition, particle can have internal structure, and this internal structure is a hollow, porous or imperforate, and perhaps any combination, as have the hollow centre of porous or solid wall.Learn for some and use that a kind of particle shape may be more suitable than other.Yet for other application, particle shape may it doesn't matter.Can learn and to use particulate combination to make final coating obtain required characteristic with different forms.

Can learn that two or more particulate mixtures with different mean particle sizes can be introduced into and give required performance of composition and characteristic in the composition of the present invention.For example, the micron particle that is particularly suitable for giving the nano-sized particles of scuff resistance and is particularly suitable for giving resistance to marring can be used in combination.

Particle can be by being selected from polymeric and non-polymeric inorganic materials, polymeric and non-polymeric organic materials, matrix material, and the formation of the material of above-mentioned substance any mixture.Be applicable to this examples of material of the present invention, in U.S. Patent No. 6,610,777 the 30th hurdle 28 row is described to the 36th hurdle 31 row, and what be incorporated herein by reference quotes part herein.

In certain embodiments, particle makes the surface tension that its surface tension is lower than does not have particulate film-forming resin through chemical modification.Be applicable to this particulate example among the present invention, in U.S. Patent No. 6,790,904 the 3rd hurdle 43 row is described to the 8th hurdle 61 row, and what be incorporated herein by reference quotes part herein.

Be present in the enough production scuff resistances of particulate amount of coating composition and/or the coating of scratch resistant, even when not enough production scuff resistances of the crosslinking degree of the crosslinkable component in the composition and/or scratch resistant coating.In certain embodiments, the particulate amount in the coating composition of being present in is 0.01 to 20.0wt%, as from 0.01 to 10wt%, perhaps, and sometimes 0.01 to 8wt%, wherein wt per-cent is based on the total weight of solids of coating composition.

Optional ingredients such as softening agent, tensio-active agent, thixotropic agent, anti-gas producing agent, organic cosolvent, flow control agent, antioxidant, the similar typical additives in UV light absorber and this area can be included in the composition.With the resin solid gross weight is benchmark, and these compositions usually exist with the amount of 40wt% at the most.

Coating composition can be applied on the base material by the whole bag of tricks.For example, this composition can be by any ordinary method as brushing, dipping, and flow coat, roller coat, conventional and electrostatic spraying applies.The most frequently used is spraying technology.Usually, the film thickness of liquid coating can between 0.5 to 3 mil, perhaps be about 1.5 mils between 0.1 and 5 mils.

According to described in the past, some method of the present invention comprises crosslinkable component in the partial cross-linked composition.Here the meaning of the term of Shi Yonging " crosslinkable component in the partial cross-linked composition " be in the composition crosslinkable component reaction so that form partial cross-linked coating.Here the term of Shi Yonging " partial cross-linked coating " is meant the formation coating, wherein a crosslinkable component part but be not that whole generations are crosslinked in the composition.In certain embodiments of the invention, the crosslinked amount of crosslinked crosslinkable component can form and have maximum cross-linking density that coating reaches (just in the partial cross-linked coating, cross-linking density/maximum the cross-linking density of 100%x after partial cross-linked step) percent 25 to 75, the coating of cross-linking density as percent 50 to 75.It will be understood to those of skill in the art that crosslinked existence and degree of crosslinking, promptly cross-linking density can be determined by the whole bag of tricks, as the dynamic mechanical analysis (DMTA) that uses TA instrument DMA 2980 DMTA analysers to carry out under at nitrogen.These methods are measured the second-order transition temperature and the cross-linking density of the free film of coating or polymkeric substance.These physicalies of solidify material are relevant with the structure of cross-linked network.

In certain embodiments, partial cross-linkedly cure and finish by making coating composition be subjected to brief heat.In this type of embodiment, coating composition can comprise heat curable composition, as use isocyanate curing agent to that is to say those compositions that usually prepare as two package systems (" 2K "), wherein solidifying agent keeps separating with the polymkeric substance that contains reactive functional.When the elevated temperature curable in minimum, the curing of this based composition is usually quickened by making composition stand high temperature for example 180 to 450 (82 ℃ to 232 ℃), and temperature mainly depends on base materials employed type.For example, adopt some plastic basis material, as TPO, normally used substrate surface temperature is 180 °F to 265 °F (82 ℃ to 129 ℃).

As described, in some method of the present invention, use " brief " heat to cure.The term of Shi Yonging " heat is cured " is meant and comprises by convective heating herein, ir radiation, perhaps their combination heating that coated substrate is carried out.The term that here uses " brief heat is cured " is meant that the residence time (be coated substrate be exposed to be the time in the solidified high temperature) enough forms partial cross-linked coating, rather than fully crosslinked coating.In fact, surprising discovery of the present invention is the coating that only can produce scuff resistance and/or scratch resistant with partial cross-linked coating, the coating of this scuff resistance and/or scratch resistant is to use brief heat to cure production, wherein the residence time than produce time little at least 25% that complete crosslinked film requires or, sometimes little at least 50% or, under other situation little at least 75%.Here the term of Shi Yonging " fully crosslinked coating " is meant that the crosslinked amount of coating can provide and has maximum cross-linking density that coating reaches (just, cross-linking density/maximum the cross-linking density of 100%x after partial cross-linked step) greater than percent 75, the coating of cross-linking density as 90 at least percent.The so significant shortening of well-known cycling time can be lowered production cost significantly.

Can learn that as those skilled in the art the complete crosslinked needed residence time of coating of production is depended on some variablees, as used solidification value, and the wet-film thickness of the coating composition that applies.For example, the exterior plastic automotive parts of coating usually needs the longer residence time (for example, substrate surface temperature at least 180 °F (82 ℃) 20-25 minute down) produces crosslinked coating fully under lower solidification value.Yet in certain embodiments of the invention, partial cross-linked continue to the substrate surface temperature of at least 180 (82 ℃) by the heating coated substrate more than 10 minutes, at the most 6 minutes sometimes, finished as 2 to 6 minutes.Therefore, as mentioned previously, when utilizing method of the present invention, anti-scratch and/or needed time of scratch resistant coating can significantly shorten on the production base material.

In certain embodiments, method of the present invention comprises and allows the coating composition after fixing.Here to refer in the composition that crosslinkable component continues partial cross-linked finishing after crosslinked for the term of Shi Yonging " after fixing " meaning, up to obtaining complete crosslinked coating.In certain embodiments, allow the step of coating composition after fixing only need under envrionment conditions, allow coated substrate place.Here the term of Shi Yonging " envrionment conditions " is meant environmental stress (being barometric point) and envrionment temperature (promptly 68 ° to 79 (20 ° to 26 ℃)).

In certain embodiments, aforementioned coating composition comprises clear coating composition, its part as the multi-component composite coatings system is coated on the base material, and this multi-component composite coatings system comprises painted foundation composition and is coated in clear coating composition at least a portion bottom.In these embodiments, before using aforementioned coating composition, apply earlier and comprise film-forming resin and usually as the foundation composition of one or more pigment of tinting material.

The useful especially resin system that is used for this foundation composition is an acrylic polymers, polyester (comprising alcohol acids), and polyurethanes.The resin glue that is used for bottom can be organic solvent type material such as U.S. Patent No. 4,220, and 679 the 2nd hurdles the 24th row is to described those materials of the 4th hurdle the 40th row, and it is incorporated herein by refere.Similarly, water base paint compositions such as U.S. Patent No. 4,403,003, U.S. Patent No. 4,147,679 and those tackiness agents that can be used as foundation composition of describing of U.S. Patent No. 5,071,904 (introducing for referencial use herein) use.

Described foundation composition can contain the pigment as tinting material.Suitable metallic pigment comprise aluminum slice, the mica of copper or bronze strip and metal oxide-coated.Except that metallic pigment, foundation composition can contain and is generally used for top coat and comprises as titanium dioxide ferric oxide, chromic oxide, lead chromate, and sooty mineral dye; And as the nonmetal tinting pigment of the pigment dyestuff of phthalocyanine blue and phthalocyanine green.

Optional components in the foundation composition comprises what the preparation technical field of surface coating was well known, as tensio-active agent, and flowing regulator, thixotropic agent, filler, anti-gas producing agent, organic cosolvent, catalyzer, and other auxiliary agent commonly used.These examples of material and suitable consumption be in U.S. Patent No. 4,220, is described in 679,4,403,003,4,147,769 and 5,071,904, and it is introduced herein as a reference.

Described foundation composition can be by any conventional coating technique as brushing, and spraying flood or mobile being applied on the base material, but they usually applies by spraying.Can use aerial spraying commonly used in manual or the automated method, Airless spraying and Electrostatic Spray Technology and equipment.

When being coated to bottom on the base material, the film thickness of the bottom that forms on base material is generally 0.1 to 5 mil (2.54 to about 127 microns), perhaps 0.1 to 2 mil (about 2.54 to about 50.8 microns).

Behind the film that forms bottom on the base material, bottom can be cured or alternatively carry out drying step, wherein evicts out of solvent in the bottom film by heating or dry air before applying Clear coating.If composition is a water-based, suitable drying conditions depends on specific foundation composition, and ambient moisture, but usually, 75 ° to 200 (21 ° to 93 ℃) temperature be following time of drying 1 to 15 minute be enough.

The solid content of basic coating composition is usually 15 to 60wt%, and perhaps 20 in the 50wt% scope.

In another embodiment, after applying bottom (and solidify, if necessary), the multiwalled clear topcoat can be coated on the bottom.This is commonly called " transparent transparent on " uses.For example, above one or more layers conventional Clear coating can be applied on the bottom and one or more layers clear coating composition of the type that will describe in the past is coated to.In addition, one or more layers Clear coating can be used as in the middle of external coating (EC) be coated on the bottom, and with one or more layers Clear coating be coated in it above.

The result is, some method of the present invention comprises: (a) first coating composition is coated on the base material, (b) second coating composition is coated at least a portion first coating composition then, wherein second coating composition comprises film-forming resin, curing catalysts, and be dispersed in particle in the film-forming resin in a large number, (c) partial cross-linked in second coating composition crosslinkable component and then (d) allow the second coating composition after fixing.In the method for the invention, step (c) and (d) between, and step (d) is afterwards, second coating composition exists with the form of scuff resistance and/or scratch resistant coating.

Can be learnt that by above description the present invention relates to base material equally, comprises plastic basis material, as the TPO base material, they are coated with the coating of being produced by the inventive method to small part.

In addition, can also learn equally that the present invention relates to surface to small part equally and is coated with scuff resistance and/or the scratch resistant coating is the goods of partial cross-linked film by aforementioned.In certain embodiments, described goods comprise trolley part or element, as exterior automotive parts or element, and as collision bumper, dashboard, mirror outer cover, door handle, (vehicle body) wing plate boards, coating layer, spoiler, fuel tank cap or the like.

The following example is used for explaining the present invention, but can not limit the present invention.Except as otherwise noted, all umber and per-cent is all by weight in embodiment and the specification sheets.

Embodiment

Embodiment 1

Mix following component by stirring by the order of their appearance and prepare transparent film-forming composition:

¹The UV light absorber of Ciba Additives.

²At room temperature slowly with 225 parts of Dowanol

(from the methyl proxitol of Dow Chemical Company) joins 1482 parts from the chemical SNOWTEX of daily output

The 20% silicon oxide colloid aqueous solution.One temperature sensor is housed, in the suitable reactors of feed hopper and vacuum distillation plant with mixture heating up to 50 ℃.When mixture reached 50 ℃, the pressure of reactor was reduced to about 60 and distills to 100mmHg, simultaneously with all the other DOWANOL of 1442 parts

Slowly add in the reaction mixture.Remove 2162 parts overhead product, make that the solids content in the reactor is about 30%.Poly-(butyl acrylate) that in reaction mixture, adds 4.9 parts then.395 parts of tetrahydroxy functional silicones (putting down in writing in the US6387519 patent) mix with 296 parts of n-propyl alcohols, with about one hour time mixture are joined in the reactor then.Remove about 460 parts of solvents by vacuum distilling then.At last, in reactor, add 343 parts of Methyl amyl ketones and from reaction mixture, remove 343 parts of overhead products by vacuum distilling subsequently with about 15 minutes clock times.Cool off final reacting mixture a little, be poured into suitable containers then.The finished product are that the solid content measured is 58% and the muddy slightly solution of Gardner-Holt viscosity＜A.

³Acrylic acid or the like polyvalent alcohol: the methacrylic acid of vinylbenzene/1% of 2-EHA/20% of methacrylic acid 2-ethylhexyl/20.8% of 34.8% hydroxyethyl methylacrylate/23.4%---60% solid and Mw in n-butyl acetate and methyl ether propylene glycol acetic ester are about 6700.

⁴Polyester polyol: the 4-methylhexahydrophthalic anhydride of hexanodioic acid/31.8% of neopentyl glycol/18.5% of TriMethylolPropane(TMP)/8.3% of 23% 1,6 hexylene glycol/18.6%---80% solid and Mw in n-butyl acetate are about 5000.

⁵The hindered amine as light stabilizer of Ciba Additives.

⁶The dispersion of the R812 calcined silica (available from Degussa) in the acrylic acid or the like polyvalent alcohol (40% Propylene glycol monoacrylate/20% vinylbenzene/19% n-butyl acrylate/18.5% methacrylic acid n-butyl/2% vinylformic acid/0.5% methyl methacrylate and Mw are about 7000); Wherein dispersion contains 7.7% silicon-dioxide, 33.5% acrylic acid or the like polyvalent alcohol, 58.8% solvent.

⁷The flowing additive of BYK-Chemie.

⁸The flowing additive of BYK-Chemie.

⁹The polyisocyanates of Bayer.

Sample E is that (TKU2000 derives from PPG Industries, Inc) to commercially available two component polyurethane Clear coating.

Sample A and sample E are sprayed onto and obtain the dry film of thickness between 1.5 to 1.7 mils on Sequel 1440 TPO (TPO) thin plate (deriving from Custom Precision).The thin plate that described Clear coating applies was at room temperature placed 10 minutes before temperature is set in 250 the convection oven to bake and bank up with earth by table 1 specific time.After cool to room temperature, Clear coating is removed as the successive free film from the TPO thin plate and is used to measure Tg (second-order transition temperature) and cross-linking density.Provide the result of initial (on the same day) and after fixing (7 days) free film in the table 1.On free film, use 20 microns of amplitudes, frequency 1Hz, temperature cycle-50 is to 150 ℃, and the TA Instruments 2980 DMTA types that speed is 3 ℃/minute are measured Tg and cross-linking density (10 in the stretched film pattern ³Mole/cc), and sample is of a size of 15x6.5mm x film thickness.

[0050] in addition, MPP4100D (from PPG Industries, the commercially available adhesion promotor of Inc.) is sprayed onto Sequel 1440 thin plates and obtains the dry film that thickness is 0.2 to 0.4 mil.The tackify plate was placed under envrionment conditions after 10 minutes, PPG Industries, and the two-pack solvent-borne type black bottom (TKPS8555) of Inc. market supply is sprayed onto and obtains the dry film that thickness is 0.9 to 1.1 mil on the plate that scribbles MPP4100D.After the bottom plate was placed 4 minutes under envrionment conditions, sample A-E was applied to and obtains the dry film that thickness is the 1.5-2.0 mil on the bottom plate.The plate that Clear coating applies is after envrionment temperature is placed 10 minutes, and this plate cured in 250 convection oven 10 minutes.Make test board do aforesaid scuff resistance test then.Mar resistance results sees Table 1 and 2.

Table 1

Table 2

	Inorganic particle	Catalyzer	Coating is baked and banked up with earth	Original gloss	Initial scratch gloss retention	13 days after fixing scratch gloss retentions
							Sample A	Have	Have	10’/250°F	87	82	70
Sample B	Have	Do not have	10’/250°F	87	75	61
							Sample C	Do not have	Do not have	10’/250°F	88	56	22
Sample D	Do not have	Have	10’/250°F	86	27	26

In table 1, notice that 250 °F were only cured after 10 minutes, sample A of the present invention all has excellent scuff resistance at initial and 7 days after fixing; Even by showing it not near completely solidified with the measurement of aging Tg that compares of after fixing and cross-linking density at first, it shows excellent scuff resistance at first.By comparison, 250 °F cure 40 minutes after, commercially available sample E has even worse significantly initial sum after fixing scuff resistance, even it is by at first showing that with the measurement of aging Tg that compares of after fixing and cross-linking density it almost completely solidifies.

In table 2, notice that 250 °F down short were cured 10 minutes, sample A (containing inorganic particle and catalyzer) is initial and all had excellent scuff resistance in 7 days behind the after fixing; Sample B (contain particle, do not contain catalyzer) has good scuff resistance, but poorer slightly than the sample A that contains inorganic particle and catalyzer.Sample C (not comprising particle and catalyzer) has even worse initial sum after fixing scuff resistance than sample A and sample B.Sample D (contain catalyzer, do not contain particle) compares with sample A has even worse significantly initial sum after fixing scuff resistance.

Those skilled in the art learn easily on the basis that does not break away from above-mentioned conception can carry out modification to the present invention.Get rid of some claim unless they specialize, described modification is believed to comprise in following claim.Therefore, the specific embodiment of Xiang Ximiaoshuing only is to be used for illustrating the present invention herein, can not limit the scope of the invention, and scope of the present invention is claim and any and complete width all coordinators thereof.

Claims (19)

1, a kind of time method that shortens the coating requirement that on base material, produces scuff resistance and/or scratch resistant, this method comprises:

(a) coating composition is coated on the base material, then

(b) make crosslinkable component in the described composition partial cross-linked and then

(c) allow described coating composition after fixing,

Wherein, step (b) and (c) between, and in step (c) afterwards, on base material, have the coating of scuff resistance and/or scratch resistant.

2, method according to claim 1, wherein said base material comprises plastic basis material.

3, method according to claim 2, wherein said plastic basis material comprises TPO.

4, method according to claim 1, wherein said coating composition comprises film-forming resin, curing catalysts, and be dispersed in a large amount of particles in the described film-forming resin.

5, method according to claim 4, wherein said film-forming resin comprises the polymkeric substance that (i) contains reactive functional, and (ii) has the respond solidifying agent of active functional group of reactive functional to polymkeric substance.

6, method according to claim 5, the wherein said polymkeric substance that contains reactive functional comprises the acrylic copolymer of hydroxyl and/or the polyester polymers of hydroxyl.

7, method according to claim 4, wherein said particle is by being selected from polymeric and non-polymeric inorganic materials, polymeric and non-polymeric organic materials, matrix material, and the formation of the material of their mixture.

8, method according to claim 4, wherein said particle makes the surface tension that its surface tension is lower than does not have particulate film-forming resin through chemical modification.

9, method according to claim 8, wherein said particle have the structure of F-L-Z by connection compound carries out modification, and wherein F is the structure division that contains functional group; Z reduces the capillary structure division of particulate that it connected; And L is the group that connects F and Z.

10, method according to claim 4 wherein when described composition exists with partial cross-linked coating form, is present in the enough production scuff resistances of particulate amount in the coating composition and/or the coating of scratch resistant.

11, method according to claim 10, the total weight of solids of coating based composition wherein, the particulate amount that is present in the coating composition is 0.01 to 20wt%.

12, method according to claim 6, the step of crosslinkable component is cured and is finished by making coating composition be subjected to brief heat in the wherein partial cross-linked described composition.

13, method according to claim 12, the residence time that wherein said brief heat is baked and banked up with earth is at least than producing the residence time short 25% that complete cross-linked coating requires.

14, method according to claim 13, wherein said brief heat are baked and banked up with earth and are comprised that coated substrate is heated at least 180 substrate surface temperature continues to be no more than 10 minutes.

15, method according to claim 14, wherein said brief heat are baked and banked up with earth and are comprised that coated substrate is heated at least 180 substrate surface temperature continues 2-6 minute.

16, method according to claim 1 wherein makes the step of coating composition after fixing be included in the base material of placing coating under the envrionment conditions.

17, be coated with the base material of the coating of the described method preparation of claim 1 to small part.

18, a kind of time method that shortens the coating requirement that on base material, produces scuff resistance and/or scratch resistant, this method comprises:

(a) coating composition is coated on the base material, wherein said coating composition comprises film-forming resin, curing catalysts and be dispersed in a large amount of particles in the described film-forming resin, then

(b) make crosslinkable component in the described composition partial cross-linked and then

(c) allow described coating composition after fixing,

Wherein, step (b) and (c) between, and in step (c) afterwards, on base material, have the coating of scuff resistance and/or scratch resistant.

19, a kind of surface to small part is coated with the goods that the coating of scuff resistance and/or scratch resistant is partial cross-linked film.