CN101168631A - Film-forming binders containing nanoscale particles and featuring enhanced scratch resistance and flexibility, processes for their preparation, and high-transparency coating materials containing them - Google Patents

Abstract

Film-forming binder comprising a matrix based on one polymer or on a plurality of polymers and, on the basis of 100% by weight of the total binder, a stabilized suspension of nanoscale particles, in an amount of 0.5% to 25% by weight, measured as the solids fraction of the suspension, the binder being distinguished by the fact that the suspension of the particles is obtainable by a) grinding the particles with addition of a solvent in a high-pressure mill which under a pressure in the range from > 500 - approximately 10000 bar breaks down agglomerates and/or aggregates of the particles into nanoscale fragments; and b) adding one or more dispersing additives to stabilize the surface of the ground particles, the dispersing additive(s) being present in an amount of 1 to 25 parts by weight, based on 100 parts by weight of the particles. Process for preparing the film-forming binder and its use in coating materials. Coating materials containing the binder produce transparent coatings with high scratch resistance and flexibility.

Description

Contain nano-scale particle and tool more high scratch resistance and flexible lacquer binding agent, its preparation method and contain its high clear lacquer

Technical field

The present invention relates to contain nano-scale particle and tool more high scratch resistance and flexible lacquer binding agent, its preparation method and contain its high clear lacquer.

Background technology

The polyester lacquer that for example is used for the metallizing bar is characterised in that the scratch resistance with very high snappiness and appropriateness.Snappiness can be checked by the T-pliability test especially, wherein will will bend 180 ° through the bar that applies.The web that applies with the polyester of cured with isocyanates lacquer can pass through this test, its doped envelope and crack-free or layering.In production practice, more and more need the coating of more scratch resistance, but requiring it can or not be very little being weakened in flexibility.Can improve degree of crosslinking for improving scratch resistance, and this can obviously reduce snappiness.Fill in the japanning and can successfully improve scratch resistance equally, but this measure depends on that for varnish the difference of filler granularity can cause painted surface muddiness, delustering and/or become coarse with granulated filler.Be coated with in the paint formula and introduce particle and also can be accompanied by the loss that coating ductility occurs, and for example can show as and stretching or be subjected to the tensile position loss of gloss phenomenon or delustering effect can occur during crooked base material through applying.

Open among the EP1204701B1, contain a large amount of particles and wherein the concentration of particle in the coatingsurface zone greater than the curing of internal volume concentration after coating, compare to unmodified coating and be more scratch resistance.Use the organosol that contains single dispersed silicon stone granulate as nano particle.This class painted is characterised in that special binding agent and solidifying agent of can the induced nano particle moving on the painted surface.This patentee has confirmed the migration situation of particle to the phase interface place of surface between japanning and air by transmission electron microscope photo (TEM photo), and ascribes the improvement through testing the scratch resistance that confirms the enrichment of nano particle in the surface to.Also put down in writing a kind of embodiment in this patent documentation, wherein, on enrichment particulate layer, still existed a very thin no granule agglomerant layer.That can use surface modification here also can use undressed particle (the 6th page, 0047 section).If but use undressed particle, then japanning must contain polysiloxane compound, and its energy and nano particle play the effect that improves scratch resistance together.If do not use siloxanes, then particle is understood agglomeration and is not had ideal effect (the 33rd page, 11 row).

In order to lure nanoparticle enrichment on painted surface, then to use the prescription that contains siloxanes, it helps binding agent and nano particle takes off mixed.Use organosol as nano particle, itself and polysiloxane be combined to play the effect that improves scratch resistance.The required amount of stablizing dispersed nano particulate siloxanes is higher relatively.In embodiment 2A, for the SiO of 6.7 weight parts ₂The polysiloxane (with the value of solid calculating) that needs 10.3 weight parts.In embodiment 1C for the SiO of 6.7 weight parts ₂Even the polysiloxane of needs 15.3 weight parts.According to the method for costliness,, can make organosol by silicon sol via sol-gel process or about exchange of solvent and surface modification.The cost of organosol and polysiloxane is very high and has limited use range for big industrial production to paint into original measuring and calculating.

Bauer, the Macromol.Mater.Eng.2002 of Mehnert etc., 287, disclose among the 546-552, come the modified inorganic nano particle and can use it in the highly cross-linked japanning of radiation-hardenable with silane to improve scratch resistance.The nano particle of modification is can be better compatible with japanning and also can be coupled to be coated with by active group and paint.If use four functional linking agents then can obtain better attrition value.Utilize gentle monofunctional reactant thinner, effect then only just can be improved under high compactedness.

Abrasion-resistant coatings based on surface-modified nano particles and blocked isocyanate has been described among the DE10326538.Coating has remarkable wear resistance under high filler content.Properties-correcting agent as nano particle can use the silane that contains the proton group, perhaps the precursor of this silane.

Put down in writing the coating procedure in a kind of two steps among the DE19920801, it will pass through the light and heat chemosetting.Coating contains monodispersed Highlink OG 103-31 type nano particle.After to be partly solidified do not contain the particulate the first layer, apply second and contain the particulate layer and then solidify once more.In certain scheme, use pyrogenic silica (aerosil) to replace monodispersed particle.But wherein do not describe the aerosil that has used which kind of type in detail.

Described a kind of coating that contains nano particle and have carbaminate official energy earth silicon material among the US5853809, and it is to obtain by colloid silica and the carbaminate functional silane reaction that had before made.This type coating contain very high amount of filler and in the scraping experiment that carries out with Crockmeter its show than unfilled japanning or wherein silica filler not with the japanning loss of gloss percentage still less of coupling agent reaction.

Described among the US6916368 to contain to be essentially the unmodified basically particle of spheric and after the Crockmeter test, to have better gloss and kept the percentile japanning that contains pure aluminium silicate.Contain the japanning of 5 or 40% Nano filling because the difference of specific refractory power is arranged under the state without scraping, thereby than more muddy without the japanning of filling.

Put down in writing the nanocrystal particulate abrasive coating that contains surface modification among the WO0245129 (nanophase), it is the deposition by one or more polysiloxane, preferably makes by deposition star polymer on the particle surface.Obtain thus attrition resistantly filming or having filming of higher pencil hardness, they have better transparency with respect to containing filming of microparticle.

Put down in writing the composition that contains microparticle and nano particle among the WO03040223 (nanophase).There is not non-linear effect in it, but does not have the film of clear owing to contain microparticle.

Put down in writing the nonaqueous dispersion that contains nano particle among the WO03084871 (nanophase), wherein used have repeating unit and such as the polymerization dispersing additive of the anchoring group of Polyvinylpyrolidone (PVP) in order to play a stabilization.

Put down in writing the water dispersion of the long-term stability that contains metal oxide nanoparticles among the WO0400916A2 (nanophase), wherein used the water-soluble polymeric dispersing additive that contains close pigment and water soluble group.Also can use annular phosphate in some cases.

WO2005119359 (nanophase) has put down in writing the scratch resistance article of the coating with substantial transparent, has wherein used the dispersion (the 2nd section of page 5) of the not agglomerant nanocrystal primary particles of great majority, polymeric dispersant and surface active material.A theme of described document is that more a small amount of nano assistant of high scratch resistance is moved on the phase interface and determined thus to be used to obtain to nano particle.Basically nano particle spherical in shape has non-pore structure.Stable and the transporting action of nano particle mainly is subjected to the control that used molecular weight surpasses 1000 the character of polymerization dispersing additive own.

Put down in writing a kind of injection method of pulverizing nano level primary particle agglomerate and aggregate among the EP-A-0766997, made two strands of pressure in a plurality of passages, collide and in this process, grind the particle that is scattered in the liquid each other in this method up to the liquid flow of 200bar.

EP943664B1 has put down in writing a kind of preparation scratch resistance painted method, has wherein used the agglomerate of the nano-scale particle that ground through gunite.This subject matter of an invention is the transparent lacquer binding that is coated with that contains nano particle, and it contains with respect to the japanning solid counts the elementary nanoparticle that 0.5 to 25 weight % sneaks into as solid, and described particle is to make by the nanometer particle in the jet spread binding agent.(EP943664B1，0016)。Disclose in the document and also can use the particle of surface modification valuably or for example after depolymerization, carry out surface modification.Preferred use pyrogenic silica and especially preferably use through those kinds surface modification, that have hydrophobic surface.Particularly preferred resin is polyester polyol especially.End capped polymeric polyisocyanate also can be considered as solidifying agent.Described composition can allow to have better scratch resistance simultaneously in reservation transparency and glossy.The theme of EP943664B1 is that also a kind of preparation contains the transparent method that is coated with lacquer binding of nano particle, it is characterized in that, guiding to make by nano particle and be coated with the preparation that lacquer binding forms and at least one passage, passing a device, and wherein also describing size range and structure arrange (referring to 0034 in the above-mentioned quoted passage) with at least one nozzle or slit.When implementing this method, adopt 5 to 50MPa, preferred 7 to 30MPa pressure.But this does not reach significantly " the broken and grinding effect of structure " that only just can occur under obviously higher grinding pressure.In EP943664B1, preferred especially with oligomeric or high poly-organic compound, for example resin and binding agent commonly used adds in the dispersion agent as other materials in japanning and paint-on technique.Can improve the viscosity of preparation by adding resin and binding agent, limit the maximum of nano-scale particle thus and can operate concentration.In preferred scheme, in dissolver, pulverous elementary nanometer particle is blended into solvent cut in the polyhydroxy reactant that is lower than 2000mPas and carry out the de-agglomerate effect.Just mentioned the pyrogenic silica that makes by flame pyrolysis in an embodiment as nano-scale particle.Silicon-dioxide has low refractive index, and itself and the common refractive index that is coated with coating resins are more or less the same.Therefore for silicon-dioxide, the existence of a certain amount of non-nano level composition, its effect does not resemble for remarkable the metal oxide of high refractive index.

Under the condition described in the EP943664 de-agglomerate can only take place, and grinding does not take place.The aggregate of nano-scale particle can not decompose under the pressure that is not higher than 50MPa.Can not grind the accumulative metal oxide particle with described method.

Although record the method that many preparations are used for the scratch resistance coating of different substrate materials, but need a kind of scratch resistance, wear-resisting and transparent coating, and require it to have only the prescription of limited scratch resistance not have significant performance degradation with respect to non-modified.

For the most effectively, based on such as the scratch resistance additive that mainly is the high refractive index metal oxide of aluminum oxide, especially the painted mist degree is too high for the application in the varnish of clear.Can not realize having the japanning of the clear of very little haze value even use a spot of nanocrystal primary particle (WO2005119359).

Other height through nano particle and low-refraction pigment such as organic silicon sol concentrates and the defective of the approach of acquisition scratch resistance coating is that the snappiness of comparing plated film with the material of non-modified has tangible loss.This to adhere to, the serious effects of jamming of coating and long-term storage performance is very crucial and still must further study once more.

Therefore, for production practice, need a kind of scratch resistance japanning system that has fully or keep most important japanning performance at least to a great extent.Required improve effect and should in a very wide work range, embody and can in a simple japanning system, realize.In 2 components and 1 component PU japanning system, be unfavorable for stable nanoparticles uses a large amount of siloxanes, because s known as technical staff, siloxanes can cause adhesion problem and may cause liquid painted unstable and take off mixed when high addition very.The cost that another very important factor is the japanning system for production practice.

Task of the present invention be to provide a kind of be used to the system of painting with the nano-scale particle modification be coated with lacquer binding and a kind of with the nano-scale particle modification japanning and be used for the Ginding process of nano inorganic particles agglomerate, described method is from cheap raw material and reproducibly implement with industrial scale.Because siloxanes and nano-scale particle, for example organosol is significant cost factor, so they should seldom promptly can bring enough effects or the more cheap system of quilt to replace under the amount.

Hitherto known, the Ginding process that for example prepares nano-scale particle by agitating ball mill, even under the situation that adopts the little mill ball of hard that for example constitutes, also can cause very important wearing and tearing material by cerium oxide or zirconium white, the clarity of the coating that makes thus and transparency can not be removed and can destroy to this wearing and tearing material (referring to J.Winkler from abrasive material, Farbe+Lack, 2/2006).

Dispersing method described in EP766997 and the EP943664B1 is to work to the pressure of possible 500bar at the 230bar that can not realize grinding.Hydrofluidic is not adapted at working under the elevated pressures at the equipment described in the EP766997, because can destroy opposite nozzles after than the short operation time with described grinding chamber size and described nozzle arrangements.

Also put down in writing scratch resistance coating in this patent documentation with high-content mono-dispersed nano filler.Have to the gathering filler of small part micron order size if use, though then can realize the raising of hardness, transparency and especially clarity can descend consumingly owing to scattering of light.By nano level and micron order raw material combination and the system that constitutes even be not largely, but also can be lost its transparency and clarity.

Now be surprised to find, aforesaid problem can be solved aspect the lacquer binding being coated with, described binding agent contain based on the matrix of one or more polymkeric substance and in 100 all binding agents of weight % and be the stabilized suspension of the nano-scale particle of 0.5 to 25 weight % with the amount that the solids component of suspension records, and it is characterized in that particulate suspension obtains by the following method:

A) add solvent and abrasive grains in the high pressure shredder, this shredder is ground into nano level fragment with particulate agglomerate and/or aggregate in greater than the pressure range of the about 10000bar of 500-; And b) add one or more dispersing additives with the particulate surface of stabilization through grinding, dispersing additive wherein is that the amount of 1 to 25 weight part exists with the particle with respect to 100 weight parts.

Summary of the invention

The lacquer binding that is coated with of the present invention can be mixed with japanning or japanning system with traditional method.Now be surprised to find, use of the present invention be coated with lacquer binding prepare obtain and can satisfy requirement by the japanning that following one-tenth is grouped into to Clear coating with better scratch resistance and/or better wear resistance:

A) resin system,

B) curative systems,

C) filler systems,

Solvent when d) needing and

Other additives commonly used in japanning and coating when e) needing,

Wherein at least composition a) and c) derive from and be coated with lacquer binding, condition is that described composition is selected from the product system of the following stated and utilizes the high pressure polishing mineral filler to be made the form of nano-scale particle.The mode of being put down in writing among the DE10204470C1 (US6991190) " preparation method of dispersion liquid " of suitable high pressure polishing according to the DE10360766 on December 23rd, 2003 " method and apparatus of preparation dispersion liquid " or on February 5th, 2002 is carried out.

The singularity that is coated with lacquer binding/japanning system of the present invention is to have used the nano-scale particle that obtains with special methods, and the suitable form of suspension with stabilization of described nano-scale particle uses.Term " nano-scale particle " refers to its particle diameter and determines at 1.0 those particles to about 500nm nanometer range as the primary particle aggregate form.The particle diameter of so-called primary particle aggregate refers to the mean particle size d50 that utilizes Horiba LA 920 particle size analyzers to record.Nano-scale particle aggregate (primary particle aggregate) can not be assembled in japanning system of the present invention becomes bigger tissue (agglomeration/formation aggregate).

In category of the present invention, being coated with lacquer binding is particularly important, wherein is present in the mean particle size d50 that nano-scale particle in the stabilized suspension has utilization 0.05 to the 10 μ m that scattering of light records according to Michaelis (Mie).Particularly preferred those are coated with lacquer binding and are characterised in that, nano-scale particle has the d50 value in 0.05 to 0.5 μ m, preferred 0.1 to 0.5 mu m range.As mentioned above, distinguish the granularity of the granularity of the primary particle in stabilized suspension/dispersion, the granularity of primary particle aggregate (" nano level ") and particle aggregate.

The particular embodiment that the present invention is coated with lacquer binding is characterised in that, nano level particle is being made up of less than 3 primary particle between 5 to 30nm and by the irregular fragment degree (Fraktalit  t) that the N2-absorption method records in p/p0 is 0.5 to 0.8 pressure range globular and particle diameter.

Particle with afore-mentioned characteristics can be selected from the material substance of a whole series.The important lacquer binding that is coated with has nano level particle, and this particle is selected from the group of being made up of with the mixture of metal carbonization and semi metallic compound and above-mentioned two or more materials oxidation, nitrogenize.The wherein particularly preferred nano-scale particle that is coated with in the lacquer binding is selected from by Alpha-alumina, gama-alumina, δ-aluminum oxide, θ-aluminum oxide, zirconium dioxide, the zirconium dioxide of doped with yttrium, titanium dioxide, rutile, anatase octahedrite, brookite, silicon-dioxide, weisspiessglanz, zinc oxide, cerium dioxide, ferric oxide, palladium dioxide, tin indium oxide, antimony tin, the spinel type compound, aluminate, hercynite, picotite, ulvospinel, cobalt spinel, ceramic particle, boron nitride, norbide, silicon carbide, silicon nitride, the mixing cpd of above-mentioned these elements and mixed oxide and contain one group that the mixture of above-mentioned two or more materials is formed.

Crucial especially for being used for particle that the present invention is coated with lacquer binding is its surface.Therefore, the suitable embodiment that the present invention is coated with lacquer binding is characterised in that, the surface that makes nano-scale particle cooperates to come modification by rear oxidation effect, absorption, surface reaction or with inorganic and/or organic reaction reagent.Just can in the japanning of making, obtain wonderful positive performance thus.

In the particularly preferred therein modification that is coated with lacquer binding, the surface of nano particle is by the functional group modification of two or more types that have nothing in common with each other.It is stable particulate suspension to be obtained thus.

Add the suspension of dispersing additive in the lacquer binding to of the present invention being coated with stabilization nano level primary particle aggregate.Can consider that to this a series of additive is arranged.Particularly preferred the present invention is coated with lacquer binding and is characterised in that, the dispersing additive that is added is selected from one group that is made up of following, promptly

A) alkyltrialkoxysilaneand of general formula R-Si-O-R ' 3, R wherein can be aliphatic series or mixed aliphatic series/aromatic group and can contain and be selected from N, O, S, the heteroatoms of the main chain capable of blocking of Cl; And wherein R ' is an aliphatic group;

B) hexamethyldisilazane and its derivative;

C) have by [SiR ₂-O]-the silicon resin base compound of unit and the end group different and [SiRR '-O]-main chain that the unit constitutes with it, R ' expression wherein grafts on the aliphatic group on the main chain;

D) have functional group's Lustrex or multipolymer or oligopolymer, described functional group is selected from by Cl, wherein R=H, the aryl with optional other functional groups or the CO of alkyl ₂R; OH, NH ₂, wherein R can be hydrogen, can contain the NR of other heteroatomic fat bases and/or aryl ₂Wherein R can be hydrogen, can contain the C=ONR of other heteroatomic fat bases and/or aryl ₂Form one group;

E) contain the segmented copolymer of polar protic or aprotic, polar functional group at least one block;

F) polycondensate is as polyester and polymeric amide;

G) general formula R-(CH ₂-CH ₂-X) _nThe compound of-R ', the wherein aliphatic series that randomly replaced by the functional group of R and R ' expression and/or the group of aromatics, X are represented O, the NR of R=H, alkyl wherein;

H) hyperbranched oligomer or polymkeric substance, as have grafting on it polyethers and/or the poly-imines of polyester side chains, hyperbranched Polyglycerine;

I) star polymer;

J) has on it and the compound that be selected from the side chain of polyethers, polyester of polymine main chain and grafting;

K) phosphorated oligopolymer, for example tego dispers 655;

With comprise at least a compound a) to k) and mixture.

The particular composition of particulate material and dispersing additive also can constitute the specially suitable lacquer binding that is coated with.The particular embodiment that the present invention is coated with lacquer binding comprises as the aluminum oxide of nano particle with as the phosphorous oligopolymer of dispersing additive.Wherein, as the preferred especially tego dispers 655 of phosphorous oligopolymer.

Except the grinding step that in the high pressure shredder, carries out can also before connect/after connect other treatment step.Therefore, a kind of special lacquer binding that is coated with of the present invention is characterised in that, by in the rotor stator operational outfit that particle is pre-dispersed in liquid phase before the grinding steps in high-energy mills, can obtain particulate suspension.This will cause further unexpectedly improving the effect of stability of suspension.

Grinding step also can be assisted by other measures and be carried out.Key is to add solvent.The suitable scheme variant that the present invention is coated with lacquer binding is characterised in that, is selected from by aliphatic series and alicyclic compound, aromatics and replacement aromatic substance for grinding the solvent that adds, the mixture of the oil in can be used for painting and gasolene ingredient, ester, lactone, ether, glycol ether, ketone, alcohol, two or more above-claimed cpds and contain a group that the mixture of the compound of at least a above-mentioned substance is formed.

For the lacquer binding that is coated with of the present invention, the solvent combination that makes solvent include different boiling and/or evaporation number and/or opposed polarity also is very useful.Some special embodiments is characterized in that used solvent compositions comprises Solvesso 150/ butyleneglycol and/or Solvesso 150/ acetic acid methoxyl group propyl ester and/or Solvesso 150/ divalent ester mixture DBE and/or contains dimethylbenzene or the solvent compositions of N-BUTYL ACETATE.

Consider from the resin aspect that plays the matrix effect, exist some other scheme possibility for japanning binder liquid of the present invention.These suitable schemes are characterised in that, matrix be selected from by have can with the organic oligomer of the free hydroxyl group of solidifying agent reaction, organic polymer with the free hydroxyl group that is suitable for curing reaction, the composition of above-mentioned oligopolymer and polymkeric substance and containing have one group that can form with the oligopolymer of the free hydroxyl group of solidifying agent reaction and/or mixture of polymers.

In addition, the feature that preferably is coated with lacquer binding is that matrix comprises any mixture of polyacrylate resin, vibrin, polycaprolactone resin, polyether resin, polycarbonate resin, polyurethane polyol resin, above-mentioned substance or comprises the mixture of at least a aforementioned polymer.Wherein, specially suitable is that wherein matrix comprises the lacquer binding that is coated with of vibrin and/or polyacrylate resin.

The lacquer binding that is coated with of the present invention has high-clarity and can realize high transparent plated film.Preferably be coated with lacquer binding and have high-clarity, be preferably greater than 85% transmissivity especially, more be preferably greater than 88% greater than 70% transmissivity.

The present invention also relates to the method that a kind of preparation is coated with lacquer binding, in the method,

I) provide matrix based on one or more polymkeric substance;

Ii) the matrix that is provided is mixed mutually with the stabilized suspension of nano particle; With

Iii) randomly in mixture ii), add other conventional additives;

Wherein, sneaking into suspension solid content meter consumption based on total binding agent of 100 weight % is the nano particle of 0.5 to 25 weight %;

And described method is characterised in that particulate suspension obtains by as described below:

A) use solvent to come abrasive grains in the high pressure shredder, described shredder is ground into the nano level fragment with particle agglomeration body and/or aggregate under greater than the pressure range of the about 10000bar of 500-; With

B) add one or more dispersing additives with the surface of stabilization through abrasive grains, the amount of wherein said dispersing additive is particle 1 to 25 weight part in 100 weight parts.

Of the present invention be coated with that lacquer binding and the method according to this invention obtain be coated with lacquer binding can be extremely aptly with aliphatic polymeric isocyanate and be used for two component varnish.Another advantageous applications that is coated with lacquer binding is combined with the solidifying agent of energy and hydroxyl reaction, in order to preparation plated film and coating.Wherein preferred especially and solidifying agent is used in combination, and described solidifying agent is selected from by the mixture of polymeric polyisocyanate, the polymeric polyisocyanate of sheltering, isocyanate prepolymer, melamine, silane, the compound that contains silyl, one or more aforesaid compounds and contains one group of material that the mixture of at least a aforesaid compound is formed.

Belong to the foregoing japanning that is coated with lacquer binding that contains in addition of the present invention.Belong to equally of the present invention contain in addition by contain aforementioned be coated with lacquer binding through solidifying the coated product of the plated film that japanning constitutes.

Embodiment

Following description according to each composition/method steps more at large sets forth the present invention:

Japanning of the present invention is composed as follows:

A) the oligomeric or high poly-resin or the mixture of oligomeric and/or high poly-resin, this resin can contain and can be used for painting the solidified functional group,

B) curative systems, itself can contain oligomeric composition,

C) filler systems, it is made up of nanoparticle fillers or the mixture that is essentially nano level granular filler basically, wherein said filler is selected from inorganic amorphous or crystalline material or organically-modified from the teeth outwards inorganic materials, and described filler or filler mixture grind in solvent and use the high pressure shredder to grind, described shredder can be under high pressure be ground into nano level fragment with the agglomerate and/or the aggregate of filler very much, and by adopting silane and/or P contained compound; Silane and/or oligomeric dispersing additive; Perhaps thereby the composition of P contained compound and oligomeric dispersing additive comes inhibition particulate in stable particle surface to reassociate or reagglomeration,

D) randomly solvent or solvent compositions and

E) other be usually used in painting and coating in additive, it is selected from flow promotor, wetting agent, dispersion agent, antioxidant, curing catalysts, siccative, reaction diluent, pigment, separant, slip additive, adhesion promoter, silane, phosphorus compound, phosphonate ester.

The feature of japanning system of the present invention is that also the silane, phosphorus compound or the oligomeric dispersing additive that are used for the surface stabilization processing are selected from as next group material:

A) alkyltrialkoxysilaneand of general formula R-Si-O-R ' 3, R wherein can be aliphatic series or mixed aliphatic series/aromatic group and can contain and be selected from N, O, S, the heteroatoms of Cl and main chain capable of blocking; And wherein R ' is an aliphatic group;

B) hexamethyldisilazane;

C) have by [SiR ₂-O]-the silicon resin base dispersing additive of unit and the end group different and [SiRR '-O]-main chain that the unit constitutes with it, R ' expression wherein grafts on the aliphatic group on the main chain;

D) have functional group's Lustrex or multipolymer or oligopolymer, described functional group is selected from by Cl, wherein R=H, the aryl with optional other functional groups or the CO of alkyl ₂R; OH, NH ₂, wherein R can be hydrogen, can contain the NR of other heteroatomic fat bases and/or aryl ₂Wherein R can be hydrogen, can contain the C=ONR of other heteroatomic fat bases and/or aryl ₂Form one group;

E) contain the segmented copolymer of polar protic or aprotic, polar functional group at least one block;

F) polycondensate is as polyester and polymeric amide;

G) general formula R-(CH ₂-CH ₂-X) _nThe compound of-R ', and the wherein aliphatic series that randomly replaced by the functional group of R and R ' expression and/or the group of aromatics, X are represented O, R=H wherein, the NR of alkyl;

H) hyperbranched oligomer or polymkeric substance;

I) star polymer;

J) has thereon and the compound that be selected from the side chain of polyethers, polyester of polymine main chain and grafting;

K) phosphorated oligopolymer, for example tego dispers 655.

Very crucial for the present invention is to grind nano level filler under extremely high pressure, thereby makes in conventional dispersion process can the ground grains aggregate can be not its component by pulverizing.

The explanation of grinding system of the present invention:

Experiment showed, in specially suitable method, at first import less than 1000kJ/m ³Energy disperse to form simultaneously predispersion (for example dissolver or rotor-stator-device), predispersion is assigned as at least two bursts of tributaries, these tributaries are inserted in the high-energy mills of pressure for 500bar at least, discharged and make it in the reaction compartment of aerification or liquid, to collide mutually and randomly repeat this high energy milling process one or many via nozzle.

Owing in dispersion soln, exists and is selected from a) to j) the suitable surfactant of group, therefore can stablize the surperficial of generation newly and stop particulate to reassociate or reagglomeration.

The explanation of japanning system:

The japanning system is grouped into by following one-tenth:

Resin or resin compound

Solvent or solvent mixture

Solidifying agent or curing agent mixture

Additive

Nanoparticle fillers, and

Composition during other are usually used in painting

Below each composition of explanation japanning system is to set forth the present invention:

Resin of the present invention be have can with the organic polymer of the free hydroxyl group of solidifying agent reaction; For example vibrin and polyacrylic ester.

But saturated polyester resin is in most cases by making the derivative of saturated polycarboxylic acid such as dicarboxylic acid or their acid anhydrides or other esterifications, with polyvalent alcohol such as glycol or triol condensation and make.Their character depends on the kind and the usage ratio of raw material to a great extent.

Be used to prepare the acid of polyester or the suitable example of acid derivative is phthalic acid, m-phthalic acid, terephthalic acid, 1,4-cyclohexane dicarboxylic acid, succsinic acid, sebacic acid, methyl tetrahydrophthalic acid, methylhexahydrophthaacid acid, pyromellitic acid, dimer (fatty acid) yl and/or trihemellitic acid, their acid anhydrides and/or lower alkyl esters such as methyl esters.

The example of suitable polyvalent alcohol is: ethylene glycol, 1, the 2-propylene glycol, 1, ammediol, glycol ether, dipropylene glycol, triglycol, Tetraglycol 99,1, the 4-butyleneglycol, 1,3-butyl ethyl propylene glycol, the 2-methyl isophthalic acid, ammediol, 1, the 5-pentanediol, cyclohexanedimethanol, glycerine, 1, the 6-hexylene glycol, neopentyl glycol, trimethylolethane, TriMethylolPropane(TMP), 1,2,6-trihydroxy-six erythritols, trihydroxy-ethyl chlorinated isocyanurates, tetramethylolmethane, sorbyl alcohol, N.F,USP MANNITOL, Xylitol, 1,4-benzyl dimethanol, 1,4-benzyl di-alcohol, 2,4-dimethyl-2-ethyl hexane-1,3-glycol, Dicidol.

Polyester of the present invention can according to known method (referring to Dr.P.Oldring, Resins forSurface Coatings, III volume, the Sita Technology of publisher, 203 Gardiness House, Bromhill Road, London SW 184JQ, Britain 1987) make by condensation.

Saturated polyester of the present invention can have the acid number of 0 to 10mg KOH/g, and preferred 0 to 5mgKOH/g and preferred especially 0 to 3mg KOH/g; Hydroxyl value with 3 to 80mg KOH/g, preferred 10 to 50mg KOH/g and preferred especially 15 to 30mg KOH/g.

The number-average molecular weight Mn of the polyester of straight or branched, preferred straight chain or slight side chain is between 2000 to 20000; Second-order transition temperature (Tg) between-20 ℃ to+60 ℃, preferred-10 ℃ to+40 ℃.

Curative systems

As curing agent component, can adopt can with the compound of hydroxyl reaction.Suitable compound is a polymeric polyisocyanate, polymeric polyisocyanate, isocyanate prepolymer, melamine, the silane of sheltering and the compound that contains silyl, other are under room temperature or higher temperature and choose wantonly in that catalyzer is auxiliary and can and produce chainpropagation or crosslinked compound with hydroxyl reaction down.

Suitable compound for example is documented in: Bodo M ü ller/Ulrich Poth:Lackformulierung und Lackrezeptur, Vincentz-press Hanover 2003 is in part ii the 2nd chapter: Einbrennlacke and the document wherein quoted.

The explanation of filler systems:

Filler systems is made up of nano level granular filler or the mixture that is essentially nano level granular filler basically, the filler that wherein is selected from inorganic amorphous or crystalline material or organically-modified from the teeth outwards inorganic materials is the key component of japanning of the present invention and coating, and can be by careful dispersion and/or grinding and combined and provide with nano shape with suitable surface active ingredient.

Select suitable particle:

The inorganic particle that suitable is has specific size and specific structure.Just can realize this point by in polymkeric substance, adding ceramic particle with non-spherical morphology.These particles can be made of the aggregate of spheric primary particle (size of primary particle: 5 to 30nm), this primary particle for realize higher surface area to have less than 3, preferably less than 2.8, especially preferably less than 2.5 irregular fragment degree.Irregular fragment degree according to the method described in the DE1976840 by being that N2 absorption method in 0.5 to 0.8 the pressure range records at p/p0.Estimate measuring result for multiple charge absorption according to irregular fragment BET theory and according to Pfeifer, Obert and the described method of Cole (Proc.R.Soc.London, A423,169 (1989)).

Particle is so that the disposable size distribution that obtains only can stand the mode of variation to a certain degree adds, and described variation only can change required improved performance effect indistinctively.

Amount of filler changes in the scope of counting 0.1 to 20 weight %, preferred 0.2 to 10 weight % and preferred especially 0.5 to 3 weight % with solid resin.

The particulate method that suitable preparation has the fractal structure is the combustion heat solution that Degussa AG company prepares the calcined oxide thing.The fractal structure can be for example by spherical, ellipsoidal crystallization or erose particle in preparation process, perhaps directly formation hot flame after takes place to assemble and form during the combustion and pyrolysis in hot flame for example.Particle with irregular tile structure can for example constitute to reaching hundreds of individual sphere, the crystallization of oval shape or the aggregate of irregular shape primary particle by at least two.But also be fit to according to the particle that additive method makes with irregular tile structure.The example of the method that other are suitable is the precipitator method, hydrothermal method or plasma method.

Make particle of the present invention compatible by surface modification with polymeric matrix.Term " surface modification " comprises the complexing of rear oxidation effect, absorption, surface reaction or inorganic and/or organic reagent.

In a special embodiment, particle is carried out modification make them be loaded with to interact and/or the hydrogen bond bridge combine and/or the functional group of static combination and/or ionic linkage and/or coordinate bond and/or covalent linkage in the Van der Waals force type that realizes forward between particle and the polymkeric substance.

In another special embodiment, particle comprises at least two, the functional group of preferred especially at least three different activities, thereby can both realize that in all stages of the preparation and the course of processing particle is combined on the polymeric matrix well.

Usually preferred oxidation, nitrogenize and carbonization metal and semi metallic compound are:

Aluminum oxide (α, β, δ, θ), zirconium dioxide, the zirconium dioxide of doped with yttrium, titanium dioxide, (rutile, anatase octahedrite and brookite), silicon-dioxide, weisspiessglanz, zinc oxide, cerium oxide, ferric oxide, palladium dioxide, the mixed oxide of above-mentioned element.Also have oxidation relation by marriage tin, antimony tin in addition.The material that the spinel type is arranged in addition is as aluminate, hercynite, picotite, ulvospinel and cobalt spinel.Also has following ceramic particle, as nitrogenize canopy, norbide, silicon carbide, silicon nitride.According to selected preparation method's difference, oxide particle also has the free hydroxyl group of different amounts except oxide groups.In surface modification process thereafter, preferably make hydroxyl reaction.

In a preferred implementation, particle is carried out surface modification, thereby guarantee to adapt with polymeric matrix.Surface modification can multistep be carried out and can carry out in building-up process.Preferable methods is the rear oxidation effect, and lip-deep hydroxy number can reduce in this process.Just can obtain having the particle of littler gathering behavior by this modification, and these particles have the characteristics of favorable dispersity.

In embodiments of the present invention, only in a step, particle is carried out surface modification.

Particularly preferably be the surface modification effect of carrying out with two or more different functional groups.Particulate first surface modifying function is the particle synthesis step and then, is for example undertaken by the reaction of pyrolytic oxide and reactive lower molecular weight functional oligomers or reactive oligomers.The example of suitable properties-correcting agent is a silicon-containing compound, as silane, substituted silane, silicone oil, hexamethyldisilazane, alkyltrialkoxysilaneand, alkyl trihalosilane, dialkyl dialkoxy silicane, dialkyl group dihalide halosilanes, trialkyl organoalkoxysilane, trialkyl halogenated silanes, glycidyl oxygen propyl trialkoxy silane, aminopropyl trialkoxy silane, methacryloxypropyl trialkoxy silane, perfluoro and part fluoric alkyltrialkoxysilaneand, have other functional groups' silane.

Other suitable compound are phosphorated materials, as the phosphoric acid ester of organic modification, phosphonic acid ester, two or polyphosphide, phosphonate ester, have the phosphorus compound, the mixture of phosphorus compound or oligopolymer and superpolymer such as the Degussa that mix organic group, the tego dispers 655 of Essen company with phosphorus-containing groups.Phosphorus compound is particularly suitable for modified aluminum oxide effectively, but also can be used for other calcined oxide thing.At least one modification procedure promptly is enough to come according to the present invention modified aluminum oxide.One preferred embodiment in, in a method steps, adopt multiple properties-correcting agent to come the modified aluminum oxide particle.

In certain embodiment, adopt dispersion agent to come modification.In a special embodiment, adopt dispersion agent to carry out the second step modification.So-called dispersion agent be interpreted as can be by reducing interfacial tension convenient particles dispersed be those reagent in the liquid phase of dispersion to dispersion agent.If the particle of the present invention in the organic liquid is converted into dispersion, just can embody dispersion agent is easy to particles dispersed by the interfacial tension between the reduction solid-liquid two-phase character.Dispersion agent helps to break agglomerate, and is wetting or cover the surface treat discrete particles and stablize it in order to avoid agglomeration once more undesirablely as surface active material.

Optional second functionalization of particulate can with first functionalization simultaneously, be right after after first functionalization or preferably before the dispersion process, among or afterwards, before process of lapping of the present invention, in or carry out afterwards.In a preferred implementation, the material that the second surface modifying function is required added to before dispersion process in the dispersion of solvent-laden nano-sized filler or its precursor and goes, and perhaps added in the dispersion that contains binding agent of filler in organic solvent or precursor.

What be used for that the properties-correcting agent of second surface modifying function can be with first modifying function is identical or different.The properties-correcting agent that is applicable to second modifying function is that the silicon compound mentioned in first modifying function, phosphorus compound and other have the oligomeric dispersing additive of appropriate functional group.The selection of functional group will make that they can or not be to disturb solidification process unimportantly.Therefore, even do not consider the chemical nature of functional group, attainability in the molecule and position also play certain effect.Preferred oligomeric dispersing additive contains non-proton polar group, especially preferably ether, ester group and amide group.Proton or ionic functional group prove and help dispersion process, but their may also can react with curing system under situation.Therefore, if the situation of cured with isocyanates, then proton that contains in the dispersion agent or ionic functional base can not be ignored.But also can introduce the proton of specified quantitative or ionic group to improve dissemination.Particularly when the japanning system can tolerate the change of resin-solidifying agent ratio, this point was effective especially.If the situation of aluminum oxide, useful especially is the oligomeric dispersing additive with phosphorus-containing groups, as tego dispers 655.

The detailed description of dispersion agent:

The silane, phosphorus compound or the oligomeric dispersing additive that are used for surface-stable can be selected from as follows:

A) alkyltrialkoxysilaneand of general formula R-Si-O-R ' 3, R wherein can be aliphatic series or mixed aliphatic series/aromatic group and can contain and be selected from N, O, S, the heteroatoms of Cl and main chain capable of blocking; And wherein R ' is an aliphatic group;

B) hexamethyldisilazane and its derivative;

C) have by [SiR ₂-O]-the silicon resin base dispersing additive of unit and the end group different and [SiRR '-O]-main chain that the unit constitutes with it, R ' expression wherein grafts on the aliphatic group on the main chain;

D) have functional group's Lustrex or multipolymer or oligopolymer, described functional group is selected from by Cl, wherein R=H, the aryl with optional other functional groups or the CO of alkyl ₂R; OH, NH ₂, wherein R can be hydrogen, can contain the NR of other heteroatomic fat bases and/or aryl ₂Wherein R can be hydrogen, can contain the C=ONR of other heteroatomic fat bases and/or aryl ₂Form one group;

E) contain the segmented copolymer of polar protic or aprotic, polar functional group at least one block;

F) polycondensate is as polyester and polymeric amide;

G) general formula R-(CH ₂-CH ₂-X) _nThe compound of-R ', and the wherein aliphatic series that randomly replaced by the functional group of R and R ' expression and/or the group of aromatics, X are represented O, R=H wherein, the NR of alkyl;

H) hyperbranched oligomer or polymkeric substance, as have the grafting polyethers thereon and/or the poly-imines of polyester side chains, hyperbranched Polyglycerine;

I) star polymer;

J) has on it and the compound that be selected from the side chain of polyethers, polyester of polymine main chain and grafting;

K) phosphorated oligopolymer, for example tego dispers 655.

Suitable wetting agent and dispersion agent are the products such as the commodity tegodispers by name of Degussa AG (Essen), the product of EFKA (present Ciba) company or Byk Chemie (Wesel).Suitable silane can be from Degussa AG, Gesch  ftsbereich Aerosil﹠amp; Silane, Rheinfelden obtains.

Suitable granulated filler is product or the Degussa AG of for example commodity Aerosil , Aeroxide  by name, AdNano , Gesch  ftsbereich Aerosil﹠amp; The product of Silane with metal oxide chemical name.

Ginding process:

Under high pressure very and containing in the solvent of at least a low-molecular-weight oligomeric or high poly-dispersing additive by nozzle extruding Nano filling.When passing nozzle, very high shearing force can occur, and in this dispose procedure, material be accelerated to very high speed.Preferably, the acceleration hydrofluidic that one tributary is at least emitted and will produce by second nozzle concentrates on the common ground, to scheme also to grind bigger aggregate by impact effect.Hydrofluidic is collided mutually from relative direction.In this process, under the best setting state, be actually and adopt kinetic energy to come abrasive grains or be converted into heat, just can avoid grinding locular wall thus and be subjected to too high erosion damage.But because be difficult to realize best adjustment state, if adopt 180 ° angle, then the opposite nozzles pillar will be impaired.For avoiding this phenomenon; thereby will adopt less angle and reduce action effect therefrom and grind locular wall, and perhaps in a particularly preferred embodiment, will choose three bursts of tributaries and planar be adjusted to 120 ° angle respectively also owing to occur not having complete arresting particle must be subjected to the protection of mechanically resistant material all the time.Here also still to prophylactically adopt mechanically resistant material to protect the grinding chamber inwall of metal.To suitably regulate during grinding and obtain high as far as possible solid content.

Adopt the grinding plant that under high pressure agglomerate and/or the aggregate of filler can be ground into the nanometer fraction to grind.By adopting silane and/or P contained compound; Silane and/or oligomeric dispersing additive; The composition stable particle surface of P contained compound and oligomeric dispersing additive suppresses that particle reassociates or reagglomeration.

Suitable two-step approach be in Ystral Conti TDS type rotor stator operational outfit with nano material pre-dispersed in liquid phase and then in high-energy mills in more than the 500bar, preferred 500 to 5000bar and for example grind predispersion under the pressure of 2500bar.

Adopt Ginding process of the present invention to obtain the nano-scale particle of fractal, therefore its one side is little also can not cause the japanning that makes thus to produce muddiness to being enough to that scattering of light is not played significant effect, and the feature of their irregular shred can be not impaired yet on the other hand.Therefore, the purpose of grinding is not to produce primary particle, and dispersion composite also can contain a certain amount of primary particle after wet grinding.Be stabilising dispersions, adopt above-mentioned wetting and dispersing additive.About the other guide that uses and make up of suitable surfactant is described among the embodiment.

Solvent system:

The optional combination that can adopt single solvent or solvent.The solvent of preparation nanoparticle dispersion is compatible with the solvent in the japanning.Suitable solvent is selected from as next group: the solvent of aliphatic and alicyclic solvent, aromatics and replacement aromatics, the oil in being usually used in painting and gasolene ingredient, ester, lactone, ether, glycol ethers, ketone, pure and mild other solvents in being usually used in painting.The combination that preferably has the solvent of different boiling (evaporation number) and opposed polarity.The example of suitable solvent compositions is Sovesso 150/ butyleneglycol; Solvesso 150/ acetic acid methoxyl group propyl ester and Solvesso 150/ divalent ester mixture DBE; The solvent compositions that contains dimethylbenzene or N-BUTYL ACETATE.

Additive commonly used in other japannings:

Also can choose wantonly and use other additives commonly used in japanning and coating, it is selected from flow promotor, wetting agent and dispersion agent, antioxidant, curing catalysts, siccative, reactive diluent, pigment, separant, slip additive, anti-skinning agent, adhesion promoter, silane, phosphorus compound, phosphonate ester, corrosion inhibitor, defoamer.

For bubble problem, suitable have a degasifier that also can be used for diesel oil fuel:

Tego Antifoam MR 465

Tego Antifoam MR 467

Tego Antifoam MR 2057

Tego Flow ZFS 460

Anti-foam system sometimes can 6ppm to 0.5% (flow) consumption use.

The explanation of coating method

Coating procedure can carry out under laboratory scale according to conventional methods.The example of washing is to come the metallizing can according to the roller painting coating metal strip with the can cladding process under the industrial scale.Painted solidifies and can carry out in very short time He under the high temperature for economic consideration.Japanning of the present invention should have been given play to its required performance under working condition.Being suitable for breadboard method is blade coating.Utilize boxlike scraper, slot type scraper or spiral formula scraper to apply doped envelope, ventilate in short-term and in drying cupboard according to curing system and between 130 ℃ to 310 ℃ solidified coating.Select wet-film thickness, make desciccator diaphragm thickness between 5 to 100 μ m, preferred 30 to 60 μ m.The solidified time length can be 30 seconds under the top temperature of the 60min under the low temperature.The hydroxyl-functional composition of recommending according to raw materials producers and the activity of curing agent component are selected to solidify the time length.Suitable time/temperature combination can reference: Bodo M ü ller/Ulrich Poth:Lackformulierung undLackrezeptur, Vincentz-press, Hanover, 2003, part ii, the 2nd chapter: Einbrennlacke.

The coating explanation

The key property of coating of the present invention is to obtain transparent clarification or transparent as far as possible clarifying plated film.Nano-sized filler with high refractive index is under equal particle diameter condition, and than near the filler of refractive index resin-curative systems refractive index, nature can bring more intensive turbid phenomenon.Behind coating curing, also to leave standstill 24 hours.Test the japanning performance then.Test all japanning performances and compare with unmodified check sample.The japanning performance that test is following: MEK tolerance, cohesiveness (crosscut), bed thickness, K  nig pendulum hardness, Erichsen deep-draw value, ball hardness, wear resistance (Taber Abraser, emery wheel CS10,1000 change (standard), and reaching 5000 when needing changes), according to before the wet-milling test of internalist methodology, the wet test that rubs and backflow (Reflow), pencil hardness, Erichsen sliding injury hardness after following 2 days of glossiness afterwards, 60 ℃ of following 2h or the room temperature.

The explanation of japanning performance and test process thereof

Japanning of the present invention is pliable and tough and scratch resistance, anti-wiping and/or attrition resistant than unmodified japanning.The prerequisite that scratch resistance and/or wear resistance improve is to grind according to the present invention, disperse and the granular filler of stable fractal.If do not have enough dispersions or suitable stabilization treatment, then just uniform distribution or meeting agglomeration sufficiently of the granular filler of fractal.In addition, if do not grind fully, painted viscosity also may be too high for the course of processing of the best.In both cases, corresponding japanning all can show muddiness and scratch resistance, erasibility and/or wear resistance and also all can descend with respect to unmodified japanning.Therefore, a key character of the present invention also is to adopt above-mentioned those surface-active agents to stablize the nano particle in dispersion that makes by the high energy milling method.Japanning of the present invention has aspect the Erichsen deep-draw value and the quite or better snappiness of unmodified japanning.

If there are not other explanations, then those skilled in the art can utilize above-mentioned these schemes in wide region.Therefore, be descriptive preferred embodiment, and be that disclosure is limited to some extent anything but with embodiment.Below will further set forth the present invention according to embodiment.Replacement embodiment of the present invention can obtain similarly.

Embodiment 1:

The preparation and the character thereof of suspension and contrast suspension

Suspension 1A (S1A):

15% AEROXIDE  Alu 65,10%Hostaphat OPS (octyl phosphonic acid) is with Al ₂O ₃Meter is in dimethylbenzene;

In a stainless steel measuring container of 100 liters that is equipped with jet mixer, insert the Hostaphat OPS of the diformazan benzo stirring and dissolving 1.05kg of 58.45kg.Then, in the dispersing apparatus Ystral Conti-TDS 3 (wheel of stator slot: 4mm and the wheel of 1mm, the about 1mm of rotor/stator spacing) of operation and under shearing condition, be AEROXIDE  Alu 65 (the BET 65m of the 10.5kg of Degussa company with the manufacturer ²/ g) insert in the measuring container.Add the re-shearing 30min under 3000 commentaries on classics/min conditions afterwards that finishes.

Make this predispersion under the pressure of 2500bar, pass high-energy mills Sugino Ultimaizer HJP-25050 and be the diamond shape nozzle of 0.25mm, the grinding of further strengthening thus by diameter with two logical journeys.

The embodiment (S1A) that other embodiment are similar to suspension 1A carries out, and wherein uses the composition of its amount corresponding to following table.The per-cent of surface active material (value in the bracket) is in the nano particle solid.

Label	Dimethylbenzene [kg]	AEROXIDE  Alu 65 [kg]	Hostaphat OPS [kg]	Dynasylan  Glymo [kg]	Dynasylan  OCTMO [kg]	d 50 [μm]
							S1A	58.45	10.5	1.05	-	-	0.301
S1B	58 14	10.5	1.05	0.315(3％) **	-	0.224
							S1C	57.82	10.5	1.05	0.630(6％)	-	0.213
S1D	57.40	10.5	1.05	1.05(10)	-	0.192
							S2A	64.23	5.6	-	0.168(3％)	-	4.2
S2B	64.12	5.6	-	0.28(5％)	-	3.0
							S2C	63.84	5.6	-	0.56(10％)	-	2.7
S3D	63.28	5.6	-	0.56(10％)	0.56(10％)	2.6
							Label	Dimethylbenzene [kg]	AEROXIDE  Alu C 805 [kg]	Hostaphat OPS [kg]	Dynasylan  Glymo [kg]	Dynasylan  OCTMO [kg]	d 50 [μm]
S4A	59.19	10.5	-	0.315(3％)	-	0.226
							S4B	58.98	10.5	-	0.525(5％)	-	0.222
Label	Dimethylbenzene [kg]	AEROXIDE  R 8200 [kg]	Hostaphat OPS [kg]	Dynasylan  Glymo [kg]	Dynasylan  OCTMO [kg]	d 50 [μm]
							S5A *	56.0	14.0		0.56(4％)		0.239
Comparative Examples	Dimethylbenzene [kg]	AEROXIDE  Alu 65 [kg]	Hostaphat OPS [kg]	Dynasylan  Glymo [kg]	Dynasylan  OCTMO [kg]	d 50 [μm]
							V1	66.3	3.7	-	-	-	***
		Kg AEROSIL  200	-	-	-
							V2	67.9	2.1	-	-	-	****

^*Adopt defoamer BYK-05;

^*% refers to AEROXIDE or AEROSIL;

^{* *}5.3% the solid of only having an appointment when not adding additive can be sneaked into, because viscosity is too high;

^{* * *}3% the solid of only having an appointment when not adding additive can be sneaked into, because viscosity is too high;

Prepare other contrast dispersions (suspension):

A) dispersion of not adding dispersing additive and on high-energy mills, not grinding

B) contain the dispersion that dispersing additive does not grind on high-energy mills

Disperse dispersion 15min or move shearing device (Ystral company) dispersion 30min with dissolver with rotor stator.

Experiment confirm, by use traditional rotor stator mixing tank or by dissolver can not be in suspension the refinement median size, and this does not depend on whether used dispersing additive.

Label	Dimethylbenzene [kg]	AEROXIDE  Alu 65 [kg]	Hostaphat OPS [kg]	Dynasylan  Glymo [kg]	Dynasylan OCTMO [kg]	d 50 [μm]
							VS1A	58.45	10.5	-	-	-	7.6
VS1B1	58.14	10.5	1.05	-	-	4.7
							VS1B2	58.45	10.5	1.05	0.315(3％) **	-	0.332
VS1C	57.82	10.5	1.05	0.630(6％)	-	7.84
							VS1D	58.45	10.5	1.05	1.05(10％) **	-	7.62
VS2A	64.23	5.6	-	0.168(3％)	-	6.17
							VS2B	64.12	5.6	-	0.28(5％)	-	n.a.
VS2C	63.84	5.6	-	0.56(10％)	-	6.85
							VS3D	63.28	5.6	-	0.56(10％)	0.56(10％)	n.a.
Label	Dimethylbenzene [kg]	AEROXIDE  Alu C 805 [kg]	Hostaphat OPS [kg]	Dynasylan  Glymo [kg]	Dynasylan OCTMO [kg]	d 50 [μm]
							VS4A1	59.19	10.5	-	-	-	6.4
VS4A2	59.19	10.5	-	0.315(3％)	-	5.95
							VS4B	58.98	10.5	-	0.525(5％)	-	8.6
Label	Dimethylbenzene [kg]	AEROSIL  R 8200 [kg]	Hostaphat OPS [kg]	Dynasylan  Glymo [kg]	Dynasylan OCTMO [kg]	d 50 [μm]
							VS5A1 *	56.0	14.0	-	-	-	12.4
VS5A2 *	56.0	14.0	-	0.56(4％)	-	11.8

^*Adopt defoamer BYK-05;

^*% refers to AEROXIDE or AEROSIL;

^{* *}5.3% the solid of only having an appointment when not adding additive can be sneaked into, because viscosity is too high;

Utilization is according to the light-scattering analysis method of Michaelis theory and measure the particle diameter and the size distribution of nanoparticle dispersion by means of Horiba LA 920 LASER Light Scattering Spectroscopy instrument.

Other suspension S6 to S10 makes in N-BUTYL ACETATE according to identical method.Substitute above-mentioned surface active cpd and only be to use based on the polymine that is grafted with polyethers and polyester side chains on it (test products, Degussa AG, polymerization dispersing additive Essen):

Contain the nanoparticle dispersion in the N-BUTYL ACETATE of polymerization dispersing additive:

Label	Nano particle	Granule content [%]	Dispersing additive content [%] **)	d 50 [μm]
					S6	Aerosil R9200	25.9	10	7.71
S7	Aerosil OX 50	39.5	10	0.179
					S8	Aeroxide Alu C	36.0	10	0.104
S9	Aeroxide Alu 65	42.1	10	0.111
					S10	Aeroxide Alu C	45	10 Tego Dispers 655	0.105 *)

^*) Tego Dispers 655 is used as dispersing additive

^*) absolute value, in whole system

Other contrast dispersions (contrast suspension) have been prepared.

For comparing the following dispersion of preparation:

C) dispersion that does not contain dispersing additive and on high-energy mills, do not grind

D) contain the dispersion that dispersing additive does not grind on high-energy mills

Disperse dispersion 15min with having 35mm dish and the Pendraulik LD 50 type dissolver under 930 rev/mins of conditions.Not adding dispersing additive, is the lotion of viscosity sometimes, thereby can not obtain the amount of filler the same with the situation of adding dispersing additive.

Experiment confirm adopts traditional dispersion process can't obtain the effect of the refinement median size of the equivalence as in the high-energy mills by dissolver, and this with whether adopt dispersing additive irrelevant.

In some cases, the combination of dispersing additive and nano particle just can realize reaching the median size of hundreds of μ m.But high-energy mills can realize that in this case further refinement is until very low granularity.

Simultaneous test: the N-BUTYL ACETATE dispersion liquid that contains the polymerization dispersing additive of nano particle, disperse on dissolver and do not adopt high-energy mills to grind:

Label	Nano particle	Granule content [%]	Dispersing additive content [%] ****)	d 50 [μm]
					VS6-1 **)	Aerosil R9200	45.0	-	9.75
VS6-2	Aerosil R9200	25.9	10	11.1
					VS7-1 ***)	Aerosil OX 50	20.4	-	0.479
VS7-2	Aerosil OX 50	39.5	10	0.291
					VS8-1	Aeroxide Alu C	7.6 *)	-	8.47
VS8-2	Aeroxide Alu C	26.0 *)	10	6.25
					VS9-1 ****)	Aeroxide Alu 65	8.7	-	6.91
VS9-2	Aeroxide Alu 65	42.1	10	0.194
					VS10-1	Aeroxide Alu C	45	10 Tego Dispers 655	Can't make dispersion owing to multiviscosisty
VS10-2 *****)	Aeroxide Alu C	25	4.5 Tego Dispers 655	6.85

^*) surpass 7.6 parts Alu C because viscosity is strong under not adding the dispersing additive situation raises and can't sneak in the dispersion.Adopt dispersing additive not have high energy milling then can sneak into 26 parts at most.Adopt dispersing additive and high energy milling, then can sneak into 36 parts.

^*) 4600 rev/mins of times dispersions, the viscosity lotion

^{* *}) 2800 rev/mins of times dispersions, the viscosity lotion

^{* * *}) 1860 rev/mins of times dispersions, the viscosity lotion

^{* * * *}) absolute value, in whole system

^{* * * *}) the solid content absolute value of maximum adjustable joint is 25% when the polymeric dispersant that contains 4.5%.Be higher than this concentration value and the pudding-like thickness will occur.

Embodiment 2:

Japanning, preparation and performance

Nano granule suspension and resin and solidifying agent and other additives are mixed, and also available if needed dissolver disperses once, leaves standstill with the degassing, is coated on the sheet material and thermofixation.The combination of the solidification value/time of selection makes and can test by MEK, but Shang Buhui is owing to flavescence appears in over-curing.Owing to add nano particle, can require a little prolongation is arranged set time with respect to unmodified japanning.Usually under 160 ℃ and set time of 10 to 30min, solidify.During various composition of the present invention is listed in the table below.Japanning of the present invention is made up of the nano-scale particle filler (according to a kind of above-mentioned particle suspension liquid/dispersion) of polyester, resol, solvent mixture, curing catalysts, flow promotor and the surface modification of for example hydroxyl-functional.

The japanning example of forming by polyester and resol:

Following examples have confirmed by improved hardness (pencil hardness) and scratch resistance (sliding injury hardness) with modified by nano particles.

The japanning scheme	Contrast is through painted	Through painted	Contrast varnish	Varnish
						Japanning 1	Japanning 2	Japanning 3	Japanning 4
nfA	50.8	50.8	50.8	50.8
					The OH number	22	22	22	22
Degree of crosslinking	80∶20	80∶20	80∶20	80∶20
					Polyester liquid 1	48.6	46.5	64.1	59.0
Nanodispersion S7 2		8.2		10.4
					TiO 2 3	27.2	26.0
Resol 4	6.1	5.9	8.3	7.7
					Catalyzer 5	0.4	0.4	0.5	0.5
Flow promotor 6	1.1	1.0	1.4	1.3
					Solvent 7	16.6	12.0	19.2	21.2
Viscosity DIN 4	118 seconds	132 seconds	103 seconds	116 seconds

1) aliphatic series/aromatic polyester of linear hybrid, Mn=is about 6000, and OH value=20,50% do not contain naphthalene in water-sol A200

2) 39.5% SiO ₂In N-BUTYL ACETATE (Aerosil OX 50)

3) pigment such as Kronos 2310

4) Cymel 303 for example

5) an acidic catalyst such as Nacure 2500

6) as Disparlon 1984/50% in SN200

7) for example glycol, ester, ether, aromatic fractions etc.

To be coated with paint formula is applied on the priming paint as the lining lacquer.Layer thickness is 20 μ m, and furnace temperature is that 310 ℃ and the residence time are 30 seconds.

The japanning numbering	1	2	3	4
					Base material	Aluminium	Aluminium	Aluminium	Aluminium
Flow	Fine	Good	Good	Good
					The MEK test	＞100	＞100	＞100	＞100
Pencil hardness	F	2H	F-H	2H
					Erichsen sliding injury hardness	17N	28N	24N	32N

Simultaneous test

For comparing, preparation contains Aerosil OX 50 and does not have dispersing additive and contain the japanning of Aerosil OX 50 with dispersing additive, and does not all grind on high-energy mills.Simultaneous test confirms, does not grind on high-energy mills and just can not improve sliding injury hardness (scratch resistance) and pencil hardness.With traditional dissolver dispersive contrast japanning have owing to agglomerate form bittiness, the japanning that disperseed via high-energy mills then be outward appearance without a doubt.

	OX 50	OX 50 + LA-D 1045	OX 50	OX 50 + LA-D 1045
					The japanning scheme	Contrast is through painted	Through painted	Contrast varnish	Varnish
	Japanning 5	Japanning 6	Japanning 7	Japanning 8
					nfA	50.5	50.5	50.5	50.5
The OH number	21	21	21	21
					Degree of crosslinking	80∶20	80∶20	80∶20	80∶20
Polyester liquid 1	47.7	49.7	70.0	68.9
					AEROSIL OX 50 2	3.3	3.3	4.9	4.8
Dispersing additive LA-D 1045		1.2		1.7
					TiO 2 3	26.7	27.8
Resol 4	6.1	6.4	9.0	8.8
					Catalyzer 5	0.4	0.4	0.3	0.6
Flow promotor 6	1.0	1.1	1.5	1.5
					Solvent 7	14.8	10.0	14.0	13.8
Viscosity DIN 4	139s	155s	105s	112s

Being coated with paint formula is applied on the priming paint as the lining lacquer.Bed thickness is 20 μ m, and furnace temperature is that 310 ℃ and the residence time are 30 seconds.

The japanning numbering	5	6	7	8
					Base material	Aluminium	Aluminium	Aluminium	Aluminium
Painted surface	Mute light, groove	Mute light, groove	Muddiness, groove	Muddiness, groove
					Flow	Satisfied	Satisfied	Satisfied	Satisfied
The MEK test	100-2	100-2	＞100	＞100
					Pencil hardness	F	F	F-H	H
Erichsen sliding injury hardness	16N	17N	26N	23N

Claims (25)

1. be coated with lacquer binding, it contains based on the matrix of one or more polymkeric substance and is the stabilized suspension of the nano-scale particle of 0.5 to 25 weight % in total binding agent of 100 weight % and with the amount of the solid content measuring of suspension, it is characterized in that described particle suspension liquid obtains by following steps:

A) add solvent and abrasive grains in the high pressure shredder, this shredder is ground into nano level fragment in the pressure range greater than the about 10000bar of 500-with particulate agglomerate and/or aggregate; With

B) add one or more dispersing additives with the surface of stabilization through abrasive grains, wherein said dispersing additive exists with the amount of counting 1 to 25 weight part with respect to the particle of 100 weight parts.

2. the lacquer binding that is coated with as claimed in claim 1 is characterized in that, is present in the median size d that nano-scale particle in the suspension of stabilization has 0.05 to 10 μ m ₅₀, this value is measured by mie light scattering.

3. the lacquer binding that is coated with as claimed in claim 2 is characterized in that, the d50 value that nano-scale particle has is between 0.05 to 0.5 μ m, preferred 0.1 to 0.5 μ m.

4. as or the multinomial described lacquer binding that is coated with of claim 1 to 3, it is characterized in that, nano-scale particle is made up of the spheric primary particle, described primary particle size is between 5 to 30nm, and its irregular fragment degree is less than 3, and irregular fragment degree is adsorbed on p/p0 by N2 and records in 0.5 to 0.8 the pressure range.

5. as one or the multinomial described lacquer binding that is coated with in the above-mentioned claim, it is characterized in that nano-scale particle is selected from one group that is made up of two or more the mixture in oxidation, nitrogenize and metallic compound carbonization and semi metallic compound and the above-mentioned substance.

6. the lacquer binding that is coated with as claimed in claim 5, it is characterized in that nano-scale particle is selected from by Alpha-alumina, gama-alumina, δ-aluminum oxide, θ-aluminum oxide, zirconium dioxide, the zirconium dioxide of doped with yttrium, titanium dioxide, rutile, anatase octahedrite, brookite, silicon-dioxide, weisspiessglanz, zinc oxide, cerium oxide, ferric oxide, palladium dioxide, tin indium oxide, antimony tin, the spinel type compound, aluminate, hercynite, picotite, ulvospinel, cobalt spinel, ceramic particle, boron nitride, norbide, silicon carbide, silicon nitride, the mixing cpd of above-mentioned element and mixed oxide and contain one group that the mixture of above-mentioned two or more materials is formed.

7. as the described lacquer binding that is coated with of one of above-mentioned claim, it is characterized in that modification is come by rear oxidation effect, absorption, surface reaction or with cooperation inorganic and/or organic reaction reagent in the surface of nano-scale particle.

8. as the described lacquer binding that is coated with of above-mentioned claim 7, it is characterized in that, with the surface of the functional group modification nano-scale particle of two or more types that have nothing in common with each other.

9. as claim 7 or the 8 described lacquer bindings that are coated with, it is characterized in that the dispersing additive that is added is selected from one group that is made up of following:

A) alkyltrialkoxysilaneand of general formula R-Si-O-R ' 3, wherein R can be aliphatic series or mixed aliphatic series/aromatic group and can contain the heteroatoms that is selected from N, O, S, Cl and main chain capable of blocking; And wherein R ' is an aliphatic group;

B) hexamethyldisilazane and its derivative;

C) have by [SiR ₂-O] the silicon resin base compound of the main chain that constitutes of unit and the end group different and [SiRR '-O] unit with it, wherein R ' expression grafts on the aliphatic group on the main chain;

D) have functional group's Lustrex or multipolymer or oligopolymer, described functional group is selected from by Cl, wherein R=H, have randomly the aryl of other functional groups or the CO of alkyl ₂R; OH, NH ₂, wherein R can be hydrogen, can contain the NR of other heteroatomic aliphatic groups and/or aryl ₂Wherein R can be hydrogen, can contain the C=ONR of other heteroatomic aliphatic groups and/or aryl ₂Form one group;

E) contain the segmented copolymer of polar protic or aprotic, polar functional group at least one block;

F) polycondensate is as polyester and polymeric amide;

G) general formula R-(CH ₂-CH ₂-X) _nThe compound of-R ', the aliphatic series and/or the aromatic group that are randomly replaced by the functional group of R and R ' expression wherein, X are represented O, the NR of R=H, alkyl wherein;

H) hyperbranched oligomer or polymkeric substance, as have the grafting polyethers thereon and/or the poly-imines of polyester side chains, hyperbranched Polyglycerine;

I) star polymer;

J) has thereon and the compound that be selected from the side chain of polyethers, polyester of polymine main chain and grafting;

K) phosphorated oligopolymer, for example tego dispers 655;

With contain at least a compound a) to k) and mixture.

10. the lacquer binding that is coated with as claimed in claim 9 is characterized in that, nano-scale particle is that aluminum oxide and dispersing additive are the phosphorated oligopolymer.

11. the lacquer binding that is coated with as claimed in claim 10 is characterized in that, dispersing additive is tego dispers 655.

12. the one or more of described lacquer binding that is coated with of claim is characterized in that as described above, by in the rotor stator operational outfit that particle is pre-dispersed in liquid phase before the grinding steps in high-energy mills, obtains particulate suspension.

13. one or the multinomial described lacquer binding that is coated with in the claim as described above, it is characterized in that, be selected from by the mixture of aliphatic series and alicyclic compound, aromatics and replacement aromatic substance, oil in can be used for painting and gasolene ingredient, ester, lactone, ether, glycol ethers, ketone, alcohol, two or more above-claimed cpds and contain one group that the mixture of the compound of at least a above-mentioned substance is formed for grinding the solvent that adds.

14. the lacquer binding that is coated with as claimed in claim 13 is characterized in that, solvent comprises the combination of the solvent of different boiling and/or evaporation number and/or opposed polarity.

15. the lacquer binding that is coated with as claimed in claim 14, it is characterized in that used solvent combination comprises Solvesso 150/ butyleneglycol and/or Solvesso 150/ acetic acid methoxyl group propyl ester and/or Solvesso 150/ divalent ester mixture DBE and/or contains dimethylbenzene or the combination of the solvent of N-BUTYL ACETATE.

16. one or the multinomial described lacquer binding that is coated with in the claim as described above, it is characterized in that matrix is selected from can be with the composition of organic oligomer, the organic polymer with the free hydroxyl group that is suitable for curing reaction, above-mentioned oligopolymer and the polymkeric substance of the free hydroxyl group of solidifying agent reaction and contain and have one group that can form with the oligopolymer of the free hydroxyl group of solidifying agent reaction and/or mixture of polymers by having.

17. the lacquer binding that is coated with as claimed in claim 16, it is characterized in that matrix comprises any mixture of polyacrylate resin, vibrin, polycaprolactone resin, polyether resin, polycarbonate resin, polyurethane polyol resin, above-mentioned substance or comprises the mixture of at least a aforementioned polymer.

18. the lacquer binding that is coated with as claimed in claim 16 is characterized in that matrix comprises vibrin and/or polyacrylate resin.

19. one or the multinomial described lacquer binding that is coated with in the claim as described above, it has the high-clarity that surpasses 85% transmittance.

20. one or the multinomial described method that is coated with lacquer binding in preparation as the above-mentioned claim, in this method,

I) provide matrix based on one or more polymkeric substance;

Ii) the matrix that is provided is mixed mutually with the stabilized suspension of nano-scale particle; With

Iii) randomly in mixture ii), add other conventional additives;

Wherein, sneaking into solid content meter consumption in the suspension based on total binding agent meter of 100 weight % is the nano-scale particle of 0.5 to 25 weight %;

And described method is characterised in that particulate suspension obtains by as described below:

A) add solvent in the high pressure shredder and come abrasive grains, described shredder is ground into the nano level fragment in the pressure range greater than the about 10000bar of 500-with particle agglomeration body and/or aggregate; And

B) add one or more dispersing additives with the surface of stabilization through abrasive grains, the amount of wherein said dispersing additive is particle 1 to 25 weight part in 100 weight parts.

21. one or multinomial described lacquer binding and the aliphatic polymeric isocyanate of being coated with are common to purposes in the two-pack varnish in the claim 1 to 19 as described above.

22. as described above in the claim 1 to 19 one or multinomial described be coated with lacquer binding with have can with the combined purposes of the solidifying agent of hydroxyl reaction, be used to prepare plated film and coating.

23. as claimed in claim 22 and the combined purposes of solidifying agent, described solidifying agent are selected from by the mixture of polymeric polyisocyanate, the polymeric polyisocyanate of sheltering, isocyanate prepolymer, melamine, silane, the compound that contains silyl, one or more aforesaid compounds and contain one group of material that the mixture of at least a aforesaid compound is formed.

24. contain the described japanning that is coated with lacquer binding of claim 1 to 19.

25. contain article through applying by the described curing plated film that japanning constitutes of claim 24.