CN108950459A

CN108950459A - The purposes of powder coating material in the method for the method for substrate coating and containing additive

Info

Publication number: CN108950459A
Application number: CN201810874735.5A
Authority: CN
Inventors: S·赫费纳; M·鲁普雷希特; C·沃尔夫鲁姆; M·格莱布; A·赖斯
Original assignee: Eckart GmbH
Current assignee: Eckart GmbH
Priority date: 2011-07-25
Filing date: 2012-07-25
Publication date: 2018-12-07
Also published as: EP2737100A2; KR20140061422A; WO2013014213A3; US20140230692A1; CN103827344A; EP2737100B1; WO2013014213A2; JP2014527575A

Abstract

The present invention relates to purposes of the powder coating material containing particle in coating method, wherein additive has at least partly been applied to the surface of particle, the coating method in particular cold air spraying, flame-spraying, high speed flame spraying, hot plasma spraying and Athermal plasma spraying.In addition, the present invention relates to coating method, especially with the above method of powder coating material according to the present invention.

Description

Powder coating material for the method for substrate coating and containing additive is in the party Purposes in method

The application be by Eckart GmbH & Co. KG in the international application no submitted on July 25 in 2012 be PCT/EP2012/ 064638 it is entitled " for the method for substrate coating and powder coating material containing additive in the method The divisional application of the international application of purposes ".The date that the International Application Serial No. PCT/EP2012/064638 enters National Phase in China is On March 24th, 2014, national application number 201280046396.2.

Technical field

The present invention relates to the purposes that powder coating material is used to apply cloth base material.In addition, the present invention includes using this powder The method that coating material is used for substrate coating.In addition, the present invention includes the powdery paints material suitable for such use and/or method Material.

Background technique

Known many coating methods for being used for different substrate materials.For example, by metal or its precursor from vapor deposition in substrate table On face, see, for example, PVD or CVD method.Furthermore it is possible to for example deposit corresponding substance by electrochemical method from solution. In addition, for example coating can be applied on surface in the form of varnish.However, all methods all have the advantages that it is specific and Disadvantage.For example, need a large amount of water and/or organic solvent in the case where being deposited in the form of varnish, need drying time, Coating material to be administered must be compatible with basic varnish, and the residue of basic varnish is equally maintained on substrate.For example, passing through PVD method application needs big energy to bring nonvolatile matter into gas phase.

In view of above-mentioned limitation, a large amount of coating methods have been developed to provide for property needed for respective desired use. Known method is using such as kinetic energy, thermal energy or their mixing to generate coating, and wherein thermal energy may originate from such as conventional combustion Flame or plasma flame.The latter is further divided into heat and Athermal plasma, this refers to gas by partially or completely It is separated into free charge carrier such as ion or electronics.

In the case of cold-gas spraying, coating is formed by applying powder to substrate surface, wherein powder particle quilt It greatly accelerates.For this purpose, heated process gas is accelerated to supersonic speed by expanding in De Laval nozzle, then will Powderject.As kinetic energy as a result, they form compacted zones when particles hit substrate surface.

For example, WO2010/003396 A1, which is disclosed, applies wear-resistant protection painting as coating method using cold air spraying Layer.In addition, for example in 1 363 811 A1, EP 0 911 425 of EP discovery cold air spraying in B1 and 7,740,905 B2 of US The disclosure of method.

Flame-spraying belongs to thermal coating method group.Here, powder coating material is introduced into fuel gas/oxygen mixture Flame.Here, it can reach a maximum of about of 3200 DEG C of temperature, such as use oxyacetylene torch.The details of this method can be from disclosure such as 5,207,382 A of EP 830 464 B1 and US is acquired.

In the case where hot plasma spraying, powder coating material is injected into hot plasma.In usually used heat In plasma, reach a maximum of about of temperature of 20,000K, to make the powder melts of injection and be deposited on substrate as painting Layer.

The method and its specific embodiment and method parameter of hot plasma spraying are known to those skilled in the art 's.For example, which depict use hot plasma to spray to apply amorphous coating with reference to WO 2004/016821.In addition, EP 0 344 781 for example disclose flame-spraying and hot plasma are used to spray as the coating side for using tungsten-carbide powder mixture Method.Repeatedly describe the particular device used in plasma spraying process in the literature, for example, 0 342 428 A2 of EP, 7,678,428 B2, US 7,928,338 of US is in B2 and 1 287 898 A2 of EP.

In the case where high speed flame spraying, fuel burns under high pressure, wherein fuel gas, liquid fuel and they Mixture can be used as fuel.The flame that powder coating material injecting height is accelerated.This method characteristic known is phase To fine and close spray-on coating.High speed flame spraying is also well known to those skilled in the art, and in many publications It is described.For example, 0 825 272 A2 of EP discloses the substrate being coated with copper alloy using high speed flame spraying.This Outside, such as 0 492 384 A1 of WO 2010/037548 A1 and EP discloses the method for high speed flame spraying and makes wherein Equipment.

Athermal plasma spraying is largely analogous to hot plasma spraying and flame-spraying carries out.Powdery paints Material is therewith deposited on substrate surface by injection Athermal plasma.Such as can for example it be obtained from 1 675 971 B1 of EP Know, the method is characterized in that the especially low thermic load of coated substrate.In this method, specific embodiment and phase The method parameter answered is also that those skilled in the art are known from different publications.Such as 2 104 750 A2 of EP description The purposes of this method and the equipment for implementing this method.For example, 103 20 379 A1 of DE describe using this method can electricity The manufacture of the element of heating.The further disclosure of equipment about this method or for Athermal plasma spraying is found in for example EP 1 675 971 B1、DE 10 2006 061 435 A1、WO 03/064061 A1、WO 2005/031026 A1、DE 198 07 086 A1、DE 101 16 502 A1、WO 01/32949 A1、EP 0 254 424 B1、EP 1 024 222 195 32 412 A1, DE 199 55 880 of A2, DE is in A1 and 198 56 307 C1 of DE.

General considerations using the coating method of powder coating material is the transmission of powder.Powder coating material very Even charging is necessary, and is especially, for example, to produce extremely thin layer.Therefore, it has been found that the various conveyers specially designed are set Standby is the theme of individual patent application.Example is found in 2011/032807 A1 of WO 03/029762 A1 and WO.

Summary of the invention

Present invention aims to must be possible to produce novel coating or improve the production of known coating.In addition, this The purpose of invention is to make it possible to produce extremely thin quality coating.It is further an object that solve about For the powder coating material in coating method can transporting Problems Existing.

Another object of the present invention is to provide the method for substrate coating, it is characterised in that novel coating or improvement Coating quality.

Another object of the present invention is to provide powder coating material, it is especially suitable for the such use of coating method it One.

On the whole, the present invention relates to following embodiments:

1. purposes of the powder coating material containing particle in coating method, wherein the coating method is sprayed selected from cold air Painting, flame-spraying, high speed flame spraying, hot plasma spraying and Athermal plasma spraying, wherein powder coating material Particle is at least partially at least one additive.

2. according to purposes described in embodiment 1, wherein the total weight relative to coating material and additive, it is described at least A kind of weight ratio of additive is at most 32 weight %.

3. the purposes according to embodiment 1 or 2, wherein the total weight relative to coating material and additive, has The carbon content of the powder coating material of at least one additive is 0.01 weight % to 15 weight %.

4. the purposes according to any one of embodiment 1 to 3, wherein the gross weight relative to coating material and additive Amount, the weight ratio of at least one additive is at least 0.02 weight %.

5. the purposes according to any one of embodiment 1 to 4, wherein being used as one or more compounds of additive With at least six carbon atom.

6. the purposes according to any one of embodiment 1 to 5, wherein the particle includes metallic particles or is golden Metal particles, and the metal be selected from silver, gold, platinum, palladium, vanadium, chromium, manganese, cobalt, germanium, antimony, aluminium, zinc, tin, iron, copper, nickel, titanium, silicon, Their alloys and mixts.

7. the purposes according to any one of embodiment 1 to 6, wherein the coating method is selected from flame-spraying and non- Hot plasma spraying, and preferably Athermal plasma sprays.

8. the purposes according to any one of embodiment 1 to 7, wherein at least one additive does not include tristearin Acid and/or oleic acid.

9. the purposes according to any one of embodiment 1 to 8, wherein at least one additive is selected from polymerization Object, monomer, silane, wax, oxidized wax, carboxylic acid, phosphonic acids, above-mentioned derivative and its mixture.

10. the purposes according to any one of embodiment 1 to 9, wherein can be used organic and/or aqueous solvent from warp The particle of coating removes at least one additive.

11. the purposes according to any one of embodiment 1 to 10, wherein the size distribution of powder coating material is D₅₀ Value is in the range of 1.5 to 53 μm.

12. a kind of method for applying cloth base material, the method be selected from cold air spraying, flame-spraying, high speed flame spraying, Hot plasma spraying and Athermal plasma spraying,

It is characterized by:

It the described method comprises the following steps:

Powder coating material containing particle is introduced to the medium being directed on substrate to be coated, wherein the particle has There is at least one additive.

13. according to method described in embodiment 12, wherein the coating method is selected from flame-spraying and non-thermal plasma Body spraying, and preferably Athermal plasma sprays.

14. the method according to embodiment 12 or 13, wherein powder coating material is transmitted as aerosol.

15. the method according to any one of embodiment 12 to 14, wherein the medium being directed on substrate is air Or it is generated from air.

Detailed description of the invention

Fig. 1 and 2 shows the chip for being coated with solar energy contact paste, has used non-thermal etc. according to embodiment 14 Ionomer spray is coated with powder coating material according to the present invention.

Specific embodiment

The present invention relates to purposes of the powder coating material containing particle in coating method, wherein powder coating material Particle is at least partially at least one additive, and wherein the coating method is selected from cold air spraying, flame-spraying, high speed Flame-spraying, hot plasma spraying and Athermal plasma spraying.

It is one or more relative to the total weight of coating material and additive in the specific embodiment of such use The weight ratio of additive is at most 32 weight %.

In the specific embodiment of such use, the gross weight relative to coating material and additive in each case Amount, the weight ratio of one or more additives is between 0.02 weight % and 32 weight %.

In the specific embodiment of such use, the gross weight relative to coating material and additive in each case Amount, the carbon content of the particle containing additive of powder coating material are 0.01 weight % to 15 weight %.

It is one or more relative to the total weight of coating material and additive in the specific embodiment of such use The weight ratio of additive is at least 0.02 weight %.

In the specific embodiment of such use, one or more compounds as additive have at least six carbon Atom.

In the specific embodiment of such use, the particle of powder coating material includes metallic particles or is metal Grain, and the metal be selected from silver, gold, platinum, palladium, vanadium, chromium, manganese, cobalt, germanium, antimony, aluminium, zinc, tin, iron, copper, nickel, titanium, silicon, they Alloys and mixts.

In the specific embodiment of such use, coating method is selected from flame-spraying and Athermal plasma sprays.It is special Not preferred Athermal plasma spraying.

In the specific embodiment of such use, at least one additive does not include stearic acid and/or oleic acid, preferably not Comprising saturated or unsaturated C18 carboxylic acid, saturated or unsaturated C14 is not included more preferably to C18 carboxylic acid, even more preferably from not wrapping Containing saturated or unsaturated C12 to C18 carboxylic acid, saturated or unsaturated C10 is not included most preferably to C20 carboxylic acid.

In the specific embodiment of such use, one or more additives are selected from polymer, monomer, silane, wax, oxygen Change wax, carboxylic acid, phosphonic acids, above-mentioned derivative and its mixture.

In the specific embodiment of such use, powder coating material has the span value in 0.4 to 2.9 range, It is defined as follows:

In the specific embodiment of such use, organic and/or aqueous solvent can be used to remove from coated particle One or more additives.

In the specific embodiment of such use, the size distribution of powder coating material is D₅₀Value is at 1.5 to 53 μm In range.

In the specific embodiment of such use, the size distribution of powder coating material is D₉₀It is worth the model at 9 to 103 μm In enclosing.

In the specific embodiment of such use, the size distribution of powder coating material is D₁₀It is worth the model at 0.2 to 5 μm In enclosing.

In addition, the method is selected from cold air spraying, flame-spraying, high speed the present invention relates to the method for applying cloth base material Flame-spraying, hot plasma spraying and Athermal plasma spraying, used in powder coating material particle at least portion Divide ground that there is at least one additive.

In the specific embodiment of the above method, the method is selected from flame-spraying and Athermal plasma sprays.It should Method is preferably Athermal plasma spraying, especially those of the embodiment above.

In the specific embodiment of the above method, powder coating material is transmitted as aerosol.

In the specific embodiment of the above method, the medium being directed on substrate is air or generates from air. Above-mentioned air is available from surrounding atmosphere.In the specific embodiment of coating for wherein for example needing special high-purity, using Air is purified before, wherein such as dust and/or water vapour are separated off.Equally it may be preferred that other than nitrogen and oxygen The gas component of air is also largely separated completely, wherein the total amount of impurity preferably < 0.01 volume %, more preferably < 0.001 volume %.

In implication scope of the invention, term " powder coating material " is related to the particle for being administered to substrate as coating Mixture.Herein, the surface of the powder coating material that provides and one or more additive granules need not be completely in order to It is able to use according to the present invention.The limitation present invention is not understood to, inventors believe that the additivated effect of institute is among other things Caused by being the effect as the interval between individual particle, wherein be applied to surface or covering beyond particular range Surface with significantly improve can transporting it is unrelated, but need more using one or more additives, therefore this is only improved into This, thus it is economically unworthy for being.In specific embodiments, it is therefore preferable that at most 90%, preferably up to 85%, more preferably up to 80%, even more preferably from most 75%, most preferably up to 70% particle surface by one or more additions Agent covering.But simultaneously, the covering of particle surface as complete as possible provides certain protective effect, such as to from environment Oxidation influences.In certain particularly preferred embodiment of the present invention, it is therefore preferable that at least 20%, preferably at least 25%, more preferably at least 30%, still more preferably at least 35% particle surface is covered by one or more additives.In above-mentioned reality Apply in scheme it is special it is some in, preferably especially at least 40%, preferably at least 50%, more preferably at least 55%, also more Preferably at least 60% particle surface is covered by one or more additives.It covers on the surface of powder coating material according to the present invention The measurement of lid is carried out by SEM, wherein 30 particles selected at random are detected.

We have surprisingly discovered that by the surface at least partly covering particle at least one additive, Powder coating material can transporting dramatically increase.In order to obtain high quality and repeatable as a result, in coating method, especially It is that this is of great significance in wherein those of thin layer to be administered coating method.The raising of the repeatability of method and powder The charging of coating material more evenly is further such that be possible to generate coating uniformly much, the coating uniformly much has The very high-crosslinking-degree of less defect and particle.This feature is important, especially for the extremely thin coating of production.In addition, Improve in this way can transporting cause the powder coating material greatly simplified to feed and expenditure in equipment It substantially reduces.

It can be used for constructing spraying according to the method for the present invention for the spraying of such as cold air, hot plasma for coating, it is non-thermal etc. Ionomer spray, flame-spraying and high speed flame spraying.It has been proved that improve can transporting especially for following coating methods It is especially important: generates the thermic load of alap substrate in the coating method, and there is no or almost no heat Component is used for applied coatings.In specific embodiments, therefore, powder coating material according to the present invention is in flame-spraying, non- Hot plasma spraying, using being preferred in cold air spraying and high speed flame spraying.Under specific circumstances, additionally needing can Also it is coated with exquisite substrate with method of the invention, is applied this is why limited kinetic energy can be only used only in powder coating material Cloth.In the above-described embodiment it is special it is some in, therefore the method is preferably selected from flame-spraying and Athermal plasma sprays It applies.But the industrial use of flame-spraying is needed using a large amount of gases used, and in order to guarantee that continuous operation needs gas used The mass storage of body.Due to being necessary to generate flame fuel gas in flame-spraying, storage is related to corresponding peace Full blast danger, it is therefore desirable to special security legislation.In contrast, incombustible gas generation also can be used in plasma, as a result It is that the storage of the gas of corresponding amount is related to lower safety standard, therefore is related to reduced cost.It is special in the above-described embodiment In more other, therefore, Athermal plasma spraying be particularly preferred very much and is used as coating method.

In implication scope of the invention, term " additive " is present in being related to uncrosslinked (i.e. they are not crosslinked) Substance on the particle surface of powder coating material.In particular, in a preferred embodiment of the invention, term " additive " relates to And the carbon compound not being crosslinked on the particle surface of powder coating material.In implication scope of the invention, " not on surface Upper crosslinking " mean apply additive to powder coating material particle during or later, each additive molecule it Between do not set up covalent bond, thus post-crosslinking does not occur on the surface of the pigment.In particular, term " additive " is not intended to crosslinking Polymer, as disclosed in 2115075 A1 of EP.

In specific embodiments, particularly preferred additive is only to pass through physical bond, such as pass through Van der Waals phase interaction The particle of powder coating material is bound to, dipole-dipole interaction or hydrogen bridge.However, it is also possible to be additive in addition Ground or alternately through chemical bonding, such as it is bound to by covalent bond or ionic bond the particle surface of powder coating material.

Generally, it is preferred to which by using organic and/or aqueous solvent additive according to the present invention can be removed from particle again. These additives have the advantages that especially to be easy to application and apply them cheaply.In specific embodiments, especially excellent The additive of choosing is dispersed in such as solvent and is applied to powder particle by mechanical force.Additionally or alternatively, specific In embodiment, additive is dissolvable in water in suitable solvent, is then mixed merga pass with powder particle and is steamed on powder particle It sends out solvent and applies.

It is not understood to that the limitation present invention, inventor think that additive according to the present invention reduces the phase interaction between particle With and thereby increase can transporting.

In implication scope of the invention, substance as additive is specifically for being physically and/or chemically bound to powder The carbon compound of the particle surface of last coating material.

It is not understood to that the limitation present invention, inventor think that the king-sized improvement of coating produced by the invention is: Pass through the combustion additive in flame and make where there is powder coating material rupture of agglomerates, cause with high-carbon content Use of the additive in combustion flame or plasma flame.In specific embodiments, it is therefore preferable that adding The weight ratio of carbon atom is at least 0.01 weight %, preferably at least 0.05 weight % in the powder coating material of agent covering, more Preferably at least 0.1 weight %, still more preferably at least 0.17 weight %.In specific embodiments, it is particularly preferably adding The weight ratio of carbon atom is at least 0.22 weight %, preferably at least 0.28 weight % in the powder coating material of agent covering, more Preferably at least 0.34 weight %, still more preferably at least 0.4 weight %.Gross weight of the above-mentioned weight % based on coating material and additive Amount.

On the other hand, in specific embodiments, the carbon atom preferably in the powder coating material of additive covering Weight ratio be at most 15 weight %, preferably up to 10 weight %, more preferably up to 7 weight %, even more preferably from most 5 weights Measure %.In the above-described embodiment it is special it is some in, particularly preferably carbon content is at most 4 weight %, preferably up to 3 weights %, more preferably up to 2 weight % are measured, even more preferably from most 1 weight %.Above-mentioned weight % is total based on coating material and additive Weight.

In specific embodiments, particularly preferably additive covering powder coating material in carbon atom weight Range of the ratio between 0.01 weight % and 15 weight %, preferably between 0.05 weight % and 10 weight % It is interior, more preferably between 0.1 weight % and 7 weight %, even more preferably between 0.17 weight % and 5 weight % In range.In the above-described embodiment it is special it is some in, particularly preferably in the powder coating material of additive covering The weight ratio of carbon atom between 0.22 weight % and 4 weight %, preferably 0.28 weight % and 3 weight % it Between in the range of, more preferably between 0.34 weight % and 2 weight %, even more preferably from 0.4 weight % and 1 weight It measures between %.Total weight of the above-mentioned weight % based on coating material and additive.Relative to coating material and addition The weight ratio of the carbon atom of the total weight of agent using 200 equipment of CS derived from Leco Instruments GmbH by for example being surveyed It is fixed.

In specific embodiments, excellent moreover it is preferred that the compound for being used as additive contains at least six carbon atom Select at least seven carbon atom, more preferably at least 8 carbon atoms, still more preferably at least 9 carbon atoms.It is special in the above-described embodiment In more other, it is therefore particularly preferred that the compound as additive contains at least ten carbon atom, preferably at least 11 carbon originals Son, more preferably at least 12 carbon atoms, still more preferably at least 13 carbon atoms.The carbon contained in additive according to the present invention is former Subnumber mesh can be measured for example, by measuring each additive.It may be used herein all known to those skilled in the art for surveying The method of earnest matter.For example, organic and/or aqueous solvent can be used to remove from the particle of powder coating material for additive, then Pass through HPLC, GCMS, NMR, CHN or above-mentioned means combination from each other or above-mentioned means and other conventional use of methods Combination identification.

In specific embodiments, it is further preferred that the weight ratio of one or more additives is at least 0.02 weight Measure %, preferably at least 0.08 weight %, more preferably at least 0.17 weight %, still more preferably at least 0.30 weight %.In above-mentioned reality Apply in scheme it is special it is some in, the carbon content of particularly preferably coating material and additive is at least 0.35 weight %, excellent Select at least 0.42 weight %, more preferably at least 0.54 weight %, still more preferably at least 0.62 weight %.Above-mentioned weight % is based on applying Expect the total weight of material and additive.

In further specific embodiment, it is further preferred that the weight ratio of additive is at most 32 weights %, preferably up to 18 weight %, more preferably up to 13 weight % are measured, even more preferably from most 9 weight %.In the above-described embodiment It is special it is some in, the carbon content of particularly preferably coating material and additive is at most 7 weight %, preferably up to 6 weights %, more preferably up to 4.5 weight % are measured, even more preferably from most 2.3 weight %.Above-mentioned weight % is based on coating material and additive Total weight.

In further specific embodiment, it is further preferred that the weight ratio of additive in 0.02 weight % and Between 32 weight %, preferably between 0.08 weight % and 18 weight %, more preferably in 0.17 weight It measures between % and 13 weight %, even more preferably between 0.30 weight % and 9 weight %.In above-mentioned reality Apply in scheme it is special it is some in, the weight ratio of carbon atom is in 0.35 weight particularly preferably in coating material and additive It measures between % and 7 weight %, preferably between 0.42 weight % and 6 weight %, more preferably 0.54 Between weight % and 4.5 weight %, even more preferably between 0.62 weight % and 2.3 weight %.On State total weight of the weight % based on coating material and additive.

In implication scope of the invention, it can be used as the example of the substance of additive are as follows:

It is polymer (such as polysaccharide, plastics), monomer, silane, wax, oxidized wax, carboxylic acid (such as fatty acid), phosphonic acids, above-mentioned Derivative (especially carboxylic acid derivates and phosphoric acid derivatives) and their mixture.In specific embodiments, preferably , polysaccharide, plastics, silane, wax, oxidized wax, carboxylic acid (such as fatty acid) carboxylic acid derivates, phosphonic acids, phosphoric acid derivatives or it Mixture, preferred polysaccharide, silane, wax, oxidized wax, carboxylic acid (such as fatty acid) carboxylic acid derivates, phosphonic acids, phosphoric acid derivatives Or their mixture, more preferable polysaccharide, silane, wax, oxidized wax, phosphonic acids, phosphoric acid derivatives or their mixture, which are used as, to be added Add agent.

Above-mentioned wax includes native paraffin and synthetic wax.The example of this kind of wax be paraffin, pertroleum wax, lignite wax, animal wax (such as Beeswax, lac, lanocerin), vegetable wax (such as Brazil wax, candelila wax, rice bran wax), fatty acid amide wax (such as erucic acid Amide), polyolefin-wax (such as polyethylene wax, polypropylene wax), grafted polyolefin chloroflo, fischer-tropsch wax and oxidized polyethylene wax and modification Polyethylene and polypropylene wax (such as metallocene wax).In specific embodiments, wax according to the present invention preferably passes through physics In conjunction with and combine.It is, however not excluded that in further specific embodiment, wax have alternately or additionally be capable of forming from The functional group of sub-key and/or covalent bond.

In implication scope of the invention, term " polymer " " it also include oligomer.But in particularly preferred embodiment party In case, polymer used in accordance with the present invention is preferably combined at least 25 monomeric units, is more preferably combined at least 35 lists Body unit, even more preferably from being combined at least 45 monomeric units, most preferred combinations at least 50 monomeric units.Here, it can incite somebody to action Polymer is bound to the particle of powder coating material without forming covalent bond or ionic bond.However in specific embodiments, excellent Select additive according to the present invention that can form at least one ionic bond or covalent bond with the particle of powder coating material.In above-mentioned reality Apply in scheme it is special it is some in, this, which is combined, preferably sends out by the inclusion of phosphoric acid, carboxylic acid, silane or sulfonic acid group in the polymer It is raw.

In implication scope of the invention, term " polysaccharide " also includes oligosaccharides.However, in particularly preferred embodiment In, polysaccharide used in accordance with the present invention is preferably combined at least four monomeric unit, it is more preferably combined at least eight monomeric unit, Even more preferably from being combined at least ten monomeric unit, most preferred combinations at least 12 monomeric units.In specific embodiments, Particularly preferred polysaccharide is cellulose, cellulose derivative, such as methylcellulose, ethyl cellulose, carboxymethyl cellulose, hydroxyl second Base cellulose, hydroxypropyl methyl cellulose, NC Nitroncellulose (such as the ethyl cellulose derived from Dow Wolff Cellulosics Element or methylcellulose), cellulose esters (such as cellulose acetate, acetobutyrate and cellulose propionate), starch, such as Cornstarch, potato starch and wheaten starch and modified starch.

In implication scope of the invention, term " plastics " includes thermoplasticity, thermosetting property or elastomer plastic.Thermoplastic herein Property plastics are particularly preferred, wherein all thermoplastics well known by persons skilled in the art are contemplated that.Corresponding heat The summary of thermoplastic plastic is found in such as Kunststoff-Taschenbuch, edits Saechtling, and the 25th edition, Hanser- Verlag, Munich, 1992 are especially chapter 4 and document cited therein and Kunststoff-Handbuch, compile G.Becker and D.Braun is collected, 1 to 11, Hanser-Verlag, Munich, 1966 to 1996 are rolled up.It is without being limited thereto, in order to illustrate For example, following thermoplastics: polyoxyalkylene, polycarbonate (PC), polyester such as polybutylene terephthalate (PBT) are referred to (PBT) or polyethylene terephthalate (PET), polyolefin such as polyethylene or polypropylene (PP), poly- (methyl) acrylate, Polyamide, aromatic vinyl (co) polymer such as polystyrene, impact-resistant modified polystyrene, such as HIPS or ASA, ABS or AES polymer, polyarylether such as polyphenylene oxide (PPE), polysulfones, polyurethane, polyactide, halogen-containing polymer contain imide group Polymer, cellulose esters, organosilicon polymer and thermoplastic elastomer (TPE).The mixture of different thermoplastic plastics can also be single-phase Or the form of the blend polymer of multiphase uses.

The homopolymer or copolymer of polyoxyalkylene, especially (total) polyformaldehyde (POM) and its production method itself are abilities Field technique personnel are known and describe in the literature.The main polymer chain of these polymer has the repetition of at least 50 moles % - CH₂O- unit.Homopolymer usually (preferred catalytic) passes through the production of the polymerization reaction of formaldehyde or trioxane.Example is poly- first Aldehyde copolymer and polyformaldehyde terpolymer.

Suitable polycarbonate is known per se, and can for example be contracted according to 1 300 266 B1 of DE by interface Gather or reacts to obtain with bis-phenol by carbonic acid Biphenyl Ester according to 14 95 730 A1 of DE.

Itself is also known and describe in the literature for suitable polyester.Polyester can be by making aromatic dicarboxylic acid, their ester Or their other derivatives for forming ester react preparation with aliphatic dihydroxy compounds in a way known.Specific In embodiment, or mixtures thereof naphthalenedicarboxylic acid, terephthalic acid (TPA), M-phthalic acid are used as dicarboxylic acids.At most 10 moles of %'s Aromatic dicarboxylic acid can be by aliphatic or alicyclic dicarboxylic acid such as adipic acid, azelaic acid, decanedioic acid, dodecanedioic acid, hexamethylene Dicarboxylic acids substitution.The example of aliphatic dihydroxy compounds be the glycol with 2 to 6 carbon atoms, especially 1,2- ethylene glycol, Or mixtures thereof 1,4- butanediol, 1,6-HD, 1,4- hexylene glycol, 1,4- cyclohexanediol and neopentyl glycol.

The example of said polyolefins is polyethylene and polypropylene, and based on ethylene or propylene (optionally also with it is more advanced Alpha-olefin) copolymer.In the meaning of the present invention, term " polyolefin " also includes ethylene-propylene elastomeric and ethylene-the third Alkene terpolymer.

The example of above-mentioned poly- (methyl) acrylate is polymethyl methacrylate (PMMA) and is based on methyl methacrylate The copolymer of other copolymerisable monomers of ester and at most 40 weight %, other described copolymerisable monomers such as n-butyl acrylate, third Enoic acid ter-butyl ester or 2-EHA.

Above-mentioned polyamide further includes polyetheramides, such as polyether block amide, is described in for example following disclosures: US 2,071, 250、US 2,071,251、US 2,130,523、US 2,130,948、US 2,241,322、US 2,312,966、US 2, 512,606 and US 3,393,210.In addition, above-mentioned polyamide includes acyl in such as polycaprolactam, poly capryllactam, poly- 12 Amine and the polyamide as obtained from dicarboxylic acids and diamine reactant.The example for being suitable for this dicarboxylic acids is with 6 to 12, especially It is the alkane dicarboxylic acid of 6 to 10 carbon atoms, and aromatic dicarboxylic acid can be used.The example of suitable diamines is that have 6 to 12, The alkane diamine and m-xylene diamine, two-(4- aminophenyl) methane, two-(4- aminocyclohexyls of especially 6-8 carbon atom Base) methane, 2,2- bis- (4- aminophenyl) propane or 2,2- bis- (4- aminocyclohexyl) propane.

The example of above-mentioned aromatic vinyl (co) polymer be polystyrene, styrene-acrylonitrile copolymer (SAN) and resist Rush modified polystyrene (HIPS=high impact polystyrene).The production of such aromatic vinyl (co) polymer is ability Known to field technique personnel, and it is found in such as EP-A-302 485.Further example is ASA, ABS and AES polymer (ASA=acrylonitrile-styrene-acrylic ester, ABS=acrylonitrile-butadiene-styrene (ABS), AES=acrylonitrile-EPDM rubber- Styrene).The production of abs polymer is found in such as 197 28 629 A1 of DE, and the production of ASA polymer is found in such as EP 99 532 A2.The details of the production of AES polymer is further found in such as US 3,055,859 or US 4,224,419.

The example of above-mentioned polyarylether is polyarylether itself, polyarylether sulfide, polyether sulphone and poly(aryl ether ketone).Its arlydene Can be identical or different, and can be the aromatic group for example with 6 to 18 C atoms independently of one another.Suitable sub- virtue The example of base is phenylene, and biphenylene, sub- terphenyl, 1,5- naphthylene, 1,6- naphthylene, 1,5- anthrylene, 9,10- is sub- Anthryl or 2,6- anthrylene.EP 113 112 A1 and EP 135 130 are seen for the example of the production details of polyether sulphone A2。

The other examples that can be used as the plastics of additive in specific embodiments are polyurethane, poly-isocyanurate and gather Urea.

The example of the polymer of lactic acid, polyactide and its production method is known to the skilled in the art.In specific reality It applies in scheme, particularly preferably uses copolymer or block copolymer based on lactic acid and other monomers.

The example of halogen-containing polymer is the polymer of vinyl chloride, such as polyvinyl chloride (PVC) (such as hard PVC and soft Matter PVC) and vinyl chloride copolymer (for example, PVC-U molding composite).

It can be used as the other examples of the plastics of additive in specific embodiments are as follows: fluoropolymer, such as polytetrafluoroethyl-ne Copolymer, the second of alkene (PTFE), tetrafluoroethylene-hexafluoro-propylene copolymer (FEP), tetrafluoroethene and perfluoroalkyl vinyl ether Alkene-TFE copolymer (ETFE), polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), polytrifluorochloroethylene (PCTFE), Ethylene-chlorotrifluoro-ethylene copolymer (ECTFE).

The example of above-mentioned polymer containing imide group is polyimides, polyetherimide and polyamide-imides.This A little polymer are described in for exampleChemie Lexikon, CD-ROM 1.0 editions, Thieme Verlag Stuttgart 1995。

Above-mentioned thermoplastic elastomer (TPE) (TPE) is characterized in that they can be processed as thermoplastic, but have Rubber-elastic properties.More detailed information sees such as G.Holden et al., Thermoplastic Elastomers, second edition, Hanser Verlag, Munich 1996.Example is thermoplastic polyurethane elastomer (TPE-U or TPU), styrene oligomeric block Copolymer (TPE-S), such as SBS (s-B-S-oxygroup block copolymer) and SEES (styrene-ethylene- Butylene-styrene block copolymer can be obtained by SBS's plus hydrogen), thermoplastic polyolefin elastomer (TPE-O), thermoplastic polyester Elastomer (TPE-E), thermoplastic polyamide elastomer (TPE-A) and thermoplastic vulcanizates (TPE-V).

The example of above-mentioned polyacrylate is poly- (methyl) acrylate, they are preferably as homopolymer or block polymer In the presence of.These polymer are for example by Evonik with trade name Degalan sale.

In specific embodiments, preferable additives are selected from the copolyreaction of PE or PP and maleic acid (acid anhydride) or acrylic acid Product.

In specific embodiments, it is preferred that the molecular weight of the polymer as additive is at most 200,000, excellent Choosing at most 170,000, more preferably up to 150,000, even more preferably from most 130,000.In the above-described embodiment special one In a little, it is therefore particularly preferred that the molecular weight of the compound as additive is at most 110,000, preferably up to 90,000, more excellent Choosing at most 70,000, even more preferably from most 50,000.

In specific embodiments, above-mentioned carboxylic acid also particularly includes dicarboxylic acids, tricarboxylic acids and tetrabasic carboxylic acid.The example of dicarboxylic acids Son is succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and decanedioic acid.

In specific embodiments, above-mentioned carboxylic acid derivates particularly carboxylate.

The example of above-mentioned fatty acid be capric acid, hendecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, Hexadecanoic acid, Heptadecanoic acide, nonadecylic acid, arachidic acid, behenic acid, lignoceric acid, hexacosoic acid, melissic acid, Undecenoic acid, palmitoleic acid, elaidic acid, vaccenic acid, eicosenoic acid, docosenoic acid, erucic acid, two Tetradecenoic acid, sorbic acid, linoleic acid, linolenic acid, eleostearic acid, arachidonic acid, eicosapentaenoic acid, 22 carbon of 4,7,11- Triolefin -18- acetylenic acid, docosahexaenoic acid, stearic acid and oleic acid.In especially specific preferred embodiment of the invention, Additive does not include stearic acid or oleic acid, does not preferably include saturated or unsaturated C18 carboxylic acid, more preferably not comprising saturation or not C14 to the C18 carboxylic acid of saturation does not include saturation most preferably even more preferably from saturated or unsaturated C12 is not included to C18 carboxylic acid Or unsaturated C10 is to C20 carboxylic acid.In implication scope of the invention, followed by number term " C (carbon) " be related to include Carbon atom in molecule or molecular composition, the wherein quantity of the carbon atom of digital representation.

Above-mentioned phosphonic acids is indicated with formula (I):

(X)_mP (=0) Y_nR_(3-m) (I),

Wherein m is 0,1 or 2, and n is 0 or 1, and X can be identical or different and be hydrogen, hydroxyl, halogen or-NR'₂, R' can be with Identical or different and be hydrogen, substituted or unsubstituted C1-C9 alkyl or substituted or unsubstituted aryl, Y can be identical or not It together and is-O- ,-S- ,-NH- or-NR-, R can be identical or different and be selected from C1-C30 alkyl, C2-C30 alkenyl, C2- C30 alkynyl, C5-C30 aryl, C6-C30 aryl alkyl, C4-C30 heteroaryl, C5-C30 heteroaryl alkyl, C3-C30 naphthenic base, C4-C30 cycloalkyl-alkyl, C2-C30 Heterocyclylalkyl, C3-C30 hetercycloalkylalkyl, C1-C30 ester group, C1-C30 alkylether radicals, C1-C30 naphthenic base ether, C1-C30 cycloalkenyl ether, C6-C30 aryl ether, C7-C30 aryl alkyl ether, wherein above-mentioned Group can be substituted or unsubstituted, and optionally straight chain or branched chain.

In implication scope of the invention, at least one hydrogen atom that term " substituted " describes related group is following Replace: halogen, hydroxyl, cyano, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C1-C5 alkanoyl, C3-C8 naphthenic base, Heterocycle, aryl, heteroaryl, C1-C7 alkyl-carbonyl, C1-C7 alkoxy, C2-C7 alkenyloxy group, C2-C7 alkynyloxy group, aryloxy group, Acyl group, C1-C7 acryloyl group oxygroup, C1-C7 methylacryloyl oxygroup, C1-C7 epoxy group, C1-C7 vinyl, C1-C5 alkane Epoxide carbonyl, aroyl, amino carbonyl, alkyl amino-carbonyl, dialkyl amino carbonyl, amino carbonyl oxygroup, C1-C7 alkyl ammonia Base carbonyl oxygroup, C1-C7 dialkyl amino carbonyl oxy, C1-C7 alkanoyl amine, C1-C7 alkoxy carbonyl amine, C1-C7 alkyl Sulfonyl amine, amino-sulfonyl, C1-C7 alkyl amino sulfonyl, C1-C7 dialkyl amino sulfonyl, carboxyl, cyano, trifluoro Methyl, trifluoromethoxy, nitro, sulfonic acid, phosphoric acid, amine, amide (wherein nitrogen-atoms independently of one another optionally by C1-C5 alkyl or Aryl replace once or twice), urea groups (wherein nitrogen-atoms independently of one another optionally by C1-C5 alkyl or aryl replaces once or Twice) or C1-C5 alkyl sulfenyl.

In implication scope of the invention, term " naphthenic base " and " Heterocyclylalkyl " include full other than aromatic systems Sum, fractional saturation and unsaturated system, aromatic systems are referred to as " aryl " or " heteroaryl ".

In implication scope of the invention, unless otherwise specified, term " alkyl " is preferred to indicate straight chain or branched chain C1 extremely C27, more preferable straight chain or branched chain C1 to C25, even more preferably from straight chain or branched chain C1 to C20 carbochain.In meaning of the invention In range, unless otherwise specified, term " alkenyl " and " alkynyl " preferably indicate straight chain or branched chain C2 to C27, more preferably straight Chain or branched chain C2 to C25, even more preferably from straight chain or branched chain C2 to C20 carbochain.In implication scope of the invention, term " aryl " indicates aromatic carbocyclic, preferably has up to the aromatic carbocyclic of 7 carbon atoms, more preferable benzyl ring, wherein above-mentioned aromatics Carbocyclic ring can be the component part of fused ring system.The example of aryl is phenyl, hydroxyphenyl, xenyl and naphthalene.Of the invention In implication scope, term " heteroaryl " indicates aromatic ring, wherein the carbon atom of similar aryl rings is formally replaced by hetero atom It changes, is preferably replaced by the atom selected from O, S and N.

Above-mentioned silane is characterized in that the structure according to formula (II):

R_pSiX_(4-p) (II),

Wherein p is 0,1,2 or 3, and X can be identical or different and be hydrogen, hydroxyl, halogen or-NR'₂, R' can it is identical or It is different and be hydrogen, substituted or unsubstituted C1-C9 alkyl or substituted or unsubstituted aryl, R can it is identical or different and Selected from C1-C30 alkyl, C2-C30 alkenyl, C2-C30 alkynyl, C5-C30 aryl, C6-C30 aryl alkyl, C4-C30 heteroaryl Base, C5-C30 heteroaryl alkyl, C3-C30 naphthenic base, C4-C30 cycloalkyl-alkyl, C2-C30 Heterocyclylalkyl, C3-C30 heterocycle alkane Base alkyl, C1-C30 ester group, C1-C30 alkylether radicals, C1-C30 naphthenic base ether, C1-C30 cycloalkenyl ether, C6-C30 aryl Ether, C7-C30 aryl alkyl ether, wherein above-mentioned group can be substituted or unsubstituted, and optionally straight chain or branch Change chain.

Additive for example can chemically or physically be bound to the particle surface of powder coating material.Particle is carried out herein Complete surface covering it is not necessary to, even if it is preferred in specific embodiment of the invention.

In specific embodiments, preferably additive is bound to the particle table of powder coating material as far as possible weakly Face.For example, in the above-described embodiment it is special it is some in, additive preferably used according to the invention is without functional group. In implication scope of the invention, term " functional group " refers to the physical property and reflex action for clearly influencing molecule in molecule Molecular radical.The example of these functional groups are as follows: carboxylic acid group, sulfonic acid group, phosphate group, silane group, carbonyl, hydroxyl, amine Base, diazanyl, halogen group and nitro.

In other specific embodiments, in contrast, preferable additives cannot easily be removed from surface very much, such as be made For the result of frictional force.In the above-described embodiment it is special it is some in, additive band particularly preferably used according to the invention There are at least one functional group, preferably at least Liang Ge functional group, more preferably at least three functional groups.

We have surprisingly discovered that when using the powder coating material covered by additive according to the present invention When, also allow using with unexpected dystectic coating material.It is not understood to that the limitation present invention, the present inventor recognize For the transmission more evenly of the particle with reduced agglomeration tendency allows particle individually to hit substrate surface, and can be more Fully using existing kinetic energy so that shaping particles.In the case where (thus being local) application agglomerate heterogeneous, Part kinetic energy due to agglomerate disintegration and be obviously used up, the particle hit later is present in the site but still uncured Coating material buffering.If powder coating material is made to pass through flame in advance, in uniform feeding particle and agglomerate-free feelings Under condition, then thermal energy is more likely to preferably be transferred to particle.

For example, in specific embodiments, according to the present invention, if the fusing point of coating material measured with [K] is with [K] At most the 50% of the temperature of the medium for being related in the coating method of the substrate measured, preferably up to 60%, more preferably extremely More 65%, even more preferably from most 70%, then the powder coating material for being covered at least one additive can also be used for preparation uniformly Layer, the medium such as gas streams, combustion flame and/or plasma flame.In other above-mentioned implementations according to the present invention In scheme it is special it is some in, if the fusing point of coating material measured with [K] is to be measured with [K] for being related to the substrate At most the 75% of the temperature of medium in coating method, preferably up to 80%, more preferably up to 85%, even more preferably from most 90%, then the powder coating material for being covered at least one additive can also be used for preparing conforming layer, the medium such as gas Stream, combustion flame and/or plasma flame.Above-mentioned percentage be related to the melting temperature of the coating material in terms of [K] with it is cold Gas blowout apply in the temperature of gas streams, in flame-spraying and high speed flame spraying the temperature of combustion flame it is non-thermal or it is hot etc. from Daughter sprays the ratio of the temperature of plasma flame.

In implication scope of the invention, term " conforming layer ", which describes related coatings, to be had less than 10%, preferably smaller than 5%, more preferably less than 3%, even more preferably less than 1%, more preferably less than 0.1% hole.In particular it is preferred to cannot know at all It Chu not hole.In implication scope of the invention, above-mentioned term " hole " is described relative to the painting being contained in two-dimensional surface Layer, is incorporated to the ratio in the hole in coating in the two-dimensional surface of the cross section of coated substrate.The measurement of this ratio is in root It is carried out on 30 randomly selected sites according to SEM is passed through on coating produced by the invention, wherein for example detecting substrate coating 100 μm of length.

It has surprisingly been found that by using coating material and additive, there is only what powder coating material improved to pass Defeated property, and the powder coating material that can not even previously transmit can also easily be transmitted and can be used for producing the painting of high-quality Layer.

The size distribution of particle is preferably measured by laser granulometry.In the method, measurement in powder form Grain.The laser of irradiation is scattered in different direction in space detections and is evaluated according to Fraunhofer diffraction theory.Particle is made Computer disposal is carried out for sphere.Therefore, measured diameter is always related to the equivalent ball measured on all direction in spaces Body diameter, and it is unrelated with the true form of particle.The size distribution shape average with the volume relative to equivalent sphere diameter Formula measurement calculates.Volume average particle sizes distribution is represented by cumulative frequency distribution.Cumulative frequency distribution is characterized in that by not With characteristic value such as D₁₀、D₅₀Or D₉₀The simplified way of value.

Measurement can be for example using Sympatec GmbH be derived from, and the granularity of Clausthal-Zellerfeld, Germany are divided Analyzer HELOS is carried out.Rodos T4.1 type dispersal unit can be used to disperse dry powder under such as 4 bars of initial pressure herein. Optionally, the size distribution curve of particle can be for example using device (device: the Cilas 1064) root for deriving from Quantachrome It is measured according to the specification of manufacturer.For this purpose, 1.5g powder coating material is suspended in about 100ml isopropanol, in ultra sonic bath (dress Set: Sonorex IK 52, Bandelin) middle processing 300 seconds, the sample of measuring device is then introduced by Pasteur suction pipe Product are prepared in pond and are measured multiple.Averaging of income value is formed by each measurement result.Scattered light signal is according to Fraunhofer method Evaluation.

In specific embodiment of the invention, preferably powder coating material has following size distributions: D₅₀Value is At most 53 μm, preferably up to 51 μm, more preferably up to 50 μm, even more preferably from most 49 μm.It is special in the above-described embodiment In some, particularly preferably powder coating material has following size distributions: D₅₀At most 48 μm of value, preferably up to 47 μm, More preferably up to 46 μm, even more preferably from most 45 μm.

In implication scope of the invention, term " D₅₀" refer to 50% by laser granulometry volume it is average described in Granularity of the size distribution under the designated value.Measurement can be used for example according to above-mentioned measurement method and derive from Sympatec GmbH, The Particle Size Analyzer HELOS of Clausthal-Zellerfeld, Germany are carried out.

In specific embodiment of the invention, preferably powder coating material has following size distributions: D₅₀Value is At least 1.5 μm, preferably at least 2 μm, more preferably at least 4 μm, still more preferably at least 6 μm.In the above-described embodiment special one In a little, particularly preferably powder coating material has following size distributions: D₅₀Value is at least 7 μm, preferably at least 9 μm, more excellent At least 11 μm, still more preferably at least 13 μm of choosing.

In specific embodiments, more preferably powder has following size distributions: D₅₀Value is in 1.5 to 53 μ ms It is interior, preferably in 2 to 51 μ ms, more preferably in 4 to 50 μ ms, even more preferably from 6 to 49 μ ms.In above-mentioned reality Apply in scheme it is special it is some in, particularly preferably powder has following size distributions: D₅₀Value is excellent in 7 to 48 μ ms It is selected in 9 to 47 μ ms, more preferably in 11 to 46 μ ms, even more preferably from 13 to 45 μ ms.

In other embodiments, such as preferably powder has following size distributions: D₅₀Value is in 1.5 to 45 μ ms It is interior, preferably in 2 to 43 μ ms, more preferably in 2.5 to 41 μ ms, even more preferably from 3 to 40 μ ms.Above-mentioned In embodiment it is special it is some in, particularly preferably powder has following size distributions: D₅₀Value is in 3.5 to 38 μ ms It is interior, preferably in 4 to 36 μ ms, more preferably in 4.5 to 34 μ ms, even more preferably from 5 to 32 μ ms.

In other embodiments, in contrast, such as preferably powder has following size distributions: D₅₀Value 9 to In 53 μ ms, preferably in 12 to 51 μ ms, more preferably in 15 to 50 μ ms, even more preferably from 17 to 49 μ ms It is interior.In the above-described embodiment it is special it is some in, particularly preferably powder has following size distributions: D₅₀Value is 19 to 48 In μ m, preferably in 21 to 47 μ ms, more preferably in 23 to 46 μ ms, even more preferably from 25 to 45 μ ms It is interior.

In other specific embodiments of the invention, preferably powder coating material has following size distributions: D₉₀ Value is at most 103 μm, preferably up to 99 μm, more preferably up to 95 μm, even more preferably from most 91 μm, most preferably up to 87 μm.? In the embodiment above it is special it is some in, the particularly preferably D of powder coating material₉₀Value is at most 83 μm, preferably up to 79 μm, more preferably up to 75 μm, even more preferably from most 71 μm.

In implication scope of the invention, term " D₉₀" refer to 90% by laser granulometry volume it is average described in Granularity of the size distribution under the designated value.Measurement can be used for example according to above-mentioned measurement method and derive from Sympatec GmbH, The Particle Size Analyzer HELOS of Clausthal-Zellerfeld, Germany are carried out.

In specific embodiments, it is preferable that powder coating material has following size distributions: D₉₀Value is at least 9 μm, preferably at least 11 μm, more preferably at least 13 μm, still more preferably at least 15 μm.In the above-described embodiment it is special it is some in, Particularly preferably powder coating material has following size distributions: D₉₀Value is at least 17 μm, preferably at least 19 μm, more preferably extremely It is 21 μm, still more preferably at least 22 μm few.

According to particularly preferred embodiment, powder coating material has following size distributions: D₉₀Value is in 42 to 103 μm of models In enclosing, preferably in 45 to 99 μ ms, more preferably in 48 to 95 μ ms, even more preferably from 50 to 91 μ ms.? In the embodiment above it is special it is some in, the particularly preferably D of powder coating material₉₀Value is excellent in 52 to 87 μ ms It is selected in 54 to 81 μ ms, more preferably in 56 to 75 μ ms, even more preferably from 57 to 71 μ ms.

Furthermore, it was surprisingly found that by additive covering obtain it is fine-grained can transporting significantly improve.This Provide the advantage that can be used in Athermal plasma spraying have large scale particulate and thus with can more preferably activate The powder coating material of property.In other specific embodiments of the invention, preferably powder coating material has following grains Degree distribution: D₁₀Value is at most 5 μm, preferably up to 4 μm, more preferably up to 3 μm, even more preferably from most 2.5 μm.In above-mentioned embodiment party In case it is special it is some in, particularly preferably powder coating material has following size distributions: D₁₀Value is at most 2.2 μm, excellent At most 2 μm of choosing, more preferably up to 1.8 μm, even more preferably from most 1.7 μm.

In implication scope of the invention, term " D₁₀" refer to 10% by laser granulometry volume it is average described in Granularity of the size distribution under the designated value.Measurement can be used for example according to above-mentioned measurement method and derive from Sympatec GmbH, The Particle Size Analyzer HELOS of Clausthal-Zellerfeld, Germany are carried out.

On the other hand, it is micro- that the powder coating material that the additive with high particulate ratio covers remains on strong formation The tendency of fine dust, this to handle corresponding powder more difficult.Therefore, in specific embodiment of the invention, preferably Be additive covering powder coating material have following size distributions: D₁₀Value is at least 0.2 μm, preferably at least 0.4 μm, more Preferably at least 0.5 μm, still more preferably at least 0.6 μm.In the above-described embodiment it is special it is some in, particularly preferably add The powder coating material of agent covering has following size distributions: D₁₀Value is at least 0.7 μm, preferably 0.8 μm, more preferable 0.9 μm, is gone back More preferably at least 1.0 μm.

In particularly preferred embodiments, the powder coating material of additive covering is characterized in that it with following granularities Distribution: D₁₀Value is also more excellent more preferably in 0.5 to 3 μ m preferably in 0.4 to 4 μ m in 0.2 to 5 μ m It is selected in 0.6 to 2.5 μ m.In the above-described embodiment it is special it is some in, the particularly preferably powder of additive covering Last coating material has following size distributions: D₁₀Value is more excellent preferably in 0.8 to 2.1 μ m in 0.7 to 2.2 μ m It is selected in 0.9 to 2.0 μ m, even more preferably from 1.0 to 1.9 μ ms.

For example, in specific embodiments, particularly preferred powder coating material has following size distributions: D₁₀Value is 3.7 To 26 μm, D₅₀Value is 6 to 49 μm, D₉₀Value is 12 to 86 μm.In the above-described embodiment it is special it is some in, particularly preferred powder Last coating material has following size distributions: D₁₀Value is 5.8 to 26 μm, D₅₀Value is 11 to 46 μm, D₉₀Value is 16 to 83 μm.? In the embodiment above it is special it is some in, it is even more preferred that powder coating material has following size distributions: D₁₀Value for 9 to 19 μm, D₅₀Value is 16 to 35 μm, D₉₀Value is 23 to 72 μm.

In other specific embodiments, such as preferably powder coating material has following size distributions: D₁₀Value is 0.8 to 28 μm, D₅₀Value is 1.5 to 45 μm, D₉₀Value is 2.5 to 81 μm.In the above-described embodiment it is special it is some in, especially It is preferred that powder coating material has following size distributions: D₁₀Value is 2.2 to 22 μm, D₅₀Value is 4 to 36 μm, D₉₀Value is 4 to 62 μ m.In the above-described embodiment it is special it is some in, it is even more preferred that powder coating material has following size distributions: D₁₀Value It is 2.8 to 17 μm, D₅₀Value is 6 to 28 μm, D₉₀Value is 9 to 49 μm.

In other specific embodiments, such as preferably powder coating material has following size distributions: D₁₀Value is 4.8 to 29 μm, D₅₀Value is 9 to 53 μm, D₉₀Value is 13 to 97 μm.In the above-described embodiment it is special it is some in, particularly preferably Powder coating material has following size distributions: D₁₀Value is 12 to 26 μm, D₅₀Value is 23 to 46 μm, D₉₀Value is 35 to 87 μm.? In the embodiment above it is special it is some in, it is even more preferred that powder coating material has following size distributions: D₁₀Value is 15 To 24 μm, D₅₀Value is 28 to 44 μm, D₉₀Value is 41 to 78 μm.

It was furthermore observed that additive covering powder coating material can transporting depend on size distribution width.This Width can such as be given a definition by specifying so-called span value to calculate:

It has been found by the present inventors that in specific embodiments, for example, the also more homogeneous of powder coating material is transmitted Property be by using being realized with the powder coating material of smaller span, which further simplifies more evenly with it is higher-quality The formation of layer.Therefore, in specific embodiments, the span of preferably powder coating material is at most 2.9, preferably up to 2.6, more preferably up to 2.4, even more preferably from most 2.1.In the above-described embodiment it is special it is some in, particularly preferably powder The span of last coating material is at most 1.9, and preferably up to 1.8, more preferably up to 1.7, even more preferably from most 1.6.

On the other hand, it has been found by the present inventors that necessarily require very narrow span with provide it is required can transporting, this makes It must be easier production powder coating material.Therefore, in specific embodiments, the span value of preferably powder coating material is At least 0.4, preferably at least 0.5, more preferably at least 0.6, still more preferably at least 0.7.In specific embodiments, preferably powder The span value of last coating material is at least 0.8, preferably at least 0.9, more preferably at least 1.0, still more preferably at least 1.1.

On the basis of teachings disclosed herein, those skilled in the art can choose any combination, especially above-mentioned The limiting value of span value, to provide the required combination of performance.In specific embodiments, such as preferably powder coating material Span value in the range of 0.4 to 2.9, preferably in the range of 0.5 to 2.6, more preferably in the range of 0.6 to 2.4, also More preferably in the range of 0.7 to 2.1.In the above-described embodiment it is special it is some in, particularly preferably powdery paints material The span value of material is in the range of 0.8 to 1.9, preferably in the range of 0.9 to 1.8, more preferably in the range of 1.0 to 1.7, Even more preferably from the range of 1.1 to 1.6.

On the basis of teachings disclosed herein, skilled in the art realises that, depending on the combination of required advantage, across The range and above-mentioned preferred D of degree limiting value or value₅₀The specific combination of the range of value is preferred.For example, particularly preferred In embodiment, powder coating material has following size distributions: span is in the range of 0.4 to 2.9 and D₅₀Value is 1.5 To 53 μ ms, preferably in 2 to 51 μ ms, more preferably in 4 to 50 μ ms, even more preferably from 6 to 49 μ ms It is interior, most preferably in 7 to 48 μ ms.In more particularly preferred in the above-described embodiment, under powder coating material has State size distribution: span is in the range of 0.5 to 2.6 and D₅₀Value is in 1.5 to 53 μ ms, preferably in 2 to 51 μ ms It is interior, more preferably in 4 to 50 μ ms, even more preferably from 6 to 49 μ ms, most preferably in 7 to 48 μ ms.Special In further preferred embodiment, powder coating material have following size distributions: span in the range of 0.6 to 2.4, with And D₅₀Value is in 1.5 to 53 μ ms, preferably in 2 to 51 μ ms, more preferably in 4 to 50 μ ms, even more preferably from 6 To 49 μ ms, most preferably in 7 to 48 μ ms.In embodiment especially still further preferably, powdery paints material Material has following size distributions: span is in the range of 0.7 to 2.1 and D₅₀Value in 1.5 to 53 μ ms, preferably 2 to In 51 μ ms, more preferably in 4 to 50 μ ms, even more preferably from 6 to 49 μ ms, most preferably in 7 to 48 μ ms It is interior.

It moreover has been found that the density of powder coating material can influence the powder with the transmission of aerosol form.It is not understood to The limitation present invention, inventors believe that, the same size but intrinsic difference of particle with different densities leads to have identical grain Spend the different behaviors of the aerosol stream of the powder coating material of distribution.Therefore can prove to be difficult to will be to specific D₅₀It is excellent The transmission method of change is converted into the transmission method of the powder coating material with other density.Therefore, in specific embodiments The upper limit of the density correction span value of powder coating material used in being preferably dependent upon.

Here, span UC is corrected span value, and span U is upper limit span value, ρ_AluFor the density (2.7g/ of aluminium cm³), ρ_XFor the density of used powder coating material.However, it has further been found that having in powder coating material lower than aluminium In the case where density, difference be it is slight, not will lead to the optimum choice of powder coating material in this respect can transporting It is obviously improved.Thus, to the powder coating material with the low density density than aluminium, using with uncorrected upper limit span The powder coating material of value.

Can coating method used according to the invention be those skilled in the art with the spraying of title cold air, hot plasma spray It applies, well known to Athermal plasma spraying, flame-spraying and high speed flame spraying.

Cold air spray characteristics is that powder to be administered is not melted in gas jet, but particle is greatly accelerated, and Result as its kinetic energy forms coating on the surface of the substrate.Here a variety of gases well known by persons skilled in the art can be used As carrier gas, such as nitrogen, helium, argon gas, air, krypton, neon, xenon, carbon dioxide, oxygen or their mixture.In specific change In body, particularly preferred air, helium or their mixture are used as gas.

The at most gas velocity of 3000m/s is obtained by controlled expansion of the above-mentioned gas in corresponding nozzle.Here may be used By Particle Acceleration at most 2000m/s.However, in the specific variants of cold air spraying preferably, the particle reaches for example Speed between 300m/s and 1600m/s, between preferably 1000m/s and 1600m/s, between more preferable 1250m/s and 1600m/s Degree.

The disadvantage is that for example, noise strong caused by high speed as used gas streams generates.

In flame-spraying, make for example, powder is converted to liquid or plasticity state and then is applied on substrate by flame For coating.Here, for example, the mixture of combustion oxygen and imflammable gas such as acetylene or hydrogen.In the specific change of flame-spraying In body, some oxygen are used to powder coating material being conveyed into combustion flame.In the conventional variant of this method, particle reaches Speed between 24m/s and 31m/s.

It is similar with flame-spraying, in high speed flame spraying, for example, powder is converted to liquid or plasticity also by flame State.However, compared to the above, particle is accelerated to significant higher speed.In the specific example of the above method, example Such as, the speed of designated gas stream is 1220 to 1525m/s, and the speed of particle is about 550 to 795m/s.However, in this method Other variants in, also reach more than the gas velocity of 2000m/s.In general, in the conventional variant of preceding method, preferred flame Speed between 1000m/s and 2500m/s.In addition, in conventional variant, preferably flame temperature 2200 DEG C and 3000 DEG C it Between.The temperature of flame is thus suitable with the temperature of flame-spraying.This is by firing gas under being about 515 to 621kPa in pressure It burns, then burning gases expand in nozzle and reached.In general, viewpoint be the coating that produces here with for example by flame spraying The coating of acquisition, which is compared, has more high density.

Pinking/explosive flame spraying can be regarded as a kind of hypotype of high speed flame spraying.Here, powder coating material is Accelerated by admixture of gas such as acetylene/oxygen repetition pinking strength, wherein for example reach the particle speed of about 730m/s Degree.The detonation frequency of this method is for example between about 4 and 10Hz.However, in variant such as so-called high-frequency gas pinking spraying, Also select detonation frequency for about 100Hz.

Resulting layer should usually have extra high hardness, intensity, density and the good combination to substrate surface.It is above-mentioned The shortcomings that method is increased safety cost, and, for example, the strong noise load as caused by high gas velocity.

In hot plasma spraying, for example, making predominant gas such as argon gas with the speed of 40l/min, second gas is such as Hydrogen passes through direct current electric arc furnace with the speed of 2.5l/min, wherein generating hot plasma.Then, for example, in carrier gas stream The powder coating material of 40g/min is fed under auxiliary, the carrier gas is sent into plasma flame with the speed of 4l/min.? In the common variant of hot plasma spraying, the transmission rate of powder coating material is more excellent between 5g/min and 60g/min It is selected between 10g/min and 40g/min.

, it is preferable to use argon gas, helium or their mixture are as ionizable gas in the specific variants of this method. In specific variants, entire gas streams further preferred 30 to 150SLPM (standard liter/min).Disregard as cooling knot Fruit and the thermal energy to dissipate, be alternatively used for ionized gas stream electrical power be for example 5 between 100kW, preferably 40 to Between 80kW.Here, it can reach in 4000K to the plasma temperature between tens of thousands of K.

In Athermal plasma spraying, Athermal plasma is used for activated powder coating material.It is used herein it is equal from Daughter is generated using the barrier discharge or corona discharge that such as frequency is 50Hz to 1MHz.In the specific of Athermal plasma spraying In variant, it is preferred that in the operation at frequencies of 10kHz to 100kHz.Here, the temperature of plasma is preferably smaller than 3000K, Preferably smaller than 2500K, even more preferably less than 2000K.This reduces process overheads to the maximum extent, and keeps to painting to be administered Expect that the energy input in material is low as far as possible, to allow the mild coating of substrate.The magnitude of the temperature of plasma flame Therefore preferably suitable with the magnitude of flame-spraying or the temperature of high speed flame spraying.DIE Temperature is lower than in nucleus The Athermal plasma of 1173K or even lower than 773K can also be generated by M8003 line parameter.Here, in nucleus Temperature for example using NiCr/Ni thermocouple and the spraying diameter for being 3mm apart from jet expansion 10mm formed plasma It is measured under ambient pressure in the core of body jet stream.Such Athermal plasma is particularly suitable for very temperature sensitive substrate Coating.

Have the coating on clearly boundary without the overlay area in a manner of targeted to produce, it has therefore proved that advantageous Be design especially plasma flame outlet so that generated coating track widths in 0.2mm between 10mm. This makes it possible to prepare very accurate, flexible, energy-efficient coating, and utilizes used coating material as far as possible simultaneously.For example, Select the distance of 1mm as the distance of spray gun to substrate.This enables coating to have flexibility as big as possible, and protects simultaneously Demonstrate,prove the coating of high-quality.Spray gun is to the distance between substrate advantageously in 1mm between 35mm.

In Athermal plasma spray coating method, multiple gases well known by persons skilled in the art and its mixture can be used as can Ionized gas.The example of these gases is helium, argon gas, xenon, nitrogen, oxygen, hydrogen or air, preferably argon gas or sky Gas.Particularly preferred ionizable gas is air.

Noise load is for example, reduced, also the speed of preferable plasma stream is lower than 200m/s here.Such as it may be selected 0.01m/s is between 100m/s, and preferably 0.2m/s to the value between 10m/s is as flow velocity.In specific embodiments, especially excellent Select the volume flow of such as carrier gas 10 between 25l/min, more preferably 15 between 19l/min.

According to preferred embodiment, the particle of powder coating material is preferably metallic particles or the particle containing metal. Particularly preferably the tenor of metallic particles or the particle containing metal is at least 95 weight %, preferably at least 99 weights Measure %, still more preferably at least 99.9 weight %.In particularly preferred embodiments, one or more metals be selected from silver, gold, Platinum, palladium, vanadium, chromium, manganese, cobalt, germanium, antimony, aluminium, zinc, tin, iron, copper, nickel, titanium, silicon, their alloys and mixts.In above-mentioned implementation In scheme it is special it is some in, preferably one or more metals be selected from silver, gold, aluminium, zinc, tin, iron, copper, nickel, titanium, silicon, they Alloys and mixts, be preferably selected from silver, gold, aluminium, zinc, tin, iron, nickel, titanium, silicon, their alloys and mixts.

Further preferred embodiment according to the method for the present invention, one or more gold of the particle of powder coating material Belong to and is selected from silver, aluminium, zinc, tin, copper, their alloys and mixts.Particularly, it has therefore proved that wherein one or more metal choosings It is specially suitable particle in a particular embodiment from the metallic particles of silver, aluminium and tin or metalliferous particle.

In other embodiments of the present invention, powder coating material is made of inorganic particle, and the inorganic particle is preferred Selected from carbonate, oxide, hydroxide, carbide, halide, nitride and their mixture.Mineral and/or metal oxygen Compound particle is specially suitable.

In other embodiments, inorganic particle is alternately or additionally selected from carbonaceous particle or graphite particle.

Another possibility is using the mixture of metallic particles and above-mentioned inorganic particle, above-mentioned inorganic particle such as mineral And/or metal oxide particle, and/or selected from carbonate, oxide, hydroxide, carbide, halide, nitride and it Mixture particle.

In addition, powder coating material may include glass particle or be made of glass particle.In specific embodiments, especially Preferably powder coating material includes that the glass particle of coating or the glass particle by being coated with form.

In addition, in specific embodiments, powder coating material includes organic and/or inorganic salts, or by organic and/or nothing Machine salt composition.

In other embodiment of the present invention, powder coating material includes plastic grain or is made of plastic grain.On Plastic grain is stated for example by pure or mixed homopolymer, copolymer, block polymer or prepolymer or their mixture shape At.Here, plastic grain can be for pure crystal or be mixed crystal or with amorphous phase.Plastic grain can for example pass through plastics Mechanical crushing obtains.

In particular embodiment of the process according to the invention, powder coating material includes the mixed of the particle of different materials It closes object or is made of the mixture of the particle of different materials.In particularly preferred embodiments, powder coating material is particularly It is made of the variable grain of at least two (preferably three kinds) different materials.

Particle can be produced by different methods.For example, metallic particles can pass through spraying or atomization molten metal It obtains.Glass particle can be prepared by the mechanical crushing of glass or be prepared from melt.In the latter case, glass melt can It is similarly atomized or spraying.Optionally, the glass of melting can also be crushed in rotating element such as rotary drum.

Selected from oxide, hydroxide, carbonate, carbide, nitride, halide and their mixture mineral Particle, metal oxide particle and inorganic particle, can be by crushing naturally occurring mineral, stone etc. then by size by it Screening obtains.

Screening can be carried out for example, by cyclone separator, air separator, sieve etc. by size.

In specific embodiment of the invention, before being covered with additive, the particle of powder coating material has had There is coating.

In particularly preferred embodiment of the invention, above-mentioned coating may include metal or be made of metal.This grain Son coating be formed as it is closed or granular, wherein it is preferred that with enclosed construction coating.The layer of this metal coating Thickness is preferably shorter than 1 μm, more preferably less than 0.8 μm, still more preferably less than 0.5 μm.In specific embodiments, this coating tool There is at least 0.05 μm, more preferably at least 0.1 μm of thickness.In specific embodiments particularly preferred in one of above-mentioned coating The metal of (preferably as main component) be selected from copper, titanium, gold, silver, tin, zinc, iron, silicon, nickel and aluminium, be preferably selected from gold, silver, tin and Zinc is more preferably selected from silver, tin and zinc.In the implication scope of above-mentioned coating, term " main component " refers to, related metal or on State metal mixture account for coating tenor at least 90 weight %, preferably 95 weight %, more preferable 99 weight %.It is necessary Understand, in the case where partial oxidation, does not consider the ratio of the oxygen in corresponding oxide skin(coating).Such metal coating can For example to be prepared by gas phase synthesis method or wet chemical method.

In other specific embodiments, the particle according to the present invention of powder coating material additionally or alternatively applies There is metal oxide layer.Preferably, the metal oxide layer is substantially by silica, aluminium oxide, boron oxide, zirconium oxide, oxidation Cerium, iron oxide, titanium oxide, chromium oxide, tin oxide, molybdenum oxide, its oxide hydrate, its hydroxide and their mixing Object composition.In particularly preferred embodiments, metal oxide layer is substantially made of silica.In meaning model of the invention In enclosing, above-mentioned term "consisting essentially of ..." refers at least 90%, preferably at least 95%, more preferably at least 98%, also more excellent Choosing at least 99%, most preferably at least 99.9% metal oxide layer is made of above-mentioned metal oxide, in each case phase For the granule number of metal oxide layer, included in any water do not consider.The composition of metal oxide layer can pass through Method known to those skilled in the art, such as the combination of sputtering method and XPS or TOF-SIMS measure.In the embodiment above In it is special it is some in, particularly preferred metal oxide layer does not represent the oxidation product of the metal core below it.It can example Such as this metal oxide layer is applied using sol-gel method.

In particularly preferred embodiments, substrate be selected from plastic basis material, inorganic substrate, cellulose-containing substrate and they Mixture.

The formed body that plastic basis material can be such as plastic film or be made of plastics.The formed body can have geometrically simple Single or complicated shape.The plastic shaped body can be such as component from auto industry or building industry.

Cellulose-containing substrate can be hardboard, paper, timber, substrate containing timber etc..

Inorganic substrate can be such as metal base, such as sheet metal or metal forming body or ceramics or mineral substrates or molding Body.Inorganic substrate can also be solar battery or silicon wafer, apply such as conductive coating or contact to it.

The substrate as made from glass, such as glass plate, it is also possible to make inorganic substrate.It, can using according to the method for the present invention So that glass (especially glass plate) has for example electrochromic coating.

A variety of different purposes are suitable for using the substrate being coated with according to the method for the present invention.

In specific embodiments, coating has optics and/or galvanomagnetic-effect.Here, coating can bring reflection or absorption. In addition, coating can be conductive, semiconductive or non-conductive.

Conductive layer can be applied to component in the form of such as tape conductor.This can be used for for example providing in automobile component Vehicle power supply frame in make it possible current-carrying.However in addition, such tape conductor can also be formed as such as antenna, Shielding, electric contact etc..This is for example particularly advantageous RFID using (radio frequency identification).In addition, coating according to the present invention can For for example for heating purposes or for particular elements or the heating of the target of the specific part of bigger component.

In other specific embodiments, coating produced is used as sliding layer, the diffusion barrier of gas and liquid, abrasion And/or corrosion protection layer.In addition, coating produced can influence the surface tension of liquid or have adhesion promotion performance.

Coating prepared in accordance with the present invention can be further used as sensor surface, for example, as man-machine interface (HMI), For example, in the form of touch screen.The coating may also used to shielding electromagnetic interference (EMI) or prevent static discharge (ESD).It should Coating can also be used for bringing Electro Magnetic Compatibility (EMC).

In addition, by using particle according to the present invention, can applied layer, apply the layer for example to increase corresponding component Stability after reparation.One example is the maintenance in aviation field, wherein the loss of material caused by such as processing step must It must be compensated, or application coating is for example for stabilizing.For such as aluminium component, this is proved to be difficult, aluminium component Post-processing step is usually required as being sintered.In contrast, by that according to the method for the present invention, can apply under very mild conditions The coating adhered to securely, even without post-processing step as being sintered.

In other embodiments, the coating is as electric contact, and allows the electrical connection between different materials.

Those skilled in the art recognize, the particle for powder coating material and wherein contained about of the invention The above description of method also correspondingly applies to the purposes of powder coating material and the particle wherein contained, and vice versa.

Embodiment

Used material and method.

The size distribution of the particle of powder coating material used is surveyed by HELOS device (Sympatec, Germany) It is fixed.For the measurement, before measuring, by 3 grams of powder coating material be introduced into the measuring device and with ultrasonic treatment 30 Second.For dispersion, using Rodos T4.1 dispersal unit, wherein initial pressure is 4 bars.The standard for evaluating use device is soft Part carries out.

It is explained in greater detail according to the method for the present invention referring now to following embodiments, and is not limited to these embodiments.

Embodiment 1: it is covered with the powder coating material of acrylic polymer (polyisobutyl methacrylate)

0.3g is based on to the acrylic polymer of Isobutyl methacrylate (Degalan P 675 derives from Evonik) As additive, and it is dissolved in 50g ethyl acetate.Then by the mixture and 240g alumina particles (D₅₀=17.5 μm) draw together Enter kneader (Duplex kneader comes from IKA) and is mediated 30 minutes at (20 DEG C) of RT.Then 40 DEG C of temperature and 250 is set The vacuum degree of millibar.It is dried 1 hour, then removes the particle containing additive from kneader, be then sieved (71 μm).

Embodiment 2: it is covered with the powder coating material of ethyl cellulose

The application of additive is similar to embodiment 1 and carries out.By 1g ethyl cellulose, (Ethocel Standard 10, is derived from Dow Wolff Cellulosics) it is used as additive.

Embodiment 3: it is covered with the powder coating material of acrylic polymer (polymethyl methacrylate)

The application of additive is similar to embodiment 1 and carries out.2g is based on methyl methacrylate and the positive fourth of methacrylic acid The acrylic polymer (Degalan LP AL 23 comes from Evonik) of ester is used as additive.

Embodiment 4: it is covered with the powder coating material of 1,10- decane dicarboxylic acid

By 3g 1,10- decane dicarboxylic acid making coatings excipient and it is dissolved in 50g ethyl acetate.Then by the mixing Object and 240g alumina particles (D₅₀=2 μm) it is concomitantly introduced into kneader (Duplex kneader comes from IKA) and mediates 30 at (20 DEG C) of RT Minute.Then 40 DEG C of temperature and 250 millibars of vacuum degree are set.It is dried 1 hour, then will be covered with coating excipient Particle removed from kneader, then be sieved (71 μm).

Embodiment 5: it is covered with the powder coating material of monomethyl ester

The application of coating excipient is similar to embodiment 4 and carries out.3g monomethyl ester making coatings excipient.

Embodiment 6: it is covered with the powder coating material of monoethyl adipatee

The application of coating excipient is similar to embodiment 4 and carries out.3g monoethyl adipatee making coatings excipient.

Embodiment 7: it is covered with the powder coating material of triethylene glycol monomethyl ether

The application of coating excipient is similar to embodiment 4 and carries out.3g triethylene glycol monomethyl ether making coatings excipient.

Embodiment 8: it is covered with the powder coating material of monoethyl adipatee

The application of coating excipient is similar to embodiment 4 and carries out.However, used here as D₅₀For 34 μm of copper particle.3g oneself Diacid mono ethyl ester making coatings excipient.

Embodiment 9: it is covered with the powder coating material of triethylene glycol monomethyl ether

The application of coating excipient is similar to embodiment 4 and carries out.However, used here as D₅₀For 34 μm of copper particle.3g tri- Glycol monomethyl ether making coatings excipient.

Embodiment 10: it is covered with the powder coating material of ethyl cellulose

The application of coating excipient is similar to embodiment 4 and carries out.However, used here as D₅₀The copper particle that value is 34 μm.3g Ethyl cellulose (Ethocel Standard 10 derives from Dow Wolff Cellulosics) uses making coatings excipient.

Embodiment 11: it is covered with the powder coating material of monomethyl ester

The application of coating excipient is similar to embodiment 4 and carries out.However, used here as D₅₀The copper particle that value is 34 μm.It will 3g DEGALAN PM 381 (copolymer of methyl methacrylate and Isobutyl methacrylate derives from Evonik), which is used as, to be applied Layer excipient.

Embodiment 12: it is covered with the powder coating material of Aerosil 200

Additive kind is similar to the application of embodiment 4.Used here as the D of 100g₅₀For 28 μm of spherical tin particles.3g Aerosil 200 (pyrogenic silicic acid derives from Evonik) are used as additive.

Embodiment 13: can transporting measurement

In order to determine be covered with additive according to the present invention powder coating material can transporting improvement, use From 100 fluidimeter of AS of Sames.Here, the various particles according to embodiment 1 to 3 of 250g are poured into and uses gas streams Change.Nitrogen is herein used as gas.Then the hole of calibration is opened 30 seconds, records the weight of the material during this period of time flowed out Measure the variable of (W) as measurement.

Embodiment 14: the Athermal plasma spraying of tin particles

Powder coating material is applied by the Plasmatron system derived from Inocon, Attnang-Puchheim, Austria With.Nitrogen is used as ionizable gas.Used here as standard process parameters.The chip for being coated with solar energy contact paste is used as base Material.It is used as powdery paints material according to the tin particles of the additive of embodiment 12 covering and additive-free similar tin particles Material.

In terms of consistency needed for coating, the transmission of additive-free tin particles is impossible.Transmission failure rapidly, And a small amount of of transmission is obviously fed into flame intermittently.In contrast, according to the powder coating material energy of embodiment 12 It is trouble-freely transmitted, the First look evaluation of obtained coating shows uniformly to apply.The SEM photograph of gained coating is seen Fig. 1 and Fig. 2.

Embodiment 15: according to the flame-spraying of the powder coating material of embodiment 4 to 11

Using the flame-spraying system for deriving from CASTOLIN, by oxyacetylene torch by the D of uncoated excipient₅₀Value is 2 μ The alumina particles of m and metal sheet is administered to according to the alumina particles of embodiment 4-7.In addition, similarly applying uncoated excipient D₅₀The copper particle that value is 34 μm and the copper particle according to embodiment 8 to 11.Gained metal sheet is detected by SEM.

For its optics and its tactile, the metal sheet being coated with according to the present invention is far more evenly.The SEM on surface Photo shows the formation of the larger homogeneous area of coating, and the surface characteristics of comparative example is the particle largely isolated.In addition, The cross section show the hole contained in the coating of metal sheet according to the present invention is significantly smaller.

Claims

1. purposes of the powder coating material containing particle in coating method, wherein the coating method be selected from cold air spraying, Flame-spraying, high speed flame spraying, hot plasma spraying and Athermal plasma spray, wherein the particle of powder coating material It is at least partially at least one additive,

Wherein the span of powder coating material is at most 2.9, the span is defined as:

2. purposes according to claim 1, wherein the total weight relative to coating material and additive, at least one The weight ratio of additive is at most 32 weight %.

3. purposes according to claim 1 or 2, wherein the total weight relative to coating material and additive, has at least A kind of carbon content of the powder coating material of additive is 0.01 weight % to 15 weight %.

4. purposes according to any one of claim 1 to 3, wherein the total weight relative to coating material and additive, The weight ratio of at least one additive is at least 0.02 weight %.

5. purposes according to any one of claim 1 to 4, wherein being used as one or more compounds of additive has At least six carbon atom.

6. purposes according to any one of claim 1 to 5, wherein the particle includes metallic particles or is metal Grain, and the metal be selected from silver, gold, platinum, palladium, vanadium, chromium, manganese, cobalt, germanium, antimony, aluminium, zinc, tin, iron, copper, nickel, titanium, silicon, they Alloys and mixts.

7. purposes according to any one of claim 1 to 6, wherein the coating method is selected from flame-spraying and non-thermal etc. Ionomer spray, and preferably Athermal plasma sprays.

8. purposes according to any one of claim 1 to 7, wherein at least one additive does not include stearic acid And/or oleic acid.

9. purposes according to any one of claim 1 to 8, wherein at least one additive is selected from polymer, list Body, silane, wax, oxidized wax, carboxylic acid, phosphonic acids, above-mentioned derivative and its mixture.

10. purposes according to any one of claim 1 to 9, wherein can be used organic and/or aqueous solvent from coated Particle remove at least one additive.

11. purposes according to any one of claim 1 to 10, wherein the size distribution of powder coating material is D₅₀Value exists In the range of 1.5 to 53 μm.

12. a kind of method for applying cloth base material, the method is selected from cold air spraying, flame-spraying, high speed flame spraying, heat etc. Ionomer spray and Athermal plasma spraying,

It is characterized by:

It the described method comprises the following steps:

Powder coating material containing particle is introduced to the medium being directed on substrate to be coated, wherein the particle has extremely A kind of few additive,

13. according to the method for claim 12, wherein the coating method is selected from flame-spraying and Athermal plasma sprays It applies, and preferably Athermal plasma sprays.

14. method according to claim 12 or 13, wherein powder coating material is transmitted as aerosol.

15. method described in any one of 2 to 14 according to claim 1, wherein the medium being directed on substrate is air or Through being generated from air.