FI118303B - Preparation of artificial patination material to substrates comprises stopping reaction between raw material and alkali metal hydroxide with water, and dispersing precipitate with powerful mixing and addition of dispersing agent - Google Patents

Abstract

Artificial patination material to substrates preferably made of copper or copper alloys is prepared by stopping reaction between raw material and alkali metal hydroxide with water, dispersing precipitate with powerful mixing and addition of dispersing agent, and using oxidative agent and carbon as agent for catalyzing natural patina. Preparation of artificial patination material to substrates preferably made of copper or copper alloys comprises using copper salt(s) as raw material that is precipitated with alkali metal hydroxide, filtering formed sludge for forming precipitate, stopping reaction between raw material and alkali metal hydroxide with water, dispersing precipitate with powerful mixing and addition of dispersing agent, and using oxidative agent and carbon as agent for catalyzing natural patina. An independent claim is also included for an artificial patination material to substrate preferably made of copper or copper alloys comprising copper salt as raw material, oxidative agent and carbon for catalyzing natural patina, and stable metal compound as color pigment for achieving desired color and/or color tinge.

Description

*, 118303

METHOD FOR THE MANUFACTURE OF PATENTING SUBSTANCES AND PATENTING SUBSTANCE

The present invention relates to a process for producing an artificial patinating agent of the desired color and / or 5 shades on a substrate material preferably made of copper or a copper alloy and to the patinating agent produced by the method.

Copper and copper alloys are covered with an oxide layer under normal atmospheric conditions. Outside, a copper oxide is formed on the copper surface and later a patina at varying speeds depending on where and how the surface is exposed. The color of the patina is green in urban and rural climates and blue-green or blue in maritime climates. Copper is known to be a durable and maintenance-free material for roofs and facades. Natural patina is the result of the corrosion of the metal in the atmosphere. The patina layer has a certain protective effect. It takes many years for patina to form on the surface of the copper substrate. Time is particularly long in a clean, rural climate where patina may not occur at all.

* · ·· • ·: mt] * 20 Numerous artificial patination methods have been described previously.

U.S. Patent 3,152,927 refers to a process and a paste wherein the patin gel is formed from basic copper nitrate and ferric sulfate.

• · · \ .I Alkaline copper nitrate is not thermodynamically stable in rainwater, but · · *** it gradually becomes stable to basic copper sulfate. The basic 25 copper sulfate and nitrate are blue in color and iron sulfate precipitation • «[··«. the resulting yellow dye compounds give the product a green color.

• *

The patinating agent is applied to the oxidized copper surface.

US Patent 5,160,381 describes a process for forming a · · 30 «artificial patina on copper by a) removing impurities, b) * * by polishing acetic acid, copper sulfate, sodium chloride, sodium hydroxide. and with copper acetate until a brown color is formed, c) washing 2 118303 polished copper surface, d) brushing, and e) placing the substrate after drying in a filtered solution of hydrochloric acid, copper carbonate, ammonium chloride, copper acetate, arsenic trioxide and copper nitrate.

U.S. Patent No. 5,714,052 refers to a process for producing a broccoli patina on a copper surface using a copper material to be treated, such as copper coils, as an anode in an electrolytic bath containing, for example, sodium carbonate. During this step, a green carbonate sulphite patina is formed on the surface of the material to be treated. The material is rinsed and transported through an attachment-10 bath where the original carbonate-sulphite patina is almost completely converted to a basic alkaline copper sulphate, i.e., brocantite. The fixative solution contains at least one of the oxidizing agents hydrogen peroxide, potassium chlorate, potassium peroxide sulfate, potassium permanganate and copper sulfate.

US Patent 6,176,905 describes a process and reaction solution especially for pre-oxidized or partially patinated copper surfaces. Copper surfaces are treated with a reaction solution comprising an aqueous solution of a copper salt and a basic salt. Suitable copper salts include copper (!) Carbonate, copper (II) carbonate, copper (II) chloride, copper (II) chloride, copper (II) sulfate, copper acetate, copper nitrate and mixtures thereof. The basic salt is selected from the group consisting of potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium sulfate, etc. The reaction solution in the example contains copper sulfate, sodium sulfate, and sodium chloride.

WO 95/29207, WO 95/29207, discloses a process for forming a patina, wherein copper sulfate and optionally iron sulfate react with an inorganic hydroxide compound followed by the use of a suitable binder.

i »·

The binder is added to the patina before the patina is applied to the surface of the substrate.

• · * "1 'The binder is an inorganic silicate and is present in an amount of 100-1000 g of patina ···: V 30 powder per liter of binder. Carboxylic acid can be used as an additional excipient to improve adhesion.

U.S. Patent No. 5,691,001 to 3,118,303 relates to a method for surface treatment of a copper-containing material. The coating agent is formed by mixing at least one aqueous solution of the copper salt and an alkali metal hydroxide, the coating agent is filtered and washed with a capillary filter. The solids content of the coating material 5 is adjusted to a range of 15-50% by weight and the coating material is stored at a temperature below 5 ° C until the surface treatment of the copper-containing material.

U.S. Patent No. 6,063,480 discloses a process for making a patinated copper sheet, first forming a layer of copper sulfide, black, on the surface of the copper sheet. A resin solution containing basic copper carbonate and / or basic copper sulfate is sprayed onto the sulfide layer so that it covers 25 to 80% of the surface. Because part of the surface remains free of artificial patina, natural patina can form at these points. The copper material having the patina manufactured in the manner described in the patent has good formability, i.e. the patin layer is also resistant to bending. The variation in color tone is limited to changing the ratio of the basic carbonate / sulfate particles in the resin mixture and the degree of coverage of the surface to be sprayed.

As noted above, basic copper nitrate is not thermodynamically stable but gradually becomes more stable basic copper sulfate • * due to oxidation reactions of sulfates or sulfur dioxide on the metal surface of the rainwater. • · However, reduced due to improved air pollution control and thus 25 changes from alkaline copper nitrate to basic copper sulfate • «[···. More time. Rainwater can cause artificial patina • · ./* discoloration in the first months and years Part of the patina • · ·:. .f may initially dissolve to reveal the brown or black oxide or sulfide surface • · "* and darken the patina surface in these areas. Part of the patina surface may react with ·: V 30 to form copper oxide, which also turns part of the patina surface * '* black or brown.

4, 118303

The former method uses iron salts to impart a green tinge to the patina, since the basic copper nitrate and sulfate coatings are blue in color without iron. The problem with the addition of iron is the formation of rust and the consequent discoloration of the patina surface 5. The iron compounds also make the patina surface more oxidative, which is advantageous for the formation of a new patina during its presence. However, a sufficient oxidation effect is achieved with less iron * than is required to achieve the required green hue.

ίο All of the above methods have attempted to give the substrate material a green, bluish-green, or blue shade that mimics the natural patina. As noted above, success depends not only on the copper salts used, but also on the amount of other additives used.

15 One important characteristic of visible parts of buildings, such as roofs and facades, is color. The visual compatibility of parts of the building made of different materials is a very important factor in new projects. Nowadays, for example, in architectural design, it is desired to create different shades of · · ··· surfaces on buildings, and even completely different colors than traditional · * ».. 20 patina.

This invention relates to a process for the preparation of an artificial patinating agent: **], wherein the desired color and / or color tone is formed on the patina.

A copper oxide layer is first formed on a substrate material such as copper or copper alloy, and a patinating agent is added thereto. Size * ·: ·· The patina layer is made as similar as possible to the natural ··· patina layer. According to the method, the patinating agent is prepared from at least one copper salt which is precipitated with an alkali metal hydroxide.

The copper salt is preferably copper sulfate, but may also be copper nitrate, copper chloride, copper carbonate, or a mixture thereof.

··· · »· 118303 5

We have found that the grain size and color of the product formed during the precipitation process can be adjusted by changing the concentration of the copper salt and / or alkali metal hydroxide in the solutions used for the precipitation. Dilute solutions give a precipitate with a small particle size. The grain size of the precipitate increases with 5 concentrations. The reaction of the copper salt and hydroxide is quenched with water, the precipitate washed and filtered with a suitable filter. Small grain size gives a lighter color and large grain size a darker color to the patinating agent and the patina surface made with it.

It is advantageous to disperse the precipitate by effective mixing with the possible addition of a dispersant. The dispersant may be a suitable commercial product. It separates the agglomerated particles of the precipitate and prevents them from agglomerating again. The dispersion makes it easy to apply the finished patinating agent. Another advantage of dispersion is that the pasta is stored at room temperature instead of the previous refrigerator temperature. In addition, the shelf life increases from four weeks to several months, for example six months.

m * * The addition of a suitable oxidizing chemical to the patinating agent is advantageous, as well as the use of substances such as carbon which catalyze the formation of sulfate without sulfur dioxide. When it is desired to obtain ··· m * [; ·; * colors or shades different from the normal patina color, it is preferable to * * · add at least one inorganic metal compound «· **** to the patinating agent as the color pigment. These compounds are chemically patinated particles. 25 and they do not react with climate pollutants. The colors of the patinating agent dyed according to the invention are essentially different shades of green and blue from light to dark, but they can also be the desired shades of gray, black, red, yellow or brown.

The invention also relates to a patinating agent whose color and hue can be adjusted to the desired size by adjusting the grain size of the patinating agent and / or using at least one metal compound as a color pigment. Preferably, the compound is an inorganic metal compound.

The invention is characterized by what is stated in the claims.

5

The iron salt can also be used as a raw material for a patinating agent. The iron salt is preferably iron (III) sulfate, but it may also be iron (III) nitrate or iron (III) chloride.

ίο We have found that patinating agents with different grain size, grain shape and grain size distribution can be obtained by adjusting the chemical concentration and feed rate of the alkali metal hydroxide during the precipitation process. Grain size, grain size distribution and grain shape have an effect on color tone and durability of the patina layer. A grain size of 0.2 to 100 µm has proven to be advantageous.

A suitable oxidizing chemical is added to the precipitate of copper salt and alkali hydroxide. This is done before or after the dispersion, depending on the material used. In addition to their oxidizing effect, the substances also act as coloring agents. In this case, the oxidizing chemical may be an iron compound, but it is preferable to use, for example, manganese dioxide (MnO2) as the main oxidizing agent. Iron can be added as iron hydroxide, iron (III) oxide or a mixture thereof. Commercial metal pigment compounds may also be used as oxidizing agents. The purpose of this addition; v <25 is to make the slurry more oxidative, which is advantageous in terms of stability and adhesion of the · · [* · *, patina layer. When other oxidizing chemicals are added, it is possible to obtain a non-iron or • · * 'patinating agent (f is less than normal and thus reduce rust formation and discoloration problems).

·· «• · ·:. · 30

It is also advantageous to use substances which catalyze the formation of sulfate from atmospheric sulfur dioxide, i.e. substances which increase the conditions for the natural formation of patina. Such a catalyst is, for example, carbon. The carbon can be added as carbon powder, carbon black or graphite. Commercial pigments such as Mineral Black (C + SiO 2) or Black Earth (C) can also be used. The addition of carbon also affects the color of the patina paste.

5

In addition to the aforementioned color effect provided by anoxic and catalysts, it is also advantageous to use other stable inorganic metal compounds to achieve the desired color. Since the basic copper sulfate and alkaline nitrate patinating agent are blue in color, the addition of yellow or brown particles makes them greener. The yellow color pigments based on stable metal compounds have a more intense coloring effect than the iron compounds of the precipitation process. It is preferable to use color pigments containing compounds of iron and aluminum, iron, aluminum and manganese, iron, aluminum manganese and isine or manganese in place of iron or in addition to iron added to the precipitation process. These include, for example, Mars Yellow (FezOyHaO + Al 2 O 3), Yellow Ocher (Fe (OH) 3), Raw Amber Earth (Fe 2 O * MnO 2 * nH 2 O + Si + Al 2 O 3) or Sienna Natural Earth (Fe 2 O 3 * nH 2 O + MnO 2 + AI 2 O 3 + SiO 2 *). 2 (H20)). Can also use brown ·: ··: color pigments such as Iron Brown (Fe203>, Manganese Brown (Μηθ2, 20 Μη2θ7), Sienna Burnt (Fe203 * nH20 + Al203 + Mn02), Burnt Umber (Fe203-Mn02 * nH20 + Si + AI2O3) Magnetite and tenorine (CuO) give a beautiful dark shade of green paste.

· ♦ * • · · • * • 1

The chromium and copper compounds, either alone or separately, are also suitable color pigments. It has been found that stable inorganic metail pigments to obtain a green color are, for example, Malacite Green (CuCO3 * Cu (0H) 2), »·· * ···: Opaq Chromium Green (Cr203), in which the chromium is trivalent ,

Chrysocolla (CuSiO3 * nH2O + Cu2CO3 (0H) 2 + CuCO3 (0H) 2) and Magnesium, Aluminum and Potassium pigment Green Earth (Mg, Al, *; 30 K). The amount of metal compounds used as pigments is small, generally less than M * * to achieve a patina color.

·; · *: 1% of the amount of the patinating agent when the pigment is used in organic h 118303

In addition to, or in place of, the above-mentioned conventional patina coloring or color-enhancing metals, other, particularly inorganic, metal pigments may be added to the patinating agent to provide the desired color or color tone. The amount of pigment used is still quite small, on the order of 1-5% of the dry matter of the patinating agent. The black, yellow, brown and green pigments have already been mentioned above and their use in obtaining a suitable organic patina tone. However, by adjusting the amount of these pigments, a corresponding colored ίο (yellow, brown and green) patina is also obtained. Different shades of blue are obtained, for example, by using Egyptian blue, calcium copper silicate, CaCuSi4Oi0), which is a chemically resistant pigment. The above-mentioned black pigments can also be used to make the green color gray or to provide different shades of blue-gray.

15

When copper sulphate is used as a raw material for a patinating agent, the reaction with an alkali metal hydroxide forms either brocantite (Cu 4 SO 4 (OH) 6) or posnaite (Cu 4 SO 4 (O H) 6 * 2H 2 O). Pancreatitis is a product that is formed ·: ·· * in nature and gradually turns into a brokant in a few years.

f * · .. 20 It may be advantageous that patina also be present in the patina, as it gives the surface liveliness as it becomes a brocade.

• · «· * • * • · ···

The purpose of the patinating agent is also to ensure that the patina adheres well to its substrate and has a durable surface. This can be improved by adding 25 binders to the patinating agent. Sodium silicate is commonly used as a binder for the patina * «: * · * and is sprayed onto the patina surface after the patina * ·· has been applied to its substrate. We have now found it advantageous to use: an alkyd-based compound as a binder and add it to the actual patinating agent during the preparation of the pasta. Addition of binder to the pasta during preparation does not shorten the shelf life. The amount of binder is up to 10% of the dry matter of the patinating agent, preferably 2 to 3%. The amount of dry matter in the patinating agent is 15-50%. The amount of binder is adjusted so that after application, the patina layer is firmly adhered to its substrate. The patina particles are not completely but only partially covered with binder. This leaves the patina particles exposed to the air so that natural patination reactions can proceed.

5

The use of a binder is not always mandatory but desirable. The grain size of the patinating agent is important for the durability of the patina surface. Certain test periods, in which the posjite was the major component, with a grain size between 0.2 and 80 µm with a uniform distribution, produced good results. This type of paste gives a very durable patina surface with good adhesion without any binder.

The patinating agent of the invention may be applied by brush, roller or spray. The pasta can also be stored for longer periods at room temperature. The paste can be applied directly to the application as well as pre-patinated elements or sheets. The durability of the formed patina layer also makes it possible to manufacture patinated sheets and make profiles for architectural use. Oxidizing agents and catalyzing carbon compounds in the patina layer facilitate natural reactions with air:: ··· and the formation of a new natural patina.

20: * · *: The invention will be further described by the following example.

· · ··· * · • · t ···: Λ Example 1 ·· *

The precipitation process is carried out in a five cubic meter reactor. A good mixing is achieved by placing the mixer at a height of about 400 mm from the bottom of the reactor ·: V. Therefore, it is possible, if desired, to use a relatively low concentration in the process solution. This is important if you are going to »: **]: make bets with different grain size and grain shape.

30 475 liters of urban water are added to the reactor. Stir evenly with 100 kg copper sulphate containing 27% copper. When the copper sulfate is completely dissolved, 4 kg of ferrous sulfate containing 21-23% iron are added.

, 0 1 18303

714 L of 1 M sodium hydroxide solution is pumped into the reactor and allowed to precipitate. The process is stopped by pumping 1960 L of tap water. The precipitate is allowed to settle for a few hours. The clear solution is pumped off and the precipitate is led to a ceramic filter for washing. After washing and filtration, the precipitate contains 20-30% solids and less than 0.1% alkaline ions.

The precipitate formed is pumped into a leaching tank for dispersion. Add 200 g of carbon powder, 300 g of manganese dioxide (MnO2), 1 liter of Malachite Green pigment (CuC031Cu (0H) 2) and 2 liters of commercial dispersant. After the dispersion process, 15 liters of the alkyd binder in the aqueous solution is added with slow stirring. The product is predominantly broccoli with a solids content of 20-30% and a grain size of 0.5-12 micrometres. The product is packed in plastic containers and stored at 15 room temperature.

The prepared product was applied to the surface of three brown oxidized copper plate sets. The application was done either with a brush, a brush and a roller or with a spray gun. Two plates from each set were taken for the cabinet test.

..... 20 Brown, oxidized, and bare copper plates were included for reference.

• · ... Cabinet Test: • ·· ..... Solution: Artificial Rainwater • *. ···. chemical mmol • ·: v. NaCI 10.0000 # ·. ***. 25 NH4NO3 0.0400 • · K2S04 0.0031: MgS0417H20 0.0049 ··· ·

CaS04x2H20 0.0050 • · 1. ···. H2S04 0.0230 • · ··· * • · • «• · 1 • · · · ·“ 118303

Temperature: 50 ° C

Spraying: 30 min / h at 0.8l / h

Duration: 250 h 5 Visual examination showed that all patinated specimens were almost intact. The bare copper samples had turned dark brown. The oxidized plates had white areas and some black oxide disappearance from the surfaces, similar to that seen in oxidized copper samples placed for two years at the sea-water corrosion station.

* • • t · ** ** ** ** * * * · · · · • · • · · * * * * * * * * * * * *

Claims (40)

A process for preparing an artificial patinating agent for a substrate material, preferably copper or copper alloy, wherein the slurry formed by at least one copper salt doped with an alkali metal hydroxide is filtered to form a patinating agent, characterized in that the reaction between the raw material and the alkali metal hydroxide the precipitate is dispersed by vigorous mixing and addition of a dispersant, and additionally, an oxidizing agent and carbon are used to catalyze the formation of a natural patina and at least one stable metal compound as a color pigment to obtain the desired color and / or color tone. The process according to claim 1, characterized in that at least one of the groups copper sulfate, copper nitrate, copper chloride, copper carbonate or a compound thereof is used as a raw material for an artificial patinating agent. The process according to claim 1 or 2, characterized in that the copper sulphate is used as a raw material for the artificial patinating agent. II: 1 '. · 2. Förfarande enligt patentkrav 1, kännetecknat av att ätminstone et • **: ** site ur Gruppen copar sulfate, copar nitrate, copechloride, carbonyl eller en förening av dessa används som rämaterial för 30 det konstgjorda patineringsämnet. • · • · · • φ * • · * • · 18 1 1 8303 3. Förfarande enligt patentkrav 1 eller 2, kännetecknat av att kopparsulfat används som rämaterial för det konstgjorda patineringsämnet. 5 4. Förfarande enligt verge av de föregäende patentkraven 1-3, kännetecknat av att mangandioxid används som oxiderande ämne. Process according to any one of claims 1 to 3, characterized in that manganese dioxide is used as an oxidizing agent. The process according to any one of claims 1 to 4, characterized in that the iron compound is used as a raw material for an artificial patinating agent. · * · 1 • · · »M 1 118303 5. Förfarande enligt avgot av de föregäende patentkraven 1-4, kännetecknat av att en järnförening används som rämaterial för det ίο konstgjorda patineringsämnet. 6. Förfarande enligt vorte av av föregaende patentkraven 1-5, kännetecknat av att en järnförening används som oxiderande ämne. 7. Förfarande enligt face av de föregäende patentkraven 1-6, kännetecknat av att en oorganisk metallförening används som färgpigment. Process according to any one of claims 1 to 5, characterized in that the iron compound is used as an oxidizing agent. Process according to any one of claims 1 to 6, characterized in that an inorganic metal compound is used as the color pigment. 8. Förfarande enligt face av de föregäende patentkraven 1-7, * * 20 kännetecknat av att en järnförening används som färgpigment. ·· • · · »· · •»:> t; * 9. Förfarande enligt nägot av de föregäende patentkraven 1-7, • · kännetecknat av att en järn- och aluminumförening, en järn-, • ♦ ·: .. f mangan- och aluminiumförening eller en järn-, manganese, kisel och • · ***** 25 aluminumförening används som färgpigment. • · • «· • · · · · 10. 10. Förfarande enligt förfarande enligt face a de föregäende patentkraven 1-7, * * [·] kännetecknat av att en manganförening används som färgpigment. face av de föregäende patentkraven 1-7, • · kännetecknat av att en kopparförening används som färgpigment. t · 118303 Process according to any one of claims 1 to 7, characterized in that the iron compound is used as a color pigment. 10 A process according to any one of claims 1 to 7, characterized in that the iron and aluminum compound, the iron, manganese and aluminum compound or the iron, manganese, silicon and aluminum compound are used as the color pigment. is Process according to any one of claims 1 to 7, characterized in that the manganese compound is used as a color pigment. . A process according to any one of claims 1 to 7, characterized in that the copper compound is used as a color pigment. • · · ·· · • · · · ·. ··. The process according to claim 11, characterized in that * · copper carbonate compound, copper silicate-copper carbonate compound • *. ♦ · *. or a calcium copper silicate compound is used as the color pigment. • · ·· · 25 12. Förfarande enligt patentkrav 11, kännetecknat av att en kopparkarbonatförening, en kopparsarbonikat-kopparkarbonatförening eller en calcium koparsilikatförening används som färgpigment. s 13. Förfarande enligt face av de föregäende patentkraven 1-7, kännetecknat av att en krom (III) förening används som färgpigment. 12 118303 13. A method according to any one of claims 1-7, characterized in that the chromium (III) compound is used as a color pigment. The process according to any one of claims 1 to 7, characterized in that the magnesium aluminum and potassium compound is used. as a pigment. '* 118303 14. Förfarande enligt arc av de föregäende patentkraven 1-7, kännetecknat av att en magnesium-, aluminum- and potassiumförening ίο används som färgpigment. 15. Förfarande enligt face av de föregäende patent kraven 1-7, kännetecknat av att koi används som färgpigment. is 16. Förfarande enligt face av de föregäende patentkraven 1-15, kännetecknat av att toyden av färgpigment utgör högst 5% av patineringsämnetstorrsubstanshalt. Process according to one of claims 1 to 7, characterized in that the carbon is used as a color pigment. Process according to one of Claims 1 to 15, characterized in that the amount of color pigment in the dry matter of the patinating agent is not more than 5%. 17. Förfarande enligt ägot av de föregäende patentkraven 1-16,:: 20 kännetecknat av att en alkydbaserad förening används som · j "bindemedel och att bindemedlet tillsätts i patineringsämnet under • · ♦: · * framställningen av en pasta. • · · ·· · • ♦ « Process according to any one of claims 1 to 16, characterized in that the alkyd-based compound is used as a binder and that the binder is added to the patinating agent during the preparation of the pasta. 18. Förfarande enligt patentkraven 17, kännetecknat av att mängden • · '"** 25 bindemedel utgör högst 10% av patineringsämnets torrsubstanshalt. • · • φ · • · ·" 1/19. Förfarande enligt face av de föregäende patentkraven 1-18 , • ♦ Hl kännetecknat av att mängden torr substans i patineringsämnet är 15-: ··· 5 50%. • ♦ 30 • · Process according to claim 17, characterized in that the amount of binder is not more than 10% of the dry matter content of the patinating agent. 15 Process according to any one of claims 1 to 18, characterized in that the amount of dry matter in the patinating agent is 15-50%. 20. Constants for patching underlagsmaterial som företrädesvis bestär av koppar eller en copparlegering, colors 20 1 1 8303 ätminstone et bulgant anv somämaterial, som utfälls med alkali metal hydroxides, den picture suspensionen filtrehas ox patne picture , och ko för att catalysera bildandet av naturlig 5 patina, och att ätminstone en stable metalförening använts som färgpigment för att ästadkomma omaskad färg och / eller färgton. An artificial patinating agent for a substrate material, preferably 20 copper or copper alloy, wherein the raw material used is at least one · ·; · formed by a · · · · · · · · · · slurry formed to form a patinating agent, characterized in that: . that the patinating agent contains an oxidizing agent, and carbon to catalyze the formation of a natural patina, and that at least one is stable. The 25 metal compounds have been used as a color pigment to achieve the desired color and / or ··· color tone. • 1 • · · · · · 1 · 21. Patineringsämne enligt patentkrav 20, kännetecknat av att en alkydbaserad förening använts som bindemedel. 10 A patinating agent according to claim 20, characterized in that ♦ ··. ·· 1. the alkyd-based compound has been used as a binder. • · ··· 30 • · · • · · · · · t m 2 • · 15 1 1 8303 22. Patineringsämne enligt patentkrav 20 eller 21, kangnetecknat av att ätminstone that you received ur Group crude sulphate, crude nitrate, copolymer, carbonate eller en förening av dessa används som rämaterial för patineringsämnet. 15 A patinating agent according to claim 20 or 21, characterized in that at least one of the group copper sulphate, copper nitrate, copper chloride, copper carbonate or a compound thereof is a raw material for the patinating agent. 23. Patineringsämne enligt nägot av de föregäende patentkraven 20-22, kännetecknat av att kopparsulfat används som rämaterial för patineringsämnet. A patinating agent according to any one of claims 20 to 22, characterized in that the copper sulphate is the raw material of the patinating agent. 24. Patineringsämne enligt ärag av de föregäende patentkraven 20-23, â &#x20AC; &#x201C; â &#x20AC; &#x201C; p (cu4SO4 (0H) e-2H2O), particle size range 0.2 to 80 pm. • · • · ··· M · • «·:,. F 25. Patineringsämne enligt nägot av de föregäende patentkraven 20-24, • · ***** 25 kännetecknat av att patineringsämnespartiklar har en storlek av 0,2 -. .100 um. • · · 1 • · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · back The quenching agent according to any one of the preceding claims 20 to 23, characterized in that part of the quenching agent is posnite mica (Cu 4 SO 4 (0H) 6 * 2H 2 O) having a grain size of 0.2 to 80 µm. The patinating agent according to any one of claims 20 to 24, characterized in that the patinating agent has a particle size of 0.2 to 100 μιτι. 26. Patineringsämne enligt nägot av de föregäende patentkraven 20-25, • φ * ···] kännetecknat av att play in torr substans i patineringsämnet 15 30 -50%. • · • ♦ ♦ • ♦ · • ♦ · 118303 The patinating agent according to any one of claims 20 to 25, characterized in that the dry substance in the patinating agent is 15 to 50%. 20 • · 27. Patineringsämne enligt verge av de föregäende patent kraven 20-26, the kännetecknat av att bindemedlet täcker itself delvis patinerings -ämämpartpartama. 27. An M patinating agent according to any one of claims 20 to 26, characterized in that the binder only partially covers the · · · ···. patinointiainepartikkelit. A patinating agent according to any one of claims 20 to 27, characterized in that the color pigment is an inorganic metal compound. ··· • · * · • * ». ···. A patinating agent according to any one of claims 20 to 27, characterized in that the iron compound is used as a color pigment. »· I« I • 118303 28. Patineringsämne enligt verge av de föregäende patentkraven 20-27, kännetecknat av att en oorganisk metallförening använts som färgpigment. 29. Patineringsämne enligt verge av de föregäende patentkraven 20-27, to kännetecknat av att en jämförening använts som färgpigment. 30. Patineringsämne enligt ägot av de föregäende patentkraven 20-27, kännetecknat av att en jäm-och aluminum-förening, en mangan, and mangan-och aluminum-förening använts som färgpigment. The patinating agent according to any one of claims 20 to 27, characterized in that the iron and aluminum compound, the iron, manganese and aluminum compound or the iron, manganese, silicon and aluminum compound are used as the color pigment. 5 31. Patineringsämne enligt verge av de föregäende patentkraven 20-27, kännetecknat av att en manganförening använts som färgpigment. • ·: ·. 20 32. Patineringsämne enligt nägot av de föregäende patentkraven 20-27, * · kännetecknat av att en kopparförening använts som färgpigment. * · · ** • · * * A patinating agent according to any one of claims 20 to 27, characterized in that the manganese compound is used as a color pigment. 10 A patinating agent according to any one of claims 20 to 27, characterized in that the copper compound is used as a color pigment. Is patinating agent according to claim 32, characterized in that the copper carbonate compound, copper silicate-copper carbonate compound or calcium copper silicate compound is used as a color pigment. 33. Patineringsämne enligt patentkrav 32, kännetecknat av att en · ·; ***; kopparkarbonatförening, en kopparsarbonikat-kopparkarbonatförening eller 25 en potassium kopparsiiikkaförening använts som färgpigment. 4 4 4 4 4 44 4 34. Patineringsämne enligt verge av de föregäende patent kraven 20-27,. λ kännetecknat av att en krom (lll) förening använts som färgigment. ··· ♦ ·· • · • · ···. *. 30 35. Patineringsämne enligt nägot av de föregäende patentkraven 20-27, * · · kännetecknat av att en magnesium, aluminum och kaiumförening t använts som färgpigment. 22 1 18303 34. § · according to any one of claims 20 to 27. 20 patinating agent, characterized in that the chromium (III) compound has been used. color pigment. • · * · # • · • · «·· The * * patinating agent according to any one of claims 20 to 27, characterized in that the magnesium aluminum and * · · 25 potassium compounds are used as a color pigment. · * • · • · ♦ 36. Patineringsämne enligt verge av de föregäende patent kraven 20-27, kännetecknat av att koi använts som färgpigment. 36. A process according to any one of claims 20 to 27. patinating agent, characterized in that carbon has been used as a color pigment. * * • * * • · • * «··:! ·. 37. ··· * .... according to any one of claims 20 to 36, characterized in that the amount of binder is up to 10% of the dry matter content of the patinating agent. 17 1 18303 37. The patineringsämne enligt face av patent föregäende patentkraven 20-36, the kännetecknat av att toyden bindemedel utgör högst 10% av patineringsämnets torrsubstanshalt. 38. Patineringsämne enligt verge av de föregäende patentkraven 20-37, änd kännetecknat av att lagringstiden är flera mezader. A patinating agent according to any one of claims 20 to 37, characterized in that the storage period is several months. A patinating agent according to any one of claims 20 to 38, characterized in that the pasta is stored at room temperature. The ozο patinating agent according to any one of claims 20 to 39, characterized in that the amount of color pigment in the dry substance of the patinating agent is not more than 5%. 15 1. Förfarande för framställning av konstgjort patineringsämne Pärt underlagsmaterial som företrädesvis bestär av koppar eller kopparlegering, vid flashing förfarande som raw material anvätänstät tarskarsalt, som utfälls med alkaline metal hydroxide, den bildadeören atten mellan jämaterialet och • ·: * · alkali metal hydroxide stop med watten, fällningen disppergeras ·· ·: V genome kraftig omröring och tiilsats av dispergeringsmed och därtill • · · an oxidant ämne och koi för att catalysera bildandet · * naturlig patina samt ätminstone en stable metalförening som * · * ··· * 25 färgpigmentförattästadkommaönskadfärgoch / ellerfärgton. • · • · · 39. Patineringsämne enligt Face to face patent code 20-38, kännetecknat av att pastan kan förvaras vid rumstemperatur. is 40. Patineringsämne enligt face av patent föregäende patentkraven 20-39, kännetecknat av att mängden färgpigment utgör högst 5% av patineringsämnets torrsubstanshalt. • a · aa • · • »» · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · 2 • · · 3 · ··· · • a »• a aa * a • · • aa aa # aaaaaaaaaaaaaa