CN109518176B - Alkaline phosphating solution, preparation method and phosphating process - Google Patents
Alkaline phosphating solution, preparation method and phosphating process Download PDFInfo
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- CN109518176B CN109518176B CN201811532494.2A CN201811532494A CN109518176B CN 109518176 B CN109518176 B CN 109518176B CN 201811532494 A CN201811532494 A CN 201811532494A CN 109518176 B CN109518176 B CN 109518176B
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- complexing agent
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
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Abstract
The invention discloses an alkaline phosphating solution, a preparation method and a phosphating treatment process. The alkaline phosphating solution comprises an aqueous solution of a polyvalent metal phosphate and a weakly alkaline complexing agent. The preparation method of the alkaline phosphating solution comprises the step of dissolving the polyvalent metal phosphate and the alkalescent complexing agent in water. The phosphating treatment process comprises the steps of applying the alkaline phosphating solution to the surface of a metal substrate and drying. The invention can effectively control the quality of the phosphating film, the phosphating film is uniformly adhered, and the phosphating treatment process has simple steps.
Description
Technical Field
The invention relates to an alkaline phosphating solution, a preparation method and a phosphating treatment process.
Background
The use of phosphating processes has been in industry for over 90 years. The phosphating film can provide protection for base metal and prevent the metal from being corroded to a certain degree; the primer can be used for priming before painting, and the adhesive force and the corrosion resistance of a paint film layer are improved; the lubricant is used for antifriction and lubrication in a metal cold working process.
Almost all phosphating solutions are currently acidic. By adding acidic substances such as phosphoric acid and the like into the phosphating solution, the indissolvable phosphate is promoted to be dissolved in water; during the phosphating treatment, the free acid reacts with the metal substrate to increase the pH value of the phosphating solution, so that phosphate dissolved in water is separated out, and a phosphating film is formed on the surface of the metal substrate. Therefore, the quality of the phosphating film is closely related to the pH value of the phosphating solution, and after the phosphating solution is used for a period of time, sediment can appear in the phosphating solution due to the increase of the pH value, so that the quality of the phosphating film is reduced and the phosphating film needs to be adjusted or replaced; the treatment process is complicated, and usually water washing and neutralization are required after phosphating to remove the acidic phosphating solution attached to the phosphating film.
Disclosure of Invention
The invention provides the alkaline phosphating solution, the preparation method and the phosphating process for overcoming the defects of easy occurrence of dregs, poor quality of a phosphating film, uneven adhesion, complicated treatment process and the like in the phosphating process in the prior art, and can effectively control the quality of the phosphating film, realize even adhesion and simplify the treatment process steps.
In order to achieve the above object, the present invention adopts the following technical solutions.
The invention provides an alkaline phosphating solution which comprises an aqueous solution of polyvalent metal phosphate and a weakly alkaline complexing agent.
In the present invention, the molar ratio of the polyvalent metal phosphate to the weakly basic complexing agent may be conventional in the art, and is preferably 1: (1-100), more preferably 1: (5-60), more preferably 1: (5-11).
In the present invention, the molar concentration of the weakly basic complexing agent may be conventional in the art, and is preferably 0.1 to 5mol/L, such as 0.25mol/L, or 0.875mol/L, or 1.2mol/L, or 1.75mol/L, or 2.5mol/L, or 3mol/L, or 3.5 mol/L.
In the present invention, the polyvalent metal phosphate may be one or more of a polyvalent metal orthophosphate, a polyvalent metal polyphosphate and hydrates thereof.
Wherein the polyvalent metal orthophosphate can be conventional in the art, and preferably is one or more of zinc phosphate, aluminum phosphate, nickel phosphate, cobalt phosphate and manganese phosphate. The hydrate of the polyvalent metal orthophosphate may be a conventional hydrate thereof in the art, and preferably one or more of zinc phosphate tetrahydrate, zinc phosphate dihydrate, aluminum phosphate tetrahydrate and manganese phosphate trihydrate. The polyvalent metal polyphosphate may be conventional in the art, and preferably is one or more of aluminum tripolyphosphate, zinc pyrophosphate, aluminum pyrophosphate, zinc hexametaphosphate, and aluminum hexametaphosphate.
In the present invention, the weakly basic complexing agent may be conventional in the art, and is preferably one or more of an amine complexing agent, an alcamine complexing agent, an aminocarboxylate, and ammonia water.
Wherein, the amine complexing agent can be conventional in the field, and preferably is one or more of ethylenediamine, trimethylamine and triethylamine. The alkanolamine complexing agent may be conventional in the art, and is preferably one or more of monoethanolamine, diethanolamine and triethanolamine. The aminocarboxylate may be conventional in the art, and is preferably ethylenediamine tetraacetate, more preferably sodium ethylenediamine tetraacetate. The concentration of the aqueous ammonia may be conventional in the art, and is preferably 0.01 to 5 mol/L.
In the present invention, the preferable combination of the polyvalent metal phosphate and the weakly basic complexing agent is one or more of the following combinations: polyvalent metal orthophosphate and aminocarboxylate, polyvalent metal orthophosphate and ammonia water, polyvalent metal orthophosphate hydrate and amine complexing agent, and polyvalent metal polyphosphate and alcohol amine complexing agent.
In the present invention, a more preferred combination of the polyvalent metal phosphate and the weakly basic complexing agent is one or more of the following combinations: zinc phosphate tetrahydrate and ethylenediamine, wherein the molar ratio of the zinc phosphate tetrahydrate to the ethylenediamine is preferably 1: 10.7; zinc phosphate tetrahydrate and trimethylamine, wherein the molar ratio of zinc phosphate tetrahydrate to trimethylamine is preferably 1: 9.17; zinc phosphate tetrahydrate and triethylamine, wherein the molar ratio of the zinc phosphate tetrahydrate to the triethylamine is preferably 1: 57; aluminum phosphate and sodium ethylenediaminetetraacetate, wherein the molar ratio of aluminum phosphate to sodium ethylenediaminetetraacetate is preferably 1: 1; aluminum tripolyphosphate and triethanolamine, wherein the molar ratio of the aluminum tripolyphosphate to the triethanolamine is preferably 1: 7.5; nickel phosphate and ammonia; cobalt phosphate and ammonia; cobalt phosphate and ethylenediamine; and manganese phosphate and sodium edetate.
The invention also provides a preparation method of the alkaline phosphating solution, which comprises the following steps: dissolving the polyvalent metal phosphate and the alkalescent complexing agent in water. Preferably, the alkalescent complexing agent is dissolved in water to obtain an alkalescent complexing agent aqueous solution; and dissolving the polyvalent metal phosphate in the weak alkaline complexing agent aqueous solution.
The invention also provides a phosphating treatment process, which comprises the following steps: and (3) applying the alkaline phosphating solution to the surface of the metal substrate, and drying.
Wherein, the applying mode can be dripping, coating or soaking; the applying may comprise applying one or more layers. The drying may be conventional in the art, preferably natural drying; the temperature of the drying preferably does not exceed 100 ℃.
The metal matrix may be conventional in the art, and is preferably one or more of steel, iron, aluminum, zinc, copper and tin.
In the invention, the alkaline phosphating solution can also be used with a water-based coating in a matching way, namely the alkaline phosphating solution and the water-based coating are uniformly mixed and then applied to the surface of a metal substrate. The water-based paint can be conventional in the field, and is preferably one or more of a water-based polyurethane solution, a water-based alkyd resin, a water-based epoxy resin and a water-based acrylic resin. The volume ratio of the alkaline phosphating solution to the water-based paint can be selected according to actual needs, and is usually 1: 1.
In a preferred phosphating treatment process of the invention, the alkaline phosphating solution is an aqueous solution of zinc phosphate tetrahydrate and triethylamine, and the water-based paint is an aqueous polyurethane solution. Wherein, the volume concentration of the aqueous polyurethane solution is preferably 8%.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows:
the alkaline phosphating solution provided by the invention does not react with a metal base material, the composition of the phosphating solution is not changed during phosphating, the quality of a phosphating film can be well controlled, and the phosphating film is uniformly adhered. Moreover, after the phosphating film is formed, subsequent washing or neutralizing operation is not needed, so that the process steps are reduced, and the phosphating efficiency is improved. In addition, the alkaline phosphating solution can be matched with a water-based coating for use, and the alkaline phosphating solution and the water-based coating form films respectively and complete phosphating and coating simultaneously.
Drawings
FIG. 1 is a photograph of a phosphating film formed in example 1 of the invention.
FIG. 2 is a photograph of a phosphating film formed in example 2 of the invention.
FIG. 3 is a photograph of a phosphating film formed in example 3 of the invention.
FIG. 4 is a photograph of a phosphating film formed in example 4 of the invention.
FIG. 5 is a photograph of a phosphating film formed in example 5 of the invention.
FIG. 6 is a photograph of a phosphating film formed in example 6 of the invention.
FIG. 7 is a photograph of a phosphating film formed in example 7 of the invention.
FIG. 8 is a photograph of a phosphating film formed in example 8 of the invention.
Fig. 9 is a photograph of a coating layer formed in example 9 of the present invention.
FIG. 10 is a photograph of a phosphating film formed in comparative example 1 of the invention.
FIG. 11 is a photograph of a phosphating film formed in comparative example 2 of the invention.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
In the following examples, the metal surface was observed with an optical microscope (model Zeiss, Axio Imager M2M) and recorded by photographing.
Example 1
A colorless transparent alkaline phosphating solution was prepared by dissolving 1.5g of zinc phosphate tetrahydrate in 10mL of a 3.5mol/L aqueous solution of ethylenediamine. The obtained alkaline phosphating solution was dropped on an iron plate, and after natural drying, a circular phosphating film was observed to be formed on the iron plate, as shown in fig. 1.
Example 2
A colorless and transparent alkaline phosphating solution was prepared by dissolving 0.75g of zinc phosphate tetrahydrate in 10mL of a 1.75mol/L aqueous solution of ethylenediamine. The obtained alkaline phosphating solution was dropped on an iron plate, and after natural drying, a circular phosphating film was observed to be formed on the iron plate, as shown in fig. 2.
Example 3
A colorless and transparent alkaline phosphating solution was prepared by dissolving 0.375g of zinc phosphate tetrahydrate in 10mL of a 0.875mol/L aqueous solution of ethylenediamine. The obtained alkaline phosphating solution was dropped on an iron plate, and after natural drying, a circular phosphating film was observed to be formed on the iron plate, as shown in fig. 3.
Example 4
A colorless transparent alkaline phosphating solution was prepared by dissolving 1.5g of zinc phosphate tetrahydrate in 10mL of a 3.5mol/L aqueous solution of ethylenediamine. The obtained alkaline phosphating solution was dropped on an aluminum plate, and after natural drying, a circular phosphating film was observed to be formed on the aluminum plate, as shown in fig. 4.
Example 5
0.3g of aluminum phosphate was dissolved in 10mL of a 0.25mol/L aqueous solution of ethylenediaminetetraacetic acid to prepare a colorless and transparent alkaline phosphating solution, which was dropped on an iron plate and dried at 60 ℃ to see that a circular phosphating film was formed on the iron plate, as shown in FIG. 5.
Example 6
0.3g of aluminum phosphate was dissolved in 10mL of a 0.25mol/L aqueous solution of ethylenediaminetetraacetic acid to prepare a colorless and transparent alkaline phosphating solution, which was dropped on a copper plate and dried at 60 ℃ to thereby form a circular phosphating film on the copper plate, as shown in FIG. 6.
Example 7
0.5g of aluminum tripolyphosphate was dissolved in 10mL of a 1.2mol/L triethanolamine aqueous solution to prepare a colorless and transparent alkaline phosphating solution, which was dropped on an iron plate, and after natural drying, a circular phosphating film was observed to be formed on the iron plate, as shown in FIG. 7.
Example 8
1.5g of zinc phosphate tetrahydrate was dissolved in 10mL of a 3mol/L aqueous trimethylamine solution to prepare a colorless and transparent alkaline phosphating solution, which was dropped on an iron plate and naturally dried to show that a circular phosphating film was formed on the iron plate, as shown in FIG. 8.
Example 9
1g of zinc phosphate tetrahydrate is dissolved in 50mL of 2.5mol/L triethylamine aqueous solution at the temperature of below 18 ℃ to prepare colorless and transparent alkaline phosphating solution, the solution is uniformly mixed with 50mL of aqueous polyurethane solution with the volume concentration of 8% and then dripped on an iron plate, a circular polyurethane layer is formed on the iron plate after natural drying, and a phosphating film is arranged below the circular polyurethane layer, as shown in figure 9.
Comparative example 1
A colorless and transparent acidic phosphating solution was prepared by dissolving 0.5g of zinc phosphate tetrahydrate in 10mL of a 3mol/L aqueous phosphoric acid solution. The obtained acidic phosphating solution was dropped on an iron plate, and after natural drying, a circular phosphating film was observed to be formed on the iron plate, but the film had a large number of voids formed by bubbles and sediment, as shown in fig. 10.
Comparative example 2
A colorless and transparent acidic phosphating solution was prepared by dissolving 0.19g of zinc phosphate tetrahydrate in 10mL of a 0.75mol/L aqueous phosphoric acid solution. The obtained acidic phosphating solution was dropped on an iron plate, and after natural drying, a circular phosphating film was observed to be formed on the iron plate, but the film had a large number of voids formed by bubbles and sediment, as shown in fig. 11.
Claims (8)
1. An alkaline phosphating solution is characterized by comprising an aqueous solution of a polyvalent metal phosphate and a weakly alkaline complexing agent;
the molar ratio of the polyvalent metal phosphate to the weakly basic complexing agent is 1: (5-11);
the alkalescent complexing agent is an amine complexing agent and/or an alcamine complexing agent; wherein, the amine complexing agent is ethylenediamine; the alcohol amine complexing agent is triethanolamine;
the molar concentration of the alkalescent complexing agent is 0.875-3.5 mol/L;
the polyvalent metal phosphate is zinc phosphate tetrahydrate and/or aluminum tripolyphosphate.
2. The alkaline phosphating solution of claim 1 wherein the molar concentration of the weakly basic complexing agent is 0.875mol/L, or 1.2mol/L, or 1.75mol/L, or 2.5mol/L, or 3mol/L, or 3.5 mol/L.
3. The alkaline phosphating solution of claim 1 wherein the combination of the polyvalent metal phosphate and the weakly basic complexing agent is one or more of the following combinations: zinc phosphate tetrahydrate and ethylenediamine; and aluminum tripolyphosphate and triethanolamine.
4. The alkaline phosphating solution of claim 3 wherein when the combination of the polyvalent metal phosphate and the weakly basic complexing agent is zinc phosphate tetrahydrate and ethylenediamine, the molar ratio of the zinc phosphate tetrahydrate to the ethylenediamine is 1: 10.7;
when the combination of the polyvalent metal phosphate and the weakly basic complexing agent is aluminum tripolyphosphate and triethanolamine, the molar ratio of the aluminum tripolyphosphate to the triethanolamine is 1: 7.5.
5. A method for preparing the alkaline phosphating solution according to any one of claims 1 to 4, which comprises the following steps: dissolving the polyvalent metal phosphate and the alkalescent complexing agent in water.
6. The method of preparing an alkaline phosphating solution according to claim 5, wherein the weakly basic complexing agent is dissolved in water to obtain a weakly basic complexing agent aqueous solution; and dissolving the polyvalent metal phosphate in the weak alkaline complexing agent aqueous solution.
7. A phosphating treatment process comprises the following steps: applying the alkaline phosphating solution according to any one of claims 1 to 4 to the surface of a metal substrate and drying.
8. The phosphating process of claim 7 wherein the application is by dropping, coating or dipping;
and/or, the applying comprises applying one or more layers;
and/or, the drying is natural drying;
and/or, the temperature of the drying does not exceed 100 ℃;
and/or the metal matrix is one or more of steel, iron, aluminum, zinc, copper and tin.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104746063A (en) * | 2013-12-29 | 2015-07-01 | 董林祥 | Metal surface liquid rust inhibitor |
| CN104962893A (en) * | 2015-06-30 | 2015-10-07 | 大连碧城环保科技股份有限公司 | Environmental phosphating solution |
| CN106521476A (en) * | 2016-12-20 | 2017-03-22 | 粟飞 | Alkaline passivation solution |
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| DE3815179A1 (en) * | 1988-05-04 | 1989-11-16 | Schmidt Geb Ganzenmueller Trau | SILK CYLINDER (SILK FELT), METHOD FOR THE PRODUCTION THEREOF AND THE COMPOSITION FOR IMPLEMENTING THE METHOD |
| DE19634685A1 (en) * | 1996-08-28 | 1998-03-05 | Metallgesellschaft Ag | Aqueous solution and process for phosphating metallic surfaces |
| ES2405841T3 (en) * | 2001-02-26 | 2013-06-04 | Nippon Steel & Sumitomo Metal Corporation | Surface treated steel product, its production method and chemical conversion treatment solution |
| JP4509425B2 (en) * | 2001-06-08 | 2010-07-21 | 日本パーカライジング株式会社 | Paint surface treatment agent, surface treatment method, metal material, processing method, and metal product |
| CN100471995C (en) * | 2007-04-09 | 2009-03-25 | 湖南大学 | Triple cationic phosphorizing fluid containing calcium, zinc and manganese for steel plate and zinc-coated plate treatment |
| CN106637178A (en) * | 2016-12-13 | 2017-05-10 | 苏州赛斯德工程设备有限公司 | Alkaline surface bluing liquid and bluing treatment process thereof |
| CN108251830B (en) * | 2018-02-02 | 2020-09-08 | 上海耀岩化学品有限公司 | Surface conditioner containing manganese phosphate |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104746063A (en) * | 2013-12-29 | 2015-07-01 | 董林祥 | Metal surface liquid rust inhibitor |
| CN104962893A (en) * | 2015-06-30 | 2015-10-07 | 大连碧城环保科技股份有限公司 | Environmental phosphating solution |
| CN106521476A (en) * | 2016-12-20 | 2017-03-22 | 粟飞 | Alkaline passivation solution |
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