CN114773950B - High-temperature-resistant fireproof basalt flake coating and preparation method thereof - Google Patents

High-temperature-resistant fireproof basalt flake coating and preparation method thereof Download PDF

Info

Publication number
CN114773950B
CN114773950B CN202210391351.4A CN202210391351A CN114773950B CN 114773950 B CN114773950 B CN 114773950B CN 202210391351 A CN202210391351 A CN 202210391351A CN 114773950 B CN114773950 B CN 114773950B
Authority
CN
China
Prior art keywords
basalt
parts
coating
epoxy resin
mixture
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202210391351.4A
Other languages
Chinese (zh)
Other versions
CN114773950A (en
Inventor
张新新
刘希帅
王立春
姜慧娉
宋吉照
白兆起
王怡翔
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Yantai Wanhua New Material Technology Co ltd
Original Assignee
Yantai Wanhua New Material Technology Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Yantai Wanhua New Material Technology Co ltd filed Critical Yantai Wanhua New Material Technology Co ltd
Priority to CN202210391351.4A priority Critical patent/CN114773950B/en
Publication of CN114773950A publication Critical patent/CN114773950A/en
Application granted granted Critical
Publication of CN114773950B publication Critical patent/CN114773950B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D177/00Coating compositions based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D177/06Polyamides derived from polyamines and polycarboxylic acids
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08Anti-corrosive paints
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/18Fireproof paints including high temperature resistant paints
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • C08K2003/2227Oxides; Hydroxides of metals of aluminium
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/011Nanostructured additives

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

The invention discloses a high-temperature-resistant fireproof basalt flake coating which comprises the following substances in parts by weight: 100-180 parts of epoxy resin, 80-150 parts of polyamide emulsion, 30-70 parts of amine curing agent, 60-150 parts of basalt flakes, 40-80 parts of nano glass beads, 20-40 parts of nano aluminum oxide and 5-25 parts of dispersing agent. The high-temperature-resistant fireproof basalt scale coating disclosed by the invention has the advantages that the surface of the basalt scale is corroded by hydrofluoric acid, the surface area of the basalt scale is increased, the area of the basalt scale combined with a polymer base material of the coating is larger, the bonding force between sections is increased, the corrosion resistance is also increased, the basalt scale is arranged in the middle layer of the coating, the corrosion resistance of the coating is ensured, the surface strength is not reduced, and the high-temperature resistance and the fireproof performance of the coating can be improved by adding the nano glass beads and the nano aluminum oxide on the surface of the coating.

Description

High-temperature-resistant fireproof basalt flake coating and preparation method thereof
Technical Field
The invention relates to the field of coatings, in particular to a high-temperature-resistant fireproof basalt flake coating and a preparation method thereof.
Background
The anticorrosive paint is mostly applied to the appearance of outdoor large-scale equipment, and along with the improvement of the use requirement, the paint with single anticorrosive performance is more and more difficult to meet the requirement, and functional components are usually added into the anticorrosive paint to endow the anticorrosive paint with other performances such as high temperature resistance, impact resistance, ultraviolet resistance, wave absorption and the like.
The basalt flakes are used as flaky inorganic granules and are good additive components of the polymer base material anticorrosive paint, and due to the high specific surface area and flaky morphology, the basalt flakes can greatly improve the anticorrosive performance of the paint. However, the existing basalt flake anticorrosive paint directly mixes basalt flakes into the paint, and the flaky structure of basalt is not fully utilized.
Disclosure of Invention
Aiming at the problems, the invention provides a high-temperature-resistant fireproof basalt flake coating which is prepared from the following substances in parts by weight: 100-180 parts of epoxy resin, 80-150 parts of polyamide emulsion, 30-70 parts of amine curing agent, 60-150 parts of basalt flakes, 40-80 parts of nano glass beads, 20-40 parts of nano aluminum oxide and 5-25 parts of dispersing agent.
Specifically, the epoxy equivalent of the epoxy resin is 200 to 350g/mol; the polyamide is selected from one of PA6, PA66, PA610 or PA56 with the number average molecular weight of 800-2000; the amine curing agent is ethylenediamine, p-phenylenediamine or polyether amine with the molecular weight of 500-1000; the dispersing agent is selected from one or more of magnesium stearate, polyethylene glycol or propylene glycol methyl ether.
The preparation method of the high-temperature-resistant fireproof basalt flake coating comprises the following steps:
1) Screening basalt scales with the particle size not less than 200 mu m, loading the basalt scales into a spray barrel with a polytetrafluoroethylene inner container, spraying a 4-10% hydrofluoric acid aqueous solution after starting to rotate, stirring for 10-30min, washing with deionized water, recovering washing liquid, and introducing hot nitrogen into the spray barrel to dry the basalt scales to obtain surface-etched basalt scales;
2) Weighing the components in parts by weight, adding the basalt flakes with etched surfaces obtained in the step 1) into polyamide emulsion, and uniformly stirring and dispersing for later use;
3) Mixing 1/4-1/3 of epoxy resin and 1/3-1/2 of amine curing agent, coating the mixture to serve as a primer, curing the primer, uniformly mixing 1/5-1/2 of epoxy resin by weight of polyamide emulsion and the mixture obtained in the step 2), coating the mixture on the primer, mixing the rest epoxy resin, the amine curing agent, the nano glass beads, the nano aluminum oxide and the dispersing agent, coating the mixture on the surface layer, and curing.
The high-temperature-resistant fireproof basalt scale coating disclosed by the invention has the advantages that the surface of the basalt scale is corroded by hydrofluoric acid, the surface area of the basalt scale is increased, the area of the basalt scale combined with a polymer base material of the coating is larger, the bonding force between sections is increased, the corrosion resistance is also increased, the basalt scale is arranged in the middle layer of the coating, the corrosion resistance of the coating is ensured, the surface strength is not reduced, and the high-temperature resistance and the fireproof performance of the coating can be improved by adding the nano glass beads and the nano aluminum oxide on the surface of the coating.
Detailed Description
The present invention is described below with reference to examples, which are provided for illustration only and are not intended to limit the scope of the present invention.
Example 1
The high-temperature-resistant fireproof basalt flake coating consists of the following substances in parts by weight: 180 parts of epoxy resin with the epoxy equivalent of 200g/mol, 100 parts of PA66 polyamide emulsion with the number average molecular weight of 2000, 70 parts of ethylenediamine, 150 parts of basalt scales, 80 parts of nano glass microspheres, 30 parts of nano aluminum oxide and 25 parts of magnesium stearate.
The preparation method of the high-temperature-resistant fireproof basalt flake coating comprises the following steps of: 1) Screening basalt scales with the particle size of 200 mu m, putting the basalt scales into a spray barrel with a polytetrafluoroethylene inner container, spraying a 4% hydrofluoric acid aqueous solution after starting to rotate, stirring for 30min, washing with deionized water, recovering washing liquid, introducing hot nitrogen into the spray barrel, and drying the basalt scales to obtain basalt scales with etched surfaces; 2) Weighing the components in parts by weight, adding the basalt flakes with etched surfaces obtained in the step 1) into PA66 polyamide emulsion, and uniformly stirring and dispersing for later use; 3) Mixing 45 parts of epoxy resin and 35 parts of ethylenediamine, coating, heating at 55 ℃ for curing to obtain a primer, uniformly mixing 50 parts of epoxy resin and the mixture obtained in the step 2) after the primer is cured, coating the mixture on the primer, heating at 60 ℃ for curing, mixing the rest epoxy resin, ethylenediamine, nano glass microspheres, nano aluminum oxide and magnesium stearate, coating the mixture on the surface layer, and curing.
Example 2
The high-temperature-resistant fireproof basalt flake coating consists of the following substances in parts by weight: 100 parts of epoxy resin with the epoxy equivalent of 350g/mol, 150 parts of PA610 polyamide emulsion with the number average molecular weight of 800, 50 parts of p-phenylenediamine curing agent, 60 parts of basalt flakes, 40 parts of nano glass beads, 20 parts of nano aluminum oxide and 5 parts of polyethylene glycol.
The preparation method of the high-temperature-resistant fireproof basalt flake coating comprises the following steps: 1) Screening basalt scales with the particle size of 300 mu m, putting the basalt scales into a spray barrel with a polytetrafluoroethylene inner container, spraying a 5% hydrofluoric acid aqueous solution after starting to rotate, stirring for 15min, washing with deionized water, recovering washing liquid, introducing hot nitrogen into the spray barrel, and drying the basalt scales to obtain basalt scales with etched surfaces; 2) Weighing the components in parts by weight, adding the basalt scales with etched surfaces obtained in the step 1) into PA610 polyamide emulsion, and uniformly stirring and dispersing for later use; 3) And (3) mixing and coating 30 parts of epoxy resin and 18 parts of p-phenylenediamine, heating and curing at 70 ℃ to obtain a primer, uniformly mixing another 30 parts of epoxy resin and the mixture obtained in the step 2) after the primer is cured, coating the mixture on the primer, heating and curing at 65 ℃ to obtain a mixture, mixing the rest epoxy resin, the phenylenediamine, the nano glass beads, the nano aluminum oxide and the polyethylene glycol, coating the mixture on the surface layer, and curing.
Example 3
The high-temperature-resistant fireproof basalt flake coating consists of the following substances in parts by weight: 120 parts of epoxy resin with the epoxy equivalent of 300g/mol, 80 parts of PA56 polyamide emulsion with the number average molecular weight of 1500, 30 parts of polyetheramine curing agent with the molecular weight of 1000, 100 parts of basalt flakes, 60 parts of nano glass beads, 20 parts of nano aluminum oxide and 15 parts of propylene glycol methyl ether.
The preparation method of the high-temperature-resistant fireproof basalt flake coating comprises the following steps: 1) Screening basalt scales with the particle size of 250 micrometers, loading into a spray barrel with a polytetrafluoroethylene inner container, spraying 10% hydrofluoric acid aqueous solution after starting to rotate, stirring for 10min, washing with deionized water, recovering washing liquid, introducing hot nitrogen into the spray barrel, and drying the basalt scales to obtain basalt scales with etched surfaces; 2) Weighing the components in parts by weight, adding the basalt flakes with etched surfaces obtained in the step 1) into PA56 polyamide emulsion, and uniformly stirring and dispersing for later use; 3) Mixing 40 parts of epoxy resin and 10 parts of polyetheramine, coating, heating and curing at 60 ℃ to obtain a primer, uniformly mixing 35 parts of epoxy resin and the mixture obtained in the step 2) after the primer is cured, coating the mixture on the primer, heating and curing at 65 ℃, mixing the rest epoxy resin, the polyetheramine, the nano glass beads, the nano aluminum oxide and the propylene glycol monomethyl ether, coating the mixture on the surface layer, and curing.
The high-temperature-resistant fireproof basalt flake coating obtained in examples 1 to 3 was coated on a steel plate, the coating thickness was 4mm, and the detection performance was as shown in table 1.
TABLE 1 Properties of the coatings of examples 1-3
Detecting the index Execution criteria Example 1 Example 2 Example 3
Tensile strength/MPa GB/T528-92 65 58 57
Shore hardness/A GB/T1698-2003 84 79 82
Salt spray resistance per hour GB/T1771-2007 3800 4100 3600
Solids content/%) GB/T1725-2007 76 68 70
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (6)

1. The high-temperature-resistant fireproof basalt flake coating is characterized by comprising the following substances in parts by weight: 100-180 parts of epoxy resin, 80-150 parts of polyamide emulsion, 30-70 parts of amine curing agent, 60-150 parts of basalt scales, 40-80 parts of nano glass beads, 20-40 parts of nano aluminum oxide and 5-25 parts of dispersing agent;
the preparation method of the high-temperature-resistant fireproof basalt flake coating comprises the following steps:
1) Screening basalt scales with the particle size not less than 200 mu m, putting the basalt scales into a spray barrel with a polytetrafluoroethylene inner container, spraying a hydrofluoric acid aqueous solution with the concentration of 4% -10% after starting to rotate, stirring for 10-30min, washing with deionized water, recovering washing liquid, and introducing hot nitrogen into the spray barrel to dry the basalt scales to obtain basalt scales with etched surfaces;
2) Weighing the components in parts by weight, adding the basalt flakes with etched surfaces obtained in the step 1) into polyamide emulsion, and uniformly stirring and dispersing for later use;
3) Mixing 1/4-1/3 of epoxy resin and 1/3-1/2 of amine curing agent, coating the mixture to serve as a primer, curing the primer, uniformly mixing 1/5-1/2 of epoxy resin by weight of polyamide emulsion and the mixture obtained in the step 2), coating the mixture on the primer, mixing the rest epoxy resin, the amine curing agent, the nano glass beads, the nano aluminum oxide and the dispersing agent, coating the mixture on the surface layer, and curing.
2. The high temperature resistant fireproof basalt scale coating of claim 1, wherein the epoxy resin has an epoxy equivalent weight of 200 to 350g/mol.
3. The high temperature resistant fire proof basalt scale coating of claim 1, wherein the polyamide is selected from one of PA6, PA66, PA610 or PA56 with number average molecular weight of 800-2000.
4. The high temperature resistant and fire resistant basalt flake coating of claim 1, wherein the amine curing agent is ethylenediamine, p-phenylenediamine, or polyetheramine with a molecular weight of 500-1000.
5. The high temperature resistant and fire resistant basalt flake coating of claim 1, wherein the dispersant is selected from one or more of magnesium stearate, polyethylene glycol, or propylene glycol methyl ether.
6. A preparation method of the high temperature resistant and fire resistant basalt flake coating as claimed in any one of claims 1 to 5, characterized by comprising the following steps:
1) Screening basalt scales with the particle size not less than 200 mu m, loading the basalt scales into a spray barrel with a polytetrafluoroethylene inner container, spraying a 4-10% hydrofluoric acid aqueous solution after starting to rotate, stirring for 10-30min, washing with deionized water, recovering washing liquid, and introducing hot nitrogen into the spray barrel to dry the basalt scales to obtain surface-etched basalt scales;
2) Weighing the components in parts by weight, adding the basalt flakes with etched surfaces obtained in the step 1) into polyamide emulsion, and uniformly stirring and dispersing for later use;
3) Mixing 1/4-1/3 of epoxy resin and 1/3-1/2 of amine curing agent, coating the mixture to serve as a primer, curing the primer, uniformly mixing 1/5-1/2 of epoxy resin by weight of polyamide emulsion and the mixture obtained in the step 2), coating the mixture on the primer, mixing the rest epoxy resin, the amine curing agent, the nano glass beads, the nano aluminum oxide and the dispersing agent, coating the mixture on the surface layer, and curing.
CN202210391351.4A 2022-04-14 2022-04-14 High-temperature-resistant fireproof basalt flake coating and preparation method thereof Active CN114773950B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210391351.4A CN114773950B (en) 2022-04-14 2022-04-14 High-temperature-resistant fireproof basalt flake coating and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210391351.4A CN114773950B (en) 2022-04-14 2022-04-14 High-temperature-resistant fireproof basalt flake coating and preparation method thereof

Publications (2)

Publication Number Publication Date
CN114773950A CN114773950A (en) 2022-07-22
CN114773950B true CN114773950B (en) 2023-01-17

Family

ID=82430203

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210391351.4A Active CN114773950B (en) 2022-04-14 2022-04-14 High-temperature-resistant fireproof basalt flake coating and preparation method thereof

Country Status (1)

Country Link
CN (1) CN114773950B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115029064A (en) * 2022-04-14 2022-09-09 烟台万华新材料技术有限公司 Thin wave-absorbing basalt flake water-based silicone coating and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108997887A (en) * 2018-07-13 2018-12-14 山东七维新材料有限公司 One kind containing the double-component aqueous corrosion-resistant epoxy paint of glass flake and its preparation, application method
CN112831252A (en) * 2021-01-29 2021-05-25 烟台万华新材料技术有限公司 Water-based high-temperature-resistant anticorrosive composition
CN113801558A (en) * 2021-11-01 2021-12-17 烟台万华新材料技术有限公司 Corrosion-resistant basalt flake polyurethane coating and coating method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108997887A (en) * 2018-07-13 2018-12-14 山东七维新材料有限公司 One kind containing the double-component aqueous corrosion-resistant epoxy paint of glass flake and its preparation, application method
CN112831252A (en) * 2021-01-29 2021-05-25 烟台万华新材料技术有限公司 Water-based high-temperature-resistant anticorrosive composition
CN113801558A (en) * 2021-11-01 2021-12-17 烟台万华新材料技术有限公司 Corrosion-resistant basalt flake polyurethane coating and coating method thereof

Also Published As

Publication number Publication date
CN114773950A (en) 2022-07-22

Similar Documents

Publication Publication Date Title
CN101643615B (en) Polyaniline modified glass flake heavy-duty anti-corrosive coating and preparation method thereof
RU2615410C2 (en) Liquid epoxy coating composition, methods and products
CN1035622C (en) Glass flake anticorrosion paint and its making method
CN114773950B (en) High-temperature-resistant fireproof basalt flake coating and preparation method thereof
CN105086772A (en) Anticorrosive coating used on inner wall of desulfurization and denitrification device and preparation method thereof
CN103298568B (en) The coating process of aluminium alloy rim and aluminium alloy rim
CN102911544B (en) Modified epoxy solvent-free coating
CN111117436A (en) Zinc-rich base powder super-anticorrosion paint
CN114686070A (en) Water-based epoxy zinc-rich primer and preparation method thereof
CN110669205A (en) Water-based double-component zinc-rich special epoxy curing agent and preparation method thereof
CN108017979A (en) A kind of graphene-based single-component epoxy anticorrosive paint of high temperature resistant and its preparation method and application
CN104673057A (en) Water-based, environment-friendly and corrosion-resistant two-component coating
CN103205179A (en) Quick-drying type organic zinc-rich coating and preparation method thereof
CN103254736A (en) Polyaniline powder paint with acid-resistant self-repair function and preparation method thereof
CN111057443A (en) Aqueous heavy-duty anticorrosive epoxy resin emulsion and preparation method thereof
CN100343352C (en) Stick-proof anti corrosion paint for internal wall of water steam pipeline
CN110845937A (en) Solvent-free pipeline inner wall anticorrosion hydrophobic coating and preparation method thereof
CN112852260B (en) Durable epoxy resin anticorrosive paint and preparation method and application thereof
CN114369249B (en) Water-based epoxy resin toughening agent and preparation method and application thereof
CN113698847B (en) Bottom-surface-integrated high-performance graphene heavy-duty anticorrosive paint and preparation method and forming process thereof
CN101643322B (en) Vinyl ester heavy-duty anticorrosive coating with polyaniline-modified glass flakes, and preparation method thereof
CN111849143B (en) High-corrosion-resistance environment-friendly water-based epoxy curing agent and preparation method thereof
CN113861807A (en) Application method of blade battery insulating anticorrosive paint
CN112457724A (en) Water-resistant anticorrosive paint and preparation method thereof
CN111808495A (en) Impact-resistant interpenetrating network anticorrosive paint

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant