CN110951308B - Preparation method of near-infrared reflecting material based on spherical MCM-41 - Google Patents
Preparation method of near-infrared reflecting material based on spherical MCM-41 Download PDFInfo
- Publication number
- CN110951308B CN110951308B CN201911203585.6A CN201911203585A CN110951308B CN 110951308 B CN110951308 B CN 110951308B CN 201911203585 A CN201911203585 A CN 201911203585A CN 110951308 B CN110951308 B CN 110951308B
- Authority
- CN
- China
- Prior art keywords
- mcm
- preparing
- material based
- stirring
- dispersion liquid
- 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
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/004—Reflecting paints; Signal paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING 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
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/03—Powdery paints
- C09D5/033—Powdery paints characterised by the 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)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
The invention provides a preparation method of a near-infrared reflecting material based on spherical MCM-41, which comprises the following steps: s1, preparing an MCM-41 dispersion liquid, wherein the MCM-41 dispersion liquid comprises the following components: 4-5 g of spherical MCM-41, 1-2 g of surfactant, 0.5-1 ml of silane coupling agent, 8-10 ml of titanate and 100 ml of solvent; s2, ultrasonically oscillating the prepared MCM-41 dispersion liquid for 5-10 minutes, and then stirring for 30-60 minutes at room temperature with the stirring speed of 300-; s3, dropwise adding 10 ml of deionized water into the dispersion liquid at a speed of 0.5 ml/min under the stirring condition, and stirring for 4-6 hours after dropwise adding; s4, filtering and washing the mixed solution, and drying for 8-12 hours at 80 ℃; s5, heat-treating the dried sample in air at the temperature of 350-500 ℃ for 1-3 hours, and fully cooling to obtain the white near-infrared reflection powder material. The near-infrared reflecting material prepared by the method not only has the decorative effect of common paint, but also has high near-infrared reflectivity.
Description
Technical Field
The invention relates to the technical field of building materials, in particular to a preparation method of a near-infrared reflecting material based on spherical MCM-41.
Background
In modern society, people's requirements for building coating not only pay attention to beautiful appearance, but also pay more and more attention to green environmental protection and low-carbon energy conservation of buildings, namely so-called green buildings.
Sunlight mainly comprises ultraviolet light, visible light and infrared light, wherein the infrared light accounts for 45% of solar radiation energy, the visible light accounts for 50%, and the ultraviolet light accounts for 5%. The surface of a common building can only reflect 10-20% of solar energy, and most of the solar energy is absorbed by the building.
Therefore, it is an urgent technical problem to be solved by those skilled in the art to improve the reflectivity of building exterior wall materials, especially the reflectivity of near infrared.
Disclosure of Invention
In view of the above situation, the invention provides a method for preparing a near-infrared reflecting material based on spherical MCM-41, and the material prepared by the method has high near-infrared reflectivity and the decorative effect of common paint.
The technical scheme of the invention is as follows:
a preparation method of a near-infrared reflecting material based on spherical MCM-41 comprises the following steps:
s1, preparing an MCM-41 dispersion liquid, wherein the MCM-41 dispersion liquid comprises the following components:
s2, ultrasonically oscillating the prepared MCM-41 dispersion liquid for 5-10 minutes, and then stirring for 30-60 minutes at room temperature with the stirring speed of 300-;
s3, dropwise adding 10 ml of deionized water into the dispersion liquid at a speed of 0.5 ml/min under the stirring condition, and stirring for 4-6 hours after dropwise adding;
s4, filtering and washing the mixed solution, and drying for 8-12 hours at 80 ℃;
s5, heat-treating the dried sample in air at the temperature of 350-500 ℃ for 1-3 hours, and fully cooling to obtain the white near-infrared reflection powder material.
According to the preparation method of the near-infrared reflecting material based on the spherical MCM-41, the prepared near-infrared reflecting material not only has the decoration effect of common paint, but also can reflect the near-infrared radiant heat of the sun, and has a remarkable heat insulation effect, and the actual measurement shows that the near-infrared reflectivity of the near-infrared reflecting material is as high as 92.41 percent, so that the near-infrared reflecting material can reflect the solar radiant heat to reduce the surface temperature of a coating film, and a series of problems caused by overhigh surface temperature of the coating film in summer are reduced, so that the near-infrared reflecting material is energy-saving and environment-friendly.
In addition, the preparation method of the near infrared reflecting material based on the spherical MCM-41, provided by the invention, also has the following technical characteristics:
further, the surfactant is a nonionic surfactant, and is preferably any one of polyvinylpyrrolidone, polyethylene glycol, and polyvinyl alcohol.
Further, the silane coupling agent is an amino functional silane coupling agent, preferably KH-550 or KH-792.
Further, the titanate is tetraethyl titanate or tetrabutyl titanate.
Further, the solvent is short-chain alcohol such as ethanol, propanol or isopropanol.
Further, the ultrasonic oscillation in step S2 was performed in an ultrasonic cleaning machine of 800 watts, and the stirring was performed on a magnetic stirrer.
Further, the deionized water dropping in step S3 is performed using a programmed syringe pump.
Further, the drying in step S4 is performed in the electric drying box.
Further, the high-temperature heat treatment in step S5 is performed in a muffle furnace.
Drawings
Fig. 1 is a graph showing a reflectance distribution of a near infrared reflective material prepared in example 1 of the present invention.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Several embodiments of the invention are presented in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
The embodiment of the invention provides a method for preparing a near-infrared reflecting material based on spherical MCM-41, which comprises the steps of S1-S5.
S1, preparing an MCM-41 dispersion liquid, wherein the MCM-41 dispersion liquid comprises the following components:
wherein, MCM-41 (MCM for short) is an ordered mesoporous material, which is a molecular sieve with a nano structure and has the characteristics of hexagonal ordered arrangement of pore channels, uniform size, continuously adjustable pore diameter within the range of 2-10nm, large specific surface area and the like.
Wherein the surfactant is a nonionic surfactant, preferably any one of polyvinylpyrrolidone, polyethylene glycol and polyvinyl alcohol.
Wherein, the silane coupling agent is amino functional silane coupling agent, preferably KH-550 or KH-792.
Wherein the titanate is tetraethyl titanate or tetrabutyl titanate.
Wherein the solvent is short-chain alcohol such as ethanol, propanol or isopropanol
S2, ultrasonically oscillating the prepared MCM-41 dispersion liquid for 5-10 minutes, and then stirring for 30-60 minutes at room temperature with the stirring speed of 300-;
wherein the ultrasonic oscillation in step S2 is performed in an ultrasonic cleaning machine of 800 watts, and the stirring is performed on a magnetic stirrer.
S3, dropwise adding 10 ml of deionized water into the dispersion liquid at a speed of 0.5 ml/min under the stirring condition, and stirring for 4-6 hours after dropwise adding;
the deionized water dropping in step S3 is performed using a programmed syringe pump.
S4, filtering and washing the mixed solution, and drying for 8-12 hours at 80 ℃;
here, the drying in step S4 is performed in the electric drying box.
S5, heat-treating the dried sample in air at the temperature of 350-500 ℃ for 1-3 hours, and fully cooling to obtain the white near-infrared reflection powder material.
Wherein the high-temperature heat treatment in step S5 is performed in a muffle furnace.
The following examples are intended to illustrate the invention in more detail. The embodiments of the present invention are not limited to the following specific examples. The present invention can be modified and implemented as appropriate within the scope of the main claim.
Example 1:
a method for preparing a near-infrared reflecting material based on spherical MCM-41 comprises the following steps:
s1, preparing an MCM-41 dispersion liquid, wherein the MCM-41 dispersion liquid comprises the following components:
s2, ultrasonically oscillating the prepared MCM-41 dispersion liquid in an ultrasonic cleaning machine of 800 watts for 5 minutes, and then stirring the solution on a magnetic stirrer for 30 minutes at room temperature, wherein the stirring speed is 500 revolutions per minute;
s3, dripping 10 ml of deionized water into the dispersion liquid at a speed of 0.5 ml/min under the stirring condition, wherein the dripping of the deionized water is finished by using a program-controlled injection pump, and stirring for 5 hours after the dripping is finished;
s4, filtering and washing the mixed solution, and drying the mixed solution in an electric drying oven for 8 hours at the temperature of 80 ℃;
and S5, heat-treating the dried sample in a muffle furnace in air at the temperature of 500 ℃ for 2 hours, and fully cooling to obtain the white near-infrared reflection powder material.
The near-infrared reflection material prepared by the method of the embodiment has a near-infrared reflectivity of 92.41%, and the reflectivity distribution is shown in fig. 1.
Example 2:
a method for preparing a near-infrared reflecting material based on spherical MCM-41 comprises the following steps:
s1, preparing an MCM-41 dispersion liquid, wherein the MCM-41 dispersion liquid comprises the following components:
s2, ultrasonically oscillating the prepared MCM-41 dispersion liquid in an ultrasonic cleaning machine of 800 watts for 7 minutes, and then stirring the solution on a magnetic stirrer at room temperature for 45 minutes at the stirring speed of 450 revolutions per minute;
s3, dripping 10 ml of deionized water into the dispersion liquid at a speed of 0.5 ml/min under the stirring condition, wherein the dripping of the deionized water is finished by using a program-controlled injection pump, and stirring for 4 hours after the dripping is finished;
s4, filtering and washing the mixed solution, and drying the mixed solution in an electric drying oven for 10 hours at the temperature of 80 ℃;
and S5, heat-treating the dried sample in air at the temperature of 450 ℃ for 2 hours in a muffle furnace, and fully cooling to obtain the white near-infrared reflection powder material.
The near-infrared reflection material prepared by the method of the embodiment has a near-infrared reflectivity of 91.55%.
Example 3:
a method for preparing a near-infrared reflecting material based on spherical MCM-41 comprises the following steps:
s1, preparing an MCM-41 dispersion liquid, wherein the MCM-41 dispersion liquid comprises the following components:
s2, ultrasonically oscillating the prepared MCM-41 dispersion liquid in an ultrasonic cleaning machine of 800 watts for 9 minutes, and then stirring the solution on a magnetic stirrer for 50 minutes at room temperature, wherein the stirring speed is 480 revolutions per minute;
s3, dripping 10 ml of deionized water into the dispersion liquid at a speed of 0.5 ml/min under the stirring condition, wherein the dripping of the deionized water is finished by using a program-controlled injection pump, and stirring for 4 hours after the dripping is finished;
s4, filtering and washing the mixed solution, and drying the mixed solution in an electric drying oven for 10 hours at the temperature of 80 ℃;
and S5, heat-treating the dried sample in air at 350 ℃ in a muffle furnace for 3 hours, and fully cooling to obtain the white near-infrared reflection powder material.
The near-infrared reflection material prepared by the method of the embodiment has a near-infrared reflectivity of 90.45%.
Example 4:
a method for preparing a near-infrared reflecting material based on spherical MCM-41 comprises the following steps:
s1, preparing an MCM-41 dispersion liquid, wherein the MCM-41 dispersion liquid comprises the following components:
s2, ultrasonically oscillating the prepared MCM-41 dispersion liquid in an ultrasonic cleaning machine of 800 watts for 10 minutes, and then stirring the solution on a magnetic stirrer at room temperature for 60 minutes at the stirring speed of 300 revolutions per minute;
s3, dripping 10 ml of deionized water into the dispersion liquid at a speed of 0.5 ml/min under the stirring condition, wherein the dripping of the deionized water is finished by using a program-controlled injection pump, and stirring for 6 hours after the dripping is finished;
s4, filtering and washing the mixed solution, and drying the mixed solution in an electric drying oven for 12 hours at the temperature of 80 ℃;
and S5, heat-treating the dried sample in a muffle furnace in air at the temperature of 400 ℃ for 1 hour, and fully cooling to obtain the white near-infrared reflection powder material.
The near infrared reflectivity of the near infrared reflective material prepared by the method of the embodiment is 92.17% through actual measurement.
Example 5:
a method for preparing a near-infrared reflecting material based on spherical MCM-41 comprises the following steps:
s1, preparing an MCM-41 dispersion liquid, wherein the MCM-41 dispersion liquid comprises the following components:
s2, ultrasonically oscillating the prepared MCM-41 dispersion liquid in an ultrasonic cleaning machine of 800 watts for 6 minutes, and then stirring the solution on a magnetic stirrer for 35 minutes at room temperature, wherein the stirring speed is 390 revolutions per minute;
s3, dripping 10 ml of deionized water into the dispersion liquid at a speed of 0.5 ml/min under the stirring condition, wherein the dripping of the deionized water is finished by using a program-controlled injection pump, and stirring for 5 hours after the dripping is finished;
s4, filtering and washing the mixed solution, and drying the mixed solution in an electric drying oven for 9 hours at the temperature of 80 ℃;
and S5, heat-treating the dried sample in air at the temperature of 450 ℃ for 2 hours in a muffle furnace, and fully cooling to obtain the white near-infrared reflection powder material.
The near-infrared reflection material prepared by the method of the embodiment has a near-infrared reflectivity of 91.2%.
Table 1 compares the test results of the above examples and comparative example, comparative example 1 being a prior art reflective construction material, wherein the thermal insulation temperature range is according to JC/T1040-2007 test:
TABLE 1 comparison of results table
In conclusion, according to the preparation method of the near-infrared reflecting material based on the spherical MCM-41, the prepared near-infrared reflecting material not only has the decoration effect of common paint, but also can reflect the near-infrared radiant heat of the sun, and has a remarkable heat insulation effect, the actual measurement shows that the near-infrared reflectivity of the near-infrared reflecting material is as high as 92.41 percent, the near-infrared reflecting material can reflect the solar radiant heat to reduce the surface temperature of a coating film when being used for the reflective heat insulation paint for buildings, a series of problems caused by overhigh surface temperature of the coating film in summer are reduced, and the near-infrared reflecting material is energy-saving and environment-friendly.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (9)
1. A preparation method of a near-infrared reflecting material based on spherical MCM-41 is characterized by comprising the following steps:
s1, preparing an MCM-41 dispersion liquid, wherein the MCM-41 dispersion liquid comprises the following components:
wherein the surfactant is any one of polyvinylpyrrolidone, polyethylene glycol and polyvinyl alcohol;
s2, ultrasonically oscillating the prepared MCM-41 dispersion liquid for 5-10 minutes, and then stirring for 30-60 minutes at room temperature with the stirring speed of 300-;
s3, dropwise adding 10 ml of deionized water into the dispersion liquid at a speed of 0.5 ml/min under the stirring condition, and stirring for 4-6 hours after dropwise adding;
s4, filtering and washing the mixed solution, and drying for 8-12 hours at 80 ℃;
s5, heat-treating the dried sample in air at the temperature of 350-500 ℃ for 1-3 hours, and fully cooling to obtain the white near-infrared reflection powder material.
2. The method for preparing a near-infrared reflective material based on spherical MCM-41 according to claim 1, wherein the silane coupling agent is an amino functional silane coupling agent.
3. The method of preparing a near-infrared reflective material based on spherical MCM-41 according to claim 2, wherein the silane coupling agent is KH-550 or KH-792.
4. The method for preparing a near-infrared reflecting material based on spherical MCM-41 of claim 1, wherein the titanate is tetraethyl titanate or tetrabutyl titanate.
5. The method for preparing a near-infrared reflective material based on spherical MCM-41 according to claim 1, wherein the solvent is any one of ethanol, propanol, and isopropanol.
6. The method for preparing a near-infrared reflective material based on spherical MCM-41 according to claim 1, wherein the ultrasonic oscillation in step S2 is performed in an ultrasonic cleaning machine of 800 watts, and the stirring is performed on a magnetic stirrer.
7. The method for preparing a near-infrared reflective material based on spherical MCM-41 according to claim 1, wherein the dropping of the deionized water in step S3 is performed using a program-controlled syringe pump.
8. The method for preparing a near-infrared reflective material based on spherical MCM-41 according to claim 1, wherein the drying in step S4 is performed in an electric drying box.
9. The method for preparing a near-infrared reflective material based on spherical MCM-41 according to claim 1, wherein the high temperature heat treatment in step S5 is performed in a muffle furnace.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911203585.6A CN110951308B (en) | 2019-11-29 | 2019-11-29 | Preparation method of near-infrared reflecting material based on spherical MCM-41 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911203585.6A CN110951308B (en) | 2019-11-29 | 2019-11-29 | Preparation method of near-infrared reflecting material based on spherical MCM-41 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110951308A CN110951308A (en) | 2020-04-03 |
| CN110951308B true CN110951308B (en) | 2021-07-27 |
Family
ID=69979039
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911203585.6A Active CN110951308B (en) | 2019-11-29 | 2019-11-29 | Preparation method of near-infrared reflecting material based on spherical MCM-41 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110951308B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101974314A (en) * | 2010-09-29 | 2011-02-16 | 北京航空航天大学 | Silica-based porous bulk for heat insulating material and coating-dry pressing preparation method thereof |
| CN102875787A (en) * | 2012-09-21 | 2013-01-16 | 中国科学院长春应用化学研究所 | Catalyst of mesoporous material with titanic compound loaded and preparation method thereof |
| US20160346766A1 (en) * | 2015-05-28 | 2016-12-01 | Exxonmobil Chemical Patents Inc. | Templated Active Material |
| CN106554704A (en) * | 2016-10-08 | 2017-04-05 | 江苏大使同丰涂料有限公司 | A kind of solar energy reflective insulation coating and preparation method thereof |
-
2019
- 2019-11-29 CN CN201911203585.6A patent/CN110951308B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101974314A (en) * | 2010-09-29 | 2011-02-16 | 北京航空航天大学 | Silica-based porous bulk for heat insulating material and coating-dry pressing preparation method thereof |
| CN102875787A (en) * | 2012-09-21 | 2013-01-16 | 中国科学院长春应用化学研究所 | Catalyst of mesoporous material with titanic compound loaded and preparation method thereof |
| US20160346766A1 (en) * | 2015-05-28 | 2016-12-01 | Exxonmobil Chemical Patents Inc. | Templated Active Material |
| CN106554704A (en) * | 2016-10-08 | 2017-04-05 | 江苏大使同丰涂料有限公司 | A kind of solar energy reflective insulation coating and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110951308A (en) | 2020-04-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101891395B (en) | Method for preparing thermal-insulation, self-cleaning and film-coated toughened glass | |
| CN106700789A (en) | Waterborne energy-saving building coating and preparation method thereof | |
| CN105860717B (en) | Colour reflective insulating moulding coating and its preparation, construction method | |
| CN103770404A (en) | Weather-resistant solar glass surface anti-reflective film and preparation method thereof | |
| CN103897462A (en) | Colorized heat reflecting paint as well as preparation method and application thereof | |
| CN110951308B (en) | Preparation method of near-infrared reflecting material based on spherical MCM-41 | |
| CN104910726A (en) | Flame-retardant reflective heat-insulating paint and preparation technique thereof | |
| CN107722751A (en) | A kind of novel aqueous heat insulating reflecting coating and preparation method thereof | |
| CN102964957A (en) | Heat insulation and heat control coating material and preparation method thereof | |
| CN104194525A (en) | Novel heat-insulating coating for buildings | |
| CN105328751A (en) | Method for generating silicon-titanium double-element oxidation film on surface of timber | |
| CN115772351B (en) | Passive radiation refrigerating material, preparation method and application | |
| CN107216758A (en) | A kind of cross-linking reaction type water-water reflective heat-insulation paint | |
| CN107935405B (en) | Preparation method of antimony-doped tin oxide electrochromic film | |
| CN106336741A (en) | Preparation method of nanometer composite water-based thermal insulation coating | |
| CN110643244A (en) | Reflective heat-insulating coating for buildings and preparation method thereof | |
| CN115340331A (en) | Preparation method of heat reflection cement-based material | |
| CN109536011A (en) | Colored insulating moulding coating of middle high brightness and preparation method thereof | |
| CN106905805B (en) | A kind of cooling shines the preparation method of multi-functional combined wall coating | |
| CN113185859B (en) | Nano SiO2/TiO2 composite material, anti-reflection self-cleaning coating based on composite material and preparation method thereof | |
| CN102260442A (en) | Water-based solar heat radiation reflective paint and preparation process thereof | |
| CN115124253A (en) | Antireflection coating optical cover plate with high transmittance and preparation method | |
| KR102073880B1 (en) | Coating composition for solar cell module and Solar cell module coated by using the same | |
| CN105504896A (en) | Thermal insulation paint | |
| CN113024893A (en) | Temperature-sensitive cellulose intelligent window |
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 |