CN111117444A - Water-based polyester-acrylic amino resin hybrid baking paint and preparation method thereof - Google Patents
Water-based polyester-acrylic amino resin hybrid baking paint and preparation method thereof Download PDFInfo
- Publication number
- CN111117444A CN111117444A CN201911396832.9A CN201911396832A CN111117444A CN 111117444 A CN111117444 A CN 111117444A CN 201911396832 A CN201911396832 A CN 201911396832A CN 111117444 A CN111117444 A CN 111117444A
- Authority
- CN
- China
- Prior art keywords
- hydrolysis
- resistant
- amino resin
- polyester
- water
- 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.)
- Granted
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
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/682—Polyesters containing atoms other than carbon, hydrogen and oxygen containing halogens
- C08G63/6824—Polyesters containing atoms other than carbon, hydrogen and oxygen containing halogens derived from polycarboxylic acids and polyhydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/682—Polyesters containing atoms other than carbon, hydrogen and oxygen containing halogens
- C08G63/6824—Polyesters containing atoms other than carbon, hydrogen and oxygen containing halogens derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6826—Dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
Abstract
The invention belongs to the technical field of coatings, and particularly relates to a water-based polyester-acrylic amino resin hybrid baking paint and a preparation method thereof, wherein the hybrid baking paint comprises the following components in parts by weight: 45-55 parts of hydrolysis-resistant polyester acrylate aqueous dispersion, 15-25 parts of amino resin, 8-15 parts of water, 0.1-0.5 part of wetting agent, 0.1-0.5 part of flatting agent and 0.1-0.8 part of defoaming agent. According to the invention, the hydrolysis-resistant polyester acrylate dispersion is added into the baking varnish system, so that the water resistance of a paint film is effectively improved, the polyester part of the hydrolysis-resistant polyester acrylate dispersion contains hydrolysis-resistant monomers, and the hydrolysis-resistant monomers contain trifluoromethyl groups, so that the water resistance of the aqueous dispersion can be fundamentally and obviously improved; the hydrolysis-resistant intermediate is obtained by polymerizing a hydrolysis-resistant monomer and isoprene glycol, and the hydrolysis-resistant monomer, polybasic acid, polyalcohol and hydroxy acrylic resin are reacted together to obtain the hydrolysis-resistant polyester acrylate dispersoid, so that the hydrolysis-resistant intermediate is firmly combined in vivo, and the water resistance of a paint film is fundamentally improved.
Description
Technical Field
The invention belongs to the technical field of coatings, and particularly relates to a water-based polyester-acrylic amino resin hybrid baking varnish and a preparation method thereof.
Background
The polyester resin has higher glossiness and fullness, and simultaneously has good adhesive force and impact resistance, but the water resistance and the acid and alkali resistance of the polyester resin are not ideal enough, while the acrylate resin has excellent light and color retention, weather resistance and chemical resistance, but the fullness is not enough, so that the two resins are combined to realize effective advantage complementation, and meet the performance requirements of the industry on various aspects of appearance, adhesive force, weather resistance and the like of the coating.
With the increasing attention of people on environmental protection, some traditional solvent-based coatings are gradually replaced by water-based coatings, but the water-based coatings have the defect of poor water resistance which is not negligible.
Chinese patent document CN109836943A discloses a high hardness water-based acrylate/amino baking varnish and a preparation method thereof, and specifically discloses that the water-based varnish composition comprises water-based acrylic resin and amino resin, and the water resistance of a coating film is improved by controlling the addition amount of the water-based acrylic resin and the amino resin and the actual addition sequence of the water-based amino resin, although the water-based varnish composition can have a certain improvement effect, the problem cannot be fundamentally solved.
Disclosure of Invention
In order to solve the problem that the water resistance of the prior acrylic amino resin is insufficient to cause adverse effect on the whole performance, the invention discloses a water-based polyester-acrylic amino resin hybrid baking varnish and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
the water-based polyester-acrylic amino resin hybrid baking paint comprises the following components in parts by weight: 45-55 parts of hydrolysis-resistant polyester acrylate aqueous dispersion, 15-25 parts of amino resin, 8-15 parts of water, 0.1-0.5 part of wetting agent, 0.1-0.5 part of flatting agent and 0.1-0.8 part of defoaming agent.
Preferably, the hydrolysis-resistant polyester acrylate aqueous dispersion is obtained by reacting a hydroxyl acrylic resin, a polyol, a polybasic acid and a hydrolysis-resistant intermediate, wherein the hydrolysis-resistant intermediate has a structural formula as follows:
the preparation method of the hydrolysis-resistant intermediate comprises the following steps: adding neopentyl glycol and a hydrolysis-resistant monomer into a reaction kettle according to a molar ratio of 2-3:1, adding a small amount of deionized water and a catalyst of dibutyl tin dilaurate, introducing nitrogen, slowly heating to 160 ℃, reacting until the water content in a water separator is basically unchanged, slowly heating to 210 ℃, and continuously reacting until the acid value is less than or equal to 5mgKOH/g to obtain a hydrolysis-resistant intermediate, wherein the reaction equation is as follows:
the preparation method of the hydrolysis-resistant polyester acrylate aqueous dispersion comprises the following steps:
(1) weighing hydroxyl acrylic resin, polybasic acid, polyalcohol and hydrolysis-resistant intermediate, wherein the molar ratio of the four is 1:0.5-1.5:0.5-1.5: 0.05-0.1;
(2) adding 30-40 wt% of hydroxyl acrylic resin, polybasic acid, polyalcohol and hydrolysis-resistant intermediate into a reaction kettle, slowly heating to 160 ℃ in a nitrogen environment, preserving heat for 1h, continuously heating to 220 ℃, preserving heat for 2h, then cooling to 140 ℃, adding the rest hydroxyl acrylic resin, heating to 220 ℃, reacting until the acid value of the system is less than or equal to 15mgKOH/g, transferring into a dispersion machine, and adding water to disperse until the solid content is 50-70%.
Preferably, the hydrolysis-resistant intermediate is obtained by polymerizing a hydrolysis-resistant monomer and neopentyl glycol, wherein the hydrolysis-resistant monomer has a structural formula:
the preparation method of the hydrolysis-resistant monomer comprises the following steps:
(1) weighing cuprous chloride, potassium tert-butoxide, phenanthroline, trifluoromethyltrimethylsilane and 5-iodoisophthalic acid dimethyl ester in a molar ratio of 2:2:2:1, adding the cuprous chloride and the potassium tert-butoxide into a reaction kettle under the protection of nitrogen, adding the phenanthroline dissolved in DMF into the reaction kettle, stirring and reacting for 30min at room temperature, dropwise adding trifluoromethyl trimethylsilane into the reaction kettle, stirring and reacting for 1h at room temperature, adding the 5-iodoisophthalic acid dimethyl ester dissolved in DMF into the reaction kettle, heating to 60 ℃, stirring and reacting for 20h, filtering with diatomite after the reaction is finished, extracting the filtrate with ethyl acetate, washing the extract with saturated salt water, drying with anhydrous magnesium sulfate, filtering, and performing rotary evaporation to obtain a product I, wherein the reaction equation is as follows:
(2) dissolving 10g of product I in 100mL of DMF, then adding 200mL of a mixed solution of water and DMF (the volume ratio of the two is 1:1), adding 20mL of methanol and 50mL of sodium hydroxide with the concentration of 3mol/L, stirring for reaction for 3h, filtering by using kieselguhr, extracting the filtrate by using ethyl acetate, washing the extract by using saturated saline solution, drying by using anhydrous magnesium sulfate, then filtering, and performing rotary evaporation to obtain a hydrolysis-resistant monomer, wherein the reaction equation is as follows:
preferably, the polyhydric alcohol is one or more of ethylene glycol, butanediol, hexanediol, neopentyl glycol, trimethylolethane, and trimethylolpropane.
Preferably, the polybasic acid is one or more of terephthalic acid, isophthalic acid and adipic acid.
Preferably, the amino resin is a methylated melamine formaldehyde resin.
Preferably, the wetting agent is a silicone-based wetting agent.
Preferably, the leveling agent is an acrylate leveling agent.
Preferably, the defoaming agent is a silicone defoaming agent.
A preparation method of a water-based polyester-acrylic amino resin hybrid baking paint comprises the following steps: adding the hydrolysis-resistant polyester acrylate aqueous dispersion into a container at the rotating speed of 400-.
The invention has the following beneficial effects: according to the invention, the hydrolysis-resistant polyester acrylate dispersion is added into the baking varnish system, so that the water resistance of a paint film is effectively improved, the polyester part of the hydrolysis-resistant polyester acrylate dispersion contains hydrolysis-resistant monomers, and the hydrolysis-resistant monomers contain trifluoromethyl groups, so that the water resistance of the aqueous dispersion can be fundamentally and obviously improved; the hydrolysis-resistant intermediate is obtained by polymerizing a hydrolysis-resistant monomer and isoprene glycol, and the hydrolysis-resistant monomer, polybasic acid, polyalcohol and hydroxy acrylic resin are reacted together to obtain the hydrolysis-resistant polyester acrylate dispersoid, so that the hydrolysis-resistant intermediate is firmly combined in vivo, and the water resistance of a paint film is fundamentally improved.
Drawings
The invention is further illustrated with reference to the following figures and examples.
FIG. 1 is a nuclear magnetic characteristic absorption spectrum of the hydrolysis-resistant intermediate prepared by the invention.
Detailed Description
The present invention will now be described in further detail with reference to examples.
FIG. 1 is a nuclear magnetic characteristic absorption spectrum of the hydrolysis-resistant intermediate prepared by the invention, and nuclear magnetic data are as follows: δ is 8.21 to 8.40 (benzene ring), δ is 4.20 to 4.29(a, 2H), δ is 3.91 to 4.01(b, 4H), δ is 3.31 to 3.36(c, 4H), δ is 0.82 to 0.88(d, 12H). The absorption peak and the integral value of each proton obtained by the test are completely consistent with those of the protons in the hydrolysis-resistant intermediate, which indicates that the hydrolysis-resistant intermediate is obtained.
The preparation method of the water-based polyester-acrylic amino resin hybrid baking paint comprises the following steps: adding the hydrolysis-resistant polyester acrylate aqueous dispersion into a container at the rotating speed of 400-.
The preparation method of the hydrolysis-resistant polyester acrylate aqueous dispersion comprises the following steps:
(1) weighing hydroxyl acrylic resin, polybasic acid, polyalcohol and hydrolysis-resistant intermediate, wherein the molar ratio of the four is 1:0.5-1.5:0.5-1.5: 0.05-0.1;
(2) adding 30-40 wt% of hydroxyl acrylic resin, polybasic acid, polyalcohol and hydrolysis-resistant intermediate into a reaction kettle, slowly heating to 160 ℃ in a nitrogen environment, preserving heat for 1h, continuously heating to 220 ℃, preserving heat for 2h, then cooling to 140 ℃, adding the rest hydroxyl acrylic resin, heating to 220 ℃, reacting until the acid value of the system is less than or equal to 15mgKOH/g, transferring into a dispersion machine, and adding water to disperse until the solid content is 50-70%.
The components and their parts by weight in examples 1 to 3 and comparative examples 1 to 3 are shown in Table 1.
TABLE 1
In Table 1, the preparation of a conventional polyester acrylate aqueous dispersion was the same as that of a hydrolysis-resistant polyester acrylate aqueous dispersion except that no hydrolysis-resistant intermediate was added; the molar ratio of the hydroxyl acrylic resin to the hydrolysis-resistant intermediate in the aqueous dispersion of the low hydrolysis-resistant intermediate is 1: 0.03; the molar ratio of the hydroxyl acrylic resin to the hydrolysis-resistant intermediate in the aqueous dispersion of the high hydrolysis-resistant intermediate is 1: 0.15.
Comparative example 4 is substantially the same as example 3 except that in comparative example 4, the hydrolysis-resistant polyester acrylate aqueous dispersion was replaced with the polyester acrylate aqueous dispersion one, and in the preparation process of the polyester acrylate aqueous dispersion one, the hydrolysis-resistant intermediate was replaced with hydrolysis-resistant monomers and neopentyl glycol in equal proportions.
Comparative example 5 is substantially the same as example 3 except that in comparative example 5, the hydrolysis-resistant polyester acrylate aqueous dispersion is replaced with a polyester acrylate aqueous dispersion two, and in the preparation process of the polyester acrylate aqueous dispersion two, the hydrolysis-resistant intermediate is replaced with an equal molar number of hydrolysis-resistant monomers.
The paint films prepared in examples 1 to 3 and comparative examples 1 to 5 were subjected to performance tests, the results of which are shown in Table 2.
TABLE 2
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (10)
1. The water-based polyester-acrylic amino resin hybrid baking varnish is characterized by comprising the following components in parts by weight: 45-55 parts of hydrolysis-resistant polyester acrylate aqueous dispersion, 15-25 parts of amino resin, 8-15 parts of water, 0.1-0.5 part of wetting agent, 0.1-0.5 part of flatting agent and 0.1-0.8 part of defoaming agent.
2. The aqueous polyester-acrylic amino resin hybrid baking varnish according to claim 1, wherein: the hydrolysis-resistant polyester acrylate aqueous dispersion is obtained by reacting hydroxyl acrylic resin, polyalcohol, polybasic acid and a hydrolysis-resistant intermediate, wherein the structural formula of the hydrolysis-resistant intermediate is as follows:
3. the aqueous polyester-acrylic amino resin hybrid baking varnish according to claim 2, characterized in that: the hydrolysis-resistant intermediate is obtained by polymerizing a hydrolysis-resistant monomer and neopentyl glycol, and the structural formula of the hydrolysis-resistant monomer is as follows:
4. the aqueous polyester-acrylic amino resin hybrid baking varnish according to claim 2, characterized in that: the polyhydric alcohol is one or more of ethylene glycol, butanediol, hexanediol, neopentyl glycol, trimethylolethane and trimethylolpropane.
5. The aqueous polyester-acrylic amino resin hybrid baking varnish according to claim 2, characterized in that: the polybasic acid is one or more of terephthalic acid, isophthalic acid and adipic acid.
6. The aqueous polyester-acrylic amino resin hybrid baking varnish according to claim 1, wherein: the amino resin is methylated melamine formaldehyde resin.
7. The aqueous polyester-acrylic amino resin hybrid baking varnish according to claim 1, wherein: the wetting agent is polysiloxane wetting agent.
8. The aqueous polyester-acrylic amino resin hybrid baking varnish according to claim 1, wherein: the leveling agent is an acrylate leveling agent.
9. The aqueous polyester-acrylic amino resin hybrid baking varnish according to claim 1, wherein: the defoaming agent is an organic silicon defoaming agent.
10. A method for preparing the water-based polyester-acrylic amino resin hybrid baking paint as claimed in any one of claims 1 to 9, which is characterized in that: the method comprises the following steps: adding the hydrolysis-resistant polyester acrylate aqueous dispersion into a container at the rotating speed of 400-.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911396832.9A CN111117444B (en) | 2019-12-30 | 2019-12-30 | Water-based polyester-acrylic amino resin hybrid baking paint and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911396832.9A CN111117444B (en) | 2019-12-30 | 2019-12-30 | Water-based polyester-acrylic amino resin hybrid baking paint and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111117444A true CN111117444A (en) | 2020-05-08 |
| CN111117444B CN111117444B (en) | 2021-11-30 |
Family
ID=70505238
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911396832.9A Active CN111117444B (en) | 2019-12-30 | 2019-12-30 | Water-based polyester-acrylic amino resin hybrid baking paint and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111117444B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111393959A (en) * | 2020-05-09 | 2020-07-10 | 深圳市深赛尔股份有限公司 | Mildew-proof antibacterial water-based baking varnish coating and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101033365A (en) * | 2006-03-09 | 2007-09-12 | 上海威肯化学品有限公司 | Water-based baking varnish |
| CN101613465A (en) * | 2009-07-21 | 2009-12-30 | 武汉理工大学 | A kind of Weather-proof self-cleaning transparent material and preparation method thereof |
| CN109337487A (en) * | 2018-09-21 | 2019-02-15 | 武汉同发科技有限公司 | A kind of water soluble acrylic acid amino-stoving varnish |
| CN110330597A (en) * | 2019-05-24 | 2019-10-15 | 广东锐涂精细化工有限公司 | A kind of fluorinated silicone modified polyester acrylic aqueous dispersion and preparation method thereof |
-
2019
- 2019-12-30 CN CN201911396832.9A patent/CN111117444B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101033365A (en) * | 2006-03-09 | 2007-09-12 | 上海威肯化学品有限公司 | Water-based baking varnish |
| CN101613465A (en) * | 2009-07-21 | 2009-12-30 | 武汉理工大学 | A kind of Weather-proof self-cleaning transparent material and preparation method thereof |
| CN109337487A (en) * | 2018-09-21 | 2019-02-15 | 武汉同发科技有限公司 | A kind of water soluble acrylic acid amino-stoving varnish |
| CN110330597A (en) * | 2019-05-24 | 2019-10-15 | 广东锐涂精细化工有限公司 | A kind of fluorinated silicone modified polyester acrylic aqueous dispersion and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111393959A (en) * | 2020-05-09 | 2020-07-10 | 深圳市深赛尔股份有限公司 | Mildew-proof antibacterial water-based baking varnish coating and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111117444B (en) | 2021-11-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100410286C (en) | Silicone modified polyacrylate and its prepn and application | |
| CN107805291B (en) | Aqueous hydroxy acrylic acid dispersion and preparation method thereof | |
| CN111073427B (en) | Dual UV (ultraviolet) curing coating for automotive interior parts, preparation method thereof and paint film formed by dual UV curing coating | |
| CN106634476B (en) | A kind of curable epoxide high-flexibility polyester resin for powder coating and preparation method thereof | |
| CN109852221B (en) | Low-VOC high-performance double-component waterborne polyurethane wood coating and preparation method thereof | |
| CN102653595B (en) | Preparation method of polyester modified hydroxyl polyacrylate, and paint containing polyester modified hydroxyl polyacrylate | |
| CN103540217B (en) | The double-component aqueous car paint of acrylate resin that a kind of aziridine is crosslinked and its preparation method | |
| CN103261345A (en) | Organic-inorganic hybrid paint composition | |
| CN111117444B (en) | Water-based polyester-acrylic amino resin hybrid baking paint and preparation method thereof | |
| CN100386356C (en) | Improved epoxy acrylic ester and its prepn | |
| CN112321774B (en) | Waterborne polyurethane/acrylate composite emulsion for single-component plastic silver paint and preparation method thereof | |
| CN105367746A (en) | Preparation method of scratch-resistant MDI and IPDI polymer polyurethane curing agent | |
| CN105367745A (en) | Preparation method of scratch-resistant TDI and IPDI polymer polyurethane curing agent | |
| CN105838204B (en) | A kind of colored steel coil coating composition and preparation method thereof | |
| CN115368795A (en) | Water-based high-solid amino baking paint and preparation method thereof | |
| CN110003788B (en) | Water-based single-component nano-modified self-crosslinking weather-resistant finish paint | |
| CN107033288B (en) | Antioxidant emulsion and antioxidant water-based coating gloss oil prepared by using same | |
| CN109401424A (en) | A kind of cured high temperature sintering varnish of LED-UV cold light source and preparation method thereof | |
| CN110423333A (en) | A kind of soft cryobranding color-changing polyurethane resin and its preparation method and application | |
| CN114213918A (en) | Water-based wood clear primer and preparation method thereof | |
| CN113462210A (en) | Water-based environment-friendly coating and preparation method thereof | |
| CN110358414B (en) | Silicon modified matte UV resin and preparation method thereof | |
| CN113637396A (en) | Single-component acrylic acid modified wrinkle paint and resin preparation method | |
| CN113637354A (en) | High-reflectivity water-based ink for photovoltaic module backboard glass | |
| CN112898531B (en) | Polyaryletherketone modified waterborne polyurethane resin |
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 |