CN112646351A - PPE/PS alloy material and preparation method and application thereof - Google Patents
PPE/PS alloy material and preparation method and application thereof Download PDFInfo
- Publication number
- CN112646351A CN112646351A CN202011558092.7A CN202011558092A CN112646351A CN 112646351 A CN112646351 A CN 112646351A CN 202011558092 A CN202011558092 A CN 202011558092A CN 112646351 A CN112646351 A CN 112646351A
- Authority
- CN
- China
- Prior art keywords
- pentaerythritol
- ppe
- alloy material
- resin
- film
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/06—Polystyrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
- C08J2325/04—Homopolymers or copolymers of styrene
- C08J2325/06—Polystyrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08J2371/12—Polyphenylene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2425/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2425/02—Homopolymers or copolymers of hydrocarbons
- C08J2425/04—Homopolymers or copolymers of styrene
- C08J2425/06—Polystyrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Wrappers (AREA)
Abstract
The invention discloses a PPE/PS alloy material and a preparation method and application thereof, wherein the PPE/PS alloy material comprises the following components in parts by weight: 30-70 parts of PPE resin; 30-70 parts of PS resin; 0.3-3 parts of pentaerythritol ester. According to the invention, the pentaerythritol ester with an active-OH structure is added into a PPE/PS system, so that the processing film forming property of the PPE/PS alloy material can be obviously improved, the PPE/PS film is easy to form, the prepared PPE/PS film has high transparency and good flexibility, the application of the PPE/PS alloy in the field of food packaging is further widened, and the PPE/PS film is particularly suitable for the field of food flexible packaging.
Description
Technical Field
The invention relates to the technical field of engineering plastics, in particular to a PPE/PS alloy material and a preparation method and application thereof.
Background
Polyphenylene Ether (PPE) is one of five engineering plastics, and has the defects of difficult processing and the like, and the practical application is limited, and the PPE is very excellent in heat resistance, chemical property, electrical property, dimensional stability and water resistance. At present, the processing performance is mainly improved by blending with Polystyrene (PS), thereby widening the application range. The PPE/PS alloy material has balanced rigidity and toughness required by food packaging, and has good application prospect in the field of food packaging. For example, GE plastics corporation in the United states has introduced a series of PPE resins that are blends of PPE and PS for use in the food packaging industry, which are suitable for a wide range of temperature applications from refrigerated storage to microwave ovens and can be used to make various food containers (dishes, trays, lids, etc.).
However, the PPE/PS alloy material has poor film forming property, has the problems of film cracking, film hardness and the like in the extrusion and film drawing process, cannot be made into a thin film grade material, can only be applied to hard packages such as food containers and the like at present, and is limited to be applied in the field of food flexible packages. The main research direction of the invention is how to improve the processing film forming property of the PPE/PS alloy material, prepare the PPE/PS film with high transparency and good flexibility, and widen the application of the PPE/PS alloy material in the field of food packaging.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention mainly aims to provide a PPE/PS alloy material which is easy to process into a film and can be prepared into a film material with good flexibility and high transparency.
The invention also aims to provide a preparation method of the PPE/PS alloy material.
The invention is realized by the following technical scheme:
the PPE/PS alloy material comprises the following components in parts by weight:
30-70 parts of PPE resin;
30-70 parts of PS resin;
0.3-3 parts of pentaerythritol ester.
The pentaerythritol ester has 2 or more than 2 active-OH groups.
According to the invention, through research, pentaerythritol ester is selected to be added into the PPE/PS alloy material, and the end-capped hydroxyl group of the pentaerythritol ester has strong activity, so that the pentaerythritol ester can be well combined with matrix resin and uniformly dispersed on the surface of the matrix resin, the film forming property of the PPE/PS alloy material is obviously improved, and the PPE/PS film with good flexibility and high transparency can be prepared. Preferably, the pentaerythritol ester is selected from one or more of pentaerythritol stearate, pentaerythritol oleate or pentaerythritol laurate; more preferably, the pentaerythritol ester is selected from pentaerythritol stearate.
The pentaerythritol stearate is selected from one or more of pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate or pentaerythritol tetrastearate; the pentaerythritol oleate is selected from any one or more of pentaerythritol monooleate, pentaerythritol dioleate, pentaerythritol trioleate or pentaerythritol tetraoleate; the pentaerythritol laurate is selected from one or more of pentaerythritol monolaurate, pentaerythritol dilaurate, pentaerythritol trilaurate or pentaerythritol tetralaurate.
The addition amount of the pentaerythritol ester is too small, so that the film layer is not uniform, and the toughness of the film is insufficient; if the addition amount is too large, the film is too soft, the stiffness is not enough, and the wrinkling is easy. Preferably, the pentaerythritol ester accounts for 0.8-1.5 parts by weight.
The viscosity average molecular weight of the PPE resin adopted by the invention is 13000-60000, and the viscosity average molecular weight is calculated by a solution viscometer measured in a dichloromethane solvent at 25 ℃; the PPE resin has an excessively high viscosity-average molecular weight, which results in poor uniformity of the extruded film; preferably, the viscosity average molecular weight of the PPE resin is 30000-50000.
The number average molecular weight of the PS resin adopted by the invention is more than 20000. The PS resin has too low a molecular weight and poor miscibility with the PPE resin, resulting in non-uniform film layer and defects.
The invention also provides a preparation method of the PPE/PS alloy material, which comprises the following steps: weighing the components according to the proportion, putting the components into a first section of a feed opening of a double-screw extruder, heating and melting the components by the double-screw extruder, extruding the components into strips through a die opening, cooling the strips by water, air-drying the strips, and cutting the strips into granules to obtain the PPE/PS alloy material; wherein the temperature of the extruder is 240-290 ℃; the rotation speed is 250rpm to 600 rpm.
The PPE/PS alloy material can be prepared into a thin film material with the thickness of less than 0.35mm by an extrusion film-drawing process.
The invention also provides application of the PPE/PS alloy material, which can be used for preparing film materials and is particularly applied to the field of food flexible packaging.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, researches show that the processing film forming property of the PPE/PS alloy material can be obviously improved by adding pentaerythritol ester with an active-OH structure into the PPE/PS system, the PPE/PS film is easy to prepare into a film material, the prepared PPE/PS film has high transparency and good flexibility, the problem that the PPE/PS alloy material in the prior art cannot be prepared into a film material is solved, the application of the PPE/PS alloy in the field of food packaging is further widened, and the PPE/PS film is particularly suitable for the field of food flexible packaging.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
The raw materials used in the examples and comparative examples are now described below, but are not limited to these materials:
PPE resin 1: PX100L, Mitsubishi chemical industry, viscosity average molecular weight 40000-46000;
PPE resin 2: LXR050, Lanxing chemical Co., Ltd., viscosity average molecular weight 50000-56000;
PS resin 1: GPPS 818K, Taida chemical, number average molecular weight 170000-180000;
PS resin 2: GPPS 1441, Trinseo, number average molecular weight 95000-105000;
pentaerythritol distearate: purchasing in market;
pentaerythritol tetrastearate: purchasing in market;
pentaerythritol dioleate: purchasing in market;
n-butyl stearate: purchasing in market;
glycerol tristearate: purchasing in market;
803 a terpene resin: purchasing in market;
erucamide: is commercially available.
Examples and comparative examples preparation of PPE/PS alloy materials:
weighing the components according to the proportion, putting the components into a first section of a feed opening of a double-screw extruder, heating and melting the components by the double-screw extruder, extruding the components into strips through a die opening, and then carrying out water cooling, air drying and grain cutting to obtain the PPE/PS alloy material. Wherein the temperature of the extruder is 240-290 ℃; the rotation speed is 250rpm to 600 rpm.
The PPE/PS alloy materials prepared in the above examples and comparative examples are extruded and drawn into films with the thickness of 0.3mm in a Haake rheometer, and the extrusion temperature is 270-300 ℃.
The related performance test method comprises the following steps:
(1) and (3) processing and film forming: evaluating the processing film-forming property of the material according to the film-discharging condition of the extruded and drawn film; the case where a thin film could not be made is denoted as XX; a film can be formed, but the case where the film cracks is represented as X; the case where a uniform film can be made is represented by O.
(2) Light transmittance: the higher the light transmission, the lower the haze, as determined by reference to the standard GB/T2410-2008 method, indicating the better the transparency of the material.
(3) Film softness: evaluating by adopting a touch rating mode, and dividing the evaluation into 5 grades (I grade, II grade, III grade, IV grade and V grade), wherein the lower the grade is, the harder the film is; a higher rating indicates a softer film.
(4) And (3) testing the impact resistance: the test was carried out according to method A in standard GB/T9639.1-2008. The better the impact resistance, the better the film toughness.
Table 1: specific proportions (by weight) of the components and performance test results in examples 1-7
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | |
| PPE resin 1 | 50 | 50 | 50 | 60 | 65 | ||
| PPE resin 2 | 50 | 55 | |||||
| PS resin 1 | 50 | 50 | 50 | 50 | 35 | ||
| PS resin 2 | 40 | 45 | |||||
| Pentaerythritol distearate | 1 | 0.3 | 2.5 | 1 | 0.8 | ||
| Pentaerythritol Tetrastearate | 1.5 | ||||||
| Pentaerythritol dioleate | 3 | ||||||
| Film forming property | O | O | O | O | O | O | O |
| Light transmittance | 85% | 82% | 82% | 87% | 80% | 88% | 83% |
| Softness of film | Ⅳ | Ⅲ | Ⅳ | Ⅳ | Ⅳ | Ⅴ | Ⅴ |
| Impact resistance | 150g | 145g | 140g | 145g | 160g | 145g | 135g |
Table 2: the specific proportions (by weight) of the components in comparative examples 1-6 and the results of performance tests
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | |
| PPE resin 1 | 50 | 50 | 50 | 50 | 50 | 50 |
| PS resin 1 | 50 | 50 | 50 | 50 | 50 | 50 |
| Pentaerythritol distearate | 5 | |||||
| Stearic acid n-butyl ester | 1 | |||||
| Glycerol tristearate | 1 | |||||
| 803 terpene resin | 1 | |||||
| Erucamide | 1 | |||||
| Film forming property | O | X | O | X | XX | XX |
| Light transmittance | 87% | / | 70% | / | / | / |
| Softness of film | V | / | Ⅱ | / | / | / |
| Impact resistance | <120g | / | <120g | / | / | / |
The embodiment shows that the processing film forming property of the PPE/PS alloy material can be obviously improved by adding the pentaerythritol ester with an active-OH structure, and the prepared PPE/PS film has high light transmittance, excellent impact resistance and good flexibility. Comparative example 1, with an excess of pentaerythritol distearate, the PPE/PS films produced were too soft, had poor impact resistance, and had inadequate film toughness. Comparative example 2/3/4/5/6, no PPE/PS film with high clarity and good flexibility was obtained without the addition of pentaerythritol ester.
Claims (9)
1. The PPE/PS alloy material is characterized by comprising the following components in parts by weight:
30-70 parts of PPE resin;
30-70 parts of PS resin;
0.3-3 parts of pentaerythritol ester.
2. The PPE/PS alloy material according to claim 1, wherein the pentaerythritol ester is 0.8-1.5 parts.
3. The PPE/PS alloy material of claim 1 wherein the pentaerythritol ester has 2 or more than 2 reactive-OH groups.
4. The PPE/PS alloy material according to claim 1, wherein the pentaerythritol ester is selected from any one or more of pentaerythritol stearate, pentaerythritol oleate or pentaerythritol laurate; preferably, the pentaerythritol ester is selected from any one or more of pentaerythritol stearate.
5. The PPE/PS alloy material according to claim 4, wherein the pentaerythritol stearate is selected from any one or more of pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate or pentaerythritol tetrastearate; the pentaerythritol oleate is selected from any one or more of pentaerythritol monooleate, pentaerythritol dioleate, pentaerythritol trioleate or pentaerythritol tetraoleate; the pentaerythritol laurate is selected from one or more of pentaerythritol monolaurate, pentaerythritol dilaurate, pentaerythritol trilaurate or pentaerythritol tetralaurate.
6. The PPE/PS alloy material according to claim 1, wherein the viscosity average molecular weight of the PPE resin is 13000-60000; preferably, the viscosity average molecular weight of the PPE resin is 30000-50000.
7. The PPE/PS alloy material of claim 1 wherein the PS resin has a number average molecular weight greater than 20000.
8. The method for preparing the PPE/PS alloy material according to any one of claims 1 to 7, comprising the following steps: weighing the components according to the proportion, putting the components into a first section of a feed opening of a double-screw extruder, heating and melting the components by the double-screw extruder, extruding the components into strips through a die opening, cooling the strips by water, air-drying the strips, and cutting the strips into granules to obtain the PPE/PS alloy material; wherein the temperature of the extruder is 240-290 ℃; the rotation speed is 250rpm to 600 rpm.
9. The use of the PPE/PS alloy material according to any one of claims 1-7 in the field of food packaging.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011558092.7A CN112646351B (en) | 2020-12-25 | 2020-12-25 | PPE/PS alloy material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011558092.7A CN112646351B (en) | 2020-12-25 | 2020-12-25 | PPE/PS alloy material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112646351A true CN112646351A (en) | 2021-04-13 |
| CN112646351B CN112646351B (en) | 2022-06-10 |
Family
ID=75362910
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011558092.7A Active CN112646351B (en) | 2020-12-25 | 2020-12-25 | PPE/PS alloy material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112646351B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102712770A (en) * | 2009-11-30 | 2012-10-03 | 帝人株式会社 | High-insulating film |
| CN104169757A (en) * | 2012-03-15 | 2014-11-26 | 日本瑞翁株式会社 | Phase difference film laminate, method for producing phase difference film laminate, and method for producing phase difference film |
| CN109796717A (en) * | 2018-12-27 | 2019-05-24 | 会通新材料股份有限公司 | A kind of low-density PPE composite material and preparation method and application |
-
2020
- 2020-12-25 CN CN202011558092.7A patent/CN112646351B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102712770A (en) * | 2009-11-30 | 2012-10-03 | 帝人株式会社 | High-insulating film |
| CN104169757A (en) * | 2012-03-15 | 2014-11-26 | 日本瑞翁株式会社 | Phase difference film laminate, method for producing phase difference film laminate, and method for producing phase difference film |
| CN109796717A (en) * | 2018-12-27 | 2019-05-24 | 会通新材料股份有限公司 | A kind of low-density PPE composite material and preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112646351B (en) | 2022-06-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106674962B (en) | A kind of PC/ABS alloy and preparation method thereof that heat aging performance is excellent | |
| WO2019237914A1 (en) | Polylactic acid 3d printing material and preparation method therefor | |
| CN112625404A (en) | Glass fiber reinforced PBT/PC alloy with high strength, low warpage and high thermal deformation temperature, and preparation method and application thereof | |
| CN113549323A (en) | High-strength high-flow low-warpage long glass fiber reinforced polyamide composite material, and preparation method and application thereof | |
| CN114716764A (en) | Polypropylene composite material and preparation method and application thereof | |
| CN112646351B (en) | PPE/PS alloy material and preparation method and application thereof | |
| CN112625361A (en) | Low-odor high-thermal-oxidative-aging-resistance glass fiber reinforced polypropylene composite material and preparation method thereof | |
| CN111073209B (en) | High-hydrophobicity PC/ABS alloy and preparation method thereof | |
| CN109749389A (en) | A kind of isobide type polycarbonate of weatherability and ABS resin alloy material and preparation method thereof | |
| CN109627656B (en) | Transparent permanent antistatic PMMA material and preparation method and application thereof | |
| CN106009052B (en) | Resin composition and resin molded article | |
| CN115627063B (en) | Flame-retardant PBT/PC alloy material and preparation method and application thereof | |
| CN114989544B (en) | Odorless high-transparency low-migration PVC material, blood transfusion tube and preparation method thereof | |
| CN115710422A (en) | High-performance PC/ABS blending material, preparation method and application | |
| CN106893250A (en) | A kind of blowing high fondant-strength, the ABS resin composition of good outward appearance | |
| CN108299805A (en) | A kind of high-impact, antistatic polyester class composite material and preparation method | |
| CN109320827B (en) | Polyethylene resin suitable for preparing blow molding tray and preparation method and application thereof | |
| CN110982211A (en) | Antistatic 3D printing material and preparation method thereof | |
| CN112812313A (en) | Antistatic agent and preparation method and application thereof | |
| CN112480637A (en) | Floating fiber-free flame-retardant PC/ABS composite material | |
| CN112759879B (en) | Low-warpage ASA composite material for 3D printing and preparation method thereof | |
| CN115948040B (en) | Polycarbonate composition and preparation and application thereof | |
| CN111320856A (en) | Composite material for high-performance PC, PBT and PTFE and preparation method thereof | |
| CN114957953B (en) | Hydrolysis-resistant low-temperature impact-resistant halogen-free flame-retardant PC/PBT alloy material and preparation method thereof | |
| CN114276638B (en) | Application of acrylic ester compound as water binding agent in preparation of hydrolysis-resistant PMMA (polymethyl methacrylate) composition |
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 |