CN116463747A - Preparation method of light-colored conductive nylon - Google Patents
Preparation method of light-colored conductive nylon Download PDFInfo
- Publication number
- CN116463747A CN116463747A CN202310464033.0A CN202310464033A CN116463747A CN 116463747 A CN116463747 A CN 116463747A CN 202310464033 A CN202310464033 A CN 202310464033A CN 116463747 A CN116463747 A CN 116463747A
- Authority
- CN
- China
- Prior art keywords
- light
- conductive
- filler
- nylon
- colored conductive
- 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.)
- Pending
Links
- 239000004677 Nylon Substances 0.000 title claims abstract description 26
- 229920001778 nylon Polymers 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000009987 spinning Methods 0.000 claims abstract description 30
- 239000011231 conductive filler Substances 0.000 claims abstract description 29
- 239000000835 fiber Substances 0.000 claims abstract description 22
- 239000000945 filler Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000004093 laser heating Methods 0.000 claims abstract description 5
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 8
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 6
- 235000019253 formic acid Nutrition 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 238000004804 winding Methods 0.000 claims description 3
- 239000011258 core-shell material Substances 0.000 claims description 2
- 229920006052 Chinlon® Polymers 0.000 claims 1
- 238000002074 melt spinning Methods 0.000 abstract description 5
- 239000012530 fluid Substances 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 239000000155 melt Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 11
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 238000005325 percolation Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/90—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D1/00—Treatment of filament-forming or like material
- D01D1/02—Preparation of spinning solutions
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/04—Dry spinning methods
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Artificial Filaments (AREA)
Abstract
The invention provides a preparation method of light-colored conductive nylon, which adopts solution fluid spinning to replace traditional melt spinning, and because the viscosity of the solution fluid is smaller than that of a melt, the fluidity is good, the rotation resistance of conductive whiskers in the spinning solution is also relatively smaller, the orientation is easier to control, and the problem of suddenly reduced fluidity after the spinning solution is sprayed out is avoided. And the subsequent stretching induced orientation method is utilized to further improve the orientation degree of the conductive filler in the axial direction of the fiber, improve the axial conductivity of charges and realize the high conductivity of the fiber with lower addition. The traditional hot roller is replaced by the laser heating device in the drafting system, so that the temperature is quickly and accurately increased, the drafting effect is improved, and the spinning rate is improved. The conductive filler in different shapes has great influence on the heat-conducting property and mechanical property of the material, and the conductive filler in the invention is preferably mixed by adopting spherical and needle-shaped fillers, wherein the weight ratio of the spherical to the needle-shaped fillers is 1:0.5-2, and the conductive filler can obtain good conductive property by adding a small amount of the conductive filler, thereby being beneficial to improving the mechanical property.
Description
Technical Field
The invention belongs to the technical field of textile processing, and particularly relates to a preparation method of light-colored conductive nylon.
Background
The main implementation means of the existing light-colored conductive fiber is to add titanium dioxide, potassium titanate and the like which are subjected to conductive coating treatment as light-colored conductive filler in the melt spinning process. The spherical conductive filler has small influence on the viscosity and fluidity of the spinning melt and small spinning difficulty, so that the spherical filler is added to carry out melt spinning in the prior art. However, when spherical fillers are used for preparing conductive fibers, the percolation threshold of the fibers is high, and the ideal conductivity can be achieved only by high addition, so that the problem that the spinnability, mechanical property and conductivity of the fibers cannot be achieved is caused. The whisker-shaped conductive filler has higher length-diameter ratio, so that a conductive path is formed by lap joint more easily and is not easily damaged due to fiber deformation when the whisker-shaped conductive filler is used than a spherical filler, the conductivity is better and more stable, the higher the orientation degree of the filler is, the better the conductivity of the fiber is, but the addition of the whisker-shaped filler easily causes the viscosity of a spinning melt to be overlarge, the high-power drafting is not facilitated, and the orientation degree of the filler along the axial direction of the fiber is not high.
When the melt spinning method is used for preparing the light-colored conductive fibers, the conductive whiskers are generally randomly oriented and have low axial charge conduction capability because of high viscosity of the spinning solution and high orientation and arrangement resistance of the conductive whiskers. The multi-stage drawing method can induce the conductive whisker to be oriented along the axial direction of the fiber to a certain extent through multiple drawing, thereby improving the conductivity of the fiber. However, the melt viscosity of the spinning is high, the temperature is suddenly reduced after the spinning is extruded from a spinning nozzle, and the fluidity is reduced, so that the drawing is not facilitated. And the traditional hot roller used for multistage hot drawing has low heating efficiency and low spinning speed.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method of light-colored conductive nylon, which comprises the following steps:
(1) Firstly, weighing light-colored conductive filler, adding the light-colored conductive filler into formic acid solution, and fully dispersing the light-colored conductive filler by using an ultrasonic dispersing instrument, wherein the dispersing process is carried out in an ice bath;
(2) Placing the evenly dispersed formic acid suspension on a stirrer for rapid stirring, and simultaneously adding nylon chips into the suspension to obtain spinning solution after complete dissolution;
(3) Adding spinning solution into a screw extrusion device for extrusion, introducing hot air into a spinning channel, realizing high-power drafting through a first drafting roller which rotates rapidly, continuously volatilizing a solvent in the drafting process of the spinning solution, forming and winding fibers on the first drafting roller, rapidly heating the fibers by using a laser auxiliary heating method, and carrying out secondary drafting through a second drafting roller, thus obtaining the light-colored conductive nylon.
The light-colored conductive filler in the step (1) is at least one of conductive TiO 2, conductive potassium titanate and the like with a core-shell structure, the shell layer of the light-colored conductive filler is a conductive component, the component is at least one of antimony doped tin oxide, tin doped indium oxide, aluminum doped zinc oxide and the like, the light-colored conductive filler is at least one of spherical, needle-shaped and the like, the diameter is within 250nm, preferably the spherical and needle-shaped blended conductive filler is prepared by mixing the following components in percentage by weight: 0.5-2.
The concentration of nylon in the spinning solution in step (2) is 25-35wt.%.
The temperature of the first drafting roller in the step (3) is 40-60 ℃, and the drafting multiple is 8-15; the draft multiple of the second draft roller is 6-12, and the laser heating power is 1.2W.
The weight ratio of nylon to filler is 1:0.2-0.6.
The technical scheme of the invention has at least the following beneficial effects: the invention provides a preparation method of light-colored conductive nylon, which adopts solution fluid spinning to replace traditional melt spinning, and because the viscosity of the solution fluid is smaller than that of a melt, the fluidity is good, the rotation resistance of conductive whiskers in the spinning solution is also relatively smaller, the orientation is easier to control, and the problem of suddenly reduced fluidity after the spinning solution is sprayed out is avoided. And the subsequent stretching induced orientation method is utilized to further improve the orientation degree of the conductive filler in the axial direction of the fiber, improve the axial conductivity of charges and realize the high conductivity of the fiber with lower addition. The laser heating device is used for replacing the traditional hot roller in the drafting system, so that the rapid temperature rise of the fiber is rapidly and accurately realized, the drafting effect is improved, and the spinning rate is improved. The conductive filler in different shapes has great influence on the heat-conducting property and mechanical property of the material, and the conductive filler in the invention is preferably mixed by adopting spherical and needle-shaped fillers, wherein the weight ratio of the spherical to the needle-shaped fillers is 1:0.5-2, and the conductive filler can obtain good conductive property by adding a small amount of the conductive filler, thereby being beneficial to improving the mechanical property.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for the purpose of illustration and explanation only and is not intended to limit the present invention.
Example 1:
the preparation method of the light-colored conductive nylon comprises the following steps:
1) Firstly weighing light-colored conductive filler TiO 2 Adding the mixture into formic acid solution, fully dispersing the mixture by using an ultrasonic dispersing instrument, and performing the dispersing process in an ice bath;
2) Placing the evenly dispersed formic acid suspension on a stirrer for rapid stirring, and simultaneously adding nylon chips into the suspension to obtain spinning solution after complete dissolution;
3) Adding spinning solution into a screw extrusion device for extrusion, introducing hot air into a spinning channel, realizing high-power drafting through a first drafting roller which rotates rapidly, continuously volatilizing a solvent in the drafting process of the spinning solution, forming and winding fibers on the first drafting roller, rapidly heating the fibers by using a laser auxiliary heating method, and carrying out secondary drafting through a second drafting roller, thus obtaining the light-colored conductive nylon.
The conductive filler is in a spherical shape and is used by blending, and the weight ratio of the needle shape to the spherical shape is 1:1.5.
the concentration of nylon in the dope in step (2) was 25wt.%.
The weight ratio of nylon to filler was 1:0.3.
The temperature of the first drafting roller in the step (3) is 50 ℃, and the drafting multiple is 12; the draft multiple of the second draft roller was 8, and the laser heating power was 1.2W.
Example 2:
the filler was needle-shaped only, and the rest was the same as in example 1.
Example 3:
the filler was spherical only, and the rest was the same as in example 1.
Comparative example 1:
the remainder was the same as in example 1, except that no laser-assisted heating was used.
Comparative example 2:
the concentration of the dope nylon in step (2) was 15wt.%, and the rest was the same as in example 1.
Comparative example 3:
the weight ratio of nylon to filler was 1:0.7, the remainder being the same as in example 1.
Comparative example 4:
the weight ratio of needle-like and spherical fillers was 1:0.4, the remainder being the same as in example 1.
Comparative example 5:
the weight ratio of needle-like and spherical fillers was 1:2.2, the remainder being the same as in example 1.
Conductive properties and mechanical properties were tested on the conductive fibers obtained in examples 1 to 3 and comparative examples 1 to 5, as shown in the following table:
| unit resistance omega/cm | Breaking strength cN/dtex | |
| Example 1 | 10 7 | 2.1 |
| Example 2 | 10 9 | 1.9 |
| Example 3 | 10 9 | 2.1 |
| Comparative example 1 | 10 8 | 1.8 |
| Comparative example 2 | 10 7 | 1.9 |
| Comparative example 3 | 10 5 | 1.4 |
| Comparative example 4 | 10 8 | 1.9 |
| Comparative example 5 | 10 8 | 2.1 |
It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (6)
1. The preparation method of the light-colored conductive nylon is characterized by comprising the following steps of:
(1) Firstly, weighing light-colored conductive filler, adding the light-colored conductive filler into formic acid solution, and fully dispersing the light-colored conductive filler by using an ultrasonic dispersing instrument, wherein the dispersing process is carried out in an ice bath;
(2) Placing the evenly dispersed formic acid suspension on a stirrer for rapid stirring, and simultaneously adding nylon chips into the suspension to obtain spinning solution after complete dissolution;
(3) Adding spinning solution into a screw extrusion device for extrusion, introducing hot air into a spinning channel, realizing high-power drafting through a first drafting roller which rotates rapidly, continuously volatilizing a solvent in the drafting process of the spinning solution, forming and winding fibers on the first drafting roller, rapidly heating the fibers by using a laser auxiliary heating method, and carrying out secondary drafting through a second drafting roller, thus obtaining the light-colored conductive nylon.
2. The method for preparing light-colored conductive nylon according to claim 1, wherein the light-colored conductive filler in the step (1) is conductive TiO with a core-shell structure 2 At least one of conductive potassium titanate and the like, wherein the shell layer of the light-colored conductive filler is a conductive component, the filler is at least one of spherical, needle-shaped and the like, and the diameter is within 250 nm.
3. The preparation method of the light-colored conductive chinlon, according to claim 2, wherein the filler is spherical and needle-shaped blended conductive filler, and the weight ratio is 1:0.5-2.
4. The method for preparing light-colored conductive nylon according to claim 1, wherein the concentration of nylon in the spinning solution in the step (2) is 15-35wt.%.
5. The preparation method of light-colored conductive nylon according to claim 1, wherein in the step (3), the temperature of the first drawing roller is 40-60 ℃ and the drawing multiple is 8-15; the draft multiple of the second draft roller is 6-12, and the laser heating power is 1.2W.
6. The method for preparing light-colored conductive nylon according to claim 1, wherein the weight ratio of nylon to filler is 1:0.2-0.6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310464033.0A CN116463747A (en) | 2023-04-26 | 2023-04-26 | Preparation method of light-colored conductive nylon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310464033.0A CN116463747A (en) | 2023-04-26 | 2023-04-26 | Preparation method of light-colored conductive nylon |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116463747A true CN116463747A (en) | 2023-07-21 |
Family
ID=87182294
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310464033.0A Pending CN116463747A (en) | 2023-04-26 | 2023-04-26 | Preparation method of light-colored conductive nylon |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116463747A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101676450A (en) * | 2008-09-19 | 2010-03-24 | 东丽纤维研究所（中国）有限公司 | Multicomponent white conductive fiber and preparation method thereof |
| CN103173886A (en) * | 2013-04-08 | 2013-06-26 | 周焕民 | Method for manufacturing nylon conductive fibers |
| CN111235655A (en) * | 2020-03-04 | 2020-06-05 | 江南大学 | Light-colored conductive TiO2Preparation method of whisker/high polymer composite antistatic fiber |
| CN111636114A (en) * | 2020-06-12 | 2020-09-08 | 东华大学 | Preparation of high-strength high-conductivity polyvinyl alcohol/graphene composite fiber |
| CN114934325A (en) * | 2022-05-31 | 2022-08-23 | 江南大学 | Preparation method of light-color photothermal fibers, and obtained material and application thereof |
-
2023
- 2023-04-26 CN CN202310464033.0A patent/CN116463747A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101676450A (en) * | 2008-09-19 | 2010-03-24 | 东丽纤维研究所（中国）有限公司 | Multicomponent white conductive fiber and preparation method thereof |
| CN103173886A (en) * | 2013-04-08 | 2013-06-26 | 周焕民 | Method for manufacturing nylon conductive fibers |
| CN111235655A (en) * | 2020-03-04 | 2020-06-05 | 江南大学 | Light-colored conductive TiO2Preparation method of whisker/high polymer composite antistatic fiber |
| CN111636114A (en) * | 2020-06-12 | 2020-09-08 | 东华大学 | Preparation of high-strength high-conductivity polyvinyl alcohol/graphene composite fiber |
| CN114934325A (en) * | 2022-05-31 | 2022-08-23 | 江南大学 | Preparation method of light-color photothermal fibers, and obtained material and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3626758B1 (en) | Graphene composite material and preparation method therefor | |
| US9263171B2 (en) | Conductive masterbatches and conductive monofilaments | |
| EP0631638B1 (en) | Polyester fibres and process for producing the same | |
| US20090111950A1 (en) | Polyester high-strength fiber | |
| CN106238726B (en) | A kind of flexible compound nano-silver thread and preparation method thereof | |
| CN110257947B (en) | Antibacterial polyester industrial yarn and preparation method thereof | |
| CN103774271A (en) | Functional nylon-6 fiber and preparation method thereof | |
| CN112853521B (en) | Production method of anti-static POY (polyester pre-oriented yarn) | |
| CN100395381C (en) | Method of continuously preparing poly terephthaloyl-p-phenylene diamine fibre | |
| US8262980B2 (en) | Sol-gel composition for fabricating conductive fibers | |
| CN108728924B (en) | Halogen-free flame-retardant reinforced nylon 66 nano fiber and preparation method thereof | |
| TW200928027A (en) | Fiber and method of forming the same | |
| CN116463747A (en) | Preparation method of light-colored conductive nylon | |
| US3591565A (en) | Polyamides containing alkali metal halide additives as void formation inhibitors | |
| CN111218732A (en) | Preparation method of graphene twisted fiber | |
| CN1035395C (en) | Fibers with improved hydrolytic stability | |
| CN110922575A (en) | Colored conductive polyester fiber and preparation method thereof | |
| CN113265717B (en) | Manufacturing method of antibacterial polyester fiber | |
| CN115233334A (en) | High-brightness composite noctilucent fiber and preparation method thereof | |
| CN112680811B (en) | Graphene/polyacrylonitrile composite fiber, spinning solution and preparation method thereof | |
| JPS61258019A (en) | Production of antistatic polyamide fiber | |
| CN1167837C (en) | Superfine fiber and its making process | |
| TWI758596B (en) | Fabricating method of fiber | |
| CN115305598B (en) | Core-shell structure shielding material and preparation method thereof | |
| JPS61201008A (en) | Production of electrically conductive monofilament |
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 |