CN114593990A - Method for evaluating spinnability of pulp for tencel - Google Patents
Method for evaluating spinnability of pulp for tencel Download PDFInfo
- Publication number
- CN114593990A CN114593990A CN202011391736.8A CN202011391736A CN114593990A CN 114593990 A CN114593990 A CN 114593990A CN 202011391736 A CN202011391736 A CN 202011391736A CN 114593990 A CN114593990 A CN 114593990A
- Authority
- CN
- China
- Prior art keywords
- pulp
- spinning solution
- paper
- strength
- spinnability
- 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
- 229920000433 Lyocell Polymers 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 19
- 239000000835 fiber Substances 0.000 claims abstract description 40
- 238000009987 spinning Methods 0.000 claims abstract description 34
- 238000011156 evaluation Methods 0.000 claims description 13
- 239000011248 coating agent Substances 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 12
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 claims description 9
- 229920000742 Cotton Polymers 0.000 claims description 5
- 230000004913 activation Effects 0.000 claims description 5
- 238000005520 cutting process Methods 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 3
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 3
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 3
- 239000011425 bamboo Substances 0.000 claims description 3
- 244000025254 Cannabis sativa Species 0.000 claims description 2
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 claims description 2
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 claims description 2
- 235000009120 camo Nutrition 0.000 claims description 2
- 235000005607 chanvre indien Nutrition 0.000 claims description 2
- 238000007766 curtain coating Methods 0.000 claims description 2
- 239000011121 hardwood Substances 0.000 claims description 2
- 239000011487 hemp Substances 0.000 claims description 2
- 239000011122 softwood Substances 0.000 claims description 2
- 244000082204 Phyllostachys viridis Species 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 3
- 238000004451 qualitative analysis Methods 0.000 abstract description 2
- 238000004445 quantitative analysis Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 19
- 230000008569 process Effects 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 4
- 239000011550 stock solution Substances 0.000 description 4
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- 229920000297 Rayon Polymers 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000011144 upstream manufacturing Methods 0.000 description 3
- 241001330002 Bambuseae Species 0.000 description 2
- 229920000875 Dissolving pulp Polymers 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- 239000012209 synthetic fiber Substances 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 244000144730 Amygdalus persica Species 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 235000006040 Prunus persica var persica Nutrition 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 206010061592 cardiac fibrillation Diseases 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000002600 fibrillogenic effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000013441 quality evaluation Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N3/00—Investigating strength properties of solid materials by application of mechanical stress
- G01N3/08—Investigating strength properties of solid materials by application of mechanical stress by applying steady tensile or compressive forces
-
- 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
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N11/00—Investigating flow properties of materials, e.g. viscosity, plasticity; Analysing materials by determining flow properties
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/84—Systems specially adapted for particular applications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/36—Textiles
- G01N33/365—Filiform textiles, e.g. yarns
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/84—Systems specially adapted for particular applications
- G01N2021/8405—Application to two-phase or mixed materials, e.g. gas dissolved in liquids
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/84—Systems specially adapted for particular applications
- G01N2021/8444—Fibrous material
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N2203/00—Investigating strength properties of solid materials by application of mechanical stress
- G01N2203/0014—Type of force applied
- G01N2203/0016—Tensile or compressive
- G01N2203/0017—Tensile
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N2203/00—Investigating strength properties of solid materials by application of mechanical stress
- G01N2203/02—Details not specific for a particular testing method
- G01N2203/026—Specifications of the specimen
- G01N2203/0262—Shape of the specimen
- G01N2203/0278—Thin specimens
- G01N2203/028—One dimensional, e.g. filaments, wires, ropes or cables
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Immunology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Pathology (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Food Science & Technology (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Artificial Filaments (AREA)
Abstract
The invention discloses a method for evaluating the spinnability of pulp for tencel, which evaluates the dissolving performance, spinnability and strength performance of the pulp respectively, simulates the preparation process of tencel fiber, carries out qualitative and quantitative analysis on the fiber strength after dissolving, spinning and spinning of the pulp, effectively links the pulp performance with the spinning process, has simple operation and better practical value.
Description
Technical Field
The invention relates to a method for evaluating spinnability of pulp for tencel, and particularly relates to the technical field of tencel fibers.
Background
Tencel fiber as an upgraded viscose fiber is produced by using dissolving pulp, cotton fiber and the like as main raw materials and N-methylmorpholine-N-oxide (NMMO) as a solvent through a solvent spinning method. As chemical reagents such as carbon disulfide and the like are not needed to be added during production, toxic and harmful waste water, waste gas and waste residue are not generated, NMMO is only used as a solvent, the production is carried out by a physical method, and the fiber can be naturally degraded 3-6 months after being buried in soil, therefore, the tencel fiber is called as 'green fiber' in the 21 st century.
The tencel fiber integrates the advantages of natural fiber and synthetic fiber, has the moisture absorption, air permeability and comfort of cotton fiber, and has the strength performance far higher than that of cotton and common viscose fiber and close to that of polyester fiber. Furthermore, lyocell fibers also have a fibrillation effect, producing a surface effect similar to that of polyester peach skin, which cannot be obtained by conventional fibers. Based on the excellent natural fiber and synthetic fiber characteristics of tencel fiber, various woven and knitted products with high added values are developed and widely applied to the fields of clothes and textile, and the industrial fields of non-woven fabrics, industrial filter cloth, industrial yarn, special paper and the like.
The upper reaches of the tencel fiber industry mainly comprise pulp and solvent such as wood pulp and bamboo pulp, and the lower reaches of the tencel fiber industry are the textile industry. Wherein the upstream product pulp is a key factor for restricting the development of tencel fiber. At present, the dependence of the pulp raw material import is high, and the problems of low average quality level, general processing performance and the like of the domestic pulp generally exist. Under the large background of trade war, the import policy will gradually become stricter, and the development of native pulp products with high quality and low price is the key to realizing the breakthrough of productivity in tencel fiber industry.
The influence of the pulp on the production of tencel fiber and the quality of the product is mainly summarized into two aspects: firstly, impurities except cellulose contained in the pulp, such as hemicellulose, lignin, extract, metal ions and the like, mostly play a negative role, and the impurities cannot be removed in the working procedure of filtering stock solution along with the pulp entering a stock solution system to influence the spinnability of the stock solution; meanwhile, along with the recycling of the solvent, the concentration of impurities in the system is continuously increased to influence the recovery of the solvent; secondly, the internal structure of the pulp, such as crystallinity and molecular weight distribution, influences the swelling effect of the pulp in an NMMO solution system, and further influences the performance of the stock solution. From the aspect of product quality evaluation, different from viscose fibers, an evaluation system for tencel fiber dissolving performance is not established at home, and the existing dissolving pulp indexes such as alpha cellulose content, alkali dissolving performance, extract content, metal ion content and the like cannot be used as the standard for evaluating the quality of tencel pulp, so that the upstream pulp product of the tencel fiber cannot be effectively connected with the downstream spinning performance. Therefore, it is necessary to establish a system for evaluating the spinnability of the pulp for tencel fiber, so as to refine and improve the existing pulp in a targeted manner, thereby achieving the standard of the pulp for tencel fiber.
Disclosure of Invention
Aiming at the problems of the existing pulp evaluation system for tencel fiber, the invention provides a method for evaluating the spinnability of pulp for tencel fiber, which can well combine the upstream pulp raw material with the downstream spinning industry and provide reference for upgrading the pulp for tencel fiber.
The invention provides a method for evaluating spinnability of pulp for tencel, which comprises the following steps:
(1) evaluation of solubility: tearing pulp into small pieces, mixing the small pieces with a 50% NMMO solution according to a certain proportion, forming an amber uniform spinning solution under reduced pressure distillation, recording the dissolving time, observing the spinning solution by using a polarizing microscope to see whether undissolved fibers exist or not, wherein the shorter the dissolving time is, and the pulp without the undissolved fibers in the spinning solution is better pulp;
(2) evaluation of spinnability of the spinning solution: measuring the zero-shear viscosity, Newton index, viscous flow activation energy and structural viscosity index of the spinning solution by using a rheometer in a steady-state shear flow mode; the lower the zero-cut viscosity of the measured pulp spinning solution, the higher the Newton index, the lower the viscous flow activation energy and the structural viscosity index, the good spinnability of the pulp and the easy formation of fibers;
(3) evaluation of spinning strength performance: uniformly coating the uniform spinning solution prepared in the step (1) on paper, placing the paper on an oven for drying to constant weight, then cutting the paper into a standard size, measuring the strength of a paper sample on a paper tensile strength tester, comparing the tensile strength of the paper sample under the same coating weight, and if the measured strength is higher, proving that the pulp has better performance and the spun fiber has higher strength;
preferably, the pulp in the step (1) is one or more of hardwood pulp, softwood pulp, bamboo pulp, cotton pulp, hemp pulp and the like;
preferably, the size of the small pulp blocks in the step (1) is 1-5 cm2；
Preferably, the mixing ratio of the pulp in the step (1) and the 50% NMMO solution is 1-10%;
preferably, the reduced pressure distillation temperature in the step (1) is 50-99 ℃;
preferably, the coating mode in the step (3) can be one or more of blade coating, bar coating and curtain coating;
preferably, the drying temperature in the step (3) is 80-115 ℃;
preferably, the cutting size in the step (3) is 100-200 mm in length and 15mm in width;
the invention is characterized in that: the method simulates the preparation process of tencel fiber, carries out qualitative and quantitative analysis on the fiber strength after dissolving, spinning and spinning the pulp, effectively links the pulp performance with the spinning process, has simple operation and better practical value.
Detailed Description
To facilitate an understanding of the invention, the following examples are set forth. It should be understood by those skilled in the art that the examples are only for the purpose of facilitating the understanding of the present invention and should not be construed as specifically limiting the present invention.
Example 1:
a method for evaluating spinnability of a pulp for tencel, the method comprising the steps of:
(1) evaluation of solubility: tearing pulp A and pulp B into small pieces with a size of about 1cm2Mixing the solution with 50% NMMO solution in a proportion of 3%, forming amber uniform spinning solution at a reduced pressure distillation temperature of 95 ℃, recording the dissolution time, and observing the spinning solution by using a polarization microscope to determine whether undissolved fibers exist;
(2) evaluation of spinnability of the spinning solution: measuring the zero-shear viscosity, Newton index, viscous flow activation energy and structural viscosity index of the spinning solution by using a rheometer in a steady shear flow mode of the uniform spinning solutions A and B prepared in the step (1);
(3) evaluation of spinning strength performance: uniformly coating the uniform spinning solutions A and B prepared in the step (1) on printing paper, placing the printing paper in an oven at 105 ℃ for drying to constant weight, then cutting the printing paper into a standard size of 180mm in length and 15mm in width, measuring the strength of a paper sample on a paper tensile strength tester, and comparing the tensile strength of the paper sample under the same coating weight;
the preparation of spinning solutions A and B of example 1 were compared and the results are shown in Table 1.
As can be seen from Table 1, the pulp A and the pulp B are evaluated by the method for evaluating the spinnability of the pulp for tencel fibers, wherein the dissolving performance, the spinnability and the strength performance of the pulp A are better than those of the pulp B.
The applicant states that the present invention is illustrated by the above examples to show the process parameters and process flow of the present invention, but the present invention is not limited to the above detailed process parameters and process flow, i.e. it is not meant that the present invention must rely on the above detailed process parameters and process flow to be practiced. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (3)
1. The invention provides a method for evaluating spinnability of pulp for tencel, which comprises the following steps:
(1) evaluation of solubility: tearing pulp into small pieces, mixing the small pieces with a 50% NMMO solution according to a certain proportion, forming an amber uniform spinning solution under reduced pressure distillation, recording the dissolving time, observing the spinning solution by using a polarizing microscope to see whether undissolved fibers exist or not, wherein the shorter the dissolving time is, and the pulp without the undissolved fibers in the spinning solution is better pulp;
(2) evaluation of spinnability of the spinning solution: measuring the zero-shear viscosity, Newton index, viscous flow activation energy and structural viscosity index of the spinning solution by using a rheometer in a steady-state shear flow mode; the lower the zero-cut viscosity, the higher the Newton index, the lower the viscous flow activation energy and the structural viscosity index of the pulp spinning solution are measured, the good spinnability of the pulp spinning solution is, and the fibers are easy to form;
(3) evaluation of spinning Strength Property: and (2) uniformly coating the uniform spinning solution prepared in the step (1) on paper, placing the paper on an oven to be dried to constant weight, then cutting the paper into a standard size, measuring the strength of a paper sample on a paper tensile strength tester, comparing the tensile strength of the paper sample under the same coating weight, and if the measured strength is higher, proving that the pulp has better performance and the spun fiber has higher strength.
2. The evaluation method according to claim 1, wherein the pulp in step (1) is one or more selected from hardwood pulp, softwood pulp, bamboo pulp, cotton pulp, hemp pulp, etc.;
preferably, the size of the small pulp blocks in the step (1) is 1-5 cm2；
Preferably, the mixing ratio of the pulp in the step (1) and the 50% NMMO solution is 1-10%;
preferably, the reduced pressure distillation temperature in the step (1) is 50-99 ℃.
3. The evaluation method according to claim 1, wherein the coating manner in the step (3) can be one or more of blade coating, bar coating and curtain coating;
preferably, the drying temperature in the step (3) is 80-115 ℃;
preferably, the cutting size in the step (3) is 100-200 mm in length and 15mm in width.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011391736.8A CN114593990A (en) | 2020-12-03 | 2020-12-03 | Method for evaluating spinnability of pulp for tencel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011391736.8A CN114593990A (en) | 2020-12-03 | 2020-12-03 | Method for evaluating spinnability of pulp for tencel |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114593990A true CN114593990A (en) | 2022-06-07 |
Family
ID=81812800
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011391736.8A Pending CN114593990A (en) | 2020-12-03 | 2020-12-03 | Method for evaluating spinnability of pulp for tencel |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114593990A (en) |
-
2020
- 2020-12-03 CN CN202011391736.8A patent/CN114593990A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110546317B (en) | Cellulose fiber | |
| De Silva et al. | Utilization of cotton waste for regenerated cellulose fibres: Influence of degree of polymerization on mechanical properties | |
| Jiang et al. | A review on raw materials, commercial production and properties of lyocell fiber | |
| Sayyed et al. | A critical review of manufacturing processes used in regenerated cellulosic fibres: viscose, cellulose acetate, cuprammonium, LiCl/DMAc, ionic liquids, and NMMO based lyocell | |
| EP2981641B1 (en) | Process for the production of shaped cellulose articles | |
| Ma et al. | Upcycling of waste paper and cardboard to textiles | |
| EP3529282A1 (en) | Recycling of cellulosic textiles | |
| KR20150139594A (en) | Polysaccharide fibres and method for the production thereof | |
| RU2636547C2 (en) | Lyocell material for tobacco filter and method of its preparing | |
| CN109267318B (en) | Flame-retardant lyocell fiber and preparation method thereof | |
| CN109402756A (en) | A kind of preparation method of fire-retardant Lyocell fibers | |
| WO2021001780A1 (en) | Process for upcycling textile waste | |
| Määttänen et al. | Pre-treatments of pre-consumer cotton-based textile waste for production of textile fibres in the cold NaOH (aq) and cellulose carbamate processes | |
| CN115537954A (en) | Preparation method of cellulose spinning solution, product prepared by preparation method and application of product | |
| KR102662301B1 (en) | Solvent-spun cellulose fiber | |
| JP3852631B2 (en) | Regenerated cellulose fiber and method for producing the same | |
| CN111788340A (en) | Lyocell fibres having viscose-like properties | |
| CN114593990A (en) | Method for evaluating spinnability of pulp for tencel | |
| CN114174572A (en) | Method for producing lyocell staple fibers | |
| AT505476A1 (en) | Production of cellulose products e.g. artificial fiber from cellulosic raw materials containing bamboo cellulose comprises performing amine oxide method, where the bamboo cellulose contains specified concentration range of iron | |
| Kvarnlöf | Activation of dissolving pulps prior to viscose preparation | |
| CN110983501A (en) | Regeneration process for producing spinnable fiber by using jean broken fabric | |
| CN110616584A (en) | Feasibility research method for bamboo willow raw material used for preparing dissolving pulp and viscose spinning | |
| Chen et al. | Upgrading Paper-Grade Pulp as Dissolving Pulp for Lyocell Fiber Preparation | |
| Schlapp‐Hackl et al. | From postconsumer cotton towels to new cotton textile fibers |
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 |