CN106589923A - Polyamide ecological environmental masterbatch and preparation method thereof - Google Patents
Polyamide ecological environmental masterbatch and preparation method thereof Download PDFInfo
- Publication number
- CN106589923A CN106589923A CN201611113482.7A CN201611113482A CN106589923A CN 106589923 A CN106589923 A CN 106589923A CN 201611113482 A CN201611113482 A CN 201611113482A CN 106589923 A CN106589923 A CN 106589923A
- Authority
- CN
- China
- Prior art keywords
- ecological
- chinlon
- masterbatch
- pigment
- environmental protective
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid amides
-
- 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
- D01F1/04—Pigments
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/12—Applications used for fibers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2310/00—Masterbatches
Abstract
The invention discloses polyamide ecological environmental masterbatch and a preparation method thereof. According to the invention, a static processed environmental-friendly coloring agent is employed, so that the dispersion properties of masterbatch is better, agglomeration is not easily generated between particles, during the preparation method, adhesion between the harmful substances such as residual solvents and polycyclic aromatic hydrocarbon and a pigment is reduced, a carcinogenic azo dye and polycyclic aromatic hydrocarbon content is less than millionth, the filtering performance is less than 1 Mpa/g, the masterbatch is used for polyamide fiber melt spinning, the screen changing period is long, and yarn flying and yarn breaking conditions are less. The polyamide ecological environmental masterbatch is suitable for polyamide fiber melt spinning.
Description
Technical field
The invention belongs to polymeric material field, is related to a kind of Masterbatch and preparation method thereof, and in particular to a kind of chinlon
Ecological, environmental protective Masterbatch and preparation method thereof.
Background technology
Requirement more and more higher of the country to environmental protection, due to pollution greatly, national management and control will for traditional dyeing of textile
Gradually strengthen, its cost more and more higher, and chinlon fused mass directly spinning is few due to pollution, will be put into national textile industry " 13 "
Development plan.But because chinlon has very strong reproducibility in high temperature spinning process, colour the pigment for using and synthesizing
The harmful substances such as the organic solvent and polycyclic aromatic hydrocarbon of a small amount of residual are not removed in journey.Directly carried out using these pigment
Color cannot meet the requirement of ecological textile.While pigment is all Nano grade due to primary partical, due to model between particle
The factors such as De Huali form aggregate, and traditional technique is difficult its aggregate to open, therefore, it is difficult to reaching good disperse water
Flat, because aggregation size is big in spinning process, blocking filter and spray are inflexible, cause fracture of wire to float silk.
Therefore, a kind of preferable Masterbatch of dispersibility is studied, is had great importance.
The content of the invention
The technical problem to be solved in the present invention, is to provide a kind of chinlon ecological, environmental protective Masterbatch and preparation method thereof, adopts
The environmentally friendly coloring agent of Electrostatic Treatment, enables to the dispersive property of Masterbatch more preferably, is difficult to reunite between particle, in preparation process
The adhesion between harmful substance and pigment such as residual solvent and polycyclic aromatic hydrocarbon weakens, and master batch tests carcinogenic azo dye and many
Aromatic hydrocarbon ring content is both less than hundred a ten thousandths, and strainability is less than 1Mpa/g.
To solve above-mentioned technical problem, the technical solution used in the present invention is：
A kind of chinlon ecological, environmental protective Masterbatch, in terms of parts by weight, the raw material group of described chinlon ecological, environmental protective Masterbatch
Cheng Shi：
50～90 parts of polyamide, 1～5 part of dispersant, 5～49 parts of the environmentally friendly coloring agent of Electrostatic Treatment.
A kind of as the present invention limits, and the preparation method of the environmentally friendly coloring agent of described Electrostatic Treatment is：
10kV～30kV high pressure produces electric field, and environmentally friendly coloring agent forms the granule with same sex electric charge, both by high voltage electric field
Obtain the environmentally friendly coloring agent of Electrostatic Treatment.
Used as the further restriction of above-mentioned restriction, described high voltage electric field is positive electric field or negative electric field.
Another kind of as the present invention is limited, and described polyamide is polyamide 6 or polyamide 66.
Used as the third restriction of the present invention, described dispersant is grafting hydroxyl ethylene bis-fatty acid amides, Oleic acid acyl
Amine or erucyl amide.
Used as the 4th kind of restriction of the present invention, the environmentally friendly coloring agent of described Electrostatic Treatment is the pigment of Electrostatic Treatment, its
In, pigment is pigment red 122, pigment red 48:2nd, pigment blue 15:3rd, pigment Violet 23, pigment Green 7, pigment yellow 191 or pigment black 7.
Present invention also offers the method for preparing above-mentioned chinlon ecological, environmental protective Masterbatch, it enters according to following steps order
OK：
1) the environmentally friendly coloring agent of Electrostatic Treatment is carried out the flash distillation under high-temperature low-pressure in flash vaporization kettle, obtain flash distillation environmental protection
Toner；
2) flash distillation environmental protection coloring agent is mixed with polyamide and dispersant in high-speed kneading machine, is then squeezed through extruder
Go out pelletize.
A kind of as the present invention limits, described step 1) in flash conditions be：Condition of negative pressure be -90Kpa～-
10Kpa, temperature is 60 DEG C～180 DEG C, and the time is 6-12h.
Another kind of as the present invention is limited, described step 2) in high-speed kneading machine be 500L, extruder is in the same direction
Double screw extruder, the screw diameter D=25mm of extruder, draw ratio L/D=60, engine speed is 100～110Hz, is fed intake
Machine rotating speed is 15～20Hz, and pelletizing is water-cooled pelletizing, and extrusion temperature is 230～270 DEG C of subsection setups.
Used as the further restriction of above-mentioned restriction, described extrusion temperature is divided into 7 sections, respectively the extrusion temperature of first paragraph
For 270 DEG C, the extrusion temperature of second segment is 270 DEG C, and the 3rd section of extrusion temperature is 230 DEG C, and the 4th section of extrusion temperature is 230
DEG C, the 5th section of extrusion temperature is 230 DEG C, and the 6th section of extrusion temperature is 230 DEG C, and the 7th section of extrusion temperature is 260 DEG C.
As a result of above-mentioned technical scheme, compared with prior art, acquired technological progress is the present invention：
The present invention produces electric field by high pressure, and pigment particles form charged particle, due to same sex phase by high voltage electric field
Scold, the repulsive force between particle offsets the Van der Waals force between the particle of a part, so as to improve the dispersibility of pigment particles
Energy；Also due to harmful substance and the face such as the repulsive force of charged particle, residual solvent and polycyclic aromatic hydrocarbon in pigment building-up process
Adhesion between material weakens, and is separated by vacuum flash.In addition, by environmentally friendly coloring agent and dispersant, polyamides after Electrostatic Treatment
Amine is mixed with high-speed kneading machine, and by screw extruder pelletize chinlon ecological, environmental protective Masterbatch is obtained, and master batch tests carcinogenic azo
Dyestuff and polycyclic aromatic content are both less than hundred a ten thousandths, and strainability is less than 1Mpa/g.Multi-ring fragrance in chinlon Masterbatch
Hydrocarbon and carcinogenic azo dye content meet ecological textile technical requirements, and carcinogenic azo dye and polycyclic aromatic content are both less than
Hundred a ten thousandths, strainability is less than 1Mpa/g, and using the Masterbatch chinlon melt spinning is carried out, and the draping cycle is long, the silk that floats, disconnected
Silk is few.
The present invention is applied to chinlon melt spinning.
The present invention is described in further detail below in conjunction with specific embodiment.
Specific embodiment
A kind of chinlon ecological, environmental protective Masterbatch of embodiment 1 and preparation method thereof
A kind of chinlon ecological, environmental protective Masterbatch, in terms of parts by weight, the raw material group of described chinlon ecological, environmental protective Masterbatch
Cheng Shi：
Polyamide 6 50g, oleamide 4g, the pigment red 122 20g of Electrostatic Treatment.
The preparation method of the wherein environmentally friendly coloring agent of Electrostatic Treatment is：
10kV high pressure produces positive electric field, and environmentally friendly coloring agent forms the granule with same sex electric charge by high voltage electric field, has both obtained Jing
The environmentally friendly coloring agent of allusion quotation process.
The method for preparing above-mentioned chinlon ecological, environmental protective Masterbatch, is carried out according to following steps order：
1) the environmentally friendly coloring agent of Electrostatic Treatment is carried out the flash distillation under high-temperature low-pressure in flash vaporization kettle, obtain flash distillation environmental protection
Toner；Wherein, flash conditions are：Condition of negative pressure is -90Kpa, and temperature is 60 DEG C, and the time is 6h.
2) flash distillation environmental protection coloring agent is mixed with polyamide and dispersant in high-speed kneading machine, is then squeezed through extruder
Go out pelletize；Wherein, high-speed kneading machine is 500L, and extruder is parallel dual-screw extruding machine, the screw diameter D=of extruder
25mm, draw ratio L/D=60, engine speed is 100Hz, and batch charger rotating speed is 15Hz, and pelletizing is water-cooled pelletizing, and extrusion temperature is
230～270 DEG C of subsection setups, specifically, extrusion temperature is divided into 7 sections, and the respectively extrusion temperature of first paragraph is 270 DEG C, and second
The extrusion temperature of section is 270 DEG C, and the 3rd section of extrusion temperature is 230 DEG C, and the 4th section of extrusion temperature is 230 DEG C, the 5th section
Extrusion temperature is 230 DEG C, and the 6th section of extrusion temperature is 230 DEG C, and the 7th section of extrusion temperature is 260 DEG C.
Carcinogenic azo dye content is tested to the Masterbatch Jing obtained by the present embodiment and polycyclic aromatic content is respectively less than
Hundred a ten thousandths, gained Masterbatch strainability is less than 0.3Mpa/g；Chinlon melt spinning, draping week are carried out using the Masterbatch
Phase is long, and the silk that floats, fracture of wire are few.
Embodiment 2-7 chinlon ecological, environmental protective Masterbatch and preparation method thereof
Embodiment 2-7 is respectively a kind of chinlon ecological, environmental protective Masterbatch and preparation method thereof, raw material used in it and
Preparation method is similar, the difference is that only technical parameter involved in involved raw material type, consumption and preparation method
Difference, shown in table specific as follows：
The above, is only presently preferred embodiments of the present invention, is not the restriction for making other forms to the present invention, is appointed
What those skilled in the art is changed or is modified as equivalent variations possibly also with above-mentioned technology contents as enlightenment
Equivalent embodiments.But, it is every without departing from the technology of the present invention design, above example is made according to the technical spirit of the present invention
The simple modification for going out, equivalent variations and remodeling, still fall within the protection domain of the claims in the present invention.
Claims (10)
1. a kind of chinlon ecological, environmental protective Masterbatch, it is characterised in that in terms of parts by weight, described chinlon ecological, environmental protective Masterbatch
Raw material composition be：
50～90 parts of polyamide, 1～5 part of dispersant, 5～49 parts of the environmentally friendly coloring agent of Electrostatic Treatment.
2. chinlon ecological, environmental protective Masterbatch according to claim 1, it is characterised in that：The environmental protection of described Electrostatic Treatment
The preparation method of toner is：
10kV～30kV high pressure produces electric field, and environmentally friendly coloring agent forms the granule with same sex electric charge by high voltage electric field, has both obtained Jing
The environmentally friendly coloring agent of allusion quotation process.
3. chinlon ecological, environmental protective Masterbatch according to claim 2, it is characterised in that：Described high voltage electric field is positive electric field
Or negative electric field.
4. chinlon ecological, environmental protective Masterbatch according to claim 1, it is characterised in that：Described polyamide is polyamide 6
Or polyamide 66.
5. chinlon ecological, environmental protective Masterbatch according to claim 1, it is characterised in that：Described dispersant is grafting hydroxyl
Ethylene bis-fatty acid amides, oleamide or erucyl amide.
6. chinlon ecological, environmental protective Masterbatch according to claim 1, it is characterised in that：The environmental protection of described Electrostatic Treatment
Toner is the pigment of Electrostatic Treatment, wherein, pigment is pigment red 122, pigment red 48:2nd, pigment blue 15:3rd, pigment Violet 23, pigment
Green 7, pigment yellow 191 or pigment black 7.
7. a kind of method of the chinlon ecological, environmental protective Masterbatch prepared as any one of claim 1～6, it is characterised in that
It is carried out according to following steps order：
1) the environmentally friendly coloring agent of Electrostatic Treatment is carried out the flash distillation under high-temperature low-pressure in flash vaporization kettle, flash distillation environmental protection coloring is obtained
Agent；
2) flash distillation environmental protection coloring agent is mixed with polyamide and dispersant in high-speed kneading machine, is then made through extruder extrusion
Grain.
8. the method for preparing chinlon ecological, environmental protective Masterbatch according to claim 7, it is characterised in that：Described step 1)
In flash conditions be：Condition of negative pressure is -90Kpa～-10Kpa, and temperature is 60 DEG C～180 DEG C, and the time is 6-12h.
9. the method for preparing chinlon ecological, environmental protective Masterbatch according to claim 7, it is characterised in that：Described step 2)
In high-speed kneading machine be 500L, extruder is parallel dual-screw extruding machine, the screw diameter D=25mm of extruder, draw ratio
L/D=60, engine speed is 100～110Hz, and batch charger rotating speed is 15～20Hz, and pelletizing is water-cooled pelletizing, and extrusion temperature is
230～270 DEG C of subsection setups.
10. the method for preparing chinlon ecological, environmental protective Masterbatch according to claim 9, it is characterised in that：Described extrusion
Temperature is divided into 7 sections, and respectively the extrusion temperature of first paragraph is 270 DEG C, the extrusion temperature of second segment is 270 DEG C, and the 3rd section is squeezed
Go out temperature for 230 DEG C, the 4th section of extrusion temperature is 230 DEG C, and the 5th section of extrusion temperature is 230 DEG C, the 6th section of extrusion temperature
Spend for 230 DEG C, the 7th section of extrusion temperature is 260 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611113482.7A CN106589923B (en) | 2016-12-06 | 2016-12-06 | Polyamide fibre ecological, environmental protective Masterbatch and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611113482.7A CN106589923B (en) | 2016-12-06 | 2016-12-06 | Polyamide fibre ecological, environmental protective Masterbatch and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106589923A true CN106589923A (en) | 2017-04-26 |
| CN106589923B CN106589923B (en) | 2019-04-12 |
Family
ID=58596456
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611113482.7A Active CN106589923B (en) | 2016-12-06 | 2016-12-06 | Polyamide fibre ecological, environmental protective Masterbatch and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106589923B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106968024A (en) * | 2017-05-08 | 2017-07-21 | 福建景丰科技有限公司 | A kind of production method of the blue nylon-6 fiber of original liquid coloring |
| CN109054360A (en) * | 2018-07-26 | 2018-12-21 | 苏州宝丽迪材料科技股份有限公司 | The preparation method of PA fiber master batch |
| CN109183176A (en) * | 2018-06-29 | 2019-01-11 | 中润科技股份有限公司 | A kind of preparation process of the wear-resisting color silk fiber of high resiliency high convergency |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101603255A (en) * | 2009-07-10 | 2009-12-16 | 潘志强 | A kind of colouring method of cloth and dyeing machine |
| CN103131119A (en) * | 2013-01-31 | 2013-06-05 | 杜县南 | Color master batch and manufacturing method thereof |
-
2016
- 2016-12-06 CN CN201611113482.7A patent/CN106589923B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101603255A (en) * | 2009-07-10 | 2009-12-16 | 潘志强 | A kind of colouring method of cloth and dyeing machine |
| CN103131119A (en) * | 2013-01-31 | 2013-06-05 | 杜县南 | Color master batch and manufacturing method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106968024A (en) * | 2017-05-08 | 2017-07-21 | 福建景丰科技有限公司 | A kind of production method of the blue nylon-6 fiber of original liquid coloring |
| CN109183176A (en) * | 2018-06-29 | 2019-01-11 | 中润科技股份有限公司 | A kind of preparation process of the wear-resisting color silk fiber of high resiliency high convergency |
| CN109183176B (en) * | 2018-06-29 | 2021-03-02 | 中润科技股份有限公司 | Preparation process of high-elasticity high-shrinkage wear-resistant colored silk fiber |
| CN109054360A (en) * | 2018-07-26 | 2018-12-21 | 苏州宝丽迪材料科技股份有限公司 | The preparation method of PA fiber master batch |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106589923B (en) | 2019-04-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106589923A (en) | Polyamide ecological environmental masterbatch and preparation method thereof | |
| CN103215656B (en) | The solvent carrier of polyester fiber spins front original liquid coloring technique | |
| CN103203810A (en) | Continuous manufacturing method for rubber masterbatch, rubber masterbatch prepared by using continuous manufacturing method and rubber product | |
| CN103113597A (en) | Continuous manufacturing method of rubber masterbatch and rubber masterbatch prepared by same | |
| CN112063166B (en) | Blue-phase black master batch for polyamide 6 fiber and preparation method and application thereof | |
| CN103205001B (en) | Process for dispersing of the filler in rubber solutions | |
| CN103046144A (en) | Trichromatic theory pun-dyed fiber production method and trichromatic theory pun-dyed fiber production equipment | |
| CN106436021A (en) | Edible food fresh keeping electrospinning fiber membrane | |
| CN103204479A (en) | Production method for high-content insoluble sulfur | |
| CN103243414A (en) | Method for preparing nylon 66 colored and low-denier industrial yarns | |
| CN102766352A (en) | Preparation method and system of toner pre-dispersing material | |
| CN113881125A (en) | Nano pigment dispersed high-molecular color master batch and preparation method thereof | |
| CN107033672A (en) | A kind of big red ink of refractory ceramics and preparation method thereof | |
| CN103342918A (en) | Highlight high hardness acrylic resin water-based ink | |
| CN103183986A (en) | Offset printing ink and preparation method thereof | |
| CN104451916A (en) | Production process for black nylon stretch yarns | |
| CN106589846B (en) | Terylene ecological, environmental protective Masterbatch and preparation method thereof | |
| CN103556245A (en) | Processing machine for producing textile thread made of polyester fiber | |
| CN106567152A (en) | Colored ultrahigh molecular weight polyethylene fiber and production method thereof | |
| CN110437479B (en) | Antibacterial antistatic color master batch for polypropylene fiber spinning and preparation method thereof | |
| CN108727900B (en) | Disperse dye ink with good storage stability and redispersibility and preparation method thereof | |
| CN104327315B (en) | A kind of application of rubber masterbatch prepared by continuous way in car tire base rubber | |
| CN114292420B (en) | Masterbatch with ultraviolet resistance function and preparation method thereof | |
| CN114561031B (en) | High-pigment-content color master batch and preparation method and application thereof | |
| CN114381141B (en) | Nanometer liquid disperse dye with high washing fastness as well as preparation method and application thereof |
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 |