CN1316554A - Electrically conductive polyphenylamine/polyamide fibre and its preparing process - Google Patents
Electrically conductive polyphenylamine/polyamide fibre and its preparing process Download PDFInfo
- Publication number
- CN1316554A CN1316554A CN 01112803 CN01112803A CN1316554A CN 1316554 A CN1316554 A CN 1316554A CN 01112803 CN01112803 CN 01112803 CN 01112803 A CN01112803 A CN 01112803A CN 1316554 A CN1316554 A CN 1316554A
- Authority
- CN
- China
- Prior art keywords
- polyamide
- polyaniline
- adulterant
- conductive fibers
- sulfuric acid
- 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
Landscapes
- Artificial Filaments (AREA)
Abstract
A polyaniline/polyamide conductive fibre consists of three components: polyaniline, polyamide and dopant. It is made by extruding the concentrated sulfuric acid mixed solution containing polyaniline, polyamide and dopant into the coagulation bath under the wet spining process conditions and then through drawing process. The electric conductivity of the produced fibre could be controlled within the range of 10 to the power -6 (cm.omega) to the power -1 - 10 (cm.omega) to the power -1.
Description
The invention belongs to polyaniline/polyamide conductive fibers and preparation method thereof.This conductive fiber is made up of polyaniline, polyamide and adulterant three components, adopts the wet spinning technology that the concentrated sulfuric acid blend solution of polyaniline and polyamide and adulterant is clamp-oned in the coagulating bath, makes conductive fiber behind the drawn.
Most of macromolecular materials are very good insulators, volume conductance 10
-18～10
-13(cm Ω)
-1, in use being easy to accumulate a large amount of electric charges, the meeting electrion easily causes various accidents, even causes major disaster when other object of contact.Chemical fibre is one of macromolecule three big materials, used widely in every field, but static takes place chemical fibre easily, thereby its application has been subjected to many restrictions.
People adopt the whole bag of tricks to improve the electric conductivity of synthetic fiber in recent decades, as adopt antistatic finish, and promptly at the surface of fiber absorption layer of surface activating agent, but it is insecure, and washing process removes easily.General at home and abroad at present using method is that a certain amount of conducting particles (leading carbon black, graphite, metal powder, metal oxide etc. as electricity) is joined in the fiber in the fibre spinning process, makes fiber have certain electric conductivity.Thisly add in the type conducting polymer composite conduction component and high-molecular organic material is inconsistent, mainly reach certain decentralization by mechanical dispersion, make the conduction component in the matrix material reach continuous conductive channel, just require the amount that adds bigger, as the dosage (being called conductivity threshold) of carbon black/polymeric system, will surpass 16%; For the blend dispersion of metal as the conduction component, conductivity threshold usually surpasses 50%, and this dispersion is easy to generate stress raisers and damages the mechanical property of material, and its Direct Spinning is made fiber difficulty more, therefore limited the application and development of material.
Polyaniline belongs to conducting polymer composite, itself has electric conductivity after mixing, this big molecule is dispersed in as the conduction component and is spun into fiber in the matrix polymer, conductivity threshold less (2%-5%), help spinning technique, the electrical conductivity of fiber is also higher, therefore can be widely used in conduction, antistatic, microwave absorbs and high-tech sector such as electromagnetic shielding.United States Patent (USP) 5788897 and 5882566 discloses the blend in solvent with polyaniline and poly terephthalic acid p-phenylenediamine (PPD), by the dry-wet spinning prepared have a superior blend conductive fiber of high-strength and high-modulus electric conductivity.But poly terephthalic acid p-phenylenediamine (PPD) price is higher, the dissolving difficulty, and spinning technique is restive, and Application Areas is restricted.
The objective of the invention is to overcome above-mentioned shortcoming, a kind of polyaniline/polyamide conductive fibers with high electrical conductivity energy and preparation method thereof is provided.
Purpose of the present invention also provides a kind of preparation method of above-mentioned polyaniline/polyamide conductive fibers.
Polyaniline/polyamide conductive fibers provided by the invention, system is made up of conduction component polyaniline, polyamide and adulterant three components, wherein the weight ratio of polyaniline, polyamide and adulterant is 1: 1.5～100: 0.1～4.0, described polyaniline derivative, and structure is as follows:
Wherein, R=H, CH
3, C
2H
5, OCH
3, OC
2H
5, SO
3H, y between 0～1, n=8～1000.
Polyamide used in the present invention comprises polyamide 6, polyamide 66, polyamide 1010, polyamide 12.
Adulterant used in the present invention comprises hydrochloric acid, camphorsulfonic acid, alkyl sulfonic acid and derivative thereof, alkyl benzene sulphonate and derivative thereof, phosphoric acid and derivative thereof.The molecular formula of described alkyl sulfonic acid and derivative thereof is RSO
3H.Described alkyl benzene sulphonate and derivative molecular formula thereof are R
1C
6H
5SO
3H, described phosphoric acid and derivative molecular formula thereof are (R
1O)
2POOH.Wherein, R=H, Cl, Br, CH
3Or R
1, R
1=H, C
mH
M+1, m=2～15.
In the polyaniline/polyamide conductive fibers of the present invention's preparation, polyaniline and adulterant sum can account for 1～75% of fibre weight, and polyamide accounts for 25～99%.Polyaniline and adulterant sum preferably account for 5～30% of fibre weight in polyaniline/polyamide conductive fibers, and polyamide accounts for 70～95%.
Polyaniline/polyamide conductive fibers the preparation method of the present invention's spinning adopts the preparation of wet spinning technology.At first polyaniline, polyamide and adulterant solvent are prepared into spinning slurry in the concentrated sulfuric acid, again this spinning slurry are clamp-oned the dilute sulfuric acid coagulating bath by spinneret orifice and make through the water-bath stretching.
In the spinning slurry that the present invention prepared, polyaniline, polyamide and the adulterant concentration in the concentrated sulfuric acid is 14～33%.
The wet spinning technology of the conductive fiber of the present invention's preparation is, under nitrogen gas pressure, it is 0～20% aqueous sulfuric acid that the concentrated sulfuric acid blend solution of polyaniline, polyamide and adulterant is clamp-oned coagulating bath through spinneret orifice, adopts circulation to bathe and keeps the coagulating bath concentration stabilize; Be stretching in the aqueous solution of pH=4 and carry out, draw ratio is 1.5～5.5.
Polyaniline/the polyamide conductive fibers that obtains with above-mentioned material and preparation method has excellent conducting performance, and electrical conductivity is different because of the difference of polyaniline content in the fiber, can be from 10
-6(cm Ω)
-1To 10 (cm Ω)
-1Scope in change, reach semi-conductive electric conductivity, can be widely used in conduction and antistatic and microwave and absorb and the electromagnetic shielding field, also can be used as the lead use in some occasion.
The tow fineness of conductive fiber of the present invention does not wait to 5000 dtex from 5dtex, and does not wait in hole count from 1 to 1000 hole.The conductive fiber of the present invention's preparation has intensity preferably, generally at 1.3CN/dtex～3.5CN/dtex, can satisfy the instructions for use in weaving and other field substantially.
Following illustrative embodiment will be further understood that the present invention.
Embodiment 1
Taking by weighing 200 gram polyamide 6s is dissolved in the 750 gram concentrated sulfuric acids, treat that polyamide 6 dissolves fully in the concentrated sulfuric acid after, again 20 gram polyanilines and 30 gram camphorsulfonic acids are joined in the above solution, make its dissolving by stirring, thereby be mixed with polyaniline/polyamide/adulterant/concentrated sulfuric acid blend solution, be referred to as spinning slurry.
Adopt the wet spinning technology path, under the nitrogen pressure of 0.25MPa, above polyaniline/polyamide/adulterant/concentrated sulfuric acid spinning slurry is clamp-oned in the coagulating bath by the spinneret orifice in 30 holes, coagulating bath is 1% dilute sulfuric acid aqueous solution.After solidifying,, be to stretch 2.5 times in 4 the water in the pH value by deflector roll, dry afterwards, reel, promptly obtain polyaniline/polyamide conductive fibers, the adulterant of this fiber is a camphorsulfonic acid.The electrical conductivity of conductive fiber is 1.32 (cm Ω)
-1, intensity 2.15CN/dtex.
Embodiment 2
Repeat embodiment 1, following difference is arranged: polyamide 6 is 100 grams, and the conduction component is polyaniline 80 grams, and adulterant is camphorsulfonic acid 120 grams, and the concentrated sulfuric acid 806 grams are mixed with polyaniline/polyamide/adulterant/concentrated sulfuric acid spinning slurry.Nitrogen pressure 0.35MPa, spinneret orifice is several 500, and coagulating bath concentration is 3.4% dilute sulfuric acid aqueous solution, stretches 1.5 times.The conductive fiber electrical conductivity of this example preparation is 9.5 (cm Ω)
-1, intensity 1.32CN/dtex.
Embodiment 3
Repeat embodiment 1, following difference is arranged: polyamide 1010 is 225 grams, and the conduction component is polyortho methylaniline 20 grams, and adulterant is p-chlorobenzenesulfonic acid 20 grams, and the concentrated sulfuric acid 900 grams are mixed with polyaniline/polyamide/adulterant/concentrated sulfuric acid spinning slurry.Coagulating bath concentration is 8% dilute sulfuric acid aqueous solution, stretches 2.5 times.The conductive fiber electrical conductivity of this example preparation is 1.21 (cm Ω)
-1, intensity 2.12CN/dtex.
Embodiment 4
Repeat embodiment 1, following difference is arranged: polyamide 66 is 150 grams, and the conduction component is polymethoxy aniline 20 grams, and adulterant is DBSA 90 grams, and the concentrated sulfuric acid 750 grams are mixed with polyaniline/polyamide/adulterant/concentrated sulfuric acid spinning slurry.Nitrogen pressure 0.35MPa, spinneret orifice is several 50, and water circulation is adopted in coagulating bath, stretches 2.1 times.The conductive fiber electrical conductivity of this example preparation is 3.51 (cm Ω)
-1, intensity 1.63CN/dtex.
Embodiment 5
Repeat embodiment 1, following difference is arranged: polyamide 66 is 230 grams, and the conduction component is polyaniline 20 grams, and adulterant is p-methyl benzenesulfonic acid 20 grams, and the concentrated sulfuric acid 1000 grams are mixed with polyaniline/polyamide/adulterant/concentrated sulfuric acid spinning slurry.Nitrogen pressure 0.35MPa, spinneret orifice is several 30, and coagulating bath concentration is 15.5% dilute sulfuric acid aqueous solution, stretches 3.5 times.The conductive fiber electrical conductivity of this example preparation is 0.25 (cm Ω)
-1, intensity 2.43CN/dtex.
Embodiment 6
Repeat embodiment 1, following difference is arranged: polyamide 66 is 150 grams, and the conduction component is polyphenylethyl amine 5 grams, and adulterant is to pyrovinic acid 3 grams, and the concentrated sulfuric acid 650 grams are mixed with polyaniline/polyamide/adulterant/concentrated sulfuric acid spinning slurry.Nitrogen pressure 0.35MPa, spinneret orifice is several 10, and coagulating bath concentration is 5% dilute sulfuric acid aqueous solution, stretches 3.6 times.The conductive fiber electrical conductivity of this example preparation is 0.02 (cm Ω)
-1, intensity 3.21CN/dtex.
Embodiment 7
Repeat embodiment 1, following difference is arranged: polyamide 1010 is 95 grams, and the conduction component is poly-sulfonation aniline 5 grams, and adulterant is to pyrovinic acid 0.1 gram, and the concentrated sulfuric acid 600 grams are mixed with polyaniline/polyamide/adulterant/concentrated sulfuric acid spinning slurry.Nitrogen pressure 0.35MPa, spinneret orifice is several 10, and coagulating bath concentration is 7% dilute sulfuric acid aqueous solution, stretches 4.5 times.The conductive fiber electrical conductivity of this example preparation is 0.025 (cm Ω)
-1, intensity 2.95CN/dtex.
Embodiment 8
Repeat embodiment 1, following difference is arranged: polyamide 12 is 75 grams, and the conduction component is polyaniline 20 grams, and adulterant is dodecyl sodium sulfonate 30 grams, and the concentrated sulfuric acid 300 grams are mixed with polyaniline/polyamide/adulterant/concentrated sulfuric acid spinning slurry.Nitrogen pressure 0.35MPa, spinneret orifice is several 100, and coagulating bath is a recirculated water, stretches 2.1 times.The conductive fiber electrical conductivity of this example preparation is 0.79 (cm Ω)
-1, intensity 1.71CN/dtex.
Embodiment 9
Repeat embodiment 1, following difference is arranged: polyamide 12 is 53 grams, and the conduction component is polyethoxy aniline 20 grams, adulterant (C
2H
5O)
2POOH is 15 grams, and the concentrated sulfuric acid 440 grams are mixed with polyaniline/polyamide/adulterant/concentrated sulfuric acid spinning slurry.Nitrogen pressure 0.35MPa, spinneret orifice is several 100, and coagulating bath concentration is 2% dilute sulfuric acid aqueous solution, stretches 2.3 times.The conductive fiber electrical conductivity of this example preparation is 0.15 (cm Ω)
-1, intensity 1.41CN/dtex.
Embodiment 10 repeats embodiment 1, and following difference is arranged: polyamide 6 is 225 grams, and the conduction component is polyaniline 5 grams, adulterant (C
12H
25O)
2POOH is 20 grams, and the concentrated sulfuric acid 540 grams are mixed with polyaniline/polyamide/adulterant/concentrated sulfuric acid spinning slurry.Nitrogen pressure 0.35MPa, spinneret orifice is several 1000, coagulating bath concentration be 18% rare
Claims (8)
1. polyaniline/polyamide conductive fibers, it is characterized in that this conductive fiber is made up of conduction component polyaniline, polyamide and adulterant three components, wherein the weight ratio of polyaniline, polyamide and adulterant is 1: 1.5～100: 0.1～4.0, described polyaniline derivative, and structure is as follows:
, wherein, R=H, CH
3, C
2H
5, OCH
3, OC
2H
5, SO
3H, y between 0～1, n=8～1000, employed adulterant is a hydrochloric acid, camphorsulfonic acid, molecular formula is RSO
3The alkyl sulfonic acid of H and derivative thereof, molecular formula are R
1C
6H
5SO
3The alkyl benzene sulphonate of H and derivative thereof, molecular formula are (R
1O)
2The phosphoric acid of POOH and derivative thereof, wherein, R=H, Cl, Br, CH
3Or R
1, R
1=H, C
mH
M+1, m=2～15.
2. polyaniline/polyamide conductive fibers according to claim 1 is characterized in that described polyamide is a polyamide 6, polyamide 66, polyamide 1010, polyamide 12.
3. polyaniline/polyamide conductive fibers according to claim 1, it is characterized in that in described polyaniline/polyamide conductive fibers that polyaniline and adulterant sum account for 1～75% of fibre weight in polyaniline/polyamide conductive fibers, polyamide accounts for 25～99%.
4. according to the described polyaniline/polyamide conductive fibers of claim 1～5, it is characterized in that polyaniline and adulterant sum preferably account for 5～30% of fibre weight in described polyaniline/polyamide conductive fibers, polyamide accounts for 70～95%.
5. the preparation method of polyaniline/polyamide conductive fibers according to claim 1, it is characterized in that adopting the preparation of wet spinning technology, at first polyaniline, polyamide and adulterant are dissolved in and are prepared into spinning slurry in the concentrated sulfuric acid, again this spinning slurry is clamp-oned the dilute sulfuric acid coagulating bath by spinneret orifice and make through the water-bath stretching.
6. the preparation method of polyaniline/polyamide conductive fibers according to claim 4 is characterized in that described polyaniline, polyamide and the adulterant concentration in the concentrated sulfuric acid is 14～33%.
7. the preparation method of polyaniline/polyamide conductive fibers according to claim 4 is characterized in that coagulating bath is 0～20% aqueous sulfuric acid in the wet spinning technology of described conductive fiber employing, and adopts circulation to bathe.
8. the preparation method of polyaniline/polyamide conductive fibers according to claim 4 is characterized in that adopting in the described drawing process aqueous solution of pH=4, and draw ratio is 1.5～5.5 times.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011128038A CN1185377C (en) | 2001-04-29 | 2001-04-29 | Electrically conductive polyphenylamine/polyamide fibre and its preparing process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011128038A CN1185377C (en) | 2001-04-29 | 2001-04-29 | Electrically conductive polyphenylamine/polyamide fibre and its preparing process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1316554A true CN1316554A (en) | 2001-10-10 |
| CN1185377C CN1185377C (en) | 2005-01-19 |
Family
ID=4659556
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011128038A Expired - Fee Related CN1185377C (en) | 2001-04-29 | 2001-04-29 | Electrically conductive polyphenylamine/polyamide fibre and its preparing process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1185377C (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1313525C (en) * | 2002-08-08 | 2007-05-02 | 帝斯曼知识产权资产管理有限公司 | Polyamide composition, process of preparation and use for making moulded articles |
| CN1323199C (en) * | 2005-12-05 | 2007-06-27 | 西安交通大学 | Preparation method of conductive polymer polyanilinc nano fiber |
| CN100343332C (en) * | 2006-03-02 | 2007-10-17 | 东北师范大学 | Prepn. process of lithium ion cell anode-phosphate/polyphenylpropane composite material |
| CN101949095A (en) * | 2010-09-02 | 2011-01-19 | 荣盛石化股份有限公司 | Conductive fiber preparation method and product thereof |
| CN101934591B (en) * | 2009-07-03 | 2012-12-12 | 中国科学院理化技术研究所 | Method for improving conductivity of polyaniline and polyaniline composite film by cold drawing |
| CN103396664A (en) * | 2013-08-06 | 2013-11-20 | 深圳市沃特新材料股份有限公司 | Poly-p-phenylene terephthamide/polyaniline conductive composite material and conductive fiber and preparation methods thereof |
| CN105624824A (en) * | 2016-01-29 | 2016-06-01 | 苏州大学 | Preparation method of polyaniline electroconductive fibers |
| CN107287686A (en) * | 2017-06-06 | 2017-10-24 | 青岛大学 | A kind of electrically conductive filament and preparation method thereof |
| CN110396730A (en) * | 2019-07-30 | 2019-11-01 | 江苏锵尼玛新材料股份有限公司 | A kind of electrically conductive polyaniline blended fiber and its preparation method and application |
| CN111996805A (en) * | 2020-06-01 | 2020-11-27 | 国网吉林省电力有限公司电力科学研究院 | Anti-static fiber and manufacturing method thereof |
-
2001
- 2001-04-29 CN CNB011128038A patent/CN1185377C/en not_active Expired - Fee Related
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1313525C (en) * | 2002-08-08 | 2007-05-02 | 帝斯曼知识产权资产管理有限公司 | Polyamide composition, process of preparation and use for making moulded articles |
| CN1323199C (en) * | 2005-12-05 | 2007-06-27 | 西安交通大学 | Preparation method of conductive polymer polyanilinc nano fiber |
| CN100343332C (en) * | 2006-03-02 | 2007-10-17 | 东北师范大学 | Prepn. process of lithium ion cell anode-phosphate/polyphenylpropane composite material |
| CN101934591B (en) * | 2009-07-03 | 2012-12-12 | 中国科学院理化技术研究所 | Method for improving conductivity of polyaniline and polyaniline composite film by cold drawing |
| CN101949095A (en) * | 2010-09-02 | 2011-01-19 | 荣盛石化股份有限公司 | Conductive fiber preparation method and product thereof |
| CN101949095B (en) * | 2010-09-02 | 2013-09-11 | 荣盛石化股份有限公司 | Conductive fiber preparation method and product thereof |
| CN103396664A (en) * | 2013-08-06 | 2013-11-20 | 深圳市沃特新材料股份有限公司 | Poly-p-phenylene terephthamide/polyaniline conductive composite material and conductive fiber and preparation methods thereof |
| CN103396664B (en) * | 2013-08-06 | 2016-06-22 | 深圳市沃特新材料股份有限公司 | PPTA/polyaniline composite material, conductive fiber and preparation method thereof |
| CN105624824A (en) * | 2016-01-29 | 2016-06-01 | 苏州大学 | Preparation method of polyaniline electroconductive fibers |
| CN107287686A (en) * | 2017-06-06 | 2017-10-24 | 青岛大学 | A kind of electrically conductive filament and preparation method thereof |
| CN110396730A (en) * | 2019-07-30 | 2019-11-01 | 江苏锵尼玛新材料股份有限公司 | A kind of electrically conductive polyaniline blended fiber and its preparation method and application |
| CN110396730B (en) * | 2019-07-30 | 2022-05-03 | 江苏锵尼玛新材料股份有限公司 | Conductive polyaniline blend fiber and preparation method and application thereof |
| CN111996805A (en) * | 2020-06-01 | 2020-11-27 | 国网吉林省电力有限公司电力科学研究院 | Anti-static fiber and manufacturing method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1185377C (en) | 2005-01-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1226472C (en) | Conducting fiber containing nano car bon tube and its prepn. method | |
| CN1185377C (en) | Electrically conductive polyphenylamine/polyamide fibre and its preparing process | |
| CN103031617B (en) | A kind of carbon nano-tube/poly ammonia ester/polyacrylonitrile composite conductive fibre and preparation method thereof | |
| KR101028984B1 (en) | Conductive polyvinyl alcohol fiber | |
| CN114108132B (en) | Preparation method of high-strength high-conductivity PEDOT fiber | |
| Zhang et al. | Morphology of conductive blend fibers of polyaniline and polyamide-11 | |
| CN1569939A (en) | Carbon nanotube electrically conductive fibre and method for making same | |
| CN1840750A (en) | Electrically conductive composite fibre containing carbon nanotube and method for making same | |
| US6127033A (en) | Solvent spinning of fibers containing an intrinsically conductive polymer | |
| CN102409422A (en) | Method for preparing antistatic polyacrylonitrile fibers from double-component nano electroconductive agent | |
| CN111363346A (en) | Method for preparing antistatic black master batch by using graphene coated carbon black and product | |
| CN112663162A (en) | Antistatic bacteriostatic ultrahigh molecular weight polyethylene fiber and preparation method thereof | |
| CN1209508C (en) | Polyaniline/polyacrylonitrile composite conductive fibre and preparation process thereof | |
| CN1478928A (en) | Preparation method of nanometer microgranule modified polyacrylonitrile anti static fiber | |
| CN109763184A (en) | A kind of production method of the magnetic oxygenated graphene-carbon nano tube conductive fiber of orientationization | |
| KR100851431B1 (en) | A method to align carbon nanotubes by electrospining process with a immiscible polymer blend | |
| CN103668529A (en) | Method of preparing compound conductive fibers, compound conductive fibers obtained by method and application of compound conductive fibers | |
| CN116288797A (en) | Flexible PEDOT (polyether-ether-ketone) PSS (power supply system) conductive composite fiber and preparation method thereof | |
| Gao et al. | Polyacrylonitrile/electroconductive TiO 2 nanoparticles composite fibers via wet-spinning | |
| CN110344160B (en) | Antibacterial and antistatic sportswear fabric and preparation method thereof | |
| US5135696A (en) | Process for forming fibers of sulfonated polyaniline compositions and uses thereof | |
| Hsu et al. | High tenacity, high modulus conducting polyaniline composite fibers | |
| CN110042499A (en) | The preparation method of the alginate fibre of electric conductivity enhancing | |
| CN101906677B (en) | Preparation method of anti-ultraviolet aging polyphenylene benzodioxazole fiber | |
| CN110396730B (en) | Conductive polyaniline blend fiber and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |