CN101280127B - Preparation of deposited white carbon black for plastic film anti-block agent - Google Patents
Preparation of deposited white carbon black for plastic film anti-block agent Download PDFInfo
- Publication number
- CN101280127B CN101280127B CN2008103018872A CN200810301887A CN101280127B CN 101280127 B CN101280127 B CN 101280127B CN 2008103018872 A CN2008103018872 A CN 2008103018872A CN 200810301887 A CN200810301887 A CN 200810301887A CN 101280127 B CN101280127 B CN 101280127B
- Authority
- CN
- China
- Prior art keywords
- carbon black
- white carbon
- sodium silicate
- aqueous solution
- reactor
- 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.)
- Expired - Fee Related
Links
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000006229 carbon black Substances 0.000 title claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 12
- 239000002985 plastic film Substances 0.000 title claims abstract description 10
- 229920006255 plastic film Polymers 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title claims description 8
- 239000004115 Sodium Silicate Substances 0.000 claims abstract description 16
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052911 sodium silicate Inorganic materials 0.000 claims abstract description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000007864 aqueous solution Substances 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000035484 reaction time Effects 0.000 claims abstract description 5
- 239000002245 particle Substances 0.000 claims abstract description 4
- 230000032683 aging Effects 0.000 claims abstract description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- 235000012239 silicon dioxide Nutrition 0.000 claims description 10
- 230000008021 deposition Effects 0.000 claims description 9
- 239000001117 sulphuric acid Substances 0.000 claims description 9
- 235000011149 sulphuric acid Nutrition 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 238000010521 absorption reaction Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 3
- 238000012546 transfer Methods 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 230000001143 conditioned effect Effects 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 239000000243 solution Substances 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 2
- 238000000034 method Methods 0.000 abstract description 2
- 238000012545 processing Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract 3
- 239000000047 product Substances 0.000 description 8
- 229960001866 silicon dioxide Drugs 0.000 description 8
- 239000000706 filtrate Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- 206010024769 Local reaction Diseases 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229960003742 phenol Drugs 0.000 description 1
- 239000012254 powdered material Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Landscapes
- Silicon Compounds (AREA)
Abstract
The invention relates to a method for preparing precipitated white carbon black for plastic film anti-block agents, with the following steps: water is added to a reactor, followed by white carbon black; when the mixture in the reactor is heated to 87 DEG C, a small amount of sodium silicate aqueous solution is added to the reactor, and the pH value of the reaction solution is adjusted to reach 10.2; the remaining sodium silicate aqueous solution and 20% dilute sulfuric acid are added to the reactor at the same time, wherein, the flow rate of dilute sulfuric acid should ensure that the pH value maintains 10.2, the temperature maintains 87 DEG C and the reaction time is 85 minutes; then 20% dilute sulfuric acid is continuously added to the reactor, and the mixture is reacted for 22 minutes, while the pH value is adjusted to reach 3.8 and the aging time is 25 minutes; then the mixture is washed, pulped and spray-dried to get the finished products. The white carbon black has uniform particles, low structures, low surface area, easy-dispersing products, good smoothness, mobility and dispersibility, which is provided with good processing performances in the plastic film production and ensures the quality of the packaged objects; besides, the production technology is simple and the production cost is low.
Description
Technical field
The invention belongs to the chemical industry technical field of powdered material preparation, relate to a kind of preparation method of silicon dioxide for plastic film anti-block agent.
Background technology
In the time of the plastics industry development, also promoted the development of plastic film open agent, the opening agent of Shi Yonging the earliest is inorganic talcum powder, and diatomite etc. develop into organic amine hydroxybenzene mid-term, erucicamide EBS derivative etc.The synthesis of nano grade silicon dioxide is used more extensive at present.All these auxiliary agents all in various degree have a weak point, show that mainly organic opening agent has a large amount of precipitates at film surface, influences the printing and the color of film; Inorganic opening agent bad dispersibility, if add lubricant and the just same precipitate that produces of organic dispersing agent in prescription, precipitate is very serious to the pollution of packing material; The synthesis of nano silicon-dioxide that uses has solved the problems referred to above substantially at present.But the nano silicon specific surface area is big, the oil-absorption(number) height, and complex manufacturing, cost is high and mobile bad, poor processability.
Summary of the invention
The present invention seeks to provides a kind of preparation method who improves the silicon dioxide for plastic film anti-block agent of performance at above-mentioned deficiency.
Technical scheme of the present invention may further comprise the steps
(1) raw material:
A, sodium silicate solid, modulus are 3.1-3.5, after dissolving, add water and are made into density 1.11-1.15g/cm
3, remove water-insoluble after filtration, must make with extra care sodium silicate aqueous solution;
The dilute sulphuric acid of b, concentration 20%-25%;
C, deposition white carbon black: the apparent density of prepared beforehand is 0.25-0.30g/cm
3White carbon black;
(2) the first step reaction: the 20-40% by the sodium silicate aqueous solution total amount adds water in reactor, the 2-3% that presses the sodium silicate aqueous solution total amount then adds deposition white carbon black, be warming up to 85-95 ℃, add sodium silicate aqueous solution conditioned reaction liquid PH10-11, add excess silicon acid sodium aqueous solution and dilute sulphuric acid in the reactor simultaneously, reaction times is 60-90 minute, keeps PH10-11 in the reaction process, temperature 85-95 ℃;
The reaction of second step: continue to add dilute sulphuric acid in 20-30 minute, transfer the suspension pH value to stop heating to 3.0-4.0, ageing 20-30 minute, reaction finished;
(3) filtration washing: squeeze into suspension in the filter and add water washing, be washed till and stop washing below the filtrate specific conductivity 300us/cm;
(4) step (3) filtrate is put into the hollander pulp, send into Highspeedcentrifugingandsprayingdrier then and carry out the drying and crushing classification and get product, 450-550 ℃ of dry-heat air temperature, product is moisture≤and 4.0%.
The concrete property of deposition white carbon black provided by the invention is:
1, outward appearance: greyish white mobile powder
2, silicon-dioxide 〉=92%
3, weight loss on heating≤4.0%
4, burning decrement≤6.0%
5, DBP absorption value 0.6-1.0ml/g
6, median size (laser particle analyzer)≤7 μ m
7, BET specific surface area 20-50m
2/ g
8, heavy real density 0.6-0.68g/cm
3
Advantage of the present invention is: 1, use deposition white carbon black as crystal seed, and adopt the dilute sulphuric acid reaction, be difficult for causing local reaction, the white carbon black particle of generation is even, and structure is low, has low specific surface area.2, the reaction process pH value is controlled in the strong basicity scope, and adopts spraying drying, and product easily disperses.3, product is pulverized and is adopted micronizer mill to pulverize, and the granularity of the product of production is tiny, has good smooth property, flowability and dispersed, has good processing properties in plastics film production.4, do not contain any volatile matter and precipitate, guaranteed that the quality of packed article and production technique are simple, production cost is low.
Below in conjunction with embodiment embodiments of the present invention are described in further detail.
Embodiment:
Embodiment 1
Preparation method's step of silicon dioxide for plastic film anti-block agent is as follows: get sodium silicate solid, modulus is 3.1-3.5, after dissolving, adds water and is made into density 1.12g/cm
3, remove water-insoluble after filtration, it is standby to make with extra care sodium silicate aqueous solution; The stainless steel cauldron that the 2000L band stirs adds water 200L, adds the deposition white carbon black 20kg of prepared beforehand, is warming up to 87 ℃ with open steam, gets the refining sodium silicate solution of 720L, a small amount of earlier the adding in the end water, water ph value is adjusted to 10.2; All the other sodium silicate aqueous solutions and 20% dilute sulphuric acid add in the reactor simultaneously.85 minutes reaction times; Reaction process keeps temperature, pH value constant.Continue to add 22 minutes 20% dilute sulphuric acid reaction times then, transfer to reaction solution pH value 3.8, digestion time 25 minutes; Squeeze into suspension in the filter and add water washing, be washed till and stop washing below the filtrate specific conductivity 260us/cm; Filtrate is put into the hollander pulp, sends into Highspeedcentrifugingandsprayingdrier then and carry out drying, 500 ℃ of dry-heat air temperature, product is moisture≤4.0%, through the micronizer mill crushing and classification to median size less than 7 μ m, pack finished product.
Embodiment 2
As different from Example 1: temperature of reaction is 92 ℃.
Embodiment 3
Adding white carbon black as different from Example 1 is 16kg.
Product after testing, the deposition white carbon black technical indicator is listed in the table below
| Project name | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Outward appearance | Greyish white mobile powder | Greyish white mobile powder | Greyish white mobile powder |
| Silicon-dioxide % | 94.10 | 94.15 | 94.03 |
| Burning decrement % | 5.23 | 5.20 | 5.48 |
| Weight loss on heating % | 3.30 | 3.50 | 3.55 |
| PH value | 6.4 | 6.6 | 6.48 |
| Project name | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| DBP absorption value ml/g | 0.75 | 0.72 | 0.8 |
| Median size μ m | 6.5 | 6.20 | 6.4 |
| Specific surface area m 2/g | 35 | 28 | 41 |
| Heavy real density g/cm 3 | 0.63 | 0.65 | 0.60 |
Claims (2)
1. the preparation method of a silicon dioxide for plastic film anti-block agent is characterized in that may further comprise the steps
(1) raw material:
A, sodium silicate solid, modulus are 3.1～3.5, after dissolving, add water and are made into density 1.11～1.15g/cm
3, remove water-insoluble after filtration, must make with extra care sodium silicate aqueous solution;
The dilute sulphuric acid of b, concentration 20%～25%;
C, deposition white carbon black: the apparent density of prepared beforehand is 0.25～0.30g/cm
3White carbon black;
(2) the first step reaction: in reactor, add water by 20～40% of sodium silicate aqueous solution total amount, press 2～3% of sodium silicate aqueous solution total amount then and add deposition white carbon black, be warming up to 85～95 ℃, add sodium silicate aqueous solution conditioned reaction liquid pH10～11, add excess silicon acid sodium aqueous solution and dilute sulphuric acid in the reactor simultaneously, reaction times is 60～90 minutes, keeps pH10～11 in the reaction process, 85～95 ℃ of temperature;
The reaction of second step: continue to add dilute sulphuric acid in 20～30 minutes, transfer pH of suspension value to 3.0～4.0 to stop heating, ageing 20～30 minutes, reaction finishes;
(3) filtration washing, pulp, the dry product that gets.
2. according to the preparation method of the described silicon dioxide for plastic film anti-block agent of claim 1, it is characterized in that the deposition white carbon black BET specific surface area that obtains is 20～50m
2/ g, DBP absorption value 0.6～1.0ml/g, detecting median size through laser particle analyzer is less than 7 μ m, heavy real density 0.6～0.68g/cm
3
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008103018872A CN101280127B (en) | 2008-06-02 | 2008-06-02 | Preparation of deposited white carbon black for plastic film anti-block agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008103018872A CN101280127B (en) | 2008-06-02 | 2008-06-02 | Preparation of deposited white carbon black for plastic film anti-block agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101280127A CN101280127A (en) | 2008-10-08 |
| CN101280127B true CN101280127B (en) | 2010-11-17 |
Family
ID=40012805
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008103018872A Expired - Fee Related CN101280127B (en) | 2008-06-02 | 2008-06-02 | Preparation of deposited white carbon black for plastic film anti-block agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101280127B (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101830474B (en) * | 2010-05-17 | 2012-01-11 | 浙江建业化工股份有限公司 | Method for preparing white carbon black |
| CN102198942B (en) * | 2011-02-25 | 2013-01-23 | 福建远翔化工有限公司 | Preparation method of silicon dioxide |
| CN102372272A (en) * | 2011-08-15 | 2012-03-14 | 万载县辉明化工有限公司 | Preparation method of silicon dioxide for plastic film opening agent |
| CN102887515A (en) * | 2012-09-14 | 2013-01-23 | 横店集团浙江英洛华硅材料有限公司 | Production equipment of white carbon black |
| CN102887514A (en) * | 2012-09-14 | 2013-01-23 | 横店集团浙江英洛华硅材料有限公司 | Improved structure of white carbon black-producing equipment |
| CN103466635B (en) * | 2013-08-23 | 2015-04-22 | 确成硅化学股份有限公司 | Preparation method for silicon dioxide |
| CN104231955B (en) * | 2014-04-24 | 2016-05-04 | 陆志平 | Evaporimeter sticks with glue film and production method thereof |
| CN106315546A (en) * | 2015-06-19 | 2017-01-11 | 大连瑞贤达塑胶有限公司 | Preparation method of silicon carbide plastic film opening agent |
| CN105949812A (en) * | 2016-07-01 | 2016-09-21 | 刘素英 | Preparation method for improved master batch |
| CN108997795A (en) * | 2018-07-10 | 2018-12-14 | 丰城黑豹炭黑有限公司 | A kind of carbon black materials and preparation process |
| CN113105762A (en) * | 2021-04-13 | 2021-07-13 | 云南云维飞虎化工有限公司 | Method for improving dispersibility of carbon black |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1058381A (en) * | 1990-07-24 | 1992-02-05 | 董葆华 | Method for preparing white carbon black with cacoxenite slag |
| CN1693194A (en) * | 2005-06-10 | 2005-11-09 | 卢元健 | Technology for producing white carbon black, sodium sulfite, sodium bisulfite by sodium sulfate method |
| WO2006131066A1 (en) * | 2005-06-08 | 2006-12-14 | Degussa Wellink Silica (Nanping) Co. Ltd. | A process for producing silica and sodium sulfite with sodium sulfate |
-
2008
- 2008-06-02 CN CN2008103018872A patent/CN101280127B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1058381A (en) * | 1990-07-24 | 1992-02-05 | 董葆华 | Method for preparing white carbon black with cacoxenite slag |
| WO2006131066A1 (en) * | 2005-06-08 | 2006-12-14 | Degussa Wellink Silica (Nanping) Co. Ltd. | A process for producing silica and sodium sulfite with sodium sulfate |
| CN1693194A (en) * | 2005-06-10 | 2005-11-09 | 卢元健 | Technology for producing white carbon black, sodium sulfite, sodium bisulfite by sodium sulfate method |
Non-Patent Citations (2)
| Title |
|---|
| 李素英 等.液相沉淀法制备超细白炭黑的改性研究.《材料导报》.2007,第21卷269－271. |
| 李素英等.液相沉淀法制备超细白炭黑的改性研究.《材料导报》.2007,第21卷269-271. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101280127A (en) | 2008-10-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101280127B (en) | Preparation of deposited white carbon black for plastic film anti-block agent | |
| CN101407324B (en) | Method of preparing silicon dioxide delustrant by large pore volume gel | |
| CN102924979B (en) | Method for preparing inorganic and organic coating titanium dioxide | |
| CN104098932B (en) | A kind of preparation method of white mineral-titanium dioxide composite powder pigment | |
| CN106311199B (en) | A kind of stable dispersion and the controllable SiO of photocatalytic activity2@TiO2Core-shell structure, preparation method and its application | |
| CN101423257B (en) | Method for preparing nano grade iron oxide red | |
| CN101585539B (en) | Prepartion method of highly anti-yellow resistance white carbon black for silastic | |
| CN107032382B (en) | Nano calcium carbonate and preparation method thereof | |
| CN100366533C (en) | Mesoporous silica particles and production process thereof | |
| CN102924980B (en) | Surface modified titanium dioxide particles and preparation method thereof | |
| CN110395740A (en) | A kind of high fluidity high oil absorption value washing powder silica and preparation method thereof | |
| CN102491354B (en) | Preparation method of nano-scale tourmaline powder | |
| CN108439414A (en) | A kind of method that pH value swing method prepares high dispersive macropore appearance precipitated silica | |
| WO2020140358A1 (en) | Method for preparing silica microspheres for acidifier carrier | |
| CN1830788B (en) | Technology of transforming common magnesium hydrexide into hexagonal sheel shaped magnesium hydroxide by hydrothermal method | |
| WO2020078029A1 (en) | High-dispersion silica and preparation method therefor | |
| CN102249247A (en) | Circulatory production process for superfine silicon dioxide | |
| CN114854278B (en) | Preparation process of nano iron oxide coating dispersion system | |
| CN101870828A (en) | Method for producing superfine talcum powder by adopting mixed grinding technology | |
| CN101805017B (en) | Preparation method of rutile type titanium dioxide nano particle | |
| CN101544387A (en) | Preparation technology of hexagonal plate magnesium hydroxide | |
| CN107130458B (en) | A kind of preparation method of colloidal microcrystalline cellulose | |
| CN102092723A (en) | Method for preparing high dispersing white carbon black with ammonia precipitation method | |
| CN105271344A (en) | Preparation method of pine-cone-shaped calcite type micron-size calcium carbonate particles | |
| CN110156034A (en) | A kind of production method of efficient beer anti-clouding agent nano silica |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20171013 Address after: 134006 Tonghua City, Jilin Province, iron town Erdaojiang District /1-1 Patentee after: TONGHUA SHUANG LONG SILICON MATERIAL TECHNOLOGY CO.,LTD. Address before: Tonghua City, Jilin province 134006 Iron Town Patentee before: Tonghua Shuanglong Chemical Co.,Ltd. |
|
| TR01 | Transfer of patent right | ||
| CP01 | Change in the name or title of a patent holder |
Address after: Tonghua City, Jilin province 134006 Iron Town Erdaojiang District /1-1 Patentee after: Tonghua Shuanglong Chemical Co.,Ltd. Address before: Tonghua City, Jilin province 134006 Iron Town Erdaojiang District /1-1 Patentee before: TONGHUA SHUANG LONG SILICON MATERIAL TECHNOLOGY Co.,Ltd. |
|
| CP01 | Change in the name or title of a patent holder | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20101117 |