CN102382509A - Water-based ink, elastic emulsion used for water-based ink and preparation method of elastic emulsion - Google Patents
Water-based ink, elastic emulsion used for water-based ink and preparation method of elastic emulsion Download PDFInfo
- Publication number
- CN102382509A CN102382509A CN2011102647525A CN201110264752A CN102382509A CN 102382509 A CN102382509 A CN 102382509A CN 2011102647525 A CN2011102647525 A CN 2011102647525A CN 201110264752 A CN201110264752 A CN 201110264752A CN 102382509 A CN102382509 A CN 102382509A
- Authority
- CN
- China
- Prior art keywords
- parts
- emulsion
- color ink
- elastic emulsion
- water
- 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
Landscapes
- Polymerisation Methods In General (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The invention discloses an elastic emulsion for water-based ink, which is prepared by the following raw materials comprising, by weight, 5 to 8 parts of styrene, 3 to 5 parts of ethyl acrylate, 32 to 35 parts of butyl acrylate, 1 to 2 parts of itaconic acid mono-n-butyl ester, 1 to 2 parts of N-hydroxymethyl acrylamide, 5 to 10 parts of acrylic ester resin liquid, 0.05 to 0.1 part of sodium bicarbonate, 2 to 3 parts of composite emulsifying agent, 0.35 to 0.5 part of composite initiating agent and 35 to 45 parts of deionized water. The invention further discloses a preparation method of the elastic emulsion for the water-based ink and the water-based ink utilizing the elastic emulsion. The water-based ink prepared by utilizing the elastic emulsion serving as a binder has good rheological property, printing adaptability and folding resistance, and the elasticity is good after a film is formed.
Description
Technical field
The present invention relates to a kind of used for water color ink elastic emulsion and preparation method thereof, and relate to a kind of water color ink of this elastic emulsion of usefulness.
Background technology
Elastic emulsion is widely used in elastic emulsion paint, bouncing putty and elastic coating etc. owing to have performances such as excellent rebound resilience, snappiness, cementability, weathering resistance, and is especially more common in the application of building field.But be applied in the water color ink rarely found.
Rheological is one of most important fundamental property of water color ink.Rheological is to the deposition coalescence of pigment in the water color ink, and printing transitivity and levelling film-forming properties have great decisive action, and directly affect the rheological of water color ink as the emulsion of used for water color ink.Patent of invention publication number CN101638452A " high-solid content pure acrylate elastic emulsion "; CN1557850A " preparation method of organosilicon-modified acrylic elastic emulsion "; The elastic emulsion viscosity of preparation such as CN101358049A " being used for elastic emulsion of curing building putty and preparation method thereof " is low; Rheological is not good, is difficult to be applicable to water color ink.
Summary of the invention
Defective based on the prior art existence; The object of the present invention is to provide a kind of elastic emulsion and preparation method who is suitable for water color ink; And a kind of water color ink of this elastic emulsion of usefulness is provided, order has good rheological, printing adaptability with this elastic emulsion as connecting the water color ink that material is mixed with; Good springiness after the film forming, folding quality is excellent.
To achieve these goals, solution of the present invention is:
A kind of used for water color ink elastic emulsion, formulated by following raw materials by weight portion:
5～8 parts of vinylbenzene;
3～5 parts of ethyl propenoates;
32～35 parts of Bing Xisuandingzhis;
1～2 part of methylene-succinic acid mono;
1～2 part of N hydroxymethyl acrylamide;
5～10 parts of acrylate resin liquid;
0.05～0.1 part of sodium hydrogencarbonate;
2～3 parts of compound emulsifying agents;
0.35～0.5 part of composite initiator;
35～45 parts of deionized waters.
The acid number of described acrylate resin liquid is 120～160, and molecular weight is 5～100,000, Tg=70～80 ℃, and pH=9.5～10.0, solid content is 28～30%.The acrylate resin liquid proportional increases, and performances such as the stability of elastic emulsion, leveling characteristics also improve thereupon.If but when the acrylate resin liquid proportional was too high, the water-repellancy of elastic emulsion can descend.Take all factors into consideration, the optimum proportion of propenoate is to account for 5～10 parts of elastic emulsion massfraction.
Described compound emulsifying agent is made up of for three kinds polymerizable negative ion emulsifying agent allyl polyethenoxy ether ammonium sulfate, anionic emulsifier alkyl polyoxyethylene ether sodium sulfate and nonionic emulsifying agent alkyl polyoxyethylene ether (containing 40 EO oxyethane), and the effective constituent weight ratio is 1:3:2.
Described composite initiator is made up of for three kinds ammonium persulphate, rongalite (rongalite) and tertbutyl peroxide, and weight ratio is 7:2:1.
A kind of preparation method of used for water color ink elastic emulsion comprises the steps:
The first step: prefabricated component:
A, still bottom is divided: with anionic emulsifier alkyl polyoxyethylene ether sodium sulfate raw material weight 10～20% with the nonionic emulsifying agent alkyl polyoxyethylene ether raw material weight that contains 40 EO 5～10%, all sodium hydrogencarbonate and 20 parts of deionized waters mix, form the still bottom and divide;
B, ammonium persulfate aqueous solution: all ammonium persulphates and 10 parts of deionized waters are mixed, obtain ammonium persulfate aqueous solution;
C, pre-emulsion: all monomers, polymerizable negative ion emulsifying agent allyl polyethenoxy ether ammonium sulfate, remaining anionic emulsifier alkyl polyoxyethylene ether sodium sulfate and the nonionic emulsifying agent alkyl polyoxyethylene ether and the 13 parts of deionized waters that contain 40 EO are mixed; Stirring and emulsifying obtains pre-emulsion;
D, the rongalite aqueous solution: all rongalite are mixed with 1 part of deionized water, obtain the rongalite aqueous solution;
Second step: polymerization:
5%～10% of still bottom branch and pre-emulsion weight is heated to 80～85 ℃, adds 10～20% of ammonium persulfate aqueous solution weight, reacted 30 minutes; Keep 80～85 ℃ of temperature in the kettle, drip remaining ammonium sulfate solution and pre-emulsion simultaneously, the dropping time is 4～4.5 hours; After dropwising,, then be cooled to 70～75 ℃, add tertbutyl peroxide, after 10 minutes, dripped off the rongalite aqueous solution with 30 minutes, be incubated 15 minutes then in 65～70 ℃ in 85 ℃ of insulations 1 hour; At last, slowly add acrylate resin liquid, disperse after 10 minutes, filter, discharging obtains the used for water color ink elastic emulsion.
The water color ink that contains above-mentioned elastic emulsion, formulated by following raw materials by weight:
Water color ink base China ink 40%～50%;
Elastic emulsion 30%～45%;
Fischer-Tropsch wax emulsion 3%～5%;
Flatting silica 0%～6%;
Silicone antifoam agent 0.3%～0.5%;
Wetting agent 0.5%～1%.
Deionized water 5%～10%.
Described water color ink base China ink is the water soluble acrylic resin.
Described Fischer-Tropsch wax emulsion is a kind of mixture, and the wax powder content is 45%～50%.
Described flatting silica is the aerosil flatting silica.
Described wetting agent is a kind of dynamic wetting agent, and its structure is a non-ionic type, has outstanding performances such as hydrophilic, wetting, low bubble, like the 104E tensio-active agent of U.S.'s gas companies.
After adopting such scheme, the present invention compared with prior art, useful is:
(1) in conventional ACRYLIC EMULSION production process, add acrylate resin liquid, fundamentally change the rheological property of emulsion liquid, make it near Newton type fluid, and key propertys such as the stability of raising emulsion and printing adaptability;
(2) in elastic emulsion, introduce the methylene-succinic acid mono, its long ester chain has certain plasticising (toughness reinforcing, and improve sticking power) effect, and one can improve wettability and the dispersiveness of emulsion to pigment, can also improve the snappiness after the film forming.
Embodiment
Embodiment one:
In having the there-necked flask of whisking appliance; Add 70 parts of solid contents and be 42%, acid number is 150, molecular weight is 5～100,000, the caustic solubility ACRYLIC EMULSION of Tg=78 ℃, adds 16.8 parts of deionized waters and 8 parts of Virahols again, while stir the Monoethanolamine MEA BASF that adds 5.2 parts then; Obtain solid content and be 29.4% transparent acrylate resin liquid; Recording viscosity is 150～200 seconds (the homemade 4# of being coated with cup, probe temperature are 40 ℃), and pH value is 9.6.
Embodiment two:
1 ﹑ (stirs and opens in a round-bottomed flask that has a stirring; 300-500 rev/min), (100%, Clariant annotates: 100% effective content of emulsifying agent for this reason to add 130 gram deionized waters, 5 gram polymerisable emulsifier Emulsogen APS 100; Germany's Clariant product; Be polymerizable anionic emulsifier allyl polyethenoxy ether ammonium sulfate), 12 gram Emulsogen EPA073 (28%, Clariant, i.e. anionic emulsifier alkyl polyoxyethylene ether sodium sulfate), 9 gram Emulsogen LCN 407 (70%; Clariant; The nonionic emulsifying agent alkyl polyoxyethylene ether that promptly contains 40 EO), stirred 5 minutes, then in continuous whipping process; Add 50 gram benzene second alkene ﹑, 30 grams, the third alkene acetoacetic ester ﹑, 350 grams, the third alkene acid butyl ester ﹑, 20 gram N hydroxymethyl acrylamides (48%), 10 gram methylene-succinic acid monos, make pre-emulsion;
2, with 100 gram deionized water dissolvings, 3.5 gram ammonium persulphates, make ammonium persulfate aqueous solution;
3, in 1 liter of four-hole round-bottomed flask that has paddle agitator, thermopair and a condensing surface; Add 200 gram deionized waters, 1 gram sodium hydrogencarbonate, 3 gram Emulsogen EPA073 (28%; Clariant), 1 gram Emulsogen LCN 407 (70%; Clariant), stir the ammonium persulfate aqueous solution that is warming up to adding 10% pre-emulsion and 20% (accounting for the ammonium persulfate aqueous solution total amount) about 80 ℃; Be warmed up to 85 ℃ again, treat to continue reaction 30 minutes when emulsion becomes blue, make seed emulsion;
4 ﹑ drip remaining pre-emulsion and initiator solution simultaneously at 85 ℃, and the dropping time is 4～4.5 hours;
5,85 ℃ of down insulations 1 hour, then be cooled to 70～75 ℃, add 0.5 gram tertbutyl peroxide, after 10 minutes, in 65～70 ℃ with dripping off the aqueous solution that 1 gram rongalite and 10 water are formed in 30 minutes, be incubated 15 minutes then;
6, last, slowly add 65 gram acrylate resin liquid, disperse after 10 minutes, to filter, discharging obtains used for water color ink elastic emulsion A.
Embodiment three:
In implementing the pre-emulsion of row one, change the consumption of methylene-succinic acid mono into 20 grams, the consumption of Bing Xisuandingzhi changes 340 grams into, and other prescription is identical with embodiment one with implementing process, makes used for water color ink elastic emulsion B.
Embodiment four:
In implementing row two, the consumption of acrylate resin liquid is brought up to 100 grams, other prescription is identical with embodiment two with implementing process, makes used for water color ink elastic emulsion C.
The application implementation example:
Be mixed with soft mute light China ink with elastic emulsion of the present invention as connecting material, can be widely used in improving the performances such as folding resistance, snappiness and feel of White Board in the water-based coating China ink, reach packing instructions such as gift box.Below be to adopt the elastic emulsion PRIMAL 2438M (U.S.'s ROHM AND HAAS) of import and three kinds of elastic emulsions of the present invention to be mixed with four kinds of soft mute light China inks of blueness, its prescription is as shown in table 1.
The blue mute light China ink of these four kinds of water-baseds is carried out the detection of some fundamental propertys, and the result is as shown in table 2:
Test condition:
PH value: use the accurate pH meter of PHS-3B under 25 ℃, to test.
Viscosity: adopt the homemade 4# of being coated with cup under 25 ℃, to test.
Leveling characteristics: use is scraped inker printing ink is scraped on White Board, observes the smooth degree and the degree of uniformity of black laminar surface after the thorough drying; If the China ink layer is even inadequately and scratch is arranged, explain that this ink flow levelling is relatively poor.
Colourity: with reference to National Standard GB/T 13217.1-2009 liquid ink method for detecting color " detect (with test color and standard specimen color distortion degree as measurement index).
Folding resistance: printing ink is scraped on White Board, after the thorough drying, observed the whether explosion of China ink layer after the doubling 3 times; If folding line is not obvious, this printing ink film forming is described after folding quality preferable.
Stability: the 100g sample is packed in the test bottle, place the 24h postcooling to room temperature for 60 ℃; If it is little not have deposition and viscosity (measuring with the homemade 4# cup that is coated with) variation, [viscosity changes with Δ T=T then to be regarded as qualified stability
The end -T
Just Expression, T
Just, T
The end Be respectively sample to be tested put into baking oven before, through 60 ℃ of viscositys (s) of placing the 24h postcooling to room temperature; T is more little for Δ, and it is more little to explain that viscosity changes, and stability is good more].
Can be known by test result: ink O viscosity is low excessively, and levelling is relatively poor after the coating, colourity is not full, and the viscosity of ink A, B, C is suitable, and especially ink C over-all properties is preferable.So elastic emulsion C joins black best results, the adding of this explanation acrylate resin liquid has not only improved the viscosity of system, has also increased the performances such as stability of system.
Claims (7)
1. used for water color ink elastic emulsion is characterized in that by following raw materials by weight portion formulated:
5～8 parts of vinylbenzene;
3～5 parts of ethyl propenoates;
32～35 parts of Bing Xisuandingzhis;
1～2 part of methylene-succinic acid mono;
1～2 part of N hydroxymethyl acrylamide;
5～10 parts of acrylate resin liquid;
0.05～0.1 part of sodium hydrogencarbonate;
2～3 parts of compound emulsifying agents;
0.35～0.5 part of composite initiator;
35～45 parts of deionized waters.
2. a kind of used for water color ink elastic emulsion as claimed in claim 1 is characterized in that: the acid number of described acrylate resin liquid is 120～160, and molecular weight is 5～100,000, Tg=70～80 ℃, and pH=9.5～10.0, solid content is 28～30%.
3. a kind of used for water color ink elastic emulsion as claimed in claim 1; It is characterized in that: described compound emulsifying agent is made up of for three kinds polymerizable negative ion emulsifying agent allyl polyethenoxy ether ammonium sulfate, anionic emulsifier alkyl polyoxyethylene ether sodium sulfate and the nonionic emulsifying agent alkyl polyoxyethylene ether that contains 40 EO, and the effective constituent weight ratio is 1:3:2.
4. a kind of used for water color ink elastic emulsion as claimed in claim 1 is characterized in that: described composite initiator is made up of for three kinds ammonium persulphate, rongalite and tertbutyl peroxide, and weight ratio is 7:2:1.
5. a kind of according to claim 1 preparation method of used for water color ink elastic emulsion is characterized in that comprising the steps:
The first step: prefabricated component:
A, still bottom is divided: with anionic emulsifier alkyl polyoxyethylene ether sodium sulfate raw material weight 10～20% with the nonionic emulsifying agent alkyl polyoxyethylene ether raw material weight that contains 40 EO 5～10%, all sodium hydrogencarbonate and 20 parts of deionized waters mix, form the still bottom and divide;
B, ammonium persulfate aqueous solution: all ammonium persulphates and 10 parts of deionized waters are mixed, obtain ammonium persulfate aqueous solution;
C, pre-emulsion: all monomers, polymerizable negative ion emulsifying agent allyl polyethenoxy ether ammonium sulfate, remaining anionic emulsifier alkyl polyoxyethylene ether sodium sulfate and the nonionic emulsifying agent alkyl polyoxyethylene ether and the 13 parts of deionized waters that contain 40 EO are mixed; Stirring and emulsifying obtains pre-emulsion;
D, the rongalite aqueous solution: all rongalite are mixed with 1 part of deionized water, obtain the rongalite aqueous solution;
Second step: polymerization:
5%～10% of still bottom branch and pre-emulsion weight is heated to 80～85 ℃, adds 10～20% of ammonium persulfate aqueous solution weight, reacted 30 minutes; Keep 80～85 ℃ of temperature in the kettle, drip remaining ammonium sulfate solution and pre-emulsion simultaneously, the dropping time is 4～4.5 hours; After dropwising,, then be cooled to 70～75 ℃, add tertbutyl peroxide, after 10 minutes, dripped off the rongalite aqueous solution with 30 minutes, be incubated 15 minutes then in 65～70 ℃ in 85 ℃ of insulations 1 hour; At last, slowly add acrylate resin liquid, disperse after 10 minutes, filter, discharging obtains the used for water color ink elastic emulsion.
6. the application of a kind of according to claim 1 used for water color ink elastic emulsion in water color ink is characterized in that this water color ink is formulated by following raw materials by weight:
Water color ink base China ink 40%～50%;
Elastic emulsion 30%～45%;
Fischer-Tropsch wax emulsion 3%～5%;
Flatting silica 0%～6%;
Silicone antifoam agent 0.3%～0.5%;
Wetting agent 0.5%～1%
Deionized water 5%～10%.
7. like the application of the said a kind of used for water color ink elastic emulsion of claim 6 in water color ink, it is characterized in that: described water color ink base China ink is the water soluble acrylic resin; Described Fischer-Tropsch wax emulsion is a kind of mixture, and the wax powder content is 45%～50%; Described flatting silica is the aerosil flatting silica; Described wetting agent is a kind of dynamic wetting agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011102647525A CN102382509A (en) | 2011-09-08 | 2011-09-08 | Water-based ink, elastic emulsion used for water-based ink and preparation method of elastic emulsion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011102647525A CN102382509A (en) | 2011-09-08 | 2011-09-08 | Water-based ink, elastic emulsion used for water-based ink and preparation method of elastic emulsion |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102382509A true CN102382509A (en) | 2012-03-21 |
Family
ID=45822370
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011102647525A Pending CN102382509A (en) | 2011-09-08 | 2011-09-08 | Water-based ink, elastic emulsion used for water-based ink and preparation method of elastic emulsion |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102382509A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103409027A (en) * | 2013-07-08 | 2013-11-27 | 上海欣旺壁纸有限公司 | High-glossiness aqueous medium for wallpaper printing and preparation method of high-glossiness aqueous medium |
| CN106085084A (en) * | 2016-06-29 | 2016-11-09 | 无锡伊佩克科技有限公司 | A kind of preparation method of water soluble acrylic acid antirust emulsion |
| CN106318031A (en) * | 2016-08-24 | 2017-01-11 | 广东德康化工实业有限公司 | Water-based multi-functional printing ink |
| CN111500113A (en) * | 2020-06-05 | 2020-08-07 | 杭州海维特化工科技有限公司 | Copper plate paper gravure water-based ink and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101851316A (en) * | 2010-06-13 | 2010-10-06 | 东莞市英科水墨有限公司 | Alkali-soluble emulsion, preparation method thereof and application thereof in water-based ink |
-
2011
- 2011-09-08 CN CN2011102647525A patent/CN102382509A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101851316A (en) * | 2010-06-13 | 2010-10-06 | 东莞市英科水墨有限公司 | Alkali-soluble emulsion, preparation method thereof and application thereof in water-based ink |
Non-Patent Citations (2)
| Title |
|---|
| 周志伟等: "乳胶漆的增稠及其流变性", 《化学建材》, no. 3, 30 June 1987 (1987-06-30), pages 12 - 14 * |
| 黄宏志等: "功能性单体对苯丙乳液性能的影响", 《粘接》, vol. 28, no. 3, 1 June 2007 (2007-06-01), pages 31 - 32 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103409027A (en) * | 2013-07-08 | 2013-11-27 | 上海欣旺壁纸有限公司 | High-glossiness aqueous medium for wallpaper printing and preparation method of high-glossiness aqueous medium |
| CN103409027B (en) * | 2013-07-08 | 2016-01-20 | 上海欣旺壁纸有限公司 | High glossiness aqueous medium of a kind of wallpaper printing and preparation method thereof |
| CN106085084A (en) * | 2016-06-29 | 2016-11-09 | 无锡伊佩克科技有限公司 | A kind of preparation method of water soluble acrylic acid antirust emulsion |
| CN106085084B (en) * | 2016-06-29 | 2018-07-24 | 安德士化工（中山）有限公司 | A kind of preparation method of water soluble acrylic acid antirust emulsion |
| CN106318031A (en) * | 2016-08-24 | 2017-01-11 | 广东德康化工实业有限公司 | Water-based multi-functional printing ink |
| CN106318031B (en) * | 2016-08-24 | 2020-04-07 | 广东德康化工实业有限公司 | Water-based multifunctional printing ink |
| CN111500113A (en) * | 2020-06-05 | 2020-08-07 | 杭州海维特化工科技有限公司 | Copper plate paper gravure water-based ink and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108864359A (en) | A kind of preparation method of high performance water-soluble high solid low viscosity acrylic resin | |
| CN101817906B (en) | Aqueous acrylic acid series wooden ware sealing paint and method for preparing special emulsion thereof | |
| CN102695730B (en) | Environmentally friendly dye compositions and emulsion paint/coating | |
| CN102906131B (en) | Thickening polymer | |
| CN105368150B (en) | A kind of water-based weather-proof glass ink | |
| CN103467672B (en) | Waterborne organic silicon modified epoxy and preparation method thereof | |
| CN102643380B (en) | Acrylate emulsion used for vacuum aluminum plating and laser embossing and preparation method thereof | |
| CN104263184B (en) | A kind of preparation method of aqueous low luster coating | |
| CN108359047B (en) | Graphene-modified water-based acrylate resin and preparation method thereof | |
| CN104870498B (en) | Including the gap filler without plasticiser and sealant of water-borne acrylic type polymerism compound and the method for manufacturing it | |
| CN107163761A (en) | A kind of colorful base paint emulsion of excellent performance and preparation method thereof | |
| CN101798776A (en) | Water-based paper polishing oil and preparation method thereof | |
| CN109929081A (en) | A kind of random copolymerization colour macromole emulsifying agent and preparation method thereof | |
| CN102382509A (en) | Water-based ink, elastic emulsion used for water-based ink and preparation method of elastic emulsion | |
| CN103965676A (en) | Special reactive typehigh-activityleveling agent for epoxy powder coatings as well as preparation method and application of leveling agent | |
| CN107459953A (en) | A kind of preparation method of the polyacrylate pressure-sensitive of enhanced water resistance | |
| CN109575175B (en) | Styrene-acrylic emulsion for interior and exterior walls and preparation method thereof | |
| CN107311568A (en) | A kind of hydrophobic type polymer cement waterproof paint and preparation method thereof | |
| CN102399344B (en) | Self-thickening pure acrylic latex used in art paints, and preparation method thereof | |
| CN105367697A (en) | Silicone acrylic emulsion having core-shell structure and preparation method thereof | |
| CN1281643C (en) | Silicofluoride containing acrylic copolyresin emulsion and paint | |
| CN111534149B (en) | High-adhesion ink and preparation method thereof | |
| CN105732909B (en) | A kind of preparation method of acrylic polysiloxane water-based emulsion | |
| WO2012122722A1 (en) | Fluorocarbon anti-cratering levelling agent for coatint and ink | |
| CN110305326B (en) | Water-based acrylic resin for engineering machinery paint and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20120321 |