CN101735706A - Waterborne polyurethane modified epoxy steel structure anti-corrosive paint and preparation method thereof - Google Patents

Waterborne polyurethane modified epoxy steel structure anti-corrosive paint and preparation method thereof Download PDF

Info

Publication number
CN101735706A
CN101735706A CN201010022502A CN201010022502A CN101735706A CN 101735706 A CN101735706 A CN 101735706A CN 201010022502 A CN201010022502 A CN 201010022502A CN 201010022502 A CN201010022502 A CN 201010022502A CN 101735706 A CN101735706 A CN 101735706A
Authority
CN
China
Prior art keywords
waterborne polyurethane
modified epoxy
corrosive paint
polyurethane modified
component
Prior art date
Application number
CN201010022502A
Other languages
Chinese (zh)
Other versions
CN101735706B (en
Inventor
任天斌
蒋志恒
黄超
钟震
钱志国
韩宇
Original Assignee
同济大学
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by 同济大学 filed Critical 同济大学
Priority to CN2010100225026A priority Critical patent/CN101735706B/en
Publication of CN101735706A publication Critical patent/CN101735706A/en
Application granted granted Critical
Publication of CN101735706B publication Critical patent/CN101735706B/en

Links

Abstract

The invention belongs to the paint technical field, in particular relates to a waterborne polyurethane modified epoxy steel structure anti-corrosive paint and a preparation method thereof. The component A of the paint is a dispersion of modified E-20 and the component B used as curing agent is a waterborne dispersion which is prepared through modification by using epoxy and hydrophilic groups. The system has the advantages of common waterborne paints, overcomes the defects of the waterborne epoxy anti-corrosive paint and has the advantages of polyurethane and epoxy materials. The waterborne epoxy anti-corrosive paint prepared by using the system as the base material has great development prospect in the field of steel structures such as bridges, pipes, containers, industrial plants and public facilities.

Description

A kind of waterborne polyurethane modified epoxy steel structure anti-corrosive paint and preparation method thereof
Technical field
The invention belongs to technical field of coatings, be specifically related to a kind of waterborne polyurethane modified epoxy steel structure anti-corrosive paint and preparation method thereof.
Background technology
Along with the requirement on environmental protection increasingly stringent, low VOC or zero VOC with and the research of the water-borne coatings of HAPs (hazardous air pollutants, hazardous airpollution), to develop the product innovation that adapts to market demand, be the important development direction of coating.
When aqueous epoxy resins uses as the coating of base materials such as steel construction, timber, solidify that back hardness and tensile strength are big, coating film gloss degree height, good to all kinds of ground bonding strengths, chemical-resistant is excellent, electrical insulating property good and advantage such as numerous in variety, cheap and easy to get, has used the paint field of base materials such as various steel knots, timber widely.But people find that also also there are some shortcomings in aqueous epoxy resins, and not enough such as the flexibility of film, ageing-resistant, anti-atomizing performance is bad etc.
Urethane resin is widely used, excellent performance.When it uses as the topcoating of base materials such as steel construction, woodenware, the formed good mechanical property of filming, wear resistance is good, hardness is high, water-fast, chemically-resistant, ageing resistance excellence, belong to high-performance coating, its Application Areas comprises floor coating, kitchen furniture coating, office furniture coating, mechanical means (OEM) coating.It is all very strong to the sticking power of various base materials, and is not only to multi-hole type base materials such as timber, cement based, also very strong to porous surface adhesion forces such as metal, glass.
Some shortcomings at the aqueous epoxy coating appearance, in recent years coating was carried out various modifications with Resins, epoxy both at home and abroad, polyurethane modified epoxy gained steel structure anti-corrosion paint wherein, some defectives of water corrosion-resistant epoxy paint itself have not only been overcome, make made coating possess the advantage of urethane and epoxy simultaneously, thereby having improved the over-all properties of coating, is that the water-base epoxy anticorrosive coating that base-material prepares has huge development prospect in iron structure fields such as bridge, pipeline, freight container, industrial premises and communal facilitys with it.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of waterborne polyurethane modified epoxy steel structure anti-corrosive paint.
The waterborne polyurethane modified epoxy steel structure anti-corrosive paint that the present invention proposes, its component consists of by weight:
Wherein: A component and B component gross weight satisfy 100%.
Among the present invention, described defoamer is a kind of modified polyorganosiloxane base polymer, as Defom W-0505 or DefomW-092.
Among the present invention, described dispersion agent is that high-molecular weight modified polyacrylate base polymer and carboxylic-acid alkanolamine salt are composite, and is composite as AFCONA-4560 or AFCONA-4550 and AFCONA-5071.
Among the present invention, described flow agent is polyether-modified polydimethylsiloxane solution, as BYK346.
Among the present invention, described rust-stabilising pigment is that red iron oxide and aluminium triphosphate are composite.
Among the present invention, the agent of described anti-sudden strain of a muscle rust is an alkylphosphonic, as RAYBO 60.
Among the present invention, described solidifying agent is the epoxide modified polyamine dispersion of non-ionic type, by the gained of the partially end-blocked polyamine of block copolymer-modified process of PEG and E-51 Resins, epoxy.And change polyamine is triethylene tetramine (TETA), and the end-blocking ratio is within the 0.5-1 scope.
The preparation method of the waterborne polyurethane modified epoxy steel structure anti-corrosive paint that the present invention proposes, concrete steps are as follows:
1, A component preparation: under 1000-1500r/min stirs, successively rust-stabilising pigment, process white, talcum powder, anti-rust agent, dispersion agent and the water of dodging are mixed to join in the waterborne polyurethane modified epoxy emulsion, and add half defoamer, below colo(u)rant dispersion to 50 order, under the 300r/min-500r/min stir speed (S.S.), add second half defoamer and flow agent then.Stir, slaking obtains the A component after the filtration;
2, the B component be by to how by carrying out after end-blocking, the addition with a kind of aqueous dispersion that is prepared from after the reactive emulsifier emulsification.Polyamine is carried out modification, not only increased the consistency with Resins, epoxy, reduced the activity of amine, prolonged the working life of coating.
3, with A, B two components according to 10: 1 mixed of mass ratio, in agitator, mix, obtain waterborne polyurethane modified epoxy steel structure anti-corrosive paint.
The performance of gained coating is as follows:
The test event test result
Dry surface drying/min 35
Time does solid work/h≤12
Shock resistance/kgcm>50
Sticking power/level 1
Snappiness/Φ mm≤2
Pencil hardness/H 3
400h is no abnormal for salt water resistance (3%NaCl)
Anti-neutral mist (5%NaCl) 600h, a small amount of blackspot, the cut infiltration<<3mm
The waterborne polyurethane modified epoxy steel structure anti-corrosive paint of the present invention's development, both kept the epoxy resin coating acid and alkali-resistance, the performance that sticking power is good has polyurethanes coating oil resistant class again, resistant to chemical media, the characteristics that coating strength and wear resisting property are good, simultaneously it, cheap, odorlessness, does not fire as dispersion medium with water, and the security in storage, transportation and the use improves greatly, and the application performance of aqueous epoxy coating is good, and the service tool used water is directly cleaned.
Embodiment
Further specify the present invention below by embodiment.
Embodiment 1:
Unit takes by weighing following raw materials according by weight: waterborne polyurethane modified epoxy emulsion 25; Process white 10; Rust-stabilising pigment 22; Talcum powder 8; Defoamer 1; Dispersion agent 2.5; Flow agent 0.5; Anti-rust agent 2, the water 18 of dodging.Flow agent adopts BYK346, and dispersion agent adopts AFCONA-4560, and raybo75 is adopted in the agent of anti-sudden strain of a muscle rust, and defoamer adopts Defom W-0505.
Under high-speed stirring, successively zinc powder, rust-stabilising pigment, talcum powder, anti-rust agent, dispersion agent and the water of dodging are mixed to join in the waterborne polyurethane modified epoxy emulsion and add half defoamer, below colo(u)rant dispersion to 50 order, under the 300r/min-500r/min stir speed (S.S.), add auxiliary agents such as second half defoamer and flow agent then.Stir, obtain the A component after the filtration.
To how by carrying out after end-blocking, the addition, get this dispersion 7g and mix with 4g water and be made into B and organize with a kind of aqueous dispersion of preparation after the reactive emulsifier emulsification.
Then A, B two components are stirred, slaking 15 minutes, promptly obtain the waterborne polyurethane modified epoxy steel structure anti-corrosive paint that directly to construct, this coating is brushed or is sprayed on the tinplate sheet, can obtain filming of surface drying in 45 minutes, dry filming in a week can completely solidified, the test film performance:
The test event test result
Dry surface drying/min 35
Time does solid work/h≤12
Shock resistance/kgcm 50
Sticking power/level 2
Snappiness/Φ mm≤2
Pencil hardness/H 4
400h is no abnormal for salt water resistance (3%NaCl)
Anti-neutral mist (5%NaCl) 600h, a small amount of blackspot, the infiltration of cut place<<2mm
Embodiment 2:
Unit takes by weighing following raw materials according by weight: waterborne polyurethane modified epoxy emulsion 35; Process white 7; Rust-stabilising pigment 16; Talcum powder 4; Defoamer 0.3; Dispersion agent 1.5; Flow agent 0.2; The agent 1 of anti-sudden strain of a muscle rust; Water 15.Flow agent adopts BYK346, and dispersion agent adopts AFCONA-4550 and AFCONA-5071, and raybo75 is adopted in the agent of anti-sudden strain of a muscle rust, and defoamer adopts DefomW-092.
Under high-speed stirring, successively process white, rust-stabilising pigment, talcum powder, anti-rust agent, dispersion agent and the water of dodging are mixed to join in the waterborne polyurethane modified epoxy emulsion and add half defoamer, below colo(u)rant dispersion to 50 order, under the 300r/min-500r/min stir speed (S.S.), add auxiliary agents such as second half defoamer and flow agent then.Stir, obtain the A component after the filtration.
To how by carrying out after end-blocking, the addition, get this dispersion 10g and mix with 10 water and be made into the B component with a kind of aqueous dispersion of preparation after the reactive emulsifier emulsification.
Then A, B two components are stirred, slaking 15 minutes, promptly obtain the waterborne polyurethane modified epoxy steel structure anti-corrosive paint that directly to construct, this coating is brushed or is sprayed on the tinplate sheet, can obtain filming of surface drying in 45 minutes, dry filming in a week can completely solidified, the test film performance:
The test event test result
Dry surface drying/mmin 40
Time does solid work/min≤12
Shock resistance/kgcm 60
Sticking power/level 1
Snappiness/Φ mm≤2
Pencil hardness/H 3
400h is no abnormal for salt water resistance (3%NaCl)
Anti-neutral mist (5%NaCl) 600h, a small amount of blackspot, the cut place does not have infiltration substantially
Embodiment 3:
Unit takes by weighing following raw materials according by weight: waterborne polyurethane modified epoxy emulsion 45; Process white 6; Rust-stabilising pigment 12; Talcum powder 4; Defoamer 0.3; Dispersion agent 1.5; Flow agent 0.2; The agent 1 of anti-sudden strain of a muscle rust; Water 10.Flow agent adopts BYK346, and dispersion agent adopts AFCONA-4550 and AFCONA-5071, and raybo75 is adopted in the agent of anti-sudden strain of a muscle rust, and defoamer adopts DefomW-092.
Under high-speed stirring, successively process white, rust-stabilising pigment, talcum powder, anti-rust agent, dispersion agent and the water of dodging are mixed to join in the waterborne polyurethane modified epoxy emulsion and add half defoamer, below colo(u)rant dispersion to 100 order, under the 300r/min-500r/min stir speed (S.S.), add auxiliary agents such as second half defoamer and flow agent then.Stir, obtain the A component after the filtration.
To how by carrying out after end-blocking, the addition, get this dispersion 13g and mix with 7g water and be made into B and organize with a kind of aqueous dispersion of preparation after the reactive emulsifier emulsification.
Then A, B two component mixing and stirring, slaking 15 minutes, promptly obtain the waterborne polyurethane modified epoxy steel structure anti-corrosive paint that directly to construct, this coating is brushed or is sprayed on the tinplate sheet, can obtain filming of surface drying in 45 minutes, dry filming in a week can completely solidified, the test film performance:
The test event test result
Dry surface drying/min 35
Time does solid work/min≤12
Shock resistance/kgcm 60
Sticking power/level 1
Snappiness/Φ mm≤2
Pencil hardness/H 2
400h is no abnormal for salt water resistance (3%NaCl)
Anti-neutral mist (5%NaCl) 600h, a small amount of blackspot, the cut infiltration<<2mm

Claims (8)

1. waterborne polyurethane modified epoxy steel structure anti-corrosive paint is characterized in that component consists of by weight:
Wherein: A component and B component gross weight satisfy 100%.
2. waterborne polyurethane modified epoxy steel structure anti-corrosive paint according to claim 1 is characterized in that described defoamer adopts the modified polyorganosiloxane base polymer.
3. waterborne polyurethane modified epoxy steel structure anti-corrosive paint according to claim 1 is characterized in that described dispersion agent employing high-molecular weight modified polyacrylate base polymer and carboxylic-acid alkanolamine salt are composite.
4. waterborne polyurethane modified epoxy steel structure anti-corrosive paint according to claim 1 is characterized in that described flow agent adopts polyether-modified polydimethylsiloxane solution.
5. waterborne polyurethane modified epoxy steel structure anti-corrosive paint according to claim 1 is characterized in that described rust-stabilising pigment is that red iron oxide and aluminium triphosphate are composite.
6. waterborne polyurethane modified epoxy steel structure anti-corrosive paint according to claim 1 is characterized in that described anti-sudden strain of a muscle rust agent employing alkylphosphonic.
7. waterborne polyurethane modified epoxy steel structure anti-corrosive paint according to claim 1, it is characterized in that described solidifying agent is the epoxide modified polyamine dispersion of non-ionic type, gained by the partially end-blocked polyamine of block copolymer-modified process of PEG and E-51 Resins, epoxy, changing polyamine is triethylene tetramine, and the end-blocking ratio is within the 0.5-1 scope.
8. the preparation method of a waterborne polyurethane modified epoxy steel structure anti-corrosive paint as claimed in claim 1 is characterized in that concrete steps are as follows:
(1), A component preparation: under 1000-1500r/min stirs, successively rust-stabilising pigment, talcum powder, anti-rust agent, dispersion agent and the water of dodging are mixed to join in the waterborne polyurethane modified epoxy emulsion, and add half defoamer, below colo(u)rant dispersion to 50 order, under the 300r/min-500r/min stir speed (S.S.), add second half defoamer and flow agent then.Stir, slaking obtains the A component after the filtration;
(2), the B component be by to how by carrying out after end-blocking, the addition with a kind of aqueous dispersion that is prepared from after the reactive emulsifier emulsification;
(3), with A, B two components according to 10: 1 mixed of mass ratio, in agitator, mix, obtain waterborne polyurethane modified epoxy steel structure anti-corrosive paint.
CN2010100225026A 2010-01-07 2010-01-07 Waterborne polyurethane modified epoxy steel structure anti-corrosive paint and preparation method thereof CN101735706B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN2010100225026A CN101735706B (en) 2010-01-07 2010-01-07 Waterborne polyurethane modified epoxy steel structure anti-corrosive paint and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN2010100225026A CN101735706B (en) 2010-01-07 2010-01-07 Waterborne polyurethane modified epoxy steel structure anti-corrosive paint and preparation method thereof

Publications (2)

Publication Number Publication Date
CN101735706A true CN101735706A (en) 2010-06-16
CN101735706B CN101735706B (en) 2012-02-29

Family

ID=42459746

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2010100225026A CN101735706B (en) 2010-01-07 2010-01-07 Waterborne polyurethane modified epoxy steel structure anti-corrosive paint and preparation method thereof

Country Status (1)

Country Link
CN (1) CN101735706B (en)

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101880508A (en) * 2010-06-24 2010-11-10 同济大学 Preparation method of high abrasion water-borne wood coating
CN101993645A (en) * 2010-11-22 2011-03-30 洛阳七维防腐工程材料有限公司 Water-based heavy corrosion protection ceramic paint
CN102020909A (en) * 2010-12-15 2011-04-20 湖南三力达化工有限公司 High-performance aqueous epoxy anticorrosive paint for steel structures
CN102533053A (en) * 2011-12-29 2012-07-04 上海门普来新材料股份有限公司 Environmental-friendly waterborne epoxy zinc phosphate anti-corrosion paint for steel structures and preparation method thereof
CN102676029A (en) * 2012-06-07 2012-09-19 青岛海洋新材料科技有限公司 Polyurethane anti-corrosion priming paint sprayed on steel structure in abyssal environment
CN102732125A (en) * 2011-04-11 2012-10-17 浙江飞鲸漆业有限公司 Aqueous epoxy resin anticorrosion coating
CN103360894A (en) * 2012-03-27 2013-10-23 比亚迪股份有限公司 Waterborne paint and preparation method thereof
CN103666197A (en) * 2013-12-03 2014-03-26 常州市拉特涂料有限公司 Aqueous anticorrosive epoxy coating for steelworks
CN103694848A (en) * 2013-12-03 2014-04-02 常州市拉特涂料有限公司 Water-borne epoxy anticorrosive paint for concrete surface
US20140350141A1 (en) * 2011-05-05 2014-11-27 Allnex Austria Gmbh Multifunctional primary amine, process for its preparation, and use thereof
CN105176347A (en) * 2015-09-08 2015-12-23 天长市银狐漆业有限公司 Weather-resistant shock-resistant anticorrosive coating
CN106634506A (en) * 2016-10-31 2017-05-10 湖南航天三丰科工有限公司 Coating for protecting aerostat capsule material and preparation method and application thereof
CN106742699A (en) * 2016-12-20 2017-05-31 江苏百瑞尔包装材料有限公司 A kind of tinplate overlay film of corrosion resistance
CN106752663A (en) * 2015-11-25 2017-05-31 湖南开磷雁峰塔涂料有限公司 A kind of aqueous steel construction paint special
US9914800B2 (en) 2012-11-06 2018-03-13 Allnex Austria Gmbh Aqueous dispersions of a multifunctional primary amine, process for its preparation, and use therof
CN109439145A (en) * 2018-11-08 2019-03-08 苏州圣杰特种树脂有限公司 Wear resistant corrosion resistant aqueous epoxide resin paint and preparation method thereof

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101880508A (en) * 2010-06-24 2010-11-10 同济大学 Preparation method of high abrasion water-borne wood coating
CN101993645A (en) * 2010-11-22 2011-03-30 洛阳七维防腐工程材料有限公司 Water-based heavy corrosion protection ceramic paint
CN101993645B (en) * 2010-11-22 2013-06-19 洛阳七维防腐工程材料有限公司 Water-based heavy corrosion protection ceramic paint
CN102020909A (en) * 2010-12-15 2011-04-20 湖南三力达化工有限公司 High-performance aqueous epoxy anticorrosive paint for steel structures
CN102732125A (en) * 2011-04-11 2012-10-17 浙江飞鲸漆业有限公司 Aqueous epoxy resin anticorrosion coating
US10023547B2 (en) 2011-05-05 2018-07-17 Allnex Austria Gmbh Multifunctional primary amine, process for its preparation, and use thereof
US9440911B2 (en) * 2011-05-05 2016-09-13 Allnex Austria Gmbh Multifunctional primary amine, process for its preparation, and use thereof
US20140350141A1 (en) * 2011-05-05 2014-11-27 Allnex Austria Gmbh Multifunctional primary amine, process for its preparation, and use thereof
CN102533053A (en) * 2011-12-29 2012-07-04 上海门普来新材料股份有限公司 Environmental-friendly waterborne epoxy zinc phosphate anti-corrosion paint for steel structures and preparation method thereof
CN102533053B (en) * 2011-12-29 2014-07-09 上海门普来新材料股份有限公司 Environmental-friendly waterborne epoxy zinc phosphate anti-corrosion paint for steel structures and preparation method thereof
CN103360894A (en) * 2012-03-27 2013-10-23 比亚迪股份有限公司 Waterborne paint and preparation method thereof
CN102676029A (en) * 2012-06-07 2012-09-19 青岛海洋新材料科技有限公司 Polyurethane anti-corrosion priming paint sprayed on steel structure in abyssal environment
US9914800B2 (en) 2012-11-06 2018-03-13 Allnex Austria Gmbh Aqueous dispersions of a multifunctional primary amine, process for its preparation, and use therof
CN103694848A (en) * 2013-12-03 2014-04-02 常州市拉特涂料有限公司 Water-borne epoxy anticorrosive paint for concrete surface
CN103666197A (en) * 2013-12-03 2014-03-26 常州市拉特涂料有限公司 Aqueous anticorrosive epoxy coating for steelworks
CN103666197B (en) * 2013-12-03 2016-04-20 常州市拉特涂料有限公司 A kind of steel construction use corrosion-resistant epoxy paint
CN105176347A (en) * 2015-09-08 2015-12-23 天长市银狐漆业有限公司 Weather-resistant shock-resistant anticorrosive coating
CN106752663A (en) * 2015-11-25 2017-05-31 湖南开磷雁峰塔涂料有限公司 A kind of aqueous steel construction paint special
CN106634506A (en) * 2016-10-31 2017-05-10 湖南航天三丰科工有限公司 Coating for protecting aerostat capsule material and preparation method and application thereof
CN106742699A (en) * 2016-12-20 2017-05-31 江苏百瑞尔包装材料有限公司 A kind of tinplate overlay film of corrosion resistance
CN109439145A (en) * 2018-11-08 2019-03-08 苏州圣杰特种树脂有限公司 Wear resistant corrosion resistant aqueous epoxide resin paint and preparation method thereof

Also Published As

Publication number Publication date
CN101735706B (en) 2012-02-29

Similar Documents

Publication Publication Date Title
CN105038464B (en) Aqueous highly corrosion resistant coating and preparation method and application with excellent punching
CN104140738B (en) For finish paint preparation method at the bottom of the aqueous of railway support system
CN103788343B (en) A kind of Diamond Search aqueous epoxy curing agent
CN102731052B (en) Aqueous organic-inorganic composite coating and preparation method thereof
CN103450719B (en) A kind of long-acting aqueous, environmental protective steel construction protection coating
CN101292003B (en) Polyfunctional epoxy resin coating composition containing rust-preventive pigment, coating film obtained therefrom, base coated with the coating film, and method of rust prevention
CN102906188B (en) Eco-friendly aqueous epoxy resins composition and use thereof
CN101792285B (en) Chromium-free environment-friendly epoxy anticorrosion primer
CN105462496B (en) A kind of antibacterial and mouldproof polymer modification spraying asphalt waterproofing paint and its application method
CN100383205C (en) Anticorrosive waterproof nano industrial coating and its preparing method
CN106189719A (en) A kind of Graphene anticorrosive paint and preparation method thereof
CN105733405A (en) Graphene-based enhanced high-solid epoxy anticorrosive coating and method for preparing same
CN106118295A (en) A kind of aqueous bottom surface unification Corrosion resisting paint without need of cleaning rust and preparation method thereof
CN105838195B (en) A kind of water corrosion-resistant epoxy paint and preparation method thereof containing graphene oxide
CN102533029B (en) Aqueous asphalt imitation anticorrosion coating for container chassis and preparation method thereof
CN108285718B (en) A kind of epoxidation zone rust graphene anticorrosive paint and its preparation method and application
CN104277664A (en) Marine anticorrosive coatings
CN103254701B (en) Novel anti-corrosion, anti-ultraviolet, anti-bacteria and wear-resistant paint and preparation method for same
CN101560355B (en) Heavy anti-corrosion antirust powder paint
CN104877526A (en) Paint containing water-based acrylic modified epoxy phosphate resin and preparation method thereof
CN101215438B (en) Anti-soiling aging-resisting stainless steel paint and preparation method thereof
CN106047091A (en) Waterproof and corrosion-resistant coating for coastal region
CN101701126B (en) Aqueous rusty anti-corrosion paint and preparation method thereof
CN101525519B (en) Polysiloxane coating composition
CN102719170B (en) Flake heavy-duty coating for desulfurizing flues 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
C14 Grant of patent or utility model
GR01 Patent grant
EXPY Termination of patent right or utility model
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20120229

Termination date: 20150107