CN103602220A - Siloxane hybrid anticorrosive paint - Google Patents
Siloxane hybrid anticorrosive paint Download PDFInfo
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- CN103602220A CN103602220A CN201310565609.9A CN201310565609A CN103602220A CN 103602220 A CN103602220 A CN 103602220A CN 201310565609 A CN201310565609 A CN 201310565609A CN 103602220 A CN103602220 A CN 103602220A
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Abstract
The invention relates to a siloxane hybrid anticorrosive paint. Every 100 parts by mass of component A is composed of 20 parts of epoxy resin, 8-12 parts of modified resin, 50-55 parts of pigment and filler, 1-3 parts of assistant and the balance of mixed solvent, wherein the epoxy resin is composed of one or more of low-molecular-weight bisphenol A or bisphenol F liquid epoxy resins; and the modified resin is an organic silicon modified epoxy resin prepared from 42 parts of ethyl orthosilicate, 8 parts of phenyltrimethoxysilane, 4.5 parts of gamma-aminopropyl trialkoxysilane, 4 parts of water, 1.5 parts of hydrochloric acid, 25 parts of isopropanol, 10 parts of E-51 epoxy resin and 5 parts of acetone. Every 100 parts by mass of component B is composed of 50 parts of polyamide, 10-15 parts of aminosiloxane resin and the balance of mixed solvent. By properly matching the components A and B, the obtained paint can satisfy the technical requirements in ISO20340, and provides long-acting protection for ocean engineering.
Description
Technical field
The present invention relates to a kind of silicone hybrid anticorrosive coating.
Background technology
Fast development along with national economy, and the Devoting Major Efforts To Developing of China to oceanic resources, in ocean and periphery, build the positive expanding day of scale of steel construction, the ocean steel construction such as bridge spanning the sea, offshore platform particularly, be subject to the impact of the factors such as high humidity in oceanic climate, high salt fog and intense UV rays, the corrosion speed of its steel construction and degree will, far away higher than inland atmospheric environment, have been formulated oceanographic engineering protection against corrosion standard for this reason.The oceanographic engineering coating standard of being accepted extensively by industry is at present ISO20340.The organic coating that this standard-required atmospheric marine environment is used is after 4200h circulation weathering test, and the corrosion of the supporting coating system that the zinc-rich paint of take is priming paint spreads monolateral expansion erosion≤3mm; The corrosion of the supporting coating system that the non-zinc-rich paint of take is priming paint spreads monolateral expansion erosion≤8mm.The high solids epoxy anticorrosive coating the most often using at present, after its 4200h circulation of filming is aging, its monolateral painting erosion spreads over 8mm, does not meet this standard-required; In atmospheric marine environment, be widely used as the zinc-rich paint of priming paint, wherein the erosion resistance of inorganic zinc coating is better than epoxy zinc-enriched paint, after its 4200h circulation of filming is aging, monolateral spread≤3mm of painting erosion, meet this standard-required, but the impact of its erosion resistance Shou Xia road coating (for example, the intermediate coat of inorganic zinc silicate primer) is larger.
Summary of the invention
The object of the invention is: a kind of silicone hybrid anticorrosive coating is provided, on steel, has excellent sticking power and corrosion resistance nature and for the intermediate coat of inorganic zinc silicate primer, have excellent permeability, erosion resistance.
The technical scheme that realizes the object of the invention is: a kind of silicone hybrid anticorrosive coating composition, it is characterized in that, and A component and B component, consist of, A component is 100:20 with the mass parts ratio of B component;
A component is by epoxy resin, modified resin, pigment, filler, auxiliary agent and solvent composition, in the A of every 100 mass parts component, 20 parts of epoxy resin, 8～12 parts of modified resin, pigment and 50～55 parts of fillers, 1～3 part of auxiliary agent, surplus are mixed solvent, wherein, epoxy resin be low-molecular-weight bisphenol A-type or Bisphenol F type liquid epoxy one or more, modified resin is modifying epoxy resin by organosilicon, it is to contain 42 parts of tetraethoxys in every 100 mass parts materials, 8 parts of phenyltrimethoxysila,e, 4.5 parts of gamma-amino propyl trialkoxy silanes, 4 parts, water, 1.5 parts of hydrochloric acid, 25 parts of Virahols, 5 parts, 10 parts of E-51 epoxy resin and acetone are raw material, by tetraethoxy, phenyltrimethoxysila,e, Virahol adds in reaction vessel, be warming up to 40 ℃, start to drip the mixture of hydrochloric acid and water, after 1h dropwises, at 60～70 ℃ of insulation 4h, then add gamma-amino propyl trialkoxy silane, insulation 1h, formation contains amino silicone resin, under stirring, add again the solution of epoxy resin and acetone in batches, continue stirring reaction 4h, be cooled to normal temperature to make,
B component is comprised of polymeric amide, aminosiloxane resin, organic solvent, in the B of every 100 mass parts component, 50 parts of polymeric amide, 10～15 parts of aminosiloxane resins, surplus are mixed solvent, and wherein, polymeric amide is the low polymerization degree product of dimeracid and the many ammonia of many ethene; Aminosiloxane resin is DOW CORNING
In above-mentioned silicone hybrid anticorrosive coating composition, the epoxy resin in described A component is one or more in E51, E44, F51; Pigment is one or more in titanium dioxide, carbon black, medium chrome yellow medium yellow, phthalocyanine blue; Filler is one or more in talcum powder, calcium carbonate, barium sulfate, silica powder, mica powder, Feldspar Powder, wollastonite powder, molochite; Auxiliary agent is one or more in dispersion agent, defoamer, thixotropic agent, anti-settling agent.
In above-mentioned silicone hybrid anticorrosive coating composition, the polymeric amide in described B component is a kind of in Versmide v-140, BS850A, 350A, and its amine value is at 300～400mgKOH/g.
In above-mentioned silicone hybrid anticorrosive coating composition, the mixed solvent using in A component and B component be dimethylbenzene and butanols mixture, both mass ratioes are 2:1.
Technique effect of the present invention is: the silicone hybrid anticorrosive coating of technical solution of the present invention mainly improves with existing similar coating and is: the modified resin that has 1. adopted special formulation and method to make in A component, i.e. modifying epoxy resin by organosilicon.The main body component of this modified resin is tetraethoxy, part oxyethyl group in preparation process tetraethoxy and phenyltrimethoxysila,e generation hydrolysis-condensation reaction, use subsequently gamma-amino propyl trialkoxy silane end-blocking, form containing amino silicone resin, the epoxy group(ing) of the epoxy resin then adding is reacted with the formed amino containing amino silicone resin before, make modified resin, it is modifying epoxy resin by organosilicon, its contained epoxy group(ing) is after mixing with B component, react with the amino that forms the aminosiloxane resin of B component, participate in crosslinking curing, form cross-linked network structure, by in modified resin-O-Si-O-key introduces in network, form hybrid inorganic-organic coating, thermotolerance and the chemical-resistant of coating have been strengthened, increased sticking power, improved solidity to corrosion, on the modified resin molecular chain of A component in tetraethoxy unhydrolysed oxyethyl group in the solidification process of filming, can continue hydrolysis, form silicon hydroxyl, form chemical bond with the active group on metal substrate, increase the sticking power that is coated with interlayer, and then improved the erosion resistance of coating on metal substrate, hybridization coating is tightly adhered on metal substrate by chemical bonding, water molecules or other corrosive mediums are difficult to, at metal interface displacement erosion shield, improve coating and resisted the ability that corrosion spreads, simultaneously adding of modified resin, improved the consistency of aminosiloxane resin in coating system in B component, the two collaborative use, has increased the inorganic components of coating, has improved the overall performance of coating,
2. the epoxy resin in A component adopt low-molecular-weight bisphenol A-type or Bisphenol F type liquid epoxy one or more, they are diglycidylethers of dihydroxyphenyl propane or Bisphenol F, oxirane value is greater than 0.4, therefore, can provide high crosslink density and shielding properties, and be in a liquid state under this based epoxy resin normal temperature, the viscosity of resin own is lower, molecular weight, is particularly conducive to and makes the coating with excellent permeability, and the also solids content of favourable raising coating of low viscosity;
3. the polymeric amide in B component is the low polymerization degree reactant of dimeracid and divinyl triammonium or triethylene four ammonia, one end of its molecular chain is the long carbochain of dimeracid, there is hydrophobicity, the other end is the hydrophilic-structure of polyamines, there is the effect of similar nonionic emulsifying agent, therefore, many grounds are had to good wetting action, flexility is good;
4. contain in a large number-O-Si-O-key of the aminosiloxane resin in B component itself is incorporated into it in the lump in cross-linked network when curing reaction, has further improved chemical resistant properties, thermotolerance and the erosion resistance of coating.The present invention provides oceanographic engineering long-effective protection by A component and the supporting silicone hybrid anticorrosive coating forming of B component, can be by the technical requirements of ISO20340.
Embodiment
Below in conjunction with embodiment, the present invention is described further, but is not limited to this.
Embodiment and comparative example raw materials are unless otherwise indicated commercially available industrial goods, can buy by commercial channel.
Embodiment 1 prepares modified resin
1. fill a prescription:
In the raw material of 100 mass parts, 42 parts of tetraethoxys, 8 parts of phenyltrimethoxysila,e, 4.5 parts of gamma-amino propyl trialkoxy silanes, 4 parts of distilled water, 1.5 parts of hydrochloric acid, 25 parts of Virahols, 10 parts of E-51 epoxy resin, 5 parts, acetone, in above-mentioned raw materials, demineralizing acid is that outside analytical pure, all the other are industrial goods.
2. preparation method
Tetraethoxy, phenyltrimethoxysila,e, Virahol are added in reaction vessel, be warming up to 40 ℃, start to drip the mixture of hydrochloric acid and water, after 1h dropwises, at 60～70 ℃ of insulation 4h, then add gamma-amino propyl trialkoxy silane, insulation 1h, formation contains amino silicone resin, under stirring, add at least at twice again the solution of epoxy resin and acetone, continue stirring reaction 4h, be cooled to normal temperature to make modified resin, be modifying epoxy resin by organosilicon, save backup.
Embodiment 2 preparation A components
1. fill a prescription:
In the A of every 100 mass parts component, 10 parts of the modified resin that epoxy resin E5120 part, embodiment 1 make, pigment titanium white R-90210 part, filler comprise that 25 parts of process whites and 20 parts of talcum powder, auxiliary agent comprise 12 parts of dispersant B YKATU1 part, defoamer AFCONA27220.5 part, organobentonite G-19581 part and aerosil R-9720.5 part, mixed solvents (dimethylbenzene that mass ratio is 2:1 and butanols mixture).
2. preparation method
In dispersion tank, add epoxy resin, solvent, dispersion agent, defoamer, after stirring, add organobentonite and aerosil, high-speed stirring 15min, makes organobentonite and aerosil fully soak and disperse.Then add respectively titanium dioxide, talcum powder, process white, after stirring, move in sand mill, discharging when grinding distribution to the fineness of slurry is 40 μ m slowly adds modified resin in this slurry, stirs, filters, packs, make A component, save backup.
Embodiment 3 preparation B components
1. fill a prescription:
In the B of every 100 mass parts component, 50 parts of polymeric amide (Versmide v-140, cognis), aminosiloxane resin (DOW CORNING
) 38 parts of 12 parts, mixed solvent (dimethylbenzene that mass ratio is 2:1 and butanols mixture).
2. preparation method
Mixed solvent is added in dispersion tank, add successively polymeric amide and aminosiloxane resin under stirring, stir, filter, packing, obtains B component, saves backup.
Embodiment 4 prepares silicone hybrid anticorrosive coating
During use, after the A component first embodiment 2 being made and embodiment 3 make B component and stir respectively, by mass parts, than for 100:20, take respectively A component and B component, remix also stirs, and then slaking 15～30min can carry out application.
Comparative example 1 is prepared the A component of comparative example high-solid epoxy resin anticorrosive coating
1. fill a prescription (not using modified resin)
In the Comparative examples A component of every 100 mass parts, epoxy resin E5126 part, pigment titanium white R-90210 part, filler comprises 20 parts of 25 parts of process whites and talcum powder, auxiliary agent comprises dispersant B YK ATU1 part, defoamer AFCONA27220.5 part, organobentonite G-19581 part and aerosil R-9720.5 part, 16 parts of mixed solvents (dimethylbenzene that mass ratio is 2:1 and butanols mixture).
2. preparation method
In dispersion tank, add epoxy resin, solvent, dispersion agent, defoamer, after stirring, add organobentonite and aerosil, high-speed stirring 15min, makes organobentonite and aerosil fully soak and disperse.Then add respectively titanium dioxide, talcum powder, process white, after stirring, move in sand mill, when grinding distribution to the fineness of slurry is 40 μ m, discharging, filtration, packing, make Comparative examples A component, saves backup.
Comparative example 2 is prepared the B component of comparative example high-solid epoxy resin anticorrosive coating
1. fill a prescription (not using aminosiloxane resin)
In the comparative example B of every 100 mass parts component, 50 parts of 50 parts of polymeric amide (Versmide v-140, cognis), mixed solvent (dimethylbenzene that mass ratio is 2:1 and butanols mixture).
2. preparation method
Mixed solvent is added in dispersion tank, under stirring, add polymeric amide, stir, filter, packing, obtains comparative example B component, saves backup.
Comparative example 3 is prepared comparative example high-solid epoxy resin anticorrosive coating
During use, the B component that the A component first comparative example 1 being made and comparative example 2 make stirs respectively, by mass parts, than for 100:20, takes respectively A component and B component, remix and stir after, slaking 15～30min can carry out application.
detect coating property
(1) detect the performance of coating own
1. method
Snappiness is pressed GB/T1731-1993 and is measured, and test plate (panel) is tinplate, coating thickness 20 ± 3 μ m;
Shock test is pressed GB/T1732-1993, and test plate (panel) is tinplate, thickness 20 ± 3 μ m;
Pull open method adhesion test by GB/T5210-2006, test plate (panel) is sandblast steel plate, thickness 320 ± 20 μ m.
2. detected result is in Table 1.
Table 1
As shown in Table 1, silicone hybrid anticorrosive coating of the present invention (embodiment 4 system) is because A component has been used the modified resin in technical scheme containing epoxy group(ing), and with by polymeric amide, DOW CORNING
the B component that aminosiloxane resin forms coordinates, and makes coating have good mechanical property to impact 50cm, snappiness 1mm, and sticking power 16Mpa, its film performance reaches the level of current high-solid epoxy resin anticorrosive coating (comparative example 3 systems).
(2) detect the matching property of coating and coating system
1. sample making
Test plate (panel) for detection of the matching performance of embodiment and comparative example paint coatings system is the sandblast steel plate that 3～5mm is thick;
A) model of non-zinc-rich coating system
By priming paint, intermediate coat and finish paint, form painting system, described each layer all adopts identical coating, the coating that embodiment 4 or comparative example 3 make, and every coating all sprays twice, build 320 ± 20 μ m of coating system;
B) model of zinc-rich coating system
The MC-SP-2 alcohol dissolubility zinc-rich coating of take is priming paint, the coating that embodiment 4 or comparative example 3 make is that intermediate coat and finish paint form coating system, its dry film zinc content >80% after priming paint spraying, thickness 90 μ m, then spray successively intermediate coat and finish paint, build 320 ± 20 μ m of coating system.
2. detection method
Resistance to salt water test is undertaken by GB/T1763;
Circulation weathering test is undertaken by the appendix A of ISO20340-2009.
Pull open method sticking power and place and test for 2 weeks after salt water resistance and circulation weathering test, test is undertaken by GB/T5210-2006;
3. detected result
A) non-zinc-rich coating system model
Use the model of silicone hybrid anticorrosive coating (embodiment 4 systems):
Initially pull open method sticking power 16Mpa;
Resistance to salt water test (4200 hours) outward appearance is non-foaming, non-corrosive; Pull open method sticking power 11Mpa;
Circulation weathering test (4200 hours) outward appearance is non-foaming, non-corrosive; Pull open method sticking power 13.6Mpa, monolateral expansion erosion 7.5mm;
Use the model of comparative example high-solid epoxy resin anticorrosive coating (comparative example 3 systems):
Initially pull open method sticking power 16.4Mpa;
Resistance to salt water test (4200 hours) outward appearance is non-foaming, non-corrosive; Pull open method sticking power 11.2Mpa;
Circulation weathering test (4200 hours) outward appearance is non-foaming, non-corrosive; Pull open method sticking power 8.1Mpa, monolateral expansion erosion 13.7mm;
From above-mentioned detected result:
Silicone hybrid anticorrosive coating of the present invention (embodiment 4) is in non-zinc-rich coating system, priming paint, intermediate coat and finish paint as coating system, this coating system has good sticking power and erosion resistance, especially resistance to expansion erosion performance is good, monolateral expansion erosion is 7.5mm, reach that ISO20340 requires≤technical indicator of 8mm, applicable ocean environment steel construction protection;
Comparative example high-solid epoxy resin anticorrosive coating (comparative example 3 system) in non-zinc-rich coating system, as priming paint, intermediate coat and the finish paint of coating system, the initial sticking power 16.4MPa of this coating system, salt water resistance performance might as well.But the performance of the cycle weathering test of coating system is not good: the sticking power of coating is down to 8.1Mpa, decline obviously, monolateral expansion erosion reaches 13.7mm, higher than in ISO20340≤technical requirements of 8mm.This shows that modified resin has obvious effect.
B) zinc-rich coating system model
Use the model of silicone hybrid anticorrosive coating (embodiment 4 systems):
Initially pull open method sticking power 12.8Mpa;
Resistance to salt water test (4200 hours) outward appearance is non-foaming, non-corrosive; Pull open method sticking power 10.5Mpa;
Circulation weathering test (4200 hours) outward appearance is non-foaming, non-corrosive; Pull open method sticking power 13.3Mpa, monolateral expansion erosion 2.8mm;
Use the model of comparative example high-solid epoxy resin anticorrosive coating (comparative example 3 systems):
Initially pull open method sticking power 13.5Mpa;
Resistance to salt water test (4200 hours) outward appearance is non-foaming, non-corrosive; Pull open method sticking power 8.2Mpa;
Circulation weathering test (4200 hours) outward appearance is non-foaming, non-corrosive; Pull open method sticking power 8.9Mpa, monolateral expansion erosion 4.2mm;
From above-mentioned detected result:
Silicone hybrid anticorrosive coating of the present invention (embodiment 4) is in zinc-rich coating system, as intermediate coat and finish paint, on zinc-rich coating, show excellent sticking power, circulation weathering test 4200h sticking power does not reduce rising on the contrary, coating has rear strengthening effect, and this is the technical characterstic of silicone hybrid coating just.Coating system is resisted corrosion, and to spread performance very excellent, monolateral expansion erosion 2.8mm, the technical requirements of reached in ISO20340≤3mm, silicone hybrid anticorrosive coating of the present invention is used on zinc rich primer, can give full play to the electro-chemical protection of inorganic zinc coating, the monolateral expansion erosion of coating is little, proves that silicone hybrid anticorrosive coating of the present invention can be used as intermediate coat and zinc rich primer supports the use;
Comparative example high-solid epoxy resin anticorrosive coating (comparative example 3 systems) is in zinc-rich coating system, as intermediate coat and finish paint, this coating system is loss of adhesion obvious through salt water resistant test and circulation weathering test coating, prove that the attachment fastness of this coating on zinc rich primer is inadequate, monolateral expansion erosion also obviously exceeds the standard range of ISO20340, is starkly lower than the corresponding performance of coating of the present invention.
Claims (4)
1. a silicone hybrid anticorrosive coating composition, is characterized in that, A component and B component, consists of, and A component is 100:20 with the mass parts ratio of B component;
A component is by epoxy resin, modified resin, pigment, filler, auxiliary agent and solvent composition, in the A of every 100 mass parts component, 20 parts of epoxy resin, 8～12 parts of modified resin, pigment and 50～55 parts of fillers, 1～3 part of auxiliary agent, surplus are mixed solvent, wherein, epoxy resin be low-molecular-weight bisphenol A-type or Bisphenol F type liquid epoxy one or more, modified resin is modifying epoxy resin by organosilicon, it is to contain 42 parts of tetraethoxys in every 100 mass parts materials, 8 parts of phenyltrimethoxysila,e, 4.5 parts of gamma-amino propyl trialkoxy silanes, 4 parts, water, 1.5 parts of hydrochloric acid, 25 parts of Virahols, 5 parts, 10 parts of E-51 epoxy resin and acetone are raw material, by tetraethoxy, phenyltrimethoxysila,e, Virahol adds in reaction vessel, be warming up to 40 ℃, start to drip the mixture of hydrochloric acid and water, after 1h dropwises, at 60～70 ℃ of insulation 4h, then add gamma-amino propyl trialkoxy silane, insulation 1h, formation contains amino silicone resin, under stirring, add again the solution of epoxy resin and acetone in batches, continue stirring reaction 4h, be cooled to normal temperature to make,
B component is comprised of polymeric amide, aminosiloxane resin, organic solvent, in the B of every 100 mass parts component, 50 parts of polymeric amide, 10～15 parts of aminosiloxane resins, surplus are mixed solvent, and wherein, polymeric amide is the low polymerization degree product of dimeracid and the many ammonia of many ethene; Aminosiloxane resin is DOW CORNING
2. according to the silicone hybrid anticorrosive coating composition described in right 1, it is characterized in that, the epoxy resin in described A component is one or more in E51, E44, F51; Pigment is one or more in titanium dioxide, carbon black, medium chrome yellow medium yellow, phthalocyanine blue; Filler is one or more in talcum powder, calcium carbonate, barium sulfate, silica powder, mica powder, Feldspar Powder, wollastonite powder, molochite; Auxiliary agent is one or more in dispersion agent, defoamer, thixotropic agent, anti-settling agent.
3. silicone hybrid anticorrosive coating composition according to claim 1, is characterized in that, the polymeric amide in described B component is a kind of in Versmide v-140, BS850A, 350A, and its amine value is at 300～400mgKOH/g.
4. silicone hybrid anticorrosive coating composition according to claim 1, is characterized in that, the mixed solvent using in A component and B component be dimethylbenzene and butanols mixture, both mass ratioes are 2:1.
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| CN201310565609.9A CN103602220B (en) | 2013-11-14 | 2013-11-14 | A kind of Siloxane hybrid anticorrosive paint |
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| CN113045919A (en) * | 2021-03-23 | 2021-06-29 | 石家庄市油漆厂 | Low-temperature curing high-solid epoxy coating and preparation method thereof |
| CN113045919B (en) * | 2021-03-23 | 2022-04-05 | 石家庄市油漆厂 | Low-temperature curing high-solid epoxy coating and preparation method thereof |
| CN114045051A (en) * | 2021-12-07 | 2022-02-15 | 常州威斯敦粘合材料有限责任公司 | Environment-friendly high-performance marble coating and preparation method thereof |
| CN115637094A (en) * | 2022-10-24 | 2023-01-24 | 中昊北方涂料工业研究设计院有限公司 | Protective coating system for cast magnesium alloy and preparation and use methods thereof |
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Address after: Chinese CNOOC Building No. 25 Beijing 100010 Dongcheng District Chaoyangmen North Street, room 1414 Applicant after: China National Offshore Oil Corporation Applicant after: CNOOC CHANGZHOU PAINT CHEMICAL RESEARCH INSTITUTE CO., LTD. Applicant after: CNOOC Energy Development Co., Ltd. Applicant after: CNOOC Changzhou EP Coating Co., Ltd. Address before: Chinese CNOOC Building No. 25 Beijing 100010 Dongcheng District Chaoyangmen North Street, room 1414 Applicant before: China National Offshore Oil Corporation Applicant before: CNOOC Changzhou Paint & Coatings Industry Research Institute Applicant before: CNOOC Energy Development Co., Ltd. Applicant before: CNOOC Changzhou EP Coating Co., Ltd. |
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Address after: China CNOOC Building No. 25 Beijing 100010 Dongcheng District Chaoyangmen North Street, room 1414 Co-patentee after: CNOOC CHANGZHOU PAINT CHEMICAL RESEARCH INSTITUTE Co.,Ltd. Patentee after: CHINA NATIONAL OFFSHORE OIL Corp. Co-patentee after: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. Co-patentee after: CNOOC CHANGZHOU EP COATING Co.,Ltd. Address before: China CNOOC Building No. 25 Beijing 100010 Dongcheng District Chaoyangmen North Street, room 1414 Co-patentee before: CNOOC CHANGZHOU PAINT CHEMICAL RESEARCH INSTITUTE Co.,Ltd. Patentee before: CHINA NATIONAL OFFSHORE OIL Corp. Co-patentee before: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. Co-patentee before: CNOOC CHANGZHOU EP COATING Co.,Ltd. |
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