CN1844272A - Method for producing nontoxic inorganic anti-rust anti-fouling ship bottom paint and its coating layer - Google Patents
Method for producing nontoxic inorganic anti-rust anti-fouling ship bottom paint and its coating layer Download PDFInfo
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- CN1844272A CN1844272A CN 200510063252 CN200510063252A CN1844272A CN 1844272 A CN1844272 A CN 1844272A CN 200510063252 CN200510063252 CN 200510063252 CN 200510063252 A CN200510063252 A CN 200510063252A CN 1844272 A CN1844272 A CN 1844272A
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Abstract
The invention provides a nontoxic inorganic rust preventive and anti-fouling shipbottom paint and a multi-layer overlayer. The invention provides a method for preparation of nontoxic inorganic rust preventive and anti-fouling bottom paint which is of good water resistance, salt endurance and drug tolerance and can be used in preventing the adherence of the microorganism in the seawater, which solves the multi-layer overlayer including nontoxic inorganic rust preventive shipbottom paint selecting crosslinked polymers of modified ethyl aluminosilicate, ground coat comprised by nontoxic inorganic rust preventive and anti-fouling shipbottom paint, intermediate layer and upper layer. The obtained paint can be used for any iron structures contacted with seawater such as marine and subbottom structure.
Description
Technical field
The present invention relates to a kind of nontoxic inorganic anti-rust, the manufacture method and the overlay thereof of anti-fouling ship bottom paint, this coating as carrier, is suitable for preventing getting rusty and preventing benthic adhering to of boats and ships, subbottom structure thing etc. with modified water glass.
Background technology
In the past as preventing that epibiota is attached to the method for boats and ships, subbottom structure thing etc. and the part of contact with sea water, what adopt is to add the big inorganic and organic toxic agent of toxicity and make it the method for slow stripping in the seawater in antifouling paint, but, therefore can't accomplish according to season, tsunami (stream) and the suitable antifouling effect of change of water quality performance owing to the dissolution rate that can not regulate as the toxic agent of antifouling effective constituent.
Under normal conditions, the toxic agent of a threshold quantity can only be contained in the antifouling paint, therefore approximately primary coating will be carried out in per 2 years; and because the stripping of toxic agent; can cause very serious pollution to seawater, therefore serious to the public hazards in marine site, aspect the global environment protection also be a bigger problem.A kind of anticorrosion nontoxicity ship-bottom paint is disclosed in English Patent GB02284822 (nineteen ninety-five), in European patent EP 0881269 (1998), disclose can make at normal temperatures paint solidification, can be used for preventing hull or the contaminated antifouling paint of subbottom structure thing, in the open WO9727751 (1997) of Japanese Patent, the material that is used for the anti-organic pollution of sealing as the antifouling paint use of fishing net and hull bottom is disclosed in addition.
Yet these are not complete inanimate matter coating, are the suitable mixtures of organic system and inorganic system.
In addition, as water glass is the solidifying agent of coating, known have phosphoric acid and as phosphatic polyphosphoric acid silicon, titanium phosphate with as the calcium oxide of metal oxide, aluminum oxide etc., and glass fibre, carbon fiber have been proposed as its strengthening agent, in addition a lot of relevant technology have also been proposed, but wherein all do not solve the essence defective of water glass class coating, promptly lack water tolerance and flexible problem.
In addition, proposed by solving the scheme of antirust antifouling problem with contact nobody with special functional the filming of inorganic silicic acid salt formation.
Recently, world's public hazards prevent that international body from just preventing that the marine site public hazards from having proposed to forbid the scheme of toxic antifouling paint, and have taked legal measure, but effective nontoxicity antifouling paint also do not occur so far.
Summary of the invention
The present invention be iron in the environments such as subsea is corroded before and propose adhering on the basis that survival condition studies of seabed settled organism, its purpose is to provide a kind of nontoxic inorganic anti-rust, the manufacturing technology and the overlay thereof of anti-fouling ship bottom paint.
Nontoxic inorganic anti-rust, the carrier of anti-fouling ship bottom paint are with the ethyl ester modified water glass polymkeric substance of manosil AS.This polymkeric substance is made up of water glass and tetraethyl silicate and sodium aluminate.
1) water glass is SiO
2/ Na
2The mol ratio of O is 2~5 alkali-metal aqueous silicate solution.
Alkali-metal silicate can dissociate in the aqueous solution, formation monomer, dimer or polymer colloidal ion, and it is as follows for its structure.
The concentration of the colloidal ion of silicate monomer is with SiO
2/ Na
2The increase of the mol ratio of O and increasing, and the rerum natura of filming also can improve thereupon.
2) manufacture method of tetraethyl silicate
At SiO
2/ Na
2The mol ratio of O is to add ethanol while stirring in 2~5 the sodium silicate aqueous solution, makes C
2H
5OH/SiO
2Mol ratio reach 0.1~0.5, and make tetraethyl silicate thus, its reaction formula is as follows.
3) manufacture method of sodium aluminate
In aluminum water solution, add sodium hydroxide, make Al
2O
3/ Na
2The mol ratio of O reaches 1.0~3.0, stirs 2~10 hours at 80 ℃ afterwards, and makes sodium aluminate thus.Its reaction formula is as follows.
4) tetraethyl silicate and the sodium aluminate that makes added in the sodium silicate solution, stirred 1~1.5 hour at 20~90 ℃, just can make the water glass polymkeric substance of modification, its structural formula is as follows.
Wherein, R
1Be C
2H
5, n is the mole number of water.
2. nontoxic inorganic anti-rust, anti-fouling ship bottom paint are made of priming paint, intermediate layer coating and last coating, and therefore above-mentioned manufacture method is the manufacture method of these three kinds of coating.
1) manufacturing of priming paint (rust proof paint)
Priming paint mixes manosil AS ethyl ester carrier and rust-preventive agent and weighting agent, and described weighting agent is that mica powder and kyanite constitute.
The characteristics of priming paint are with the tack and the rust-preventing characteristic of hull metallic surface good, and its ratio of components (weight ratio) is as follows.
Carrier: zinc powder: mica powder: kyanite=40~60 part: 30~50 parts: 2~5 parts: 2~5 parts, and the content of ambient cure promotor is for the weighting agent that comprises Fang Rust agent 2~5%.
The main technical characteristics of priming paint
Form and aspect and outward appearance: gray viscous liquid
The content of non-volatility component (%): 50~70
Viscosity (20 degree, No. 4 viscometers, second): 20~50
Surface drying time (hour): 0.5~1
The complete drying time (hour): below 24
Flexural strength (mm): below 5
Shock strength (kg/cm2): more than 40
Serviceable time (hour): below 3
2) manufacturing of intermediate layer coating (rust proof paint)
Intermediate layer coating mixes rust-preventive agent and weighting agent in manosil AS ethyl ester carrier, wherein said weighting agent is made of mica powder, kyanite, zeolite, barite.
The characteristics of intermediate layer coating are to film with priming paint and to go up consistency, tack and rust-preventing characteristic that coating films good, and its ratio of components (weight ratio) is as follows.
Carrier: zinc powder: mica powder: kyanite: zeolite=40~60 part: 20~30 parts: 5~10 parts: 5~10 parts: 3~7 parts, the content of ambient cure promotor with respect to comprise Fang Rust agent weighting agent for 2~5%.
The main technical characteristics of intermediate layer coating
Form and aspect and outward appearance: gray viscous liquid
The content of non-volatility component (%): 50~70
Viscosity (20 degree, No. 4 viscometers, second): 20~25
Surface drying time (hour): below 1
The complete drying time (hour): below 24
Flexural strength (mm): below 5
Shock strength (kg/cm
2): more than 40
Serviceable time (hour): below 3
3) the upward manufacturing of coating (antifouling paint)
Last coating mixes stain control agent, anti-Rust agent, weighting agent and inorganic color and forms in manosil AS ethyl ester carrier, wherein said weighting agent is to be made of mica powder, kyanite, zeolite, barite, and described needed inorganic color is the chromic oxide (Cr as metal oxide
2O
3), ferric oxide (Fe
2O
3), titanium oxide (TiO
2), and lead chromate (PbCrO
4PbSO
4), ultramarine (Na
6AlSi6O
24S
4) etc.
The characteristics of last coating are good with the consistency and the tack of intermediate layer coating, and the physical strength of filming and resistance to salt water, chemical proofing are good, and its ratio of components (mass ratio) is as follows.
Carrier: pure aluminium silicate: zinc powder: barite: mica powder: kyanite=40~60 part: 30~50 parts: 5~10 parts: 6~13 parts: 5~10 parts: 5~10 parts, the content of ambient cure promotor is 2~5% with respect to weighting agent.
The addition of needed inorganic color is equivalent to remove in the material of coating on constituting
Unload 20% amount of all powdered material mixture amounts beyond the body.
The main technical characteristics of last coating
Form and aspect and outward appearance: versicolor viscous liquid
The content of non-volatility component (%): 50~60
Viscosity (20 degree, No. 4 viscometers, second): 20~25
Surface drying time (hour): 0.5~1
The complete drying time (hour): below 24
Flexural strength (mm): below 5
Shock strength (kg/cm
2): more than 40
Serviceable time (hour): below 3
3. the manufacturing of ambient cure promotor
Ambient cure promotor mixes muriates such as zinc chloride, calcium chloride, sodium-chlor and sodium sulphite anhydrous 99.3 and oxalic acid at normal temperatures.
The characteristics of ambient cure agent promotor are can coating is cured at short notice, and its ratio of components (weight ratio) is as follows:
Zinc chloride: calcium chloride: sodium-chlor: sodium sulphite anhydrous 99.3: oxalic acid=70~80 part: 2~3 parts: 8~9 parts: 8~9 parts: in 0.1~1 part the scope.
4. nontoxic inorganic anti-rust, the coating structure of anti-fouling ship bottom paint and overlay should solve following basic problem earlier if will realize the purpose of nontoxic inanimate matter antifouling paint.
1. film to tack, rust-preventing characteristic and the didirtresistance of hull metallic surface;
2. film stability under various ocean conditions and salinity condition;
3. can be anti-in colliding, scrape off, impact and the obdurability of filming and the physical strength of other external force;
4. coating easily, and working procedure of coating is simple, films to have flatness.
In the present invention, design by formation and coating structure ship-bottom paint, reached that can to make full use of with the ethyl ester modified water glass of manosil AS be the purpose of the excellent specific property of coating, and introduced the triplex coating layer that is suitable for this coating, thereby solved above-mentioned basic problem fully.
Formation angle from coating, nontoxic inorganic anti-rust of the present invention, anti-fouling ship bottom paint are made of priming paint, intermediate layer coating and last coating, also carry out according to priming paint overlay, intermediate layer coating overlay and this triplex coating layer of upper strata applying coating layer when therefore constructing.In addition, the formation angle from filming is made of anti-rust coating and antifouling coat.
Priming paint is that rust proof paint constitutes by the inanimate matter zinc powder, can guarantee the tack of hull metallic surface and rust-preventing characteristic and the consistency of filming with intermediate layer coating.The thickness of the desciccator diaphragm that is made of this priming paint is 90~105 microns.
Intermediate layer coating is made of complete inanimate matter coating, can guarantee to film with priming paint and goes up consistency that coating films and tack and to the rust-preventing characteristic of hull metallic surface, also can making films has obdurability and high mechanical strength.The thickness of the desciccator diaphragm that is made of this intermediate layer coating is 30~35 microns.
Last coating is made of consistency of filming with intermediate layer coating and the high complete inanimate matter Nonpoisonous, non-environmental-pollution antifouling paint of tack, resistance to salt water and physical strength.The thickness of the desciccator diaphragm that is made of coating on this is 60~70 microns.
In the present invention, the coating structure of nontoxic inorganic anti-rust, anti-fouling ship bottom paint is designed to anti-rust coating and antifouling coat, and has formed by priming paint, intermediate layer coating, the triplex coating layer of going up coating and to be suitable for this coating structure and modified water glass is the overlay of coating characteristic.
Priming paint, intermediate layer coating, last coating all can be implemented coating by any coating method in spraying, brushing, the roller coat.
At this moment, the thickness of the dry coating of non-toxic and non-pollution inorganic anti-rust, anti-fouling ship bottom paint is 180 to 200 microns.
5. embodiment
1. test film test
Test film specification: 500 * 500 * 8mm
Test place: waters, the Korea Xihai sea
Duration of test: 18 months
The nontoxic inorganic anti-rust that uses when making test film, composition and its ratio of components of anti-fouling ship bottom paint are as follows:
Carrier
Water glass is SiO
2/ Na
2The mol ratio of O is 2.8 alkali-metal aqueous silicate solution.In described aqueous silicate solution, add ethanol and stirring, make C
2H
5OH/SiO
2Mol ratio reach 0.3, and prepare tetraethyl silicate thus.
In addition, in aluminum water solution, add sodium hydroxide, make Al
2O
3/ Na
2The mol ratio of O reaches 1.5, stirs 6 hours the preparation sodium aluminate afterwards down at 80 ℃.
Prepared tetraethyl silicate and sodium aluminate are added in the sodium silicate solution, stir 1 hour preparation modified water glass polymkeric substance (carrier) down at 80 ℃.
Ambient cure promotor
Use zinc chloride: calcium chloride: sodium-chlor: sodium sulphite anhydrous 99.3: oxalic acid=79 part: 2.8 parts: 9 parts: 9 parts: 0.2 part ratio of components, mix at normal temperatures and prepare.
Priming paint (rust proof paint)
With carrier: zinc powder: mica powder: kyanite=50 part: 43 parts: 2.5 parts: 2.5 parts ratio of components, in the coating that mixes at normal temperatures and prepare, add 2% the ambient cure promotor be equivalent to the filling dose that comprises rust-preventive agent that cooperated in this coating, be used for the making of test film.
The dried film thickness of priming paint is 100 microns.
Intermediate layer coating (rust proof paint)
With carrier: zinc powder: mica powder: kyanite: zeolite=50 part: 23 parts: 8 parts: 8 parts: in the coating that 8 parts ratio of components is made, add 3% the ambient cure promotor be equivalent to the filling dose that comprises rust-preventive agent that cooperated in this coating, be used for the making of test film.
The thickness of intermediate layer coating is 35 microns.
Last coating (antifouling paint)
With carrier: pure aluminium silicate: zinc powder: barite: mica powder: kyanite=50 part: 32 parts: 5 parts: 6 parts: 2 parts: in the coating that 2 parts ratio of components is made, add 3% the ambient cure promotor be equivalent to the filling dose that comprises rust-preventive agent and stain control agent that cooperated in this coating, be used for the making of test film.。
The addition of needed inorganic color is equivalent to remove in the coating 20% amount of all powdered material mixture amounts beyond the carrier on constituting.
The thickness of last coating is 70 microns.
The applying coating of made on test film, is solidified and carried out simultaneous test after 7 days.
Table 1
The coating name | Nontoxic inorganic anti-rust, anti-fouling ship bottom paint | China's bitumen carrier base paint 832 | ||
Distinguish | Number (only) | Weight in wet base (g) | Number (only) | Weight in wet base (g) |
The settled organism number | 6 | 14.15 | 15 | ?69.2 |
As shown in Table 1, nontoxic inorganic anti-rust, anti-fouling ship bottom paint of the present invention have very good anti-fouling effect.
2. actual hull test
Subjects: defend asterisk (3750 tonnes, freighter)
Test place: the Korea Xihai sea, the Korea East Sea, straits, Japanese Okinawa
Duration of test: year June in April, 2000 to 2004
Composition and its ratio of components of the nontoxic inorganic anti-rust of use, anti-fouling ship bottom paint are as follows in this test:
Carrier
Water glass is SiO
2/ Na
2The mol ratio of O is 2.9 alkali-metal aqueous silicate solution.In described aqueous silicate solution, add ethanol and stirring, make C
2H
5OH/SiO
2Mol ratio reach 0.25, and prepare tetraethyl silicate thus.
In addition, in aluminum water solution, add sodium hydroxide, make Al
2O
3/ Na
2The mol ratio of O reaches 2, stirs 7 hours the preparation sodium aluminate afterwards down at 80 ℃.
Prepared tetraethyl silicate and sodium aluminate are added in the sodium silicate solution, stir 1.5 hours preparation modified water glass polymkeric substance (carrier) down at 80 ℃.
Ambient cure promotor
Use zinc chloride: calcium chloride: sodium-chlor: sodium sulphite anhydrous 99.3: oxalic acid=79.2 part: 3 parts: 8.8 parts: 8.8 parts: 0.2 part ratio of components has prepared ambient cure promotor.
Priming paint (rust proof paint)
With carrier: zinc powder: mica powder: kyanite=50 part: 44 parts: 2 parts: 2 parts ratio of components mixes and in the coating made at normal temperatures, add 2% the ambient cure promotor be equivalent to the weighting agent that comprises rust-preventive agent that cooperated in this coating, be used for the making of test film.
The dried film thickness of priming paint is 100 microns.
Intermediate layer coating (rust proof paint)
With carrier: zinc powder: mica powder: kyanite: zeolite=50 part: 25 parts: 7.5 parts: 7.5 parts: 7 parts ratio of components mixes and in the coating made at normal temperatures, add 3% the ambient cure promotor be equivalent to the weighting agent that comprises rust-preventive agent that cooperated in this coating, be used for the making of test film.
The thickness of intermediate layer coating is 35 microns.
Last coating (antifouling paint)
With carrier: pure aluminium silicate: zinc powder: barite: mica powder: kyanite=50 part: 30 parts: 6 parts: 7 parts: 2 parts: 2 parts ratio is mixed and in the coating made at normal temperatures, add 3% the ambient cure promotor be equivalent to the weighting agent that comprises rust-preventive agent and stain control agent that cooperated in this coating, be used for the making of test film.
The dried film thickness of last coating is 70 microns.
Test-results is found not get rusty, and average every square meter is attached with 4 to 6 microorganisms, but its sticking power is less, is enough to extract with hand.
In addition, has the speed of ship improved 0.7 because the coating characteristic of coating of the present invention in seawater? / hour.
Claims (12)
1. nontoxic antirust, the anti-fouling ship bottom paint of a coating and the multilayer hull bottom overlay that forms comprises undercoat, inter coat, goes up coating is characterized in that:
Described undercoat and inter coat are to use inorganic anti-rust ship-bottom paint (I) respectively, and form to wherein adding ambient cure agent III,
Described upward coating is added ambient cure agent (III) and is formed in inanimate matter anti-fouling ship bottom paint (II), wherein
Described inorganic anti-rust ship-bottom paint (I) is mixed by carrier, rust-preventive agent, weighting agent and to constitute, and when it forms undercoat when using coating, the ratio of components of described carrier, rust-preventive agent and weighting agent is 40~60 parts: 30~50 parts: 2~10 parts by weight; When it forms inter coat when using coating, the ratio of components of described carrier, rust-preventive agent and weighting agent is 40~60 parts: 20~30 parts: 3~27 parts by weight;
Described inanimate matter anti-fouling ship bottom paint (II), mixing the inorganic color that needs in carrier, stain control agent, rust-preventive agent, weighting agent makes, and the ratio of components of described carrier, stain control agent, rust-preventive agent, weighting agent and inorganic color is 40~60 parts: 30~50 parts: 5~10 parts: 5~33 parts: 10~20 parts by weight;
Described carrier all adopts the carrier of polymer system of the crosslinking structure of modification manosil AS ethyl ester;
Total film thickness is 180~200 microns behind the dried coating film of described overlay.
2. multilayer coated layer according to claim 1 is characterized in that:
Described carrier is with tetraethyl silicate and sodium aluminate silicate polymer to be carried out rust proof paint and antifouling paint carrier after the modification.
3. multilayer coated layer according to claim 1 and 2 is characterized in that:
Described carrier is at SiO
2/ Na
2The mol ratio of O is in 2~5 the sodium silicate aqueous solution, to add the C as properties-correcting agent respectively
2H
5OH/SiO
2Mol ratio be 0.1~0.5 tetraethyl silicate and Al
2O
3/ Na
2The mol ratio of O is behind 1.0~3.0 the sodium aluminate aqueous solution, under 20~90 ℃ temperature of reaction, stir to react in 1~1.5 hour to form, and the structural formula of described carrier is as follows,
Wherein, R
1Be C
2H
5, n is the mole number of water.
4, multilayer coated layer according to claim 1 is characterized in that:
Described rust-preventive agent is zinc powder.
5. multilayer coated layer according to claim 1 is characterized in that:
The stain control agent of described nontoxic inanimate matter anti-fouling ship bottom paint is a pure aluminium silicate, and described pure aluminium silicate is that structural formula is M (I)
2OAl
2O
3NSiO
2MH
2O, wherein M (I) is 1 valency metallic cation, n is Al
2O
3/ SiO
2Mol ratio, in 0.2~2.0 scope, m is the mole number of water.
6, multilayer coated layer according to claim 1 is characterized in that described weighting agent is mica powder, kyanite, zeolite, barite; Wherein
When the priming paint of nontoxic inanimate matter anti-fouling ship bottom paint (I), constitute by mica powder, kyanite, during intermediate layer coating, constitute by mica powder, kyanite, zeolite;
When nontoxic inanimate matter anti-fouling ship bottom paint (II), constitute by barite, mica powder, kyanite.
7. multilayer coated layer according to claim 1, it is characterized in that: wherein said nontoxic inanimate matter anti-fouling ship bottom paint (II), contain required inorganic color, described inorganic color is chromic oxide, ferric oxide, titanium oxide and lead chromate, the ultramarine as metal oxide.
8. multilayer coated layer according to claim 1, it is characterized in that: the ambient cure agent (III) that cooperates in the described coating, be made of zinc chloride, calcium chloride, sodium chloride muriate and sodium sulphite anhydrous 99.3 and oxalic acid, its ratio of components is a zinc chloride: calcium chloride: sodium-chlor: sodium sulphite anhydrous 99.3: oxalic acid=70~80 part: 2~3 parts: 8~9 parts: 8~9 parts: 0.1~2 part.
9. multilayer coated layer according to claim 8 is characterized in that: the use level of described ambient cure agent is with respect to 2~5% of the filling dose that is cooperated in nontoxic inorganic anti-rust ship-bottom paint (I) and nontoxic inanimate matter anti-fouling ship bottom paint (II).
10. the formation method of the described non-toxic and non-pollution inorganic anti-rust of claim 1, the multilayer coated layer of antifouling hull bottom is characterized in that: may further comprise the steps:
1) preparation of carrier:
At SiO
2/ Na
2The mol ratio of O is in 2~5 the sodium silicate aqueous solution, to add the C as properties-correcting agent respectively
2H
5OH/SiO
2Mol ratio be 0.1~0.5 tetraethyl silicate and Al
2O
3/ Na
2The mol ratio of O is behind 1.0~3.0 the sodium aluminate aqueous solution, stirs to react in 1~1.5 hour and form the polymer system carrier of the crosslinking structure of the modification manosil AS ethyl ester of being made up of water glass and tetraethyl silicate and sodium aluminate under 20~90 ℃ temperature of reaction;
2) nontoxic inorganic anti-rust, the preparation of anti-fouling ship bottom paint:
In the polymer system carrier and rust-preventive agent of the crosslinking structure of modification manosil AS ethyl ester, interpolation is by weighting agent and needed inorganic color that mica powder, kyanite constitute, mixes at normal temperatures and is mixed with the priming paint of nontoxic inorganic anti-rust ship-bottom paint;
At the polymer system carrier of the crosslinking structure of modification manosil AS ethyl ester with in the Fang Rust agent, add constitute by mica powder, kyanite, zeolite and weighting agent, mix at normal temperatures and be mixed with the intermediate layer coating of inorganic anti-rust ship-bottom paint;
In the polymer system carrier of the crosslinking structure of modification manosil AS ethyl ester and stain control agent, rust-preventive agent, weighting agent that interpolation is made of barite, mica powder, kyanite and required inorganic color mix at normal temperatures and are mixed with the last coating of nontoxic inanimate matter anti-fouling ship bottom paint;
3) by above-mentioned 2) in the coating that obtains, add 2~5% ambient cure agent respectively with respect to the filling dose that comprises rust-preventive agent and stain control agent, and form respectively with conventional coating method film, after the drying, obtain having undercoat, inter coat and 3 layers multilayer coated layer going up coating
Total thickness behind the dried coating film of described overlay is 180~210 microns.
11. the formation method of multilayer coated layer according to claim 10 is characterized in that:
The formation of filming of wherein said undercoat, inter coat, last coating is to be undertaken by arbitrary method of spraying, brushing or roller coat.
12., go for all iron structures of boats and ships, subbottom structure thing, bottom culture field, canal etc. and contact with sea water according to each described nontoxic inorganic anti-rust in the claim 1~8, the multilayer coated layer of antifouling hull bottom.
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101864240A (en) * | 2010-06-13 | 2010-10-20 | 徐友志 | Self-releasing anti-fouling ship paint suitable for marine environment and preparation method and application thereof |
WO2017020147A1 (en) * | 2015-08-03 | 2017-02-09 | 天津纳微华瑞科技有限公司 | Cationic type antifouling and anti-drag composite functional paint and coating |
-
2005
- 2005-04-07 CN CN 200510063252 patent/CN1844272A/en active Pending
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101864240A (en) * | 2010-06-13 | 2010-10-20 | 徐友志 | Self-releasing anti-fouling ship paint suitable for marine environment and preparation method and application thereof |
CN101864240B (en) * | 2010-06-13 | 2012-08-08 | 徐友志 | Self-releasing anti-fouling ship paint suitable for marine environment and preparation method and application thereof |
WO2017020147A1 (en) * | 2015-08-03 | 2017-02-09 | 天津纳微华瑞科技有限公司 | Cationic type antifouling and anti-drag composite functional paint and coating |
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