CN1618893A - Water moistening type non-toxic antifouling paint and its preparation method - Google Patents
Water moistening type non-toxic antifouling paint and its preparation method Download PDFInfo
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- CN1618893A CN1618893A CN 200310113364 CN200310113364A CN1618893A CN 1618893 A CN1618893 A CN 1618893A CN 200310113364 CN200310113364 CN 200310113364 CN 200310113364 A CN200310113364 A CN 200310113364A CN 1618893 A CN1618893 A CN 1618893A
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Abstract
A water-wettable non-toxic anti-fouling paint without pollution is composed of the hydroscopic priming paint containing paint and hydroscopic resin and the porous surface paint containing paint and water-soluble compound. It can prevent the ocean living things from being attached on object.
Description
Technical field
The invention belongs to the antifouling paint field, particularly a kind of nontoxic pollution-free is met water wet type antifouling varnish.
Background technology
Boats and ships are in the ocean environment for a long time, and seawater is more than the land intensive to corrosion of metal.Marine paint is the tailor-(made) coating on the boats and ships, is used for protecting marine iron structures such as ship, naval vessel, offshore drilling platforms, harbour piling bar etc. not to be subjected to sea-water corrosion.Antifouling varnish is a kind of special coating that is coated on hull bottom and ocean underwater facility.Its main effect is that the modes such as the oozing out of material, diffusion or hydrolysis of poisoning by paint film progressively discharge the poison material, reaches to prevent that marine attaching organism is attached to the purpose of hull bottom or ocean underwater facility.
Of a great variety in the ocean attached to the settled organism on hull and the ocean underwater facility, it can bring a lot of troubles and financial loss to the mankind, in the time of on attached to the boats and ships housing, it can make running resistance increase, thereby increase fuel consumption, cause loss economically, not only endanger the work-ing life of boats and ships, and especially serious to the threat on military naval vessel.
The mechanism of action of antifouling varnish is behind the poison material and contact with sea water in the paint film, with the form of lewis' acid, progressively to the seawater dissolving, forms the thin layer of poisonous solution at coating surface, and in the immobilized seawater, its thickness is about tens microns.The lewis' acid of " thin layer " toxic substance can repel or kill sporozoite or larva that attempt is docked to the marine attaching organism on the paint film.
In recent years,, ecotope and human beings'health have been constituted great threat with existence, started the tide of protecting environment at present in the world because environmental pollution is serious day by day.This all is a new challenge to all trades and professions, and is all the more so concerning the marine finish industry.World economy develop rapidly, maritime industry are prosperous day by day, and shipping amount in ocean also increases thereupon.Yet consequent problem is protective system and the antifouling paint that all scribbles toxic substances such as containing various poison material, heavy metal compound on the hull of these ship's and crafts; these objectionable impuritiess have caused serious pollution to ocean environment; in order to adapt to development of times and requirement on environmental protection, the exploitation environment-friendly type coating has become the major objective of each marine finish production firm.China National Bureau of Oceanography also classifies developmental research non-toxic anticorrosion technology as the emphasis schedule in the new millennium agenda of formulating.
U.S. Chemical ﹠amp; Engineering News magazine report in November calendar year 2001: answer ocean environment to protect the requirement of the council, International Navigation Transportation Organization (IMO) passes a resolution, and requires to forbid in the world being coated with the paint that contains tributyl tin organic tin compounds such as (TBT) at boats and ships from January 1st, 2003; From on January 1st, 2008, all operation naval vessels all must not re-use this type of paint.
Organic tin application of compound scopes such as TBT are wider, are mainly used in the stain control agent in the marine paints, with apposition growths such as preventing microorganism, plant, animals in hull; The anticorrosion and bactericidal agent that also is used for textiles (wrapping up in large scale industry textiless such as canvas as tent, truck outward), leatherware, timber etc. in addition.But organic tin human body such as TBT and environment all have very big harm.
Therefore, many novel anti-fouling materials begin to be applied to ship bottom anti-fouling paint and substitute organic tin.Mainly contain following several solution at present, one: improve the content of Red copper oxide poison material in the antifouling varnish, reach identical effect.Shortcoming is to cause cost to increase, and the rate of release of Red copper oxide is fast, will increase the coat-thickness of antifouling varnish, and benefit further descends.Two: adopt biological stain control agent, adopting many at present is peppery element.As the Chinese patent publication number is the natural stain control agent of the pungent type of employing of CN1296044A report.The Chinese patent publication number is the peptides that extracts in the alkaloid that extracts in the employing marine alga of CN1392208A report and the spongy biological in addition.The material of these alternative organic tins still adopts the mechanism of poisoning, and marine organisms are had bigger harm.
Summary of the invention
It is environmental protection that one of purpose of the present invention provides a kind of, can play again to prevent the chance water wet type nontoxic antifouling paint of marine organisms attached to ocean underwater facilities such as hulls, to overcome the defective of existing antifouling paint contaminate environment; And prepared coating has, and chance water is moistening, smooth, the character of low resistance.
A further object of the present invention provides a kind of method of meeting water wet type nontoxic antifouling paint of using High hydrophilous resin to combine with marine anti-fouling paint to prepare.
Marine organisms are to make it to be attached on body surface by self excretory adhering liquid, at this phenomenon, the present invention has adopted a kind of new anti-adhesion mechanism, change the contact angle of marine organisms adhering liquid with retouching agent and tensio-active agent, to eliminate marine organisms, make the ocean underwater facility have soft-surface, and contain a large amount of water layer (skin of similar hydrocoles) attached to the ability on the object, to weaken halobiontic sticking power, even also can break away from by very fast quilt after adhering to.This coating does not contain any toxic substance, can not cause environmental pollution and biological the murder by poisoning.
Chance water wet type nontoxic antifouling paint of the present invention is made up of water-absorbent priming paint and porosity surface coating, described water-absorbent priming paint is mixed with High hydrophilous resin by paint and forms, wherein paint accounts for 10wt%～90wt%, and High hydrophilous resin accounts for 90wt%～10wt%; Described water-absorbent surface coating material is made up of paint and water-soluble cpds, and wherein, paint accounts for 20wt%～95wt%, and water-soluble cpds accounts for 80wt%～5wt%.
Chance water wet type nontoxic antifouling paint preparation method step of the present invention comprises:
One. the preparation of water-absorbent priming paint and application
The paint that accounts for water-absorbent priming paint gross weight 10wt%～90wt% is mixed with the High hydrophilous resin that accounts for water-absorbent priming paint gross weight 90wt%～10wt%, stir, make the water-absorbent priming paint, wherein, the particle diameter of High hydrophilous resin is 30 orders～3000 orders.
High hydrophilous resin is coated on the good matrix surface of cleaning with after paint mixes, and places certain hour and make it drying.High hydrophilous resin must be uniformly dispersed during stirring, prevent that it from reuniting causing partial overplumping, the homogeneity of coating surface is damaged.And partial overplumping might break through the constraint of porous surface layer, causes become estranged coating surface cracking of water-absorbing resin excess flow.In making coating, should adopt short grained High hydrophilous resin to reach homodisperse.And the water absorbent rate of High hydrophilous resin does not require very high.
Two. the preparation of porosity surface coating and application
The paint that accounts for porosity surface coating gross weight 20wt%～95wt% is mixed with the water-soluble cpds that accounts for porosity surface coating gross weight 80wt%～5wt%, stir, make porosity surface coating.
Water-soluble cpds is coated on the surface of water-absorbent priming paint with after paint mixes, and places certain hour and make it drying.
Coating of the present invention all will eliminate rust coated body material when concrete coating, applies priming paint after the cleaning again.The body material that is suitable for has iron and steel, wood, and concrete, pottery etc. generally need the material of protection.
The present invention has two compound coatings, and base coat contains meets the moistening material of water, and extexine contains water-soluble substances.Paint in the two composite bed coating can be selected with a kind of paint, also can select paint not of the same race.
Described paint can be various paint such as asphalt rubber lacquer, chloroprene rubber lacquer, acrylic acid resin paint, polyurethane paint, polyester lacquer, alkyd varnish, pyroxylin(e)finish, epoxy resin-based paint, natural resin paint, silicone rubber kinds lacquer or other elementary organic paint.
The key of base coat is to contain High hydrophilous resin, and the suction back generates a loose waterbearing stratum on the surface, completely cut off halobiontic adhering to.
High hydrophilous resin is a kind of functional high molecule material.It is different with traditional water-absorbing material, can the heavy hundred times of specific absorption self to several thousand times water, when being in the suction state, good water-retaining property, water can therefrom not overflow yet under pressure, and traditional water-absorbing material can only absorb the water of more than 20 times of own wt, and its high-hydroscopicity is main relevant with the distribution of its chemical structure and the polarity group in the state of aggregation, and it has the hydrophilic three-dimensional space network structure of low crosslinking degree.
Described High hydrophilous resin mainly contains starch system, cellulose-based, synthetic resins system or their any mixture by raw material sources classification.
Described starch system is to be selected from starch-grafted third rare nitrile, starch-grafted acrylic acid salt, starch-grafted third rare acid amides, carboxymethylated starch, starch, acrylic acid, third rare acid amides, br dilute anhydride graft copolymer wherein a kind of or their any mixture etc.
Cellulose-based have: carboxymethylation Mierocrystalline cellulose, cellulose graft third rare nitrile, cellulose graft acrylic acid salt or the sulfonated grafting acrylic acid of Mierocrystalline cellulose salt etc.
Synthetic resins system has: polypropylene hydrochlorate, polyacrylamide, acrylic acid and third rare acid amides copolymerization product, polyvinyl alcohol-acid anhydrides copolymerzation with cross-linking product, polyvinyl alcohol-acrylic acid graft copolymerization product or vinyl acetate between to for plastic-acrylic acid fat copolymerization hydrolysate etc.
In order to prevent the loss of High hydrophilous resin, at the surface applied layer protective layer of High hydrophilous resin.The present invention adopts the water-soluble cpds of the certain content of (protective layer) interpolation on the top layer; immerse water-soluble the taking off of back water-soluble cpds chance in the water; produce trickle hole; both can allow water-absorbing resin touch moisture; can produce constraint to water-absorbing resin again; be fixed in the surface, reduce the loss of water-absorbing resin.
Described water-soluble cpds can be polyoxyethylene glycol, polyvinyl alcohol or their materials such as any mixture.
Two composite beds of the present invention, bottom includes High hydrophilous resin, can produce softness after the suction, slick upper layer, the skin of similar fish.Softish is rich in surface layer of water can allow marine organisms not have attachment point, is difficult to be fixed on the surface.Slick low resistance surface energy reduces running resistance, makes the boats and ships operation more economical.The top layer is one deck porous surface, can allow seawater infiltrate, and High hydrophilous resin is produced fixed action, prevents that High hydrophilous resin from coming off, running off.
The present invention has following characteristics:
High hydrophilous resin in the coating in immersing water after, can water-swelling, produce a softish, rich aqueous top layer allows marine organisms not have attachment point, can't adhere to.And nontoxic, pollution-free, can protect environment.
2. after the coating water-swelling, moistened surface reduces with the contact angle of water, forms a slick top layer, can reduce resistance, to ship's navigation generation favorable influence.
3. after water-soluble cpds dissolves in the upper layer of two coatings, can produce porous surface in water, can either allow water-absorbing resin expand, can reduce the loss of water-absorbing resin to working the constraint effect that produces again.
Embodiment
Embodiment 1. meets the preparation of the moistening polyurethane paint of water
1. the preparation of water-absorbent priming paint.Adding 2.11 gram particles in 36.17 gram polyurethane paints directly is 50 order crosslinked polypropylene diluted acid sodium High hydrophilous resins.Be coated on ceramic surface after stirring, place under the natural condition and made it dry in 24 hours.
2. the preparation of porosity surface coating.In 11.86 gram polyurethane paints, add polyoxyethylene glycol (molecular weight 600) 0.23 gram, stir.Treat to be coated on the surface after the priming paint drying.Place and made it complete drying in 24 hours.
3. performance test.Measuring as above, the contact angle of coatingsurface and water is 98.9 °.Be soaked in the distilled water after 48 hours, its surface energy form one smooth, soft top layer.Taking out the contact angle of measuring top layer and water is 41.9 °.
Embodiment 2. meets the preparation of the moistening polyurethane paint of water
1. the preparation of water-absorbent priming paint.Adding 0.56 gram particle in 11.28 gram polyurethane paints directly is the rare acid amides of 500 order crosslinked polypropylenes.Be coated on ceramic surface after stirring, placed 24 hours under the natural condition.
2. the preparation of porosity surface coating.In 11.86 gram polyurethane paints, add polyoxyethylene glycol (molecular weight 600) 0.23 gram, stir.Treat to be coated on the surface after the priming paint drying.Place and made it complete drying in 24 hours.
3. performance test.Measuring as above, the contact angle of coatingsurface and water is 96.3 °.Be soaked in the distilled water after 48 hours, its surface energy form one smooth, soft top layer.Taking out the contact angle of measuring top layer and water is 43.1 °.
Embodiment 3. meets the preparation of the moistening polyurethane paint of water
1. the preparation of water-absorbent priming paint.Adding 2.11 gram particles in 36.17 gram polyurethane paints directly is 1000 order crosslinked polypropylene diluted acid sodium High hydrophilous resins.Be coated on the iron plate surface after stirring, placed 24 hours under the natural condition.
2. the preparation of porosity surface coating.In 10.83 gram polyurethane paints, add polyoxyethylene glycol (molecular weight 600) 0.52 gram, stir.Treat to be coated on the surface after the priming paint drying.Place and made it complete drying in 24 hours.
3. performance test.Measuring as above, the contact angle of coatingsurface and water is 84.1 °.Be soaked in the distilled water after 48 hours, its surface energy form one smooth, soft top layer.Taking out the contact angle of measuring top layer and water is 38.9 °.
Embodiment 4. meets the preparation of the moistening polyurethane paint of water
1. the preparation of water-absorbent priming paint.Adding 2.11 gram particles in 36.17 gram polyurethane paints directly is 2000 order crosslinked polypropylene diluted acid sodium High hydrophilous resins.Be coated on the iron plate surface after stirring, placed 24 hours under the natural condition.
2. the preparation of porosity surface coating.In 9.44 gram polyurethane paints, add polyvinyl alcohol (molecular weight 1000) 0.95 gram, stir.Treat to be coated on the surface after the priming paint drying.Place and made it complete drying in 24 hours.
3. performance test.Measuring as above, the contact angle of coatingsurface and water is 87.0 °.Be soaked in the distilled water after 48 hours, its surface energy form one smooth, soft top layer.Taking out the contact angle of measuring top layer and water is 48.6 °.
Embodiment 5. meets the preparation of the moistening bituminous ship bottom anti-fouling paint of water
1. the preparation of water-absorbent priming paint.Adding 2.68 gram particles in 26.81 gram bituminous ship bottom anti-fouling paints directly is 3000 order crosslinked polypropylene diluted acid sodium High hydrophilous resins.Be applied to the iron plate surface after stirring, place 48 hours dryings under the natural condition.
2. the preparation of porosity surface coating.In 24.39 gram bituminous ship bottom anti-fouling paints, add 1.24 gram polyoxyethylene glycol (molecular weight 600), stir.Treat to be coated on the surface after the priming paint drying.Place and made it complete drying in 48 hours.
3. performance test.Measuring as above, the contact angle of coatingsurface and water is 79.7°。Be soaked in the distilled water after 48 hours, its surface energy form one smooth, soft top layer.Taking out the contact angle of measuring top layer and water is 40.9 °.
Claims (10)
1. meet water wet type nontoxic antifouling paint for one kind, it is characterized in that: described coating is made up of water-absorbent priming paint and porosity surface coating, described water-absorbent priming paint is mixed with High hydrophilous resin by paint and forms, wherein paint accounts for 10wt%～90wt%, and High hydrophilous resin accounts for 90wt%～10wt%; Described water-absorbent priming paint is made up of paint and water-soluble cpds, and wherein, paint accounts for 20wt%～95wt%, and water-soluble cpds accounts for 80wt%～5wt%; The particle diameter of High hydrophilous resin is 30 orders～3000 orders.
2. coating as claimed in claim 1 is characterized in that: described paint is asphalt rubber lacquer, chloroprene rubber lacquer, acrylic acid resin paint, polyurethane paint, polyester lacquer, alkyd varnish, pyroxylin(e)finish, epoxy resin-based paint, natural resin paint or silicon rubber lacquer.
3. coating as claimed in claim 1 is characterized in that: described High hydrophilous resin is starch system, cellulose-based, synthetic resins system or their any mixture.
4. coating as claimed in claim 3, it is characterized in that: described starch is is to be selected from starch-grafted third rare nitrile, starch-grafted acrylic acid salt, starch-grafted third rare acid amides, carboxymethylated starch, starch, acrylic acid, third rare acid amides, br dilute anhydride graft copolymer wherein a kind of or their any mixture;
Described cellulose-based be carboxymethylation Mierocrystalline cellulose, cellulose graft third rare nitrile, cellulose graft acrylic acid salt or the sulfonated grafting acrylic acid of Mierocrystalline cellulose salt;
Described synthetic resins is is polypropylene hydrochlorate, polyacrylamide, acrylic acid and third rare acid amides copolymerization product, polyvinyl alcohol-acid anhydrides copolymerzation with cross-linking product, polyvinyl alcohol-acrylic acid graft copolymerization product or vinyl acetate between to for plastic-acrylic acid fat copolymerization hydrolysate.
5. coating as claimed in claim 1 is characterized in that: described water-soluble cpds is polyoxyethylene glycol, polyvinyl alcohol or their any mixture.
6. as the preparation method of the described chance water of claim 1～5 wet type nontoxic antifouling paint, it is characterized in that: described preparation method's step comprises:
One. the preparation of water-absorbent priming paint
The paint that accounts for water-absorbent priming paint gross weight 10wt%～90wt% is mixed with the High hydrophilous resin that accounts for water-absorbent priming paint gross weight 90wt%～10wt%, stir, make the water-absorbent priming paint, wherein, the particle diameter of High hydrophilous resin is 30 orders～3000 orders;
Two. the preparation of porosity surface coating
The paint that accounts for porosity surface coating gross weight 20wt%～95wt% is mixed with the water-soluble cpds that accounts for porosity surface coating gross weight 80wt%～5wt%, stir, make porosity surface coating.
7. method as claimed in claim 6 is characterized in that: described paint is asphalt rubber lacquer, chloroprene rubber lacquer, acrylic acid resin paint, polyurethane paint, polyester lacquer, alkyd varnish, pyroxylin(e)finish, epoxy resin-based paint, natural resin paint or silicone rubber kinds lacquer.
8. method as claimed in claim 6 is characterized in that: described High hydrophilous resin is starch system, cellulose-based, synthetic resins system or their any mixture.
9. method as claimed in claim 8, it is characterized in that: described starch is is to be selected from starch-grafted third rare nitrile, starch-grafted acrylic acid salt, starch-grafted third rare acid amides, carboxymethylated starch, starch, acrylic acid, third rare acid amides, br dilute anhydride graft copolymer wherein a kind of or their any mixture.
Described cellulose-based be carboxymethylation Mierocrystalline cellulose, cellulose graft third rare nitrile, cellulose graft acrylic acid salt or the sulfonated grafting acrylic acid of Mierocrystalline cellulose salt;
Described synthetic resins is is polypropylene hydrochlorate, polyacrylamide, acrylic acid and third rare acid amides copolymerization product, polyvinyl alcohol-acid anhydrides copolymerzation with cross-linking product, polyvinyl alcohol-acrylic acid graft copolymerization product or vinyl acetate between to for plastic-acrylic acid fat copolymerization hydrolysate.
10. the method for claim 1, it is characterized in that: described water-soluble cpds is polyoxyethylene glycol, polyvinyl alcohol or their any mixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310113364 CN1261506C (en) | 2003-11-17 | 2003-11-17 | Water moistening type non-toxic antifouling paint and its preparation method |
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200310113364 CN1261506C (en) | 2003-11-17 | 2003-11-17 | Water moistening type non-toxic antifouling paint and its preparation method |
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| CN1618893A true CN1618893A (en) | 2005-05-25 |
| CN1261506C CN1261506C (en) | 2006-06-28 |
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| CN 200310113364 Expired - Fee Related CN1261506C (en) | 2003-11-17 | 2003-11-17 | Water moistening type non-toxic antifouling paint and its preparation method |
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| CN102887205A (en) * | 2012-08-31 | 2013-01-23 | 李宏江 | Three methods for saving energy and increasing speed of water shipping boats and machinery equipment for various marine purposes |
| CN103865396A (en) * | 2014-03-31 | 2014-06-18 | 南通长青沙船舶工程有限公司 | Anticorrosion and antifouling paint for ships and preparation method of paint |
| WO2014178873A1 (en) * | 2013-05-02 | 2014-11-06 | Empire Technology Development Llc | Composition of hydrophilic painted surface |
| CN102307956B (en) * | 2009-02-06 | 2014-12-24 | 汉伯公司 | Enzyme-based self-polishing coating compositions |
| CN104845467A (en) * | 2015-04-29 | 2015-08-19 | 天津纳微华瑞科技有限公司 | Environment-friendly antifouling damping complex-function coating and preparation method thereof |
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| CN106281024A (en) * | 2016-08-23 | 2017-01-04 | 柳州市国正机电物资有限责任公司 | Building water-proof paint |
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- 2003-11-17 CN CN 200310113364 patent/CN1261506C/en not_active Expired - Fee Related
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| CN102307956B (en) * | 2009-02-06 | 2014-12-24 | 汉伯公司 | Enzyme-based self-polishing coating compositions |
| CN102887205A (en) * | 2012-08-31 | 2013-01-23 | 李宏江 | Three methods for saving energy and increasing speed of water shipping boats and machinery equipment for various marine purposes |
| US10017651B2 (en) | 2013-05-02 | 2018-07-10 | Empire Technology Development Llc | Composition of hydrophilic painted surface |
| WO2014178873A1 (en) * | 2013-05-02 | 2014-11-06 | Empire Technology Development Llc | Composition of hydrophilic painted surface |
| CN103865396A (en) * | 2014-03-31 | 2014-06-18 | 南通长青沙船舶工程有限公司 | Anticorrosion and antifouling paint for ships and preparation method of paint |
| CN104845467A (en) * | 2015-04-29 | 2015-08-19 | 天津纳微华瑞科技有限公司 | Environment-friendly antifouling damping complex-function coating and preparation method thereof |
| CN106118167A (en) * | 2016-07-14 | 2016-11-16 | 太仓卡斯特姆新材料有限公司 | A kind of high-quality anti-rusting antibiotic coating and preparation thereof and application process |
| CN106281023A (en) * | 2016-08-23 | 2017-01-04 | 柳州市国正机电物资有限责任公司 | Building water-proof paint preparation method |
| CN106281024A (en) * | 2016-08-23 | 2017-01-04 | 柳州市国正机电物资有限责任公司 | Building water-proof paint |
| CN107604667A (en) * | 2017-09-30 | 2018-01-19 | 界首市远航织带有限公司 | A kind of preparation method of antifouling ribbon |
| CN108409914A (en) * | 2018-03-07 | 2018-08-17 | 浙江飞鲸新材料科技股份有限公司 | A kind of acrylic resin modified preparation method and the long-acting antifouling paint using acrylic resin modified preparation |
| CN109355016A (en) * | 2018-08-27 | 2019-02-19 | 大连理工高邮研究院有限公司 | Sterilizing environmental protection coating and preparation method thereof |
| CN109468035A (en) * | 2018-10-15 | 2019-03-15 | 广东工业大学 | One kind is except moss anti-corrosion slurry sprayed on material and its preparation method and application |
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