CN104693970A - Contact type inshore fishing boat anti-fouling paint and preparation method thereof - Google Patents
Contact type inshore fishing boat anti-fouling paint and preparation method thereof Download PDFInfo
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- CN104693970A CN104693970A CN201310671278.7A CN201310671278A CN104693970A CN 104693970 A CN104693970 A CN 104693970A CN 201310671278 A CN201310671278 A CN 201310671278A CN 104693970 A CN104693970 A CN 104693970A
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- fishing boat
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- antifouling varnish
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1612—Non-macromolecular compounds
- C09D5/1618—Non-macromolecular compounds inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention discloses contact type inshore fishing boat anti-fouling paint and a preparation method thereof. The contact type inshore fishing boat anti-fouling paint comprises a component A and a component B, wherein the component A comprises the following components in percentage by weight: 10%-30% of epoxy resin, 0-15% of rosin resin, 3%-15% of anti-rusting pigments, 15%-25% of an anti-fouling agent, 0.2%-1.0% of fumed silica, 0.2%-1.5% of an aid, 5%-30% of functional pigments and 15%-40% of a solvent; the component B comprises the following components in percentage by weight: 60%-100% of an epoxy curing agent and 0-40% of a solvent. The contact type inshore fishing boat anti-fouling paint has the advantages that the anti-fouling paint does not contain internationally forbidden pesticide poisons such as organic tributyltin (TBT) and dichlorodiphenyltrichloroethane (DDT); the manufacturing and construction environments are relatively good, the poisons and resin emitted to ocean are reduced; the contact type inshore fishing boat anti-fouling paint is environmentally friendly and is non-toxic to the environment.
Description
Technical field
The present invention relates to a kind of antifouling varnish, especially a kind of high solid contact-type ship bottom anti-fouling paint with versatility, can be used for hull bottom and the water contact site of steel hull.
Background technology
In recent years, shipbuilding, shipping, exploitation of offshore oil and gas and sea farming aspect are flourish, but various marine attaching organism brings significant damage in the process of human development ocean.As barnacle, marine alga, shellfish etc. are attached on hull bottom, buoy, harbour, bridge pier, seawater pipeline and aquaculture net cage netting gear in a large number, their substantial amounts, the speed of growth are exceedingly fast, and can make that ship speed slows down, fuel increases, accelerate metallic corrosion, blocking pipe and net cage mesh, make underwater facility unbalance.
In the method preventing sea organism attachment, stained boats and ships and all kinds of facility, most popular is antifouling paint based on poison material releasing mechanism, as the self-polishing coating containing the organic tributyl tin of poisonous material (TBT), dichloro-diphenyl-trichloroethane (DDT), organic copper.Antifouling paint, by release stain control agent, makes to form one is killed effect stain control agent concentration layer to marine plant spore and animal larvae around it, can realize anti-fouling effect.Such as, but while antifouling, the stain control agent of release can cause water pollution, and organotin can accumulate in fish, body of shellfish, causes heritable variation, and also causes potential hazard to the health of the mankind.
At present, antifouling paint product main on market is generally poisonous substance release property antifouling varnish and the antifouling varnish from polishing type, stops halobiontic attachment with the stripping of dissolving gradually of the release of poisonous substance or coating.But along with the release of poisonous substance, the usefulness of antifouling coating reduces gradually.From the antifouling varnish of polishing type As time goes on, coat-thickness reduces, and antifouling property also can produce reduction.
Number of patent application: 200810088860.x discloses a kind of environment-friendly marine antifouling coating for finishing boat, respectively by acrylic resin, rosin, the organic stain control agent of compound, pigment, mixed solvent and anti-settling agent, stain control agent in coating is relied on constantly to be dissolved in ocean, prevent the attachment of marine life, stain control agent is cuprous thiocyanate, copper pyrithione and m-tetrachlorophthalodinitrile.There is anti-pollution function to a certain degree, but its coating is still to discharge low toxicity stain control agent as the halobiontic main method of control in ocean.Anti-fouling effect is only about 1 year, still has limitation.
Number of patent application: 201210095881.0 application discloses that a kind of environmental protection fishing boat antifouling varnish, be made up of modified acroleic acid zinc, rosin, liquid bisphenol A epoxy resin and composite anti-fouling agent, its stain control agent is pyrithione and copper system stain control agent, its main antifouling mechanism is that Toxic is released in water, produce coating and there is certain anti-fouling effect, but still have heavy metal ion and agricultural chemicals to infiltrate ocean.There is certain limitation.
Number of patent application 201180001644.7 discloses a kind of marine organisms antifouling varnish, its main antifouling mechanism is utilize polyacrylic-capsaicine resinoid to produce the antifouling function of fungi-proofing sterilization, belong to a type of bioantifouling paint, but, in antifouling varnish, capsaicine has strong and stimulating smell, in production process, environment has strong and stimulating, has certain production limitation.
Summary of the invention
The object of the invention is to overcome the weak point existed in existing antifouling paint technology, provides a kind of contact-type offshore-fishing boat antifouling varnish and preparation method.
Described contact-type offshore-fishing boat antifouling varnish is made up of first, second group two component;
The weight percent of first component is as follows:
The per-cent sum of component is 100%;
Preferably, the weight percent of first component is as follows:
The per-cent sum of component is 100%;
The weight percent of second component formula is as follows:
Epoxy hardener 60% ~ 100%
Solvent 0% ~ 40%
Preferably, the weight percent of second component is as follows:
Epoxy hardener 80% ~ 100%
Solvent 0% ~ 20%
First and second composition weight proportionings are: 6 ~ 12:1, and wherein, the ratio that first component epoxy base is corresponding with second component reactive hydrogen mol ratio is 1:1;
Preferably, the first and second composition weight proportionings are 8 ~ 10:1;
Described epoxy resin is bisphenol A type epoxy resin and modifier thereof, and being preferably epoxy equivalent (weight) is the bisphenol A epoxide resin of 0.18 ~ 0.46, as the epoxy resin for the domestic trade mark E20, E42, E44, and the EPIKOTE874l-x-90 etc. of import epoxy Mai Tu company;
Described Gum Rosin is limed rosin;
Described rust-stabilising pigment is phosphoric acid salt, molybdate, chromic salt, borate, one or more in phospho-molybdic acid zinc, is preferably zinc phosphate, aluminum phosphate, zinc borate, one or more in phospho-molybdic acid zinc;
The metal ion complex that described stain control agent is is carrier with layered inorganic nano material, metal ion is cupric ion and silver ions, layered inorganic nano material is the ceramic matric composite with phosphate metal salt, adopt direct precipitation method by metal ion compound and stratiform phosphate metal salt compound, after dry, sintering forms, the stain control agent of preparation is submicron particles, particle diameter is between 100nm to 500nm, the preparation method of layered inorganic nano material can refer to document " Chinese Journal of Inorganic Chemistry " 14 volume the 1st phase 79 pages to the 84 pages contents " Preparation and characterization of lamellar compound alpha zirconium phosphate " of publishing or the NAFUR series stain control agent adopting commercially available prod Shanghai Runhe Nanometer Material Technology Co., Ltd to produce.
Described wetting dispersing agent is selected from the metal carboxylate dispersion agent of unsaturated polyamine acid amides, as BYK-Anti-Terra-U or BYK-Anti-Terra-204 of German Bi Ke chemical company;
Described silicon-dioxide is aerosil, as the related products of German goldschmidt chemical corporation;
Described auxiliary agent is defoamer, and described defoamer is type siloxane solution or non-silicon defoamer, as BYK-141, BYK-066N of German Bi Ke chemical company or the Tegoairex900 etc. of German goldschmidt chemical corporation;
Described functional filler is zinc oxide, is submicron particles, and particle diameter is between 50nm to 200nm;
Described solvent is selected from aromatic hydrocarbon, alcohols, ketone or alcohol ethers, the mixture of preferred dimethylbenzene and butanols, and weight ratio is: dimethylbenzene: butanols=0.5 ~ 2:1;
Described epoxy hardener is one or more in polyamide-based, modified fat amine or cashew nut oil modified pnenolic aldehyde amine hardener, as the epoxy polyamide solidifying agent that the German Kening Co., Ltd trade mark is Versmid115 × 70, domestic 650 polyamide curing agents, the NC-541 solidifying agent of Ka Delai company of the U.S., one or more of the solidifying agent such as US Air chemistry Ancamine2636 modified fatty amine curing agent;
Wherein: described daiamid epoxy curing agent comprises epoxy hardener A, epoxy hardener B or epoxy hardener C; Wherein, described epoxy hardener A is domestic 650 polyamide curing agents, and epoxy hardener B is Ka Delai NX-2041 solidifying agent, and epoxy hardener C is Versmid115 × 70 polyamide curing agent;
The solvent that second component adopts is selected from aromatic hydrocarbon, alcohols or alcohol ethers, preferred dimethylbenzene;
The preparation method of described contact-type offshore-fishing boat antifouling varnish, comprises the following steps:
The preparation of antifouling varnish:
(1) solvothermal of epoxy resin and gross weight 11 ~ 25% is dissolved, then wetting dispersing agent, Gum Rosin is added successively, rust-stabilising pigment, the solvent of gross weight 3 ~ 10%, auxiliary agent, grinding, add the mixed slurry of scattered stain control agent and functional filler and solvent, add the solvent of anti-settling agent silicon-dioxide and surplus, obtain first component, the first component rotary viscosity of 25 DEG C is more than 1.0pa.s;
(2) by epoxy hardener and solvent, stir slaking, obtain component B;
During use, after the first and second component mixing, finish using in 4 hours.
The product that the present invention is corresponding, antifouling property is excellent, and have good antiseptic property, ocean link plate result, through trimestral ocean board experiment, marine growth rate, lower than 2%, can be used for the fishing boat hull-bottom antifouling sterilization in coastal waters and inland river simultaneously.
The present invention be not containing at the bottom of the coastal waters of release property poison material and river steamer with the antifouling varnish of asepsis environment-protecting antifouling and antibiosis, and there is certain antirust function.
Described antifouling varnish forms the firmly fine and close protective layer of one deck alow after application, when being soaked in water, washing away of current, Gum Rosin dissolves gradually, the pore space structure that varnish formation is fine and closely woven, nano inorganic stain control agent migrates to coatingsurface, the metal ion of stain control agent forms the metal ion that one deck is made up of cupric ion and silver ions, the lewis' acid of " thin layer " interior material, spore or larva that attempt rests on the marine attaching organism on paint film can be repelled, stop the growth of mould simultaneously, sterilization is provided and prevents the effect of marine growth, simultaneously, the inorganic ceramic material grappling metal ion of stain control agent, because stratiform gap is very little, control the travelling speed of silver-bearing copper ion, make the silver-bearing copper ion in stratiform gap can continue slow stripping.Rely on the lower concentration silver-bearing copper ion being adsorbed on carrier surface, the long-acting to algae can be realized.
Compared with prior art, the invention has the advantages that antifouling varnish does not use the agricultural chemicals poison material of international forbidding as organic tributyl tin (TBT), dichloro-diphenyl-trichloroethane (DDT) etc., compared with the pungency biotechnological formulations such as capsaicine, manufacture and construction environment better, having no irritating odor, is the healthy and beneficial of workmen.Compared with the antifouling varnish of polishing type, decrease the discharge of poisoning material and resin to ocean.A kind of environmental protection, the antifouling paint nontoxic to environment.
Embodiment
Embodiment 1 ~ 3
Antifouling varnish: formula is in table 1.(weight percent)
Table 1
First and second component proportions are (8 ~ 12): 1, and concrete test according to calculating and reality is as the criterion.
Stain control agent in embodiment is the silver-bearing copper ion composite nano-powder of alpha zirconium phosphate, the product of the NAFUR series stain control agent adopting Shanghai Runhe Nanometer Material Technology Co., Ltd to produce;
Embodiment 1 preparation method:
The preparation of antifouling varnish:
(1) solvothermal of epoxy resin and gross weight 18% is dissolved, add wetting dispersing agent, Gum Rosin successively, the solvent of rust-stabilising pigment, gross weight 3%, other auxiliary agents, grinding, add the mixed slurry of scattered stain control agent and functional filler and solvent, add the solvent of anti-settling agent silicon-dioxide and surplus, obtain first component, the first component rotary viscosity of 25 DEG C is more than 1.0pa.s;
(2) by daiamid epoxy curing agent and solvent, stir slaking, obtain component B;
First and second composition weight proportionings are the ratio that first component epoxy equivalent is corresponding with second component active hydrogen equivalent weight mol ratio is 1:1, after the first and second component mixing, finishes using in 4 hours.
The preparation method of embodiment 2 ~ 3 with embodiment 1, wherein:
The preparation method of antifouling varnish is as follows:
The solvothermal of epoxy resin and gross weight 15% is dissolved, add wetting dispersing agent, Gum Rosin successively, the solvent of rust-stabilising pigment, gross weight 8%, other auxiliary agents, grinding, add the mixed slurry of scattered stain control agent and functional filler and solvent, add the solvent of anti-settling agent silicon-dioxide and surplus, obtain first component, the first component rotary viscosity of 25 DEG C is more than 1.0pa.s.
The above; be only the present invention's preferably embodiment; but protection scope of the present invention is not limited thereto; also not because the succession of each embodiment causes any restriction to the present invention; anyly be familiar with those skilled in the art in the technical scope that the present invention discloses; the change that can expect easily or replacement, all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of claim.
Claims (7)
1. contact-type offshore-fishing boat antifouling varnish, is characterized in that, is made up of first, second group two component;
The weight percent of first component is as follows:
The per-cent sum of component is 100%;
The weight percent of second component formula is as follows:
Epoxy hardener 60% ~ 100%
Solvent 0% ~ 40%.
2. contact-type offshore-fishing boat antifouling varnish according to claim 1, it is characterized in that, the weight percent of first component is as follows:
The per-cent sum of component is 100%;
The weight percent of second component is as follows:
Epoxy hardener 80% ~ 100%
Solvent 0% ~ 20%.
3. contact-type offshore-fishing boat antifouling varnish according to claim 1, is characterized in that, the first and second composition weight proportionings are: 6 ~ 12:1, and wherein, the ratio that first component epoxy base is corresponding with second component reactive hydrogen mol ratio is 1:1.
4. contact-type offshore-fishing boat antifouling varnish according to claim 1, is characterized in that, the first and second composition weight proportionings are 8 ~ 10:1.
5. the contact-type offshore-fishing boat antifouling varnish according to any one of Claims 1 to 4, is characterized in that, described epoxy resin is bisphenol A type epoxy resin and modifier thereof;
Described Gum Rosin is limed rosin;
Described rust-stabilising pigment is phosphoric acid salt, molybdate, chromic salt, borate, one or more in phospho-molybdic acid zinc;
The metal ion complex that described stain control agent is is carrier with layered inorganic nano material, metal ion is cupric ion and silver ions, and layered inorganic nano material is the ceramic matric composite with phosphate metal salt;
Described wetting dispersing agent is selected from the metal carboxylate dispersion agent of unsaturated polyamine acid amides;
Described auxiliary agent is defoamer;
Described functional filler is zinc oxide;
Described solvent is selected from aromatic hydrocarbon, alcohols, ketone or alcohol ethers;
Described epoxy hardener is one or more in polyamide-based, modified fat amine or cashew nut oil modified pnenolic aldehyde amine hardener;
The solvent that second component adopts is selected from aromatic hydrocarbon, alcohols or alcohol ethers.
6. contact-type offshore-fishing boat antifouling varnish according to claim 5 is characterized in that, described solvent is the mixture of dimethylbenzene and butanols, and weight ratio is: dimethylbenzene: butanols=0.5 ~ 2:1.
7. the preparation method of contact-type offshore-fishing boat antifouling varnish according to claim 5, is characterized in that, comprise the following steps:
The preparation of antifouling varnish:
(1) solvothermal of epoxy resin and gross weight 11 ~ 25% is dissolved, then wetting dispersing agent, Gum Rosin is added successively, rust-stabilising pigment, the solvent of gross weight 3 ~ 10%, auxiliary agent, grinding, add the mixed slurry of scattered stain control agent and functional filler and solvent, add the solvent of anti-settling agent silicon-dioxide and surplus, obtain first component, the first component rotary viscosity of 25 DEG C is more than 1.0pa.s;
(2) by epoxy hardener and solvent, stir slaking, obtain component B;
During use, after the first and second component mixing, finish using in 4 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310671278.7A CN104693970A (en) | 2013-12-10 | 2013-12-10 | Contact type inshore fishing boat anti-fouling paint and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201310671278.7A CN104693970A (en) | 2013-12-10 | 2013-12-10 | Contact type inshore fishing boat anti-fouling paint and preparation method thereof |
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| CN104693970A true CN104693970A (en) | 2015-06-10 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107022280A (en) * | 2017-05-26 | 2017-08-08 | 芜湖威灵数码科技有限公司 | Epoxy anti-fouling coating |
| CN107118597A (en) * | 2017-05-26 | 2017-09-01 | 芜湖威灵数码科技有限公司 | Antifouling paint |
| CN107177279A (en) * | 2017-05-26 | 2017-09-19 | 芜湖威灵数码科技有限公司 | A kind of antifouling paint |
| CN107418367A (en) * | 2017-05-26 | 2017-12-01 | 芜湖威灵数码科技有限公司 | A kind of epoxy anti-fouling coating |
| WO2018221266A1 (en) * | 2017-05-30 | 2018-12-06 | 中国塗料株式会社 | Epoxy-resin-based anticorrosive coating composition, anticorrosive coating film, multilayered antifouling coating film, antifouled base, and production methods therefor |
| CN111205694A (en) * | 2020-03-18 | 2020-05-29 | 深圳海龙舰船涂料科技有限公司 | Long-acting ship bottom antifouling paint blended by crystal active particles |
| CN114292589A (en) * | 2021-12-29 | 2022-04-08 | 江苏海耀化工有限公司 | Preparation method of antifouling paint for low-modulus fishing net |
-
2013
- 2013-12-10 CN CN201310671278.7A patent/CN104693970A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107022280A (en) * | 2017-05-26 | 2017-08-08 | 芜湖威灵数码科技有限公司 | Epoxy anti-fouling coating |
| CN107118597A (en) * | 2017-05-26 | 2017-09-01 | 芜湖威灵数码科技有限公司 | Antifouling paint |
| CN107177279A (en) * | 2017-05-26 | 2017-09-19 | 芜湖威灵数码科技有限公司 | A kind of antifouling paint |
| CN107418367A (en) * | 2017-05-26 | 2017-12-01 | 芜湖威灵数码科技有限公司 | A kind of epoxy anti-fouling coating |
| WO2018221266A1 (en) * | 2017-05-30 | 2018-12-06 | 中国塗料株式会社 | Epoxy-resin-based anticorrosive coating composition, anticorrosive coating film, multilayered antifouling coating film, antifouled base, and production methods therefor |
| CN111205694A (en) * | 2020-03-18 | 2020-05-29 | 深圳海龙舰船涂料科技有限公司 | Long-acting ship bottom antifouling paint blended by crystal active particles |
| CN114292589A (en) * | 2021-12-29 | 2022-04-08 | 江苏海耀化工有限公司 | Preparation method of antifouling paint for low-modulus fishing net |
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Application publication date: 20150610 |