CN104559635A - High-performance environment-friendly water-based ship inner cabin coating - Google Patents
High-performance environment-friendly water-based ship inner cabin coating Download PDFInfo
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- CN104559635A CN104559635A CN201310487844.9A CN201310487844A CN104559635A CN 104559635 A CN104559635 A CN 104559635A CN 201310487844 A CN201310487844 A CN 201310487844A CN 104559635 A CN104559635 A CN 104559635A
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- 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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- 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
- C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
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- 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
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
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- C08K3/20—Oxides; Hydroxides
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Abstract
本发明公开了一种高性能环保型水性船舶内舱涂料组合物的制备方法和应用。高性能环保型水性船舶内舱涂料采用双组份含氟烷基侧链的改性环氧树脂乳液涂料体系，其中A组分为经结构改性的含氟烷基侧链环氧树脂乳液为基料的混合物，B组分为含端环氧基的聚醚化合物与胺的加成物组成的水性胺类固化剂。A、B组分按比例配匀进行涂装。固化后漆膜的有害物质限量满足挥发性有机化合物含量（VOC）≤120g/L的环保标准，漆膜的水接触角达到100°以上并保持稳定，复涂容易，具有优良的防霉、抗玷污、耐腐蚀性能，适用于船舶内舱的防护装饰。
The invention discloses a preparation method and application of a high-performance and environment-friendly water-based coating composition for interior cabins of ships. The high-performance environment-friendly water-based ship interior coating adopts a two-component modified epoxy resin emulsion coating system containing fluorine-containing alkyl side chains, in which component A is a structure-modified epoxy resin emulsion containing fluorine-containing alkyl side chains. The mixture of base materials, component B is a water-based amine curing agent composed of adducts of epoxy-terminated polyether compounds and amines. A and B components are evenly mixed in proportion for coating. The limit of harmful substances in the cured paint film meets the environmental protection standard of volatile organic compound content (VOC) ≤ 120g/L, the water contact angle of the paint film reaches above 100° and remains stable, easy to recoat, and has excellent anti-mildew and anti-corrosion properties. Pollution and corrosion resistance, suitable for protective decoration of ship interior cabins.
Description
Technical field
The present invention relates to macromolecule chemical industry paint field, specifically with fluorine richness epoxy resin latex for base-material prepare a kind of there is excellent mildew-resistant, anti-to stain, the environment-friendly type aqueous inner cabin of ship coating of corrosion resistance nature.
Background technology
Inner cabin of ship application of paints is in the decoration of interior cabin steel plate and soft clad surface and protection, and traditional inner cabin of ship coating mostly is solvent based coating, applies maximum having: alkydpaints, acrylic coating and epoxypaint etc.But coating easy presence of fire in construction in cabin in solvent-borne type, the accident such as poisoning, particularly insulation layer Soft Roll covers in construction, Soft Roll covers cloth and insulated heat material is porous material, larger to the absorbed dose of coating, and easily organic solvent is enclosed in porous substrate inside, affect cabin office work and life personnel healthy.Therefore pay the utmost attention to during the coating of cabin in selecting that VOC content is low, nonflammable, blast, and once burning or the less coating variety of explosion gases toxicity.
Water-based inner cabin of ship coating not only has the feature such as environmental protection, use safety, and coincide with the requirement of accommodation coating half light, sub-light, more and more receives the concern of people.Water-based inner cabin of ship coating take water as dispersion medium, petroleum resources can be saved in a large number, reduce VOC discharge, alleviate environmental pollution, do not fire in coating material production and coating process, not quick-fried, the fire in the coating application of interior cabin and poisoning hidden danger can be eliminated, compartment environment in remarkable improvement, and make some cross-operation become possibility, be conducive to improving work efficiency, obtain the accreditation of shipyard and shipowner, have a extensive future.In water-based, cabin coating to mainly contain in cabin coating in water alcohol acid (or water-based acrylic acid modified alcoholic acid coating), water soluble acrylic acid cabin coating and Waterborne Epoxy Coatings for Inner Cabin of Naval Ships in cabin coating, water-based epoxy acrylic.In early stage water-based, cabin coating is mainly used in the application of interior on-deck paint, except environmental-protecting performance, less demanding to other performance, so mostly be water alcohol acid system or aqueous acrylamide acid system, single-component system, easy construction, but in antiseptic property, hardness, solvent resistant Shortcomings, anti-staining difference, does not also possess the performances such as mildew-resistant.Water-borne epoxy systems is two-pack, VOC content is low, smell is little, use safety, can solidify in room temperature and wet environment, have rational set time and ensure higher cross-linking density, antiseptic property, hardness, solvent resistant and anti-stain in better, become one of optimal coating system of cabin coating in water-based.
Due to inner cabin of ship narrow space, ventilate not smooth; in the winter time or temperature is lower time, indoor and outdoor also exists the temperature difference, causes wall to condense; if things go on like this; the problems such as appearance wall is mouldy, therefore modern ships production internal cabin coating has had higher requirement, except safety non-toxic, easy construction; also should possess anti-to stain, Anti-dew, mildew-resistant and the characteristic such as corrosion-resistant; reach cabin environment in significantly improving, prevent cabin mildew, the object of personnel health in protection cabin.
Low surface energy coatings has hydrophobic, oleophobic, mildew-resistant, the excellent properties such as antifouling, is applied in building coating, anti-drag paint, antifouling paint, protective system, waterproof paint, antifog antiicing coating, anti-doodling paint etc.There is not been reported low surface energy coatings to be applied to cabin coating in boats and ships water-based.
Open (bulletin) number CN102603991A of Chinese patent discloses formula and the preparation technology of the environment-friendly type aqueous protected decoration coating of a kind of inner cabin of ship, and it is a kind of with cabin coating in the acrylic modified alkyd emulsion water-based that is base-material.First this patent has synthesized that VOC content is low, the acrylic modified alkyd emulsion of Heat stability is good, fast drying, then with this emulsion for base-material mixes with pigment, auxiliary agent, is processed into coating through operations such as grinding, dispersions.This coating VOC content is low, not containing benzene homologues, nontoxic, does not fire, environmentally safe, healthy harmless to workmen, can adopt the multiple method construction such as brushing, spraying, dip-coating, fast drying, safe and convenient to use.Paint film physical strength is high, strong adhesion, good decorative property, is mainly used in inner cabin of ship steel plate and soft clad surface as protection and decorative coveringn.Also can be used for protection and the decoration of the facility part ferrous materials such as the vehicles, bridge, basin, pipeline, mechanical means.This kind of not mentioned low surface energy characteristic of coating.
Chinese Patent Application No. CN200910311766.0 discloses a kind of water-soluble low surface energy paint and preparation method thereof, and this patent mainly uses fluorine-containing emulsion, fungicidal preservative, defoamer, wetting dispersing agent, pH value regulator, color stuffing, nano powder, film coalescence aid, thickening material, flow agent and water etc. to prepare the water-soluble low surface energy paint of single component by techniques such as stirring, dispersions.
Comprehensive invention both domestic and external and document, the preparation method of water-soluble low surface energy paint emulsion is mainly fluorine-carbon modified ACRYLIC EMULSION, fluorine/silicon modified polyurethane emulsion etc., it mainly make use of, and acrylic resin self weather resistance is excellent, the advantage of good decorative property, by with fluorine with chemical bonds, by chemical modification technique, give low surface energy performance, but there is the not good defect of antiseptic property.At present both at home and abroad patent and document also do not introduce the preparation method that fluorine carries out surface modification to epoxy resin latex and the relevant information applied in inner cabin of ship for water-soluble low surface energy paint prepared by base-material with it.
The present invention carries out skill upgrading to existing water-based inner cabin of ship coating products performance, is ensureing, under safety, nontoxic prerequisite, to make it have low surface energy, mildew-resistant, prevent function and certain corrosion resistance natures such as staining.Prepare the high-performance environment protection type water-based inner cabin of ship coating of a kind of environmental friendliness, safety non-toxic, the low surface energy of coating is conducive to that paint film mildew-resistant is anti-stains, and the barrier propterty of aqueous epoxy coating can reach cabin coating protecting performance in corresponding solvent-borne type.
Summary of the invention
The technical problem to be solved in the present invention be for cabin coating in common ship mildew-resistant, anti-to stain etc. in deficiency, a kind of environment-protecting asepsis is provided, have mildew-resistant resist stain characteristic be film forming matter high-performance environment protection type water-based inner cabin of ship method for preparing coatings composition and the application thereof of fluorine richness epoxy resin latex and aqueous epoxy curing agent.
The object of the invention is to be achieved through the following technical solutions:
For reaching inner cabin of ship coating, there is high in environmental protection security and long-acting use properties requirement, the high-performance environment protection type water-based inner cabin of ship coating that the present invention proposes have employed two-pack aqueous dispersion type epoxy resin coating system route, screening meets the starting material of environmental requirement, instead of easily brings the aqueous acrylic emulsion system of formaldehyde into.Main employing homemade through structurally-modified be base-material containing fluoroalkyl side chains epoxy resin latex, the low surface energy film forming matter prepared with the aqueous amine solidifying agent be made up of the affixture containing epoxy terminated polyether compound and amine is main.Ensure that the limits of harmful substances of paint film meets the environmental protection standard of content of volatile organic compound (VOC)≤120g/L with this.
In general, when the water contact angle of coating reaches more than 1000, water is just difficult to infiltrate at coating surface.Improve water-based inner cabin of ship coating lacquer film water contact angle, mainly introduce in molecular resin and realize compared with the fluorine atom of low surface energy, fluorine atom paint film water contact angle when coating surface enrichment just can significantly improve.In epoxy molecule structure, introduce fluoroalkyl side chains, this fluoroalkyl side chains has excellent surface transport property in film process, thus obtains very low surface energy.The present invention adopts the modified epoxy resin emulsion containing fluoroalkyl side chains to be high-performance environment protection type water-based inner cabin of ship coating prepared by base-material, overcoating is easy, water contact angle >=100 of paint film ° and stable performance, have mildew-resistant, anti-staining, be applicable to the protected decoration of inner cabin of ship.
A kind of high-performance environment protection type water-based inner cabin of ship coating, this coating composition is made up of component A and B component, and the formula of A, B component is as follows:
Component A
B component
Raw-material weight per-cent
Aqueous epoxy curing agent 65-90%
Water 10-35%
Wherein, fluorine richness epoxy resin latex is the modified epoxy resin emulsion containing fluoroalkyl side chains, comprises following structure:
X >=1 in formula; Y >=1.m=2-6；n=9，11，13；
In formula, R is the line style that divalence has 4-30 carbon atom, or branced aliphatic group, or alicyclic group, or has the aromatic group of 6-24 carbon atom.
Owing to introducing fluoroalkyl side chains in the bisphenol A type epoxy resin molecular structure of hydroxyl, the coating containing above structure has low surface energy characteristic, and keeps stable.
Described fluorine richness epoxy resin latex, its composition comprises (weight percent):
The epoxy resin of described lateral chain containing fluoroalkyl segment, its composition comprises (weight percent):
The preparation method of the epoxy resin of described lateral chain containing fluoroalkyl segment, its step joins in reactor by the vulcabond of metering, perfluoroalkyl alcohol, solvent, be filled with nitrogen or argon gas, at the uniform velocity stir, be heated to 60 ~ 95 DEG C, insulation reaction 2 ~ 3 hours after material all dissolves, adds half amount catalyzer, to continue at 60 ~ 95 DEG C insulation reaction 6 ~ 8 hours while stirring.Be cooled to the bisphenol A type epoxy resin solution (epoxy resin content is 50-60%) added at 50 DEG C containing hydroxyl, supply catalyst levels, be warming up to 65 ~ 90 DEG C, continue insulation reaction 6 ~ 8 hours, the isocyanate terminated fluorochemicals of synthesis is grafted on the side chain of bisphenol A type epoxy resin.Vacuumize 2 ~ 4 hours after having reacted, the solvent that decompression removing is unnecessary, purify and obtain the epoxy resin of the fluorine-containing side chain of long-chain-segment.
In the epoxy resin of above-mentioned lateral chain containing fluoroalkyl segment, vulcabond used is selected from following one: 4 of isophorone diisocyanate (IPDI), hexamethylene diisocyanate trimer (HDI tripolymer), carbodiimide-uretonimine-modified, 4-diphenylmethanediisocyanate (modification MDI), 4,4-diphenylmethanediisocyanate (4,4-MDI), 2,4-diphenylmethanediisocyanate (2,4-MDI) or the blend of the two, its functionality is between 2 to 2.5.
Perfluoroalkyl alcohol used in the epoxy resin of above-mentioned lateral chain containing fluoroalkyl segment does not have fluorine substituted alkyl alcohol to form by containing one section of perfluor substituted alkyl and one, and hydroxyl is connected to the long-chain-segment fluorochemicals on alkyl, and its molecular formula is CF
3(CF
2)
n(CH
2) mOH, m=2-6 in formula; N=9,11,13; Be selected from perfluoro decyl ethyl alcohol, perfluorododecyl ethyl alcohol etc.
In the epoxy resin of above-mentioned lateral chain containing fluoroalkyl segment, solvent used is selected from one or both mixing following: ethyl acetate, N-BUTYL ACETATE or dimethylbenzene.
In the epoxy resin of above-mentioned lateral chain containing fluoroalkyl segment, catalyzer used is selected from following one: dibutyltin dilaurate (DBTDL), three-(N, N-dimethyl aminoethyl) amine.
The solution of the bisphenol A type epoxy resin solution containing hydroxyl used to be epoxy resin content be 50-60% in the epoxy resin of above-mentioned lateral chain containing fluoroalkyl segment; Bisphenol A type epoxy resin containing hydroxyl is selected from one or both mixing following: the E type high molecular expoxy resins such as E20, E12, Epikote1001, Epikote1007.In solution, solvent is selected from one or both mixing following: ethyl acetate, N-BUTYL ACETATE or dimethylbenzene.
The preparation method of described fluorine richness epoxy resin latex, its step is that the epoxy resin of the above-mentioned lateral chain containing fluoroalkyl segment taking formula ratio is placed in container, add reactive thinner, the hydroxyl bisphenol A type epoxy resin of different amounts is added according to low surface energy property requirements, open mulser low rate mixing, preheating dispersing head, after epoxy resin dissolves completely, adds emulsifying agent and the defoamer of formula ratio.It is completely even to system with rotating speed to be that 1500-4500rpm carries out high-speed stirring, and be creamy white oily body; Take the hot water of formula ratio 30-100 DEG C, by dropping funnel, hot water is slowly added drop-wise in system, the viscosity of system is increased gradually, when reaching peak viscosity, system reaches inversion of phases stagnation point, now stops adding water, be after 1500-4500rpm carries out high-speed stirring 2-5 minute with rotating speed, after even to system, continue to drip remaining hot water, obtained liquid epoxies emulsion.In the preparation process of liquid epoxies emulsion, the total time for adding of hot water is 15-20 minute.Be mixed with the modified epoxy resin emulsion containing fluoroalkyl side chains that oyster white is stable.
Solid content: 50-60%
The stability of fluorine richness epoxy resin latex: under the rotating speed of 3000 revs/min centrifugal 30 minutes not stratified.
The stability in storage of fluorine richness epoxy resin latex: 6 months emulsions not breakdown of emulsion, not stratified.
Can thin up and not breakdown of emulsion.
Epoxy resin used in above-mentioned fluorine richness epoxy resin latex is the bisphenol A type epoxy resin of hydroxyl, is selected from the E type high molecular expoxy resins such as E20, E12, Epikote1001, Epikote1007.
Reactive thinner used in above-mentioned fluorine richness epoxy resin latex is the reactive epoxies thinner of ether-containing key and epoxy group(ing), be selected from one or both mixing following: 10 two to tetradecyl glycidyl ethers (AGE), butylglycidyl ether (BGE), o-tolyl glycidyl ether, BDDE, benzyl glycidyl ether etc.
Emulsifying agent used in above-mentioned fluorine richness epoxy resin latex is reactive emulsifier, is selected from one or more mixing following: vinyl alkyl phenol polyethenoxy sulfonate, vinyl alkyl phosphoric acid ester, allyl ethers hydroxyl sulfoacid sodium etc.Its end group of the type emulsifying agent is respectively epoxy group(ing) and hydroxyl, can not only carry out emulsification to epoxy resin, and participates in polymerization in emulsion polymerization process, is embedded in emulsion particle surface.Because molecular end has epoxy group(ing), the curing reaction of epoxy curing agent can be participated in, become a part for the rear corsslinking molecular of solidification, form cross-linked network structure, firmly tensio-active agent is fixed in film, effectively overcome the dialysis of additional type emulsifying agent, free problem, less on the impact of film performance.
Water used in above-mentioned fluorine richness epoxy resin latex is deionized water or distilled water.
High-performance environment protection type water-based inner cabin of ship method for preparing coatings composition of the present invention:
The first step: above-mentioned fluorine richness epoxy resin latex 28-40%, water 19-23%, film coalescence aid 1.8-2.2%, rust-stabilising pigment 3-3.8%, physique filler and pigment 35-42%, surplus is sanitas, other auxiliary agents (wetting agent, defoamer, thickening material and flow agent etc.); All be weight percentage, component percentages sum is 100%.Each raw material is stirred in material-compound tank high speed dispersion, is ground to fineness≤30 μm, filter discharging and prepare high-performance environment protection type water-based inner cabin of ship coating component A.
Second step: aqueous epoxy curing agent and water are stirred in material-compound tank high speed dispersion, obtained high-performance environment protection type water-based inner cabin of ship coating B component.
In above-mentioned high-performance environment protection type water-based inner cabin of ship coating composition, rust-stabilising pigment used is selected from one or both mixing following: zinc phosphate, aluminium triphosphate, aluminum phosphate zinc, phospho-molybdic acid zinc calcium, silicophosphate strontium etc.
In above-mentioned high-performance environment protection type water-based inner cabin of ship coating composition, color stuffing used comprises physique filler and pigment, adds according to concrete purposes.Physique filler is selected from one or more mixing following: process white, talcum powder, kaolin, ground barium sulfate, light calcium carbonate etc.; Pigment is selected from one or more mixing following: Rutile type Titanium Dioxide, red iron oxide, iron oxide black, iron oxide yellow, phthalocyanine blue, carbon black.
In above-mentioned high-performance environment protection type water-based inner cabin of ship coating composition, film coalescence aid used is selected from the low smell alcohol ethers film coalescence aid of high boiling point (more than 250 DEG C), as TEXANOL, and ester alcohol-12 etc.
In above-mentioned high-performance environment protection type water-based inner cabin of ship coating composition, auxiliary agent used is selected from extremely not low containing VOC or VOC amount auxiliary agent, comprises the mixing that defoamer, flow agent, wetting dispersing agent, thickening material, mould inhibitor and sanitas etc. are several.
In above-mentioned high-performance environment protection type water-based inner cabin of ship coating composition, aqueous epoxy curing agent used is selected from the aqueous amine solidifying agent product be made up of the affixture containing epoxy terminated polyether compound and amine, this solidifying agent and above-mentioned both fluorine richness epoxy resin latexes solubility parameter is close, matching is good.Such as commercially available Zhejiang stablizes the country the AB-HGA trade mark, Fuqing trump Kingcure630W60, Kingcure540W60 trade mark, step figure EPIKURE8545, EPIKURE6870 trade mark, the products such as air chemical industry Anquamine401, Anquamine419, Anquamine721, Sunmide WH-900 trade mark.
The preparation of high-performance environment protection type water-based inner cabin of ship coating of the present invention:
A, B two component in 8 ~ 6:1(weight ratio) ratio used in combination.Can adopt spraying, brushing, blade coating method construct.Stir by hand, be coated on surface treated tinplate, low-carbon steel plate with brush, self-vulcanizing film forming.The performance of paint film is as follows:
Overcoating: easily, sticking power (cross-hatching) 0 grade, cut edge is completely level and smooth, and none lattice comes off, and has no intermediate(coat)peeling, stripping; (GB/T1720-1979)
Fungi-growth grade (28 days): 0 grade (having no mould-growth); (GJB150.10A-2009)
Contact angle θ/2 method: coating and distilled water contact angle >=100 °;
Content of volatile organic compound (VOC) :≤120g/L; (GB/T18582-2008)
Resistance to neutral salt spray: coordinate with same system primary coat, more than 1000 hours, coating is non-foaming, non-corrosive, not come off.（GB/T1771-2007）
Coating can be used in decoration and the protection of inner cabin of ship steel plate and soft clad surface, safety non-toxic, has good mildew-resistant, anti-to stain, corrosion resistance nature.
Beneficial effect of the present invention:
High-performance environment protection type water-based inner cabin of ship coating have employed the modified epoxy resin paint system of the aqueous dispersion type fluorinated alkyl group side chain of two-pack, the mixture that wherein component A is is base-material with fluorine richness epoxy resin latex, B component is the aqueous amine solidifying agent that the affixture containing epoxy terminated polyether compound and amine forms.During use two components by proportioning used in combination, can adopt spraying, brushing, blade coating method construct.The feature of the modified epoxy resin paint system of aqueous dispersion type fluorinated alkyl group side chain in epoxy molecule structure, introduces the fluoroalkyl side chains with excellent surface transport property by chemical modification technique, then in epoxy resin, introduce hydrophilic radical thus be dispersed in water.In film process, fluoroalkyl side chains can move to coating surface, enrichment, and few addition can make film forming matter obtain very low surface energy, thus ensures that the water contact angle of coating reaches more than 100 ° and keeps stable, and coating overcoating is easy, does not find the problem such as intermediate(coat)peeling, stripping.Although and the fluorine modified aqueous ACRYLIC EMULSION adopting emulsion polymerisation process to obtain also can reach the water contact angle of more than 100 °, in use paint film water contact angle easily declines to a great extent and is difficult to recover.
In general, when the water contact angle of coating reaches more than 100 °, water is just difficult to infiltrate at coating surface.The low surface energy of coating is conducive to paint film mildew-resistant, and the amine curing agent self that epoxy resin latex is selected also has mildew-proof function, water-based inner cabin of ship coating of the present invention is made to have the over-all properties such as mildew-resistant, anti-contamination concurrently, in addition environmentally friendly, safety non-toxic, after solidification, the limits of harmful substances of paint film meets the environmental protection standard of content of volatile organic compound (VOC)≤120g/L, coordinate salt spray resistance to reach more than 1000 hours with same system primary coat, these all current water-based inner cabin of ship coating do not possess.
Accompanying drawing explanation
Fig. 1 is the surface energy water contact angle measurement effect figure of embodiment 1 high-performance environment protection type water-based inner cabin of ship coating.
Fig. 2 is the surface energy water contact angle measurement effect figure of embodiment 2 high-performance environment protection type water-based inner cabin of ship coating.
Fig. 3 is the surface energy water contact angle measurement effect figure of embodiment 3 high-performance environment protection type water-based inner cabin of ship coating.
Embodiment
Embodiment 1:
The first step: the preparation of the epoxy resin of lateral chain containing fluoroalkyl segment
6.40 parts of isophorone diisocyanates, 15.18 parts of perfluoro decyl ethyl alcohols, 7.83 parts of N-BUTYL ACETATEs are joined in reactor successively, is filled with nitrogen or argon gas, at the uniform velocity stirs, be heated to 95 DEG C, after material all dissolves, insulation reaction 2 hours.Add 0.01 part of dibutyltin dilaurate, to continue at 95 DEG C insulation reaction 7 hours while stirring.Be cooled to the 60% epoxy resin E20 solution adding 42.35 parts of epoxy resin E20 and 28.22 parts of N-BUTYL ACETATE compositions at 50 DEG C, add 0.01 part of dibutyltin dilaurate, be warming up to 70 DEG C, continue insulation reaction 7 hours, the isocyanate terminated fluorochemicals of synthesis is grafted on the side chain of bisphenol A type epoxy resin E20.Vacuumize 3 hours after having reacted, the solvent that decompression removing is unnecessary, purify and obtain the epoxy resin of the fluorine-containing side chain of long-chain-segment.
Second step: containing the preparation of the modified epoxy resin emulsion of fluoroalkyl side chains
The formula of composition and composition:
Preparation process is:
The fluorine richness epoxy resin, 10 two to the tetradecyl glycidyl ethers (AGE) that take the synthesis of formula ratio embodiment 1 the first step add in container, open mulser low rate mixing, preheating dispersing head, after epoxy resin dissolves completely, add vinyl alkyl phenol polyethenoxy sulfonate and the defoamer of formula ratio.It is completely even to system with rotating speed to be that 4000rpm carries out high-speed stirring, and be creamy white oily body; Take the hot water of formula ratio 60 DEG C, by dropping funnel, hot water is slowly added drop-wise in system, the viscosity of system is increased gradually, when reaching peak viscosity, system reaches inversion of phases stagnation point, now stops adding water, be after 4000rpm carries out high-speed stirring 2-5 minute with rotating speed, after even to system, continue to drip remaining hot water, obtained liquid fluorine modified epoxy resin emulsion.In the preparation process of liquid epoxies emulsion, the total time for adding of hot water is 15 minutes.Be mixed with milky fluorine richness epoxy resin latex, emulsion property is as follows:
Solid content: 60%
Epoxy equivalent (weight): about 430g/ equivalent;
The stability of fluorine richness epoxy resin latex: under the rotating speed of 3000 revs/min centrifugal 30 minutes not stratified.
The stability in storage of fluorine richness epoxy resin latex: 6 months emulsions not breakdown of emulsion, not stratified.
Can thin up and not breakdown of emulsion.
3rd step: the preparation of high-performance environment protection type water-based inner cabin of ship coating composition
The formula of composition and composition:
Component A
Preparation process is:
Prepared by high-performance environment protection type water-based inner cabin of ship coating component A
(1) in container with slurry, add the water, dispersion agent, defoamer, sanitas, mould inhibitor etc. of accurate-metering, stir with high speed dispersor;
(2) the fluorine richness epoxy resin latex weighed in more than half above-mentioned formula is added in container with slurry stir evenly;
(3) add aluminum phosphate zinc, titanium dioxide, talcum powder and the barium sulfate in above-mentioned formula successively, stir evenly;
(4) slurry stirring end of a period in (3) step is transferred in grinding plant, be ground to fineness and be less than 30 μm, obtain mill base;
(5) mill base in (4) step is transferred in paint container, add remaining fluorine richness epoxy resin latex by metered amount, stir evenly;
(6) add the film coalescence aid of above-mentioned formula ratio, thickening material, flow agent stir evenly;
(7) filter with 80-120 eye mesh screen, packaging, obtains coating composition component A finished product.
Prepared by high-performance environment protection type water-based inner cabin of ship coating B component
In container with slurry, add aqueous epoxy curing agent EPIKURE8545 and the water of accurate-metering, to stir obtained coating composition B component finished product with high speed dispersor.
4th step: the preparation of high-performance environment protection type water-based inner cabin of ship coating
With component A: B component=7:1(weight ratio) ratio mixing, stir, be coated on surface-treated tinplate sheet or low-carbon steel plate with brush, self-vulcanizing after application.After 14 days, the performance of coating is as follows:
Overcoating: easily, sticking power (cross-hatching) 0 grade, cut edge is completely level and smooth, and none lattice comes off, and has no intermediate(coat)peeling, stripping; (GB/T1720-1979)
Fungi-growth grade (28 days): 0 grade (having no mould-growth); (GJB150.10A-2009)
Contact angle θ/2 method: coating and distilled water contact angle 107 °;
Content of volatile organic compound (VOC): 83.6g/L; (GB/T18582-2008)
Resistance to neutral salt spray: coordinate with same system primary coat, more than 1000 hours, coating is non-foaming, non-corrosive, not come off.（GB/T1771-2007）
Embodiment 2:
The first step: the preparation of the epoxy resin of lateral chain containing fluoroalkyl segment
5.35 parts of isophorone diisocyanates, 12.75 parts of perfluoro decyl ethyl alcohols, 10.41 parts of N-BUTYL ACETATEs are joined in reactor successively, is filled with nitrogen or argon gas, at the uniform velocity stirs, be heated to 95 DEG C, after material all dissolves, insulation reaction 2 hours.Add 0.015 part of dibutyltin dilaurate, to continue at 95 DEG C insulation reaction 7 hours while stirring.Be cooled to the 60% epoxy resin E20 solution adding 42.88 parts of epoxy resin E20 and 28.58 parts of N-BUTYL ACETATE compositions at 50 DEG C, add 0.015 part of dibutyltin dilaurate, be warming up to 70 DEG C, continue insulation reaction 7 hours, the isocyanate terminated fluorochemicals of synthesis is grafted on the side chain of bisphenol A type epoxy resin E20.Vacuumize 3 hours after having reacted, the solvent that decompression removing is unnecessary, purify and obtain the epoxy resin of the fluorine-containing side chain of long-chain-segment.
Second step: containing the preparation of the modified epoxy resin emulsion of fluoroalkyl side chains
The formula of composition and composition:
Preparation process is:
The fluorine richness epoxy resin, bisphenol A type epoxy resin E12,10 two to the tetradecyl glycidyl ethers (AGE) that take embodiment 2 the first step synthesis of formula ratio add in container, open mulser low rate mixing, preheating dispersing head, after epoxy resin dissolves completely, add vinyl alkyl phenol polyethenoxy sulfonate and the defoamer of formula ratio.It is completely even to system with rotating speed to be that 4000rpm carries out high-speed stirring, and be creamy white oily body; Take the hot water of formula ratio 60 DEG C, by dropping funnel, hot water is slowly added drop-wise in system, the viscosity of system is increased gradually, when reaching peak viscosity, system reaches inversion of phases stagnation point, now stops adding water, be after 4000rpm carries out high-speed stirring 2-5 minute with rotating speed, after even to system, continue to drip remaining hot water, obtained liquid epoxies emulsion.In the preparation process of liquid epoxies emulsion, the total time for adding of hot water is 15 minutes.Be mixed with milky fluorine richness epoxy resin latex.Emulsion property is as follows:
Solid content: 50%
Epoxy equivalent (weight): about 450g/ equivalent;
The stability of fluorine richness epoxy resin latex: under the rotating speed of 3000 revs/min centrifugal 30 minutes not stratified.
The stability in storage of fluorine richness epoxy resin: 6 months emulsions not breakdown of emulsion, not stratified.
Can thin up and not breakdown of emulsion.
3rd step: the preparation of high-performance environment protection type water-based inner cabin of ship coating composition
The formula of composition and composition:
Component A
B component
Raw-material weight part
1. aqueous epoxy curing agent EPIKURE8545 77.95
2. water 22.05
Preparation process is:
Prepared by high-performance environment protection type water-based inner cabin of ship coating component A
(1) in container with slurry, add water, dispersion agent, defoamer, sanitas, the mould inhibitor of accurate-metering, stir with high speed dispersor;
(2) the fluorine richness epoxy resin latex weighed in more than half above-mentioned formula is added in container with slurry stir evenly;
(3) add aluminum phosphate zinc, titanium dioxide, talcum powder and the barium sulfate in above-mentioned formula successively, stir evenly;
(4) slurry stirring end of a period in (3) step is transferred in grinding plant, be ground to fineness and be less than 30 μm, obtain mill base;
(5) mill base in (4) step is transferred in paint container, add remaining fluorine richness epoxy resin latex by metered amount, stir evenly;
(6) add the film coalescence aid of above-mentioned formula ratio, thickening material, flow agent stir evenly;
(7) filter with 80-120 eye mesh screen, packaging, obtains coating composition component A finished product.
Prepared by high-performance environment protection type water-based inner cabin of ship coating B component
In container with slurry, add aqueous epoxy curing agent EPIKURE8545 and the water of accurate-metering, to stir obtained coating composition B component finished product with high speed dispersor.
4th step: the preparation of high-performance environment protection type water-based inner cabin of ship coating
With component A: B component=7:1(weight ratio) ratio mixing, stir, be coated on surface-treated tinplate sheet or low-carbon steel plate with brush, self-vulcanizing after application.After 14 days, the performance of coating is as follows:
Overcoating: easily, sticking power (cross-hatching) 0 grade, cut edge is completely level and smooth, and none lattice comes off, and has no intermediate(coat)peeling, stripping; (GB/T1720-1979)
Fungi-growth grade (28 days): 0 grade (having no mould-growth); (GJB150.10A-2009)
Contact angle θ/2 method: coating and distilled water contact angle 105 °;
Content of volatile organic compound (VOC): 80.5g/L; (GB/T18582-2008)
Resistance to neutral salt spray: coordinate with same system primary coat, more than 1000 hours, coating is non-foaming, non-corrosive, not come off.（GB/T1771-2007）
Embodiment 3:
The first step: the preparation of the epoxy resin of lateral chain containing fluoroalkyl segment
6.36 parts of isophorone diisocyanates, 15.12 parts of perfluoro decyl ethyl alcohols, 7.66 parts of N-BUTYL ACETATEs are joined in reactor successively, is filled with nitrogen or argon gas, at the uniform velocity stirs, be heated to 95 DEG C, after material all dissolves, insulation reaction 2 hours.Add 0.01 part of dibutyltin dilaurate, to continue at 95 DEG C insulation reaction 7 hours while stirring.Be cooled to the 60% epoxy resin E20 solution adding 42.50 parts of epoxy resin E20 and 28.34 parts of N-BUTYL ACETATE compositions at 50 DEG C, add 0.01 part of dibutyltin dilaurate, be warming up to 70 DEG C, continue insulation reaction 7 hours, the isocyanate terminated fluorochemicals of synthesis is grafted on the side chain of bisphenol A type epoxy resin E20.Vacuumize 3 hours after having reacted, the solvent that decompression removing is unnecessary, purify and obtain the epoxy resin of the fluorine-containing side chain of long-chain-segment.
Second step: containing the preparation of the modified epoxy resin emulsion of fluoroalkyl side chains
The formula of composition and composition:
Preparation process is:
Take the fluorine richness epoxy resin of formula ratio the first step synthesis in container, add the bisphenol A type epoxy resin E12 of equivalent weight, 10 two to tetradecyl glycidyl ethers (AGE) of formula ratio, open mulser low rate mixing, preheating dispersing head, after epoxy resin dissolves completely, add vinyl alkyl phenol polyethenoxy sulfonate and the defoamer of formula ratio.It is completely even to system with rotating speed to be that 4000rpm carries out high-speed stirring, and be creamy white oily body; Take the hot water of formula ratio 60 DEG C, by dropping funnel, hot water is slowly added drop-wise in system, the viscosity of system is increased gradually, when reaching peak viscosity, system reaches inversion of phases stagnation point, now stops adding water, be after 4000rpm carries out high-speed stirring 2-5 minute with rotating speed, after even to system, continue to drip remaining hot water, obtained liquid epoxies emulsion.In the preparation process of liquid epoxies emulsion, the total time for adding of hot water is 15 minutes.Be mixed with milky fluorine richness epoxy resin latex.Emulsion property is as follows:
Solid content: 60%
Epoxy equivalent (weight): about 481g/ equivalent;
The stability of fluorine richness epoxy resin latex: under the rotating speed of 3000 revs/min centrifugal 30 minutes not stratified.
The stability in storage of fluorine richness epoxy resin: 6 months emulsions not breakdown of emulsion, not stratified.
Can thin up and not breakdown of emulsion.
3rd step: the preparation of high-performance environment protection type water-based inner cabin of ship coating composition
The formula of composition and composition:
Component A
B component
Raw-material weight part
1. aqueous epoxy curing agent EPIKURE8545 73.59
2. water 26.41
Preparation process is:
Prepared by high-performance environment protection type water-based inner cabin of ship coating composition component A
(1) in container with slurry, add water, dispersion agent, defoamer, sanitas, the mould inhibitor of accurate-metering, stir with high speed dispersor;
(2) the fluorine richness epoxy resin latex weighed in more than half above-mentioned formula is added in container with slurry stir evenly;
(3) add aluminum phosphate zinc, titanium dioxide, talcum powder and the barium sulfate in above-mentioned formula successively, stir evenly;
(4) slurry stirring end of a period in (3) step is transferred in grinding plant, be ground to fineness and be less than 30 μm, obtain mill base;
(5) mill base in (4) step is transferred in paint container, add remaining fluorine richness epoxy resin latex by metered amount, stir evenly;
(6) add the film coalescence aid of above-mentioned formula ratio, thickening material, flow agent stir evenly;
(7) filter with 80-120 eye mesh screen, packaging, obtains coating composition component A finished product.
Prepared by high-performance environment protection type water-based inner cabin of ship coating composition B component
In container with slurry, add aqueous epoxy curing agent EPIKURE8545 and the water of accurate-metering, to stir obtained coating composition B component finished product with high speed dispersor.
4th step: the preparation of high-performance environment protection type water-based inner cabin of ship coating
With component A: B component=7:1(weight ratio) ratio mixing, stir, be coated on surface-treated tinplate sheet or low-carbon steel plate with brush, self-vulcanizing after application.After 14 days, the performance of coating is as follows:
Overcoating: easily, sticking power (cross-hatching) 0 grade, cut edge is completely level and smooth, and none lattice comes off, and has no intermediate(coat)peeling, stripping; (GB/T1720-1979)
Fungi-growth grade (28 days): 0 grade (having no mould-growth); (GJB150.10A-2009)
Contact angle θ/2 method: coating and distilled water contact angle 103 °;
Content of volatile organic compound (VOC): 78.8g/L; (GB/T18582-2008)
Resistance to neutral salt spray: coordinate with same system primary coat, more than 1000 hours, coating is non-foaming, non-corrosive, not come off.（GB/T1771-2007）。
Claims (10)
1. a high-performance environment protection type water-based inner cabin of ship coating, is characterized in that, this coating composition is made up of component A and B component, fills a prescription as follows:
Component A
B component
Raw-material weight per-cent
Aqueous epoxy curing agent 65-90%
Water 10-35%
A, B two components are used in combination in the ratio of 8 ~ 6:1 weight ratio.
2. high-performance environment protection type water-based inner cabin of ship coating according to claim 1, is characterized in that, described fluorine richness epoxy resin latex is the modified epoxy resin emulsion of lateral chain containing fluoroalkyl segment, comprises following structure:
X >=1 in formula; Y >=1; M=2-6; N=9,11,13;
In formula, R is line style, the branced aliphatic group that divalence has 4-30 carbon atom, or alicyclic group, or has the aromatic group of 6-24 carbon atom.
3. high-performance environment protection type water-based inner cabin of ship coating according to claim 1 and 2, it is characterized in that, described fluorine richness epoxy resin latex comprises following component:
。
4. fluorine richness epoxy resin latex according to claim 3, is characterized in that, the epoxy resin of described lateral chain containing fluoroalkyl segment comprises following component:
。
5. high-performance environment protection type water-based inner cabin of ship coating according to claim 1, is characterized in that: described rust-stabilising pigment is selected from one or both the mixture in zinc phosphate, aluminium triphosphate, aluminum phosphate zinc, phospho-molybdic acid zinc calcium, silicophosphate strontium; Described color stuffing comprises physique filler and pigment, and physique filler is selected from the mixture of one or more in process white, talcum powder, kaolin, ground barium sulfate, light calcium carbonate; Pigment is selected from the mixture of one or more in Rutile type Titanium Dioxide, red iron oxide, iron oxide black, iron oxide yellow, phthalocyanine blue, carbon black; Described film coalescence aid is selected from the low smell alcohol ethers film coalescence aid of boiling point more than 250 DEG C; Described auxiliary agent is selected from the mixing of one or more in defoamer, flow agent, wetting dispersing agent, thickening material, mould inhibitor, sanitas; Described aqueous epoxy curing agent is selected from the aqueous amine solidifying agent be made up of the affixture containing epoxy terminated polyether compound and amine.
6. high-performance environment protection type water-based inner cabin of ship coating according to claim 3, is characterized in that: described epoxy resin is the bisphenol A type epoxy resin of hydroxyl; Described reactive thinner is selected from one or both the mixture in 10 two to tetradecyl glycidyl ethers, butylglycidyl ether, o-tolyl glycidyl ether, BDDE, benzyl glycidyl ether; Described emulsifying agent is selected from the mixture of one or more in vinyl alkyl phenol polyethenoxy sulfonate, vinyl alkyl phosphoric acid ester, allyl ethers hydroxyl sulfoacid sodium; Described water is deionized water or distilled water.
7. high-performance environment protection type water-based inner cabin of ship coating according to claim 4, it is characterized in that: described vulcabond is selected from: isophorone diisocyanate, hexamethylene diisocyanate trimer, carbodiimide-uretonimine-modified 4,4-diphenylmethanediisocyanate, 4,4-diphenylmethanediisocyanate, one or both mixture in 2,4-diphenylmethanediisocyanate; Its molecular formula of described perfluoroalkyl alcohol is CF
3(CF
2)
n(CH
2) mOH, m=2-6 in formula; N=9,11,13; Described solvent is selected from one or both the mixture in ethyl acetate, N-BUTYL ACETATE, dimethylbenzene; Described catalyzer is selected from dibutyltin dilaurate, three-(N, N-dimethyl aminoethyl) amine; The solution of the described bisphenol A type epoxy resin solution containing hydroxyl to be epoxy resin content be 50-60%; Bisphenol A type epoxy resin containing hydroxyl is selected from one or both the mixture in E20, E12, Epikote1001, Epikote1007; Solvent in solution is selected from one or both the mixture in ethyl acetate, N-BUTYL ACETATE or dimethylbenzene.
8. high-performance environment protection type water-based inner cabin of ship method for preparing coatings composition according to claim 1, is characterized in that:
The first step: by fluorine richness epoxy resin latex, water, film coalescence aid, rust-stabilising pigment, color stuffing, auxiliary agent stirs in material-compound tank high speed dispersion, is ground to fineness≤30 μm, filters discharging and prepares component A;
Second step: aqueous epoxy curing agent and water are stirred in material-compound tank high speed dispersion, obtained B component;
By A, B two component by 8 ~ 6:1 weight ratio mixing.
9. the preparation method of the epoxy resin of lateral chain containing fluoroalkyl segment according to claim 4, it is characterized in that, by vulcabond, perfluoroalkyl alcohol, solvent joins in reactor, be filled with nitrogen or argon gas, at the uniform velocity stir, be heated to 60 ~ 95 DEG C, insulation reaction 2 ~ 3 hours after material all dissolves, add half catalyzer, to continue at 60 ~ 95 DEG C insulation reaction 6 ~ 8 hours while stirring, be cooled to 50 DEG C of bisphenol A type epoxy resin solution added containing hydroxyl, epoxy resin solid content is 50-60%, supply catalyst levels, be warming up to 65 ~ 90 DEG C, continue insulation reaction 6 ~ 8 hours, 2 ~ 4 hours are vacuumized after having reacted, the solvent that decompression removing is unnecessary, purify and obtain the epoxy resin of lateral chain containing fluoroalkyl segment.
10. the preparation method of fluorine richness epoxy resin latex according to claim 3, it is characterized in that, the epoxy resin taking lateral chain containing fluoroalkyl segment is placed in container, adds reactive thinner, adds epoxy resin, open mulser low rate mixing, preheating dispersing head, after epoxy resin dissolves completely, adds emulsifying agent and defoamer, it is completely even to system with rotating speed to be that 1500-4500rpm carries out high-speed stirring, and be creamy white oily body; Take the hot water of formula ratio 30-100 DEG C, by dropping funnel, hot water is slowly added drop-wise in system, the viscosity of system is increased gradually, and when reaching peak viscosity, system reaches inversion of phases stagnation point, now stop adding water, be after 1500-4500rpm carries out high-speed stirring 2-5 minute with rotating speed, after even to system, continue to drip remaining hot water, the total time for adding of hot water is 15-20 minute, is mixed with the epoxy resin latex of the stable lateral chain containing fluoroalkyl segment of oyster white.
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