CN1052317A - Waterborne rusted paint - Google Patents

Waterborne rusted paint Download PDF

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Publication number
CN1052317A
CN1052317A CN 90108650 CN90108650A CN1052317A CN 1052317 A CN1052317 A CN 1052317A CN 90108650 CN90108650 CN 90108650 CN 90108650 A CN90108650 A CN 90108650A CN 1052317 A CN1052317 A CN 1052317A
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emulsion
agent
freeze
synthetic resin
film
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CN 90108650
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CN1020196C (en
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魏宽文
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NAVY REAR SERVICE TECHNOLOGY APPARATUS INST CPLA
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NAVY REAR SERVICE TECHNOLOGY APPARATUS INST CPLA
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Publication of CN1052317A publication Critical patent/CN1052317A/en
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Abstract

The present invention is a kind of waterborne rusted paint, can directly spray it or brush on the steel structural part of rust.Coating of the present invention is made up of synthetic resin emulsion, transforming agent, thickening material, film coalescence aid, freeze-thaw stabiliser and other auxiliary agents, it forms weight percent: synthetic resin emulsion 60-80, transforming agent 4-6, inversion accelerating agent 1-3, thickening material 5-9, film coalescence aid 1-3, other auxiliary agents of freeze-thaw stabiliser 1-3 1-3, water 8-12.The characteristics of this coating are phosphoric acid not, and film-forming temperature is low, and excellent storage stability does not add softening agent.

Description

Waterborne rusted paint
The invention belongs to a kind of anti-corrosive paints, belong to a kind of waterborne rusted paint that is used for steel and iron member in more detail.
In order to protect the steel and iron member non-corrosive, often adopt the method for coating.Before using coating, must thoroughly eliminate rust to base material, the labour intensity of rust cleaning work is very big in the past, and concerning large-scale and baroque steel and iron member, thoroughly rust cleaning almost is impossible comprehensively.On rust paint has been arranged at present, and it need not thoroughly eliminate rust before using, and can directly be coated on the rust face of steel and iron member, can receive antirust effect equally.The spy opens in clear 57-18766 and No. 2160877 patents of GB and has narrated a kind of anti-corrosive paints of being made up of emulsion, film coalescence aid, transforming agent, inversion accelerating agent, freeze-thaw stabiliser, defoamer, tackifier and water etc., and this is a class waterborne rusted paint preferably at present.But the shortcoming that also also has film-forming temperature height, package stability difference.
The object of the present invention is to provide a kind of waterborne rusted paint, more definite theory provides a kind of film-forming temperature low, excellent storage stability, not the transformant waterborne rusted paint of phosphoric acid.This coating is made up of synthetic resin emulsion, transforming agent, inversion accelerating agent, film coalescence aid, freeze-thaw stabiliser, defoamer and mould inhibitor etc.
Synthetic resin emulsion is the important component part of waterborne rusted paint, all adopt the way of soft or hard monomer blend to synthesize usually, but film-forming temperature is all higher.Be lowered into film temperature, must reduce rigid monomer content, film like this, be clamminess with regard to deliquescing; Improve hardness of film, must improve rigid monomeric content, so just improved film-forming temperature.When preparing coating with this film-forming temperature high emulsion, need to add a large amount of auxiliary agents, particularly softening agent, this will influence the package stability and the film performance of coating.
The present invention adopts that step polymerization is synthetic to have an emulsion of laminate structure particle, so-called laminate structure emulsion, be exactly by the different polymkeric substance of two or more components, being not, homogeneous phase is present among the same particle, with a kind of polymkeric substance is core, another kind of polymkeric substance wraps in core outer layer, so, also claim core-shell emulsion.With the coating of this emulsion preparation, have following advantage: one, make rigid polymer be in the center, soft polymer wraps in the outside, helps particle like this and is melting, and helps the surface bonding of coated article or adheres to.And film-forming temperature is low, after the film forming, can obtain the hardness height simultaneously, the filming of good combination property; Its two, make the polymkeric substance that is difficult for dispersive wetting ability difference occupy the center, the polymkeric substance that wetting ability is strong wraps in the periphery, can improve the dispersion stabilization of emulsion.After the film forming, present hydrophobicity again, therefore can improve the water tolerance of filming.
Preparation example 240 parts (by weight, down together) distilled water, 1.0 parts of sodium bicarbonates and 2.2 portions of anion surfactants add in the reactor, be that 5 parts of butyl acrylates and 35 parts of vinylbenzene are scattered in the above-mentioned aqueous solution again with the first step monomer, be warming up to 70 ℃, add initiator i.e. 0.17 part of ammonium persulphate and 0.20 part of sodium bisulfite, make it polymerization in 30 minutes, be incubated 20 minutes, obtain the emulsion that particle diameter is the even particle size distribution of 0.155 μ; Drip the second step monomer with the speed of 2~3 milliliters of per minutes then, promptly 88 parts butyl acrylate, vinylbenzene and 2 parts of vinylformic acid of 30 parts added in about one hour, be incubated 1 hour, obtain the composition polymer emulsion of laminate structure, its particle diameter is 0.250 μ, and viscosity (is coated with 4 #Cup) 15.6 seconds, pH value 4~5,5 ℃ of minimum film-forming temperatures.
Adopt the synthetic laminate structure emulsion of step polymerization, to micelle-forming concentration, this is a key problem in technology of the present invention emulsifying agent in the polymerization system (for example tensio-active agent) concentration adjustment in requirement.If emulsifying agent deficiency, the stability of letex polymerization with regard to non-constant, gel often occurs in polymerization process; If emulsifier concentration surpasses micelle-forming concentration, can form new micella, emulsion particle is inhomogeneous, after the film forming, does not reach and gives the phase purpose.
With above-mentioned step polymerization synthetic benzene emulsion (vinylbenzene~acrylate), nitrile acrylic emulsion (vinyl cyanide~acrylate), styrene-butadiene emulsion (divinyl~vinylbenzene), butyronitrile emulsion (divinyl~vinyl cyanide), vinyl acetate emulsion (vinyl-acetic ester~acrylate), second second emulsion (vinyl-acetic ester~ethene), as long as mechanical stability and chemical stability reach requirement, all can be used for the present invention.Synthetic resin emulsion can account for 60~80% of gross weight among the present invention.
Transforming agent also is the weight integral part of this coating, and is rapid, thorough for corrosion is transformed, and also will add inversion accelerating agent in transforming agent, promptly has infiltrative acidulous material.The waterborne rusted paint great majority were to be base-material with various synthetic resin emulsions in the past, cooperate gallic acid, tannic acid, Protocatechuic Acid, M-nitro benzoic acid and derivative thereof as transforming agent,, also have and use phosphoric acid and yellow prussiate of potash as inversion accelerating agent simultaneously as transforming agent promotor with phosphoric acid or yellow prussiate of potash.Yellow prussiate of potash has influence significantly to the package stability of waterborne rusted paint, cooperates the coating of phosphoric acid, is coated in position rustless or that rusty scale is thin, often causes new corrosion hidden danger.The present invention adopts tannic acid or gallic acid to make transforming agent, replaces phosphoric acid and yellow prussiate of potash to make inversion accelerating agent with pyrocatechol or benzenetriol.Pyrocatechol and benzenetriol and tannin or tannic acid have only lightly crosslinked effect, can not influence the package stability of coating.Simultaneously, pyrocatechol and benzenetriol all have stronger rust inhibition and osmosis, can generate the black complex compound with iron rust, therefore, it makes rust conversion agent with tannic acid or gallic acid, has not only overcome the problems referred to above, and it is rapid, thorough that corrosion is transformed.Thereby give this coating and have rust-proof effect preferably.Transforming agent can account for 4~6% of gross weight among the present invention, and inversion accelerating agent accounts for 1~3%.
For increasing coat-thickness, in water-borne coatings, be added with thickening material usually.Because the transforming agent used of waterborne rusted paint has stronger complex ability, can with chemical compound lot complexing or crosslinked, therefore, when preparation coating, except that requiring emulsion to have the advantages of higher stability, other auxiliary agents all need conscientiously to select, otherwise will influence package stability.Thickening material commonly used, as polyvinyl alcohol, methylcellulose gum, polyvinyl formal, though have thickening power preferably, crosslinked with transforming agent, can make coating store instability or gel; Carboxymethyl cellulose, refining agar, alginates, polyacrylate can be used for the present invention, and wherein best is alginates and polyacrylate.Thickening material accounts for 5~9% of gross weight in this coating.
In order to help the latex particle film forming, also be added with film coalescence aid such as ethylene glycol ethyl ether, butyl glycol ether in this coating, consumption is preferably 1~3%(weight).Also be added with freeze-thaw stabiliser in this coating, can deposit at a lower temperature, be unlikely because of the gel of enduring cold, ethylene glycol, 1,2-propylene glycol, hexylene glycol etc. all can be used for the present invention, and its consumption can be 1~3%(weight).In addition, also be added with 0.1~1%(weight) tributyl phosphate or water-based silicon oil foam killer and 0.1~1%(weight) Sodium Benzoate and Sodium Nitrite as mould inhibitor.Contain 8~12%(weight in this coating) water.
Embodiment 5.0 parts (by weight, transforming agent (tannic acid) down together), 2.0 parts inversion accelerating agent (benzenetriol), 10.0 parts water, 2.0 parts film coalescence aid (butyl glycol ether) and 2.2 parts of freeze-thaw stabilisers (ethylene glycol) mix, heat is dissolved it fully a little.Stir on the limit again, the limit joins the good above-mentioned solution of dissolving among 70.2 parts the emulsion (benzene emulsion for preparing in preparation example), and then add 7.0 parts of thickening materials (14.2% polyacrylic acid sodium water solution) while stirring, add other auxiliary agent at last, comprise 0.8 part defoamer (tributyl phosphate) and 0.8 part mould inhibitor (5% Sodium Benzoate).Here note, can not add conversion fluid or thickening material in the emulsion quickly,, make the emulsion breaking gel in order to avoid partial concn is too high.
The coating for preparing, outward appearance is oyster white, and is tasteless, pH value 5~6, viscosity (is coated with 4 #Cup) 12.6 seconds, solid content 36.1%, 1 ℃ of minimum film-forming temperature, package stability is more than 1 year.This coating is coated onto on the iron and steel test specimen of corrosion, by the leucismus orchid, approximately need 1-1.5 minute by this process of blue blackening, about 30 minutes of surface drying is done solid work and is no more than 24 hours, 1 grade of sticking power (drawing the circle method), above-mentioned test specimen is immersed in distilled water and 3% salt solution, nothing had corrosion in 7 days, after 1 year, had only indivedual rust spots through atmospheric exposure.Above-mentioned coating is coated onto bin in the naval vessel, and through real ship examination 3 years, not having had corrosion.
This coating can be used for shipbuilding industry, petroleum industry, mechanical industry, building trade and other industry-by-industries that needs steel rust prevention to protect.

Claims (4)

1, a kind of waterborne rusted paint, it includes synthetic resin emulsion, transforming agent, thickening material, film coalescence aid, freeze-thaw stabiliser and other auxiliary agents, it is characterized in that its composition weight percent is: synthetic resin emulsion 60~80, transforming agent 4-6, inversion accelerating agent 1-3, thickening material 5-9, film coalescence aid 1-3, freeze-thaw stabiliser 1-3, defoamer 0.1-1, mould inhibitor 0.1-1, water 8-12; Optimum weight per-cent is: synthetic resin emulsion 70.2, transforming agent 5.0, inversion accelerating agent 2.0, water 10.0, thickening material 7.0, film coalescence aid 2.0, freeze-thaw stabiliser 2.2, defoamer 0.8, mould inhibitor 0.8.
2, waterborne rusted paint as claimed in claim 1, it is characterized in that described synthetic resin emulsion system by the low emulsion of step polymerization synthetic film-forming temperature, i.e. a kind of in benzene emulsion, pure acrylic emulsion, nitrile acrylic emulsion, styrene-butadiene emulsion, butyronitrile emulsion, vinyl acetate emulsion, the second second emulsion;
3, waterborne rusted paint as claimed in claim 1 is characterized in that described thickening material is alginates or polyacrylate; Described freeze-thaw stabiliser is ethylene glycol or 1,2-propylene glycol or hexylene glycol;
4, waterborne rusted paint as claimed in claim 1 is characterized in that described inversion accelerating agent is pyrocatechol or benzenetriol.
CN 90108650 1990-10-31 1990-10-31 Watery coating with rust Expired - Fee Related CN1020196C (en)

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CN 90108650 CN1020196C (en) 1990-10-31 1990-10-31 Watery coating with rust

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CN 90108650 CN1020196C (en) 1990-10-31 1990-10-31 Watery coating with rust

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CN1052317A true CN1052317A (en) 1991-06-19
CN1020196C CN1020196C (en) 1993-03-31

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Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1037354C (en) * 1992-12-27 1998-02-11 延边安装公司机械修造厂 Emulsified paint for rusted, oiled and watered steel and its preparing method
CN102212299A (en) * 2010-10-29 2011-10-12 立邦涂料(中国)有限公司 Long-acting antibacterial ultra-low volatility interior wall coating compound
CN101760095B (en) * 2008-11-07 2011-12-07 马其才 Multi-functional brushing liquid
CN101161739B (en) * 2006-10-12 2012-06-06 上海路丰助剂有限公司 Aqueous rust-conversion rust-inhibiting primer
CN102533018A (en) * 2011-12-23 2012-07-04 上海奇想青晨新材料科技股份有限公司 Antirust paint emulsion and its preparation method
CN102911565A (en) * 2012-09-30 2013-02-06 合肥华清方兴表面技术有限公司 Waterborne rusty coating for protecting coating of steel-structure work pieces and preparation method thereof
CN103183990A (en) * 2013-03-16 2013-07-03 安徽巢湖南方膜业有限责任公司 Environment-friendly water-based anticorrosive paint and preparation method thereof
CN103183991A (en) * 2013-03-16 2013-07-03 安徽巢湖南方膜业有限责任公司 Antirust coating with high acid resistance and preparation method thereof
CN103183989A (en) * 2013-03-16 2013-07-03 安徽巢湖南方膜业有限责任公司 Water-borne rust-based anticorrosion coating and preparation method thereof
CN103627264A (en) * 2013-11-08 2014-03-12 吴江邻苏精密机械有限公司 Polystyrene antirust paint
CN103665994A (en) * 2013-11-29 2014-03-26 江苏太平洋液压机械制造有限公司 Antirust styrene-acrylic emulsion paint in light yellow color
CN104031482A (en) * 2013-03-06 2014-09-10 山西鑫山生物工程集团有限公司 Environment friendly persimmon base membrane
CN104046149A (en) * 2014-07-01 2014-09-17 国家电网公司 Water-based on-rust paint and preparation method thereof
CN104356780A (en) * 2014-11-14 2015-02-18 无锡伊佩克科技有限公司 Water-based residual rust paint and preparation method thereof
CN105017884A (en) * 2014-04-16 2015-11-04 镇江德马化工有限公司 Aqueous rotating rust steel iron surface treatment liquid and preparation method thereof
CN107880664A (en) * 2017-12-22 2018-04-06 江苏怡成屏障科技有限公司 Environmentally friendly low-carbon rotation rust coating and preparation method thereof
US11407921B2 (en) 2016-12-22 2022-08-09 Henkel Ag & Co. Kgaa Reaction products of catechol compounds and functionalized co-reactant compounds for metal pretreatment applications
US11891534B2 (en) 2016-12-22 2024-02-06 Henkel Ag & Co. Kgaa Treatment of conversion-coated metal substrates with preformed reaction products of catechol compounds and functionalized co-reactant compounds

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1037354C (en) * 1992-12-27 1998-02-11 延边安装公司机械修造厂 Emulsified paint for rusted, oiled and watered steel and its preparing method
CN101161739B (en) * 2006-10-12 2012-06-06 上海路丰助剂有限公司 Aqueous rust-conversion rust-inhibiting primer
CN101760095B (en) * 2008-11-07 2011-12-07 马其才 Multi-functional brushing liquid
CN102212299B (en) * 2010-10-29 2013-12-04 立邦涂料(中国)有限公司 Long-acting antibacterial ultra-low volatility interior wall coating compound
CN102212299A (en) * 2010-10-29 2011-10-12 立邦涂料(中国)有限公司 Long-acting antibacterial ultra-low volatility interior wall coating compound
CN102533018A (en) * 2011-12-23 2012-07-04 上海奇想青晨新材料科技股份有限公司 Antirust paint emulsion and its preparation method
CN102911565A (en) * 2012-09-30 2013-02-06 合肥华清方兴表面技术有限公司 Waterborne rusty coating for protecting coating of steel-structure work pieces and preparation method thereof
CN102911565B (en) * 2012-09-30 2015-05-13 合肥华清方兴表面技术有限公司 Waterborne rusty coating for protecting coating of steel-structure work pieces and preparation method thereof
CN104031482A (en) * 2013-03-06 2014-09-10 山西鑫山生物工程集团有限公司 Environment friendly persimmon base membrane
CN103183990A (en) * 2013-03-16 2013-07-03 安徽巢湖南方膜业有限责任公司 Environment-friendly water-based anticorrosive paint and preparation method thereof
CN103183991A (en) * 2013-03-16 2013-07-03 安徽巢湖南方膜业有限责任公司 Antirust coating with high acid resistance and preparation method thereof
CN103183989A (en) * 2013-03-16 2013-07-03 安徽巢湖南方膜业有限责任公司 Water-borne rust-based anticorrosion coating and preparation method thereof
CN103183989B (en) * 2013-03-16 2015-06-10 安徽巢湖南方膜业有限责任公司 Water-borne rust-based anticorrosion coating and preparation method thereof
CN103183991B (en) * 2013-03-16 2015-03-25 安徽巢湖南方膜业有限责任公司 Antirust coating with high acid resistance and preparation method thereof
CN103183990B (en) * 2013-03-16 2015-03-25 安徽巢湖南方膜业有限责任公司 Environment-friendly water-based anticorrosive paint and preparation method thereof
CN103627264A (en) * 2013-11-08 2014-03-12 吴江邻苏精密机械有限公司 Polystyrene antirust paint
CN103665994A (en) * 2013-11-29 2014-03-26 江苏太平洋液压机械制造有限公司 Antirust styrene-acrylic emulsion paint in light yellow color
CN105017884A (en) * 2014-04-16 2015-11-04 镇江德马化工有限公司 Aqueous rotating rust steel iron surface treatment liquid and preparation method thereof
CN104046149A (en) * 2014-07-01 2014-09-17 国家电网公司 Water-based on-rust paint and preparation method thereof
CN104356780A (en) * 2014-11-14 2015-02-18 无锡伊佩克科技有限公司 Water-based residual rust paint and preparation method thereof
CN104356780B (en) * 2014-11-14 2017-01-18 河北晨阳工贸集团有限公司 Water-based residual rust paint and preparation method thereof
US11407921B2 (en) 2016-12-22 2022-08-09 Henkel Ag & Co. Kgaa Reaction products of catechol compounds and functionalized co-reactant compounds for metal pretreatment applications
US11891534B2 (en) 2016-12-22 2024-02-06 Henkel Ag & Co. Kgaa Treatment of conversion-coated metal substrates with preformed reaction products of catechol compounds and functionalized co-reactant compounds
CN107880664A (en) * 2017-12-22 2018-04-06 江苏怡成屏障科技有限公司 Environmentally friendly low-carbon rotation rust coating and preparation method thereof

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