CN103409002A - Environment-friendly anticorrosive acrylic acid water-based coating and preparation method thereof - Google Patents
Environment-friendly anticorrosive acrylic acid water-based coating and preparation method thereof Download PDFInfo
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- CN103409002A CN103409002A CN2013102499537A CN201310249953A CN103409002A CN 103409002 A CN103409002 A CN 103409002A CN 2013102499537 A CN2013102499537 A CN 2013102499537A CN 201310249953 A CN201310249953 A CN 201310249953A CN 103409002 A CN103409002 A CN 103409002A
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Abstract
The invention relates to an environment-friendly anticorrosive acrylic acid water-based coating and a preparation method thereof. The environment-friendly anticorrosive acrylic acid water-based coating comprises deionized water, a film forming auxiliary agent, a wetting agent, a dispersant, a filler, and acrylic emulsion which comprises fluoroketone hydroxyl acrylic resin, adipic acid dihydrazide used as a crosslinking agent and water-soluble amino resin. The preparation method comprises the following steps of: preparing a water-based dispersoid; adding the water-based dispersoid into stirred acrylic emulsion, adding the film forming auxiliary agent and a thickening agent, and stirring and uniformly dispersing the film forming auxiliary agent and the thickening agent; adding a pigment; and replenishing water and adjusting the viscosity to obtain the water-based coating. In the invention, the environment-friendly anticorrosive acrylic acid water-based coating has certain hardness, low VOC (volatile organic compounds) and formaldehyde contents, does not have heavy metals, and has excellent corrosion resistance.
Description
Technical field
The present invention relates to technical field of aqueous paint, relate in particular to acrylic type water-borne coatings of a kind of environment friendly corrosion protection and preparation method thereof.
Background technology
Aqueous acrylic emulsion is widely used in water-borne coatings, and for example interior outer wall building coating almost all adopts aqueous acrylic emulsion.Usually aqueous acrylic emulsion, is formed through letex polymerization by monomers such as Acrylic Acid Monomer, vinyl acetate between to for plastic and vinylbenzene in water under emulsifying agent exists.
There are two significant shortcomings in aqueous acrylic emulsion: be at first that paint film is softer, this is because aqueous acrylic emulsion need to the fusion by micro emulsion form continuous paint film after the water solvent volatilization, there is no crosslinking reaction, if polymer glass temperature (Tg) is too high, cause the film forming difficulty, the inevitable hardness of the low paint film of Tg is low, and nail can scratch usually; Second shortcoming is that Corrosion Protection is bad, this is because water soluble acrylic acid relies on the wetting ability of monomer or the wetting ability of emulsifying agent to form stable emulsion, these hydrophilic radicals just cause the water tolerance extreme difference of paint film after film forming, thereby the general salt spray resistance of rust proof paint that common water soluble acrylic acid is made can only reach 100-200 hour, and solvent typely generally can reach 500-1000 hour.
Simultaneously, along with people improve constantly the requirement of coating safety and environmental protection used, the material of these serious harm human-body safeties such as the hazardous and noxious substances in coating such as volatile organic compounds (VOC), formaldehyde, heavy metal content also becomes one of problem that fears are entertained that.Therefore, a kind of not only Environmental Safety of exploitation but also coating with excellent use properties such as antiseptic property become and pay close attention to essential technical problem solved of HUMAN HEALTH.
Summary of the invention
The invention provides a kind of acrylic type water-borne coatings of environment friendly corrosion protection, both had certain degree of hardness, low VOC, formaldehyde, heavy metal free, and have excellent antiseptic property.
In the present invention, a kind of acrylic type water-borne coatings of environment friendly corrosion protection, contain by weight following component: 5～25 parts of deionized waters, 3～20 parts of film coalescence aid, 0.1～1.5 part of wetting agent, 2.0～5.0 parts of dispersion agents, 3～20 parts of fillers, 35～60 parts of ACRYLIC EMULSION, wherein, ACRYLIC EMULSION comprises fluorine ketone Hydroxylated acrylic resin, as adipic dihydrazide and the water soluble amino resin of linking agent.
The present invention utilizes the coating that ACRYLIC EMULSION makes, and not only sticking power is good, hardness is high, snappiness is excellent, and the non-corrosibility ability also is significantly improved.
ACRYLIC EMULSION provided by the present invention, the preparation method is as follows: be at first to use emulsion polymerization technology through copolymerization, to obtain fluorine ketone Hydroxylated acrylic resin in water, then in emulsion, add linking agent adipic dihydrazide and water soluble amino resin.Before adding ADH, need to adjust emulsion pH with ammoniacal liquor or amine is 7-9.
Preferably, described film coalescence aid is selected one or more mixture of Macrogol 200, Liquid Macrogol, poly(oxyethylene glycol) 400, propylene glycol phenylate PPH, alcohol ester-12.Film coalescence aid is selected the organic compound without physiology toxicity, VOC free.Film coalescence aid is selected a kind of or its combination of Macrogol 200, Liquid Macrogol, poly(oxyethylene glycol) 400, propylene glycol phenylate PPH, alcohol ester-12.
Preferably, described filler is selected one or more mixture of ultra-fine fine particle calcium carbonate, talcum powder, process white, silicon calcium powder, Zinic stearas.Filler is selected a kind of or its combination of the ultra-fine fine particle calcium carbonate that do not contain heavy metal, talcum powder, process white, silicon calcium powder, Zinic stearas.
Preferably, described fluorine ketone Hydroxylated acrylic resin carries out radical polymerization by the fluorine-containing unsaturated monomer of the vinyl monomer of the unsaturated monomer that contains the ketone carbonyl that accounts for total monomer weight 0.5-15%, 60-95% and 2-25% and obtains in water.It is not contain free monomer that unsaturated monomer, vinyl monomer and the fluorine-containing unsaturated monomer that contains the ketone carbonyl selected, and does not contain triphen, the raw material of content≤65g/L of VOC.
Radical polymerization is a kind of polymerization technique that those of ordinary skills commonly use, and under the guidance of relevant high molecular polymer textbook, just can obtain fluorine ketone Hydroxylated acrylic resin of the present invention.
Preferably, the described unsaturated monomer that contains the ketone carbonyl is selected from one or more mixture of diacetone-acryloamide(DAA), propenal, Methylacrylaldehyde, methyl vinyl ketone, vinylformic acid acetoxy ethyl ester and methacrylic acid acetoxy ethyl ester, preferred propenal or Methylacrylaldehyde, or its mixture;
Described vinyl monomer is selected from following one or more mixture: vinylbenzene, alpha-methyl styrene, vinyl acetate between to for plastic, vinyl cyanide, optimization styrene or alpha-methyl styrene, or its mixture;
Described fluorine-containing unsaturated monomer is selected from one or more mixture of trifluorochloroethylene, vinylformic acid trifluoro ethyl ester, trifluoroethyl methacrylate, vinylformic acid hexafluoro butyl ester, Hexafluorobutyl mathacrylate, vinylformic acid ten difluoro fat in heptan, methacrylic acid ten difluoro fat in heptan, vinylformic acid ten trifluoro monooctyl esters and methacrylic acid ten trifluoro monooctyl esters, preferred trifluorochloroethylene, vinylformic acid trifluoro ethyl ester, trifluoroethyl methacrylate or vinylformic acid hexafluoro butyl ester, or two or more mixtures.
Preferably, described water soluble amino resin, be selected from the terpolycyantoamino-formaldehyde resin of complete methyl-etherified or the urea-formaldehyde resin of complete methyl-etherified, or its mixture.
In optimal technical scheme, the acrylic type water-borne coatings of environment friendly corrosion protection provided by the invention, also comprise conventional auxiliary agent, preferred pigments, thickening material, sanitas, the mixture of one or more in defoamer.
Conventional adding of auxiliary agent can be so that the coating property made be more outstanding.Pigment can make coating have predetermined color and luster, and pigment optimization of the present invention does not contain the anti-corrosion paint of heavy metal, as red lead, zinc yellow, zinc phosphate, strontium chromate and zinc molybdate.Thickening material can be so that coating has thixotropy preferably, and the present invention selects the nonionic polyurethane compounds.Sanitas can suppress the mould-growth in coating, makes coating keep steady quality.In the present invention, sanitas is isothiazolinone.Defoamer can suppress foam, while making the coating brushing, is difficult for producing shrinkage cavity and flake, and defoamer of the present invention can adopt the mixture of water drain silica and mineral oil.The addition of conventional auxiliary agent can add according to those skilled in the art's general knowledge.
The present invention also provides a kind of preparation method of acrylic type water-borne coatings of environment friendly corrosion protection, comprises the steps:
The weight percent of S1, setting, by deionized water, wetting agent, dispersion agent, defoamer mixing and stirring, add filler, with 1000～3000rpm, carries out high speed dispersion even, obtains aqueous dispersion;
S2, the aqueous dispersion that S1 is obtained add in the ACRYLIC EMULSION of stirring, then add film coalescence aid, thickening material dispersed with stirring even, then add pigment;
S3, moisturizing adjusting viscosity are 65～90KU, make the acrylic type water-borne coatings of environment friendly corrosion protection.
In the present invention, the acrylic type water-borne coatings of described environment friendly corrosion protection, both had certain degree of hardness, hangs down VOC, formaldehyde, heavy metal free, and have the coating of excellent antiseptic property, is the water-borne coatings that a kind of use properties and environmental-protecting performance all can be taken into account.
Embodiment
The acrylic type water-borne coatings of the environment friendly corrosion protection that the present invention proposes, ACRYLIC EMULSION adopt ingredient requirement not contain free monomer, do not contain triphen, VOC low (≤65g/L).Film coalescence aid in water-borne coatings is selected without the organic compound of physiology toxicity, VOC free such as Macrogol 200, Liquid Macrogol or poly(oxyethylene glycol) 400, propylene glycol phenylate PPH, alcohol ester-12 etc.In coating, pigment selects heavy metal to meet the hygienic safety standard.Filler generally is used in aqueous putty or solid color enamel, selects and meets ultra-fine fine particle calcium carbonate, talcum powder, process white, silicon calcium powder and the Zinic stearas that hygienic requirements does not contain heavy metal.Other auxiliary agent such as dispersion agent, defoamer, thickening material, sanitas etc. are close with common coating, select zero or low VOC, do not contain the product of APE.Therefore, the acrylic type water-borne coatings of described environment friendly corrosion protection, both had certain degree of hardness, hangs down VOC, formaldehyde, heavy metal free, and have the coating of excellent antiseptic property, is the water-borne coatings that a kind of use properties and environmental-protecting performance all can be taken into account.
Embodiment 1:
In the present embodiment, a kind of acrylic type water-borne coatings of environment friendly corrosion protection, contain following component: 25 parts of deionized waters, 20 parts of film coalescence aid, 0.1 part of wetting agent, 2 parts of dispersion agents, 3 parts of fillers, 35 parts of ACRYLIC EMULSION, 5 parts of pigment, 1.5 parts of thickening materials by weight; Wherein, ACRYLIC EMULSION, comprise fluorine ketone Hydroxylated acrylic resin, as the adipic dihydrazide of linking agent and the terpolycyantoamino-formaldehyde resin of methyl-etherified fully, fluorine ketone Hydroxylated acrylic resin is obtained by radical polymerization by diacetone-acryloamide(DAA), vinylbenzene, trifluorochloroethylene.
Embodiment 2:
In the present embodiment, a kind of acrylic type water-borne coatings of environment friendly corrosion protection, contain following component: 5 parts of deionized waters, 3 parts of film coalescence aid by weight, 1.5 parts of wetting agents, 5 parts of dispersion agents, 20 parts of fillers, 60 parts of ACRYLIC EMULSION, 0.5 part of sanitas, 1.2 parts of defoamers, 3 parts of pigment; Wherein, ACRYLIC EMULSION, comprise fluorine ketone Hydroxylated acrylic resin, as the adipic dihydrazide of linking agent and the terpolycyantoamino-formaldehyde resin of methyl-etherified fully, fluorine ketone Hydroxylated acrylic resin is obtained by radical polymerization by propenal, vinyl cyanide, vinylformic acid trifluoro ethyl ester.
Embodiment 3:
In the present embodiment, a kind of acrylic type water-borne coatings of environment friendly corrosion protection, contain following component: 10 parts of deionized waters, 15 parts of film coalescence aid by weight, 1.1 parts of wetting agents, 3.5 parts of dispersion agents, 16 parts of fillers, 45 parts of ACRYLIC EMULSION, 0.06 part of sanitas, 3 parts of defoamers, 2.5 parts of pigment, 4 parts of thickening materials; Wherein, ACRYLIC EMULSION, comprise fluorine ketone Hydroxylated acrylic resin, as the adipic dihydrazide of linking agent and the urea-formaldehyde resin of methyl-etherified fully, fluorine ketone Hydroxylated acrylic resin is obtained by radical polymerization by vinylformic acid acetoxy ethyl ester, alpha-methyl styrene, vinylformic acid hexafluoro butyl ester.
Based on the acrylic type water-borne coatings of above-mentioned environment friendly corrosion protection, its preparation method comprises the steps:
The weight percent of S1, setting, by deionized water, wetting agent, dispersion agent, defoamer mixing and stirring, add filler, with 1000～3000rpm, carries out high speed dispersion even, obtains aqueous dispersion;
S2, the aqueous dispersion that S1 is obtained add in the ACRYLIC EMULSION of stirring, then add film coalescence aid, thickening material dispersed with stirring even, then add pigment;
S3, moisturizing adjusting viscosity are 65～90KU, make the acrylic type water-borne coatings of environment friendly corrosion protection.
The above; it is only preferably embodiment of the present invention; but protection scope of the present invention is not limited to this; anyly be familiar with those skilled in the art in the technical scope that the present invention discloses; according to technical scheme of the present invention and inventive concept thereof, be equal to replacement or changed, within all should being encompassed in protection scope of the present invention.
Claims (8)
1. the acrylic type water-borne coatings of an environment friendly corrosion protection, it is characterized in that, contain by weight following component: 5～25 parts of deionized waters, 3～20 parts of film coalescence aid, 0.1～1.5 part of wetting agent, 2.0～5.0 parts of dispersion agents, 3～20 parts of fillers, 35～60 parts of ACRYLIC EMULSION, wherein, ACRYLIC EMULSION comprises fluorine ketone Hydroxylated acrylic resin, as adipic dihydrazide and the water soluble amino resin of linking agent.
2. the acrylic type water-borne coatings of environment friendly corrosion protection as claimed in claim 1, it is characterized in that, described film coalescence aid is selected one or more mixture of Macrogol 200, Liquid Macrogol, poly(oxyethylene glycol) 400, propylene glycol phenylate PPH, alcohol ester-12.
3. the acrylic type water-borne coatings of environment friendly corrosion protection as claimed in claim 1 is characterized in that: described filler is selected one or more mixture of ultra-fine fine particle calcium carbonate, talcum powder, process white, silicon calcium powder, Zinic stearas.
4. as the acrylic type water-borne coatings of the described environment friendly corrosion protection of any one in claim 1-3, it is characterized in that, described fluorine ketone Hydroxylated acrylic resin carries out radical polymerization by the fluorine-containing unsaturated monomer of the vinyl monomer of the unsaturated monomer that contains the ketone carbonyl that accounts for total monomer weight 0.5-15%, 60-95% and 2-25% and obtains in water.
5. the acrylic type water-borne coatings of environment friendly corrosion protection as claimed in claim 4, it is characterized in that, the described unsaturated monomer that contains the ketone carbonyl is selected from one or more mixture of diacetone-acryloamide(DAA), propenal, Methylacrylaldehyde, methyl vinyl ketone, vinylformic acid acetoxy ethyl ester and methacrylic acid acetoxy ethyl ester, preferred propenal or Methylacrylaldehyde, or its mixture;
Described vinyl monomer is selected from following one or more mixture: vinylbenzene, alpha-methyl styrene, vinyl acetate between to for plastic, vinyl cyanide, optimization styrene or alpha-methyl styrene, or its mixture;
Described fluorine-containing unsaturated monomer is selected from one or more mixture of trifluorochloroethylene, vinylformic acid trifluoro ethyl ester, trifluoroethyl methacrylate, vinylformic acid hexafluoro butyl ester, Hexafluorobutyl mathacrylate, vinylformic acid ten difluoro fat in heptan, methacrylic acid ten difluoro fat in heptan, vinylformic acid ten trifluoro monooctyl esters and methacrylic acid ten trifluoro monooctyl esters, preferred trifluorochloroethylene, vinylformic acid trifluoro ethyl ester, trifluoroethyl methacrylate or vinylformic acid hexafluoro butyl ester, or two or more mixtures.
6. as the acrylic type water-borne coatings of the described environment friendly corrosion protection of any one in claim 1-3, it is characterized in that, described water soluble amino resin is the terpolycyantoamino-formaldehyde resin of complete methyl-etherified or urea-formaldehyde resin or both mixtures of complete methyl-etherified.
7. as the acrylic type water-borne coatings of the described environment friendly corrosion protection of any one in claim 1-6, it is characterized in that, described water-borne coatings also comprises conventional auxiliary agent, preferred pigments, thickening material, sanitas, the mixture of one or more in defoamer.
8. preparation method as the acrylic type water-borne coatings of the arbitrary described environment friendly corrosion protection of claim 1-7 comprises following step:
The weight percent of S1, setting, by deionized water, wetting agent, dispersion agent, defoamer mixing and stirring, add filler, with 1000～3000rpm, carries out high speed dispersion even, obtains aqueous dispersion;
S2, the aqueous dispersion that S1 is obtained add in the ACRYLIC EMULSION of stirring, then add film coalescence aid, thickening material dispersed with stirring even, then add pigment;
S3, moisturizing adjusting viscosity are 65～90KU, make the acrylic type water-borne coatings of environment friendly corrosion protection.
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| CN104341946A (en) * | 2014-10-14 | 2015-02-11 | 凤阳徽亨商贸有限公司 | Glass paint with functions of refreshing mind and inducing resuscitation and preparation method thereof |
| CN104804125A (en) * | 2015-04-16 | 2015-07-29 | 佛山市顺德区巴德富实业有限公司 | Adipic dihydrazide modified acrylic ester emulsion for removing formaldehyde and preparation method of emulsion |
| CN105273542A (en) * | 2015-11-05 | 2016-01-27 | 苏州明轩地坪涂料有限公司 | Flame-retardant latex paint |
| CN106189587A (en) * | 2016-07-19 | 2016-12-07 | 安徽圣德建材科技有限公司 | A kind of preparation method of acrylic coating used for building exterior wall |
| CN106833247A (en) * | 2017-02-28 | 2017-06-13 | 广州聚澜健康产业研究院有限公司 | A kind of environment-friendly type fluorine carbon anticorrosive paint and preparation method thereof |
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| CN109161260A (en) * | 2018-09-05 | 2019-01-08 | 马鞍山市金韩涂料制造有限公司 | A kind of production technology for road mark paint |
| CN109679421A (en) * | 2018-11-21 | 2019-04-26 | 镇江禹亨新材料有限公司 | A kind of single-component water-based acrylic acid antisepsis finishing paint of normal temperature self-drying type |
| CN109880467A (en) * | 2019-02-20 | 2019-06-14 | 哈尔滨绿科科技有限公司 | One kind being suitable for oilfield environment metal base corrosion-resistant environment protecting water-based paint |
| CN110079169A (en) * | 2014-09-09 | 2019-08-02 | 霍尼韦尔国际公司 | Low VOC and high solid fluoropolymer for coating application |
| CN111138932A (en) * | 2019-12-19 | 2020-05-12 | 湖南太子化工涂料有限公司 | High-wear-resistance water-based paint for agricultural machinery and preparation method thereof |
| CN111560100A (en) * | 2020-06-28 | 2020-08-21 | 广西贵港和乐门业有限公司 | Novel acrylic resin and preparation method and application thereof |
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| CN110079169A (en) * | 2014-09-09 | 2019-08-02 | 霍尼韦尔国际公司 | Low VOC and high solid fluoropolymer for coating application |
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| CN104341946A (en) * | 2014-10-14 | 2015-02-11 | 凤阳徽亨商贸有限公司 | Glass paint with functions of refreshing mind and inducing resuscitation and preparation method thereof |
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| CN107652820A (en) * | 2016-07-23 | 2018-02-02 | 天津市新丽华色材有限责任公司 | A kind of lead-free environment-friendly type silver mirror mirror-back protective coating |
| CN106833247A (en) * | 2017-02-28 | 2017-06-13 | 广州聚澜健康产业研究院有限公司 | A kind of environment-friendly type fluorine carbon anticorrosive paint and preparation method thereof |
| CN109161260A (en) * | 2018-09-05 | 2019-01-08 | 马鞍山市金韩涂料制造有限公司 | A kind of production technology for road mark paint |
| CN109679421A (en) * | 2018-11-21 | 2019-04-26 | 镇江禹亨新材料有限公司 | A kind of single-component water-based acrylic acid antisepsis finishing paint of normal temperature self-drying type |
| CN109880467A (en) * | 2019-02-20 | 2019-06-14 | 哈尔滨绿科科技有限公司 | One kind being suitable for oilfield environment metal base corrosion-resistant environment protecting water-based paint |
| CN109880467B (en) * | 2019-02-20 | 2021-01-08 | 哈尔滨绿科科技有限公司 | Environment-friendly water-based paint suitable for corrosion prevention of metal base material in oil field environment |
| CN111138932A (en) * | 2019-12-19 | 2020-05-12 | 湖南太子化工涂料有限公司 | High-wear-resistance water-based paint for agricultural machinery and preparation method thereof |
| CN111560100A (en) * | 2020-06-28 | 2020-08-21 | 广西贵港和乐门业有限公司 | Novel acrylic resin and preparation method and application thereof |
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Application publication date: 20131127 |