CN100368495C - Water epoxy resin paint and its making process - Google Patents
Water epoxy resin paint and its making process Download PDFInfo
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- CN100368495C CN100368495C CNB2004100679818A CN200410067981A CN100368495C CN 100368495 C CN100368495 C CN 100368495C CN B2004100679818 A CNB2004100679818 A CN B2004100679818A CN 200410067981 A CN200410067981 A CN 200410067981A CN 100368495 C CN100368495 C CN 100368495C
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- epoxide resin
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Abstract
The present invention discloses a composition of water epoxy resin paint and a preparation method thereof, which is characterized in that the paint is composed of an A component and a B component, wherein the A component uses chemically modified water epoxy resin as base materials, and the B component as a curing agent uses chemically modified water polybasic amine as base materials. The paint has the characteristics of high storage stability of epoxy resin emulsion, long service life, favorable brushing performance, easy observation of a using end, and good water resistance and corrosion resistance of a paint film.
Description
Technical field
The present invention relates to a kind of eco-friendly protective system and manufacture method thereof, specifically, relate to a kind of protective system and manufacture method thereof based on aqueous epoxy resins.
Background technology
Traditional epoxypaint is solvent type, and its feature is to have good sticking power, corrosion-resistant, wear-resisting, but this class coating has a large amount of solvent evaporates in preparation and construction process, and not only contaminate environment also endangers health of operators.
For this reason, people have developed eco-friendly aqueous epoxide resin paint, are made up of first and second liang of components usually, and the first component is that epoxy resin latex, component B are waterborne curing agent.Because Resins, epoxy itself is water insoluble, can not directly add entry and carry out emulsification, adopts the method for mechanical disintegration usually, solid epoxy is worn into micron-sized fine powder in advance, under heating condition, add emulsifying agent and water again,, make it to form epoxy resin latex by the intensive mechanical stirring.But Zhi Bei emulsion owing to the distribution of sizes broad of solids, causes the stable not enough of emulsion in this way, collides and the generation coacervation mutually easily between the particle.Another kind of common method is to adopt " phase reversion " method, promptly under the high speed shear effect, at first outer emulsifying agent and Resins, epoxy are mixed, under suitable shearing condition, in system, add distilled water subsequently lentamente, at this moment, with the increase of rate of water added, whole system progressively is converted into " oil-in-water " by " water-in-oil ", thus form can dilute with water system.But, adopt this method to be difficult to judge whether " phase reversion " process has reached terminal point completely, thereby deal with the stability that also can influence emulsion improperly.
In addition, have advantages such as curing speed is fast, viscosity is low though be commonly used for the aliphatic polyamine of aqueous epoxide resin paint solidifying agent, have that construction time limit weak point, frowziness, pungency are strong, the moisture absorption, and the compatibility of resin is poor, easily cause paint film shrinkage cavity, tangerine peel, return disadvantages such as white.Use polymeric amide instead as solidifying agent, price is higher, and not obviously raising of paint film property, and curing speed is also slow.
Summary of the invention
The present invention is intended to overcome the deficiency of above-mentioned existing aqueous epoxide resin paint, a kind of strong adhesion that had both kept solvent epoxy varnish coating, excellent properties such as corrosion-resistant, wear-resisting are provided, have again the construction time limit suitably, the aqueous epoxide resin paint of the smooth characteristic such as smooth of good, fast dried, water-fast, the shelf-stable of brushing performance, paint film.
This coating is a kind of room temperature-cured aqueous epoxy cold coating that comprises the first and second two components, it is characterized in that the first component is a base-material with the aqueous epoxy resins through chemical modification, as the component B of solidifying agent based on water-based polyamine through chemical modification.
Wherein, chemical modification aqueous epoxy resins as the first component, the cardinal principle of modification is that ionic group or polar group are incorporated on the Resins, epoxy apolar chain, make it become the amphiphilic polymers of hydrophilic and oleophilic, thereby can produce the surfactivity effect, for example, in epoxy-resin systems, add the polyoxyethylene nonionic surface active agent, make hydroxyl on the polyoxyethylene segment and the epoxy reaction in the Resins, epoxy, thereby hydrophilic polyoxyethylene segment is introduced in the Resins, epoxy molecular chain, can be obtained containing the aqueous epoxy resins of nonionic hydrophilic segment.During emulsification, these hydrophilic segment are distributed in the surface of hydrophobic polymer particulate, repel mutually because of having like charges, so can form stable epoxy resin latex under certain dynamic conditions.In view of the above, aqueous epoxide resin paint of the present invention is characterized in that, described first component comprises the material of following gradation composition:
Weight %
Resins, epoxy 40～80
Emulsifying agent 0～10
Auxiliary agent I 0～10
Auxiliary agent II 0～10
Deionized water 20～60.
Resins, epoxy wherein can be to be selected from a kind of among Resins, epoxy E-51, E-42, E-44, the E-20 or several mixture wherein.Described emulsifying agent is a kind of nonionic surface active agent, can be to be selected from a kind of in the condenses of stearin, oxyethylene, lipid acid and oxyethane or several mixture; Described auxiliary agent I is a kind of associative thickener, is to be selected from a kind of in acrylic acid type thickening material, polyurethane associative thickener, the lithium bentonite or several mixture; Described auxiliary agent II is a kind of solubility promoter, is to be selected from a kind of in pure ether solvent, toluene, the ketone or several mixture.
The preparation technology of this first component is as follows: the proportioning by above-mentioned setting drops into Resins, epoxy, emulsifying agent in the high-speed stirring cylinder, under 1400 ± 100 rev/mins rotating speed, be uniformly dispersed, 40 ± 5 ℃ deionized waters are added drop-wise in the system, after dropwising, stablized 12～18 minutes, adding auxiliary agent I, II then stirs, stablized 25～35 minutes, filtration, discharging, packing, stand-by;
The component B of aqueous epoxide resin paint of the present invention comprises the material of following gradation composition:
Weight %
Resins, epoxy 20～60
Aliphatic amide 20～65
Aliphatic cyclic amine 0～20
Alcohol ether solvent 5～30
Deionized water 10～40
Also promptly this component B comes down to the solidifying agent of the present invention's aqueous epoxide resin paint, what adopt is the modifier of aliphatic amide, and it is by aliphatic polyamine is carried out the epoxy waterborne curing agent that part primary amine end-blocking obtains a kind of water-dispersion with a small amount of Resins, epoxy reaction and with unitary aliphatic glycidyl ether.After adopting this class solidifying agent, paint film be difficult for the moisture absorption return white, stink is slight; After joining lacquer, needn't slaking just can directly use, unhindered amina content is low, toxicity is little; Because it improves with the consistency as the aqueous epoxy resins of first component, the cross-linking density of paint film improves.
Aliphatic amide in the above-mentioned gradation composition can be to be selected from a kind of in quadrol, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, the hexanediamine or several mixture; Described aliphatic cyclic amine can be to be selected from 1,3-diamino hexahydroaniline, 1,2-diamino hexahydroaniline, 1, a kind of in 4-diamino hexahydroaniline, the m-xylene diamine or several mixture; Described pure ether solvent can be to be selected from a kind of in ethylene glycol ethyl ether, phenylate, the propylene glycol propyl ether or several mixture.
The preparation technology of this component B is: by setting proportioning aliphatic amide, aliphatic cyclic amine are dropped in the reactor, heating, stirring are warming up to 60 ± 2 ℃, insulation, the mixed solution of dropping Resins, epoxy and pure ether solvent is after dropwising, 80 ± 2 ℃ of insulations 1.5～2.5 hours, add deionized water, be warming up to 80 ± 2 ℃, be incubated 1.5～2.5 hours, when the amine value reaches 340 ± 20, stopped reaction, cooling, filtration, discharging, packing, stand-by.
Certainly, except above-mentioned first, second two components, at body of the present invention in change can be with addition of various suitable coating cooperation machine commonly used, for example color stuffing and anticorrosion auxiliary agents such as barium sulfate, iron mica, talcum powder play functions such as corrosion-resistant, antirust.
Once the stability of the present invention's aqueous epoxy resin emulsion was made overtesting, the result is as follows:
| Test number | Storage stability | 50 ℃ of storage stabilitys | -5～18 ℃ of storage stabilitys |
| 1 | Half a year | Passed through in 30 days | 5 cycle through |
| 2 | Half a year | Passed through in 30 days | 5 cycle through |
| 3 | Half a year | Passed through in 30 days | 5 cycle through |
| 4 | Half a year | Passed through in 30 days | 5 cycle through |
As seen,, have suitable storage stability, can satisfy the demand in market according to epoxy resin latex of the present invention.
Aqueous epoxide resin paint with the present invention is mixed with antiseptic varnish, and the result who makes corrosion resistance test is as follows:
| Test number | 19%NaOH liquid | Tap water | Distilled water | Gasoline | Diesel oil |
| 1 | One week passed through | One week passed through | One week passed through | One week passed through | One week passed through |
| 2 | One week passed through | One week passed through | One week passed through | One week passed through | One week passed through |
| 3 | One week passed through | One week passed through | One week passed through | One week passed through | One week passed through |
| 4 | One week passed through | One week passed through | One week passed through | One week passed through | One week passed through |
In a word, the present invention's aqueous epoxide resin paint have long service life, brushing performance good, use advantages such as easily observation of terminal point, shelf-stable, paint film appearance be smooth, smooth, it also keeps the advantage of happy Resins, epoxy itself simultaneously: to the strong adhesion of ground, and the matching capacity of other lacquer is good, chemical resistance is excellent.
Embodiment
The invention will be further described with embodiment below, but the present invention never is confined to these embodiment.
Embodiment 1
First component prescription:
Weight %
E-51 Resins, epoxy 40
501 reactive thinners 28
Emulsifying agent 10
Auxiliary agent I 10
Auxiliary agent II 5
Deionized water 15
Emulsifying agent wherein is the condenses of glycerin fatty acid ester and oxyethane, and auxiliary agent I is a kind of thickening material of acrylic acid, and auxiliary agent II is a kind of ether alcohol class solubility promoter.Compound method is as follows: E-51 Resins, epoxy, reactive thinner, emulsifying agent are dropped into reactor, make it to be uniformly dispersed with 1400 rev/mins of high-speed stirring, add auxiliary agent II, heat temperature raising to 80 ℃ when continuing to stir drips 40 deionized waters, in 0.5h, add, at the uniform velocity stir 0.5h, add auxiliary agent I, restir 0.5h, stable, the about 35min of cooling, discharging.
The component B prescription:
Weight %
E-51 Resins, epoxy 30.57
Triethylene tetramine 37.51
M-phthalic acid 5.00
Butyl glycol ether 8.00
Deionized water 18.92
Blending process: E-51 Resins, epoxy is mixed as dropping liquid with butyl glycol ether.Triethylene tetramine and m-phthalic acid are dropped into reactor, be heated to 60 ℃, drip epoxy resin solution.Dropwise, be warming up to 80 ℃, insulation 2h adds deionized water, continues insulation 2h, and survey the amine value and reach 340 ± 20, stopped reaction, cooling is filtered, discharging, packing.
Lacquer formulation (units)
A component first component 60
B component component B 20
Propylene glycol monomethyl ether 10
Deionized water 30
Join lacquer: the A component: B component=1: 1
Test-results to this varnish is as follows:
Paint film appearance is transparent, nothing whitens, no shrinkage cavity
Build, μ m 100
Wet-film thickness, μ m 150
Surface drying time, h 2
Do solid work the time, h 24
Completely solidified, d 14
In the construction time limit, h 2～4
Hardness (H) 2
Shock-resistant, kg-cm 50
Sticking power, level (cross-hatching) 2
Anti-boiling water (24h) no change
Anti-10%NaOH (24h) no change
The construction time limit of traditional aqueous epoxide resin paint is generally about 0.5h, because rate of drying is too fast, internal moisture is not fully overflowed as yet, and the surface has cured, so that internal crosslinking density deficiency, one-pass film-forming thickness can only be 40～50 μ m.Yet, adopt the present invention, because its rate of drying is suitable, cross-linking density height, one-pass film-forming thickness can reach 100 μ m, thereby not only can reduce construction times, improve operating efficiency, but also have good water-fast, corrosion resistance nature, paint film does not have phenomenons such as foaming, whiting, tangerine peel.
Embodiment 2
The prescription of first, second two components is with embodiment 1, and wherein the Resins, epoxy of first component changes E-44 and E-22 into 1: 1 and usefulness, and auxiliary agent I adopts stearin, and auxiliary agent II changes toluene and butanone into 1: 1 usefulness also; The Resins, epoxy of component B also changes E-44 and E-22 into 1: 1 and usefulness, and triethylene tetramine changes hexanediamine into, and m-xylene diamine changes 1 into, 4-diamino hexahydroaniline.The preparation technology of this two component is also identical with embodiment 1.With this two components modulation colored paint, prescription (unit: kg) as follows:
A component: first component 50.00
B component: component B 9.40
Iron mica 40.60
Process white 12.50
Talcum powder 6.25
Iron black 6.25
Deionized water 25.00
Join lacquer: the A component: B component=1: 2
Test-results to this colored paint is as follows:
Paint film appearance black, clear saturating, do not have whiting, a no shrinkage cavity
Build, μ m 100
Wet-film thickness, μ m 150
Surface drying time, h 2～4
Do solid work the time, h 24
Completely solidified, d 14
In the construction time limit, h 2～4
Hardness (H) 2
Shock-resistant, kg-cm 40
Sticking power, level (cross-hatching) 2
Salt spray resistance, h 1500
Moisture-proof heat, h 500
The salt spray resistance of general aqueous epoxide resin paint is no more than 500h, and the present invention can reach 1500h, illustrates that its antiseptic property is very outstanding.
Claims (7)
1. a room temperature-cured aqueous epoxy cold coating that comprises the first and second two components is characterized in that the first component is a base-material with the aqueous epoxy resins through chemical modification, as the component B of solidifying agent based on water-based polyamine through chemical modification; Described first component comprises the material of following gradation composition:
Weight %
Resins, epoxy 40～80
Emulsifying agent 0～10
Auxiliary agent I 0～10
Auxiliary agent II 0～10
Deionized water 20～60;
Described component B comprises the material of following gradation composition:
Weight %
Resins, epoxy 20～60
Aliphatic amide 20～65
Aliphatic cyclic amine 0～20
Alcohol ether solvent 5～30
Deionized water 10～40;
Described Resins, epoxy is selected from a kind of among Resins, epoxy E-51, E-42, E-44, the E-20 or several mixture wherein; Described emulsifying agent is a kind of nonionic surface active agent, is to be selected from a kind of in the condenses of stearin, oxyethylene, lipid acid and oxyethane or several mixture.
2. aqueous epoxide resin paint according to claim 1 is characterized in that, described auxiliary agent I is a kind of associative thickener, is to be selected from a kind of in acrylic acid type thickening material, polyurethane associative thickener, the lithium bentonite or several mixture.
3. aqueous epoxide resin paint according to claim 1 is characterized in that, described auxiliary agent II is a kind of solubility promoter, is to be selected from a kind of in pure ether solvent, toluene, the ketone or several mixture.
4. aqueous epoxide resin paint according to claim 1 is characterized in that, described aliphatic amide is to be selected from second two by a kind of in, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, the hexanediamine or several mixture.
5. aqueous epoxide resin paint according to claim 1 is characterized in that, described aliphatic cyclic amine is to be selected from 1,3-diamino hexahydroaniline, 1,2-diamino hexahydroaniline, 1, a kind of in 4-diamino hexahydroaniline, the m-xylene diamine or several mixture.
6. aqueous epoxide resin paint according to claim 1 is characterized in that, described pure ether solvent is to be selected from a kind of in glycol butyl ether, phenylate, the propylene glycol propyl ether or several mixture.
7. by the manufacture method of the described aqueous epoxide resin paint of claim 1, it is characterized in that described first, second two components are produced as follows respectively:
A) first component: Resins, epoxy, emulsifying agent are dropped in the high-speed stirring cylinder by setting proportioning, under 1400 ± 100 rev/mins rotating speed, be uniformly dispersed, 40 ± 5 ℃ deionized waters are added drop-wise in the system, after dropwising, stablized 12～18 minutes, add auxiliary agent I, II then and stir, stablized filtration, discharging, packing, stand-by 25～35 minutes;
B) component B: by setting proportioning aliphatic amide, aliphatic cyclic amine are dropped in the reactor, heating, stirring are warming up to 60 ± 2 ℃, insulation, the mixed solution of dropping Resins, epoxy and pure ether solvent is after dropwising, 80 ± 2 ℃ of insulations 1.5～2.5 hours, add deionized water, be warmed up to 80 ± 2 ℃, be incubated 1.5～2.5 hours, when the amine value reaches 340 ± 20, stopped reaction, cooling, filtration, discharging, packing, stand-by.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100679818A CN100368495C (en) | 2004-11-10 | 2004-11-10 | Water epoxy resin paint and its making process |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100679818A CN100368495C (en) | 2004-11-10 | 2004-11-10 | Water epoxy resin paint and its making process |
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| CN1772823A CN1772823A (en) | 2006-05-17 |
| CN100368495C true CN100368495C (en) | 2008-02-13 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104086749A (en) * | 2014-07-04 | 2014-10-08 | 中国船舶重工集团公司第七二五研究所 | Side-group long-chain azidated epoxy resin and synthesis technique thereof |
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| CN101392143B (en) * | 2008-10-28 | 2011-11-09 | 深圳市广田环保涂料有限公司 | Water epoxy seal coat and preparation method and use method thereof |
| CN102352024B (en) * | 2011-07-08 | 2014-06-18 | 南京博物院 | Application of waterborne epoxy resin to protection of historic tombs |
| CN106147517A (en) * | 2012-03-23 | 2016-11-23 | 大日本涂料株式会社 | Aqueous epoxide resin paint compositions, corrosion-proof coating method and coated-body |
| CN104479087B (en) * | 2014-12-08 | 2018-04-17 | 上海涂料有限公司技术中心 | A kind of quick-dry type water-base epoxy ester lotion and its preparation method and application |
| CN104513590B (en) * | 2014-12-23 | 2017-01-25 | 上海海隆石油化工研究所 | High-corrosion resistance two-component waterborne epoxy coating capable of quickly drying at room temperature |
| CN104893498A (en) * | 2015-05-27 | 2015-09-09 | 芜湖县双宝建材有限公司 | Water-borne double-component epoxy coating |
| CN105062308A (en) * | 2015-08-05 | 2015-11-18 | 天长市开林化工有限公司 | Heatproof corrosion-resistant aqueous epoxy resin coating for ships |
| CN110628301B (en) * | 2019-09-06 | 2021-10-22 | 广州市五羊油漆(翁源)有限公司 | Special water-based paint for ceramic tiles and application method thereof |
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2004
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Patent Citations (4)
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| CN1084864A (en) * | 1991-12-17 | 1994-04-06 | 陶氏化学公司 | The miscible end capped resin of amine of water as cured epoxy resin |
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| CN1460698A (en) * | 2003-05-16 | 2003-12-10 | 广州秀珀化工有限公司 | Room temperature solidification water epoxy paint and its production method |
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| CN104086749A (en) * | 2014-07-04 | 2014-10-08 | 中国船舶重工集团公司第七二五研究所 | Side-group long-chain azidated epoxy resin and synthesis technique thereof |
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| CN1772823A (en) | 2006-05-17 |
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