CN100551982C - Douple-component water-thinned epoxy zinc-rich silane metal paint - Google Patents
Douple-component water-thinned epoxy zinc-rich silane metal paint Download PDFInfo
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- CN100551982C CN100551982C CNB200610022492XA CN200610022492A CN100551982C CN 100551982 C CN100551982 C CN 100551982C CN B200610022492X A CNB200610022492X A CN B200610022492XA CN 200610022492 A CN200610022492 A CN 200610022492A CN 100551982 C CN100551982 C CN 100551982C
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- tetraethoxysilane
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Abstract
The invention discloses a kind of by zinc powder/sheet; Resins, epoxy; water; the metal protection barrier Emulgating polymers that auxiliary agent is formed and the combination liquid of silane and solidifying agent combine; the waterborne metal anti-corrosive paint that is used for the non-solvent on the metallic substrate surface; also claim aqueous priming paint; wherein silane is by two-(the silica-based propyl group of trimethoxy first) amine; vinyltriacetoxy silane and tetraethoxysilane combine; the present invention utilizes the known characteristic that is cross-linked of tetraethoxysilane; help the coupling between the silane; it has and impels the molecule crosslinked of two (trimethoxy-silylpropyl) amine and vinyltriacetoxy silane and from strengthening the characteristic of silane combination liquid water resisting property in essence; this silane combination can be wrong crosslinked with the intermolecular horizontal stroke that carries out of metal protection barrier Emulgating polymers; change the performance and the microstructure of their interpenetrating net polymer, improve the antiseptic property of Douple-component water-thinned epoxy zinc-rich silane metal paint significantly.
Description
Technical field
The present invention relates to a kind of bi-component waterborne metal anti-corrosive paint; especially relating to a kind of metal protection barrier Emulgating polymers of being made up of zinc powder/sheet, Resins, epoxy, water, auxiliary agent and the combination liquid of silane and solidifying agent combines; the waterborne metal anti-corrosive paint that is used for the non-solvent on the metallic substrate surface also claims aqueous priming paint.
Background technology
Corrosion of metal is that metal is subjected to the chemistry of surrounding medium or electrochemical action and ruined phenomenon.Corrosion of metal spreads all over the national economy every field, has brought tremendous loss to national economy.In the flourishing country of industry, the direct economic loss that corrosion causes accounts for 1%～4% of total value of production in national economy, and the iron and steel of annual rust corrosion accounts for 20% of output, has 30% equipment to scrap because of corrosion approximately.In China, owing to up to more than 30,000,000,000 yuan, account for 4% of gross national product financial loss every year that metallic corrosion causes.For a long time, people adopt multiple technologies that metal is protected always, prevent that corrosive from taking place.Wherein, one of method that the hardware protection against corrosion is effective, the most the most frequently used is at metallic surface coating erosion shield, with isolated corrosive medium and metallic matrix.Protective system is the same with other coating, and its prescription is formed and mainly comprised base-material (resin), color stuffing and solvent.Binder resin is a filmogen, is the main component in the coating, and its molecular structure is determining the salient features of coating; Color stuffing is used for assisting isolates corrosion factor, can be divided into rust-stabilising pigment and laminal filler again according to the mechanism of action; Solvent is divided into organic solvent or water, is used for dissolving binder resin, is convenient to film forming.
Traditional coating mostly is solvent-borne type greatly, and the content height of volatile organic compounds (VOC) causes environmental pollution very easily; Along with expanding economy, water-based anticorrosive paint is energy-conservation with it, the characteristics of low consumption, environmental protection have also obtained significant progress.
Along with the reinforcement of people to environmental consciousness, the upsurge of one development " green aseptic technic " starts in the world in recent years.Research and development about the surrogate of chromium cpd (or claim " green sanitas ") are just in the ascendant, and silane is a kind of of wherein tool potentiality.
Silane is the silica-based hybrid thing of a class, and its basic molecular formula is: R ' is nSi (OR) (CH2)
3Wherein OR is hydrolyzable group, and R is an organo-functional group.The glueability that its excellent preservative property reach organic coating mainly shows: the formation of silane film is back to cohesion from the interface of the hydrogen bond enrichment before condensing on the metallic surface: the forming process of Si-O-Si and Si-O-Me covalent linkage, remaining silane molecule then form the silane film with Si-O-Si tridimensional network by the aggregation between the SiOH group on the metallic surface.It is generally acknowledged that the formation of Si-O-Me key makes silane film closely be bonded in the metallic surface.The thickness of silane film depends primarily on the concentration of solution of silane, when the silane film forming after the metallic surface because the MeOH group of SiOH group and metallic surface in the solution of silane produces aggregation, the very strong Si-O-Me covalent linkage of formation adhesive power on the interface.This key is with the Si-O-Si key, and interface zone forms a kind of new structure, or title " interfacial layer ".Because the silane interfacial layer combine with the metallic surface closely, the corrosion product of the generation of spot corrosion is in early days covered under the interfacial layer and more difficult mobile securely.So former spot corrosion has time enough passivation once more.And therefore the corrosion of metal on the macroscopic view also has been suppressed.Make firm being bonded together of silane and metallic surface though it should be noted that the Si-O-Me covalent linkage on the interface, the water stability of this key itself is also bad.When a large amount of water intrusion, the Si-O-Me covalent linkage can hydrolysis, forms Si-OH and Me-OH group again.Obviously, after Si-O-Me covalent linkage hydrolysis a large amount of on the interface, the bounding force at interface can reduce greatly, thereby causes silane film to peel off and further lose its antiseptic property from the metallic surface.Therefore, the water resisting property of silane film is to prevent the hydrolysis of Si-O-Me covalent linkage, keeps the key of interface good bond strength.Below two kinds of methods can effectively improve the water resisting property of silane film.The one, the Si-OH group is fully condensed, form the good Si-O-Si tridimensional network of water resisting property; Second method is to adopt the silane that has hydrophobic grouping.Along with the raising of silane film water resisting property, the water yield in the film is greatly diminished.Prevent the hydrolysis of Si-O-Me covalent linkage thus, kept the interface good adhesive strength, and further guaranteed the antiseptic property of silane film.
For viscosity and the solid content that makes coating averages out, the normal composition that adopts silane, generally combine by two kinds of silane, such as CN1360644 disclosed " aqueous mixture with vinyl silanes and bis-silyl aminosilane is handled the protectiveness of metallic surface ", 6 kinds of array modes are provided, vinyltriacetoxy silane and two-(triethoxysilylpropyltetrasulfide) amine; Vinyltrimethoxy silane and two-(triethoxysilylpropyltetrasulfide) amine; Vinyltriethoxysilane and two-(triethoxysilylpropyltetrasulfide) amine; Vinyltrimethoxy silane and two-(trimethoxy-silylpropyl) amine; Vinyltriethoxysilane and two-(trimethoxy-silylpropyl) amine.
U.S. Patent application 20030049486 disclosed " silane coating that is used for metal ", the process metal surfaces corroding method of the solution of silane of at least a vinyl of the application that provides and at least a bis-silyl amino.
Chinese patent 200610054285.2 disclosed " aqueous nano zinc-riched epoxy silicane paint " provides following six kinds of silane combination: vinyltriacetoxy silane and two-(triethoxysilylpropyltetrasulfide) amine; Vinyltriacetoxy silane and two-(trimethoxy-silylpropyl) amine; Vinyltriethoxysilane and two-(trimethoxy-silylpropyl) amine; Vinyltriethoxysilane and two-(triethoxysilylpropyltetrasulfide) amine; Vinyltrimethoxy silane and two-(trimethoxy-silylpropyl) amine; Vinyltrimethoxy silane and two-(triethoxysilylpropyltetrasulfide) amine.
From in October ,-2005 in 1991, United States Patent (USP) 20050179011,6955728,6855768,6677047,6432191,6409874,5807921,5750197,5013771 and the paper delivered on " Progress in Organic Coatings " in January, 2004 of Zhu.D has stated that two-(the silica-based propyl group of trimethoxy first) amine and vinyltriacetoxy silane make up that liquid is used for anti-corrosion of metal and to the adherent passivation of metal base.
Can learn from above prior art, two-(the silica-based propyl group of trimethoxy first) amine (bis-[tri methoxy silyl propyl] amine C12H
31NO
6Si
2) and vinyltriacetoxy silane (Vinyltriacetoxysilane C
8H
12O
6Si) composition of two kinds of silane is most widely used.Use two (trimethoxy-silylpropyl) amine and vinyltriacetoxy silane combination liquid, be based on it to clagging with to the characteristics of the strong anticorrosion interfacial layer of the adhesivity of metal covering, and preceding a kind of effect that a kind of silane in back is also had bonding auxiliary agent.Basic chemical ingredients and performance characteristics according to zinc-base at present commonly used, magnesium base and three kinds of sacrificial anode materials such as aluminium base; select for use zinc powder to make protection barrier in the aqueous silane anticorrosive coating; the film forming base-material uses Resins, epoxy; paint solvent uses pure water; in conjunction with above-mentioned silane, form the protective system of water-based.Aqueous silane protective system according to the disclosed formulated of paper of United States Patent (USP) 20050179011 and Zhu.D; on 480 hours resisting salt fog corrosion detected result; its antiseptic property is relatively poor; the reason of searching to the bottom; be that the Si-O-Si tridimensional network is crosslinked inadequately between the silane, water resisting property is also relatively poor because this protective system also exists; and can not protect the barrier Emulgating polymers to carry out intermolecular network interpenetrating with zinc powder; thereby reduced silane film after crosslinked to the protection of metal base, directly influenced the antiseptic property of water-borne coatings.
Summary of the invention
The objective of the invention is to overcome the shortcoming of above-mentioned prior art and a kind of silane is provided; this silane has stronger water resisting property; and can form intermolecular inierpeneirating network structure, thereby form the waterborne metal anti-corrosive paint of antiseptic property excellence with the metal protection barrier Emulgating polymers that mainly forms by zinc powder and Resins, epoxy.
The object of the present invention is achieved like this:
A kind of Douple-component water-thinned epoxy zinc-rich silane metal paint, the metal protection barrier Emulgating polymers that the A component is made up of zinc powder/sheet, Resins, epoxy, water, auxiliary agent, the B component is silane and solidifying agent synthetic combination liquid.
Described silane is to be combined by two-(trimethoxy-silylpropyl) amine, vinyltriacetoxy silane and tetraethoxysilane;
Wherein, above-mentioned silane is to combine by following weight proportion: two-(trimethoxy-silylpropyl) amine: vinyltriacetoxy silane: the tetraethoxysilane proportion is 3-6: 1: 3-6, be preferably 6: 1: 6 or 5: 1: 5, best is 4: 1: 4 or 3: 1: 3;
Wherein, the weight proportion of the combination liquid that metal protection barrier Emulgating polymers and silane and solidifying agent form is 86-90%: 14-10%, is preferably 88%: 12%, 86%: 14%, and best is 89.5%: 10.5%.
Preparation method of the present invention is very simple, is to choose by the weight ratio of various materials in the two-pack prescription, synthesizes after the mediation respectively.Prepare the A component at first according to a conventional method, soon Resins, epoxy, ethanol, deionization pure water stirred 10-20 minute after choosing by weight proportion together, put zinc powder into be stirred liquid lentamente again, stirred 20 minutes, add viscosifying agent again, disperse the anti-settling agent stirring airtight after 10-20 minute; The preparation of B component is in proportion three kinds of silane and solidifying agent to be mixed stirring 30 minutes; At last A, B component are mixed to stir and promptly got Douple-component water-thinned epoxy zinc-rich silane metal paint in 40 minutes.
The present invention is because added tetraethoxysilane in the silane combination; utilize its known characteristic that is cross-linked; help the coupling between the silane; it has and impels the molecule crosslinked of two (trimethoxy-silylpropyl) amine and vinyltriacetoxy silane and from strengthening the characteristic of silane combination liquid water resisting property in essence; this silane can be crosslinked with the intermolecular horizontal stroke mistake of carrying out of the metal protection barrier Emulgating polymers of two (the silica-based propyl group amine of trimethoxy first) and vinyltriacetoxy silane and A component; change the performance and the microstructure of bi-component waterborne interpenetrating net polymer, improve the antiseptic property of Douple-component water-thinned epoxy zinc-rich silane metal paint significantly.
Embodiment
Be the specific descriptions that the present invention is carried out below; but protection scope of the present invention has more than and is limited to these examples; can be such as the zinc powder in the A component by other metal substitutes; as magnesium base or alumina-base material; or the formula rate of suitable variation A component; as long as guarantee the fundamental property of metallic barrier Emulgating polymers, these change all is conventional variation, does not constitute limiting the scope of the invention.
In order fully to prove antiseptic property of the present invention, at first make Comparative Examples according to Chinese patent 200610054285.2.
Comparative Examples: the weight with whole components is 100%, prepares according to following weight percent:
The A component: 1000 order nano zinc powders 75%, from newborn type Resins, epoxy 15%, ethanol 1%, deionization pure water 2%, viscosifying agent 0.5% disperses anti-settling agent 0.5%.
The B component: combined according to 0.20 cooperation ratio by vinyltriacetoxy silane and two-(trimethoxy-silylpropyl) amine, accounting for part by weight altogether is 3%, solidifying agent 3%.
Be prepared into protective system according to its disclosed method, its neutral salt spray test (NSS), film thickness measurement, sticking power (cross-hatching) test-results such as table 1.
Embodiment 1: the weight with whole components is 100%, prepares according to following weight percent:
The A component: 800 order zinc powders 65%, from newborn type Resins, epoxy 11%, ethanol 4%, deionization pure water 5%, viscosifying agent 2% disperses anti-settling agent 1%.
The B component: combined by two-(trimethoxy-silylpropyl) amine, vinyltriacetoxy silane and the tetraethoxysilane ratio according to 4: 1: 4, accounting for part by weight altogether is 4%, solidifying agent 8%.
Wherein, viscosifying agent is selected DSX3256 for use, disperses anti-settling agent to select Texaphor 963 for use, and solidifying agent is selected HTS-4518 for use.
Be prepared as follows metal anti-corrosive paint: prepare the A component at first according to a conventional method, soon Resins, epoxy, ethanol, deionization pure water stirred 10-20 minute after choosing by weight proportion together, put zinc powder into be stirred liquid lentamente again, stirred 20 minutes, and added viscosifying agent, anti-settling agent again and stir after 10-20 minute airtight; The preparation of B component is in proportion three kinds of silane and solidifying agent to be mixed stirring 30 minutes; At last A, B component are mixed to stir and promptly got Douple-component water-thinned epoxy zinc-rich silane metal paint in 40 minutes.
Resisting salt fog corrosion of the present invention 500 hours, film adhesive, hardness of film, the acid resistance of filming, the anti-gasoline and be coated with film heat resistance and detect of filming, detected result sees Table 2.
Embodiment 2: the weight with whole components is 100%, prepares according to following weight percent:
The A component: 900 order zinc powders 75%, from newborn type Resins, epoxy 11%, ethanol 1%, deionization pure water 2.6%, viscosifying agent 0.2% disperses anti-settling agent 0.2%.
The B component: combined by two-(trimethoxy-silylpropyl) amine, vinyltriacetoxy silane and the tetraethoxysilane ratio according to 3: 1: 3, accounting for part by weight altogether is 5%, solidifying agent 5%.
Wherein, viscosifying agent is selected SD-301 for use, disperses anti-settling agent to select Hydorpalat 5040 for use, and solidifying agent is selected 1425B for use;
Make the present invention according to the method among the embodiment 1, resisting salt fog corrosion of the present invention 500 hours, film adhesive, hardness of film, the acid resistance of filming, the anti-gasoline and be coated with film heat resistance and detect of filming, detected result sees Table 2.
Embodiment 3: the weight with whole components is 100%, prepares according to following weight percent:
The A component: 1000 order zinc powders 70%, from newborn type Resins, epoxy 12%, ethanol 2%, deionization pure water 2%, viscosifying agent 2% disperses anti-settling agent 1%.
The B component: combined by two-(trimethoxy-silylpropyl) amine, vinyltriacetoxy silane and the tetraethoxysilane ratio according to 5: 1: 5, accounting for part by weight altogether is 2.5%, solidifying agent 8.5%.
Wherein, viscosifying agent is selected T-2038 for use, disperses anti-settling agent to select TEXAPHOR963 for use, and solidifying agent selects 2040 for use;
Make the present invention according to the method among the embodiment 1, resisting salt fog corrosion of the present invention 500 hours, film adhesive, hardness of film, the acid resistance of filming, the anti-gasoline and be coated with film heat resistance and detect of filming, detected result sees Table 2.
Embodiment 4: the weight with whole components is 100%, prepares according to following weight percent:
The A component: 800 order zinc powders 74%, from newborn type Resins, epoxy 9%, ethanol 1%, deionization pure water 2%, viscosifying agent 0.5% disperses anti-settling agent 0.5%.
B component: by two-(trimethoxy-silylpropyl) amine, vinyl triacetyl oxygen base
Silane and tetraethoxysilane combine according to 6: 1: 6 ratio, and accounting for part by weight altogether is 4%, solidifying agent 9%.
Wherein, viscosifying agent is selected RHEOLATE266 for use, disperses anti-settling agent to select Hydorpalat100 for use, and solidifying agent is selected HTS-4518 for use;
Make the present invention according to the method among the embodiment 1, resisting salt fog corrosion of the present invention 500 hours, film adhesive, hardness of film, the acid resistance of filming, the anti-gasoline and be coated with film heat resistance and detect of filming, detected result sees Table 2,3.
Table 2: film adhesive, hardness of film, the acid resistance of filming, the anti-gasoline and be coated with film heat resistance, resisting salt fog corrosion examining report of filming
Table 3: specific embodiment 1-4 examining report
From detected result as can be seen, the present invention contrast is only used the silane combination of two (trimethoxy-silylpropyl) amine and vinyltriacetoxy silane and the antiseptic property of the rotproofing coating that forms, the antiseptic property that adds the water-thinned epoxy zinc-rich silane metal protective system behind the tetraethoxysilane is the raising of how much multiples, is only with two (trimethoxy-silylpropyl amine) and vinyltriacetoxy silane rotproofing coating 2 times-8.23 times as: monolateral average anti-corrosion capability of the present invention; Appearance of film anti-corrosion capability of the present invention is its 3 times-15 times; The monolateral average anti-corrosion capability of drawn area of the present invention is higher 13.846 times-18 times than it.
What need explanation once more is that the monolateral average anti-corrosion capability difference of filming of four kinds of prescriptions providing of present embodiment is little, but difference is very big on the appearance of film anti-corrosion capability, and this has also proved tetraethoxysilane importance and three kinds of silane proportioning values key in protective system.Simultaneously film adhesive of the present invention, hardness of film, the acid resistance of filming, the anti-gasoline and be coated with and strengthened silane combination liquid water resisting property and network interpenetrating after the film heat resistance detected result has also proved the use tetraethoxysilane indirectly of filming.
Especially water-thinned epoxy zinc-rich silane metal protective system of the present invention, it is a kind of green environmental friendly coatings, tasteless the filming of coating is light grey, but at room temperature 4 minutes and 50 seconds surface dryings of coating, and its organic volatile of every liter have only 93 the gram, be lower than the environmental requirement that European Union will implement in 2007 to coating and paint, owing to its surface hardness be H, filming can anti-scratch sassafras, and this is a not comparability of solvent paint.
Claims (8)
1; a kind of Douple-component water-thinned epoxy zinc-rich silane metal paint; comprise A; the B component; the A component is by zinc powder/sheet; Resins, epoxy; water; the metal protection barrier Emulgating polymers that auxiliary agent is formed; the B component is silane and solidifying agent synthetic combination liquid; it is characterized in that described silane is by two-(trimethoxy-silylpropyl) amine; vinyltriacetoxy silane and tetraethoxysilane are pressed column weight amount proportioning and combined: two-(trimethoxy-silylpropyl) amine: vinyltriacetoxy silane: the tetraethoxysilane proportion is 3-6: 1: 3-6; wherein, A; the weight ratio of B component is 86-90%: 14-10%.
2, metal anti-corrosive paint according to claim 1 is characterized in that silane is to combine by following weight proportion: two-(trimethoxy-silylpropyl) amine: vinyltriacetoxy silane: tetraethoxysilane 3: 1: 3.
3, metal anti-corrosive paint according to claim 1 is characterized in that silane is to combine by following weight proportion: two-(trimethoxy-silylpropyl) amine: vinyltriacetoxy silane: tetraethoxysilane 4: 1: 4.
4, metal anti-corrosive paint according to claim 1 is characterized in that silane is to combine by following weight proportion: two-(trimethoxy-silylpropyl) amine: vinyltriacetoxy silane: tetraethoxysilane 5: 1: 5.
5, metal anti-corrosive paint according to claim 1 is characterized in that silane is to combine by following weight proportion: two-(trimethoxy-silylpropyl) amine: vinyltriacetoxy silane: tetraethoxysilane 6: 1: 6.
6, metal anti-corrosive paint according to claim 1 is characterized in that the weight proportion of the combination liquid that metal protection barrier Emulgating polymers and silane and solidifying agent form is 88%: 12%.
7, metal anti-corrosive paint according to claim 1 is characterized in that the weight proportion of the combination liquid that metal protection barrier Emulgating polymers and silane and solidifying agent form is 89.5%: 10.5%.
8, metal anti-corrosive paint according to claim 1 is characterized in that the weight proportion of the combination liquid that metal protection barrier Emulgating polymers and silane and solidifying agent form is 86%: 14%.
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| CNB200610022492XA CN100551982C (en) | 2006-12-14 | 2006-12-14 | Douple-component water-thinned epoxy zinc-rich silane metal paint |
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| CN100551982C true CN100551982C (en) | 2009-10-21 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101104771B (en) * | 2007-08-20 | 2010-06-23 | 维新环保涂料（深圳）有限公司 | Water-based epoxy zinc-rich primer |
| CN101116855B (en) * | 2007-09-04 | 2010-10-13 | 中国船舶重工集团公司第七二五研究所 | Method for preparing corrosion-protection composite coating for the steel metalwork |
| CN102304704A (en) * | 2011-09-09 | 2012-01-04 | 重庆大学 | Aqueous silane treatment agent for improving metal surface protection performance |
| US11021614B1 (en) * | 2020-03-10 | 2021-06-01 | Tesla Nanocoatings, Inc. | Self-stratifying coatings |
| CN113416431B (en) * | 2021-06-23 | 2022-06-10 | 上海兴赛尔表面材料有限公司 | Preparation method of environment-friendly anticorrosive pigment with self-repairing function |
| CN118344593B (en) * | 2024-06-17 | 2024-08-30 | 中国电力科学研究院有限公司 | Organic silicon resin and preparation method thereof, water-based zinc-aluminum alloy anticorrosive paint and preparation method thereof |
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