CN101892012B - Coating composition and steel composite material - Google Patents
Coating composition and steel composite material Download PDFInfo
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- CN101892012B CN101892012B CN200910202922A CN200910202922A CN101892012B CN 101892012 B CN101892012 B CN 101892012B CN 200910202922 A CN200910202922 A CN 200910202922A CN 200910202922 A CN200910202922 A CN 200910202922A CN 101892012 B CN101892012 B CN 101892012B
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Abstract
The invention provides a coating composition, which comprises maleic anhydride modified abietic resin, a water-soluble alkaline substance, a film-forming substance and a solvent. The solid content of the composition is 30 to 45 weight percent, and the pH value is 7 to 11. The invention also provides a steel composite material, which comprises a base material and an anticorrosive coating which is attached to the surface of the base material. The anticorrosive coating is a product which is cured by the provided coating composition. The coating composition can provide short-term anticorrosion for steel, in particular steel rails. Therefore, the coating composition can improve the appearance quality and service life of the steel. The coating composition does not contain Pb, Cd, Hg, Cr6+, polybrominated diphenyl ethers (PBDE) and polybrominated biphenyls (PBB) regulated in a RoHS instruction, and is environment-friendly.
Description
Technical field
The present invention relates to a kind of coating composition, also relate to a kind of steel composite material, this steel composite material comprises the corrosion protection coating that is solidified to form by this coating composition.
Background technology
Steel enterprise is producing, is storing and transportation steel for example in the process of rail, and steel are easy to directly and the corrosive medium generation electrochemical reaction in the external environment and being corroded.Especially with rail when ships such as harbour, outer of shipment and the sea transport, the corrosive medium Cl in rail and the seawater
-, Na
+, Mg
2+And H
2Redox reaction takes place in O, makes the rail surface serious red rust occur, thereby influences the exterior quality and the work-ing life of rail product.
And rail except (as in dark moist tunnel) uses in receiving the corrosive particular surroundings easily need carry out long-term anticorrosion, use is unwanted rot-resistant in common outside atmosphere environment.Therefore, when rail storing, etc. in the process of to be transported and transportation, need carry out in short-term anticorrosion, in case rail corrosion takes place and influences exterior quality and work-ing life in this process.Do not contain Pb, Cd, Hg, Cr but also need satisfy in the fungicidal wash of the RoHS of European Union instruction defined
6+, polybromodiphenyl ether (PBDE) and PBBs compositions such as (PBB), to satisfy international environmental requirement.
Summary of the invention
The object of the present invention is to provide a kind of rail that makes to obtain rot-resistant coating composition in short-term, a kind of steel composite material also is provided, this steel composite material comprises the corrosion protection coating that is solidified to form by this coating composition.
Coating composition provided by the invention contains maleic-modified rosin resin, water-soluble alkaline material, filmogen and solvent; And the solids content of said compsn is that 30-45 weight %, pH value are 7-11.
Steel composite material provided by the invention comprises base material and attached to the corrosion protection coating of this substrate surface, the product of said corrosion protection coating for being formed after solidifying by coating composition provided by the invention.
Coating composition of the present invention can for steel particularly rail provide anticorrosion in short-term, in salt spray corrosion test, can make the as many as of steel just occur red rust in 24 hours, thereby can improve the exterior quality and the work-ing life of steel.And do not contain Pb, Cd, Hg, the Cr of regulation in the RoHS instruction in the coating composition of the present invention
6+, polybromodiphenyl ether (PBDE) and PBBs (PBB) composition, environmentally friendly.
Embodiment
Coating composition of the present invention contains maleic-modified rosin resin, water-soluble alkaline material, filmogen and solvent; And the solids content of said compsn is that 30-45 weight %, pH value are 7-11, and the pH value of said compsn is preferably 9-11.
According to coating composition provided by the invention; Under preferable case; Total amount based on said coating composition; The content of maleic-modified rosin resin is 100-200g/L, be preferably 120-180g/L, and the content of water-soluble alkaline material is 0.5-2.5g/L, be preferably 0.8-1.8g/L, and the content of said filmogen is 80-200g/L, be preferably 100-160g/L.
According to coating composition provided by the invention, under the preferable case, the acid number of maleic-modified rosin resin is 250-350mgKOH/g, and softening temperature is 180-195 ℃.The maleic-modified rosin resin can be commercially available; Also can obtain through rosin and MALEIC ANHYDRIDE being carried out diels-alder (Dieds Alder) reaction (being also referred to as " diene synthesis reaction "), wherein, MALEIC ANHYDRIDE and rosiny weight ratio can be 1: 2-8; Reaction process does; MALEIC ANHYDRIDE and rosin are joined in the container, can be under the situation of catalyst-free, under agitation; This mixture heating up to 200 ℃ is made its congruent melting and reacted 1-3 hour, obtain the maleic-modified rosin resin; Perhaps can be in the presence of catalyzer ZnO, and under agitation, with this mixture heating up to 120 ℃ and make its reaction 2 hours, obtain the maleic-modified rosin resin.
According to coating composition provided by the invention; Said filmogen can be for well known to a person skilled in the art the various filmogens that can be used for coating, for example can be in vinyl acetate-acrylic copolymer, copolymer in cinnamic acrylic ester, ZGK 5-Yodo Sol GH 28, vinylformic acid-2-hydroxyl polymerizable methacrylate thing, vinyl resin, acrylic acid epoxy resin and the silicon sol one or more.Vinyl acetate-acrylic copolymer can obtain through being purchased acrylate and vinyl acetate emulsion; Copolymer in cinnamic acrylic ester can obtain through being purchased benzene emulsion; ZGK 5-Yodo Sol GH 28 can obtain through being purchased organosilicon crylic acid latex; Vinyl resin can obtain through being purchased pure-acrylic emulsion, and acrylic acid epoxy resin and silicon sol all can be commercially available in addition, and above-mentioned filmogen also can be synthesized into through those skilled in the art's known method.
In the above-mentioned filmogen, the weight-average molecular weight of vinyl acetate-acrylic copolymer, copolymer in cinnamic acrylic ester, ZGK 5-Yodo Sol GH 28, vinyl resin, acrylic acid epoxy resin and vinylformic acid-2-hydroxyl polymerizable methacrylate thing can be 3000-302000 separately; Wherein, to be preferably the weight-average molecular weight of 10000-30000 and vinylformic acid-2-hydroxyl polymerizable methacrylate thing be 3000-5000 to the weight-average molecular weight of the vinyl acetate-acrylic copolymer weight-average molecular weight that is preferably 15000-24000, the copolymer in cinnamic acrylic ester weight-average molecular weight that is preferably 100000-302000, the ZGK 5-Yodo Sol GH 28 weight-average molecular weight that is preferably 100000-220000, the vinyl resin weight-average molecular weight that is preferably 100000-300000, acrylic acid epoxy resin; SiO in the said silicon sol
2Content be 20-30 weight %.
According to coating composition provided by the invention, said water-soluble alkaline material can for example can be NH for well known to a person skilled in the art various water-soluble alkaline materials
3, in sodium hydroxide, Pottasium Hydroxide and the yellow soda ash one or more.In order in coating composition, not introduce new metallic salt composition, prevent that alkalimetal ion penetrates coated membrane when coating composition solidifies back formation coating, thereby destroy coated membrane, so preferably water dissolubility alkaline matter is NH
3
According to coating composition provided by the invention, under preferable case, said solvent is water and/or water-soluble solvent, and more preferably said solvent is a water.
The preparation method of the coating composition of the invention described above can adopt the whole bag of tricks to obtain; Under the preferable case; According to the content range of above-mentioned each composition, earlier maleic-modified rosin and the solution of water-soluble alkaline material in solvent are mixed, add filmogen then and stir.In the method, can the water-soluble alkaline substance dissolves all obtained the solution of water-soluble alkaline material in solvent in the solvent; Also can earlier the water-soluble alkaline substance dissolves be obtained the solution of water-soluble alkaline material in solvent in a part of solvent, in the end add the solvent of residual content then.
Steel composite material provided by the invention comprises base material and attached to the corrosion protection coating of this substrate surface, the product of said corrosion protection coating for being formed after solidifying by coating composition provided by the invention.
According to steel composite material provided by the invention, under the preferable case, the adhesion amount of said corrosion protection coating is 500-2000mg/m
2, more preferably 600-1200mg/m
2The adhesion amount of corrosion protection coating both can make steel obtain sufficient erosion resistance protection in this scope, thereby can prevent that also this corrosion protection coating appearance be full of cracks makes corrosive medium lose the problem of antirust function along crackle slit and steel generation corrosion reaction when coating composition is solidified.
According to steel composite material provided by the invention, under the preferable case, said solidified condition comprises that solidification value is 60-120 ℃, preferred 65-110 ℃, and be 0.5-2 second set time.Curing both can make coating composition fully solidify in this TR, can prevent the corrosion protection coating generation of cracks that forms again.
The preparation method of above-mentioned steel composite material of the present invention is preferably; Adopt method known to those skilled in the art that coating composition of the present invention is coated in rot-resistant steel surface in short-term; Be cured then; As long as in the temperature of steel is 60-120 ℃ scope, get final product dry solidification, the method for coating can adopt special-shaped roller coat to apply or spray applies.Preferably when the steel temperature on production line is reduced to 200 ℃; Apply coating composition of the present invention; Utilize the waste heat of steel to be cured then, like this, carry out the on-line continuous coating processing and can save production cost, simplify the operation, also can reduce the place space requirement.
Steel composite material of the present invention can completely cut off the approach that steel and corrosive medium react, and corrosion does not take place the protection steel surface.Simultaneously, the preparation method of this steel composite material is simple, cost is low and anti-corrosion effective.
When coating composition of the present invention is coated in steel surface; Faint film formation reaction takes place in coating composition and steel surface; Formed coating of coating composition and steel surface are combined as a whole, and simultaneously, filmogen can play sealing and auxiliary and film forming effect; Can completely cut off extraneous corrosive medium well and contact and prevent corrosion reaction with steel surface, thereby play preservative effect.
The solids content of coating composition of the present invention is higher, can reach 30-45 weight %, and the coated weight of coating is very low; The thickness that is solidified formed corrosion protection coating by coating composition is 0.6-1.2 μ m; Thereby can reduce cost, and solidification value is low, can handled easily.
Preservative challenge testing for steel composite material can carry out anti-corrosion test according to the salt spray corrosion test of defined among the GB/T 10125-1997.
Adopt the mode of embodiment that the present invention is explained in further detail below.
Embodiment 1
1, preparation coating composition
In 1.5 liters container, add 100g rosin and 30g MALEIC ANHYDRIDE, and add 5g catalyzer ZnO, under agitation; Be heated to 120 ℃ and kept 2 hours; Treat that solution is uniform and stable, obtain maleic-modified rosin resin (acid number is 250mgKOH/g, and softening temperature is 195 ℃) 130g.
Ammoniacal liquor 8.4ml and the above-mentioned maleic-modified rosin resin that obtains of getting concentration and be 10 weight % are mixed, add vinylformic acid-2-hydroxyethyl ester polymer (weight-average molecular weight is 5000) 50ml then, stir, and making the pH value of mixed liquid is 9; Then add benzene emulsion (molecular weight is 200000) 50ml, it is even under the rotating speed of 1300r/min, to stir 20 minutes extremely mixed liquid, adds zero(ppm) water at last to the long-pending 1L of being of mixed liquid, and skimmer (the SD-236 water-based skimmer) froth breaking of back with 0.5g stirs.
Obtain the coating composition that solids content is 30 weight %.
2, preparation steel composite material
Adopt spray to apply the above-mentioned coating composition that obtains is coated in rail (model PD4) surface, drying is 2 seconds under 100 ℃, and obtaining coated weight on the rail surface is 600mg/m
2Corrosion protection coating.
Embodiment 2
1, preparation coating composition
In 1.5 liters container, add 150g rosin and 20g MALEIC ANHYDRIDE, and add 10g catalyzer ZnO, under agitation; Be heated to 120 ℃ and kept 2 hours; Treat that solution is uniform and stable, obtain maleic-modified rosin resin (acid number is 350mgKOH/g, and softening temperature is 180 ℃) 170g.
Ammoniacal liquor 18.8ml and the above-mentioned maleic-modified rosin resin that obtains of getting concentration and be 10 weight % are mixed; Add organosilicon crylic acid latex (weight-average molecular weight is 200000) 160ml then; It is even under the rotating speed of 1300r/min, to stir 20 minutes extremely mixed liquid, and making the pH value of mixed liquid is 11; , adding zero(ppm) water at last to the long-pending 1L of being of mixed liquid, the back that stirs is with 1.0g skimmer (SD-236 water-based skimmer) froth breaking.
Obtain the coating composition that solids content is 45 weight %.
2, preparation steel composite material
Adopt spray to apply the above-mentioned coating composition that obtains is coated in rail (model PD4) surface, drying is 2 seconds under 110 ℃, and obtaining coated weight on the rail surface is 1200mg/m
2Corrosion protection coating.
Embodiment 3
1, preparation coating composition
In 1.5 liters container, add 130g rosin and 40g MALEIC ANHYDRIDE, and add 10g catalyzer ZnO, under agitation; Be heated to 120 ℃ and kept 2 hours; Treat that solution is uniform and stable, obtain maleic-modified rosin resin (acid number is 300mgKOH/g, and softening temperature is 190 ℃) 170g.
Ammoniacal liquor 12.5ml and the above-mentioned maleic-modified rosin resin that obtains of getting concentration and be 10 weight % are mixed; Add pure-acrylic emulsion (weight-average molecular weight 150000) 140ml then; It is even under the rotating speed of 1300r/min, to stir 20 minutes extremely mixed liquid, and making the pH value of mixed liquid is 10; , adding zero(ppm) water at last to the long-pending 1L of being of mixed liquid, the back that stirs is with 1.0g skimmer (SD-236 water-based skimmer) froth breaking.
Obtain the coating composition that solids content is 40 weight %.
2, preparation steel composite material
Adopt spray to apply the above-mentioned coating composition that obtains is coated in rail (model PD4) surface, drying is 5 seconds under 65 ℃, and obtaining coated weight on the rail surface is 900mg/m
2Corrosion protection coating.
Performance test
Salt spray corrosion test according to defined among the GB/T 10125-1997 carries out anti-corrosion test.
The rail that the steel composite material that obtains among the embodiment 1-3 promptly is coated with corrosion protection coating places salt fog cabinet, and under 35 ℃ temperature, using concentration is the sodium chloride brine spray of 5 weight %.Observe the rail surface then and time of red rust occurs.
As a result, the time that red rust appears in the steel composite material of embodiment 1 is 24 hours, and embodiment's 2 is 23 hours, and embodiment's 3 is 23.5 hours.
Rail with uncoated coating composition of the present invention carries out salt spray corrosion test according to the method described above as contrast then, and the time that red rust appears in this rail is 1 hour.
Can find out that from above-mentioned test result coating composition of the present invention can carry out anticorrosion in short-term to steel, thereby improve the exterior quality and the work-ing life of steel product.
Claims (8)
1. a coating composition is characterized in that, said coating composition contains maleic-modified rosin resin, water-soluble alkaline material, filmogen and solvent; And the solids content of said compsn is that 30-45 weight %, pH value are 7-11; Wherein, Based on the total amount of said coating composition, the content of said maleic-modified rosin resin is 100-200g/L, and the content of said water-soluble alkaline material is 0.5-2.5g/L; The content of said filmogen is 80-200g/L, and said water-soluble alkaline material is NH
3, in sodium hydroxide, Pottasium Hydroxide and the yellow soda ash one or more; Said filmogen is one or more in vinyl acetate-acrylic copolymer, copolymer in cinnamic acrylic ester, ZGK 5-Yodo Sol GH 28, vinylformic acid-2-hydroxyl polymerizable methacrylate thing, vinyl resin, acrylic acid epoxy resin and the silicon sol, and said solvent is water and/or water-soluble solvent.
2. coating composition according to claim 1; Wherein, based on the total amount of said coating composition, the content of maleic-modified rosin resin is 120-180g/L; The content of said water-soluble alkaline material is 0.8-1.8g/L, and the content of said filmogen is 100-160g/L.
3. coating composition according to claim 1 and 2, wherein, the acid number of maleic-modified rosin resin is 250-350mgKOH/g, softening temperature is 180-195 ℃.
4. coating composition according to claim 1; Wherein, the weight-average molecular weight of vinyl acetate-acrylic copolymer, copolymer in cinnamic acrylic ester, ZGK 5-Yodo Sol GH 28, vinyl resin and the acrylic acid epoxy resin 3000-302000 that respectively does for oneself; SiO in the said silicon sol
2Content 20-30 weight %.
5. coating composition according to claim 1 and 2; Wherein, Said coating composition prepares through following method, and maleic-modified rosin resin and the solution of water-soluble alkaline material in solvent are mixed, and mixes with filmogen then.
6. steel composite material, this steel composite material comprise base material and attached to the corrosion protection coating of this substrate surface, it is characterized in that, said corrosion protection coating is for by any product that described coating composition forms after solidifying among the claim 1-5.
7. steel composite material according to claim 6, wherein, said corrosion protection coating is 500-2000mg/m at the adhesion amount of said substrate surface
2
8. steel composite material according to claim 6, wherein, said solidified condition comprises that solidification value is 60-120 ℃, be 0.5-2 second set time.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910202922A CN101892012B (en) | 2009-05-18 | 2009-05-18 | Coating composition and steel composite material |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910202922A CN101892012B (en) | 2009-05-18 | 2009-05-18 | Coating composition and steel composite material |
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| CN101892012A CN101892012A (en) | 2010-11-24 |
| CN101892012B true CN101892012B (en) | 2012-08-29 |
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| CN103436146B (en) * | 2013-08-23 | 2016-01-06 | 苏州长盛机电有限公司 | A kind of Steel anticorrosive paint |
| CN103740216B (en) * | 2013-12-20 | 2016-09-07 | 南通昂申金属材料有限公司 | A kind of anti-rust coating composition and preparation method thereof |
| CN106047022A (en) * | 2016-05-31 | 2016-10-26 | 无锡伊佩克科技有限公司 | Anti-corrosion metal coating and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1043330A (en) * | 1989-06-24 | 1990-06-27 | 北京丰台光海电器开发公司 | The compound method of thermo-smelting coating for road mark post |
| CN1286283A (en) * | 1999-08-26 | 2001-03-07 | 中国林业科学研究院林产化学工业研究所 | Antirust precoating paint for printed circuit board |
-
2009
- 2009-05-18 CN CN200910202922A patent/CN101892012B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1043330A (en) * | 1989-06-24 | 1990-06-27 | 北京丰台光海电器开发公司 | The compound method of thermo-smelting coating for road mark post |
| CN1286283A (en) * | 1999-08-26 | 2001-03-07 | 中国林业科学研究院林产化学工业研究所 | Antirust precoating paint for printed circuit board |
Non-Patent Citations (2)
| Title |
|---|
| JP特开2002-322400A 2002.11.08 |
| 范洪波等."新型环保高效水基防锈剂的研制".《材料保护》.2004,第37卷(第12期),42-43. |
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