CN102286242B - Acrylic polyurethane hot galvanizing substrate paint and preparation method thereof - Google Patents
Acrylic polyurethane hot galvanizing substrate paint and preparation method thereof Download PDFInfo
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Abstract
The invention discloses acrylic polyurethane hot galvanizing substrate paint and a preparation method thereof. The acrylic polyurethane hot galvanizing substrate paint is characterized by comprising an ingredient A and an ingredient B, wherein the ingredient A comprises epoxy modified hydroxyl acrylic resin, aerosil, organic bentonite or polyamide wax powder, hyper dispersants, xylol-butyl acetate-ethylene glycol methyl ether acetate mixed solvents, non-floating type aluminum silver paste and mica iron oxide pigment, coloring pigment, fluorine modified acrylic flowing agents, driers, organic siloxane adherence promoters and industrial alcohol, the ingredient B comprises low-molecular-weight polyalcohol polymers (TP hydroxyl value 500), trimethylolpropane (TMP), toluene diisocynate (TDI) and 4, 4'-diphenylmethane diisocyanate (MDI), and mixed solvents of xylol and butyl aetate are used as addition product carriers. The prepared products have excellent adhesive strength on hot galvanizing substrates.
Description
Technical field
The present invention relates to a kind of coating, particularly a kind of galvanizing base material anticorrosive coating with good chemical anticorrosion and splendid adhesive strength.
Background technology
Galvanizing (galvanizing) also be galvanizing and galvanizing by dipping: be a kind of effective anti-corrosion of metal mode, be mainly used on the metal structure facility of every profession and trade.Be that the steel part after the rust cleaning is immersed in about the 500 ℃ zinc liquid that melt, make the steel component surface adhere to the zinc layer, thereby play the corrosion-resistant purpose.Galvanizing is to be developed by more ancient hot-dipping method, since France in 1836 is applied to industry to galvanizing, in 1 hundred 40 history has been arranged.Yet galvanizing industry is to follow in the last thirty years the develop rapidly of cold-strip steel and obtained extensive development.
Hot galvanized layer is more much better than paint or plastic layer to the protection effect of iron and steel.During galvanizing, spread between zinc and the iron and steel, generate the zinc-iron intermetallic compounds layer, i.e. alloy-layer.Be metallurgical binding between alloy-layer and iron and steel and the zinc, more firm than the combination of lacquer class and steel.The hot galvanized layer many decades that is exposed in the atmospheric environment can not come off yet, until by complete spontaneous corrosion.
When zinc coat has little crackle or damage, zinc will continue with the form of sacrificial anode to prevent that the iron and steel of crackle or breakage from getting rusty, and this is the zinc coat main feature more superior than other coated layers.Fe-zn alloy layer contains zinc more than 90%, and iron and steel is had the electro-chemical protection approximate with zinc; And the pure zinc of fe-zn alloy layer hardness ratio much higher (near pure iron), thereby the coating Collision-free is higher with the ability of scraping damage.Because zinc can be dissolved in acid and highly basic, hot galvanized layer can only be applicable in general atmosphere and the natural water environment.Zinc coat can produce slight electrochemical corrosion when ingress of air and water.In rural area and the clean area of air ratio, zinc coat can be kept a lot of years, and at the dirty Liang Qu of industry and coastal area, the service life of zinc coat is just shorter.This serving is thicker, and the service life is also longer, and the service life almost is directly proportional with thickness.
Because coating can consume in application, when fe-zn alloy layer exposed gradually, it is gloomy unglazed that coating surface becomes.And contain a small amount of iron rust (ferric iron) in the corrosion product, can make coating surface present local iron rust color.For the plating piece that is prone to dim coating, coating surface seldom or does not substantially have pure zinc layer, uses at plating piece this " rusty stain " to occur in a short time, although do not affect its protective effect, can affect outward appearance.Therefore, in order to increase the service life and to strengthen appearance effect, generally at hot galvanizing surface coating paint again.
Coating paint on zinc-plated base material is because adhesion problem is relatively more difficult thing, the domestic coating variety that is used on the galvanizing base material traditionally is MIO epoxy primer, but there is following defective in MIO epoxy primer: 1. adhesive force, wet-heat resisting moisture are poor, the problem of usually bubbling, come off under the harsh and unforgiving environments such as coastal area; 2. dryness is slow, especially in winter severe cold weather situation, and the construction of the lower road of impact paint.
Summary of the invention
Goal of the invention of the present invention is in order to overcome the defective in the above-mentioned background technology, develops a kind ofly to have excellent adhesion intensity for the application of galvanizing base material, and wet-heat resisting moisture is good, quick-drying, the acroleic acid polyurethane hot galvanizing substrate paint of environmental protection.
Another goal of the invention of the present invention is to provide a kind of rational practicable preparation method for the described acroleic acid polyurethane hot galvanizing substrate paint of first goal of the invention.
First goal of the invention of the present invention is achieved by the following technical solution.A kind of acroleic acid polyurethane hot galvanizing substrate paint, comprise A component and B component, wherein the A component is addition product, its each constituent take and the percentage of weight as low molecular weight polyols polymer (the grand chemical industry TP of Co., Ltd hydroxyl value 500 is encouraged by the Foshan City) 6%～10%, trimethylolpropane (TMP) 6%～10%, toluene di-isocyanate(TDI) (TDI) 20%～30%, 4,4 '-methyl diphenylene diisocyanate (MDI) 5%～10%, the mixed solvent of dimethylbenzene and butyl acetate (35:65) 45%～55%, phosphoric acid c.p 0.01%～0.03%.
Each constituent of B component take and the percentage of weight as epoxy modified hydroxyl acrylic resin 18%～55%, aerosil 0.01%～0.5%, organobentonite 0.01%～0.6%, polyamide wax pulp 0.01%～0.5%, hyper-dispersant ST-88 0.01%～0.4%, mixed solvent (dimethylbenzene: butyl acetate: ethyl lactate=60:35:15) 10%～15%, non-floating type aluminum paste 0.01%～5%, mica-iron oxide pigment 0.01%～50%, dicalcium powder 0.01%～10%, coloring pigment 6～25%, fluorin modified crylic acid levelling agent 0.1%～0.2%, organotin drier 0.01%～0.05%, organosiloxane adhesive agent 0.1%～0.5%, industrial alcohol 0.1%～0.3%.
The weight proportion of A component and B component is: A:B=1:9～5
The preparation method of acroleic acid polyurethane hot galvanizing substrate paint of the present invention comprises the following steps:
A), preparation A component: first solvent acetic anhydride butyl ester 99.9% or more of the purity of formula ratio, low molecular weight polyols polymer TP, trimethylolpropane TMP, 1/2 phosphoric acid C.P are dropped in the reactor, stir, intensification; When rising to 60～65 ℃, temperature drops into 4,4 when treating that trimethylolpropane TMP dissolves fully '-methyl diphenylene diisocyanate MDI and toluene di-isocyanate(TDI) TDI, 70～75 ℃ of maintenances of temperature 4～5 hours, NCO% content and free TDI % content are surveyed in sampling, index request is: Gu Ti Han Liang ﹙ 50 ± 2) %, NCO Zhi ﹙ 6.8 ± 0.3) %, drop into solvent anhydrous dimethyl benzene behind the qualified, be cooled to below 50 ℃, filter packing, sealed type storage;
B), preparation B component: resin and auxiliary agent mixed dissolution: (1) drops into epoxy modified hydroxyl acrylic resin, organobentonite, polyamide wax powder, mixed solvent, dicalcium powder, aerosil, hyper-dispersant ST-88 in order successively; Start mixer, with the rotating speed dispersed with stirring of 500 ~ 800r/min 20 ~ 30 minutes, make it fully that dissolving mixes, the limit is dropped into mica-iron oxide pigment or coloring pigment successively in middling speed dispersed with stirring process; (2) in another container, drop into non-floating type aluminum paste and dimethylbenzene, transfer with 500 ~ 800r/min disperseed 30 minutes, non-floating type aluminum paste fully is uniformly dispersed, then with in the container of the material in this container in dropping into step (1), the input process stirs with the rotating speed of 500 ~ 800r/min; (3) high speed dispersion: the complete rear continuation that feeds intake was with the rotating speed high speed dispersion more than the 1200r/min 60 minutes; (4) upper sand mill grinds, and after the mill base fineness will meet specification requirement, squeezes in the paint mixing cylinder; (5) drop into successively levelling agent, drier, industrial alcohol and adhesive agent, feed intake complete after with the rotating speed high speed dispersion more than the 1200r/min 10 minutes; (6) finely tune color to meeting the requirements with the acrylic resin mill base; (7) inspection by sampling, qualified in can after the filtration of 180 order screen packs; In this technical process indices require be: fineness of grind: priming paint is not more than 80 microns, and finish paint is not more than 20 microns, viscosity: 60～100 seconds/be coated with-425 ℃, color and outward appearance: smooth smooth or bright;
C) before the construction with A component and B component by A:B=1:9～5 part by weight proportionings and stir then spraying application.
Beneficial effect of the present invention is as follows:
1. the coating of excellent adhesive strength and anti-boiling water boiling performance acroleic acid polyurethane hot galvanizing substrate paint has excellent adhesive strength to the galvanizing base material, excellent anti-boiling water boiling, and water is medium-term and long-term to be soaked.The compactness of filming is good, can effectively keep out the Korrosionsmediums such as water, oxygen and see through coating.
2. the organic solvent of environmental protection and hypotoxicity acroleic acid polyurethane hot galvanizing substrate paint is low toxicity or nontoxic, (VOC) is lower for content, reduced the requirement to ventilation, the wasting of resources and environmental pollution that the organic matter volatilization causes have been reduced, and to workmens' infringement, and the acroleic acid polyurethane hot galvanizing substrate paint meets the sanitary standard requirement through check.
3. bottom surface unification coating paint film was through outdoor exposure test in 3 years, and efflorescence is lower than 2 grades, and change color is less than ∑ △ 3, and filming has showed good weatherability.
4. the technology of the present invention product can be applicable to various tower classes, bridge, freeway guardrail, steel construction etc.
The monologue story-telling with gestures accompanying drawing
Fig. 1 is A component technological process of production schematic diagram of the present invention;
Fig. 2 is bottom surface unification coating producing process schematic flow sheet of the present invention;
The specific embodiment
Illustrate as follows to of the present invention further describing:
Example 1:
A kind of propylene acid cloud iron galvanizing priming paint.
A component proportion table:
Table 1 A component proportion table
The preparation method of A component as shown in Figure 1 comprises the following steps:
First the acetic anhydride butyl ester (more than 99.9%) of formula ratio, low molecular weight polyols polymer TP, trimethylolpropane (TMP), 1/2 phosphoric acid are dropped in the reactor, stir, heat up.Drop into MDI and TDI when treating that TMP dissolves fully when temperature rises to 60～65 ℃, 70～75 ℃ of temperature kept 4～5 hours, and NCO% content and free TDI % content are surveyed in sampling, the qualified rear input solvent anhydrous dimethyl benzene that touches the mark is cooled to below 50 ℃, filters, packing, sealed type storage.
B component proportion table:
Table 2 B component proportion table
Above-mentioned preparation method comprises the following steps:
Resin and auxiliary agent mixed dissolution:(1) in container, drops into successively in order the epoxy modified hydroxyl acrylic resin, organobentonite, polyamide wax powder, dimethylbenzene, butyl acetate, and the mixed solvent of ethyl lactate.Start mixer, (500 ~ 800r/min) stirrings 20 ~ 30 minutes make it fully dissolving mixing to middle low speed, and (500 ~ 800r/min) disperse also to drop into successively micaceous iron oxide gray, dicalcium powder, anatase thpe white powder, permanent yellow to middling speed.(2) in another container, drop into non-floating type aluminum paste and dimethylbenzene, middling speed was disperseed 30 minutes, non-floating type aluminum paste fully is uniformly dispersed, and then with in the container of the material in this container in dropping into step (1), the input process stirs with the rotating speed of 500 ~ 800r/min.
High speed is pre-dispersed: the complete rear continuation high speed (more than the 1200r/min) that feeds intake was disperseed 60 minutes.(4) then drop into successively levelling agent, drier, industrial alcohol and adhesive agent.The complete rear continuation high speed (more than the 1200r/min) that feeds intake was disperseed 10 minutes.(5) inspection by sampling, qualified rear filtration (180 order) can.
C) before the construction with A component and B component in the ratio proportioning of A:B=1:9 (quality) and stir then spraying application.
Example 2:
A kind of light gray acroleic acid polyurethane galvanizing base material bottom surface unification coating
A set of dispense when preparation method is same as Example 1.
The B component proportion sees Table 3.
Table 3 light gray acroleic acid polyurethane galvanizing base material bottom surface unification coating formula
Preparation method as shown in Figure 2 comprises the following steps:
Resin and auxiliary agent mixed dissolution:(1) drops into successively in order the epoxy modified hydroxyl acrylic resin, aerosil, hyper-dispersant, dimethylbenzene, butyl acetate, and the mixed solvent of ethyl lactate.Start mixer, (500 ~ 800r/min) stirred 20 ~ 30 minutes middle low speed, and making it fully, dissolving mixes.
High speed is pre-dispersed: (2) in (1) the limit middling speed (500 ~ 800r/min) disperse limits to drop into successively titanium dioxide, iron oxide red, high-carbon black pigment and phthalocyanine blue.The complete rear continuation high speed (more than the 1200r/min) that feeds intake was disperseed 30 minutes.
Sand milling:(3) advance the sand mill grinding distribution, the mill base fineness will meet specification requirement, then squeezes in the paint mixing cylinder.
Paint:⑷ drop into successively acrylic resin, levelling agent, drier, industrial alcohol and adhesive agent in paint mixing cylinder.The complete rear continuation high speed (more than the 1200r/min) that feeds intake was disperseed 10 minutes.⑸ inspection by sampling, qualified rear filtration (180 order) can.
C) before the construction with A component and B component in the ratio proportioning of A:B=1:5 (quality) and stir then spraying application.
The technology of the present invention product and traditional MIO epoxy primer properties of product relatively see Table 4.
Table 4 the technology of the present invention product and MIO epoxy primer (being applied to the galvanizing base material) properties of product technical indicator relatively
Other performance and the workability of the technology of the present invention product see Table 5.
Other performance of table 5 the technology of the present invention product and workability
Annotate: HG/T3668-2000 " zinc rich primer " coating and pigment standard compilation coating products universal lacquer volume 2007 editions, China Standard Press
GB/T 1728--1978(1989) " paint film, putty membrane determination method drying time " coating and pigment standard compilation coating test method general use volume is 2007 editions, China Standard Press
GB/T 9754-1988 " paint and varnish is the mensuration of 20 °, 60 ° and 85 ° bright lusters of the colored paint paint film of containing metal pigment not " coating and pigment standard compilation coating test method general use volume 2007 editions, China Standard Press
GB/T 6739-2006 " paint and varnish pencil method is measured hardness of paint film " coating and pigment standard compilation coating test method general use volume 2007 editions, China Standard Press
GB/T 1732--1993 " paint film resistance to impact determination method " coating and pigment standard compilation coating test method general use volume 2007 editions, China Standard Press
GB/T 1720--1979(1989) " paint film adhesion determination method " coating and pigment standard compilation coating test method general use volume is 2007 editions, China Standard Press
GB/T 1733-1993 " paint film resistance to water determination method " coating and pigment standard compilation coating test method general use volume 2007 editions, China Standard Press
GB/T 9276-1986 " coating natural climate exposure test method " coating and pigment standard compilation coating test method general use volume 2007 editions, China Standard Press
GB/T 6753.3--1996 " coating bin stability determination method " coating and pigment standard compilation coating test method general use volume 2007 editions, China Standard Press
GB/T 5208-2008 " flashing test Fast-Balance closed-cup method " coating and pigment standard compilation coating test method general use volume 2007 editions, China Standard Press
GB/T 9264-1988 " mensuration of colored paint flow " coating and pigment standard compilation coating test method general use volume 2007 editions, China Standard Press
2007 China Standard Press of national standardization administration committee of GB5749-2006 " drinking water sanitary standard " Ministry of Public Health
Can find out that from table 4, table 5 this invention products and marketing conventional products is compared has following characteristics:
1. the coating of excellent adhesive strength and anti-boiling water boiling performance acroleic acid polyurethane hot galvanizing substrate paint has excellent adhesive strength to the galvanizing base material, excellent anti-boiling water boiling, and water is medium-term and long-term to be soaked.The compactness of filming is good, can effectively keep out the Korrosionsmediums such as water, oxygen and see through coating.
2. the organic solvent of environmental protection and hypotoxicity acroleic acid polyurethane hot galvanizing substrate paint is low toxicity or nontoxic, (VOC) is lower for content, reduced the requirement to ventilation, the wasting of resources and environmental pollution that the organic matter volatilization causes have been reduced, and to workmens' infringement, and the acroleic acid polyurethane hot galvanizing substrate paint meets the sanitary standard requirement through check.
3. bottom surface unification coating paint film was through outdoor exposure test in 3 years, and efflorescence is lower than 2 grades, and change color is less than ∑ △ 3, and filming has showed good weatherability.
4. the technology of the present invention product can be applicable to various tower classes, bridge, freeway guardrail, steel construction etc.
Claims (2)
1. an acroleic acid polyurethane hot galvanizing substrate paint comprises A component and B component, and the proportioning of its weight is A:B=9～5:1; Wherein the A component is addition product, its each constituent take and the percentage of weight as low molecular weight polyols polymer TP:6%～10%, trimethylolpropane TMP:6%～10%, toluene di-isocyanate(TDI) TDI:20%～30%, 4,4 '-methyl diphenylene diisocyanate MDI:5%～10%, the mixed solvent of dimethylbenzene and butyl acetate: 45%～55%, phosphoric acid C.P:0.01%～0.03%, wherein the mixed proportion in the mixed solvent of dimethylbenzene and butyl acetate is: dimethylbenzene: butyl acetate=35:65;
Each constituent of B component take and the percentage of weight as epoxy modified hydroxyl acrylic resin: 18%～55%, aerosil: 0.01%～0.5%, organobentonite: 0.01%～0.6%, polyamide wax pulp: 0.01%～0.5%, hyper-dispersant ST-88:0.01%～0.4%, mixed solvent: 10%～15%, non-floating type aluminum paste: 0.01%～5%, mica-iron oxide pigment: 0.01%～50%, dicalcium powder: 0.01%～10%, coloring pigment: 6～25%, the fluorin modified crylic acid levelling agent: 0.1%～0.2%, the organotin drier: 0.01%～0.05%, organosiloxane adhesive agent: 0.1%～0.5%, industrial alcohol: 0.1%～0.3%, wherein the component ratio of above-mentioned mixed solvent is: dimethylbenzene: butyl acetate: ethyl lactate=60:35:15.
2. the preparation method of acroleic acid polyurethane hot galvanizing substrate paint claimed in claim 1 is characterized in that its preparation method comprises the following steps:
A), preparation A component: first solvent acetic anhydride butyl ester 99.9% or more of the purity of formula ratio, low molecular weight polyols polymer TP, trimethylolpropane TMP, 1/2 phosphoric acid C.P are dropped in the reactor, stir, intensification; When rising to 60～65 ℃, temperature drops into 4,4 when treating that trimethylolpropane TMP dissolves fully '-methyl diphenylene diisocyanate MDI and toluene di-isocyanate(TDI) TDI, 70～75 ℃ of maintenances of temperature 4～5 hours, NCO% content and free TDI % content are surveyed in sampling, index request is: Gu Ti Han Liang ﹙ 50 ± 2) %, NCO Zhi ﹙ 6.8 ± 0.3) %, drop into solvent anhydrous dimethyl benzene behind the qualified, be cooled to below 50 ℃, filter packing, sealed type storage;
B), preparation B component: resin and auxiliary agent mixed dissolution: (1) drops into epoxy modified hydroxyl acrylic resin, organobentonite, polyamide wax powder, mixed solvent, dicalcium powder, aerosil, hyper-dispersant ST-88 in order successively; Start mixer, with the rotating speed dispersed with stirring of 500 ~ 800r/min 20 ~ 30 minutes, make it fully that dissolving mixes, the limit is dropped into mica-iron oxide pigment or coloring pigment successively in middling speed dispersed with stirring process; (2) in another container, drop into non-floating type aluminum paste and dimethylbenzene, transfer with 500 ~ 800r/min disperseed 30 minutes, non-floating type aluminum paste fully is uniformly dispersed, then with in the container of the material in this container in dropping into step (1), the input process stirs with the rotating speed of 500 ~ 800r/min; (3) high speed dispersion: the complete rear continuation that feeds intake was with the rotating speed high speed dispersion more than the 1200r/min 60 minutes; (4) upper sand mill grinds, and after the mill base fineness will meet specification requirement, squeezes in the paint mixing cylinder; (5) drop into successively levelling agent, drier, industrial alcohol and adhesive agent, feed intake complete after with the rotating speed high speed dispersion more than the 1200r/min 10 minutes; (6) finely tune color to meeting the requirements with the acrylic resin mill base; (7) inspection by sampling, qualified in can after the filtration of 180 order screen packs; In this technical process indices require be: fineness of grind: priming paint is not more than 80 microns, and finish paint is not more than 20 microns, viscosity: 60～100 seconds/be coated with-425 ℃, color and outward appearance: smooth smooth or bright;
C) before the construction with A component and B component by A:B=1:9～5 part by weight proportionings and stir then spraying application.
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| CN113402961A (en) * | 2021-06-10 | 2021-09-17 | 广州盛门新材料科技有限公司 | Protective coating for zinc-plated material and preparation method and application thereof |
| CN113683929A (en) * | 2021-09-11 | 2021-11-23 | 蒋炜 | Protective coating for zinc-plated material and preparation method and application thereof |
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| CN1583912A (en) * | 2004-05-27 | 2005-02-23 | 解居会 | Coiled material priming paint coating and preparing method thereof |
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