CN109778159A - A kind of chromium-free zinc aluminum anticorrosive paint using phosphomolybdic acid as passivator - Google Patents

A kind of chromium-free zinc aluminum anticorrosive paint using phosphomolybdic acid as passivator Download PDF

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Publication number
CN109778159A
CN109778159A CN201910066116.8A CN201910066116A CN109778159A CN 109778159 A CN109778159 A CN 109778159A CN 201910066116 A CN201910066116 A CN 201910066116A CN 109778159 A CN109778159 A CN 109778159A
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China
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coating
kilograms
phosphomolybdic acid
zinc
acid
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Inventor
殷跃军
杨宏强
李庆鹏
张亮
严川伟
韩长智
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SHENYANG HANGDA TECHNOLOGY Co Ltd
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SHENYANG HANGDA TECHNOLOGY Co Ltd
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Abstract

The aqueous chromium-free zinc aluminum anticorrosive paint that the invention discloses a kind of using phosphomolybdic acid as passivator, each component including following mass parts ratio: zinc powder 250-310, aluminium powder 10-30, phosphomolybdic acid 3-10, polyethylene glycol 110-150, silane coupling agent 70-140, ethylene glycol ether acetate 3-8, surfactant 1-18, defoaming agent 1-6, tetraisopropyl titanate 10-60, boric acid 10-18, deionized water 380-480.By polyethylene glycol, 35-50%, ethylene glycol ether acetate, surfactant and the defoaming agent of silane coupled agent prescription total amount, equal component A is made in stirring;B component is made in the deionized water of the weight ratio, phosphomolybdic acid, the 50-65% of silane coupled agent prescription total amount, tetraisopropyl titanate, boric acid stirring;Two component of A, B is mixed evenly by the weight ratio of 1:1~1.4 using preceding, is configured to finished product coating.Its thermal stability of product prepared by the present invention is improved, the coating after coating have meet fastening parts of automobiles requirement coating is thin, adhesive strength is high and the comprehensive performances such as antiseptic property is good require.

Description

A kind of chromium-free zinc aluminum anticorrosive paint using phosphomolybdic acid as passivator
Technical field
The invention belongs to anticorrosive paint technology fields, and in particular to a kind of chromium-free zinc aluminum using phosphomolybdic acid as passivator is anti- Rotten coating.
Background technique
In existing metallic matrix corrosion-inhibiting coating, zinc-chromium coating (also known as Dacromet/steel) technology is contained pair due to coating The harmful Cr VI of human body is not met " about the instruction for using certain harmful components in electronic and electrical equipment is limited in " (i.e. RoHS standard).RoHS standard is the environmental protection mandatory standard formulated by European Union's legislation, for specification electronic and electrical equipment Material and technological standards.The standard has been extended to many military use product fields and related to the people's livelihood at present.Countries in the world The use for the measure limitation zinc-chromium coating technology being increasingly stringenter is begun to take.Substitute the Non-chromium Zn-al Coating skill of zinc-chromium coating Art has become the new technology in metal coated anti-corrosion collar domain, and the update substitute technology as zinc-chromium coating has been obtained in numerous areas To application.
It emerges both at home and abroad there are many Non-chromium Zn-al Coating, is divided into aqueous and organic solvent type two by paint solvent type Major class.Wherein aqueous chromium-free Aluminum Coating environmental-protecting performance is more preferable, and zinc-aluminium powder passivation difficulty is bigger, and technology complexity is higher. There is harsher requirement in the preservative treatment application of automotive field fastener, basic demand is sought to aqueous chromium-free zinc aluminum Coating technology.Fastener is due to needing lesser mechanical engagement tolerance, it is desirable that chromium-free zinc aluminum corrosion-inhibiting coating is thin with coating, adheres to Intensity height and the stable particular/special requirement of antiseptic property.The passivation of sheet zinc-aluminium powder in Non-chromium Zn-al Coating and composition coating Carrier phase structure is an important factor for meeting these particular/special requirements.
The passivator of substitution chromic anhydride or chromate in Non-chromium Zn-al Coating formula is applied to have molybdenum trioxide, phosphoric acid at present Salt, dihydric phosphate, borate, molybdate, silicate, tungstates etc.;Or several aforementioned substances compounds, such as molybdate and tungsten Hydrochlorate is compound to be used as passivator.Such as proprietary term are as follows: a kind of non-chrome water-based metal anti-corrosive paint and preparation method, application No. is Molybdenum trioxide is used in the patent of CN201410534326.2;A kind of proprietary term are as follows: non-chrome water-based metal anti-corrosive paint of two-component And preparation method, application No. is in the patent of CN201610033182.1 use sodium molybdate and ammonium molybdate combination be used as chromium-free zinc aluminum Passivator in coating formula.
The passivation effect and coating thermal stability of above-mentioned technical proposal are all ideal not to the utmost.For aqueous chromium-free Aluminum Coating Coating, there is water-soluble bad, dispersions to be not thorough for the passivator of metal oxide-type;There is zinc-aluminium powders for salt passivator It is passivated the problems such as insufficient and unstable, is not met by the proposed coating thermostabilization of fastening parts of automobiles, coating is thin, adhesive strength High and stable antiseptic property comprehensive performance requirement.
Summary of the invention
The aqueous chromium-free zinc aluminum anticorrosive paint that the object of the present invention is to provide a kind of using phosphomolybdic acid as passivator, heat are steady Qualitative to be improved, coating after coating has that the coating for meeting fastening parts of automobiles requirement is thin, adhesive strength is high and anti-corrosive properties Comprehensive performances can be waited to require well.
The present invention is achieved through the following technical solutions:
Composition quality portion rate
Zinc flake 250-310
Flake aluminum 10-30
Phosphomolybdic acid 3-10
Polyethylene glycol 110-150
Silane coupling agent 70-140
Ethylene glycol ether acetate 3-8
Surfactant 1-18
Defoaming agent 1-6
Tetraisopropyl titanate 10-60
Boric acid 10-18
Deionized water 380-480
Further: zinc flake, flake aluminum, piece diameter is no more than 20 μm, and thickness is no more than 0 .3 μm;
Further: phosphomolybdic acid is industrial phosphomolybdic acid;
Further: polyethylene glycol is room temperature liquid polyethylene glycol, and molecular weight is 200~400;
Further: silane coupling agent is Silane coupling agent KH550, KH560, KH570;
Further: ethylene glycol ether acetate is industrial CAC solvent;
Further: surfactant is polyethoxylated fatty alcohols EN90, EN20;Or nonylphenol polyoxyethylene ether NP-4, NP- 15;
It is further: defoaming agent W-052 or organosilicon 3270 or W-052 and 3270 intermixtures, ratio 1:1;
Further: tetraisopropyl titanate is industrial tetraisopropyl titanate;
Further: boric acid is industrial boric acid;
Further: deionized water used, conductivity are 0.1-30 us/cm.
Using phosphomolybdic acid as the preparation method of the chromium-free zinc aluminum anticorrosive paint of passivator, the specific steps of which are as follows:
(1) with the zinc flake and flake aluminum of the weight ratio, polyethylene glycol, silane coupled agent prescription total amount is added 35-50%, ethylene glycol ether acetate, surfactant and defoaming agent, dispersion is sufficiently stirred, and that uniform sheet zinc-aluminium is made is mixed It closes slurry (component A);
(2) by the deionized water of the weight ratio, phosphomolybdic acid, the 50-65% of silane coupled agent prescription total amount, four isopropyl of metatitanic acid Paint solvent (B component) is made until being dispersed with stirring into uniform liquid in ester, boric acid mixed hydrolysis under agitation;
(3) zinc-aluminium is being mixed into slurry and two component of paint solvent A, B by the weight ratio mixing of the .4 of 1:1~1 using preceding Uniformly, it is configured to finished product coating;Coating mode can brush, spray or dip coating manner carries out;Curing mode uses heat-agglomerating, 70 DEG C~100 DEG C dry 10~30 minutes, are warming up to 320 DEG C~350 DEG C with furnace and are sintered solidification, and 20~40 minutes.
It is prepared as described above the chromium-free zinc aluminum anticorrosive paint using phosphomolybdic acid as passivator of method preparation, technical conditions requirement Its viscosity is 90-150 seconds (No. 2 cups of Cai Shi).Corresponding thickener improvement coating mobility can be added to obtain corresponding viscosity. Thickener used is hydroxyethyl cellulose.
The invention has the advantages that
1, corrosion-inhibiting coating thickness is in 6-10 μm of (coating amount 190-320mg/dm2) under conditions of, using phosphomolybdic acid as the painting of passivator The neutral salt spray test that layer can meet 720~1500 hours reaches the requirement for anticorrosion of fastening parts of automobiles;Using phosphomolybdic acid as passivator The compound coating that tetraisopropyl titanate is added, further improves antiseptic property, can meet greater than in 1200~2000 hours The requirements at the higher level of property salt spray test;
2, corrosion-inhibiting coating thickness is in 6-10 μm of (coating amount 190-320mg/dm2) under conditions of, with tape method (Japanese gummed tape Pyatyi Rating method JDIS K53114-4) coating adhesive strength reached 4-5 grades;
3, the chromium without any price, coating and coating process meet environmental requirement;
4, polyethoxylated fatty alcohols are more friendly to environment as surfactant;
5, it is compound to form molybdenum oxide, titanium oxide in hot setting sintering process for phosphomolybdic acid and tetraisopropyl titanate compound action Ceramic phase plays ideal invigoration effect in coated substrate ceramic bonding phase.
6, the thermal stability of coating is improved, and tests, applies through 45 DEG C × 7 × 24 hours high temperature hot storage stabilities Material does not generate gelatin phenomenon, and viscosity increases less than 20%, and the antiseptic property of coating does not change.
For the present invention using phosphomolybdic acid as passivator, addition tetraisopropyl titanate, boric acid, silane coupling agent are carrier, the technology The non-chrome water-based metal anti-corrosive paint that scheme obtains, coating thermostabilization, coating is thin, adhesive strength is high and antiseptic property is stable High comprehensive performance has obtained the approval of automobile major client.
In the present invention, phosphomolybdic acid is added in aqueous chromium-free zinc aluminum anticorrosive paint system as a kind of ideal passivator, It so that corrosion resisting property, strength of coating and the adhesive force of coating is had significant improvement, the storage of coating can also be improved Thermal stability.
The molecular structural formula of phosphomolybdic acid is H3[P(Mo3O10)4], molecular formula H3PO4·12MoO3;CAS No.:51429- 74-4.Phosphomolybdic acid is a kind of phosphoric acid with the sour general character and oxidation molybdenum complex.
Phosphomolybdic acid the positive effect of coating be in the water-based system of coating, can with molybdenum trioxide existing for complex status It is dispersed among aqueous solution with admirably dissolving, complexing passivation is carried out to zinc powder and aluminium powder, to ensure that zinc-aluminium to a certain degree The stability of powder.But the complexing passivation for relying only on phosphomolybdic acid is difficult to prevent the evolving hydrogen reaction of aluminum zinc powder completely, and phosphorus is being added in we Silanization treatment is carried out to aluminum zinc powder surface before molybdic acid, phosphomolybdic acid be complexed to the incomplete aluminum zinc powder of cladding blunt Change, plays the role of joint filling leak repairing, can also be complexed in silane film surface further progress, play the role of reinforcing.Sheet zinc Double action of the aluminium powder body by silane cladding and phosphomolybdic acid complexing passivation, effective solution liberation of hydrogen of the aluminum zinc powder in coating Problem, to ensure that the hot storage stability of coating.
The positive effect of phosphomolybdic acid in the coating is to improve the comprehensive performance of coating.Coating is by silane cladding and sufficiently For the sheet zinc-aluminium powder of passivation in solidification sintering process, the coating ceramic carrier of formation mutually has good solid phase binding, improves The compactness of coating.Phosphomolybdic acid, tetraisopropyl titanate, silane coupling agent, the boric acid added in this programme, it is solid in high temperature sintering The coated body composition to form the oxide glass-ceramics phase such as molybdenum, titanium, boron, silicon, phosphorus is mutually provided during changing for coated carrier Substance forms firm and fine and close coating structure with the sheet aluminum zinc powder body of passivation.Sexavalence molybdenum in phosphomolybdic acid passes through high temperature Partial reduction forms fine and close film layer, to improve the corrosion resistance of coating at trivalent molybdenum.Tetraisopropyl titanate is in hot setting Titanium oxide ceramics phase is formed in sintering process, is combined with the film forming that phosphomolybdic acid is formed, in coated substrate ceramic bonding carrier phase In play ideal invigoration effect, improve the intensity and adhesive force of coating.
Specific embodiment
It, will the invention will be further described by specific embodiment in order to preferably verify effect of the invention.
Raw material selected by embodiment:
Selected zinc flake and flake aluminum is that Germany's love blocks (ECKART) Products;
Selected polyethylene glycol is Nanjing chemical reagent limited liability company product, molecular weight 200-400;
Selected Silane coupling agent KH550, KH560, KH570 are Nanjing Chen Gong organosilicon material Co., Ltd product;
Selected ethylene glycol ether acetate is that industrial CAC(molecular formula is C6H12O3) manufacturer be Jinan benefit Yang Huagong Co., Ltd;
Selected surfactant polyethoxylated fatty alcohols be Sha Suo Chemical Co., Ltd., the U.S., Sha Suo group EN90 and EN20;
Selected surfactant nonylphenol polyoxyethylene ether is the NP-4 and NP- of Nanjing chemical reagent limited liability company 15;
Selected defoaming agent is W-052 product and the Qingdao Penn spy Chemical Co., Ltd. of modest (Shanghai) Chemical Co., Ltd. of moral 3270 product;
Selected tetraisopropyl titanate, character are slight yellowish transparency liquid, and CAS No.:546-68-9 is the remote city in Wuhan The product of development in science and technology Co., Ltd;
Selected tetraethyl titanate, character be it is colourless to pale yellowish oil thick liquid, CAS No.:3087-36-3 is The product of Yixing City southern Jiangsu petrochemical additive Co., Ltd;
Selected phosphomolybdic acid is industrial phosphomolybdic acid, and character is orange crystals powder, and CAS No.:51429-74-4 is The product of Shanghai prophyll Biotechnology Co., Ltd;
Selected ammonium molybdate be industrial ammonium molybdate, character be baby-blue (white) crystal powder, CAS No.: 51429-74-4, Taizhou City Southern Star tungsten products factory product;
Selected boric acid is industrial boric acid, and character is white powder crystallization, CAS No.:10043-35-3;
Selected is industrial deionized water, and conductivity is 0.1-30 us/cm;
Selected thickener is the hydroxyethyl cellulose of Shanghai Mai Ruier chemical technology Co., Ltd production.
Embodiment 1
A kind of chromium-free zinc aluminum anticorrosive paint and preparation method thereof using phosphomolybdic acid as passivator, the specific steps are as follows:
(1) by 250 kilograms of zinc flake, 10 kilograms of flake aluminum, 110 kilograms of polyethylene glycol are added, silane coupling agent (KH550) 25 kilograms, 3 kilograms of ethylene glycol ether acetate, polyethoxylated fatty alcohols (EN20 is 0.2 kilogram, and EN90 is 0.8 kilogram) totally 1 Kilogram, 0.5 kilogram of defoaming agent (W-052), (3270) 0.5 kilograms of defoaming agent organosilicon are sufficiently stirred dispersion and sheet zinc are made Aluminium mixes slurry, is directly prepared into component A;
(2) by 3 kilograms of phosphomolybdic acid, 45 kilograms of silane coupling agent (KH550), 10 kilograms of boric acid, is gone by 10 kilograms of tetraisopropyl titanate B component is made until being dispersed with stirring into uniform liquid in 400 kilograms of ionized water mixed hydrolysis under agitation;
(3) two component of A, B is mixed evenly using preceding by the weight ratio of the .4 of 1:1~1, is configured to finished product coating;Make The coating mode that used time is used can be carried out by brushing, spraying or dip coating manner;Curing mode use heat-agglomerating, 70 DEG C~ 100 DEG C dry 10~30 minutes, then are sintered solidification at 320 DEG C~350 DEG C, 20~40 minutes, i.e. completion coating decoration.
Through detecting, the present embodiment coating is after coating, and coating coated weight is in 220mg/dm2When left and right, resistance to neutral salt The mist time can be more than 1600 hours, and coating hardness is greater than 5H, coating adhesion tape method (Japanese gummed tape Pyatyi rating method JDIS K53114-4) coating adhesive strength reaches 4 grades or more.It is tested through 45 DEG C × 7 × 24 hours high high-temp stabilities, coating Gelatin phenomenon is not generated, and antiseptic property does not change.
For different coating modes if it is desired, corresponding hydroxyethyl cellulose thickening can be added to obtain corresponding viscosity Agent improves coating mobility.
Embodiment 2
A kind of chromium-free zinc aluminum anticorrosive paint and preparation method thereof using phosphomolybdic acid as passivator, the specific steps are as follows:
(1) by 310 kilograms of zinc flake, 30 kilograms of flake aluminum, addition polyethylene glycol: 150 kilograms, silane coupling agent (KH560) 60 kilograms, 8 kilograms of ethylene glycol ether acetate, (NP-4 is 2 kilograms to nonylphenol polyoxyethylene ether, and NP-15 is 16 public Jin) totally 18 kilograms, 3 kilograms of defoaming agent (W-052), (3270) 3 kilograms of defoaming agent organosilicon are sufficiently stirred dispersion and sheet are made Zinc-aluminium mixes slurry, is directly prepared into component A;
(2) by 10 kilograms of phosphomolybdic acid, 80 kilograms of silane coupling agent (KH560), 60 kilograms of tetraisopropyl titanate, 18 kilograms of boric acid, B component is made until being dispersed with stirring into uniform liquid in 480 kilograms of deionized water mixed hydrolysis under agitation;
(3) two component of A, B is mixed evenly using preceding by the weight ratio of the .4 of 1:1~1, is configured to finished product coating; The coating mode used when use can be carried out by brushing, spraying or dip coating manner;Curing mode uses heat-agglomerating, at 70 DEG C ~100 DEG C dry 10~30 minutes, then are sintered solidification at 320 DEG C~350 DEG C, 20~40 minutes, i.e. completion coating decoration.
Through detecting, the present embodiment coating is after coating, and coating coated weight is in 220mg/dm2When left and right, resistance to neutral salt The mist time can be more than 2000 hours, and coating hardness is greater than 5H, coating adhesion tape method (Japanese gummed tape Pyatyi rating method JDIS K53114-4) coating adhesive strength reaches 4 grades or more.It is tested through 45 DEG C × 7 × 24 hours high high-temp stabilities, coating Gelatin phenomenon is not generated, and antiseptic property does not change.
For different coating modes if it is desired, corresponding hydroxyethyl cellulose thickening can be added to obtain corresponding viscosity Agent improves coating mobility.
Embodiment 3
A kind of chromium-free zinc aluminum anticorrosive paint and preparation method thereof using phosphomolybdic acid as passivator, the specific steps are as follows:
(1) by 290 kilograms of zinc flake, 25 kilograms of flake aluminum, addition polyethylene glycol: 130 kilograms, silane coupling agent (KH570) 50 kilograms, 4 kilograms of ethylene glycol ether acetate, (EN20 is 2 kilograms to polyethoxylated fatty alcohols, and EN90 is 10 public Jin) totally 12 kilograms, 2 kilograms of defoaming agent (W-052), (3270) 1 kilograms of defoaming agent organosilicon are sufficiently stirred dispersion and sheet are made Zinc-aluminium mixes slurry, is directly prepared into component A;
(2) by 8 kilograms of phosphomolybdic acid, 70 kilograms of silane coupling agent (KH570), 15 kilograms of boric acid, is gone by 55 kilograms of tetraisopropyl titanate B component is made until being dispersed with stirring into uniform liquid in 450 kilograms of ionized water mixed hydrolysis under agitation;
(3) two component of A, B is mixed evenly using preceding by the weight ratio of the .4 of 1:1~1, is configured to finished product coating; The coating mode used when use can be carried out by brushing, spraying or dip coating manner;Curing mode uses heat-agglomerating, at 70 DEG C ~100 DEG C dry 10~30 minutes, then are sintered solidification at 320 DEG C~350 DEG C, 20~40 minutes, i.e. completion coating decoration.
Through detecting, the present embodiment coating is after coating, and coating coated weight is in 220 mg/dm2When left and right, resistance to neutral salt The mist time can be more than 2000 hours, and coating hardness is greater than 5H, coating adhesion tape method (Japanese gummed tape Pyatyi rating method JDIS K53114-4) coating adhesive strength reaches 4 grades or more.It is tested through 45 DEG C × 7 × 24 hours high high-temp stabilities, coating Gelatin phenomenon is not generated, and antiseptic property does not change.
For different coating modes if it is desired, corresponding hydroxyethyl cellulose thickening can be added to obtain corresponding viscosity Agent improves coating mobility.
Embodiment 4
A kind of chromium-free zinc aluminum anticorrosive paint and preparation method thereof using phosphomolybdic acid as passivator, the specific steps are as follows:
(1) by 280 kilograms of zinc flake, 15 kilograms of flake aluminum, addition polyethylene glycol: 140 kilograms, silane coupling agent (KH560) 50 kilograms, 4 kilograms of ethylene glycol ether acetate, (EN20 is 2 kilograms to polyethoxylated fatty alcohols, and EN90 is 10 public Jin) totally 12 kilograms, 2 kilograms of defoaming agent (W-052), (3270) 1 kilograms of defoaming agent organosilicon are sufficiently stirred dispersion and sheet are made Zinc-aluminium mixes slurry, is directly prepared into component A;
(2) by 4 kilograms of phosphomolybdic acid, 60 kilograms of silane coupling agent (KH560), 13 kilograms of boric acid, is gone by 30 kilograms of tetraisopropyl titanate B component is made until being dispersed with stirring into uniform liquid in 430 kilograms of ionized water mixed hydrolysis under agitation;
(3) two component of A, B is mixed evenly using preceding by the weight ratio of the .4 of 1:1~1, is configured to finished product coating;Make The coating mode that used time is used can be carried out by brushing, spraying or dip coating manner;Curing mode use heat-agglomerating, 70 DEG C~ 100 DEG C dry 10~30 minutes, then are sintered solidification at 320 DEG C~350 DEG C, 20~40 minutes, i.e. completion coating decoration.
Through detecting, the present embodiment coating is after coating, and coating coated weight is in 220 mg/dm2When left and right, resistance to neutral salt The mist time can be more than 1800 hours, and coating hardness is greater than 5H, coating adhesion tape method (Japanese gummed tape Pyatyi rating method JDIS K53114-4) coating adhesive strength reaches 4 grades or more.It is tested through 45 DEG C × 7 × 24 hours high high-temp stabilities, coating Gelatin phenomenon is not generated, and antiseptic property does not change.
For different coating modes if it is desired, corresponding hydroxyethyl cellulose thickening can be added to obtain corresponding viscosity Agent improves coating mobility.
Embodiment 5
A kind of chromium-free zinc aluminum anticorrosive paint and preparation method thereof using phosphomolybdic acid as passivator, the specific steps are as follows:
(1) by 280 kilograms of zinc flake, 25 kilograms of flake aluminum, addition polyethylene glycol: 130 kilograms, silane coupling agent (KH560) 40 kilograms, 4 kilograms of ethylene glycol ether acetate, (EN20 is 2 kilograms to polyethoxylated fatty alcohols, and EN90 is 10 public Jin) totally 12 kilograms, 2 kilograms of defoaming agent (W-052), (3270) 2 kilograms of defoaming agent organosilicon are sufficiently stirred dispersion and sheet are made Zinc-aluminium mixes slurry, is directly prepared into component A;
(2) by 8 kilograms of phosphomolybdic acid, 70 kilograms of silane coupling agent (KH560), 13 kilograms of boric acid, is gone by 35 kilograms of tetraisopropyl titanate B component is made until being dispersed with stirring into uniform liquid in 400 kilograms of ionized water mixed hydrolysis under agitation;
(3) two component of A, B is mixed evenly using preceding by the weight ratio of the .4 of 1:1~1, is configured to finished product coating;Make The coating mode that used time is used can be carried out by brushing, spraying or dip coating manner;Curing mode use heat-agglomerating, 70 DEG C~ 100 DEG C dry 10~30 minutes, then are sintered solidification at 320 DEG C~350 DEG C, 20~40 minutes, i.e. completion coating decoration.
Through detecting, the present embodiment coating is after coating, and coating coated weight is in 220 mg/dm2When left and right, resistance to neutral salt The mist time can be more than 1900 hours, and coating hardness is greater than 5H, coating adhesion tape method (Japanese gummed tape Pyatyi rating method JDIS K53114-4) coating adhesive strength reaches 4 grades or more.It is tested through 45 DEG C × 7 × 24 hours high high-temp stabilities, coating Gelatin phenomenon is not generated, and antiseptic property does not change.
For different coating modes if it is desired, corresponding hydroxyethyl cellulose thickening can be added to obtain corresponding viscosity Agent improves coating mobility.
Embodiment 6
One kind is using phosphomolybdic acid as passivator, the chromium-free zinc aluminum anticorrosive paint and preparation method thereof without tetraisopropyl titanate, tool Steps are as follows for body:
(1) by 260 kilograms of zinc flake, 15 kilograms of flake aluminum, addition polyethylene glycol: 130 kilograms, silane coupling agent (KH560) 50 kilograms, 4 kilograms of ethylene glycol ether acetate, (NP-4 is 2 kilograms to nonylphenol polyoxyethylene ether, and NP-15 is 10 public Jin) totally 12 kilograms, 2 kilograms of defoaming agent (W-052), (3270) 2 kilograms of defoaming agent organosilicon are sufficiently stirred dispersion and sheet are made Zinc-aluminium mixes slurry, is directly prepared into component A;
(2) by 8 kilograms of phosphomolybdic acid, 70 kilograms of silane coupling agent (KH560), 12 kilograms of boric acid, 420 kilograms of deionized water are being stirred Under the conditions of mixed hydrolysis B component is made until be dispersed with stirring into uniform liquid;
(3) two component of A, B is mixed evenly using preceding by the weight ratio of the .4 of 1:1~1, is configured to finished product coating; The coating mode used when use can be carried out by brushing, spraying or dip coating manner;Curing mode uses heat-agglomerating, at 70 DEG C ~100 DEG C dry 10~30 minutes, then are sintered solidification at 320 DEG C~350 DEG C, 20~40 minutes, i.e. completion coating decoration.
Through detecting, the coating of the present embodiment is after coating, and coating coated weight is in 220 mg/dm2When left and right, resistance to neutrality The salt fog time can reach 1200 hours, and coating hardness is greater than 4H, coating adhesion tape method (Japanese gummed tape Pyatyi rating method JDIS K53114-4) coating adhesive strength reaches 4 grades.It is tested through 45 DEG C × 7 × 24 hours high high-temp stabilities, coating part Gelatin phenomenon is generated, antiseptic property does not change.
For different coating modes if it is desired, corresponding hydroxyethyl cellulose thickening can be added to obtain corresponding viscosity Agent improves coating mobility.
Embodiment 7
A kind of chromium-free zinc aluminum anticorrosive paint and preparation method thereof using ammonium molybdate as passivator, the specific steps are as follows:
(1) by 26 kilograms of zinc flake, 1.2 kilograms of flake aluminum, addition polyethylene glycol: 12 kilograms, silane coupling agent (KH560) 4 kilograms, 0.4 kilogram of ethylene glycol ether acetate, polyethoxylated fatty alcohols (EN20 is 0.1 kilogram, and EN90 is 0.6 kilogram) are altogether 0.7 kilogram, 0.3 kilogram of defoaming agent (W-052), (3270) 0.3 kilograms of defoaming agent organosilicon are sufficiently stirred dispersion and sheet are made Zinc-aluminium mixes slurry, is directly prepared into component A;
(2) by 0.5 kilogram of ammonium molybdate, 8.5 kilograms of silane coupling agent (KH560), 1.2 kilograms of boric acid, 40 kilograms of deionized water exists B component is made until being dispersed with stirring into uniform liquid in mixed hydrolysis under stirring condition;
(3) two component of A, B is mixed evenly using preceding by the weight ratio of the .4 of 1:1~1, is configured to finished product coating;Make The coating mode that used time is used can be carried out by brushing, spraying or dip coating manner;Curing mode use heat-agglomerating, 70 DEG C~ 100 DEG C dry 10~30 minutes, then are sintered solidification at 320 DEG C~350 DEG C, 20~40 minutes, i.e. completion coating decoration.
Through detecting, the coating of the present embodiment is after coating, and coating coated weight is in 220 mg/dm2When left and right, resistance to neutrality The salt fog time can reach 1080 hours, and coating hardness is greater than 4H, coating adhesion tape method (Japanese gummed tape Pyatyi rating method JDIS K53114-4) coating adhesive strength reaches 4 grades.It is tested through 45 DEG C × 7 × 24 hours high high-temp stabilities, coating generates Gelatin phenomenon.
For different coating modes if it is desired, corresponding hydroxyethyl cellulose thickening can be added to obtain corresponding viscosity Agent improves coating mobility.
Embodiment 8
A kind of chromium-free zinc aluminum anticorrosive paint and preparation method thereof using phosphomolybdic acid as passivator, the specific steps are as follows:
(1) by 270 kilograms of zinc flake, 20 kilograms of flake aluminum, addition polyethylene glycol: 130 kilograms, silane coupling agent (KH550) 50 kilograms, 5 kilograms of ethylene glycol ether acetate, (NP-4 is 2 kilograms to nonylphenol polyoxyethylene ether, and NP-15 is 10 public Jin) totally 12 kilograms, 1.5 kilograms of defoaming agent (W-052), (3270) 1.5 kilograms of defoaming agent organosilicon are sufficiently stirred dispersion and are made Sheet zinc-aluminium mixes slurry, is directly prepared into component A;
(2) by 10 kilograms of phosphomolybdic acid, 70 kilograms of silane coupling agent (KH550), 50 kilograms of tetraisopropyl titanate, 15 kilograms of boric acid, B component is made until being dispersed with stirring into uniform liquid in 420 kilograms of deionized water mixed hydrolysis under agitation;
(3) two component of A, B is mixed evenly using preceding by the weight ratio of the .4 of 1:1~1, is configured to finished product coating;Make The coating mode that used time is used can be carried out by brushing, spraying or dip coating manner;Curing mode use heat-agglomerating, 70 DEG C~ 100 DEG C dry 10~30 minutes, then are sintered solidification at 320 DEG C~350 DEG C, 20~40 minutes, i.e. completion coating decoration.
Through detecting, the present embodiment coating is after coating, and coating coated weight is in 220 mg/dm2When left and right, resistance to neutral salt The mist time can be more than 2000 hours, and coating hardness is greater than 5H, coating adhesion tape method (Japanese gummed tape Pyatyi rating method JDIS K53114-4) coating adhesive strength reaches 4 grades or more.It is tested through 45 DEG C × 7 × 24 hours high high-temp stabilities, coating Gelatin phenomenon is not generated, and antiseptic property does not change.
For different coating modes if it is desired, corresponding hydroxyethyl cellulose thickening can be added to obtain corresponding viscosity Agent improves coating mobility.
Embodiment 9
A kind of chromium-free zinc aluminum anticorrosive paint and preparation method thereof using phosphomolybdic acid as passivator, the specific steps are as follows:
(1) by 260 kilograms of zinc flake, 20 kilograms of flake aluminum, polyethylene glycol: 120 kg, silane coupling agent is added (KH560) 50 kilograms, 4 kilograms of ethylene glycol ether acetate, (EN20 is 2 kilograms to polyethoxylated fatty alcohols, and EN90 is 10 public Jin) totally 12 kilograms, (3270) 4 kilograms of defoaming agent organosilicon, dispersion is sufficiently stirred, sheet zinc-aluminium mixing slurry is made, directly made At component A;
(2) by 10 kilograms of phosphomolybdic acid, 70 kilograms of silane coupling agent (KH560), 55 kilograms of tetraisopropyl titanate, 15 kilograms of boric acid, B component is made until being dispersed with stirring into uniform liquid in 420 kilograms of deionized water mixed hydrolysis under agitation;
(3) two component of A, B is mixed evenly using preceding by the weight ratio of the .4 of 1:1~1, is configured to finished product coating;Make The coating mode that used time is used can be carried out by brushing, spraying or dip coating manner;Curing mode use heat-agglomerating, 70 DEG C~ 100 DEG C dry 10~30 minutes, then are sintered solidification at 320 DEG C~350 DEG C, 20~40 minutes, i.e. completion coating decoration.
Through detecting, the present embodiment coating is after coating, and coating coated weight is in 220 mg/dm2When left and right, resistance to neutral salt The mist time can be more than 2000 hours, and coating hardness is greater than 5H, coating adhesion tape method (Japanese gummed tape Pyatyi rating method JDIS K53114-4) coating adhesive strength reaches 4 grades or more.It is tested through 45 DEG C × 7 × 24 hours high high-temp stabilities, coating Gelatin phenomenon is not generated, and antiseptic property does not change.
For different coating modes if it is desired, corresponding hydroxyethyl cellulose thickening can be added to obtain corresponding viscosity Agent improves coating mobility.
Embodiment 10
A kind of chromium-free zinc aluminum anticorrosive paint and preparation method thereof using phosphomolybdic acid as passivator, the specific steps are as follows:
(1) by 300 kilograms of zinc flake, 25 kilograms of flake aluminum, addition polyethylene glycol: 140 kilograms, silane coupling agent (KH570) 50 kilograms, 6 kilograms of ethylene glycol ether acetate, (EN20 is 2 kilograms to polyethoxylated fatty alcohols, and EN90 is 10 public Jin) totally 12 kilograms, (3270) 4 kilograms of defoaming agent organosilicon, dispersion is sufficiently stirred, sheet zinc-aluminium mixing slurry is made, directly made At component A;
(2) by 10 kilograms of phosphomolybdic acid, 70 kilograms of silane coupling agent (KH570), 25 kilograms of tetraisopropyl titanate, 15 kilograms of boric acid, B component is made until being dispersed with stirring into uniform liquid in 420 kilograms of deionized water mixed hydrolysis under agitation;
(3) two component of A, B is mixed evenly using preceding by the weight ratio of the .4 of 1:1~1, is configured to finished product coating;Make The coating mode that used time is used can be carried out by brushing, spraying or dip coating manner;Curing mode use heat-agglomerating, 70 DEG C~ 100 DEG C dry 10~30 minutes, then are sintered solidification at 320 DEG C~350 DEG C, 20~40 minutes, i.e. completion coating decoration.
Through detecting, the present embodiment coating is after coating, and coating coated weight is in 220 mg/dm2When left and right, resistance to neutral salt The mist time can be more than 2000 hours, and coating hardness is greater than 5H, coating adhesion tape method (Japanese gummed tape Pyatyi rating method JDIS K53114-4) coating adhesive strength reaches 4 grades or more, it is tested through 45 DEG C × 7 × 24 hours high high-temp stabilities, coating Gelatin phenomenon is not generated, and antiseptic property does not change.
For different coating modes if it is desired, corresponding hydroxyethyl cellulose thickening can be added to obtain corresponding viscosity Agent improves coating mobility.
Embodiment 11
A kind of chromium-free zinc aluminum anticorrosive paint and preparation method thereof using phosphomolybdic acid as passivator, the specific steps are as follows:
(1) by 280 kilograms of zinc flake, 20 kilograms of flake aluminum, addition polyethylene glycol: 130 kilograms, silane coupling agent (KH560) 50 kilograms, 4 kilograms of ethylene glycol ether acetate, (EN20 is 2 kilograms to polyethoxylated fatty alcohols, and EN90 is 10 public Jin) totally 12 kilograms, 2 kilograms of defoaming agent (W-052), (3270) 2 kilograms of defoaming agent organosilicon are sufficiently stirred dispersion and sheet are made Zinc-aluminium mixes slurry, is directly prepared into component A;
(2) by 8 kilograms of phosphomolybdic acid, 70 kilograms of silane coupling agent (KH560), 50 kilograms of tetraethyl titanate, 15 kilograms of boric acid, B component is made until being dispersed with stirring into uniform liquid in mixed hydrolysis under stirring condition in 420 kilograms of deionized waters;
(3) two component of A, B is mixed evenly using preceding by the weight ratio of the .4 of 1:1~1, is configured to finished product coating;Make The coating mode that used time is used can be carried out by brushing, spraying or dip coating manner;Curing mode use heat-agglomerating, 70 DEG C~ 100 DEG C dry 10~30 minutes, then are sintered solidification at 320 DEG C~350 DEG C, 20~40 minutes, i.e. completion coating decoration.
Through detecting, the present embodiment coating is after coating, and coating coated weight is in 220 mg/dm2When left and right, resistance to neutral salt The mist time can be more than 1800 hours, and coating hardness is greater than 4H, coating adhesion tape method (Japanese gummed tape Pyatyi rating method JDIS K53114-4) coating adhesive strength reaches 4 grades or more.It is tested through 45 DEG C × 7 × 24 hours high high-temp stabilities, coating Generate gelatin phenomenon.
For different coating modes if it is desired, corresponding hydroxyethyl cellulose thickening can be added to obtain corresponding viscosity Agent improves coating mobility.

Claims (10)

1. a kind of chromium-free zinc aluminum anticorrosive paint using phosphomolybdic acid as passivator, it is characterised in that the material quality number of each component Are as follows:
Composition quality portion rate
Zinc flake 250-310
Flake aluminum 10-30
Phosphomolybdic acid 3-10
Polyethylene glycol 110-150
Silane coupling agent 70-140
Ethylene glycol ether acetate 3-8
Surfactant 1-18
Defoaming agent 1-6
Tetraisopropyl titanate 10-60
Boric acid 10-18
Deionized water 380-480.
2. anticorrosive paint according to claim 1, it is characterised in that: the piece diameter of the zinc flake and flake aluminum is not Greater than 20 μm, thickness is not more than 0.3 μm.
3. phosphomolybdic acid according to claim 1 is industrial phosphomolybdic acid;Phosphomolybdic acid be a kind of phosphoric acid with the sour general character and Aoxidize molybdenum complex, molecular structural formula H3[P(Mo3O10)4], molecular formula H3PO4·12MoO3
4. anticorrosive paint according to claim 1, it is characterised in that: the polyethylene glycol is room temperature liquid polyethylene glycol, Its molecular weight is 200~400;Ethylene glycol ether acetate is industrial CAC solvent;Tetraisopropyl titanate is industrial metatitanic acid four Isopropyl ester;Boric acid is industrial boric acid.
5. anticorrosive paint according to claim 1, it is characterised in that: the silane coupling agent is silane coupling agent KH550, KH560, KH570;The surfactant is polyethoxylated fatty alcohols or nonylphenol polyoxyethylene ether;It is described to disappear Infusion is W-052 or organosilicon 3270 or the intermixture of 1:1 in mass ratio of W-052 and 3270.
6. anticorrosive paint according to claim 1, it is characterised in that: the deionized water, conductivity 0.1-30 us/cm。
7. using phosphomolybdic acid as the preparation method of the chromium-free zinc aluminum anticorrosive paint of passivator, which comprises the steps of:
(1) with the zinc flake and flake aluminum of the mass ratio, polyethylene glycol, silane coupled agent prescription total amount is added 35-50%, ethylene glycol ether acetate, surfactant and defoaming agent are made sheet zinc-aluminium mixing slurry, are directly prepared into A group Point;
(2) first by the phosphomolybdic acid of the weight ratio, 50-65%, tetraisopropyl titanate, the boric acid of silane coupled agent prescription total amount B component is made until being dispersed with stirring into uniform liquid in mixed hydrolysis under agitation;
(3) using it is preceding by two component of A, B by 1:(1~1.4) mass ratio be mixed and stirred for uniformly, as finished product coating.
8. preparation method as claimed in claim 7, it is characterised in that: further include step (4), mixed in step (3) Corresponding thickener is added in finished product.
9. preparation method as claimed in claim 8, it is characterised in that: the thickener is hydroxyethyl cellulose.
10. the preparation method as described in claim 7~9 is any, it is characterised in that: carry out coating, coating mode after mixing Can brush, spray or dip coating manner carry out;Curing mode uses heat-agglomerating, dries 10~30 minutes at 70 DEG C~100 DEG C, then It is sintered solidification at 320 DEG C~350 DEG C, 20~40 minutes.
CN201910066116.8A 2019-01-24 2019-01-24 A kind of chromium-free zinc aluminum anticorrosive paint using phosphomolybdic acid as passivator Pending CN109778159A (en)

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CN116445078A (en) * 2023-03-27 2023-07-18 上海德修化工有限公司 Chromium-free anti-corrosion coating for automobile fasteners and preparation method thereof

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Application publication date: 20190521