CN104312246A - Metallic cathode electrophoretic paint and preparation method thereof - Google Patents
Metallic cathode electrophoretic paint and preparation method thereof Download PDFInfo
- Publication number
- CN104312246A CN104312246A CN201410520121.9A CN201410520121A CN104312246A CN 104312246 A CN104312246 A CN 104312246A CN 201410520121 A CN201410520121 A CN 201410520121A CN 104312246 A CN104312246 A CN 104312246A
- Authority
- CN
- China
- Prior art keywords
- electrophoretic paint
- modified epoxy
- metallic cathode
- acrylamide
- cathode electrophoretic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Paints Or Removers (AREA)
Abstract
The invention discloses metallic cathode electrophoretic paint and a preparation method thereof. The metallic cathode electrophoretic paint comprises the following components: modified epoxy resin, methyl trimethoxy silane, hydroxy propyl cellulose acetic ester, 2-cyan ethyl acrylate, acrylamide, 2-acrylamide-2-methyl propanesulfonic acid, propanesulfonic acid and zinc stearate. The preparation method comprises the following steps: adding modified epoxy resin, hydroxy propyl cellulose acetic ester and 2-cyan ethyl acrylate into a reaction kettle, heating till the above components are molten, adding hydroxypropyl methylcellulose and methyl trimethoxy silane, heating, stirring to react, further adding deionized water, further reacting at certain temperature and vacuum degree, finally adding acrylamide, heating, stirring, subsequently cooling, adding 2-acrylamide-2-methyl propanesulfonic acid and zinc stearate, stirring, reacting, and finally cooling to room temperature, thereby obtaining the metallic cathode electrophoretic paint. By adopting the metallic cathode electrophoretic paint disclosed by the invention, the properties of a coated paint membrane are greatly improved, and the use range of the cathode electrophoretic paint is further widened and expanded.
Description
Technical field
The invention belongs to field of metal surface treatment technology, particularly a kind of metallic cathode electrophoretic paint and preparation method thereof.
Background technology
Electrophoretic painting is a kind of newer coating process at present.It is a kind of water miscible organic coating with just (or negative) electric charge, with the dissolving of rarer even concentration (or dispersion) in aqueous, using the workpiece (coated article) with electroconductibility as negative electrode (or anode) separately using metal sheet or carbon plate as anode (or negative electrode), under certain processing condition, people's galvanic current (higher voltage must be applied) is led at two interpolars, electrophoretic paint is deposited equably on workpiece, forms a kind of water-fast organic coating film.Through certain temperature baking and curing, and obtain the higher organic coating film of a kind of hardness, play anticorrosion and effect that is surface decoration.
Cathode electrophoresis dope, compared with traditional technology, has unrivaled superiority.
(1) there is excellent Corrosion Protection and sticking power.
(2) there is the features such as smooth coating, water tolerance, chemical resistant properties be good.
(3) there is outstanding environment-friendly advantage, using water as solvent, reduce the volatilization of VOC.
(4) have and easily realize automatic continuous production, enhance productivity.
(5) there is the application of applicable complex-shaped workpieces, as edge corner angle, hole workpiece, inner chamber, gap etc.
(6) have electrophoretic painting efficiency high, adopt closed circulating system, coating almost 100% utilizes.
In phase early 1960s, PPG company of the U.S. helps Ford Motor Company to establish Article 1 electrophoretic coating production line in the world, for vehicle paint base, thus makes electrophoretic painting formally proceed to industrial production from conceptual phase.20 century 70s, PPG company of the U.S. developed in the first the stronger cathode electrophoresis dope of antiseptic property, make Ford Motor Company of the U.S. and General Motors Corporation establish cathode electro-coating production line in 1977, for the electrophoretic painting of body of a motor car, facilitate electrophoretic painting industrial expansion.
Since the eighties in 20th century, the states such as the U.S., France, Japan, Italy have developed thick film cathode electrophoresis coating, color electrophoresis coating, low-temperature curing electrophoretic coating, dumb light electrophoretic paint etc. in succession, facilitate developing rapidly of electrophoretic painting industry, make electrophoretic painting apply to the industry-by-industries such as automobile, light industry, material of construction, furniture, electrical equipment widely.Nineteen eighty-two, the states such as Japan have started and carried out electrophoretic painting on electrolytic coatings.Along with the increase of electrophoretic paint kind, the raising of quality, electrophoresis coating technique constantly perfect, has further developed the application of plating in decoration protection field, has also promoted electrophoretic painting industrial expansion.
In China, electrophoretic painting originates in phase early 1970s, as the bottoming for sewing machine fuselage, not only increases quality product, improves the operational condition of workman simultaneously, is conducive to environment protection.Since late 1980s, the provinces and cities such as Beijing, Guangdong, Sichuan, Jiangsu start the electrophoretic paint developing urethane, vinylformic acid, epoxide resin type.Meanwhile, electrophoresis application technique is also introduced China by some external manufacturers such as Britain, the U.S., Japan gradually, has promoted the utilization of electrophoresis application technique at China's electroplating industry.Electrophoretic painting applies to the industries such as clock and watch, glasses, lamp decoration, hardware (pen, smoking set, belt hook, slide fastener etc.) widely.
Cathode electrophoresis dope owing to having a series of advantage, therefore more and more by people are paid attention to, particularly in the country of automotive industry prosperity.But along with the continuous progress of society, the higher specification of quality of application product can not have been met for the use range of current electrophoretic paint and performance, the composition and engineering condition of lot of domestic and international paint company anticathode electrophoretic paint is updated, achieve certain achievement, but also there are some places had much room for improvement at present, as higher in the electrophoretic paint solidification value based on the epoxy resin of excellent property, acidproof, alkaline-resisting and salt fog resistance can meet higher specification of quality further, also have for the corner angle of workpiece and the spreadability of most advanced and sophisticated film poor etc., these aspects become cathode electrophoresis dope and further develop the difficult problem needing to solve.
Application number be 201210363919.8 Chinese patent disclose a kind of high throwing power cathode electrophoresis dope resin emulsion and preparation method thereof, emulsion by the modified epoxy of multiple unit molecule amine amination and one or both Totally-enclosed-type aromatic polyisocyanates heat blended after, neutralize with organic acid, obtained with deionized water dispersion again, provide a kind of content of volatile organic compound low, Ford box method throwing power reaches the high throwing power cathode electrophoresis dope resin emulsion of more than 22cm; Application number be 03132255.7 Chinese patent disclose a kind of cathode electrophoresis dope resin emulsion of low-temperature curing, by modified epoxy, polyamine and blocked polyisocyanate through chemical reaction and mixing, after using organic acid center again, form resin emulsion, its object is to eliminate many drawbacks that hot setting causes, 120-140 DEG C of film curing is abundant, and good decorative property, does not turn yellow.But the improvement for cathode electrophoresis dope performance in above disclosed document is not highly significant, little for the improvement of the performance such as acidproof, alkaline-resisting, salt spray resistance, resistance to boiling water of paint film, therefore need to further investigate further, develop a kind of cathode electrophoresis dope of excellent performance.
Summary of the invention
The object of the invention is to provide a kind of metallic cathode electrophoretic paint and preparation method thereof to overcome above the deficiencies in the prior art, improve acidproof, alkaline-resisting, resistance to neutral salt spray and the resistance to boiling water energy of coating paint film, overcome the problem of workpiece corner angle or most advanced and sophisticated paint film adhesion difference simultaneously.
The present invention is realized by following technique means:
A kind of metallic cathode electrophoretic paint, comprise in components by weight percent: modified epoxy 20-30 part, methyltrimethoxy silane 0.5-2 part, hydroxypropylcellulose acetic ester 2-8 part, 2-cyanacrylate 5-10 part, acrylamide 0.8-2 part, 2-acrylamide-2-methylpro panesulfonic acid 0.6-1.5 part, hypromellose 1-4 part, Zinic stearas 0.8-3 part; The formula of wherein said modified epoxy comprises in components by weight percent: epoxy resin 10-20 part, alkylphenol polyoxyethylene 4-8 part, tolylene diisocyanate 2-8 part, Diisopropyl azodicarboxylate 1-3 part, maleic anhydride 2-5 part.
Described metallic cathode electrophoretic paint, can preferably comprise in components by weight percent: modified epoxy 25-28 part, methyltrimethoxy silane 0.8-1.3 part, hydroxypropylcellulose acetic ester 5-7 part, 2-cyanacrylate 8-10 part, acrylamide 1.2-1.6 part, 2-acrylamide-2-methylpro panesulfonic acid 1-1.3 part, hypromellose 2-4 part, Zinic stearas 2-2.5 part; The formula of wherein said modified epoxy comprises in components by weight percent: epoxy resin 14-18 part, alkylphenol polyoxyethylene 5-7 part, tolylene diisocyanate 4-7 part, Diisopropyl azodicarboxylate 2-3 part, maleic anhydride 3-5 part.
Above-described metallic cathode electrophoretic paint, the particle diameter of described Zinic stearas can be 100-200 μm.
In above-described metallic cathode electrophoretic paint, the preparation method of described modified epoxy is as follows:
Step one, joins epoxy resin in reactor, adds alkylphenol polyoxyethylene and Diisopropyl azodicarboxylate, be uniformly mixed, then under the condition of protection of inert gas, be warming up to 60-70 DEG C, continue stirring reaction 60-150 minute, be down to room temperature, obtain reactant one;
Step 2, joins maleic anhydride and tolylene diisocyanate in reactant one, under the condition of protection of inert gas, is heated to 70-80 DEG C, and keeps vacuum tightness to be 0.03-0.06MPa, and stirring reaction 60-100 minute, is down to room temperature, obtains modified epoxy.
The condition be uniformly mixed in step one in the preparation method of described modified epoxy can be mixing speed 100-120 rev/min, stirs 20-30 minute.
The stirring velocity continuing stirring reaction in the preparation method of described modified epoxy in step one can be 60-70 rev/min.
In the preparation method of described modified epoxy, in step 2, the stirring velocity of stirring reaction can be 70-80 rev/min.
The preparation method of the metallic cathode electrophoretic paint described in more than one, comprises the following steps:
Step one, joins in reactor by modified epoxy, hydroxypropylcellulose acetic ester and 2-cyanacrylate, is heated to melting, stirs, obtain mixture one;
Step 2, joins hypromellose and methyltrimethoxy silane in mixture one, is heated to 40-50 DEG C, stirring reaction 2-8 hour, then adds 5-10 part deionized water, and maintenance temperature is 50-60 DEG C, vacuum tightness 0.04-0.08MPa, continues to stir 1-3 hour, obtains mixture two;
Step 3, joins acrylamide in mixture two, is warming up to 90-100 DEG C, be uniformly mixed 40-60 minute, be then cooled to 70-80 DEG C, add 2-acrylamide-2-methylpro panesulfonic acid and Zinic stearas, continue to stir 60-90 minute, be down to room temperature, obtain cathode electrophoresis dope.
The preparation method of above-described metallic cathode electrophoretic paint, in step one, stirring velocity can be 150-200 rev/min.
The preparation method of above-described metallic cathode electrophoretic paint, in step 2, the stirring velocity of stirring reaction can be 80-100 rev/min.
Mutual Synergistic Mechanisms in metallic cathode electrophoretic paint provided by the invention between each component is as follows:
Metallic cathode electrophoretic paint provided by the invention is first by carrying out modification by epoxy resin, obtain and pass through netted modified epoxy mutually, can better and other components merge, the introducing of methyltrimethoxy silane and hypromellose makes mutually to soak between each component invades with crosslinked, can locate well to form paint film at the corner angle of workpiece with most advanced and sophisticated; Hydroxypropylcellulose acetic ester and adding of 2-cyanacrylate define high performance polymer with modified epoxy by the effect of acrylamide, enhance the performances such as the acidproof, alkaline-resisting of coating paint film and resistance to neutral salt spray, and the introducing of 2-acrylamide-2-methylpro panesulfonic acid enhances coating stability in aqueous while serving neutralizing agent effect cleverly, improve the binding ability of paint film and matrix.
Metallic cathode electrophoretic paint provided by the invention compared with prior art, has following clear superiority:
(1) performance of metallic cathode electrophoretic paint provided by the invention compared with prior art has obvious advantage, wherein pencil hardness reaches 4H, solvent resistance reaches more than 205 times, acid resistance reaches more than 880h, alkali resistance reaches more than 912h, resistance to boiling water reaches more than 10h, weathering resistance reaches more than 625h, erosion resistance (CASS) reaches more than 530h, neutral salt spray test reaches more than 1062h, workpiece corner angle and most advanced and sophisticated paint film cover mean thickness and account for the per-cent that workpiece smooth place paint film covers mean thickness and reach more than 99.6%.
(2) metallic cathode electrophoretic paint solidification value provided by the invention is low, is 105-110 DEG C, and existing is that the electrophoretic paint solidification value of main raw is generally 160-200 DEG C with epoxy resin, and progress of the present invention is remarkable.
Embodiment:
Embodiment 1
A kind of metallic cathode electrophoretic paint, comprise in components by weight percent: modified epoxy 20 parts, methyltrimethoxy silane 0.5 part, hydroxypropylcellulose acetic ester 2 parts, 2-cyanacrylate 5 parts, acrylamide 0.8 part, 2-acrylamide-2-methylpro panesulfonic acid 0.6 part, hypromellose 1 part, Zinic stearas 0.8 part; The formula of wherein said modified epoxy comprises in components by weight percent: epoxy resin 10 parts, alkylphenol polyoxyethylene 4 parts, tolylene diisocyanate 2 parts, Diisopropyl azodicarboxylate 1 part, maleic anhydride 2 parts.
The particle diameter of above Zinic stearas is 100 μm.
(1) preparation method of above modified epoxy is:
Step one, epoxy resin is joined in reactor, add alkylphenol polyoxyethylene and Diisopropyl azodicarboxylate, be uniformly mixed, the condition be wherein uniformly mixed is mixing speed 100 revs/min, stirs 20 minutes, then under the condition of nitrogen protection, 60 DEG C are warming up to, continue the speed stirring reaction 60 minutes with 60 revs/min, be down to room temperature, obtain reactant one;
Step 2, joins maleic anhydride and tolylene diisocyanate in reactant one, is heated to 70 DEG C under the condition of nitrogen protection; and keep vacuum tightness to be 0.03MPa; with the stirring velocity stirring reaction 60 minutes of 70 revs/min, be down to room temperature, obtain modified epoxy.
(2) preparation method's step of above-described metallic cathode electrophoretic paint is as follows:
Step one, join in reactor by modified epoxy, hydroxypropylcellulose acetic ester and 2-cyanacrylate, be heated to melting, stir, wherein stirring velocity is 150 revs/min, obtains mixture one;
Step 2, joins hypromellose and methyltrimethoxy silane in mixture one, is heated to 40 DEG C, stirring reaction 2 hours, stirring velocity is 80 revs/min, then adds 5 parts of deionized waters, keeps temperature to be 50 DEG C, vacuum tightness 0.04MPa, continues stirring 1 hour, obtains mixture two;
Step 3, joins acrylamide in mixture two, is warming up to 90 DEG C, is uniformly mixed 40 minutes, is then cooled to 70 DEG C, adds 2-acrylamide-2-methylpro panesulfonic acid and Zinic stearas, continues stirring 60 minutes, is down to room temperature, obtains cathode electrophoresis dope.
Embodiment 2
A kind of metallic cathode electrophoretic paint, comprise in components by weight percent: modified epoxy 25 parts, methyltrimethoxy silane 0.8 part, hydroxypropylcellulose acetic ester 5 parts, 2-cyanacrylate 8 parts, acrylamide 1.2 parts, 2-acrylamide-2-methylpro panesulfonic acid 1 part, hypromellose 2 parts, Zinic stearas 2 parts; The formula of wherein said modified epoxy comprises in components by weight percent: epoxy resin 14 parts, alkylphenol polyoxyethylene 5 parts, tolylene diisocyanate 4 parts, Diisopropyl azodicarboxylate 2 parts, maleic anhydride 3 parts.
The particle diameter of above Zinic stearas is 120 μm.
(1) preparation method of above modified epoxy is:
Step one, epoxy resin is joined in reactor, add alkylphenol polyoxyethylene and Diisopropyl azodicarboxylate, be uniformly mixed, the condition be wherein uniformly mixed is mixing speed 105 revs/min, stirs 22 minutes, then under the condition of argon shield, 65 DEG C are warming up to, continue the speed stirring reaction 70 minutes with 63 revs/min, be down to room temperature, obtain reactant one;
Step 2, joins maleic anhydride and tolylene diisocyanate in reactant one, is heated to 73 DEG C under the condition of argon shield; and keep vacuum tightness to be 0.04MPa; with the stirring velocity stirring reaction 70 minutes of 75 revs/min, be down to room temperature, obtain modified epoxy.
(2) preparation method's step of above-described metallic cathode electrophoretic paint is as follows:
Step one, join in reactor by modified epoxy, hydroxypropylcellulose acetic ester and 2-cyanacrylate, be heated to melting, stir, wherein stirring velocity is 160 revs/min, obtains mixture one;
Step 2, joins hypromellose and methyltrimethoxy silane in mixture one, is heated to 45 DEG C, stirring reaction 4 hours, stirring velocity is 88 revs/min, then adds 6 parts of deionized waters, keeps temperature to be 55 DEG C, vacuum tightness 0.05MPa, continues stirring 2 hours, obtains mixture two;
Step 3, joins acrylamide in mixture two, is warming up to 96 DEG C, is uniformly mixed 48 minutes, is then cooled to 76 DEG C, adds 2-acrylamide-2-methylpro panesulfonic acid and Zinic stearas, continues stirring 72 minutes, is down to room temperature, obtains cathode electrophoresis dope.
Embodiment 3
A kind of metallic cathode electrophoretic paint, comprise in components by weight percent: modified epoxy 27 parts, methyltrimethoxy silane 1 part, hydroxypropylcellulose acetic ester 6 parts, 2-cyanacrylate 9 parts, acrylamide 1.5 parts, 2-acrylamide-2-methylpro panesulfonic acid 1.2 parts, hypromellose 3 parts, Zinic stearas 2.3 parts; The formula of wherein said modified epoxy comprises in components by weight percent: epoxy resin 16 parts, alkylphenol polyoxyethylene 6 parts, tolylene diisocyanate 5 parts, Diisopropyl azodicarboxylate 3 parts, maleic anhydride 4 parts.
The particle diameter of above Zinic stearas is 150 μm.
(1) preparation method of above modified epoxy is:
Step one, epoxy resin is joined in reactor, add alkylphenol polyoxyethylene and Diisopropyl azodicarboxylate, be uniformly mixed, the condition be wherein uniformly mixed is mixing speed 110 revs/min, stirs 25 minutes, then under the condition of nitrogen protection, 68 DEG C are warming up to, continue the speed stirring reaction 100 minutes with 70 revs/min, be down to room temperature, obtain reactant one;
Step 2, joins maleic anhydride and tolylene diisocyanate in reactant one, is heated to 78 DEG C under the condition of protection of inert gas; and keep vacuum tightness to be 0.05MPa; with the stirring velocity stirring reaction 85 minutes of 75 revs/min, be down to room temperature, obtain modified epoxy.
(2) preparation method's step of above-described metallic cathode electrophoretic paint is as follows:
Step one, join in reactor by modified epoxy, hydroxypropylcellulose acetic ester and 2-cyanacrylate, be heated to melting, stir, wherein stirring velocity is 180 revs/min, obtains mixture one;
Step 2, joins hypromellose and methyltrimethoxy silane in mixture one, is heated to 50 DEG C, stirring reaction 6 hours, stirring velocity is 90 revs/min, then adds 8 parts of deionized waters, keeps temperature to be 58 DEG C, vacuum tightness 0.06MPa, continues stirring 2 hours, obtains mixture two;
Step 3, joins acrylamide in mixture two, is warming up to 98 DEG C, is uniformly mixed 55 minutes, is then cooled to 75 DEG C, adds 2-acrylamide-2-methylpro panesulfonic acid and Zinic stearas, continues stirring 80 minutes, is down to room temperature, obtains cathode electrophoresis dope.
Embodiment 4
A kind of metallic cathode electrophoretic paint, comprise in components by weight percent: modified epoxy 28 parts, methyltrimethoxy silane 1.3 parts, hydroxypropylcellulose acetic ester 7 parts, 2-cyanacrylate 10 parts, acrylamide 1.6 parts, 2-acrylamide-2-methylpro panesulfonic acid 1.3 parts, hypromellose 4 parts, Zinic stearas 2.5 parts; The formula of wherein said modified epoxy comprises in components by weight percent: epoxy resin 18 parts, alkylphenol polyoxyethylene 7 parts, tolylene diisocyanate 7 parts, Diisopropyl azodicarboxylate 3 parts, maleic anhydride 5 parts.
The particle diameter of above Zinic stearas is 180 μm.
(1) preparation method of above modified epoxy is:
Step one, epoxy resin is joined in reactor, add alkylphenol polyoxyethylene and Diisopropyl azodicarboxylate, be uniformly mixed, the condition be wherein uniformly mixed is mixing speed 120 revs/min, stirs 28 minutes, then under the condition of nitrogen protection, 66 DEG C are warming up to, continue the speed stirring reaction 130 minutes with 70 revs/min, be down to room temperature, obtain reactant one;
Step 2, joins maleic anhydride and tolylene diisocyanate in reactant one, is heated to 76 DEG C under the condition of protection of inert gas; and keep vacuum tightness to be 0.05MPa; with the stirring velocity stirring reaction 85 minutes of 80 revs/min, be down to room temperature, obtain modified epoxy.
(2) preparation method's step of above-described metallic cathode electrophoretic paint is as follows:
Step one, join in reactor by modified epoxy, hydroxypropylcellulose acetic ester and 2-cyanacrylate, be heated to melting, stir, wherein stirring velocity is 180 revs/min, obtains mixture one;
Step 2, joins hypromellose and methyltrimethoxy silane in mixture one, is heated to 50 DEG C, stirring reaction 7 hours, stirring velocity is 95 revs/min, then adds 9 parts of deionized waters, keeps temperature to be 56 DEG C, vacuum tightness 0.07MPa, continues stirring 3 hours, obtains mixture two;
Step 3, joins acrylamide in mixture two, is warming up to 100 DEG C, is uniformly mixed 55 minutes, is then cooled to 75 DEG C, adds 2-acrylamide-2-methylpro panesulfonic acid and Zinic stearas, continues stirring 90 minutes, is down to room temperature, obtains cathode electrophoresis dope.
Embodiment 5
A kind of metallic cathode electrophoretic paint, comprise in components by weight percent: modified epoxy 30 parts, methyltrimethoxy silane 2 parts, hydroxypropylcellulose acetic ester 8 parts, 2-cyanacrylate 10 parts, acrylamide 2 parts, 2-acrylamide-2-methylpro panesulfonic acid 1.5 parts, hypromellose 4 parts, Zinic stearas 3 parts; The formula of wherein said modified epoxy comprises in components by weight percent: epoxy resin 20 parts, alkylphenol polyoxyethylene 8 parts, tolylene diisocyanate 8 parts, Diisopropyl azodicarboxylate 3 parts, maleic anhydride 5 parts.
The particle diameter of above Zinic stearas is 200 μm.
(1) preparation method of above modified epoxy is:
Step one, epoxy resin is joined in reactor, add alkylphenol polyoxyethylene and Diisopropyl azodicarboxylate, be uniformly mixed, the condition be wherein uniformly mixed is mixing speed 120 revs/min, stirs 30 minutes, then under the condition of nitrogen protection, 70 DEG C are warming up to, continue the speed stirring reaction 150 minutes with 70 revs/min, be down to room temperature, obtain reactant one;
Step 2, joins maleic anhydride and tolylene diisocyanate in reactant one, is heated to 80 DEG C under the condition of protection of inert gas; and keep vacuum tightness to be 0.06MPa; with the stirring velocity stirring reaction 100 minutes of 80 revs/min, be down to room temperature, obtain modified epoxy.
(2) preparation method's step of above-described metallic cathode electrophoretic paint is as follows:
Step one, join in reactor by modified epoxy, hydroxypropylcellulose acetic ester and 2-cyanacrylate, be heated to melting, stir, wherein stirring velocity is 200 revs/min, obtains mixture one;
Step 2, hypromellose and methyltrimethoxy silane are joined in mixture one, be heated to 50 DEG C, stirring reaction 8 hours, stirring velocity is 100 revs/min, then adds 10 parts of deionized waters, temperature is kept to be 60 DEG C, vacuum tightness 0.08MPa, continues stirring 3 hours, obtains mixture two;
Step 3, joins acrylamide in mixture two, is warming up to 100 DEG C, is uniformly mixed 60 minutes, is then cooled to 80 DEG C, adds 2-acrylamide-2-methylpro panesulfonic acid and Zinic stearas, continues stirring 90 minutes, is down to room temperature, obtains cathode electrophoresis dope.
Voltage when the metallic cathode electrophoretic paint that above embodiment prepares uses is 200-220V, and solidification value is 105-110 DEG C, can reach and solidify completely.Performance test is carried out to the film of the cathode electrophoresis dope that above embodiment prepares, and adopts Japanese ELECOAT CM cathod coating to carry out performance comparison as a comparison case, the results are shown in Table 1.
As can be seen from above test-results, the performance of metallic cathode electrophoretic paint provided by the invention compared with prior art has obvious advantage, wherein pencil hardness reaches 4H, solvent resistance reaches more than 205 times, acid resistance reaches more than 880h, alkali resistance reaches more than 912h, resistance to boiling water reaches more than 10h, weathering resistance reaches more than 625h, erosion resistance (CASS) reaches more than 530h, neutral salt spray test reaches more than 1062h, workpiece corner angle and most advanced and sophisticated paint film cover mean thickness and account for the per-cent that workpiece smooth place paint film covers mean thickness and reach more than 99.6%, the negative electrophoretic paint performance wherein prepared in embodiment 3 is best, can as most preferred embodiment.
Metallic cathode electrophoretic paint provided by the invention is first by carrying out modification by epoxy resin, obtain and pass through netted modified epoxy mutually, can better and other components merge, the introducing of methyltrimethoxy silane and hypromellose makes mutually to soak between each component invades with crosslinked, can locate well to form paint film at the corner angle of workpiece with most advanced and sophisticated; Hydroxypropylcellulose acetic ester and adding of 2-cyanacrylate define high performance polymer with modified epoxy by the effect of acrylamide, enhance the performances such as the acidproof, alkaline-resisting of coating paint film and resistance to neutral salt spray, and the introducing of 2-acrylamide-2-methylpro panesulfonic acid enhances coating stability in aqueous while serving neutralizing agent effect cleverly, improve the binding ability of paint film and matrix.
Comprehensively the above can be found out, metallic cathode electrophoretic paint provided by the invention well solves the problem of acidproof, alkaline-resisting, the resistance to neutral salt spray poor performance of the negative coating based on epoxy resin, enhance film adhesion simultaneously, overcome the problem of workpiece corner angle or most advanced and sophisticated paint film adhesion difference, compared with prior art reach the progress of highly significant, expand further and the use range extending negative electrophoretic paint.
Claims (10)
1. a metallic cathode electrophoretic paint, it is characterized in that, comprise in components by weight percent: modified epoxy 20-30 part, methyltrimethoxy silane 0.5-2 part, hydroxypropylcellulose acetic ester 2-8 part, 2-cyanacrylate 5-10 part, acrylamide 0.8-2 part, 2-acrylamide-2-methylpro panesulfonic acid 0.6-1.5 part, hypromellose 1-4 part, Zinic stearas 0.8-3 part; The formula of wherein said modified epoxy comprises in components by weight percent: epoxy resin 10-20 part, alkylphenol polyoxyethylene 4-8 part, tolylene diisocyanate 2-8 part, Diisopropyl azodicarboxylate 1-3 part, maleic anhydride 2-5 part.
2. metallic cathode electrophoretic paint according to claim 1, it is characterized in that, comprise in components by weight percent: modified epoxy 25-28 part, methyltrimethoxy silane 0.8-1.3 part, hydroxypropylcellulose acetic ester 5-7 part, 2-cyanacrylate 8-10 part, acrylamide 1.2-1.6 part, 2-acrylamide-2-methylpro panesulfonic acid 1-1.3 part, hypromellose 2-4 part, Zinic stearas 2-2.5 part; The formula of wherein said modified epoxy comprises in components by weight percent: epoxy resin 14-18 part, alkylphenol polyoxyethylene 5-7 part, tolylene diisocyanate 4-7 part, Diisopropyl azodicarboxylate 2-3 part, maleic anhydride 3-5 part.
3. metallic cathode electrophoretic paint according to claim 1 and 2, is characterized in that, the particle diameter of described Zinic stearas is 100-200 μm.
4. metallic cathode electrophoretic paint according to claim 1, is characterized in that, the preparation method of described modified epoxy is as follows:
Step one, joins epoxy resin in reactor, adds alkylphenol polyoxyethylene and Diisopropyl azodicarboxylate, be uniformly mixed, then under the condition of protection of inert gas, be warming up to 60-70 DEG C, continue stirring reaction 60-150 minute, be down to room temperature, obtain reactant one;
Step 2, joins maleic anhydride and tolylene diisocyanate in reactant one, under the condition of protection of inert gas, is heated to 70-80 DEG C, and keeps vacuum tightness to be 0.03-0.06MPa, and stirring reaction 60-100 minute, is down to room temperature, obtains modified epoxy.
5. metallic cathode electrophoretic paint according to claim 4, is characterized in that, the condition be uniformly mixed in step one in the preparation method of described modified epoxy is mixing speed 100-120 rev/min, stirs 20-30 minute.
6. metallic cathode electrophoretic paint according to claim 4, is characterized in that, the stirring velocity continuing stirring reaction in the preparation method of described modified epoxy in step one is 60-70 rev/min.
7. metallic cathode electrophoretic paint according to claim 4, is characterized in that, in the preparation method of described modified epoxy, in step 2, the stirring velocity of stirring reaction is 70-80 rev/min.
8. a preparation method for metallic cathode electrophoretic paint according to claim 1, is characterized in that, comprise the following steps:
Step one, joins in reactor by modified epoxy, hydroxypropylcellulose acetic ester and 2-cyanacrylate, is heated to melting, stirs, obtain mixture one;
Step 2, joins hypromellose and methyltrimethoxy silane in mixture one, is heated to 40-50 DEG C, stirring reaction 2-8 hour, then adds 5-10 part deionized water, and maintenance temperature is 50-60 DEG C, vacuum tightness 0.04-0.08MPa, continues to stir 1-3 hour, obtains mixture two;
Step 3, joins acrylamide in mixture two, is warming up to 90-100 DEG C, be uniformly mixed 40-60 minute, be then cooled to 70-80 DEG C, add 2-acrylamide-2-methylpro panesulfonic acid and Zinic stearas, continue to stir 60-90 minute, be down to room temperature, obtain cathode electrophoresis dope.
9. the preparation method of metallic cathode electrophoretic paint according to claim 8, is characterized in that, in step one, stirring velocity is 150-200 rev/min.
10. the preparation method of metallic cathode electrophoretic paint according to claim 8, is characterized in that, in step 2, the stirring velocity of stirring reaction is 80-100 rev/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410520121.9A CN104312246B (en) | 2014-09-30 | 2014-09-30 | Metallic cathode electrophoretic paint and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410520121.9A CN104312246B (en) | 2014-09-30 | 2014-09-30 | Metallic cathode electrophoretic paint and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104312246A true CN104312246A (en) | 2015-01-28 |
| CN104312246B CN104312246B (en) | 2017-02-08 |
Family
ID=52367571
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410520121.9A Active CN104312246B (en) | 2014-09-30 | 2014-09-30 | Metallic cathode electrophoretic paint and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104312246B (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106883690A (en) * | 2017-04-06 | 2017-06-23 | 广德瑞邦涂料有限公司 | A kind of inventive thick film paste solvent-borne type electrophoretic paint |
| CN106883748A (en) * | 2017-04-06 | 2017-06-23 | 广德瑞邦涂料有限公司 | A kind of anti-cissing cathode electrodip painting |
| CN106893389A (en) * | 2017-04-06 | 2017-06-27 | 广德瑞邦涂料有限公司 | A kind of high-performance antique copper electrophoretic paint |
| CN106905748A (en) * | 2017-04-06 | 2017-06-30 | 广德瑞邦涂料有限公司 | A kind of transparent aluminum alloy electrophoresis paint |
| CN106947328A (en) * | 2017-04-06 | 2017-07-14 | 广德瑞邦涂料有限公司 | A kind of dumb light cathode electrodip painting |
| WO2018022792A1 (en) * | 2016-07-26 | 2018-02-01 | Ppg Industries Ohio, Inc. | Electrodepositable coating compositions containing 1,1-di-activated vinyl compounds |
| CN109641237A (en) * | 2016-07-26 | 2019-04-16 | Ppg工业俄亥俄公司 | The acid catalyzed curable coating composition and relevant coating and method of vinyl compound containing 1,1- bis--activation |
| US10934411B2 (en) | 2016-09-30 | 2021-03-02 | Ppg Industries Ohio, Inc. | Curable compositions containing 1,1-di-activated vinyl compounds that cure by pericyclic reaction mechanisms |
| US10987697B2 (en) | 2016-07-26 | 2021-04-27 | Ppg Industries Ohio, Inc. | Multi-layer curable compositions containing 1,1-di-activated vinyl compound products and related processes |
| US11078376B2 (en) | 2016-07-26 | 2021-08-03 | Ppg Industries Ohio, Inc. | Polyurethane coating compositions containing 1,1-di-activated vinyl compounds and related coatings and processes |
| US11130867B2 (en) | 2016-07-26 | 2021-09-28 | Ppg Industries Ohio, Inc. | Curable compositions containing 1,1-di-activated vinyl compounds and related coatings and processes |
| US11466159B2 (en) | 2016-07-26 | 2022-10-11 | Ppg Industries Ohio, Inc. | Particles having surfaces functionalized with 1,1-di-activated vinyl compounds |
| US11613076B2 (en) | 2016-07-26 | 2023-03-28 | Ppg Industries Ohio, Inc. | Three-dimensional printing processes using 1,1-di-activated vinyl compounds |
| US11634524B2 (en) | 2016-07-26 | 2023-04-25 | Ppg Industries Ohio, Inc. | Acid-catalyzed curable coating compositions containing 1,1 di-activated vinyl compounds and related coatings and processes |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5725911A (en) * | 1995-06-22 | 1998-03-10 | Dai Nippon Toryo Co., Ltd. | Method for forming a metal spray coating |
| CN104004448A (en) * | 2014-05-04 | 2014-08-27 | 四川理工学院 | Single-component cathodic electrophoretic coating for automotive primer |
-
2014
- 2014-09-30 CN CN201410520121.9A patent/CN104312246B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5725911A (en) * | 1995-06-22 | 1998-03-10 | Dai Nippon Toryo Co., Ltd. | Method for forming a metal spray coating |
| CN104004448A (en) * | 2014-05-04 | 2014-08-27 | 四川理工学院 | Single-component cathodic electrophoretic coating for automotive primer |
Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11078376B2 (en) | 2016-07-26 | 2021-08-03 | Ppg Industries Ohio, Inc. | Polyurethane coating compositions containing 1,1-di-activated vinyl compounds and related coatings and processes |
| US11634524B2 (en) | 2016-07-26 | 2023-04-25 | Ppg Industries Ohio, Inc. | Acid-catalyzed curable coating compositions containing 1,1 di-activated vinyl compounds and related coatings and processes |
| US10961403B2 (en) | 2016-07-26 | 2021-03-30 | Ppg Industries Ohio, Inc. | Electrodepositable coating compositions containing 1,1-di-activated vinyl compounds |
| US11859101B2 (en) | 2016-07-26 | 2024-01-02 | Ppg Industries Ohio, Inc. | Curable compositions containing 1,1-di-activated vinyl compounds and related coatings and processes |
| US10987697B2 (en) | 2016-07-26 | 2021-04-27 | Ppg Industries Ohio, Inc. | Multi-layer curable compositions containing 1,1-di-activated vinyl compound products and related processes |
| WO2018022792A1 (en) * | 2016-07-26 | 2018-02-01 | Ppg Industries Ohio, Inc. | Electrodepositable coating compositions containing 1,1-di-activated vinyl compounds |
| CN109642098A (en) * | 2016-07-26 | 2019-04-16 | Ppg工业俄亥俄公司 | Electrodepositable coating composition comprising the vinyl compound activated of 1,1- bis- |
| CN109641237A (en) * | 2016-07-26 | 2019-04-16 | Ppg工业俄亥俄公司 | The acid catalyzed curable coating composition and relevant coating and method of vinyl compound containing 1,1- bis--activation |
| US20190153244A1 (en) * | 2016-07-26 | 2019-05-23 | Ppg Industries Ohio, Inc. | Electrodepositable Coating Compositions Containing 1,1-Di-Activated Vinyl Compounds |
| US11629257B2 (en) | 2016-07-26 | 2023-04-18 | Ppg Industries Ohio, Inc. | Particles having surfaces functionalized with 1,1-di-activated vinyl compounds |
| US12005475B2 (en) | 2016-07-26 | 2024-06-11 | Ppg Industries Ohio, Inc. | Multi-layer curable compositions containing 1,1-di-activated vinyl compound products and related processes |
| US11613076B2 (en) | 2016-07-26 | 2023-03-28 | Ppg Industries Ohio, Inc. | Three-dimensional printing processes using 1,1-di-activated vinyl compounds |
| US11136469B2 (en) | 2016-07-26 | 2021-10-05 | Ppg Industries Ohio, Inc. | Acid-catalyzed curable coating compositions containing 1,1-di-activated vinyl compounds and related coatings and processes |
| US11130867B2 (en) | 2016-07-26 | 2021-09-28 | Ppg Industries Ohio, Inc. | Curable compositions containing 1,1-di-activated vinyl compounds and related coatings and processes |
| EP4151689A1 (en) * | 2016-07-26 | 2023-03-22 | PPG Industries Ohio, Inc. | Curable compositions containing 1,1-di-activated vinyl compounds and related coatings and processes |
| CN109641237B (en) * | 2016-07-26 | 2021-11-30 | Ppg工业俄亥俄公司 | Acid catalyzed curable coating compositions containing 1, 1-di-activated vinyl compounds and related coatings and methods |
| US11466159B2 (en) | 2016-07-26 | 2022-10-11 | Ppg Industries Ohio, Inc. | Particles having surfaces functionalized with 1,1-di-activated vinyl compounds |
| US11583891B2 (en) | 2016-07-26 | 2023-02-21 | Ppg Industries Ohio, Inc. | Multi-layer curable compositions containing 1,1-di-activated vinyl compound products and related processes |
| US10934411B2 (en) | 2016-09-30 | 2021-03-02 | Ppg Industries Ohio, Inc. | Curable compositions containing 1,1-di-activated vinyl compounds that cure by pericyclic reaction mechanisms |
| CN106883690A (en) * | 2017-04-06 | 2017-06-23 | 广德瑞邦涂料有限公司 | A kind of inventive thick film paste solvent-borne type electrophoretic paint |
| CN106883748A (en) * | 2017-04-06 | 2017-06-23 | 广德瑞邦涂料有限公司 | A kind of anti-cissing cathode electrodip painting |
| CN106947328A (en) * | 2017-04-06 | 2017-07-14 | 广德瑞邦涂料有限公司 | A kind of dumb light cathode electrodip painting |
| CN106905748A (en) * | 2017-04-06 | 2017-06-30 | 广德瑞邦涂料有限公司 | A kind of transparent aluminum alloy electrophoresis paint |
| CN106893389A (en) * | 2017-04-06 | 2017-06-27 | 广德瑞邦涂料有限公司 | A kind of high-performance antique copper electrophoretic paint |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104312246B (en) | 2017-02-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104312246A (en) | Metallic cathode electrophoretic paint and preparation method thereof | |
| CN102181214B (en) | Baking varnish for magnesium aluminum alloy base material and preparation and using methods thereof | |
| CN103554378B (en) | The preparation method that ketone resin is room temperature self-crosslinking acrylic ester emulsion modified and application | |
| CN105036178B (en) | A kind of preparation method of modified nano zinc oxide | |
| CN104371497A (en) | Cathode water-soluble electrophoretic paint | |
| CN103408755A (en) | Low-viscosity cyano resin monomer and polymer, and preparation method thereof | |
| CN108441069B (en) | Mirror back anticorrosive coating modified based on graphene, graphene oxide and nano filler | |
| CN113046800A (en) | Gold sodium sulfite electroplating solution and preparation method thereof | |
| CN114230805A (en) | Organic polymer flame retardant, water-based fireproof flame-retardant coating and preparation method thereof | |
| CN104962961B (en) | Improve the pre-plating process of non-cyanide silver coating adhesion | |
| CN109225227B (en) | Ordered mesoporous carbon catalyst for preparing hexahydrophthalic anhydride and preparation method thereof | |
| CN108424680A (en) | A kind of high-performance self-crosslinking acrylic resin Cathode Electrophoretic Paint of Environment Protection and preparation method | |
| CN104725909A (en) | High weather resistant cathode electrophoresis coating with screening function and manufacture method thereof | |
| CN103923551A (en) | Low-film-thickness and high-covering-power black cathode electrophoretic paint and using method thereof | |
| CN104231856B (en) | High anticorrosion epoxy modified aqueous leaching spray paint and preparation method thereof | |
| CN103819028B (en) | Aluminum profile modification wastewater treatment method | |
| CN105694670A (en) | Anti-oxidation coating with added zinc oxide and preparation method of anti-oxidation coating | |
| CN104559667A (en) | Cathode electrophoresis paint with high outdoor weather resistance and preparation method thereof | |
| CN106047110A (en) | Electric cooker antistatic coating and preparation method thereof | |
| CN103897581A (en) | Nylon paint | |
| CN109399658A (en) | A kind of preparation method of compound mica | |
| CN108929615A (en) | A kind of preparation method of anticorrosive paint | |
| CN109957818A (en) | The preparation method of zincate galvanizing brightener | |
| CN107557767A (en) | Nickel ecology copper facing water-based process material and its copper electroplating method | |
| CN106756652A (en) | A kind of manufacture method of automotive hub |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| CB03 | Change of inventor or designer information |
Inventor after: Zhang Xueping Inventor after: Zhu Zhonghai Inventor after: Wang Weigen Inventor after: Yang Xiaojing Inventor before: Zhang Xueping Inventor before: Zhu Zhonghai |
|
| COR | Change of bibliographic data | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20160922 Address after: 211111 Jiangsu Province, Nanjing Zijin (Jiangning) technology start-ups in particular communities (Jiangning District Mo Zhou Road No. 12) Applicant after: Nanjing Valley Intellectual Property Service Co., Ltd. Address before: 215000 Jiangsu city of Suzhou province high tech Zone No. 121 Hua Feng Lu Applicant before: Suzhou Changsheng Electromechanical Co., Ltd. |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |