CN104312246B - Metallic cathode electrophoretic paint and preparation method thereof - Google Patents
Metallic cathode electrophoretic paint and preparation method thereof Download PDFInfo
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- CN104312246B CN104312246B CN201410520121.9A CN201410520121A CN104312246B CN 104312246 B CN104312246 B CN 104312246B CN 201410520121 A CN201410520121 A CN 201410520121A CN 104312246 B CN104312246 B CN 104312246B
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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 to a kind of metallic cathode electrophoretic coating and its preparation side
Method.
Background technology
Electrophoretic painting is the new coating process of a kind of comparison at present.It is a kind of water miscible with just (or negative) electric charge
Organic coating, the dissolving (or dispersion) with diluter even concentration in aqueous, will have the workpiece (coated article) of electric conductivity
As negative electrode (or anode) another using metallic plate or carbon plate as anode (or negative electrode), under certain process conditions, in two interpolars
Logical people's DC current (must apply higher voltage), makes electrophoretic coating equably be deposited on workpiece, forms one kind not
It is dissolved in the organic coating film of water.Through certain temperature baking and curing, and obtain a kind of higher organic coating film of hardness, play anti-corrosion
Effect with incrustation.
Cathode electrophoresis dope, compared with traditional handicraft, has unrivaled superiority.
(1) there is excellent Corrosion Protection and adhesive force.
(2) have smooth coating, resistance to water, chemical resistance good the features such as.
(3) there is prominent environment-friendly advantage, using water as solvent, reduce the volatilization of VOC.
(4) have and easily realize automatic continuous production, improve production efficiency.
(5) there is the application of suitable complex-shaped workpieces, such as edge corner angle, hole workpiece, inner chamber, gap etc.
(6) there is electrophoretic painting efficiency high, using closed circulating system, coating almost 100% utilization.
In phase early 1960s, PPG company of the U.S. helps Ford Motor Company to establish first electrophoresis in the world
Paint line, for vehicle paint base, so that electrophoretic painting has formally proceeded to industrial production from conceptual phase.70 years 20th century
In generation, PPG company of the U.S. develops the stronger cathode electrophoresis dope of antiseptic property first, makes Ford Motor Company of the U.S. and general vapour
Che company established cathode electro-coating production line in 1977, for the electrophoretic painting of body of a motor car, promoted electrophoretic painting
Industrial expansion.
Since the eighties in 20th century, the state such as the U.S., France, Japan, Italy in succession have developed thick film cathode electrophoresis and applies
Material, color electrophoresis coating, low-temperature curing electrophoretic coating, dumb light electrophoretic coating etc., promote developing rapidly of electrophoretic painting industry,
Electrophoretic painting is made widely to apply to the industry-by-industries such as automobile, light industry, construction material, furniture, electrical equipment.Nineteen eighty-two, Japan
Start in state and electrophoretic painting has been carried out on electrodeposited coating.With the increase of electrophoretic coating kind, the raising of quality, electrophoretic painting work
The constantly improve of skill, has developed the application electroplated in decoration protection field further, has also promoted electrophoretic painting industrial expansion.
In China, electrophoretic painting originates in phase early 1970s, such as the bottoming of sewing machine fuselage, not only improves
Product quality, improves the operating condition of workman simultaneously, is conducive to environmental protection.Since late 1980s, Beijing,
The provinces and cities such as Guangdong, Sichuan, Jiangsu start to develop polyurethane, acrylic acid, the electrophoretic coating of epoxide resin type.Meanwhile, Britain, U.S.
Electrophoresis application technique is also gradually introduced China by some external manufacturers such as state, Japan, has promoted electrophoresis application technique in China
The utilization of electroplating industry.Electrophoretic painting widely applies to clock and watch, glasses, lamp decoration, hardware (pen, smoking set, belt fastener, draw
Chain etc.) etc. industry.
Cathode electrophoresis dope, due to having a series of advantage, is therefore increasingly paid attention to by people, particularly in automobile
The country of industry prosperity.However as social continuous progress, the range for current electrophoretic coating and performance are
Application product higher quality can not be met require, lot of domestic and international paint company is to the formula of cathode electrophoresis dope and technique bar
Part is updated, and achieves certain achievement, but the current place that also there are some and have much room for improvement, such as with the ring of function admirable
Oxygen tree fat is that the electrophoretic coating solidification temperature of main body is higher, and acidproof, alkaline-resisting and salt fog resistance can meet higher further
Quality requirement, the corner angle also for workpiece are poor with the spreadability of most advanced and sophisticated film etc., and these aspects become ability cathode electrophoresis
The difficult problem that the further development need of coating solves.
The Chinese patent of Application No. 201210363919.8 discloses a kind of high throwing power cathode electrophoresis dope resin
Emulsion and preparation method thereof, emulsion is fragrant with one or two Totally-enclosed-types by the modified epoxy of multiple unimolecule amine aminations
After race's polyisocyanates heating blending, neutralized with organic acid, then deionized water dispersion is obtained, there is provided a kind of volatility is organic
Compounds content is low, and Ford box method throwing power reaches the high throwing power cathode electrophoresis dope resin emulsion of more than 22cm；Application number
Chinese patent for 03132255.7 discloses a kind of cathode electrophoresis dope resin emulsion of low-temperature setting, by modified epoxy tree
Fat, polyamine and blocked polyisocyanate are through chemical reaction and mixing, then with after organic acid center, form resin emulsion, its
Purpose is to eliminate the many drawbacks caused by hot setting, and 120-140 DEG C of film curing is abundant, and good decorative property does not turn yellow.
But be not highly significant for the improvement of cathode electrophoresis dope performance in document disclosed above, for paint film acidproof,
Alkaline-resisting, the performance such as salt spray resistance, resistance to boiling water improvement, simultaneously less it is therefore desirable to be furtherd investigate further, develops a kind of performance
Excellent cathode electrophoresis dope.
Content of the invention
It is an object of the invention in order to overcome above the deficiencies in the prior art to provide a kind of metallic cathode electrophoretic coating
And preparation method thereof, improve acidproof, alkaline-resisting, resistance to neutral salt spray and the boiling water resistance energy of coating paint film, overcome workpiece rib simultaneously
Angle or the problem of most advanced and sophisticated paint film adhesion difference.
The present invention is realized by following technological means：
A kind of metallic cathode electrophoretic coating, includes by weight part：Modified epoxy 20-30 part, methyl trimethoxy oxygen
Base silane 0.5-2 part, hydroxypropyl cellulose acetate 2-8 part, 2- cyanacrylate 5-10 part, acrylamide 0.8-2 part,
2- acrylamide-2-methylpro panesulfonic acid 0.6-1.5 part, Hydroxypropyl methylcellulose 1-4 part, zinc stearate 0.8-3 part；Wherein said
The formula of modified epoxy includes by weight part：Epoxy resin 10-20 part, APES 4-8 part, toluene
Diisocyanate 2-8 part, azodiisobutyronitrile 1-3 part, maleic anhydride 2-5 part.
Described metallic cathode electrophoretic coating is it may be preferred to be to include by weight part：Modified epoxy 25-28
Part, MTMS 0.8-1.3 part, hydroxypropyl cellulose acetate 5-7 part, 2- cyanacrylate 8-10 part,
Acrylamide 1.2-1.6 part, 2- acrylamide-2-methylpro panesulfonic acid 1-1.3 part, Hydroxypropyl methylcellulose 2-4 part, zinc stearate
2-2.5 part；The formula of wherein said modified epoxy includes by weight part：Epoxy resin 14-18 part, alkyl phenol polyoxy
Vinethene 5-7 part, toluene di-isocyanate(TDI) 4-7 part, azodiisobutyronitrile 2-3 part, maleic anhydride 3-5 part.
Above-described metallic cathode electrophoretic coating, the particle diameter of described zinc stearate can be 100-200 μm.
In above-described metallic cathode electrophoretic coating, the preparation method of described modified epoxy is as follows：
Step one, epoxy resin is added in reactor, adds APES and azodiisobutyronitrile, stirs
Mix and mix, be then warming up to 60-70 DEG C under conditions of inert gas shielding, continue stirring reaction 60-150 minute, fall
To room temperature, obtain reactant one；
Step 2, maleic anhydride and toluene di-isocyanate(TDI) is added in reactant one, in the bar of inert gas shielding
It is heated to 70-80 DEG C under part, and keep vacuum to be 0.03-0.06MPa, stirring reaction 60-100 minute, it is down to room temperature, obtain
Modified epoxy.
The condition stirring mixing in step one in the preparation method of described modified epoxy can be speed of agitator
100-120 rev/min, stir 20-30 minute.
The mixing speed continuing stirring reaction in step one in the preparation method of described modified epoxy can be 60-
70 revs/min.
In step 2 in the preparation method of described modified epoxy, the mixing speed of stirring reaction can be 70-80
Rev/min.
The preparation method of more than one described metallic cathode electrophoretic coatings, comprises the following steps：
Step one, modified epoxy, hydroxypropyl cellulose acetate and 2- cyanacrylate are added to reaction
In kettle, it is heated to melting, stirs, obtain mixture one；
Step 2, Hydroxypropyl methylcellulose and MTMS is added in mixture one, is heated to 40-50
DEG C, stirring reaction 2-8 hour, it is subsequently adding 5-10 part deionized water, keeping temperature is 50-60 DEG C, vacuum 0.04-
0.08MPa, continues stirring 1-3 hour, obtains mixture two；
Step 3, acrylamide is added in mixture two, is warming up to 90-100 DEG C, stirring mixing 40-60 minute, so
After be cooled to 70-80 DEG C, add 2- acrylamide-2-methylpro panesulfonic acid and zinc stearate, continue stirring 60-90 minute, fall
To room temperature, obtain cathode electrophoresis dope.
The preparation method of above-described metallic cathode electrophoretic coating, in step one mixing speed can turn for 150-200/
Minute.
The preparation method of above-described metallic cathode electrophoretic coating, in step 2, the mixing speed of stirring reaction can be
80-100 rev/min.
In the metallic cathode electrophoretic coating that the present invention provides, the mutual Synergistic Mechanisms between each component are as follows：
The metallic cathode electrophoretic coating that the present invention provides first passes through and is modified epoxy resin, has obtained mutually passing through netted
Modified epoxy, can preferably be merged with other components, MTMS and Hydroxypropyl methylcellulose
Introducing makes mutually leaching between each component invade and crosslinking, can form paint film at the corner angle of workpiece with tip well；Hydroxypropyl
Cellulose acetate defines height with modified epoxy by the effect of acrylamide with the addition of 2- cyanacrylate
The polymer of performance, enhances the performances such as acidproof, the alkaline-resisting and resistance to neutral salt spray of coating paint film, and 2- acrylamido -2- first
The introducing of base propane sulfonic acid enhances coating stability in aqueous while cleverly serving nertralizer effect, improves
Paint film and the binding ability of matrix.
The metallic cathode electrophoretic coating that the present invention provides compared with prior art, has following clear superiority：
(1) performance of the metallic cathode electrophoretic coating that the present invention provides compared with prior art has obvious advantage, its
Middle pencil hardness has reached 4H, and solvent resistance has reached more than 205 times, and acid resistance has reached more than 880h, and alkali resistance reaches
More than 912h, boiling water resistance has reached more than 10h, and weatherability has reached more than 625h, and corrosion resistance (CASS) has reached 530h
More than, neutral salt spray test has reached more than 1062h, and workpiece corner angle and most advanced and sophisticated paint film cover average thickness and account for workpiece smooth place paint
The percentage that film covers average thickness has reached more than 99.6%.
(2) present invention provide metallic cathode electrophoretic coating solidification temperature low, be 105-110 DEG C, existing with asphalt mixtures modified by epoxy resin
Fat is generally 160-200 DEG C of the electrophoretic coating solidification temperature of main material, and progress of the present invention is notable.
Specific embodiment：
Embodiment 1
A kind of metallic cathode electrophoretic coating, includes by weight part：20 parts of modified epoxy, methyl trimethoxy epoxide silicon
0.5 part of alkane, 2 parts of hydroxypropyl cellulose acetate, 5 parts of 2- cyanacrylate, 0.8 part of acrylamide, 2- acrylamido-
0.6 part of 2- methyl propane sulfonic acid, 1 part of Hydroxypropyl methylcellulose, 0.8 part of zinc stearate；The formula of wherein said modified epoxy with
Components by weight percent meter includes：10 parts of epoxy resin, 4 parts of APES, 2 parts of toluene di-isocyanate(TDI), azo two isobutyl
1 part of nitrile, 2 parts of maleic anhydride.
The particle diameter of above zinc stearate is 100 μm.
(1) preparation method of above modified epoxy is：
Step one, epoxy resin is added in reactor, adds APES and azodiisobutyronitrile, stirs
Mix and mix, the condition wherein stirring mixing is 100 revs/min of speed of agitator, stir 20 minutes, then in nitrogen protection
Under the conditions of be warming up to 60 DEG C, continue the speed stirring reaction 60 minutes with 60 revs/min, be down to room temperature, obtain reactant one；
Step 2, maleic anhydride and toluene di-isocyanate(TDI) are added in reactant one, under conditions of nitrogen protection
It is heated to 70 DEG C, and keeps vacuum to be 0.03MPa, with 70 revs/min of mixing speed stirring reaction 60 minutes, be down to room
Temperature, obtains modified epoxy.
(2) the preparation method step of above-described metallic cathode electrophoretic coating is as follows：
Step one, modified epoxy, hydroxypropyl cellulose acetate and 2- cyanacrylate are added to reaction
In kettle, it is heated to melting, stirs, wherein mixing speed is 150 revs/min, obtains mixture one；
Step 2, Hydroxypropyl methylcellulose and MTMS is added in mixture one, is heated to 40 DEG C, stirs
Mix reaction 2 hours, mixing speed is 80 revs/min, is subsequently adding 5 parts of deionized waters, keeping temperature is 50 DEG C, vacuum
0.04MPa, continues stirring 1 hour, obtains mixture two；
Step 3, acrylamide is added in mixture two, is warming up to 90 DEG C, stirring mixing 40 minutes, then lowers the temperature
To 70 DEG C, add 2- acrylamide-2-methylpro panesulfonic acid and zinc stearate, continue stirring 60 minutes, be down to room temperature, obtain the moon
Pole electrophoretic coating.
Embodiment 2
A kind of metallic cathode electrophoretic coating, includes by weight part：25 parts of modified epoxy, methyl trimethoxy epoxide silicon
0.8 part of alkane, 5 parts of hydroxypropyl cellulose acetate, 8 parts of 2- cyanacrylate, 1.2 parts of acrylamide, 2- acrylamido-
1 part of 2- methyl propane sulfonic acid, 2 parts of Hydroxypropyl methylcellulose, 2 parts of zinc stearate；The formula of wherein said modified epoxy is with weight
Component meter includes：14 parts of epoxy resin, 5 parts of APES, 4 parts of toluene di-isocyanate(TDI), azodiisobutyronitrile 2
Part, 3 parts of maleic anhydride.
The particle diameter of above zinc stearate is 120 μm.
(1) preparation method of above modified epoxy is：
Step one, epoxy resin is added in reactor, adds APES and azodiisobutyronitrile, stirs
Mix and mix, the condition wherein stirring mixing is 105 revs/min of speed of agitator, stir 22 minutes, then in argon gas protection
Under the conditions of be warming up to 65 DEG C, continue the speed stirring reaction 70 minutes with 63 revs/min, be down to room temperature, obtain reactant one；
Step 2, maleic anhydride and toluene di-isocyanate(TDI) are added in reactant one, under conditions of argon gas protection
It is heated to 73 DEG C, and keeps vacuum to be 0.04MPa, with 75 revs/min of mixing speed stirring reaction 70 minutes, be down to room
Temperature, obtains modified epoxy.
(2) the preparation method step of above-described metallic cathode electrophoretic coating is as follows：
Step one, modified epoxy, hydroxypropyl cellulose acetate and 2- cyanacrylate are added to reaction
In kettle, it is heated to melting, stirs, wherein mixing speed is 160 revs/min, obtains mixture one；
Step 2, Hydroxypropyl methylcellulose and MTMS is added in mixture one, is heated to 45 DEG C, stirs
Mix reaction 4 hours, mixing speed is 88 revs/min, is subsequently adding 6 parts of deionized waters, keeping temperature is 55 DEG C, vacuum
0.05MPa, continues stirring 2 hours, obtains mixture two；
Step 3, acrylamide is added in mixture two, is warming up to 96 DEG C, stirring mixing 48 minutes, then lowers the temperature
To 76 DEG C, add 2- acrylamide-2-methylpro panesulfonic acid and zinc stearate, continue stirring 72 minutes, be down to room temperature, obtain the moon
Pole electrophoretic coating.
Embodiment 3
A kind of metallic cathode electrophoretic coating, includes by weight part：27 parts of modified epoxy, methyl trimethoxy epoxide silicon
1 part of alkane, 6 parts of hydroxypropyl cellulose acetate, 9 parts of 2- cyanacrylate, 1.5 parts of acrylamide, 2- acrylamido -2-
1.2 parts of methyl propane sulfonic acid, 3 parts of Hydroxypropyl methylcellulose, 2.3 parts of zinc stearate；The formula of wherein said modified epoxy is with weight
Amount component meter includes：16 parts of epoxy resin, 6 parts of APES, 5 parts of toluene di-isocyanate(TDI), azodiisobutyronitrile 3
Part, 4 parts of maleic anhydride.
The particle diameter of above zinc stearate is 150 μm.
(1) preparation method of above modified epoxy is：
Step one, epoxy resin is added in reactor, adds APES and azodiisobutyronitrile, stirs
Mix and mix, the condition wherein stirring mixing is 110 revs/min of speed of agitator, stir 25 minutes, then in nitrogen protection
Under the conditions of be warming up to 68 DEG C, continue the speed stirring reaction 100 minutes with 70 revs/min, be down to room temperature, obtain reactant one；
Step 2, maleic anhydride and toluene di-isocyanate(TDI) is added in reactant one, in the bar of inert gas shielding
It is heated to 78 DEG C under part, and keeps vacuum to be 0.05MPa, with 75 revs/min of mixing speed stirring reaction 85 minutes, be down to
Room temperature, obtains modified epoxy.
(2) the preparation method step of above-described metallic cathode electrophoretic coating is as follows：
Step one, modified epoxy, hydroxypropyl cellulose acetate and 2- cyanacrylate are added to reaction
In kettle, it is heated to melting, stirs, wherein mixing speed is 180 revs/min, obtains mixture one；
Step 2, Hydroxypropyl methylcellulose and MTMS is added in mixture one, is heated to 50 DEG C, stirs
Mix reaction 6 hours, mixing speed is 90 revs/min, is subsequently adding 8 parts of deionized waters, keeping temperature is 58 DEG C, vacuum
0.06MPa, continues stirring 2 hours, obtains mixture two；
Step 3, acrylamide is added in mixture two, is warming up to 98 DEG C, stirring mixing 55 minutes, then lowers the temperature
To 75 DEG C, add 2- acrylamide-2-methylpro panesulfonic acid and zinc stearate, continue stirring 80 minutes, be down to room temperature, obtain the moon
Pole electrophoretic coating.
Embodiment 4
A kind of metallic cathode electrophoretic coating, includes by weight part：28 parts of modified epoxy, methyl trimethoxy epoxide silicon
1.3 parts of alkane, 7 parts of hydroxypropyl cellulose acetate, 10 parts of 2- cyanacrylate, 1.6 parts of acrylamide, 2- acrylamide
1.3 parts of base -2- methyl propane sulfonic acid, 4 parts of Hydroxypropyl methylcellulose, 2.5 parts of zinc stearate；The formula of wherein said modified epoxy
Include by weight part：18 parts of epoxy resin, 7 parts of APES, 7 parts of toluene di-isocyanate(TDI), azo two is different
3 parts of butyronitrile, 5 parts of maleic anhydride.
The particle diameter of above zinc stearate is 180 μm.
(1) preparation method of above modified epoxy is：
Step one, epoxy resin is added in reactor, adds APES and azodiisobutyronitrile, stirs
Mix and mix, the condition wherein stirring mixing is 120 revs/min of speed of agitator, stir 28 minutes, then in nitrogen protection
Under the conditions of be warming up to 66 DEG C, continue the speed stirring reaction 130 minutes with 70 revs/min, be down to room temperature, obtain reactant one；
Step 2, maleic anhydride and toluene di-isocyanate(TDI) is added in reactant one, in the bar of inert gas shielding
It is heated to 76 DEG C under part, and keeps vacuum to be 0.05MPa, with 80 revs/min of mixing speed stirring reaction 85 minutes, be down to
Room temperature, obtains modified epoxy.
(2) the preparation method step of above-described metallic cathode electrophoretic coating is as follows：
Step one, modified epoxy, hydroxypropyl cellulose acetate and 2- cyanacrylate are added to reaction
In kettle, it is heated to melting, stirs, wherein mixing speed is 180 revs/min, obtains mixture one；
Step 2, Hydroxypropyl methylcellulose and MTMS is added in mixture one, is heated to 50 DEG C, stirs
Mix reaction 7 hours, mixing speed is 95 revs/min, is subsequently adding 9 parts of deionized waters, keeping temperature is 56 DEG C, vacuum
0.07MPa, continues stirring 3 hours, obtains mixture two；
Step 3, acrylamide is added in mixture two, is warming up to 100 DEG C, stirring mixing 55 minutes, then lowers the temperature
To 75 DEG C, add 2- acrylamide-2-methylpro panesulfonic acid and zinc stearate, continue stirring 90 minutes, be down to room temperature, obtain the moon
Pole electrophoretic coating.
Embodiment 5
A kind of metallic cathode electrophoretic coating, includes by weight part：30 parts of modified epoxy, methyl trimethoxy epoxide silicon
2 parts of alkane, 8 parts of hydroxypropyl cellulose acetate, 10 parts of 2- cyanacrylate, 2 parts of acrylamide, 2- acrylamido -2-
1.5 parts of methyl propane sulfonic acid, 4 parts of Hydroxypropyl methylcellulose, 3 parts of zinc stearate；The formula of wherein said modified epoxy is with weight
Component meter includes：20 parts of epoxy resin, 8 parts of APES, 8 parts of toluene di-isocyanate(TDI), azodiisobutyronitrile 3
Part, 5 parts of maleic anhydride.
The particle diameter of above zinc stearate is 200 μm.
(1) preparation method of above modified epoxy is：
Step one, epoxy resin is added in reactor, adds APES and azodiisobutyronitrile, stirs
Mix and mix, the condition wherein stirring mixing is 120 revs/min of speed of agitator, stir 30 minutes, then in nitrogen protection
Under the conditions of be warming up to 70 DEG C, continue the speed stirring reaction 150 minutes with 70 revs/min, be down to room temperature, obtain reactant one；
Step 2, maleic anhydride and toluene di-isocyanate(TDI) is added in reactant one, in the bar of inert gas shielding
It is heated to 80 DEG C under part, and keeps vacuum to be 0.06MPa, with 80 revs/min of mixing speed stirring reaction 100 minutes, fall
To room temperature, obtain modified epoxy.
(2) the preparation method step of above-described metallic cathode electrophoretic coating is as follows：
Step one, modified epoxy, hydroxypropyl cellulose acetate and 2- cyanacrylate are added to reaction
In kettle, it is heated to melting, stirs, wherein mixing speed is 200 revs/min, obtains mixture one；
Step 2, Hydroxypropyl methylcellulose and MTMS is added in mixture one, is heated to 50 DEG C, stirs
Mix reaction 8 hours, mixing speed is 100 revs/min, is subsequently adding 10 parts of deionized waters, keeping temperature is 60 DEG C, vacuum
0.08MPa, continues stirring 3 hours, obtains mixture two；
Step 3, acrylamide is added in mixture two, is warming up to 100 DEG C, stirring mixing 60 minutes, then lowers the temperature
To 80 DEG C, add 2- acrylamide-2-methylpro panesulfonic acid and zinc stearate, continue stirring 90 minutes, be down to room temperature, obtain the moon
Pole electrophoretic coating.
Voltage when the metallic cathode electrophoretic coating that above example prepares uses is 200-220V, and solidification temperature is
105-110 DEG C, can reach and be fully cured.The film of the cathode electrophoresis dope that above example is prepared carries out performance survey
Examination, and performance comparison is carried out as a comparison case using Japanese ELECOAT CM cathod coating, the results are shown in Table 1.
Performance and the prior art phase of the metallic cathode electrophoretic coating of present invention offer is provided from above result of the test
Ratio has obvious advantage, and wherein pencil hardness has reached 4H, and solvent resistance has reached more than 205 times, and acid resistance reaches
More than 880h, alkali resistance has reached more than 912h, and boiling water resistance has reached more than 10h, and weatherability has reached more than 625h, corrosion resistant
Corrosion (CASS) has reached more than 530h, and neutral salt spray test has reached more than 1062h, and workpiece corner angle and most advanced and sophisticated paint film cover flat
The percentage that equal thickness accounts for workpiece smooth place paint film covering average thickness has reached more than 99.6%, prepares wherein in embodiment 3
The negative electrophoretic coating performance obtaining preferably, can be used as most preferred embodiment.
The metallic cathode electrophoretic coating that the present invention provides first passes through and is modified epoxy resin, has obtained mutually passing through netted
Modified epoxy, can preferably be merged with other components, MTMS and Hydroxypropyl methylcellulose
Introducing makes mutually leaching between each component invade and crosslinking, can form paint film at the corner angle of workpiece with tip well；Hydroxypropyl
Cellulose acetate defines height with modified epoxy by the effect of acrylamide with the addition of 2- cyanacrylate
The polymer of performance, enhances the performances such as acidproof, the alkaline-resisting and resistance to neutral salt spray of coating paint film, and 2- acrylamido -2- first
The introducing of base propane sulfonic acid enhances coating stability in aqueous while cleverly serving nertralizer effect, improves
Paint film and the binding ability of matrix.
The metallic cathode electrophoretic coating that comprehensively the above can be seen that present invention offer solves well with asphalt mixtures modified by epoxy resin
Fat is the problem of acidproof, alkaline-resisting, the resistance to neutral salt spray poor performance of negative coating of main body, enhances film adhesion simultaneously, gram
Take workpiece corner angle or the problem of most advanced and sophisticated paint film adhesion difference, compared with prior art reached the progress of highly significant, entered one
Step expands and the range extending negative electrophoretic coating.
Claims (8)
1. a kind of metallic cathode electrophoretic coating is it is characterised in that include by weight part：Modified epoxy 20-30 part, first
Base trimethoxy silane 0.5-2 part, hydroxypropyl cellulose acetate 2-8 part, 2- cyanacrylate 5-10 part, acrylamide
0.8-2 part, 2- acrylamide-2-methylpro panesulfonic acid 0.6-1.5 part, Hydroxypropyl methylcellulose 1-4 part, zinc stearate 0.8-3 part；
The formula of wherein said modified epoxy includes by weight part：Epoxy resin 10-20 part, APES 4-
8 parts, toluene di-isocyanate(TDI) 2-8 part, azodiisobutyronitrile 1-3 part, maleic anhydride 2-5 part；
The preparation method of described modified epoxy is as follows：
Step one, epoxy resin is added in reactor, adds APES and azodiisobutyronitrile, and stirring is mixed
Close uniformly, be then warming up to 60-70 DEG C under conditions of inert gas shielding, continue stirring reaction 60-150 minute, be down to room
Temperature, obtains reactant one；
Step 2, maleic anhydride and toluene di-isocyanate(TDI) is added in reactant one, under conditions of inert gas shielding
It is heated to 70-80 DEG C, and keep vacuum to be 0.03-0.06MPa, stirring reaction 60-100 minute, it is down to room temperature, obtain modification
Epoxy resin；
The preparation method of described metallic cathode electrophoretic coating, comprises the following steps：
Step one, modified epoxy, hydroxypropyl cellulose acetate and 2- cyanacrylate are added in reactor,
It is heated to melting, stir, obtain mixture one；
Step 2, Hydroxypropyl methylcellulose and MTMS is added in mixture one, is heated to 40-50 DEG C, stirs
Mix reaction 2-8 hour, be subsequently adding 5-10 part deionized water, keeping temperature is 50-60 DEG C, vacuum 0.04-0.08MPa continues
Continuous stirring 1-3 hour, obtains mixture two；
Step 3, acrylamide is added in mixture two, is warming up to 90-100 DEG C, stirring mixing 40-60 minute, then drops
Temperature, to 70-80 DEG C, adds 2- acrylamide-2-methylpro panesulfonic acid and zinc stearate, continues stirring 60-90 minute, is down to room
Temperature, obtains cathode electrophoresis dope.
2. metallic cathode electrophoretic coating according to claim 1 is it is characterised in that include by weight part：Modified ring
Oxygen tree fat 25-28 part, MTMS 0.8-1.3 part, hydroxypropyl cellulose acetate 5-7 part, 2- alpha-cyanoacrylate
Ethyl ester 8-10 part, acrylamide 1.2-1.6 part, 2- acrylamide-2-methylpro panesulfonic acid 1-1.3 part, Hydroxypropyl methylcellulose 2-4
Part, zinc stearate 2-2.5 part；The formula of wherein said modified epoxy includes by weight part：Epoxy resin 14-18
Part, APES 5-7 part, toluene di-isocyanate(TDI) 4-7 part, azodiisobutyronitrile 2-3 part, maleic anhydride 3-5 part.
3. metallic cathode electrophoretic coating according to claim 1 and 2 is it is characterised in that the particle diameter of described zinc stearate is
100-200μm.
4. metallic cathode electrophoretic coating according to claim 1 is it is characterised in that the preparation of described modified epoxy
The condition stirring mixing in step one in method is 100-120 rev/min of speed of agitator, stirs 20-30 minute.
5. metallic cathode electrophoretic coating according to claim 1 is it is characterised in that the preparation of described modified epoxy
The mixing speed continuing stirring reaction in step one in method is 60-70 rev/min.
6. metallic cathode electrophoretic coating according to claim 1 is it is characterised in that the preparation of described modified epoxy
In step 2 in method, the mixing speed of stirring reaction is 70-80 rev/min.
7. metallic cathode electrophoretic coating according to claim 1 is it is characterised in that prepared by described metallic cathode electrophoretic coating
In method and step one, mixing speed is 150-200 rev/min.
8. metallic cathode electrophoretic coating according to claim 1 is it is characterised in that prepared by described metallic cathode electrophoretic coating
In method and step two, the mixing speed of stirring reaction is 80-100 rev/min.
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| US10961403B2 (en) * | 2016-07-26 | 2021-03-30 | Ppg Industries Ohio, Inc. | Electrodepositable coating compositions containing 1,1-di-activated vinyl compounds |
| EP3490784B1 (en) | 2016-07-26 | 2022-10-12 | 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 |
| ES2930756T3 (en) * | 2016-07-26 | 2022-12-21 | Ppg Ind Ohio Inc | Acid-Catalyzed Curable Coating Compositions Containing 1,1-Diactivated Vinyl Compounds and Related Coatings and Processes |
| ES2930531T3 (en) | 2016-07-26 | 2022-12-16 | Ppg Ind Ohio Inc | Particles having surfaces functionalized with 1,1-diactivated vinyl compounds |
| WO2018022780A1 (en) | 2016-07-26 | 2018-02-01 | 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 |
| EP3490726B1 (en) | 2016-07-26 | 2022-11-30 | 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 |
| 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 |
| 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 |
| 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 |
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| CN104004448B (en) * | 2014-05-04 | 2016-07-13 | 四川理工学院 | A kind of one pack system cathode electrophoresis dope for vehicle paint base |
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