CN105885640A - Corrosion-resistant low-temperature-curing cathode electrophoretic paint - Google Patents
Corrosion-resistant low-temperature-curing cathode electrophoretic paint Download PDFInfo
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- CN105885640A CN105885640A CN201610455743.7A CN201610455743A CN105885640A CN 105885640 A CN105885640 A CN 105885640A CN 201610455743 A CN201610455743 A CN 201610455743A CN 105885640 A CN105885640 A CN 105885640A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D17/00—Pigment pastes, e.g. for mixing in paints
- C09D17/001—Pigment pastes, e.g. for mixing in paints in aqueous medium
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
- C09D5/4419—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained otherwise than by polymerisation reactions only involving carbon-to-carbon unsaturated bonds
- C09D5/443—Polyepoxides
- C09D5/4457—Polyepoxides containing special additives, e.g. pigments, polymeric particles
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
- C09D5/4473—Mixture of polymers
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09F—NATURAL RESINS; FRENCH POLISH; DRYING-OILS; DRIERS (SICCATIVES); TURPENTINE
- C09F9/00—Compounds to be used as driers (siccatives)
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The invention relates to the field of paint, in particular to corrosion-resistant low-temperature-curing cathode electrophoretic paint which comprises 1-2 parts of color paste, 4-6 parts of an emulsion and 5-7 parts of deionized water. The color paste comprises 20-30 parts of main resin, 5-10 parts of an alcohol-ether cosolvent, 3-8 parts of organic acid, 0.3-0.7 part of an emulsifier, 1-5 parts of a compound drier, 30-40 parts of deionized water, 3-7 parts of a first solid additive, 1.5-6 parts of a second solid additive, 6-9 parts of a first compound regulator, 7-11 parts of a second compound regulator, 8-14 parts of a third compound regulator, 3-7 parts of a fourth compound regulator composed of polyacrylate-2-cross-linked polymer and corrosion-resistant liquid, and 15-20 parts of a filler, and the emulsion comprises 40-50 parts of modified epoxy resin A, 10-20 parts of modified epoxy resin B, 10-30 parts of a cross-linking agent, 5-9 parts of a curing agent, 3-8 parts of monomolecular amine, 0.1-2 parts of an emulsifier, 0.1-2 parts of a neutralizing agent and 30-50 parts of deionized water. Different compound formulations are used in the emulsion and the color paste in an improved, so that the cathode electrophoretic paint is corrosion-resistant, supportive of low-temperature curing and resistant to yellowing.
Description
Technical field
The present invention relates to paint field, be specifically related to a kind of anti-corrosion type low-temperature curing cathode electrophoresis paint.
Background technology
Come out from cathode electrodip painting, because its paint film formed has the corrosion resistance of excellence, mechanical performance, be suitable for again automatically
Changing application, the most quickly popularized, the baking temperature scope of traditional cathode electrodip painting is typically 170～180
℃.At present, many industrial workpiece are with rubber, plastic or other material, it is desirable to together dry with electrophoretic paint after processing, thus
Reduce operative's intensity, control cost.But such material toasts under the high temperature conditions and is easily deformed or melts.For adapting to be somebody's turn to do
The demand of class technique, market occurs the low temperature curing type cathode electrodip painting of few kind.Low temperature curing type cathode electrodip painting is not
Only being conducive to plastics and the application of the auto parts and components of rubber, and can be substantially reduced energy consumption, cathode electrodip painting is with habitually in the past
Organic leadP and tin catalyst, due to toxicity greatly, not environmentally etc. shortcoming limit the use of in Europe and developed country.Unleaded, nothing
Stannum environment-friendly type high anti-corrosive properties cathode electrodip painting is a significant improvement in electrophoretic paint evolution.Therefore in electrophoretic paint, choosing
The best environment-friendly type drier is to improve electrophoresis product quality, and the competitiveness of in use improving product is particularly important.
CN104497786A(2015-4-8) disclose a kind of electrophoretic paint, but the environmental-protecting performance of this electrophoretic paint need to change
Enter.
Summary of the invention
The purpose of the present invention, is the problem in order to solve in background technology, it is provided that a kind of anti-corrosion type low-temperature curing cathode
Swimming paint.
The above-mentioned technical purpose of the present invention has the technical scheme that
A kind of anti-corrosion type low-temperature curing cathode electrophoresis paint, cathode electrodip painting includes mill base, emulsion and deionized water, including by quality
Part meter, 1-2 part mill base, 4-6 part emulsion and 5-7 part deionized water；
Described paste formula includes, 20-30 part matrix resin, 5-10 part alcohol ethers cosolvent, 3-8 part organic acid, 0.3-0.7 part
Emulsifying agent, 1-5 part composite drier, 30-40 part deionized water, 3-7 part the first solid additive, 1.5-6 part the second solid add
Add agent, first composite regulator 6-9 part, the diphenylamines of the proportioning of 1:2-4:1-3 in mass ratio, 2,6-di-t-butyl and benzo three nitrogen
Second composite regulator 7-11 part of azoles composition；
The sulfuration Oleum Gossypii semen of the proportioning of 1:0.5-0.8:1.3-1.7 in mass ratio, two (2-sulfydryl-4-n-propylamine base-1,3,5-three
Piperazine) thioether and two (2-sulfydryl-4-Aminocyclopentane base-1,3,5-triazine) thioether composition the 3rd composite regulator 8-14 part；
Polyacrylate-2-the cross linked polymer of the proportioning of 1:1-4 in mass ratio and the 4th composite regulator 3-7 of impregnating fluid composition
Part；
And 15-20 part filler；
Described impregnating fluid compound method:
Add AVC 10-18 part, sodium fluoride 20-40 the most successively
Part, ammonium acid fluoride 30-60 part, potassium permanganate 10-20 part, Neutral potassium chromate 40-50 part；Stirring 5-10min, it is thus achieved that the second the most mixed liquid；
Zinc phosphate 15-25 part, sodium nitrate 8-18 part, praseodymium chloride 5-is added successively the most in order in the described second the most mixed liquid
12 parts, ethylenediaminetetraacetic acid 10-16 part, malic acid 7-14 part, dodecyl phenenyl sulfate 8-12 part, nickel sulfate 6-13 part, three
Ethanolamine 15-25 part, stirs 1-4min；
The particle size range of the first solid additive is 0.8-5 micron；Wherein, the granule of 0.8-1 micron accounts for described solid additive
The 20-40% of gross weight；The granule of 1-2 micron accounts for the 10-30% of described solid additive gross weight；Surplus is the granule of 3-5 micron；
Described first solid additive is following formula I polymer, wherein MwIt is 6.10 × 106, MnIt is 2.0 × 106, molecular weight divides
Cloth index is 3.1:
I
Described second solid additive be the molybdenum disulfide nano ball of particle diameter 10-20 nanometer with the regulation grain of particle diameter 6-9 micron by
Mixture according to mass ratio 1:2-5 composition；
Described first composite regulator is the tricaprylmethyl ammonium bromide of the proportioning of 1:3-4:1-2 in mass ratio, glycerol and poly-four
Fluorothene forms；
Described emulsion formulations includes, 40-50 part modified epoxy A, 10-20 part modified epoxy B, 10-30 part cross-linking agent,
5-9 part firming agent, 3-8 part unimolecule amine, 0.1-2 part emulsifying agent, 0.1-2 part nertralizer 30-50 part deionized water；
Described cross-linking agent is type semienclosed and/or blocked polyurethane includes, 4-4-methyl diphenylene diisocyanate 5-20 part,
Alcohol ether compound, heterocycle compound one of them or two or more mixing 3-30 part, polyethers or PCDL 0-
80 parts, ketones solvent 0-40 part；
Described modified epoxy A formula includes, 10-20 part bisphenol-A, 40-60 part epoxy resin, 8-16 part solvent, 4-16 part
Plasticizer, 10-35 part flexible polymer；Described modified epoxy B formula includes, 10-20 part Bisphenol F, 40-60 part asphalt mixtures modified by epoxy resin
Fat, 5-10 part nonyl phenol, 2-6 part dimethylbenzene, 0.1-1 part triphenyl phosphite；
Described composite drier preparation method is
(1). vanadic anhydride is mixed into vanadium ion and isooctyl acid radical ion molal weight ratio 1: 4 to 1: 5 with isooctyl acid
Row reaction, reaction temperature is 220 to 230 DEG C, and the response time is 0.5-0.8 hour；
(2). continuously add manganese carbonate, add lanthanum carbonate or cerous carbonate, and isooctyl acid carry out compound reaction, herein manganese ion with
Isooctyl acid root molal weight ion ratio is 1: 2 to 1: 3, and lanthanum ion or cerium ion with isooctyl acid radical ion molal weight ratio are
1: 4 to 1: 5, reaction temperature 100 to 180 DEG C, the response time is 0.4-0.6 hour；
(3). the liquid obtained after reaction is cooled to less than 140 DEG C and is blended into catalyst and Porous deproteinized bone solvent naphtha, stir-, obtain
Composite dryer for paint product, in described composite drier product, it is whole that each variable valency metal ions and isooctyl acid root form complexation
Body；Described catalyst is 1:5-8 with the mass ratio of vanadic anhydride；
This catalyst is zinc oxide, yittrium oxide, rubidium oxide, cobalt oxide, bismuth oxide, zirconium oxide, manganese oxide, cerium oxide, hydroxide
Cerium, zinc hydroxide, Bismuth hydrate., Yttrium trihydroxide, rubidium hydroxide, calcium hydroxide, cobalt nitrate, bismuth nitrate, manganese nitrate, nitroxylic acid
One of which in bismuth, cobalt octoate；
Anti-corrosion type low-temperature curing cathode electrophoresis paint comprises the following steps:
Prepared by A mill base, be sequentially added in a reservoir 20-30 part matrix resin, 5-10 part alcohol ethers cosolvent, 3-8 part organic acid,
0.3-0.7 part emulsifying agent and 30-40 part deionized water, composite drier 1-5 part, add 15-20 part filler at 700-1100
Stand more than 8 hours after dispersion under rev/min, sequentially add 3-7 part the first solid additive, the interpolation of 1.5-6 part the second solid
Agent, first composite regulator 6-9 part, second composite regulator 7-11 part, the 3rd composite regulator 8-14 part and the 4th are compound to be adjusted
Joint agent 3-7 part；
Disperse under 600-800 rev/min again 20-40 minute, then grind with sand mill, use after the μm of sand milling fineness≤13
Bag type filtering machine i.e. obtains mill base after filtering；
Prepared by B emulsion, 1. prepare modified epoxy A；2. modified epoxy B is prepared；3. by 40-50 part modified epoxy
After A and 10-20 part modified epoxy B stirring mixing, it is heated to 100-120 DEG C, adds unimolecule amine, continue mixing 2 little
Time；4. drip or be dividedly in some parts 10-30 part cross-linking agent, 5-9 part firming agent, be incubated 1.5-2.5 hour；5. 70-90 DEG C is cooled to,
Add 0.1-2 part emulsifying agent and 0.1-2 part nertralizer, dispersed with stirring 30-60 minute；6. cool to 30-70 DEG C, extract organic molten
Agent, adds 30-50 part deionized water, obtains emulsion after filtration, and emulsion Con trolling index is, solids content 35 ± 2%, and particle diameter≤
0.20 μm, ph value 6.0 ± 0.5；
C electrophoretic paint is allocated, and adds 2-3 part deionized water and 2-3 part emulsion, start circulation mixing pump in electrophoresis tank, incite somebody to action both
Circulation mixing；In premix groove, put into 2-3 part emulsion start stirring, the most slowly put into 1-2 part mill base, will after stirring
Premix groove mixed liquor the most uniformly inputs in electrophoresis tank；Throw 3-4 part deionized water and 4-7 part composite dispersing agent again to cleaning premix
Groove the water after cleaning the most uniformly pump into electrophoresis tank, i.e. obtain carrying out application in constantly circulation after tank liquor transconversion into heat
Electrophoretic paint；
Described composite dispersing agent forms according to following weight:
Oligomer diacetyl acetate alkylene diester metal chelate 35-45 part
Dispersant 5-9 part
Wetting agent 4-6 part
Defoamer 1-2 part.
The present invention uses specific paste formula, composite drier formula and emulsion formulations especially emulsion formulations, at breast
Liquid improves and uses 4-4-methyl diphenylene diisocyanate, make cathode electrodip painting green safety environmental protection, and when actually used
Reach to accelerate the oxidation of paint film, be polymerized and be dried, reach quick-drying purpose.Have excellent after the present invention the first composite regulator proportioning
Different dispersion, coagulate the soup and anti-wear and wear-resistant performance；Different-grain diameter and the first solid additive of kind and the second solid additive exist
While increasing cathode electrodip painting film uniformity and throwing power, moreover it is possible to give the good anti-wear performance of cathode electrodip painting paint film and
Water repelling property.The present invention the second composite regulator and the 3rd composite regulator proportioning have antioxidation and bright and clean corrosion resistant by after adding
Erosion function；So that paint film also has the effect of color inhibition.
Stage by stage add different material especially dispersion after add the first solid additive, the second solid additive and
First composite regulator, contributes to while increasing cathode electrodip painting film uniformity and throwing power, moreover it is possible to give negative electrode electricity
The good anti-wear performance of paint film and water repelling property are painted in swimming.
The solidification temperature of a kind of low-temperature curing cathode electrophoresis coating of the present invention is 140 DEG C, and coating film thickness is at 10-30
μm is adjustable, uses nontoxic formula simultaneously, environmental friendliness and more energy-conservation.Inventor finds, time prepared by impregnating fluid mix and blend,
The performance of paint film is had an impact by the order that various compositions add.The impregnating fluid prepared according to the inventive method order of addition makes paint film
Stability more preferable, have more anti-corrosive properties, color inhibition and curability at low temperatures.
As preferably, described impregnating fluid also includes potassium borohydride 1-3 part, bicyclohexane also-18-crown-6 4-6 part and two
Benzylbiphenyl phenol polyoxyethylene polyoxypropylene ether 5-8 part.
Inventor finds, adds the impregnating fluid of described material, can make paint film stability when preparing cathode electrodip painting and resist
Corrosive nature is more preferable.
As preferably, the preparation method of described polyacrylate-2-cross linked polymer is:
(1) prepared polymer P by weight (MMA-MAh)-PEG6000 30-40 part, regulation liquid 40-60 part form first and just mix
Liquid；Described regulation liquid is to include the sodium perchlorate that concentration is 0.4-0.7mol/L and the N-butyl benzene that concentration is 0.3-0.8mol/L
And the carbonic allyl ester solution of imidazoles；MMA in described polymer P (MMA-MAh)-PEG4000 is methyl methacrylate,
MAh is maleic anhydride, and P (MMA-MAh) is the copolymer of methyl methacrylate and maleic anhydride, and PEG6000 is that molecular weight is
The Polyethylene Glycol of 6000；
(2) in the described first the most mixed liquid, add 2-7 part ten dihydroxystearic acid, be heated to 30-45 DEG C under nitrogen protection instead
Answer 5-9min；
(3) polyacrylate-2-cross linked polymer is obtained after drying with deionized water rinsing.
Polyacrylate-2-the cross linked polymer using the present invention to prepare has hot property and the dimensional stability of excellence,
Paint film is made to possess more excellent anti-yellowing property.As preferably, described hardener formula includes, 20-66 part dimer (fatty acid) yl,
5-18 part vegetable oil acid, 5-25 part fatty amine, 10-34 part ketone, 5-20 part ethers, 0.01-0.02 part terminator；Described plant
Thing oleic acid is castor oil acid, cotton oil acid, the one in Semen Allii Tuberosi oleic acid or behenic acid, and described fatty amine is ethylenediamine, divinyl
Triamine, triethylene tetramine, TEPA or the one of mixed amine, described mixed amine is aminoethyl ethanolamine, aminoethyl piperazine or three
Mixing two or more in ethylene tetramine, described terminator is quinone, nitro polyol, nitroso-group polyhydroxy chemical combination
Thing, aryl polyol or the one of boric acid.
As preferably, described unimolecule amine at least contains the ketimide of aminoethyl ethanolamine or the two of diethylenetriamines
One in ketimide, its consumption at least accounts for the 50% of the total consumption of unimolecule amine.
As preferably, other compositions in described unimolecule amine are butylamine, octylame, diethylamine, methylbutylamine, an ethanol
One or more in amine, diethanolamine or N-methylethanolamine.
As preferably, the epoxide equivalent of described modified epoxy A is 200～1000, the ring of described modified epoxy B
Oxygen equivalent is 600～800.
As preferably, described flexible polymer is polyether Glycols, polyester diol or polyethers diamine, its equal molecule of number
Amount is 400～1500.
As preferably, the number-average molecular weight of described modified epoxy A is 1500～3500, described modified epoxy B
Number-average molecular weight is 1200～3000.
As preferably, described plasticizer is bisphenol A polyethenoxy ether or bisphenol-A polyethenoxy ether.
As preferably, described nertralizer is formic acid, acetic acid, propanoic acid, lactic acid, oxalic acid or other organic acid.
As preferably, in described hardener formula ketone be acetone, butanone, Ketohexamethylene, methyl iso-butyl ketone (MIBK), methyl
One in nezukone, methyl butyl ketone or 1-Phenylethanone., described ethers is ether, butyl cellosolve, ethylene glycol only son
One in ether or ethyl methyl ether.
As preferably, described composite dispersing agent forms according to following weight:
Oligomer diacetyl acetate alkylene diester metal chelate 35-45 part
Dispersant 5-9 part
Wetting agent 4-6 part
Defoamer 1-2 part.
Above material selects to may is that dispersant is DP 19 or EFKA 4550, and wetting agent is the secondary octyl phenol of polyoxyethylene
Ether, defoamer is 090 or EFKA 2526, wherein dispersant DP 19, and defoamer 090 is the TaiWan, China moral limited public affairs of modest chemistry
The product of department, EFKA 4550, EFKA 2526 is Holland's EFKA auxiliary agent Products.
As preferably, described modified epoxy A preparation method is, by 10-20 part bisphenol-A, 40-60 part epoxy resin,
8-16 part methyl iso-butyl ketone (MIBK) is added sequentially in reactor, after stirring is warmed up to 110 DEG C of holdings 0.5-1 hour, lowers the temperature subsequently
To 90 DEG C, add 10-35 part flexible polymer, be heated to 120 DEG C carry out chain extending reaction or heating catalyst in the presence of enter
Row chain extending reaction, is incubated 2 hours；It is cooled to 100 DEG C, after 4-16 part plasticizer, is incubated 1-2 hour.
As preferably, described modified epoxy B preparation method is, by 40-60 part epoxy resin, 5-10 part nonyl phenol,
2-6 part dimethylbenzene, 10-20 part Bisphenol F are added sequentially in reactor, and stirring is warmed up to 125 DEG C；Maintain the temperature at 130 DEG C, will
0.1-1 part triphenyl phosphite furnishing pasty state in dimethylbenzene, is gradually added in reactor subsequently, controls the joining day at 0.5-
1 hour；Cool to 100 DEG C, be incubated 1-2 hour.
As preferably, described firming agent preparation method is, adds dimer (fatty acid) yl, vegetable oil in the reactor of logical nitrogen
Acid and fatty amine, then stir the mixture for 30-90 minute；Then it is warmed up to dehydration, continues to be heated to 180-280 DEG C, keep
React 1-5 hour, be cooled to 100-145 DEG C and add ketone, temperature rising reflux 1-6 hour；Backflow reheats to reclaim after terminating and dissociates
Ketone, keeps 1-3 hour to 180-230 DEG C, then evacuation, controls vacuum-0.08MPa～-0.1 MPa, keeps 1-3 little
Time；It is cooled to 180 DEG C and adds terminator, be cooled back to 100-140 DEG C, add ethers；Finally it is stirred for after adding ethers
0.5-1 hour.
In sum, beneficial effects of the present invention:
The solidification temperature of a kind of color inhibition cathode electrodip painting the most of the present invention is 140 DEG C, and coating film thickness can in 10-30 μm
Adjust, use nontoxic formula simultaneously, environmental friendliness and more energy-conservation.
A kind of color inhibition cathode electrodip painting the most of the present invention, the heat stability of tank liquor is high, tank liquor electrophoresis temperature >=35
DEG C, electrodeposited paint film uniformity is good, the breakdown voltage >=380V of coating, and Ford box method records throwing power >=22cm, in workpiece
Chamber film ability is strong.
A kind of color inhibition cathode electrodip painting the most of the present invention, uses the heavy metals such as the most leaded, stannum, cadmium, chromium, hydrargyrum
Environment-friendly composite drier, is modified epoxy resin obtaining excellent cationic macromolecules amount resin, obtains without high-rise
Unleaded, the Tin-free environment-friendlyelectrophoretic electrophoretic paint of air pollution.
4. the present invention uses specific paste formula, composite drier formula and emulsion formulations especially emulsion formulations,
Emulsion is improved and uses 4-4-methyl diphenylene diisocyanate, make cathode electrodip painting green safety environmental protection, and actually used
Time reach accelerate paint film oxidation, be polymerized and be dried, reach quick-drying purpose.
5. there is after the first composite regulator proportioning the dispersion of excellence, coagulate the soup and anti-wear and wear-resistant performance；Different-grain diameter and kind
First solid additive of class and the second solid additive are while increasing cathode electrodip painting film uniformity and throwing power, also
The good anti-wear performance of cathode electrodip painting paint film and water repelling property can be given.The present invention the second composite regulator and the 3rd compound tune
Joint agent proportioning has antioxidation and bright and clean corrosion-resistant function by after adding；So that paint film also has the effect of color inhibition.
The solidification temperature of low-temperature curing cathode electrophoresis coating the most of the present invention is 140 DEG C, and coating film thickness is in 10-30 μm
Adjustable, use nontoxic formula, environmental friendliness and more energy-conservation simultaneously.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in detail.
Embodiment 1:
A kind of color inhibition cathode electrodip painting, including in parts by mass, 1 part of mill base, 4 parts of emulsions and 5 parts of deionized waters；
Described paste formula includes, 20 parts of matrix resins, 5 parts of alcohol ethers cosolvents, 3 parts of organic acid, 0.3 part of emulsifying agent, 1 part multiple
Conjunction drier, 30 parts of deionized waters, 15 parts of fillers, the first solid additive 3 parts and the second solid additive 6 parts, in mass ratio
The tricaprylmethyl ammonium bromide of 1:3:2 proportioning, glycerol and first composite regulator 6 parts of politef composition；With by matter
Measure the diphenylamines than 1:2:3 proportioning, 2,6-di-t-butyl and second composite regulator 7 parts of BTA composition；And press
The sulfuration Oleum Gossypii semen T404 of mass ratio 1:0.5:1.7 proportioning, two (2-sulfydryl-4-n-propylamine base-1,3,5-triazine) thioether and two
3rd composite regulator 8 parts of (2-sulfydryl-4-Aminocyclopentane base-1,3,5-triazine) thioether composition；Gathering of the proportioning of 1:1 in mass ratio
Acrylate-2-cross linked polymer and the 4th composite regulator 3 parts of impregnating fluid composition；
Impregnating fluid compound method:
Add AVC 15 parts, sodium fluoride 28 parts, fluorination the most successively
Hydrogen ammonium 50 parts, 15 parts of potassium permanganate, Neutral potassium chromate 47 parts；Stirring 8min, it is thus achieved that the second the most mixed liquid；
Zinc phosphate 19 parts, sodium nitrate 12 parts, praseodymium chloride 9 parts, ethylenediamine is added successively the most in order in the second the most mixed liquid
Tetraacethyl 14 parts, malic acid 11 parts, dodecyl phenenyl sulfate 10 parts, nickel sulfate 8 parts, triethanolamine 20 parts, stir 3min.The
The particle size range of one solid additive is 0.8-5 micron；Wherein, the granule of 0.8-1 micron accounts for the 20% of solid additive gross weight；
The granule of 1-2 micron accounts for the 10% of solid additive gross weight；Surplus is the granule of 3 microns；Second solid additive is that particle diameter 10 is received
The mixture that the molybdenum disulfide nano ball of rice forms according to mass ratio 1:2 with the tungsten disulfide of particle diameter 6 microns；
Described emulsion formulations includes, 40 parts of modified epoxy A, 10 parts of modified epoxy B, 10 parts of cross-linking agent, 9 parts of solidifications
Agent, the diketimine of 3 parts of diethylenetriamines and 2 parts of N-methylethanolamines, 0.1 part of emulsifying agent, 0.1 part of acetic acid and 30 parts go from
Sub-water；Described modified epoxy A formula includes, 10 parts of bisphenol-As, 40 parts of epoxy resin, 8 parts of solvents, 4 parts of bisphenol-A polyoxy second
Alkene ether, 10 number average molecular weights are the polyether Glycols of 400～1500；Described modified epoxy B formula includes, 10 parts of bis-phenols
F, 40 portions of epoxy resin, 5 portions of nonyl phenols, 2 portions of dimethylbenzene, 0.1 portion of triphenyl phosphite；Described hardener formula includes, 20
Part dimer (fatty acid) yl, 5 parts of castor oil acids, 5 parts of ethylenediamines, 10 parts of acetone, 5 parts of ether, 0.01 part of boric acid.
Cross-linking agent is type semienclosed and/or blocked polyurethane includes, 4-4-methyl diphenylene diisocyanate 5 parts, alcohol
Ether compound, heterocycle compound one of them or two or more mixing 3 parts, polyethers or PCDL 80 parts, ketone
Kind solvent 40 parts.
Above-mentioned anti-corrosion type low-temperature curing cathode electrophoresis paint, comprises the following steps:
Prepared by A mill base, be sequentially added into 20 parts of matrix resins, 5 parts of alcohol ethers cosolvents, 3 parts of organic acid, 0.3 part of breast in a reservoir
Agent and 30 parts of deionized waters, composite drier 1 part, add standing 8 after 15 parts of fillers disperse under 700-1100 rev/min little
More than time, then sequentially add the first solid additive 3 parts and the second solid additive 6 parts, the proportioning of 1:3:2 in mass ratio
Tricaprylmethyl ammonium bromide, glycerol and first composite regulator 6 parts of politef composition；The proportioning of 1:2:3 in mass ratio
Diphenylamines, 2,6-di-t-butyl and BTA composition the second composite regulator 7 parts；And 1:0.5 in mass ratio:
The sulfuration Oleum Gossypii semen T404 of 1.7 proportionings, two (2-sulfydryl-4-n-propylamine base-1,3,5-triazine) thioether and two (2-sulfydryl-4-rings
Amylamine base-1,3,5-triazine) thioether composition the 3rd composite regulator 8 parts；4th composite regulator 3 parts；
Disperse under 600-800 rev/min again 20-40 minute, then grind with sand mill, use behind sand milling fineness≤13 micron
Bag type filtering machine i.e. obtains mill base after filtering；
Composite drier preparation method is:
(1). vanadic anhydride and isooctyl acid are mixed with isooctyl acid radical ion molal weight ratio 1: 5 with vanadium ion carry out anti-
Should, reaction temperature is 230 DEG C, and the response time is 0.8 hour；
(2). continuously add manganese carbonate, add lanthanum carbonate or cerous carbonate, and isooctyl acid carry out compound reaction, herein manganese ion with
Isooctyl acid root molal weight ion ratio is 1: 3, and lanthanum ion or cerium ion are 1: 5 with isooctyl acid radical ion molal weight ratio,
Reaction temperature 180 DEG C, the response time is 0.6 hour；
(3). the liquid obtained after reaction is cooled to less than 140 DEG C and is blended into catalyst and Porous deproteinized bone solvent naphtha, stir-, obtain
Composite dryer for paint product, in described composite drier product, it is whole that each variable valency metal ions and isooctyl acid root form complexation
Body；Described catalyst is 1:8 with the mass ratio of vanadic anhydride；
Prepared by B emulsion, 1. prepare modified epoxy A, 10 parts of bisphenol-As, 40 parts of epoxy resin, 8 parts of methyl iso-butyl ketone (MIBK)s is depended on
Secondary join in reactor, stirring be warmed up to 110 DEG C keep 0.5-1 hour after, cool to 90 DEG C subsequently, add 10 numbers and divide equally
Son amount is the polyether Glycols of 400～1500, be heated to 120 DEG C carry out chain extending reaction or heating catalyst in the presence of carry out
Chain extending reaction, is incubated 2 hours；It is cooled to 100 DEG C, after adding 4 parts of bisphenol A polyethenoxy ethers, is incubated 1-2 hour, obtains epoxy
The modified epoxy A that equivalent is 200～1000, number-average molecular weight is 3000；2. modified epoxy B is prepared, by 40 parts of rings
Epoxy resins, 5 parts of nonyl phenols, 2 parts of dimethylbenzene, 10 parts of Bisphenol F are added sequentially in reactor, and stirring is warmed up to 125 DEG C；Keep temperature
Degree, at 130 DEG C, by 0.1 part of triphenyl phosphite furnishing pasty state in dimethylbenzene, is gradually added in reactor subsequently, controls to add
Time was at 0.5-1 hour；Cool to 100 DEG C, be incubated 1-2 hour, obtain epoxide equivalent be 600～800, number-average molecular weight be
The modified epoxy B of 2000；3. by after 40 parts of modified epoxy A and 10 parts of modified epoxy B stirring mixing, it is heated to
100-120 DEG C, add diketimine and 2 parts of N-methylethanolamines, the continuation mixing 2 hours of 3 parts of diethylenetriamines；4. drip
Adding or be dividedly in some parts 10 parts of cross-linking agent, 9 parts of firming agent, be incubated 1.5-2.5 hour, wherein, described firming agent preparation method is,
The reactor of logical nitrogen adds 20 parts of dimer (fatty acid) yls, 5 parts of castor oil acids and 5 parts of ethylenediamines, then stirs the mixture for 30-
90 minutes；Then it is warmed up to dehydration, continues to be heated to 180-280 DEG C, keep reaction 1-5 hour, be cooled to 100-145 DEG C of addition
10 parts of acetone, temperature rising reflux 1-6 hour；Backflow reheats after terminating and reclaims free acetone, keeps 1-3 little to 180-230 DEG C
Time, then evacuation, control vacuum-0.08MPa～-0.1 MPa, keep 1-3 hour；It is cooled to 180 DEG C and adds 0.01 part of boron
Acid, is cooled back to 100-140 DEG C, adds 5 parts of ether；Finally it is stirred for after adding ether 0.5-1 hour；5. 70-is cooled to
90 DEG C, add 0.1 part of emulsifying agent and 0.1 part of acetic acid, dispersed with stirring 30-60 minute；6. cool to 30-70 DEG C, extract organic molten
Agent, adds 30-50 part deionized water, obtains emulsion after filtration, and emulsion Con trolling index is, solids content 35 ± 2%, and particle diameter≤
0.20 μm, ph value 6.0 ± 0.5；
C electrophoretic paint is allocated, and adds 2 parts of deionized waters and 2 parts of emulsions, starts circulation mixing pump, both circulated in electrophoresis tank
Mixing；In premix groove, put into 2 parts of emulsions start stirring, the most slowly put into 1 part of mill base, will be pre-after stirring 30 minutes
Mixed groove mixed liquor the most uniformly inputs in electrophoresis tank；Throw 3 parts of deionized waters again
Water after cleaning premix groove with 7 parts of composite dispersing agents and will clean the most uniformly pumps into electrophoresis tank, in constantly circulation
Tank liquor transconversion into heat i.e. obtains carrying out the electrophoretic paint of application after 48 hours；
Composite dispersing agent forms according to following weight:
Oligomer diacetyl acetate alkylene diester metal chelate 35 parts
Dispersant 5 parts
Wetting agent 4 parts
Defoamer 2 parts.
Embodiment 2:
Color inhibition cathode electrodip painting, including in parts by mass, 2 parts of mill bases, 6 parts of emulsions and 5 parts of deionized waters；
Described paste formula includes, 30 parts of matrix resins, 10 parts of alcohol ethers cosolvents, 8 parts of organic acid, 0.7 part of emulsifying agent, 5 parts
Composite drier, 40 parts of deionized waters, 20 parts of fillers, the first solid additive 7 parts, the second solid additive 1.5 parts, by quality
Tricaprylmethyl ammonium bromide, glycerol and first composite regulator 9 parts of politef composition than 1:4:1 proportioning；By matter
Measure the diphenylamines than 1:4:1 proportioning, 2,6-di-t-butyl and second composite regulator 7-part of BTA composition；With press
The sulfuration Oleum Gossypii semen T404 of mass ratio 1:0.8:1.3 proportioning, two (2-sulfydryl-4-n-propylamine base-1,3,5-triazine) thioether and two
3rd composite regulator 14 parts of (2-sulfydryl-4-Aminocyclopentane base-1,3,5-triazine) thioether composition；The proportioning of 1:4 in mass ratio
Polyacrylate-2-cross linked polymer and impregnating fluid composition the 4th composite regulator 7 parts；
Impregnating fluid compound method:
Add AVC 10 parts, sodium fluoride 20 parts, fluohydric acid gas the most successively
Ammonium 30 parts, 10 parts of potassium permanganate, Neutral potassium chromate 50 parts；Stirring 5min, it is thus achieved that the second the most mixed liquid；
Zinc phosphate 15 parts, sodium nitrate 8 parts, praseodymium chloride 5 parts, ethylenediamine tetrem is added successively the most in order in the second the most mixed liquid
Acid 10 parts, malic acid 7 parts, dodecyl phenenyl sulfate 8 parts, nickel sulfate 6 parts, triethanolamine 25 parts, stir 1min.First solid
The particle size range of additive is 0.8-5 micron;Wherein, the granule of 0.8-1 micron accounts for the 40% of solid additive gross weight；1-2 is micro-
The granule of rice accounts for the 30% of solid additive gross weight；Surplus is the granule of 5 microns；
Second solid additive is that the micro powder graphite of molybdenum disulfide nano ball and the particle diameter 9 microns of particle diameter 20 nanometer is according to mass ratio
The mixture of 1:5 composition.
Described emulsion formulations includes, 50 parts of modified epoxy A, 20 parts of modified epoxy B, 30 parts of cross-linking agent, 5 parts solid
Agent, the ketimide of 4 parts of aminoethyl ethanolamines and 3 parts of diethanolamine, 2 parts of emulsifying agents, 1 part of acetic acid and 50 parts of deionized waters；Institute
State modified epoxy A formula to include, 20 parts of bisphenol-As, 60 parts of epoxy resin, 16 parts of solvents, 16 parts of bisphenol-A polyethenoxy ethers,
35 number average molecular weights are the polyethers diamine of 400～1500；Described modified epoxy B formula includes, 20 parts of Bisphenol F, 60
Part epoxy resin, 10 portions of nonyl phenols, 6 portions of dimethylbenzene, 1 portion of triphenyl phosphite；Described hardener formula includes, 66 parts of dimerization
Fatty acid, 18 parts of Semen Allii Tuberosi oleic acid, 25 parts of triethylene tetramines, 34 parts of acetone, 20 parts of butyl cellosolves, 0.02 part of boric acid；
Described cross-linking agent is type semienclosed and/or blocked polyurethane includes, 4-4-methyl diphenylene diisocyanate 20 parts, alcohol
Ether compound, heterocycle compound one of them or two or more mixing 30 parts.
Above-mentioned anti-corrosion type low-temperature curing cathode electrophoresis paint, comprises the following steps:
Prepared by A mill base, be sequentially added into 30 parts of matrix resins, 10 parts of alcohol ethers cosolvents, 8 parts of organic acid, 0.7 part of breast in a reservoir
Agent and 40 parts of deionized waters, composite drier 5 parts, add standing 8 after 20 parts of fillers disperse under 700-1100 rev/min little
More than time, then it is sequentially added into the first solid additive 7 parts, the second solid additive 1.5 parts, the proportioning of 1:4:1 in mass ratio
Tricaprylmethyl ammonium bromide, glycerol and first composite regulator 9 parts of politef composition；The proportioning of 1:4:1 in mass ratio
Diphenylamines, 2,6-di-t-butyl and BTA composition second composite regulator 7-part；1:0.8:1.3 in mass ratio
The sulfuration Oleum Gossypii semen T404 of proportioning, two (2-sulfydryl-4-n-propylamine base-1,3,5-triazine) thioether and two (2-sulfydryl-4-Aminocyclopentanes
Base-1,3,5-triazine) thioether composition the 3rd composite regulator 14 parts；4th composite regulator 7 parts；
Disperse under 600-800 rev/min again 20-40 minute, then grind with sand mill, use after the μm of sand milling fineness≤13
Bag type filtering machine i.e. obtains mill base after filtering；
Composite drier preparation method is:
(1). vanadic anhydride and isooctyl acid are mixed with isooctyl acid radical ion molal weight ratio 1: 4 with vanadium ion carry out anti-
Should, reaction temperature is 220 DEG C, and the response time is 0.5 hour；
(2). continuously add manganese carbonate, add lanthanum carbonate or cerous carbonate, and isooctyl acid carry out compound reaction, herein manganese ion with
Isooctyl acid root molal weight ion ratio is 1: 2, and lanthanum ion or cerium ion are 1: 4 with isooctyl acid radical ion molal weight ratio,
Reaction temperature 100 DEG C, the response time is 0.4 hour；
(3). the liquid obtained after reaction is cooled to less than 140 DEG C and is blended into catalyst and Porous deproteinized bone solvent naphtha, stir-, obtain
Composite dryer for paint product, in described composite drier product, it is whole that each variable valency metal ions and isooctyl acid root form complexation
Body；Described catalyst is 1:5 with the mass ratio of vanadic anhydride；
Prepared by B emulsion, 1. prepare modified epoxy A, 20 parts of bisphenol-As, 60 parts of epoxy resin, 16 parts of methyl iso-butyl ketone (MIBK)s is depended on
Secondary join in reactor, stirring be warmed up to 110 DEG C keep 0.5-1 hour after, cool to 90 DEG C subsequently, add 35 numbers and divide equally
Son amount is the polyether Glycols of 400～1500, be heated to 120 DEG C carry out chain extending reaction or heating catalyst in the presence of carry out
Chain extending reaction, is incubated 2 hours；It is cooled to 100 DEG C, after adding 16 parts of bisphenol-A polyethenoxy ethers, is incubated 1-2 hour, obtains epoxy
The modified epoxy A that equivalent is 200～1000, number-average molecular weight is 2400；2. modified epoxy B is prepared, by 60 parts of rings
Epoxy resins, 10 parts of nonyl phenols, 6 parts of dimethylbenzene, 20 parts of Bisphenol F are added sequentially in reactor, and stirring is warmed up to 125 DEG C；Keep
Temperature, at 130 DEG C, by 1 part of triphenyl phosphite furnishing pasty state in dimethylbenzene, is gradually added in reactor subsequently, controls to add
Time was at 0.5-1 hour；Cool to 100 DEG C, be incubated 1-2 hour, obtain epoxide equivalent be 600～800, number-average molecular weight be
The modified epoxy B of 1600；3. by after 50 parts of modified epoxy A and 20 parts of modified epoxy B stirring mixing, it is heated to
100-120 DEG C, add ketimide and 3 parts of diethanolamine, the continuation mixing 2 hours of 4 parts of aminoethyl ethanolamines；4. drip or divide
Criticizing and add 30 parts of cross-linking agent, 5 parts of firming agent, be incubated 1.5-2.5 hour, wherein, described firming agent preparation method is, at logical nitrogen
Reactor in add 66 parts of dimer (fatty acid) yls, 18 parts of Semen Allii Tuberosi oleic acid and 25 parts of triethylene tetramines, then stir the mixture for 30-
90 minutes；Then it is warmed up to dehydration, continues to be heated to 180-280 DEG C, keep reaction 1-5 hour, be cooled to 100-145 DEG C of addition
10 parts of acetone, temperature rising reflux 1-6 hour；Backflow reheats after terminating and reclaims free acetone, keeps 1-3 little to 180-230 DEG C
Time, then evacuation, control vacuum-0.08MPa～-0.1 MPa, keep 1-3 hour；It is cooled to 180 DEG C and adds 0.02 part of boron
Acid, is cooled back to 100-140 DEG C, adds 20 parts of butyl cellosolves；Finally it is stirred for after adding ether 0.5-1 hour；⑤
Cool to 70-90 DEG C, add 0.1 part of emulsifying agent and 0.1 part of acetic acid, dispersed with stirring 30-60 minute；6. cool to 30-70 DEG C, take out
Carrying organic solvent, add 30-50 part deionized water, obtain emulsion after filtration, emulsion Con trolling index is, solids content 35 ± 2%,
Particle diameter≤0.20 μm, ph value 6.0 ± 0.5；
C electrophoretic paint is allocated, and adds 3 parts of deionized waters and 3 parts of emulsions, starts circulation mixing pump, both circulated in electrophoresis tank
Mixing；In premix groove, put into 3 parts of emulsions start stirring, the most slowly put into 2 parts of mill bases, will be pre-after stirring 30 minutes
Mixed groove mixed liquor the most uniformly inputs in electrophoresis tank；Throw 2 parts of deionized waters again
Water after cleaning premix groove with 7 parts of composite dispersing agents and will clean the most uniformly pumps into electrophoresis tank, in constantly circulation
Tank liquor transconversion into heat i.e. obtains carrying out the electrophoretic paint of application after 48 hours；
Composite dispersing agent forms according to following weight:
Oligomer diacetyl acetate alkylene diester metal chelate 45 parts
Dispersant 9 parts
Wetting agent 6 parts
Defoamer 1 part.
Embodiment 3
Color inhibition cathode electrodip painting, including in parts by mass, 1.2 parts of mill bases, 5 parts of emulsions and 6 parts of deionized waters；
Paste formula includes, 25 parts of matrix resins, 8 parts of alcohol ethers cosolvents, 5 parts of organic acid, 0.5 part of emulsifying agent, 4 parts compound urge
Dry agent, 35 parts of deionized waters, 15-20 part filler, the first solid additive 4 parts and the second solid additive 5 parts and press quality
Tricaprylmethyl ammonium bromide, glycerol and first composite regulator 7 parts of politef composition than 1:3:1 proportioning；By matter
Measure the diphenylamines than 1:3:2 proportioning, 2,6-di-t-butyl and second composite regulator 9 parts of BTA composition；With by matter
Measure sulfuration Oleum Gossypii semen T404, two (2-sulfydryl-4-n-propylamine base-1,3,5-triazine) thioether and the two (2-than 1:0.7:1.5 proportioning
Sulfydryl-4-Aminocyclopentane base-1,3,5-triazine) thioether composition the 3rd composite regulator 12 parts；Poly-the third of the proportioning of 1:3 in mass ratio
Olefin(e) acid ester-2-cross linked polymer and the 4th composite regulator 5 parts of impregnating fluid composition；
The particle size range of the first solid additive is 0.8-5 micron;Wherein, the granule of 0.8-1 micron accounts for solid additive gross weight
30%;The granule of 1-2 micron accounts for the 20% of solid additive gross weight；Surplus is the granule of 3-5 micron；
Second solid additive be the calcium carbonate of molybdenum disulfide nano ball and the particle diameter 8 microns of particle diameter 15 nanometer according to mass ratio 1:
The mixture of 3 compositions；
Composite drier preparation method is
(1). vanadic anhydride and isooctyl acid are mixed with isooctyl acid radical ion molal weight ratio 1: 4.5 with vanadium ion carry out anti-
Should, reaction temperature is 225 DEG C, and the response time is 0.6 hour；
(2). continuously add manganese carbonate, add lanthanum carbonate or cerous carbonate, and isooctyl acid carry out compound reaction, herein manganese ion with
Isooctyl acid root molal weight ion ratio is 1: 2.5, and lanthanum ion or cerium ion are 1 with isooctyl acid radical ion molal weight ratio:
4.5, reaction temperature 160 DEG C, the response time is 0.5 hour；
(3). the liquid obtained after reaction is cooled to less than 140 DEG C and is blended into catalyst and Porous deproteinized bone solvent naphtha, stir-, obtain
Composite dryer for paint product, in described composite drier product, it is whole that each variable valency metal ions and isooctyl acid root form complexation
Body；Catalyst is 1:6 with the mass ratio of vanadic anhydride；
This catalyst is Yttrium trihydroxide；
Emulsion formulations includes, 45 parts of modified epoxy A, 12 parts of modified epoxy B, 20 parts of cross-linking agent, 20 parts of 4-4-hexichol
Dicyclohexylmethane diisocyanate, 8 parts of firming agent, 6 parts of unimolecule amine, 1 part of emulsifying agent, 1 part of nertralizer and 40 parts of deionized waters.
Described cross-linking agent is type semienclosed and/or blocked polyurethane includes, 4-4-methyl diphenylene diisocyanate 10
Part, alcohol ether compound, heterocycle compound one of them or two or more mixing 10 parts, polyethers or PCDL 10
Part, ketones solvent 10 parts；
Anti-corrosion type low-temperature curing cathode electrophoresis paint comprises the following steps:
Prepared by A mill base；
Prepared by B emulsion；
C electrophoretic paint is allocated, and adds 2.5 parts of deionized waters and 2.5 parts of emulsions, start circulation mixing pump in electrophoresis tank, incite somebody to action both
Circulation mixing；In premix groove, put into 2.5 parts of emulsions start stirring, the most slowly put into 1.2 parts of mill bases, stir 30 minutes
Afterwards premix groove mixed liquor is the most uniformly inputted in electrophoresis tank；Throw 3.4 parts of deionized waters and 4.7 parts of composite dispersing agents again to clearly
Water after washing premix groove and cleaning the most uniformly pumps into electrophoresis tank, and in constantly circulation, tank liquor transconversion into heat i.e. obtained after 48 hours
The electrophoretic paint of application can be carried out；
Composite dispersing agent forms according to following weight:
Oligomer diacetyl acetate alkylene diester metal chelate 40 parts
Dispersant 8 parts
Wetting agent 5 parts
Defoamer 1.5 parts.
Above material selects to may is that dispersant is DP 19 or EFKA 4550, and wetting agent is the secondary octyl phenol of polyoxyethylene
Ether, defoamer is 090 or EFKA 2526, wherein dispersant DP 19, and defoamer 090 is the TaiWan, China moral limited public affairs of modest chemistry
The product of department, EFKA 4550, EFKA 2526 is Holland's EFKA auxiliary agent Products.
Impregnating fluid compound method:
Add AVC 18 parts, sodium fluoride 40 parts, fluohydric acid gas the most successively
Ammonium 60 parts, 20 parts of potassium permanganate, Neutral potassium chromate 40 parts；Stirring 10min, it is thus achieved that the second the most mixed liquid；
Zinc phosphate 25 parts, sodium nitrate 18 parts, praseodymium chloride 12 parts, ethylenediamine tetraacetic is added successively the most in order in the second the most mixed liquid
Acetic acid 16 parts, malic acid 14 parts, dodecyl phenenyl sulfate 12 parts, nickel sulfate 13 parts, triethanolamine 15 parts, stir 4min.
Embodiment 4
With embodiment 1, except for the difference that
The preparation method of polyacrylate-2-cross linked polymer is:
(1) prepared polymer P by weight (MMA-MAh)-PEG6000 35 parts, regulation liquid 50 parts form the first the most mixed liquid；Adjust
Joint liquid is the carbonic acid including sodium perchlorate that concentration is 0.5mol/L and N-butyl benzimidazole that concentration is 0.3-0.8mol/L
Propylene solution；MMA in polymer P (MMA-MAh)-PEG4000 is methyl methacrylate, and MAh is maleic anhydride, P
(MMA-MAh) be the copolymer of methyl methacrylate and maleic anhydride, PEG6000 be molecular weight be the poly-second two of 6000
Alcohol；
(2) in the first the most mixed liquid, add 4 part of ten dihydroxystearic acid, be heated to 38 DEG C of reaction 5-9min under nitrogen protection；
(3) polyacrylate-2-cross linked polymer is obtained after drying with deionized water rinsing.
Impregnating fluid also includes potassium borohydride 1 part, bicyclohexane also-18-crown-64 parts and dibenzyl xenol polyoxy third
Alkene polyoxyethylene ether 8 parts.
Embodiment 5
With embodiment 2, except for the difference that
The preparation method of polyacrylate-2-cross linked polymer is:
(1) prepared polymer P by weight (MMA-MAh)-PEG6000 30 parts, regulation liquid 40 parts form the first the most mixed liquid；Adjust
Joint liquid is the propylene carbonate including sodium perchlorate that concentration is 0.4mol/L and N-butyl benzimidazole that concentration is 0.3mol/L
Ester solution；MMA in polymer P (MMA-MAh)-PEG4000 is methyl methacrylate, and MAh is maleic anhydride, P (MMA-
MAh) be the copolymer of methyl methacrylate and maleic anhydride, PEG6000 be molecular weight be the Polyethylene Glycol of 6000；
(2) in the first the most mixed liquid, add 2 part of ten dihydroxystearic acid, be heated to 30 DEG C of reaction 5min under nitrogen protection；
(3) polyacrylate-2-cross linked polymer is obtained after drying with deionized water rinsing.
Impregnating fluid also includes potassium borohydride 3 parts, bicyclohexane also-18-crown-66 parts and dibenzyl xenol polyoxy third
Alkene polyoxyethylene ether 5 parts.
Embodiment 6
With embodiment 3, except for the difference that
The preparation method of polyacrylate-2-cross linked polymer is:
(1) prepared polymer P by weight (MMA-MAh)-PEG6000 40 parts, regulation liquid 60 parts form the first the most mixed liquid；Adjust
Joint liquid is the propylene carbonate including sodium perchlorate that concentration is 0.7mol/L and N-butyl benzimidazole that concentration is 0.8mol/L
Ester solution；MMA in polymer P (MMA-MAh)-PEG4000 is methyl methacrylate, and MAh is maleic anhydride, P (MMA-
MAh) be the copolymer of methyl methacrylate and maleic anhydride, PEG6000 be molecular weight be the Polyethylene Glycol of 6000；
(2) in the first the most mixed liquid, add 7 part of ten dihydroxystearic acid, be heated to 45 DEG C of reaction 9min under nitrogen protection；
(3) polyacrylate-2-cross linked polymer is obtained after drying with deionized water rinsing.
Impregnating fluid also includes potassium borohydride 2 parts, bicyclohexane also-18-crown-65 parts and dibenzyl xenol polyoxy third
Alkene polyoxyethylene ether 7 parts.
Table 1 is the film performance table of various embodiments of the present invention
This specific embodiment is only explanation of the invention, and it is not limitation of the present invention, and those skilled in the art exist
As required the present embodiment can be made after reading this specification and there is no the amendment of creative contribution, but as long as in the present invention
Right in all protected by Patent Law.
Claims (10)
1. an anti-corrosion type low-temperature curing cathode electrophoresis paint, it is characterised in that in parts by mass, described electrophoretic paint includes, 1-2 part
Mill base, 4-6 part emulsion and 5-7 part deionized water；
Described paste formula includes, 20-30 part matrix resin, 5-10 part alcohol ethers cosolvent, 3-8 part organic acid, 0.3-0.7 part
Emulsifying agent, 1-5 part composite drier, 30-40 part deionized water, 3-7 part the first solid additive, 1.5-6 part the second solid add
Add agent, first composite regulator 6-9 part, the diphenylamines of the proportioning of 1:2-4:1-3 in mass ratio, 2,6-di-t-butyl and benzo three nitrogen
Second composite regulator 7-11 part of azoles composition；
The sulfuration Oleum Gossypii semen of the proportioning of 1:0.5-0.8:1.3-1.7 in mass ratio, two (2-sulfydryl-4-n-propylamine base-1,3,5-three
Piperazine) thioether and two (2-sulfydryl-4-Aminocyclopentane base-1,3,5-triazine) thioether composition the 3rd composite regulator 8-14 part；
Polyacrylate-2-the cross linked polymer of the proportioning of 1:1-4 in mass ratio and the 4th composite regulator 3-7 of impregnating fluid composition
Part；
And 15-20 part filler；
Described impregnating fluid compound method:
Add AVC 10-18 part, sodium fluoride 20-40 the most successively
Part, ammonium acid fluoride 30-60 part, potassium permanganate 10-20 part, Neutral potassium chromate 40-50 part；Stirring 5-10min, it is thus achieved that the second the most mixed liquid；
Zinc phosphate 15-25 part, sodium nitrate 8-18 part, praseodymium chloride 5-is added successively the most in order in the described second the most mixed liquid
12 parts, ethylenediaminetetraacetic acid 10-16 part, malic acid 7-14 part, dodecyl phenenyl sulfate 8-12 part, nickel sulfate 6-13 part, three
Ethanolamine 15-25 part, stirs 1-4min；
The particle size range of the first solid additive is 0.8-5 micron；Wherein, the granule of 0.8-1 micron accounts for described first solid and adds
Add the 20-40% of agent gross weight；The granule of 1-2 micron accounts for the 10-30% of described first solid additive gross weight；Surplus is 3-5 micron
Granule；
Described first solid additive is following formula I polymer, wherein MwIt is 6.10 × 106, MnIt is 2.0 × 106, molecular weight distribution
Index is 3.1:
I
Described second solid additive be the molybdenum disulfide nano ball of particle diameter 10-20 nanometer with the regulation grain of particle diameter 6-9 micron by
Mixture according to mass ratio 1:2-5 composition；
Described first composite regulator is the tricaprylmethyl ammonium bromide of the proportioning of 1:3-4:1-2 in mass ratio, glycerol and poly-four
Fluorothene forms；
Described emulsion formulations includes, 40-50 part modified epoxy A, 10-20 part modified epoxy B, 10-30 part cross-linking agent,
5-9 part firming agent, 3-8 part unimolecule amine, 0.1-2 part emulsifying agent, 0.1-2 part nertralizer 30-50 part deionized water；
Described cross-linking agent is type semienclosed and/or blocked polyurethane includes, 4-4-methyl diphenylene diisocyanate 5-20 part,
Alcohol ether compound, heterocycle compound one of them or two or more mixing 3-30 part, polyethers or PCDL 0-
80 parts, ketones solvent 0-40 part；
Described modified epoxy A formula includes, 10-20 part bisphenol-A, 40-60 part epoxy resin, 8-16 part solvent, 4-16 part
Plasticizer, 10-35 part flexible polymer；Described modified epoxy B formula includes, 10-20 part Bisphenol F, 40-60 part asphalt mixtures modified by epoxy resin
Fat, 5-10 part nonyl phenol, 2-6 part dimethylbenzene, 0.1-1 part triphenyl phosphite；
Described composite drier preparation method is:
(1). vanadic anhydride is mixed into vanadium ion and isooctyl acid radical ion molal weight ratio 1: 4 to 1: 5 with isooctyl acid
Row reaction, reaction temperature is 220 to 230 DEG C, and the response time is 0.5-0.8 hour；
(2). continuously add manganese carbonate, add lanthanum carbonate or cerous carbonate, and isooctyl acid carry out compound reaction, herein manganese ion with
Isooctyl acid root molal weight ion ratio is 1: 2 to 1: 3, and lanthanum ion or cerium ion with isooctyl acid radical ion molal weight ratio are
1: 4 to 1: 5, reaction temperature 100 to 180 DEG C, the response time is 0.4-0.6 hour；
(3). the liquid obtained after reaction is cooled to less than 140 DEG C and is blended into catalyst and Porous deproteinized bone solvent naphtha, stir-, obtain
Composite dryer for paint product, in described composite drier product, it is whole that each variable valency metal ions and isooctyl acid root form complexation
Body；
Described catalyst is 1:5-8 with the mass ratio of vanadic anhydride；
This catalyst is zinc oxide, yittrium oxide, rubidium oxide, cobalt oxide, bismuth oxide, zirconium oxide, manganese oxide, cerium oxide, hydroxide
Cerium, zinc hydroxide, Bismuth hydrate., Yttrium trihydroxide, rubidium hydroxide, calcium hydroxide, cobalt nitrate, bismuth nitrate, manganese nitrate, nitroxylic acid
One of which in bismuth, cobalt octoate；
Anti-corrosion type low-temperature curing cathode electrophoresis paint comprises the following steps:
Prepared by A mill base, be sequentially added in a reservoir 20-30 part matrix resin, 5-10 part alcohol ethers cosolvent, 3-8 part organic acid,
0.3-0.7 part emulsifying agent and 30-40 part deionized water, composite drier 1-5 part, add 15-20 part filler at 700-1100
Stand more than 8 hours after dispersion under rev/min, sequentially add 3-7 part the first solid additive, the interpolation of 1.5-6 part the second solid
Agent, first composite regulator 6-9 part, second composite regulator 7-11 part, the 3rd composite regulator 8-14 part and the 4th are compound to be adjusted
Joint agent 3-7 part；
Disperse under 600-800 rev/min again 20-40 minute, then grind with sand mill, use after the μm of sand milling fineness≤13
Bag type filtering machine i.e. obtains mill base after filtering；
Prepared by B emulsion, 1. prepare modified epoxy A；2. modified epoxy B is prepared；3. by 40-50 part modified epoxy
After A and 10-20 part modified epoxy B stirring mixing, it is heated to 100-120 DEG C, adds unimolecule amine, continue mixing 2 little
Time；4. drip or be dividedly in some parts 10-30 part cross-linking agent, 5-9 part firming agent, be incubated 1.5-2.5 hour；5. 70-90 DEG C is cooled to,
Add 0.1-2 part emulsifying agent and 0.1-2 part nertralizer, dispersed with stirring 30-60 minute；6. cool to 30-70 DEG C, extract organic molten
Agent, adds 30-50 part deionized water, obtains emulsion after filtration, and emulsion Con trolling index is, solids content 35 ± 2%, and particle diameter≤
0.20 μm, ph value 6.0 ± 0.5；
C electrophoretic paint is allocated, and adds 2-3 part deionized water and 2-3 part emulsion, start circulation mixing pump in electrophoresis tank, incite somebody to action both
Circulation mixing；In premix groove, put into 2-3 part emulsion start stirring, the most slowly put into 1-2 part mill base, will after stirring
Premix groove mixed liquor the most uniformly inputs in electrophoresis tank；Throw 3-4 part deionized water and 4-7 part composite dispersing agent again to cleaning premix
Groove the water after cleaning the most uniformly pump into electrophoresis tank, i.e. obtain carrying out application in constantly circulation after tank liquor transconversion into heat
Electrophoretic paint；
Described composite dispersing agent forms according to following weight:
Oligomer diacetyl acetate alkylene diester metal chelate 35-45 part
Dispersant 5-9 part
Wetting agent 4-6 part
Defoamer 1-2 part.
A kind of anti-corrosion type low-temperature curing cathode electrophoresis paint the most according to claim 1, it is characterised in that
Described hardener formula includes, 20-66 part dimer (fatty acid) yl, 5-18 part vegetable oil acid, 5-25 part fatty amine, 10-34
Part ketone, 5-20 part ethers, 0.01-0.02 part terminator；Described vegetable oil acid is castor oil acid, cotton oil acid, Semen Allii Tuberosi oleic acid or
One in behenic acid, described fatty amine is ethylenediamine, diethylenetriamine, triethylene tetramine, TEPA or mixed amine
One, described mixed amine is mixing two or more in aminoethyl ethanolamine, aminoethyl piperazine or triethylene tetramine, described termination
Agent is quinone, nitro polyol, nitroso-group polyol, aryl polyol or the one of boric acid；
Ketone in described hardener formula is acetone, butanone, Ketohexamethylene, methyl iso-butyl ketone (MIBK), methyl isopropyl Ketone, methyl fourth
One in base ketone or 1-Phenylethanone., described ethers is in ether, butyl cellosolve, ethylene glycol monobutyl ether or ethyl methyl ether
Kind.
A kind of anti-corrosion type low-temperature curing cathode electrophoresis paint the most according to claim 1, it is characterised in that in described impregnating fluid
Also include potassium borohydride 1-3 part, bicyclohexane also-18-crown-6 4-6 part and dibenzyl xenol polyoxyethylene polyoxypropylene ether
5-8 part.
A kind of anti-corrosion type low-temperature curing cathode electrophoresis paint the most according to claim 3, it is characterised in that described unimolecule amine
In other unimolecule amine be in butylamine, octylame, diethylamine, methylbutylamine, monoethanolamine, diethanolamine or N-methylethanolamine
One or more.
A kind of anti-corrosion type low-temperature curing cathode electrophoresis paint the most according to claim 4, it is characterised in that described modified epoxy
The epoxide equivalent of Resin A is 200～1000, and the epoxide equivalent of described modified epoxy B is 600～800.
A kind of anti-corrosion type low-temperature curing cathode electrophoresis paint the most according to claim 4, it is characterised in that described flexible polymer
Thing is polyether Glycols, polyester diol or polyethers diamine, and its number-average molecular weight is 400～1500.
A kind of anti-corrosion type low-temperature curing cathode electrophoresis paint the most according to claim 6, it is characterised in that described modified epoxy
The number-average molecular weight of Resin A is 1500～3500, and described modified epoxy B number-average molecular weight is 1200～3000.
A kind of anti-corrosion type low-temperature curing cathode electrophoresis paint the most according to claim 7, it is characterised in that described plasticizer is
Bisphenol A polyethenoxy ether or bisphenol-A polyethenoxy ether.
A kind of anti-corrosion type low-temperature curing cathode electrophoresis paint the most according to claim 8, it is characterised in that described nertralizer is
Formic acid, acetic acid, propanoic acid, lactic acid, oxalic acid or other organic acid.
A kind of anti-corrosion type low-temperature curing cathode electrophoresis paint the most according to claim 1, it is characterised in that
The preparation method of described polyacrylate-2-cross linked polymer is:
(1) prepared polymer P by weight (MMA-MAh)-PEG6000 30-40 part, regulation liquid 40-60 part form first and just mix
Liquid；Described regulation liquid is to include the sodium perchlorate that concentration is 0.4-0.7mol/L and the N-butyl benzene that concentration is 0.3-0.8mol/L
And the carbonic allyl ester solution of imidazoles；MMA in described polymer P (MMA-MAh)-PEG4000 is methyl methacrylate,
MAh is maleic anhydride, and P (MMA-MAh) is the copolymer of methyl methacrylate and maleic anhydride, and PEG6000 is that molecular weight is
The Polyethylene Glycol of 6000；
(2) in the described first the most mixed liquid, add 2-7 part ten dihydroxystearic acid, be heated to 30-45 DEG C under nitrogen protection instead
Answer 5-9min；
(3) polyacrylate-2-cross linked polymer is obtained after drying with deionized water rinsing.
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| CN201610455743.7A CN105885640A (en) | 2016-06-22 | 2016-06-22 | Corrosion-resistant low-temperature-curing cathode electrophoretic paint |
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| CN109321027A (en) * | 2018-09-21 | 2019-02-12 | 合肥市君科合成材料有限公司 | A kind of novel aqueous drier and preparation method thereof |
| CN111055603A (en) * | 2019-12-31 | 2020-04-24 | 安徽省粤隆印刷科技有限公司 | Packaging box printing process for preventing excessive emulsification of residual ink and formation of residues |
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