CN106047052A - Environment-friendly cathode electrophoretic coating - Google Patents
Environment-friendly cathode electrophoretic coating Download PDFInfo
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- CN106047052A CN106047052A CN201610382555.6A CN201610382555A CN106047052A CN 106047052 A CN106047052 A CN 106047052A CN 201610382555 A CN201610382555 A CN 201610382555A CN 106047052 A CN106047052 A CN 106047052A
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- modified epoxy
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- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- IWPWMAJDSLSRIP-UHFFFAOYSA-N nezukone Chemical compound CC(C)C1=CC=CC(=O)C=C1 IWPWMAJDSLSRIP-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000012974 tin catalyst Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- 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
-
- 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
- C09D5/4434—Polyepoxides characterised by the nature of the epoxy binder
- C09D5/4438—Binder based on epoxy/amine adducts, i.e. reaction products of polyepoxides with compounds containing amino groups only
-
- 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
-
- C—CHEMISTRY; METALLURGY
- 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; OIL DRYING AGENTS, i.e. SICCATIVES; TURPENTINE
- C09F9/00—Compounds to be used as driers, i.e. siccatives
-
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Paints Or Removers (AREA)
Abstract
The invention relates to the field of coatings, in particular to an environment-friendly cathode electrophoretic coating. The environment-friendly cathode electrophoretic coating is prepared from, by mass, 1-2 parts of color paste, 4-6 parts of emulsion and 5-7 parts of deionized water; the color paste is prepared from 20-30 parts of matrix resin, 5-10 parts of alcohol-ether cosolvent, 3-8 parts of organic acid, 0.3-0.7 part of emulsifying agent, 1-5 parts of compound drier, 30-40 parts of deionized water and 15-20 parts of filler. A preparation method of the compound drier comprises the steps that one of oxalic acid, citric acid, glycolic acid and the like is selected to be mixed with deionized water according to the proportion of (1-10):10, premixing is conducted for 1 h at 60 DEG C to 80 DEG C, 1-10 parts of catalyst is added to the mixed solution in a batched mode under stirring, a reaction is conducted for 4 h to 10 h at 70 DEG C to 90 DEG C, precipitates are filtered out, and the water-soluble compound drier can be obtained. The emulsion is prepared from 40-50 parts of modified epoxy resin A, 10-20 parts of modified epoxy resin B, 10-30 parts of curing agent, 3-8 parts of single-molecule amine, 0.1-2 parts of emulsifying agent, 0.1-2 parts of neutralizing agent and 30-50 parts of deionized water.
Description
Technical field
The present invention relates to paint field, be specifically related to a kind of environment protection type cathode electrophoresis coating.
Background technology
Come out from cathode electrophoresis dope, because its paint film formed has the corrosion resistance of excellence, mechanical performance, be suitable for again certainly
Dynamicization application, is the most quickly popularized, the baking temperature scope of traditional cathode electrophoresis dope typically 170～
180℃.At present, many industrial workpiece are with rubber, plastic or other material, it is desirable to together dry with electrophoretic coating after processing
Dry, 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 the demand of such technique, market occurs the low temperature curing type cathode electrophoresis dope of few kind.Low temperature curing type is cloudy
Pole electrophoretic coating not only contributes to plastics and the application of the auto parts and components of rubber, and can be substantially reduced energy consumption, negative electrode
Organic leadP that electrophoretic coating was commonly used in the past and tin catalyst, due to toxicity, greatly, not environmentally etc. shortcoming is in European and flourishing state
Family limits the use of.Unleaded, Wuxi environment-friendly type high anti-corrosive properties cathode electrophoresis dope is a significant improvement in electrophoretic coating evolution.
Therefore in electrophoretic coating, select excellent environment-friendly type drier improving electrophoresis product quality, and in use improving product
Competitiveness is particularly important.
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 environment protection type cathode electrophoresis coating.
The above-mentioned technical purpose of the present invention has the technical scheme that
A kind of environment protection type cathode electrophoresis coating, including in parts by mass, 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 and 15-20 part filler；Described composite drier preparation method is
Choose oxalic acid, citric acid, hydroxyacetic acid, dihydromethyl propionic acid, acetic acid, lactic acid, formic acid, sulfamic acid, hydroxyl sulfoacid, cycloalkanes
Acid, isooctyl acid a kind of acid therein and deionized water and by 1-10: 10 ratio mixed be incorporated in 60-80 DEG C premix 1 hour after, stir
Mix down and be dividedly in some parts 1-10 part catalyst, in above-mentioned mixed liquor, after 70 DEG C-90 DEG C reactions 4-10 hour, finally will precipitation
Filtering out and can prepare water-soluble composite drier, this catalyst is zinc oxide, yittrium oxide, rubidium oxide, cobalt oxide, oxidation
Bismuth, zirconium oxide, manganese oxide, cerium oxide, cerium hydroxide, zinc hydroxide, Bismuth hydrate., Yttrium trihydroxide, rubidium hydroxide, hydroxide
One of which in calcium, cobalt nitrate, bismuth nitrate, manganese nitrate, bismuth subnitrate, cobalt octoate；
Described emulsion formulations includes, 40-50 part modified epoxy A, 10-20 part modified epoxy B, 10-30 part firming agent,
3-8 part unimolecule amine, 0.1-2 part emulsifying agent, 0.1-2 part nertralizer and 30-50 part deionized water.
As preferably, 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 epoxy resin, 5-10 part nonyl phenol, 2-6 part dimethylbenzene, 0.1-1 part triphenyl phosphite；Described hardener formula
Including, 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, and the one in Semen Allii Tuberosi oleic acid or behenic acid is described
Fatty amine be ethylenediamine, diethylenetriamine, triethylene tetramine, TEPA or the one of mixed amine, described mixed amine is ammonia second
Mixing two or more in ethylethanolamine, aminoethyl piperazine or triethylene tetramine, described terminator is that quinone, nitro are polyhydroxylated
Compound, nitroso-group polyol, 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.
The preparation technology of this programme environment protection type cathode electrophoresis coating, 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, then disperse 20-40 minute under 600-800 rev/min, then grind with sand mill
Mill, i.e. obtains mill base after filtering with bag type filtering machine after the μm of sand milling fineness≤13；
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 firming agent, be incubated 1.5-2.5 hour；5. cool to 70-90 DEG C, 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 solvent, add 30-
50 parts of deionized waters, 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 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, stir 30 minutes
Afterwards premix groove mixed liquor is the most uniformly inputted in electrophoresis tank；Throw 3-4 part deionized water again and clean premix groove and by after cleaning
Water the most uniformly pump into electrophoresis tank, in constantly circulation, tank liquor transconversion into heat i.e. obtained carrying out the electrophoresis of application after 48 hours
Paint.
As preferably, the preparation method of described composite drier is, takes oxalic acid, citric acid, hydroxyacetic acid, dihydroxymethyl third
Acid, acetic acid, lactic acid, formic acid, sulfamic acid, hydroxyl sulfoacid, a kind of acid therein of aphthenic acids, isooctyl acid and deionized water and press 1-
The ratio of 10: 10 is mixed was incorporated in 60-80 DEG C of premix after 1 hour, was dividedly in some parts 1-10 part catalyst to above-mentioned mixed liquor under stirring
In, 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, after 70 DEG C-90 DEG C reactions 4-10 hour, finally leaches precipitation, obtains water-soluble
Composite drier.
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 environment protection type 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.
A kind of environment protection type cathode electrophoresis coating 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, and the breakdown voltage >=380V of coating, Ford box method records throwing power >=22cm, to workpiece
Inner chamber film ability is strong.
A kind of environment protection type cathode electrophoresis coating the most of the present invention, uses the heavy metals such as the most leaded, stannum, cadmium, chromium, hydrargyrum
Environment-friendly composite drier, be modified epoxy resin obtaining excellent cationic macromolecules amount resin, obtain without high
Unleaded, the Wuxi environment-friendly type electrophoretic coating that layer of air pollutes.
Detailed description of the invention
Specific examples below is only explanation of the invention, and it is not limitation of the present invention, art technology
The present embodiment can be made after reading this specification by personnel as required does not has the amendment of creative contribution, but as long as
All protected by Patent Law in scope of the presently claimed invention.
Below in conjunction with specific embodiment, the present invention is described in detail.
Embodiment 1:
A kind of environment protection type cathode electrophoresis coating, 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
Close drier, 30 parts of deionized waters and 15 parts of fillers；
Described emulsion formulations includes, 40 parts of modified epoxy A, 10 parts of modified epoxy B, 10 parts of firming agent, 3 part of two sub-second
The diketimine of base triamine and 2 parts of N-methylethanolamines, 0.1 part of emulsifying agent, 0.1 part of acetic acid and 30 parts of deionized waters；Described change
Property epoxy resin A formula includes, 10 parts of bisphenol-As, 40 parts of epoxy resin, 8 parts of solvents, 4 parts of bisphenol A polyethenoxy ethers, 10 numbers
Average molecular weight is the polyether Glycols of 400～1500；Described modified epoxy B formula includes, 10 parts of Bisphenol F, 40 parts of epoxies
Resin, 5 portions of nonyl phenols, 2 portions of dimethylbenzene, 0.1 portion of triphenyl phosphite；Described hardener formula includes, 20 parts of dimer fatty
Acid, 5 parts of castor oil acids, 5 parts of ethylenediamines, 10 parts of acetone, 5 parts of ether, 0.01 part of boric acid.
Above-mentioned environment protection type cathode electrophoresis coating preparation technology, comprises the following steps:
Prepared by A mill base, choose oxalic acid and deionized water and in 1: 10 ratio mixed be incorporated in 60-80 DEG C of premix 1 hour after, stirring
Under be dividedly in some parts 2 parts of bismuth oxide in above-mentioned mixed liquor, after 70 DEG C-90 DEG C reactions 4-10 hour, finally precipitation is filtered out
Water-soluble composite drier can be prepared, be sequentially added in a reservoir 20 parts of matrix resins, 5 parts of alcohol ethers cosolvents, 3 parts
Organic acid, 0.3 part of emulsifying agent and 30 parts of deionized waters, composite drier 1 part, add 15 parts of fillers at 700-1100 rev/min
Stand more than 8 hours after lower dispersion, then disperse under 600-800 rev/min 20-40 minute, then grind with sand mill, treat sand
Mill base is i.e. obtained after filtering with bag type filtering machine after the μm of grinding rate≤13；
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 firming agent, being incubated 1.5-2.5 hour, wherein, described firming agent preparation method is, anti-at logical nitrogen
Answer and still adds 20 parts of dimer (fatty acid) yls, 5 parts of castor oil acids and 5 parts of ethylenediamines, then stir the mixture for 30-90 minute；Connect
And be warmed up to dehydration, continue to be heated to 180-280 DEG C, keep reaction 1-5 hour, be cooled to 100-145 DEG C and add 10 parts of acetone,
Temperature rising reflux 1-6 hour；Backflow reheats after terminating and reclaims free acetone, keeps 1-3 hour to 180-230 DEG C, then takes out true
Sky, controls vacuum-0.08MPa～-0.1 MPa, keeps 1-3 hour；It is cooled to 180 DEG C and adds 0.01 part of boric acid, then cool down
To 100-140 DEG C, add 5 parts of ether；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, extract organic solvent, add 30-
50 parts of deionized waters, 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 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 the water after 3 parts of deionized waters clean premix groove and will clean again the most equal
Even pumping into electrophoresis tank, in constantly circulation, tank liquor transconversion into heat i.e. obtained carrying out the electrophoretic paint of application after 48 hours.
Embodiment 2:
A kind of environment protection type cathode electrophoresis coating, 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 and 20 parts of fillers；
Described emulsion formulations includes, 50 parts of modified epoxy A, 20 parts of modified epoxy B, 30 parts of firming agent, 4 parts of aminoethyls
The ketimide of ethanolamine and 3 parts of diethanolamine, 2 parts of emulsifying agents, 1 part of acetic acid and 50 parts of deionized waters；Described modified epoxy A
Formula includes, 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 parts of epoxy resin, 10 parts of nonyls
Base phenol, 6 portions of dimethylbenzene, 1 portion of triphenyl phosphite；Described hardener formula includes, 66 parts of dimer (fatty acid) yls, 18 portions of Oleum Brassicae campestriss
Acid, 25 parts of triethylene tetramines, 34 parts of acetone, 20 parts of butyl cellosolves, 0.02 part of boric acid；
Above-mentioned environment protection type cathode electrophoresis coating preparation technology, comprises the following steps:
Prepared by A mill base, choose formic acid and deionized water and in 3: 10 ratio mixed be incorporated in 60-80 DEG C of premix 1 hour after, stirring
Under be dividedly in some parts 8 parts of zinc oxide in above-mentioned mixed liquor, after 70 DEG C-90 DEG C reactions 4-10 hour, finally precipitation is filtered out
Water-soluble composite drier can be prepared, be sequentially added in a reservoir 30 parts of matrix resins, 10 parts of alcohol ethers cosolvents, 8
Part organic acid, 0.7 part of emulsifying agent and 40 parts of deionized waters, composite drier 5 parts, add 20 parts of fillers 700-1100 turn/
Stand more than 8 hours after dispersion under point, then disperse under 600-800 rev/min 20-40 minute, then grind with sand mill, treat
Mill base is i.e. obtained after filtering with bag type filtering machine after the μm of sand milling fineness≤13；
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 firming agent, be incubated 1.5-2.5 hour, wherein, described firming agent preparation method is, in the reactor of logical nitrogen
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 minute；Connect
And be warmed up to dehydration, continue to be heated to 180-280 DEG C, keep reaction 1-5 hour, be cooled to 100-145 DEG C and add 10 parts of acetone,
Temperature rising reflux 1-6 hour；Backflow reheats after terminating and reclaims free acetone, keeps 1-3 hour to 180-230 DEG C, then takes out true
Sky, controls vacuum-0.08MPa～-0.1 MPa, keeps 1-3 hour；It is cooled to 180 DEG C and adds 0.02 part of boric acid, then cool down
To 100-140 DEG C, add 20 parts of butyl cellosolves；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 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 the water after 2 parts of deionized waters clean premix groove and will clean again the most equal
Even pumping into electrophoresis tank, in constantly circulation, tank liquor transconversion into heat i.e. obtained carrying out the electrophoretic paint of application after 48 hours.
Table 1 is the film performance table of 2 embodiments of the present invention
Claims (10)
1. an environment protection type cathode electrophoresis coating, including mill base, emulsion and deionized water, it is characterised in that in parts by mass, institute
State electrophoretic coating to include, 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 and 15-20 part filler；Described composite drier preparation method is
Choose oxalic acid, citric acid, hydroxyacetic acid, dihydromethyl propionic acid, acetic acid, lactic acid, formic acid, sulfamic acid, hydroxyl sulfoacid, cycloalkanes
Acid, isooctyl acid a kind of acid therein and deionized water and by 1-10: 10 ratio mixed be incorporated in 60-80 DEG C premix 1 hour after, stir
Mix down and be dividedly in some parts 1-10 part catalyst, in above-mentioned mixed liquor, after 70 DEG C-90 DEG C reactions 4-10 hour, finally will precipitation
Filtering out and can prepare water-soluble composite drier, this catalyst is zinc oxide, yittrium oxide, rubidium oxide, cobalt oxide, oxidation
Bismuth, zirconium oxide, manganese oxide, cerium oxide, cerium hydroxide, zinc hydroxide, Bismuth hydrate., Yttrium trihydroxide, rubidium hydroxide, hydroxide
One of which in calcium, cobalt nitrate, bismuth nitrate, manganese nitrate, bismuth subnitrate, cobalt octoate；Described emulsion formulations includes, 40-50 part
Modified epoxy A, 10-20 part modified epoxy B, 10-30 part firming agent, 3-8 part unimolecule amine, 0.1-2 part emulsifying agent,
0.1-2 part nertralizer 30-50 part deionized water.
A kind of environment protection type cathode electrophoresis coating the most according to claim 1, it is characterised in that 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
Thing；Described modified epoxy B formula includes, 10-20 part Bisphenol F, 40-60 part epoxy resin, 5-10 part nonyl phenol, 2-6 part
Dimethylbenzene, 0.1-1 part triphenyl phosphite；Described hardener formula includes, 20-66 part dimer (fatty acid) yl, 5-18 part plant
Oleic 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
Oleum Sesami acid, cotton oil acid, the one in Semen Allii Tuberosi oleic acid or behenic acid, described fatty amine is ethylenediamine, diethylenetriamine, triethylene
Tetramine, TEPA or the one of mixed amine, described mixed amine is in aminoethyl ethanolamine, aminoethyl piperazine or triethylene tetramine two
Planting above mixing, described terminator is quinone, nitro polyol, nitroso-group polyol, aryl polyhydroxy
Compound or the one of boric acid.
A kind of environment protection type cathode electrophoresis coating the most according to claim 2, it is characterised in that in described unimolecule amine at least
One in ketimide containing aminoethyl ethanolamine or the diketimine of diethylenetriamines, its consumption at least accounts for unimolecule
The 50% of the total consumption of amine.
A kind of environment protection type cathode electrophoresis coating the most according to claim 3, it is characterised in that its in described unimolecule amine
His composition is the one or several in butylamine, octylame, diethylamine, methylbutylamine, monoethanolamine, diethanolamine or N-methylethanolamine
Kind.
A kind of environment protection type cathode electrophoresis coating the most according to claim 4, it is characterised in that described modified epoxy A
Epoxide equivalent be 200～1000, the epoxide equivalent of described modified epoxy B is 600～800.
A kind of environment protection type cathode electrophoresis coating the most according to claim 4, it is characterised in that described flexible polymer is poly-
Ether dihydroxylic alcohols, polyester diol or polyethers diamine, its number-average molecular weight is 400～1500.
A kind of environment protection type cathode electrophoresis coating the most according to claim 6, it is characterised in that described modified epoxy A
Number-average molecular weight be 1500～3500, described modified epoxy B number-average molecular weight is 1200～3000.
A kind of environment protection type cathode electrophoresis coating the most according to claim 7, it is characterised in that described plasticizer is bisphenol-A
Polyoxyethylene ether or bisphenol-A polyethenoxy ether.
A kind of environment protection type cathode electrophoresis coating the most according to claim 8, it is characterised in that described nertralizer be formic acid,
Acetic acid, propanoic acid, lactic acid, oxalic acid or other organic acid.
A kind of environment protection type cathode electrophoresis coating the most according to claim 9, it is characterised in that in described hardener formula
Ketone be acetone, butanone, Ketohexamethylene, in methyl iso-butyl ketone (MIBK), methyl isopropyl Ketone, methyl butyl ketone or 1-Phenylethanone.
Kind, described ethers is the one in ether, butyl cellosolve, ethylene glycol monobutyl ether or ethyl methyl ether.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002294141A (en) * | 2001-03-29 | 2002-10-09 | Nippon Paint Co Ltd | Cationic electrodeposition coating material composition |
| CN101054487A (en) * | 2007-04-30 | 2007-10-17 | 袁兴 | Method of preparing low temperature solidifying environment protection type cathode electrophoresis coating |
| CN101368057A (en) * | 2008-09-25 | 2009-02-18 | 江泽平 | High-performance 150 DEG C oven dry type bi-component epoxy-polyurethane cathode electrophoretic paint |
| CN101602854A (en) * | 2009-07-23 | 2009-12-16 | 福州百盛精细化学品有限公司 | A kind of daiamid epoxy curing agent and preparation method thereof |
| CN102838846A (en) * | 2012-09-26 | 2012-12-26 | 中国海洋石油总公司 | Resin emulsion for cathode electrophoretic coating with high throwing power and preparation method thereof |
| CN103965760A (en) * | 2014-05-07 | 2014-08-06 | 广东科德化工实业有限公司 | Cathode electrophoretic paint containing environmental-friendly type drier and preparation and use method thereof |
| CN105969054A (en) * | 2016-06-02 | 2016-09-28 | 广德县中银化工有限责任公司 | Environment-friendly cathode electrophoretic coating and preparation process thereof |
-
2016
- 2016-06-02 CN CN201610382555.6A patent/CN106047052A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002294141A (en) * | 2001-03-29 | 2002-10-09 | Nippon Paint Co Ltd | Cationic electrodeposition coating material composition |
| CN101054487A (en) * | 2007-04-30 | 2007-10-17 | 袁兴 | Method of preparing low temperature solidifying environment protection type cathode electrophoresis coating |
| CN101368057A (en) * | 2008-09-25 | 2009-02-18 | 江泽平 | High-performance 150 DEG C oven dry type bi-component epoxy-polyurethane cathode electrophoretic paint |
| CN101602854A (en) * | 2009-07-23 | 2009-12-16 | 福州百盛精细化学品有限公司 | A kind of daiamid epoxy curing agent and preparation method thereof |
| CN102838846A (en) * | 2012-09-26 | 2012-12-26 | 中国海洋石油总公司 | Resin emulsion for cathode electrophoretic coating with high throwing power and preparation method thereof |
| CN103965760A (en) * | 2014-05-07 | 2014-08-06 | 广东科德化工实业有限公司 | Cathode electrophoretic paint containing environmental-friendly type drier and preparation and use method thereof |
| CN105969054A (en) * | 2016-06-02 | 2016-09-28 | 广德县中银化工有限责任公司 | Environment-friendly cathode electrophoretic coating and preparation process thereof |
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