CN105969056A - High-throwing-power cathodic electrophoretic paint - Google Patents

High-throwing-power cathodic electrophoretic paint Download PDF

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Publication number
CN105969056A
CN105969056A CN201610382585.7A CN201610382585A CN105969056A CN 105969056 A CN105969056 A CN 105969056A CN 201610382585 A CN201610382585 A CN 201610382585A CN 105969056 A CN105969056 A CN 105969056A
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parts
epoxy resin
throwing power
resin
power cathode
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彭德琼
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GUANGDE ZHONGYIN CHEMICAL CO Ltd
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GUANGDE ZHONGYIN CHEMICAL CO Ltd
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D163/00Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/44Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
    • C09D5/4419Coating 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
    • C09D5/443Polyepoxides
    • C09D5/4434Polyepoxides characterised by the nature of the epoxy binder
    • C09D5/4438Binder based on epoxy/amine adducts, i.e. reaction products of polyepoxides with compounds containing amino groups only
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025Polymer 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
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035Polymer 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)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Paints Or Removers (AREA)

Abstract

The invention relates to the field of paint, in particular to high-throwing-power cathodic electrophoretic paint. The paint is prepared from, by mass, 2-3 parts of mill base, 4-6 parts of emulsion and 5-7 parts of deionized water. The mill base is prepared from 20-40 parts of water-borne cationic epoxy resin, 10-40 parts of pigment filler, 10-20 parts of solvent, 05-1.5 parts of non-toxic drying catalyst, 0.5-2 parts of dispersion agent and 20-50 parts of deionized water. The emulsion is prepared from 40-50 parts of aminated modified epoxy resin, 10-20 parts of epoxy polyurethane resin, 10-30 parts of cross-linking agent, 0.1-2 parts of emulsifying agent, 0.1-2 parts of neutralizer and 30-50 parts of deionized water. The aminated modified epoxy resin is prepared from 40-60 parts of bisphenol A epoxy resin, 8-16 parts of solvent methyl isobutyl ketone, 4-16 parts of plasticizer, 10-35 parts of flexible polymer and 3-8 parts of single molecule amine. The epoxy polyurethane resin is prepared from 10-30 parts of alcohol ether and ketone solvents, 20-35 parts of epoxy resin, 0.5-2 parts of aliphatic amine and 10-25 parts of ketimine resin.

Description

A kind of high throwing power cathode electrophoresis dope
Technical field
The present invention relates to paint field, be specifically related to a kind of high throwing power cathode electrophoresis dope.
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 automation paint, the most quickly popularized.Owing to body of a motor car and parts are complex-shaped, containing many concave volumes, cavity and gap.Usually because producing electric screen phenomenon during electrophoretic painting, making to be coated the paint film became uneven of workpiece surfaces externally and internally, inner surface paint film is relatively thin, has a strong impact on the Corrosion Protection of whole workpiece.Can make to be coated at the recessed depths of workpiece, gap or be uniformly coated with paint film by shielding, becoming the important indicator i.e. throwing power weighing cathode electrophoresis dope quality.Throwing power is the highest, and the film thickness coated by painting workpiece surfaces externally and internally is the most uniform, and workpiece entirety Corrosion Protection is the highest.Along with the fast development of auto industry, the cathode electrophoresis dope preparing high throwing power is the most very urgent.
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 high throwing power cathode electrophoresis dope.
The above-mentioned technical purpose of the present invention has the technical scheme that
A kind of high throwing power cathode electrophoresis dope, including in parts by mass, mill base 2-3 part, emulsion 4-6 part and deionized water 5-7 part;
Described paste formula includes, waterborne cation epoxy resin 20-40 part, color stuffing 10-40 part, solvent 10-20 part, nontoxic drier 0.5-1.5 part, dispersant 0.5-2 part, deionized water 20-50 part;
Described emulsion formulations includes, amination modifying epoxy resin 40-50 part, epoxy polyurethane resin 10-20 part, cross-linking agent 10-30 part, emulsifying agent 0.1-2 part, nertralizer 0.1-2 part and deionized water 30-50 part;
Described amination modifying Formulaion of epoxy resin includes, bisphenol A type epoxy resin 40-60 part, solvent methylisobutyl ketone 8-16 part, plasticizer 4-16 part, flexible polymer 10-35 part and unimolecule amine 3-8 part;
Described epoxy polyurethane resin formula includes, alcohol ethers and ketones solvent 10-30 part, epoxy resin 20-35 part, fatty amine 0.5-2 part, ketimide resin 10-25 part;
Described ketimide resin formula includes, polyetheramine or polyamide 6 0-80 part, butanone or methyl iso-butyl ketone (MIBK) 20-40 part;
Described cross-linking agent is type semienclosed and/or blocked polyurethane includes, aromatic polyisocyanate 5-20 part, alcohol ether compound, heterocycle compound one of them or two or more mixing 3-30 part, polyethers or PCDL 0-80 part, ketones solvent 0-40 part.
By using, the amination modifying epoxy resin of mixing and epoxy polyurethane resin are as emulsion main material, make electrophoretic paint have stronger throwing power and electrophoretic paint tank liquor has higher breakdown voltage, the heat stability of tank liquor is the highest, and the salt spray resistance of this electrophoretic paint, chemicals-resistant, alkaline-resisting, water resistance is outstanding.
As preferably, described aromatic polyisocyanate is TDI or MDI;Alcohol ether compound is butyl glycol ether, diethylene glycol first/second/butyl ether, 2-hydroxyl first/second/butyl ether or propylene glycol first/second/butyl ether;Heterocycle compound is N-methylpyrrole alkanol, tetrahydrofurfuryl alcohol, acetylacetone,2,4-pentanedione or ethyl acetoacetate;Polyethers is molecular weight polypropylene glycol ether between 400-3000, polyglycol ether or admixtured polyether;The molecular weight of PCDL is between 1000-3000;Ketones solvent is butanone, ring ethyl ketone or methyl iso-butyl ketone (MIBK).
As preferably, described unimolecule amine at least contains the one in the ketimide of aminoethyl ethanolamine or the diketimine of diethylenetriamines, its consumption at least accounts for the 50% of the total consumption of unimolecule amine, and other compositions in unimolecule amine are one or more in butylamine, octylame, diethylamine, methylbutylamine, monoethanolamine, diethanolamine or N-methylethanolamine.
As preferably, the epoxide equivalent of described bisphenol A type epoxy resin is 200~1000.
As preferably, described flexible polymer is polyether Glycols, polyester diol or polyethers diamine, and its number-average molecular weight is 400~1500.
As preferably, the number-average molecular weight of described amination modifying epoxy resin is 1500~3500.
As preferably, described plasticizer is bisphenol A polyethenoxy ether or bisphenol-A polyethenoxy ether.
As preferably, described epoxy resin be epoxide equivalent be the bisphenol A type epoxy resin between 180-1000 or phenol aldehyde modified epoxy resin, described fatty amine is methylethanolamine, dimethylethanolamine, diethylamine, diethanolamine, triethanolamine, di-n-propylamine or di-n-butylamine.
As preferably, the amine number of described polyamide is 80-380, and molecular weight is 1000-3000.
As preferably, described nertralizer is formic acid, acetic acid, propanoic acid, lactic acid, oxalic acid or other organic acid.
The preparation technology of this programme coating, comprises the following steps:
Prepared by A mill base, by waterborne cation epoxy resin 20-40 part, color stuffing 10-40 part, solvent 10-20 part, nontoxic drier 0.5-1.5 part, dispersant 0.5-2 part, deionized water 20-50 part, puts into dispersion pot, stands more than 8 hours under 700-1100 rev/min after dispersion, disperse 20-40 minute under 600-800 rev/min again, enter sand mill and be ground to fineness≤15 μm;
Prepared by B emulsion, 1. prepare amination modifying epoxy resin;2. epoxy polyurethane resin is prepared;3., after amination modifying epoxy resin 40-50 part and epoxy polyurethane resin 10-20 part being stirred mixing, it is heated to 100-120 DEG C;4. drip or be dividedly in some parts cross-linking agent 10-30 part, be incubated 1.5-2.5 hour;5. cool to 70-90 DEG C, add emulsifying agent 0.1-2 part and nertralizer 0.1-2 part, dispersed with stirring 30-60 minute;6. cool to 30-70 DEG C, add deionized water 30-50 part, continue stirring and obtain emulsion in 30-60 minute;
C electrophoretic paint is allocated, and adds 2-3 part deionized water and 2-3 part emulsion, start circulation mixing pump, both are circulated mixing in electrophoresis tank;In premix groove, put into 2-3 part emulsion start stirring, the most slowly put into 2-3 part mill base, after stirring 30 minutes, premix groove mixed liquor is the most uniformly inputted in electrophoresis tank;Throwing the water after 3-4 part deionized water cleans premix groove and will clean again and the most uniformly pump into electrophoresis tank, in constantly circulation, tank liquor transconversion into heat i.e. obtained carrying out the electrophoretic paint of application after 48 hours.
As preferably, described amination modifying epoxy resin preparation method is, by bisphenol A type epoxy resin that epoxide equivalent is 200~1000 and solvent methylisobutyl ketone, it is heated to 110 DEG C together, until bisphenol A type epoxy resin is the most melted, cool to 90 DEG C subsequently, add flexible polymer, be heated to 120 DEG C carry out chain extending reaction or heating catalyst in the presence of carry out chain extending reaction, be incubated 2 hours;It is cooled to 100 DEG C, after adding appropriate plasticizer and solvent mix homogeneously, adds unimolecule amine, continue mixing 2 hours.
As preferably, described epoxy polyurethane process for preparing resins is, by epoxy resin 20-35 part, alcohol ethers and ketones solvent 10-30 part stirring and dissolving at 50 DEG C-80 DEG C, is subsequently added fatty amine 0.5-2 part, reacts 2-3 hour at 80 DEG C-90 DEG C;After having reacted, at 75 DEG C-90 DEG C, drip ketimide resin 10-25 part, be incubated 1.5-2.5 hour.
As preferably, described cross-linking agent preparation method is, aromatic polyisocyanate 5-20 part is put into reaction pot, is dividedly in some parts or drips alcohol ether compound or heterocycle compound 3-30 part, polyethers or PCDL 0-80 part at 20-50 DEG C;It is warming up to 70 DEG C-90 DEG C again after being incubated 0.5-2 hour at 30-80 DEG C subsequently and is incubated 1.5-3 hour, add ketones solvent 0-40 part, obtain type semienclosed and/or blocked polyurethane curing agent;Wherein, described alcohol ether compound is alcohol ethers monohydroxy compound, and described heterocycle compound is heterocyclic hydroxy-containing compounds.
In sum, beneficial effects of the present invention:
① Breakdown voltage >=the 380V of a kind of high throwing power cathode electrophoresis dope of the present invention, Ford box method records throwing power >=22cm, strong to the inner chamber film ability of workpiece.
② One of the present invention high throwing power cathode electrophoresis dope, the heat stability of tank liquor is high, and tank liquor electrophoresis temperature >=35 DEG C, electrodeposited paint film uniformity is good.
③ One of the present invention high throwing power cathode electrophoresis dope, solidification temperature is 160 DEG C of energy-conserving and environment-protective, when tank liquor working solvent content is less than 1.5%, still can normal film.
Detailed description of the invention
Specific examples below is only explanation of the invention; it is not limitation of the present invention; the present embodiment can be made after reading this specification by those skilled in the art as required does not has the amendment of creative contribution, but as long as all being 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 high throwing power cathode electrophoresis dope, including in parts by mass, mill base 2 parts, emulsion 6 parts and deionized water 5 parts;
Described paste formula includes, waterborne cation epoxy resin 20 parts, color stuffing 40 parts, solvent 10 parts, nontoxic drier 0.5 part, dispersant 0.5 part, deionized water 50 parts;
Described emulsion formulations includes, number-average molecular weight is amination modifying epoxy resin 40 parts, epoxy polyurethane resin 10 parts, cross-linking agent 30 parts, emulsifying agent 0.1 part, acetic acid 0.5 part and the deionized water 40 parts of 2500;
Described amination modifying Formulaion of epoxy resin includes, polyether Glycols 10 parts and the unimolecule amine 8 parts that bisphenol A type epoxy resin 60 parts that epoxide equivalent is 200~1000, solvent methylisobutyl ketone 12 parts, bisphenol A polyethenoxy ether 8 parts, number-average molecular weight are 1400;Wherein unimolecule amine is made up of the diketimine 4 parts of methylethanolamine 4 parts He diethylenetriamines;
Described epoxy polyurethane resin formula includes, alcohol ethers and ketones solvent 15 parts, and epoxide equivalent is the bisphenol A type epoxy resin 20 parts of 400, diethanolamine 0.5 part, ketimide resin 10 parts;Described ketimide resin formula includes, amine number is 80-380, and molecular weight is the polyamide 80 parts of 1000-3000, methyl iso-butyl ketone (MIBK) 20 parts;
Described cross-linking agent is that blocked polyurethane formula includes, TDI20 part, butyl glycol ether 15 parts, PCDL 50 parts, methyl iso-butyl ketone (MIBK) 30 parts.
Above-mentioned high throwing power cathode electrophoresis dope preparation technology, comprises the following steps:
Prepared by A mill base, by waterborne cation epoxy resin 20 parts, color stuffing 40 parts, solvent 10 parts, nontoxic drier 0.5 part, dispersant 0.5 part, deionized water 50 parts, puts into dispersion pot, stands more than 8 hours under 700-1100 rev/min after dispersion, disperse 30 minutes under 600-800 rev/min again, enter sand mill and be ground to fineness≤15 μm;
Prepared by B emulsion, 1. amination modifying epoxy resin is prepared, by bisphenol A type epoxy resin 60 parts that epoxide equivalent is 200~1000 and solvent methylisobutyl ketone 12 parts, it is heated to 110 DEG C together, until bisphenol A type epoxy resin is the most melted, cool to 90 DEG C subsequently, add the polyether Glycols 10 parts that number-average molecular weight is 1400, be heated to 120 DEG C carry out chain extending reaction or heating catalyst in the presence of carry out chain extending reaction, be incubated 2 hours;It is cooled to 100 DEG C, after adding bisphenol A polyethenoxy ether 8 parts and solvent mix homogeneously, adds the diketimine 4 parts of methylethanolamine 4 parts and diethylenetriamines, continue mixing 2 hours;2. prepare epoxy polyurethane resin, by epoxy resin 20 parts, alcohol ethers and ketones solvent 10-30 part stirring and dissolving at 50 DEG C-80 DEG C, be subsequently added diethanolamine 0.5 part, react 2-3 hour at 80 DEG C-90 DEG C;After having reacted, at 75 DEG C-90 DEG C, drip ketimide resin 10 parts, be incubated 1.5 hours;3. by after amination modifying epoxy resin 40 parts and epoxy polyurethane resin 10 parts stirring mixing, it is heated to 100-120 DEG C;4. dripping or be dividedly in some parts cross-linking agent 30 parts, be incubated 1.5-2.5 hour, described cross-linking agent preparation method is, 20 parts of TDI is put into reaction pot, is dividedly in some parts butyl glycol ether 3-30 part, PCDL 50 parts at 20-50 DEG C;It is warming up to 70 DEG C-90 DEG C again after being incubated 0.5-2 hour at 30-80 DEG C subsequently and is incubated 1.5-3 hour, methylate isobutyl ketone 30 parts, obtain blocked polyurethane curing agent;5. cool to 70-90 DEG C, add emulsifying agent 0.1-2 part and nertralizer 0.1-2 part, dispersed with stirring 30-60 minute;6. cool to 30-70 DEG C, add deionized water 30-50 part, continue stirring and obtain emulsion in 30-60 minute;
C electrophoretic paint is allocated, and adds 2 parts of deionized waters and 3 parts of emulsions, start circulation mixing pump, both are circulated mixing in electrophoresis tank;In premix groove, put into 3 parts of emulsions start stirring, the most slowly put into 2 parts of mill bases, after stirring 30 minutes, premix groove mixed liquor is the most uniformly inputted in electrophoresis tank;Throwing the water after 3 parts of deionized waters clean premix groove and will clean again and the most uniformly pump 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 high throwing power cathode electrophoresis dope, including in parts by mass, mill base 2 parts, emulsion 4 parts and deionized water 6 parts;
Described paste formula includes, waterborne cation epoxy resin 30 parts, color stuffing 30 parts, solvent 10 parts, nontoxic drier 0.5 part, dispersant 0.5 part, deionized water 40 parts
Described emulsion formulations includes, number-average molecular weight is 2000 amination modifying epoxy resin 50 parts, epoxy polyurethane resin 10 parts, cross-linking agent 20 parts, emulsifying agent 0.5 part, acetic acid 0.1 part and deionized water 50 parts;
Described amination modifying Formulaion of epoxy resin includes, epoxide equivalent be 200~1000 bisphenol A type epoxy resin 50 parts, solvent methylisobutyl ketone 16 parts, bisphenol-A polyethenoxy ether 8 parts, number-average molecular weight be polyether Glycols 10 parts and the unimolecule amine 5 parts of 1000;Wherein unimolecule amine is made up of the ketimide 4 parts of diethanolamine 4 parts He aminoethyl ethanolamine;
Described epoxy polyurethane resin formula includes, alcohol ethers and ketones solvent 30 parts, and epoxide equivalent is the bisphenol A type epoxy resin 30 parts of 400, diethanolamine 0.5-2 part, ketimide resin 20 parts;Described ketimide resin formula includes, molecular weight is the polyamide 60 part of 1000-3000, butanone 40 parts;
Described cross-linking agent is that type semienclosed polyurethane includes, TDI20 part, diethylene glycol ether 20 parts, PCDL 40 parts, butanone 30 parts.
Above-mentioned high throwing power cathode electrophoresis dope preparation technology, comprises the following steps:
Prepared by A mill base, by waterborne cation epoxy resin 30 parts, color stuffing 30 parts, solvent 10 parts, nontoxic drier 0.5 part, dispersant 0.5 part, deionized water 40 parts, puts into dispersion pot, stands more than 8 hours under 700-1100 rev/min after dispersion, disperse 20-40 minute under 600-800 rev/min again, enter sand mill and be ground to fineness≤15 μm;
Prepared by B emulsion, 1. amination modifying epoxy resin is prepared, by bisphenol A type epoxy resin 50 parts that epoxide equivalent is 200~1000 and solvent methylisobutyl ketone 16 parts, it is heated to 110 DEG C together, until bisphenol A type epoxy resin is the most melted, cool to 90 DEG C subsequently, add the polyether Glycols 10 parts that number-average molecular weight is 1000, be heated to 120 DEG C carry out chain extending reaction or heating catalyst in the presence of carry out chain extending reaction, be incubated 2 hours;It is cooled to 100 DEG C, after adding bisphenol-A polyethenoxy ether 8 parts and solvent mix homogeneously, adds the ketimide 4 parts of diethanolamine 4 parts and aminoethyl ethanolamine, continue mixing 2 hours;2. prepare epoxy polyurethane resin, by epoxy resin 30 parts, alcohol ethers and 30 parts of stirring and dissolving at 50 DEG C-80 DEG C of ketones solvent, be subsequently added diethanolamine 0.5-2 part, react 2-3 hour at 80 DEG C-90 DEG C;After having reacted, at 75 DEG C-90 DEG C, drip ketimide resin 20 parts, be incubated 2 hours;3. by after amination modifying epoxy resin 50 parts and epoxy polyurethane resin 10 parts stirring mixing, it is heated to 100-120 DEG C;4. dripping or be dividedly in some parts cross-linking agent 20 parts, be incubated 1.5-2.5 hour, described cross-linking agent preparation method is, 20 parts of TDI is put into reaction pot, is dividedly in some parts or diethylene glycol ether 20 parts at 20-50 DEG C, PCDL 40 parts;It is warming up to 70 DEG C-90 DEG C again after being incubated 0.5-2 hour at 30-80 DEG C subsequently and is incubated 1.5-3 hour, butanone 30 parts, obtain type semienclosed polyurethane curing agent;5. cool to 70-90 DEG C, add emulsifying agent 0.5 part and acetic acid 0.1 part, dispersed with stirring 30-60 minute;6. cool to 30-70 DEG C, add deionized water 50 parts, continue stirring and obtain emulsion in 30-60 minute;
C electrophoretic paint is allocated, and adds 3 parts of deionized waters and 2 parts of emulsions, start circulation mixing pump, both are circulated mixing in electrophoresis tank;In premix groove, put into 2 parts of emulsions start stirring, the most slowly put into 2 parts of mill bases, after stirring 30 minutes, premix groove mixed liquor is the most uniformly inputted in electrophoresis tank;Throwing the water after 3 parts of deionized waters clean premix groove and will clean again and the most uniformly pump 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 3:
A kind of high throwing power cathode electrophoresis dope, including in parts by mass, mill base 3 parts, emulsion 4 parts and deionized water 6 parts;
Described paste formula includes, waterborne cation epoxy resin 30 parts, color stuffing 40 parts, solvent 20 parts, nontoxic drier 1 part, dispersant 1 part, deionized water 35 parts
Described emulsion formulations includes, number-average molecular weight is 3000 amination modifying epoxy resin 45 parts, epoxy polyurethane resin 20 parts, cross-linking agent 25 parts, emulsifying agent 1 part, acetic acid 0.5 part and deionized water 50 parts;
Described amination modifying Formulaion of epoxy resin includes, epoxide equivalent be 200~1000 bisphenol A type epoxy resin 45 parts, solvent methylisobutyl ketone 10 parts, bisphenol A polyethenoxy ether 10 parts, number-average molecular weight be polyether Glycols 20 parts and the unimolecule amine 7 parts of 800;Wherein unimolecule amine is made up of the ketimide 4 parts of diethanolamine 4 parts He aminoethyl ethanolamine;
Described epoxy polyurethane resin formula includes, alcohol ethers and ketones solvent 20 parts, and epoxide equivalent is the bisphenol A type epoxy resin 35 parts of 600, diethanolamine 1 part, ketimide resin 20 parts;Described ketimide resin formula includes, molecular weight is the polyamide 60 part of 1000-3000, butanone 40 parts;
Described cross-linking agent is that type semienclosed polyurethane includes, TDI20 part, diethylene glycol ether 20 parts, PCDL 40 parts, butanone 30 parts.
A kind of high throwing power cathode electrophoresis dope preparation technology, comprises the following steps:
Prepared by A mill base, by waterborne cation epoxy resin 30 parts, color stuffing 40 parts, solvent 20 parts, nontoxic drier 1 part, dispersant 1 part, deionized water 35 parts, puts into dispersion pot, stands more than 8 hours under 700-1100 rev/min after dispersion, disperse 20-40 minute under 600-800 rev/min again, enter sand mill and be ground to fineness≤15 μm;
Prepared by B emulsion, 1. amination modifying epoxy resin is prepared, by bisphenol A type epoxy resin 45 parts that epoxide equivalent is 200~1000 and solvent methylisobutyl ketone 10 parts, it is heated to 110 DEG C together, until bisphenol A type epoxy resin is the most melted, cool to 90 DEG C subsequently, add the polyether Glycols 20 parts that number-average molecular weight is 800, be heated to 120 DEG C carry out chain extending reaction or heating catalyst in the presence of carry out chain extending reaction, be incubated 2 hours;It is cooled to 100 DEG C, after adding bisphenol A polyethenoxy ether 10 parts and solvent mix homogeneously, adds the ketimide 4 parts of diethanolamine 4 parts and aminoethyl ethanolamine, continue mixing 2 hours;2. prepare epoxy polyurethane resin, by epoxy resin 35 parts, alcohol ethers and 20 parts of stirring and dissolving at 50 DEG C-80 DEG C of ketones solvent, be subsequently added diethanolamine 1 part, react 2-3 hour at 80 DEG C-90 DEG C;After having reacted, at 75 DEG C-90 DEG C, drip ketimide resin 20 parts, be incubated 2 hours;3. by after amination modifying epoxy resin 45 parts and epoxy polyurethane resin 20 parts stirring mixing, it is heated to 100-120 DEG C;4. dripping or be dividedly in some parts cross-linking agent 25 parts, be incubated 1.5-2.5 hour, described cross-linking agent preparation method is, 20 parts of TDI is put into reaction pot, is dividedly in some parts or diethylene glycol ether 20 parts at 20-50 DEG C, PCDL 40 parts;It is warming up to 70 DEG C-90 DEG C again after being incubated 0.5-2 hour at 30-80 DEG C subsequently and is incubated 1.5-3 hour, butanone 30 parts, obtain type semienclosed polyurethane curing agent;5. cool to 70-90 DEG C, add emulsifying agent 1 part and nertralizer 0.5 part, dispersed with stirring 30-60 minute;6. cool to 30-70 DEG C, add deionized water 50 parts, continue stirring and obtain emulsion in 30-60 minute;
C electrophoretic paint is allocated, and adds 3 parts of deionized waters and 2 parts of emulsions, start circulation mixing pump, both are circulated mixing in electrophoresis tank;In premix groove, put into 2 parts of emulsions start stirring, the most slowly put into 3 parts of mill bases, after stirring 30 minutes, premix groove mixed liquor is the most uniformly inputted in electrophoresis tank;Throwing the water after 3 parts of deionized waters clean premix groove and will clean again and the most uniformly pump 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 3 embodiments of the present invention
Index embodiment Embodiment 1 Embodiment 2 Embodiment 3
Outward appearance Flat smooth is without shrinkage cavity Flat smooth is without shrinkage cavity Flat smooth is without shrinkage cavity
Throwing power (Ford box method) 22.4mm 22.5mm 22.3mm
Voltage thickness V/ μm 310/20 312/20 308/20
Gloss 60% 80 82 79
Impact strength Kg cm ≥50 ≥50 ≥50
Cupping mm 6.8 6.8 6.8
Adhesive force/level 0 0 0
Pencil hardness/H 2 2 2
Alkali resistance (5%) >120h >120h >120h
Acid resistance (0.05mol) >48h >48h >48h
Resistance to water (40 DEG C), 360h Qualified Qualified Qualified
Salt water resistance (3%) 25 DEG C, 360h Qualified Qualified Qualified
Salt spray test phosphatization plate 21 ± 2 μ, 800h Qualified Qualified Qualified
Resistance to gasoline (93#) >240h >240h >240h

Claims (10)

1. a high throwing power cathode electrophoresis dope, including mill base, emulsion and deionized water, it is characterised in that in parts by mass, described electrophoretic coating includes, mill base 2-3 part, emulsion 4-6 part and deionized water 5-7 part;
Described emulsion formulations includes, amination modifying epoxy resin 40-50 part, epoxy polyurethane resin 10-20 part, cross-linking agent 10-30 part, emulsifying agent 0.1-2 part, nertralizer 0.1-2 part and deionized water 30-50 part;
Described amination modifying Formulaion of epoxy resin includes, bisphenol A type epoxy resin 40-60 part, solvent methylisobutyl ketone 8-16 part, plasticizer 4-16 part, flexible polymer 10-35 part and unimolecule amine 3-8 part;
Described epoxy polyurethane resin formula includes, alcohol ethers and ketones solvent 10-30 part, epoxy resin 20-35 part, fatty amine 0.5-2 part, ketimide resin 10-25 part;
Described ketimide resin formula includes, polyetheramine or polyamide 6 0-80 part, butanone or methyl iso-butyl ketone (MIBK) 20-40 part;
Described cross-linking agent is type semienclosed and/or blocked polyurethane includes, aromatic polyisocyanate 5-20 part, alcohol ether compound, heterocycle compound one of them or two or more mixing 3-30 part, polyethers or PCDL 0-80 part, ketones solvent 0-40 part.
One the most according to claim 1 high throwing power cathode electrophoresis dope, it is characterised in that described paste formula includes, waterborne cation epoxy resin 20-40 part, color stuffing 10-40 part, solvent 10-20 part, nontoxic drier 0.5-1.5 part, dispersant 0.5-2 part, deionized water 20-50 part.
One the most according to claim 2 high throwing power cathode electrophoresis dope, it is characterized in that, described unimolecule amine at least contains the one in the ketimide of aminoethyl ethanolamine or the diketimine of diethylenetriamines, its consumption at least accounts for the 50% of the total consumption of unimolecule amine, and other compositions in unimolecule amine are one or more in butylamine, octylame, diethylamine, methylbutylamine, monoethanolamine, diethanolamine or N-methylethanolamine.
One the most according to claim 3 high throwing power cathode electrophoresis dope, it is characterised in that the epoxide equivalent of described bisphenol A type epoxy resin is 200~1000.
One the most according to claim 4 high throwing power cathode electrophoresis dope, it is characterised in that described flexible polymer is polyether Glycols, polyester diol or polyethers diamine, its number-average molecular weight is 400~1500.
One the most according to claim 5 high throwing power cathode electrophoresis dope, it is characterised in that the number-average molecular weight of described amination modifying epoxy resin is 1500~3500.
One the most according to claim 6 high throwing power cathode electrophoresis dope, it is characterised in that described plasticizer is bisphenol A polyethenoxy ether or bisphenol-A polyethenoxy ether.
One the most according to claim 2 high throwing power cathode electrophoresis dope, it is characterised in that described epoxy resin be epoxide equivalent be the bisphenol A type epoxy resin between 180-1000 or phenol aldehyde modified epoxy resin.
One the most according to claim 8 high throwing power cathode electrophoresis dope, it is characterised in that the amine number of described polyamide is 80-380, molecular weight is 1000-3000.
One the most according to claim 9 high throwing power cathode electrophoresis dope, it is characterised in that described nertralizer is formic acid, acetic acid, propanoic acid, lactic acid, oxalic acid or other organic acid.
CN201610382585.7A 2016-06-02 2016-06-02 High-throwing-power cathodic electrophoretic paint Pending CN105969056A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108384308A (en) * 2018-03-12 2018-08-10 镇江百胜千隆新材料科技有限公司 A kind of aqueous cathode electrophoresis dope and its manufacture craft
CN108587413A (en) * 2018-05-30 2018-09-28 安徽润晟建设有限公司 A kind of exterior wall waterborne epoxy coatings
CN110105845A (en) * 2019-05-27 2019-08-09 枣阳市旺前电泳涂料有限公司 A kind of cathode epoxy electrophoretic paint and its production method
CN111088515A (en) * 2019-12-31 2020-05-01 枣阳市旺前电泳涂料有限公司 High-throwing-power electrophoretic paint mixing tank method
CN112812273A (en) * 2021-02-26 2021-05-18 美高微球(南通)科技有限公司 Polyepoxy quaternary ammonium salt emulsion for cathode electrophoretic coating and preparation method and application thereof
CN114736353A (en) * 2022-03-01 2022-07-12 天津市新丽华色材有限责任公司 Special toughening resin for cathode electrophoretic coating and preparation method and application thereof

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CN101362919A (en) * 2008-09-25 2009-02-11 江泽平 Single-component cationoid water-soluble epoxy-polyurethane anticorrosion primer system drying at 150 DEG C
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

Patent Citations (2)

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Publication number Priority date Publication date Assignee Title
CN101362919A (en) * 2008-09-25 2009-02-11 江泽平 Single-component cationoid water-soluble epoxy-polyurethane anticorrosion primer system drying at 150 DEG C
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

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108384308A (en) * 2018-03-12 2018-08-10 镇江百胜千隆新材料科技有限公司 A kind of aqueous cathode electrophoresis dope and its manufacture craft
CN108587413A (en) * 2018-05-30 2018-09-28 安徽润晟建设有限公司 A kind of exterior wall waterborne epoxy coatings
CN110105845A (en) * 2019-05-27 2019-08-09 枣阳市旺前电泳涂料有限公司 A kind of cathode epoxy electrophoretic paint and its production method
CN111088515A (en) * 2019-12-31 2020-05-01 枣阳市旺前电泳涂料有限公司 High-throwing-power electrophoretic paint mixing tank method
CN112812273A (en) * 2021-02-26 2021-05-18 美高微球(南通)科技有限公司 Polyepoxy quaternary ammonium salt emulsion for cathode electrophoretic coating and preparation method and application thereof
CN114736353A (en) * 2022-03-01 2022-07-12 天津市新丽华色材有限责任公司 Special toughening resin for cathode electrophoretic coating and preparation method and application thereof

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