CN103436153B - Weather resistant cathode electrophoretic coating composition - Google Patents
Weather resistant cathode electrophoretic coating composition Download PDFInfo
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- CN103436153B CN103436153B CN201310398181.3A CN201310398181A CN103436153B CN 103436153 B CN103436153 B CN 103436153B CN 201310398181 A CN201310398181 A CN 201310398181A CN 103436153 B CN103436153 B CN 103436153B
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Abstract
The present invention provides a kind of weather resistant cathode electrophoretic coating composition, primary raw material is by propylene glycol monomethyl ether, ethyl acetate, bisphenol-A, epoxy resin, curing agent and deionized water etc. form, preparation method is i.e. prepared as composition 1 and composition 2 by component feeding, on the basis of composition 1 and composition 2, reprocessing is product A, product B it is prepared as again after being prepared by composition 3, during use, use after taking product A and product B mixing by technique, the product weatherability of institute of the present invention structure and decay resistance are stable, can be used for automobile chassis, accessory and various engineering machinery or processing equipment etc. use as film.
Description
Technical field
The present invention relates to a kind of for automobile or other mechanical fitting as the composition of external paint, specifically one
Plant weather resistant cathode electrophoretic coating composition.
Background technology
In automobile industry and various mechanical industry, various accessories and automobile chassis etc. use electrophoretic coating to make the most substantially
For coating, but in a lot of use fields, such as wiper, offroad vehicle spare wheel carrier, automobile chassis, wheel and the engineering machinery of automobile
Etc. the various various components being exposed to outdoor use, all can, condition of work big due to climate change severe, resistance to electrophoretic coating
Wait performance and decay resistance requires the highest, in existing electrophoretic coating product, be difficult to fully meet in currently practical use
Needs.
Summary of the invention
It is an object of the invention to meet the urgent need of existing market needs, it is provided that a kind of weather resistant cathode electrophoresis dope combination
Thing, has fabulous weather resistance and decay resistance, and does not haves precipitation in storage and go bad, constant product quality
Fabulous.
The technical solution adopted in the present invention is as follows: cathode electrophoretic coating composition is made up of product A and product B,
Wherein product A is to prepare composition on the basis of prepared composition 1 and composition 2 again:
1) composition 1, it may be assumed that acrylic resin
Parts by weight of raw materials percentage is as follows:
Propylene glycol monomethyl ether 14%
Ethyl acetate 14%
Dimethylaminoethyl acrylate methyl ammonia ethyl ester 10.5%
Hydroxy-ethyl acrylate 18%
Methyl methacrylate 18%
Styrene 6%
Butyl acrylate 16.5%
Lauryl mercaptan 1.5%
Azodiisobutyronitrile 1.5%
Preparation method is as follows:
1. by propylene glycol monomethyl ether, ethyl acetate puts into band stirring water knockout drum, the stainless steel cauldron of condenser is stirred,
Being simultaneously heated to 95 DEG C has phegma to produce；
2. by dimethylaminoethyl acrylate methyl ammonia ethyl ester, hydroxy-ethyl acrylate, methyl methacrylate, styrene, acrylic acid fourth
Ester, lauryl mercaptan, azodiisobutyronitrile add reactor top head tank in stir, temperature of reaction kettle keep 90
～95 DEG C, the mixture of head tank was added drop-wise in reactor with the time more than 3h, is incubated 3h after adding and treats resin conversion ratio
>=98.5% cooling, discharging is composition 1 acrylic resin,
2) composition 2, it may be assumed that amine-modified epoxy resin
Parts by weight of raw materials percentage is as follows:
Bisphenol-A 13.5%
Dodecylphenol 7.8%
Epoxy resin 44.7%
Dimethylbenzene 10.5%
Dimethyl benzyl amine 0.7%
Diethanol amine 4.5%
Butyl glycol ether 3%
Sec-butyl alcohol 10.8%
Propane diols phenylate 3%
Dimethylaminopropylamine 1.5%
Preparation method is as follows:
1. the dimethylbenzene of 1/3rd in bisphenol-A, dodecylphenol, epoxy resin and component is put into belt stirrer, divides
Hydrophone, condenser stainless steel cauldron in, be heated to 130 DEG C；
2. add dimethyl benzyl amine carry out being catalyzed to epoxide equivalent be 1000g/eq;
3. add in component the dimethylbenzene remaining 2/3rds, be diluted, be simultaneously introduced diethanol amine and be cooled to 90 DEG C
State is incubated 1 hour；
4. add butyl glycol ether, after sec-butyl alcohol, propane diols phenylate carry out mixed diluting, add dimethylaminopropylamine and exist
It is composition 2 amine-modified epoxy resin after being incubated 2 hours under 90 DEG C of states,
The composition of product A: i.e. epoxy-acrylate emulsion,
Parts by weight of raw materials percentage is as follows:
Composition 1 15～24%
Composition 2 6～15%
Curing agent 14.5%
Plasticizer 1.5%
Defoamer 0.05%
Levelling agent 0.05%
88% lactic acid 0.9%
Deionized water 53%
Preparation method is as follows:
1. composition 1, composition 2, curing agent, plasticizer, defoamer, levelling agent are joined band condenser and agitator not
Stirring mixing in rust steel emulsifying kettle；
2. add 88% lactic acid to be stirred neutralizing；
3., when continuously stirring, the deionized water added in formula i.e. constitutes emulsion；
4. above-mentioned emulsion emulsifying kettle hot water jacket be heated to 30～45 DEG C carry out decompression distillation, when distillate reaches 30%
During weight portion, still further add the deionized water of above-mentioned total amount 30%, become product A: epoxy-acrylate emulsion,
In technique scheme, curing agent is the dibutyl amine closure of HDI trimer,
Product B is by preparing after composition 3 preparation again:
Composition 3, i.e.: pigment dispersing resin
Composition of raw materials weight portion percentage is as follows:
Bisphenol-A 7.3%
Dodecylphenol 4.2%
Epoxy resin 24.1%
Dimethylbenzene 1.4%
Triphenylphosphine 0.4%
Butyl glycol ether 24.4%
Polypropylene glycol diglycidyl ether 21%
Monoethanolamine 1.9%
Dimethylaminopropylamine 1.5%
Acetic acid 1.8%
Deionized water 12%
Preparation method is as follows:
1. bisphenol-A, dodecylphenol, epoxy resin, dimethylbenzene are joined belt stirrer, water knockout drum, condenser not
In rust steel reactor, it is heated to 130 DEG C；
2. add triphenylphosphine to be catalyzed；
3., when catalysis to epoxide equivalent is 700～750 g/eq, butyl glycol ether, polypropylene glycol diglycidyl are added
Ether is diluted and lowers the temperature；
4., when temperature is down to 70 DEG C, after addition monoethanolamine is incubated 1 hour under 85 DEG C of states, dimethylamino third is added
Amine is incubated 2 hours 120 DEG C of states；
5., after above-mentioned reactant being cooled to less than 85 DEG C, add acetic acid and be neutralized；
6. add deionized water to be diluted to solids content being 60%, become composition 3 pigment dispersing resin,
Product B, i.e.: graining paste
Formulation weight part percentage is as follows:
Composition 3 25.2%
Deionized water 32.9%
Carbon black 2.4%
Ultrafine kaolin 18%
Barium sulfate 18%
Dibutyltin oxide 1.5%
Bismuth subcarbonate 2%
Preparation method is as follows:
Above-mentioned raw materials is all ground to fineness≤15 m through sand mill, becomes the face that product B solids content is 57%
Slip.
In technique scheme:
2. composition 1 preparation method is cooled to 50 DEG C, composition 1 acrylic resin acquired by discharging, the amine of its polymer
Value is 0.95mmolN/g, and the equal relative molecular weight of number is 8500.
Its epoxide equivalent of epoxy resin in raw material components in composition 2 and composition 3 is 188 g/eq.
Latex solids content after product A preparation method 3. middle addition deionized water is 35%, and MEQ value is 20, and pH value is 6.
The composition 3 preparation method 5. middle acetic acid that adds is neutralized, and the pH value after it neutralizes is 7.
Carbon black formulation material in technique scheme composition 4 is black paste, during as produced other color slurry, can change
Other colorant.
The product that the present invention is produced method in use is as follows:
Feeding by weight
Product A 38～39%
Product B 7～8%
Deionized water 53～55%
Spendable coating is i.e. constituted after mixing；First component use during coating ternary low zinc phosphating process liquid carry out anticorrosion table
Layer processes, and painting feed liquid put into by the component after then processing, and carries out electrophoretic coating under 28 DEG C of states, and during application, voltage is
280V, electrophoresis time is 3 minutes, after taking-up is rinsed with clear water, puts in electrothermal air drying box and toasts 20 points by 165 DEG C
Clock, can constitute the paint film of 28～30 m thickness on component top layer.
The present invention passes through technique scheme, owing to the acrylic resin containing amine component and epoxy resin are carried out science group
Close, and be mixed together with curing agent blocked polyisocyanates compound, then be neutralized through acid, be allowed to be dispersed in deionized water
In, defining stable emulsion, solvent is removed in finally decompression, and each component property of cathode electrophoretic coating composition making acquisition is steady
Fixed, weather resistance and decay resistance are fabulous, coating surface light durable.During use, product A and product B are needed by technique
Can be used as coating after mixing to use, the present invention efficiently solves the weatherability that existing cathode electrophoresis dope generally exists to be had
Limit and coating surface easily tarnish and the problems such as poor corrosion resistance, can be applicable to automobile industry and various machinery
Industry and electrical appliance industry use as component coating.
Detailed description of the invention
Embodiment 1: calculating with finished product 100kg, cathode electrophoretic coating composition is made up of product A and product B, wherein product
A is to prepare composition on the basis of prepared composition 1 and composition 2 again:
1) composition 1, it may be assumed that acrylic resin
Parts by weight of raw materials percentage is as follows: propylene glycol monomethyl ether 14Kg, accounts for component 14%, ethyl acetate 14Kg, account for component 14%,
Dimethylaminoethyl acrylate methyl ammonia ethyl ester 10.5Kg, accounts for component 10.5%, hydroxy-ethyl acrylate 18Kg, accounts for component 18%, methacrylic acid
Methyl esters 18Kg, accounts for component 18%, styrene 6Kg, accounts for component 6%, butyl acrylate 16.5Kg accounts for component 16.5%, dodecyl sulphur
Alcohol 1.5Kg, accounts for component 1.5%, azodiisobutyronitrile 1.5Kg, accounts for component 1.5%,
Preparation method is as follows:
1. by propylene glycol monomethyl ether, ethyl acetate puts into band stirring water knockout drum, the stainless steel cauldron of condenser is stirred,
Being simultaneously heated to 95 DEG C has phegma to produce；2. by dimethylaminoethyl acrylate methyl ammonia ethyl ester, hydroxy-ethyl acrylate, methyl methacrylate
Ester, styrene, butyl acrylate, lauryl mercaptan, azodiisobutyronitrile add in the head tank on reactor top stirring all
Even, temperature of reaction kettle keeps 90～95 DEG C, is added drop-wise in reactor with the time more than 3h by the mixture of head tank, after adding
Insulation 3h treats that resin conversion ratio >=98.5% is lowered the temperature, and discharging is composition 1 acrylic resin,
2) composition 2, it may be assumed that amine-modified epoxy resin
Parts by weight of raw materials percentage is as follows: bisphenol-A 13.5Kg, accounts for component 13.5%, dodecylphenol 7.8Kg, accounts for component
7.8%, epoxy resin 44.7Kg, accounts for component 44.7%, dimethylbenzene meter 10.5Kg, accounts for component 10.5%, dimethyl benzyl amine
0.7Kg, accounts for component 0.7%, diethanol amine 4.5Kg, accounts for component 4.5%, butyl glycol ether 3Kg, accounts for component 3%, sec-butyl alcohol
10.8Kg, accounts for component 10.8%, propane diols phenylate 3Kg, accounts for component 3%, dimethylaminopropylamine 1.5Kg, account for component 1.5%,
Preparation method is as follows:
1. the dimethylbenzene of 1/3rd in bisphenol-A, dodecylphenol, epoxy resin and component is put into belt stirrer, divides
Hydrophone, condenser stainless steel cauldron in, be heated to 130 DEG C；2. add dimethyl benzyl amine to carry out being catalyzed to epoxide equivalent
For 1000g/eq；3. add the dimethylbenzene of residue 2/3rds in component to be diluted, be simultaneously introduced diethanol amine and be cooled to 90
DEG C state is incubated 1 hour；4. add butyl glycol ether, after sec-butyl alcohol, propane diols phenylate carry out mixed diluting, add diformazan ammonia
Base propylamine is composition 2 amine-modified epoxy resin after being incubated 2 hours under 90 DEG C of states.
The composition of product A: i.e. epoxy-acrylate emulsion
Parts by weight of raw materials percentage is as follows:
Take above-mentioned prepared composition 1 16Kg, account for component 16%, composition 2 14Kg, account for component 14%, separately take curing agent 14.5Kg,
Account for component 14.5%, plasticizer 1.5Kg, account for component 1.5%, defoamer 0.05Kg, account for component 0.05%, levelling agent 0.05Kg, account for group
Divide 0.05%, 88% lactic acid 0.9Kg, account for component 0.9%, deionized water 53Kg, account for component 53%,
Preparation method is as follows:
1. composition 1, composition 2, curing agent, plasticizer, defoamer, levelling agent are joined band condenser and agitator not
Stirring mixing in rust steel emulsifying kettle；2. add 88% lactic acid to be stirred neutralizing；3., when continuously stirring, formula is added
In deionized water i.e. constitute emulsion；4. above-mentioned emulsion emulsifying kettle hot water jacket be heated to 30～45 DEG C carry out decompression distillation,
When distillate reaches 30% weight portion, still further add the deionized water of above-mentioned total amount 30%, become product A: epoxy third
Olefin(e) acid emulsion,
In technique scheme, curing agent is the dibutyl amine closure of HDI trimer, product B be by composition 3 prepare after
Prepare again:
Composition 3, i.e.: pigment dispersing resin
Composition of raw materials weight portion percentage is as follows:
Bisphenol-A 7.3Kg, accounts for component 7.3%, dodecylphenol 4.2Kg, accounts for component 4.2%, epoxy resin 24.1Kg, accounts for group
Point 24.1%, dimethylbenzene 1.4Kg, accounts for component 1.4%, triphenylphosphine 0.4Kg, accounts for component 0.4%, butyl glycol ether 24.4Kg, account for group
Point 24.4%, polypropylene glycol diglycidyl ether 21Kg, accounts for component 21%, monoethanolamine 1.9Kg, accounts for component 1.9%, dimethylamino third
Amine 1.5Kg, accounts for component 1.5%, acetic acid 1.8Kg, accounts for component 1.8%, deionized water 12Kg, account for component 12%, and preparation method is such as
Under:
1. bisphenol-A, dodecylphenol, epoxy resin, dimethylbenzene are joined belt stirrer, water knockout drum, condenser not
In rust steel reactor, it is heated to 130 DEG C；2. add triphenylphosphine to be catalyzed；3. when catalysis to epoxide equivalent be 700～750
During g/eq, add butyl glycol ether, polypropylene glycol diglycidyl ether is diluted and lowers the temperature；4. when temperature is down to 70 DEG C,
After addition monoethanolamine is incubated 1 hour under 85 DEG C of states, adds dimethylaminopropylamine and be incubated 2 hours 120 DEG C of states；5. allow
After above-mentioned reactant is cooled to less than 85 DEG C, adds acetic acid and be neutralized；6. add deionized water to be diluted to solids content
It is 60%, becomes composition 3 pigment dispersing resin,
Product B, i.e.: graining paste
Formulation weight part percentage is as follows:
Take above-mentioned prepared composition 3 25.2Kg, account for component 25.2%, separately remove ionized water 32.9Kg, account for component 32.9%, charcoal
Black 2.4Kg, accounts for component 2.4%, ultrafine kaolin 18Kg, accounts for component 18%, barium sulfate 18Kg, accounts for component 18%, Dibutyltin oxide
1.5Kg, accounts for component 1.5%, bismuth subcarbonate 2Kg, accounts for component 2%,
Preparation method is as follows:
Above-mentioned raw materials is all ground to fineness≤15 m through sand mill, becomes the face that product B solids content is 57%
Slip.
In above-described embodiment:
2. composition 1 preparation method is cooled to 50 DEG C, composition 1 acrylic resin acquired by discharging, the amine of its polymer
Value is 0.95mmolN/g, and the equal relative molecular weight of number is 8500.
Its epoxide equivalent of epoxy resin in raw material components in composition 2 and composition 3 is 188g/eq.
Latex solids content after product A preparation method 3. middle addition deionized water is 35%, and MEQ value is 20, and pH value is 6.
The composition 3 preparation method 5. middle acetic acid that adds is neutralized, and the pH value after it neutralizes is 7.
When the present invention constitutes coating composition, method is as follows:
Feeding by weight
Product A 38%
Product B 7%
Deionized water 55%
Spendable coating is i.e. constituted after feeding uniformly mixes according to the above ratio.
Embodiment 2: calculating with finished product 500kg, cathode electrophoretic coating composition is made up of product A and product B, wherein product
A is to prepare composition on the basis of prepared composition 1 and composition 2 again:
1) composition 1, it may be assumed that acrylic resin,
Parts by weight of raw materials percentage is as follows: propylene glycol monomethyl ether 70Kg, accounts for component 14%, ethyl acetate 70Kg, account for component 14%,
Dimethylaminoethyl acrylate methyl ammonia ethyl ester 52.5Kg, accounts for component 10.5%, hydroxy-ethyl acrylate 90Kg, accounts for component 18%, methacrylic acid
Methyl esters 90Kg, accounts for component 18%, styrene 30Kg, accounts for component 6%, butyl acrylate 82.5Kg accounts for component 16.5%, dodecyl
Mercaptan 7.5Kg, accounts for component 1.5%, azodiisobutyronitrile 7.5Kg, accounts for component 1.5%,
Preparation method is as follows:
1. by propylene glycol monomethyl ether, ethyl acetate puts into band stirring water knockout drum, the stainless steel cauldron of condenser is stirred,
Being simultaneously heated to 95 DEG C has phegma to produce；2. by dimethylaminoethyl acrylate methyl ammonia ethyl ester, hydroxy-ethyl acrylate, methyl methacrylate
Ester, styrene, butyl acrylate, lauryl mercaptan, azodiisobutyronitrile add in the head tank on reactor top stirring all
Even, temperature of reaction kettle keeps 90～95 DEG C, is added drop-wise in reactor with the time more than 3h by the mixture of head tank, after adding
Insulation 3h treats that resin conversion ratio >=98.5% is lowered the temperature, and discharging is composition 1 acrylic resin,
2) composition 2, it may be assumed that amine-modified epoxy resin
Parts by weight of raw materials percentage is as follows: bisphenol-A 67.5Kg, accounts for component 13.5%, dodecylphenol 39Kg, accounts for component
7.8%, epoxy resin 223.5Kg, accounts for component 44.7%, dimethylbenzene meter 52.5Kg, accounts for component 10.5%, dimethyl benzyl amine
3.5Kg, accounts for component 0.7%, diethanol amine 22.5Kg, accounts for component 4.5%, butyl glycol ether 15Kg, accounts for component 3%, sec-butyl alcohol
54Kg, accounts for component 10.8%, propane diols phenylate 15Kg, accounts for component 3%, dimethylaminopropylamine 7.5Kg, account for component 1.5%,
Preparation method is as follows:
1. the dimethylbenzene of 1/3rd in bisphenol-A, dodecylphenol, epoxy resin and component is put into belt stirrer, divides
Hydrophone, condenser stainless steel cauldron in, be heated to 130 DEG C；2. add dimethyl benzyl amine to carry out being catalyzed to epoxide equivalent
For 1000g/eq；3. add the dimethylbenzene of residue 2/3rds in component to be diluted, be simultaneously introduced diethanol amine and be cooled to 90
DEG C state is incubated 1 hour；4. add butyl glycol ether, after sec-butyl alcohol, propane diols phenylate carry out mixed diluting, add diformazan ammonia
Base propylamine is composition 2 amine-modified epoxy resin after being incubated 2 hours under 90 DEG C of states,
The composition of product A: i.e. epoxy-acrylate emulsion
Parts by weight of raw materials percentage is as follows:
Take above-mentioned prepared composition 1 95Kg, account for component 19%, composition 2 55Kg, account for component 11%, separately take curing agent 72.5Kg,
Account for component 14.5%, plasticizer 7.5Kg, account for component 1.5%, defoamer 0.25Kg, account for component 0.05%, levelling agent 0.25Kg, account for group
Divide 0.05%, 88% lactic acid 4.5Kg, account for component 0.9%, deionized water 265Kg, account for component 53%,
Preparation method is as follows:
1. composition 1, composition 2, curing agent, plasticizer, defoamer, levelling agent are joined band condenser and agitator not
Stirring mixing in rust steel emulsifying kettle；2. add 88% lactic acid to be stirred neutralizing；3., when continuously stirring, formula is added
In deionized water i.e. constitute emulsion；4. above-mentioned emulsion emulsifying kettle hot water jacket is heated to 30～45 DEG C and carries out decompression steaming
Evaporate, when distillate reaches 30% weight portion, still further add the deionized water of above-mentioned total amount 30%, become product A: epoxy
Acrylic emulsion,
In technique scheme, curing agent is the dibutyl amine closure of HDI trimer,
Product B is by preparing after composition 3 preparation again:
Composition 3, i.e.: pigment dispersing resin
Composition of raw materials weight portion percentage is as follows:
Bis-phenol 36.5Kg, accounts for component 7.3%, dodecylphenol 21Kg, accounts for component 4.2%, epoxy resin 120.5Kg, accounts for group
Point 24.1%, dimethylbenzene 7Kg, accounts for component 1.4%, triphenylphosphine 2Kg, accounts for component 0.4%, butyl glycol ether 122Kg, account for component
24.4%, polypropylene glycol diglycidyl ether 105Kg, accounts for component 21%, monoethanolamine 9.5Kg, accounts for component 1.9%, dimethylaminopropylamine
7.5Kg accounts for component 1.5%, acetic acid 9Kg, accounts for component 1.8%, deionized water 60Kg, accounts for component 12%,
Preparation method is as follows:
1. bisphenol-A, dodecylphenol, epoxy resin, dimethylbenzene are joined belt stirrer, water knockout drum, condenser not
In rust steel reactor, it is heated to 130 DEG C；2. add triphenylphosphine to be catalyzed；3. when catalysis to epoxide equivalent be 700～750
During g/eq, add butyl glycol ether, polypropylene glycol diglycidyl ether is diluted and lowers the temperature；4. when temperature is down to 70 DEG C,
After addition monoethanolamine is incubated 1 hour under 85 DEG C of states, adds dimethylaminopropylamine and be incubated 2 hours 120 DEG C of states；5. will
After above-mentioned reactant is cooled to less than 85 DEG C, adds acetic acid and be neutralized；6. add deionized water to be diluted to solids content
It is 60%, becomes composition 3 pigment dispersing resin,
Product B, i.e.: graining paste
Formulation weight part percentage is as follows:
Take above-mentioned prepared composition 3 126Kg, account for component 25.2%, separately remove ionized water 164.5Kg, account for component 32.9%, charcoal
Black 12Kg, accounts for component 2.4%, ultrafine kaolin 90Kg, accounts for component 18%, barium sulfate 90Kg, accounts for component 18%, Dibutyltin oxide
7.5Kg, accounts for component 1.5%, bismuth subcarbonate 10Kg, accounts for component 2%,
Preparation method is as follows:
Above-mentioned raw materials is all ground to fineness≤15 m through sand mill, becomes the face that product B solids content is 57%
Slip.
In the present embodiment:
2. composition 1 preparation method is cooled to 50 DEG C, composition 1 acrylic resin acquired by discharging, the amine of its polymer
Value is 0.95mmolN/g, and the equal relative molecular weight of number is 8500.
Its epoxide equivalent of epoxy resin in raw material components in composition 2 and composition 3 is 188g/eq.
Latex solids content after product A preparation method 3. middle addition deionized water is 35%, and MEQ value is 20, and pH value is 6.
The composition 3 preparation method 5. middle acetic acid that adds is neutralized, and the pH value after it neutralizes is 7.
When the present invention constitutes coating composition, method is as follows:
Feeding by weight
Product A 38.5%
Product B 7.5%
Deionized water 54%
Spendable coating is i.e. constituted after feeding uniformly mixes according to the above ratio.
Embodiment 3: calculating with finished product 1000kg, cathode electrophoretic coating composition is made up of product A and product B, wherein produces
Product A is to prepare composition on the basis of prepared composition 1 and composition 2 again:
1) composition 1, it may be assumed that acrylic resin,
Parts by weight of raw materials percentage is as follows: propylene glycol monomethyl ether 140Kg, accounts for component 14%, ethyl acetate 140Kg, accounts for component
14%, dimethylaminoethyl acrylate methyl ammonia ethyl ester 105Kg, accounts for component 10.5%, hydroxy-ethyl acrylate 180Kg, accounts for component 18%, methyl-prop
E pioic acid methyl ester 180Kg, accounts for component 18%, styrene 60Kg, accounts for component 6%, butyl acrylate 165Kg accounts for component 16.5%, 12
Alkyl hydrosulfide 15Kg, accounts for component 1.5%, azodiisobutyronitrile 15Kg, accounts for component 1.5%,
Preparation method is as follows:
1. by propylene glycol monomethyl ether, ethyl acetate puts into band stirring water knockout drum, the stainless steel cauldron of condenser is stirred,
Being simultaneously heated to 95 DEG C has phegma to produce；2. by dimethylaminoethyl acrylate methyl ammonia ethyl ester, hydroxy-ethyl acrylate, methyl methacrylate
Ester, styrene, butyl acrylate, lauryl mercaptan, azodiisobutyronitrile add in the head tank on reactor top stirring all
Even, temperature of reaction kettle keeps 90～95 DEG C, is added drop-wise in reactor with the time more than 3h by the mixture of head tank, after adding
Insulation 3h treats that resin conversion ratio >=98.5% is lowered the temperature, and discharging is composition 1 acrylic resin,
2) composition 2, it may be assumed that amine-modified epoxy resin
Parts by weight of raw materials percentage is as follows: bisphenol-A 135Kg, accounts for component 13.5%, dodecylphenol 78Kg, accounts for component
7.8%, epoxy resin 447Kg, accounts for component 44.7%, dimethylbenzene meter 105Kg, accounts for component 10.5%, dimethyl benzyl amine 7Kg, account for
Component 0.7%, diethanol amine 45Kg, account for component 4.5%, butyl glycol ether 30Kg, accounts for component 3%, sec-butyl alcohol 108Kg, accounts for component
10.8%, propane diols phenylate 30Kg, accounts for component 3%, dimethylaminopropylamine 15Kg, accounts for component 1.5%,
Preparation method is as follows:
1. the dimethylbenzene of 1/3rd in bisphenol-A, dodecylphenol, epoxy resin and component is put into belt stirrer, divides
Hydrophone, condenser stainless steel cauldron in, be heated to 130 DEG C；2. add dimethyl benzyl amine to carry out being catalyzed to epoxide equivalent
For 1000g/eq；3. add the dimethylbenzene of residue 2/3rds in component to be diluted, be simultaneously introduced diethanol amine and be cooled to 90
DEG C state is incubated 1 hour；4. add butyl glycol ether, after sec-butyl alcohol, propane diols phenylate carry out mixed diluting, add diformazan ammonia
Base propylamine is composition 2 amine-modified epoxy resin after being incubated 2 hours under 90 DEG C of states,
The composition of product A: i.e. epoxy-acrylate emulsion
Parts by weight of raw materials percentage is as follows:
Take above-mentioned prepared composition 1 230Kg, account for component 23%, composition 2 70Kg, account for component 7%, separately take curing agent 145Kg,
Account for component 14.5%, plasticizer 15Kg, account for component 1.5%, defoamer 0.5Kg, account for component 0.05%, levelling agent 0.5Kg, account for component
0.05%, 88% lactic acid 9Kg, accounts for component 0.9%, deionized water 530Kg, accounts for component 53%,
Preparation method is as follows:
1. composition 1, composition 2, curing agent, plasticizer, defoamer, levelling agent are joined band condenser and agitator not
Stirring mixing in rust steel emulsifying kettle；2. add 88% lactic acid to be stirred neutralizing；3., when continuously stirring, formula is added
In deionized water i.e. constitute emulsion；4. above-mentioned emulsion emulsifying kettle hot water jacket is heated to 30～45 DEG C and carries out decompression steaming
Evaporate, when distillate reaches 30% weight portion, still further add the deionized water of above-mentioned total amount 30%, become product A: epoxy
Acrylic emulsion,
In technique scheme, curing agent is the dibutyl amine closure of HDI trimer,
Product B is by preparing after composition 3 preparation again:
Composition 3, i.e.: pigment dispersing resin
Composition of raw materials weight portion percentage is as follows:
Bisphenol-A 73Kg, accounts for component 7.3%, dodecylphenol 42Kg, accounts for component 4.2%, epoxy resin 241Kg, accounts for component
24.1%, dimethylbenzene 14Kg, accounts for component 1.4%, triphenylphosphine 4Kg, accounts for component 0.4%, butyl glycol ether 244Kg, accounts for component
24.4%, polypropylene glycol diglycidyl ether 210Kg, accounts for component 21%, monoethanolamine 19Kg, accounts for component 1.9%, dimethylaminopropylamine
15Kg accounts for component 1.5%, acetic acid 18Kg, accounts for component 1.8%, deionized water 120Kg, accounts for component 12%,
Preparation method is as follows:
1. bisphenol-A, dodecylphenol, epoxy resin, dimethylbenzene are joined belt stirrer, water knockout drum, condenser not
In rust steel reactor, it is heated to 130 DEG C；2. add triphenylphosphine to be catalyzed；3. when catalysis to epoxide equivalent be 700～
During 750g/eq, add butyl glycol ether, polypropylene glycol diglycidyl ether is diluted and lowers the temperature；4. it is down to 70 DEG C when temperature
Time, after addition monoethanolamine is incubated 1 hour under 85 DEG C of states, adds dimethylaminopropylamine and be incubated 2 hours 120 DEG C of states；
5., after above-mentioned reactant being cooled to less than 85 DEG C, add acetic acid and be neutralized；6. add deionized water to be diluted to solid
Content is 60%, becomes composition 3 pigment dispersing resin,
Product B, i.e.: graining paste
Formulation weight part percentage is as follows:
Take above-mentioned prepared composition 3 252Kg, account for component 25.2%, separately remove ionized water 329Kg, account for component 32.9%, carbon black
24Kg, accounts for component 2.4%, ultrafine kaolin 180Kg, accounts for component 18%, barium sulfate 180Kg, accounts for component 18%, Dibutyltin oxide
15Kg, accounts for component 1.5%, bismuth subcarbonate 20Kg, accounts for component 2%,
Preparation method is as follows:
Above-mentioned raw materials is all ground to fineness≤15 m through sand mill, becomes the face that product B solids content is 57%
Slip.
In the present embodiment:
2. composition 1 preparation method is cooled to 50 DEG C, composition 1 acrylic resin acquired by discharging, the amine of its polymer
Value is 0.95mmolN/g, and the equal relative molecular weight of number is 8500.
Its epoxide equivalent of epoxy resin in raw material components in composition 2 and composition 3 is 188g/eq.
Latex solids content after product A preparation method 3. middle addition deionized water is 35%, and MEQ value is 20, and pH value is 6.
The composition 3 preparation method 5. middle acetic acid that adds is neutralized, and the pH value after it neutralizes is 7.
When the present invention constitutes coating composition, method is as follows:
Feeding by weight
Product A 39%
Product B 8%
Deionized water 53%
Spendable coating is i.e. constituted after feeding uniformly mixes according to the above ratio.
Plasticizer involved by inventive formulation, defoamer, levelling agent are existing product on market, the most preferably
For: polypropylene glycols plasticizer, alkynes alcohol defoaming agent, polyoxyethylene phenols levelling agent, but it is not limited to this preferred content, it is respectively provided with
Effect same.
Claims (1)
1. a weather resistant cathode electrophoretic coating composition, it is characterised in that: cathode electrophoretic coating composition is by product A and product
B forms,
The preparation of product A: product A is to prepare composition on the basis of prepared composition 1 and composition 2 again:
1) composition 1, it may be assumed that acrylic resin
Parts by weight of raw materials percentage is as follows:
Propylene glycol monomethyl ether 14%
Ethyl acetate 14%
Dimethylaminoethyl acrylate methyl ammonia ethyl ester 10.5%
Hydroxy-ethyl acrylate 18%
Methyl methacrylate 18%
Styrene 6%
Butyl acrylate 16.5%
Lauryl mercaptan 1.5%
Azodiisobutyronitrile 1.5%
Preparation method is as follows:
1. by propylene glycol monomethyl ether, ethyl acetate puts into band stirring water knockout drum, the stainless steel cauldron of condenser is stirred, simultaneously
Being heated to 95 DEG C has phegma to produce；
2. by dimethylaminoethyl acrylate methyl ammonia ethyl ester, hydroxy-ethyl acrylate, methyl methacrylate, styrene, butyl acrylate, ten
Dialkyl group mercaptan, azodiisobutyronitrile add reactor top head tank in stir, temperature of reaction kettle keep 90～95
DEG C, the mixture of head tank was added drop-wise in reactor with the time more than 3h, after adding be incubated 3h treat resin conversion ratio >=
98.5% cooling, discharging is composition 1 acrylic resin,
2) composition 2, it may be assumed that amine-modified epoxy resin
Parts by weight of raw materials percentage is as follows:
Bisphenol-A 13.5%
Dodecylphenol 7.8%
Epoxy resin 44.7%
Dimethylbenzene 10.5%
Dimethyl benzyl amine 0.7%
Diethanol amine 4.5%
Butyl glycol ether 3%
Sec-butyl alcohol 10.8%
Propane diols phenylate 3%
Dimethylaminopropylamine 1.5%
Preparation method is as follows:
1. the dimethylbenzene of 1/3rd in bisphenol-A, dodecylphenol, epoxy resin and component is put into belt stirrer, water knockout drum,
In the stainless steel cauldron of condenser, it is heated to 130 DEG C；
2. add dimethyl benzyl amine carry out being catalyzed to epoxide equivalent be 1000g/eq；
3. add the dimethylbenzene of remaining 2/3rds in component, be diluted, be simultaneously introduced diethanol amine and be cooled to 90 DEG C of shapes
State is incubated 1 hour；
4. add butyl glycol ether, after sec-butyl alcohol, propane diols phenylate carry out mixed diluting, add
Dimethylaminopropylamine is composition 2 amine-modified epoxy resin after being incubated 2 hours under 90 DEG C of states,
The composition of product A: i.e. epoxy-acrylate emulsion
Parts by weight of raw materials percentage is as follows:
Composition 1 15～24%
Composition 2 6～15%
Curing agent 14.5%
Plasticizer 1.5%
Defoamer 0.05%
Levelling agent 0.05%
88% lactic acid 0.9%
Deionized water 53%
Preparation method is as follows:
1. composition 1, composition 2, curing agent, plasticizer, defoamer, levelling agent are joined the stainless steel of band condenser and agitator
Stirring mixing in emulsifying kettle；
2. add 88% lactic acid to be stirred neutralizing；
3., when continuously stirring, the deionized water added in formula i.e. constitutes emulsion；
4. above-mentioned emulsion emulsifying kettle hot water jacket be heated to 30～45 DEG C carry out decompression distillation, when distillate reaches 30% weight
During part, still further add the deionized water of above-mentioned total amount 30%, become product A: epoxy-acrylate emulsion,
Described curing agent is the dibutyl amine closure of HDI trimer,
The preparation of product B:
Product B is by preparing after composition 3 preparation again:
Composition 3, i.e.: pigment dispersing resin
Composition of raw materials weight portion percentage is as follows:
Bisphenol-A 7.3%
Dodecylphenol 4.2%
Epoxy resin 24.1%
Dimethylbenzene 1.4%
Triphenylphosphine 0.4%
Butyl glycol ether 24.4%
Polypropylene glycol diglycidyl ether 21%
Monoethanolamine 1.9%
Dimethylaminopropylamine 1.5%
Acetic acid 1.8%
Deionized water 12%
Preparation method is as follows:
1. bisphenol-A, dodecylphenol, epoxy resin, dimethylbenzene are joined the stainless steel of belt stirrer, water knockout drum, condenser
In reactor, it is heated to 130 DEG C；
2. add triphenylphosphine to be catalyzed；
3. be catalyzed to epoxide equivalent be 700～750g/eq time, add butyl glycol ether, polypropylene glycol diglycidyl ether and carry out
Dilute and lower the temperature；
4., when temperature is down to 70 DEG C, after addition monoethanolamine is incubated 1 hour under 85 DEG C of states, adds dimethylaminopropylamine and exist
120 DEG C of states are incubated 2 hours；
After the most above-mentioned reactant is cooled to less than 85 DEG C, adds acetic acid and be neutralized；
6. add deionized water to be diluted to solids content being 60%, become composition 3 pigment dispersing resin,
Product B, i.e.: graining paste
Formulation weight part percentage is as follows:
Composition 3 25.2%
Deionized water 32.9%
Carbon black 2.4%
Ultrafine kaolin 18%
Barium sulfate 18%
Dibutyltin oxide 1.5%
Bismuth subcarbonate 2%
Preparation method is as follows:
Above-mentioned raw materials is all ground to fineness≤15 m through sand mill, becomes the pigment that product B solids content is 57%
Slurry,
2. composition 1 preparation method is cooled to 50 DEG C, and composition 1 acrylic resin acquired by discharging, the amine value of its polymer is
0.95mmolN/g, the equal relative molecular weight of number is 8500,
Its epoxide equivalent of epoxy resin in raw material components in composition 2 and composition 3 is 188g/eq,
Latex solids content after product A preparation method 3. middle addition deionized water is 35%, and MEQ value is 20, and pH value is 6,
The composition 3 preparation method 5. middle acetic acid that adds is neutralized, and the pH value after it neutralizes is 7,
Weather resistant cathode electrophoretic coating composition, using method is as follows:
Feeding by weight percentage
Product A 38～39%
Product B 7～8%
Deionized water 53～55%.
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| CN201310398181.3A CN103436153B (en) | 2012-09-06 | 2013-09-05 | Weather resistant cathode electrophoretic coating composition |
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| CN2012103258849A CN102850892A (en) | 2012-09-06 | 2012-09-06 | Weathering resistance type cathode electrophoresis coating material composition |
| CN2012103258849 | 2012-09-06 | ||
| CN201310398181.3A CN103436153B (en) | 2012-09-06 | 2013-09-05 | Weather resistant cathode electrophoretic coating composition |
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| CN103694751A (en) * | 2013-10-28 | 2014-04-02 | 安徽明都电气有限公司 | Instrument cabinet paint with good heat dissipation and preparation method thereof |
| CN104231827A (en) * | 2014-09-19 | 2014-12-24 | 苏州云舒新材料科技有限公司 | Anticorrosive coating for household appliances and preparation method thereof |
| CN108359348A (en) * | 2016-08-07 | 2018-08-03 | 南安市品龙新材料科技有限公司 | A kind of diethanol amine modified epoxy resin emulsion, preparation method and applications |
| WO2018124246A1 (en) * | 2016-12-28 | 2018-07-05 | 花王株式会社 | Aqueous pigment dispersion |
| CN106995524B (en) * | 2017-04-12 | 2018-11-30 | 湖南省达琪新材料有限公司 | Polynary auxiliary curing agent and its application in terms of polynary cured epoxy resin |
| CN109054571B (en) * | 2018-07-19 | 2021-01-12 | 浩力森化学科技（江苏）有限公司 | Preparation of fluorine-containing organic silicon modified anti-doodling coating |
| CN109127962A (en) * | 2018-09-12 | 2019-01-04 | 佛山市南海区大沥永太五金丝网制品有限公司 | A kind of steel wire electrophoresis formula of liquid and process flow |
| CN109735204A (en) * | 2018-12-28 | 2019-05-10 | 武汉科利尔新材料有限公司 | The cathodic acrylic epoxy electrophoretic coating and preparation method of a kind of high glaze and high plumpness |
| CN110117339A (en) * | 2019-06-13 | 2019-08-13 | 深圳市志邦科技有限公司 | A kind of ability cathode electrophoresis coating resins of high salt spray resistance and preparation method thereof |
| CN110330854A (en) * | 2019-08-14 | 2019-10-15 | 程浩源 | A kind of acrylic resin modified car paint of water-dispersion type and preparation method thereof |
| CN110903690B (en) * | 2019-11-26 | 2021-08-24 | 深圳市长丰环保新材料有限公司 | Cathode electrophoretic coating and preparation method thereof |
| CN111019441B (en) * | 2019-12-24 | 2022-05-20 | 湖北同邦达科技有限公司 | Color paste for cathode electrophoretic paint and preparation method thereof |
| CN112094574A (en) * | 2020-09-23 | 2020-12-18 | 湖北天鹅科技有限公司 | Production process of weather-resistant color cathode electrophoretic paint |
| CN112280438A (en) * | 2020-11-21 | 2021-01-29 | 浙江铭孚金属涂装科技有限公司 | Curable cathodic electrodeposition coating exhibiting weather and corrosion resistance |
| CN112409878A (en) * | 2020-12-01 | 2021-02-26 | 武汉双虎涂料有限公司 | Primer-topcoat integrated electrophoretic paint and preparation method thereof |
| CN114891412B (en) * | 2021-06-25 | 2024-01-12 | 江苏御镐智能制造有限公司 | Breakdown-resistant electrophoretic paint and application thereof |
| CN116836609A (en) * | 2023-06-16 | 2023-10-03 | 浩力森化学科技（江苏）有限公司 | High-hardness electrophoretic paint and preparation method thereof |
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