CN110511660A - Sulfur-bearing color inhibition acrylic cathodic electrophoretic coating - Google Patents
Sulfur-bearing color inhibition acrylic cathodic electrophoretic coating Download PDFInfo
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- CN110511660A CN110511660A CN201910874698.2A CN201910874698A CN110511660A CN 110511660 A CN110511660 A CN 110511660A CN 201910874698 A CN201910874698 A CN 201910874698A CN 110511660 A CN110511660 A CN 110511660A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
- C09D5/4407—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 by polymerisation reactions involving only carbon-to-carbon unsaturated bonds
- C09D5/4411—Homopolymers or copolymers of acrylates or methacrylates
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
- C09D5/4476—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications comprising polymerisation in situ
-
- 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
- C09D5/4488—Cathodic paints
- C09D5/4496—Cathodic paints characterised by the nature of the curing agents
Abstract
The invention belongs to cathode electrophoresis dopes, more particularly to sulfur-bearing color inhibition acrylic cathodic electrophoretic coating, the raw material for preparing of the sulfur-bearing color inhibition acrylic resin includes 10-21 part by weight of n-butanol, 14-22 parts by weight ethylene glycol monobutyl ether, 6-9 weight parts of methacrylic acid ethylene oxidic ester, 8-12 weight parts of methacrylic acid hydroxypropyl acrylate, 12-14 parts by weight of methylmethacrylate, 6-8 parts by weight of styrene, the 14-17 weight parts of methacrylic acid tert-butyl ester, the thio glycol of 4.5-7 parts by weight low molecular weight, 3-5 parts by weight benzoyl peroxide and 3.5-4 parts by weight dihydromethyl propionic acid, the raw material for preparing of the color inhibition blocked isocyanate curing agent includes 17-22 parts by weight methyl iso-butyl ketone (MIBK), 37-43 parts by weight isophorone diisocyanate, 2 9-33 parts by weight methyl ethyl ketoxime and 7-12 part by weight of n-butanol.Product of the present invention yellowing resistance tests 220 DEG C of high temperature bakings 10 hours or more non yellowings.
Description
Technical field
The invention belongs to cathode electrophoresis dopes, and in particular to sulfur-bearing color inhibition acrylic cathodic electrophoretic coating.
Background technique
After decades of development, develop to cathode electrophoresis dope via initial anode electrophoresis dope is electrophoretic coating
Main, because anodic electrophoretic coating technique has the shortcomings that dissolution anode (i.e. coated object), and electrophoretic coating is in order to meet not
Same application field starts the incrustation effect for taking into account material, and the high color inhibition acrylic cathodic electrophoretic coating of sulfur-bearing has
Good guarantor's color, gloss retention, good weatherability and high yellowing resistance, and monomeric species are more and source is very wide, largely answered
Coating for handwares such as 3C industry and household electrical appliances.Cathode electrophoresis dope yellowing resistance difference on the market is on 180 DEG C of left sides now
Right baking just will appear xanthochromia and be difficult to apply in industries such as oily tincture, radiators, and anode product have certain yellowing resistance but
Its chemical resistance and throwing power are poor.So be badly in need of develop it is a have higher yellowing resistance acrylic cathodic electrophoretic coating,
To further expand its application field.
Summary of the invention
The purpose of the present invention is to provide a kind of sulfur-bearing color inhibition acrylic cathodic electrophoretic coatings.
The sulfur-bearing color inhibition acrylic cathodic electrophoretic coating includes the high color inhibition acrylic resin of sulfur-bearing and color inhibition closing
Isocyanate curing agent, wherein
The raw material for preparing of the sulfur-bearing color inhibition acrylic resin includes 10-21 part by weight of n-butanol, 14-22 parts by weight
Ethylene glycol monobutyl ether, 6-9 weight parts of methacrylic acid ethylene oxidic ester, 8-12 weight parts of methacrylic acid hydroxypropyl acrylate, 12-14 weight
Amount part methyl methacrylate, 6-8 parts by weight of styrene, the 14-17 weight parts of methacrylic acid tert-butyl ester, 4.5-7 parts by weight are low
The thio glycol of molecular weight, 3-5 parts by weight benzoyl peroxide and 3.5-4 parts by weight dihydromethyl propionic acid,
The raw material for preparing of the color inhibition blocked isocyanate curing agent includes 17-22 parts by weight methyl iso-butyl ketone (MIBK),
37-43 parts by weight isophorone diisocyanate, 29-33 parts by weight methyl ethyl ketoxime and 7-12 part by weight of n-butanol.
Above-mentioned formula has the advantage that 1, film forms more crosslinking points, passes through the hydroxy propyl methacrylate of higher amount
In hydroxyl and the isocyanate group crosslinking curing that unlocks of color inhibition blocked isocyanate curing agent improve the entirety of coating
Performance；2, the thio glycol of low molecular weight is introduced also while optimizing monomeric species and proportion to replace organic amine to be vulcanized
Then neutralize using dihydromethyl propionic acid that achieve the purpose that resin water-soluble.
Above-mentioned cathode electrophoresis dope also has following prioritization scheme:
The high color inhibition acrylic resin of sulfur-bearing described in every 30~35 parts by weight adds resistance to Huang described in 10-14 parts by weight
Become blocked isocyanate curing agent.
It further include levelling agent in sulfur-bearing color inhibition acrylic cathodic electrophoretic coating.
It further include mill base, color inhibition acrylic resin: mill base weight ratio in sulfur-bearing color inhibition acrylic cathodic electrophoretic coating
For 6:1.Further, the raw material for preparing of the mill base includes 15-18 parts by weight of acrylic acid grind resin, 1-2 parts by weight table
Face activating agent and 42-50 parts by weight of deionized water, 34-38 parts by weight pigments and fillers.
The thio glycol of the low molecular weight preferably uses commercially available YL-001.
There is product of the present invention good Stability of Bath Solution, excellent in mechanical performance, non yellowing, high-wearing feature to go with artificial perspiration resistance
Advantage, especially yellowing resistance test 220 DEG C of high temperature bakings 10 hours or more non yellowings.
Specific embodiment
The principles and features of the present invention are described below, and the given examples are served only to explain the present invention, is not intended to limit
Determine the scope of the present invention.
Embodiment 1
1) the high color inhibition acrylic resin formula of sulfur-bearing:
By formula ratio by glycidyl methacrylate, hydroxy propyl methacrylate, methyl methacrylate, benzene second
Alkene, Tert-butyl Methacrylate, YL-001 (the thio glycol of low molecular weight), benzoyl peroxide are uniformly mixed for use, referred to as
Mixed liquor 1；The benzoyl peroxide of formula ratio and methyl iso-butyl ketone (MIBK) are uniformly mixed for use, referred to as mixed liquor 2.By formula ratio
N-butanol and ethylene glycol monobutyl ether are added in the reaction vessel with blender and condenser pipe, logical nitrogen is warming up to 100-110
DEG C, start that mixed liquor 1 is added dropwise, keep the temperature 1 hour after dripping off within 3-3.5 hours, mixed liquor 2 is then added dropwise, half an hour drips off, and then protects
Temperature 1 hour, then heat preservation 3 hours is added in dihydromethyl propionic acid, 45 DEG C are cooled to bottom discharge, obtain the sulfur-bearing Gao Naihuang
Become acrylic resin.
2) the color inhibition blocked isocyanate curing agent formula:
Methyl iso-butyl ketone (MIBK) and isophorone diisocyanate be added by formula ratio anti-with blender and condenser pipe
It answers in container, logical nitrogen is warming up to 70 DEG C, and methyl ethyl ketoxime is added dropwise, drips off within 1 hour, and after heat preservation 2 hours, n-butanol is added, continues
Heat preservation 1 hour, cools to 45 DEG C with bottom discharge, obtains the color inhibition blocked isocyanate curing agent.
3) formulation for coating material
Reaction is added in the high color inhibition acrylic resin of sulfur-bearing and color inhibition blocked isocyanate curing agent by formula ratio to hold
It stirs 1 hour and is uniformly mixed in device, then deionized water is added at one time reaction vessel high speed and is stirred 1 hour, be then added
Aqueous levelling agent stirs 30 minutes, and whole preparation process reaction vessel temperature is controlled at 45 DEG C or less.Gone out using filter screen filtration
Material obtains the high color inhibition acrylic cathodic electrophoretic coating of sulfur-bearing.
4) the color inhibition paste formula
Acrylic grinding resin, surfactant and deionized water are added in grinding pot by formula ratio and stirred evenly, In
Color pigment iron oxide red PR-101, phthalocyanine blue PB-15 and face are slowly added in the case where having zirconium pearl, logical condensed water in grinding pot
Material is yellow, and high speed is sanded 2 hours, until fineness≤15 μm, obtain the color inhibition colour mill base.
Embodiment 2
1) the high color inhibition acrylic resin formula of sulfur-bearing:
By formula ratio by glycidyl methacrylate, hydroxy propyl methacrylate, methyl methacrylate, benzene second
Alkene, Tert-butyl Methacrylate, YL-001 (the thio glycol of low molecular weight), benzoyl peroxide are uniformly mixed for use, referred to as
Mixed liquor 1；The benzoyl peroxide of formula ratio and methyl iso-butyl ketone (MIBK) are uniformly mixed for use, referred to as mixed liquor 2.By formula ratio
N-butanol and ethylene glycol monobutyl ether are added in the reaction vessel with blender and condenser pipe, logical nitrogen is warming up to 100-110
DEG C, start that mixed liquor 1 is added dropwise, keep the temperature 1 hour after dripping off within 3-3.5 hours, mixed liquor 2 is then added dropwise, half an hour drips off, and then protects
Temperature 1 hour, then heat preservation 3 hours is added in dihydromethyl propionic acid, 45 DEG C are cooled to bottom discharge, obtain the sulfur-bearing Gao Naihuang
Become acrylic resin.
2) the color inhibition blocked isocyanate curing agent formula:
Methyl iso-butyl ketone (MIBK) and isophorone diisocyanate be added by formula ratio anti-with blender and condenser pipe
It answers in container, logical nitrogen is warming up to 80 DEG C, and methyl ethyl ketoxime is added dropwise, drips off within 1 hour, and after heat preservation 2 hours, n-butanol is added, continues
Heat preservation 1 hour, cools to 45 DEG C with bottom discharge, obtains the color inhibition blocked isocyanate curing agent.
3) formulation for coating material
Reaction is added in the high color inhibition acrylic resin of sulfur-bearing and color inhibition blocked isocyanate curing agent by formula ratio to hold
It stirs 1 hour and is uniformly mixed in device, then deionized water is added at one time reaction vessel high speed and is stirred 1 hour, be then added
Aqueous levelling agent stirs 30 minutes, and whole preparation process reaction vessel temperature is controlled at 45 DEG C or less.Gone out using filter screen filtration
Material obtains the high color inhibition acrylic cathodic electrophoretic coating of sulfur-bearing.
4) the color inhibition paste formula
Acrylic grinding resin, surfactant and deionized water are added in grinding pot by formula ratio and stirred evenly, In
It is slowly added to titanium dioxide in the case where having zirconium pearl, logical condensed water in grinding pot, high speed is sanded 2 hours, until fineness≤15 μm, obtain
The color inhibition white colorant.
Embodiment 3
1) the high color inhibition acrylic resin formula of sulfur-bearing:
By formula ratio by glycidyl methacrylate, hydroxy propyl methacrylate, methyl methacrylate, benzene second
Alkene, Tert-butyl Methacrylate, YL-001 (the thio glycol of low molecular weight), benzoyl peroxide are uniformly mixed for use, referred to as
Mixed liquor 1；The benzoyl peroxide of formula ratio and methyl iso-butyl ketone (MIBK) are uniformly mixed for use, referred to as mixed liquor 2.By formula ratio
N-butanol and ethylene glycol monobutyl ether are added in the reaction vessel with blender and condenser pipe, logical nitrogen is warming up to 100-110
DEG C, start that mixed liquor 1 is added dropwise, keep the temperature 1 hour after dripping off within 3-3.5 hours, mixed liquor 2 is then added dropwise, half an hour drips off, and then protects
Temperature 1 hour, then heat preservation 3 hours is added in dihydromethyl propionic acid, 45 DEG C are cooled to bottom discharge, obtain the sulfur-bearing Gao Naihuang
Become acrylic resin.
2) the color inhibition blocked isocyanate curing agent formula:
Methyl iso-butyl ketone (MIBK) and isophorone diisocyanate be added by formula ratio anti-with blender and condenser pipe
It answers in container, logical nitrogen is warming up to 75 DEG C, and methyl ethyl ketoxime is added dropwise, drips off within 1 hour, and after heat preservation 2 hours, n-butanol is added, continues
Heat preservation 1 hour, cools to 45 DEG C with bottom discharge, obtains the color inhibition blocked isocyanate curing agent.
3) formulation for coating material
Reaction is added in the high color inhibition acrylic resin of sulfur-bearing and color inhibition blocked isocyanate curing agent by formula ratio to hold
It stirs 1 hour and is uniformly mixed in device, then deionized water is added at one time reaction vessel high speed and is stirred 1 hour, be then added
Aqueous levelling agent stirs 30 minutes, and whole preparation process reaction vessel temperature is controlled at 45 DEG C or less.Gone out using filter screen filtration
Material obtains the high color inhibition acrylic cathodic electrophoretic coating of sulfur-bearing.
4) the color inhibition paste formula
Acrylic grinding resin, surfactant and deionized water are added in grinding pot by formula ratio and stirred evenly, In
It is slowly added to carbon black, kaolin and titanium dioxide in the case where having zirconium pearl, logical condensed water in grinding pot, high speed is sanded 2 hours, until thin
≤ 15 μm of degree obtains the color inhibition grey mill base.
By the high color inhibition acrylic cathodic electrophoretic coating of sulfur-bearing made from above-described embodiment 1-3 and color inhibition mill base with 6:1
Ratio, be made into solid part be 10%-12% electrophoresis groove liquid, cured in electrophoresis tank for 24 hours, in electrophoretic voltage 150V, tank liquor
30 DEG C of temperature, electrophoresis time prepares template under conditions of being 30s, and solidification temperature is 160 DEG C/20min.
The high color inhibition acrylic cathodic electrophoretic coating of sulfur-bearing made from embodiment 1-3 prepares the key technical indexes of template such as
Following table
Thus the acrylic cathodic electrophoretic coating of transparent high abrasion produced by the present invention has that Stability of Bath Solution is good, mechanical property
Can excellent, non yellowing, high-wearing feature the advantages that going with artificial perspiration resistance, especially it is small to test 220 DEG C of high temperature bakings 10 for yellowing resistance
When above non yellowing.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (6)
1. a kind of sulfur-bearing color inhibition acrylic cathodic electrophoretic coating, it is characterised in that including the high color inhibition acrylic resin of sulfur-bearing and
Color inhibition blocked isocyanate curing agent, wherein
The raw material for preparing of the sulfur-bearing color inhibition acrylic resin includes 10-21 part by weight of n-butanol, 14-22 parts by weight second two
Alcohol monobutyl ether, 6-9 weight parts of methacrylic acid ethylene oxidic ester, 8-12 weight parts of methacrylic acid hydroxypropyl acrylate, 12-14 parts by weight
Methyl methacrylate, 6-8 parts by weight of styrene, the 14-17 weight parts of methacrylic acid tert-butyl ester, 4.5-7 parts by weight low molecule
The thio glycol of amount, 3-5 parts by weight benzoyl peroxide and 3.5-4 parts by weight dihydromethyl propionic acid,
The raw material for preparing of the color inhibition blocked isocyanate curing agent includes 17-22 parts by weight methyl iso-butyl ketone (MIBK), 37-43
Parts by weight isophorone diisocyanate, 29-33 parts by weight methyl ethyl ketoxime and 7-12 part by weight of n-butanol.
2. sulfur-bearing color inhibition acrylic cathodic electrophoretic coating as described in claim 1, it is characterised in that every 30 ~ 35 parts by weight institute
The high color inhibition acrylic resin of the sulfur-bearing stated adds color inhibition blocked isocyanate curing agent described in 10-14 parts by weight.
3. sulfur-bearing color inhibition acrylic cathodic electrophoretic coating as described in claim 1, it is characterised in that further include levelling agent.
4. sulfur-bearing color inhibition acrylic cathodic electrophoretic coating as described in claim 1, it is characterised in that it further include mill base, resistance to Huang
Become acrylic resin: mill base weight ratio is 6:1.
5. sulfur-bearing color inhibition acrylic cathodic electrophoretic coating as claimed in claim 4, it is characterised in that the system of the mill base
Standby raw material include 15-18 parts by weight of acrylic acid grind resin, 1-2 parts surfactant and 42-50 parts by weight of deionized water,
34-38 parts by weight pigments and fillers.
6. sulfur-bearing color inhibition acrylic cathodic electrophoretic coating as described in claim 1, it is characterised in that the low molecular weight
Thio glycol uses commercially available YL-001.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910874698.2A CN110511660A (en) | 2019-09-17 | 2019-09-17 | Sulfur-bearing color inhibition acrylic cathodic electrophoretic coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910874698.2A CN110511660A (en) | 2019-09-17 | 2019-09-17 | Sulfur-bearing color inhibition acrylic cathodic electrophoretic coating |
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| CN110511660A true CN110511660A (en) | 2019-11-29 |
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| CN201910874698.2A Pending CN110511660A (en) | 2019-09-17 | 2019-09-17 | Sulfur-bearing color inhibition acrylic cathodic electrophoretic coating |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103289553A (en) * | 2013-06-24 | 2013-09-11 | 浩力森涂料（上海）有限公司 | Transparent high wear-resistant acrylic acid cathode electrophoretic paint and preparation method thereof |
| CN103289498B (en) * | 2013-06-24 | 2015-11-04 | 浩力森涂料（上海）有限公司 | A kind of Multipurpose high weather resistant acrylic acid electrophoretic paint and preparation method thereof |
| CN106118409A (en) * | 2016-06-22 | 2016-11-16 | 广德瑞邦涂料有限公司 | A kind of color inhibition cathode electrophoresis dope |
| CN108102504A (en) * | 2017-11-20 | 2018-06-01 | 盐城安诺电泳涂料科技有限公司 | A kind of cathode electrophoresis dope for improving automobile sealant xanthochromia and preparation method and application |
-
2019
- 2019-09-17 CN CN201910874698.2A patent/CN110511660A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103289553A (en) * | 2013-06-24 | 2013-09-11 | 浩力森涂料（上海）有限公司 | Transparent high wear-resistant acrylic acid cathode electrophoretic paint and preparation method thereof |
| CN103289498B (en) * | 2013-06-24 | 2015-11-04 | 浩力森涂料（上海）有限公司 | A kind of Multipurpose high weather resistant acrylic acid electrophoretic paint and preparation method thereof |
| CN106118409A (en) * | 2016-06-22 | 2016-11-16 | 广德瑞邦涂料有限公司 | A kind of color inhibition cathode electrophoresis dope |
| CN108102504A (en) * | 2017-11-20 | 2018-06-01 | 盐城安诺电泳涂料科技有限公司 | A kind of cathode electrophoresis dope for improving automobile sealant xanthochromia and preparation method and application |
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