CN106243311A - A kind of aqueous epoxy resin emulsion and preparation method thereof, cathode electrophoresis dope - Google Patents
A kind of aqueous epoxy resin emulsion and preparation method thereof, cathode electrophoresis dope Download PDFInfo
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- CN106243311A CN106243311A CN201610628604.XA CN201610628604A CN106243311A CN 106243311 A CN106243311 A CN 106243311A CN 201610628604 A CN201610628604 A CN 201610628604A CN 106243311 A CN106243311 A CN 106243311A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/58—Epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/61—Polysiloxanes
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6275—Polymers of halogen containing compounds having carbon-to-carbon double bonds; halogenated polymers of compounds having carbon-to-carbon double bonds
- C08G18/6279—Polymers of halogen containing compounds having carbon-to-carbon double bonds; halogenated polymers of compounds having carbon-to-carbon double bonds containing fluorine atoms
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/6505—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6511—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38 compounds of group C08G18/3203
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/08—Polyurethanes from polyethers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
- C09D5/4419—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained otherwise than by polymerisation reactions only involving carbon-to-carbon unsaturated bonds
- C09D5/4465—Polyurethanes
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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
- C09D5/4488—Cathodic paints
Abstract
The invention discloses a kind of aqueous epoxy resin emulsion, make including following raw materials: 5 10% epoxy resin；5 10% diisocyanate；2 8% polyether polyol；0.5 2% dibutyl tin laurate；2 8% cyclohexanedimethanols；1 2% propylene glycol methyl ether acetate；2 4% triethylamines；1 3% benzene sulfonic acid sodium salt；5 10% butanone；1 3% terminal hydroxyl organic silicon modified by polyether or the fluorine-containing organic polymer of terminal hydroxyl；50 60% deionized waters.The present invention uses organosilicon and fluorine-containing organic polymer modified epoxy, is keeping the performance of original coating excellence simultaneously, is reducing the surface tension of this type of coating, stable performance, apply more extensive.Additionally, the preparation method that the invention also discloses above-mentioned aqueous epoxy resin emulsion and the cathode electrophoresis dope using aqueous epoxy resin emulsion to prepare.
Description
Technical field
The present invention relates to paint field, particularly relate to a kind of aqueous epoxy resins breast preparing low interfacial tension coating
Liquid；The invention still further relates to the preparation method of described aqueous epoxy resin emulsion；The invention still further relates to the moon of a kind of low interfacial tension
Pole electrophoretic coating.
Background technology
Epoxy resin has excellent process based prediction model after solidifying because of it, is widely used in the fields such as coating.Wherein
Aqueous epoxy resins, not only has the premium properties of epoxy resin, has environmental protection simultaneously, is prone to construction application, with water as medium
The advantage such as cheap, is widely used in the field such as aqueous and electrophoretic coating.But, existing property of water-bearing epoxy resin latex system
Standby cathode electrophoresis dope uses highly polar resin and using high capillary solvent as dispersion, the easy bubble of system,
And ground moistening difficulty, film forming procedure is susceptible to such as the defects such as shrinkage cavity, impression, sagging, loose colour, affects film effect.This
Outward, owing to existing coating has high surface tension, if being used for such as the metal surface such as smoke exhaust ventilator, electromotor, it is easily adhered food
The oiliness impurity such as oil, machine oil, affect the cleaning of paint film and affect paint film property further.
In order to solve the above-mentioned technical problem of this type of cathode electrophoresis dope existing, present way is at cathode electrophoresis dope
In add containing the levelling agent of organosilicon, such as Chinese patent CN103214895B organosilicon coating levelling agent and preparation method thereof,
Prepared with olefin(e) compound polyreaction by polysiloxanes, but levelling agent adding as a kind of auxiliary agent, only miscellaneous function
Add agent, add in the middle of coating, be to be present in as a mixture in the middle of coating or paint film.Add the auxiliary agent of class, changing
While kind paint film a certain item performance, another kind of film defect may be brought.As levelling agent can reduce surface tension, simultaneously can
Can cause the paint marketing such as shrinkage cavity, pinprick, it is also possible to cause the problems such as coating compatibility variation, storage stability variation；
Additionally, interpolation analog assistant, it is to exist as a mixture in the middle of coating or paint film, there is precipitation, disperse unequal problem.
To this end, need a kind of new cathode electrophoresis dope of offer badly both can reduce surface tension, the every of coating also can be made
Property retention is stable, meets industry standard.
Summary of the invention
The technical problem to be solved is, it is provided that a kind of aqueous epoxy resin emulsion and preparation method thereof, can
Produce the coating of low surface tension, increase the antifouling capacity of film.
The technical problem to be solved also resides in, it is provided that a kind of cathode electrophoresis dope, it is possible to decrease the surface of coating
Tension force, increases the antifouling capacity of film.
In order to solve above-mentioned technical problem, the invention provides a kind of aqueous epoxy resin emulsion, including following by weight
The raw material of percentage ratio is made:
Epoxy resin 5-10%；
Diisocyanate 5-10%；
Polyether polyol 2-8%；
Dibutyl tin laurate 0.5-2%；
Cyclohexanedimethanol 2-8%；
Propylene glycol methyl ether acetate 1-2%；
Triethylamine 2-4%；
Benzene sulfonic acid sodium salt 1-3%；
Butanone 5-10%；
Terminal hydroxyl organic silicon modified by polyether or terminal hydroxyl fluorine-containing organic polymer 1-3%；
Deionized water 50-60%.
As the improvement of described aqueous epoxy resin emulsion, the relative molecular mass of described polyether polyol is 2000-
4000。
As the improvement of described aqueous epoxy resin emulsion, mass content 30-of described aqueous epoxy resin emulsion solid
33%。
As the improvement of described aqueous epoxy resin emulsion, described terminal hydroxyl organic silicon modified by polyether uses γ-ammonia third
Ethyl triethoxy silicane alkane prepares as raw material.
As the improvement of described aqueous epoxy resin emulsion, the fluorine-containing organic polymer of terminal hydroxyl is by ethoxy pi-allyl
Ether, vinyl acetate and CTFE reaction prepare.
Correspondingly, the present invention also provides for the preparation method of a kind of aqueous epoxy resin emulsion, comprises the following steps:
(1) in reaction vessel, epoxy resin, diisocyanate, polyether polyol and propylene glycol methyl ether acetate are added, 100
DEG C ~ 120 DEG C under conditions of reaction backflow 2 hours；
(2) after being cooled to 60 DEG C, adding dibutyl tin laurate and butanone, under conditions of 60 DEG C ~ 80 DEG C, reaction backflow 2 is little
Time；
(3) it is cooled to 60 DEG C, adds terminal hydroxyl organic silicon modified by polyether or the fluorine-containing organic polymer of terminal hydroxyl, hexamethylene two
Methanol, butanone, reaction backflow 4 hours under conditions of 80 DEG C ~ 85 DEG C；
(4) when isocyano-content is less than 0.5%, it is cooled to 50 DEG C ~ 55 DEG C, is slowly added dropwise triethylamine under stirring condition and is incubated 1
Hour；
(5) by benzene sulfonic acid sodium salt and after, add deionized water and carry out emulsifying, be warming up to 65 DEG C ~ 80 DEG C, vacuum pumps solvent 4
Hour.
As the improvement of described aqueous epoxy resin emulsion preparation method, the relative molecular mass of described polyether polyol is
2000-4000。
As the improvement of described aqueous epoxy resin emulsion preparation method, the quality of described aqueous epoxy resin emulsion solid
Content 30-33%.
Correspondingly, the present invention also provides for a kind of cathode electrophoresis dope, including aqueous epoxy resins as claimed in claim 1 breast
Liquid, mill base and deionized water, be mixed into tank liquor by mill base, described aqueous epoxy resin emulsion, deionized water by 1:3:4 mass ratio
Rear stirring, places 24h at 25 DEG C and uses cathode electrophoresis equipment to make coating.
As the improvement of described cathode electrophoresis dope, described mill base solid content is 55%, mill base fineness≤15 μm.
Implement the embodiment of the present invention, have the advantages that
The present invention uses terminal hydroxyl organic silicon modified by polyether or the fluorine-containing organic polymer of terminal hydroxyl to change epoxy resin
Property, make the chemical bond of resin formation C-Si, O-Si and C-F, thus reduce in the case of keeping existing film excellent properties
Coating and the surface tension of film.The present invention not only avoids the coating of existing interpolation auxiliary agent to disperse uneven, the feelings of poor stability
Condition, and it reduces the capillary better of film, makes the liquid such as food oil, machine oil that surface tension is bigger the most easy to stick
Being attached on film, keep the relatively clean of film coated surface, range of application is wider.
Detailed description of the invention
For making the object, technical solutions and advantages of the present invention clearer, make to retouch the most in detail to the present invention below
State.
Existing coating is owing to using highly polar resin and using high capillary solvent as dispersion so that prepare
Coating there is high surface tension, be unfavorable for the performance of coating film forming and film.And prior art is by adding in coating
Levelling agent, to reduce the surface tension of coating, but levelling agent is poor with the compatibility of coating, easily causes precipitation, and dispersion is not
All, the problem such as storage stability is the best.Therefore the present invention changes the capillary mode of existing reduction coating, no longer adds such as
The auxiliary agent of levelling agent, but by introducing organosilicon and fluorine-containing functional group, organosilicon and fluorine-containing official in emulsion polymer
Can group be presented in chemical bond on aqueous epoxy resins, become the part in aqueous epoxy resins molecule, shape
The chemical bond energy of C-Si, O-Si and C-F of becoming greatly reduces the surface tension of coating, is also avoided that existing interpolation auxiliary agent simultaneously
Problem.
The invention provides a kind of aqueous epoxy resin emulsion, make including following raw materials:
Epoxy resin 5-10%；
Diisocyanate 5-10%；
Polyether polyol 2-8%；
Dibutyl tin laurate 0.5-2%；
Cyclohexanedimethanol 2-8%；
Propylene glycol methyl ether acetate 1-2%；
Triethylamine 2-4%；
Benzene sulfonic acid sodium salt 1-3%；
Butanone 5-10%；
Terminal hydroxyl organic silicon modified by polyether or terminal hydroxyl fluorine-containing organic polymer 1-3%；
Deionized water 50-60%.
It should be noted that the present invention uses terminal hydroxyl organic silicon modified by polyether to be modified epoxy resin, described
Terminal hydroxyl organic silicon modified by polyether is connected with epoxy resin by terminal hydroxyl so that modified epoxy resin forms C-Si
With the chemical bond of O-Si, after coating is made in this modified epoxy emulsifying, it is possible to decrease the surface tension of coating.Specifically can be according to bag
Include the raw material of following percentage by weight and make organic silicon modified aqueous epoxy resin:
Epoxy resin 5-10%；
Diisocyanate 5-10%；
Polyether polyol 2-8%；
Dibutyl tin laurate 0.5-2%；
Cyclohexanedimethanol 2-8%；
Propylene glycol methyl ether acetate 1-2%；
Triethylamine 2-4%；
Benzene sulfonic acid sodium salt 1-3%；
Butanone 5-10%；
Terminal hydroxyl organic silicon modified by polyether 1-1.5%；
Deionized water 56-58%.
Wherein, resin emulsion solids content 30-33%(records after 120 DEG C of baking 2h), epoxy resin content is 6-
8%, organic silicon modified by polyether about 1%-2%.
Similarly, the fluorine-containing organic polymer of terminal hydroxyl of the present invention is again by terminal hydroxyl with epoxy resin even
Connecing, modified epoxy resin defines the chemical bond of C-F, it is possible to reduce the surface tension of coating.Specifically can be following according to including
Fluorine-containing modified aqueous epoxy resin made by the raw material of percentage by weight:
Epoxy resin 5-10%；
Diisocyanate 5-10%；
Polyether polyol 2-8%；
Dibutyl tin laurate 0.5-2%；
Cyclohexanedimethanol 2-8%；
Propylene glycol methyl ether acetate 1-2%；
Triethylamine 2-4%；
Benzene sulfonic acid sodium salt 1-3%；
Butanone 5-10%；
Terminal hydroxyl fluorine-containing organic polymer 1.5-3%；
Deionized water 50-60%.
Wherein, resin emulsion solids content is that 30-33%(records after 120 DEG C of baking 2h), epoxy resin content is 6-
8%, fluoropolymer content is 2-3%.
Described terminal hydroxyl organic silicon modified by polyether uses gamma-aminopropyl-triethoxy-silane to prepare as raw material.
The fluorine-containing organic polymer of terminal hydroxyl is reacted system by hydroxyethyl allyl ether, vinyl acetate and CTFE
?.
Preferably, the relative molecular mass of described polyether polyol is 2000-4000.
More preferably, the relative molecular mass of described polyether polyol is 2000-3000.
Correspondingly, the embodiment of the present invention also provides for the preparation method of a kind of aqueous epoxy resin emulsion, comprises the following steps:
(1) in reaction vessel, epoxy resin, diisocyanate, polyether polyol and propylene glycol methyl ether acetate are added, 100
DEG C ~ 120 DEG C under conditions of reaction backflow 2 hours；
(2) after being cooled to 60 DEG C, adding dibutyl tin laurate and butanone, under conditions of 60 DEG C ~ 80 DEG C, reaction backflow 2 is little
Time；
(3) it is cooled to 60 DEG C, adds terminal hydroxyl organic silicon modified by polyether or the fluorine-containing organic polymer of terminal hydroxyl, hexamethylene two
Methanol, butanone, reaction backflow 4 hours under conditions of 80 DEG C ~ 85 DEG C；
(4) when isocyano-content is less than 0.5%, it is cooled to 50 DEG C ~ 55 DEG C, is slowly added dropwise triethylamine under stirring condition and is incubated 1
Hour；
(5) by benzene sulfonic acid sodium salt and after, add deionized water and carry out emulsifying, be warming up to 65 DEG C ~ 80 DEG C, vacuum pumps solvent 4
Hour.
The aqueous epoxy resin emulsion using above-mentioned formula and preparation method to prepare, adds mill base and deionized water, with
Mill base, emulsion, deionized water stir after being mixed into tank liquor by 1:3:4 mass ratio, place 24h for 25 DEG C and use cathode electrophoresis equipment system
Make coating.
It should be noted that the component of mill base includes aqueous epoxy resins, dibutyl tin laurate DBTDL, acetic acid, titanium
White lead, carbon black, deionized water.Mill base records after 120 DEG C of baking 2h containing 55%(admittedly), use milling apparatus by mill base to carefully
Degree≤15 μm.
Further illustrate below by specific embodiment.
Embodiment 1
1, the preparation of aqueous epoxy resin emulsion
(1) in reaction vessel, add 7% epoxy resin, 8% diisocyanate, 5% polyether polyol and 1% the third by weight percentage
Glycol methyl ether acetate, reaction backflow 2 hours under conditions of 100 DEG C ~ 120 DEG C；
(2) after being cooled to 60 DEG C, add 0.8% dibutyl tin laurate and 4% butanone, react under conditions of 60 DEG C ~ 80 DEG C
Reflux 2 hours；
(3) it is cooled to 60 DEG C, adds 1.2% terminal hydroxyl organic silicon modified by polyether, 5% cyclohexanedimethanol, 2% butanone, at 80 DEG C
Reaction backflow 4 hours under conditions of ~ 85 DEG C；
(4) when isocyano-content is less than 0.5%, it is cooled to 50 DEG C ~ 55 DEG C, is slowly added dropwise 3% triethylamine under stirring condition and protects
Temperature 1 hour；
(5) by benzene sulfonic acid sodium salt and after, add 57% deionized water and carry out emulsifying, be warming up to 65 DEG C ~ 80 DEG C, vacuum pumps molten
Agent 4 hours, prepares aqueous epoxy resin emulsion a.
2, the preparation of cathode electrophoresis dope
Stir after mill base, emulsion a, deionized water are mixed into tank liquor by 1:3:4 mass ratio, place 24h for 25 DEG C and use negative electrode electricity
Swimming equipment making coating A.
Embodiment 2
1, the preparation of aqueous epoxy resin emulsion
(1) in reaction vessel, 8% epoxy resin, 6% diisocyanate, 6% polyether polyol and 1.5% are added by weight percentage
Propylene glycol methyl ether acetate, reaction backflow 2 hours under conditions of 100 DEG C ~ 120 DEG C；
(2) after being cooled to 60 DEG C, add 1% dibutyl tin laurate and 3% butanone, react back under conditions of 60 DEG C ~ 80 DEG C
Flow 2 hours；
(3) be cooled to 60 DEG C, add the 2% fluorine-containing organic polymer of terminal hydroxyl, 4% cyclohexanedimethanol, 3% butanone, 80 DEG C ~
Reaction backflow 4 hours under conditions of 85 DEG C；
(4) when isocyano-content is less than 0.5%, it is cooled to 50 DEG C ~ 55 DEG C, is slowly added dropwise 4% triethylamine under stirring condition and protects
Temperature 1 hour；
(5) by benzene sulfonic acid sodium salt and after, add 55% deionized water and carry out emulsifying, be warming up to 65 DEG C ~ 80 DEG C, vacuum pumps molten
Agent 4 hours, prepares aqueous epoxy resin emulsion b.
2, the preparation of cathode electrophoresis dope
Stir after mill base, emulsion b, deionized water are mixed into tank liquor by 1:3:4 mass ratio, place 24h for 25 DEG C and use negative electrode electricity
Swimming equipment making coating B.
Reference example 1
Use the epoxy resin that is not modified as raw material, and combine conventional formulation and cathode electrophoresis dope that production technology prepares
C。
Reference example 2
In reference example 1, add organosilicon coating levelling agent, after being uniformly mixed, obtain cathode electrophoresis dope D.
In order to enable to compare further the performance of cathode electrophoresis dope of the present invention, below by above-described embodiment 1, embodiment
2, cathode electrophoresis dope A, B, C and D of reference example 1 and reference example 2 is coated on zinc phosphate pretreatment clear with deionized water
On washed cold-rolled steel sheet (170mm*70mm*1mm).
One, electrophoretic painting: the steel plate processed by zinc phosphate immerses in cathode electrophoresis dope A, B, C and D as negative electrode, 28
At a temperature of DEG C, logical 120V electric current 3 min.Take out model respectively, washing, 180 DEG C of heating 30 min cured coating films, form negative electrode
Electrophoresis film A1, B1, C1 and D1, the thickness of film is 20 ± 2mm.
Two, coating tank liquor and film performance test
Cathode electrophoresis dope A, B, C and the D that will make, and film A1, B1, C1 and D1 carry out performance test, specifically surveys
Method for testing is as follows:
1, electrical conductivity detection establishing criteria: HG/T3335-1997(1985) " electrophoretic paint conductimetric method ": EDTM-02 " conductance
Degree algoscopy ".
2, throwing power detection establishing criteria: HG-1198-79 " electrophoretic paint throwing power algoscopy (a vapour steel pipe method) ".
3, Gel divides rate detection with reference to Automobile Co., Ltd. company standard Q/SZS Q/SZS J 2101113-suitable in Shenyang
2003。
4, coulombic efficiency detection establishing criteria: HG/T3337-1977(1985) " electrophoretic paint coulombic efficiency algoscopy ".
5, mill base fineness test establishing criteria: GB1724-79 " coating fineness algoscopy ".
6, film thickness detection establishing criteria: GB/T13452.2-1992 " colored paint, varnish, the side of mensuration of film thickness
Method 5: non-destructive instrument measuring method ".
7, detection establishing criteria acidproof, alkaline-resisting: GB1763-79 " paint film chemical reagent resistance algoscopy ".
8, adhesive force detection establishing criteria: GB/T9286-1998 " cross cut test of paint and varnish paint film ".
9, impact strength detection establishing criteria: GB1732-79 " paint film impact resistance algoscopy ".
10, hardness determination establishing criteria: GB/T 6739-1996 " hardness of film pencil algoscopy ".
11, water-fast detection establishing criteria: GB/T1733-93 " paint film resistance to water algoscopy ".
12, pliability detection establishing criteria: GB/T 1731-93 " paint film flexibility algoscopy ".
13, gloss detection establishing criteria: GB/T9754-1998 " paint and varnish without metallic pigments colored paint paint film it
The mensuration of 20 °, 60 ° and 85 ° bright lusters ".
14, salt spray resistance establishing criteria: GB/51771-91 " mensuration of paint and varnish resistance to neutral salt spray performance ".
15, interfacial tension detection is according to GB6541-86 " oil product oil is to water interfacial tension algoscopy ".
Three, test result
Table 1 coatings tank liquid performance comparison table
Table 2 film performance contrast table
Table 3 film coated surface coefficient of tension contrast table
Understanding from table 1 and 2, the present invention is modified through the fluorine-containing organic polymer of terminal hydroxyl organic silicon modified by polyether or terminal hydroxyl
After aqueous epoxy resin emulsion prepare electrophoretic coating A with B identical with the cathode electrophoresis dope C of prior art and D performance,
Invent described cathode electrophoresis dope and keep the physical and chemical performance of aqueous epoxy resins excellence itself, on this basis, by changing
Property make the reduction in surface tension of film A1 and B1 to 25mN/m and 18mN/m, compare common water borne Epoxy Cathodic Electrodeposition Coating be coated with
Film D1 surface tension 47mN/m, reduction ratio is respectively 46.81% and 61.70%；The coating film C1 adding levelling agent is 35
MN/m, modified cathode electrophoretic coating film of the present invention reduces surface tension effect by comparison and becomes apparent from.
In addition, C-Si, O-Si of being formed between organosilicon and epoxy resin in the coating of existing interpolation levelling agent are
Molecular link, its active force be far from chemical bond that the present invention formed by chemical reaction on epoxy resin by force, therefore at film
In surface tension, performance is not as the coating film of the present invention.Simultaneously as organosilicon adds to coating with additive form, it is coated with
Material storage stability and the degree that is uniformly dispersed are poor.The present invention then avoids the problem of above-mentioned coating, is keeping existing film
Reduce the surface tension of film in the case of excellent properties, make the liquid such as food oil, machine oil that surface tension is bigger be difficult to adhere to
On paint film, keep the relatively clean of film coated surface.
Last institute is it should be noted that, the present invention is only protected by above example in order to technical scheme to be described
Protecting the restriction of scope, although being explained in detail the present invention with reference to preferred embodiment, those of ordinary skill in the art should
Understand, technical scheme can be modified or equivalent, without deviating from the essence of technical solution of the present invention
And scope.
Claims (10)
1. an aqueous epoxy resin emulsion, it is characterised in that include that following raw materials is made:
Epoxy resin 5-10%；
Diisocyanate 5-10%；
Polyether polyol 2-8%；
Dibutyl tin laurate 0.5-2%；
Cyclohexanedimethanol 2-8%；
Propylene glycol methyl ether acetate 1-2%；
Triethylamine 2-4%；
Benzene sulfonic acid sodium salt 1-3%；
Butanone 5-10%；
Terminal hydroxyl organic silicon modified by polyether or terminal hydroxyl fluorine-containing organic polymer 1-3%；
Deionized water 50-60%.
2. aqueous epoxy resin emulsion as claimed in claim 1, it is characterised in that the relative molecular mass of described polyether polyol
For 2000-4000.
3. aqueous epoxy resin emulsion as claimed in claim 1, it is characterised in that the matter of described aqueous epoxy resin emulsion solid
Amount content 30-33%.
4. aqueous epoxy resin emulsion as claimed in claim 1, it is characterised in that described terminal hydroxyl organic silicon modified by polyether is adopted
Prepare as raw material with gamma-aminopropyl-triethoxy-silane.
5. aqueous epoxy resin emulsion as claimed in claim 1, it is characterised in that the fluorine-containing organic polymer of terminal hydroxyl is by hydroxyl second
Base allyl ether, vinyl acetate and CTFE reaction prepare.
6. the preparation method of an aqueous epoxy resin emulsion as claimed in claim 1, it is characterised in that comprise the following steps:
(1) in reaction vessel, epoxy resin, diisocyanate, polyether polyol and propylene glycol methyl ether acetate are added, 100
DEG C ~ 120 DEG C under conditions of reaction backflow 2 hours；
(2) after being cooled to 60 DEG C, adding dibutyl tin laurate and butanone, under conditions of 60 DEG C ~ 80 DEG C, reaction backflow 2 is little
Time；
(3) it is cooled to 60 DEG C, adds terminal hydroxyl organic silicon modified by polyether or the fluorine-containing organic polymer of terminal hydroxyl, hexamethylene two
Methanol, butanone, reaction backflow 4 hours under conditions of 80 DEG C ~ 85 DEG C；
(4) when isocyano-content is less than 0.5%, it is cooled to 50 DEG C ~ 55 DEG C, is slowly added dropwise triethylamine under stirring condition and is incubated 1
Hour；
(5) by benzene sulfonic acid sodium salt and after, add deionized water and carry out emulsifying, be warming up to 65 DEG C ~ 80 DEG C, vacuum pumps solvent 4 hours.
7. the preparation method of aqueous epoxy resin emulsion as claimed in claim 6, it is characterised in that the phase of described polyether polyol
It is 2000-4000 to molecular mass.
8. the preparation method of aqueous epoxy resin emulsion as claimed in claim 6, it is characterised in that described aqueous epoxy resins breast
Mass content 30-33% of liquid-solid body.
9. a cathode electrophoresis dope, it is characterised in that include aqueous epoxy resin emulsion as claimed in claim 1, mill base and
Deionized water, stirs after mill base, described aqueous epoxy resin emulsion, deionized water are mixed into tank liquor by 1:3:4 mass ratio,
Place 24h at 25 DEG C and use cathode electrophoresis equipment to make coating.
10. cathode electrophoresis dope as claimed in claim 9, it is characterised in that described mill base solid content is 55%, mill base fineness≤
15μm。
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| CN201610628604.XA CN106243311A (en) | 2016-08-03 | 2016-08-03 | A kind of aqueous epoxy resin emulsion and preparation method thereof, cathode electrophoresis dope |
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| CN201610628604.XA CN106243311A (en) | 2016-08-03 | 2016-08-03 | A kind of aqueous epoxy resin emulsion and preparation method thereof, cathode electrophoresis dope |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107163210A (en) * | 2017-05-04 | 2017-09-15 | 广东科德环保科技股份有限公司 | A kind of polyurethane modified epoxy resin and preparation method thereof and electrophoretic coating |
| CN107936219A (en) * | 2017-12-18 | 2018-04-20 | 广州聚碳合成材料有限公司 | Modified aqueous polyurethane emulsion and preparation method thereof and water-based ink resin |
| CN108084785A (en) * | 2017-12-18 | 2018-05-29 | 广州聚碳合成材料有限公司 | Modified aqueous polyurethane dispersoid and preparation method thereof and water-based ink resin |
| CN108707414A (en) * | 2018-05-18 | 2018-10-26 | 安徽朗凯奇建材有限公司 | A kind of epoxy resin modification polyurethane water-proof paint and preparation method thereof |
| CN108864885A (en) * | 2018-04-03 | 2018-11-23 | 河北晨阳工贸集团有限公司 | A kind of cathode electrophoresis dope and preparation method thereof suitable for kitchen ventilator |
| CN108912949A (en) * | 2018-05-25 | 2018-11-30 | 河北晨阳工贸集团有限公司 | A kind of cathode electrophoresis dope and preparation method thereof suitable for gas range |
| CN109057208A (en) * | 2018-07-27 | 2018-12-21 | 江苏贝格丽新材料科技有限公司 | A kind of corrosion-resistant, anti-pollution, mould proof fungi-proofing wall decoration film and manufacturing method |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1226913A (en) * | 1996-06-05 | 1999-08-25 | 纳幕尔杜邦公司 | Cathodic electrocoating compositions containing alkane sulfonic acid |
| CN1451702A (en) * | 2003-04-29 | 2003-10-29 | 华南理工大学 | Organic silicon modified cathode electrophoresis epoxy coating and process for preparing same |
| CN1651530A (en) * | 2004-12-28 | 2005-08-10 | 华南理工大学 | Fluorinated low surface energy cathode electrophoresis paint and its preparation method |
| CN103319691A (en) * | 2013-06-24 | 2013-09-25 | 浩力森涂料（上海）有限公司 | Method for preparing organic silicon modified epoxy electrophoretic coating emulsion |
| CN104086693A (en) * | 2014-06-20 | 2014-10-08 | 安徽华箔箔业科技有限公司 | Synthesis process of waterborne fluorocarbon resin |
-
2016
- 2016-08-03 CN CN201610628604.XA patent/CN106243311A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1226913A (en) * | 1996-06-05 | 1999-08-25 | 纳幕尔杜邦公司 | Cathodic electrocoating compositions containing alkane sulfonic acid |
| CN1451702A (en) * | 2003-04-29 | 2003-10-29 | 华南理工大学 | Organic silicon modified cathode electrophoresis epoxy coating and process for preparing same |
| CN1651530A (en) * | 2004-12-28 | 2005-08-10 | 华南理工大学 | Fluorinated low surface energy cathode electrophoresis paint and its preparation method |
| CN103319691A (en) * | 2013-06-24 | 2013-09-25 | 浩力森涂料（上海）有限公司 | Method for preparing organic silicon modified epoxy electrophoretic coating emulsion |
| CN104086693A (en) * | 2014-06-20 | 2014-10-08 | 安徽华箔箔业科技有限公司 | Synthesis process of waterborne fluorocarbon resin |
Non-Patent Citations (2)
| Title |
|---|
| 祝方著: "《环境友好材料及其应用》", 31 August 2009 * |
| 詹益兴主编: "《精细化工新产品（第3集）》", 31 October 2007 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107163210A (en) * | 2017-05-04 | 2017-09-15 | 广东科德环保科技股份有限公司 | A kind of polyurethane modified epoxy resin and preparation method thereof and electrophoretic coating |
| CN107936219A (en) * | 2017-12-18 | 2018-04-20 | 广州聚碳合成材料有限公司 | Modified aqueous polyurethane emulsion and preparation method thereof and water-based ink resin |
| CN108084785A (en) * | 2017-12-18 | 2018-05-29 | 广州聚碳合成材料有限公司 | Modified aqueous polyurethane dispersoid and preparation method thereof and water-based ink resin |
| CN108864885A (en) * | 2018-04-03 | 2018-11-23 | 河北晨阳工贸集团有限公司 | A kind of cathode electrophoresis dope and preparation method thereof suitable for kitchen ventilator |
| CN108707414A (en) * | 2018-05-18 | 2018-10-26 | 安徽朗凯奇建材有限公司 | A kind of epoxy resin modification polyurethane water-proof paint and preparation method thereof |
| CN108707414B (en) * | 2018-05-18 | 2020-04-14 | 安徽朗凯奇建材有限公司 | Epoxy resin modified polyurethane waterproof coating and preparation method thereof |
| CN108912949A (en) * | 2018-05-25 | 2018-11-30 | 河北晨阳工贸集团有限公司 | A kind of cathode electrophoresis dope and preparation method thereof suitable for gas range |
| CN109057208A (en) * | 2018-07-27 | 2018-12-21 | 江苏贝格丽新材料科技有限公司 | A kind of corrosion-resistant, anti-pollution, mould proof fungi-proofing wall decoration film and manufacturing method |
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Application publication date: 20161221 |