CN107033736A - It is a kind of for cathode electrodip painting of leaf spring and preparation method thereof - Google Patents
It is a kind of for cathode electrodip painting of leaf spring and preparation method thereof Download PDFInfo
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- CN107033736A CN107033736A CN201710289485.4A CN201710289485A CN107033736A CN 107033736 A CN107033736 A CN 107033736A CN 201710289485 A CN201710289485 A CN 201710289485A CN 107033736 A CN107033736 A CN 107033736A
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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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/226—Mixtures of di-epoxy compounds
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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
- C09D5/443—Polyepoxides
- C09D5/4434—Polyepoxides characterised by the nature of the epoxy binder
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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
- C09D5/443—Polyepoxides
- C09D5/4457—Polyepoxides containing special additives, e.g. pigments, polymeric particles
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- Wood Science & Technology (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The present invention provides a kind of for cathode electrodip painting of leaf spring and preparation method thereof, and raw material includes epoxy resin, and when the epoxide number of the epoxy resin is less than 0.4, the raw material also includes epoxide diluent, conversely, then the raw material also includes chain extender；Wherein, the epoxide diluent and chain extender are flexible chain compound.The present invention is increased the epoxide diluent or chain extender of flexible chain compound, is reduced the fragility of cathode electrodip painting, and then improve anti-stone and hit ability, while also improving salt fog resistance in the feed by the epoxide number according to epoxy resin.
Description
Technical field
The present invention relates to electrophoretic paint technical field, more particularly, to the cathode electrodip painting and its system for leaf spring
Preparation Method.
Background technology
Leaf spring (Leaf Spring) leaf spring is most widely used a kind of flexible member in automotive suspension, it
If being by the spring beam for the approximately equi-strength that dry plate is wide but alloy spring piece of Length discrepancy is combined, each alloy bullet
The thickness of reed can be with equal, can also be unequal.
Because leaf spring is mounted to bottom of car, therefore leaf spring paint will bear continuous stone and hit, simultaneously
It is required that stronger salt fog resistance, in the prior art, uses epoxy resin, or epoxy resin and bis-phenol more the raw material of leaf spring
A combination, but because epoxy resin is harder, after being made as electrophoretic paint and being coated in leaf spring, has that fragility is higher, anti-stone
The problem of hitting ability, while salt fog resistance is also and not fully up to expectations.
Steel spring plate is divided into following several with paint in the prior art：
A, powdery paints, using electrostatic painting process, generating process produces a large amount of dust；
B, oil paint, using pneumatic spraying technique, production process has a large amount of VOC volatilization；
C, water paint (spraying paint), expensive using pneumatic spraying technique, utilization rate is low；
D, oil paint (dip painting), using dipping process, the problem of there is coating became uneven, and production process meeting
There is substantial amounts of VOC to volatilize；
E, water paint (dip painting), using dipping process, the problem of there is coating became uneven.
The content of the invention
The present invention provide it is a kind of overcome above mentioned problem or solve the above problems at least in part be used for leaf spring
Cathode electrodip painting and preparation method thereof.
There is provided a kind of cathode electrodip painting for leaf spring according to an aspect of the present invention, it is characterised in that raw material
Including epoxy resin and flexible chain compound；
Wherein, when the epoxide number of the epoxy resin is less than 0.4, the flexible chain compound is epoxide diluent, instead
It, the flexible chain compound is chain extender.
Preferably, when the epoxide number of the epoxy resin is less than 0.4, epoxy radicals and the epoxy of the epoxy resin dilute
The mol ratio of the epoxy radicals of agent is：0.8-0.95:1；Preferably, the epoxy of the epoxy radicals of the epoxy resin and epoxide diluent
The mol ratio of base is 0.86:1.
When the epoxide number of the epoxy resin is more than 0.4, the mass ratio of the epoxy resin and chain extender is：0.9-
1.4:1；Preferably, the weight ratio of the epoxy resin and chain extender is：0.94:1.
Preferably, when the epoxide number of the epoxy resin is more than 0.4, raw material also includes the epoxy that epoxide number is less than 0.4
Resin, and epoxide number is more than the weight fraction ratio of 0.4 epoxy resin of epoxy resin and epoxide number less than 0.4 and is：0.6-
1.6:1；Preferably, the weight ratio that epoxide number is more than the epoxy resin that 0.4 epoxy resin and epoxide number are less than 0.4 is 0.7:1.
Preferably, when the epoxide number of the epoxy resin is less than 0.4, epoxy resin is included in E10, E10P, E12, E20
One or more；Preferably, when the epoxide number of the epoxy resin is less than 0.4, epoxy resin is E12 and E20；More preferably
Ground, E12 and E20 weight ratio are 1.4-1.7:1.
Preferably, the epoxide diluent include neopentylglycol diglycidyl ether, BDDE,
1,6- hexanediol diglycidyl ether, ethylene glycol diglycidylether, resorcinolformaldehyde resin, diethylene glycol diglycidyl
In glycerin ether, Triethylene Glycol Diglycidyl Ether, polyethyleneglycol diglycidylether and polypropylene glycol diglycidyl ether
It is one or more；Preferably, the epoxide diluent is polypropylene glycol diglycidyl ether；
The chain extender includes PPG-200, PPG-400, PPG-600, PPG-1000, PEG-200, PEG-300, PEG-
400th, the one or more in PEG-600, PEG-800 and PEG-1000；Preferably, the epoxy resin is E-51, described
Chain extender is PPG-600.
The present invention also provides a kind of cathode electrodip painting preparation method, including epoxy resin toughened preparation process, the preparation
Step includes：
When the epoxide number of epoxy resin is less than 0.4, the epoxy resin, epoxide diluent and solvent are placed in reactor
In, 60-100 DEG C is warming up to, when detection is when epoxide number is decreased to 0.07-0.12, solvent is continuously added, it is glass to treat solution levelling
Glass state, is obtained epoxy resin toughened；
When the epoxide number of the epoxy resin is more than 0.4, the epoxy resin, chain extender are mixed with solvent, heated up
To 60-100 DEG C, catalyst and keeping temperature are added, when epoxide number is decreased to 0.07-0.12, solvent is added, stops stirring,
The epoxy resin that epoxide number is less than 0.4 is added, it is glassy state to treat solution levelling, is obtained epoxy resin toughened.
Preferably, the raw material of cathode electrodip painting also includes：Amine, sealer, crosslinking agent, acid acceptor and electrophoretic paint color
Slurry.
Preferably, epoxy resin toughened, amine, sealer, crosslinking agent, the weight ratio of acid acceptor are 150-160:2-
2.5:3-4:5-6:1；Preferably, the epoxy resin toughened, amine, sealer, crosslinking agent, the weight ratio of acid acceptor are
153:2.16:3.3:5.41:1。
Preferably, preparation method also includes：
By it is described it is epoxy resin toughened mixed with amine, carry out amination treatment, obtain aminate；
By aminate, for occlusive polyurethane sealer and crosslinking agent it is well mixed after, add acid acceptor
To carry out neutralization reaction, product is discharged into water and carries out emulsion reaction, emulsion is obtained；
The emulsion is mixed with electrophoretic paint mill base, deionized water is added, is configured to tank liquor, the tank liquor is cured, obtained
Obtain electrophoretic paint finished product.
Preferably, also include before acid acceptor is added：Auxiliary agent is added, the auxiliary agent includes：Octyl phenol polyoxy second
One in alkene ether, APES, polyoxyethylene sorbitan fatty acid ester and sorbitan fatty acid ester
Plant or a variety of.The application proposition is a kind of for cathode electrodip painting of leaf spring and preparation method thereof, by according to epoxy resin
Epoxide number, increase the epoxide diluent or chain extender of flexible chain compound in the feed, reduce the crisp of cathode electrodip painting
Property, and then improve anti-stone and hit ability, while also improving salt fog resistance.
Embodiment
With reference to embodiment, the embodiment to the present invention is described in further detail.Following examples are used for
Illustrate the present invention, but be not limited to the scope of the present invention.
Because leaf spring is mounted to bottom of car, therefore the cathode electrodip painting of leaf spring will bear continuous stone
Hit, while requiring stronger salt fog resistance, in the prior art, epoxy resin, or asphalt mixtures modified by epoxy resin are used the raw material of leaf spring more
The combination of fat and bisphenol-A, but because epoxy resin is harder, after being made as electrophoretic paint and being coated in leaf spring, there is fragility
The problem of higher, anti-stone hits ability, while salt fog resistance is also and not fully up to expectations.
In order to overcome above mentioned problem of the prior art, the present invention provides a kind of cathode electrodip painting for leaf spring,
Raw material includes epoxy resin and flexible chain compound；
Wherein, when the epoxide number of the epoxy resin is less than 0.4, the flexible chain compound is epoxide diluent, instead
It, the flexible chain compound is chain extender.
It should be noted that the flexibility in macromolecular chain refers to the energy for the change strand form that macromolecular chain has
Amount, flexible stronger, then the energy for changing strand form is also stronger.In general, belong to hard containing aromatic macromolecular chain
Property chain, the macromolecular chain of fatty race belongs to inclined stiff chain, and the macromolecular chain of ether-containing key belongs to flexible chain, also, molecular weight
Smaller then macromolecular chain is harder.
It should be noted that the epoxide number of epoxy resin is higher, it is meant that the molal weight of epoxy resin is smaller, strand
Length it is shorter, that is, hardness it is higher, the present invention with epoxide number 0.4 is boundary, when epoxide number is more than or equal to 0.4, is then added
Flexible chain extender, makes the length of epoxy resin, the flexibility of appropriate increase epoxy resin, when epoxide number is less than 0.4, then
By increasing epoxide diluent, the molecular chain length of epoxy resin is shortened, the flexibility of epoxy resin is suitably reduced, purpose is all
In order that the toughness enhancing of epoxy resin, make epoxy resin reach it is hard in soft, the hard effect of soft middle band.
In one alternate embodiment, when the epoxide number of epoxy resin is less than 0.4, the epoxy radicals and epoxy of epoxy resin
The mol ratio of the epoxy radicals of diluent is：0.8-0.95:1.
In a preferred embodiment, when the epoxide number of epoxy resin is less than 0.4, the epoxy radicals and epoxy of epoxy resin
The mol ratio of the epoxy radicals of diluent is 0.86:1.
In one alternate embodiment, when the epoxide number of epoxy resin is more than 0.4, the quality of epoxy resin and chain extender
Than for：0.9-1.4:1.
In a preferred embodiment, when the epoxide number of epoxy resin is more than 0.4, the weight of epoxy resin and chain extender
Than for：0.94:1.
In one alternate embodiment, when the epoxide number of epoxy resin is more than 0.4, raw material is also less than including epoxide number
0.4 epoxy resin, and epoxide number is more than the weight fraction ratio of 0.4 epoxy resin of epoxy resin and epoxide number less than 0.4
For：0.6-1.6:1.
In a preferred embodiment, epoxide number is more than 0.4 epoxy resin of epoxy resin and epoxide number less than 0.4
Weight ratio is 0.7:1.
In a preferred embodiment, when the epoxy resin epoxide number be less than 0.4 when, epoxy resin include E10,
One or more in E10P, E12, E20；It is highly preferred that when the epoxide number of the epoxy resin is less than 0.4, epoxy resin
For E12 and E20；It is highly preferred that E12 and E20 weight ratio is 1.6:1.
In one alternate embodiment, epoxide diluent includes：Neopentylglycol diglycidyl ether, BDO two contract
Water glycerin ether, 1,6- hexanediol diglycidyl ethers, ethylene glycol diglycidylether, resorcinolformaldehyde resin, diethyl
Hexanediol diglycidyl ether, Triethylene Glycol Diglycidyl Ether, polyethyleneglycol diglycidylether and polypropylene glycol two shrink
One or more in glycerin ether.
It should be noted that neopentylglycol diglycidyl ether, BDDE, 1,6- hexylene glycols two
Glycidol ether, ethylene glycol diglycidylether, resorcinolformaldehyde resin and diethylene glycol diglycidyl glycerin ether all belong to
In rigid chain compound, polyethyleneglycol diglycidylether then belongs to partially aqueous compound, polypropylene glycol diglycidyl ether
Then belong to the compound of inclined oiliness.
Chain extender include PPG-200, PPG-400, PPG-600, PPG-1000, PEG-200, PEG-300, PEG-400,
One or more in PEG-600, PEG-800 and PEG-1000.
In a preferred embodiment, epoxide diluent is polypropylene glycol diglycidyl ether.
In a preferred embodiment, epoxy resin is E-51, and chain extender is PPG-600.
In one alternate embodiment, the preparation method for the cathode electrodip painting of leaf spring includes：
When the epoxide number of epoxy resin is less than 0.4, epoxy resin, epoxide diluent and solvent are placed in reactor,
60-100 DEG C is warming up to, when epoxide number is decreased to 0.07-0.12, solvent is continuously added, it is glassy state to treat solution levelling, is obtained
It is epoxy resin toughened.
It should be noted that the solvent in the present invention includes：Dimethylbenzene, ethyl acetate, butyl acetate, ethylene glycol only son
Ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propane diols monophenyl ether, butanone, methyl
One or more in isobutyl ketone.
In a preferred embodiment, solvent is dimethylbenzene.
In an alternative embodiment, when the epoxide number of epoxy resin is more than 0.4, by epoxy resin, chain extender and solvent
Mixing, is warming up to 60-100 DEG C, adds catalyst and keeping temperature, when epoxide number is decreased to 0.07-0.12, add solvent and
Epoxide number is less than 0.4 epoxy resin, stops stirring, and it is glassy state to treat solution levelling, is obtained epoxy resin toughened.
It should be noted that why when epoxide number is decreased to 0.07-0.12, adding solvent and epoxide number being less than 0.4
Epoxy resin, be because the hardness of now epoxy resin is too low, when adding the epoxy resin that epoxide number is less than 0.4, equivalent to
Hard monomer is added in the solution, it is ensured that the toughness of solution after reaction.
In a preferred embodiment, when epoxide number is decreased to 0.0859, the ring of solvent and epoxide number less than 0.4 is added
Oxygen value.
It should be noted that the toughing ways when epoxide number of epoxy resin is more than 0.4 are realized first by the present invention,
Why currently available technology can not realize this process, be because of when the epoxide number of epoxy resin is more than 0.4, if be added without
Catalyst, the speed of reaction will be very slow, but once add catalyst, though the addition of catalyst it is considerably less (equivalent to
The number one thousandth of epoxy resin addition), the speed of reaction also can be near uncontrollable stage, and then makes the increasing of epoxy resin
Tough process exceed experimenter control, but the present inventor it has been investigated that, control temperature for 60-100 DEG C when, reaction can be in
Controllable state, simultaneous reactions speed is very good.
In one alternate embodiment, the present invention also provides a kind of leaf spring negative electrode using epoxy resin toughened preparation
Electrophoretic paint, raw material also includes：Amine, sealer, crosslinking agent, acid acceptor and electrophoretic paint mill base.
In a preferred embodiment, epoxy resin toughened, amine, sealer, crosslinking agent, the weight ratio of acid acceptor are
150-160:2-2.5:3-4:5-6:1。
In a more preferred embodiment, epoxy resin toughened, amine, sealer, crosslinking agent, the weight ratio of acid acceptor
For 153:2.16:3.3:5.41:1.
In a preferred embodiment, the amount of acid acceptor is the 70%-90% of resin degree of neutralization.
In one alternate embodiment, using the epoxy resin toughened method for preparing leaf spring cathode electrodip painting, including：
Mixed epoxy resin toughened with amine, carry out amination treatment, obtain aminate；
By aminate, for occlusive polyurethane sealer and crosslinking agent it is well mixed after, enter with acid acceptor
Row neutralization reaction, product is discharged into water and carries out emulsion reaction, emulsion is obtained；
Emulsion and electrophoretic paint mill base are pressed into 3-5:1 ratio mixing, adds deionized water, is configured to solid content for 10-
30% tank liquor, tank liquor is cured, and obtains electrophoretic paint finished product.
In a preferred embodiment, emulsion and the ratio of electrophoretic paint mill base are 4:1.
It should be noted that the sealer used in occlusive polyurethane has：Gaultherolin, 3,5- dimethyl pyrazoles, acetyl
One in aniline, phenol, caprolactam, ethylene glycol monoethyl ether, ethylene glycol ether, ethylene glycol monobutyl ether, ethylene glycol monohexylether
Plant or a variety of.
In a preferred embodiment, sealer selects ethylene glycol monoethyl ether.
It should be noted that the electrophoretic paint of the present invention is particularly suitable in leaf spring, reacted by electrophoresis by the present invention
Electrophoretic paint be coated in leaf spring, hit verification experimental verification by anti-stone, the leaf spring that the present invention is coated has 80% ratio
It is height, the significantly larger than like product of prior art that example hits the grade of ability in the resistance to stone of coating.
In one alternate embodiment, amine includes monoethanolamine, diethanol amine, N, N- dimethylethanolamines, N- methyl lists
Any two kinds in monoethanolamine, polyamide and ketimide.
It should be noted that the selection of amine is equally the place of the innovation of the present invention in the present embodiment, according to the present inventor
Research, with the combination of two of above-mentioned ammonium, the throwing power of electrophoretic paint can be significantly improved compared with prior art.Throwing power is also known as
Dispersibility, refers in electrophoretic coating, coating ability of the coating at the inner surface of coated article, the depression and back side.According to good fortune
The test of the electrophoretic paint throwing power determination method of special box, the performance of the electrophoretic paint throwing power prepared with prior art using polyetheramine is shown in
Table 1：
| Raw material | Throwing power (mm) |
| Monoethanolamine+diethanol amine | 22.7 |
| Diethanol amine+N, N- dimethylethanolamine | 22.3 |
| (2-hydroxyethyl)methylamine)+polyamide | 23.1 |
| (2-hydroxyethyl)methylamine)+ketimide | 23.4 |
| Monoethanolamine+N, N- dimethylethanolamine | 22.5 |
| Polyetheramine | 22.1 |
Table 1, the performance table for the electrophoretic paint throwing power that the present embodiment is prepared with prior art using polyetheramine
As shown in Table 1, the amine that aminating reaction of the invention is utilized can significantly improve electrophoretic paint compared with prior art
Throwing power.The wherein best (2-hydroxyethyl)methylamine)+ketimide of throwing power can reach 23.4mm throwing power, far better than existing
There is technology.
In an alternative embodiment, the step of carrying out neutralization reaction with acid acceptor also includes before：Add auxiliary agent,
Auxiliary agent includes：OPEO (OP-4, OP-7, OP-9, OP-10, OP-13, OP-15, OP-20, OP-30, OP-40,
OP-50), APES (TX-4, TX-5, TX-7, TX-9, TX-10, TX-112, TX-13, TX-15, TX-18,
TX-21, TX-30, TX-40, TX-50), polyoxyethylene sorbitan fatty acid ester (Tween-20, Tween-40, Tween-60,
Tween-80) and sorbitan fatty acid ester (Arlacel-20, Arlacel-40, Arlacel-60, Arlacel-80, Arlacel-85) in one
Plant or a variety of.
It should be noted that prior art is usually required during preparing electrophoretic paint, addition BYK etc. is expensive to be helped
Agent, the BYK market price generally in 180-220 members/kilogram fluctuation, and OP that the auxiliary agent in the present embodiment is used, TX, tween with
And sapn price be only tens of members/kilogram, well below the production cost of similar electrophoretic paint, and the anti-stone of the actual product obtained
Hit ability and be still better than prior art, the another prominent effect for the present invention that can yet be regarded as.
Embodiment 1
By 1600 parts of E-12,1000 parts of E-20,1000 parts of polypropylene glycol diglycidyl ethers (epoxide number=0.20), 764
Part polypropylene glycol diglycidyl ether (epoxide number=0.33), 200 parts of dimethylbenzene are put into reactor, are to slowly warm up to 100 DEG C,
After material is completely dissolved, 105 parts of diethanol amine are added, after 100 DEG C are reacted 1 hour, 235 parts of propylene glycol monomethyl ethers are added,
450 parts of ethylene glycol monomethyl ether acetates, add 141 parts of monoethanolamines, are reacted 2 hours at 110 DEG C, add 404 parts of polyamide
(amine value=320 ± 10mgKOH/g), reacts 2 hours, adds 1000 parts of ethylene glycol monobutyl ethers, is cooled to 90 DEG C, adds 1600 parts
Crosslinking agent, is cooled to 70 DEG C, adds 2 parts of Tween-40s, 2.4 parts of OP-7,2.4 parts of OP-15 are stirred 1 hour.At 60 DEG C, add
117 parts of acetic acid, 176 parts of lactic acid are stirred 0.5 hour.Resin is discharged into 10100 parts of water, emulsifies, obtains emulsion.Obtained breast
Liquid and mill base proportionally 4：1 ratio mixing, adds deionized water, is configured to after the solid tank liquor containing for 20%, curing 48h i.e.
Electrophoresis production can be carried out.
Embodiment 2
By 1600 parts of E-12,1000 parts of E-20,1000 parts of polypropylene glycol diglycidyl ethers (epoxide number=0.20), 764
Part polypropylene glycol diglycidyl ether (epoxide number=0.33), 200 parts of dimethylbenzene are put into reactor, are to slowly warm up to 100 DEG C,
After material is completely dissolved, 105 parts of diethanol amine are added, after 100 DEG C are reacted 1 hour, 235 parts of propylene glycol monomethyl ethers are added,
450 parts of ethylene glycol monomethyl ether acetates, add 141 parts of monoethanolamines, are reacted 2 hours at 110 DEG C, add 404 parts of polyamide
(amine value=320 ± 10mgKOH/g), reacts 2 hours, adds 1000 parts of ethylene glycol monobutyl ethers, is cooled to 90 DEG C, adds 1600 parts
Crosslinking agent, is cooled to 70 DEG C, adds 2 parts of Tween-40s, 2.4 parts of OP-7,2.4 parts of OP-15 are stirred 1 hour.At 60 DEG C, add
117 parts of acetic acid, 176 parts of lactic acid are stirred 0.5 hour.Resin is discharged into 10100 parts of water, emulsifies, obtains emulsion.Obtained breast
Liquid and mill base proportionally 4：1 ratio mixing, adds deionized water, is configured to after the solid tank liquor containing for 20%, curing 48h i.e.
Electrophoresis production can be carried out.
Embodiment 3
By 1593 parts of E-12,900 parts of E-20,1000 parts of polypropylene glycol diglycidyl ethers (epoxide number=0.20), 800 parts
Polypropylene glycol diglycidyl ether (epoxide number=0.33), 200 parts of dimethylbenzene are put into reactor, are to slowly warm up to 100 DEG C, are treated
After material is completely dissolved, 105 parts of diethanol amine are added, after 100 DEG C are reacted 1 hour, 235 parts of propylene glycol monomethyl ethers, 450 are added
Part ethylene glycol monomethyl ether acetate, adds 135 parts of monoethanolamines, is reacted 2 hours at 110 DEG C, adds 400 parts of polyamide (amine
It is worth=320 ± 10mgKOH/g), react 2 hours, add 1000 parts of ethylene glycol monobutyl ethers, be cooled to 90 DEG C, add 1600 parts of friendships
Join agent, be cooled to 70 DEG C, add 2 parts of Tween-40s, 2.4 parts of OP-7,2.4 parts of OP-15 are stirred 1 hour.At 60 DEG C, add
113 parts of acetic acid, 175 parts of lactic acid are stirred 0.5 hour.Resin is discharged into 10100 parts of water, emulsifies, obtains emulsion.Obtained breast
Liquid and mill base proportionally 4：1 ratio mixing, adds deionized water, is configured to after the solid tank liquor containing for 20%, curing 48h i.e.
Electrophoresis production can be carried out.
Embodiment 4
By 1620 parts of epoxy resin E-51,1200 parts of PPG-600,100 parts of dimethylbenzene is put into reactor, heating
To 90 DEG C, 0.5 part of BFEE is added, temperature rises to 100 DEG C, and detection epoxide number is 0.0859 ± 0.01.Add 100
The propylene glycol monomethyl ether of part, stops stirring, adds 1600 parts of E-12.110 DEG C are warming up to, is completely dissolved to E-12,403 part third is added
Glycol monomethyl ether, 450 parts of ethylene glycol monomethyl ether acetates are cooled to 90 DEG C, add 290 parts of ketimides (amine value=400 ±
10mgKOH/g), react 2 hours.Cooling, adds 800 parts of ethylene glycol monobutyl ethers, is cooled to 90 DEG C, adds 1500 parts of crosslinking agent drops
Temperature adds 2 parts of Arlacel-40s, 2.4 parts of OP-10,2.4 parts of OP-15 are stirred 1 hour to 70 DEG C.At 60 DEG C, 135 parts of breasts are added
Acid, is stirred 0.5 hour.Resin is discharged into 8000 parts of water, emulsifies, obtains emulsion.Obtained emulsion and mill base proportionally 4：1
Ratio mixing, add deionized water, electrophoresis production can be carried out after being configured to the solid tank liquor containing for 30%, curing 48h.
Embodiment 5
By 1128 parts of epoxy resin E-51,1200 parts of PPG-600,100 parts of dimethylbenzene is put into reactor, heating
To 90 DEG C, 0.5 part of BFEE is added, temperature rises to 100 DEG C, and detection epoxide number is 0.0859 ± 0.01.Add 100
The propylene glycol monomethyl ether of part, stops stirring, adds 1600 parts of E-12.110 DEG C are warming up to, is completely dissolved to E-12,403 part third is added
Glycol monomethyl ether, 450 parts of ethylene glycol monomethyl ether acetates are cooled to 90 DEG C, add 285 parts of ketimides (amine value=400 ±
10mgKOH/g), react 2 hours.Cooling, adds 800 parts of ethylene glycol monobutyl ethers, is cooled to 90 DEG C, adds 1500 parts of crosslinking agent drops
Temperature adds 2 parts of Arlacel-40s, 2.4 parts of OP-10,2.4 parts of OP-15 are stirred 1 hour to 70 DEG C.At 60 DEG C, 126 parts of breasts are added
Acid, is stirred 0.5 hour.Resin is discharged into 8000 parts of water, emulsifies, obtains emulsion.Obtained emulsion and mill base proportionally 4：1
Ratio mixing, add deionized water, electrophoresis production can be carried out after being configured to the solid tank liquor containing for 30%, curing 48h.
Embodiment 6
By 2256 parts of epoxy resin E-51,1800 parts of PPG-600,100 parts of dimethylbenzene is put into reactor, heating
To 90 DEG C, 0.35 part of BFEE is added, temperature rises to 100 DEG C, and detection epoxide number is 0.1479 ± 0.01.Add
100 parts of propylene glycol monomethyl ether, stops stirring, adds 1600 parts of E-12.110 DEG C are warming up to, is completely dissolved to E-12, cooling is added
To 90 DEG C, 420 parts of diethanol amine are added, are reacted 1 hour.122 parts of monoethanolamines are added, are reacted 2 hours at 120 DEG C.Cooling,
893 parts of ethylene glycol monobutyl ethers are added, 90 DEG C are cooled to, 1600 parts of crosslinking agents are added, 70 DEG C are cooled to, 2 parts of Tween-60s are added,
2.4 parts of OP-10,2.4 parts of TX-15, are stirred 1 hour.At 60 DEG C, 162 parts of acetic acid are added, 162 parts of lactic acid are stirred 0.5 hour.
Product is discharged into 12150 parts of water, emulsifies, obtains emulsion.Obtained emulsion and mill base proportionally 4：1 ratio mixing, plus
Enter deionized water, electrophoresis production can be carried out after being configured to the solid tank liquor containing for 10%, curing 48h.
Embodiment 7
By 2256 parts of epoxy resin E-51,1800 parts of PEG-400,100 parts of dimethylbenzene is put into reactor, heating
To 90 DEG C, 0.35 part of BFEE is added, temperature rises to 100 DEG C, and detection epoxide number is 0.1479 ± 0.01.Add
100 parts of propylene glycol monomethyl ether, stops stirring, adds 1600 parts of E-12.110 DEG C are warming up to, is completely dissolved to E-12, cooling is added
To 90 DEG C, 410 parts of diethanol amine are added, are reacted 1 hour.120 parts of monoethanolamines are added, are reacted 2 hours at 120 DEG C.Cooling,
893 parts of ethylene glycol monobutyl ethers are added, 90 DEG C are cooled to, 1550 parts of crosslinking agents are added, 70 DEG C are cooled to, 2 parts of Tween-60s are added,
2.4 parts of OP-10,2.4 parts of TX-15, are stirred 1 hour.At 60 DEG C, 152 parts of acetic acid are added, 160 parts of lactic acid are stirred 0.5 hour.
Product is discharged into 12150 parts of water, emulsifies, obtains emulsion.Obtained emulsion and mill base proportionally 4：1 ratio mixing, plus
Enter deionized water, electrophoresis production can be carried out after being configured to the solid tank liquor containing for 10%, curing 48h.
The anti-stone of coating hits the overall merit that experiment is the mechanical property progress to whole coating system, can reflect that coating is soft
The quality of toughness, each ply adhesion and matching, be also evaluate the particularly important detection project of the secondary mechanical property of coating it
One.
Anti- stone, which hits experiment (Stone chip resistance test for Surface coating) and is mainly, to be passed through
Compressed air-driven rubble impacts coating, the toughness that evaluation automobile electrophoretic paint or similar coatings are impacted by rubble.
Impact method is tested with reference to the chipping resistance of SAE J400 U.S. surface coating, the temperature according to residing for sample, instrument
Divide A (subzero), B (low temperature), three kinds of C (room temperature), damage spot occurs in coating surface after impact.To each test method, coating is used
Maximum peels off the corresponding grading of spot diameter grading corresponding with the spot frequency is peeled off, and carrys out the resistance to stone of overall merit coating and hits ability.
Peel off corresponding grading point seven grades of spot diameter, respectively 10,9+, 9,8,7,6, it is very poor.Peel off spot frequency
Secondary corresponding grading point nine grades, respectively 0,1,2,3,4,5, it is bottom, middle and high.
The specification of sample is 101.6*304.8mm (4*12in), and test prepares 3 pieces of test plate (panel)s, before on-test, and paint film should be
48h is placed under temperature (23 ± 2) DEG C, humidity (50 ± 5) % standard conditions.
After experiment, the film of loosening is pulled off with adhesive tape, by film destruction situation compared with normal pictures, take its approximately
Standard number is rated the result for resisting stone.
Comparative example 1
Difference with embodiment 1 is that epoxy resin E-12 directly carries out aminating reaction without flexible chain compound.
Comparative example 2
Difference with embodiment 5 is that epoxy resin E-51 directly carries out aminating reaction without flexible chain compound.
Inventor by above-described embodiment 1-7 and comparative example 1 and comparative example 2, and using identical enamelling process by coating
On leaf spring, hit experiment through anti-stone and find, it is height that the resistance to stone of embodiment 1,2,3,4,5,6, which hits ability rating, embodiment 7
Resistance to stone is hit during ability rating is, the resistance to stone of comparative example 1 hits ability rating to be low, and the resistance to stone of comparative example 2 is hit during ability rating is.On
State the epoxy resin toughened epoxy resin toughened far better than prepared by prior art of embodiment preparation.
Finally, the present processes are only preferably embodiment, are not intended to limit the scope of the present invention.It is all
Within the spirit and principles in the present invention, any modification, equivalent substitution and improvements made etc. should be included in the protection of the present invention
Within the scope of.
Claims (10)
1. a kind of cathode electrodip painting for leaf spring, it is characterised in that raw material includes epoxy resin and flexible chain chemical combination
Thing；
Wherein, when the epoxide number of the epoxy resin is less than 0.4, the flexible chain compound is epoxide diluent, conversely, institute
Flexible chain compound is stated for chain extender.
2. cathode electrodip painting as claimed in claim 1, it is characterised in that when the epoxide number of the epoxy resin is less than 0.4,
The mol ratio of the epoxy radicals of the epoxy resin and the epoxy radicals of epoxide diluent is：0.8-0.95:1；Preferably, the epoxy
The mol ratio of the epoxy radicals of resin and the epoxy radicals of epoxide diluent is 0.86:1；
When the epoxide number of the epoxy resin is more than 0.4, the mass ratio of the epoxy resin and chain extender is：0.9-1.4:1；
Preferably, the weight ratio of the epoxy resin and chain extender is：0.94:1.
3. cathode electrodip painting as claimed in claim 3, it is characterised in that when the epoxide number of the epoxy resin is more than 0.4,
Raw material also includes the epoxy resin that epoxide number is less than 0.4, and epoxide number is more than 0.4 epoxy resin and epoxide number is less than 0.4
The weight fraction ratio of epoxy resin is：0.6-1.6:1；Preferably, epoxy resin of the epoxide number more than 0.4 is less than with epoxide number
The weight ratio of 0.4 epoxy resin is 0.7:1.
4. cathode electrodip painting as claimed in claim 1, it is characterised in that when the epoxide number of the epoxy resin is less than 0.4,
Epoxy resin includes the one or more in E10, E10P, E12, E20；Preferably, when the epoxide number of the epoxy resin is less than
When 0.4, epoxy resin is E12 and E20；It is highly preferred that E12 and E20 weight ratio is 1.4-1.7:1.
5. cathode electrodip painting as claimed in claim 2, it is characterised in that the epoxide diluent shrinks including neopentyl glycol two
Glycerin ether, BDDE, 1,6- hexanediol diglycidyl ethers, ethylene glycol diglycidylether, isophthalic
Diphenol diglycidyl ether, diethylene glycol diglycidyl glycerin ether, Triethylene Glycol Diglycidyl Ether, polyethylene glycol diglycidyl
One or more in ether and polypropylene glycol diglycidyl ether；Preferably, the epoxide diluent is that polypropylene glycol two contracts
Water glycerin ether；
The chain extender include PPG-200, PPG-400, PPG-600, PPG-1000, PEG-200, PEG-300, PEG-400,
One or more in PEG-600, PEG-800 and PEG-1000；Preferably, the epoxy resin is E-51, the chain extension
Agent is PPG-600.
6. a kind of cathode electrodip painting preparation method as described in claim 1-5 any one, it is characterised in that including toughness reinforcing ring
The preparation process of oxygen tree fat, the preparation process includes：
When the epoxide number of epoxy resin is less than 0.4, the epoxy resin, epoxide diluent and solvent are placed in reactor,
60-100 DEG C is warming up to, when detection is when epoxide number is decreased to 0.07-0.12, solvent is continuously added, it is glass to treat solution levelling
State, is obtained epoxy resin toughened；
When the epoxide number of the epoxy resin is more than 0.4, the epoxy resin, chain extender are mixed with solvent, 60- is warming up to
100 DEG C, catalyst and keeping temperature are added, when epoxide number is decreased to 0.07-0.12, solvent is added, stops stirring, add ring
Oxygen value is less than 0.4 epoxy resin, and it is glassy state to treat solution levelling, is obtained epoxy resin toughened.
7. the preparation method of cathode electrodip painting as claimed in claim 6, it is characterised in that raw material also includes：Amine, sealer,
Crosslinking agent, acid acceptor and electrophoretic paint mill base.
8. the preparation method of cathode electrodip painting as claimed in claim 7, it is characterised in that epoxy resin toughened, amine, closing
Agent, crosslinking agent, the weight ratio of acid acceptor are 150-160:2-2.5:3-4:5-6:1；Preferably, the flexibilizing epoxy tree
Fat, amine, sealer, crosslinking agent, the weight ratio of acid acceptor are 153:2.16:3.3:5.41:1.
9. the preparation method of cathode electrodip painting as claimed in claim 8, it is characterised in that also include：
By it is described it is epoxy resin toughened mixed with amine, carry out amination treatment, obtain aminate；
By aminate, for occlusive polyurethane sealer and crosslinking agent it is well mixed after, acid acceptor is added to enter
Row neutralization reaction, product is discharged into water and carries out emulsion reaction, emulsion is obtained；
The emulsion is mixed with electrophoretic paint mill base, deionized water is added, is configured to tank liquor, the tank liquor is cured, electricity is obtained
Product are painted in swimming.
10. the preparation method of cathode electrodip painting as claimed in claim 9, it is characterised in that before acid acceptor is added
Also include：Auxiliary agent is added, the auxiliary agent includes：OPEO, APES, polyoxyethylene sorbitan mountain
One or more in pears alcohol fatty acid ester and sorbitan fatty acid ester.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110452362A (en) * | 2019-08-20 | 2019-11-15 | 湖南湘江关西涂料有限公司 | Watersoluble closed isocyanate curing agent and preparation method thereof, water paint |
| CN112375208A (en) * | 2020-11-27 | 2021-02-19 | 芜湖春风新材料有限公司 | High-throwing-power toughened cathode electrophoresis resin and preparation method thereof, and electrophoresis emulsion and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102838846A (en) * | 2012-09-26 | 2012-12-26 | 中国海洋石油总公司 | Resin emulsion for cathode electrophoretic coating with high throwing power and preparation method thereof |
| CN103467708A (en) * | 2013-08-30 | 2013-12-25 | 武汉二航路桥特种工程有限责任公司 | Flexible epoxy resin material with low elastic modulus and high elongation |
| CN106085101A (en) * | 2016-06-02 | 2016-11-09 | 广德县中银化工有限责任公司 | A kind of low-temperature curing cathode electrophoresis coating emulsion and preparation technology thereof |
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2017
- 2017-04-27 CN CN201710289485.4A patent/CN107033736B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102838846A (en) * | 2012-09-26 | 2012-12-26 | 中国海洋石油总公司 | Resin emulsion for cathode electrophoretic coating with high throwing power and preparation method thereof |
| CN103467708A (en) * | 2013-08-30 | 2013-12-25 | 武汉二航路桥特种工程有限责任公司 | Flexible epoxy resin material with low elastic modulus and high elongation |
| CN106085101A (en) * | 2016-06-02 | 2016-11-09 | 广德县中银化工有限责任公司 | A kind of low-temperature curing cathode electrophoresis coating emulsion and preparation technology thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110452362A (en) * | 2019-08-20 | 2019-11-15 | 湖南湘江关西涂料有限公司 | Watersoluble closed isocyanate curing agent and preparation method thereof, water paint |
| CN112375208A (en) * | 2020-11-27 | 2021-02-19 | 芜湖春风新材料有限公司 | High-throwing-power toughened cathode electrophoresis resin and preparation method thereof, and electrophoresis emulsion and preparation method thereof |
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