CN107033736B - A kind of cathode electrodip painting and preparation method thereof for leaf spring - Google Patents
A kind of cathode electrodip painting and preparation method thereof for leaf spring Download PDFInfo
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- CN107033736B CN107033736B CN201710289485.4A CN201710289485A CN107033736B CN 107033736 B CN107033736 B CN 107033736B CN 201710289485 A CN201710289485 A CN 201710289485A CN 107033736 B CN107033736 B CN 107033736B
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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
-
- 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
-
- 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
-
- 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
Abstract
The present invention provides a kind of cathode electrodip painting and preparation method thereof for leaf spring, and raw material includes epoxy resin, and when the epoxide number of the epoxy resin is less than 0.4, the raw material further includes epoxide diluent, conversely, then the raw material further includes chain extender；Wherein, the epoxide diluent and chain extender are flexible chain compound.The present invention increases the epoxide diluent or chain extender of flexible chain compound in the feed, reduces the brittleness of cathode electrodip painting, and then improve anti-stone and hit ability, while also improving salt fog resistance by the epoxide number according to epoxy resin.
Description
Technical field
The present invention relates to electrophoretic paint technical fields, more particularly, to the cathode electrodip painting and its system for leaf spring
Preparation Method.
Background technique
Leaf spring (Leaf Spring) leaf spring is most widely used a kind of elastic element in automotive suspension, it
If being the spring beam for the approximately equi-strength that wide by dry plate but Length discrepancy alloy spring piece is composed, each alloy bullet
The thickness of reed can be equal, can also be unequal.
Since leaf spring is mounted to bottom of car, leaf spring paint will bear continuous stone and hit, simultaneously
It is required that stronger salt fog resistance, in the prior art, the raw material of leaf spring mostly use epoxy resin or epoxy resin and bis-phenol
The combination of A, but since epoxy resin is harder, after being made as electrophoretic paint and being coated in leaf spring, there are brittleness higher, anti-stone
The problem of ability difference is hit, while salt fog resistance is also and not fully up to expectations.
Steel spring plate paint is divided into following several in the prior art:
A, powdery paints, using electrostatic painting process, generating process generates a large amount of dust；
B, oil paint, using pneumatic spraying technique, production process has the volatilization of a large amount of VOC；
C, water paint (spraying paint), expensive using pneumatic spraying technique, utilization rate is low；
D, there is coating became uneven, and production process meeting using dipping process in oil paint (dip painting)
There is a large amount of VOC to volatilize；
E, there is coating became uneven using dipping process in water paint (dip painting).
Summary of the invention
The present invention provide it is a kind of overcome the above problem or at least be partially solved the above problem for leaf spring
Cathode electrodip painting and preparation method thereof.
According to an aspect of the present invention, a kind of cathode electrodip painting for leaf spring is provided, which is characterized 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 flexibility chain compound is epoxide diluent, instead
It, the flexibility chain compound is chain extender.
Preferably, when the epoxide number of the epoxy resin is less than 0.4, the epoxy group and epoxy of the epoxy resin dilute
The molar ratio of the epoxy group of agent are as follows: 0.8-0.95:1；Preferably, the epoxy of the epoxy group of the epoxy resin and epoxide diluent
The molar ratio of base is 0.86:1.
When the epoxide number of the epoxy resin is greater than 0.4, the mass ratio of the epoxy resin and chain extender are as follows: 0.9-
1.4:1；Preferably, the weight ratio of the epoxy resin and chain extender are as follows: 0.94:1.
Preferably, when the epoxide number of the epoxy resin is greater than 0.4, raw material further includes epoxy of the epoxide number less than 0.4
Resin, and the weight fraction ratio of epoxy resin and epoxide number epoxy resin less than 0.4 of the epoxide number greater than 0.4 are as follows: 0.6-
1.6:1；Preferably, the weight ratio of epoxy resin and epoxide number epoxy resin less than 0.4 of the epoxide number greater than 0.4 is 0.7:1.
Preferably, when the epoxide number of the epoxy resin is less than 0.4, epoxy resin includes in E10, E10P, E12, E20
It is 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
The weight ratio of ground, E12 and E20 are 1.4-1.7:1.
Preferably, the epoxide diluent include neopentylglycol diglycidyl ether, 1,4-butanediol diglycidyl ether,
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-
400, one of PEG-600, PEG-800 and PEG-1000 or a variety of；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 methods, including epoxy resin toughened preparation step, 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 reaction kettle
In, it is warming up to 60-100 DEG C, when detecting when epoxide number is decreased to 0.07-0.12, continuously adds solvent, is glass to solution levelling
Glass state obtains epoxy resin toughened；
When the epoxide number of the epoxy resin is greater than 0.4, the epoxy resin, chain extender are mixed with solvent, is heated up
To 60-100 DEG C, catalyst is added and keeps temperature, when epoxide number is decreased to 0.07-0.12, solvent is added, stops stirring,
Epoxy resin of the epoxide number less than 0.4 is added, is glassy state to solution levelling, obtains epoxy resin toughened.
Preferably, the raw material of cathode electrodip painting further include: amine, sealer, crosslinking agent, acid acceptor and electrophoretic paint color
Slurry.
Preferably, epoxy resin toughened, amine, sealer, crosslinking agent, acid acceptor weight ratio be 150-160:2-
2.5:3-4:5-6:1；Preferably, the epoxy resin toughened, amine, sealer, crosslinking agent, acid acceptor weight ratio be
153:2.16:3.3:5.41:1。
Preferably, preparation method further include:
By it is described it is epoxy resin toughened mixed with amine, carry out amination treatment, obtain aminate；
By aminate, the sealer that is used for occlusive polyurethane and crosslinking agent after mixing, acid acceptor is added
To carry out neutralization reaction, product is discharged into water and carries out emulsion reaction, obtains lotion；
The lotion is mixed with electrophoretic paint mill base, deionized water is added, is configured to tank liquor, the tank liquor is cured, is obtained
Obtain electrophoretic paint finished product.
Preferably, before acid acceptor is added further include: auxiliary agent is added, the auxiliary agent includes: octyl phenol polyoxy second
One in alkene ether, alkyl phenol polyoxyethylene ether, polyoxyethylene sorbitan fatty acid ester and sorbitan fatty acid ester
Kind is a variety of.The application proposes a kind of cathode electrodip painting and preparation method thereof for leaf spring, 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.
Specific embodiment
With reference to embodiment, the embodiment of the present invention is furthur described in detail.Following embodiment is used for
Illustrate the present invention, but is not intended to limit the scope of the invention.
Since leaf spring is mounted to bottom of car, the cathode electrodip painting of leaf spring will bear continuous stone
It hits, while requiring stronger salt fog resistance, in the prior art, the raw material of leaf spring mostly uses epoxy resin or asphalt mixtures modified by epoxy resin
The combination of rouge and bisphenol-A, but since epoxy resin is harder, after being made as electrophoretic paint and being coated in leaf spring, there are brittleness
Higher, anti-stone hits the problem of ability difference, while salt fog resistance is also and not fully up to expectations.
In order to overcome the above problem in 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 flexibility chain compound is epoxide diluent, instead
It, the flexibility chain compound is chain extender.
It should be noted that the flexibility in macromolecular chain refers to the energy for changing strand form possessed by macromolecular chain
Amount, flexible stronger, then the energy for changing strand form is also stronger.In general, belong to firmly containing aromatic macromolecular chain
Property chain, the macromolecular chain of fatty race belong 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 is higher, and the present invention is boundary with epoxide number 0.4, when epoxide number is more than or equal to 0.4, is then added
Chain extender flexible makes the length of epoxy resin, the appropriate flexibility for increasing 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 to enhance the toughness of epoxy resin, reach epoxy resin in firmly with 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 group and epoxy of epoxy resin
The molar ratio of the epoxy group of diluent are as follows: 0.8-0.95:1.
In a preferred embodiment, when the epoxide number of epoxy resin is less than 0.4, the epoxy group and epoxy of epoxy resin
The molar ratio of the epoxy group of diluent is 0.86:1.
In one alternate embodiment, when the epoxide number of epoxy resin is greater than 0.4, the quality of epoxy resin and chain extender
Than are as follows: 0.9-1.4:1.
In a preferred embodiment, when the epoxide number of epoxy resin is greater than 0.4, the weight of epoxy resin and chain extender
Than are as follows: 0.94:1.
In one alternate embodiment, when the epoxide number of epoxy resin is greater than 0.4, raw material further includes that epoxide number is less than
0.4 epoxy resin, and the weight fraction ratio of epoxy resin and epoxide number epoxy resin less than 0.4 of the epoxide number greater than 0.4
Are as follows: 0.6-1.6:1.
In a preferred embodiment, epoxide number is greater 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 epoxide number of the epoxy resin is less than 0.4, epoxy resin include E10,
One of E10P, E12, E20 or a variety of；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 the weight ratio of E12 and E20 is 1.6:1.
In one alternate embodiment, epoxide diluent includes: neopentylglycol diglycidyl ether, the contracting of 1,4-butanediol two
Water glycerin ether, 1,6- hexanediol diglycidyl ether, ethylene glycol diglycidylether, resorcinolformaldehyde resin, diethyl
Hexanediol diglycidyl ether, Triethylene Glycol Diglycidyl Ether, polyethyleneglycol diglycidylether and polypropylene glycol two shrink
One of glycerin ether is a variety of.
It should be noted that neopentylglycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6- hexylene glycol 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 of PEG-600, PEG-800 and PEG-1000 or a variety of.
In a preferred embodiment, epoxide diluent is polypropylene glycol diglycidyl ether.
In a preferred embodiment, epoxy resin E-51, chain extender 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 reaction kettle,
It is warming up to 60-100 DEG C, when epoxide number is decreased to 0.07-0.12, continuously adds solvent, is glassy state to solution levelling, obtains
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, propylene glycol monophenyl ether, butanone, methyl
One of isobutyl ketone is a variety of.
In a preferred embodiment, solvent is dimethylbenzene.
In an alternative embodiment, when the epoxide number of epoxy resin is greater than 0.4, by epoxy resin, chain extender and solvent
Mixing, is warming up to 60-100 DEG C, and catalyst is added and simultaneously keeps temperature, when epoxide number is decreased to 0.07-0.12, be added solvent and
Epoxy resin of the epoxide number less than 0.4 stops stirring, is glassy state to solution levelling, obtains epoxy resin toughened.
It should be noted that solvent and epoxide number is added less than 0.4 why when epoxide number is decreased to 0.07-0.12
Epoxy resin, be, when epoxy resin of the epoxide number less than 0.4 is added, to be equivalent to because the hardness of epoxy resin at this time is too low
Hard monomer is increased in the solution, ensure 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 greater than 0.4 are realized for the first time by the present invention,
Why currently available technology cannot achieve this process, be because when the epoxide number of epoxy resin be greater than 0.4 when, if be added without
Very slowly, but catalyst once will be added in the speed of catalyst, reaction, (be equivalent to even if the additive amount of catalyst is considerably less
The number one thousandth of epoxy resin additive amount), 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, when controlled at 60-100 DEG C, reaction can be in
Controllable state, simultaneous reactions speed are very ideal.
In one alternate embodiment, the present invention also provides a kind of leaf spring cathodes using epoxy resin toughened preparation
Electrophoretic paint, raw material further include: amine, sealer, crosslinking agent, acid acceptor and electrophoretic paint mill base.
In a preferred embodiment, epoxy resin toughened, amine, sealer, crosslinking agent, acid acceptor weight ratio be
150-160:2-2.5:3-4:5-6:1。
In a more preferred embodiment, the weight ratio of epoxy resin toughened, amine, sealer, crosslinking agent, 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, the epoxy resin toughened method for preparing leaf spring cathode electrodip painting is utilized, comprising:
It is mixed epoxy resin toughened with amine, carries out amination treatment, obtain aminate；
By aminate, the sealer that is used for occlusive polyurethane and crosslinking agent after mixing, with acid acceptor into
Product is discharged into water and carries out emulsion reaction, obtains lotion by row neutralization reaction；
Lotion and electrophoretic paint mill base are mixed in the ratio of 3-5:1, deionized water is added, being configured to solid content is 10-
30% tank liquor, tank liquor is cured, and obtains electrophoretic paint finished product.
In a preferred embodiment, lotion and the ratio of electrophoretic paint mill base are 4:1.
It should be noted that sealer used in occlusive polyurethane has: gaultherolin, 3,5- dimethyl pyrazole, acetyl
Aniline, phenol, caprolactam, ethylene glycol monoethyl ether, ethylene glycol ether, ethylene glycol monobutyl ether, one in ethylene glycol monohexylether
Kind is a variety of.
In a preferred embodiment, sealer selects ethylene glycol monoethyl ether.
It should be noted that electrophoretic paint of the invention is particularly suitable in leaf spring, being reacted by electrophoresis will be of the invention
Electrophoretic paint be coated in leaf spring, hit verification experimental verification by anti-stone, the leaf spring that the present invention coats has 80% ratio
Example hits the grade of ability in the resistance to stone of coating as height, the significantly larger than similar product of the prior art.
In one alternate embodiment, amine includes monoethanolamine, diethanol amine, N, N- dimethylethanolamine, N- methyl list
Any two kinds in ethanol amine, polyamide and ketimide.
It should be noted that the selection of amine is equally the place of innovation of the invention in the present embodiment, people according to the present invention
Research can significantly improve the throwing power of electrophoretic paint compared with prior art with the combination of two of above-mentioned ammonium.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 measuring method of special box is shown in the prior art using the performance of the electrophoretic paint throwing power of polyetheramine preparation
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 |
The performance table for the electrophoretic paint throwing power that table 1, the present embodiment and the prior art are prepared 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.Wherein the best (2-hydroxyethyl)methylamine)+ketimide of throwing power can reach the throwing power of 23.4mm, far better than existing
There is technology.
In an alternative embodiment, the step of carrying out neutralization reaction with acid acceptor, before further include: auxiliary agent is added,
Auxiliary agent include: octyl phenol polyoxyethylene ether (OP-4, OP-7, OP-9, OP-10, OP-13, OP-15, OP-20, OP-30, OP-40,
OP-50), alkyl phenol polyoxyethylene ether (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
Kind is a variety of.
It should be noted that usually requiring to be added during prior art preparation electrophoretic paint, BYK etc. is expensive to be helped
Agent, the market price of BYK usually in 180-220 member/kilogram fluctuation, and OP, TX that the auxiliary agent in the present embodiment uses, 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
It hits ability and is still better than the prior art, another prominent effect of the invention of 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 reaction kettle, 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,
141 parts of monoethanolamines are added in 450 parts of ethylene glycol monomethyl ether acetates, react 2 hours at 110 DEG C, 404 parts of polyamide are added
(amine value=320 ± 10mgKOH/g) reacts 2 hours, 1000 parts of ethylene glycol monobutyl ethers is added, be cooled to 90 DEG C, is added 1600 parts
Crosslinking agent is cooled to 70 DEG C, and 2 parts of Tween-40s are added, and 2.4 parts of OP-7,2.4 parts of OP-15 are stirred 1 hour.At 60 DEG C, it is added
117 parts of acetic acid, 176 parts of lactic acid stir 0.5 hour.Resin is discharged into 10100 parts of water, emulsifies, obtains lotion.Obtained cream
The ratio of liquid and mill base proportionally 4:1 mix, and deionized water is added, is configured to the solid tank liquor containing for 20%, cure after 48h i.e.
It can carry out electrophoresis production.
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 reaction kettle, 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,
141 parts of monoethanolamines are added in 450 parts of ethylene glycol monomethyl ether acetates, react 2 hours at 110 DEG C, 404 parts of polyamide are added
(amine value=320 ± 10mgKOH/g) reacts 2 hours, 1000 parts of ethylene glycol monobutyl ethers is added, be cooled to 90 DEG C, is added 1600 parts
Crosslinking agent is cooled to 70 DEG C, and 2 parts of Tween-40s are added, and 2.4 parts of OP-7,2.4 parts of OP-15 are stirred 1 hour.At 60 DEG C, it is added
117 parts of acetic acid, 176 parts of lactic acid stir 0.5 hour.Resin is discharged into 10100 parts of water, emulsifies, obtains lotion.Obtained cream
The ratio of liquid and mill base proportionally 4:1 mix, and deionized water is added, is configured to the solid tank liquor containing for 20%, cure after 48h i.e.
It can carry out electrophoresis production.
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 reaction kettle, are to slowly warm up to 100 DEG C, to
After material is completely dissolved, 105 parts of diethanol amine are added, after 100 DEG C are reacted 1 hour, are added 235 parts of propylene glycol monomethyl ethers, 450
Part ethylene glycol monomethyl ether acetate, is added 135 parts of monoethanolamines, reacts 2 hours at 110 DEG C, 400 parts of polyamide (amine are added
It is worth=320 ± 10mgKOH/g), it reacts 2 hours, 1000 parts of ethylene glycol monobutyl ethers is added, are cooled to 90 DEG C, 1600 parts of friendships are added
Join agent, be cooled to 70 DEG C, 2 parts of Tween-40s are added, 2.4 parts of OP-7,2.4 parts of OP-15 are stirred 1 hour.At 60 DEG C, it is added
113 parts of acetic acid, 175 parts of lactic acid stir 0.5 hour.Resin is discharged into 10100 parts of water, emulsifies, obtains lotion.Obtained cream
The ratio of liquid and mill base proportionally 4:1 mix, and deionized water is added, is configured to the solid tank liquor containing for 20%, cure after 48h i.e.
It can carry out electrophoresis production.
Embodiment 4
By 1620 parts of epoxy resin E-51,1200 parts of PPG-600,100 parts of dimethylbenzene is put into reaction kettle, is heated up
To 90 DEG C, 0.5 part of boron trifluoride ether is added, temperature rises to 100 DEG C, and detection epoxide number is 0.0859 ± 0.01.It is added 100
The propylene glycol monomethyl ether of part stops stirring, 1600 parts of E-12 is added.110 DEG C are warming up to, until E-12 is completely dissolved, is added 403 part third
Glycol monomethyl ether, 450 parts of ethylene glycol monomethyl ether acetates, is cooled to 90 DEG C, be added 290 parts of ketimides (amine value=400 ±
10mgKOH/g), it reacts 2 hours.Cooling, is added 800 parts of ethylene glycol monobutyl ethers, is cooled to 90 DEG C, and 1500 parts of crosslinking agent drops are added
2 parts of Arlacel-40s are added to 70 DEG C in temperature, and 2.4 parts of OP-10,2.4 parts of OP-15 are stirred 1 hour.At 60 DEG C, 135 parts of creams are added
Acid stirs 0.5 hour.Resin is discharged into 8000 parts of water, emulsifies, obtains lotion.Obtained lotion and mill base proportionally 4:1
Ratio mixing, deionized water is added, is configured to the solid tank liquor containing for 30%, electrophoresis production can be carried out after curing 48h.
Embodiment 5
By 1128 parts of epoxy resin E-51,1200 parts of PPG-600,100 parts of dimethylbenzene is put into reaction kettle, is heated up
To 90 DEG C, 0.5 part of boron trifluoride ether is added, temperature rises to 100 DEG C, and detection epoxide number is 0.0859 ± 0.01.It is added 100
The propylene glycol monomethyl ether of part stops stirring, 1600 parts of E-12 is added.110 DEG C are warming up to, until E-12 is completely dissolved, is added 403 part third
Glycol monomethyl ether, 450 parts of ethylene glycol monomethyl ether acetates, is cooled to 90 DEG C, be added 285 parts of ketimides (amine value=400 ±
10mgKOH/g), it reacts 2 hours.Cooling, is added 800 parts of ethylene glycol monobutyl ethers, is cooled to 90 DEG C, and 1500 parts of crosslinking agent drops are added
2 parts of Arlacel-40s are added to 70 DEG C in temperature, and 2.4 parts of OP-10,2.4 parts of OP-15 are stirred 1 hour.At 60 DEG C, 126 parts of creams are added
Acid stirs 0.5 hour.Resin is discharged into 8000 parts of water, emulsifies, obtains lotion.Obtained lotion and mill base proportionally 4:1
Ratio mixing, deionized water is added, is configured to the solid tank liquor containing for 30%, electrophoresis production can be carried out after curing 48h.
Embodiment 6
By 2256 parts of epoxy resin E-51,1800 parts of PPG-600,100 parts of dimethylbenzene is put into reaction kettle, is heated up
To 90 DEG C, 0.35 part of boron trifluoride ether is added, temperature rises to 100 DEG C, and detection epoxide number is 0.1479 ± 0.01.It is added
100 parts of propylene glycol monomethyl ether stops stirring, 1600 parts of E-12 is added.110 DEG C are warming up to, until E-12 is completely dissolved, cooling is added
To 90 DEG C, 420 parts of diethanol amine are added, react 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, are cooled to 90 DEG C, 1600 parts of crosslinking agents are added, are cooled to 70 DEG C, 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 stir 0.5 hour.
Product is discharged into 12150 parts of water, emulsifies, obtains lotion.Obtained lotion and mill base proportionally 4:1 ratio mixing, add
Enter deionized water, is configured to the solid tank liquor containing for 10%, electrophoresis production can be carried out after curing 48h.
Embodiment 7
By 2256 parts of epoxy resin E-51,1800 parts of PEG-400,100 parts of dimethylbenzene is put into reaction kettle, is heated up
To 90 DEG C, 0.35 part of boron trifluoride ether is added, temperature rises to 100 DEG C, and detection epoxide number is 0.1479 ± 0.01.It is added
100 parts of propylene glycol monomethyl ether stops stirring, 1600 parts of E-12 is added.110 DEG C are warming up to, until E-12 is completely dissolved, cooling is added
To 90 DEG C, 410 parts of diethanol amine are added, react 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, are cooled to 90 DEG C, 1550 parts of crosslinking agents are added, are cooled to 70 DEG C, 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 stir 0.5 hour.
Product is discharged into 12150 parts of water, emulsifies, obtains lotion.Obtained lotion and mill base proportionally 4:1 ratio mixing, add
Enter deionized water, is configured to the solid tank liquor containing for 10%, electrophoresis production can be carried out after curing 48h.
It is the overall merit carried out to the mechanical property of entire coating system that the anti-stone of coating, which hits test, and it is soft to be able to reflect coating
Toughness, the superiority and inferiority of each ply adhesion and matching, and the particularly important detection project of the evaluation secondary mechanical property of coating it
One.
Anti- stone hits test (Stone chip resistance test for Surface coating) and mainly passes 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 the U.S. SAE J400 surface coating, according to temperature locating 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
The corresponding grading of maximum removing spot diameter grading corresponding with the removing spot frequency, carrys out the resistance to stone of overall merit coating and hits ability.
Remove corresponding grading point seven grades of spot diameter, respectively 10,9+, 9,8,7,6, it is very poor.Remove 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, and before on-test, paint film should be
Temperature (23 ± 2) DEG C places 48h under the standard conditions of humidity (50 ± 5) %.
After test, the film of loosening is pulled off with adhesive tape, and film is destroyed into situation compared with normal pictures, takes it approximate
Standard number is rated the result for resisting stone.
Comparative example 1
The difference from embodiment 1 is that epoxy resin E-12 does not add flexible chain compound, aminating reaction is directly carried out.
Comparative example 2
Difference with embodiment 5 is that epoxy resin E-51 does not add flexible chain compound, directly progress aminating reaction.
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, Jing Kangshi hits test discovery, and 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 hit ability rating be it is low, 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 prior art preparation of embodiment preparation.
Finally, the present processes are only preferable embodiment, it is 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 replacement, improvement and so on should be included in protection of the invention
Within the scope of.
Claims (12)
1. a kind of cathode electrodip painting for leaf spring, which is characterized in that raw material includes by epoxy resin and flexible chain
Close the epoxy resin toughened of object reaction generation；
Wherein, when the epoxide number of the epoxy resin is less than 0.4, the flexibility chain compound is epoxide diluent, the ring
Oxygen diluent includes neopentylglycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6- hexylene glycol 2-glycidyl
Ether, ethylene glycol diglycidylether, resorcinolformaldehyde resin, diethylene glycol diglycidyl glycerin ether, triethylene glycol two contract
One of water glycerin ether, polyethyleneglycol diglycidylether and polypropylene glycol diglycidyl ether are a variety of；Conversely, described
Flexible chain compound be chain extender, the chain extender include PPG-200, PPG-400, PPG-600, PPG-1000, PEG-200,
One of PEG-300, PEG-400, PEG-600, PEG-800 and PEG-1000 or a variety of；
The epoxy resin is reacted with flexible chain compound generates epoxy resin toughened step, specifically:
When the epoxide number of epoxy resin is less than 0.4, the epoxy resin, epoxide diluent and solvent are placed in reaction kettle,
It is warming up to 60-100 DEG C, when detecting that epoxide number is decreased to 0.07-0.12, continuously adds solvent, is glass to solution levelling
State obtains epoxy resin toughened；
When the epoxide number of the epoxy resin is greater than 0.4, the epoxy resin, chain extender are mixed with solvent, are warming up to 60-
100 DEG C, catalyst is added and keeps temperature, when epoxide number is decreased to 0.07-0.12, solvent is added, stops stirring, ring is added
Epoxy resin of the oxygen value less than 0.4 is glassy state to solution levelling, obtains epoxy resin toughened.
2. cathode electrodip painting as described in claim 1, which is characterized in that when the epoxide number of the epoxy resin is less than 0.4,
The molar ratio of the epoxy group of the epoxy group and epoxide diluent of the epoxy resin are as follows: 0.8-0.95:1.
3. cathode electrodip painting as described in claim 1, which is characterized in that when the epoxide number of the epoxy resin is less than 0.4, institute
The molar ratio for stating the epoxy group of epoxy resin and the epoxy group of epoxide diluent is 0.86:1.
4. cathode electrodip painting as described in claim 1, which is characterized in that when the epoxide number of the epoxy resin is greater than 0.4,
The mass ratio of the epoxy resin and chain extender are as follows: 0.9-1.4:1.
5. cathode electrodip painting as described in claim 1, which is characterized in that when the epoxide number of the epoxy resin is greater than 0.4,
The weight ratio of the epoxy resin and chain extender are as follows: 0.94:1.
6. cathode electrodip painting as described in claim 1, which is characterized in that when the epoxide number of the epoxy resin is greater than 0.4,
Raw material further includes epoxy resin of the epoxide number less than 0.4, and epoxy resin of the epoxide number greater than 0.4 and epoxide number are less than 0.4
The weight fraction ratio of epoxy resin are as follows: 0.6-1.6:1.
7. cathode electrodip painting as claimed in claim 6, which is characterized in that epoxide number is greater than 0.4 epoxy resin and epoxide number
The weight ratio of epoxy resin less than 0.4 is 0.7:1.
8. cathode electrodip painting as described in claim 1, which is characterized in that when the epoxide number of the epoxy resin is less than 0.4,
Epoxy resin includes one of E10, E10P, E12, E20 or a variety of.
9. cathode electrodip painting as claimed in claim 8, which is characterized in that when the epoxide number of the epoxy resin is less than 0.4,
Epoxy resin is E12 and E20.
10. cathode electrodip painting as claimed in claim 2, which is characterized in that the epoxide diluent is the shrink of polypropylene glycol two
Glycerin ether.
11. cathode electrodip painting as claimed in claim 4, which is characterized in that the epoxy resin is E-51, and the chain extender is
PPG-600。
12. cathode electrodip painting as claimed in claim 9, which is characterized in that the weight ratio of E12 and E20 is 1.4-1.7:1.
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| 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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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 |
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