CN1900191A - Resin containing biamide structure, cathode electrophoretic paint containing said resin and their preparing method - Google Patents
Resin containing biamide structure, cathode electrophoretic paint containing said resin and their preparing method Download PDFInfo
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- CN1900191A CN1900191A CN 200610028896 CN200610028896A CN1900191A CN 1900191 A CN1900191 A CN 1900191A CN 200610028896 CN200610028896 CN 200610028896 CN 200610028896 A CN200610028896 A CN 200610028896A CN 1900191 A CN1900191 A CN 1900191A
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Abstract
The present invention discloses a kind of resin with biamide structure and the following structure: R1OCO-NH-Y-NH-CO-O(CH2)nNR3-CO-Z-CO-NR3(CH2)n-O-CO-NH-Y-NH-CO-OR1, where, Y is one residual radical selected from TDI, 1, 6-HDI, MDI, PAPI, IPDI, TXDI, TMXDI, HMDI and HTDI; R1 is R1'(CH2CH2O)qCH2CH2-, with R1' being C1-C6 alkyl radical, q being integral of 0-2; Z is one selected from -(CH2)m-, pheynlene, 2, 6-naphthylene and dimeric linoleic radical, with m being integral of 0-9; R3 is H, C1-C4 alkyl radical or -(CH2)pOH, with p being integral f 2-4; and n is integral of 2-4. The resin can raise the interlayer adhesion between the electrophoretic primer and the finishing paint. The present invention also discloses the paint composition including the resin.
Description
Technical field
The present invention relates to electrodepositable cathode electrophoretic coating composition, relate more specifically to environment-friendly low-temperature cathode electrophoresis dope and the manufacture method thereof formed by emulsion and mill base.
Background technology
Cation electrodeposition coating (cathode electrophoresis dope) gains great popularity with its excellent corrosion resistance nature, high throwing power, high coulomb efficiency and low solvent, and fast development since the seventies comes out is widely used in the priming paint of motor vehicle body and vehicle frame so far in world's automotive industry, the especially application of body of a motor car (referring to US3,984,299,5,074,979,4,009,133,4,423,166,5,348,578).In recent years; along with being growing more intense of automobile market competition and day by day increasing of environmental protection cry; painting dressing automobiles is also more and more paid attention to for requirement on environmental protection, coating material and application production cost and facility investment when guaranteeing high-decoration, high Corrosion Protection.Have only those to be proved to be that the novel material and the new technology of safety and environmental protection could obtain business success more than previously used material and technology.
The cation electrodeposition coating that is used for vehicle paint base is a kind of affixture and end capped polyisocyanate mixtures of positively charged ion epoxy amine of water-dispersion, and is equipped with dispersible pigment slurry, forms electrodepositable work tank liquor.Conducting base takes out after the work of immersion tank liquor, forms one deck paint film through baking on conducting base.This paint film is attached on the phosphatization conversion film, has stronger corrosion proof function.Early stage cathode electrodip painting generally includes plumbiferous color stuffing, plumbous existence has the corrosion proof function of lifting and catalytic curing function for paint film, and unleaded now ability cathode electrophoresis has become a kind of trend, and along with the development of low-temperature curing technology has obtained using widely.Used unleaded color stuffing to substitute leaded color stuffing in the mill base of cathode electrophoresis dope, can play to reduce and expand erosion, the blistered purpose of paint film.
In addition, in the finish paint and electrocoating paint of prior art, in order to solve the compatibility problem between each component of electrocoating paint, can in coating system, add polyether monoamine compound (for example referring to US4,432,850, US4,423,166).Yet aforesaid method is coated with in the priming paint surface does not have or adopt Synolac as finish paint or solidifying priming paint adopts under the situation of non-direct-fired (as electrically heated or heat exchanger) roasting mode, tends to occur the problem of interlayer poor adhesive force between priming paint and finish paint.
Summary of the invention
The present invention is intended to solve in the prior art electrophoretic primer to the problem of the ply adhesion difference of finish paint.
An object of the present invention is to provide and a kind ofly can effectively improve the additive of electrophoretic primer sticking power between top coat layer.
Another object of the present invention provides a kind of cathode electrophoretic coating composition, and said composition has the sticking power of good priming paint to finish paint.
A further object of the invention provides the preparation method of above-mentioned additive and above-mentioned cathode electrophoretic coating composition.
A further object of the present invention provides the purposes of above-mentioned additive in the preparation cathode electrophoresis dope.
In a first aspect of the present invention, a kind of resin with biamide structure is provided, it can effectively improve electrophoretic primer to sticking power between top coat layer.This resin has following structural formula:
R
1OCO-NH-Y-NH-CO-O(CH
2)
nNR
3-CO-Z-CO-NR
3(CH
2)
n-O-CO-NH-Y-NH-CO-OR
1
In the formula, Y represents to be selected from the residue of the polyisocyanates of tolylene diisocyanate (TDI), hexamethylene diisocyanate (HDI), diphenylmethanediisocyanate (MDI), poly methylene poly phenyl poly isocyanate (PAPI), isophorone diisocyanate (IPDI), trimethylammonium hexamethylene diisocyanate (TXDI), tetramethylxylylene diisocyanate (TMXDI), dicyclohexyl methane diisocyanate (HMDI), hexahydrotoluene vulcabond (HTDI);
R
1Expression R
1' (CH
2CH
2O)
qCH
2CH
2-, R wherein
1' be selected from C
1-C
6Alkyl, q is the integer of 0-2;
Z represents to be selected from-(CH
2)
m-, phenylene, 2, the group of the linolic acid base of 6-naphthylidene or dimerization, m represents the integer of 0-9;
R
3Expression is selected from H, C
1-C
4Alkyl or-(CH
2)
pOH, the integer of p=2-4;
N represents the integer of 2-4.
Above-mentioned resin preferably, number-average molecular weight is in 500～2000 scope.Preferably, the weight-average molecular weight of above-mentioned resin is in 1000～4000 scope.
In a second aspect of the present invention, a kind of coating composition is provided, said composition comprises water-dispersion emulsion and pigment slurry, described water-dispersion emulsion comprises matrix resin and aqueous medium, described matrix resin comprises through toughening agent modified chain extension and aminating Resins, epoxy and end capped isocyanic ester, described pigment slurry comprises quaternised modified epoxy, pigment and the aqueous medium as dispersion resin, it is characterized in that described water-dispersion emulsion also comprises claim 1 or 2 described resins with biamide structure.
In aforementioned coating composition, preferably, the described weight percentage that accounts for water-dispersion emulsion total solids with resin of biamide structure is 0.5-10%.Preferably, the weight of described water-dispersion emulsion accounts for the 70-90% of coating composition gross weight, and the weight of described pigment slurry accounts for the 10-30% of coating composition gross weight.
In a third aspect of the present invention, a kind of method for preparing the resin with biamide structure of first aspect present invention is provided, this method may further comprise the steps: make polyisocyanates and alcohol or the reaction of pure ether compound, obtain half end capped isocyanic ester; Make the reaction of dicarboxylic esters and oxyamine, form the bisamide compound; Then, described half end capped isocyanic ester and described bisamide compound are reacted, obtain described resin with biamide structure.
In aforesaid method, preferably, described polyisocyanates is selected from tolylene diisocyanate (TDI), 1, hexamethylene-diisocyanate (HDI), diphenylmethanediisocyanate (MDI), poly methylene poly phenyl poly isocyanate (PAPI), isophorone diisocyanate (IPDI), trimethylammonium hexamethylene diisocyanate (TXDI), tetramethylxylylene diisocyanate (TMXDI), dicyclohexyl methane diisocyanate (HMDI), hexahydrotoluene vulcabond (HTDI); Described alcohol or pure ether compound are selected from has formula R
1' (CH
2CH
2O)
qCH
2CH
2The compound of OH, in the formula, R
1' be selected from C
1-C
6Alkyl, the integer of q=0-2; Described dicarboxylic esters is to be selected to have formula R
2O
2C-Z-CO
2R
2Compound, wherein, Z is selected from-(CH
2)
m-, the integer of m=0-9, phenylene, 2, the linolic acid base of 6-naphthylidene or dimerization, R
2Be C
1-C
6Alkyl; Described oxyamine is to be selected to have formula R
3NH (CH
2)
nThe compound of OH, in the formula, R
3Be selected from H, C
1-C
4Alkyl or-(CH
2)
pOH, the integer of p=2-4, the integer of n=2-4.
More preferably, described polyisocyanates is selected from tolylene diisocyanate (TDI) or isophorone diisocyanate (IPDI).Described alcohol or pure ether compound particularly preferably are isooctyl alcohol or butyl carbitol.Described dicarboxylic esters is dibasic acid dimethyl ester preferably, is more preferably to be selected from dimethyl adipate, dimethyl terephthalate (DMT), 2, the linolic acid dimethyl ester of 6-naphthylidene dioctyl phthalate dimethyl ester or dimerization.Described oxyamine is selected from thanomin or Mono Methyl Ethanol Amine.
In aforesaid method, preferably, the mol ratio of polyisocyanates and alcohol or pure ether compound is in 2: 1～2: 1.2 scope, and temperature of reaction is in 10～100 ℃ scope; The mol ratio of dicarboxylic esters and oxyamine is in 1.1: 1～1: 1 scope, and temperature of reaction is in 50～200 ℃ scope; Half end capped isocyanic ester and bisamide compound mol ratio are in 1: 1～1.5: 1 scope, and temperature of reaction is in 60～100 ℃ scope.
More preferably, carry out under the existence that is reflected at catalyzer of dicarboxylic esters and oxyamine.Described catalyzer can be selected from mineral acid or organic acid, and good especially for example is sulfuric acid, phosphoric acid, tosic acid, thionamic acid, methylsulphonic acid, formic acid or acetate etc.
In a fourth aspect of the present invention, a kind of method for preparing the coating composition of second aspect present invention is provided, this method may further comprise the steps:
The toughner that used for epoxy resin is selected from polyvalent alcohol, aliphatic carboxylic acid or its combination carries out the chain extension modification, and then carries out amination treatment, obtains through toughening agent modified chain extension and aminating Resins, epoxy; Make claim 1 or 2 described resins according to each described method among the claim 6-8 with biamide structure; Mix through toughening agent modified chain extension and aminating Resins, epoxy, end capped polyisocyanates, described resin and aqueous medium described, obtain the water-dispersion emulsion with biamide structure;
In addition, the properties-correcting agent that used for epoxy resin is selected from polyether amine compound, alkyl glycidyl ether or glyceryl ester or its combination carries out modification, and then carries out quaternized processing, obtains quaternised modified epoxy; Described quaternised modified epoxy, pigment and aqueous medium are mixed, obtain pigment slurry;
The water-dispersion emulsion and the pigment slurry that as above obtain are mixed, be mixed with described coating composition.
In a fifth aspect of the present invention, provide the purposes of the resin with biamide structure in the preparation cathode electrophoresis dope of first aspect present invention.
Embodiment
Below in conjunction with the specific embodiment of the present invention content of the present invention is described in further detail.
Resin with biamide structure
As indicated above, the invention provides a kind of resin with biamide structure, it can improve electrophoretic primer effectively to sticking power between top coat layer.Described synthetic method with resin of biamide structure can be following method, and this method can be divided into three links: the preparation of synthetic, the bisamide intermediate of half blocked isocyanate and resin synthetic with biamide structure.Below respectively these three links are described.
In half blocked isocyanate synthetic, half blocked isocyanate is that general formula is the polyisocyanates of OCN-Y-NCO and half end-blocking product of alcohol and pure ether compound.Wherein, polyisocyanates for example can be selected from but be not limited to: tolylene diisocyanate (TDI), 1, hexamethylene-diisocyanate (HDI), diphenylmethanediisocyanate (MDI), poly methylene poly phenyl poly isocyanate (PAPI), isophorone diisocyanate (IPDI), trimethylammonium hexamethylene diisocyanate (TXDI), tetramethylxylylene diisocyanate (TMXDI), dicyclohexyl methane diisocyanate (HMDI), hexahydrotoluene vulcabond (HTDI) particularly preferably is tolylene diisocyanate (TDI) and isophorone diisocyanate (IPDI).Pure and pure ether compound better is to be selected from C
1-C
10Alkyl alcohol and pure ether compound, be more preferably by general formula R
1' (CH
2CH
2O)
qCH
2CH
2The compound that OH represents, wherein R
1' be selected from C
1-C
6Alkyl, q is the integer of 0-2, particularly preferably is isooctyl alcohol or butyl carbitol.The temperature of reaction of polyisocyanates and alcohol and pure ether compound preferably in 10-100 ℃ temperature range, is more preferably in 50-80 ℃ scope.The mol ratio of polyisocyanates and alcohol or pure ether compound preferably in 2: 1～2: 1.2 scope, is more preferably in 2: 1～2: 1.05 scope.
The bisamide intermediate can react by dicarboxylic esters and oxyamine and prepare.Described dicarboxylic esters better is to be selected to have formula R
2O
2C-Z-CO
2R
2Compound, wherein, Z is selected from-(CH
2)
m-(integer of m=0-9), phenylene, 2, the linolic acid base of 6-naphthylidene or dimerization, R
2Be C
1-C
6Alkyl.Good especially dicarboxylic esters includes but not limited to: dimethyl adipate, dimethyl terephthalate (DMT), 2, the linolic acid dimethyl ester of 6-naphthylidene dioctyl phthalate dimethyl ester or dimerization.Described oxyamine better is to be selected to have formula R
3NH (CH
2)
nThe compound of OH, in the formula, R
3Be selected from H, C
1-C
4Alkyl or-(CH
2)
pOH, the integer of p=2-4, the integer of n=2-4.Good especially oxyamine is thanomin or Mono Methyl Ethanol Amine.The reaction of dicarboxylic esters and oxyamine is to carry out in the presence of catalyzer.Catalyzer can be selected mineral acid or organic acid for use, preferably includes but is not limited to: sulfuric acid, phosphoric acid or tosic acid.Temperature of reaction preferably in 50-200 ℃ temperature range, is more preferably in 100～150 ℃ scope.In reaction process, dicarboxylic esters should be excessive a little, with the mol ratio of oxyamine better be in 1.1: 1～1: 1 scope, be more preferably in 1.05: 1～1: 1.01 scope.
It is following synthetic to have the resin of biamide structure: the bisamide intermediate and half blocked isocyanate that as above make are reacted, temperature of reaction preferably 60-100 ℃ temperature range in, be more preferably in 70～90 ℃ scope.The mol ratio of half blocked isocyanate and bisamide intermediate is more preferably in 1.05: 1～1.15: 1 scope in 1: 1～1.5: 1 scope.
Above-mentioned three links can be represented with following reaction signal formula:
(1)
(2)
(3)
In the above reaction formula, Y represents to be selected from tolylene diisocyanate (TDI), 1, hexamethylene-diisocyanate (HDI), diphenylmethanediisocyanate (MDI), poly methylene poly phenyl poly isocyanate (PAPI), isophorone diisocyanate (IPDI), trimethylammonium hexamethylene diisocyanate (TXDI), tetramethylxylylene diisocyanate (TMXDI), dicyclohexyl methane diisocyanate (HMDI), the residue of the polyisocyanates of hexahydrotoluene vulcabond (HTDI).The above-mentioned polyisocyanates of used term " residue " expression is removed two isocyanate groups (NCO) remaining group part in back.
R
1Expression R
1' (CH
2CH
2O)
qCH
2CH
2-, R wherein
1' be selected from C
1-C
6Alkyl, q is the integer of 0-2;
Z represents to be selected from-(CH
2)
m-(integer of m=0-9), phenylene, 2, the group of the linolic acid base of 6-naphthylidene or dimerization;
R
2Expression C
1-C
6Alkyl;
R
3Expression is selected from H, C
1-C
4Alkyl or-(CH
2)
pOH, the integer of p=2-4;
The integer of n=2-4.
In the synthetic method of above-mentioned resin with biamide structure, there is not sequencing between first link (synthesizing of half blocked isocyanate) and second link (preparation of bisamide intermediate), can carry out first link earlier and carry out second link again, also can carry out second link earlier and carry out first link again, can also two links carry out side by side.Then, half blocked isocyanate and bisamide intermediate that first link and second link are made respectively react, and obtain the resin with biamide structure of the present invention.
The resin that the present invention has biamide structure can produce solidification with the matrix resin in the water-dispersion emulsion in the baking-curing after galvanic deposit as the part of linking agent in the galvanic deposit system.Resin with biamide structure can join in the system as auxiliary agent before emulsion forms.
Through toughening agent modified chain extension and aminating Resins, epoxy
Used for epoxy resin toughner is carried out the chain extension modification, and then carry out amination treatment, obtain through toughening agent modified chain extension and aminating Resins, epoxy.
Described Resins, epoxy can be obtained by polyphenolic substance and epihalohydrin reaction, and only Resins, epoxy is made by dihydroxyphenyl propane.The epoxy equivalent (weight) of Resins, epoxy is generally 180～1000, is preferably 180～500 especially.
The toughner that Resins, epoxy is carried out the chain extension modification can for example be but be not limited to: polyol compound and aliphatic carboxylic acid and combination thereof.Preferably, polyester diol, polyether Glycols, aliphatics C
1-C
18Carboxylic acid.The special preferably polyester diol or the polyether Glycols of molecular weight 200～2000, and stearic acid, isocaprylic acid etc.Above-mentioned substance has and the high-compatibility of Resins, epoxy and the hyperergy that is provided by terminal hydroxy group, therefore is suitable as very much the internal plasticizer of coating with Resins, epoxy, plays the effect to epoxy resin roughening.The consumption of plasticized modifier is preferably 10-40 weight %, and more preferably 15-30 weight % is a gross weight in resin solid in the water-dispersion emulsion.Plasticized modifier carries out in suitable solvent usually to the chain extending reaction that Resins, epoxy carries out modification, and these solvents can include but not limited to: varsol (for example toluene, dimethylbenzene), ketones solvent (for example methylethylketone, mibk and methylpentanone) etc.Usually in 100-220 ℃ scope, preferably in 120～150 ℃ scope, the reaction times is generally 1～5 hour to the temperature of reaction of chain extending reaction, is preferably 2～4 hours.Epoxy equivalent (weight) through chain extension preferably is controlled in the scope of 1000-1500, is more preferably in the scope of 1100-1400.
After the chain extension modification is finished in the Resins, epoxy reaction, make through toughening agent modified chain extension and aminating Resins, epoxy, i.e. modified epoxy amine affixture to wherein introducing amination reagent.Be used for to have an active hydrogen at least with the amination reagent of Resins, epoxy reaction.Amination reagent includes but not limited to: the primary amine of quadrol, monoethanolamine, dimethylamine, diethylamine, N-Mono Methyl Ethanol Amine, diethylenetriamine, diethanolamine, triethylene tetramine, polyoxy alkylene polyamines, alkanolamine etc. and the mixture of secondary amine or primary amine and secondary amine, the addition reaction product of perhaps above-mentioned amine and ketone (for example methylethylketone, methyl iso-butyl ketone (MIBK) etc.).
In the preparation of toughening agent modified chain extension and aminating Resins, epoxy, there is no particular restriction for the consumption of Resins, epoxy, toughner and amination reagent, can suitably adjust according to the application scenario of coating composition.Preferably, the consumption of Resins, epoxy is 40-70 weight %, and good especially is 45-65 weight %; The consumption of toughner is 10-30 weight %, and good especially is 15-25 weight %; The consumption of amination reagent is 5-20 weight %, and good especially is 6-15 weight %; Above-mentioned consumption is all in the gross weight of three kinds of reagent.
End capped polyisocyanates
The end capped isocyanic ester that relates among the present invention is polyisocyanate compound and the isocyanate-terminated dose of product by the stoichiometry addition reaction.Polyisocyanate compound includes but not limited to aromatics, aliphatic series or alicyclic compound, good especially for example is: tolylene diisocyanate, poly methylene poly phenyl poly isocyanate, phenylene vulcabond, two (isocyanic ester methyl) hexanaphthene, tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate and isophorone diisocyanate.Isocyanate-terminated dose includes but not limited to: lactan based compound (as ε-Ji Neixianan and butyrolactam); Oxime compound (as methyl ethyl ketoxime and cyclohexanone-oxime); Aliphatic alcohol class, pure ether compound (as methyl alcohol, ethanol, propyl alcohol, 2-Ethylhexyl Alcohol, diethylene glycol monobutyl ether, TriMethylolPropane(TMP) and dimethylol propionic acid) and aminated compounds (as diethylamine, dibutylamine, Di-Octyl amine etc.).Above-mentioned isocyanate-terminated dose of blocked polyisocyanates compound that is added to blocked isocyanate base in the polyisocyanate compound and forms at room temperature is stable.But, this compound at coating in storing temperature (being generally 100～200 ℃) down during heating, thereby separablely go out end-capping reagent and produce the free isocyanate group.When the end capped polyisocyanate crosslinker of preparation, the consumption of polyisocyanate compound is preferably 50-80 weight %, more preferably 55-65 weight %; Isocyanate-terminated dose consumption is preferably 20-50 weight %, more preferably 35-45 weight %; In the total weight of solids in the water-dispersion emulsion.
Water-dispersion emulsion and matrix resin thereof
Coating composition of the present invention comprises water-dispersion emulsion and pigment slurry, and wherein, the water-dispersion emulsion comprises matrix resin, has the resin and the aqueous medium of biamide structure.Described matrix resin comprises through toughening agent modified chain extension and aminating Resins, epoxy and end capped polyisocyanates, as follows through toughening agent modified chain extension and aminating Resins, epoxy (being modified epoxy amine affixture) and the ratio of mixture of blocked polyisocyanates: the amount of modified epoxy amine affixture is 55-90 weight %, more preferably 60-80 weight %; The amount of blocked polyisocyanates linking agent is 10-45 weight %, more preferably 20-40 weight %; All in the total solid weight of epoxy amine affixture and blocked polyisocyanates.
The water-dispersion emulsion is that matrix resin and the resin dispersion with biamide structure are formed in aqueous medium.As required, can use suitable acid, can also use auxiliary agents such as tensio-active agent as neutralizing agent.As neutralizing agent, the degree of neutralization of acid depends on reaction product, and common degree of neutralization is at least 30% of theoretical degree of neutralization, is preferably 35-60%.As the used acid of the neutralization that contains the amine salt resin, comprise such as but not limited to phosphoric acid, acetic acid, propionic acid, formic acid, lactic acid etc.The available tensio-active agent for example is a nonionic surface active agent, and particularly preferably being the ethylene oxide adduct of long chain alkylphenol or the model of gas companies production is the nonionic surface active agent of Surfynol 104.
In addition, aqueous medium be water and can with the mixture of the miscible organic solvent of water.As required, also can use can not be miscible with water organic solvent.Spendable solvent includes but not limited to hydro carbons, alcohols, ester class, ethers and ketones solvent.Particularly preferred solvent includes but not limited to: toluene, dimethylbenzene, Virahol, butanols, ethyl cellosolve, ethylene glycol butyl ether, ethylene glycol, propylene glycol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, methylethylketone, methyl iso-butyl ketone (MIBK) etc.
A kind of preparation method of water-dispersion emulsion of the present invention can be: aforementioned body resin, the resin with biamide structure as the sticking power toughener, optional tensio-active agent and/or neutralizing agent and aqueous medium are mixed, form aqueous dispersions, form the water-dispersion emulsion behind the extraction solvent.Consumption as the resin with biamide structure of sticking power toughener is preferably 0.5～10 weight % especially, in the total solid weight of water-dispersion emulsion.
Pigment slurry
Pigment slurry of the present invention comprises quaternised modified epoxy, pigment and the aqueous medium as dispersion resin.
Described dispersion resin is formed through modifier modification and quaternized process by Resins, epoxy.Dispersion resin is a kind of quaternary ammonium resin, and its a kind of preparation method can be: Resins, epoxy is used modifier modification earlier, carry out quaternized processing again.Properties-correcting agent is polyether amine compound, alkyl glycidyl ether or the glyceryl ester of molecular weight in about 200-2000 scope preferably, and that good especially is butyl glycidyl ester, octyl glycidyl ether, C
12-C
14Alkyl glycidyl ether or alkyl glycidyl ester.Between 300-2000, good especially is between 500-1000 through the molecular weight of modified epoxy.
Pigment slurry of the present invention can be prepared as follows: the dispersion resin that will as above obtain mixes with color stuffing, aqueous medium (for example comprising water and solubility promoter), disperses to form pigment slurry after sand mill grinds.In pigment slurry of the present invention, can add pigment as required arbitrarily, described pigment can be selected from tinting pigment, pigment extender and anti-corrosion paint.The tinting pigment preference is as titanium white, carbon black, iron oxide red, carbon black etc.; The pigment extender preference is as clay, talcum powder, lime carbonate, mica, silicon-dioxide, sedimentation type barium sulfate etc.; Anti-corrosion paint preference such as zinc phosphate, condensed phosphoric acid ammonium etc.Not leaded and other heavy metal in this pigment slurry, but combine by non-lead pigments (for example aerosil, titanium dioxide, kaolin, carbon black etc.), can play the effect of protection against corrosion and control foaming effectively.The ratio of color stuffing and dispersion resin (in the total solids of these two kinds of components) is 2: 1～5: 1, especially preferably 3: 1～4: 1.
Cathode electrophoretic coating composition
Cathode electrophoretic coating composition of the present invention comprises water-dispersion emulsion and pigment slurry.Wherein, the water-dispersion emulsion accounts for the 70-90 weight % of coating composition, especially preferably 75-80 weight %; Pigment slurry accounts for the 10-30 weight % of coating composition, especially preferably 20-25 weight %.
Cathode electrophoresis dope of the present invention can be water-dispersion emulsion and pigment slurry are mixed by a certain percentage and to be diluted to working fluid with pure water.The ratio of mixture of water-dispersion emulsion and pigment slurry is 2: 1～6: 1, particularly preferably is 3: 1～5.5: 1.
Environment-friendly low-temperature ability cathode electrophoresis coating of the present invention can followingly form: build groove and form aforesaid working fluid, slaking was carried out electrophoresis after 24 hours.Cathode electrophoresis dope can have on the ground of conductive surface by cathode electro-coating, these grounds for example include but not limited to: metal and alloys thereof such as iron, chromium, steel, zinc, concrete example is if any cold-rolled steel sheet, aluminium sheet, steel plate, steel plate galvanized, tinplate, plating iron zinc alloy steel plate etc.These grounds also can carry out surface treatments such as chromate treating, zinc phosphate processing, oxide film processing.The technology of anionic electrodeposition electrophoresis painting dressing is roughly as follows: general work liquid (tank liquor) solid part concentration is 10～30% in accordance with known methods, dilute with deionized water, adjusting pH is 5.1～7.0, with the coating of this condition as the electrophoresis working fluid, so close the bath temperature is adjusted to 20-35 ℃, carry out electrophoresis as negative electrode and under making alive 100～400 laid shoot spares with coated article.Coating behind the electrophoresis solidified 10～60 minutes under 100～200 ℃ of temperature.Operating voltage is preferably 150～250V, electrophoresis time is preferably 1-3 minute, and tank liquor solid part is preferably 16～22%, and tank liquor temperature is preferably 25～34 ℃, the wet film drying is solidified after the making sheet, and coating and curing of coating condition optimization are 160～175 ℃/30～10min.
Major advantage of the present invention is as follows:
(1) the present invention makes priming paint obtain obvious enhancing to the sticking power of finish paint by introduce the resin with biamide structure in the cathode electrophoretic coating composition system, has solved in the prior art cathode electrophoresis dope to the problem of poor adhesive force between top coat layer.
(2) cathode electrophoretic coating composition of the present invention has the characteristics of low-temperature curing and leadless environment-friendly.
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.The experimental technique of unreceipted actual conditions in the following example usually according to normal condition, or carries out according to the condition that manufacturer advises.Unless otherwise indicated, otherwise all umbers are weight part, and all per-cents are weight percentage.
The preparation of embodiment A water-dispersion emulsion matrix resin
Embodiment A-1
| Raw material | Consumption (weight part) |
| GY2600① | 273.6 |
| PPG400② | 90.4 |
| Nonyl phenol | 6.6 |
| Dihydroxyphenyl propane | 80.0 |
| Hexone | 20.8 |
| Dimethyl benzylamine | 0.60 |
| Hexone | 96.0 |
| Ketoimine (70%) 3. | 26.6 |
| Mono Methyl Ethanol Amine | 21.0 |
| Linking agent 4. | 285.0 |
| Add up to | 900.6 |
1. GY2600, the bisphenol A type epoxy resin that German Ciba company produces, epoxy equivalent (weight) 188
2. PPG400, the polyether Glycols that Japanese Sanyo company produces
3. ketoimine reacts the product that makes by diethylenetriamine and hexone, and solids content is 70%
4. linking agent is prepared by poly methylene poly phenyl poly isocyanate (PAPI2940 is available from DOW company), end-capping reagent butyl carbitol and methyl alcohol and TriMethylolPropane(TMP).The solids content of linking agent is 80%.In the reaction flask that thermometer, agitator, reflux condensing tube, dropping funnel are housed, drop into polymeric MDI, methyl iso-butyl ketone (MIBK) and dibutyl tin laurate, stirring is warming up to 50～55 ℃, begin to drip butyl carbitol and methanol mixture, strict control reaction temperature, be advisable to be no more than 65 ℃, the dropping time remained on 2～3 hours.Add the back 80 ℃ of insulations 2 hours.Add TriMethylolPropane(TMP) then 90-100 ℃ of insulation 3 hours, begin to measure free NCO content, until qualified, be cooled to 60 ℃, solids content, standby is surveyed in discharging.
In reaction flask, add 273.6 parts GY2600, PPG400 and 20.8 parts of hexones of 90.4 parts.With reaction mixture at N
2Be heated to 210 ℃ under the gas shiled, reflux to remove in 30 minutes and anhydrate.Be cooled to 120 ℃, the dimethyl benzylamine that adds 0.6 part, reacted 8 hours, add 80 parts of dihydroxyphenyl propanes and 6.6 parts of nonyl phenols reaction 4 hours then, keep reacting under this temperature, add the hexone cooling subsequently, be cooled to 100 ℃ to epoxy equivalent (weight) 1300, add ketoimine and Mono Methyl Ethanol Amine, insulation formed modified epoxy amine affixture in 2 hours about 110 ℃.Add the linking agent latting drown then, form the A-1 matrix resin.
Embodiment A-2
| Raw material | Consumption (weight part) |
| GY2600 | 273.6 |
| TONE201⑤ | 90.4 |
| Lauric acid | 6.6 |
| Dihydroxyphenyl propane | 80.0 |
| Hexone | 20.8 |
| Dimethyl benzylamine | 0.60 |
| Hexone | 96.0 |
| Ketoimine (70%) | 27.6 |
| Mono Methyl Ethanol Amine | 21.8 |
| Linking agent 6. | 285.0 |
| Add up to | 900.6 |
5. TONE201, the polycaprolactone dibasic alcohol that U.S. Union Carbide company produces
6. linking agent is prepared from by isophorone diisocyanate (IPDI) (available from degussa company), end-capping reagent methyl ethyl ketoxime and TriMethylolPropane(TMP).The solids content of linking agent is 80%.In the reaction flask that thermometer, agitator, reflux condensing tube, dropping funnel are housed, drop into IPDI, methyl iso-butyl ketone (MIBK) and dibutyl tin laurate, stirring is warming up to 50～55 ℃, begin to drip the mixture of TriMethylolPropane(TMP) and methyl iso-butyl ketone (MIBK), strict control reaction temperature, be advisable to be no more than 65 ℃, the dropping time remained on 4～5 hours.Add the back 80 ℃ of insulations 2 hours.Dripped methyl ethyl ketoxime then in 30 minutes, begin to measure free NCO content, until qualified, be cooled to 60 ℃, solids content, standby is surveyed in discharging.
In reaction flask, add 273.6 parts GY2600, TONE201 and 20.8 parts of hexones of 90.4 parts.With reaction mixture at N
2Be heated to 210 ℃ under the gas shiled, reflux to remove in 30 minutes and anhydrate.Be cooled to 120 ℃, the dimethyl benzylamine that adds 0.6 part, reacted 8 hours, add 80 parts of dihydroxyphenyl propanes and 6.6 parts of lauric acid reaction 4 hours then, keep reacting under this temperature, add the hexone cooling subsequently, be cooled to 100 ℃ to epoxy equivalent (weight) 1250, add ketoimine and Mono Methyl Ethanol Amine, insulation is 2 hours about 110 ℃.Add the linking agent latting drown then, form the A-2 matrix resin.
Embodiment A-3
| Raw material | Consumption (weight part) |
| GY2600 | 273.6 |
| PTG650⑦ | 90.4 |
| Isocaprylic acid | 6.6 |
| Dihydroxyphenyl propane | 80.0 |
| Hexone | 20.8 |
| Dimethyl benzylamine | 0.60 |
| Hexone | 96.0 |
| Ketoimine (70%) | 36.0 |
| Mono Methyl Ethanol Amine | 21.3 |
| Linking agent 8. | 285.0 |
| Add up to | 900.6 |
7. PTG650, the polyether Glycols that U.S. Dupont company produces
8. linking agent is prepared from by tolylene diisocyanate (TDI) (80/20), end-capping reagent ethylene glycol ethyl ether and TriMethylolPropane(TMP).The solids content of linking agent is 80%.Thermometer is being housed, drop into TDI (80/20), methyl iso-butyl ketone (MIBK) and dibutyl tin laurate in the reaction flask of agitator, reflux condensing tube, dropping funnel, stirring is warming up to 50～55 ℃, begin to drip the solution of the methyl iso-butyl ketone (MIBK) of TriMethylolPropane(TMP), strict control reaction temperature, make it be no more than 70 ℃, the dropping time remained on 4～5 hours.Add the back 80 ℃ of insulations 2 hours.Added ethylene glycol ethyl ether then in 30 minutes, be warming up to 90 ℃ of insulations 2 hours, begin to survey free NCO content, until qualified, be cooled to 70 ℃, solids content, standby is surveyed in discharging.
GY2600,90.4 parts PTG650 and 20.8 parts of hexones of in reaction flask, adding 273.6 parts.With reaction mixture at N
2Be heated to 210 ℃ under the gas shiled, reflux to remove in 30 minutes and anhydrate.Be cooled to 120 ℃, the dimethyl benzylamine that adds 0.6 part, reacted 8 hours, add 80 parts of dihydroxyphenyl propanes and 6.6 parts of isocaprylic acids reaction 4 hours then, keep reacting under this temperature, add the hexone cooling subsequently, be cooled to 100 ℃ to epoxy equivalent (weight) 1200, add ketoimine and Mono Methyl Ethanol Amine, insulation is 2 hours about 110 ℃.Add the linking agent latting drown then, form the A-3 matrix resin.
The preparation of Embodiment B pigment slurry
Synthesizing of Embodiment B-1 pigment dispersing resin
| Raw material | Consumption (weight part) |
| GY2600 | 424.80 |
| Dihydroxyphenyl propane | 131.00 |
| Triphenyl phosphorus | 0.42 |
| Dimethylbenzene | 10.30 |
| Properties-correcting agent 1. | 211.40 |
| The 2-Ethylhexyl Alcohol half end-blocking thing of TDI | 191.50 |
| Butyl glycol ether (I) | 39.60 |
| Quaternizing agent 2. | 332.10 |
| Pure water | 42.00 |
| Butyl glycol ether (II) | 357.20 |
| Add up to | 1740.32 |
1. D-400 (production of Huntsman company) presses the reaction product of 1: 2 mol ratio under 60 ℃ with butylglycidyl ether.
2. the preparation of quaternizing agent: 262 parts 2-Ethylhexyl Alcohols half are end capped 2, and 4-dimethyl vulcabond joins in the solution of being made up of 76.6 parts of dimethylethanolamines and 25.8 methylethylketones, and at room temperature reacts.80 ℃ of insulations 1 hour, add 91.2 parts of lactic acid and 59.7 parts of butyl glycol ethers then after the exothermic heat of reaction.Reaction mixture stirs down at 65 ℃ and obtained quaternizing agent in 1 hour.
GY2600 and dihydroxyphenyl propane are added in the reaction flask; under nitrogen protection, be heated to 125 ℃; add triphenyl phosphorus, exothermic heat of reaction is warming up to 150～160 ℃ naturally, and reaction mixture is cooled to 120 ℃; reacted 1 hour; the 2-Ethylhexyl Alcohol half end-blocking thing that adds 2,4 toluene diisocyanate, reaction remain on 120 ℃ of reactions 2 hours; add properties-correcting agent and after 1 hour, add butyl glycol ether (I) then 120 ℃ of reactions.Reaction mixture is cooled to 85～90 ℃, adds quaternizing agent and pure water, reaction mixture remains on 80～85 ℃, less than 1, adds butyl glycol ether (II) latting drown up to acid value, obtains pigment dispersing resin, and solids content is 85%.
The preparation of Embodiment B-2 pigment slurry
| Raw material | Consumption (weight part) |
| Titanium dioxide 1. | 33.15 |
| China clay 2. | 11.27 |
| Aerosil | 2.90 |
| Carbon black | 0.37 |
| Dibutyltin oxide | 2.52 |
| Dispersion resin (B-1) | 26.05 |
| Deionized water | 38.78 |
| Add up to | 115.04 |
1. Dupont company model is the titanium dioxide of Tipure R900
2. Englehard company model is the china clay of Extender ASP200
With 38.78 parts of water and 26.05 parts of dispersion resin pre-mixings.Add carbon black, aerosil, titanium dioxide, china clay and Dibutyltin oxide then, on homogenizer, mixed 30 minutes.Then this mixture was disperseed 1.5 hours in the sand milling of laboratory, less than 15 microns, in case of necessity, can be adjusted to desirable viscosity, solids content 56-58% with extra water up to fineness.
Embodiment D has resin (sticking power toughener) synthetic of biamide structure
The preparation of (1) half blocked isocyanate
Embodiment D-1a
In reaction flask, drop into 57.24 part 2, the 4-tolylene diisocyanate, feed nitrogen, stir, when temperature of charge rises to 25 ℃, evenly drip 42.76 parts of 2-Ethylhexyl Alcohols lentamente, keep temperature of reaction at 28-32 ℃, after dropwising,, detect the discharging between 132-138mg/g of NCO content in 28-32 ℃ of insulation 1 hour.
Embodiment D-1b
In reaction flask, drop into 222 parts of isophorone diisocyanates, feed nitrogen, stir, when temperature of charge during at 30 ℃, evenly dripped 81.0 parts of Diethylene Glycol butyl ether lentamente 3-4 hour, keep temperature of reaction at 30-45 ℃, after dropwising, in 40-50 ℃ of insulation 1 hour, detect NCO content, reach the 135-141mg/g discharging until index.
(2) the bisamide intermediate is synthetic
Embodiment D-2a
| Raw material | Consumption (weight part) |
| Diethyl malonate | 37.27 |
| Monoethanolamine MEA BASF | 28.43 |
| Tosic acid | 0.02 |
| Methyl alcohol | 41.96 |
| Add up to | 107.68 |
In the reaction flask of being furnished with agitator, thermometer, add diethyl malonate and tosic acid and methyl alcohol, start stirring, feed nitrogen, be heated to 50 ℃, drip Monoethanolamine MEA BASF, dripped off in 30 minutes.Rise to 65-67 ℃ after dripping off and refluxed 5 hours, to the amine value be 52-58mgKOH/g, stop heating, about 3 hours, slowly be cooled to 20-25 ℃, produce crystallization in the reaction flask this moment.With recrystallization method product is purified.
Recrystallization purification intermediate D-2a
With the xln impouring B in the reaction flask, suction filtration, be the pure white crystal with analytical pure washed with methanol to crystal till.White crystal is inserted in the clean reaction flask, add small amount of methanol, be heated to 60 ℃ of dissolvings, be cooled to 20-25 ℃ then about 3 hours, produce crystallization to bottle, crystal is carried out suction filtration again, washed with methanol obtains white fine crystals D-2a at last.Structure to products therefrom is measured, and shows 1636cm by infrared spectra
-1(vs, amido linkage carbonyl absorption), 3283cm
-1(s, the absorption of amido linkage NH).
Embodiment D-2b
| Raw material | Consumption (weight part) |
| DBE * | 60.68 |
| Mono Methyl Ethanol Amine | 61.88 |
| Tosic acid | 0.03 |
| Add up to | 122.59 |
*The DBE (aliphatic dibasic ester) that U.S. Dupont company produces, wherein dimethyl succinate accounts for 13.65%; Methyl glutarate accounts for 60.51%; Dimethyl adipate accounts for 25.58%.
Be furnished with agitator, in the reaction flask of thermometer, adding DBE and tosic acid, starting and stir feeding nitrogen, be heated to 80 ℃, dripping Mono Methyl Ethanol Amine, dripping off in 30 minutes.After dripping end, be warming up to 100-105 ℃, be incubated 6 hours, deviate from methyl alcohol, detect the amine value, obtain intermediate D-2b less than 207.25mgKOH/g.Structure to products therefrom is measured, and shows 1625cm by infrared spectra
-1(vs, amido linkage carbonyl absorption), 1733cm
-1(w, the absorption of remaining ester bond).
(3) have resin synthetic of biamide structure
Embodiment D-3a
| Raw material | Consumption (weight part) |
| Intermediate D-2a | 15.00 |
| Half blocked isocyanate that embodiment D-1a obtains | 48.16 |
| Hexone | 38.07 |
| Add up to | 101.23 |
In the reaction flask of being furnished with agitator, thermometer, add intermediate D-2a and hexone, be heated with stirring to 60 ℃, drip half blocked isocyanate that embodiment D-1a obtains.After dripping end, be warming up to 90 ℃, be incubated 5 hours, detect NCO content less than 5mg/g.
Structure to products therefrom D-3a is measured.Show by infrared spectra: 1670cm
-1(vs, amido linkage carbonyl absorption), 3309cm
-1(s, the absorption of amido linkage NH), 1707cm
-1(absorption of amino-formate bond).MS (abundance): 57 (100%); 304 (3.39%C
8H
17OCO-NH-C
7H
6-NCO fragment).C
13-NMR:168.35ppm (carbon signal of amido linkage), 154.4,154.7ppm (carbon signal of amino-formate bond); 137.2,136.7,136.3,131.1,123.6,115.3ppm (carbon signal of phenyl ring); (43.21ppm the methyl carbon signal on the phenyl ring); 53.2ppm (C
7H
14CH
2The methylene signals of OCO-NH-); 39.4ppm (NH-CO-CH
2The methylene signals of-CO-NH-); 30.7,29.3ppm (NH-CO-O (CH
2)
2Two methylene signals among the NH-CO); 25.0,24.0,23.4,22.9,17.4,14.4,11.3ppm (C
7H
14In carbon signal).Above-mentioned data show that the structure of products therefrom D-3a is as follows:
C
8H
17OCO-NH-C
7H
6-NH-CO-O (CH
2)
2NH-CO-CH
2-CO-NH (CH
2)
2O-CO-NH-C
7H
6-NH-CO-OC
8H
17, molecular weight 798 (theoretical value).
2. embodiment D-3b
| Raw material | Consumption (weight part) |
| Intermediate D-2b | 22.90 |
| Half blocked isocyanate that embodiment D-1b obtains | 83.28 |
| Methyl-isobutyl Shen ketone | 38.24 |
| Add up to | 144.42 |
In the reaction flask of being furnished with agitator, thermometer, add intermediate D-2b and hexone, be heated with stirring to 60 ℃, drip half blocked isocyanate that embodiment D-1b obtains, drip finish after, 90 ℃ of insulations 5～7 hours to NCO content less than 5mgNCO/g.
Structure to products therefrom D-3b is measured, and is shown by infrared spectra: 1641cm
-1(vs, amido linkage carbonyl absorption), 1721cm
-1(absorption of amino-formate bond).MS (abundance): 57 (100%); 385 (2.19%, C
4H
9O (CH
2)
2OCO-NH-C
10H
18-NHCO fragment).C
13-NMR:173.7,173.2,173.0ppm (carbon signal of amido linkage); 157.4,156.3ppm (carbon signal of amino-formate bond).Show that by above-mentioned data the structure of product D-3b is as follows:
C
4H
9O (CH
2)
2OCO-NH-C
10H
18-NH-CO-O (CH
2)
2NCH
3-CO-(CH
2)
n-CO-NCH
3-(CH
2)
2O-CO-NH-C
10H
18-NH-CO-O (CH
2)
2OC
4H
9, n=2-4, molecular weight=1000-1028 (theoretical value).
The preparation of embodiment A A water-dispersion emulsion
| Raw material | Consumption (weight part) |
| A series matrix resin | 188.00 |
| Sticking power strengthens resin (embodiment D-3 series) | 12.20 |
| The propylene glycol phenylate | 3.00 |
| Tensio-active agent (1. Surfynol 104E) | 1.52 |
| Lactic acid (85%) | 7.12 |
| Water (I) | 134.00 |
| Water (II) | 200.00 |
| Add up to | 545.84 |
Earlier 188 parts of A series matrix resins, 12.2 parts of sticking power are strengthened in resin (embodiment D-3 series) and 3.0 parts of propylene glycol phenylates adding reaction flasks and be heated with stirring to 110 ℃.134 parts deionized water (I), the tensio-active agent of 7.12 parts lactic acid and 3.75 parts is put into another emulsification container.Mix, then 188 parts mixed matrix resin is slowly added in the emulsification container, and high-speed stirring 15 minutes, drip water (II) to emulsion and finish, form initial latex, solids content is 32%.Remove solvent under 40 ℃, form final emulsion, solids content is 36%, and emulsion particle diameter is the 800-1000 dust.
The preparation of Embodiment C electrocoating paint work tank liquor
| Raw material | Consumption (weight part) |
| Embodiment A A water-dispersion emulsion | 1050 |
| The pigment slurry of Embodiment B-2 series | 325 |
| Deionized water | 1425 |
| Add up to | 2800 |
Above-mentioned raw materials is mixed, and the solids content that obtains electrocoating paint is 20%, and resin-pigment ratio is 0.33.
The preparation of embodiment 1:AA-3a emulsion
| Raw material | Consumption (weight part) |
| Embodiment A-1 matrix resin | 188.00 |
| Embodiment D-3a | 12.20 |
| The propylene glycol phenylate | 3.00 |
| Surfynol 104E | 1.52 |
| Lactic acid (85%) | 7.12 |
| Water (I) | 134.00 |
| Water (II) | 200.00 |
| Add up to | 545.84 |
With 188 parts of A-1 matrix resins, 12.2 parts of sticking power strengthen resin D-3a earlier, and 3.0 propylene glycol phenylates add in the reaction flask, are heated with stirring to 110 ℃.134 parts deionized water (I), the tensio-active agent Surfynol 104E of 7.12 parts lactic acid and 3.75 parts puts into another emulsification container.Mix, then 188 parts mixed matrix resin is slowly added in the emulsification container, and high-speed stirring 15 minutes, drip water (II) to emulsion and finish, form initial latex, solids content is 32%.Remove solvent under 40 ℃, form final emulsion, solids content is 36%, and emulsion particle diameter is 950 dusts.
The preparation of embodiment 2:AA-3b emulsion
| Raw material | Consumption (weight part) |
| Embodiment A-2 matrix resin | 188.00 |
| Embodiment D-3b | 12.20 |
| The propylene glycol phenylate | 3.00 |
| Alkylphenol polyoxyethylene (OP-10) | 1.52 |
| Lactic acid (85%) | 7.12 |
| Water (I) | 134.00 |
| Water (II) | 200.00 |
| Add up to | 545.84 |
The preparation of embodiment 3:AA-3c emulsion
| Raw material | Consumption (weight part) |
| Embodiment A-3 matrix resin | 188.00 |
| Embodiment D-3a | 12.20 |
| The propylene glycol phenylate | 3.00 |
| Alkylphenol polyoxyethylene (OP-10) | 1.52 |
| Lactic acid (85%) | 7.12 |
| Water (I) | 134.00 |
| Water (II) | 200.00 |
| Add up to | 545.84 |
The preparation of Embodiment C-1:C-1 electrocoating paint work tank liquor
| Raw material | Consumption (weight part) |
| Embodiment 1:AA-3a emulsion | 1050 |
| Embodiment B-2 pigment slurry | 325 |
| Deionized water | 1425 |
| Add up to | 2800 |
The preparation of Embodiment C-2:C-2 electrocoating paint work tank liquor
| Raw material | Consumption (weight part) |
| Embodiment 2:AA-3b emulsion | 1050 |
| Embodiment B-2 pigment slurry | 325 |
| Deionized water | 1425 |
| Add up to | 2800 |
The preparation of Embodiment C-3:C-3 electrocoating paint work tank liquor
| Raw material | Consumption (weight part) |
| Embodiment 1:AA-3c emulsion | 1050 |
| Embodiment B-2 pigment slurry | 325 |
| Deionized water | 1425 |
| Add up to | 2800 |
The preparation of comparative example 4:A-5 emulsion (not containing the sticking power toughener)
| Raw material | Consumption (weight part) |
| Embodiment A-1 matrix resin | 188.00 |
| The propylene glycol phenylate | 3.00 |
| Surfynol 104E | 1.52 |
| Emulsion (85%) | 7.00 |
| Water (I) | 134.00 |
| Water (II) | 200.00 |
| Add up to | 533.52 |
The preparation (not containing the sticking power toughener) of comparative example C-4:C-4 electrocoating paint work tank liquor
| Raw material | Consumption (weight part) |
| Embodiment 5:A-5 emulsion | 1050 |
| Embodiment B-2 pigment slurry | 325 |
| Deionized water | 1425 |
| Add up to | 2800 |
As indicated above, the electrocoating paint work tank liquor of C series is carried out electrophoretic painting, the plate that obtains swimming is filmed, and detects related mechanical properties, carries out performance evaluations such as finish paint sticking power, shrinkage cavity, outward appearance, thickness, and concrete outcome is as shown in Table 1 and Table 2.The result shows, compares with the contrast sample, and the finish paint ply adhesion obviously improves.
The performance of table 1 electrocoating paint work tank liquor swimming plate
| Example and comparative example are 1. | C-1 | C-2 | C-3 | C-4 (comparative example) |
| Finish paint sticking power 2. | 0 | 0 | 0 | 2 |
| Shrinkage cavity 3. | 8 | 9 | 8 | 9 |
| Outward appearance | Smooth smooth | Smooth smooth | Smooth smooth | Smooth smooth |
| Thickness | 24 | 26 | 25 | 22 |
| Pin hole | Do not have | Do not have | Do not have | Do not have |
| Cupping | 8.2 | 8.5 | 8.4 | 7.8 |
| The MEK wiping 4. | 100 | 100 | 100 | 100 |
1. the finish paint that uses in the performance test is alkyd finish, and the model that is Shanghai Jinlitai Chemical Industry Co., Ltd. is the KNT929 product.
2. finish paint sticking power adopts GB/T9286 to measure, wherein 0 grade best, 5 grades are the poorest.
3. the shrinkage cavity evaluation adopts QB8021 to measure, 10 the bests wherein, and 1 is the poorest.
4. condition of cure: 160-165 ℃/20min
The contrast of table 2 film performance
| Interventions Requested | Required value | Measured value | Inspecting standard | ||||
| C-1 | C-2 | C-3 | C-4 (comparison) | ||||
| Outward appearance | A plate L plate C plate | 8-10 7-10 7-10 | 9 9 8 | 10 9 9 | 10 9 8 | 10 9 9 | QB8021 * QB8021 * QB8021 * |
| Thickness/μ m hardness/H cupping/mm adhesive force/level pliability/mm impact/cm gloss/60 ° of salt spray resistance/h | 20-30 ≥2H ≥6 0-1 1 50 50-80 ≥1000 | 24 2H 8.2 0 1 50 62 ＞1000 | 26 2H 8.5 0 1 50 73 ＞1000 | 25 2H 8.4 0 1 50 68 ＞1000 | 22 2H 7.8 2 1 50 76 ＞1000 | GB/T1764 GB/T6739 GB/T9753 GB/T9286 GB/T1731 GB/T1732 GB/T9754 ASTMB117 | |
Annotate: QB8021: the ocular estimate index, be divided into and be 1-10 grade, wherein 1 is the poorest, and 10 is best.For the A plate, grade 8-10 represents that smooth coating is smooth, and the thickness difference is between the 1-6 micron; (for the 15cm * 7.5cm), grade 7-10 represents that the flake number is 0, and the shrinkage cavity number is 0-5, and the pit number is 0-10, and pinhole number is 1-12 for the C plate; For the L plate, grade 7-10 represents smooth smooth, and horizontal plane and facade be the outward appearance indifference relatively, and film thickness difference is on average between 0-6.
All quote in this application as a reference at all documents that the present invention mentions, just quoted as a reference separately as each piece document.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after having read above-mentioned teachings of the present invention, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Claims (10)
1. resin with biamide structure, this resin has following structural formula:
R
1OCO-NH-Y-NH-CO-O(CH
2)
nNR
3-CO-Z-CO-NR
3(CH
2)
n-O-CO-NH-Y-NH-CO-OR
1
In the formula, Y represents to be selected from the residue of the polyisocyanates of tolylene diisocyanate (TDI), hexamethylene diisocyanate (HDI), diphenylmethanediisocyanate (MDI), poly methylene poly phenyl poly isocyanate (PAPI), isophorone diisocyanate (IPDI), trimethylammonium hexamethylene diisocyanate (TXDI), tetramethylxylylene diisocyanate (TMXDI), dicyclohexyl methane diisocyanate (HMDI), hexahydrotoluene vulcabond (HTDI);
R
1Expression R
1' (CH
2CH
2O)
qCH
2CH
2-, R wherein
1' be selected from C
1-C
6Alkyl, q is the integer of 0-2;
Z represents to be selected from-(CH
2)
m-, phenylene, 2, the group of the linolic acid base of 6-naphthylidene or dimerization, m represents the integer of 0-9;
R
3Expression is selected from H, C
1-C
4Alkyl or-(CH
2)
pOH, the integer of p=2-4;
N represents the integer of 2-4.
2. resin as claimed in claim 1 is characterized in that the number-average molecular weight of described resin is in 500～2000 scope.
3. coating composition, said composition comprises water-dispersion emulsion and pigment slurry, described water-dispersion emulsion comprises matrix resin and aqueous medium, described matrix resin comprises through toughening agent modified chain extension and aminating Resins, epoxy and end capped isocyanic ester, described pigment slurry comprises quaternised modified epoxy, pigment and the aqueous medium as dispersion resin, it is characterized in that described water-dispersion emulsion also comprises claim 1 or 2 described resins with biamide structure.
4. coating composition as claimed in claim 3 is characterized in that, the described weight percentage that accounts for water-dispersion emulsion total solids with resin of biamide structure is 0.5-10%.
5. coating composition as claimed in claim 3 is characterized in that the weight of described water-dispersion emulsion accounts for the 70-90% of coating composition gross weight, and the weight of described pigment slurry accounts for the 10-30% of coating composition gross weight.
6. one kind prepares claim 1 or 2 described methods with resin of biamide structure, and this method may further comprise the steps: make polyisocyanates and alcohol or the reaction of pure ether compound, obtain half end capped isocyanic ester; Make the reaction of dicarboxylic esters and oxyamine, form the bisamide compound; Then, described half end capped isocyanic ester and described bisamide compound are reacted, obtain described resin with biamide structure.
7. method as claimed in claim 6, it is characterized in that, described polyisocyanates is selected from tolylene diisocyanate (TDI), 1, hexamethylene-diisocyanate (HDI), diphenylmethanediisocyanate (MDI), poly methylene poly phenyl poly isocyanate (PAPI), isophorone diisocyanate (IPDI), trimethylammonium hexamethylene diisocyanate (TXDI), tetramethylxylylene diisocyanate (TMXDI), dicyclohexyl methane diisocyanate (HMDI), hexahydrotoluene vulcabond (HTDI); Described alcohol or pure ether compound are selected from has formula R
1' (CH
2CH
2O)
qCH
2CH
2The compound of OH, in the formula, R
1' be selected from C
1-C
6Alkyl, the integer of q=0-2; Described dicarboxylic esters is to be selected to have formula R
2O
2C-Z-CO
2R
2Compound, wherein, Z is selected from-(CH
2)
m-, the integer of m=0-9, phenylene, 2, the linolic acid base of 6-naphthylidene or dimerization, R
2Be C
1-C
6Alkyl; Described oxyamine is to be selected to have formula R
3NH (CH
2)
nThe compound of OH, in the formula, R
3Be selected from H, C
1-C
4Alkyl or-(CH
2)
pOH, the integer of p=2-4, the integer of n=2-4.
8. method as claimed in claim 6 is characterized in that, the mol ratio of polyisocyanates and alcohol or pure ether compound is in 2: 1～2: 1.2 scope, and temperature of reaction is in 10～100 ℃ scope; The mol ratio of dicarboxylic esters and oxyamine is in 1.1: 1～1: 1 scope, and temperature of reaction is in 50～200 ℃ scope; Half end capped isocyanic ester and bisamide compound mol ratio are in 1: 1～1.5: 1 scope, and temperature of reaction is in 60～100 ℃ scope.
9. method for preparing each described coating composition among the claim 3-5, this method may further comprise the steps:
The toughner that used for epoxy resin is selected from polyvalent alcohol, aliphatic carboxylic acid or its combination carries out the chain extension modification, and then carries out amination treatment, obtains through toughening agent modified chain extension and aminating Resins, epoxy; Make claim 1 or 2 described resins according to each described method among the claim 6-8 with biamide structure; Mix through toughening agent modified chain extension and aminating Resins, epoxy, end capped polyisocyanates, described resin and aqueous medium described, obtain the water-dispersion emulsion with biamide structure;
In addition, the properties-correcting agent that used for epoxy resin is selected from polyether amine compound, alkyl glycidyl ether or glyceryl ester or its combination carries out modification, and then carries out quaternized processing, obtains quaternised modified epoxy; Described quaternised modified epoxy, pigment and aqueous medium are mixed, obtain pigment slurry;
The water-dispersion emulsion and the pigment slurry that as above obtain are mixed, be mixed with described coating composition.
10. claim 1 or the purposes of 2 described resins with biamide structure in the preparation cathode electrophoresis dope.
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| CN100457843C CN100457843C (en) | 2009-02-04 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102928329A (en) * | 2012-09-27 | 2013-02-13 | 立邦工业涂料(上海)有限公司 | Method for evaluating corrosion resistance and anti-cratering performance of coating on inner wall of electrophoretic paint packing bucket |
| CN105907284A (en) * | 2016-06-02 | 2016-08-31 | 广德县中银化工有限责任公司 | Low temperature curable cathodic electrophoretic paint |
| CN105969057A (en) * | 2016-06-02 | 2016-09-28 | 广德县中银化工有限责任公司 | Low-temperature curing cathode electrophoretic paint and preparing process thereof |
| CN106047055A (en) * | 2016-06-02 | 2016-10-26 | 广德县中银化工有限责任公司 | Preparing technology for low-temperature setting cathode electrophoresis paint |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4920162A (en) * | 1988-12-22 | 1990-04-24 | Clark Peter D | Electrocoating composition of a polyamine self-condensed epoxy adduct and coatings produced thereby |
| JP2001152088A (en) * | 1999-11-24 | 2001-06-05 | Kansai Paint Co Ltd | Cationic electrodeposition coating composition |
| JP2002188048A (en) * | 2000-12-21 | 2002-07-05 | Nippon Paint Co Ltd | Cationic electrodeposition coating composition |
| JP2002285079A (en) * | 2001-03-27 | 2002-10-03 | Nippon Paint Co Ltd | Cationic electrodeposition coating composition having low heating loss |
| CN1757683A (en) * | 2005-10-28 | 2006-04-12 | 常州市凌龙涂料有限公司 | Method for preparing high weather ability cathode electrophoresis coatings |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102928329A (en) * | 2012-09-27 | 2013-02-13 | 立邦工业涂料(上海)有限公司 | Method for evaluating corrosion resistance and anti-cratering performance of coating on inner wall of electrophoretic paint packing bucket |
| CN102928329B (en) * | 2012-09-27 | 2015-02-04 | 立邦工业涂料(上海)有限公司 | Method for evaluating corrosion resistance and anti-cratering performance of coating on inner wall of electrophoretic paint packing bucket |
| CN105907284A (en) * | 2016-06-02 | 2016-08-31 | 广德县中银化工有限责任公司 | Low temperature curable cathodic electrophoretic paint |
| CN105969057A (en) * | 2016-06-02 | 2016-09-28 | 广德县中银化工有限责任公司 | Low-temperature curing cathode electrophoretic paint and preparing process thereof |
| CN106047055A (en) * | 2016-06-02 | 2016-10-26 | 广德县中银化工有限责任公司 | Preparing technology for low-temperature setting cathode electrophoresis paint |
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| CN100457843C (en) | 2009-02-04 |
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