CN1066465C - Modified epoxy resins having a blocked isocyanate moiety and a cationic group and their use in cathodic electrodeposition paints - Google Patents
Modified epoxy resins having a blocked isocyanate moiety and a cationic group and their use in cathodic electrodeposition paints Download PDFInfo
- Publication number
- CN1066465C CN1066465C CN95103486A CN95103486A CN1066465C CN 1066465 C CN1066465 C CN 1066465C CN 95103486 A CN95103486 A CN 95103486A CN 95103486 A CN95103486 A CN 95103486A CN 1066465 C CN1066465 C CN 1066465C
- Authority
- CN
- China
- Prior art keywords
- epoxy
- block
- resin
- acyl group
- isocyanide acyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Abstract
Part of an epoxy resin of an epoxy group containing plural glycidyloxy groups is reacted with an unsymmetrical block diisocyanate compound to bond an isocyanate component to the epoxy resin skeleton by oxazolidone ring bond. Then, the residual epoxy ring is subjected to ring opening by cationic active hydrogen combination and the cationic group is introduced into the epoxy ring to give a modified epoxy resin containing the isocyanate component and the cationic group. This modified epoxy resin is mixed with a coating compound of electrodeposition as a cationic group or a pigment dispersed paste.
Description
The present invention relates to a kind of modified epoxy that is used for electrocoating paint and preparation method thereof.
The present invention also relates to contain the cathode electrodeposition paint and the pigment paste of described modified epoxy.
The modified epoxy of preparing in cathode electrodeposition paint can be made by ordinary method, as with the Resins, epoxy and first active dydrogen compounds, as alkylphenol, monocarboxylic acid or hydroxyl carboxylic acid reaction are opened the ring of part epoxide, with second active dydrogen compounds, open remaining epoxide ring then as primary amine or secondary amine reaction.With the modified resin and the linking agent of gained, mix as the organic polymeric polyisocyanate of melamine resin penta block, electricity imposes in the substrate, and baking at high temperature, obtains a cured film.Such modified epoxy has some shortcomings, is that they only just react with linking agent under comparatively high temps.Similarly also knownly open the modified epoxy for preparing self-crosslinkable on the secondary hydroxyl group that forms of reaction by half block vulcabond being connected to by the ring of oxirane ring.This resin also has some shortcomings, and when being under being higher than 200 ℃ temperature fired film, the blocked isocyanate moiety that connects by urethane bond is tending towards part at least and separates out.
An important requirement when making coating is the pigment deposit.Usually this can realize promptly preparing pigment paste by pigment and a carrier part that constitutes coating and a kind of suitable solvent or thinner and other additive are ground in paint roller mill.Then, remainder and other additive of pigment paste and carrier mixed, be scattered in wherein coating to prepare granules of pigments.The most serious problem that runs in the pigment deposit of coating is the coalescent or sedimentation of granules of pigments, and this can cause reducing storage stability, in use gets into trouble, and reduces surface smoothness, goes bad in time etc.Coalescent can the grinding mixed, and takes place in storage or the electrodeposition step.It is coalescent that granules of pigments takes place in intergranular interaction.In order to delay or to control interaction, must make dispersant resin in its structure, contain hydrophobic part, make dispersant resin be adsorbed on the granules of pigments surface well.Equally also must make dispersant resin contain hydrophilic segment, make it the dispersion that in water medium, reaches stable.
Japanese Patent publication No.4978/1979 has disclosed a kind of modified epoxy as pigment dispersing agent.This resin is connected to blocked isocyanate moiety on the modified epoxy by urethane bond and makes, and described urethane bond is by half block vulcabond and the hydroxyl reaction that is positioned on the alkanol that resin backbone or resin do not hold forms.Yet when being heated to storing temperature, blocked isocyanate moiety is easily separated out diisocyanate monomer, and causes variety of issue, for example increases the thermogravimetric loss or makes the finish paint system yellowing of using subsequently.
The invention provides a kind of blocked isocyanate moiety that is connected to the resin end and modified epoxy of cation radical of containing.The unique distinction of modified epoxy of the present invention is by Dinged the oxazolidone ring by the Re Wen that forms with oxirane ring reaction blocked isocyanate moiety to be connected on the resin.Therefore, separating out of blocked isocyanate moiety can not taken place, because half block vulcabond adds on the alcoholic extract hydroxyl group.
On the other hand; the invention provides a kind of modified epoxy that logical oxazolidone ring connects at least one blocked isocyanate moiety that contains; Suo Shu De oxazolidone ring is formed by the isocyanide acyl group reaction of the oxirane ring of many glycidyl epoxies part with organic diisocyanate; remaining isocyanide acyl group is by block reversibly or irreversibly, and this modified epoxy contains at least one cation radical of being introduced by the ring-opening reaction of remaining oxirane ring and cation activity hydrogen compound further.Such modified epoxy can be introduced in the anodic electrodeposition coating as the cationic binder resin.
On the one hand, the invention provides a kind of method of making modified epoxy again, this method comprises the steps:
To contain the organic diisocyanate reaction of the Resins, epoxy and the asymmetric block of many glycidyls, described vulcabond contains the first block isocyanide acyl group and the second block isocyanide acyl group, the specific activity first block isocyanide acyl group of this second block isocyanide acyl group is little, and than the described first block isocyanide acyl group stoichiometric number little with the ratio of glycidyl; With
With the product and the cation activity reactive hydrogen compound of gained, introduce cation radical with ring-opening reaction by residual epoxide ring and described cation activity hydrogen compound.
The present invention also provides a kind of cathode electrodeposition paint and pigment paste that contains modified epoxy of the present invention.
For the ease of understanding better, to method that make modified epoxy of the present invention be described with model reaction figure, wherein initial Resins, epoxy is diglycidyl ether epoxy resin (I), and diisocyanate cpd forms symmetrical two urethanes (II) by the full block of monohydroxy-alcohol block agent.
The first step, Resins, epoxy as described below (I) and two urethane reaction;
Second step, as described below, with the product (III) of the first step and, secondary amine HN (R ") for example
2Reaction, the modified epoxy (IV) that acquisition can need;
In aforesaid equation, R is a diglycidyl Resins, epoxy resistates, and R ' is the organic diisocyanate resistates, R
1And R
2Be monohydroxy-alcohol resistates, and R " is the secondary amine resistates as the first and second block agent.
Initial resin
Modified epoxy of the present invention is to begin to make from the Resins, epoxy that contains many glycidyls.Its typical example comprises by encircling polyphenol such as dihydroxyphenyl propane, Bisphenol F, bisphenol S, the polyphenol polyglycidyl ether type Resins, epoxy that phenol phenolic varnish or cresols phenolic varnish and Epicholorohydrin reaction make more.But various bisphenol epoxy commodity are buied, and comprise EPIKOTE 827 (epoxy equivalent (weight) 180-190), EPIKOTE 1001 (epoxy equivalent (weight) 450-500), and EPIKOTE 1010 (epoxy equivalent (weight) 3000～4000) is sold by YuKa Shell EpoxyK.K..Spendable Resins, epoxy comprises the polyglycidyl ethers of the many alcohol of aliphatic series equally, ethylene glycol for example, propylene glycol, 1,4-butyleneglycol, 1,6-hexylene glycol, trihydroxymethyl propane, tetramethylolmethane, polyglycol etc., and aliphatic series, many glycidyl esters of alicyclic or aromatic multi-carboxy acid.
As the use of initial resin, bifunctional Resins, epoxy can with bifunctional alcohol how, poly carboxylic acid, polyisocyanates, polyphenol or polyamines reaction and make chainpropagation.The example of the many alcohol of bifunctional comprises bifunctional multi-ether polyol such as polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol, their random or segmented copolymer, or dihydroxyphenyl propane-oxyethane or propylene oxide adduct, many ester polyols of bifunctional that the polycondensation of dicarboxylic acid or acid anhydrides and glycol obtains and cause the polycaprolactone glycol that the polyreaction of 6-caprolactone obtains by glycol.The molecular weight of the many alcohol of these bifunctionals is preferably 300-3000.Bis-phenol such as dihydroxyphenyl propane or Bisphenol F and aliphatic series or aromatic dicarboxylic acid such as succsinic acid, hexanodioic acid, nonane diacid, dodecandioic acid, dipolymer, phthalic acid, m-phthalic acid or terephthalic acid all can be used in the transfer reaction.
The transfer reaction of bifunctional Resins, epoxy and organic diisocyanate is at Iwakuraet al, J.Polymer Sci., and Part A-1,4,751 (1966) and Sander et al., J.Appl.Polymer Sci. has disclosure in 9.1984 (1966).The chainpropagation Resins, epoxy that is obtained by these reactions contains Xu Duo oxazolidone ring on resin backbone.
The molecular weight of initial Resins, epoxy is generally 150-2, and 000, be preferably 150-1,500.
The first step
In the first step, the epoxy group(ing) of initial resin part is reacted with the block diisocyanate cpd.The example of available vulcabond comprises aromatic diisocyanate such as toluene-2,4-diisocyanate (TDI), xylene diisocyanate (XDI), 4,4 '-diphenylmethanediisocyanate (MDI) etc.; With aliphatic series and alicyclic diisocyanate such as hexamethylene diisocyanate (HMDI), isophorone diisocyanate (IPDI), 4,4-methylene-bis (cyclic isocyanate polyhexamethylene), trimethylammonium hexamethylene diisocyanate etc.
Various block agent are well-known in the literature, and its example comprises fatty alcohol such as methyl alcohol, ethanol, and Virahol, just-and butanols, 2-Ethylhexyl Alcohol, ethylene glycol monobutyl ether, hexalin etc.; Phenols such as phenol, nitrophenol, ethyl phenol etc.; Oxime such as methyl ethyl ketoxime; With lactan such as ε-Ji Neixianan; Uncle-amino-alkane hydramine such as dimethylethanolamine, diethylethanolamine and dipropyl thanomin; With secondary amine such as diethylamine, dibutylamine and two-uncle-butylamine all can use.
Reaction by Iwakura et al.supra report also is Resins, epoxy and block vulcabond, the i.e. reaction of two urethanes.Yet in this case, two block isocyanide acyl groups are by block, and Resins, epoxy is by with the reaction of block vulcabond not and make chainpropagation.Opposite with this reaction, the first step of the present invention be in the first and second block isocyanide acyl groups preferred one with oxirane ring reaction, remaining then keeps carrying out under the situation of block.This can be by reaching with the different block agent block first and second isocyanide acyl groups.In preferable example, the first isocyanide acyl group is with methyl alcohol or ethanol block.The second isocyanide acyl group can be with the aliphatic monohydric alcohol block that contains at least 4 carbon atoms; for example butanols or 2-Ethylhexyl Alcohol; alkylphenol such as cresols or nonyl phenol; glycol monobasic ether such as ethylene glycol one-2-second hexyl ether or propylene glycol one-2-second hexyl ether; oxime such as diformazan ketoxime; methyl ethyl ketoxime or methyl isobutyl ketoxime, hexanolactam etc.Preferably, methyl alcohol or ethanol react with other block agent earlier before reaction.
Electrocoating paint contains a kind of heat flow toughener usually, as contains aliphatic monohydric alcohol, alkylphenol or the glycol monobasic ether of 4 or more a plurality of carbon atoms.The present invention adds to these flow enhancing agents in the resin with aforesaid method.Perhaps, the first isocyanide acyl group can form with methyl alcohol or ethanol block can be preferably and the block isocyanide acyl group of epoxy reaction, and the second isocyanide acyl group can form the block isocyanide acyl group of irreversible block with the active hydride block.The example of this active dydrogen compounds comprises primary amine such as methylamine, octylame or polyoxy alkylidene monoamine and aliphatic monocarboxylic acid such as sad or 2 ethyl hexanoic acid.
The performance of the visual specific resin of mol ratio of block vulcabond and Resins, epoxy and used vulcabond reach desirable amine equivalent in modified epoxy and change.Yet the mol ratio of the second block isocyanide acyl group and epoxy group(ing) always should be less than 1.In other words, the epoxy group(ing) part should keep not reacting in the reaction product of the first step.React under the temperature that is preferably in 60 ℃-200 ℃ and carry out, preferably use decantor that the by-product carbinol or the ethanol that are produced are removed from reaction system.Preferably, as mentioned above, resin with asymmetric block di-isocyanate reaction after carry out chainpropagation.
In second step, use cation activity hydrogen compound is opened the residual epoxide ring in the first step product.The example of available cation activity hydrogen compound comprises primary amine or secondary amine such as butylamine, octylame, diethylamine, dibutylamine, first butylamine, Monoethanolamine MEA BASF, diethanolamine or N-Mono Methyl Ethanol Amine, tertiary amine-acid salt such as triethylamine hydrochloride or N, N-dimethylethanolamine acetate, and sulfide-acid mixture such as diethyl sulfide-acetate mixture.Also can use ketoimine such as the amino ethyl ethanolamine or the diethylenetriamine of primary amine.Also can use the mixture of these amine and ketoimine.What it should be noted that is when using primary amine, because it also plays chainpropagation, and to make resin sticking excessively.For using as adhesive resin, the equivalents that makes the modified resin of gained contain amine is that 0.3-4.0meq/g is better.If the equivalents of amine is too low, it is difficult that emulsification in water medium or dispersion become.On the contrary, if the equivalents of amine is too high, the film that may obtain to have gratifying water resistance hardly.
The modified resin that contains quaternary ammonium or sulfonium part is useful as the pigment paste dispersion agent.For this reason, the residual epoxide ring of the first step or product ring can be by opening with the reaction of tertiary amine-acid salt or mixture or sulfide-acid mixture.The tertiary amine preferably and the sulfide that are used for this purpose comprise the substituent aliphatic tertiary amine of hydroxyl, as dimethylethanolamine or diethylethanolamine and the substituent aliphatic sulphide of hydroxyl, as thiodiethanol, 1-(2-hydroxyl second sulfo-)-2, ammediol, 1-(2-hydroxyl second sulfo-)-2-propyl alcohol, 1-(2-hydroxyl rosickyite generation)-2, ammediol, 1-(2-hydroxyl second sulfo-)-2-butanols, 1-(2-hydroxyl second sulfo-)-3-butoxy-1-propyl alcohol.The example of carboxylic acid comprises formic acid preferably, lactic acid, acetate, propionic acid, butyric acid, dimethylol propionic acid, N-acetyl-glycine, N-ethanoyl-β-An Jibingsuan etc.Being used for the alkali equivalents that the modified resin of colo(u)rant dispersion purpose should contain is 0.5-1.5meq/g.
Electrocoating paint
Modified epoxy contains two blocked isocyanates and self-crosslinking or by outside cross-linking agent such as block polyisocyanate or the crosslinked cationic moiety of melamine resin.When preparing in cathode electrodeposition paint, their characteristic performance can be revealed to the full extent.As previously mentioned, Chang Yong modified epoxy with the reactivity of linking agent on and unsatisfactory.Modified epoxy of the present invention not only with the reactivity of linking agent on, but and other performance comprise emulsifying property, thermal fluidity, erosion resistance and thermotolerance are very satisfactory.
In order to prepare electrocoating paint, modified resin of the present invention is dispersed in the water medium that contains neutralizing agent with linking agent, typical linking agent is the methylol melamine resin or the block polyisocyanate of etherificate.Certainly neutralizing agent is sour example hydrochloric acid, nitric acid, phosphoric acid, formic acid, acetate, lactic acid, thionamic acid or acetyl-glycine.
The amount of linking agent must be enough to by be contained in the resin usually amount and be the amino of the 5-50% (weight) of solid modified resin, hydroxyl or carboxyl crosslinking reaction and obtain rigid film.The amount of neutralizing agent is at least 20%, and preferably 30-60% can realize the neutralization of modified resin.
When block polyisocyanate during as linking agent, formulation for coating material can contain the catalyzer for block polyisocyanate weight 0.1-5%, as dibutyltin dilaurate, and dibutyltin oxide or other urethane catalyst for cracking.Certainly, formulation for coating material can contain many its special conventional additives that use needs of looking.Its example comprises tinting pigment such as titanium dioxide, carbon black or ferric oxide; Rust-stabilising pigment such as lead silicate white or phospho-molybdic acid lead; Pigment extender such as kaolin, talcum or clay; With other additive such as water miscibles organic solvent, tensio-active agent, oxidation inhibitor, UV absorption agent etc.The water-based paint of gained not only can be by electrodeposition process but also by spraying, and dipping and other ordinary methods impose in the substrate.
Pigment paste
When the vector resin as pigment paste was used for cathode electrodeposition paint, the modified resin that contains quaternary ammonium or sulfonium type cation radical demonstrated the performance better than existing resin.This is because blocked isocyanate moiety is Dinged the oxazolidone ring by Re Wen to be connected on the resin backbone, thereby it is difficult to separate out from resin during the baked paint film.
Can prepare pigment paste by ordinary method, be about to pigment, vector resin and deionized water are dispersed to particle size less than 10 microns.Pigment can be a kind of as above exemplified with suitable ratio blended pigment extender, the mixture of tinting pigment and rust-stabilising pigment.The vector resin of solid state is generally 1 with the ratio of pigment: 1-1: 10.The pigment paste of gained not only can add with in the coating of adhesive resin as modified resin of the present invention, and can add other and contain vinylformic acid, in the coating of epoxy or polybutadiene binder resin.In the coating that is disclosed as Japanese patent application JP-A-05306327 that pigment paste is added other, owing to the adhesive resin also Han oxazolidone ring that discloses herein, and, and can reach special benefit because the similarity and the pigment paste carrier of chemical structure have good consistency.
Following embodiment desires to further specify the present invention under situation about being not limited thereto.Except other pointed out, all umbers and percentage ratio all were parts by weight and weight percentage.All herein epoxy equivalent (weight)s and amine or alkali equivalent are benchmark with dried content all.
(embodiment 1)
Agitator is being housed, condenser, nitrogen tube adds 54.0g2 in the flask of thermometer and dropping funnel, 4-/2,6-toluene-2,4-diisocyanate (80: 20 weight ratios), 136g methyl iso-butyl ketone (MIBK) (MIBK) and 0.05g dibutyltin dilaurate.Stirring and feed under the nitrogen foaming, in 30 minutes, in mixture, be added dropwise to 10.9g methyl alcohol.At this section in the period, interior temperature rise to 60 ℃.Continue reaction after 30 minutes, in 1 hour, be added dropwise to 54.0g ethylene glycol one-2-second hexyl ether, make it 60-65 ℃ of reaction down, until the absorption peak disappearance of isocyanide acyl group on IR spectrum.In flask, add the 285g epoxy equivalent (weight) subsequently and be 475 bisphenol A epoxide resin 380g epoxy equivalent (weight) and be 950 bisphenol A epoxide resin and 0.62g benzyl dimethylamine.Then, make mixture 120 ℃ of reactions down, the by-product methanol of generation is removed in distillation, reaches 1120 until epoxy equivalent (weight).After the cooling, add the 29.1g diethanolamine in mixture, 21.5gN-Mono Methyl Ethanol Amine and 32.9g hydrogen ehtylethanolamine ketoimine (79% solution in MIBK) make it to react 2 hours in the time of 110 ℃.IR spectrum confirms at 1750cm
-1The absorption of Chu oxazolidine ketone carbonyl.Non-volatile with MIBK cut back to 80%, obtain number-average molecular weight and be 2600 and amine equivalent be the resin cation (R.C.) A of 99meq/100g.
Embodiment 2
Similar to Example 1, with 57.4g 2.4/2,6-toluene-2,4-diisocyanate (80: 20 weight ratios) reacts with 11.6g methyl alcohol, and then reacts with 60.8g ethylene glycol monobutyl ether.With the asymmetric block vulcabond of gained and 309g epoxy equivalent (weight) is that 475 bisphenol F epoxy resin and 332g epoxy equivalent (weight) are 950 bisphenol F epoxy resin reaction.With product further with the 27.0g diethanolamine, 20.0gN-Mono Methyl Ethanol Amine and 32.9g N-aminoethyl ethanolamine ketoimine (79% solution in MIBK) reaction is diluted to 80% non-volatile then with MIBK.Obtain number-average molecular weight and be 2400 and amine equivalent be the resin cation (R.C.) B of 97meq/100g.
Embodiment 3
Agitator is being housed, condenser, nitrogen tube adds 77.5g4 in the flask of thermometer and dropping funnel, 4 '-diphenylmethanediisocyanate, 136g methyl iso-butyl ketone (MIBK) (MIBK) and 0.05g dibutyltin dilaurate.Stirring and feed under the nitrogen foaming, in 30 minutes, in mixture, be added dropwise to 10.9g methyl alcohol.During this period of time, interior temperature rise is to 80C.Continue reaction after 30 minutes, in 1 hour, be added dropwise to 52.2g ethylene glycol one-2-second hexyl ether, make it 80-85 ℃ of reaction down, until the absorption peak disappearance of isocyanide acyl group on IR spectrum.Add the 309.0g epoxy equivalent (weight) subsequently and be 475 bisphenol F epoxy resin in flask, the 3323g epoxy equivalent (weight) is 950 bisphenol F epoxy resin and 0.62g benzyl dimethylamine.Then, make mixture 120 ℃ of reactions down, the by-product methanol of generation is removed in distillation, reaches 1116 until epoxy equivalent (weight).After the cooling, add the 14.6g diethanolamine in mixture, 31.8gN-Mono Methyl Ethanol Amine and 32.9g N-aminoethyl ethanolamine ketoimine (79% solution in MIBK) make it to react 2 hours in the time of 110 ℃.IR spectrum confirms at 1750cm
-1The absorption of Chu oxazolidine ketone carbonyl.Be diluted to 80% non-volatile, obtain number-average molecular weight and be 2700 and amine equivalent be the resin cation (R.C.) C of 98meq/100g.
Embodiment 4
Similar to Example 1, earlier 82.5g 4,4 '-diphenylmethanediisocyanate and 10.5g methyl alcohol are reacted, and then with the mixture reaction of 34.8g ethylene glycol one-2-second hexyl ether and 11.3g ε-Ji Neixianan.With the block vulcabond of gained and 285g epoxy equivalent (weight) is that 475 bisphenol F epoxy resin and 380g epoxy equivalent (weight) are the mixture reaction of 950 bisphenol F epoxy resin.With product further with 13.9g diethanolamine, the mixture reaction of 28.9gN-Mono Methyl Ethanol Amine and 22.0g N-aminoethyl ethanolamine ketoimine (79% solution in MIBK), and be diluted to 80% non-volatile with MIBK.Obtain number-average molecular weight and be 2600 and amine equivalent be the resin cation (R.C.) D of 95meq/100g.
Embodiment 5
Similar to Example 1, earlier with 57.0g 2,4-/2,6-toluene-2,4-diisocyanate (80: 20 weightization) reacts with 10.5g methyl alcohol, and then obtains the block vulcabond with the reaction of 54.0g ethylene glycol one-2-second hexyl ether.It with this block vulcabond and epoxy equivalent (weight) 1200 chainpropagation Resins, epoxy reaction, this chainpropagation Resins, epoxy is to be 650 bisphenol A epoxide resin and 86.0g dihydroxyphenyl propane-ethylene oxide adduct (BPE-100 by the 1012.0g epoxy equivalent (weight), by Sanyo Chemical Industries, Ltd. sell) the reaction acquisition, with product further with the 29.1g diethanolamine, 21.5gN-the mixture reaction of Mono Methyl Ethanol Amine and 32.9g N-aminoethyl ethanolamine ketoimine (79% solution in MIBK), and be diluted to 80% non-volatile, obtain number-average molecular weight and be 2800 and amine equivalent be the resin cation (R.C.) E of 98meq/100g.
The comparative example 1
In the identical reactor used, add the 285.0g epoxy equivalent (weight) and be as embodiment 1 475 bisphenol A epoxide resin 77.0g right-nonyl phenol and 82.4gMIBK.After mixing formed a solution under the heating, at 3.0g N, the N-dimethyl benzylamine existed down, mixture is reacted down at 150 ℃ reach 1140 until epoxy equivalent (weight).After the cooling, add the 19.2g diethanolamine in mixture, 27.0gN-Mono Methyl Ethanol Amine and 30.6g N-aminoethyl ethanolamine ketoimine (79% solution in MIBK) make it to react 2 hours down at 110 ℃.And be diluted to 90% non-volatile with MIBK.Obtain number-average molecular weight and be 2100 and amine equivalent be the resin cation (R.C.) a of 90meq/100g.
The comparative example 2
Except in the first step with the 99.0g12-oxystearic acid replace 77.0g right-nonyl phenol, and the diethanolamine that adds, the amount of N-Mono Methyl Ethanol Amine and N-aminoethyl ethanolamine ketoimine is respectively 27.9g, 19.8g and outside the 31.5g, by comparative example 1 step, obtain number-average molecular weight and be 2700 and amine equivalent be the resin cation (R.C.) b of 90meq/100g.
The comparative example 3
As in the used identical reactor of embodiment 1, adding 26.1g 2,4-/2,6-toluene-2,4-diisocyanate (80: 20 weight ratios) and 13.0g MIBK.Under stirring and the foaming of feeding nitrogen, in 1 hour, in mixture, be added dropwise to 26.1g ethylene glycol one-2-second hexyl ether.During this period of time, interior temperature rise to 60 ℃.Acquisition NCO equivalent is 350 half block vulcabond solution.In this solution, be added dropwise to the 95.0g epoxy equivalent (weight) and be 475 bisphenol A epoxide resin and 750g epoxy equivalent (weight) and be the solution that 950 bisphenol A epoxide resin is dissolved in 150.0gMIBK.Mixture is disappeared 120 ℃ of absorptions of reacting down until NCO on IR spectrum.After being chilled to 110 ℃, with mixture further with 35.4g diethanolamine, 25.2g N-Mono Methyl Ethanol Amine and 40.0g N-aminoethyl ethanolamine ketoimine (75% solution in MIBK) reaction 2 hours, and be diluted to 85.0% non-volatile.Obtain number-average molecular weight and be 2800 and amine equivalent be the resin cation (R.C.) c of 100meq/100g.
Pigment paste
Agitator is being housed, and adding 740g epoxy equivalent (weight) is 190 bisphenol A epoxide resin (EPIKOTE 828, YuKa Shell E-poxy K.K.) in the three-necked flask of reflux condensing tube and thermometer, 211g dihydroxyphenyl propane, 48g MIBK and 1.5g benzyl dimethylamine.Mixture was reacted 2 hours in the time of 170 ℃.With the epoxy equivalent (weight) of gained is 700 product and 244g thiodiethanol, and 268g dimethylol propionic acid and 50g deionized water mix, make it 60 ℃ down reaction 5 hours and subsequently spent glycol monobutyl ether be diluted to 30% solid.
Prepare pigment paste by grinding following mixture
The component amount, g
Pigment dispersing resin 200.0 (60g solid)
Carbon black 4.0
Kaolin 36.0
TiO
2 150.0
Lead silicate white 10.0
Deionized water 33.3
Synthesizing of linking agent
The linking agent I:
In the identical reactor used, add 125.0g 4,4 '-diphenylmethanediisocyanate, 75.0g MIBK and 0.05g dibutyltin dilaurate as embodiment 1.Stirring and feed under the nitrogen foaming, in this mixture, be added dropwise to the 45.2g ε-Ji Neixianan, 47.2g ethylene glycol monobutyl ether, the mixture of 4.0g methyl alcohol and 4.4g TriMethylolPropane(TMP).During this period of time, interior temperature rise to 60 ℃.Continuing the reaction absorption until NCO on IR spectrum in 1 hour disappears.With the product of calling gained in the following text is the linking agent I.
The linking agent II:
Similar to the above, in 32gMIBK, with 87.0g methyl ethyl ketoxime block 199g hexamethylene diisocyanate tripolymer (CORONATE HX is sold by Nippon PolyurethaneK.K.).With the product of calling gained in the following text is the linking agent II.
Embodiment 6
Thoroughly mix 148.0g solid state linking agent I, 252.0g solid state resin cation (R.C.) A and 5.0g dibutyltin oxide.After being heated to 80 ℃, under agitation, slowly adding the deionized water that 266.6g contains 6.24g acetate and make emulsifying mixture, be diluted to 36% solid with the 455g deionized water then.Evaporate this emulsion in a vacuum and remove organic solvent, be adjusted to 36% solid with deionized water again, mix, be diluted to 20% non-volatilely at last with 1400g deionized water and 32g ethylene glycol one hexyl ether, make cathode electrodeposition paint with the above-mentioned pigment paste of 270g.
The coating electricity is imposed on the steel plate as negative electrode that zinc phosphate handled, and build is 20 microns, toasts under the condition listed as table 1, and tests its performance.The experimental result that records by spectrometer and listing in the table 1 with the particle size of emulsion before pigment paste mixes.Embodiment 7-10 and comparative example 3-5
Prepare the coating of the listed various prescriptions of table 1 as embodiment 6, in all embodiment and comparative example, the ratio of resin cation (R.C.)/linking agent is 63/37 in the coating.The results are shown in Table 1 for gained.
Table 1 component embodiment comparative example 6789 10 a b c resin cation A B C D E F G H cross-linking agents Ⅰ I II II II I I I performance emulsion granules 1) 80 100 130 120 85 250 130 100 sizes; Nm curability 2) 150 * 20min glossiness, 160 * 20min apparent property, 3 carefully of the low in glossiness of good job carefully) 0.22 0.25 0.20 0.22 0.21 0.23 0.24 0.25Ra; μ m, 160 * 20min. salt spray 4) the unchanged yellowing 5 of nothing nothing 160 * 20mm variation variation detectable bubble of detectable bubble) 160 ℃ of * 20min of the no remarkable of nothing nothing nothing
The note of table 1
1) measures by Hitachi Spectrometer Model V-1110
2) baking is after 20 minutes down at 175 ℃, and sulfide film uses the fabric by the acetone dipping to rub 30 times back and forth, when observing variation on the surface of film, just thinks that curability is good.
3) the Surface Roughness MeterModel E-30A that is sold by Toyo Seimitsu K.K. measures.
4) press JIS-Z 2371
What 5) internal surface of cylindrical metal can be with routine grants automobile body as the white paint of inter coat (by Nippon Point Co., the alkyd melamine base white paint that Ltol sells) spraying.This can be transferred and place on the laboratory sample steel plate.Sulfuration is after 20 minutes in the time of 140 ℃, and its yellowness factor of coated membrane that imposes on internal surface can be by visual inspection.
Embodiment 11
Agitator is being housed, condenser, nitrogen tube adds 66.1g2 in the flask of thermometer and dropping funnel, 4-/2,6-toluene-2,4-diisocyanate (80: 20 weight ratios), 53.3g methyl iso-butyl ketone (MIBK) (MIBK) and 0.12g dibutyltin dilaurate.Stirring and feed under the nitrogen foaming, in 30 minutes, in mixture, be added dropwise to 13.6g methyl alcohol.At this section in the period, interior temperature rise to 60 ℃.Continue reaction after 30 minutes, in 1 hour, be added dropwise to the 46.8g 2-Ethylhexyl Alcohol and make it and react down, until the absorption peak disappearance of isocyanide acyl group on IR spectrum at 60-65 ℃.In flask, add the 310g epoxy equivalent (weight) subsequently and be 188 bisphenol A epoxide resin and 0.8g benzyl dimethylamine.Then, make mixture 120-125 ℃ of reaction down, the by-product methanol of generation is removed in distillation, reaches 338 until epoxy equivalent (weight).IR spectrum confirms at 1750cm
-1The absorption of Chu oxazolidine ketone carbonyl.In mixture, add the 57.0g dihydroxyphenyl propane then, and make it to reach 640 until epoxy equivalent (weight) 120 ℃ of reactions.After the cooling, in the time of 65 ℃, product and 92.3g dithioglycol and 100.5g dimethylol propionic acid are dissolved in the solution reaction of 108.0g deionized water, reach less than 5 until acid number, use the mixture diluted to 60% of 1: 1 ethylene glycol monobutyl ether and dipropylene glycol monobutyl ether non-volatile then.Obtaining the alkali equivalent is the pigment dispersing resin F of 78meq/100g.
Embodiment 12
Agitator is being housed, condenser, nitrogen tube adds 62.6g2 in the flask of thermometer and dropping funnel, 4-/2,6-toluene-2,4-diisocyanate (80: 20 weight ratios), 55.1g methyl iso-butyl ketone (MIBK) (MIBK) and 0.12g dibutyltin dilaurate.Stirring and feed under the nitrogen foaming, in 30 minutes, in mixture, be added dropwise to 13.6g methyl alcohol.At this section in the period, interior temperature rise to 60 ℃.Continue reaction after 30 minutes, in 1 hour, be added dropwise to 62.6g ethylene glycol one-2-ethylhexyl ether, make it 60-65 ℃ of reaction down, until the absorption peak disappearance of isocyanide acyl group on IR spectrum.In flask, add the 310g epoxy equivalent (weight) subsequently and be 188 bisphenol A epoxide resin and 0.8g benzyl dimethylamine.Then, make mixture 120 ℃ of reactions down, the by-product methanol of generation is removed in distillation, reaches 350 until epoxy equivalent (weight).In mixing, add the 57.0g dihydroxyphenyl propane then, make it reaction in the time of 120 ℃, reach 660 until epoxy equivalent (weight).After the cooling, in the time of 65 ℃, product and 102.2gl-(2-hydroxyethylthio)-2-propyl alcohol and 100.5g dimethylol propionic acid are dissolved in the solution reaction of 108.0g deionized water, reach less than 5 until acid number, use the mixture diluted to 60% of 1: 1 ethylene glycol monobutyl ether and dipropylene glycol monobutyl ether non-volatile then, obtain pigment dispersing resin G.
Embodiment 13
The step of using following substances to press embodiment 11:
The title umber
TDI 66.1
Methyl alcohol 13.6
Diethylene Glycol one-2-second hexyl ether 78.5
Dibutyltin dilaurate 0.12
MIBK 56.9
Bisphenol A epoxide resin (E.E.=188) 310.2
Dihydroxyphenyl propane 57.0
Diformazan benzylamine 0.8
1-(2-hydroxyethylthio)-2, ammediol 114.0
Dimethylol propionic acid 100.5
Deionized water 108.0
Amount to 726.3
Product is non-volatile with the mixture diluted to 60% of 1: 1 ethylene glycol monobutyl ether and dipropylene glycol monobutyl ether, obtains pigment dispersing resin H.Alkali equivalent=72.3meq/100g.
Embodiment 14
The step of using following substances to press embodiment 11:
The title umber
TDI 66.1
Methyl alcohol 13.6
Ethylene glycol one-2-second hexyl ether 62.6
Dibutyltin dilaurate 0.12
MIBK 55.1
Bisphenol A epoxide resin (E.E.=188) 310.2
Dihydroxyphenyl propane 57.0
Diformazan benzylamine 0.8
1-(2-hydroxyethylthio)-2, ammediol 124.5
Dimethylol propionic acid 100.5
Deionized water 108.0
Amount to 720.0
Product is non-volatile with the mixture diluted to 60% of 1: 1 ethylene glycol monobutyl ether and dipropylene glycol monobutyl ether, obtains the pigment dispersing resin I.Alkali equivalent=72.9meq/100g.
Embodiment 15
The step of using following substances to press embodiment 11:
The title umber
MDI 95.0
Methyl alcohol 13.6
Ethylene glycol one-2-second hexyl ether 62.6
Dibutyltin dilaurate 0.12
MIBK 58.3
Bisphenol A epoxide resin (E.E.=188) 310.2
Dihydroxyphenyl propane 57.0
Dithioglycol 92.3
Dimethylol propionic acid 100.5
Deionized water 108.0
Amount to 717.6
Product is non-volatile with the mixture diluted to 60% of 1: 1 ethylene glycol monobutyl ether and dipropylene glycol monobutyl ether, obtains pigment dispersing resin J.Alkali equivalent=72.0meq/100g.
Embodiment 16
The step of using following substances to press embodiment 11:
The title umber
TDI 66.1
Methyl alcohol 13.6
Ethylene glycol one-2-second hexyl ether 62.6
Dibutyltin dilaurate 0.12
MIBK 67.0
Bisphenol A epoxide resin (E.E.=475) 475.0
Diformazan benzylamine 0.8
1-(2-hydroxyethylthio)-2-propyl alcohol 81.7
Dimethylol propionic acid 80.4
Deionized water 113.0
Amount to 765.8
Product is non-volatile with the mixture diluted to 60% of 1: 1 ethylene glycol monobutyl ether and dipropylene glycol monobutyl ether, obtains pigment dispersing resin K.Alkali equivalent=55.0meq/100g.
Embodiment 17
The step of using following substances to press embodiment 11:
The title umber
TDI 26.1
Methyl alcohol 5.44
Ethylene glycol one-2-second hexyl ether 24.4
Dibutyltin dilaurate 0.12
Bisphenol A epoxide resin (E.E.=188) 310.2
Dihydroxyphenyl propane 57.0
Diformazan benzylamine 0.8
1-(2-hydroxyethylthio)-2-propyl alcohol 121.8
Dimethylol propionic acid 132.7
Deionized water 129.6
Amount to 672.0
Product is non-volatile with the mixture diluted to 60% of 1: 1 ethylene glycol monobutyl ether and dipropylene glycol monobutyl ether, obtains pigment dispersing resin L.Alkali equivalent=146.0meq/100g.
Embodiment 18
Agitator is being housed, condenser, nitrogen tube adds 62.6g2 in the flask of thermometer and dropping funnel, 4-/2,6-toluene-2,4-diisocyanate (80: 20 weight ratios), 55.1g methyl iso-butyl ketone (MIBK) (MIBK) and 0.12g butyl tin dilaurate.Stirring and feed under the nitrogen foaming, in 30 minutes, in mixture, be added dropwise to 13.6g methyl alcohol.At this section in the period, interior temperature rise to 60 ℃.Continue reaction after 30 minutes, in 1 hour, be added dropwise to 62.6g ethylene glycol one-2-second hexyl ether, make it 60-65 ℃ of reaction down, until the absorption peak disappearance of isocyanide acyl group on IR spectrum.In flask, add the 475.0g epoxy equivalent (weight) subsequently and be 475 bisphenol A epoxide resin and 0.8g benzyl dimethylamine.Then, make mixture 125 ℃ of reactions down, the by-product methanol of generation is removed in distillation, reaches 1010 until epoxy equivalent (weight).After the cooling, add the 62.3g dimethylethanolamine in mixture, 63.0g lactic acid and 108.0g deionized water make it to reach less than 1 until acid number 80 ℃ of reactions down.Product reaches less than 1 until acid number with 1: 1 ethylene glycol monobutyl ether and 2 80 ℃ of reactions down.Product is non-volatile with the mixture diluted to 60% of 1: 1 ethylene glycol monobutyl ether and dipropylene glycol monobutyl ether, obtains pigment dispersing resin M.
Embodiment 19
Agitator is being housed, condenser, nitrogen tube adds 62.6g2 in the flask of thermometer and dropping funnel, 4-/2,6-toluene-2,4-diisocyanate (80: 20 weight ratios), 55.1g methyl iso-butyl ketone (MIBK) (MIBK) and 0.12g dibutyltin dilaurate.Stirring and feed under the nitrogen foaming, in 30 minutes, in mixture, be added dropwise to 13.6g methyl alcohol.At this section in the period, interior temperature rise to 60 ℃.Continue reaction after 30 minutes, in 1 hour, be added dropwise to 62.6g ethylene glycol one-2-second hexyl ether, make it 60-65 ℃ of reaction down, until the absorption peak disappearance of isocyanide acyl group on IR spectrum.In flask, add the 475.0g epoxy equivalent (weight) subsequently and be 475 bisphenol A epoxide resin and 0.8g benzyl dimethylamine.Then, make mixture 120 ℃ of reactions down, the by-product methanol of generation is removed in distillation, reaches 1010 until epoxy equivalent (weight).After the cooling, in mixture, add 51.89g N-Mono Methyl Ethanol Amine and make it reaction, until on IR spectrum, detecting less than epoxy group(ing).Product is dissolved in further the solution reaction of 108.0g deionized water with 101.0g Racemic glycidol and 90g lactic acid, reach less than 1 until acid number, use the mixture diluted to 60% of 1: 1 ethylene glycol monobutyl ether and dipropylene glycol monobutyl ether non-volatile at last, obtain pigment dispersing resin N.
Embodiment 20
The step of using following substances to press embodiment 18:
The title umber
TDI 26.1
Methyl alcohol 5.44
Ethylene glycol one-2-second hexyl ether 24.4
Dibutyltin dilaurate 0.12
MIBK 190.5
Bisphenol A epoxide resin (E.E.=950) 950.0
Diformazan benzylamine 0.8
Dimethylethanolamine 62.3
Lactic acid (60%) 63.0
Amount to 1204.0
Product is non-volatile with the mixture diluted to 60% of 1: 1 ethylene glycol monobutyl ether and dipropylene glycol monobutyl ether, obtains pigment dispersing resin O.Alkali equivalent=48.0meq/100g.
The comparative example 7
Material umber solid
EPON?828 533.2 533.2
Dihydroxyphenyl propane 199.6 199.6
Nonyl phenol 19.2 19.2
Iodate ethyl triphenyl sulfonium 0.75-
Propylene glycol monobutyl ether 201.6-
Thiodiethanol 122.1 122.1
Dimethylol propionic acid 134.1 134.1
Deionized water 30.6-
With EPON 828, dihydroxyphenyl propane and nonyl phenol heat 107 ℃ in reactor, keep this temperature to dissolve until dihydroxyphenyl propane.After adding iodate ethyl triphenyl sulfonium, heated mixt to 125 ℃ also is chilled to 75 ℃, adds propylene glycol monobutyl ether subsequently, dithioglycol, the mixture of dimethylol propionic acid and deionized water.Make mixture 70-75 ℃ of reaction down, reach less than 3 until acid number, cooling is diluted to 30% solid with deionized water, obtains pigment dispersing resin lacquer P.
The comparative example 8
Step 1:
Material umber solid
2-second hexanol-half block TDI 320.0 304.0 in MIBK
Dimethylethanolamine 87.2 87.2
75% lactic acid 117.6 88.2
Ethylene glycol monobutyl ether 39.2-
In reactor, in 2-second hexanol-half block TDI, be added dropwise to dimethylethanolamine under stirring, thermopositive reaction takes place.In the time of 80 ℃, stir after 1 hour, stir down and in the time of 65 ℃, mixture was reacted 30 minutes with lactic acid in ethylene glycol monobutyl ether further, obtain quaternizing agent.
Step 2:
Material umber solid
EPON?829 710.0 681.2
Dihydroxyphenyl propane 289.6 298.6
2-second hexanol-half block TDI 406.4 386.1 in MIBK
The quaternizing agent 496.3 421.9 of step 1
Deionized water 71.2-
Ethylene glycol monobutyl ether 56.76-
Under nitrogen atmosphere, in 150-160 ℃ of following EPON 829 and bisphenol-a reaction 1 hour, be chilled to 120 ℃ after, product reacts with 2-second hexanol-half block TDI and 85-95 ℃ of following homogenizing.In reaction mixture, add the quaternizing agent of step 1 then and make it and reach less than 1 until acid number 80-85 ℃ of reaction down.With the product of calling gained in the following text is pigment dispersing resin lacquer Q.
Embodiment 21-30 and comparative example 9-10
Pigment paste
In the sand milling grinding machine, grind following mixture to particle size less than 10 microns, preparation pigment paste, and estimate its performance.The results are shown in Table 2.
The material umber
Pigment dispersing resin 125.0 (60.0% solid)
Deionized water 400.0
Carbon black 8.5
Kaolin 72.0
Titanium dioxide 345.0
Phospho-molybdic acid aluminium 75.0
Adhesive resin:
Agitator is being housed, condenser, nitrogen tube, adding the 285.0g epoxy equivalent (weight) in the flask of thermometer and dropping funnel is that 475 oxazolidone ring equivalents are 650, make the Resins, epoxy of De Han oxazolidone ring by bisphenol A epoxide resin and TDI, after 380.0g epoxy equivalent (weight) is 950 bisphenol A epoxide resin 77.0g right-nonyl phenol and 82.4gMIBK. adds 3.0g benzyl dimethylamine, make mixture 130 ℃ of reactions down, reach 1140 until epoxy equivalent (weight), after the cooling, in the time of 110 ℃ with this mixture and 19.2g diethanolamine, the mixture reaction of 27.0gN-Mono Methyl Ethanol Amine and 30.6g N-aminoethyl ethanolamine ketoimine (79% solution in MIBK) 2 hours.Product is diluted to 90% non-volatile with MIBK.
Linking agent
Use the linking agent II of embodiment 6-10 and comparative example 3-6.
Main emulsion:
With above-mentioned adhesive resin and linking agent with 68: 36 solid than mixing, in mixture, add ethylene glycol one hexyl ether that is equivalent to solid 2% amount.During adding acetate reaches and after 42.5%, mixture dilutes lentamente with deionized water, and MIBK to 36.0% solid is removed in evaporation in a vacuum.
Evaluation to coating
Mix the above-mentioned main emulsion of 2000.0g, above-mentioned pigment paste of 460.0g and 2252.0g deionized water prepare various cathod coatings.
With the coating electricity impose on the cold roll steel plate that zinc phosphate handled to build be 20 microns, baking is 10 minutes in the time of 160 ℃, experiment paint film performance, the results are shown in Table 2.
Table 2
The embodiment comparative example
21 22 23 24 25 26 27 28 29 30 9 10
Pigmental resin F G H I J K L M N O P Q
Thermostability 1) carefully OK
Dispersion stabilization 2) good carefully OK good
Coulombic efficiency 3) good carefully OK good
Salt spray 4) carefully OK
Yellowing 5)
160 ℃ of fashions fair carefully OK
180 ℃ of fair carefully one's likes or preferences carefully of fashion good OK
The note of table 2:
1) thermostability in 20 minutes in the time of 220 ℃
Good: no vulcabond is separated out
Bad: as to have vulcabond to separate out
2) in the time of 40 ℃, left standstill for 2 weeks after the storage stability of pigment paste
Good: as not have deposition
Bad: piece deposits or is separated
3) sedimentation effect of under the condition that obtains 20 microns thickness, representing with the mg/ coulomb
Good:＞35mg/ coulomb
Bad:＜35mg/ coulomb
4) press JIS-Z 2371
Good: no change
Bad: as on whole area, to bubble
5) middle layer white paint spraying is 160 ℃ of bakings 10 minutes or on 20 minutes membrane samples of 180 ℃ of bakings, then 140 ℃ of bakings 20 minutes down.The yellowness factor of white paint film by with the naked eye with the reference sample plate comparative measurement that directly applies with white paint.
Good: as not have yellowing
Fair: slight yellowing
Bad: significantly yellowing
Embodiment 31
Agitator is being housed, condenser, nitrogen tube adds 54.0g2 in the flask of thermometer and dropping funnel, 4-/2,6-toluene-2,4-diisocyanate (80: 20 weight ratios), 136g methyl iso-butyl ketone (MIBK) (MIBK) and 0.05g dibutyltin dilaurate.Stirring and feed under the nitrogen foaming, in 30 minutes, in mixture, be added dropwise to 10.9g methyl alcohol.At this section in the period, interior temperature rise to 60 ℃.Continue reaction after 30 minutes, in 1 hour, be added dropwise to the 36.2g dibutylamine, make it 60-65 ℃ of reaction down, until the absorption peak disappearance of isocyanide acyl group on IR spectrum.In flask, add the 285g epoxy equivalent (weight) subsequently and be 475 bisphenol A epoxide resin 380g epoxy equivalent (weight) and be 950 bisphenol A epoxide resin and 0.62g benzyl dimethylamine.Then, make mixture 120 ℃ of reactions down, the by-product methanol of generation is removed in distillation, reaches 1120 until epoxy equivalent (weight).After the cooling, add the 29.1g diethanolamine in mixture, 21.5gN-Mono Methyl Ethanol Amine and 32.9g N-aminoethyl ethanolamine ketoimine (79% solution in MIBK) make it to react 2 hours in the time of 110 ℃.IR spectrum confirms at 1750cm
-1The absorption of Chu oxazolidine ketone carbonyl.Product is non-volatile with MIBK cut back to 80%, and the resin cation (R.C.) of Huo Deing demonstrates gratifying emulsifying property like this.
Embodiment 32
Agitator is being housed, condenser, nitrogen tube adds 54.0g2 in the flask of thermometer and dropping funnel, 4-/2,6-toluene-2,4-diisocyanate (80: 20 weight ratios), 136g methyl iso-butyl ketone (MIBK) (MIBK) and 0.05g dibutyltin dilaurate.Stirring and feed under the nitrogen foaming, in 30 minutes, in mixture, be added dropwise to 10.9g methyl alcohol.At this section in the period, interior temperature rise to 60 ℃.Continue reaction after 30 minutes, it is sad to be added dropwise to 40.4g in 1 hour, makes it 60-65 ℃ of reaction down, until the absorption peak disappearance of isocyanide acyl group on IR spectrum.In flask, add the 285g epoxy equivalent (weight) subsequently and be 475 bisphenol A epoxide resin 380g epoxy equivalent (weight) and be 950 bisphenol A epoxide resin and 0.62g benzyl dimethylamine.Then, make mixture 120 ℃ of reactions down, the by-product methanol of generation is removed in distillation, reaches 1120 until epoxy equivalent (weight).After the cooling, add the 29.1g diethanolamine in mixture, 21.5gN-Mono Methyl Ethanol Amine and 32.9g N-aminoethyl ethanolamine ketoimine (79% solution in MIBK) make it to react 2 hours in the time of 110 ℃.IR spectrum confirms at 1750cm
-1The absorption of Chu oxazolidine ketone carbonyl.Product is non-volatile with MIBK cut back to 80%, and the resin cation (R.C.) of Huo Deing demonstrates gratifying emulsifying property like this.
Claims (13)
1. modified epoxy; comprise at least one blocked isocyanate moiety that Tong Guo oxazolidone ring connects; Suo Shu De oxazolidone ring is formed by the isocyanide acyl group reaction of the epoxy group(ing) of many glycidyl epoxies part with organic diisocyanate; then by block reversibly or irreversibly, this modified epoxy further contains at least one cation radical of being introduced by the ring-opening reaction of remaining oxirane ring and cation activity hydrogen compound to other isocyanate group.
2. modified epoxy as claimed in claim 1, wherein said many glycidyl epoxies are the many glycidyl ether epoxy of polyphenol, aliphatic series how pure many glycidyl ether epoxy, many glycidyls of poly carboxylic acid ester epoxy resin or its chainpropagation product.
3. modified epoxy as claimed in claim 1, wherein said other isocyanide acyl group is reversibly used butanols, 2-Ethylhexyl Alcohol, alkylphenol, glycol monobasic ether, ketoxime or lactan block.
4. modified epoxy as claimed in claim 1, wherein said other isocyanide acyl group be irreversibly with primary amine or secondary amine, uncle's aminoalkanol, or aliphatic monocarboxylic acid's block.
5. modified epoxy as claimed in claim 1, the wherein said cation activity hydrogen compound that is used to open the residual epoxide ring is a primary amine, secondary amine, the mixture of the acid salt of tertiary amine or sulfide-acid.
6. a method for preparing modified epoxy comprises the steps:
To contain the organic diisocyanate reaction of the Resins, epoxy and the asymmetric block of many glycidyls, described vulcabond contains the first block isocyanide acyl group and the second block isocyanide acyl group, the specific activity first block isocyanide acyl group of this second isocyanide acyl group is little, and than the described first block isocyanide acyl group stoichiometric number little with the ratio of glycidyl; With
The product and the cation activity reactive hydrogen compound of gained are introduced cation radical with the ring-opening reaction by residual epoxide ring and described positively charged ion hydrogen compound.
7. method as claimed in claim 6, wherein said Resins, epoxy are the many glycidyl ether epoxy of polyphenol, the how pure many glycidyl ether epoxy of aliphatic series, many glycidyls of poly carboxylic acid ester epoxy resin, or its chainpropagation product.
8. method as claimed in claim 6, the wherein said first isocyanide acyl group is with methyl alcohol or ethanol block.
9. method as claimed in claim 6, the wherein said second isocyanide acyl group is reversibly used butanols, 2-Ethylhexyl Alcohol, alkylphenol, glycol-first ether, ketoxime or lactan block.
10. method as claimed in claim 6, the wherein said second isocyanide acyl group be irreversibly with primary amine or secondary amine, uncle's aminoalkanol, or aliphatic monocarboxylic acid's block.
11. method as claimed in claim 6, wherein said cation activity hydrogen compound is primary amine or secondary amine, the acid salt of tertiary amine, or the mixture of sulfide-acid.
12. the described modified resin of claim 1 is as the application of the aqueous dispersion of cathode electrodeposition paint.
13. the described modified epoxy of claim 1 is as the application of the vector resin of pigment paste, described pigment paste is the form of the dispersion of pigment in the described vector resin aqueous solution.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07658194A JP3513665B2 (en) | 1993-05-17 | 1994-03-22 | Modified epoxy resin having a blocked isocyanate component and a cationic group bonded thereto, its production method and use thereof |
| JP76581/1994 | 1994-03-22 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1111651A CN1111651A (en) | 1995-11-15 |
| CN1066465C true CN1066465C (en) | 2001-05-30 |
Family
ID=13609252
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95103486A Expired - Lifetime CN1066465C (en) | 1994-03-22 | 1995-03-22 | Modified epoxy resins having a blocked isocyanate moiety and a cationic group and their use in cathodic electrodeposition paints |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1066465C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1324062C (en) * | 2003-02-26 | 2007-07-04 | 拜尔材料科学股份公司 | Polyurethane Coating System |
| CN106519184A (en) * | 2016-10-28 | 2017-03-22 | 苏州太湖电工新材料股份有限公司 | Preparing method of high polymer containing oxazolidinone ring |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106700028B (en) * | 2016-11-28 | 2019-03-22 | 中海油常州涂料化工研究院有限公司 | A kind of cathode electrophoresis dope sulfosalt type dispersion resin and preparation method thereof |
| CN112661935B (en) * | 2020-12-23 | 2023-01-20 | 江苏东材新材料有限责任公司 | High-heat-resistance water-soluble isocyanate modified epoxy resin for copper-clad plate, composition and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0129787A2 (en) * | 1983-06-27 | 1985-01-02 | Siemens Aktiengesellschaft | Process for the production of moulding compounds |
| WO1986001526A1 (en) * | 1984-09-01 | 1986-03-13 | Basf Lacke + Farben Ag | Aqueous electrophoretic coating by cathodic deposition and method for coating an electric conductor substrate |
| EP0342064A2 (en) * | 1988-05-13 | 1989-11-15 | Nippon Paint Co., Ltd. | A thermosetting resinous composition and preparation of heat resisting coating and molded product using said composition |
-
1995
- 1995-03-22 CN CN95103486A patent/CN1066465C/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0129787A2 (en) * | 1983-06-27 | 1985-01-02 | Siemens Aktiengesellschaft | Process for the production of moulding compounds |
| WO1986001526A1 (en) * | 1984-09-01 | 1986-03-13 | Basf Lacke + Farben Ag | Aqueous electrophoretic coating by cathodic deposition and method for coating an electric conductor substrate |
| EP0342064A2 (en) * | 1988-05-13 | 1989-11-15 | Nippon Paint Co., Ltd. | A thermosetting resinous composition and preparation of heat resisting coating and molded product using said composition |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1324062C (en) * | 2003-02-26 | 2007-07-04 | 拜尔材料科学股份公司 | Polyurethane Coating System |
| CN106519184A (en) * | 2016-10-28 | 2017-03-22 | 苏州太湖电工新材料股份有限公司 | Preparing method of high polymer containing oxazolidinone ring |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1111651A (en) | 1995-11-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1128849C (en) | Cationic resin and capped polyisocyanate curing agent suitable for use in electrodeposition | |
| CN1024416C (en) | Process for preparing amino-urethanes and their use | |
| CN1154701C (en) | Coating composition having improved adhesion to substrate | |
| CN1184249C (en) | Curable polyurethanes, coatings prepared therefrom, and method of making the same | |
| CN1016430B (en) | Cationic advanced epoxy resin compositions | |
| CN1016437B (en) | Improved cationic electrodepositable compositions through use of sulfamic acid and derivatives thereof | |
| CN1232598C (en) | Method for inhibiting trap and trap inhibitor for cation electric deposition paint composition | |
| CN1300209C (en) | Polyisocyanate composition having allophanate group and high-solid coating material | |
| CN1606578A (en) | Curable polyurethanes, coatings prepared therefrom, and method of making the same | |
| CN1086528A (en) | Reduced yellowing electrodepositable coating composition | |
| CN1047684A (en) | Waterborne coating compositions for automotive applications | |
| CN1891773A (en) | Method for making amine-modified epoxy resin and cationic electrodeposition coating composition | |
| CN1195680A (en) | Powder paints and its preparation and use | |
| CN1117979A (en) | Stable aqueous dispersive body of hydroxyleste fluoridated copolymer and acrylic copolymer and preparation and application as aqueous pait of same | |
| CN1977002A (en) | Method of stabilizing metal pigments against gassing | |
| CN1068309C (en) | Semicarbazide derivative and coating compsn. containing the derivative | |
| CN1268702C (en) | Cationic electrolytic deposition coating composition | |
| CN1077473A (en) | Water base paint compositions | |
| CN1106435A (en) | Cationic electrodeposition coating composition | |
| CN1608115A (en) | Aqueous coating compositions containing polyurethane-acrylic hybrid polymer dispersions | |
| CN1041839C (en) | Controllec film build epoxy coatings applied by cathodic electrodeposition | |
| CN87107861A (en) | Curing composition | |
| CN1066465C (en) | Modified epoxy resins having a blocked isocyanate moiety and a cationic group and their use in cathodic electrodeposition paints | |
| CN1162330A (en) | Electrodepositable coating composition having improved cure response | |
| CN1950416A (en) | Film-forming compositions substantially free of organic solvent, multi-layer composite coatings and related methods |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CX01 | Expiry of patent term |
Expiration termination date: 20150322 Granted publication date: 20010530 |